Survival and Sustainability: Environmental concerns in the 21st Century

Environmental Earth Sciences Series Editors James W. LaMoreaux P.E. LaMoreaux and Associates, Tuscaloosa, USA For fur...

Author: Hüseyin Gökçekus | Umut Türker | James W. LaMoreaux

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Environmental Earth Sciences

Series Editors James W. LaMoreaux P.E. LaMoreaux and Associates, Tuscaloosa, USA

For further volumes: http://www.springer.com/series/8394

Hüseyin Gökçeku¸s · Umut Türker · James W. LaMoreaux Editors

Survival and Sustainability Environmental Concerns in the 21st Century

123

Editors Prof. Dr. Hüseyin Gökçeku¸s Near East University Dept. Civil Engineering Nicosia, North Cyprus Mersin 10 Turkey [email protected]

Assoc. Prof. Dr. Umut Türker Near East University Dept. Civil Engineering Nicosia, North Cyprus Mersin 10 Turkey [email protected]

Prof. Dr. James W. LaMoreaux P.E. LaMoreaux and Associates 2612 University Blvd. Tuscaloosa AL 35403 USA [email protected]

ISBN 978-3-540-95990-8 e-ISBN 978-3-540-95991-5 DOI 10.1007/978-3-540-95991-5 Springer Heidelberg Dordrecht London New York Library of Congress Control Number: 2010925151 © Springer-Verlag Berlin Heidelberg 2011 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: Bauer, Thomas Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com)

Foreword

The International Conference on Environment: Survival and Sustainability, held at the Near East University, Nicosia, Northern Cyprus 19-24 February 2007, dealt with environmental threats and proposed solutions at all scales. The 21 themes addressed by the conference fell into four broad categories: Threats to Survival and Sustainability; Technological Advances towards Survival and Sustainability; Activities and Tools for Social Change; Defining Goals for Sustainable Societies. Activities and tools that move the society towards greater sustainability were emphasized at the conference. These included environmental law and ethics, environmental knowledge, technology and information systems, media, environmental awareness, education and lifelong learning, the use of literature for environmental awareness, the green factor in politics, international relations and environmental organizations. The breadth of the issues addressed at the conference made clear the need for greatly increased interdisciplinary and international collaboration in the survival and sustainability concept. The exchanges at the conference represent a step in this direction. It is hoped that this book will serve to contribute to increase in awareness towards various environmental issues as well as drawing more attention to the urgency of international cooperation and collaboration in pursuing sustainable environmental management.

Near East University, Nicosia North Cyprus

Prof. Dr. Hüseyin Gökçeku¸s

v

Contents

Part I

Conservation and Management of Biodiversity

Characterization of Serratia sp. K1RP-49 for Application to the Rhizoremediation of Heavy Metals . . . . . . . . . . . . . . . . . So-Yeon Koo and Kyung-Suk Cho

3

Predators in ‘Agri-environmental’ Sweden: Rural Heritage and Resistance Against Wolf Propagation . . . . . . . . . . . . . . . . . Annelie Sjölander-Lindqvist

15

Seas, Ecological Balance and Sustainable Environment. Heavy Metals in the Water of Lake Ohrid and in Fish Species Belbica – Alburnus alburnus alborella de Filippi . . . . . . . . . . . . . . Suzana Aliu, S. Jusufi, Majlinda Daci, and Shefket Dehari Space Analysis and the Detection of the Changes for the Follow-Up of the Components Sand-Vegetation in the Area of Mecheria, Algerie . . . . . . . . . . . . . . . . . . . . . . Haddouche Idriss, Mederbal Khaladi, and Saidi Slim Biodiversity and Actual Status of Narta and Dukati Lagoons in Albania . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Liljana Elmazi and Evelina Bazini Approximation of Sea Surface to Optimize Tide Gauge Network . . . . A.N. Vlasov, D.B. Volkov-Bogorodsky, V.A. Kurochkina, M.G. Mnushkin, and C.J. Blasi

29

37

51 61

Improvement of Germination of Three Endemic Species of the Sierra Nevada (S. Spain) . . . . . . . . . . . . . . . . . . . . . . . M. Díaz-Miguel, F. Serrano, and J.L. Rosúa

67

Early Growth of Quercus castaneifolia (C.A. Meyer) Seedlings as Affected by Weeding, Shading and Irrigation . . . . . . . . . . . . . Masoud Tabari, Javad Mirzaei, and Hadi Daroodi

75

vii

viii

Contents

The Role of Plant Diversity in Sustainable Exploitation in Highland Rangelands (Alborz Mountain – Iran) . . . . . . . . . . . . R. Safaian, H. Arzani, H. Azarnivand, and N. Safaian

85

Role of Indigenous People in Conservation of Biodiversity of Medicinal Plants: An Indian Case Study . . . . . . . . . . . . . . . . Pooja Joshi and Nilanjana Rao

91

Stand Structure and Spatial Patterns of Trees in Mixed Hyrcanian Beech Forest, Iran . . . . . . . . . . . . . . . . . . . . . . . . H. Habashi, S.M. Hosseini, R. Rahmani, and J. Mohammadi

103

Nutrient-Food Chain Modeling for Lake Prespa . . . . . . . . . . . . . Spiro Grazhdani and Spase Shumka

117

Tolerance of Different Wild Oats Biotypes to Different Oat Killers and Their Impact on Wheat . . . . . . . . . . . . . . . . . . . . Imtiaz Khan, Gul Hassan, Muhammad Ishfaq Khan, and Meher Gul

129

Effects of L-Proline and Cold Treatment on Pepper (Capsicum annuum L.) Anther Culture . . . . . . . . . . . . . . . . . . . . . . . . . Dudu Özkum and R. Tipirdamaz

137

Examination of Some Parameters for Ecological Growth of Maize in Pelic Vertisol . . . . . . . . . . . . . . . . . . . . . . . . . . I. Stoimenova, E. Djonova, A. Taleva, and N. Kaloyanova

145

Effect of Bacterial and Fungal Abundance in Soil on the Emission of Carbon Dioxide from Soil in Semi-arid Climate in India . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Rashmi Kant, Chirashree Ghosh, Lokendra Singh, and Neelam Tripathi Part II

151

Cultural Heritage and Environmental Factors

The Evaluation of Sustainability of Organic Farms in Tuscany . . . . . Chiara Certomà and Paola Migliorini Evaluation of the Sustainability on Cultural Heritage and Environmental Factors in Architecture from a Tourism Point of View: Ayvalik Historical City Center . . . . . . . . . . . . . . . Olcay Çetiner and Ay¸segül Çetiner Gökyilmaz Preserving the Mediterranean Landscape: The Role of Local Traditional Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Giovanni Quaranta and Caterina Salvia

165

179

187

Climate Change Critical to Cultural Heritage . . . . . . . . . . . . . . . P. Brimblecombe, C.M. Grossi, and I. Harris

195

Cultural Landscapes and Conservation Issues: Side Case . . . . . . . . Elmas Erdogan

207

Contents

ix

Survival of the Vernacular Environments in North Cyprus Through Sustainable Tourism Implementation . . . . . . . . . . . . . . Özlem Ogaç Türker

223

Environmental Basis of Sustainable Tourism Along Sensitive Coastal Areas – Principles and Applications . . . . . . . . . . . . . . . . D. Orhon, H. Gökçeku¸s, and Seval Sözen

235

Part III Economics, Development, Sustainability and Risks Medical Waste Survey in a University Hospital: Do Intern Doctors and Emergency Nurses Know and Pay Attention to Segregation of Wastes? . . . . . . . . . . . . . . . . . . . . . . . . . . F. Nur Aksakal, Evin Aras, Mustafa N. ˙Ilhan, and Sefer Aycan An Investigation of Appropriate Economic Instruments for Preventing the Negative Impacts of Construction Projects on the Environmental Utility . . . . . . . . . . . . . . . . . . . . . . . . Javad Jassbi, Fatemeh Razavian, and Hanieh Nikoomaram “Breaking Eco-limits” in Coal Mining in the Ústí Region in the Czech Republic: Possibilities, Decision-Making and Consequences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Iva Ritschelová, Miroslav Farský, and Egor Sidorov

245

253

267

Relationship Between Tourist Education and Development Perception About Environmental Impact of Tourism Development . . . R. Shakeri and A. Barati

279

Assessment of Dangerous Substances Release from Construction Products to Environment . . . . . . . . . . . . . . . . . . . . . . . . . . Nicoleta Schiopu, Emmanuel Jayr, Jacques Méhu, and Pierre Moszkowicz

289

Challenges of the Implementation of the WEEE Directive in the Danish Context . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chiara Gobbi

303

A Sustainable and Economically Recycling Real Estate Development Project: A Case Study for Istanbul Park . . . . . . . . . . H. Demir, F. Balik Sanli, M. Gur, and C. Goksel

315

Analysis of Land Use Changes in Nigeria: With Application of Integrated Bio-economic Spatial Model . . . . . . . . . . . . . . . . . Igbekele A. Ajibefun

329

Green Marketing Willingness of Bulgarian Market: Comparison with Italy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Teodoro Gallucci, Giovanni Lagioia, Julia Uzunova, and Vesselina Dimitrova

341

x

Contents

The Distribution of Carcinogenic Heavy Metals in Cyprus Soil . . . . . M. Ertan Akun, Rezan Fahrio˘glu Yamacı, Christophoros Charalambous, Savvas Lechtvich, and Mustafa B.A. Djamgoz

353

Biotechnology: A Powerful Tool for Human Survival and Sustainability Anwar Nasim

361

Ecotourism – Environment Relationship in Contemporary Eastern Europe Countries. Its Facts, Myths and Challenges. The Case of Albania and Macedonia . . . . . . . . . . . . . . . . . . . . Liljana Elmazi and Jovan Stojanoski Earthquake is Manmade Catastrophe Rather than a Natural Disaster: Turkey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Özgür Yilmazer, Özlem Yilmazer, Ali Özvan, Yasemin Leventeli, and Ilays Yilmazer Mitigation of Seismic Risk on Earthen Buildings . . . . . . . . . . . . . Marcial Blondet Land Use Conversion and Agricultural Intensification in Tropical Hill Slopes: A Geographical Approach . . . . . . . . . . . . David Lopez Cornelio

371

383

391

401

Part IV Energy and Development: New and Renewable Energy Role of Renewable Energy in Development of Self Sufficient Housing in Developing Countries . . . . . . . . . . . . . . . . . . . . . . Debashis Sanyal

425

Energy and Environmental Significance of an Alternative Fuels Utilization Produced with to Liquid Technology . . . . . . . . . . . . . Nenad Kukulj and Tomislav Kurevija

435

Sustainability Concept for Energy, Water and Environment Systems . . Naim Hamdia Afgan Energy and Sustainable Development: Environmental Impacts of Energy Use in Africa . . . . . . . . . . . . . . . . . . . . . . . . . . . Muawya Ahmed Hussein

447

471

Economizing the Energy Consumption in Circular Surface Aerator . . Achanta Ramakrishna Rao and Bimlesh Kumar

481

Sewage Biogas Conversion into Electricity by Using Small Systems . . . Suani Teixeira Coelho, Sílvia Maria Stortini González Velázquez, Osvaldo Stella Martins, and Fernando Castro de Abreu

491

Algae Biofuels as a Possible Alternative to Environmentally Doubtful Conventional Methods of Biodiesel Production . . . . . . . . . Tomislav Kurevija and Nenad Kukulj

499

Contents

xi

Investigation of Combustion Kinetics of Five Waste Wood Samples with Thermogravimetric Analysis . . . . . . . . . . . . . . . . Sema Yurdakul Yorulmaz and Aysel Atimtay

511

On Integration of Mirror Collector and Stirling Engine for Solar Power System . . . . . . . . . . . . . . . . . . . . . . . . . . . B.F. Yousif, Ammar Al-Shalabi, and Dirk G. Rilling

521

Part V

Environment and Health

Antioxidant Activities of Molokhia (Corchorus olitorius L.) Extracts . . Nilgün Öztürk and Filiz Savaro˘glu

535

Solid Medical Waste Management in Healthcare Centers in Palestine . Issam A. Al-Khatib, Mohamed Abu-Dayah, Hussein Hajjeh, and Tayseer Al-Shanbleh

545

Sustainable Indoor Air Quality (IAQ) in Hospital Buildings . . . . . . . Çi˘gdem Belgin Dikmen and Arzuhan Burcu Gültekin

557

The Regional Level of Microelements in the Food Materials . . . . . . . Aida Sahmurova, Gunay (Yildiz) Tore, Atakan Ongen, and Suna Ozden Celik

567

Microbiological Pollution Levels of Some Vegetable Specimens Taken From Public Markets of Three Central Towns of Konya-Turkey . K. Gur, H.N. Uçan, and S. ¸ Dursun

581

Assessment of Metal Pollution Based on Multivariate Statistical Modelling of Soils from Gediz and Buyuk Menderes Rivers . . . . . . . M. Bakaç and M.N. Kumru

591

A Commonly Used Pesticide Endosulfan in Diet Could Cause Hepatomegaly and Kidney Tumor When Combined with Nitrosamines Recai Ogur and Omer Faruk Tekbas

599

Effect of Different Time and Temperature of Various Cooking Methods on Sulfonamide Residues in Chicken Balls . . . . . . . . . . . M.R. Ismail-Fitry, S. Jinap, B. Jamilah, and A.A. Saleha

607

Reassessment of Tritium Dose Coefficients . . . . . . . . . . . . . . . . A. Melintescu, D. Galeriu, and H. Takeda Approaches on H5N1 Avian Influenza Spreading in Relation with Human Health Risk . . . . . . . . . . . . . . . . . . . . . . . . . . Monica Popa, Daniela Cur¸seu, Dana Sîrbu, Ioan Stoian, and Adriana Manciu The Relationship Between Infant Methemoglobinemia and Environmental Exposure to Nitrates . . . . . . . . . . . . . . . . . Daniela Cur¸seu, Dana Sîrbu, Monica Popa, and Alina Ionutas

615

623

635

xii

Contents

West Nile Virus: Risk Factors of Spreading, Prevention and Control Measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dana Sîrbu, Monica Popa, Daniela Cur¸seu, Ovidiu Ghiran, and Adriana Manciu The Determinants of Improved Water Supply for Rural Households in Kenya: A Differential Diagnosis Framework for Community Health . . . . . . . . . . . . . . . . . . . . . . . . . . . David W. Nerubucha Health Effects Due to Indoor Air Pollution . . . . . . . . . . . . . . . . John A. Hoskins

641

653 665

Part VI Environmental Awareness, Education and Ethics Promotion of Nursery School Teacher and Junior Grade Teacher Education for Environment and Sustainable Development in the Republic of Croatia According to the Concept of Lifelong Learning . . . . . . . . . . . . . . . . . . . . Vinka Uzelac and Dunja Andic

679

Spatial Analyses for Environmental Impacts of Landfill Areas . . . . . D.Z. Seker, S. Kaya, N. Musaoglu, H. Demirel, A. Tanik, and E. Sertel

691

The Ethical Basis of Environmental Law . . . . . . . . . . . . . . . . . Tapan Narayana

699

The Creation of New Ways of Acting in the Water Administration Field – the Implementation of the EU-WFD in Sweden . Petra Adolfsson

707

Education for “Sense of Place” in a Wide, Complex Land. A Challenge for Environmental Education . . . . . . . . . . . . . . . . Andrew Brookes

719

The Humanly Dimension of Media that Affects Masses and Various TV Programmes . . . . . . . . . . . . . . . . . . . . . . . . Arma˘gan Gökçearslan

729

Engaging the Public in Environmental Decisions: Strategies for Environmental Education and Communication . . . . . . . . . . . . Martha C. Monroe

741

Reconstruction of the Worldview as Strategy for Environmental Survival and Sustainability . . . . . . . . . . . . . . . . . . . . . . . . . Ibrahim Shogar

751

Public Participation in Environmental Decision-Making on Major Energy Projects in Turkey: The Case of BTC Crude Oil Pipeline Project . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nuriye Say and Deniz Babu¸s

759

Contents

xiii

From Human Social “Matrix” to Perception of Social Structures and Corporate Actors . . . . . . . . . . . . . . . . . . . . . . . . . . . . David Schnaiter

769

Negative Effects of Creating Environmental Awareness of Public Relations Applications by Alming of Political Propagandas . . . . . . . Emel Tozlu Aslan

777

Part VII Environmental Science and Technology Monitoring of Wetlands by Using Multitemporal Landsat Data; A Case Study from Fethiye – Turkey . . . . . . . . . . . . . . . . . . . . ˙I. Ozdemir, K. Ozkan, A. Mert, and S. Gülsoy Analyzing Changes in Coastal Biospheres using Remote Sensing and Geographic Information System Techniques, Northern Nile Delta, Egypt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . H. Effat, M.N. Hegazy, and H.El. Gameely Exploring the Egyptian Terrain Characteristics from Space for Strategic Planning . . . . . . . . . . . . . . . . . . . . . . . . . . . . M.N. Hegazy and H. Effat Composting and Solid Waste Management in Dhaka City . . . . . . . . Md. Niamul Bari, Md. Kumruzzaman, Mohammad Harun ur Rashid, and Md. Muzibur Rahman Assessment of Dissolved Pollutants in Krishna River Using Mass Balance Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . M. Chandra Sekhar and B. Shailamber Copper (II) Removal from Water by Natural Zeolites . . . . . . . . . . Sukru Dursun, M. Emin Argun, Nazan Celik, and Fatma Celebi

785

795

805 815

825 831

Biodegradation of 4-Chlorophenol in Biosurfactant Supplemented Activated Sludge . . . . . . . . . . . . . . . . . . . . . . Ayla Uysal and Aysen Turkman

841

Use of Silk Industry Waste – Silkworm Pupa: A Remediation of Environmental Pollution . . . . . . . . . . . . . . . . . . . . . . . . . B. Noroozi, S.H. Bahrami, and M. Arami

851

Using Susceptibility Measurements on Polluted Areas by Exhaust Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ali Aydin

861

Biowaste as a Resource for Bioproduct Development . . . . . . . . . . . J. Pieter H. van Wyk

875

xiv

Contents

Textile Azo Dyes Decolourization by Combined Ultrasonication and Microbial Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . H. Tu˘gba Gümü¸sdere, Tuba Artan, Afife Güvenç, Gönül Dönmez, and Ülkü Mehmeto˘glu

885

Identification of Wastewater Leaching into the Wells by HPLC-SEC Using UV and Fluorescence Detection . . . . . . . . . . Hilda Marta Szabo and Tuula Tuhkanen

893

Removal of Methylene Blue from Aqueous Solution Using Cotton Stalk: As a Bioadsorbent . . . . . . . . . . . . . . . . . . . . . . Murat Erta¸s, Bilal Acemio˘glu, M. Hakkı Alma, and Mustafa Usta

899

Removal of Cyanide from Solutions by Air Oxidation and Adsorption . Ersin Yener Yazici, Hacı Deveci, ˙Ibrahim Alp, Tu˘gba Yılmaz, and Oktay Celep

907

Effects of Various Backwash Scenarios on Membrane Fouling in a Membrane Bioreactor . . . . . . . . . . . . . . . . . . . . . . . . . N. Yigit, G. Civelekoglu, I. Harman, H. Köseo˘glu, and M. Kitis

917

NOx Formation of Co-combustion of Sweet Sorghum – Lignite (Orhaneli) Mixtures in Fluidised Beds . . . . . . . . . . . . . . . . . . . M. Handan Çubuk, Derya B. Özkan, and Özlem Emanet

931

Pretreatment of Ceftriaxone Formulation Effluents: Drawbacks and Benefits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . T. Tezgel, F. Germirli Babuna, I. Arslan-Alaton, G. Iskender, and O. Okay

943

Reducing the Toxicity and Recalcitrance of a Textile Xenobiotic Through Ozonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . F. Germirli Babuna, N. Oructut, I. Arslan-Alaton, G. Iskender, and O. Okay

955

Bioidentification of Xenobiotics in Water as a Part of Pollution Control Valerii Tonkopii

967

Biosorption of CR+6 from Aqueous Solution with Activated Sludge Biosolids (Ref. NO: MT11-OP-475) . . . . . . . . . . . . . . . . Aziz Sencan, ¸ H. Cahit Sevindir, Mehmet Kiliç, and Mustafa Karaboyaci

973

Effect of Chromium on Growth Attributes in Sunflower (Helianthus annuus L.) . . . . . . . . . . . . . . . . . . . . . . . . . . . M. Fozia Anjum, M. Anjum Zia, M. Ashraf, and Z.M. Khalid

985

Use of Surfactants in Soil and Groundwater Remediation . . . . . . . . Aras Gezer and Ahmet Karagunduz

995

Co-digestion Approaches to Organic Fraction of Municipal Solid Waste with Primary Sludge for a Municipal Treatment Plant in Turkey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005 R.K. Dereli, M.E. Ersahin, C.Y. Gomec, O. Ozdemir, and Izzet Ozturk

Contents

xv

Radiochronological Methods as Tools to Study Environmental Pollution 1015 H.N. Erten Are Certain Invertebrate Species Sensitive Bioindicators of the Air Pollution? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1023 Liliana Vasiliu-Oromulu, Viorica Honciuc, Sanda Maican, Cristina Munteanu, Minodora St˘anescu, Cristina Fiera, Mihaela Ion, and Dorina Purice Determination of Heavy Metal Pollution in Some Honey Samples from Yozgat Province, Turkey . . . . . . . . . . . . . . . . . . 1037 Ahmet Aksoy, Zeliha Leblebici, and Yavuz Ba˘gci Removal of Direct Orange-46 from Aqueous Solutions Using MN-Diatomite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1045 Selay Aksoy, Mesut Tekba¸s, Güleda Engin, and Nihal Bekta¸s Environmental Problems from the Open Dump in Gümü¸shane Province and Investigation of Biological Recycling for the Organic Solid Wastes . . . . . . . . . . . . . . . . . . . . . . . . 1055 S. Serkan Nas and Adem Bayram Adsorption Behavior of Radionuclides, 137 Cs and 140 Ba, onto Solid Humic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1065 O. Çelebi and H.N. Erten The Fate of Chlortetracycline During the Anaerobic Digestion of Manure from Medicated Calves . . . . . . . . . . . . . . . . . . . . . 1087 Osman A. Arikan Adsorption of Methylene Blue from Aqueous Solution onto Bentonite . 1097 J. Krsti´c, Z. Mojovi´c, A. Abu Rabi, D. Lonˇcarevi´c, N. Vukeli´c, and D. Jovanovi´c The Evaluation of the Pb(II) Removal Efficiency of Duckweed Lemna Minor (L.) from Aquatic Mediums at Different Conditions . . . 1107 Ya˘gmur Uysal and Fadime Taner Biodegradation of a Tannery and Chemical Plant Producing Asetilsalisilikat Wastewater Mixture . . . . . . . . . . . . . . . . . . . . 1117 E.U. Cokgor, O. Karahan, and D. Orhon Boron Removal in Seawater Desalination by Reverse Osmosis Membranes – the Impacts of Operating Conditions . . . . . . . . . . . 1127 H. Köseo˘glu, N. Kabay, M. Yüksel, S. Sarp, Ö. Arar, and M. Kitis Respirometric Evaluation of Strong Wastewater Activated Sludge Treatment for a Complex Chemical Industry . . . . . . . . . . . 1139 E. Ubay Cokgor, G. Insel, E. Aydın, S. Ozdemir, and D. Orhon

xvi

Contents

Cellulose Acetate-Polyethersulfone (CA-PS) Blend Ultrafiltration Membranes for Palm Oil Mill Effluent Treatment . . . . 1149 Ani Idris and Iqbal Ahmad Rehabilitation of Wastewater Treatment Plant of Sakhnin City in Israel by Using Advanced Technologies . . . . . . . . . . . . . . . . . 1161 Yasar Avsar, Hussein Tarabeah, Shlomo Kimchie, Izzet Ozturk, and Hadi Naamneh Removal of Mn(II) Ions from the Aqueous Solutions by Cotton Boll . . 1171 H. Duygu Ozsoy and Halil Kumbur Optimization of Electrochemical Oxidation of Textile Dye Wastewater Using Response Surface Methodology (RSM) . . . . . . . . 1181 Bahadır K. Körbahti Dynamic Modelling of Bioconversion of Domestic Wastewater Sludge for Cellulase Enzyme . . . . . . . . . . . . . . . . . . . . . . . . 1193 N.A. Kabbashi, Md. Zahangir Alam, and Khadijah B. Abdul Rahim Treatment of H-Acid Containing Wastewater by Wet Peroxide Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1203 Zhao Binxia, Li Hongya, Wang Jin, Bai Weili, Zhang Xiaoli, and Jin Qiting Ambient Ozone Levels in the Eastern Mediterranean Region and Assessment of Its Effect on the Forested Mountain Areas of Southern Turkey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1213 Evrim Akkoyunlu, Rukiye Tipirdamaz, Saime Ba¸saran, Halil Sariba¸sak, Dudu Özkum, and Gülen Güllü Physico-chemical Study of Bagasse and Bagasse Ash from the Sugar Industries of NWFP Pakistan and Remediation of Environmental Problems Caused by Refused Bagasse Ash . . . . . . 1225 Khurshid Ali, Noor-ul-Amin, Tahir Shah, and Saeed-ur-Rehman Adsorption of Different Reactive Dyes onto Surfactant-Modified Zeolite: Kinetic and Equilibrium Modeling . . . . . . . . . . . . . . . . 1237 Bulent Armagan, Mustafa Turan, and Dogan Karadag Water Quality Index for Municipal Water Supply of Attock City, Punjab, Pakistan . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1255 Humera Qasim Khan Reaction Kinetics of Spent Reactive Dye Bath Ozonation Process . . . . 1263 T. Ölmez, I. Kabda¸slı, and O. Tünay Copper Adsorption from Aqueous Solutions by Usıng Red Mud – An Aluminium Industry Waste . . . . . . . . . . . . . . . . . . . 1275 Semra Çoruh and Osman Nuri Ergun Global Warming: How Much of a Threat to Tropical Forests? . . . . . . 1283 Philip M. Fearnside

Contents

xvii

The European Sea Level Service Information System for Coastal Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1293 Christoph J. Blasi A Review on the Impact of the North Sea – Caspian Pattern (NCP) on Temperature and Precipitation Regimes in the Middle East . 1301 H. Kutiel Wave Damping and Retardance by Emergent Vegeatation . . . . . . . . 1313 Oral Ya˘gci, Umut Türker, and M. Sedat Kabda¸sli The Effect of Sludge History on Aerobic Sludge Stabilization Efficiency G. Insel, H. Gökçeku¸s, S. Sözen, E. Dulekgurgen and D. Orhon

1321

Morphological and Physiological Features of an Aerobic Granular EBPR Biomass Fed with Propionate . . . . . . . . . . . . . . 1327 Ebru Dulekgurgen, Nazik Artan and Derin Orhon Part VIII Integrated Water Resources Management Water Quality Variation in a Tank Cascade Irrigation System: A Case Study from Malagane Cascade, Sri Lanka . . . . . . . . . . . . 1345 Kushani Mahatantila, Rohana Chandrajith, H.A.H. Jayasena, and Sampath Marasinghe Investigation of Flood Event Possibility over Iran Using Flood Index . . 1355 Kazem Nosrati, Mohsen Mohseni Saravi, and Afsaneh Shahbazi Analysis of First-Flush Load from Urban Catchment in Isfahan, Iran . 1363 Afsaneh Shahbazi, Kazem Nosrati, and Mohsen Mohseni Saravi Assesment of Ecological Flow for Mountain Rivers of the Kura Basin . 1369 Rovshan Abbasov Effictiveness of Water Resources Use in Aral Sea Basin and Lower Reaches of the Amu Darya River . . . . . . . . . . . . . . . 1381 M. Ikramova, A. Khodjiev, and K. Misirkhonov Uncertainties in the Water Budget Computations of Develi Closed Basin in Turkey . . . . . . . . . . . . . . . . . . . . . . . . . . . 1397 Ibrahim Gurer and F. Ebru Yildiz Impacts Assessment of Newly Constructed Highways via Spatial Information Sciences . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1409 H. Demirel, M. Çetin, and N. Musaoglu Water Resources in the Slovak Republic and Their Protection . . . . . 1421 Jozef Kriš, Faško Martin, and Škultétyová Ivona E-Waste Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1433 Santosh M. Avvannavar, Ravi Kiran Mutnuru, and S. Shrihari

xviii

Contents

Extreme Rainfall Events and Uncertainty in the Mediterranean Basin . 1439 Hadas Reiser and Haim Kutiel Part IX Pesticides in the Environment and Food Commodities An Investigation of Pesticide Transport in Soil and Groundwater in the Most Vulnerable Site of Bangladesh . . . . . . . . . . . . . . . . . 1451 Anika Yunus and A.H.M. Faisal Anwar Conservation of Beneficial Insects for Sustainable Agriculture . . . . . 1463 M. Anjum Suhail, M. Arshad, Jalal Arif, and M. Dildar Gogi Organochlorine Pesticides in Soil and Sediment from an Urban Zone of Novi Sad, Serbia . . . . . . . . . . . . . . . . . . . . . . . . . . 1469 Nataša Ðuriši´c-Mladenovi´c, Biljana Škrbi´c, and Jelena Cvejanov Conversion of Agricultural Wastes into Value Added Product with High Protein Content by Growing Pleurotus ostreatus . . . . . . . 1483 Ahmad Al-Momany and Kholoud Ananbeh Plants as a Source of Biopesticides for Pest Control: A New Perspective E. Hassan and D. Prijono

1491

Study of Some Factors of Variation of intake on Course by Dairy Ewes T. Najar, Aziza-Guesmi Boubaker, A. Rigueiro-Rodríguez, and M.R Mosquera-Losada

1501

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1509

Contributors

Rovshan Abbasov Hydrometeorolgy Scientific Research Institute (HSRI) A2 1073, Baku, B. Agayev St. 100(A), Azerbaijan, [email protected] Fernando Castro de Abreu CENBIO – Brazilian Reference Center on Biomass, IEE – Institute of Electrotechnics and Energy, USP – University of São Paulo, Av. Prof. Luciano Gualberto, 1289 CEP 05508-010, São Paulo, Brazil, [email protected] Mohamed Abu-Dayah Institute of Community and Public Health, Birzeit University, Nir Zeit, Palestine, [email protected] Bilal Acemio˘glu Department of Chemistry, Faculty of Arts and Science, University of Kahramanmaras Sutcu Imam, Kahramanmaras 46100, Turkey, [email protected] Petra Adolfsson GRI, School of Business, Economics and Law, Göteborg University, Göteborg, Sweden, [email protected] Naim Hamdia Afgan Instituto Superior Tecnico, Lisbon, Portugal, [email protected] Iqbal Ahmad Faculty of Chemical and Natural Resources Engineering, Department of Bioprocess Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia, [email protected] Igbekele A. Ajibefun Department of Agricultural Economics and Extension, Federal University of Technology, Akure, Nigeria, [email protected] Evrim Akkoyunlu Department of Environmental Engineering, Hacettepe University, 06532 Ankara, Turkey, [email protected] F. Nur Aksakal Department of Public Health, Gazi University, Ankara, Turkey, [email protected] Ahmet Aksoy Faculty of Art and Science, Department of Biology, Erciyes University, 38039 Kayseri, Turkey, [email protected]

xix

xx

Contributors

Selay Aksoy Environmental Engineering Department, Gebze Institute of Technology, 41400, Gebze, Turkey, [email protected] M. Ertan Akun Chairman, Department of Industrial Engineering, Cyprus International University, Haspolat, North Cyprus, [email protected] Md. Zahangir Alam Bioenvironmental Engineering Research Unit (BERU), Department of Biotechnology Engineering, International Islamic University, Kuala Lumpur 50728, Malaysia, [email protected] Khurshid Ali Institute of Chemical Science, University of Peshawar, Peshawar, Pakistan, [email protected] Suzana Aliu Study of Polytechnic Center, State University of Tetovo, Tetovo, Macedonia, [email protected] Issam A. Al-Khatib Institute of Community and Public Health and Faculty of Engineering, Birzeit University, Ramallah, Palestine, [email protected] M. Hakkı Alma Department of Industrial Engineering of Forestry, Faculty of Forestry, University of Kahramanmaras Sutcu Imam, Kahramanmaras, 46100, Turkey, [email protected] Ahmad Al-Momany Faculty of Agriculture, University of Jordan, Amman, Jordan, [email protected] ˙ Ibrahim Alp Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon, Turkey, [email protected] Ammar Al-Shalabi Faculty of Engineering and Technology, Malacca Campus, Multimedia University, 75450 MMU, Malacca, Malaysia, [email protected] Tayseer Al-Shanbleh Faculty of Engineering, Near East University, Nicosia, Turkish Republic of Northern Cyprus, [email protected] Kholoud Ananbeh Faculty of Agriculture, University of Jordan, Amman, Jordan, [email protected] Dunja Andic Faculty of Teacher Education, University of Rijeka, Trg Ivana Klobuˇcari´ca 1, 51 000 Rijeka, Croatia, [email protected] M. Fozia Anjum Department of Botany, University of Agriculture, Faisalabad, Pakistan, [email protected] A.H.M. Faisal Anwar Department of Water Resources Engineering, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh, [email protected] M. Arami Textile Engineering Department, Amirkabir University of Technology, Tehran, Iran, [email protected]

Contributors

xxi

Ö. Arar Department of Chemistry, Ege University, 35100 Izmir, Turkey, [email protected] Evin Aras Department of Public Health, Resident, Gazi University, Ankara, Turkey, [email protected] M. Emin Argun Department of Environmental Engineering, Engineering Faculty, Selcuk University, Konya, Turkey, [email protected] Osman A. Arikan Department of Environmental Engineering, Istanbul Technical University, Istanbul 34469, Turkey, [email protected] Bulent Armagan Environmental Engineering Department, Engineering Faculty, Harran University, 63300 Sanlıurfa, Turkey, [email protected] M. Arshad Department of Agricultural Entomology, Insect Biodiversity and Biosystematics Research Laboratory, University of Agriculture, Faisalabad, Pakistan, [email protected] I. Arslan-Alaton Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] Nazik Artan Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, Maslak, Istanbul 34469, Turkey, [email protected] Tuba Artan Biology Department, Faculty of Science, Ankara University, Tando˘gan, 06100 Ankara, Turkey, [email protected] H. Arzani Faculty of Natural Resources, University of Tehran, Tehran, Iran, [email protected] M. Ashraf Department of Botany, University of Agriculture, Faisalabad, Pakistan, [email protected] Emel Tozlu Aslan Faculty of Communication, Near East University, T.R.N.C – Nicosia, Cyprus, [email protected]; [email protected] Aysel Atimtay Department of Environmental Engineering, Middle East Technical University (METU), 06531 Ankara, Turkey, [email protected] Yasar Avsar Faculty of Civil Engineering, Department of Environmental Engineering, Yildiz Technical University, Istanbul, Turkey, [email protected] Santosh M. Avvannavar Department of Chemical Engineering, Technische Universiteit, Eindhoven, The Netherlands, [email protected] Sefer Aycan Department of Public Health, Gazi University, Ankara, Turkey, [email protected] Ali Aydin Geophysical Engineering Department, Engineering Faculty, Pamukkale University, 20017 Kınıklı, Denizli, Turkey, [email protected]

xxii

Contributors

E. Aydın Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] Ay¸segül Çetiner Gökyilmaz AB Mimarlık, Necip Bey Sitesi Ku¸sadası, Aydin, [email protected] H. Azarnivand Faculty of Natural Resources, University of Tehran, Tehran, Iran, [email protected] F. Germirli Babuna Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] Deniz Babu¸s Department of Landscape Architecture, Çukurova University, 01330 Balcalı, Adana, Turkey, [email protected] Yavuz Ba˘gci Department of Biology, Faculty of Art and Science, Selçuk University, Konya, Turkey, [email protected]; [email protected] S.H. Bahrami Textile Engineering Department, Amirkabir University of Technology, Tehran, Iran, [email protected] M. Bakaç Buca Faculty of Education, Department of Physics, Dokuz Eylul University, Buca – Izmir, Turkey, [email protected] A. Barati Natural resources faculty, Malayer University, Malayer, Iran, [email protected] Md. Niamul Bari Department of Civil Engineering, Rajshahi University of Engineering and Technology, Rajshahi, Bangladesh, [email protected] Saime Ba¸saran Ministry of Environment and Forestry, West Mediterranean Research Institude, Antalya, Turkey, [email protected] Adem Bayram Department of Civil Engineering, Engineering Faculty, Karadeniz Technical University, 61080 Trabzon, Turkey, [email protected] Evelina Bazini Marketing and Tourism Department, Faculty of Commerce, University of Vlora, Vlora, Albania, [email protected]; [email protected] Nihal Bekta¸s Environmental Engineering Department, Gebze Institute of Technology, 41400, Gebze, Turkey, [email protected] Zhao Binxia College of Chemical Engineering, Northwest University, Taibai North Road No.229, Xi’an, 710069, People’s Republic of China, [email protected] C.J. Blasi Federal Institute of Hydrology, D-56002 Koblenz, Germany, [email protected] Marcial Blondet Catholic University of Peru, Lima, Peru, [email protected] Aziza-Guesmi Boubaker Institut National Agronomique de Tunis, 42, Av Charles Nicolle, 1082 Tunis, Tunis, [email protected]

Contributors

xxiii

P. Brimblecombe School of Environmental Sciences, University of East Anglia, Norwich, UK, [email protected] Andrew Brookes La Trobe University, Bendigo, VIC 3086, Australia, [email protected] Fatma Celebi Department of Environmental Engineering, Engineering Faculty, Selcuk University, Konya, Turkey, [email protected] O. Çelebi Department of Chemistry, Bilkent University, 06800 Bilkent, Ankara, Turkey, [email protected] Oktay Celep Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon, Turkey, [email protected] Nazan Celik Department of Environmental Engineering, Engineering Faculty, Selcuk University, Konya, Turkey, [email protected]; [email protected] Suna Ozden Celik Environmental Engineering Department, Corlu Engineering Faculty, Trakya University, 59860 Corlu-Tekirdag, Turkey, [email protected] Chiara Certomà Scuola Superiore Sant’Anna, Piazza Martiri della Libertà 33, 56127 Pisa, Italy, [email protected] M. Çetin Department of Geodesy and Photogrammetry Engineering, Gebze Institute of Technology, Muallimköy 41400, Gebze Kocaeli, Turkey, [email protected] Olcay Çetiner Department of Architecture, Yildiz Technical University, Barboros str., 34349 Besiktas, Istanbul, Turkey, [email protected]; [email protected] Rohana Chandrajith Department of Geology, University of Peradeniya, Peradeniya, Sri Lanka, [email protected] Christophoros Charalambous Frederick Institute of Technology, Nicosia, Cyprus, [email protected] Kyung-Suk Cho Department of Environmental Science and Engineering, Ewha Womans University, Seoul 120-750, Republic of Korea, [email protected] A. S. Çıggın Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, Istanbul, Turkey, [email protected] G. Civelekoglu Department of Environmental Engineering, Suleyman Demirel University, Isparta, Turkey, [email protected]; [email protected] Suani Teixeira Coelho CENBIO – Brazilian Reference Center on Biomass, IEE – Institute of Electrotechnics and Energy, USP – University of São Paulo, Av. Prof. Luciano Gualberto, 1289 CEP 05508-010, São Paulo, Brazil, [email protected]

xxiv

Contributors

E. Ubay Cokgor Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] David Lopez Cornelio Correo central de Huanuco, Huanuco, Peru, [email protected]; [email protected] Semra Çoruh Department of Environmental Engineering, Ondokuz Mayıs University, 55139 Samsun, Turkey, [email protected] M. Handan Çubuk Mechanical Engineering Faculty, Heat and Thermodynamics Division, Yıldız Technical University, 80750 Yıldız, Istanbul, Turkey, [email protected] Daniela Cur¸seu Environmental Health Department, University of Medicine and Pharmacy, Cluj Napoca, Romania, [email protected] Jelena Cvejanov Faculty of Technology, University of Novi Sad, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia, [email protected] Majlinda Daci Department of Chemistry, University of Prishtina, Prishtina, Kosova, [email protected] Hadi Daroodi Faculty of Natural Resources and Marine Siences, Tarbiat Modares University, Noor, Iran, [email protected] Shefket Dehari Study of Polytechnic Center, State University of Tetovo, Tetovo, Macedonia, [email protected] H. Demir Department of Geodesy and Photogrammetry Engineering, Yildiz Technical University, 34349-Besiktas Istanbul, Turkey, [email protected]; [email protected]; [email protected] H. Demirel Faculty of Civil Engineering, Geodesy and Photogrammetry Engineering Department, Istanbul Technical University, 34469 Maslak Istanbul, Turkey, [email protected] R.K. Dereli Department of Environmental Engineering, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey, [email protected] Hacı Deveci Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon, Turkey, [email protected] M. Díaz-Miguel Departamento de Fisiología Vegetal, Facultad de Ciencias, Universidad de Granada, Edificio Politécnico, Campus Fuentenueva s/n, 18071 Granada, Spain, [email protected] Çi˘gdem Belgin Dikmen Engineering and Architecture Faculty, Bozok University, Yozgat, Turkey, [email protected]

Contributors

xxv

Vesselina Dimitrova Department of International Economic Relations, University of Economics Varna, 77, Kniaz Boris I blv., Varna 9002, Bulgaria, [email protected] Mustafa B.A Djamgoz Imperial College of Science, Technology and Medicine, London, UK, [email protected] E. Djonova Department of Soil Microbiology, N. Poushkarov Institute of Soil Science, 7 Shosse Bankya Str., 1080, Bulgaria, [email protected] Gönül Dönmez Biology Department, Faculty of Science, Ankara University, Tando˘gan, 06100 Ankara, Turkey, [email protected] Ebru Dulekgurgen Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey, [email protected] Nataša Ðuriši´c-Mladenovi´c Faculty of Technology, University of Novi Sad, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia, [email protected] M. Sukru Dursun Department of Environmental Engineering, Engineering Faculty, Selcuk University, Konya, Turkey, [email protected] H. Effat The National Authority of Remote Sensing and Space Science (NARSS), Cairo, Egypt, [email protected] Liljana Elmazi Faculty of Economics, University of Tirana, Tirana, Albania, [email protected] Özlem Emanet Mechanical Engineering Faculty, Heat and Thermodynamics Division, Yıldız Technical University, 80750 Yıldız, Istanbul, Turkey, [email protected] Güleda Engin Environmental Engineering Department, Gebze Institute of Technology, 41400, Gebze, Turkey, [email protected] Elmas Erdogan Department of Landscape Architecture, Faculty of Agriculture, Ankara University, Di¸skapi, Ankara 06110, Turkey, [email protected] Osman Nuri Ergun Department of Environmental Engineering, Ondokuz Mayıs University, 55139 Samsun, Turkey, [email protected] M.E. Ersahin Department of Environmental Engineering, Gebze Institute of Technology, Gebze/Kocaeli, 41400, Turkey, [email protected] Murat Erta¸s Department of Industrial Engineering of Forestry, Faculty of Forestry, University of Kahramanmaras Sutcu Imam, Kahramanmaras, 46100, Turkey, [email protected] H.N. Erten Department of Chemistry, Bilkent University, 06800 Ankara, Turkey, [email protected]

xxvi

Contributors

Miroslav Farský Faculty of Environmental Studies, University of Jan Evangelista Purkyne, Usti nad Labem, Czech Republic, [email protected] Philip M. Fearnside National Institute for Reseach in Amazonia (INPA), C.P. 478, 69.011-970 Manaus-Amazonas, Brazil, [email protected] Cristina Fiera Institute of Biology, Romanian Academy, 296 Splaiul Independentei, Po Box 56–53, 060031 Bucharest, Romania, [email protected] D. Galeriu Department of Life and Environmental Sciences, Horia Hulubei National Institute of R&D for Physics and Nuclear Engineering, 407 Atomistilor St., PO Box MG-6, RO-077125 Bucharest – Magurele, Romania, [email protected]; [email protected] Teodoro Gallucci Department of Geographical and Commodity Science, Section of Commodity Science and Ecology, University of Barivia C. Rosalba, 53, I-70124 Bari, Italy, [email protected] H.El. Gameely The National Authority of Remote Sensing and Space Science,(NARSS), Cairo, Egypt, [email protected] Aras Gezer Department of Environmental Engineering, Gebze Institute of Technology, Gebze/Kocaeli, 41400, Turkey, [email protected] Ovidiu Ghiran IPA S.A. R&D Institute, Cluj Subsidiary, Romania, [email protected] Chirashree Ghosh Centre of Environmental Management of Degraded Ecosystem (CEMDE), University of Delhi, New Delhi 11007, India, [email protected] Chiara Gobbi Department of Industrial Management and Engineering, Technical University of Denmark, DTU Building 423, 2800 Lyngby, Denmark, [email protected] M. Dildar Gogi Department of Agricultural Entomology, Insect Biodiversity and Biosystematics Research Laboratory, University of Agriculture, Faisalabad, Pakistan, [email protected]; [email protected] Arma˘gan Gökçearslan Department of Graphics, Hacettepe University, Beytepe, Ankara, Turkey, [email protected] H. Gökçeku¸s Department of Civil Engineering, Near East University, Nicosia, Turkish Republic of Northern Cyprus, [email protected] C. Goksel Department of Geodesy and Photogrammetry Engineering, Istanbul Technical University, 34469-Maslak Istanbul, Turkey, [email protected] C.Y. Gomec Department of Environmental Engineering, Istanbul Technical University, 34469-Maslak, Istanbul, Turkey, [email protected]

Contributors

xxvii

Spiro Grazhdani Agricultural University of Tirana, Tirana, Albania, [email protected] C.M. Grossi School of Environmental Sciences, University of East Anglia, Norwich, UK, [email protected] Meher Gul Pakistan Sport Board, Islamabad, Pakistan, [email protected] Gülen Güllü Department of Environmental Engineering, Hacettepe University, 06532 Ankara, Turkey, [email protected] S. Gülsoy, Faculty of Forestry Department of Soil Science and Ecology, Suleyman Demirel University, Isparta, Turkey, [email protected] Arzuhan Burcu Gültekin Faculty of Technical Education, Gazi University, Ankara, Turkey, [email protected] H. Tu˘gba Gümü¸sdere Chemical Engineering Department, Faculty of Engineering, Ankara University, Tando˘gan, 06100 Ankara, Turkey, [email protected] K. Gur Environmental Engineering Department, Selcuk University, Konya, Turkey, [email protected] M. Gur Department of Geodesy and Photogrammetry Engineering, Yildiz Technical University, 34349-Besiktas Istanbul, Turkey, [email protected]; [email protected]; [email protected] Ibrahim Gurer Engineering and Architecture Faculty, Civil Engineering Department, Gazi University, Celal Bayar Bulvari Maltepe, Ankara, Turkey, [email protected] Afife Güvenç Chemical Engineering Department, Faculty of Engineering, Ankara University, Tando˘gan, 06100 Ankara, Turkey, [email protected] H. Habashi Natural Resources Faculty, Tarbiat Modarres University, P.O. Box 46414-356 Noor, Mazandaran, Iran, [email protected] Hussein Hajjeh Institute of Community and Public Health, Birzeit University, Birzeit, Palestine, [email protected] I. Harman Department of Environmental Engineering, Suleyman Demirel University, Isparta, Turkey, [email protected] I. Harris Climate Research Unit, School of Environmental Sciences, University of East Anglia, Norwich, UK, [email protected] E. Hassan Integrated Crop Management, School of Agronomy and Horticulture, University of Queensland, GATTON 4343 QLD, Australia, [email protected] Gul Hassan Department of Weed Science, Faculty of Crop Protection, NWFP Agricultural University, Peshawar 25130, Pakistan, [email protected]

xxviii

Contributors

M.N. Hegazy The National Authority of Remote Sensing and Space Science (NARSS), Cairo, Egypt, [email protected] Viorica Honciuc Ecology Taxonomy and Nature Conservation Centre, Institute of Biology Splaiul Independentei, 060031 Bucharest, Romania [email protected] Li Hongya College of Chemical Engineering, Northwest University, Xi’an, Shaanxi 710069, China John A. Hoskins Independent Toxicologist, Haslemere, Surrey GU27 2 JH, UK, [email protected] S.M. Hosseini Natural Resources Faculty, Tarbiat Modarres University, Tehran, Iran, [email protected] Muawya Ahmed Hussein University of Dhofar, Salalah, Oman, [email protected] Ani Idris Faculty of Chemical and Natural Resources Engineering, Department of Bioprocess Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia, [email protected] Haddouche Idriss Département de Foresterie, Faculté des Sciences, Université de Tlemcen BP 119, Tlemcen 13000, Algeria, [email protected] ˙ Mustafa N. Ilhan Department of Public Health, Gazi University, Ankara, Turkey, [email protected]; [email protected] M. Ikramova Central Asian Research Institute of Irrigation (SANIIRI), Karasu-4, 11, Tashkent 700187, Uzbekistan, [email protected] G. Insel Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] Mihaela Ion Romanian Academy Institute of Biology, Buila-Vânturarita National Park Administration, Romania, [email protected] Alina Ionutas Environmental Health Department, University of Medicine and Pharmacy, Cluj Napoca, Romania, [email protected] G. Iskender Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] M.R. Ismail-Fitry Faculty of Food Science and Technology, University of Putra Malaysia, [email protected] Škultétyová Ivona Faculty of Civil Engineering, Department of Sanitary and Environmental Engineering, Slovak University of Technology Bratislava, Radlinského 11, 813 68 Bratislava, Slovak Republic, [email protected] B. Jamilah Faculty of Food Science and Biotechnology, Universiti Pertanian Malaysia, 43400 UPM, Serangor, Malaysia, [email protected]

Contributors

xxix

Javad Jassbi Department of Industrial Management, Faculty of Management and Economy, Islamic Azad University, Science and Research Campus, Tehran, Iran, [email protected] H.A.H. Jayasena Department of Geology, University of Peradeniya, Peradeniya, Sri Lanka, [email protected] Emmanuel Jayr Sustainable Development Department, CSTB – Scientific and Technical Centre for the Building Industry, 24, rue Joseph Fourier, 38400 Saint Martin d’Hères, France, [email protected] Wang Jin College of Chemical Engineering, Northwest University, Xi’an 710069, People’s Republic of China, [email protected] S. Jinap Centre of Excellence for Food Safety Research (CEFSR), Faculty of food Science and Technology, Universiti Puta Malaysia, 43400 UPM, Selangor, Malaysia, [email protected] Pooja Joshi The Energy Resource Institute, New Delhi, India, [email protected] D. Jovanovi´c Department for Catalysis and Chemical Engineering, ICTM, Njegoševa12, 11000 Belgrade, Republic of Serbia, [email protected] S. Jusufi Department of Chemistry, University of Prishtina, Prishtina, Kosova, [email protected] N. Kabay Department of Chemical Engineering, Ege University, 35100 Izmir, Turkey, [email protected] N.A. Kabbashi Bioenvironmental Engineering Research Unit (BERU), Department of Biotechnology Engineering, International Islamic University, Kuala Lumpur 50728, Malaysia, [email protected] I. Kabda¸slı Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, Ayaza˘ga Kampüsü, 34469, Maslak, Istanbul, Turkey, [email protected] M. Sedat Kabda¸slı Civil Engineering Faculty, Division of Hydraulics, Istanbul Technical University, Maslak, Istanbul 34469, Turkey, [email protected] N. Kaloyanova Department of Soil Microbiology, N. Poushkarov Institute of Soil Science, 7 Shosse Bankya Str., 1080, Bulgaria, [email protected] Rashmi Kant Yamuna Biodiversity Park, School of Environmental Studies, University of Delhi, New Delhi 110007, India, [email protected] Mustafa Karaboyaci Department of Civil Engineering, Faculty of Engineering, University of Süleyman Demirel, Turkey, [email protected] Dogan Karadag Enviromental Engineering Department, Yildiz Technical University, 34669 Istanbul, Turkey, [email protected]

xxx

Contributors

Ahmet Karagunduz Department of Environmental Engineering, Gebze Institute of Technology, Gebze, Kocaeli 41400, Turkey, [email protected] O. Karahan Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] S. Kaya Civil Engineering Faculty, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey Z.M. Khalid National Institute for Biotechnology and Genetic Engineering, Faisalabad, Pakistan, [email protected] Mederbal Khaladi Centre universitaire de Mascara, 29000 Mascara, Algérie, [email protected] Imtiaz Khan Department of Weed Science, Faculty of Crop Protection, NWFP Agricultural University, Peshawar 25130, Pakistan, [email protected] Humera Qasim Khan National Center of Excellence in Geology, University of Peshawar, Peshawar, Pakistan, [email protected] Muhammad Ishfaq Khan Department of Weed Science, Faculty of Crop Protection, NWFP Agricultural University, Peshawar 25130, Pakistan, [email protected] A. Khodjiev Central Asian Research Institute of Irrigation (SANIIRI), Karasu-4, 11, Tashkent 700187, Uzbekistan, [email protected] Mehmet Kiliç Department of Civil Engineering, Faculty of Engineering, University of Süleyman Demirel, Turkey, [email protected] Shlomo Kimchie Department of Environmental and Water Resources Engineering, Faculty of Civil Engineering, Technion Institute for Research and Development, Technion City, Haifa, Israel, [email protected] M. Kitis Department of Environmental Engineering, Suleyman Demirel University, Isparta, Turkey, [email protected] So-Yeon Koo Department of Environmental Science and Engineering, Ewha Womans University, Seoul 120-750, Republic of Korea, [email protected] Bahadır K. Körbahti Faculty of Engineering, Chemical Engineering Department, University of Mersin, Çiftlikköy, 33343 Mersin, Turkey, [email protected] H. Köseo˘glu Department of Environmental Engineering, Suleyman Demirel University, Isparta, Turkey, [email protected] Jozef Kriš Department of Sanitary and Environmental Engineering, Faculty of Civil Engineering, Slovak University of Technology Bratislava, Radlinského 11, 813 68 Bratislava, Slovak Republic, [email protected] J. Krsti´c Department for Catalysis and Chemical Engineering, ICTM, Njegoševa12, 11000 Belgrade, Republic of Serbia, [email protected]

Contributors

xxxi

Nenad Kukulj Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Pierottijeva 6, Zagreb, Croatia, [email protected] Bimlesh Kumar Department of Civil Engineering, Indian Institute of Science, Bangalore, India, [email protected] Halil Kumbur Department of Environmental Engineering, Engineering Faculty, Mersin University, Mersin 33360, Turkey, [email protected] M.N. Kumru Institute of Nuclear Sciences, Ege University, Bornova-˙Izmir, Turkey, [email protected] Md. Kumruzzaman Department of Civil Engineering, Rajshahi University of Engineering & Technology, Rajshahi, Bangladesh, [email protected] Tomislav Kurevija Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Pierottijeva 6, Zagreb, Croatia, [email protected] V.A. Kurochkina Moscow State University of Civil Engineering, Moscow, Russia, [email protected] H. Kutiel Laboratory of Climatology, Department of Geography and Environmental Studies, University of Haifa, Haifa 31905, Israel, [email protected] Giovanni Lagioia Department of Geographical and Commodity Science, Section of Commodity Science and Ecology, University of Bari, via C. Rosalba, 53, I-70124 Bari, Italy, [email protected] Zeliha Leblebici Faculty of Art and Science, Department of Biology, Erciyes University, 38039 Kayseri, Turkey, [email protected] Savvas Lechtvich Frederick Institute of Technology, Nicosia, Cyprus Yasemin Leventeli Yilmazer Education, 8. Cd., 89. Sk., 9/8, 06460 A.Ovecler, Ankara, Turkey, [email protected] D. Lonˇcarevi´c Department for Catalysis and Chemical Engineering, ICTM, Njegoševa12, 11000 Belgrade, Republic of Serbia, [email protected] Kushani Mahatantila Department of Geology, University of Peradeniya, Peradeniya, Sri Lanka, [email protected] Sanda Maican Academic Românã, Institutl de Biologie Spl. Independentei nr.296, 060031 Bucureti, România, [email protected] Adriana Manciu IPA S.A. R&D Institute, Cluj Subsidiary, Romania, [email protected] Sampath Marasinghe Department of Geology, University of Peradeniya, Peradeniya, Sri Lanka, [email protected]

xxxii

Contributors

Faško Martin Faculty of Civil Engineering, Department of Sanitary and Environmental Engineering, Slovak University of Technology Bratislava, Radlinského 11, 813 68 Bratislava, Slovak Republic, [email protected] Osvaldo Stella Martins CENBIO – Brazilian Reference Center on Biomass, IEE – Institute of Electrotechnics and Energy, USP – University of São Paulo, Av. Prof. Luciano Gualberto, 1289 CEP 05508-010, São Paulo, Brazil, [email protected] Ülkü Mehmeto˘glu Chemical Engineering Department, Faculty of Engineering, Ankara University, Tando˘gan, 06100 Ankara, Turkey, [email protected] Jacques Méhu INSA de Lyon – National Institute of Applied Sciences of Lyon, Laboratory of Environmental Assessment of Industrial Systems and Process (LAEPSI), 9, Rue de la Physique, 69100 Villeurbanne, France, [email protected] A. Melintescu Department of Life and Environmental Sciences, Horia Hulubei National Institute of R&D for Physics and Nuclear Engineering, 407 Atomistilor St., PO Box MG-6, RO-077125 Bucharest – Magurele, Romania, [email protected] A. Mert Department of Forest Management, Faculty of Forestry, Suleyman Demirel University, Isparta, Turkey, [email protected] Paola Migliorini Department of Agronomy and land Management, University of Florence, Piazzale delle Cascine 18, 50141 Firenze, Italia, [email protected] Javad Mirzaei Faculty of Natural Resources and Marine Siences, Tarbiat Modares University, Noor, Iran, [email protected] K. Misirkhonov Central Asian Research Institute of Irrigation (SANIIRI), Karasu-4, 11, Tashkent 700187, Uzbekistan, [email protected] M.G. Mnushkin Institute of Applied Mechanics, RAS, Moscow, Russia, [email protected] J. Mohammadi Agriculture Faculty, Shahrekord University, Shahrekord, Iran, [email protected] Z. Mojovi´c Department for Catalysis and Chemical Engineering, Njegoševa12, 11000 Belgrade, Republic of Serbia, [email protected] Martha C. Monroe School of Forest Resources and Conservation, University of Florida, PO Box 110410, Gainesville, FL 32611-0410, USA, [email protected] M.R Mosquera-Losada Crop Production Department, University of Santiago de Compostela, 27002, Lugo, Spain, [email protected]

Contributors

xxxiii

Pierre Moszkowicz INSA de Lyon – National Institute of Applied Sciences of Lyon, Laboratory of Environmental Assessment of Industrial Systems and Process (LAEPSI), 9, Rue de la Physique, 69100 Villeurbanne, France, [email protected] Cristina Munteanu University of Bucharest, Biochemistry and Molecular Biology Research Center, Spl. Independentei, 91–95, Bucharest, Romania, [email protected] N. Musaoglu Civil Engineering Faculty, Istanbul Technical University, 34469 Maslak Istanbul, Turkey, [email protected] Ravi Kiran Mutnuru Department of Applied Physics, Technische Universiteit, Eindhoven, The Netherlands, [email protected] Hadi Naamneh Towns Association for Environmental Quality (TAEQ)-Agan Beit Natufa (ABN), 1093 Sakhnin, Israel, [email protected] T. Najar Institut National Agronomique de Tunis, 42, Av Charles Nicolle, 1082 Tunis, Tunis, [email protected] Tapan Narayana Hidayatullah National Law University, Raipur, Chhattisgarh, India, [email protected] S. Serkan Nas Gümü¸shane Engineering Faculty, Department of Civil Engineering, Karadeniz Technical University, 29000 Gümü¸shane, Turkey, [email protected] Anwar Nasim COMSTECH Secretariat, 33-Constitution Avenue, G-5/2, Islamabad, Pakistan, [email protected] David W. Nerubucha Lecturer of Economics, United States International University, Nairobi, Kenya, [email protected] Hanieh Nikoomaram Department of Environmental Management, Graduate College of the Environment and Energy, Science and Research Campus, Islamic Azad University, Tehran, Iran, [email protected] Noor-ul-Amin Institute of Chemical Science, University of Peshawar, Peshawar, Pakistan, [email protected] B. Noroozi Textile Engineering Department, Amirkabir University of Technology, Tehran, Iran, [email protected] Kazem Nosrati Faculty of Natural Resources, University of Tehran, Tehran, Iran, [email protected] Recai Ogur Department of Environmental Health, Gulhane Military Medical Faculty, Ankara, Turkey; GATA Halk Sagligi AD, 06018, Etlik, Ankara, Turkey, [email protected]; [email protected]

xxxiv

Contributors

O. Okay Faculty of Naval Architecture and Ocean Engineering, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] T. Ölmez Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, Ayaza˘ga Kampüsü, 34469, Maslak, Istanbul, Turkey, [email protected] Atakan Ongen Environmental Engineering Department, Corlu Engineering Faculty, Trakya University, 59860 Corlu-Tekirdag, Turkey, [email protected] D. Orhon Civil Engineering Faculty, Department of Environmental Engineering, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] N. Oructut Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey, [email protected] ˙ Ozdemir Department of Forest Management, Faculty of Forestry, Suleyman I. Demirel University, Isparta, Turkey, [email protected] O. Ozdemir Kayseri Water and Sewerage Administration, Mustafa Kemal Pasa Bulvari, 38090 Kocasinan, Kayseri, Turkey, [email protected] S. Ozdemir Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] K. Ozkan Faculty of Forestry Department of Soil Science and Ecology, Suleyman Demirel University, Isparta, Turkey, [email protected] Derya B. Özkan Mechanical Engineering Faculty, Heat and Thermodynamics Division, Yıldız Technical University, 80750 Yıldız, Istanbul, Turkey, [email protected] Dudu Özkum Near East University, Faculty of Pharmacy, Nicosia, Northern Cyprus, Mersin 10, Turkey, [email protected] H. Duygu Ozsoy Department of Environmental Engineering, Engineering Faculty, Mersin University, Mersin 33360, Turkey, [email protected] Izzet Ozturk Department of Environmental Engineering, Gebze Institute of Technology, Gebze/Kocaeli, 41400, Turkey, [email protected] Nilgün Öztürk Department of Pharmacognosy, Faculty of Pharmacy, University of Anadolu Tepebasi, 26470 Eskisehir, Turkey, [email protected] Ali Özvan Yilmazer Education, 8. Cd., 89. Sk., 9/8, 06460 A.Ovecler, Ankara, Turkey, [email protected]; [email protected] Monica Popa Department of Environmental Health, University of Medicine and Pharmacy Cluj-Napoca, Cluj-Napoca, Romania, [email protected]

Contributors

xxxv

D. Prijono Department of Plant Pest and Diseases, Faculty of Agriculture, Bogor Agricultural University, Bogor, Indonesia, [email protected] Dorina Purice National Institute of Wood, Romanian Academy Institute of Biology, Bucharest, Romania, [email protected] Jin Qiting College of Chemical Engineering, Northwest University, Taibai North Road No.229, Xi’an, 710069, People’s Republic of China, [email protected] Giovanni Quaranta UNIBAS, Potenza, Italy, [email protected] A. Abu Rabi Department for Catalysis and Chemical Engineering, Njegoševa12, 11000 Belgrade, Republic of Serbia, [email protected] Khadijah B. Abdul Rahim Department of Biotechnology Engineering, International Islamic University, 50728 KL, Malaysia, [email protected] Md. Muzibur Rahman Department of Civil Engineering, Bangladesh University of Engineering & Technology, Dhaka, Bangladesh R. Rahmani Natural Resources Faculty, Gorgan university, Gorgan, Iran, [email protected] Achanta Ramakrishna Rao Department of Civil Engineering, Indian Institute of Science, Bangalore, India, [email protected] Nilanjana Rao Environmental Consultant, E-50, Lajpat Nagar I, New Delhi, India, [email protected] Mohammad Harun ur Rashid Department of Civil Engineering, Khulna University of Engineering & Technology, Khulna, Bangladesh, [email protected] Fatemeh Razavian Department of Environmental Management, Graduate College of the Environment and Energy, Science and Research Campus, Islamic Azad University, Tehran, Iran, [email protected] Hadas Reiser Laboratory of Climatology, Department of Geography and Environmental Studies, University of Haifa, Haifa 31905, Israel, [email protected] A. Rigueiro-Rodríguez Crop Production Department, University of Santiago de Compostela 27002, Lugo, Spain, [email protected] Dirk G. Rilling Faculty of Engineering and Technology, Malacca Campus, Multimedia University, 75450 MMU, Malacca, Malaysia, [email protected] Iva Ritschelová University of Jan Evangelista Purkynˇe, 400 96, Ústí nad Labem, The Czech Republic, [email protected] J.L. Rosúa Departamento de Botánica, Facultad de Ciencias, Universidad de Granada, Edificio Politécnico, Campus Fuentenueva s/n 18071 Granada, Spain, [email protected]

xxxvi

Contributors

Saeed-ur-Rehman Institute of Chemical Science, University of Peshawar, Peshawar, Pakistan, [email protected] N. Safaian Faculty of Natural Resources, University of Mazandaran, Mazandaran, Iran, [email protected] R. Safaian College of Agriculture, Shiraz University, Shiraz, Iran, [email protected] Aida Sahmurova Engineering Faculty, Department of Environmental Engineering, Istanbul University, 34320 Avcilar, Istanbul, [email protected] A.A. Saleha Department of Veterinary Pathology and Microbiology, Faculty of Veterinary Medicine, Universiti Putra Malaysia, 43400 UPM, Serdang, Malaysia Caterina Salvia UNIBAS, Potenza, Italy, [email protected] F. Balik Sanli Department of Geodesy and Photogrammetry Engineering, Yildiz Technical University, 34349-Besiktas Istanbul, Turkey, [email protected], [email protected], [email protected] Debashis Sanyal Department of Architecture, National Institute of Technology Raipur, P.O. Ravishankar University, Raipur Chhattisgarh 492010, India, [email protected] Mohsen Mohseni Saravi Faculty of Natural Resources, University of Tehran, Tehran, Iran, [email protected]. Halil Sarıba¸sak Ministry of Environment and Forestry, West Mediterranean Research Institude, Antalya, Turkey, [email protected] S. Sarp Department of Chemical Engineering, Ege University, 35100 Izmir, Turkey, [email protected] Filiz Savaro˘glu Department of Biology, Faculty of Science and Arts, University of Eski¸sehir Osmangazi, 26480, Turkey, [email protected] Nuriye Say Department of Landscape Architecture, Çukurova University, 01330 Balcalı, Adana, Turkey, [email protected] Nicoleta Schiopu Sustainable Development Department, CSTB – Scientific and Technical Centre for the Building Industry, 24, rue Joseph Fourier, 38400 Saint Martin d’Hères, France; Laboratory of Environmental Assessment of Industrial Systems and Process (LAEPSI), INSA de Lyon – National Institute of Applied Sciences of Lyon, 9, Rue de la Physique, 69100 Villeurbanne, France, [email protected] David Schnaiter Division of Social Medicine, Department for Hygiene, Microbiology and Social Medicine, Medical University of Innsbruck, Sonnenburgstrasse 16, A-6020 Innsbruck, Tirol, Austria, [email protected]

Contributors

xxxvii

D.Z. Seker Civil Engineering Faculty, Istanbul Technical University, 34469 Maslak Istanbul, Turkey, [email protected] M. Chandra Sekhar Water and Environment Division, Department of Civil Engineering, National Institute of Technology, Warangal 506 004, India, [email protected] Aziz Sencan ¸ Engineering and Architecture Faculty, Environmental Engineering Department, Arts and Science Faculty, Chemistry Department, Süleyman Demirel University, Almaty, Kazakhstan, [email protected] F. Serrano Departamento de Botánica, Facultad de Ciencias, Universidad de Granada, Edificio Politécnico, Campus Fuentenueva s/n 18071 Granada, Spain, [email protected] E. Sertel Civil Engineering Faculty, Istanbul Technical University, 34469 Maslak Istanbul, Turkey, [email protected] H. Cahit Sevindir Department of Chemistry, Faculty of Science-Arts, University of Süleyman Demirel, Turkey, [email protected] Tahir shah National Center of Excellence in Geology, University of Peshawar, Peshawar, Pakistan, [email protected] Afsaneh Shahbazi Department of Environment, Faculty of Natural Resources and Marine Sciences, Tarbiat Madares University, Iran, [email protected] B. Shailamber Department of Civil Engineering, Water & Environment Division, National Institute of Technology, Warangal 506 004, India, [email protected] R. Shakeri Natural Resources Faculty, Chamran University, Ahvaz, Iran, [email protected] Ibrahim Shogar Kulliyyah of Science, International Islamic University Malaysia, Kuantan, Pahang, Malaysia, [email protected], [email protected] S. Shrihari Department of Civil Engineering, NITK, Surathkal, Srinivasnagar, Mangalore 575025, India, [email protected]; [email protected] Spase Shumka Agricultural University of Tirana, Tirana, Albania, [email protected] Egor Sidorov Jan Evangelista Purkyne University, Usti nad Labem, Czech Republic, [email protected] Lokendra Singh Centre for Inter-disciplinary Studies of Mountain & Hill Environment (CISMHE), University of Delhi, New Delhi 110007, India, [email protected] Dana Sîrbu Environmental Health Department, University of Medicine and Pharmacy, Cluj Napoca, Romania, [email protected]

xxxviii

Contributors

Annelie Sjölander-Lindqvist Centre for Public Sector Research (CEFOS), Göteborg University, Göteborg Box 720, SE-405 30, Sweden, [email protected] Biljana Škrbi´c Faculty of Technology, University of Novi Sad, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia, [email protected] Saidi Slim Département EMVT-CIRAD TA 30/E Campus International de Baillarguet, 34398 Montpellier Cedex 5, France, [email protected] Seval Sözen Civil Engineering Faculty, Department of Environmental Engineering, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] Minodora St˘anescu Institute of Biology, Department of Ecology and Natural Protection, Splaiul Indenpendentei Street 296, 060031 Bucharest, Romania, [email protected] Ioan Stoian S.C. I.P.A. – S.A. Subsidiary Cluj-Napoca, Cluj-Napoca, Romania, [email protected] I. Stoimenova N. Poushkarov Institute of Soil Science, Sofia, Bulgaria, [email protected] Jovan Stojanoski Faculty of Tourism and Hospitality, University of Bitola, Bitola, Macedonia, [email protected] M. Anjum Suhail Department of Agricultural Entomology, Insect Biodiversity and Biosystematics Research Laboratory, University of Agriculture, Faisalabad, Pakistan, [email protected] Hilda Marta Szabo Environmental Engineering and Biotechnology Laboratory, Department of Chemistry and Bioengineering, Tampere University of Technology, P.O. Box 541, Fin-33101, Tampere, Finland, [email protected] Masoud Tabari Department of Forestry, Faculty of Natural Resources and Marine Sciences, Tarbiat Modares University, Noor, Iran, [email protected] H. Takeda National Institute of Radiological Sciences, Environmental and Toxicological Sciences Research Group, Chiba, 4-9-1, Anagawa, Inage-ku, Chiba-shi 263-8555, Japan, [email protected] A. Taleva Department of Soil Microbilogy, N. Poushkarov Institute of Soil Science, 7 Shosse Bankya str., 1080, Bulgaria, [email protected] Fadime Taner Department of Environmental Engineering, Engineering Faculty, Mersin University, 33343 Mersin, Turkey, [email protected] A. Tanik Civil Engineering Faculty, Istanbul Technical University, 34469 Maslak Istanbul, Turkey, [email protected]

Contributors

xxxix

Hussein Tarabeah Towns Association for Environmental Quality (TAEQ)-Agan Beit Natufa (ABN), 1093 Sakhnin, Israel, [email protected] Omer Faruk Tekbas Department of Environmental Health, Gulhane Military Medical Faculty, Ankara, Turkey; GATA Halk Sagligi AD, 06018, Etlik, Ankara, Turkey, [email protected] Mesut Tekba¸s Environmental Engineering Department, Gebze Institute of Technology, 41400, Gebze, Turkey, [email protected] T. Tezgel Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] R. Tıpırdamaz Department of Biology, Faculty of Science, Beytepe Hacettepe University, 06800 Ankara, Turkey, [email protected] Rukiye Tıpırdamaz Department of Biology, Hacettepe University, 06532 Ankara, Turkey, [email protected] Valerii Tonkopii Institute of Limnology, Russian Academy of Sciences, 196105 St. Petersburg, Russia, [email protected] Gunay (Yildiz) Tore Environmental Engineering Department, Corlu Engineering Faculty, Trakya University, 59860 Corlu-Tekirdag, Turkey, [email protected] Neelam Tripathi Centre of Environmental Management of Degraded Ecosystem (CEMDE), University of Delhi, New Delhi 11007, India, [email protected] Tuula Tuhkanen Institute of Environmental Engineering and Biotechnology, Tampere University of Technology, P.O. Box 541, Fin-33101 Tampere, Finland, [email protected] O. Tünay Environmental Engineering Department, Civil Engineering Faculty, Istanbul Technical University, Ayaza˘ga Kampüsü, 34469, Maslak, Istanbul, Turkey, [email protected] Mustafa Turan Environmental Engineering Department, Civil Engineering Faculty, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey, [email protected] Özlem Ogaç Türker Department of Interior Architecture, Eastern Mediterranean University, Gazima˘gusa, Northern Cyprus, [email protected] Umut Türker Department of Civil Engineering, Near East University, Lefkosa, North Cyprus, Mersin 10, Turkey, [email protected] Aysen Turkman Department of Environmental Engineering, Dokuz Eylul University, Tınaztepe Campus, Buca, Izmir, Turkey, [email protected] H.N. Uçan Environmental Engineering Department, Selcuk University, Konya, Turkey, [email protected]

xl

Contributors

Mustafa Usta Department of Industrial Engineering of Forestry, Faculty of Forestry, Karadeniz Technical University, Trabzon 61080, Turkey, [email protected] Ayla Uysal Department of Environmental Engineering, Dokuz Eylul University, Tınaztepe Campus, Buca, Izmir, Turkey, [email protected] Ya˘gmur Uysal Kahramanmara¸s Sütçü ˙Imam University, Av¸sar Campus, 46100 Kahramanmara¸s, Turkey, [email protected] Vinka Uzelac Faculty of Teacher Education, University of Rijeka, Trg Ivana Klobuˇcari´ca 1, 51 000 Rijeka, Croatia, [email protected] Julia Uzunova Department of Marketing, University of Economics Varna, 77, Kniaz Boris I blv., Varna, Bulgaria, [email protected] Liliana Vasiliu-Oromulu Romanian Academy Institute of Biology, Spl. Independentei 296 Bucharest-6 Romania, [email protected] Sílvia Maria Stortini González Velázquez CENBIO – Brazilian Reference Center on Biomass, IEE – Institute of Electrotechnics and Energy, USP – University of São Paulo, Av. Prof. Luciano Gualberto, 1289 CEP 05508-010, São Paulo, Brazil, [email protected] A.N. Vlasov Institute of Applied Mechanics, RAS, Moscow, Russia, [email protected] D.B. Volkov-Bogorodsky Institute of Applied Mechanics, RAS, Moscow, Russia, [email protected] N. Vukeli´c Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, Republic of Serbia, [email protected] Bai Weili College of Chemical Engineering, Northwest University, Xi’an 710069, People’s Republic of China, [email protected] J. Pieter H. van Wyk Department of Pharmacology and Therapeutics, University of Limpopo, Box 225, Medunsa Campus, 0204, Medunsa South Africa, [email protected] Zhang Xiaoli College of Chemical Engineering, Northwest University, Taibai North Road No.229, Xi’an, 710069, People’s Republic of China, [email protected] Oral Ya˘gci Civil Engineering Faculty, Division of Hydraulics, Istanbul Technical University, Maslak, Istanbul 34469, Turkey, [email protected] Rezan Fahrio˘glu Yamacı Laboratory of Forensic Genetics, Cyprus Institute of Neurology and Genetics, Nicosia, Cyprus, [email protected] Ersin Yener Yazici Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon, Turkey, [email protected]

Contributors

xli

N. Yigit Department of Environmental Engineering, Suleyman Demirel University, Isparta, Turkey, [email protected] F. Ebru Yildiz Department of Research-Plan and Highway, Bank of Provinces, Opera, Ankara, Turkey, [email protected] Tu˘gba Yılmaz Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon, Turkey, [email protected] Ilyas Yilmazer YY University, Van, Turkey, [email protected] Özgür Yilmazer Yilmazer Education, 8. Cd., 89. Sk., 9/8, 06460 A, Ovecler, Ankara, Turkey, [email protected] Özlem Yilmazer YY University, Van, Turkey, [email protected] Sema Yurdakul Yorulmaz Environmental Engineering Department, METU, 06531 Ankara, Turkey, [email protected] B.F. Yousif Faculty of Engineering and Technology, Malacca Campus, Multimedia University, 75450 MMU, Malacca, Malaysia, [email protected] M. Yüksel Ege University, Department of Chemical Engineering, 35100 Izmir, Turkey, [email protected] Anika Yunus Department of Water Resources Engineering, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh, [email protected] M. Anjum Zia Department of Chemistry (Biochemistry), University of Agriculture, Faisalabad, Pakistan, [email protected]

Part I

Conservation and Management of Biodiversity

Characterization of Serratia sp. K1RP-49 for Application to the Rhizoremediation of Heavy Metals So-Yeon Koo and Kyung-Suk Cho

Abstract Many soil sites in industrialized areas are contaminated with high concentrations of heavy metals. These pollutants are highly accumulated to ecosystem and human body and cause serious ecotoxical effects. To remove heavy metals from the soil, a potential strategy is the ecologically sound, safe, and cost effective rhizoremediation using the symbiotic relationship of plants and microbes in the rhizosphere. Serratia sp. K1RP-49 was isolated from the rhizoplane of the barnyard grass (Echinochloa crus-galli) which had grown in oil contaminated soil. Serratia sp. K1RP-49 could produce various organic acids such as oxalic acid (174 mg l−1 ), maleic acid (137 mg l−1 ), citric acid (15 mg l−1 ), malic acid (2 mg l−1 ), formic acid (117 mg l−1 ), acetic acid (79 mg l−1 ), and succinic acid (203 mg l−1 ). The pH of the culture broth was decreased due to the accumulation of these organic acids. This bacterium could produce a indole acetic acid and a siderophore(s). The K1RP49 had a moderate resistance of Pb. The results of root elongation assay indicated that the growth of radicular root of maize could be enhanced by the inoculation of Serratia sp. K1RP-49. Keywords Metal · Phytoremediation · Plant growth-promoting rhizobacteria

1 Introduction Heavy metals have been discharged from industrialized areas, easily adsorbed at soil particles, and remain at the ecosystems for a long time [24]. Heavy metals in the soils are transferred to human body, and then cause DNA damage and carcinogenic effects.

K.-S. Cho (B) Department of Environmental Science and Engineering, Ewha Womans University, Seoul 120-750, Republic of Korea e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_1,

3

4

S.-Y. Koo and K.-S. Cho

Soils contaminated heavy metals can be remedied by chemical, physical and biological techniques. Rhizoremediation as an in-situ biological method is ecologically sound, safe and cost effective, and their efficiency of remediation is mostly satisfied [17]. For rhizoremediation, the symbiotic relationship of plants and plant growth-promoting rhizobacteria (PGPR) in the rhizosphere is very important: Plants can offer nutrients and good habitat to rhizobacteria, and PGPR can also protect plants and promote root growth. It have been reported that PGPR could promote root length under soils contaminated with Ni or Pb [4, 13]. The mechanisms of the promotion of plant growth by PGPR have not been fully understood, it has been considered that the following properties of rhizobacteria cause the promotion of plant growth: (a) the productivity of plant hormones such as indole acetic acid (IAA) [10]; (b) the synthesis of siderophores [5]; (c) the solubilization of mineral phosphates and other nutrients [14]. In this study, a novel bacterium, Serratia sp. K1RP-49, was isolated from oilcontaminated soil, and its ability to promote plant growth such as IAA and organic acid production, and siderophore(s) synthesis was characterized.

2 Materials and Methods 2.1 Isolation of a Bacterium The banyard grass (Echinochloa crus-galli) and its rhizosphere soil were sampled at an oil refinery plant, South Korea. One g (wet weight) of the banyard grass rhizoplane was ground using a mortar, and then diluted with 9 ml of sterilized water. One hundred microlitres of the rhizoplane suspension was spread onto the LB-agar plate, and then the plates were incubated at 30◦ C for 3 days. Some colonies were selected by the morphology and the color characteristics, and their abilities for IAA production and siderophore(s) synthesis were compared. A bacterium showing best ability was named as K1RP-49.

2.2 Identification of the Isolate The colony of K1RP-49 on the LB-agar plate was suspended with 0.05 N NaOH and then treated at 95◦ C for 30 min. The solution was centrifuged at 13,000 rpm for 10 min, and then the supernatant was used as the template for PCR. PCR R amplification (GeneAmp PCR System 2700, Applied Biosystem, USA) was performed using eubacterial universal primers, 27f (5 -AGA GTT TGA TCM TGG CTC AG-3 ) and 1492r (5 -TAC GGY TAC CTT GTT ACG ACT T-3 ). The conditions for PCR were as followings: 93◦ C for 2 min for pre-denaturation, followed by 35 cycles of a denaturation at 92◦ C for 1 min, an annealing at 55◦C for 1 min, and an extension at 68◦C for 45 s, and a final extension at 72◦C

Characterization of Serratia sp. K1RP-49

5

for 2 min. The sequences were determined using an ABI Prism 373A automated DNA sequencer (Perkin Elmer, Foster, CA) and were compared with those present in the GenBank database by the BLAST (basic local alignment search tool) search.

2.3 Heavy Metal Resistance The medium for the resistance assessment of heavy metal was the 10% LB media supplemented with heavy metal: Cd of 0.2−1.8 mM, Cr of 0.01–0.2 mM, Cu of 0.2–1.0 mM, Ni of 1–9 mM, Pb of 0.5–3.5 mM, or Zn of 1–5 mM. The K1RP-49 was inoculated to the each medium and incubated at 30◦ C for 3 days. The optical density (OD) of the cultures was measured every hour at 600 nm.

2.4 IAA Productivity The productivity of IAA by the strain K1RP-49 was tested in the modified DF medium [8]. The composition of the medium had the following compositions: (NH4 )2 SO4 , 2 g; KH2 PO4 , 4 g; Na2 HPO4 ·12H2 O, 15 g; MgSO4 ·7H2 O, 0.2 g; FeSO4 ·7H2 O, 1.0 mg; B (as H3 BO3 ), 10 μg; Mn (as MnSO4 ·H2 O), 11 μg; Zn (as ZnSO4 ·7H2 O), 125 μg; Cu (as CuSO4 ·5H2 O), 78 μg; Mo (as Na2 MoO4 ·2H2 O), 17 μg; distilled water, 1 l. The strain K1RP-49 was inoculated in 5 ml of the medium amended with 0.5 mg ml−1 of L-tryptophan, and incubated on a rotary shaker (160 rpm) at 30◦C for 5 days. One millilitre of the culture broth was mixed with 2 ml of Salkowski’s reagent (150 ml of concentrated H2 SO4 , 250 ml of distilled water, 7.5 ml of 0.5 M FeCl3 ·6H2 O) and allowed to stand at room temperature for 20 min. The developed pink color which indicates the production of IAA by the strain was measured at 530 nm with a spectrophotometer. The experiment was performed in triplicate.

2.5 Organic Acids Productivity The strain K1RP-49 was inoculated in the minimal salts medium (MSM; KH2 PO4 , 1.5 g l−1 ; Na2 HPO4 ·12H2 O, 9.0 g l−1 ; (NH4 )2 SO4 , 3.0 g l−1 ; FeSO4 ·7H2 O, 0.01 g l−1 ; MgSO4 ·7H2 O, 0.15 g l−1 ; CaCl2 ·2H2 O, 0.01 g l−1 ) amended with 30 g l−1 glucose, and incubated on a rotary shaker (160 rpm) at 30◦ C. During incubation, OD at 600 nm, pH, and the concentration of organic acids of culture broth were measured every 4 h. For the analysis of organic acid concentration, ionchromatograph (Dionex, DX-500 with ED40 Electro-chemical Detector, IonPac AS11 (4 × 250 mm) column, ASRS-Ultra II Anion self regenerating suppressor) was used with KOH as eluent.

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2.6 Siderophore(s) Synthesis Siderophore(s) production by the strain K1RP-49 was detected by the method of Schwyn and Neilands using blue agar plates containing chrome azurol S [25]. Orange halo around the colony on blue agar was the indicator for siderophore(s) excretion. The plate inoculated with the K1PR-49 was incubated at 30◦ C, and the surface area of orange halo around the colony was measured.

2.7 Root Elongation The promoting activity of plant root elongation by the K1RP-49 was determined using the modified root elongation assay of Belimov et al. [3]. The colony of K1RP-49 grown on LB-agar plate was suspended in sterilized water (OD 0.4–0.5 at 600 nm). Experimental conditions divided into four treatments; with/without inoculation of K1RP-49, and with/without tryptophane. The mixtures of bacterial suspension and tryptophane (0.5 mg ml−1 ) were supplemented with 0, 15 and 30 mg l−1 of Cd or Cu. Six millilitres of the solution was added to glass Petri dishes with filter paper. The seeds of Zea mays were surface-sterilized with a mixture of ethanol and 30% H2 O2 (1:1) for 10 min, washed with sterilized water and placed on wetted filter paper with 10 seeds per dish. Primary and radicular root length of seedlings was measured after incubation of closed Petri dishes for 8 days at room temperature in dark condition. The assay was repeated twice for each treatment.

3 Results and Discussion 3.1 Identification of a Plant-Growth Promoting Rhizobacterium, K1RP-49 Based on BLAST analysis, a plant-growth promoting rhizobacterium, K1RP49, was closely similar with Serratia plymuthica (accession AJ233433, 99% (1135/1139) similarity). S. plymuthica has been isolated from the rhizosphere of wheat, oat, cucumber, maize, oil-seed rape and potato, and frequently been associated with plants [1, 11, 16]. S. plymuthica had antifungal effects including antibiosis, siderophores, fungal cell-wall degrading enzymes (chitinases), and β-1,3 gluconases [16]. A strain of S. plymuthica isolated from the roots of a plant belonging to the Brassicaceae family had a heavy metal resistance and the accumulation ability of heavy metal [6]. S. plymuthica has been reported as an endophytic bacterium providing beneficial effects to plant [22].

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3.2 Heavy Metal Resistance Serratia sp. K1RP-49 could grow in the medium with Pb, although it couldn’t grow in the medium supplemented with Cd, Cr, Cu, Ni or Zn. The growth of the K1RP49 in the medium with Pb (0–1.5 mM) is shown in Fig. 1. Serratia sp. K1RP-49 could hardly grow at over 1.0 mM of Pb. In the medium with 0.5 mM of Pb, the specific growth rate of Serratia sp. K1RP-49 was approximately the half of that in the medium without Pb, and the average growth rate reflecting lag time was only 1/2 of that without Pb. Although heavy metals in the soils are almost adsorbed at the soil particles, bioavailable heavy metals are leached and formed soluble complexes by organic acids producing soil microbes and root exudates. Many soil microbes have tolerance against heavy metals or can uptake heavy metals into their cells. They can also influence the solubility and the bioavailability of the metal to the plant, thus the efficiency of the accumulation process can be modified [6]. (a)

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Fig. 1 Growth of Serratia sp. K1RP-49 in the liquid medium amended with Pb (0–1.5 mM), (a) growth curve; (b) average and specific growth rates

3.3 IAA Producing Ability IAA production by the growth of Serratia sp. K1RP-49 in the modified DF medium containing L-tryptophane is shown in Fig. 2. According to the growth of Serratia sp. K1RP-49, the amount of IAA produced was increased. Phytohormone such as auxin, gibberellin, cytokinin, and so on, can regulate the physiological functions of plant. Auxin is the general term for plant-growth hormones, and IAA is one of typical auxin [26]. IAA is a common metabolite of L-tryptophane by several microorganisms including PGPR [9]. The effects of IAA are different with the concentration: Primary root growth is promoted under low concentration of IAA. High level of IAA can induce radicular root growth, but inhibits primary root growth by the synthesis of ethylene [23]. Therefore, the PGPR can regulate the growth of plant’s root by producing of IAA. These promoted roots system of plant by beneficial PGPR can enhance the phytoextraction of heavy metal.

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3.4 Organic Acids Productivity To enhance metal-bioavailability in soils, synthetic chelates like EDTA have been used directly to the soil, but low biodegradation rate of these strong chelates enhances mobility of the metal in soil excessively. Metal leaching is associated with the risk of groundwater contamination [7, 19, 20, 27, 30]. The use of easily biodegradable chelates such as organic acids has been proposed to enhance bioavailability of heavy metals and accumulation into plants while avoiding leaching risks [21]. The production of organic acids by Serratia sp. K1RP-49 is shown in Fig. 3. The pH of the culture broth was decreased according to the growth of the K1RP-49. The amount of organic acids produced by the K1RP-49 were arranged in higher order as succinic acid (203 mg l−1 ) > oxalic acid (174 mg l−1 ) > maleic acid (137 mg l−1 ) > formic acid (117 mg l−1 ) > acetic acid (79 mg l−1 ) > citric acid (15 mg l−1 ) > malic acid (2 mg l−1 ). Many soil microbes can discharge organic (a)

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acids to the soil [15]. Therefore, heavy metals adsorbed at soil particles can be converted to bioavailable forms by the bacterial organic acids without artificial chelates, and the accumulation of heavy metal into the plant can be increased.

3.5 Siderophore(s) Synthesis Ability The expanded surface areas of the orange halo around the colony of Serratia sp. K1RP-49 on blue agar are shown in Fig. 4. The siderophore(s) synthesized by the K1RP-49 taken up the iron from a blue CAS-agar medium, and the color of medium was changed to orange color. The amount of siderophore(s) was increased steadily. Due to the physio-chemical properties of iron which exists in the trivalent state as oxyhydroxide in an aerobic and biological pH, iron is virtually insoluble [25]. Heavy metal-contaminated soil is often associated with iron deficiency in a range of different plant species [18, 28]. Iron deficiency inhibits the synthesis of a chloroplast and chlorophyll, and induces production of ethylene which acts as stress matter to plants, eventually leads to the decrease of rhizoremediation efficiency [12]. Many microorganisms use a ferric-specific ligand, termed ‘siderophore(s)’ of a high affinity low-molecular-weight to take up essential element iron [25]. These microbial iron-siderophore complexes which bound iron can be taken up by plants as an iron source [2, 29]. 10

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3.6 Promotion of Root Growth The effect of Serratia sp. K1RP-49 on root elongation of Zea mays in the existence of heavy metal (Cd or Cu) are shown Figs. 5, 6 and 7. The root length with heavy metal was shorter than that without heavy metal. It means that root

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elongation was inhibited by metal toxicity. Compared with the control, the growth of primary root with heavy metal was not significantly affected by the bacterium or tryptophane compared with the control. However, radicular root length was increased by the addition of bacterium or tryptophane except the results in 30 mg l−1 Cu. The primary and radicular root length of 30 mg l−1 Cu inoculated with the K1RP-49 was inhibited by fungal contamination. The effect of the K1RP49 was similar to that of tryptophane in the filter paper with heavy metal. As a result, the inoculation of Serratia sp. K1RP-49 can promote the growth of radicular root. It is suggested that the application of Serratia sp. K1RP-49 to rhizoremediation will be helpful to enhance the metal remediation efficiency by increasing root surface area.

References 1. Alström B, Gerhardson B (1988) Differential reactions of wheat and pea genotypes to root inoculation with growth affecting rhizobacteria. Plant Soil 109:263–269 2. Bar-Ness E Chen Y, Hadar H, Marschner H, Romeheld V (1991) Siderophores of Pseudomonas putida as an iron source for dicot and monocot plants. Plant Soil 130:231–241

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3. Belimov AA, Hontzeas N, Safronova VI, Demchinskaya SV, Piluzza G, Bullitta S, Glick BR (2005) Cadmium-tolerant plant growth-promoting bacteria associated with the roots of Indian mustard (Brassica juncea L. Czern.). Soil Biol Biochem 37:241–250 4. Burd GI, Dixon DG, Glick BR (1998) A plant growth-promoting bacterium that decreases nickel toxicity in seedlings. Appl Environ Microbiol 64:3663–3668 5. Burd GI, Dixon DG, Glick BR (2000) Plant growth promoting bacteria that decreases heavy metal toxicity in plants. Can J Microbiol 46:237–245 6. Carlot M, Giacomini A, Casella S (2002) Aspects of plant-microbe interactions in heavy metal polluted soil. Acta Biotechnol 22:13–20 7. Chen Y, Xiangdong L, Shen Z (2004) Leaching and uptake of heavy metals by ten different species of plants during an EDTA-assisted phytoextraction process. Chemosphere 57:187–196 8. Dworkin M, Foster JW (1958) Experiments with some microorganism which utilize ethane and hydrogen. J Bacteriol 75:592–603 9. Frankenberger WT Jr, Brunner W (1983) Methods of detection of auxin-indole acetic acid in soil by high performance liquid chromatography. Soil Sci Soc Am J 47:237–241 10. Gaudin V, Vrian T, Jouanin L (1994) Bacterial genes modifying hormonal balances in plants. Plant Physiol Biochem 32:11–29 11. Gimmont F, Gimmont PAD (1992) The genus Serratia. In: Balowes A, Trüper HG, Dworkin M, Harder W, Schleifer KH, (eds) The prokaryotes – a handbook on the biology of bacteria: Ecophysiology, isolation, identification, application, 2nd edn, Vol. 3. Springer Verlag, New York, pp 2823–2848 12. Glick BR (2003) Phytoremediation: synergistic use of plants and bacteria to clean up the environment. Biotechnol Adv 21:383–393 13. Grichko VP, Filby B, Glick BR (2000) Increased ability of transgenic plants expressing the bacterial enzyme ACC deaminase to accumulate Cd, Co, Cu, Ni, Pb and Zn. J Biotechnol 81:45–53 14. Gupta A, Meyer JM, Goel R (2002) Development of heavy metal resistant mutants of phosphate solubilizing Pseudomonas sp. NBRI4014 and their characterization. Current Microbiol 45:323–327 15. Halvorson HO, Keynan A, Kornberg HL (1990) Utilization of calcium phosphates for microbial growth at alkaline pH. Soil Biol Biochem 22:887–890 16. Kalbe C, Marten P, Berg G (1996) Members of the genus Serratia as beneficial rhizobacteria of oilseed rape. Microbiol Res 151:4433–4400 17. Kumino T, Seaki K, Nagaoka K, Oyaizu H, Matsumoto S (2001) Characterization of copperresistant bacterial community in rhizosphere of highly copper-contaminated soil. Eur J Soil Biol 37:95–102 18. Ma JF, Nomoto K (1993) Inhibition of mugineic acid-ferric complex in barley by copper, zinc and cobalt. Plant Physiol 89:331–334 19. Madrid F, Liphadzi MS, Kirkham MB (2003) Heavy metal displacement in chelate-irrigated soil during phytoremediation. J Hydrol 271:107–119 20. Meers E, Hopgood M, Lesage E, Tack FMG, Verloo MG (2004) Enhanced phytoextraction: in search for EDTA alternatives. Int J Phytoremed 6:95–109 21. Nascimento CWA, Amarasiriwardena D, Xing B (2006) Comparison of natural organic acids and synthetic chelates at enhancing phytoextraction of metals from a multi-metal contaminated soil. Environ Pollut 140:114–123 22. Nicole B, Serge G, Dominique LQ, Leila D (2000) Bacterial-mediated induced resistance in cucumber: beneficial effect of the endophytic bacterium Serratia plymuthica on the protection against infection by Pythium ultimum. Biochem Cell Biol 90:45–56 23. Pilet P-E, Saugy M (1987) Effect on root growth of endogenous and applied IAA and ABA. Plant Physiol 83:33–38 24. Rajkumar M, Nagendran R, Lee KJ, Lee WH, Kim SZ (2005) Influence of plant growth promoting bacteria and Cr6+ on the growth of Indian mustard. Chemosphere 62:741–748

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25. Schwyn B, Neilands JB (1987) Universal chemical assay for the detection and determination of siderphores. Anal Biochem 160:47–56 26. Sergeeva E, Liaimer A, Bergman B (2002) Evidence for production of the phytohormone indole-3-acetic acid by cyanobacteria. Planta 215:229–238 27. Sun B, Zhao FJ, Lonbi E, Mcgrath SP (2001) Leaching of heavy metals from contaminated soils using EDTA. Environ Pollut 113:111–120 28. Wallace A, Wallace GA, Cha JW (1992) Some modifications in trace elements toxicities and deficiencies in plants resulting from interactions with other elements and chelating agents. The special case of iron. J Plant Nutr 15:1589–1598 29. Wang Y, Brown HN, Crowley DE, Szaniszlo PJ (1993) Evidence for direct utilization of a siderophore, ferroxamine B. in axenically grown cucumber. Plant Cell Environ 16:579–585 30. Wenzel WW, Unterbrunner R, Sommer P, Sacco P (2003) Chelate-assisted phytoextraction using canola (Bassica napus L.) in outdoors pot and lysimeter experiments. Plant Soil 249:83–96

Predators in ‘Agri-environmental’ Sweden: Rural Heritage and Resistance Against Wolf Propagation Annelie Sjölander-Lindqvist

Abstract The politics and the underlying reasons for the recuperation of a Scandinavian wolf population are increasingly contested. According to the official policy, wolves shall be guaranteed place in the Swedish fauna. The conflict regarding whether Sweden should host a wolf population polarises between on the one hand, views and understandings as regards biodiversity and sustainable development, and on the other hand, perspectives expressing that local traditions and livelihoods are at stake as a result of wolf occurrence in the landscape. The diverging environmental imaginaries at play in the debate can be seen as constitutive of spatial indifferences. States’ and nature conservation organisations’ desires to implement measures understood to provide conditions for the survival of the wolf are counterbalanced by local actions groups and community residents who struggle to maintain the conditions for the conservation of summer pasturing agriculture, continued and unchanged opportunities to perform hunting with sporting dogs and other recreational activities such as mushrooming and the picking of berries. Considered not only by themselves as of high natural and cultural value, the European Union like wisely appoint that small-scale ways of farming are important to maintain for the upkeep of the landscape and the promotion of conditions guarding the survival of the values associated with these ‘agri-environmental’ habitats. Keywords Agricultural policy · Environmental policy · Wolf population

1 Introduction No other predatory animal has attracted as much organized opposition as the wolf. The reaction is due in part to the greediness of the wolves, and also to the fact that nobody ever eats the meat of an animal that has been touched by a wolf [25].

The above quotation illustrates an opinion of wolves that was prevalent in Sweden until 1965 when the preservation act came into force, but this view is not uncommon A. Sjölander-Lindqvist (B) Centre for Public Sector Research (CEFOS), Göteborg University, Göteborg Box 720, SE-405 30, Sweden e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_2,

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even today. At that time, the wolf was seen as a threat to humans and their activities in forest and farm landscapes. While the numbers of the wolf population were considerably reduced to as low as 10–35 individuals, mainly as a result of hunting and organised battues, they amount today to some hundred individuals and are still considered to jeopardise the lives and values of people living in the vicinity of wolves. These views illustrate the controversies we find among people regarding nature and natural assets. The above statement is not only a portrayal of views of and feelings about the wolf as a dangerous and uncertain creature, it also tells of struggles over the access to, use of, and ownership of environmental resources. Disputes over ‘Nature’ are politically charged—issues of power exercise and dominance range from the supranational level of negotiations over directives and agreements concerning sustainability and biodiversity, to the local level where global discourses are to be implemented. Politically decided regulations and practices may, however, from a local point of view be perceived as illegitimate, and hence neither receive support nor be complied with. The concerned public’s experience and perceptions of the implementation process as being fair and just has been found to influence acceptance by the public [10]. The politics and the underlying reasons for the recuperation of a Scandinavian wolf population have been, and continue to be, increasingly contested. According to the Swedish official nature conservation policy, wolves shall be guaranteed place in the Swedish fauna. The conflict regarding whether Sweden should host a wolf population polarises between on the one hand, views and understandings as regards biodiversity and sustainable development, and on the other hand, perspectives expressing that local traditions and livelihoods are at stake as a result of wolf occurrence in the landscape. Wolf sceptics maintain that the occurrence of wolves in the surrounding local environment will lead to the demise of forests and farm communities. The effects of the presence of wolves—wolf attacks on livestock and hunting dogs, potential attacks on people when growing wolf populations no longer have enough game to prey on, declining game stocks—will, according to the informants, cause increased marginalization of rural people and the depopulation of margin areas (cf. [32]). Although numbers steadily increasing, environmentalists and authorities still consider the Scandinavian wolf population1 to be in jeopardy of extinction due to not only a poor pedigree. According to the biological predator research community, the unlawful killings of wolves are another threat of considerable weight [24]. The view that the Swedish Government should take actions to make it possible for the wolf population to survive is supported by nature conservation organizations,2 the

1 The wolf population is generally referred to as ‘Scandinavian’ since some of the wolf territories is to be found to pass the national border between Sweden and Norway. 2 Such as Svenska Rovdjursföreningen (the Swedish Carnivore Association), Svenska Naturskyddsföreningen (the Swedish Society for Nature Conservation), and WWF (the World Wide Foundation).

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public at large [6, 7] and individuals.3 The ‘pro’ wolves groups withholding that wolves have the ‘right’ to exist is an argument—grounded in the environmentalist discourse recommending actions to be take to restore an ecosystem understood as being under threat—that others4 confront by emphasizing that the landscape and the local traditions of the rural Sweden are jeopardized as a result of the occurrence of wolves in Swedish countryside, and due to the present wolf policy (cf. [32, 36]). Thus, while some argues for protective measures to halt high inbreeding5 and illegal hunting,6 yet others oppose the practices in question [30]. In this paper, focus will be drawn to how the adoption and the implementation of a coherent policy for large carnivores in Sweden—the Coherent Predator Policy— besides its aim to enhance measures for an environmentally friendly society, may result in a transformation of the Swedish rural landscape—spatially as well as symbolically. Squeezed between policies promoting the safe-guarding of the predatory populations of wolves, the preventing of cruelty to animals and demanded-for activities by the agricultural program of the European Union, farmers residing in areas with residential wolf populations have come to take part in processes that may bring about a reinforcing of rural identity. The presence of wolves in the countryside of the middle parts of Sweden—where the majority of the Swedish wolf population is to be found—has caused considerable disquiet among some of the concerned stakeholders. Farmers’ and hunters worries that the survival of the rural landscape and rural heritage are at stake due to wolves residing in the local environment are encoded with symbolic meanings of the landscape and the local traditions carried out in farmed and forested areas. Disputes between different stakeholders regarding what should guide the achieving of biodiversity has besides a policy quandary given rise to discourses on morality and ethics what regards the keeping of livestock and domestic animals. A questioning is taking place pertaining to space and place—as reproducing dimensions of cultural identity.

1.1 Theoretical Departure Veined by the assumption that conflicts between people regarding the biological environment involve different dimensions, such as the aspect of place attachment and the meanings of property, the article is inspired by a ‘first world political 3 Including

informants and people who have been expressing their opinions at debate meetings, in radio and TV programs. 4 Groups and organizations such as the ‘the Swedish Forum for Predatory Animal Issues’ (authors translation for Svenskt Samarbetsforum i Rovdjursfrågor) and ‘the Swedish Hunting & Outdoor Recreation Club’ (authors translation for Svenska Jakt & Fritidsgruppen), as well as individuals. 5 It has been found that the Scandinavian wolf population was founded be three individuals. By drawing up a pedigree for 24 breeding pairs it was found that the inbreeding coefficient F varied between 0.00 and 0.41 in the period between 1983 and 2002 [13]. 6 See for example the web page of the Swedish Carnivore Association (www. rovdjursforeningen.se).

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ecology’ [18, 19]. That people in industrialized countries have relations with ‘nature’ is the main outline of this approach; irrespective of taking place in the ‘first’ or in the ‘developing’ world, environmental conflicts are socio-culturally informed [18, 23]. The article thus employs a landscape and place oriented anthropological approach in the sense that perceptions of the environment might serve as a frame for the rise of local desires and struggles to maintain social and cultural values and practices which can turn out to be in conflict with other wishes and agreements taken at other societal levels (e.g. [11, 16, 17, 20, 29]). Informed by cultural value frames that have developed during times and years of ‘dwelling’, to apply the vocabulary of anthropologist Tim Ingold [12], local residents can be said to find themselves in a ‘configurative complex of things’ ([5], p. 25). Besides relating to the natural and social worlds in ways that reproduce collective memories [26] and the meanings the traditions of the rural landscape bring to its practitioners, people’s understandings and experiences of the contemporary world is also informed by other actor’s endeavours imposing other sets of values (cf. [15, 27, 28]).

2 Promoting Environmental Diversity—The Encapsulation of Different Values and View Points Understood as being under the threat of destruction, the ecological system has become an integral part of national policy. Politically motivated, regimes for the management of natural resources have been established. Policies for collective control and the public administration of, for example, the management of the Scandinavian wolf population, have developed during the latter decades. Measures for the conservation of natural resources follows internationally negotiated treaties that have been ratified by the Swedish Parliament (e.g. the Bern Convention). These treaties, aiming for a sustainable development and caretaking, have served to inspire and direct environmental protective measures in the promotion of a biologically diversified society. In 2001, the Swedish Parliament laid down a ‘Coherent Predator Policy’, which stipulates that the Scandinavian wolf shall be ensured long-term survival through the implementation of protective measures. The recovery of the wolf have, however, been increasingly contested. Although the decision can be labelled as democratically agreed upon, the decision has turned out to be highly debated. While the view that Sweden should take actions to preserve and maintain a wolf population is widely supported by authorities, nature organizations and a large public, others disagree, emphasizing that local traditions, values and meanings are at stake as a result of recovery aims and wolf management. These disputes tell of struggles over the access to, and use of environmental resources. As an issue of power exercise, the controversy regarding whether measures should be taken or not and if the survival of the wolf is to be considered as a matter for Sweden to deal with, can be said to highlight dimensions of space and place. The controversy is thus to be regarded as not only a matter of how to understand a biological habitat, commonly referred to as ‘Nature’. Most importantly, the voices raised for or against activities taken to ensure a long-term survival of

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the Scandinavian wolf, can as well be encapsulated as a reflection regarding which values that should guide rural reconstruction. The implementation of policies for the protection of natural resources brings many interests into collision. The wolf issue is thus to be considered as a meeting-point between authorities, ‘green’ organizations such as the Swedish Carnivore Association (‘Svenska Rovdjursföreningen’), interest organizations as for example the Swedish Association for Wildlife Hunting and Management (‘Svenska Jägareförbundet’), and organizations assembling wolf sceptics—the ‘Swedish Forum for Predatory Animal Issues’ (author’s translation for ‘Svenskt Samarbetsforum i Rovdjursfrågor’), the ‘Swedish Hunting & Outdoor Recreation Club’ (author’s translation for ‘Svenska Jakt & Fritidsgruppen’). ‘The Association for Safety in Rural Communities in Sweden’ (author’s translation for ‘Sveriges Glesbygds Trygghet’) is another local/regional association, generally referred to by the acronym SGT,7 that similarly to the previous mentioned, demand that Swedish predator policy and management to a much greater extent must consider the living conditions of people residing in rural Sweden. Decision-making concerning wolf occurrence should be made locally instead of nationally and regionally, since, as they argue, such decisions must have their point of departure in local realities and knowledge. The organization ‘Peoples’ Campaign for a New Predator Policy (author’s translation for ‘Folkaktionen Ny Rovdjurspolitik’), organizes today many wolf sceptics and some of the above mentioned wolf sceptic associations have become transformed into this national organization that was founded in 2005. At the core of their demands stands that dialogue between local stakeholders and authorities must be increased since, as they say, without dialogue and real participation in decisionmaking, predator policy can never become sustainable and reach acceptance. Thus, network building and mobilization of opinion are taking place. While wolf sceptical organizations make complaints and protests concerning Swedish wolf politics and management, wolf protectionists join nature conservation organizations to support the protection of threatened species. We thus see a division between protectionists and sceptics. From reasons of solidarity with other countries efforts to protect endangered species, Sweden should also take actions for the furthering of biological diversity. That Sweden is obliged to actions since they have signed international treaties is another reason mentioned by the protectionists. But above all, as they argue, the wolf has the right to reside in the countryside since it as all other creatures has the right to exist.

3 Wolves in Scandinavia According to an integrated predator policy, laid down by the Parliament (the Swedish Riksdag) in 2001, the Scandinavian wolf (together with four other large carnivores—brown bear, lynx, wolverine and golden eagle) shall, through the 7 In

popular parlance among certain groups referred to as ‘Shoot, Dig and Shut Up’.

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implementation of protective measures, be ensured long-term survival ([21], p. 57). The politics of and the underlying reasons for the recovery of the Scandinavian wolf population have, however, been increasingly contested. While the view that Sweden should take actions to preserve and maintain a wolf population is widely supported by authorities, nature organizations and a large public, others disagree, emphasizing that local traditions, values and meanings are jeopardized as a result of recovery aims and practices of wolf management. Thus, although the political community has decided democratically that Sweden shall strive to follow international decisions and legislation in species conservation, others argue otherwise, saying that wolves do not really belong in the Swedish landscape. Whether or not we should save the wolves from extermination, is thus a highly debated matter. In order to secure the wolf population in Scandinavia, policies for collective control and public administration have been developed and adopted. The Swedish official nature conservation policy follows treaties that have been internationally negotiated and ratified by the Swedish Parliament. Serving as a background for the research carried out did the understanding that contestations over the biological environment have been an issue both in earlier times and today. While the Scandinavian wolf population of today amounts 35 territories with wolf packs,8 scent-marking pairs9 and single stationary individuals10 [35] representing 109–117 individuals,11 the population was estimated at 1,500 individuals some 180 years ago. Whereas we today see protective measures governing the wolf population, laws and opinions of the wolf as being detrimental to humans and human activities, led, in the past, to wolf persecution. Provincial laws from the 15th century, for example, stated parish members’ obligation to take an active part in wolf battues. The women of the parish, its vicar and the clerk of the parish were the only ones exempted from this duty. The hunt for wolves was successful. Until the preservation act in 1965, the larger part of the wolf population was exterminated during the 19th and 20th centuries. Using a variety of methods—traps, nets, weapons, and battues—people throughout the country managed well in their wolf hunts. Additionally, bounties were imposed in 1647 to encourage the hunt for wolves, and these remained in force until the wolf preservation act came into force more than 200 years later. Some tens of years before the wolf protection act in 1965, the wolf population was estimated at less than 40 individuals. Approximately 20 years after the establishment of the protection act, traces and observations point to a growing wolf population in Scandinavia. In the 1980s, it was estimated that there were about ten individuals and during the following years, we see a growing increase in the number of wolves, packs, scent-marking pairs and other residential individuals.

8 Estimated amount: 76–79 individuals. A wolf pack consists of a breeding

pair and their offspring. amount: 26–28 individuals. 10 Estimated amount: 7–10. 11 Besides wolf packs, scent-marking pairs and other residential individuals there are also migratory wolves. 9 Estimated

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4 Study Area and Methods Ethnographic methods were chosen as the main strategy for empirical investigation. Data was collected primarily from the conducting of in-depth interviews. Informal observations have also been carried out at various meetings. Readings of newspaper and journal articles and the visiting of different web sites have given additional insight into the ‘wolf issue’—its structures, actors and the mains of the debate. The informants were asked to discuss the situation surrounding having wolves in the forests. Through conversations, local residents expressed their opinions, values and collectively shared dimensions of everyday experiences of wolves and local practices in farming and forest communities, thus providing glimpses of the social worlds of the people interviewed. The investigation of the concerns of residents living in the wolf territories employed an ethnographic approach. Such methods have found to suit research situations when it is of crucial importance for the outcome of the research carried out to establish trustworthy relationships with the informants [3]. The interview results on which this paper rests were carried out in three separate areas; the county of Dalarna and the two wolf territories Dals-Ed/Halden and Hasselfors—although all to be found in the middle parts of Sweden neither study area are located next to one another. The fifty-two interviews that were carried out the summer and autumn of 2005 consisted of people holding ‘pro’ as well as ‘anti’ wolf attitudes and through which opinions and values related to the presence of predators in the landscape were collected. Gathered by convenience sampling, particularly the groups of hunters and farmers were interviewed. Besides interviewing residents in wolf territories, members of the research team have been carrying out observations at meetings, generally announced as ‘information meetings’, and the annually held ‘Wolf Symposium’ where interested parties have the opportunity to take part of talks regarding different aspects of wildlife management nationally as well as internationally. The interviews lasted from two to four hours and consisted of a set of general questions as well as follow-ups on issues raised by the respondent. A written list of questions and topics served as a guide throughout the conversation. Detailed notes were taken and later transcribed. A tape recorder was not used during the interview since the wolf is a rather controversial issue and in some cases the parties involved have been under threat of violence. It was therefore considered important to guarantee individual anonymity as far as possible.

5 National Environmental Conservation Policy The status of the Scandinavian wolf is based upon the classification works of plants and animals carried out by the Swedish Species Information Centre (ArtDatabanken), a body shared by the Swedish Environmental Protection Agency and the Swedish University of Agricultural Science (SLU). According to this classification, building on a system of six categories reflecting the risk of extinction

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in the Swedish flora and fauna, the Scandinavian wolf is on the Red List and is classified as Critically Endangered [9]. As such, the wolf is understood to be exceptionally endangered, facing an extremely high risk of extinction in the very near future. This classification system, built on a global classification system that was outlined by the World Conservation Union (IUCN) in 1994, is one of the measures taken to protect biodiversity. In Sweden, policies for collective control and public administration have been developed to deal with the political goal of specie conservation and today’s controversy regarding the wolf. Through the Coherent Predator Policy, laid down in 2001, the Parliament has agreed that measures to minimize conflicts regarding predatory animals must be taken to ensure their long-term survival ([21], p. 57; see also [24]). A Council for Predator Issues was founded in 2002 to assist the Swedish Environmental Protection Agency (SEPA) in implementing the Coherent Predator Policy. As an advisory consultative body, the Council deals with issues concerning general and overall policy, surveys and developments of the populations of the five carnivores covered by the Predator Policy. Besides striving for the reaching of 20 reproductions of the Swedish wolf population, representing approximately 200 individuals, the Parliament decided in 2001 that regional predatory animal management, as other environment protection, must involve local participation and strong support by those affected by the conservation efforts ([21], p. 57; [33], p. 173). The need to encourage local participation ([21], p. 57) resulted in the establishment of Regional Predator Groups (RPG) in all counties having residential large predators. Today, we find 17 of these groups across the country, comprising representatives from hunting organizations, voluntary nature conservation groups, farmers’ associations, the police and prosecutors, municipalities and county administrative boards. Besides striving for local empowerment on issues of predator management, the RGPs are by the authorities understood to be a means for an increased information exchange between different regional and local groups, and as such, facilitating the dissemination of information to the large public. Cooperation between the central authorities and the concerned NGOs and groups is by the decision-makers considered vital for the accumulation of knowledge— by the authorities assumed necessary to enhance more ‘nuanced’ perspectives and opinions of what has turned out to be a rather controversial question for the Swedish countryside. The solution on the wolf controversy, the authorities (regional as well as national ones) say, is to raise the level of ‘acceptance’. Their work focuses therefore on the process of attaining a local consensus regarding what they refer to as a politically based initiative. Local compliance with a highly debated political decision, regarding wolves’ living conditions and their future in the Swedish fauna, is thus sought for at the same time as the regional authorities strive for the realization of a national goal through the implementation of intermediate aims, such as regional minimum levels for wolf recovery in each county [31]. By incorporating concerned stakeholders and interest organizations into the RPGs, the central authorities assume that consent on the predator policy might be achieved as a dissemination of information will take place when the information given to the group members is passed on to their mother organizations ([34], p. 146). Understood as nourished by debates

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and inconsistent opinions on the causes and effects of wolves’ occurrence in the countryside, the central authorities appraises an increase of a scientifically based knowledge as central for abating worries regarding the effects of large carnivore presence [31].

6 Rural Lives at Stake According to the Common Agricultural Policy (CAP) of the European Union, the farming sector has a multiple role to play. By their use of rural land, the farmers produce a variety of products for consumption but they do also contribute to the diversity—and the survival—of the countryside. Through their work, the farmers have a role to play in the maintenance of rural area. Wolf sceptic informants, however, maintain that the occurrence of wolves in the surrounding local environment will be detrimental to the survival of forest and farm communities. According to the informants, the wolf’s presence has entailed changed routines and fear and anxiety about the future of traditional work and ways of life locally. Among local residents, the wolf is considered to be an animal with the potential of bringing harm to livestock and humans. The effects of the presence of wolves—wolf attacks on livestock and hunting dogs, potential attacks on people when growing wolf populations no longer have enough game to prey on, declining game stocks—will, according to the informants, cause increased marginalization of rural people and the depopulation of margin areas (cf. [32]). Among local residents, the wolf is considered to be an animal with the potential of bringing harm to livestock and humans. Therefore people feel that they, their families and ways of living are jeopardised as a result of wolves living in the area. Since the wolf is not in jeopardy of being exterminated internationally, informants feel further that there is no reason why the Swedish rural population should be exposed to the risks the presence of wolves brings to people living in the countryside. Fear and anxiety is not only a matter restricted to the outdoors. Peoples’ homes and households are by several of the informants experienced as threatened by wolves’ occurrence in the environs. One of the female informants mentioned that she did not dare to go down to the basement since she was afraid that wolves might enter the house meanwhile. Social anthropological research has shown that members of households draw safety and comfort from these entities when they experience that the surrounding world is exposed to threat and change [2]. Local reports that the wolves passes close to dwelling-houses and that women and children cannot feel secure, even close to their homes, show that the meanings people attach to ‘home’ and ‘property’—as fundamental social institutions—are disarranged. Implementation of goals of society may thus bring about that peoples’ self-images and ideas about society and life are put under pressure. People may feel violated when ‘agents of change’—represented here by the wolf—trespasses what people regards as basic principles upon which human activity is structured (cf. [8]). Network building and mobilization of opinion have taken place, making complaints and protests concerning Swedish wolf politics and management. The ways

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in which people sceptic to wolf presence in the Swedish landscape become involved varies. A most obvious action that has taken place to counteract the implementation of the predator policy is the ‘Dala Revolt’ (Dalaupproret). This rebellion by hunters in the county of Dalarna who during a period of approximately 1 year (2004–2005) refused to trace animals injured by traffic (otherwise a normal task for them) until their demands—unrestricted access to outdoor recreation for people living in the countryside, a continued preservation of the country’s moose stock, and a predator policy that more explicitly takes into consideration local knowledge and rural living conditions—had been met. The boycott was, however, brought to an end in spring 2005 without the movement being able to achieve their demand of a changed legislation concerning the rights of livestock and dog owners to defend their animals against attacks from predatory animals and grant permits for the controlled culling of wolves. Generally, the presence of wolves in the landscape is understood to affect not only rural livelihoods and people’s customary ways of living—in terms of restricted opportunities for hunting, fishing, berry and fungus picking, horseback-riding and orienteering—but the biological diversity is also felt to be endangered. According to the wolf sceptic informants, wolf presence has led and will lead to a depopulation of the countryside since landowners, livestock breeders and mountain pasture farmers will give up their livelihoods when the threats posed by wolves appear to be too heavy a burden. The moving of livestock to summer residences is a historically rooted tradition. Restricted possibilities to graze in the village have, since agricultural land in the county of Dalarna in the 19th century were not partitioned as in other parts of Sweden, made the way for the use of unfenced summer forest pastures. Farmers who employ agricultural seasonal foraging consider themselves as part of a local heritage. By taking their cattle to summer grazing pastures they carry on the traditions of a historical past. Besides the keeping of old customs, the informants are of the opinion that they continually contributes to the up keeping of an open landscape and that seasonal foraging have developed in correspondence with the ecological environment of the constraints and possibilities of the Swedish rural landscape. However, the presence of wolves in the landscape threatens summer pasturing agriculture since the farmers have very limited possibilities to defend their cattle from wolf attacks. They say that their way of living and the old customs of cattle grazing in summer pastures are at stake. Instead of continually contributing to the up keeping of an open landscape and a rich fauna through unfenced cattle grazing they must leave their cattle nearby the chalets on the summer pasture. Since the grazinggrounds next to the chalets are very limited they will be forced to bring fodder from the farm in the village to feed their cattle. If forced this way, the environmental benefits of summer pasturing agriculture will be lost—and the farmers will not be able to fulfil the conditions the European Union asks for when granting economic support. Besides the environmental benefits such as a rich flora and fauna, the municipality and the region do also benefit from the maintaining of the cultural heritage of agricultural seasonal foraging since it attracts many tourists during the summer months (June-August).

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Similarly to results from Norway [32], feelings of injustice prevail among farmers regarding their experiences that their activities are improperly acknowledged. As they say, their ways of small scale farming has contributed to an open landscape, a diversified flora and fauna and a cultural heritage, which they see as being under threat due to the wolf residing in the forest. The farmers believe that the traditional ways of sending livestock out to grass—fenced or unfenced—will decrease since they fear attacks by wolves. When no longer the possibility exists to deploy forest pastures, small scale farming and agricultural seasonal foraging will decline, adding to the dying out of rural Sweden. Similarly, it is argued, decreased possibilities to go hunting without exposing hunting dogs to wolves’ search of prey will leave the Swedish forests empty of hunters. Informants’ feelings of uncertainty regarding continued farming and hunting reflect that the landscape is a lived reality, holding significant meanings to people locally. As suggested by Cantrill and Senecah [4], ‘. . . our conception of the natural environment is framed by our experiences bound to local settings’ ([4], p. 186]. The landscape, then, is experienced through activities. Through practices of performance, representation and action, people socialise the landscape [1], as for example through hunting—an activity that in Sweden assemble nearly 300,000 people— meanings are created and established. When hunters gather and hunt, they establish and uphold social relationships and networks since the hunt for elks, in particularly, is carried out in hunting parties. The landscape and the locality as a dimension for social life [1] and where feelings of fellowship, solidarity, and relationship building are established, create a sense of belonging [1, 5, 14, 22].

7 Discussion The presence of wolves in the countryside of the middle parts of Sweden—where the majority of the Swedish wolf population is to be found—has caused considerable disquiet among some of the concerned stakeholders. Due to wolves’ residing in the local environments, farmers (including farmers who employ a transhumance system of agriculture) and hunters worries that the survival of the rural landscape and rural heritage are at stake. The presence of wolves in the landscape is understood to affect not only rural livelihoods and people’s customary ways of living—in terms of restricted opportunities for hunting, fishing, berry and fungus picking, horsebackriding and orienteering—but the biological diversity is also felt to be endangered. According to the movement, wolf presence has led and will lead to a depopulation of the countryside since landowners, livestock breeders and summer pasture farmers will give up their livelihoods when the threats posed by wolves appear to be too heavy a burden. According to the Common Agricultural Policy (CAP) of the European Union, the farming sector has a multiple role to play. By their use of rural land, the farmers produce a variety of products for consumption but they do also contribute to the diversity—and the survival—of the countryside. Through their work, the farmers and their farming activities are thus assigned as essential in the

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maintenance of rural area. The implementation of policies for the safeguarding of the Scandinavian wolf is giving rise to a policy quandary when farmers are expected to use production methods which are addressed as compatible with environment protection. Dependency upon the European Union’s economic grants (CAP Reform 1992)—received if environment protective production methods are employed—and authorities’ expectancy that they must adjust to the risks carnivore presence bring to the rural communities have come to cause disquiet and frustration among the informants when they are not given the possibility to safeguard their livestock from wolf attacks. Disputes between different stakeholders regarding what should guide the achieving of biodiversity has besides a policy quandary given rise to discourses on morality and ethics what regards the keeping of livestock and domestic animals but we can also see that a questioning is taking place pertaining to space and place—as reproducing dimensions of cultural identity.

References 1. Appadurai A (1995) The production of locality. In: Fardon R (ed) Counterworks. Routledge, London and New York, pp 204–225 2. Birdwell-Pheasent D, Lawrence-Zúñiga D (1999) House life: Space, place and family in Europe. Berg, Oxford 3. Boholm A (1983) Swedish Kinship: An exploration into cultural precesses of belonging and continuity. Gothenburg Studies in Social Authropology 3, Acta Universitatis, Gothoburgensis 4. Cantrill JG, Senecah LS (2001) Using the ‘sense of self-in-place’ construct in the context of environmental policy-making and landscape planning. Environ Sci Policy 4:185–203 5. Casey ES (1996) How to get from space to place in a fairly short stretch of time: Phenomenological prolegomena. In Feld S, Basso K (eds) Senses of place. School of American Research Press, Santa Fe, NM, pp 13–52 6. Ericsson G, Heberlein TA (2002) Attityder till varg och vargjakt i Sverige. SLU, Uppsala 7. Ericsson G, Sandström C (2005) Delrapport om svenskars inställning till rovdsjurspolitik och -förvaltning. SLU Umeå/FjällMistra & Umeå universitet/FjällMistra, FjällMistrarapport, Rapport nr: 10, Umeå, Sweden 8. Fitchen JM (1989) When toxic chemicals pollute residential environments: The cultural meanings of home and homeownership. Hum Organ 48:313–324 9. Gärdenfors U (2005) Rödlistade arter i Sverige 2005—The 2005 Red List of Swedish Species. ArtDatabanken. SLU, Uppsala 10. Grimes M (2005) Democracy’s infrastructure: The role of procedural fairness in fostering consent. Department of Political Science, Göteborg University, Göteborg 11. Hornborg A (1994) Environmentalism, ethnicity and sacred places: Reflections on modernity, discourse and power. Can Rev Sociol Anthropol 31:245–267 12. Ingold T (1993) The temporality of the landscape. World Archaeol 25:152–174 13. Liberg O, Andrén H, Pedersen H-C, Sand H, Sejberg D, Wabakken P, Åkesson M, Bensch S (2005) Severe inbreeding depression in a wild wolf (Canis lupus) population. Biol Lett 22:17–20 14. Lovell N (1998) Locality and belonging. Routledge, London 15. Löfgren O (1997) Mellanrum: Vita fläckar och svarta hål i storstadens utkant. In: Saltzman K, Svensson B (eds) Moderna landskap. Natur och Kultur, Stockholm, pp 45–69

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16. Mairal Buil G (1996) Social disarticulation and water policy in Aragon. In Second International Conference on Resettlement Issues: Oxford 9–14 September 1996. Refugee Studies Programme, University of Oxford and World Bank. Oxford, UK 17. Mairal Buil G (2004) The invention of a minority: A case from the Aragonese. In: Boholm Å, Löfstedt R (eds) Facility siting: Risk, power and identity in land use planning. Earthscan, London 18. McCarthy J (2002) First world political ecology: lessons from the wise use movement. Environ Plann A 34:1281–1302 19. McCarthy J (2005) Guest editorial. Environ Plann A 37:953–958 20. Nesbitt JT, Daniel W (2001) Conflicting environmental imaginaries and the politics of nature in central appalachia. Geoforum 32:333–349 21. Prop.2000/01:57. Sammanhållen rovdjurspolitik [Coherent Predator Policy]. Miljödepartementet 22. Riley RB (1992) Attachment to the ordinary landscape. In: Altman I, Low SM (eds) Human behavior and environment: Advances in theory and research. Place attachment. Plenum Press: New York, pp 13–35 23. Robbins P (2002) Obstacles to a first world political ecology? looking near without looking up. Environ Plann A 34:1509–1513 24. Sand H, Wabakken P, Liberg O (2004) Vargens biologi: karaktärer och konsekvenser för små populationer. In: Jansson G, Seiler C, Andrén H (eds) Skogsvilt III. Grimsö forskningsstation, Sveriges Lantbruksuniversitet, Riddarhyttan, pp. 58–65 25. Saxon JL (1935) Jakt och jägare i gamla tiders Närke [Hunting and hunters in old time Närke]. Saxon & Lindströms Förlag, Stockholm 26. Schama S (1995) Landscape and memory. Alfred A. Knopf Inc, New York 27. Scott JC (1998) Seeing like a state. Yale University Press, New Haven 28. Sjölander-Lindqvist A (2004a) Local environment at stake: The Hallandsås railway tunnel in a social and cultural context. Human Ecology Division, Lund 29. Sjölander-Lindqvist A (2004b) Vizualising place and belonging: Landscape redefined in a Swedish farming community. In: Boholm Å, Löfstedt R (eds) Facility siting: Risk, power and identity in land-use planning. Earthscan, London 30. Sjölander-Lindqvist A (2006) Den är ju inte i fårhagen på studiebesök—om lokala perspektiv och uppfattningar om varg och rovdjursförvaltning. CEFOS, Göteborgs universitet, Rapport 2006:1, Göteborg 31. Sjölander-Lindqvist A, Serena C (2006) Negotiating ’Dead-end’ Decisions: Organizing REGIONAL Groups in Predatory Animal Issues in Sweden. in New Perspectives on Risk Communication Conference. Göteborg 32. Skogen K, Olve K (2003) A wolf at the gate: the anti-carnivore alliance and the symbolic construction of community. Sociol Ruralis 43:309–325 33. Skr.2001/02:173. En samlad naturvårdspolitik. Miljödepartementet 34. SOU 1999:146. Rovdjursutredningen—Slutbetänkande om en sammanhållen rovdjurspolitik. Miljö- och samhällsbyggnadsdepartementet 35. Wabakken P, Åke A (2006) Ulv i Skandinavia pr. 5 april 2006. Foreløpige konklusjoner for vinteren 2005/2006. Høgskolen i Hedmark, Oppdragsrapport nr. 5 36. Wilson MA (1997) The wolf in yellow stone: science, symbol, or politics? Deconstructing the conflict between environmentalism and wise use. Soc Nat Res 10:453–469

Seas, Ecological Balance and Sustainable Environment. Heavy Metals in the Water of Lake Ohrid and in Fish Species Belbica – Alburnus alburnus alborella de Filippi Suzana Aliu, S. Jusufi, Majlinda Daci, and Shefket Dehari

Abstract Water is a must need for the life and none of the living creatures could exist without it. But, in meantime water could became a cause of some diseases and the death. With the social society development, improvement of the well-being and increase of the number of the residents in our planet, also the individual and economical need for the water is increased. The permanent human being is used only to take things from the nature not to contribute to the “nature”. However human egoism in rapport with nature and the vital environment, which is exploited without control and without any care can destroy the entire ecosystems. All of this is returned to the humans and seen in their life and health. The aim of this paper was analysis and determination of heavy metals like Cu, Zn, Cd, and Pb in water samples of different prophiles from Ohrid Lake. Studied water samples were taken in different locations and different depths (0, 20, 40, 75, 100 and 150 m). The presence of toxic heavy metals in food chain was studied in fish species – Belbica (Alburnus alburnus alborella de Filippi). Determination of analysed heavy metals was done using Atomic Absorption spectroscopy using a Perkin Elmer 370 A and 370 flame – air acetylene and AAS Peyunicam 926 model. Keywords Water Belbica · Conservarion · Heavy Meta

1 Entry Metals occur naturally in the environment and are present in rocks, soil, plants, and animals. Metals occur in different forms: as ions dissolved in water, as vapors, or as salts or minerals in rock, sand and soil. They can also be bound in organic or inorganic molecules, or attached to particles in the air. Both natural anthropogenic processes and sources emit metals into air and water. The effects of metals in the environment depend to a large extent on whether they occur in forms that can be taken up by plants or animals. Uptake of metals in S. Aliu (B) Study of Polytechnic Center, State University of Tetovo, Tetovo, Macedonia e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_3,

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an animal involves metal ions crossing a cell membrane. Often a ligand, or a carriers, executes this transport. Sometimes there are additional specific carriers within the cell. If an organism’s uptake of metal is greater than its ability to get rid of it, the metal will accumulate. Heavy metals tend to accumulate in storage compartments. For example, cadmium accumulates preferentially in the kidneys, and lean in the skeleton. The accumulation can continue throughout the organism’s life and is the major cause of chronic toxicity. In contrast to organic pollutants, metals accumulate in protein tissues and bone rather than fat.

2 Ohrid Lake Is situated in the Southeastern part of Europe, with Albania and FYR of Macedonia as the only two lakeshore states. It is peculiar for it’s rich biodiversity, that derives of it’s very old age. Ohrid Lake is the biggest and the deepest from all the lakes of the group known as “Desaret”. It is called a Museum of living fossils and it offers a living environment for too many organisms typical for mild waters, which, in the Balkans Peninsula and Central Europe are found only in the fossil form. Another typicalpeculiarity of this Lake is its the only flow – the river Drini i Zi, with an approximate flow of 22.4 m s, for most of the time. The beautiful parts of the lake can be viewed on the pictures below.

The dirty parts of the lake can be viewed on the pictures below.

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3 Living Species Ohrid Lake is well known for its 17 kinds of fish. They are all autochthonous species. Ten of them are commercially important. Another peculiar feature of this lake is its ability to self regeneration. Its water comes from different sources as well as from its water accumulating basin. Because of these peculiarities, beginning from 1980, Ohrid Lake and the city itself are under the protection of UNESCO.

4 Experimental Engagement 4.1 Material Gathering and Working Methods In this output, the presence of heavy metals (Fe, Mn, Cu, Cd, Pb, Ni, Zn) in the water on its vertical profile was analyzed, beginning from levels (0, 20, 40, 75, 100 and 150 m depth), as well as their impact in the nutrition chain. Three exemplars of fish known as Belbica (Alburnus alburnus alborella de Filippi), B1, B2 and B3 were examined. From each of them organs like gills, liver, muscular tissues and bones were dissected. After the dissection, the determination of the concentration of the heavy metals, such as: Zn, Cu, Cd and Pb in each of the organs was done. To achieve this, SAA – Spectroscopy of Atomic Absorption – the flame technique was used. The measurements were done by Spectrophotometer of the atomic absorption of the type PERKIN – ELMER 370 A and 370. Flame – Air– Acetylene and SAA PEYUNICAM 926 (4).

Belbica (Gjuca) – Alburnus alburnus alborella de Filippi 1844

5 Experimental Results Achieved results are presented in charts/graphics as follows: Charts 1–5 to represent the achieved results of the concentration of the heavy metals on the studied samples through experimental work.

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Graphic charts from A to E represent the same results – the results from the previous Charts 1–5, added is only a better visual representation of them.

6 Discussion of the Results After having thrown an analytic view on the results given above through the charts, both numeric and graphic ones, one can notice very clearly that on the vertical profile of the lake waters, the concentration of the metals were traced, as follows: Concentration of Mn goes from 0.10 mg/l in 20 m to 1.91 mg/l in 150 m deepness (Table 1, Chart 1). Iron – Fe was represented in concentrations 1.0 mg/l in 20 m up to 1.91 mg/ in 150 m deepness (Table 1, Chart 1). Zinc was registered on minimal values from 0.41 mg/l in 20 m, up to 0.45 mg/l in 100 m deepness (Table 1, Chart 1). Copper was registered from 0.07 mg/l in 20 m to 0.07 mg/l in 100 m deepness (Table 1, Chart 1). Nickel gave these results: 0.38 mg/l in 20 m up to 0–85 mg/l in 150 m deepness (Table 1, Chart 1). Table 1 Determination of heavy metals in the water on the vertical profile of the lake by SAA – mg/l Sample

0m

20 m

40 m

75 m

100 m

150 m

Fe Mn Zn Cu Cd Ni Pb

0.8 0.15 0.33 0.05 – 0.26 –

1.0 0.1 0.41 0.06 – 0.38 –

0.9 0.14 0.37 0.06 – 0.3 –

1.2 0.21 0.29 0.07 – 0.27 –

1.0 0.24 0.45 0.07 – 0.18 –

1.91 0.25 0.4 0.06 – 0.85 –

2 0m 20m 40m 75m 100m 150m

1.5 1 0.5 0 Fe

Mn

Zn

Cu

Cd

Ni

Pb

Chart 1 Concentration of Fe, Mn, Zn, Cu, Cd, Ni and Pb in water on the vertical profile of the lake, determined with SAA (mg/l)

Heavy Metals in the Water of Lake Ohrid and in Fish Species Belbica

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From the analyses done on the studied water samples, about the concentration of the above mentioned metals, one can easily understand that, with some exceptions, their concentration on the lake waters is not of a high level. That’s why, we can say that the waters on the vertical profile of the Ohrid Lake belong to the waters of the first or second class (Tables 2, 3, 4, 5, and 6). In order to have a realistic view about what was stated above, during the determination of the presence of the heavy metals in the organs of fish, our results have shown the values given below:

Table 2 Parameters of analysed fish Sample

B1

B2

B3

Length cm Weight g Gills g Liver g Muscular tissues g Bones g

14 22.205 0.183 0.255 0.725 0.05

12.5 16.67 0.242 0.205 0.506 0.02

13.5 21.37 0.241 0.203 0.672 0.02

Table 3 Determination of heavy metals on gills of fish with SAA – μg/l Sample

B1

B2

B3

Zn Cu Cd Pb

115.3 25.9 9.3 74.16

30.64 126.6 0.92 1.27

24.6 139.6 0.77 13.9

Table 4 Determination of heavy metals on liver of fish with SAA – μg/l Sample

B1

B2

B3

Zn Cu Cd Pb

127.4 285.6 1.4 −

162.2 210.3 2.38 −

142.2 164.5 6.32 48.8

Table 5 Determination of heavy metals on the fish muscular tissue with SAA – μg/l Sample

B1

B2

B3

Zn Cu Cd Pb

3.8 21.5 0.45 2.9

2.12 22.1 1.08 38.4

1.46 27.1 1.91 0.52

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S. Aliu et al. Table 6 Determination of heavy metals on fish bones with SAA – μg/l Sample

B1

B2

B3

Zn Cu Cd Pb

7.72 486 1.36 3.8

26.8 403 1.3 2.12

30.5 18.9 1.4 1.46

Chart 2 Concentration of Zn in the organs of fish, determined with SAA (μg/g)

180 160 140 120

gills

100

liver muscular tissues

80 60

bones

40 20 0 B1

B2

B3

Minimal amount of Zinc was accumulated in the muscles 1.46 μg/kg B3 (Table 5, Chart 2), up to 162.2 μg/kg in the liver B2 (Table 4, Chart 2). Copper did give these results: 21.5 μg/kg – B1 in muscles (Table 5, Chart 3) up to 486 μg/kg B1 in the bones (Table 6, Chart 3). The amount of the concentrated Lead goes from 0.52 μg/kg in muscles – B3 (Table 5, Chart 4), up to 74.16 μg/kg in gills – B1 (Table 3, Chart 4). Results of the Cadmium have shown that the gill of B3 possesses a concentration of 0.77 μg/kg (Table 3, Chart 5), up to 9.3 μg/kg in the gills of B1 (Table 3, Chart 5).

180 160 140 120 100

gills liver

80

muscular tissues bones

60

Chart 3 Concentration of Cu in the organs of fish, determined SAA (μg/g)

40 20 0 B1

B2

B3

Heavy Metals in the Water of Lake Ohrid and in Fish Species Belbica Chart 4 Concentration of Pb in the organs of fish, determined SAA (μg/g)

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80 70 60 50

gills

40

liver

30

muscular tissues bones

20 10 0 B1

Chart 5 Concentration of cadmium in the organs of fish, determined SAA (μg/g)

B2

B3

80 70 60 50

gills

40

liver

30

muscular tissues

20

bones

10 0 B1

B2

B3

7 Conclusions Presence of the heavy metals in the leaving creatures is done by their penetration through the cell membrane. This process is frequently done through some conductors specific for the cells. Metals get accumulated in the organism in cases when the conductivity of a given metal is bigger than the capacity of the organism to get rid of it. It is typical for the heavy metals to get themselves accumulated in the accumulative organs. This way, cadmium initially is accumulated in the kidney, copper in liver and Lead in skeleton. This process goes on during the whole lifetime of the organism and occasionally it brings it to the level of chronic poisoning. From the above results, one can notice that the fish belbica does accumulate a higher amount of heavy metals and this amount get bigger together with the weight of the fish. From what was stated above, one can conclude that the accumulation of heavy metals by the leaving creatures that do live within water ecosystems, is an ongoing process that is not preferred because it represents a sort of threat for their mere existence as well as for the nutrition chain to come.

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References 1. Hart B, Hines T (1995) Trace elements in rivers. In: Salbu B, Steinnes E (eds), Trace elements in natural waters. CRC, Press, Boca Raton, Ann Arbor, London, Tokyo, pp 203–221 2. Beckett R (1990) Surface and colloid chemistry in natural waters and water treatment. Plenum Press, Melbourne 3. Hong J, Calmano W, Foerstner U (1995) Interstitial waters. In: Salbu B, Steinnes E (eds), Trace elements in natural waters. CRC Press, Boca Raton, Ann Arbor, London, Tokyo, pp 117–150 4. Spirkovski Z (2002) Teški metali i pesticidi vo ribite od Ohridskoto Ezero. Hidrobiološki zavod Ohrid 5. Balvay R (1991) What is the best time reference to express biological results. The calendar year or the ecological year. Verh Int Verein Limnol 24:928–930 6. Risteski K, Davitkovski B (1997) Ekološko pravo, Shkup. pp. 18–22 7. Goldman CR (1983) Horne, limnology. McGraw-Hill Book Company, New York St. Luis-San Francisko-Auckland, Bogota- Hamburg-Toronto, pp 464 8. Arsoski M (1974) Nekoi pogledi vrz genezata na Ohridskoto Ezero. MANU. Simpozium za problematikata na regulacijata na Ohridskoto Ezero, pp 76–85 9. Naumovski T (1985) Oligomiksijata na Ohridskoto Ezero. Hidrobiološki zavod. Jubilejno izdanie, 1:217–226 10. Hadište J (1992) Dosegašnite sovetuvanja za problemite na zaštitatata na Ohridskoto Ezero so negovata okolina i novi predlozi za nivno rešavanje. DEM. Zbornik na trudovi “Ohridskoto Ezero i negovata zaštita”, pp 19–26 11. Naumovski T (2000) Fosforno optovaruvanje na Ohridskoto Ezero. Dokt. Diser. Univ. “Sv. Kiril i Metodij” PMF – Institut za biologija; Shkup, pp 1–37 12. Hecky R (1993) The eutrophication of lake Victoria. Verh Internat Verein Limnol 25:39–48 13. Ntakimazi G (1992) Conservation of the resources of the African great lakes. Mitt Internat Verein Limnol 23:5–9 14. Twenddle D (1992) Conservation and threats to the resources of Lakes Malawi. Mitt Internat Verein Limnol 23:17–24 15. Naumovski T (1999) Promeni na alkalnosta na nekoi regioni od Ohridskoto Ezero kako rezultat na nutrientnoto iskoristuvanje. Zbornik na trudovi. I Kongres na ekolozite na Makedonija so megjunarodno u´cestvo, pp 268–275 16. Ikonomi, Gj. (2002) Ndikimi i aktivitetit minerar në Liqenin e Ohrit. Kumtesë. Inst. Hidrobiologjik, Ohër 17. El-Hasani S, Al-Dhaeri S, El-Maazawi M, Kamal M (1999) Polarographic and voltammetric determination of some toxic heavy metal jones in the treated Waster water at Abu – Dhabi, UAE. Water Sci Technol 40(7):67–74. IWA Publishing 18. Meany M (1995) Determination of Pb and Cd in seawater by F – AAS using preconcentration trace elements in seawater htm. Dublin City University

Space Analysis and the Detection of the Changes for the Follow-Up of the Components Sand-Vegetation in the Area of Mecheria, Algerie Haddouche Idriss, Mederbal Khaladi, and Saidi Slim

Abstract The Algerian steppe has become for a few years the theatre of an ecological and climatic imbalance. The intense degradation for this fragile medium (stranding wind erosion, overgrazing, clearing, salinisation . . . .) inducing the turning into a desertification require a better comprehension in order to see how to fight against this plague and to adapt an adequate installation to him. Thus, this work lies within the scope of the follow-up of the phenomenon of the turning into a desertification on a space with the heart of the high Oranian southern steppe plains, in fact the area of Mecheria. Techniques of numerical cartography, since the satellite image processing until the geographic information systems (SIG) for the realization of the charts sets of themes, being able to highlight this calamity. The use of the approaches based on the exploitation of the satellite data multi dates (1998 and 2004) of the sensor Thematic Mapper (TM) of Landsat 5 permitted us to obtain a gathering of an interpretative photo maps and vegetation index which, in their turn, helped us to see the changes arrived in the medium, copiously regressive that progressive. Keywords Desertification · Remote sensing · Steppe · Mecheria · Algeria Résumé La steppe algérienne est devenue depuis quelques années le théâtre d’un déséquilibre écologique et climatique. La dégradation intense de ce milieu fragile (ensablement, érosion éolienne, surpâturage, défrichement, salinisation . . .) induisant la désertification, nécessite une meilleure compréhension en vue de voir comment lutter contre ce fléau et lui adapter un aménagement adéquat. Ainsi, ce travail s’inscrit dans le cadre du suivi du phénomène de la désertification sur un espace au cœur des hautes plaines steppiques sud oranaises, en l’occurrence la région de Mecheria. Les techniques de cartographie numérique, depuis les traitements des images satellitaires jusqu’aux systèmes d’information

H. Idriss (B) Département de Foresterie, Faculté des Sciences, Université de Tlemcen BP 119, Tlemcen 13000, Algeria e-mail: [email protected]

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géographique (SIG) pour la réalisation des cartes thématiques, pouvant mettre en relief cette calamité. L’utilisation des approches basées sur l’exploitation des données satellitaires multi dates (1998 and 2004) du capteur Thermaux Mapper (TM) de Lands 5 nous a permis l’obtention d’un ensemble de cartes photointerprétations et des indices de végétation qui, à leur tour, nous ont aidé à apercevoir les changements parvenus dans le milieu, copieusement régressifs que progressifs. Mots clés Désertification · Télédétection · Steppe · Mecheria · Algérie

1 Introduction The degradation of the dry and semi-dry ecosystems in Algeria has become a fact which shows down the progress of rural development [1]. In these milieus, the lack of vegetation is apparent and the eolian erosion predominates. The ecosystem has a long hot season and a weak rainfall. In these areas, the phenomenon is called desertification. The emergency of the struggle against this phenomenon is imposed by the process itself, when man’s intervention doesn’t come on time; it creates situations forbidding the possibility of arranging these areas [2]. In the case of the steppes located north of the Sahara, the degradation process of the soils, has been studied: the covering rate of the vegetation decreases, and hence gives birth to dunes. The sensitiveness of the desertification appears as a set of indicators synoptic adapted to the evaluation scale. Hence, an indicator may be defined as a tool which enables to characterize the milieu, the constraints and the answers. The pictures sent by the observation satellites of the earth, are an important source of information. They allow us to collect the information about the resources of earth [3]. Taking this advantage for granted, it is useful to conduct a map survey with the help of a tool “remote sensing” as an applying help over a dry area, located in the heart of the high plains south of Oran, called Mecheria.

2 The Milieu Study 2.1 The Geographical Setting As far as the administrative point of view is concerned, our area of study is located in the commune of Mecheria, wilaya of Naama. It’s geographically bordered in the North and the West by the commune of El-Biodh, in the East by the wilaya of El-Bayadh and in the South by the commune of Naama.

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Fig. 1 Localization of the zone of study

The main physical sets of the area of study are as follows: • A dune in the North; • The city of Mecheria lies in the centre of the area at the bottom of Djebel Antar which is 30 km long and 1,712 m of high point. • The “sebkha” of Naama, in the South. It could be collected on a topographic map at 1/100.000eme with following coordinates (Fig. 1): • Longitude: 0◦ 3 00 –0◦25 00 West (Greenwich meridian); • Latitude: 32◦ 40 22 –32◦51 52 North.

2.2 The Natural Milieu The climate of the area of Mecheria is a Mediterranean climate dry with cold winters [2] and [4]. It is characterized by two (02) contrasting seasons. The first is cold and wet, and goes till the end of October until early May with an average temperature of 10.05◦C and a rainfall of 147 mm, the other is dry and hot and runs from mid May to mid October with an average temperature of 21.77◦C and a rainfall of 86.49 mm. The area of Mecheria is composed of three (03) types of formation (Fig. 2): • Djebel Antar corresponds to an anticlinal composed essentially of formations of Jurassic age; • The plains; • The recent depots.

40

Fig. 2 The geological setting of the area of Mecheria

Fig. 3 The slope map of the area of Mecheria

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The map allows us to distinguish 4 categories showing the geomorphologic diversity of the milieu: Category 1: 0–3% Category 2: 3–12% Category 3: 12–25% Category 4: 25–88%. This information varies between 0% (the lowest points) until 88% (the highest point) that of Djebel Antar (Fig. 3). The types of soils in the area of Mecheria are lithological, like greys types, calcareous, marine and clay. We can distinguish: • • • •

The sand soils; The colluviums; The alluviums; The calcareous glacis.

3 Used Data For this application, we have used satellite pictures data of two different dates (Figs. 4 and 5).

Fig. 4 Picture TM 4.3.1 (1998)

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Fig. 5 Picture TM 4.3.1 (2004)

• Picture LANDSAT 5 Thematic Mapper (scene 198/37) of October 24 1998; • Picture LANDSAT 5 Thematic Mapper (scene 198/37) of March 27, 2004. We got interested in the spectral field of the TM captor by the combination of three bands (4, 3 and 1) for the two pictures. The picture extracts are 1000 × 1000 pixels, whose contours are more or less equidistant from the city of Mecheria. The resolution of the pixel of TM picture is 30 × 30 m.

4 Methodology The work conducted on the area of study (set of treatments and photo interpretation through computer) based on the use of satellite multi temporal pictures and different software of the treatment of pictures. The approaches used are synthesized and represented in the form of an organisation diagram (Fig. 6). The mapping way is based on two types of criteria:

Space Analysis and the Detection of the Changes in Mecheria, Algerie

LANDSAT TM image (1998)

Auxiliary data

Pretreatments: -Geometric correction -Radiometric correction

43

LANDSAT TM image (2004)

Extraction of windows of region study

Image extract TM 4.3.1 (2004)

Image extract TM 4.3.1 (1998) Specific treatments Classified image (1998) NDVI 1998

Ground reality

COMPARISON Index change

Sand map (1998)

Classified image (2004) NDVI 2004

Sand map (2004)

Comparison and detection of changements Fig. 6 Organisation diagram methodology

• the criteria related to the satellite picture: geographical location; colours; geometric forms; • the criteria of environment: topography, vegetation, climatic data, . . .etc. These criteria allow the recognition of the homogeneous units of the level of vegetation cover, there delimitation and there representation [4] and [5]. Consequently, the diachronic approach contributes to the evolution of the milieu between two (02) dates (1998 and 2004). Thus, the mixing of the two NDVI will help us get a final image presenting different changes which happened in the steppic area.

5 Results and Discussion The interpretation allows providing a thematic cartography. The superposition of three bands of the TM, hence the supervised classification (Figs. 7 and 8) and the indices of vegetation (Figs. 9 and 10) have shown that there has been a very

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Fig. 7 Classified image by maximum likelihood (1998)

Fig. 8 Classified image by maximum likelihood (2004)

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Space Analysis and the Detection of the Changes in Mecheria, Algerie

Fig. 9 Vegetation index “NDVI” (1998)

Fig. 10 Vegetation index “NDVI” (2004)

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46

Fig. 11 Change index

Fig. 12 Sand map (1998)

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Fig. 13 Sand map (2004)

important regression during the last 6 years between 1998 and 2004 (Fig. 11). This is due to the degradation of the vegetal cover caused by an over exploitation. The sand remains a very important factor in the area. The sand map obtained by the unsupervised classification for the two dates, showed us a reverse effect (Figs. 12 and 13), due essentially to the date of the two pictures, one in autumn and the other in spring. We have compared the physiognomic types of the units in 1998 and those of 2004 where there is a change for the elements on the surface of the ground (Fig. 14). The rate of recovering of Alpha (Stipa Tenacissima) group has a decrease from 11.18 to 2.37%. It’s a species which regenerates because of the problems of overexploitation. Unlike the Alfa, the “psammophites” species have known a high increase of their recovering rate from 1.42 to 40.66%. The appearance of species of Peganum harmala, Salsola vermiculata and Noea microphila is the sign of the degradation of the vegetal cover. This is due to the impact of the human actions on our milieu principally with an increase of the urbanisation rate 0.38–2.52%. However, other mutations less significative are due to the shade effect, considering the difference between the angles of elevation and also the dates when the images were taken.

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Fig. 14 Comparison between the physiognomic types (1998–2004)

6 Conclusion The use of these approaches based on the exploitation of the satellite data (1998– 2004) of the captor Thematic Mapper (TM) of the Landsat 5 allowed us to obtain a set of maps photo interpretative and signs of vegetation which helped us to see the changes which happened in the milieu. Hence the movies of the degradation of the milieu in the area of Mecheria. The area of Mecheria identified as degraded on the whole, is the result of human actions. If urgent measures are not taken, this degradation, stressed by the phenomenon of dryness, may engender one or many processes of desert advance, endangering the natural milieu and the sustainability of the resources (soil, fauna and flora). Thanks to remote sensing, it’s possible to bring a help to the prospector provided the elements of surface may be discriminated and to reduce the duration of the prospection of the field in varied milieu and difficult of access.

References 1. Haddouche I, Mederbal K, Bouazza M, Benhanifia K (2004) Utilisation de la télédétection pour l’étude de la déforestation. Cas de la région de Djelfa. Colloque Méditerranéen sur la Gestion Durable des Espaces Montagnards. Dept. Sc. de la Terre et Agronomie, Univ. Tlemcen, 10–11 Oct. 2004. 10p 2. Halem M (1997) La steppe Algérienne : causes de la désertification et propositions pour un développement durable. Thèse de magistère. UNIV Sidi Bel Abes. 180p 3. Scanvic JY (1983) Utilisation de la télédétection dans les sciences de la terre. Manuels et méthodes dans les sc. de la terre. Manuels et méthodes. BRGM. France. 158p 4. Haddouche I, Benhamouda F, Djili K (2001) Cartographie pédopaysagique de synthèse par télédétection «images Landsat TM.». Cas de la région de Ghassoul (El Bayadh). Actes du

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3ème COLLOQUE « Géophysique des sols et des Formations Superficielles » 25–26 Septembre 2001 Orlérans, France. INRA, Paris. ISBN: 2-7380-0991-3, pp 61–65 5. Benhanifia K, Haddouche I, Smahi Z, Bensaid K, Hamimed A (2003) Characterization of the deforestation effect in a semi-arid region by the use of satellite images. Proc. SPIE vol. 5232, RS 2003, pp 324–332, Remote sensing for agriculture, Ecosystems, and Hydrology V; eds. Feb. 2004 ISBN-0-8194-5142-8

Biodiversity and Actual Status of Narta and Dukati Lagoons in Albania Liljana Elmazi and Evelina Bazini

Abstract In this paper we have emphasise that sustainable tourism depends on community involvement and participation, communities should benefit from sustainable tourism, tourism is closely linked to the preservation of a healthy environment, which in turn is an essential element of tourism development and helps to raise public awareness on some biodiversity issues. An assessment of the interlinkages biological diversity and tourism was endorsed. This included consideration of the economic importance of tourism and its interrelationship with the conservation and sustainable use of biological diversity, as well as the potential impacts of tourism on biological diversity, including economic, social and environmental impacts. The management process comprises ten steps for management of sustainable tourism and biodiversity: (1) Baseline information and review; (2) Vision and goals; (3) Objectives; (4) Review of legislation and control measures; (5) Impact assessment; (6) Impact management; (7) Decision making; (8) Implementation; (9) Monitoring; (10) Adaptive management. Also we analyse the biological diversity in Albania, especially in Narta and Dukati lagoons. Keywords Biodiversity · Lagoon · Sustainable tourism

1 Biological Diversity and Tourism Within the Convention on Biological Diversity The fact that tourism is expanding in all regions, including in remote and sensitive areas such as islands and new mountain areas, and Antarctica, and that the main areas where tourism is based include: small island developing states and coastal

L. Elmazi (B) Faculty of Economics, University of Tirana, Tirana, Albania e-mail: [email protected]

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regions; mountains; species-rich and protected areas; and urban areas, emphasise the growing pressure on biological diversity [3]. Tourism has been discussed in the context of the Convention on Biological Diversity (CBD) as a cross-cutting issue for a number of years. The CBD was signed at the 1992 United Nations Conference on Environment and Development in Rio de Janeiro [1]. With 182 parties ratified so far, it is the most successful environmental convention. The Convention has three basic objectives: • Conservation of Biological Diversity • Sustainable use of its components • Fair and equitable sharing of benefits At the fifth Conference of the Parties (COP5) in May 2000 in Nairobi, Decision V/25 on Biological diversity and tourism was adopted, which recognized that the scale and expansion of tourism has major implications for the conservation and sustainable use of biodiversity, and for attainment of the Convention’s objectives. Decision V/25 noted the increasing importance of tourism for social and economic development at local, national and regional levels, and that, in relation to the provisions of the Convention on Biological Diversity: • sustainable tourism depends on community involvement and participation, • communities should benefit from sustainable tourism, • tourism is closely linked to the preservation of a healthy environment, which in turn is an essential element of tourism development and helps to raise public awareness on some biodiversity issues. An assessment of the inter-linkages biological diversity and tourism was endorsed. This included consideration of the economic importance of tourism and its interrelationship with the conservation and sustainable use of biological diversity, as well as the potential impacts of tourism on biological diversity, including economic, social and environmental impacts [2]. Furthermore, Decision V/25 accepted the invitation to participate in the international work program on sustainable tourism development under the Commission on Sustainable Development process with regard to biological diversity, in particular, with a view to contributing to international guidelines for activities related to sustainable tourism development in vulnerable terrestrial, marine and coastal ecosystems and habitats of major importance for biological diversity and protected areas, including fragile riparian and mountain ecosystems, bearing in mind the need for such guidelines to apply to activities both within and outside protected areas, and taking into account existing guidelines, and requests the Executive Secretary to prepare a proposal for the contribution guidelines, for example by convening an international workshop.

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2 Draft International Guidelines for Activities Related to Sustainable Tourism Development in Vulnerable Areas The International Guidelines for activities related to sustainable tourism development drafted at the Santo Domingo Workshop are intended to assist Parties to the Convention on Biological Diversity, public authorities and stakeholders at all levels, to apply the provisions of the Convention to the sustainable development and management of tourism activities. They will provide technical guidance to policy makers, decision makers and managers with responsibilities covering tourism and/or biodiversity, whether in national or local government, the private sector, indigenous and local communities, non governmental organizations or other organizations, on ways of working together with key stakeholders involved in tourism and biodiversity in order to contribute, interalia, to functioning ecosystems; sustainable tourism in functioning ecosystems; fair and equitable sharing of benefits; information and capacity-building; restoration of past damage.

2.1 Scope The guidelines cover all forms and activities of tourism, which should all come under the framework of sustainable development, in all geographic regions. These include, but are not limited to, conventional mass tourism, ecotourism, nature-and culture-based tourism, cruise tourism, leisure and sports tourism.

2.2 Management Process Steps The management process needs to be undertaken through a multi-stakeholder process. Interdepartmental and inter-organizational structure and processes should be established to ensure coordination to guide policy development and implementation and to improve awareness and exchange of knowledge among stakeholders at all levels. A consultative process, based on multi-stakeholder participation, should be established to ensure ongoing and effective dialogue and information sharing and the stakeholder engagement and participation in the whole process. The establishment of partnership should be encouraged. The management process comprises ten steps for management of sustainable tourism and biodiversity: 1. 2. 3. 4. 5.

Baseline information and review; Vision and goals; Objectives; Review of legislation and control measures; Impact assessment;

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6. 7. 8. 9. 10.

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Impact management; Decision making; Implementation; Monitoring; Adaptive management.

2.3 Notification Process and Information Requirements Proposals for tourism development and activities at particular locations in relation to biodiversity, are to be submitted through the notification process. Proposers of tourism projects, including government agencies, should provide full and timely advance notice to relevant authorities and all stakeholders who may be affected, including indigenous and local communities, of proposed developments through a formal process of prior informed approval. Information provided should be made public, and public comment invited on all proposals for tourism development and activities. Government response to notification of proposals for tourism development may range from approvals, with or without conditions, to refusal of the proposal. Further information from the proposer and further research by other agencies may be requested by Governments.

2.4 Public Education and Awareness Raising Public education and awareness raising campaigns need to be addressed to both the professional sectors and the general public to inform them about the impacts of tourism on biological diversity, and good practices in this area. Public awareness campaign will need to be tailored for various audiences, particularly stakeholders including consumers of tourism, developers and tourism operators. The private sector could play an active role encouraging conservation among clients. Education and awareness-raising is required at all levels of government. Awareness should also be increased within and outside governments that vulnerable ecosystems and habitats are often located within lands and waters occupied or used by indigenous and local communities. It is also important to raise awareness within the academic sector responsible for training and research on issues regarding the harmonious interaction between biological diversity and sustainable tourism.

2.5 Capacity Building Capacity-building activities should aim to develop and strengthen the capacities of governments and all stakeholders to facilitate the effective implementation of

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these guidelines, and may be necessary at local, national, regional and international levels. Capacity-building activities can include strengthening human resources and institutional capacities; the transfer of know-how; the development of appropriate facilities; training in relation to biological diversity and sustainable tourism issues, and impact assessment and impact management techniques. Local communities should also be equipped with the necessary decision-making abilities, skills and knowledge in advance of future tourist in-flows, as well as with relevant capacity and training regarding tourism services and environmental protection. Capacity-building activities should provide assistance to stakeholders in undertaking all the steps of the management processes and in strengthening mechanisms for impact assessment. Capacity-building should also include the establishment of multi-stakeholder processes and the training of tourism professionals. Information exchange and collaboration regarding sustainable tourism implementation through networking and partnerships between all stakeholders affected by, or involved in tourism, including the private sector, should be encouraged.

3 Case Study: Narta and Dukati Lagoons 3.1 Historical Introduction The fisheries activities in Narta and Dukati lagoons are some of the oldest and most traditional activities in our country. Due to sensible alterations of the productions in different years, there were made important studies such as: “Study of the Narta lagoon in its hydrological, hydro chemical, hydro biological and fishing aspects (1987–1988)”. The same studies were carried out for Dukati lagoon in 1990. The coastal area of Narta and Dukati lagoons was monitored for the heavy metal presence, the physical and chemical parameters, the bacterial abundance and the dynamics of bivalve mussel populations (the mussels that have socio-economic importance). In 1994–1996 in cooperation with the Montpellier University (Hydrobiology lab) were made some expeditions in Narta lagoon about phytoplankton, the suspension matter and some physical chemical parameters. From the statistical data, the production has had great alterations in years and in species components. The species with the greatest alterations are: for the fish group, eel (Anguilla anguilla), gilthead seabream (Sparus aurata), sand smelt (Aterina sp.) and crab (Carcinus aestuarii), and for the mussel group we have in Dukat, grooved carpet shell (Ruditapes decussatus), golden carpet shell (Venerupis aurea) and in Narta donax (Donax sp.)

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3.2 Mussel and Ichtyc Species Status It’s important to say that we don’t have species going toward extinction. However we must not forget the dystrophic crises and hydrological conditions and in the recent years also the irresponsible fishing and human intervention, which have caused serious problems for these ecosystems, which are crucial in the renovation of the fishery stock of the coastal area. These ecosystems have a typical Mediterranean hydrological structure and are similar with other Albanian lagoons. There some changes, especially for the Narta lagoon: The growth rate compared with other Albanian lagoons is lower of 20–40% The species compositions is worse than elsewhere High yield is obtained by high intensity fishing efforts and efficient fishery tools. The total of species are included in important species, threatened species and species that have socio-economic value. In this lagoon we don’t have species that are in extinction danger, and actually it is a clean area and we don’t have any critical conditions. However these ecosystems are threatened by: Uncontrolled fishing The income of polluted waters, which are potentially eutrophic The development of tourism and the urbanization, which threatens the biotopes of the species. 3.2.1 Rare Species These lagoons are typical Mediterranean and their ichtyofauna and malacofauna in general is the one that is present in Adriatic and Ionian coast. Studies show that the only rare species is the gastropod (Hydrobia ventosa) of Fam. Hydrobidae in the Narta lagoon. This gastropod inhabits the western side of the lagoon Priority for the existence of this species like for all the other species remains the improvement of the lagoon connection with the near coast. 3.2.2 Endemic Species The Narta and Dukati lagoon don’t have endemic species because their ecosystem has active connections with the near coast. However the experience of other Mediterranean countries suggest us that in function of the abiotic conditions the most representative species form local populations. The new FAO Codes (Art. 9–10) aim that the lagoon has to be populated only by its local population, made possible by an extensive aquaculture center.

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We must emphasize that the lagoon ichtyofauna is subject of coast-lagoon migrations, happening all year due to factors such as: abiotic, nutrient, habitat and reproduction conditions. 3.2.3 Important Species Narta Lagoon The main species of Narta lagoon, not only in the socio-economic meaning, but also as an indicator of the ecosystem state, are: Eel (A. anguilla), katadrom fish is the main species for the most of fishermen. Its production in different years changes with a maximum rate of 1:6 due to lagoon state, distrophic crises and in recent years related with decline eel stock in Mediterranean. When the eel migrates massively toward sea, its size shows the state of ecosystems, because although it’s eurihaline and euriterm species, temperature and especially high salinity are very restraining factors for its growth, often accompanied with massive losses during distrophic crises. Mullets Fam. Mugilidae, flathead grey mullet (Mugil cephalus), thinlip mullet (Liza ramada), leaping mullet (Liza saliens) have economic importance, especially (M. cephalus) who is also an indicator of the coast exploitment rate, sea communication and the fishery tools used, things that create conditions for a normal and sustainable of the lagoon and of the coastal area. The lagoon is rich with detrits, that shows the growth dynamic and a very high production over the past years but that nowadays is deteriorated. Sea breams, especially the gilthead sea bream (S. aurata) is a species that indicates the abundance of the mollusks in the lagoon, because they are its normal feed. It is also an indicator of the hydro chemical conditions, because often in winter due to lack of wintering places and low temperatures, the new generations are very reduced. Sea bass, European sea bass (Dicentrarchus labrax), stotted sea bass (D. punctatus) are very greedy species, which hunt the lagoon ichtyofauna such as mullets, sand smelt etc. They are euriterm and eurihalin species and their production is in function of the coastal stock state and reproduction conditions, because it’s from the coast that their feed comes. Sand smelts, Mediterranean sand smelt (Atherina hepsetus), big-scale sand smelt (A. boyeri) can reach the 30% of lagoon production, they grow in weed areas, and migrates toward sea only in winter when temperature is lower than 5–6 C. The production alterations for this species is linked with hydro meteorological conditions and water level in the lagoon [Dedei Z, Bego F, Marika K, Kapedani R (2005) Unpublished]. Mussels Donax clams (Donax trunculus, D. semistriatus) are spanned in the coastal area of the Narta lagoon communications channels. They are not only of economic importance, but also of an environmental one, because their population dynamic shows the coast state alluvium and the area clearance.

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Dukati Lagoon The most important species are the one that we met in Narta lagoon, but we must note some other mussels of great importance. Grooved carpet shell (Ruditapes decussatus) and golden carpet shell (V. aurea) are concentrated in the lagoon-sea communication area. The density for surface unit is linked with the intensity of the communication lagoon-sea and from the respecting of biological exploitment parameters.

3.3 Species Habitats in Narta Lagoon Mullets, sand smelts and eels are widespread during the spring season and located in central and western side during other seasons. Their biggest concentration is near the lagoon-sea communication channels. Sea bass, sea bream and other fish of the Sparidae family are located in the areas with at least 50 cm. Depth and in the western side of the lagoon. In Dukati lagoon the ichtyc species have a uniform dispersion, meanwhile R. decussates and V. aurea are in great quantity near the channel. Ichtyofauna and malacofauna have had great alteration in their population dynamic, the maximum and constant production was reached in 1990 with great deterioration during 1994–1998 and now it has some improvements.

3.4 Main Endangered Species M. cephalus has had a drastically decline in the last years, for these reasons: the intensification of the fishing being one of the preferred species (especially his salted eggs), the diminution of the juveniles in the coastal area and the lagoon-sea channel malfunction. The endangered sea bream species are: stripped sea bream (Lithognathus mormyrus), common two bonded sea bream (Diplodus vulgaris), white sea bream (D. sargus), annular sea bream (D. annularis) and saddled sea bream (Oblada melanura). Their situation is deteriorated especially in 1997–1999 from bad communication lagoon-sea and the bad wintering conditions. The species that live in the aquatic plants populated area like: million (Lebistes reticulates), (A. fasciatus), (A. ibrus), (A. dispar) are threatened because nearly 900 ha of their habitat during summer and autumn is converted in soil, aggravating their population situation. These species are important because they feed with Anopheles, controlling their breeding. In the lagoon outfall we noted a sensible diminution of greater amberjack (Seriola dumerili) intensified fishing with trawling nets often under 20 m depth, which is prohibited [Dedei Z, Bego F, Marika K, Kapedani R (2005) Unpublished].

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In the Dukati lagoon the most endangered species is gilthead sea bream (S. aurata) because of the reduction of mussel (Mytilus galloprovincialis), and of the small quantity of fingerlings that enters in lagoon. R. decussates and V. aurea due to the great export demand were overfished, which has led to drastical diminution of the production. In Narta lagoon M. cephalus is, in function of the age widespread in the lagoon. The sea bream populates the central and western part of the lagoon, meanwhile L. reticulates and Aphanius sp. Populates the shallow areas and the economy channels with great concentration in the northern part. In Dukati lagoon S. aurata is located in the northyern and central part, meanwhile Ruditapes sp. and Venerupies sp. inhabit the lagoon side of the communication channel. The communities status in Narta lagoon: M. cephalus has become a rare species from a common one, it was before. The sparidae has become rare and concentrated only in the western part, Lebistes sp. and Aphanis sp. has passed from abundant to less that common. In Dukati lagoon S. aurata has a low abundance index, especially in the last 5 years, meanwhile R. decussates and V. aurea are in the normal abundance level [4].

3.5 Species Use and Exploitation In Narta & Dukati lagoon the main activities has been fishing, grapes and olives cultivation. Fishing has always been primal, not only for fish and mussel catch but also for the lagoon maintenance. The main activity of fishing are linked with the sea communication channels where the main part of the fish is caught, were the migration gates. A great number of fishermen are occupied all year in fishing with tools like eel nets etc. The mussel catch, which is a big activity, is made by hand or by dragging nets. In the fishing activity of the lagoon are other activities such as communication channel maintainment, the opening of channels inside lagoon for fish wintering, fresh water fish in order to attract fish to the lagoon. In the last decade these ecosystems were overfished from illegal fishermen, which are the double of the legal one. This has led to the diminution of the production and alterations and to selective high quality fishing, due to external demand. The same phenomena has happen with the mussel exploitation. The mullets are destinated for the national market, except for (M. cephalus), which altogether with its eggs is exported. Until 1990 the main part of eels captured were conserved and exported as smoke-cured eels. Sea bass, sea bream and sand smelt were exported and marketed internally. Today, with the great market value fish have, the trend is to catch 3–4 times more than lagoon capacity. It’s imperative the strengthening of fish administration and ecosystems protection as it occurs in all Mediterranean countries. Coastal lagoons are intermediate areas between land and sea, so they require a very special attention, even more than other coastal areas. In the surround

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area of Narta lagoon are caught mainly from 50,000–80,000 kg of mussel/year exported. Studies made by I.K.P. Durres show that are caught also the under 22 mm individuals, problem that need attention and further monitorization. In Dukati lagoon the average production in 1990 has been of 7,000 kg of fish and 1,500–2,000 of very high quality mussels Fish and mussel value in the lagoons is growing up and these ensure big incomes. In Narta lagoon are employed 100 fishermen and 20 mussel collectors and this makes it the main activity of the area. With the improvement that must be made in the fishing and administrable aspects and the improvement of the extensive aquaculture, this lagoon can stabilize production and be well administrated in order to grow socio economic value. In the Dukati lagoon are employed 12 people with fishery and mussel activity. The fishery administration must be seen in a wider point of view and analyzing its physical, biological, economical, social and cultural components [4].

4 Recommendations and Outlook While the guidelines were developed focusing on vulnerable terrestrial, marine and coastal ecosystems and habitats of major importance for biological diversity and protected areas, they are appropriate for tourism and biological diversity in all areas. The participants of the Santo Domingo Workshop strongly recommended that the guidelines should be demonstrated through the implementation of pilot projects, including new or existing projects. Parties should be actively encouraged to submit to the Secretariat reports and cases- studies on the findings of such projects which could be based on different levels of protection and tourism development impact in different types of ecosystems. There is no doubt that such regional alliances and cross-sector partnerships imply certain risks like national egoism, industry opposition and NGO difficulties to link with government and industry in a common scheme While a SADC-based agency would do the actual auditing and accreditation on a regional and cost-effective basis it could link to the global process being investigated by the Sustainable Tourism Stewardship Council, a process described in other papers presented at this event.

References 1. Antolovi´c J (1998) Mediterranean monk seal (Monachus monachus) habitat in Vis Archipelago, the Adriatic Sea. Monachus science. The Monachus Guard 1(2):8–9 December 1998 2. Antolovi´c J (2005) Mediterranean news. The Monachus Guard 8(2):20–21 December 2005 3. Casale P, Freggi D, Basso R, Argano R (2005) Oceanic habitats for loggerhead turtles in the Mediterranean sea. Marine Turtle Newl 107:10–11 4. Haxhiu I, Uruci S (1998) Some data on marine turtles in Albania. UNEP (OCA)/MED WG.145/4 Annex IV, 1–5

Approximation of Sea Surface to Optimize Tide Gauge Network A.N. Vlasov, D.B. Volkov-Bogorodsky, V.A. Kurochkina, M.G. Mnushkin, and C.J. Blasi

Abstract Nearly all kind of activities on coastal areas need water data. These data are mostly provided by water authorities who are also responsible for the tide gauge. These gauges are located on various positions and for different purposes. Despite today’s possibility of remote control systems, tide gauges have to controlled and maintained by technicians, which means that this has a time and costly effect. Therefore investigations have been undertaken to find methods and tools which can the network optimize without the loss of information. There are various methods which can be used to find the best network. Most methods are using the required accuracy of the network purpose, the installation and the maintenance cost to find the optimized network under the given constrains. The methods are quiet well used on networks on inland waters. For coastal waters and especially with tidal influence the established methods are sparse. The allocation of tide gauges on coastal area depends mainly on the behaviour of the water surface. The physical processes which are in involved can be described and used by numerical models. But numerical models are not always present at every authority. Therefore a new method was required which only uses water level data. The new method is based on the Meshless Method were weight functions play a major role. The area of investigation is divided in sub domains were the tide gauges are the associated nodes. The paper describes the new method show an example. Keywords Coast · Meshfree Method · Tide

1 Introduction Nearly all kind of activities on coastal areas need water data. These data are mostly provided by water authorities who are also responsible for the tide gauge. These gauges are located on various positions and for different purposes. Despite today’s C.J. Blasi (B) Federal Institute of Hydrology, Koblenz, Germany e-mail: [email protected]

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possibility of remote control systems, tide gauges have to controlled and maintained by technicians, which mean that this has a time and costly effect. Therefore investigations have been undertaken to find methods and tools which can the network optimize without the loss of information. There are various methods which can be used to find the best network. Most methods are using the required accuracy of the network purpose, the installation and the maintenance cost to find the optimized network under the given constrains. The methods are quiet well used on networks on inland waters. For coastal waters and especially with tidal influence the established methods are sparse. The allocation of tide gauges on coastal area depends mainly on the behaviour of the water surface. The physical processes which are in involved can be described and used by numerical models. But numerical models are not always present at every authority. Therefore a new method was required which only uses water level data. The new method is based on the Meshless Method. The area of investigation is divided in sub domains were the tide gauges are the associated nodes.

2 Applied Methodology As the allocation of the tide gauges depend mainly on the physical processes of the particular region a method have to developed which is able to reconstruct sea surface in the given area by using the water readings of stations within the region. To optimizing the location of the tide gauges presents as a problem of limited number of gauges in a huge area. In the area of investigation gauges appear in linear position (along the coast line). In addition to these, each tide gauge has an immense huge amount of data. The above mentioned special conditions determine the mathematical methods to solve the problem. The probability theory and mathematical statistics methods were used for statistical data processing. Data concerning each tide gauge were considered as realization of a random variable. Correlation and regression analyses were performed to optimally position of gauges. Approximation theory methods were applied for data approximation for the whole region of investigation and illustratively representing water surface level as well as differential geometry methods (curvature determination) to optimize positioning of tide gauges in the observed area. A new methodology was suggested which uses radial basis functions. The approximation method being developed for the region can be classified as the “Meshless Method” [1], based on the idea of local approximations in sub domain blocks, which means areas of influence. For each tide gauge with its abundance of minute-by-minute measurement data an analysis and one-dimensional approximation were performed in order to considerably reduce the volume of stored information without loss of accuracy. The accuracy of the applied methodology is in the same range as the accuracy of tide gauge itself.

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To solve the problem of optimally positioning tide gauges, an approach based on differential geometry methods was offered which allowed determining the most critical locations in the water area through analyzing the curvature of the constructed surface of the value being approximated [5]. If the surface is defined by equation ϕ = ϕ (x, y), the first and second quadratic form coefficients will be respectively determined as follows: E = 1 + ϕx2 , F = ϕx ϕy , G = 1 + ϕy2 , ϕxy ϕyy ϕxx L= , M= , N= . 1 + ϕx2 + ϕy2 1 + ϕx2 + ϕy2 1 + ϕx2 + ϕy2

(1)

Principal curvatures κ 1 and κ 2 are determined as roots of quadratic equation: κ 2 (EG − F 2 ) − κ(LG − 2MF + NE) + (LN − M 2 ) = 0

(2)

As principal curvatures κ 1 and κ 2 of the surface are determined from a quadratic equation, in accordance with the Vi˙eta theorem for mean H and Gaussian (total) K curvature we get their formulae through the first and second quadratic form coefficients as follows: H=

1 LN − M 2 1 LG − 2MF + NE , K = κ κ = . (κ1 + κ2 ) = 1 2 2 2 EG − F 2 EG − F 2

(3)

Substituting expressions (2) for the first and second quadratic form coefficients into (3), we obtain the expressions for the mean i Gaussian curvature: 2 ϕ − 2ϕ ϕ ϕ + 1 + ϕ 2 ϕ 2 1 + ϕ xx x y xy yy ϕxx ϕyy − ϕxy y x 1 H= , K = 2 . 3 2 2 + ϕ2 1 + ϕ 2 2 x y 1 + ϕx + ϕy

(4)

To solve the above problems the Sea Mirror program was developed and implemented which allows accumulating, ordering, storing and processing raw data within the database. For each tide gauge, the Sea Mirror database collects water surface level extremes Uk and instants tk at which they are attained. Approximation is applied over the intervals between extremes, which significantly reduces the data volume to store. The approximating function in the interval tk , tk+1 etween two subsequent extremes has the form: U(t) = φ0 (t) + Uδ (t),

Uk+1 − Uk Uk+1 + Uk + cos φ0 (t) = 2 2

π tk+1 − t 2 tk+1 − tk

, (5)

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Fig. 1 Local data approximation

Uδ (t) =

Mk

Aj φj (t),

φj (t) = sin

i=1

tk+1 − t , πj tk+1 − tk

Mk ≤ 8.

(6)

There are measurement errors in the neighborhood of the extremes which contribute to the estimation error of its attainment instant (Fig. 1). Therefore, additional approximation to obtain more accurate instants textr and extremes Uextr is used in these neighborhoods. As a result, high accuracy is achieved comparable to the accuracy of gauge itself. To reconstruct water surface in the given area, the approximation based on the least squares technique was performed using measurement data for the whole region. The approximation used the system of basis functions that are bound to specific tide gauges and represented analytically as those with a set of free parameters. The distinguishing feature of the system is that it simulates the data at the measuring points identically. Functions used are modified Gaussian functions [4] which belong to the class of radial basis functions [3, 2, 6]:

(x − xk ) cos θk + (y − yk ) sin θk Ak

(y − yk ) cos θk − (x − xk ) sin θk 2 − Bk

2

ϕk (x, y) = exp −

(7)

where (xk , yk ) are local coordinates of a tide gauge in the approximation region; Ak , Bk and θ k are parameters of some ellipse with center (xk , yk ). This ellipse defined by semi-axes Ak , Bk and rotated by angle θ k is the influence domain of the function in approximation. In the interior of the influence domain, function ϕ k (x, y) varies no more than e times the value at the tide gauge itself (e is the base of natural logarithms). In the exterior of the influence domain, function decreases exponentially and asymptotically approaches zero at infinity. The function represents a specific bell-shaped surface with level curves in the form of ellipses.

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Fig. 2 Region of investigation and locations of tide gauges

The proposed approach was developed and tested in the North Sea area near the Port of Wilhelmshaven, Jade Bay, Germany. Figure 2 shows the region of investigation and the location of the tide gauges. The areas of influence of each tide gauge, which called sub-domain blocks are shown as circles in this case. The data relevant to this region were entered into the database of the Sea Mirror program and statistical processing and analysis were performed over a long time span. Statistical series comprised the data starting from 1935 up to the present. The water level time-dependent deviation was calculated using the Sea Mirror program by the algorithm employing measurement data approximation with Meshless Methods. Figure 3 shows the fluctuation dynamics of the sea level in August, 2001, on the change of tide (time span was taken equal to 20 minutes). These plots clearly demonstrate just the opposite behavior of flow and ebb tidal waves at the mouth of the bay: where the flow wave level rises, the ebb wave level decreases.

Fig. 3 Fluctuation dynamics of the sea level in August, 2001

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3 Conclusions The analysis of data approximation with harmonic and trigonometric polynomials and Gaussian exponential basis functions in the total observation region demonstrated that the best results are obtained using Gaussian basis functions. The approximating functions simulate the water level values up to the accuracy of tide gauges at the measuring points and smoothly connect these values accordingly to the form of the influence domains between the points. There is an opportunity to control the approximating surface by varying α k and β k values, thus making it more or less smooth in the domain of drastic data changes by means of enlarging or reducing the influence domain of these functions. It is also possible to take into account the features of the flow wave advance nearby the coastline by choosing the influence domains geometry. Trigonometric polynomials prove most effective in one-dimensional case for time smoothing and approximation of data at an individual measuring point.

References 1. Belytschko T, Krongauz Y, Organ D, Fleming M, Krysl P (1996) Meshless methods: an overview and recent developments. Comput Method Appl Mech Eng 139:3–47 2. Broomhead DS, Lowe D (1988) Multivariable functional interpolation and adaptive networks. Compl Syst 2:321–355 3. Buhmann MD (1990) Multivariate cardinal interpolation with radial-basis functions. Constr Approx 6:225–255 4. Haykin S (1994) Neural networks: a comprehensive foundation. Macmillan, New York 5. Pogorelov AV (1974) Differential geometry. Nauka, Moscow 6. Wendland H (1995) Piecewise polynomial, positive definite and compactly supported radial basis functions of minimal degree. Adv Comput Math 4:389–396

Improvement of Germination of Three Endemic Species of the Sierra Nevada (S. Spain) M. Díaz-Miguel, F. Serrano, and J.L. Rosúa

Abstract Three shrub species—Genista versicolor, Reseda complicata and Thymus serpylloides subsp. serpylloides—endemic of the Sierra Nevada (Spain) and used in the process of replanting the ski slopes of this zone have been studied with the aim of improving their germinative capacity. This work presents the results from a laboratory experiment conducted at three different temperatures (15, 20 and 25◦ C), studying the effect on germination percentage and rate after the application of certain plant-growth regulators: Inabarplant IV, Ethrel, benzyladenine, and gibberellic acid 3. From the results, it can be concluded that the three species studied present different optimal germination temperatures: 15◦ C for G. versicolor, 25◦C for R. complicata and 20◦ C for T. serpylloides. With respect to the phytoregulators treatments, both in G. versicolor as well as T. serpylloides, the action of the benzyladenine was notable at 10 ppm and 25◦ C, which prompted an increase of 114 and 49% over their respective controls. In the case of R. complicata seeds, the treatments were generally more effective. Thus, Ethrel at 10 and 100 ppm improved the germination indices by 60 and 76%, respectively, benzyladenine at 10 ppm registered a 60% improvement, and GA3 at 100 ppm a 60% improvement, in all cases at 25◦ C, the optimal temperature for seed germination in this species. Keywords Endemic species · Germination · Mediterranean high mountain · Plant growth regulators · Sierra Nevada National Park

1 Introduction The Sierra Nevada massif in the SE of the Iberian Peninsula, forming part of the Betic Sierras, measures some 90 km in length and covers roughly 200,000 ha. In contrast with the other Betic mountains, which are predominantly calcareous, the M. Díaz-Miguel (B) Departamento de Fisiología Vegetal, Facultad de Ciencias, Universidad de Granada, Edificio Politécnico, Campus Fuentenueva s/n, 18071 Granada, Spain e-mail: [email protected]

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central core of the massif, with the highest peaks, is siliceous and furthermore presents the highest elevations in Europe, after the Alps, reaching 3,482 m asl (Mulhacen). In addition, the Betic range is the most southerly of the continent, at 37◦ north. All of these characteristics have contributed to make the Sierra Nevada one of the richest reserves of plant diversity in Europe. Its great floristic importance, harbouring more than 2,100 vascular plants and, among these, more than 80 endemic species [8], has been one of the main reasons for granting this area the highest degree of legal and environmental protection, being declared a National Park in 1999. Within the geographical limits of the park, stands the Sierra Nevada Ski Station, between 2,000 and 3,325 m asl. As in other Alpine systems in which skiing is practised seasonally, this zone is subjected to perturbations related to the presence of the ski slopes. It has been amply demonstrated that the conditioning the slopes in summer with heavy equipment disturbs the uppermost layers of the soil, damaging the vegetation [6, 14, 22, 24, 27, 29, 32]. In winter, the preparation of the slopes and the skiing itself compacts the snow, which loses its isolating capacity, exposing the underlying vegetation to temperatures as low as –10◦C [24]. By contrast, in the areas with loose snow, temperatures rarely fall below 0◦ C [23, 25] All this disturbance has consequences for the composition, diversity, and productivity of plant species in these habitats, exerting a negative impact on the functionality and stability of the ecosystem [19, 28, 32]. Restoration of the plant cover on the Sierra Nevada began in a partial way in 1986 [11]. With the World Ski Cup, held on the mountain in 1995, the slopes were submitted to ambitious conditioning work that inflicted heavy impact on this zone, which harbours many of the endemic species of the Sierra Nevada. Therefore, in 1992, more extensive corrective measures were implemented in an effort to counteract the deterioration. Among the actions taken, the affected zones were replanted, using a series of species that form part of the natural dynamics of the plant communities of this habitat [26] in accord with the authors that point out the need to use autochthonous species in recovery processes of Alpine vegetation [20, 30]. In the Sierra Nevada, the recovery involved asexual reproduction as well as direct sowing, which was more economical and advantageous in relation to gene variability [12, 15], although in the latter case the results desired were not achieved. As the first step in any type of replanting of altered zones, knowledge of the different factors governing germination success is essential in these types of wild species, which often present some type of dormancy [5, 7]. Temperature is one of the most important environmental factors related to the regulation of the germination. In addition, phytohormones are presumed to be determinant in this process [17]. Despite that studies on autochthonous plants of the Iberian Peninsula are becoming more frequent [10, 13, 18, 21] little information is available on the endemic species of the Sierra Nevada [2, 3]. Therefore, we undertook the present laboratory study on the behaviour of three endemic species used in restoration work in the zones affected by the ski station, examining the above-mentioned factors in order to contribute to better knowledge of the germinative process of these species for their potential use in the currently degraded areas as well as others that might be affected in the future by any type of habitat alteration.

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2 Material and Methods From three endemic species of the Sierra Nevada, Genista versicolor (Leguminosae), Reseda complicata (Resedaceae), and Thymus serpylloides subsp. serpylloides (Labiatae), seeds were collected in the natural habitat of the plants, between 1,900–2,650, 2,400–3,050, 2,200–2,800 m, respectively. Once separated from their fruits, the seeds were cleaned and sorted for uniformity in size and colour, eliminating those having any type of seed-coat damage. The seeds were stored in a chamber at 4◦ C for at least 2 months before beginning the experiments. For the germination study, the seeds were surface sterilized with sodium hypochlorite at 1% for 5 min and then washed with abundant distilled, sterilized water. Samples of 50 seeds from each of the species were placed in Petri dishes 10 cm in diameter, over filter paper moistened with 10 ml of sterile distilled water (control) or with the same quantity of the solutions of the different treatments tested: Inabarplant IV (0.2% indolbutyric acid, 2% naphthalenacetic acid, and 15% fungicide captan), Ethrel (2-cloroethylphosphonic acid), benzyladenine, and type-3 gibberellic acid. All solutions were applied at concentrations of 1, 10, and 100 ppm and adjusted to pH 6.2. In total for each species, four replicates were used for each treatment and concentration. All the manipulations were performed in a laminarflow chamber with green light. The germination assays were made in darkness in a thermostatically controlled chamber at 15, 20 and 25◦C. Each day, in all cases over the 20 days, samples were taken from the dishes to calculate the germination percentage, considering a seed to have germinated when radicle protrusion was visible. In addition, the T50 was calculated as an estimate of the germination rate, expressed as the time needed to reach half of the maximum germination level in each case. Lost moisture was replenished every 6–7 days with sterile distilled water. The data were submitted to an analysis of variance and the means were compared using Duncan’s test.

3 Results and Discussion From the data presented in Tables 1, 2, and 3 as well as a comparison of the data of the respective controls (seeds incubated in water), it can be concluded that the germination of the three species studied differed in their behaviour with respect to temperature. Thus, G. versicolor germinated better the lower the temperature, although these differences were not statistically significant (37.5, 32.5 and 17.5% at 15, 20 and 25◦ C, respectively). In any case, at 15◦ C the germination rate expressed by the T50 value was higher than for the other temperatures (6.6 vs. 10.5 and 9). In the case of the R. complicata seeds (Table 2), the opposite was true, and 25◦C (the highest temperature of those assayed) presented the best results (50% germination), doubling the values registered at the other two temperatures (20% at 15◦ C and 25% at 20◦ C), in this case with statistical significance. It is noteworthy that the germination rate at this temperature had a T50 value of 2.3, as opposed to 11.8 and 11.0 at 15 and 20◦ C,

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M. Díaz-Miguel et al. Table 1 Degree of germination and T50 in Genista versicolor seeds 15◦ C

20◦ C

25◦ C

Treatment

% germination

T50

% germination

T50

% germination

T50

Control IP 1 IP 10 IP 100 E1 E 10 E 100 BA 1 BA 10 BA 100 GA 1 GA 10 GA 100

37 ± 12 a,b,A 30 ± 4 a,b,A 20 ± 4 b,A,B 20 ± 4 b,A 33 ± 9 a,b,A 43 ± 3 a,b,A 53 ± 5 a,A 48 ± 12 a,A 50 ± 4 a,A 33 ± 5 a,b,A 30 ± 4 a,b,A 30 ± 11 a,b,A 30 ± 0 a,b,A

6.6 6.0 12.0 12.0 8.7 6.2 5.2 11.2 8.3 12.8 9.3 13.0 9.3

32 ± 5 a,b,c,d,A 17 ± 6 d,A 32 ± 6 a,b,c,d,A 30 ± 7 a,b,c,d,A 20 ± 7 c,d,A,B 18 ± 6 d,B 40 ± 0 a,A,B 35 ± 3 a,b,c,A 38 ± 5 a,b,A 28 ± 6 a,b,c,d,A 22 ± 3 b,c,d,A 22 ± 5 b,c,d,A 22 ± 3 b,c,d,A

10.5 14.1 5.4 7.4 10.2 7.2 7.2 10.0 5.8 7.6 5.5 12.6 11.0

17 ± 3 b,c,A 22 ± 13 a,b,A 7 ± 5 b,c,B 17 ± 8 b,c,A 3 ± 3 c,B 10 ± 4 b,c,B 28 ± 6 a,b,B 28 ± 5 a,b,A 38 ± 6 a,A 10 ± 4 b,c,B 27 ± 6 a,b,A 10 ± 5 b,c,B 10 ± 4 b,c,B

9.0 7.0 15.0 8.6 5.0 5.0 6.9 8.4 10.2 5.4 6.7 10.0 13.1

Concentrations of treatments are expressed in ppm. Values of T50 are expressed in days. Each value of germination is the mean of four replicates and is accompanied by its standard error. Results followed by the same letters in lower case in each column and by upper case in each row show no significant differences (p = 0.05) IP: Inabarplant IV, E: Ethrel, BA: Benzyladenine, GA: Gibberellic acid type 3

Table 2 Degree of germination and T50 in Reseda complicata seeds 15◦ C

20◦ C

25◦ C

Treatment

% Germination

T50

% Germination

T50

% Germination

T50

Control IP 1 IP 10 IP 100 E1 E 10 E 100 BA 1 BA 10 BA 100 GA 1 GA 10 GA 100

20 ± 4 c,d,e,B 8 ± 2 d,e,C 8 ± 2 d,e,B 3 ± 2 e,C 60 ± 0 a,A 38 ± 10 b,c,B 58 ± 6 a,B 23 ± 8 c,d,B 43 ± 3 a,b,C 23 ± 6 c,d,B 33 ± 10 b,c,A 20 ± 7 c,d,e,B 13 ± 3 d,e,B

11.8 6.7 14.8 4.5 10.4 7.7 5.9 11.6 10.5 11.6 13.2 10.0 9.4

25 ± 5 c,d,e,B 20 ± 4 c,d,e,B 8 ± 5 e,B 22 ± 3 c,d,e,B 48 ± 14 b,A 68 ± 6 a,A 68 ± 3 a,B 65 ± 2 a,A 70 ± 0 a,B 33 ± 3 b,c,A,B 30 ± 4 c,d,A 28 ± 5 c,d,B 13 ± 6 d,e,B

11.0 10.0 10.8 9.4 9.3 11.4 8.8 9.2 9.5 10.2 10.3 9.7 9.5

50 ± 8 b,c,A 40 ± 0 c,A 50 ± 8 b,c,A 63 ± 3 a,b,c,A 60 ± 4 a,b,c,A 80 ± 4 a,A 88 ± 6 a,A 60 ± 0 a,b,c,A 83 ± 5 a,A 48 ± 8 b,c,A 50 ± 4 b,c,A 63 ± 3 a,b,c,A 80 ± 4 a,A

2.3 2.7 2.3 2.2 2.2 1.7 1.5 3.4 2.9 3.7 2.4 2.7 3.4

Concentrations of treatments are expressed in ppm. Values of T50 are expressed in days. Each Value of germination is the mean of four replicates and is accompanied by its standard error. Results followed by the same letters in lower case in each column and by upper case in each row show no significant differences (p = 0.005) IP: Inabarplant IV, E: Ethrel, BA: Benzyladenine, GA: Gibberellic acid type 3

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Table 3 Degree of germination and T50 in Thymus serpylloides seeds 15◦ C

20◦ C

25◦ C

Treatment

% Germination

T50

% Germination

T50

% Germination

T50

Control IP 1 IP 10 IP 100 E1 E 10 E 100 BA 1 BA 10 BA 100 GA 1 GA 10 GA 100

60 ± 4 a,b,c,B 70 ± 5 a,b,A 50 ± 4 b,c,A 48 ± 8 b,c,A 59 ± 5 a,b,c,A 58 ± 3 a,b,c,A 60 ± 7 a,b,c,A 40 ± 4 c,A 63 ± 3 a,b,c,A 40 ± 4 c,A 70 ± 4 a,b,A 78 ± 9 a,b,A 78 ± 9 a,b,A

2.8 2.8 3.2 3.3 3.5 5.0 4.7 4.0 4.1 4.0 3.1 2.8 2.3

72 ± 5 a,b,A 88 ± 5 a,A 47 ± 11 c,d,A 41 ± 3 c,d,A 35 ± 3 d,B 28 ± 3 d,A 44 ± 11 c,d,A 38 ± 10 d,A 50 ± 10 c,d,A 28 ± 3 d,A,B 72 ± 3 a,b,A 38 ± 5 d,B 60 ± 3 b,c,A

2.0 2.5 3.8 1.8 2.3 3.2 3.2 2.8 2.0 5.4 3.6 2.6 2.8

50 ± 4 b,c,B 38 ± 5 b,c,d,e,B 28 ± 3 c,d,e,A 60 ± 8 a,b,A 15 ± 3 e,C 47 ± 16 b,c,A 54 ± 6 a,b,A 28 ± 3 c,d,e,A 75 ± 9 a,A 22 ± 6 d,e,B 40 ± 3 b,c,d,B 47 ± 8 b,c,B 60 ± 3 a,b,A

3.3 4.7 3.7 4.5 5.6 3.8 3.3 1.8 4.1 4.6 3.5 1.6 3.2

Concentrations of treatments are expressed in ppm. Values of T50 are expressed in days. Each value of germination is the mean of four replicates and is accompanied by its standard error. Results followed by the same letters in lower case in each column and by upper case in each row show no significant differences (p = 0.05) IP: Inabarplant IV, E: Ethrel, BA: Benzyladenine, GA: Giberrellic acid type 3

respectively. In the case of T. serpylloides (Table 3), the germination percentage in no case fell below 50% (25◦ C), reaching a maximum of 72% at 20◦ C, this value being statistically significant in comparison with the other two (60% at 15◦C and 50% at 25◦C). In the zones to be restored, within the area of the ski slopes of the Sierra Nevada Ski Station, previous field assays used the phytoregulator inabarplant IV as a rooting stimulant [26], and thus, given that the auxins in some cases promote germination [4, 17], whether directly or indirectly, by inducing ethylene production [1], in the present work this compound was used to determine whether it encouraged germination. In none of the cases studied, was any beneficial effect detected, and at times it in fact inhibited germination, as in the case of R. complicata at 15◦ C. In G. versicolor, only the application of de 10 ppm at 20◦ C matched the germination rate reached by control, though the germination rate was higher given that a T50 of 5.4 was registered, as opposed to 10.5 control. These results reflect that its effect is post-germinative, favouring the formation of roots but not directly promoting germination. On the other hand, in G. versicolor and R. complicata, the imbibition of the seeds in ethrel, a compound which at pH > 4.0 hydrolyses and produces ethylene, acts positively on germination, implying that, at least in these two species, inabarplant IV does not promote ethylene synthesis. In any event, in G. versicolor, ethrel did not provoke significantly higher germination percentages than control, although germination values did surpass control by 40%, as in the treatment E100 at 15◦C. More notable were the results for R. complicata, where E 1 ppm at 15◦C surpassed control values by 200%, E 10 and E 100 at

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20◦ C by 170%, and E100 at 25◦ C by 75%, all these differences being statistically significant. On the other hand, the ethrel treatments in general notably increased the germination rate in these two species, as reflected in the T50 data (Tables 2 and 3). This was not the case with T. serpylloides, in which ethrel did not encourage germination and at 20◦ C even caused inhibition at the three concentrations tested. The imbibition of the seeds in benzyladenine gave quite similar to those described for ethrel. In fact, this phytoregulator boosted germination of G. versicolor and R. complicata seeds, which reached total germination values that practically equalled those reached in the case of soaking with ethrel, although the germination rate was not so high. Similarly, for T. serpylloides, in all cases except at 25◦ C (where 10 ppm benzyladenine surpassed control by almost 50%) this compound behaved the same as ethrel, inhibiting germination (Table 3). The fact that cytokines can stimulate ethylene production [9] could explain the similar results for BA and ethrel application. Many reports credit gibberellins with promoting seed germination [16] and in fact the exogenous application of this type of phytohormone not only augments germination but can often break dormancy [7]. Nevertheless, this same type of gibberellic acid is not always involved in these processes. In the case of G. versicolor, it is clear that GA3 is incapable of breaking primary dormancy of seeds at any of the temperatures assayed (Table 1) and the same occurred in R. complicata at 15 and 20◦ C. Nevertheless, at 25◦ C, the behaviour of this phytohormone proved more favourable and in fact with 100 ppm reached a germination rate of 80%, this being statistically significant as opposed to control seeds at the three temperatures studied, despite the increase of more than 28% with 10 and 100 ppm (Table 3). From the results of the present work, it can be concluded that, at least under the experimental conditions tested, the germination of seeds from the three species studied improved with some of the treatments applied, a step preparatory to future studies under field conditions.

References 1. Abeles FB, Morgan PW, Salveit ME Jr (1992) Ethylene in plant biology, 2nd edn. Academic Press, San Diego, CA 2. Angosto T, Matilla AJ (1993) Variations in seeds of three endemic leguminous species at different altitudes. Plant Physiol 87:329–334 3. Ayerbe L, Ceresuela JL (1982) Germinación de especies endémicas españolas. An. INIA. Ser. Forest 6:17–41 4. Bandursky RS, Cohen JD, Slovin JP, Reinecke DM (1995) Auxin biosynthesis and metabolism. In: Davies PJ (ed) Plant hormones: physiology, biochemistry and molecular biology. Kluwer Academic Publisher, Dordrecht, The Netherlands, pp 39–65 5. Baskin CC, Baskin JH (1998) Seeds: ecology, biogeography and evolution of dormancy and germination. Academic Press, San Diego, CA 6. Bayfield NG (1996) Long-term changes in colonization of bulldozed ski pistes at Cairn Gorm, Scotland. J Appl Ecol 33:1359–1365 7. Bewley JD, Black M (1994) Seeds: physiology and development and germination, 2nd edn. Plenum Press, New York

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8. Blanca G (2002) Flora amenazada y endémica de Sierra Nevada. Junta de Andalucía Ed., Granada 9. Brault M, Maldiney R (1999) Mechanisms of cytokinin action. Plant Physiol Biochem 37:403–412 10. Castro J, Romero AT (1999) Dormancy and germination in Cistus clusii (Cistaceae): effect of biotic and abiotic factors. Rev. Ecol. (Terre Vie) 54:19–28 11. Chacón J, Ortega F, Pulido A, Rosúa JL (1989) Estudio de impacto ambiental del anteproyecto de reparación y acondicionamiento de la pista del río para el Campeonato del Mundo de Esquí Alpino con instalación de nieve artificial y nuevos remontes. University of Granada, Spain 12. Cuisance P (1988) La multiplicación de las plantas y el vivero. Mundi-Prensa, Madrid 13. Escudero A, Carnes LF, Pérez- García F (1997) Seed germination of gypsophytes in semi-arid central Spain. J Arid Environ 36:487–497 14. Haeberli W (1992) Construction, environmental problems and natural hazards in periglacial mountain belts. Permafrost Periglac Process 3:111–124 15. Hartman HT, Kester DE (1989) Propagación de plantas, principios y prácticas. C.E.S.A., México 16. Karssen CM, Zaórski S, Kepczyñski J, Groot SPC (1989) Key role for endogenous gibberellins in the control of seed germination. Ann Bot 63:71–80 17. Kucera B, Cohn MA, Leubner-Metzgor G (2005) _ Plant hormone interactions during seed dormancy release and germination. Seed Sci Res 15(4):281–307 18. Merlo E, Alemán MM (1996) Efecto de la temperatura sobre la germinación de especies de Astragalus L. y Genista L. (Leguminosae). Monogr. Fl. Veg. Béticas 9:135–146 19. Mulder CPH, Uliassi DD, Doak DF (2001) Physical stress and diversity-productivity relationships: the role of positive interactions. PNAS 98:6704–6708 20. Papst WA, Morgan JW (1992) Using indigenous species for alpine rehabilitation. Indigenotes 5:5 21. Peña J, Aparicio-Tejo P, Sánchez-Díaz M (1988) Dormancy mechanism and the effect of scarification in the germination of Halimium halimifolium seeds. J Plant Physiol 132:54–58 22. Pröbstl U (1990) Skisport und vegetation. Stöppel, Weildheim, Germany 23. Rixen C (2002) Artificial snow and snow additives on ski pistes: interactions between snow cover, soil and vegetation. PhD Thesis. University of Zurich, Zurich, Switzerland 24. Rixen C, Casteller A, Schweingruber FH, Stoeckli V (2004) Age analysis helps to estimate plant performance on ski pistes. Bot Helvetica 114:127–138 25. Rixen C, Stoeckli V, Ammann W (2003) Does artificial snow production affect soil and vegetation of ski pistes? Perspect Plant Ecol Evolut Syst 5:219–230 26. Rosúa JL, Martín JC (1996) Propagación de especies propias de la alta montaña mediterránea y su utilización en la restauración de la cubierta vegetal. In: Chacón J, Rosúa JL (eds) 1st Conferencia Internacional Sierra Nevada: Conservación y Desarrollo Sostenible, vol V, Granada, pp 77–87 27. Ruth-Balaganskaya E, Myllynem-Malinem K (2000) Soil nutrient status and revegetation practices of downhill sking areas in Finnish Lapland: a case study of Mt Ylläs. Landscape Urban Plann 50:259–268 28. Tilman D (1996) Biodiversity: population versus ecosystem stability. Ecology 77:350–363 29. Titus JH, Tsuyuzaki S (1999) Ski slope vegetation of Mount Hood, Oregon, USA. Arct Antarct Alp Res 31:283–292 30. Tsuyuzaki S (1995) Ski slope vegetation in Central Honshu. Japan Environ Manag 19: 773–777 31. Watson A (1985) Soil erosion and vegetation damage near ski lifts at Cairn Gorm, Scotland. Biol Conserv 33:363–381 32. Wipf S, Rixen C, Fischer M, Schmid B, Stoeckli V (2005) Effects of ski piste preparation on alpine vegetation. J Appl Ecol 42(2):306–316

Early Growth of Quercus castaneifolia (C.A. Meyer) Seedlings as Affected by Weeding, Shading and Irrigation Masoud Tabari, Javad Mirzaei, and Hadi Daroodi

Abstract The influence of shading, irrigation and weeding on survival, growth and morphology of 1-year Quercus castaneifolia seedlings was studied in north of Iran. The seedlings were grown under eight treatments including full-light versus artificial shading, irrigation versus non-irrigation and weed presence versus weed removing at three replicates. At the end of the first growing season seedling survival in all treatments was 100%. Weed removing had positive effect on height, diameter growth, slenderness coefficient and leaf area of Q. castaneifolia. Irrigation enhanced diameter growth and leaf area, and shading increased leaf area. Irrigation had no significant effect on plant growth where the weed was removed. In weed plots seedlings growth and leaf area were greater in shading than in full-light. The results indicated that for 1-year Q. castaneifolia seedlings, weeding, in contrast to irrigation, is an essential factor. Where the weed competition is a difficulty, plantation with higher stem length should be applied. Keywords Growth · Irrigation · Quercus castaneifolia · Seedling · Shading · Weed competition

1 Introduction Caspian forests are the most valuable forests in north of Iran covering the northern slopes and foothills of Alborz mountain range in southern part of the Caspian Sea. Quercus castaneifolia (C. A. Mey) is one of the most prevalent species growing in these forests [12]. Reduction of standing volume as well as defect of natural regeneration in Quercus stands has made concerned Iranian silviculturists. To this reason, its natural regeneration problem has led forest managers to use the artificial M. Tabari (B) Department of Forestry, Faculty of Natural Resources and Marine Sciences, Tarbiat Modares University, Noor, Iran e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_8,

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regeneration, where regeneration establishment is difficult [27]. Some factors negatively affect growth and establishment of artificial regeneration. In literature has been referred that weeds directly compete with seedlings for soil moisture and nutrients, and have a negative effect on its survival and growth [4]. Likewise, strong radiation can limit plant survival and growth by photo damage [22] and by reducing soil water content through evaporation and transpiration [28]. Numerous studies have addressed the issues of how the performance of planted or naturally established woody seedlings are affected by shade [33, 28, 1, 10, 23, 30, 21], herb competition [24, 2, 25, 9, 11, 13, 25] and irrigation [6, 15]. The interaction of irrigation, shading and weeds on this performance is complicated. For instance, shading may have a positive direct effect on seedling establishment and humid content [19], but a negative indirect effect mediated by an enhancement of weed growth. In addition, weeds directly compete with seedlings for resources (especially water and nutrient), a negative effect, but they also diminish radiation and may increase low winter temperatures at the ground level, indirect positive effects that may facilitate seedling establishment and increase seedlings growth [25]. Furthermore, soil moisture may have a negative effect due to enhancement of weed growth, but a positive effect on seedling growth and establishment. Generally, it was believed that in Caspian forests intensive sun light, low water availability and weed competition are the major factors negatively affecting growth and establishment of man-made Q. castaneifolia seedlings, particularly in dry season (summer). So, in this experiment, the interaction of shading, irrigation and weeding on early growth and establishment of Q. castaneifolia seedlings was studied in the first growing season.

2 Materials and Methods A field experiment was carried out at Tarbiat Modares University, north of Iran (51◦46 E, 36◦47 N, 15 m a.s.l.) (Fig. 1). The experiment was conducted in a flat, deep soil and homogenous area that was formerly a mixed oak stand. Mean annual

Turkey Afghanistan Iran Noor Iraq Pakistan

Fig. 1 Position of the study area in north of Iran

Growth of Q. castaneifolia Seedlings as Affected by Weeding, Shading and Irrigation Temperature ( o C)

77

Precipitation (mm)

80

160 Temperature (° c)

70

140

Rain (mm)

60

120

Dec.

0

Nov.

0

Oct.

20 Sep.

10 Aug.

40

Jul.

20

Jun.

60

May

30

Apr.

80

Mar.

40

Feb.

100

Jan.

50

Fig. 2 Embrotermic curve of the study area, based on meteorological data

rainfall is 803.4 mm and a distinct rainy season occurs between August and May. Mean annual temperature is 17◦C and the dry season comes about between May and August (Fig. 2). In April 2005, 384 naturally regenerated oak seedlings with height = 10.9 (±0.1) cm, diameter = 2.7 (±0.2) mm and age∼30 days were collected together with acorns connected to root, under a mature tree near the experimental area to minimize the variation in genetic composition. The eight treatments were included of the factorial combination of artificial shading (shaded (SH) versus full-light (L) plots), weed removing (weeding (W) versus weed (G) plots) and irrigation (irrigation (I) versus rainfed (R). There were three replicated plots per treatment (24 plots 1 m × 1 m, in total). Some sixteen 1-year old seedlings were transplanted with a regular distribution in each plot, being separated from each other by 20 cm. The experiment was set up as factorial with completely randomized design. In the field, several wooden frames (120 wide × 120 cm long × 100 cm tall) were built to support neutral density shade fabric. Fabric densities were draped over the frames to provide two levels of light availability, 100% of full sunlight (no fabric) and 50% of full sunlight. Irrigation was carried out using a sprinkler at 4-day intervals (1.5 l for each seedling) over the growing season. Weeds were removed manually six times through out the growing season. The main weed species in the field experiment have been listed in Table 1. Diameter (D) and height (H) of seedlings were recorded at the beginning and end of first growing season. Seedling diameter was measured 5 cm above the ground. Survival was calculated at the end of period following recording the seedlings number. Leaf area was registered by measuring leaves of two seedlings randomly

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M. Tabari et al. Table 1 The list of weed species grown in the field experiment

Species

Family

Age

Growth form

Frequency (%)

Myosoroides alopecorus Calystegia sepium Carex rogusa Digitaris sanguinea Equisetum ramosissimum Geranium pyrenaicum Oxalis corniculata Paspalum distichum Potentila raptanse Setaria verticilata Solanum nigrum Halepense sorghum Vicia sp.

Poaceae Convolvulaceae Cyperaceae Poaceae Equisetaceae Geraminaceae Oxalidaceae Poaceae Rocaceae Poaceae Solanaceae Poaceae Papilionaceae

Annual Perennial Perennial Annual Perennial Annual Perennial Perennial Perennial Annual Annual Perennial Annual

Ph Th Cr Th Cr He He He He Th He Cr Th

5 1 5 15 4 3 5 5 5 25 1 10 2

Ph = Phanerophyte, Ch = Chamaephyte, Th = Therophyte, He = Hemicriptopyte

selected in each plot and measured with a Leaf Area Meter at the end of the growing season. Height growth and diameter growth, leaf area and slenderness coefficient (H/D ratio) were tested with Kolmogorov-Smironov for normality of data. The resulting data were subjected to ANOVA. Means were compared for significant differences using Duncan’s multiple range tests.

3 Results Seedling survival was not affected by any treatment. It was 100% in all treatments, showing no died seedling was found in any treatment at the end of the first growing season. Only weeding (p = 0.000, df = 1) and interactions of shading and weeding (p = 0.000, df = 1) affected seedlings height growth (Table 2). The best response Table 2 Three-way-ANOVA for seedlings height growth Source

df

f

p

Artificial shading Weeding Irrigation Shading × irrigation Shading × weeding Irrigation × weeding Shading × irrigation × weeding Error Total

1 1 1 1 1 1 1 374 382

0.348 189.74 1.53 0.115 14.68 1.43 1.19

0.556 0.000∗∗ 0.216 0.735 0.000∗∗ 0.232 0.274

∗∗

Significant at the 1% level of probability

Growth of Q. castaneifolia Seedlings as Affected by Weeding, Shading and Irrigation 30

a

ab bc

25

c

20 15

d

d

10

de

L+I+G

SH+R+G

SH+I+G

SH+R+W

SH+I+W

L+I+W

0

L+R+G

e

5 L+R+W

Hight growth (cm)

Fig. 3 Height growth of Q. castneifolia seedlings at different treatments (L = full-light, I = irrigation, G = grass, W = weeding, SH = shading, R = rainfed, Values are Mean ± SE). Columns with the same letter have no significant difference (p = 0.01)

79

Treatment of height growth was found in weeding-full-light areas, with and no watering (LRW and LIW) (Fig. 3). In weed plots height growth was lower in shading than full-light. Where the grass was present the greatest height growth was in irrigated- and rainfedshaded plots; the lowest in rainfed-full-light plots (LRG) and the intermediate in irrigated-full-light (LIG) plots. Seedling diameter growth was affected by weeding (p = 0.000, df = 1), irrigation (p = 0.000, df = 1) and interaction of shading and weeding (p = 0.008, df = 1) (Table 3). It was greatest in LRW, LIW and SHIW treatments (Fig. 4). This showed where the weeding was done; the seedlings had greater diameter growth particularly in irrigated plots. Where the grass was kept, diameter growth was lowest, particularly in non-irrigated plots. Seedlings obtained intermediate diameter growth in SHRW and SHIG treatments. Weeding and its interaction with shading, as well as interaction of all treatments had significant effect on seedling slenderness (Table 4). In rainfed-full-light plot, where the weeds were removed (LRW), seedlings attained the highest slenderness (Fig. 5). The smallest slenderness coefficient was found in rainfed-shaded treatment Table 3 Three-way-ANOVA for seedling diameter growth Source

df

f

p

Artificial shading Weeding Irrigation Shading × irrigation Shading × weeding Irrigation × weeding Shading × irrigation × weeding Error Total

1 1 1 1 1 1 1 374 382

2.41 779.21 20.72 2.76 7.18 0.00 0.84

0.121 0.000∗∗ 0.000∗∗ 0.097 0.008∗∗ 0.967 0.357

∗∗

Significant at the 1% level of probability

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M. Tabari et al. a

4.5

a

4 3.5

a b

3 2.5 cd

2

d

1.5

d

d

SH+R+G

L+R+G

L+I+G

SH+I+G

SH+R+W

L+R+W

0.5 0

SH+I+W

1

L+I+W

diameter growth (mm)

Fig. 4 Seedling diameter growth at different treatments (L = full-light, I = irrigation, G = grass, W = weeding, SH = shading, R = rainfed, Values are Mean ± SE). Columns with the same letter have no significant difference (p =0.01)

Treatment

Table 4 Three-way-ANOVA for slenderness coefficient Source

df

f

p

Artificial shading Weeding Irrigation Shading × irrigation Shading × weeding Irrigation × weeding Shading × irrigation × weeding Error Total

1 1 1 1 1 1 1 376 384

0.183 32.06 0.00 0.532 7.18 8.91 6.84

0.669 0.000∗∗ 0.974 0.466 0.003∗∗ 0.146 0.009∗∗

Significant at the 1% level of probability

70

a

60

ab

abc

bc

bc

c

c

50

d

40 30 20

Treament

L+R+G

L+I+G

SH+I+G

SH+R+G

SH+R+W

SH+I+W

0

L+I+W

10 L+R+W

Fig. 5 Sslenderness coefficient at different treatments (L = full-light, I = irrigation, G = grass, W = weeding, SH = shading, R = rainfed, Values are Mean ± SE)

Slenderness coefficient %

∗∗

Growth of Q. castaneifolia Seedlings as Affected by Weeding, Shading and Irrigation

81

where the weeds were kept (LRG). In weed plots the highest slenderness could be detected in rainfed-shaded treatment (SHRW). Artificial shading, weed removing, their interaction and irrigation increased seedling leaf area (Table 5). Where the herbaceous species were eliminated, leaf area did not significantly differ in shaded and full-light plots or irrigated and rainfed plots but it was greater in weeding than weed plots. In weed plots greater leaves were found in irrigated- and rainfed-shaded plots and the smaller in rainfed-full-light plots (Fig. 6). Table 5 Three-way-ANOVA for seedlings leaf area Source

df

f

p

Artificial shading Weeding Irrigation Shading × irrigation Shading × weeding Irrigation × weeding Shading × irrigation × weeding Error Total

1 1 1 1 1 1 1 376 384

5.79 147.02 4.42 0.41 5.1 0.01 0.00

0.017∗∗ 0.000∗∗ 0.036∗ 0.520 0.025∗ 0.901 0.943

∗

Significant at the 5% level of probability; level of probability

Significant at the 1%

35 30

a

a

a

a

25 b

20

b bc

15

c

10

L+R+G

L+I+G

Sh+R+G

Sh+R+w

Sh+I+W

L+I+W

0

Sh+I+G

5 L+R+W

Leaf area (cm2)

Fig. 6 Seedlings leaf area at different treatments (L = full-light, I = irrigation, G = grass, W = weeding, SH = shading, R = rainfed, Values are Mean ± SE). Columns with the same letter have no significant difference (p = 0.01)

∗∗

Treatment

4 Discussion The study revealed that all treatments influenced height growth, diameter growth, leaf area and slenderness of seedlings but had no effect on seedling survival. Seedling survival in all treatments was very high (100%). Weeding and its interaction with shading had positive effect on height growth and diameter growth, whereas both characteristics were greater in weeding plots than in weed plots.

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The same results were obtained by Kolb and Steiner [14] and Lorimer et al. [18]. Generally, weeds compete with oak seedlings for moisture and soil nutrient, and influence negatively plant growth [17, 5, 16]. So, weeding is essential for young oaks [25]. The results of current research showed that shading did not significantly affect diameter growth and height growth. This confirms the results reported by Gardiner [8] on Q. pagoda, Welander and Ottosson [32] on Q. robur and Fagus sylvatica and Fuchs et al. [7] on Q. garryana. In the current research the newly regenerated seedlings along with their acorns were transplanted in plots. Acorn reserve could be probably the main reason for growth homogeneity in shaded plot as well as in full-light plots [9, 8]. This reveals that in the first growing season nutrient reserve of oak acorn is caused growth and establishment become independent of lighting (or shading). In this study it was found that diameter growth was prominently depended on irrigation. This result is supported by Fotelli et al. [6] and Kolb et al. [15] on oak seedling and Madsen [20] on beech seedling. It was revealed that weeding and its interaction with shading had positive effect on slenderness of seedlings. In fact where the weeds were present, seedlings attained a higher slenderness in shaded than full-light plots. In the similar studies, Phares [26] and Thadani and Ashton [31] showed that higher slenderness occurred at low light intensity. Leaf area was affected by weeding, irrigation and shading. As a matter of fact, oak seedlings obtained larger leaves in shaded than in full-light plots. Similar finding was reported by Ziegenhagen and Kausch [33] on Q. robur and Cardillo and Bernal [3] on Q. suber. Generally based on results of this study, weeding-full-light, with and without irrigation (LRW and LIW) and weeding-shaded with irrigation (SHIW) treatments increased growth and development of seedlings. With respect to similarity in some growth characteristics of seedlings grown in irrigated and non-irrigated plots, irrigation is not a demand for Q. castaneifolia seedling during the first growing season. However, for better seedling establishment weeding is necessary. Where the weed was present; seedlings in shaded plots compared to full-light plots had higher growth and development. So in clear-cut areas, where the weed is dense, seedling plantation with taller shoot length is advised. Shelter is not essential for seedling growth in its first growth season, so, Q. castaneifolia seedlings can be grown in full-light, but weed control is a critical point.

References 1. Bardon RE, Countryman DW, Hall RB (1999) Tree shelters reduced growth and survival of under planted red oak seedlings in southern Iowa. Northern J Appl For 16:103–107 2. Caldwell JM, Sucoff EI, Dixon RK (1995) Grass interference limits resource availability and reduces growth of juvenile red pine in the field. New Forests 10:1–15 3. Cardillo E, Bernal CJ (2005) Morphological response and growth of cork oak (Quercus suber L.) seedlings at different shade levels. For Ecol Manage 222: 296–301 4. Davis MA, Wrage KJ, Reich PB, Tjoelker MG, Schaeffer T, Muermann C (1999) Survival, growth, and photosynthesis of tree seedlings competing with herbaceous vegetation along a water–light–nitrogen gradient. Plant Ecol 145:341–350

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5. Duplissis J, Yin X, Banghman MJ (2000) Effects of site preparation, seedling quality and tree shelters on planted northern red oak. University of Minnesota, Staff Paper Service, No: 141, 29 p 6. Fotelli MN, Radoglou KM, Constantinidou HIA (2000) Water stress of seedlings four Mediterranean oak species. Tree Physiol 20:1065–1075 7. Fuchs MA, Krannitz PG, Harestad AS (2000) Factors affecting emergence and first-year survival of seedlings of Garry oak (Quercus garrayana) in British Colombia, Canada. For Ecol Manage 137:209–219 8. Gardiner H (1998) Growth and biomass distribution of cherry bark oak (Quercus pagoda Raf.) seedling as influenced by light availability. For Ecol Manage 108:127–134 9. Gemmel P, Nilsson U, Welander T (1996) Development of oak and beech seedlings planted under varying shelterwood densities and with different site preparation methods in southern Sweden. New Forests 12:141–161 10. Guo K, Werger MJA (1999) Different responses to shade of evergreen and deciduous oak seedlings and the effect of acorn size. Acta Oecol 20(6):576–586 11. Holl KD (1998) Effects of above- and below-ground competition of shrubs and grass on Calophyllum brasiliense (Camb.) seedling growth in abandoned tropical pasture. For Ecol Manage 10:187–195 12. Jafari M (1977) Four article on forest. Technical Publication of Research Institute of Forest and Rangelands, No: 176–1977, 121 p 13. Jose S, Merritt S, Ramsey CL (2002) Growth, nutrition, photosynthesis and transpiration responses of longleaf seedling to light, water and nitrogen. For Ecol Manage 180:335–344 14. Kolb TE, Steiner KC (1990) Growth and biomass partitioning of northern red oak and yellow poplar seedlings: effect of shading and grass root competition. For Sci 36:34–44 15. Kolb TE, Steiner KC, McCormick LH, Bowersox TW (2003) Growth response of northern red oak and yellow poplar seedling to light, soil moister and nutrients in relation to ecological strategy. For Ecol Manage 1–2:675–678 16. Lhotka JM, Zaczek J (2001) The use of soil scarification to enhance oak regeneration in a mixed oak bottomland forest of southern Illinois. Proceedings of the 11th Biennial Southern Silvicultural Research, Knoxville, TN, USA, pp 392–395 17. Lof M, Gemmel P, Nilsson U, Welander NT (1998) The influence of site preparation on growth of Quercus robur L. seedling in a southern Sweden clear cut and shelterwood. For Ecol Manage 109:241–249 18. Lorimer CG, Chapman JW, Lambert WD (1994) Tall understorey vegetation as a factor in the poor development of oak seedlings beneath mature stands. J Ecol 82:227–237 19. Madsen P (1994) Growth and survival of Fagus sylvatica seedlings in relation to light intensity and soil water content. Scand J For Res 9:316–322 20. Madsen P (1995) Effects of soil water content, fertilization, light, weed competition and seedbed type on natural regeneration of beech (Fagus sylvatica). For Ecol Manage 72:251–264 21. McLaren KP, McDonald MA (2003) The effects of moisture and shade on seed germination and seedling survival in a tropical dry forest in Jamaica. For Ecol Manage 183:61–75 22. Méthy M, Damesin C, Rambal S (1996) Drought and photosystem II activity in two Mediterranean oaks. Ann For Sci 53:255–262 23. Morris HM, Castillo PN, Mize C (2000) Sowing date, shade, and irrigation affect big-leaf mahogany (Swietenia macrophylla King). For Ecol Manage 132:173–181 24. Morris LA, Moss SA, Garbett WS (1993) Competitive interference between selected herbaceous and woody plants and Pinus taeda L. during two growing seasons following planting. For Sci 39:166–187 25. Owens MK, Wallace RB, Archer SR (1995) Landscape and micro site influences on shrub recruitment in disturbed semiarid Quercus-Juniperus woodland. Oikos 74:493–502 26. Phares RE (1970) Growth of red oak (Quercus robur L.) seedlings in relation to light and nutrients. Ecology 52:669–672

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27. Rasaneh Y, Moshtagh Kahnamooi MH, Salehi, P. (2001) Northern Iran forests qualitative and quantitative investigation. The Proceeding of Northern Iran Forests Management and Sustainable Development 1:56–82 28. Rey Benayas JM (1998) Growth and mortality in Quercus ilex L. seedlings after irrigation and artificial shading in Mediterranean set-aside agricultural lands. Ann For Sci 55:801–807 29. Rey Benayas JM, Navarro J, Espigares T, Nicolau JM, Zavala MA (2005) Effect of artificial shading and weed mowing in reforestation of Mediterranean abandoned cropland with contrasting Quercus species. For Ecol Manage 212:302–314 30. Sack L, Grubb PJ (2002) The combined impacts of deep shade and drought on the growth and biomass allocation of shade-tolerant woody seedlings. Oecologia 131:175–185 31. Thadani R, Ashton PMS (1995) Regeneration of banj-oak (Q. leucotrichophoraA. Camus) in the Central Himalaya. For Ecol Manage 78:217–224 32. Welander NT, Ottosson B (1998) The influence of shading on growth and morphology in seedlings of Quercus robur L. and Fagus sylvatica L. For Ecol Manage 107:117–126 33. Ziegenhagen B, Kausch W (1995) Productivity of young shaded oak (Quercus robur L.) as corresponding to shoot morphology and leaf anatomy. For Ecol Manage 72:97–108

The Role of Plant Diversity in Sustainable Exploitation in Highland Rangelands (Alborz Mountain – Iran) R. Safaian, H. Arzani, H. Azarnivand, and N. Safaian

Abstract The rangeland managers, by understanding the importance and role of diversity in sustainable exploitation of rangelands, paid much attention to evaluation of plant relative frequency. This has been worked out in this research. As there is the probability that social and economic factors dominate the ecologic importance of this procedure (biodiversity conservation) and plant diversity is endangered by the kind of use, which in this research, was carried out in part of Alborz rangelands of Iran, the plants of the region were investigated as follows based on regional conditions: Endangered (EN), Vulnerable (VU), Low Risk (LR), (IUCN: International Union Conservation of Nature, classification system was used). In this research the following botanical structure of 375 plant species were recognized: Poaceae: 12%, Papilionaceae: 26%, Rosaceae: 12%, Lamiaceae: 24%, Asteraceae: 17% and other species: 9%. Based on comparison of Critical areas with Reference areas, the highest plant species decrease, in the first place is from family Poaceae for excessive animal grazing and then from Papilionaceae as forage and industrial plants and Finally from Lamiaceae as medicinal, industrial and fragrant plants. It seems that endangered condition and change in plant structure can be controlled by rangeland management, but change in rangeland use for development along with ecosystem degradation are the main threat and danger for plant diversity destruction in the region. Keywords Diversity · Conservation · Exploitation · Sustainable · Highland rangelands · Alborz mountain · Iran

1 Introduction Plant diversity indicates sustainability and kind of exploitation from an ecosystem. In degraded rangelands, use of plant diversity (food, medicinal and recreational uses) is a management tool procedure. If we accept that by correct use of natural R. Safaian (B) College of Agriculture, Shiraz University, Shiraz, Iran e-mail: [email protected]

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habitat, the biodiversity is also sustained, then the next question is that the exploitation should be at what level, so that beside sustainable use, the plant diversity is also sustained. It is because the complete conservation may not give maximum plant diversity [10]. Koojimam and smith in 2001 investigated the effect of grazing on organic matter and soil nutrition dynamics in Netherland rangelands and showed that grazing decreases tall grasses and increases species diversity. Chapin et al. [1] stated that interference of human being in world environment, has destroyed world organisms. They recommended human interference for world environment conversation and biodiversity. Gough and Galus [3] investigated tundra richness of species in north Alaska. It was concluded in this research that species diversity in northern area is a function of non-alive environmental gradients (topography, soil moisture, pH and soil natural fertility). Yuguang et al. [13] investigated the relationship between species diversity and grass land conditions. This results showed that species diversity has increased from poor to good condition and decreased from good to excellent conditions. Due to importance of conservation of species diversity, to be informed of hazards or reasons for plant species reduction, the ecosystem researchers at world level [2] in species duration commission IUCN (November 30, [4] in Gland, Switzerland), determined the plant species situation and approved and wrote in red book of species classification. As the species extinction is a world loss [1], this study was carried out in mountainous Alborz rangelands (Iran) to be informed of the hazards, decrease and or increase of plant species.

2 Materials and Methods The mountainous rangelands under study is located in central Alborz, 90 Km north of Tehran. The area is 13, 250,000 ha. The longitude is 50, 36, 50 to 50, 53, 20 and latitude is 36, 19, 19. The elevation is 1,700–4,100 m MSL, the mean annual ◦ temperature is 4.48 C, the mean annual precipitation is 698 mm. The climate is semi-arid cold and cold humid based on Emberger method of classification [12].

3 Research Method Sampling in ecological unit (homogeneous plant types) was carried out by randomsystematic method and using bar-point, by setting 56 transects 50 m apart and at different rangeland condition. In this method, the relative frequency of plants in study unit was evaluated. The species diversity was calculated from Shanon-Wiener formula (1948) [10]:

The Role of Plant Diversity in Sustainable Exploitation in Highland Rangelands

H=−

s ni i=1

N

ln

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ni N

where, H is Shanon-Wiener indicator ni is the amount of importance of each species N is the total showing the importance of species. Plant recognition and their places in IUCN classification were carried out with the help of references [4, 5, 7, 8, 9].

4 Results In Table 1 the plant diversity is observed in different rangelands condition. In Table 2, the evaluated plants are observed in IUCN classification. Table 1 Diversity in different rangeland conditions (poor, good, excellent) Sample

Rangeland Rangeland Rangeland condition Diversity Sample condition Diversity Sample condition Diversity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Poor Poor Poor Good Good Good Excellent Good Poor Poor Good Excellent Good Good Excellent Excellent Excellent Excellent Poor

2.9 1.95 1.1 5.44 4.1 3.96 3 3.81 2 2.12 3.9 3.67 4 4.56 3 3.76 3.5 3.68 1

20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38

Good Good Good Excellent Poor Poor Excellent Poor Good Poor Good Excellent Good Excellent Good Excellent Excellent Good Poor

4.06 4.99 3.8 3 1.83 1 3.62 2 3.83 2.99 3.83 3.2 3.9 3 4.12 3.01 3.67 4.07 2.83

39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56

Good Excellent Poor Good Poor Good Good Excellent Excellent Poor Poor Excellent Poor Poor Good Poor Excellent Excellent

4.8 3.73 1.4 3.85 2.2 3.9 4.8 3.74 3 2.17 2.9 3.3 2.6 2.35 4.9 2.02 3.5 3.57

Table 2 The evaluated plants in IUCN classification Page of red book Status Life form

Scientific name

Family

Habitat Number

294 306 312 325 339

Ajuga chamaecistus Mentha longifolia Nepeta denudata Salvia hypoleuca Thymus daenensis

Lamiaceae Lamiaceae Lamiaceae Lamiaceae Lamiaceae

IT IT IT IT-EU IT

LR LR LR LR LR

Ch H Ch H Ch

1 2 3 4 5

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Page of red book Status Life form 340 341 25 45

LR VU DD DD

Ch H H H

673 682 682 685 696 96 105 115

EN DD LR LR LR LR LR LR

H H H H H H H H

125 128 129 169 22

LR LR DD LR IT

H H H H Ch

178 202 559 559 214 374 343 347 216 18 606

LR LR LR LR LR LR LR LR LR LR LR

H H Ch Ch H H H H H Th Ch

Scientific name

Family

Habitat Number

Thymus kotschyanus Ziziphora clinopodioides Caccinia strigosa Trachelanthus cerinthoides Ferula persica Malabaila dasyantha Malabaila porphyrodiscus Pimpinella tragioides Zosima radians Achillea talagonica Centaurea aucheri Cephalorrhynchus brassicifolius Cousinia calocephala Cousinia commutata Cousinia crispa Echinops polygamus Helichrysum oligocephalum Jurinea heterophylla Tragopogon caricifolius Acantholimon scorpius Acantholimon sorchense Aethionema stenopterum Alcea longipedicellata Allium derderianum Allium shelkovnikovii Alyssum bracteatum Amaranthus blitoides Amygdalus eburnea

Lamiaceae Lamiaceae Boraginaceae Boraginaceae

IT IT IT IT

Umbelliferae Umbelliferae Umbelliferae Umbelliferae Umbelliferae Asteraeae Asteraeae Asteraeae

IT IT IT IT IT IT IT IT-EU

Asteraeae Asteraeae Asteraeae Asteraeae Asteraeae

IT IT IT IT LR

Asteraeae Asteraeae Plumbaginaceae Plumbaginaceae Brassicaceae Malvaceae Alliaceae Alliaceae Brassicaceae Amaranthaceae Rosaceae

IT IT-EU IT-SS IT IT-EU IT IT-EU IT IT IT IT-SS

6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 173 23 24 25 26 27 28 29 30 31 32 33

Note: IT – Irano–touranian region floristic; M – Mediteranean region floristic; SS – SaharoSindian region floristic; E – Euro-Siberian region floristic; LR – Lower risk; DD – Data deficient; EN – Endangered; VU – Vulnerable; Th – Therophyts; H – Hemicryptophyts; Ch – Chamophyts; G – Geophyts; Ph – Phanerophyts; En – Endemic.

5 Discussion and Conclusion Based on the results of this study, the variations in plant species is effected by exploitation and activities of living organisms (human being and animals) in the nature. The results showed that plant diversity increases in poor to good conditions, but decreases from good to excellent conditions. The result confirms the results obtained by Yuguang et al. [13]. This phenomenon can be useful and efficient as management procedure (use of medicinal plants, aromatic plants, etc) for planners.

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Botanic formation and floristic composition show decrease in the family Poaceae and increase in plants of the family Labiatae. The result is similar to the results of [6]. Use of special plants, those plants that people like: Ferula, Prangus, Thymus and Astragalus, made them susceptible to damages. Due to world importance of these species [1], their conservation is necessary by managers. Prangus, as one of the best rangeland species, is under extinction, and is not mentioned in Iranian Red Book. Due to difference in climatic-ecologic condition in the world, it seems that the classification made by species duration commission (IUCN) for each region floristic is necessary.

References 1. Chapin FS, Zavaleta ES, Eviner VT, Naylor RL, Vitousek PM, Reynolds HL, Hooper DU, Lavorel S, Sala OE, Hobbie SE, Mack MC, Diaz S (2000) Functional and societal consequences of changing biotic diversity. Nature 405:234–242 (ISP 3-018/CRN-012) 2. Fitter R, Fitter M (1987) The road to extinction. IUCN, Gland, Switzerland 3. Gough L, Galus R (2000) Vascular plant species richness in Alaskan arctic tundra: the importance of soil pH. Ecology 88:54–66 4. IUCN – International Union of Nature Conservation (1993) Draft IUCN red list categories. IUCN, Gland, Switzerland 5. Jalili A, Jamzad Z (1999) Red data book of Iran (A preliminary survey of endemic, rare & endangered plant species in Iran), Research Institute of Forests and Rangelands (RIFR), Iran, 748 pp 6. Koojimam AM, Smith A (2001) Grazing as a measure to reduce nutrient availability in acid dune grasslands and pine forests in the Netherlands. Journal Ecological Engineering 17:63–77 7. Mace GM, Stuart SN (1994) Draft IUCN red list categories, Version 2.2. Species 22:13–24 8. Mace GM, Lande R (1991) Assessing extinction threats: toward a reevaluation of IUCN threatened species categories. Conserv Biol 5(2):148–157 9. Mace GM, Collar N, Cooke J, Gaston K, Ginsberg J, Williams NL, Maunder M, MilnerGulland EJ (1992) The development of new criteria for listing species on the IUCN red list. Species 19:16–22 10. Odum EP (1983) Basic ecology. Saunders College Publishing, Philadelphia, PA, 613 pp 11. Rechinger KH (ed.), (1963–1998): Flora iranica, Nos 1–173, Academische Druk-u Verlagasantalt, Graz 12. Safaian R (2005) The multiple use of rangeland in Taleghan, Ms Thesis, Faculty of Natural Resources, University of Tehran, Tehran, 200 pp 13. Yuguang B, Abougundia Z, Redmann RE (2001) Relationship between plant species diversity and grassland condition. J Range Manage 54:177–183

Role of Indigenous People in Conservation of Biodiversity of Medicinal Plants: An Indian Case Study Pooja Joshi and Nilanjana Rao

Abstract Medicinal and aromatic plants (MAPs) have become a part of traditional system of medicines and have gained importance, more so in today’s world. According to the estimate of World Health Organization (WHO), about 80% of the population of developing world are making use of traditional medicines. The medicinal plants have been used for widespread purposes since ancient times in countries particularly India, China, Greece, Persia etc. In India, according to a report of AICEP, Anthropological Survey of India, 1994, it is estimated that over 7,500 species of medicinal plants are used for therapeutic uses. The major floral species which are widely used as medicinal and aromatic plants (MAPs) include Ephedra gerardiana Wall., Rauvolfia serpentina, Swertia chirata, Aconitum heterophyllum Wall. ex Royle, Rhododendron anthopogon D. Dun., Peganum harmala L. etc. The widespread use of these medicinal plants for both internal consumption and export purposes have led to their large-scale exploitation, resulting in loss of biological diversity (both at genetic and species level). Most of the medicinal plants like Rauvolfia serpentina, Gentiana kurro, Alpinia galanga, Saussurea lappa have become endangered and threatened. Overexploitation along with lack of initiatives from government bodies, absence of proper management systems and loss of traditional knowledge are some of the factors responsible for rapid biodiversity loss. Indigenous people and biodiversity complement each other and the former has played an important role in conservation of biodiversity since time immemorial. The rural communities over the period of time have gathered a pool of indigenous knowledge/know-how for cultivation of the medicinal plants and their propagation. In the meantime, the importance of local knowledge systems in conservation and preservation of the germplasm of medicinal plants have also attained global significance. In India, various programmes on medicinal plants and their conservation based on traditional knowledge are being carried out by the local people, Non Government Organizations (NGOs), Community

P. Joshi (B) The Energy Resource Institute, New Delhi, India e-mail: [email protected]

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Based Organizations (CBOs) at various grass root levels such as the districts and villages. Though an unorganized sector, the local people are playing their role in the propagation as well as conservation of the medicinal plants through the application of the concepts of herbal gardens and local “mandis” (markets). There is a need to strengthen these linkages and build upon the indigenous knowledge base of the local people through proper documentation and building of a strong database. This paper deliberates upon the importance (therapeutic, ecological and economic) of medicinal plants and threats to their biodiversity. The communication also describes the details of some of the local efforts, which are being carried out at local levels in India for conservation of medicinal plants through the use of indigenous knowledge of traditional medicines. The paper also highlights the need to integrate indigenous knowledge into national policies and strengthen the participation of the indigenous communities in order to harness maximum potential of medicinal plant biodiversity along with sustainable management of these resources. Keywords Aromatic plants · Biodiversity · Medical plants

1 Introduction India occupies only 2.4% of the world’s land area and yet contributes 8% to the world’s biodiversity [8]. India’s biogeographic location at the tri-junction of Afro-Tropical, Indo-Malayan and Paleo- Arctic realms (http://www.envfor.nic.in) is responsible for its unique and rich biodiversity. Ten distinct biogeographical zones have been identified in Indian peninsula, each characterized by distinct topography, climate and biodiversity. Among the 25 hotspots identified all over the world [11], two, namely, the Western Ghats and Indo-Burma region (covering Eastern Himalayas) extend into India. India has 47,000 species of flowering and nonflowering plants (representing almost 12% of the world’s recorded flora) of which 2,532 species are endemic to Himalayan region and the remaining 1,782 to peninsular India (http://www.envfor.nic.in). This floral diversity is an important natural resource, which makes a rich contribution to the gross domestic product of the country. Besides contributing directly to the economy of the country, the floral diversity is a source of fuel, fodder, food and medicine for rural communities of the country. The floral diversity, especially the medicinal plants has been an integral part of Indian culture and heritage. In fact indigenous communities in India and their traditions, rituals, beliefs as well as the age-old systems of medicines such as the Ayurveda, Siddha, Unani and Amchi have evolved deriving sumptuously from the rich floral and faunal diversity of the region. The Ayurvedic system of medicine, first described in Agnivesh Tantra by Agnivesha, is believed to have originated in the Himalayas, about 5,000 years ago (1,000–600 BC). Charaka Samhita, one of the earliest treatises of Indian medicines, reported the use of about 2,000 herbs for medicinal use.

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The Siddha system of medicine originated and flourished in Southern India, owes its origin to Lord Shiva. Indigenous communities, as defined by the United Nations are those which having a historical continuity with pre-invasion and pre-colonial societies that developed on their territories, consider themselves distinct from other sectors of societies now prevailing in those territories, or parts of them. They form at present non-dominant sectors of society and are determined to preserve, develop, and transmit to future generations their ancestral territories, and their ethnic identity, as the basis of their continued existence as peoples, in accordance with their own cultural patterns, social institutions and legal systems. These include the tribal people, the natives of the area concerned, marginalized sections such as the scheduled castes and also the farmers living on the fringes of forest areas. The association of medicinal plants and indigenous people has made the two traditionally, ecologically and economically inseparable. These communities have their day-to-day practices, rituals and traditions linked with the indigenous flora of the area, which essentially happens to be of medicinal value. For instance, Saussurea lappa locally called brahma kamal, is an important ethno-religious medicinal herb of Garhwal Himalayas where it is offered during prayers to Lord Shiva. Similarly, plants such as Ocimum (tulsi), Azadirachta (neem), Aegle marmelos (bel) are all considered sacred, ethno-religious plants used for prayers and rituals and most importantly recognized for their medicinal uses. The Naga tribes of Nagaland make use of the leaves of Psidium guajava, Houttuynia cordata and the stalk of Lasia spinosa for their anti helminthic properties for tapeworm infections. The anti-fatigue properties of Arogyapcha plant (Trichopus zeylanicus) were known to the Kani tribes of Western Ghats in the Thiruvanthapuram district of the state of Kerela. The legacy of traditional systems of medicines is still carried on by approximately two million traditional and village “dais” or mid wives, vaidyas, bonesetters, herbal practitioners and wandering monks. Besides, being the bearers of this unique traditional knowledge, the indigenous communities have strong conservation ethics. The religious beliefs of these communities have contributed to the conservation of biodiversity. The sacred groves or virgin patches of forests dedicated to local deities are befitting examples of conservation. The present day depletion of medicinal plants and traditional system of medicines is directly linked with the dwindling population of indigenous people and the erosion of their traditions and culture. The efforts, which are currently made for conservation of medicinal plants, need to be integrated with conservation of the traditional customs, practices, rituals, knowledge and wisdom of the indigenous people. The present communication is an attempt to highlight the importance of medicinal and aromatic plants vis-à-vis India’s traditional systems, its economy, their depleting status and efforts towards conservation of medicinal plants with active involvement of the indigenous communities.

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2 Significance of Medicinal and Aromatic Plants (MAPs) The significance of medicinal plants is highlighted by the fact that worldwide more than 50,000 plant species, covering about 13% of all flowering plants, are estimated to be medicinally important [14]. According to estimates of World Health Organization (WHO), 80% of the population in developing countries relies on traditional medicines [6, 2]. It is very important to realize that traditional systems of medicine are important for the poor and marginalized sections of the society, especially in the remote areas where modern medical facilities are not available [3]. This is validated by case study of India where per capita annual consumption of drugs is Rs.124 only (∼ = US $3), the lowest in the world. Additionally, interest in herbal medicines and natural products has increased substantially in developed as well as developing nations, mainly due to non-toxic nature of plant materials and no known side effects. This scenario is well reflected by the available trade figures. The international medicinal plant trade, estimated at US $60 billion, is presently growing at a rate of 7% per year [3]. This is besides the fact that a substantial part of the trade goes unrecorded, partly because much of it is illegal. Further, a large proportion of medicinal plant material is used domestically (India) and these figures are again not documented, hence the total trade of medicinal plants remains far greater than the suggested figures. The leading suppliers of the world market are China, Singapore, Brazil, India and Egypt. China and India constitute more than 40% of the global biodiversity. India is the second largest producer, second only to China. China earns US $5 billion per year from herbal trade, while India manages US $1.43 billion only, which is estimated to increase by US $2.2 billion by the year 2010 [2]. The international demand is largely from the United States and European Union (EU), with Germany as the leading trade center [3]. Besides contributing to the trade and economics at international level, the cultivation and collection of MAPs is an important means of livelihood generation among the rural and marginalized sections. Though the local and indigenous communities had always been dependant on forest resources for fuel, fodder, food and medicines, a substantial increase in collection of local medicinal and aromatic plants have been reported over the last 50 years, implicating that the collections are usually for commercial utilization. It has also been observed that it is the marginalized section of the society such as the scheduled tribes, scheduled castes, and women and the poor that depend on collection of MAPs for their livelihood. It is reported that the total income from sales of MAPs and Non Timber Forest Products (NTFPs) from forests in Madhya Pradesh, India was around US $2,000 per year [16]. The government in the state of Meghalaya benefits from the gathering and collection of MAPs where a single district provides around US $1,000,000 per year of revenue from the sale of about 3,000 tons of Bay Leaf products [7, 17]. Also, the cultivation of medicinal plants, hitherto not much in vogue, is slowly gaining acceptance among the farmers and commercial plantation of MAPs namely, Cholorophytum, Mentha, Geranium etc have proved to be economically beneficial. On the whole, it is evident that MAPs form an integral part of

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the rural society and have an important role to play in socio-economics of the local/indigenous communities.

3 Threat to Medicinal and Aromatic Plant (MAP) Biodiversity The established medicinal and emerging socio-economic importance of MAPs is having serious implications on these resources. A drastic decline in species diversity has been observed over the years. This is basically attributed to increasing anthropological pressures, habitat destruction, over exploitation, and lack of cultivation of the much-demanded medicinal and aromatic species. Of these, habitat destruction due to developmental projects is one major reason of genetic erosion of the biodiversity. It is estimated that India has lost 4,696 million hectares of forestland to non-forestry purposes in the period spanning 50 years after independence [10]. Such increasing human encroachments leads to fragmentation of large populations of species into small fragmented and scattered groups, which are rendered vulnerable to inbreeding depressions, high mortality rates and are more prone to extinction. Similarly, the rising demand by pharmaceutical industry leads to overexploitation of the medicinal plant species from the wild. Despite the immense importance of medicinal plants, the raw material is still not cultivated and about 95% of the medicinal plants are collected from the wild. According to a study, more than 1,300 tons of MAPs are collected and traded in a single district of Pithoragarh in Uttaranchal state, most of which is illegal [13]. A case study of Ayurveda industry showed that over 70% of the plant collections involves destructive harvesting mainly because of the use of plant parts like roots, bark, wood and whole plants. The estimates show that the various plant parts used by the Ayurvedic industry in India are as follows: bark 13.5%, roots 29.6%, rhizome 4%, stem 6%, whole plant 16.3%, wood 2.8% and the rest being contributed by flowers, fruits, leaves and seeds [2]. These medicinal plants include both herbs and trees and have major implications for conservation and management of supplies of raw material. Further, indiscriminate collection of medicinal plants from the natural stands leads to change in community organization, which in turn effects the regeneration potential of the rare and endemic species resulting in their endangered status [9]. Medicinally important species like Picrorhiza kurrooa, Rauvolfia serpentina, Saussurea lappa, Taxus wallichiana, already figure in the list of threatened and endangered species of Convention on International Trade in Endangered Species of Wild Fauna and Flora http://www.cites.org/eng/resources/species.html. As per the recent International Union of Conservation of Nature and Natural Resources (IUCN) guidelines, Southern and Northern India has around 200 species of medicinal plants that are rare, endangered and threatened [15]. This could mean a tremendous loss to the world of modern allopathic medicine as well as traditional system of Ayurveda, Unani and Siddha, which the human race surely cannot afford.

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4 Loss of Indigenous Knowledge and Threats to MAPs As stated earlier, the traditional knowledge of the indigenous communities and the medicinal plants are inseparable. A decline in the traditions, rituals and age-old systems of the indigenous communities directly reflects on the conservation status of the medicinal plants. Though, India has one of the richest traditions of using medicinal plants in health care, most of the traditional and indigenous knowledge associated with the rich natural resource of the country remains undocumented and is passed down either by word of mouth from generation to generation or is described in ancient classical literature, and therefore remains inaccessible to common man. Even our traditional health systems such as Ayurveda, Siddha and Unani, which are very well documented, are codified in languages such as the Persian, Sanskrit and Tamil, which are not well understood internationally. The undocumented Indian Traditional Knowledge (ITK) is facing challenges from the developed countries in the form of “biopiracy” and “gene robbing” [5]. The need for protecting Indian traditional knowledge (ITK) has been vehemently brought forth by many well-known cases of misappropriation of traditional knowledge that includes the patents granted for medicinal properties of brinjal (Solanum melongena), bitter gourd (Momordica charantia), neem (Azadirachta indica) and turmeric (Curcuma longa) to name a few. Therefore, documentation of existing knowledge on various traditional systems of medicine, which is available in the public domain has become imperative in order to safeguard it from patenting of non-original inventions. Further, the effects of urbanization are fast catching up with these native people as it has with their plants. The effects of urbanization are not only evident on the declining species diversity but also have resulted in developmental and socio-cultural adaptations among the indigenous people. Due to technological advancement and change in lifestyles, the traditional knowledge in these local communities is disappearing, with younger generations opting for new livelihood options. Also, the impacts of urbanization on the socio-cultural lifestyle has led to erosion of religious and cultural values, which in turn has repercussions on the status of medicinal plants. This is exemplified by the scared groves or community forests, rich in medicinal flora, which were once dedicated to the local gods/goddesses by indigenous communities. Ecologically speaking scared groves form a compact community structure at its climax and harbor many rare and endemic species. The dilution of religious values and socio-cultural aspects has led many communities to lose their unified identity, instrumental to their conservation practice, and to destroy resources in their sacred groves in return for short-term commercial gain. The losses incurred due to such changes in socio-cultural patterns are further augmented by developmental projects such as highways, dams and railway tracks, which have either totally destroyed the sacred grooves or else have irreversibly disturbed their community structure, which has left many of the rare and endemic species vulnerable to threats of extinction.

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5 Conservation of Traditional Knowledge and MAPs – Requirements and Current Efforts 5.1 Documentation of the MAPs and Traditional Knowledge The first and foremost task is to document the vast traditional knowledge, which the indigenous communities possess. Unless and until this vast knowledge is preserved, we will not only lose the traditional system of medicines but also the genetic diversity of the medicinal and aromatic plants. The medicinal plants are known by their local names and it is often seen that different plants have the same name in different parts of the country, which creates unnecessary confusion. Therefore, taxonomic databases of ethno medicinal plants with the help of traditional practioners and experienced taxonomists should be prepared immediately. The role of research institutes and universities come into the foray for proper and scientific identification of plants and plant products. With this perspective, National Institute of Science Communication and Information Resources (NISCAIR) and the Department of Indian Systems of Medicine and Homoeopathy (ISM&H) have come up with a novel concept of traditional knowledge digital library (TKDL), in which all information for a target species is available in world languages such as English, French, German, Japanese and Spanish (www.niscair.res.in). This attempt at digitalization of ITK gives legitimacy to the existing traditional knowledge and enables protection of such information from getting patented illegally. A well documented database will help in “bioprospecting” a term used to assign economic value to plant species. Bioprospecting will further strengthen the value of traditional system of Indian medicine in the international market. Thus, documentation and conservation of these resources will simultaneously lead to an understanding and awareness towards the medicinal plants and hence care for them.

5.2 Protection of Intellectual Rights of Indigenous People and Benefit Sharing The indigenous knowledge, which is the dominion of the local communities, should be protected and cases of bio-piracy should be prevented as discussed earlier. Further, the indigenous people should also get a profit sharing from the marketing of their medicinal plant use. One prominent example is the development of “Jeevani” medicine based on the traditional knowledge of the Kani tribals of Kerala. The tribals used fruits of a tree that they called aarogyapyappacha which kept them energetic and agile during their arduous treks across the forests. The detailed investigation of the plant revealed that it contained certain glycolipids and non-steroidal compounds that had anti-stress, anti-hepatotoxic and immuno-modulatory/immunorestorative properties. Eventually the drug “Jeevani” was formulated from this plant, which was later, identified as Trichopus zeylanicus, with three other plants’

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ingredients. The license to manufacture “Jeevani” was given to a private company for a fee of one million rupees (∼ = US $22,000) for a period of 7 years. The Kani tribals received 50% of the license fee as well as 50% of the royalty obtained from sale of the drug. Such instances not only enhance the livelihood means of the communities, but also instill a sense of pride and utility for indigenous traditional knowledge. The communities become more conscious of their inherent traditional resources and hence more aware towards their conservation.

5.3 Cultivation of MAPs and Enhancement of Livelihood Opportunities Cultivation of medicinal plants is one of the viable options for not only meeting the market demands and in improving the socio-economic position of the local people, but also helps in conservation of the endangered species in their natural habitat. The case in point of Nardostachys jatamansi, an endangered plant of the Northwestern Himalayas illustrates this. The plant have been included the schedule of CITES to ensure its conservation. In India there is a need of 300 metric tons of the plant [1, 18]. This increased demand can certainly not be met through wild collections only and hence cultivation is the only viable solution. This scenario holds true not only for N. jatamansi in particular, but also for other rare and endangered medicinal plants such as Picrorhiza kurroa, Swertia chirayita, etc. Keeping this in view many cultivation/domestication studies have been conducted for different medicinal plants [4, 12]. In a study in Ghese village of Chamoli district, Uttaranchal (India), cultivation of a highly prioritised medicinal plant, Picrorhiza kurrooa (commonly called kutki) was conducted on an experimental basis [12]. According to the calculations, the net benefit to the farmer that comes from conventional crops such as potato and rajma (Phaseolus vulgaris) is a mere US $280 and US $118 per acre, respectively. On the contrary, kutki cultivation would yield a net profit of US $1961. Such studies augur well for conservation of medicinal plants as well as the local people who will definitely benefit from cultivation of elite germplasm of economically valuable medicinal and aromatic plants.

5.4 Policy Initiatives at the National Level In the present scenario of increasing demand of medicinal and aromatic plant species with a simultaneous decline of the resources, conservation and sustainable management are the need of the day. The Ministry of Forest and Environment (MoEF), the nodal environmental regulatory agency of Government of India, has devised many policies and programs to enhance the conservation of the medicinal and aromatic plants throughout the country. A number of institutions affiliated with the ministry are involved towards implementing these programs. Almost 4.2% area of

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the country has been earmarked for the extensive in situ conservation of habitats and ecosystems and under this program various national parks, Biosphere Reserve Programs have been initiated. Similarly, concept of botanic and herbal gardens have been instituted under the ex situ conservation programs. More recently, under the aegis of Ministry of Health and Family welfare, the government has set up the National Medicinal Plant Board (http://www.nmpb.nic.in), with the objective to establish a board that would be responsible for co-ordination of all matters relating to medicinal plants, including drawing up policies and strategies for conservation, proper harvesting, cost-effective cultivation, research and development, processing, marketing of raw material in order to protect, sustain and develop this sector.

5.5 Involvement of Local Communities, Non-Government Organizations/Community Based Organizations Cultivation of the medicinal plants can serve as one of the potential employment avenues for local communities, youth and women. Community based approaches have been successful in the conservation and livelihood generation programmes. Many non-government organizations (NGOs) and community-based organizations (CBOs) are doing commendable work in this arena. In India, the Foundation for Revitalization of Local Health Traditions (FRLHT) is the pioneer and has been recognized by the Government of India as the “centre of excellence” in the field of medicinal plants. Many programmes and projects of such NGOs are running successfully in this country. Amongst many others, one such initiative is the Medicinal Plant Conservation Area (MPCA) programme, created by the FRLHT and implemented by another NGO, Medicinal Plant Conservation Centre (MPCC). The programme is a multi-approach effort to conserve the medicinal plants within their natural ecosystem and production of traditional medicines aimed at providing primary health aid through participation of local people. This also provides a supplementary source of income. However, for any such community based effort to be successful, the direct beneficiaries i.e. indigenous people, marginalized and poor farmers, women and youth should be involved right from the project conceptualization and planning stage.

5.6 Role of International Organizations Realizing the importance of the MAPs and the efforts of local NGOs/CBOs and the local communities in conservation of biodiversity, many international organizations like World Bank, United Nations Development Programme (UNDP), International Development Research Centre (IDRC) are sponsoring many conservation programmes. One of the core areas of the UNDP’s Global Environment Facility (GEF) under its Small Grant Fund (SGF) is the conservation of biodiversity including medicinal plants. The Medicinal and Aromatic Plants Program in Asia is

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another initiative aimed at long-term sustainable and equitable use of MAPs of the IDRC and Ford Foundation. The involvement of international bodies in the existing national and local programmes further strengthens the efforts, which are currently being made towards the conservation of medicinal plant biodiversity and enhances India’s position in the global scenario of traditional medicines.

6 Conclusion India occupies an advantageous position related to the rich diversity of medicinal and aromatic plants and have an old lineage of traditional knowledge in indigenous medicines. In spite of this fact, the current scenario is that the age-old indigenous knowledge of the local and tribal communities is at a threat, thereby endangering the diversity of many of the species of medicinal plants. Over-exploitation of the plants from the wild due to excessive commercialization of herbal medicines and effects of urban trends on the socio-economic lifestyle of the rural and indigenous people are the major reasons cited for the alarming situation of the medicinal plants and the traditional system of medicines associated with them. Though efforts are being carried by the government, research organizations, local NGOs and even the local communities at their individual levels, however an integration of all the parties is required for not only enhancing the income levels of the indigenous communities and safeguarding the traditional knowledge, but also for conservation of medicinal plants and the promotion of the traditional system of medicines.

References 1. Ahuja PS (2003) Medicinal plants in India. In report and directory. Institute of Economic and Market Research, New Delhi 2. Anonymous (2000) Report of the taskforce on medicinal plants in India. Planning Commission, Government of India, Yojana Bhawan, New Delhi, India. http://planning commission.nic.in/aboutus/taskforce/tsk_medi.pdf 3. Belt J, Lengkeek A, Van Der Zant J (2003) Cultivating a healthy enterprise – developing a sustainable medicinal plant chain in Uttranchal – India Bulletin 350. KIT Publishers, Amsterdam 4. Chauhan RS, Nautiyal MC (2005) Commercial viability of cultivation of an endangered medicinal herb Nardostachys jatamansi at three different agroclimatic zone. Curr Sci 89:1481–1488 5. Dubey NK, Kumar R, Tripathi P (2004) Global promotion of herbal medicine: India’s opportunity. Curr Sci 86:37–41 6. Holley, J., Cherla, K. (1998) The medicinal plants sector in India. Medicinal and Aromatic Plants Programme in Asia (MAPPA) ADRC/SARO, New Delhi 7. Karki M, Tiwari B, Badoni A, Bhattarai N (2003) Creating livelihood enhancing medicinal and aromatic plants based biodiversity rich production systems: Preliminary lessons from South Asia. Oral Paper Presented at the 3rd world congress on medicinal and aromatic plants for human welfare (WOCMAP III), Chiang Mai, Thailand

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8. Khoshoo TN (1996) India needs a national conservation board, Current Science, 71: 506–513 9. Laloo RC, Kharlukhi L, Jeeva S, Mishra BP (2006) Status of medicinal plants in the disturbed and the undisturbed sacred forests of Meghalaya, northeast India: population structure and regeneration efficacy of some important species. Curr Sci 90:225–232 10. MoEF (1999) National policy and macrolevel action strategy on biodiversity. Ministry of Environment and Forests, Government of India, New Delhi 11. Myers N, Muttermeier RA, Muttermeier CA, da Fonseca GAB, Kent J (2000) Biodiversity hotspots for conservation priorities. Nature 403:853–858 12. Nautiyal MC, Nuatiyal BP (2004) Collaboration between farmers, research institutions and industry: experiences of Picrorhiza kurroa cultivation at Ghese village in Chamoli district, Uttaranchal, India. In: Alam G, Belt J (eds) Searching synergy: stakeholders views on developing a sustainable medicinal plant chain in Uttranchal, India. KIT Publishers, Amsterdam. KIT Bulletin No. 359, pp 63–72 13. Regmi S, Bista S (2002) Best practices in collection and cultivation of medicinal plants for sustainable livelihoods in Himalayan communities. Paper presented at the regional workshop at wise practices and experimental learning in the conservation and management of Himalayan medicinal plant, 15–20 Dec, Kathmandu, CECI-Nepal 14. Schippmannn U, Leaman DJ, Cunningham CB (2002) Impact of cultivation and gathering of medicinal plants in biodiversity: global trends and issues. FAO, Biodiversity and the Ecosystem Approach in Agriculture, Forestry and Fisheries, Interdepartmental Working Group on Biological Diversity for Food and Agriculture, Rome 15. Shankar D (1998) Medicinal plants: a global heritage. Proceedings of the international conference on medicinal plants for survival, 16–19 February. IDRC, New Delhi 16. Singh MK (2003) Non-wood forest products based joint forest management in good forests. Indian Council of Forestry Research and Education (ICFRE), Dehradun, India 17. Tiwari BK (2003) Biodiversity enriching and livelihood enhancing forest management practice of war Khasis of Meghalaya, India. Proceedings of wise practices in sustainable management of Himalayan medicinal plants, PPI and IDRC 18. Uniyal MR Uniyal RC (2002) Utilization of medicinal plants by pharmaceutical industries in India. Paper presented in workshop on ‘Vanaspati van’ WII, Dehdradun

Stand Structure and Spatial Patterns of Trees in Mixed Hyrcanian Beech Forest, Iran H. Habashi, S.M. Hosseini, R. Rahmani, and J. Mohammadi

Abstract The mixed beech forests (Fagus orientalis) are the most important industrial forests with the highest degree of naturalness in Hyrcanian forest, Iran. These forests commonly dominate by shade tolerance species with irregular uneven age stand structure. The aim of this study was to analyze the stand structure and spatial pattern in order to identify specific structural patterns. We investigated the stand structure and spatial pattern of trees in mixed Beech forest in the Shastkolate Educational Forest to examine the coexistence strategies of different species. Data was collected from an 16 ha permanent plot on an 400 × 400 m quadrate area that divided to 64 micro-quadrate (50 × 50 m). We mapped all stems >7.5 cm in diameter at breast height (dbh) on permanent plot. The stand contained nine woody plant species and 4,901 living stems with a combined basal area of 32.8 m2 ha−1 . The density of living trees >7.5 cm dbh averaged 291.7 ha−1 . The six main species were divided into two groups based on density and stand structure. Group A (F. orientalis, Carpinus betulus and Parrotia persica) had higher density than group B, as well as reverse J or L-shaped dbh distribution of live stems. Species in group B (Alnus subcordata, Acer velutinum and Diospurus lotus) had bell-shaped dbh distributions. Species in group A have clump spatial distribution pattern in all layers but clump intensity is more than in under storey layer and size of patch clump is small in this group. This phenomenon for group A may explaining by having numerous coppice, sucker and patch regeneration in the under storey layer. Middle storey and under storey stems of the six major tree species were patchily distributed throughout the plot but for Alder and Maple species common pattern in canopy layer was complete spatial randomness. The distribution of Beech and Hornbeam trees were negatively associated with other species. These results suggest species differences in favorable canopy condition. Differences in life history strategies and site preferences may explain the coexistence of these species.

H. Habashi (B) Natural Resources Faculty, Tarbiat Modarres University, P.O. Box 46414-356 Noor, Mazandaran, Iran e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_11,

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Keywords Stand structure · Spatial distribution pattern · Spatial association · Beech forest · Iran

1 Introduction Beech forests commonly dominate the intermediate elevation regions of the northern temperate zone of Iran. These forests are the most important forest communities in natural forest landscape in Iran and usually consist of several canopy tree species. In this site, including Fagus orientalis, Carpinus betulus, Acer velutinum and Alnus subcordate are the most dominant, while Prunus spinosa and Diospyrus lotus often co-occur. Because Beech forests are widespread and represent the potential natural vegetation of many areas of Hyrcanian landscape, it’s of interest to identified stand structure and spatial pattern of major trees in these forests. The spatial and temporal pattern and the consequences of that pattern for the dynamics of populations and ecosystems are two fundamental and related themes in ecology [23]. Patterns can exist at various scales in time and space [2, 44, 34]. In nature, these patterns can appear as patches, gradients, or other kinds of spatial structures at spatial scales ranging from ecosystems to the area occupied by an individual organism [45, 43, 37, 18, 23, 13, 27]. Accordingly, many studies have attempted to quantify the patterns of heterogeneity within plant communities. These studies described and tested the effects of environmental heterogeneity on individual plants and plant-plant interactions at scales of centimeters to dozens of meters [7, 37, 18, 16, 11]. The results have demonstrated that significant spatial variations exist in soil attributes at finer spatial scales, and that plants appear to respond to these variations. It is possible that the pattern and dynamics of the fine-scale variations in soil resources may hold the key to understand mechanisms of plant-plant interactions. Furthermore, some studies have revealed that plants can modify the spatial variability of soil attributes through litter production and its composition, absorption of moisture, oxygen and nutrients, and the release from roots of organic molecules [36], suggesting the significance of plants in creation and maintenance of soil resource heterogeneity. The relationship of plant species and communities to site factors has also been the subject of extensive study [19]. Plants that repeatedly occur to gather in areas with similar combination of soil water, nutrients, light, and other factors are perceived to have similar recruitments or tolerance and are therefore grouped together [4]. The structure of different forest vegetation has also been analyzed in the context of scale dependency [1, 6, 26]. This was because various ecological phenomena often depend on the scales analyzed. Thus, we must pay attention to scales observed and analyzed in evaluating the characteristics of vegetation. Traditional research on plant spatial pattern has emphasized testing for departures from complete spatial randomness (CSR). Tests of the CSR hypothesis have also been applied in studies of competition effects on dynamics of even aged homogeneous forests [47, 12, 20, 21], mixed species temperate forests [8, 41], semi-arid shrub dominated stands [46], and savanna vegetation [40]. In general,

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the competition is assumed to cause a systematic change in the spatial pattern from random or aggregated to a regular pattern as a result of density-dependent mortality. Model of forest dynamics that incorporate spatial interactions among trees and other forest vegetation have been used as an alternative approach to testing hypotheses about the influence of forest structure on spatial pattern. This mechanistic approach has been applied to describe the spatial structure of tropical and temperate forests [24] and as a component of models simulating forest dynamics (e.g., Busing [5]). The objective of this paper is to identify stochastic point processes that can simulate the non-random spatial patterns of trees in mixed Beech forests, Iran. The point processes were selected to provide realistic reproduction of the observed patterns under a simple set of biologically plausible assumptions. This study assessed: (1) the characteristics of stand structure, including the stand structure of the six major species and canopy and (2) the characteristics of spatial distribution patterns of the major species. On the basis of the results of this large-scale study, we discuss the coexistence of Fagus and other species in the Shastkolate Forest permanent plot.

2 Methods 2.1 Study Area The study area is located at the Shastkolate educational forest in the North-East of the Hyrcanian forest, Iran (36◦ 45 N and 41◦54 E) (Fig. 1). Permanent plot located in parcel 32, district 1 with 79.9 ha. Near the study stand (at Gorgan city), mean annual precipitation is about 6,506,144 mm and the mean monthly temperature is highest in May (27.9◦C) and lowest in November (8.71◦C). The study stand is situated at an elevation between 820 and 960 m up to see level. There were no signs of human or major natural disturbance. Canopy height was typically about 30 m and Canopy cover is about 55–100%.

2.2 Field Methods In February 2005, a 16 ha (400 m × 400 m) permanent plot was established. The forest on the 16 ha plot was well developed and contained many species within the study stand. All woody stems >7.5 cm dbh were measured to the nearest 0.1 cm and the location of all stems was mapped. The trees were tagged, identified to species level, and classified according to state (living or dead) and position in the canopy by measuring height of all trees. In our analysis of spatial distribution patterns and spatial associations among the tree species, we considered layer I to be the canopy layer (height is greater than 40 m) and layers II (height between 20 and 40 m) and III the understorey (height is less than 20 m). The plot was divided into 64 contiguous 50 m × 50 m quadrates, and all trees coordinate were recorded. The condition of the forest floor within a quadrate was recorded by visual estimation as percentage coverage [39].

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Fig. 1 Location of study site

2.3 Data Analysis We described the stand structure of the major tree species using stem density, maximum dbh, basal area, dbh distribution. We determined the spatial distribution of each species using the number of stems in each layer. The spatial distribution of stems of major species >7.5 cm dbh in different layers was analyzed using First-order Nearest Neighbour Tests; Clark-Evans Statistic. Probably the simplest measure of spatial pattern is the first-order nearest neighbour distance; that is, the distance from an event to its closest counterpart. The measure was described in an ecological context by Clark and Evans [9] who provide estimates of the expected nearest neighbour distance under CSR (Complete Spatial Randomness) as well as significance tests for detecting departure from CSR in spatial point processes. The Clark Evans statistic (RCE ) is the ratio of the observed (rA ) nearest neighbour distance to that expected (rE ) under CSR. Under CSR, RCE ∼1.0. When RCE < 1.0 the point process is aggregated (RCE = 0 for maximum possible aggregation) and when RCE > 1.0 it is maximally spaced (the maximum value of RCE is 1.0746/λ). In any given distribution the mean observed distance to the nearest neighbour is RCE times as great as would be expected under CSR (at the same density). Thus, an RCE

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value of 0.5 would indicate that nearest neighbours are on average half as far apart as expected under CSR. Spatial associations among major tree species and stems in different layers were analyzed using Morisita’s index of interspecific correlation, Rδ [30, 31]. First, we considered the following function:

q nxi nyi − Nx Ny 2 q Rδ =

i=1

q(δx × δy )Nx Ny

(1)

where q

δx =

nxi (nxi − 1)

i=1

(2)

Nx (Nx − 1)

and q

δy =

nyi (nyi − 1)

i=1

(3)

Ny (Ny − 1)

Where nxi is the number of stems of species X occurring in the ith quadrate, nyi the number of stems of species Y in the ith quadrate, Nx and Ny are the total number of stems of species X and Y, respectively, and q the number of quadrates. If Rδ ≥ 0, then Rδ = Rδ

(4)

And if Rδ < 0, then ⎛

q

⎞

nxi nyi ⎟ ⎜q ⎜ i=1 ⎟ Rδ = ⎜ ⎟ ⎝ Nx Ny ⎠

(5)

Rδ expresses the degree of spatial associations, taking a positive value when the distributions of the two species or layers are positively associated and a negative value when they are negatively associated. If the two species or layers are distributed independently of one other, Rδ = 0. The scale of spatial associations is determined by computing Rδ values for quadrates. The size of quadrates is same at Iδ . Because both Iδ and Rδ tend to vary erratically where the number of samples (stems) is small, layers II and III were pooled to increase the sample size for the analysis of spatial

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distributions and spatial associations. There are various examples for the use of the Rδ index in the analysis of spatial associations of tree stems [25, 17].

3 Results 3.1 Floristic and Physical Characteristics In the 16 ha permanent plot, we found nine tree and shrub species with a dbh >7.5 cm: F. Orientalis, C. betulus, A. velutinum, A. cappadocicum, Alnus subcordata, Ulmus glabra, P. spinosa, D. lotus and P. persica. We counted 4,901 living stems (292 stems ha−1 ) and 314 dead stems (18.7 stems ha−1 ), with a total basal area of 55.2 m2 ha−1 (living) and 24.3 m3 ha−1 (dead). Here we considered only the living stems of the six main species that each made up >95% of the total stem density: F. orientalis Lipsky, C. betulus, P. persica, A. subcordata, A. velutinum and D. lotus (Table 1). Most of the ground surface was covered by Ruscus hyrcanus, although bare rock and exposed mineral soil occurred locally. Table 1 Stand parameters of living stems >7.5 cm dbh for major tree species in the 16 ha permanent plot of the Shastkolate Forest Iran

Species F. oreintalis C. betulus P. persica A. subcordata A. velutinum D. Lotus

Stem density (ha−1 ) 107.5 71.5 76.4 2.5 8.5 23.7

DBH (cm) Mean 6S.D.

Maximum

Height (m)

33.84630.01 29.19623.9 22.45616.4 62.99621.6 38.6628.6 12.464.3

150 112 98 119 154 40

21.29 21.03 15.03 32.25 24.29 13.39

Basal area (m2 ha−1 )

Crown diameter (m)

17.3 8.0 4.6 0.87 1.53 0.32

6.16 6.02 6.64 5.9 5.66 6.36

3.2 Size and Stand Structure Stand parameters varied among the major tree species (Table 1). A. Subcordata had the largest mean dbh and basal area, whereas F. Orientalis had the highest stem density. The dbh distributions of living stems of D. lotus, A. velutinum and A. subcordata were bell-shaped. The mode of A. subcordata was 60–70 cm and that of A. velutinum was 20–30 cm and fot D. lotus was 10–15 cm (Fig. 2). Live stems of F. orientalis, C. betulus and P. persica exhibited reverse J or L-shaped distributions. Canopy layers varied among species (Table 2). The four species had stems in all layers but D. lotus hadn’t stems in layer I and 68.3% this species stems is related on layer III. A. subcordata had far fewer stems in layer III than in layers I and II. P. persica had more stems in the lowest layer, and A. velutinum had more stems in the layer II.

Fig. 2 The Stand structure and dbh class distributions of the major tree species in the 16 ha permanent plot of the Shastkolate Forest Iran

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Table 2 Density (ha−1 ) by canopy height of living stems >7.5 cm dbh for major tree species in each layer in the 16 ha permanent plot of the Shastkolate forest, Iran Layera I

II

III

Species

Number

Percent

Number

Percent

Number

Percent

F.oreintalis C. betulus P. persica A. subcordata A. velutinum D. Lotus

17.7 5.9 0.48 1.1 0.95 0.0

16.5 8.2 0.6 45.2 11.2 0.0

47.2 43.4 31.7 1.3 6.0 7.5

43.9 60.7 41.5 52.4 70.6 31.7

42.5 22.2 44.2 0.05 1.5 16.2

39.6 31.1 57.9 2.4 18.2 68.3

a Layer

I: Canopy with height is greater than 35 m, Layer II: middle storey canopy with height between 15 and 35 m, Layer III: Under storey canopy with height less than 15 m

3.3 Spatial Distribution Pattern Dispersion maps of individual stems of Beech and Hornbeam species in each layer illustrate their spatial distributions (Figs. 3 and 4). Stems of four species in the plot were clumped in canopy, middle and understorey layers, but A. subcordata and A. velutinum were complete spatial randomness pattern and RCE > 1 illustrate maximum space between stems. In the canopy layer, A. velutinum stems were aggregated in a large sized clump (4,518 m2 ), P. persica was clustered in large sized clump (8,885 m2 ); and A. subcordata, C. betulus and F. orientalis were aggregated in small clump (552 and 400 and 144 m2 ). Because we found few A. subcordata stems in the understorey, we did not analyze the data for this species. Understorey stems of F. orientalis were aggregated in small patch (41 m2 ) and P. persica were (32 m2 ) patches, whereas stems of A. velutinum and A. subcordata were aggregated in intermediate (1,038 and 862 m2 ) clumps. Stems of all species were found in the understorey, distributed independently of canopy conditions. The following tables illustrate spatial distribution analysis in three layers with use of Clark and Evan’s indices (Table 3) [9].

3.4 Spatial Association In permanent plot, F. orientalis and C. betulus stems were negatively associated with A. subcordata and A. velutinum stems, although the relation was stronger with A. subcordata. The sole exception to this result was that C. betulus was distributed independently of other species specification A. velutinum and P. persica in big quadrate size. A. subcordata were positively associated with D. lotus in quadrates 145,000 m2 but were negatively associated with other species in the smallest quadrates. Stems of A. velutinum were distributed independently of the D. lotus

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Fig. 3 Distribution of individual stems of Beech tree in the 16 ha permanent plot of the Shastkolate Forest, Iran. Large circles: stem with dbh greater or equal than 80 cm; medium circle: stems with dbh greater or equal than 40 cm and less than 80 cm; small circles: stems with dbh greater than 40 cm. Scale in meters

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Fig. 4 Distribution of individual stems of Hornbeam tree in the 16 ha permanent plot of the Shastkolate Forest Iran. Large circles: stem with dbh greater or equal than 80 cm; medium circle: stems with dbh greater or equal than 40 cm and less than 80 cm; small circles: stems with dbh greater than 40 cm. Scale in meters

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Table 3 Spatial distribution analysis parameters of living stems >7.5 cm dbh for major tree species in the 16 ha permanent plot of the Shastkolate forest – Iran Species

Parameter

Canopy layer

Middle layer

Understorey layer

F. oreintalis

Point analyzed Average NN distance Clark and Evan’s R Point analyzed Average NN distance Clark and Evan’s R Point analyzed Average NN distance Clark and Evan’s R Point analyzed Average NN distance Clark and Evan’s R Point analyzed Average NN distance Clark and Evan’s R Point analyzed Average NN distance Clark and Evan’s R

294 12.02 0.38 98 20.03 0.39 7 94.26 0.45 19 23.5 2.31 15 67.22 0.91 0 0 0

789 6.72 0.34 729 6.91 0.36 528 8.66 0.35 20 29.36 0.25 99 17.01 0.33 124 13.33 0.27

718 6.39 0.30 372 7.85 0.27 740 5.68 0.28 0 0 0 26 32.22 0.32 271 8.17 0.25

C. betulus

P. persica

A. subcordata

A. velutinum

D. lotus

and P. persica in quadrates 12,500 m2 but were negatively associated the smallest quadrates. D. lotus was strong negatively associated with P. persica in all quadrates (Fig. 5).

1

F.orientalis with all other species

0.5

Rδ

0

2500

37500

75000

1125000

130000

–0.5

137500

145000 160000

Fagus&Carpinus Fagus &Alnus Fagus&Acer Fagus&Diospyrus Fagus&Parrotia

–1 Quadratee size (m2)

Fig. 5 Rδ quadrate size relations of living stems >7.5 cm dbh for tree species in the 16 ha permanent plot of the Shastkolate Forest, Iran. Rδ is the Morisita’s index of interspecific correlation [31]. Rδ quadrate size relations stems in F. orientalis with other species

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4 Discussion 4.1 Stand Characteristics In many mixed Beech forests, Fagus. spp are found at a much greater density than other species [38, 35, 22]. In the study stand, the density of F. orientalis was much higher than that of C. betulus, A. subcordata and A. velutinum although A. subcordata and A. velutinum occupied the largest basal area. Total dead wood volume is similar to other reported from Hyrcanian mixed beech forest [15, 14].

4.2 Stand Structure Beech forests (F. orientalis) represent the most important forest communities in natural forested landscapes in Hyrcanian forest, Iran [29]. In Beech forest of central Europe mean density of living trees >7 cm dbh amounted to 263 ha−1 and about one-third of the trees (95 ha−1 ) occurred in the upper canopy layer [33]. In our study, mean density of living trees >7.5 cm dbh amounted to 107.4 ha−1 and 16.5% of the trees (17.7 ha−1 ) occurred in the upper canopy layer. On the basis of our results, we divided the species into two groups. The species in group A were F. orientalis, C. betulus and P. persica and in group B were D. lotus, A. subcordata and A. velutinum. The species in group A were the most common, characterized by continuously reverse L-shaped dbh distributions (live stems). Stand structure of beech forest most dominant with L-shaped dbh distributions [29, 33]. The species in group B had bell-shaped dbh distributions (live stems). Group A species dominated the canopy layer and very most stems in the middle layer understorey layer too. Despite their low density in the understorey, however, their longevity may allow for continued coexistence of these two species groups in the canopy layer. In RuscoFagetum association, Diospyrus is usually more abundant in understorey [3] and in mixed beech forest studied Diospyrus trees occurred in understorey canopy layer (68.3%). Group A’s dominance of the understorey may be due to shade tolerance, a characteristic of Fagus species.

4.3 Spatial Distribution Pattern and Spatial Association Individuals of many tree species in various forest communities tend to be patchily distributed [10, 42, 32, 26]. We found a similar situation in our study site; stems of four species in each layer had clumped distributions and the size of the clumps differed among species and canopy layers. A. subcordata and A. velutinum had complete spatial randomness pattern in out site that reflected pioneer species. In our study, spatial associations varied among intra- and inter-specific cohorts in stand structure. Some of species such as A. subcordata were negatively associated with other species in small quadrate size but were positively associated with other

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species in their big quadrate size. F. orientalis stems were negatively associated with all other species. D. lotus stems was occupied in layer II and III and had strong negatively associated with P.perica that occupied same layer. Acknowledgements We thank numerous institutions and persons for their contribution of the study: Educational Shastkolate forest, Gorgan University. Shaban Shataii, Habib Zare, Gholamreza Daneshvar, Alireza Aliarab, Mohamad Hadi Moayeri and Mr Mirzaii.

References 1. Akashi N (1996) The spatial pattern and canopy-understory association of trees in a cool temperate, mixed forest in western Japan. Ecol Res 11:311–319 2. Allen TFH, Starr TB (1982) Hierarchy: perspectives for ecological diversity. University of Chicago Press, Chicago, IL 3. Asadollahi F (2001) Study of Hyrcanian plant association in north Iranian forest. 1st national conference of north forest management and sustainable development, Ramsar, Iran 4. Barnes BV (1998) Forest ecology. Wiley, New York. 773 pp 5. Busing R (1991) A spatial model of forest dynamics. Vegetatio 92:167–179 6. Busing RT, White PS (1993) Effects of area on old-growth forest attributes: importance for the equilibrium landscape concept. Landscape Ecol 8:119–126 7. Caldwell MM, Pearcy RW (1994) Causes of soil nutrient heterogeneity at different scales. In Caldwell MM, Pearcy RW (eds) Exploitation of environmental heterogeneity by plants. Academic Press, Boston, MA, pp 255–282 8. Collins SL, Klahr SC (1991) Tree dispersion in oak-dominated forests along an environmental gradient. Oecologia 86(4):471–477 9. Clark PJ, Evans FC (1954) Distance to nearest neighbor as a measure of spatial relationships in populations. Ecology 35:445–453 10. Denslow JS (1980) Gap partitioning among tropical rainforest trees. Biotropica 12:47–55 11. Ehrenfeld JG, Han X, Parsons WFJ, Zhu W (1997) On the nature of environmental gradients: temporal and spatial variability of soils and vegetation in the New Jersey Pinelands. J Ecol 85:785–798 12. Franklin J, Michaelsen J, Strahler AH (1985) Spatial analysis of density dependent pattern in coniferous forest stands. Vegetation 64:29–36 13. Gross KL, Pregitzer KS, Burton AJ (1995) Spatial variation in nitrogen availability in three successional plant communities. J Ecol 83:357–367 14. Habashi H, Hosseini SM, Mohajer M (2004) The importance of necromass in virgin oriental beech forests (Mazandaran, Iran). 7th IUFRO international beech symposium, Tehran, Iran 15. Habashi H, Mahmoudi J (2005) The ecological importance of dead trees in virgin oriental beech forests (Mazandaran, Iran). 10th European ecological congress, Turkey 16. Halvorson JJ, Bolton H Jr, Smith JL, Rossi RE (1994) Geostatistical analysis of resource islands under Artemisia tridentata in the shrub-steppe. Great Basin Nat 54:313–328 17. Hoshino D, Nishimura N, Yamamoto S. (2001) Age, size structure and spatial patterns of major tree species in an old growth Chamaecyparis obusa forest, central Japan. For Ecol Manage 152:31–43 18. Jackson RB, Caldwell MM (1993) Geostatistical patterns of soil heterogeneity around individual plants. J Ecol 81:683–692 19. Kashian DM, Barnes BV, Walker WS (2003) Ecological species groups of landform level ecosystems dominated by jack pine in northern lower Michigan, USA. Plant Ecol 166:75–91 20. Kenkel NC (1988) Pattern of self-thinning in jack pine: testing the random mortality hypothesis. Ecology 69(4):1017–1024 21. Kenel NC, Hoskins JA, Hoskins WD (1989) Local competition in naturally established jack pine stand. Can J Bot 67:2630–2635

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22. Leibundgut H (1993) Europäische Urwälder. Haupt Bern, Stuttgart 23. Levin SA (1992) The problem of pattern and scale in ecology: the Robert H. MacArthur award lecture. Ecology 73:1943–1967 24. Maguire D, Batista JLF, McKenzie D (1993) Horizontal structure of uneven-aged mixed species forests modeled as an inhomogeneous poisson process. In: Reynolds K (ed) Proceedings IUFRO S4.11 Conference on stochastic spatial models in forestry, University of Greenwich, Thessaloniki, Greece, pp 163–170 25. Manabe T, Yamamoto S (1997) Spatial distribution of Eurya japonica in an old-growth evergreen broad-leaved forest, SW Japan. J Veg Sci 8:761–772 26. Manabe T, Nishimura N, Miura M, Yamamoto S (2000) Population structure and spatial patterns for trees in a temperate old-growth evergreen broad-leaved forest in Japan. Plant Ecol 151:181–197 27. Miller RE, Ver Hoef JM, Fowler NL (1995) Spatial heterogeneity in eight central Texas grasslands. J Ecol 83:919–928 28. Mitchell A, Arnott J (1995) Effects of shade on the morphology and physiology of amabilis fir and western hemlock seedlings. New Forests 10(1):79–98 29. Mohajer MM (2005) Silviculture. Tehran University Press, Tehran, p 387 30. Morisita M (1959a) Measuring of the dispersion of individuals and analysis of the distributional patterns. Mem Fac Sci Kyushu Univ Ser E 2:215–235 31. Morisita M (1959b) Measuring of interspecific association and similarity between communities. Mem Fac Sci Kyushu Univ Ser E 3:65–80 32. Nakashizuka T (1999) Structure, dynamics and disturbance regime of temperate broad-leaved forests in Japan. J Veg Sci 10:805–814 33. Oheimb G, Westphal C, Tempel H, Härdtle W (2005) Structural pattern of a near-natural beech forest (Fagus sylvatica) (Serrahn, North-east Germany). For Ecol Manage 212:253–263 34. Pickett STA, Cadenasso ML (1995) Landscape ecology: spatial heterogeneity in ecological systems. Science 269:331–334 35. Rademacher C, Neuert C, Grundmann V, Wissel C, Grimm V (2004) Reconstructing spatiotemporal dynamics of Central European natural beech forests: the rule-based forest model before. For Ecol Manage 194:349–368 36. Robinson, D., Van Vuuren MMI (1998) Responses of wild plants to nutrient patches in relation to growth rate and life-form. In: Lambers H, Poorter H (eds) Inherent variation in plant growth. Physiological mechanisms and ecological consequences. Backhuys Publishers, Leiden, The Netherlands, pp 237–257 37. Robertson GP, Crum JR, Ellis BG (1993) The spatial variability of soil resources following long-term disturbance. Oecologia 96:451–456 38. Saniga M, Schütz J-P (2001) Dynamics of changes in dead wood share in selected beech virgin forests in Slovakia within their development cycle. J For Sci 47:557–565 39. Sinclair DF (1985) On tests of spatial randomness using mean nearest neighbour distance. Ecology 66:1084–1085 40. Skarpe C (1991) Spatial patterns and dynamics of woody vegetation in an arid savanna. J Veg Sci 2:565–572 41. Szwagrzyk J, Czerwczak M (1993) Spatial pattern of trees in natural forests of East-Central Europe. J Veg Sci 4:469–476 42. Taylor AH, Qin Z (1988) Regeneration patterns in old-growth Abies–Betula forests in the Wolong natural reserve, Sichuam, China. J Ecol 76:1204–1218 43. Trangmar BB, Yost RS, Wade MK, Uehara G, Sudjadi M (1987) Spatial variation of soil properties and rice yield on recently cleared land. Soil Sci Soc Am J, 51:668–674 44. Urban DL, O’Neill RV, Shugart HH (1987) Landscape ecology. BioScience 37:119–127 45. Webster R, Oliver MA (1992) Sample adequately to estimate variograms of soil properties. J Soil Sci 43:177–192 46. Welden C, Slauson W, Ward R (1990) Spatial pattern and interference in PinÄon-Juniper woodlands of northwest Colorado. Great Basin Nat 50(4):313–319 47. West PW (1984) Inter-tree competition and small-scale pattern in monoculture of Eucalyptus obilqua L’Herit. Austr J Ecol 9:405–411

Nutrient-Food Chain Modeling for Lake Prespa Spiro Grazhdani and Spase Shumka

Abstract This research presents an approach to modeling nutrient/food-chain interactions in a stratified lake, which gives a general picture of the eutrophication level for lake Prespa and shows general trends of the trophic state of this aquatic ecosystem. Man – made eutrophication, in absence of control measures, provides much faster than the natural phenomenon and is the major reason for pollution of lake Prespa. The model presented provides informations on temporal resolution of eutrophication effects that is extremely useful to water quality managers. This study also provides a means to identify nutrient and light limitation, which is a critical step in controlling eutrophication. The specific nature of the lake has been taken account and embodied in the model. The adequacy of the simulation is assessed by experimental measurements in the lake. The results taken are encouraging. Keywords Nutrient/food-chain · Eutrophication · Algae · Phytoplankton · Zooplankton · Non-living organic carbon

1 Introduction Water quality modeling has evolved a great deal since its innovation in the early years of the twentieth century. In the 1970s the principal water quality problem addressed was eutrophication. As a consequence, modelers broadened their own scope to include more mechanistic representations of biological processes. Capitalizing on oceanographic research environmental engineers developed elaborate nutrient/food-chain models [2–6, 8, 9]. The major modeling advance in this period has been to recognize the prominent role of solid matter in the transport and fate of toxicants. In particular, the association of toxicants with settling and

S. Grazhdani (B) Agricultural University of Tirana, Tirana, Albania e-mail: [email protected]

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resuspending particles represents a major mechanism controlling their transport and fate in natural waters. Further, small organic particles such as phytoplankton and detritus, can be ingested and passed along to higher organisms. Such food-chain interactions have led the modelers to view nature’s organic carbon cycle as more than an end in itself. Rather, the food chain is viewed as a conveyer and concentrator of contaminants [6]. This research focuses on a seasonal nutrient/food- chain model for a stratified lake. A limiting nutrient is integrated into algal – zooplankton scheme to complete the picture of nutrient/food chain interactions. Following a simple kinetic scheme the resulting equations are written. The equations form a completely closed system where nutrients are turned into biomass by net production and recycled by respiration/excretion and death. We are focused in this research on a specific group of microorganisms, algae. We refined the plant growth framework by developing a more complete model of an important group of algae, the free-floating microorganism called phytoplankton. Chlorophyll a is considered to be directly proportional to the concentration of phytoplanktonic algal biomass. Below are given the factors that contribute to algal growth. The growth rate of algae is not a simple constant, but varies in response to environmental factors, such as temperature, nutrients and light. At low levels and in some instances at high levels, these factors can limit growth. A variety of formulations have been developed to represent the effect of temperature on plant growth [10]. A more commonly used form is theta model. There are several ways in which the nutrient limitation term can be refined. The most important relates to how nutrients are handled. For such cases, separate limitation terms would be developed for each nutrient. At the other extreme is the case where the nutrient in shortest supply controls growth. This type of approach, which is similar in spirit to Liebig’s law of the minimum [6], is the most commonly accepted formulation. The effect of light on phytoplankton growth is complicated by the fact that several factors have to be integrated to come up with the total effect. These factors are diurnal surface light variation, light attenuation with depth and dependence of the growth rate on light. In the previous paragraphs are outlined some external physical and chemical factors, such as temperature, light and nutrients, that limit phytoplankton growth in natural waters. There are a number of processes contribute to the loss of phytoplankton. Some of these are transport related such as settling and diffusion/dispersion. Others are kinetic such as respiration, excretion and death by predation. In water quality modeling, two losses are emphasized: non-predatory and predatory losses. The non-predatory losses consist primarily of respiration and excretion. Respiration reefers to the opposite process to photosynthesis where the plant utilizes oxygen and release carbon dioxide. Excretion is a process focused on the release of nutrients. However, algae can also release organic carbon as extracellular byproducts. It should be noted that although they are often treated as a single

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process, the division between respiration and excretion should not be considered a trivial distinction. This is particularly true as nutrient/food-chain models evolve toward more accurate representation of the organic carbon cycle. In such cases, processes that tend to generate carbon dioxide and liberate available nutrients (respiration) should be separated from processes that liberate organic forms of carbon and nutrients (excretion). Predatory losses include the factors that limit algal populations by causing their death due to grazing by zooplankton that employ the algae as a food source. To provide background for this phytoplankton – zooplankton interactions, general mathematical models have been developed to simulate predator-prey interactions. Summaries of the data for all aforementioned parameters can be found in Chapra [6] and Bowie et al. [1]. This research has been designed to illustrate how predator-prey kinetics works, and to show how they can be integrated into a more comprehensive nutrient/foodchain computation. It relates to the ecological state of Lake Prespa.

2 Materials and Methods The present framework handles physical segmentation (two vertical layers), loadings and transport in the same way as the two-component model described in [6]. Mass balance for a substance in the epilimnion and the hypolimnion (Fig. 1), can be written as: V1

dc1 = W(t) − Qc1 + vt At (c2 − c1 ) + S1 dt dc2 = vt At (c1 − c2 ) + S2 V2 dt

(1) (2)

where V = volume, c = concentration, t = time, W(t) = loading, Q = outflow, vt = thermocline transfer coefficient, At = thermocline area, and S = sources and sinks.

Fig. 1 Physical segmentation scheme and transport representation

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As depicted in Fig. 2, the model consists of eight state variables. These can be divided into three major groups (Table 1). Mass balance equations are written for each of the state variables for each of the layers. The source and sink terms for each state variables are described below.

Fig. 2 Kinetic segmentation

Table 1 Model state variables State Variable

Symbol

Units

Food-chain 1. Algae 2. Herbivorous zooplankton 3. Carnivorous zooplankton

a zh zc

mgCha m−3 gC m−3 gC m−3

Non-living organic carbon 1. Particulate 2. Dissolved

cp cd

gC m−3 gC m−3

Nutrients 1. Ammonium nitrogen 2. Nitrate nitrogen 3. Soluble reactive phosphorus

na ni ps

mgN m−3 mgN m−3 mgP m−3

2.1 Food Chain The food chain consists of a single plant group along with two zooplankton groups.

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2.1.1 Algae The algae growth is a function of temperature, nutrients and solar radiation. For the hypolimnion, algae are also gained by settling from the surface layer. Sinks include respiration/excretion, grazing and settling losses. The differential equation that governs the growth and production of algae (chlorophyll a) is formulated as following: V

da = kg (T, nt , ps, I)Va − kra (T)Va − Cgh (T, a, zh )Va + νa At au − νa At a dt

(3)

where kg (T, nt , ps , I) = the algal growth rate [d−1 ], kra (T) = losses due to respiration and excretion [d−1 ], Cgh (T, a, zh ) = grazing losses [d−1 ], νa = phytoplankton settling velocity [m d−1 ], and the subscript “u” designates an upper layer. The growth and the grazing rates are dependent on environmental factors as in [8]: kg (T, nt , ps , I) = kg,

20

1.066

T−20 2.718

ke H

−α e 1 − e−α0 min

p nt , ksn + nt ksp + p (4)

and Cgh (T, a, zh ) =

a Cgh θ T−20 zh kSa + a

(5)

where nt = total inorganic nitrogen = na + ni , and other parameters are defined in [6]. In addition, the respiration rate is corrected for temperature with the theta model: kra (T) = kra, 20θ T−20

(6)

All other temperature-dependencies are corrected in this fashion. 2.1.2 Herbivorous Zooplankton Part of the consumed algae is converted into herbivorous zooplankton. The herbivores are depleted by carnivore grazing and respiration/excretion losses: V

dzh = aca εh Cgh (T, a, zh ) Va − Cgc (T, zc ) Vzh − krh (T) Vzh dt

(7)

where aca = the stoichiometric coefficient for the conversion of algal chlorophyll a to zooplankton carbon [mgChla/gC]. 2.1.3 Carnivorous Zooplankton Part of the consumed herbivorous zooplankton is converted into carnivorous zooplankton. The carnivores are depleted by respiration/excretion losses and the

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first-order death due to grazing by organisms higher on the food chain (primarily fish): V

dzc = εc Cgc (T, zc )Vzh − krc (T) Vzc − kdc (T) Vzc dt

(8)

2.2 Non-living Organic Carbon The non-living organic carbon is divided into particulate and organic fractions in order to distinguish between settleable and non-settleable forms.

2.2.1 Particulate Inefficient grazing (egestion) along with carnivore death results in gains to the particulate non-living organic carbon (POC) pool. For the hypolimnion, POC is also gained by settling from the surface layer. Sinks include a first-order dissolution reaction and settling losses: V

dcp = rca (1 − εh ) Cgh (T, a, zh ) Va + (1 − εc ) Cgc (T, zc ) Vzh dt + kdc (T) Vzc − kp (T)Vcp + νp At cpu − νp At cp

(9)

2.2.2 Dissolved DOC is gained via the first-order dissolution reaction and lost by hydrolysis: V

dcd = kp (T) Vcp − kh (T) Vcd dt

(10)

2.3 Nutrients The nutrients are divided into inorganic nitrogen and phosphorus. The former is split into ammonium and nitrate nitrogen. 2.3.1 Ammonium Nitrogen Ammonium ion is gained due to hydrolysis of dissolved organic carbon and from food-chain respiration. It is lost via uptake and nitrification: V

dna = rnc kh (T) Vcd + rna kra (T) Va + rnc krh (T) Vzh + rnc krc (T) Vzc dt − Fa rna kg (T, nt , ps , I) Va − kn (T) Vna

(11)

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where Fa = the fraction of the inorganic nitrogen that is taken from the ammonium pool by plant uptake: Fa =

na ka + n a

(12)

where k = a half-saturation constant for ammonium preference.

2.3.2 Nitrate Nitrogen Nitrate is gained due to nitrification and it is lost via plant uptake: V

dni = kn (T) Vna − (1 − Fa ) rna kg (T, nt , ps , I) Va dt

(13)

2.3.3 Soluble Reactive Phosphorus (SRP) SRP is gained due to hydrolysis of dissolved organic carbon and from food-chain respiration. It is lost via plant uptake: V

dpS = rpc kh (T) Vcd + rpa kra (T) Va + rpc krh (T) Vzh + rpc krc (T) Vzc dt − rpa kg (T, nt , ps , I) Va

(14)

By employing the kinetic interaction from Eqs. 3 through 14, Eqs. 1 and 2 can be written for each of the eight state variables. The resulting sixteen ordinary differential equations can be integrated simultaneously using a numerical method such as the fourth-order Runge-Kutta method [7].

3 Results and Discussions Physical parameters for Lake Prespa during the 2001 are summarized in Table 2. Note that the hypolimnetic temperatures are simulated with a heat balance model. Loads and initial conditions are summarized in Table 3, and model parameters are listed in Table 4. The model equations were solved numerically for year 2001. The results are summarized in Fig. 3. Figure 3a shows results for the food chain in the epilimnion. Note that zooplankton is expressed in chlorophyll units to allow comparison among the variables. The results indicate that predator – prey interactions are taking place with peak of the algae, herbivores, and carnivores occurring at approximately days 160, 180, and 240, respectively.

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Symbol

Surface area Thermocline area Epilimnion volume Hypolimmnion volume Thermocline thickness Epilimnion thickness Hypolimnion thickness Outflow Thermocline difussion: Summer stratified Winter mixed Start of summer stratification Time to establish stratification Onset of end of stratification End of stratification

As At Ve Vh Ht He Hh Q νt

Value

Units m2 m2 m3 m3 m m m rn3 yr−1 cm2 s−1

0.13 13 100 58 315 20

d d d d

Table 3 Boundary (loading) and initial conditions for Lake Prespa Variable

Units

Loadinga

Initial conditionsb

Algae Herbivorous zooplankton Carnivorous zooplankton Particulate organic carbon Dissolved organic carbon Ammonium Nitrate Solube reactive phosphorus

μgchla L−1 mgC L−1 mgC L−1 mgC L−1 mgC L−1 μgN L−1 μgN L−1 μgP L−1

1 0 0 0.8 0.8 15 220 14.3

1 0.005 0.005 0.12 0.12 15 250 12

a Multiply b Same

by outflow to convert to mass loading rate for epilimnion and hypolimnion

Table 4 Model parameter values used for Lake Prespa Parameter

Symbol

Value

Units

Algae Growth rate Temperature factor Respiration rate Temperature factor Settling velocity Optimal light P half-saturation

kg,20 θa kra θ ra νa Is ksp

2 1.066 0.025 1.08 0.2 350 2

d−1 d−1 m d−1 Ly d−1 μgP d−1

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Table 4 (continued) Parameter

Symbol

Value

Units

N half-saturation Background light extinction

ksn ke

15 0.2

μgN d−1 m−1

Herbivorous zooplankton Grazing rate Temperature factor Grazing efficiency Respiration rate Temperature factor Algae half-saturation

Cgh θ gh εh krh θ rh ksa

5 1.08 0.7 0.1 1.08 10

L mgC−1 d−1

Carnivorous zooplankton Grazing rate Temperature factor Grazing efficiency Respiration rate Temperature factor Death rate Temperature factor Herbivore – half-saturation

Cgh θ gh εc krc θ rc kdc θ dc ksh

5 1.08 0.7 0.04 1.08 0.04 1.08 0.4

L mgC−1 d−1

Non – living carbon Particulate settling Dissolution rate Temperature factor Hydrolysis rate Temperature factor

νp kp θp kh θh

0.2 0.1 1.08 0.075 1.08

m d−1 d−1

Nutrients Nitrification rate Temperature factor Ammonia preference half − saturation

kn θn ksam

0.1 1.08 50

d−1 μgcha L−1

d−1 d−1 mgC L−1

d−1

d−1 μgN L−1

Results for epilimnetic inorganic nitrogen and phosphorus are illustrated in Fig. 3b. According to the calculation, the lake is overwhelmingly phosphorus limited during the summer stratified period. The fact that there is excess nitrogen and phosphorus in the water indicates that lake’s production is light limited during the remained of the year. The organic carbon cycle for the epilimnion is shown in Fig. 3c. This plot indicates a clear difference between the productive summer months and the rest of the year. High organic carbon generation during the stratified period has several implications. First, it eventual decomposition can have an impact on oxygen content of bottom waters. This would be particularly important for water bodies with smaller hypolimnion (and, hence smaller oxygen reserves) than for lake Prespa. Second, the transport and fate of toxic substances can be strongly associated with organic matter.

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Fig. 3 Simulation results for the epilimnion of Lake Prespa as computed with a nutrient/foodchain model. (a) Food chain with all components expressed as chlorophyll, (b) inorganic nutrients, and (c) organic carbon

4 Conclusions The model provides predictions of features like peak chlorophyll levels and, hence, produces information that is extremely useful to water-quality managers. This is because the public is often most concerned with extreme events in water body, rather than in seasonal or long-term average conditions. Because of its daily time step, the nutrient/food chain model is capable of generating both types of information. Identifying the limiting nutrient or whether the system has significant light limitation is a critical step in controlling eutrophication. By mechanistically including

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several nutrients and light, the nutrient/food-chain model provides a means to make such identifications. By providing predictions of organic carbon levels, nutrient/food-chain framework provides a means to assess both oxygen and toxic substances in lakes.

References 1. Bowie GL, Mills WB, Porcella DB, Campbell CL, Pagenkopf JR, Rupp GL, Jonson KM, Chan PWH, Gherini SA, Chamberlin CE (1985) Rates, constants, and kinetic formulations in surface water quality modeling. US Environmental Protection Agency, ORD, Athens, GA, ERL, EPA/600/3-85/040 2. Canale RP, Owens EM, Auer MT, Effler SW (1995) The validation of a water quality model for the Seneca river, New York. J Water Resour Plan Manage 121(3):241–250 3. Canale RP, de Palma LM, Vogel AH (1976) A plankton- based food web model for lake Michigan. In: Canale RP (ed) Modeling biochemical processes in aquatic ecosystems. Ann Arbor Science, Ann Arbor, MI, p 33 4. Cerco CF, Cole T (1993) Three dimensional eutrophication model of chesapeake bay. J Environ Eng ASCE 119(6):1006–1025 5. Chan CW, Orlob GT (1975) Ecological simulation for aquatic environment. In Patton BC (ed) Analysis and simulation in ecology, vol III. Academic, New York, p 474 6. Chapra SG (1996) Surface water quality modeling. McGraw-Hill, New York 7. Chapra SG, Canale RP (1888) Numerical methods for engineers, 2nd ed. McGraw – Hill, New York 8. Di Toro DM, Fitzpatrick JJ (1993) Chesapeake bay sediment flux model. US Army Crops of Engineers, Waterways Experiment Station, Tech. Report EL-93-2 9. Mitreski K, Koneski Z, Davcev D, Naumoski T, Mitic V, Sumka S, Guseka D (1998) An ecological model of lake Ohrid. Proceedings of the IASTED international conference: Applied Modeling and Simulation, Honolulu, Hawaii, USA, 12–14 Aug 1998, pp 32–35 10. Thorton KW, Lessen AS (1978) A temperature algorithm for modifying rates. Trans Am Fish Soc 107(2):284–287

Tolerance of Different Wild Oats Biotypes to Different Oat Killers and Their Impact on Wheat Imtiaz Khan, Gul Hassan, Muhammad Ishfaq Khan, and Meher Gul

Abstract The ecological starting point for crop health requires knowledge of what is in the soil (microbes, insects, weed seeds, etc.), methods to prevent herbicides resistance build up in the crop, and knowledge to maximize the plants ability to defend itself. The focus of most current crop production practices is weed control with little effort applied by herbicides. Cropping practices that degrade soil and limit genetic diversity contribute to increasing weed populations. A field experiment was initiated at Malkandher Research Farm, NWFP (North West Frontier Province) Agricultural University, Peshawar during Rabi 2005–2006 to figure out the tolerance of different wild oats (noxious weed) biotypes to herbicides. The experiment was laid out in randomized complete block design under a split-plot arrangement, with three replications. The experiment comprised of four wild oats biotypes assigned to the main plots, while 3 herbicides along with a weedy check (Sencor, Isoproturon, Affinity and Weedy check treatment) were kept in sub-plots. The Ghaznavi-98 variety of wheat in a sub-plot size of 5 × 1m2 was planted on November 13, 2005. The data were recorded on tillers plant−1 , wheat spikes m−2 , number of grains spike−1 , 1,000 grain weight (g), biological yield (t ha−1 ), grain yield (t ha−1 ) and the protein content (%) in grain. The statistical analyses of data exhibited non-significant differences for tolerance of biotypes to herbicides in all the morphological and agronomic traits, while herbicides and their interaction with biotypes were significant for all the traits examined except wheat plant height. As a consequence of phytotoxic effect on weeds, the herbicides increased grain yield and yield components. The herbicide Affinity out yielded rest of the herbicides. In general, the highest grain yield was harvested in Affinity treated plots across all the wild oats biotypes. The interaction of biotypes with the herbicides exhibited a differential competitive ability or tolerance to different herbicides. It is thus recommended that judicious thinking is desired to control different biotypes infesting farmers’ fields because wild oat (Avena fatua L.) is one of the most troublesome weeds in the weed community. The I. Khan (B) Department of Weed Science, Faculty of Crop Protection, NWFP Agricultural University, Peshawar 25130, Pakistan e-mail: [email protected]

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Pakistani prairies are a semiarid region prone to soil erosion, and appears to be an appropriate site to adopt conservation tillage practices. Due to the environmental concerns and the development of herbicide resistance, it would be desirable to integrate all aspects of crop management systems, rather than solely rely on herbicides, to manage wild oat problems. Keywords Wild oat · Biotypes · Herbicides

1 Introduction Production losses due to weed in wheat may occur from initial stages to the last stage of maturity, harvest, Threshing, winnowing and storing of wheat grains. Weeds of wheat such as, wild oats and Phalaris minor mimic wheat morphologically, hence weeds could be segregated from the crop, consequently could not be removed manually during the early growth stages. Weed plants are more resistant, hardy and making faster growth than wheat. Because, until the wheat plants establish, weeds bind over the plants and wheat fails to capture the space and weed deprive it from nutrients, solar radiation, space and moisture. Some weed species, nourish insects pests and diseases and provide shelter to them. Wild oat causes yield reductions directly by competing with the crop for moisture, light, and nutrients. Such losses occur early in the growing season. Most of the yield loss occurs before the crop is 45 to 50 days old. In addition to yield losses, wild oat may cause dockage at the elevator, increased tillage, reduced yields from delayed seeding, and increased expenditures for herbicides. Compared to herbicides used to control broadleaf weeds in small grains, effective wild oat control herbicides are expensive. Wild oat infests 28 million acres of land in the United States only. Wild oat is extremely competitive and difficult to control because i.e. it has delayed germination. It shatters its seed before most crops are harvested. Its growth habit is similar to that of wheat, barley, and domesticated oats (Paterson, 1976). Wild oat plants rarely produce more than 200 seed, but viable seed are produced rapidly, generally within 7 to 10 days after heading. The twisted, bent awn that rises from the back of each seed is straightened and rewound repeatedly by moist conditions and often serves as a mechanism for covering freshly shattered seed [7].

2 Experimental An experiment was conducted at Malkandher Research Farm, N.W.F.P Agricultural University, Peshawar during the Rabi season 2004–2005. The experiment was laid out in Randomized complete block (RCB) design with a split plot arrangement having four replications. In each replication, there were four main plots (wild oats biotypes). Each main plot consisted of four sub-plots. The number of rows in each

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sub-plot were five 5 m long spaced at 25 cm. Four wild oats biotypes collected from across the NWFP were assigned to main plots and herbicides were kept in the subplots. The sub plot size was kept at 5 × 1 m2 . The seed of Ghaznavi-98 wheat variety was seeded at the rate of 120 kg ha−1 on 13th November, 2005 at Malkandher farm with the rabi drill. The wild oats biotypes were sown right after wheat sowing. All the recommended cultural practices were carried out uniformly in all the treatments during the experiment. The detail of the experimental materials are as under: Wild oats biotypes (main plots) i. ii. iii. iv.

Peshawar D.I. Khan (White) Mardan Malakand

Herbicides (Rate kg ha−1 (sub-plots)) v. vi. vii. viii.

Isoproturon 1.25 kg i.e. ha−1 Sencor 1.25 kg i.e. ha−1 Affinity 1.75 kg ha−1 Weedy check.

3 Results and Discussion 3.1 Wheat Tillers Plant−1 Data regarding wheat tiller plant−1 are presented in Fig. 1. Analysis of the data showed that wild oat biotypes had no effect while herbicide and their interaction had significant effect on wheat tiller plant−1 . Among the herbicides means maximum (8.77) wheat tiller plant−1 was recorded in Affinity treated plots, while minimum (5.37) wheat tiller plant−1 was recorded in Weedy check treatment. For interaction of wild oats biotypes with the herbicides, the maximum (9.07) wheat tiller plant−1 was recorded in D.I. Khan (W) × Affinity. While minimum wheat tiller plant−1 (5.00) was recorded in Mardan X Weedy check (Fig. 1). The logic behind significant interaction could be the various control techniques that affected wild oat biotypes and their growth was checked thereby diverting nutrients. Solar radiation and moisture channel towards the development of wheat (clum), fully utilizing space and converting assimilates into various food components for vigorous growth of wheat. Similar results are also reported by Akhtar et al. [1], who reported that application of herbicides increased fertile tiller density.

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Number of grains spike−1

80 a

70 ab b b

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Fig. 1 Wheat tiller plant−1 as affected by different wild oats biotypes and herbicides

3.2 Number of Grains Spike−1 Number of grains spike−1 is another important component of yield. Change in number of grains spike−1 drastically influence the final yield. The analysis of the data showed that biotypes of wild oat, herbicides and their interaction were evaluated as significant. The data in Fig. 2 exhibits that among the wild oats biotypes, maximum (43.20) number of grains spike−1 was recorded in Malakand biotype while minimum (40.00) number of grains spike−1 was recorded in D.I. Khan (W) wild oat treated plots. Among the herbicides means maximum (56.15) number of grains spike−1 was recorded in Affinity treated plots, while minimum (27.18) number of grains spike−1 was recorded in weedy check treatment. For interaction of wild oats biotypes with the herbicides, the maximum (61.33) number of grains spike−1 was

Number of grains spike–1

80 a

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60 50

d d

cd

cd

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Peshawar

c cd cd

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20 10 0

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Fig. 2 Number of grains spike−1 as affected by different wild oats biotypes and herbicides

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recorded in Malakand × Affinity. The minimum number of grains spike−1 (25.13) was recorded in D.I. Khan (W) × Weedy check. The results are corroborated with results of Khan et al. [3, 4, 5], who concluded that herbicidal applications produce more grains spike−1 than untreated control.

3.3 1000 Grains Weight (g) Thousand grain weights is an important yield parameter. It is evident from the data (Fig. 3) that the 1,000-grain weight (g) was non-significantly affected by wild oats biotype, while herbicides and their interaction had a significant effect. The mean data manifest that among the wild oats biotypes, maximum (28.17 g) 1,000-grain weight was recorded in D.I. Khan white biotype while minimum (25.25 g) 1,000grain weight was recorded in Mardan wild oat treated plots. Among the herbicides means maximum (32.24 g) 1,000-grain weight was recorded in Affinity treated plots, while minimum (21.15 g) grain size was recorded in Weedy check treatment. For interaction of wild oats biotypes with the herbicides, the maximum (33.17 g) 1,000-grain weight was recorded in D.I. Khan (W) × Affinity. The minimum 1,000grain weight (21.15 g) was recorded in Malakand × Weedy check. Sohail [9] reported similar results, who concluded that herbicides significantly increased the 1,000 grains weight in wheat.

1000 grains weight (g)

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Isoproturon

Affinity

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Fig. 3 1,000 grains weight (g) as affected by different wild oats biotypes and herbicides

3.4 Biological Yield (t ha−1 ) The total dry matter produced by a plant as the result of photosynthesis and nutrients uptake, minus that lost by respiration is called biological yield [8]. Statistical analysis of the data revealed that wild oat biotypes had non-significant while herbicides and their interaction with wild oat biotypes had significant effect

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on biological yield (t ha−1 ). The data show that among the wild oats biotypes, maximum (8.033) biological yield (t ha−1 ) was recorded in Malakand biotype while minimum (7.567) biological yield (t ha−1 ) was recorded in Peshawar wild oat treated plots. Among the herbicides means maximum (9.867) biological yield (t ha−1 ) was recorded in Affinity treated plots, while minimum (4.167) biological yield (t ha−1 ) was recorded in Weedy check treatment. For interaction of wild oats biotypes with the herbicides, the maximum (10.27) biological yield (t ha−1 ) was recorded in Peshawar × Affinity. While minimum wheat biological yield (3.467 t ha−1 ) was recorded in Peshawar X Weedy check

3.5 Grain Yield (t ha−1 ) The grain yield is the most important attribute for obtaining higher production from wheat crop. The components that determine grain yield include the number of plants, number of heads per plant, number of seeds per head, and weight per seed. A decrease in any of these factors can decrease wheat yield. Statistical analysis of the data showed that wild oats biotypes had a non-significant, while herbicides and their interaction with wild oats biotypes had significant differences on grain yield. The data in (Figs. 4 and 5) show that among the wild oats biotypes, maximum (1.961) grain yield (t ha−1 ) was recorded in Malakand biotype while minimum (1.604) grain yield (t ha−1 ) was recorded in Peshawar wild oat treated plots. Among the herbicides means maximum (2.600) grain yield (t ha−1 ) was recorded in Affinity treated plots, while minimum (1.043) grain yield (t ha−1 ) was recorded in Weedy check treatment. For interaction of wild oats biotypes with the herbicides, the maximum (2.867) grain yield (t ha−1 ) was recorded in D.I. Khan (W) × Affinity. While minimum wheat grains yield (0.908 t ha−1 ) was recorded in Peshawar X Weedy check. The significant increase in grain yield might be attributed to the effective weed control in affinity treatments and consequently wheat crop efficiently utilized all the

Biological yield (t ha–1)

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4 2 0 Sencor

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Affinity

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Fig. 4 Biological yield (t ha−1 ) as affected by different wild oats biotypes and herbicides

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Fig. 5 Grain yield (t ha−1 ) as affected by different wild oats biotypes and herbicides

available resources. These results are in line with Awan et al. [2] and Tunio et al. [10] who reported more grain yield in plots applied with herbicides.

3.6 Wheat Grain Protein Content (%)

Wheat grain Protein content (%)

Proteins are some of the most important basic nutrients and are essential for growth and development. The data regarding the grain protein content in Fig. 6 show that there were significant differences in the herbicides, wild oat biotypes and their interaction. Evidently, protein content increased by herbicides tested for different wild oat biotypes as compared to weedy check. Among the wild oat biotypes, maximum grain protein content (12.02%) was recorded by Mardan biotypes. The minimum grain protein content (11.05%) was recorded in the Malakand biotype. 16 14 cd

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Fig. 6 Wheat grain Protein content (%) as affected by different wild oats biotypes and herbicides

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Among the herbicides, maximum (12.73%) grain protein content was recorded in Affinity treated plot while minimum (10.65%) grain protein content was observed in weedy check. Taking into consideration the interaction of herbicides and wild oat biotypes maximum (13.10%) grain protein content was observed in Mardan × Affinity interaction. Minimum (10.17%) was recorded in Malakand × Weedy check.

4 Conclusion Herbicide affinity show best results control both grassy and broadleaf weeds. It increased grain yield and protein content (%). So it is thus recommended that judicious thinking is desired to control different biotypes infesting farmers’ fields. Acknowledgement Acknowledgement goes to HEC (Higher Education Commission) of Pakistan for their kind and financial cooperation through out my research.

References 1. Akhtar M, Hamyn Q, Gill MB, Nazair MS (1991) Comparative study of various crop management practices on weed growth and wheat yield. Sarhad J Agric 7(2):91–94 2. Awan IU, Iqbal M, Ahamad HK (1990) Screening of different herbicides for the control of weeds in wheat corp. Gomal Univ J Res 10(2):77–83 3. Khan I, Muhammad Z, Hassan G, Marwat KB (2001) Efficacy of different herbicides for controlling weeds in wheat crop-I. Response of agronomic and morphological traits in wheat variety Ghanznavi-98. Sci Khyber 14(1):51–57 4. Khan I, Hassan G, Marwat KB (2002). Efficacy of different herbicides for controlling weeds in wheat crop-II. Weed dynamics and herbicides. Pak J Weed Sci Res 8(1–2):41–47 5. Khan N, Hassan G, Marwat KB, Khan MA (2003) Efficacy of different herbicides for controlling weeds in wheat crop at different time of application-II. Asian J Plant Sci 2(3):310–313 6. Peterson JG (1976) The distribution of avena spp naturalized in western Australia. J Appl Ecol 13:257–264 7. Radford BJ, WilsonBJ, Cartledge O, Watkins FB (1980) Effect of wheat seeding rate on wild oat competition. Aust J Exp Agric Anim 120:77–81 8. Shah P, Nazir S, Bashir E, Bantel R, eds. (1994) Crop production. National Book Foundation, Islamabad, pp 238–245, pp 499 9. Sohail N (1993) Efficacy of weedicides to control weeds in wheat. M.Sc. thesis, Department of Agronomy, University of Agriculture. Faisalabad, Pakistan 10. Tunio SD, Kaka SN, Jarwar AD (2004) Effect of integrated weed management practices on wheat yield. Pak J Agric Eng Vet Sci 20(1):5–10

Effects of L-Proline and Cold Treatment on Pepper (Capsicum annuum L.) Anther Culture Dudu Özkum and R. Tipirdamaz

Abstract Comparison of cold-shock treatments (at 4◦ C for 48 and 96 h) of pepper buds with a control (not subjected to cold treatments) has no effect on the production of embryo from cultured pepper anthers. The effects of cold shock treatments were not changed when the L-proline was added to the induction medium (40, 125 and 500 mg L−1 ). Cold treated anthers showed a lower response or non response than control anthers. Regeneration frequency did not appear to be affected by the presence of L-proline in the induction medium. The highest numbers of embryos (12.5 embryos/100 anthers) were obtained from the control anthers that were cultured on induction medium, MS medium, containing 4 mg L−1 naphthalene acetic acid (NAA) and 1 mg L−1 benzyladenine (BA) and activated charcoal without L-proline. Keywords Anther culture · Pepper (Capsicum annuum L.) · Cold shock treatment · L-Proline

1 Introduction Anther culture has been used for producing haploid plants in a variety of higher plants but the low frquencies of haploid plants restrict the use of this technique in plant breeding [2, 8]. Altough many species have been successfully anther-cultured, others have not, even among those that do respond there is considerable variation in embryo yields within the species [8]). However, the yield has remained extremely low in many cases. It is possible that low embryo yields from particular plants may be a consequence of the environmental conditions improved during the anther culture period rather than absolute non-responsiveness [3]. The method can only

D. Özkum (B) Near East University, Faculty of Pharmacy, Nicosia, North Cyprus, Mersin 10, Turkey e-mail: [email protected]

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become useful for applied agricultural projects when the haploids are produced in large numbers. Some treatments can be applied before or during culture in order to increase the success in anther culture. It has been shown that the addition of activated charcoal [1, 25, 24, 16], inclusion of different concentration of L-proline in the culture medium [5, 4, 9, 19, 7] and cold pretreatment of whole buds or anthers [12] or different concentrations of NAA and BA combination [20, 21, 18] could increase embryo production. Beneficial effects of temperature shock treatments on anther culture productivity were known. Although the mode action is unknown, temperature shocks are believed to improve androgenesis by diverting normal gametophytic development into a sporophytic pathway leading to the formation of haploid embryos [14]. To date, very little work has been done relative to the effects of L-proline on androgenesis [23, 19, 7]. The present study was conducted to investigate the effects of cold shock treatments in combination with L-proline on pepper anther culture.

2 Materials and Methods Plants of Capsicum annuum L. cultivar Malatya were grown under field conditions. After a cold pretreatment (at +4◦ C for 48 and 96 h) of buds, with anthers containing uninucleate or 1st polen mitosis microspores [16], were selected and surface streilized (20% v/v sodyum hypochloride for 15 min). The control buds were not subjected to cold conditions. The anthers were then cultured on induction medium. The induction medium consist of MS basal salts [13] with the addition of 30 g L−1 sucrose, 8 g L−1 agar and 4 mg L−1 NAA and 1 mg L−1 BA or 1 mg L−1 NAA and 4 mg L−1 BA with or without 0.25 % activated charcoal and with different concentrations (0, 40, 125 and 500 mg L−1 ) of L-proline, adjusted to pH 5.8. The cultures were incubated at 29ºC in continous light conditions (40 μmol m−2 .sn−1 ). Three months after culture initiation, embryos were counted and transferred to regeneration medium (hormone-free growth medium, MS basal salts, 20 g L−1 sucrose, 7 g L−1 agar, pH 5.8, at 29ºC in continous light conditions (50 μmol m−2 .sn−1 ). Experiments were performed on 20 replication per each treatment (each replication consisted of one petri dishes, with 10 anthers). Data were collected after 3 months’ culture. Data were analyzed by Multiple-way anaysis of variance using ANOVA and the differences in the means were evaluated statistically at p = 0.05 by LSD test. Statistical analyses were done angular transformed percentage data [22].

3 Results and Discussion Production of embryoids was differently affected from cold pretreatment of buds, different concentrations of NAA/BA combination, activated charcoal and L-proline in pepper anther culture (Table 1). According to the results of the statistical analyses,

0 0 0 0 40 40 40 40 125 125 125 125 500 500 500 500

4+1 4+1 1+4 1+4 4+1 4+1 1+4 1+4 4+1 4+1 1+4 1+4 4+1 4+1 1+4 1+4

+ − + − + − + − + − + − + − + −

Activated charcoal

84.5 100 88 99 100 100 100 100 100 100 100 100 100 100 100 100

Percentage of callus in anthers

0h Percentage of callus in anthers 97 100 97 99.5 100 100 100 100 100 100 100 100 100 100 100 100

12.5∗ 0 6.5 0.5 0 0 0 0 0 0 0 0 0 0 0 0

48 h Numbers of embryo/100 anthers

α = 0.05 significance level difference observed (p < 0.05) based on LSD

(mg. L−1 )

∗ For

L-Proline

NAA+BA (mg L−1 )

Cold Pretreatment

2.5∗ 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0

Numbers of embryo/100 anthers 98 99 100 100 100 100 100 100 100 100 100 100 100 100 100 100

Percentage of callus in anthers

96 h

2 0.5 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Numbers of embryo/100 anthers

Table 1 Effects of cold shock treatments combined with L-proline containing (0, 40, 125 and 500 mg L−1 ) induction medium on the production of embryo from anther culture of pepper (200 anthers were cultured for each combination)

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the effects of all the factors as well as interactions between the factors, except few, on androgenetic capacity of pepper were found statistically significant (p ≤ 0.05). There are significantly differences among the treatments. Activated charcoal and additions of different concentrations of NAA/BA combination to MS medium were significantly increased embryo formation compared to the other treatments. Besides there are significant differences between used hormone combinations and concentrations. Control anthers of C. annuum L. cultured in MS medium containing 4 mg L−1 NAA and 1 mg L−1 BA and activated charcoal were most responsive, producing 12.5 embryos/100 anthers. Anthers cultured in MS medium containing 1 mg L−1 NAA and 4 mg L−1 BA and activated charcoal were producing 6.5 embryos/100 anthers. Likewise it has been suggested that the additions of NAA/BA combination and also concentrations to MS medium can increase androgenetic embryo formation [20, 21]. On the other hand the promotive effect of activated charcoal in anther culture medium has been described earlier. Generally, the effect has been attributed to the adsorption of inhibitory substances (phenolics, abscisic acid) from the medium [10, 6, 24, 15]. The cold pretreatment of flower buds before excising the anthers for culture has been described as a means of increasing the androgenetic response [11, 12]. However Vagera and Havranek [25] in pepper and Tipirdamaz and Ellialtio˘glu [24] in eggplant anther culture reported that no significant effect of cold pretreatment of flower buds. Likewise in our study 1–2% embryos were obtained from the cold treated anthers. On the other hand a considerably higher number of embyros (12.5%) were produced in the control cultures which were cultivated (Fig. 1). Pretreating flower buds with cold at 4ºC for 48 or 96 h and addition of different concentrations of L-proline resulted in a lower number of responding anthers mainly by causing callus induction from anthers (Fig. 2). And this showed that the pretreatments of flowers buds and addition of L-proline to the culture medium had no significant effect on embryo production. The results

Fig. 1 An embryo obtained from the control anther culture of Malatya pepper cultivar on MS medium, containing 4 mg L−1 NAA and 1 mg L−1 BA and activated charcoal

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Fig. 2 Callus initiation from the cold treated anthers

of some studies showed that considerable improvement in embryo production were achieved by the inclusion of the L-proline. But it is probably just one factor in a complex series of interactions between genotypes and tissue culture environment. In our study the inclusion of L-proline was not effect embryo formation. In the absence of L-proline better responds of embryo production is obtained. However, Redha et al. [19], working with wheat anther culture, reported that although L-proline significantly reduced embryogenesis but improved embryoid quality. The sensitivity of anthers and pollen to cold stress [26] has been proposed to be related to their endogenous L-proline content. The present results are contrary to this assumption and demonstrate that L-proline, as a component of the induction medium, combined with a cold treatment of incubated anthers, results in not improve embryo production. It has been demonstrated that L-proline is involved in the synthesis of hydroxylproline rich proteins which are known as components of pollen cell wall [27]. L-proline also has been proposed to cause a drop in the water potential inside pollen resulting in dormancy-like conditions [26]. This could results in a reduced sensitivity to unfavourable temperatures. Further, L-proline was found to protect enzymes from inactivation by extreme temperature conditions [17]. It is conceivable that cold stress of inoculated anthers not only provides positive effects with regard to sporophytic development, but may also cause damage within the anther. If this is the case, L-proline, when present in the induction medium, could possibly reduce this damage without interfering with the beneficial effects on embryo production. However work with other species suggests that L-proline may promote anther culture embryogenesis; the promotive effect of L-proline on anther culture appears to be cultivar-dependent [19, 7]. In conclusion these results, together with what is known about L-proline action and cold treatment effect in plant tissue, suggest that the combination of L-proline application with cold shock treatments had no effect on embryo formation frequency in pepper anther culture when compared to the use of different concentrations of NAA/BA combination and activated charcoal.

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References 1. Anagnostakis SL (1974) Haploid plants from anthers of tobacco-enhancement with charcoal. Planta 115:281–283 2. Bajaj YPS (1983) In vitro production of haploids. In: Evans DA, Sharp VR, Ammairato PV, Yamada Y (eds) Handbook of plant cell culture, vol I, Chap 6. MacMillan Publ. Co., New York, pp 228–287 3. Biddington NL, Robinson HT (1990) Variations to high temperature treatments in anther culture of Brussels sprouts. Plant Cell Tissue Organ Cult 22:48–54 4. Büter B, Schmid JE, Stamp P (1991) Effects of L-proline and post-plating temperature treatment on Maize (Zea mays L.) anther culture. Plant Cell Rep 10:325–328 5. Chu CC, Hill RD (1988) An improved anther culture method for obtaining higher frequency of pollen embryoids in Triticum aestivum L. Plant Sci 55:175–181 6. Chunling L (1992) Successful development of new sweet (hot) pepper cultivars by anther culture. Asia-Pasific Conference on Agricultural Biotechnology (APAB), Beijing, China, 20–24 August 7. Deepinder, G., Raman, G., Gosal, S. (2006) Role of cysteine in enhancing androgenesis and regeneration of Indica rice (Oryza sativa L.). Plant Growth Regul 49(1):43–47 8. Dunwell JM (1986) Pollen, ovule and embryo culture as tools in plant breeding. In: Wither LA, Alderson PG (eds) Plant tissue culture and its applications. Butterworths, London, pp 377–404. 9. Huang C, Yan H, Yan Q, Zhu M, Yuan M, Xu A (1993) Establishment and characterization of embryogenic cell susension cultures from immature and mature embryos of barley (Hordeum vulgare L.). Plant Cell Tissue Organ Cult 32:19–25 10. Johansson L (1983) Effects of activated charcoal in anther cultures. Plant Physiol 59:397–403 11. Maheswari SC, Rashid A, Tayag AK (1982) Haploids from pollen grains-retrospect and prospect. Amer J Bot 69:865–879 12. Morrison RA, Köning RE, Evans DA (1986) Anther culture of an inter specific hybrid of Capsicum. J Plant Physiol 126(1):1–9 13. Murashige T, Skoog F (1962) A revised medium for rapid growth and bio-assays with tabacco tissue cultures. Plant Physiol 15:473–497 14. Nitsch C, Andersen S, Godard M, Neuffer MG, Sheridan WF (1987) Production of Haploid Plants of Zea mays and Pennisetum Through Androgenesis. In: Earle E. D., Demarly Y. (eds) Variability in Plants Regenerated from Tissue Culture. Praeger, NY 69–91 15. Özkum D, Tipirdamaz R, Ellialtio˘glu S¸ (2001) Relationship between endogenous abscisic acid content of anthers and in vitro androgenesis in pepper (Capsicum annuum L.). 4th international symposium on in vitro culture and horticultural breeding. ActaHort 560, ISHS, Tampere, Finland, 2–7 July, pp 327–329 16. Özkum Çiner D, Tipirdamaz R (2002) The effects of cold treatment and charcoal on the in vitro androgenesis in pepper (Capsicum annuum L.). Turk J Bot 26:131–139 17. Paleg LG, Douglas TJ, van Doal A, Keech DB 1981, Proline, Betaine and Other Organic Solutes Protect Enzymes Against Heat Inactivation, Aust, J., Plant Physiol., 8:107–114 18. Qin X, Rotino GL (1993) Anther culture of several seweet and hot pepper genotypes. Capsicum and Eggplant Newsletter 12:59–62 19. Redha A, Attia T, Büter B, Stamp P, Schmid JE (1998) Single and combined effects of colchicine, L-proline and post-inoculation low temperature on anther culture of wheat, Triticum aestivum L. Plant Breed 117(4):335–340 20. Rotino G, Falavigna A, Restaino F (1987a) Production of anther-derived plantlets of eggplant. Capsicum Newsl 6:89–90 21. Rotino G, Falavigna A, Fiume F, Nervo G., Restaino, F. (1987b) Possibility of eggplants (Solanum melongena L.) improvement through in vitro technique. Genetica Agrar XLI(3):314–315

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22. Sokal RR, Rohlf FJ (1995) Biometry. The principles and practice of statistics in biological research, 3rd edn. W.H. Freeman and Co., New York, USA, p 887 23. Sozinov A, Lugjanjuk S, Lgnatova S (1981) Anther Cultivation and Induction of Haploid Plants in Triticale, Z. Pflanzenzücht, 86:272–285 24. Tipirdamaz R, Ellialtio˘glu S¸ (1998) The effects of cold treatments and activated charcoal on ABA contents of anthers and in vitro androgenesis in eggplant (Solanum melongena L.). In: Tsekos I, Moustakas M (eds) Progress in botanical research, Proceedings of the 1st Balkan botanical congress. Kluwer Academic Publishers, The Netherlands 25. Vagera J, Havranek P (1985) In vitro induction of androgenesis in Capsicum annuum L. and its genetic aspests. Biol Plant 27(1):10–21 26. Zhang HQ, Croes AF (1983) Protection of Pollen Germination from Adverse Temperature; A Possible Role for Proline, Plant Cell Environ., 6:471–476 27. Zhang HQ, Croes AF, Linkens HF (1982) Proline Synthesis in Germination of Pollen of Petunia; Role of Proline, Planta, 154:199–203

Examination of Some Parameters for Ecological Growth of Maize in Pelic Vertisol I. Stoimenova, E. Djonova, A. Taleva, and N. Kaloyanova

Abstract The increases in doses of nitrogen fertilization decreased the depressing effect of the used herbicides and stimulated their biological degradation. The bacteria, microscopic fungi and cellulose decomposing microorganisms took part in the biological herbicide degradation process during the first days of application of herbicides, whereas the actinomicetes and microbes, utilizing nitrogen, took part at the later phases of the process. The observed soil chemical changes and the ratio between the main groups of soil microorganisms had a temporary effect and did not influence negatively the maize development. Keywords Fertilization · Nitrogen · Maize

1 Dynamics of the Soil Microflora, Depending on the Level of Nitrogen Fertilization and Application of Herbicides The herbicide substances show different effectiveness in specific soil and climatic conditions, which is reflected both in the number and the content of the weeds, as well as in the dynamics and the diversity of the soil microflora [1–4]. Therefore their examination during the growth of maize in the particular agro-ecological conditions is required in order to determine the herbicide effect and the danger of contamination of the soil with residual quantities. The purpose of the experiment is to study the effect of the Lacorn combi herbicide (applied independantly and in combination with Atrazine) and its interaction with other forms of nitrogen fertilization on the dynamics and the diversity of the soil microflora. The variations in the species and quantitative structure of the microbial population (at depth from 0 to 20 cm), depending on the studied factors, are studied in the dynamics on selective nutrition media by the decimal dilution test. I. Stoimenova (B) N. Poushkarov Institute of Soil Science, Sofia, Bulgaria e-mail: [email protected]

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3.70 4.15 4.20 4.10 4.65 3.70

N20 + herbicide N40 + herbicide N80 + herbicide N20 N40 N80

4.85 6.30 5.60 5.65 5.95 7.80

6.20 6.60 7.00 7.00 7.90 6.90

90

35

Days after treatment

60

Amonifying bacteria 1 × 106

Variants

1.35 1.40 1.08 0.99 0.81 0.95

35 2.42 3.55 2.65 3.20 1.90 2.90

60 1.70 3.10 2.90 1.65 2.05 2.40

90

Actinomycetes 1 × 106

13.00 28.60 20.00 23.35 41.70 38.35

35 28.45 36.35 31.65 21.75 35.30 18.30

60

39.95 36.70 37.00 35.25 56.65 49.95

90

Microscopic tungi 1 × 104

11.34 76.30 106.80 56.80 72.95 68.35

35

29.35 83.40 97.33 72.20 69.40 71.33

60

Cellulose decomposing microorganisms 1 × 104

Table 1 Dynamics of some main groups soil microorganisms after application of Lacorn combi (5,500 ml/ha)

61.65 96.45 104.80 81.50 94.95 80.00

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7.43 8.51 4.92 8.05 6.45 6.86

N20 + herbicide N40 + herbicide N80 + herbicide N20 N40 N80

5.20 8.60 5.60 5.90 8.93 7.13

4.13 8.00 3.23 4.20 7.60 8.33

90

35

Days after treatment

60

Amonifying bacteria 1 × 104

Variants

3.43 6.55 5.64 4.32 4.03 4.05

35 3.56 5.66 4.83 5.63 10.20 6.56

60 5.56 7.46 5.13 9.96 5.60 8.30

90

Actinomycetes 1 × 104

59.50 36.50 13.00 68.00 33.00 91.50

35 36.00 63.00 10.00 33.00 60.00 53.00

60

30.00 16.00 20.00 26.00 23.00 50.00

90

Microscopic tungi 1 × 103

20.00 81.50 93.00 69.50 99.50 75.00

35

56.00 66.00 71.00 53.00 83.00 93.00

60

23.00 100.00 143.00 70.00 53.00 126.00

90

Cellulose decomposing microorganisms 1 × 103

Table 2 Dynamics of some main groups soil microorganisms after application of Lacorn combi (5,500 ml/ha) + atrazine (1,600 g/ha)

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In maize growth it is found that the soil microorganisms actively participate in the biological decomposition of the herbicide combination Lacorn combi (5,500 ml/ha), and the relative part taken by the different physiological groups depends on the nitrogen fertilization and the climatic conditions (Table 1). On the 35th day after the introduction of the herbicide substance the amonifying bacteria, the microscopic fungi and the cellulose decomposing microorganisms decrease their number up to 30% in the variant with N20 in comparison to higher doses of nitrogen fertilization. In the same period a some stimulation of the development of the actinomicetes from the applied herbicide established, where no effect of the tested doses of nitrogen fertilization is examined. On the 60th day the negative effect of the herbicide substance continues on the amonifying bacteria, the microscopic fungi and the cellulose decomposing microorganisms, again most strongly shown at N20 . With the actinomicetes no significant changes in the population are observed. Until the 90th day the numbers and the structure of the population is almost completely restored. The data on Table 1 show that the applied nitrogen in increasing doses decreases the suppressing effect of Lacorn combi and stimulates the biological detoxification of the herbicide substance. The examined herbicide contributes to the increase of the numbers of microorganisms in the soil, related to the nutrition and the development of the maize. In a field experiment with maize the effect of the herbicide substances Lacorne combi (5,500 ml/ha)+Atrazine (1,600 g/ha) on the same groups of microorganisms in the soil layer 0–20 cm. The experiment has been carried out in dynamic and includes the same periods of soil sampling after herbicide application. The data presented in Table 2 show that the herbicide substances applied in combination with nitrogen norm N40 leads to increase of the population of the amonifying microorganisms, actinomicetes, and the microscopic fungi through the whole experimental period. With the cellulose decomposing microorganisms such stimulation is observed at N80 , distinctly displayed on the 90th day after the treatment. This is probably related to the products, received as a result of the decomposition of the herbicide substance in the soil and the deir different influence on the examined groups of soil microorganisms. In the process of biological degradation of the herbicide substance Lacorn combi+Atrazine the amonifying bacteria, the actinomicetes and the microscopic fungi participate in the first days after the treatment, whereas the cellulose decomposing microorganisms participate at the later stages of detoxification of the herbicides.

2 Conclusions 1. The application of higher doses of nitrogen fertilization decreases the depressing effect of the tested herbicide – for Lacorn combi up to N80 and for the combination Lacorn combi+Atrazine up to N40.

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2. The determined changes in the microbial population during the two experiments have temporary effect and do not have negative effect on the structure of the microbial population.

References 1. Assae NA, Turco RF (1995) Accelerated biodegradation of atrazine by microbial consortium is possible in culture and soil. Biodegradation 5:29–35 2. Dovies DH et al (1995) Risk evaluation of reduced dose approaches to weed control in cereals. 9th Symposium, Challenges for weed science in a changing Europe, Budapest, vol 2, pp 459–467 3. Parry KP (1989) Herbicide use and invention. In: Dodge AP (ed) Herbicides and plant metabolism. Cambridge University Press, Cambridge, pp 1–20 4. Rocha F (1995) Reducing inputs of herbicides on dryland areas. 9th Symposium, Challenges for weed science in a changing Europe, Budapest, vol 2, pp 478–482

Effect of Bacterial and Fungal Abundance in Soil on the Emission of Carbon Dioxide from Soil in Semi-arid Climate in India Rashmi Kant, Chirashree Ghosh, Lokendra Singh, and Neelam Tripathi

Abstract Carbon dioxide concentration in atmosphere is actively increasing since industrial revolution (1800) from 285 ppmv to 378 ppmv in 2005. Carbon dioxide efflux from soil due to floral and faunal respiration in soil, called soil respiration, is the second largest source of increasing concentration of CO2 in atmosphere. Soil respiration produces almost 11 times more carbon dioxide in atmosphere than that produced due to fossil fuel burning [18]. Microorganisms are the most abundant biotic group in soil and huge amount of CO2 is evolved from soil due to bacterial and fungal respiration. The present study investigated soil respiration and distribution of bacteria and fungi in the soil. The study was conducted in semi arid (subtropical) climate around New Delhi in India. Two different sites (Aravali Biodiversity Park and Yamuna Biodiversity Park) with ecologically different soil and vegetation conditions were studied. Three different locations were selected at each site and at each location CO2 efflux and microbial population were measured at three depths, topsoil (0–5 cm depth), midsoil (15–20 cm depth) and Deep soil (40–45 cm depth). Higher soil activity was found at Yamuna Biodiversity Park (YBP) having profuse ground vegetation, sandy soil with high organic matter and moisture content than Aravali Biodiversity Park (ABP) having scares vegetation, rocky area and dry soil with low organic matter content. Higher soil respiration is recorded in the surface and mid soil at YBP than ABP. However the soil respiration rate was slightly more in deep soil at ABP. In most of the cases soil respiration was found increasing from surface soil to deeper soil till 50 cm depth. Rate of soil respiration is highly correlated (R 2 = 0.7) to fungal population. Our study suggests that soil respiration process is a function of bacterial and fungal abundance in the soil. However, fungal population is more responsible for CO2 evolution in atmosphere from soil than bacterial population. Better understanding of soil respiration process can help in reducing CO2 emission and carbon sequestration process.

R. Kant (B) Yamuna Biodiversity Park, School of Environmental Studies, University of Delhi, New Delhi 110007, India e-mail: [email protected]

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Keywords Soil respiration · Bacterial and fungal abundance · CO2 efflux and semi-arid

1 Introduction Carbon dioxide is one of the Green House Gasses (GHGs) whose increasing concentration leads to global warming. The concentration of Carbon dioxide in atmosphere has increased significantly form 280 ppmv (0.55 g m−3 ) in 1750 to 370 ppmv (0.73 g m−3 ) in 2005 [7, 31] and is increasing at 0.5% (about 3.4 pg) per year [15] (Table 1). The principal sources of increase in atmospheric CO2 concentration are the change in land use pattern and fossil fuel burning. Soil C is distributed among five active global C pools: (i) oceanic pool having 38,000 Pg C (1 Pg = 1015 g), (ii) fossil fuel pool 5,000 Pg C, (iii) soil C pool 2,300 Pg, (iv) atmospheric pool 720 Pg C, and (v) biotic pool 550 Pg C. The soil C pool which is 3.2 times the total atmospheric C pool and 4.1 times the total biotic C pool is very active and play a major role in global C cycle processes. Majority of the C pool in the soil is found on the upper 1 m depth of soil horizon and about 60% is in the organic form. The agricultural and forestry activities are major sources for disturbing the existing carbon pool in the soil. The annual losses from soil C pool are estimated to be 1–2 Pg [3]. It is estimated that about 1,100–1,600 Pg C is sequestered in soil worldwide [14] and around 40–80 Pg of carbon can be sequestered in cropland soils over next 50–100 years [11]. The restoration of degraded soils and ecosystems can led to sequestration of 60–80% C lost due to past mismanagement. People are worried about rate of fossil fuel burning (including vehicular and industrial emission) and its long-term consequences. It may be difficult to reduce the rate of fossil fuel burning substantially enough, to minimize the CO2 emissions in the atmosphere. However, it is worth thinking other sources of carbon emission and the possible steps to minimise their contribution in the emission process. Soil respiration is the second largest carbon flux in terrestrial ecosystems and plays a critical role in Table 1 Atmospheric concentration of CO2 over 6,000 years ([7], BBC News 31 March 2005)

Year

CO2 concentration (ppmv)

4000 BC–AD 1700 1750 1800 1850 1900 1950 1959 1990 1994 1998 2000 2005

260–280 280 285 291 300 312 316 340 358 367 370 378

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global carbon cycling [35]. Soil respiration contributes almost 11 times more carbon dioxide emission in atmosphere than the total CO2 evolved from fossil fuel burning [18]. Carbon dioxide evolved from soil due to respiration activities of various soil floral and faunal populations is called soil respiration. It includes heterotrophic and autotropic respiration. Both abiotic and biotic factors control the rate of CO2 emission. Soil is not inactive, what it looks like, but it harbours a huge number of different living organisms which makes it dynamic. Microorganisms are the most abundant group of organisms in the soil. The contribution of different heterotrophic organisms in soil respiration is important to understand the soil respiration and carbon sequestration process. However, their contribution is unknown [10]. In this study we concentrated on heterotrophic bacteria (the most abundant microbes in soil) and fungi, which are responsible for majority of CO2 efflux in the atmosphere from the soil. Out of the total organic carbon metabolised by the microbes, only one in three parts is utilised and the remainder is lost in the atmosphere in the form of CO2 . Soil factors like moisture, temperature, porosity, pH, and electrical conductivity decide the quality of soil and govern activity in the soil. These factors ultimately regulate the floral and faunal population in the soil. Microbial growth and metabolism can be limited by temperature, moisture and available carbon in the soil [33]. The pore spaces in between the mineral particles are filled with water or air in different combinations. The relative quantity of air and water in the pore spaces determines the property and activity of living organisms in the soil. The availability of water has various physiological and physical effects on ecosystem metabolism [16] and hence it is an important factor influencing soil respiration processes [24]. However, the air in the pore spaces provides the substrate (Oxygen) for respiration. Temperature is an important factor that regulates the soil respiration process. Optimum temperature is always required by organisms for their activities. According to Luo and Zhou [17], global warming can instigate the positive feedback on soil respiration. Vegetation structure and species composition strongly influence the C allocation pattern [34] and microbial population. Recent changes in land use pattern by intensive agriculture and forestry substantially contribute to increased concentration of carbon dioxide in atmosphere [11]. Study of soil respiration has a long history. Soil respiration has been used as index for measuring soil fertility earlier [27]. The dynamic nature of soil respiration process and its importance in global warming attract scientists to work in this area. The objective of the study was to study soil respiration processes at two ecologically different sites. We estimated the fungal and the bacterial population at these two sites. The study further correlated the soil respiration rate with the bacterial and fungal abundance. This study gives us idea about ecological health of the sites. The information on soil respiration is crucial to understand the terrestrial carbon budgets and to determine whether terrestrial ecosystems are sink or sources of carbon dioxide [23]. Soil respiration, once well understood, can be utilised as a measure for determining the health and quality of an ecosystem [9].

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2 Methodology 2.1 Experimental Sites and Soil Sampling The study was conducted in semi arid (subtropical) climate around New Delhi in India. Two separate sites Aravali Biodiversity Park and Yamuna Biodiversity Park were selected for this study. Aravali Biodiversity Park (ABP) is situated on the Aravali Hill next to the Great Indian Thar Desert. The area is dry and soil has very limited moisture. The soil in the area is rocky type and loam in texture having slightly acidic pH. The area is dominated by scrub forest with Prosopis juliflora as predominant species and lacking ground vegetations. This made the area dry and limited organic matter in the soil. Another site Yamuna biodiversity Park (YBP) is situated on the flood plain of river Yamuna. The soil is sandy and moist being near to river. Area is dominated by ground vegetation especially Desmostachya bipinnate other grass species. The soil has high organic matter content with alkaline pH. Three different locations were selected for soil respiration measurement and microbial estimation at both the sites.

2.2 Soil Respiration Measurement Soil respiration efflux was measured at three different depths, topsoil (0–5 cm depth), midsoil (15–20 cm depth) and Deep soil (40–45 cm depth) at all the six experimental locations. We used the modified alkali absorption method [6] for quantifying soil respiration. The method is economical and easy [26]. It has been reported that the method underestimates the amount of CO2 efflux [25]. However, Yim et al. [37] found little difference in the amount of CO2 efflux measured using dynamic infrared gas analysis (IRGA) compared with alkali absorption method. Respiration chambers were installed at all the locations of ABP and YBP experimental sites for estimating soil respiration. Glass jar containing NaOH (1M) was placed inside the respiration chamber for trapping the evolved CO2 from soil. The chambers were closed and made airtight. Aluminium foil was also wrapped around the chambers to minimise the carbon dioxide escape. The alkali was exposed for different durations 12, 24, 48 and 72 h while CO2 measurement at each location. The samples were precipitated with BaCl2 and further titrated with HCl (IM) using Thymolphthaleine indicator to quantify the trapped Carbon dioxide. The amount of CO2 -C evolved was calculated using the formula CO2 − C (mg) = (B − X) ME B is amount of HCl needed to titrate NaOH from blank, X is the amount of HCl required to titrate the carbon dioxide absorbed NaOH solution. M is molarity of HCl i.e. 1.0, E is the equivalent wt. of carbon i.e. 6 for C and 22 for CO2 . Soil respiration was measured during different duration like 12, 14, 24, 48 and 72 h at a stretch. Finally the respiration rate mg of C-CO2 per h is calculated for each duration.

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2.3 Soil Sampling Soil samples for microbial analysis were collected at all the three depths topsoil with 5 cm depth, midsoil with 20 cm depth and deepsoil with 40 cm depth from all the three locations of ABP and YBP sites. Metallic soil core cutter with diameter 10 cm and length 60 cm was used for collecting these soil samples. Soil samples were collected in the evening of the day on which the respiration was measured. The soil samples collected were kept in airtight zip bag and stored in a dark cool place for microbial analysis.

2.4 Microbial Enumeration Bacterial and fungal population was estimated by colony counting, Most Probable Number (MPN) procedure [21, 36]. MPN method is used to estimate the population density of viable microorganisms in soil, water and food products. Soils are heterogeneous and it is not possible to estimate the exact cell count in the soil. One mg of soil was taken from each sample and appropriate ten serial dilutions were prepared. ◦ The plates were incubated at 37 C for 3–5 days before counting the Bacterial and fungal colonies.

3 Results 3.1 Soil Respiration (SR) Rate at Aravali Biodiversity Park Soil respiration measurement was done at three different locations at Aravali Biodiversity Park (ABP) site is shown in Fig. 1. Soil reparation was observed for different durations at a stretch at each location. Finally, the respiration rate was calculated per hour by dividing the total respiration by total duration. Highest respiration rate recorded was 7.8 mg of CO2 per h at 40 cm deep soil while the lowest respiration recorded was 0.8 mg C per h in the top surface

Soil Respirtation at ABP site

Fig. 1 Soil respiration rate (milligram of CO2 emission per hour per 300 sq. cm) at three locations of Aravali Biodiversity Park site

9 8 7 6 5 4 3 2 1 0 TopSoil

MidSoil

DeepSoil

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soil. The average soil respiration rate at top, medium and deep soil is 0.97, 3.7 and 7.2 mg C per h respectively. The trend in soil respiration variation along the depth is similar at all the locations at Aravali Biodiversity Park site. Higher respiration rate is observed in the deep soil at 40 cm and least on the surface soil.

3.2 Soil Respiration (SR) Rate at Yamuna Biodiversity Park The respiration rate was found maximum in mid soil in most of locations at YBP site. However the difference in respiration rate at mid soil and deep soil was not significant except at one location. The highest respiration rate observed was 6.5 mg C per h at depth 20 cm while the lowest on surface soil. The mean respiration rate at top, mid and deep soil was 3.07, 5.4 and 4.53 mg C per h respectively. The soil respiration rate at YBP site is shown in Fig. 2. Fig. 2 Soil respiration rate (milligram of CO2 emission per hour per 300 sq. cm) at three locations of Yamuna Biodiversity Park site

Soil Respiration at YBP site

7 6 5 4 3 2 1 0 TopSoil

MidSoil

DeepSoil

3.3 Bacterial Abundance at ABP and YBP Sites Microbial population is an important parameter for understanding the soil activity. Bacterial population pays an important role in soil decomposition processes. The bacterial abundance, estimated by Most Probable Number (MPN) count, was measured at both the experimental sites and is shown in Fig. 3. Bacteria are more abundant at the YBP than the ABP site. But bacterial count is more in the deep soil at Aravali Biodiversity Park site. Variation in bacterial population at ABP site has no fixed trend. However, there is a decreasing trend bacterial population from surface to deep soil in YBP.

3.4 Fungal Abundance at ABP and YBP Sites MPN method is used for estimating the soil fungal population. The fungal abundance is shown in Fig. 4. The fungal population is more confined to deep soil in most of the locations at the both sites. Increasing fungal population trend from surface soil

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Variation in Bacterial Population

250 200 150 100 50 0 DeepSoil

MidSoil

TopSoil

Fig. 3 Bacterial count (× 105 per mg of soil) at ABP and YBP sites. (Black bar indicates ABP and White bars YBP)

Variation in Fungal Population 135

146

Deep Soil

160

130

Mid Soil

0

50

134

128

Top Soil

100

150

200

250

300

350

Fungal count in (100,000)

Fig. 4 Fungal count (× 105 per mg of soil) at ABP and YBP sites. (Black bar indicates ABP and White bars YBP)

to deep inside is observed at ABP site. However at YBP site fungal abundance is more in the deep soil than the surface soil. The maximum fungal population (160 × 105 per mg of soil) was observed in the middle soil depth at Yamuna Biodiversity Park site.

3.5 Relation Between Soil Respiration Rate and Microbial Population Relationship between soil respiration and microbial population at Yamuna Biodiversity Park and Aravali Biodiversity Park sites is studied. Soil respiration

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8

SR correlated with bacterial population at YBP

SR correlated with bacterail population at ABP

6 4

y = 0.0574 x – 6.4068 R2 = 0.542

2 0 120

140

160 180 200 220 Bacterial Count (100,000)

6

SR rate mg C/hr

SR rate mg C/hr

158

5 4 y = -0.0212 x + 8.6035 R2 = 0.2938

3

2 150

240

170 190 210 230 Bacterial Count (100,000)

250

Fig. 5 Soil respiration correlated with fungal population at ABP site

8

SR rate mg C/hr

SR rate mg C/hr

SR correlated w ith fungal population at ABP 6 4

y = 0.2973 x – 36.074 R2 = 0.8819

2 0 125

130 135 140 145 Fungal Count (100,000)

150

6

SR correlated with fungal population at YBP

5 y = 0.0644 x – 4.8694 R2 = 0.6483

4 3 2 130

140

150

160

170

Fungal Count (100,000)

Fig. 6 Soil respiration correlated with fungal population at YBP site

increases with increase in bacterial population from topsoil to deepsoil at ABP. However, a negative correlation exists between soil respiration and bacterial count at YBP (Fig. 5). Soil respiration rate is directly associated with fungal abundance at both the sites. Strong positive correlation exists between soil respiration and fungal population at both sites (Fig. 6). It also shows that rate soil respiration is more influenced by fungal abundance than bacterial population.

4 Discussion Soil activity below the ground is very much dependent on vegetation cover. Vegetation density and type is responsible for variation in organic matter content of soil. Soil with high vegetation cover contributes to high organic carbon in the soil [20]. Post and Kwon [22] found significant higher soil carbon stock in high vegetation area. Yamuna Biodiversity Park (YBP) site is dominated by ground vegetation than the Aravali Biodiversity Park (ABP). Soil respiration rate at YBP is 3 times more on the surface soil and 1.5 times more in deepsoil than ABP. The result is supported by Campos [5] findings that soil respiration was 2.5 times higher in grassland than the forest in humid subtropical climate in Mexico. Salimon et al. [28] have also found higher soil surface CO2 -C flux in grassland (2,400 g CO2 m−2 ) than mature forest (1,700 g CO2 m−2 ) in Amazonia. The large CO2 efflux in soil is probably due to high rate of gross primary productivity. Wagai et al. [32]

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indicated greater fine root biomass and respiration rate in prairie ecosystem than forest. A similar trend was reported by Raich and Schlesinger, in 1992, a higher soil respiration in grassland than agroecosystem. The vegetation at YBP conserves more moisture in soil which led to high soil respiration. Campos [5] found that soil water content in grassland (51%) was more than cloud forest (40%), which also influences higher respiration in grassland than the forest. Howard and Howard [12] found that soil CO2 emission decreases with draught condition and increases after rain. Bacteria and fungi are actively involved in biogeochemical processes that occur in soil. The microbial biomass is affected by biotic and abiotic factor like N mineralization, soil type, moisture, soil depth and vegetation [13]. Plants influence organic matter content and microbial abundance in soil [1, 4]. Abundant ground vegetation at YBP causes high organic matter content in soil and conserves moisture in soil. This probably harbours more microbial population at YBP than ABP. A significantly high microbial population in YBP than ABP. High C content in soil supports greater level of microbial activity [8]. Soil moisture content is an important factor in controlling microbial population [30]. Higher combined population of bacteria and fungi is observed in topsoil, midsoil and deepsoil at YBP than ABP. High soil moisture might have supported the microbial population at YBP. Orchard and Cook [19] found that low soil moisture could reduce the CO2 efflux by limiting microbial contact with available substrate in the soil. The high fungal population in observed at YBP site. Bardgett et al. [2] also found that fungi play a significant role in grassland soil. The microbial activity in soil directly influences the ecosystem fertility and stability [29]. Soil respiration integrates physical and biological parameters of soil. Activity in soil is higher in area with dense vegetation. Grassland is found ecologically more active than scrub forest. Vegetation influences the soil moisture content and soil microbial population. Soil respiration process is a function of Fungal and Bacterial abundance in soil. However, fungal population is more responsible for higher soil respiration rate. Deeper soil is more active than the surface soil in dry forest. Our study suggests surface vegetation determines the physical and chemical properties of soil, which influence the microbial activity that controls the soil respiration rate and obviously, the global warming and climate change processes. Acknowledgement We wish to thank Mr. VG Gogate, Dr. Anupam Joshi and Dr. Sah Hussain for their help and cooperation during my work at Arawali Biodiversity Park and Yamuna Biodiversity Park. We are also grateful to Ms. Pallavi Saxena and Mamta Singh for their help in sample analysis. The financial support came from department fund CEMDE, University of Delhi, New Delhi.

References 1. Allen MF, Morris SJ, Edwards F, Allen EB (1995) Microbe-plant interactions in Mediterranean-type habitats: shifts in fungal symbiotic and saprophytic functioning in response to global change. In: Moreno JM, Oechel WC (eds),Global Change in mediterranean-type ecosystems Springer, New York, pp. 287–305

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26. Rochette P, Ellert B, Gregorich EG, Desjardins RL, Pattey Lessard ER, Johnson BG (1997) Description of a dynamic closed chamber for measuring soil respiration and its comparison with other techniques. Can J Soil Sci 77:195–203 27. Russell EJ, Appleyard A (1915) The atmosphere of the soil, its composition and causes of variation. J Agric Sci 7:1–48 28. Salimon CI, Dadvidson EA, Victoria RL, Melo AWF (2004) CO2 flux from soil in pastures and forests in Southwestern Amazonia. Global Change Biol 10:833–843 29. Smith JL, Papendick RI, Bezdicek DF, Lynch JM (1993) Soil organic matter dynamics and crop residue management. In: Blaine Metting F Jr (ed) Soil microbial ecology – Applications in agricultural and environmental management. Marcel Dekker, New York, Basel, Hong Kong, pp 65–94 30. Sotta ED, Meir P, Malhi Y, Nobre AD, Hodnett M, Grace J (2004) Soil CO2 efflux in a tropical forest in the central Amazon. Global Change Biol 10:601–617 31. Sukhman D (2005) Carbon dioxide continues its rise. BBC News, 31 March 2005. http://news.bbc.co.uk/2/hi/science/nature/4395817.stm 32. Wagai R, Brye KR, Gower ST, Norman JM, Bundy LG (1998) Land use and environmental factors influencing soil surface CO2 flux and microbial biomass in natural and managed ecosystems in southern Wisconsin. Soil Biol Biochem 30:1501–1509 33. Waldrop MP, Firestone MK (2006) Seasonal dynamics of microbial community composition and function in oak canopy and grassland soils. Microb Ecol 52:470–479 34. Wang C, Gower ST, Wang Y, Zhao H, Yan P, Bond-Lamberty B (2001) Influence of fire on carbon distribution and net primary production of boreal Larix gmelinii forests in northeastern China. Global Change Biol 7:719–730 35. Wang CK, Yang JY, Zhang QZ (2006) Soil respiration in six temperate forests in China. Global Change Biol 12:2103–2114 36. Woomer PL (1994) Most probable number counts. In: Weaver RW (ed) Methods of soil analysis. Part 2. Microbiological and biochemical properties SSSA Book Series 5. SSSA, Madison, WI, pp 59–79 37. Yim MH, Joo SJ, Nakane K (2002) Comparison of field methods for measuring soil respiration: a static alkali absorption method and two dynamic closed chamber methods. Forest Ecol Manag 170:189–197

Part II

Cultural Heritage and Environmental Factors

The Evaluation of Sustainability of Organic Farms in Tuscany Chiara Certomà and Paola Migliorini

Abstract Sustainability evaluation with an updated version of MESMIS Framework has been conducted in 5 organic farms in Tuscany, characterised by different management approach. The real differences is, indeed, determined by motivations that explain how the landscape, the work structure and the cultural heritage are organized, giving the present assessment of the Tuscan rural world. Keywords Sustainable agriculture · Social sustainability · Organic farms · MESMIS

1 Introduction The implementation and evaluation of agricultural sustainable methods are one of the most challenging goal in political and scientific research. The use of sustainability indicators is becoming a frequent tool to evaluate agricultural systems [6, 12]. Several lists of indicators exist [26]. Evaluation strategies and methodologies were worked out in order to quantitative describe and qualitative evaluate ecosystem management [9, 7]. A significant research experience with an holistic approach was carried out in 17 countries by a European network for prototype agroecosystem [34–38, 33]. The network developed a management methodology with a list of indicators on the following criteria: abiotic environment, income/profit, nature/landscape, employment, health/well-being. The methodology was applied in Tuscany where a specific long term experiment to evaluate the organic vs conventional sector was established in 1992 at the experiment farm of Montepaldi. Other indicators to evaluate biodiversity and soil fertility were developed [23] and other methodologies to evaluate sustainability were implemented. A network in France [4] proposed different agroecological indicators. C. Certomà (B) Scuola Superiore Sant’Anna, Piazza Martiri della Libertà 33, 56127 Pisa, Italy e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_17,

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In Switzerland some researches [5] adopted five criteria: abiotic environment; biotic environment; cultural value; social aspects; economic aspects. In small rice agroecosystem a quantitative approach to evaluate productive and environmental performance has been applied [8]. An environmental account methodology has been developed in order to combine economic with ecological aspects [29, 16, 17]. Other approaches are based on rapid evaluation with on-farm indicators for farmers [28] or on-farm questioners [30] and the environmental impact of agriculture at form level (der Werf et al. 2002). Organic agriculture nowadays, is no more a nice (Willer and Yoursy, 2009). Italy is the third country of the world for presence of organic land and in Tuscany 10% of total agricultural surface is growing organic with 3,000 organic farms (ARSIA, 2006). As an alternative propose to conventional agricultural production, IFOAM organic norms (IFOAM, 2005) include principle1 and social justice in the standards for organic production and processing. Although, some researches (Michelsen, 2001; Guthman, 2004) show that the organic regulations (Reg. CE 2092/91, NOP-USDA, etc.) do not include all the principle of organic movements.

2 Rethinking MESMIS Framework in Tuscan Context Since 1996, when Miguel Altieri and his researching team elaborated the MEMSIS Framework (Marco para la evaluacion de sistemas de manejo de recursos naturales incorporando indicadores de sustentabilidad), this methodology was used in several studies in Mexico and Latin America and it is part of academic programs in United States and Spain. Considering that traditional evaluation systems are not always able to reflect the typical complexity of socio-economic and agro-ecosystems (such as cost-benefit analysis), MESMIS gives a redefinition of problems from a qualitative point of view and provides a multi-criteria model to handle the management of ecological systems [27]. It is a cyclic process. The final assessment is positive when it helps to improve social and environmental profile of managing systems of natural resources and when the whole evaluation has been developed through a dialogic process with experts. The most part of MESMIS framework focuses its attention on small rural villages in the Andes area in which modern conventional agriculture encounters traditional, organic or alternative farm management. The difference between Italian, and above all the Tuscan context, and indigenous systems is deeply rooted in social, geographical and political history but it is a profitable to apply the same methodology on the western farmers activities in order to highlight values and development possibilities of a “non-conventional agriculture” and the social net in rural areas.

1 At the general assembly of Adelaide, the 4 principle of health, ecology, fairness and care were included as preamble of the IFOAM Basic Standards (IBS).

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In rural Tuscany towns, villages and farms are strictly interconnected in the way that it’s impossible to consider isolated agricultural systems without social, economic and political factors. That is why in the research here presented, MESMIS Framework is used as a methodological reference: it represents a good model to evaluate both agroecological and socio-economic sustainability [21, 19, 13, 31, 24, 14]. In comparison with the present Community Agricultural Policy (CAP) and EU policy support to Rural Development (Reg. CE 1698/05) oriented towards environmental care, the application of MESMIS methodology, for the first time in Italy, was an innovative experience, despite the fact that modifying some passage of the original framework was needed. The phases of the updated method, used in the present work, are the following (Table 1): Table 1 Phases of updated method Step A

• •

Step B

• •

Step C

• •

Step D

• • •

Step E

• • •

Definitions of a key concept on which the research focuses its attention (here “sustainability”); Definitions of attributes, consequent criteria and subsequent general indicators (parameters and indices) referred to the key concept; Individuation of study cases. Setting out of a specific questionnaire for interviews based on the general indicators; Collection of data (multimedia documents, interviews, direct experiments. . . . ). Description of studies through the processing of the collected data according to general indicators. Elaboration of critical points suggested or noticed during the data collection in topic areas; Choice of strategic indicators for every topic area; Normalization of results for strategic indicators and representation by Amoeba diagrams. Problem analysis and individuation of good practices; Discussion with farmers; Elaboration of a report.

3 Materials and Methods In the research applied on Tuscan context, the chosen key-word (Step A) is “sustainability”. It is considered sustainable a system, in a defined time and space, that: – maintains or increases the basis of existent resources – maintains or increases the biological and socio-cultural diversity – satisfies the necessities of biotic component – hangs in or fit in changed conditions – generates risk and consumption distributive structures

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– shows cooperative mechanism in order to improve the efficiency of productive processes – allows the internal “emergence” of auto-organised phenomena. The following table resume the attributes and related criteria for farms sustainability evaluation settled out from the previous definition. For each criterion, specific indicators (qualitative descriptions,2 parameters or indices) were found and related. As an example, the following table concerns the choosing of socials indicators and sub-indicators for the analysis of concrete case studies. Every indicator is referred to different criteria (indicated by numbers as in Tables 2 and 3).

Table 2 List of “attribute” and corresponding “criteria” used in the research to evaluate farms sustainability

Attribute

Criteria

Complexity

1. Availability (natural and social elements) 2. Diversity 3. Connectivity (richness of relations) 4. Efficiency 5. Productivity 6. Fairness 7. Durability and stability 8. Flexibility 9. Accessibility 10. Multifunctional capability 11. Self organization

Functionality

Interactivity

Creativity

Table 3 List of social indicators and sub-indicators with reference to sustainability criteria Social features of a farm Reference criteria

Indicator

1,2,6,7,1,6

Composition, organization

1,8,10,11 3,9,8,10,11

Movements Territorial relations, activities, projects

Sub-indicators (d=qualitative description, p=parameter, i=index) Social composition (d), managing (d), residents (p), hectare per resident (i), gender (p), age (p), instruction (p) Origin (p), turnover (p), employment situation (i) Training courses (p), agro-ecological projects (p), associations (p), cooperation with private or public organizations (p), syndicates (p), willingness at experimental projects (p)

2 To calculate same indicators, it was used a Likert scale in order to give an evaluation of personal judgment and non-numerical data, based on a five step scale.

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After having identified the cases studies, the collecting data step (Step B) starts from the ideological, historical and organizational situation of farms, including biophysical, agro-ecological, economical and social characteristics, always referring to the general grid related to the attributes of sustainability (Table 2). The relevance of social matters in the research leads to the integration of MESMIS method with the Participatory Action Research approach [Cuadernos del program de manejo partecipativo de recursos naturales, 1993 2]. It suggests to involve farmers, peasants and institutional delegates in the most part of the research. Considering that peasants’ and farmers’ time has to be respected and not wasted, it is very important to spend time working with them, sharing food and spare time [10]. The aim is collecting the largest part of information informally, before using a questionnaire specifically arranged for a formal interview. During the interviews, it is suggested a Rapid Rural Appraisal3 setting-up: a not rigid grid in which active listen, that allows an “appropriate inaccuracy” for fuzziness typical of complex systems, is preferred to a dual-purpose structure. That is particularly true for qualitative data that, sometimes, give more precise results with respect to the quantitative ones and stress the real perception and intentions of people involved in the interview. The structure of ad hoc-created interview model is the following: 1. 2. 3. 4.

Determination of farm: administrative, juridical and agronomical classification Orientation: history, ideal choices, philosophical issues of the farm Biophysical features: weather, soil, geological characteristics, water Agro-ecological features: landscape description, wood area, crop rotation and cattle-breeding 5. Economical features: production characteristics, material and financial assets, employment, financial management, marketing management, energy 6. Social features: participants, relationship, organization, connection with territory and research institutions, socio-political and cultural activities 7. Opinions Five organic farms, according to the Reg. CE 2092/91, are chosen in different areas of the region and represent different approaches to eco-agricultural and social managing [20]. In Tuscany controlled foodstuffs, environmental politics and social welfare have a good standard, so it would be important to make breakthrough and pick up samples cases in which a basic involvement in sustainability matters is assumed by the farmers. That is the reason why organic farms managed by farmers with a high socio-environmental awareness are preferred. The sampled analysed farms are located in five different areas, socially and legally organized in different ways and show excellent results in sustainability path (Table 4).

3 See:

http://www.fao.org/documents/advanced_s_result.asp

2005 10 8,3 Olive and fruit trees, vegetables C28.000,00 37% 2 females, 2 males A 4, S 3

1992 79,5 34

Mixed crop

C94.000,00

33%

8 females, 15 males

A 4, S 2

A 4, S 14

1 female, 1 male

3%

C120.000,00

Olive and grapevine

1992 14,5 11,6

Paterna Valdarno (Arezzo), flat, 300 m asl Cooperative Organic

C

A 6, S 1

1 female, 1 male

0%

C18.000,00

Olive and grapevine

1993 3,3 2,1

Podere di Peciano Val di Chiana (Arezzo), flat, 330 m asl Familiar Permaculture

D

A1

7 females, 7 males

0%

C361.000,00

Olive and grapevine

2002 49 24,5

Tenuta di Valgiano Lucca hills, 250 m asl Society Biodynamic

E

b On

a Agricultural

management are define as follows: organic = Reg. CE 2092/91; synergic = [11]; permaculture = Mollison, 1989; biodynmaic = Steiner, 1968 the total outcomes c A = agro-ecological activity; S = socio-cultural activity

Gross production value (2003/04) Percentage of public financingb Farm habitants (2003/04) Numbers of projects runsc

Podere del Grillo San Miniato (Pisa), hills, 47–100 m asl Familiar Organic

La Comune di Bagnaia Siena hills, 350 m asl Communitarian Organic-synergic

Farms name Province Landform Legal organisation Agriculture managementa Organic certified since total farm area (ha) Utilised agricultural area (ha) Crops

B

A

Study cases

Table 4 General description of the case studies farms in Tuscany

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Another very relevant, but not really simple identifiable, feature of the farms, is the motivational approach to farming and the choice of living in the countryside. In the present research, it was given an overview on the different motivations. Specifically, it was considered – the case of a communitarian farm (A) in which participants decided to share all the properties and the work in order to build up an alternative live style that it is at odds with respect to the individualistic style of western societies; – the case of a young couple (B) who decided to rebuilt the grandparents’ farm by taking into account the possibility, according to modern economic and technical instruments, to restore the ancient water managing system and the landscape; – the case of a cooperative farm (C) from which began all of the most significant cultural developments in rural area; – the case of a farm managed by a farmer (D) who is involved in increasing the permaculture approach in Italy; – the case of a classical wine producer farm (E) biodynamical oriented. After having set out a good description platform (Step C), the analysis of the critical points starts (Step D). Taking inspiration from the critical point, focused as weakness or strength points by farmers, five distinguished areas of analysis are settled: agro-ecological structure, work and production, composition and competences, availability, social network. For each one of these, only few indicators, called “strategic” and considered deeply relevant for sustainability in the observed region, are evaluated by using data collected in the previous phase of the research (Table 5). Table 5 List of strategic indicators with reference to the area of interests, algorithm and unit measure Area

Strategic indicators

Algorithm

Unit

Agro-ecological assessment

Wood area Herbaceous strips area Hedges Wood borders

Wood area/total area Herbaceous area/total area Hedges/boundaries Wood borders of the farm/total borders Cultures/lot Computation of kinds of crops in the farm

% % % %

Variety of cultures Crops Work and production

Level of employment Age classes

Agricultural employers/total area Computation of person for farm represented in each class Farm employers farm employers /farms habitants Products (different Computation of different product by kinds) each farm Olive grove productivity Quantity of olives/ha Vineyard productivity Quantity of grapes/ha

% n. n./ha n. % n. kg/ha kg/ha

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C. Certomà and P. Migliorini Table 5 (continued)

Area

Strategic indicators

Algorithm

Unit

Composition and competences

Gender ratio City, village, countryside origin Geographical origin

Female/male Quantity of people for farm represented in each class Quantity of people for farm represented in each class Quantity of people for farm represented in each class Incoming people/out coming people production self consumed/ total production Amount of public financing/gross production value Gross profit/production costs External income/total income

n/n n.

Previous employment

Availability

Turnover4 Self consumption Dependency

Social Network

n. n. n. kg/kg %

Gross margin External income influence Availability of capital Perception of availability of capital Availability of credit Perception of availability of credit Availability of assistance Perception of availability of assistance

% %

Association forms

n.

Likert Scale Likert Scale Likert Scale

Number of association in which the farm in involved Citizens involvement Average of citizen involved in each happening Participation Average of farm habitants involved in each happening Cooperation with public Computation of collaboration with institutions public institutions Projects Computation of active projects in the farm Involvement in Perception of involvement in territorial policies territorial policies definition

n. n. n. n. Likert Scale

Table 6 Example of normalization for the strategic indicator “Association forms” included in the Social Network Area Not normalised value of strategic indicator “Association forms” (included in Social Network Area): it represent the effective number of different kind of association in which the farm take part. Farm a: 10 Farm b: 6 Farm c: 5 Farm d: 2 Farm e: 3

4 Turnover

Sustainability value [1,5] Value “10” (farm a) = 5 maximum sustainability value6

is calculated on the last ten years. The others indicators, on the last years.

5 3 2,5 1 1,5

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Table 7 Amoeba diagram of strategic sustainability indicator concerning the social network area Social Network

association forms 5 4 territorial policies

3

involvement of citizens

farm a

2

farm b

1

farm c

0

farm d farm e

projects

collaboration with public institutions

participation

The results of each strategic indicator is calculated for each farm. The following step is to normalise the obtained results on a five step scale not weighted. The value “5” represent the highest sustainability result in our reference system (Table 6).5 The result of all the normalized value for each strategic indicator are represented in an amoeba diagram. Five amoeba diagrams were elaborated in reference to each five different areas, as shown in Table 7, concerning Social network area. The attribution of maximum sustainability value was decided on a related literature basis considering some features as more positive for social and agro-ecological aspect: • environmental and social diversification useful to empower the reliance of the system; • long term planning and flexibility; • social and economic network organization to have an increasing contractual power and help in new enterprises, information and technical support; • multi-functional capability; • decrease of external energy dependence; • easier acquisition of land and financial resources for familiar agriculture; 5 This form of evaluation was choosen in a wide range of possibilities because we found it more suitable to use. The goal of the research was, in fact, to show a friendly methodology that presents understandable results for farmers, citizen, public authority. Moreover, according to MESMIS philosophy, we consider sustainability as a relative characteristic of a complex system, so we establish the cluster of farms as our reference system. 6 0 is not considered as the minimum sustainability value but as the real value 0.

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C. Certomà and P. Migliorini Table 8 General amoeba diagram of sustainability General sustainability evaluation

agro-ecological assesment 5 4 3 social network

2

farm a work and production

1

farm b farm c

0

farm d farm e availability

composition and competences

• revitalization of territorial society and offer of public utility services; • introduction of farming method complementary to biological standard (such as biodynamic, synergic, permaculture)

At the end a general Amoeba diagram of sustainability related to the farm considered in the research, was drawn in five different areas, calculating how many “5” each farm obtained in the different Areas and normalizing them. It can be used as a guideline for the farmers who take part into the research to have an idea of the path they have gone towards sustainability in order to plan how to proceed in their management (Table 8). A discussion at the end of the research with the stakeholders was considered as a good starting point for a participatory development plan and suggests interesting conclusion to the researchers and the farmers.

4 Conclusions The perception of farmers, who has a good or an increasing feeling about environmental and social matters, is generally correct according to the result of the research, but not always. It is due probably to the fact that farmers, even if nonconventional agriculture oriented, go on evaluating their farms according to the dominant paradigm of conventional agriculture: that produces a persistent feeling of inadequacy to the general standard [3].

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In the observed farms rural development shows good examples in which, unfortunately, the economic factor is often constraining for a non-market oriented agriculture supported by value and practices that enforces the social structure and the environmental maintenance. Generally a strong relation is evident between social and environmental awareness. Such kind of agriculture goes forth the modernity values, re-interpreters work, land, society and development with new suggestions. In the reviewed MESMIS method, the approach towards involved subjects is essentially dialogic in order to valorise the human aspects of the analysed experiences to create bonds among different but complementary ideas, to get suggestions from a selected group of peculiar cases useful for the whole typology of farms. In the study here presented the social aspect has a particular relevance: it wants to give room to the singular commitment in the general mosaic work. The real differences is, indeed, determined by motivations that explain how the landscape, the work structure and the cultural heritage organize themselves giving the present assessment of the Tuscan rural work. In general, except the agricultural benefits arising from specific managing models or positive economic results, it’s possible to find some peculiar features, for the considered case studies, especially useful for sustainability: the willingness to create social network, to interact with local administrations and to collaborate in organizing social or agricultural projects that involve citizens, the participatory decision processes and the inclusion association with others farmers on particular foci in order to develop cooperative commitments and self aid groups. History, expectations and symbolical value of farmers derived by motivation have had a crucial role in the pattern designed by the research. Moreover the motivational factor probably could explain the reason why, after the modern age in which agricultural activity held the negative sign of “past”, a lot of people, coming from very different productive sectors, decided to engage themselves in agriculture, conceiving it as a “post-modern” choice of live.

References 1. ARSIA (2006) Agricoltura biologica in Toscana. Gestione Elenco Regional Operatori biologici L.R. 49/97, Report N. 10. Firenze 2. Bacon C, Mendez E, Brown M (2005) Participatory action research and support for community development and conservation: Examples from shade coffee landscapes in Nicaragua and El Slavador. Centre for Agroecology and Sustainable food system, Santa Cruz, paper brief 3. Bans C, Dunlap R (1990) Conflict paradigms in agriculture. Rural Sociol 4:592–611 4. Boockstaller C, Girardin P, van der Werf HMG (1997) Use of agro-ecological indicators for the evaluation of farming systems. Eur J Agron 7:261–270 5. Bosshard A (2000) A methodology and terminology of sustainability assessment and its perspectives for rural planning. Agriculture, Ecosystems and Environment 77:29–41 6. Conway GR (1987) The Properties of Agroecosystems. Agricultural Systems 24:95–117 7. Cuadernos del Programa de Manejo Participativo de Recursos Naturales Instituto de los Recursos Mundiales & Grupo de Estudios Ambientales A.C. México, agosto de 1993 8. Dalsgaard JPT, Oficial RT (1997) A quantitative approach for assessing the productive performance and ecological contributions of smallholders farms. Agric Syst 55(4):503–533 9. Douglass G (1984) The meaning of agricultural sustainability. In Agricultural sustainability in a changing world order, West ù Press, Colorado, pp 3–30

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10. Freire P (1970) Pedagogy of the oppressed. Continuum, New York 11. Fukuoka M (1980) La rivoluzione del filo di paglia. Libreiria editrice fiorentina, p 205 12. Girardin P, Bockstaller C, van der Werf HMG (1999) Indicators: Tools to evaluate the environmental impacts of farming systems. J Sustain Agric 4:5–21 13. Gomes de Almeida S, Bianconi Fernandes G (2003) Monitoreo económico de la transición agroecológica: estudio de caso de una propiedad familiar del sur de Brasil. LEISA Revista de Agroecología, ocho estudios de caso, pp 58–63 14. Gonzalez-Esquivel L, Brunett-Pérez C et al (2003) Sustainability and dairy cattle production in highlands of central Mexico. Presented at the IX World Conference on Animal Production, Porto Alegre, Brasil 15. Gulthman J (2004) Agrarian dreams: the paradox of organic farming in California. University of California press 16. Halberg N (1999) Indicators of resources use and environmental impact for use in decision aid for Danish livestock farmers. Agric Ecosyst Environ 76:17–30 17. Halberg N, Verschur G, Goodlass G (2005) Farm level environmental indicators. Are they useful? An overview of green accounting systems for European farms. Agric Ecosyst Environ 105:195–212 18. IFOAM (2005) Basic Standards for organic production and processing. International Federation of Organic Movements, Bonn 19. Lopez-Ridaura S, Masera O, Astier M (2000) Evaluating the sustainability of integrated peasantry systems: The MESMIS framework. Ilea, Dicembre, pp 28–30 20. Lotter D (2003) Organic agriculture. J Sustain Agric 21:59–124 21. Masera O, Astier M, Lopez Ridaura S (2000) Sustentabilidad y manejo de recursos naturals. Mundi Prensa, Michoacan, Mexico 22. Michelson J (2001) Organic farming in a regulatory prospective. The Danish case. Sociologia ruralis 41 (1) 23. Migliorini P (2006) Valutazione della sostenbiltià in sistemi agricoli e colturali bioloici della Toscana. Tesi di dottorato di ricerca. Università degli Studi di Firenze 24. Moya García X, Caamal A, Ku Ku B, Chan Xool C, Armendariz I, Flores J, Moguel J, Noh Poot M, Rosales M, Dominguez JX (2003) La agricultura campesina de losmayas en Yucatán. LEISA Revista de Agroecología, ocho estudios, pp 7–16 25. Mollison B (1989) Permaculture: A Designers’ Manual Tagari Publications, Australia 26. Morse S, Namara Mc N, Acholo M, Okwoli B (2001) Sustainability indictors: The problem of integration sustainable development. Sustain Dev 9:1–15 27. Nicholls CI, Altieri MA, Dezanet A, Lana M, Feistrauer D, Ouriques M (2004) A rapid, framer-friendly agroecological method to estimate soil quality and crop health in vineyars systems. Biodynamics n. 250 p. 33–39 28. Pacini C, Wossink A, Giesen G, Vazzana C, Omodei Zorini L (2003) Evaluation of sustainability of organic, integrated and conventional farming systems: A farm ad field-scale analysis. Agric Ecosyst Environ 95:273–288 29. Piorr HP (2003) Environmental policy, agri-environmental indicators and landscape indicators. Agric Ecosyst Environ 93:17–33 30. Rigby D, Caceres D (2001) Organic farming and the sustainability of agriculturale systems. Agric Syst 68:21–40 31. Santillánt A, Nahed Toral J, López Méndez T (2003) Sostenibilidad y agricultura campesina: la producción agrosilvopastoril en Los Altos de Chiapas, México. LEISA Revista de Agroecología, ocho estudios de caso, pp. 18–23 32. Steiner R (1968) The Roots of Education, Five Lectures Given in 1924, London, Rudolf Steiner Press 33. Vazzana C, Raso E, Pier S (1997) Una nuova metodologia europea per la progettazione e la gestione di agroecosistemi integrati ed ecologici: Applicazione in un area agricola toscana. Rivista di Agronomia 31(2):423–440 34. Vereijken P (1994) Progress Report n 1 Designing prototype. Research Network on integrated and Ecological Arable Farming System for EU AB/DLO Wageningen, 87p

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35. Vereijken P (1995) Progress Report n 2 Designing and testing prototype. Research Network on integrated and Ecolgical Arable Farming System for EU AB/DLO Wageningen, 90p 36. Vereijken P (1996) Progress Report n 3 Testing and improving prototype. Research Network on integrated and Ecolgical Arable Farming System for EU AB/DLO Wageningen, 87p 37. Vereijken P (1998) Progress Report n 4 Improving and disseminate prototype. Research Network on integrated and Ecological Arable Farming System for EU AB/DLO Wageningen 55p 38. Vereijken P (1999) Manual for prototype integrated and ecological arable farming system in interaction with pilot farms, AB/DLO Wageninen, 87p 39. der Werf, van HMG, Petit J (2002) Evaluation of the environmental impact of agriculture at the farm level: A comparison and analysis of 12 indicator-based methods. Agric Ecosyst Environ 93:131–145 40. Willer H. e L. Kilcher (2009) The World of Organic Agriculture. Statistics and Emerging Trends 2009, International Federation of Organic Agriculture Movements (IFOAM), Bonn, Germany and Research Institute of Organic Agriculture (FiBL), Frick-ITC, Ginevra

Evaluation of the Sustainability on Cultural Heritage and Environmental Factors in Architecture from a Tourism Point of View: Ayvalik Historical City Center Olcay Çetiner and Ay¸segül Çetiner Gökyilmaz

Abstract Tourism should be evaluated as a sustainable progress tool to obtain the continuity in the areas which acquires cultural heritage and natural values. It is observed that, the two important visual features in tourism are the environmental characteristics and the architectural characteristics of the accommodation buildings that belong to cultural heritage. Environmental protection conception and returning back to nature also affected the architecture. Today, people that have a certain intellectual and cultural level, prefer and look for environmentally interrelated facilities that are peculiar to that district, that are completely in nature, that are providing an interactivity with the local people, and have cultural heritage, rather than facilities that have a common architectural style, that have a good comfort of a luxury hotel and that are indented and self-sufficient. These kinds of facilities are mostly developed by Small Sized Tourism Firms (STF) and Micro Entrepreneurs/Very Small Sized firms. The STF’s are obtained from a lot of different source. Most of them are developed by special investors using small capitals. Some others, especially micro entrepreneurs/very small sized firms are mostly owned and ran by a family. In this study, evaluation of the sustainability on cultural heritage and environmental factors in architecture from a tourism point of view and the characteristic features and design approaches of the STF’s that are already located in or might be located in Ayvalik historical city center are analysed. Keywords Cultural heritage · Environmental factors · Sustainability · Tourism in architecture · Small sized tourism firms, and micro entrepreneurs/very small sized firms · Ayvalik historical city center

O. Çetiner (B) Department of Architecture, Yildiz Technical University, Barboros str., 34349 Besiktas, Istanbul, Turkey e-mail: [email protected]; [email protected]

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1 Introduction Understanding the space requires understanding the physical and social relations behind the space in an unlimited vivacity caused by various civilizations changing places, expanding and being affected by the geographies they live in throughout the history and today. In other words, social and cultural continuity and changes requires reidentification and explanation of the space. There are places that are left to decay and buildings to be protected in many cities. As a result of the movements in tourism that have become a need, people begin to see and experience the city textures that are the products of different cultures and consequently, reviving old city areas becomes a must. Being a pattern of climate, building materials, tradition and ethnic groups, historical city center areas are the areas that must be protected because of their cultural values. There are civil architecture examples that are not decayed and still protect their old characters in several cities. Recovering and functionalizing city textures in compliance with today’s conditions are very important historical and cultural factors not only in terms of social, economical and cultural quality but also in terms of communicating information to following generations [3].

2 The Evaluation of the Sustainability of Cultural Heritage and Environmental Factors in Architecture in Terms of Tourism In terms of cultural heritage and environmental factors, sustainable tourism should attract individual tourists or small tourist groups instead of mass tourism for maximum profit, diversify tourism activities, extend tourism to a longer period and apply tourism to different places. Today’s travelers are people that develop their holiday concepts, personal hobbies and interests, prefer regions where they can experience these, integrate with the environment, endeavor to know people and cultures and show respect to the environment. The expectations of these new types of travelers with their new conceptions are to spend their holidays in clean and environment-friendly facilities that integrate with nature. Quebec Declaration includes principles regarding active contribution to the protection of natural and cultural heritage, participation of the local community, preference of independent travelers and small tourist groups, services provided by small-scaled organizations/companies among the principles of sustainable tourism. As Turkey is a developing country of which the historical heritage mostly continues its presence lively with its natural and cultural values, it is certain that there is a significant potential in several regions of our country in terms of sustainable tourism [7]. Sustainable tourism should be developed without giving any harm to the environment; society; historical, natural and cultural assets so as to contribute to the regional economy and social life. Integration with nature and hospitality of the regional people are considered as the two factors that give the maximum satisfaction to travelers in accommodations.

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For this reason, it was observed that the studies and plannings made without the participation of the local community are unsuccessful in the long term although they seem to be successful in the short term. It is seen that tourists expect local cultural properties of the place they spend their holidays, a healthy environment and a certain level of prosperity especially in the regions of which the economy is planned according to tourism. These expectations show that the local community and touristical developments should complete each other. The cultural components in the social life are cultural elements in natural and historical protected areas, folkloric properties, regional life style, eating-drinkingdressing habits, traditional architecture, handicrafts, customs & traditions, linguistic properties, songs, lullabies, folk dances, folk architecture, etc. These components are used to describe the local identity of the city [1]. It is thought that natural values can be reproduced or can replace each other like cultural values. As the number of regions with cultural and natural values have started to decrease and the concept of locality has begun to stand out, especially the groups that conduct studies with the purpose of protection have started to develop approaches that aim to emphasize the meaning and feeling of places instead of the process of consuming areas/places. Thus, tourism is considered as an “instrument” rather than a “purpose” in order to ensure economic continuity especially in areas that have historical, cultural and natural values [4]. Utilizing old building stocks cause less structuring by using the idle space potential. These buildings cover the expectations of environmentalist travelers by creating visual and cultural variety and providing comfortable accommodation. Thus, historical city textures are protected, infrastructures are functionalized, the interaction between tourism and environment starts to protect and develop both parties by reducing the impact of structuring on the environment [5]. This includes smallscaled and/or micro-scaled tourism enterprises that are acts sensitively about the environment, cultural and social structure. It is a fact that design criteria that include all the plans and designs, which aim to ensure sustainability while using or creating environment, will shape tourism architecture. Because success, future and sustainability in tourism will be achieved with the help of structuring and design that reflect the importance given to environmental values.

3 Certain Features and Design Approaches of Ste’s that Are/May Be Located in Ayvalik Historical City Center 3.1 Tourism Potential and Properties of Historical City Center in Ayvalik Turkey is a country that has the traces of many civilizations. Therefore, it will always attract the attention of the entire world with its universally important historical and cultural values that are richer and more intense than any country in the world not only in terms of geographical position but also long history [8].

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Photograph 1 General view from the studied area [2]

From the tourism potential point of view that have been examined in the study have a very rich source in terms of antique cities and historical buildings. They hosted many civilizations until today. The developing civilizations that lived in these regions left several artworks that succeeded to reach today. Touristic properties natural properties, coastal facilities, natural port, climate and physical data positively affect the tourism potential of these regions. This historical and natural heritage that integrates with the green texture managed to reach today. Access possibilities and rich archeological values are also important factors. Ayvalik: It is a very old residential area surrounded by rich forests. Very old artworks can be observed in Ayvalik. Late Byzantine buildings are also seen in the region. Saatli Church, Alibey Mosque, Yeni Mosque and Biberli Mosque are among the significant historical buildings in the city. Being constructed by Abdülhamit II in the 19th century, Hamidiye Mosque is the only building in Ayvalik that was designed as a mosque. There are totally 22 big and small islands in Ayvalik. The main islands are Alibey, Timarhane and Tav¸sanli. Sarimsakli, Altinkum and Duma are the most significant beaches. Çamlik, Ba˘gyüzü Village, Kazak and Alibey Island are green areas that are still being used with their unique views. Being 4 km away from the city, Seytan ¸ Sofrasi is located on a hill where you can see the islands. Natural beauties in Alibey Island and Sarimsak, thermal springs that are good for skin problems and the unspoiled nature along the coast increase the population in Ayvalik by two or three times during summer. There are many springs among the pine and acorn trees in the forests that have touristical values and that surround Ayvalik. This forest region is used for camping and hunting activities. Vacation, cultural-historical, hunting and health tourism are available in Ayvalik. The area that begins with the antique city of Troy in the north and ends in Foça in the south affect the tourism in Ayvalik (Photograph 1).

3.2 Accommodation Design Approaches in Small Tourism Enterprises Most of the S.T.E.’s in tourism sector was formed by private investors that use small capitals. Others are generally micro enterprises that are owned and managed by families.

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Enterprises give importance firstly to accommodation quality. However, the existing facilities in the region should be used by attracting the attention to interesting regional objects and events. They should make applications that improve the promotion of the regions. These applications should include properties that are not known/will attract by the incoming guests [6]. Historical centers are tourism areas where visitors stop off; that are strong in terms of economical and social factors, settling geography and culture and that were once residential areas. The facilities that provide accommodation in historical places are facilities that are easy to manage and that provide catering services or facilities where guests can prepare their own meals in addition to lodging services. In some of these regions, home pensioning has become widespread with the house owners renting some rooms of their houses to the guests. There are two important points regarding the contribution of good design to efficiency in Small Tourism Enterprises; (a) The first impression of the guests can be positive with the help of a well-designed Small Tourism Enterprise. This makes the guests spend longer time in the facility and visit it several times, (b) Well-designed and well-organized service areas can reduce the cost of employees and increase the efficiency by affecting the motivation of employees, as these areas are aesthetical [6]. The texture and technology that is used with the purpose of increasing customer satisfaction are important in terms of customers’ preference. For this, the belowmentioned conditions should be met; • The infrastructure of the communication system should be flexible for improvement (TV, cable distribution system, fast Internet system), • Bathrooms should have sufficient facilities, • There should be more alternatives for artistical objects, antiques and ornamentations, • Designs should be created in order to reflect the regional environment by using artistical objects, • Healthy environments should be created, as there will be guests that give importance to personal health, • Natural materials that are in compliance with the environment should be used, • Modern concepts and objects that reflect history should be combined.

3.3 Design Recommendations for the Usage of Accommodation Spaces It is seen that the most important visual properties that attract the interest of travelers are environmental properties and the architectural characteristics of the accommodation facilities. Among these, environmental properties are the ones that belong to the historical city centers. These buildings that are in historical centers should have facades with properties that will attract attention. In order to establish a traditional place that reflects

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Table 1 Examples from accomadation buildings that can be renovated for reusage and exterior facade recommendations that are in compliance with their architectural components of the small turism enterprises [2] Examples from accommodation buildings that will be reopened for usage

Exterior facade recommendations

the regional life style, the first thing to do should be examining the regional architectural style and combining these properties with the interior and exterior design (Table 1). Architecture and interior design for Small Tourism Enterprises should be in compliance with the natural environment and connected to the main properties of the environment. The most important reason of why a guest prefers a specific place for holiday is the natural view and surroundings. This preference depends on transferring interior design components into this atmosphere. To achieve this, design concept should be identified and room and common space design should be examined. Identifying design concept is affected by the answers of the below-stated questions; who are the people that will stop off? What kind of an experience would they like to have? Is there any interior design style that people would like to experience? How is the image of our existing market and is this image a desired image or should a new image be created? Where is settling area? How is the settling area associated with the interior design style? Space can be regarded as a special place in historical centers for residents. Moreover, the materials to be used in interior and exterior designs should be determined. Accommodation facilities can be designed with one or two floors that compose of entrance, reception, kitchen, dining room and bedrooms.

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Table 2 Interior spaces that lead the design for accomodation places that are examined in this study [2] Interior spaces that lead the design Example from rooms

Common usage examples

Objects that enable the connection

For room design; room measurement, room layout, room groups that include the number and type of rooms, recommended furniture and lighting, objectives of the sector, etc. should be taken into account [6]. Rooms of the accommodation facilities that are examined in the study have been observed in two different categories (Table 2). Only basic furniture has been selected for the room furnishing. Special attention paid for the optimum use of regional furniture according to the requirements. The purpose was to make the room look bigger and create well-used interior spaces. Spaces gave been decorated with traditional objects and motifs. Common space design; another point is to create common spaces that will ensure differentiating. Reception, meeting room, dining room and recreational areas can become nice spaces if they are organized with a good programming and design. Regardless of the type of accommodation, all these common spaces should be places around the lobby in terms of design and planning. The guests should be enabled to find different functions with minimum difficulties. A good relation of the common spaces and the rooms should be obtained. Designers should take functional properties into consideration while creating the atmosphere, layout, lighting and furniture.

4 Conclusion The functional usage areas in historical buildings are nearly in the same number with the ones in new buildings. Historical buildings can also be used in every field and every subject. However, usage has a different usage in tourism field. Because historical and cultural values are the biggest resources of the tourism potential of a

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country. Countries, which have rich historical and cultural values and give importance to tourism, always utilize these values in order to develop tourism industry. Therefore, there is a very close relationship between the factor of history and culture and tourism sector. For this reason, tourism is the most appropriate and most useful way in the usage of historical buildings [8]. When renewing historical city areas, recommendations that meet today’s needs and increase the image quality of that area should be prioritized and contemporary concepts should be adapted. Environmental properties should be well analyzed for the innovations to be made. Architectural character should definitely be protected and the innovations to be made should emphasize the character. It should be remembered that a careful and authentic innovation would provide urban and architectural richness. The new functions to be brought during renovation should be made by considering the cultural value, spatial requirement and aesthetical preference and livable space should be created. Only a study like this would add richness and dynamism to the space. Facilities that are constructed unconsciously cause changes in the natural appearance, unorganized settlement areas become problems in the most preferred regions and natural resources may be affected negatively. Therefore, tourism can be sustainable by protecting the natural environment, historical heritage and cultural texture.

References 1. Beyhan SG ¸ (2006) Kültürel, Do˘gal Ve Tarihi Mirasın Sürdürülebilir Turizm Açısından De˘gerlendirilmesi Ve Isparta Örne˘gi. Turizm ve Mimarlık Sempozyumu-Turizmde Sosyal, Kültürel, Fiziksel Geli¸smeler: Sorunlar ve Öneriler, Antalya. (in Turkish) 2. Çetiner O, Gökyılmaz ÇA (2006) Photos of Ayvalık (Balıkesir – Ayvalık ˙Ilçesi Turizmde Tanıtma ve Pazarlamada Yeni Yakla¸sım – Konaklama Mekânlarında Tasarım Etkileri-, II. Balıkesir Ulusal Turizm Kongresi Balıkesir Üni. Turizm ˙I¸sl. ve Otelcilik Y.O., Balıkesir. (in Turkish) 3. Çetiner O, Gökyılmaz ÇA (2006) Antalya Turizmi Konaklama Mekanlarının Kullanımında Tasarım Etkilerine Öneri, Turizm ve Mimarlık Sempozyumu-Turizmde Sosyal, Kültürel, Fiziksel Geli¸smeler: Sorunlar ve Öneriler, Antalya 4. Hovardao˘glu SÇ, Hovardao˘glu O (2006) Turizm Ve Do˘gal – Kültürel De˘gerler Ba˘glamında Yerin Anlamı Üzerine: Erciyes Da˘gı Ve Seyh¸ ¸ saban Yerle¸smesi, Turizm ve Mimarlık Sempozyumu-Turizmde Sosyal, Kültürel, Fiziksel Geli¸smeler: Sorunlar ve Öneriler, Antalya. (in Turkish) 5. Kısa OP (2006) Farklı Turist, Farklı Turizm, Farklı Mimari: Çevreci Turist, Ekolojik Turizm, Ekolojik Turizm Mimarisi, Turizm ve Mimarlık Sempozyumu-Turizmde Sosyal, Kültürel, Fiziksel Geli¸smeler: Sorunlar ve Öneriler, Antalya. (in Turkish) 6. Negrusa A, Ionescu CE (2005) Design implications in creating a competitive advantege for hospitality small business. Studia Universitatias Babes-Bolyai Negotia, No.1/2005, ISSN 1224-8738. Cluj-Napoca, Romanya, pp 102–112 7. Tosun Ç, ve Sahin ¸ SZ (2006) Geli¸sen ve De˘gi¸sen E˘gilim: Ekoturizm, II. Balıkesir Ulusal Turizm Kongresi, Balıkesir Üniversitesi Turizm ˙I¸sletmecili˘gi ve Otelcilik Yüksekokulu, Balıkesir. (in Turkish) 8. Türk A, Kıstır R, Sataf M (2006) Tarhi ve Kültürel De˘gerlerin Turizm Amaçlı Kullanımları Ba˘glamında Isparta Aya Baniye ve Aya Yorgi Kiliselerinin De˘gerlendirilmesi, Turizm ve Mimarlık Sempozyumu-Turizmde Sosyal, Kültürel, Fiziksel Geli¸smeler: Sorunlar ve Öneriler, Antalya. (in Turkish)

Preserving the Mediterranean Landscape: The Role of Local Traditional Food Giovanni Quaranta and Caterina Salvia

Abstract It is largely recognised that the Mediterranean and its landscape symbolises a cultural heritage for the world as a whole. It represents the place where different countries with different languages and cultures converge. Today all this culture and history seems clearly threatened by extensive desertification phenomena. This paper focuses on the role played by the gastronomic landscape and local traditional food into the process of Mediterranean cultural landscape making and conservation. By conceptualising local traditional food as a part of the entire cultural heritage of a place, the intend here has been to discuss how traditional knowledge, particularly traditional food and food processing, can both environmentally and culturally preserve the identity of a place. The rediscovering of typical agri-food products can guarantee the protection of landscape quality both from an aesthetic and an environmental point of view. It implies the reorganisation of productive systems through the adoption of traditional techniques. In fact, differently from the conventional products, the traditional ones belong to the historical memory of a territory and they have particular characteristics linked to geographical factors, quality of raw materials and processing techniques. This implies that there is a strict relationship between agri-food products and local community heritage and identity. The paper investigates the capacity of typical agri-food products to safeguard and sustain landscapes in a environmental fragile context. The approach leaded to a development of an empirical model validated through a case study located in Southern Italy (Costiera Amalfitana – Campania region), an outstanding example of Mediterranean landscape, with exceptional cultural and natural scenic values resulting from its peculiar topography and historical evolution and with a vital gastronomic heritage. Keywords Mediterranean · Local traditional food · Environment · Cultural heritage · Conservation

G. Quaranta (B) UNIBAS, Potenza, Italy e-mail: [email protected]

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1 Introduction The Mediterranean contains a variety of landscapes, all of which have been shaped by the social, economic, cultural and religious activities of people over thousands of years. Scholars agree in describing this territory as the cradle of civilisation, where different and important cultures have followed one another. But the Mediterranean derives also from the combination of its climate, its plants, its sea and its soil. Indeed, then, it is the result of the historical interaction between human and nature. Citing Braudel [5, p. 26] “in both the physical and human sphere, the Mediterranean is a crossroads, the Mediterranean is a heteroclite and coherent image into which everything emerges and settles back into an original unit”. The term Mediterranean, however, evokes also the image of the desert. While the existing deserts are considered as a part of the Mediterranean landscape, it is necessary to underline that desertification or land degradation represents one of its main threats. Desertification, that properly means the creation or enlargement of a desert by natural processes and human activities leading to changes such as the loss of soil exposing, affect, in a differ manner and intensity, almost all the Countries of the Basin [10]. For millennia, the equilibrate use of both natural resources and traditional techniques has guaranteed the survival of people and their territories and the maintenance of a singular landscape. When this synergy broke, the entire ecosystem collapsed generating phenomena of degradation and land abandonment, often irreversible, such as desertification [20]. Thus, coping with desertification and, consequently, preserving the Mediterranean landscape implies the restoration of this equilibrium and, as a consequence, the elaboration of a new paradigm involving environment respect and economic, social and cultural sustainability. Namely, this underpins the “re-connection of people, land and nature” [19]. Moving from this idea, the recuperation and the valorisation of traditional techniques and knowledge, such as those linked with the traditional agri-food products, appears as a new challenge for regenerating territories at risk of desertification. They could start, in fact, virtuous processes of environment conservation and, in so doing, promote a sustainable safeguarding of all the landscape components, including its cultural heritage. As Austad (2000 in Antrop [1, p. 189]) points out “local knowledge and traditions should be combined with concepts of landscape ecology to develop ‘new’ cultural landscapes and agro-systems”. Nonetheless, encouraging these mechanisms is not easy. Their implementation, in fact, needs to take into account all the existing differences in economic, spatial, socio and cultural settings so that it might be possible asses their practical effects. Bearing this in mind, the explicit aim of this paper is then to analyse how traditional agri-food sustains the process of landscape preservation through the exploration of a case study. It is organised in four sections. The first section critically examines three key concepts: landscape, heritage and tradition. The second part focuses on the role played by typical agri-food products in the process of landscape protection. The third section examines the case of Costiera Amalfitana, in Italy. Finally, the last section, draws some conclusions.

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2 Landscape, Heritage and Tradition There is a general consensus that landscape is an evolving concept, generally characterised as ambivalent, fuzzy and multifaceted. Often, scholars [10] prefer its century-old sense of “a tract of land with its distinguishing characteristics and features [. . .], (Oxford English Dictionary)”. While, according to Tuan (1979 in Arriaza et al. [2, p. 115]) “landscape [. . .] is not to be defined by itemising its parts. The parts are subsidiary clues to an integrated image”. Following the definition used in the European Landscape Convention [7], however, “landscape means an area, as perceived by people, whose character is the result of the action and interaction of natural and/or human factors”. This definition clearly underlines what Antrop [1, p. 187] summarises stating “landscapes evolve continuously in a more or less chaotic way and reflect social and economics needs of a particular society at a given moment”. It, thus, needs to be contextualised, as it results from the overlapping of different complementary aspects: aesthetical, geographical, historical, etc., forming a whole, whose natural and cultural components are taken together, not separately [7]. The expression cultural landscape, therefore, has been coined to emphasise “the combined works of nature and man [8, p. 18]” and embraces the diversity of manifestations resulting from the interaction between humankind and its natural environment. Once shaped into a landscape, this interaction becomes an historical and cultural piece of document constituting the cultural heritage of both people and places. In other words, landscapes are part of the cultural heritage in which the cultural identity is rooted. Comes to the light, then, that heritage must be considered both as a sort of intellectual capital [1] and as an “identity marker” of groups [4]. In accordance with the Cambridge Dictionary definition, in fact, heritage is the set of “features belonging to the culture of a particular society, such as traditions, languages or buildings, which still exist from the past and which have a historical importance”. More specifically, the United Nations Educational, Scientific and Cultural Organization (UNESCO) defines heritage as a legacy from the past, what people live with today and pass on the future generations. Furthermore, this set of shared practices and understandings, inherited and adapted through generations, represents what Ray [21] identifies as local knowledge. The term local here, derives from the concept of locality, which is usually characterised by a twofold meaning: one physical and another social. In physical terms, it refers to a place where people live, work and resolve their activities [23]. In social terms, as Lowe and Murdoch (1993 cited in Selman [23, p. 4]) argue, “locality represents groups of individuals who are associated through common responsibilities, occupations, cultures or interests”. It comes to the fore, then, that the heritage preservation assures the continuity between past and present. Using the Bessière [4, p. 26] words “heritage provides historical depth and permanent pattern in a perpetually changing world”. The notion of heritage becomes clearly the same of tradition. Etymologically, tradition comes from the Latin, particularly, from the verb tradere, that literally means “to transmit or to deliver” [4]. In other words, it suggests the idea of handing something down

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or over, in order to transmit theoretical and practical know how, behaviour, attitudes and to ensure the continuity among generations [11]. Yet, summarising and following Antrop [1], landscapes posses heritage values and traditional knowledge, such as those linked with typical agri-food products, that should be preserved. The protection of cultural landscapes can contribute to the implementation of sustainable development strategies, maintaining and enhancing the quality of life for the local population and, in doing so, preventing land abandonment. Furthermore, it can sustain and improve natural values of the landscape contributing to preserve ecological functioning and diversity as well as to continue and reintroduce traditional practices, recognised as sustainable.

3 Traditional Agri-Food Products as a Tool of Landscape Safeguarding According to different authors (Giardiello [9], Torquati and Frascarelli 2000 in Miele and Murdoch [13]), typical agri-food products are different from other products existing on the market as they belong to the historical memory of a territory. “Tipicality” here indicates the historical memory, geographic localisation and the quality of raw materials and techniques of preparations. This implies that there is a strict relationship between agri-food products and local community heritage and identity. Given this, typical agri-food products seem to encompass the Sage’s [22] definition of good food. He correctly states that a good food should embrace three basic attributes: specific properties and both ecological and social embeddedness [12, 18]. It is, in the author words, “a heuristic hybrid term for it embodies both nature and culture [. . .] [22, p. 50] ”. Essentially, the mixture of human skills and knowledge with the character of the surrounding ecosystem becomes the main quality of typical foods that needs to be culturally appreciate [13]. Moran (1993 in Ray [21]), referring to French wines, states “each wine is a product of the physical characteristics of the locality and accumulated local know-how, the combination of which, it is claimed, ‘cannot be replicated elsewhere’. To put it in another way, the specific characteristics of the typical food originate from the interaction with the landscape of production or terroir [25], generating what authors [16, 6, 22] identify as gastronomic landscape. The rediscovering of typical agri-food products and the preservation of the gastronomic landscape can guarantee the protection of the landscape as a whole both from an aesthetic and an environmental point of view. It implies, in fact, the reorganisation of traditional productive systems through the adoption of traditional techniques. Furthermore, it is widely recognised that moving towards valorisation of local or endogenous resources, such as typical agri-food products, territories, particularly those marginalised and at risk of land degradation and abandonment, can create new sources of wealth [24]. Some researchers state that “in an era of increasingly competitive agri-food production (competition based on cost and price), there is an emerging hope that the promotion of regionally distinctive products may offer

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an alternative development trajectory for regions less able to compete in a globalised, commodity driven, market place” (Gilg and Battershill, 1998; Jenkins and Parrot, 2001 in Parrott et al. [17, p. 243]). As Parrott et al. [17, p. 257] argue, “the existence of well-known regional products may act as a ‘flagship’ for a region, creating positive associations which may, in turn, create other synergies in terms of tourism and regional development”. They can help to “maintain agricultural profitability in zones that are considered difficult or marginal (. . .) [and] create rural employment, both directly and indirectly, in associated industries such as tourism (Bessière [4] in Barham [3, p. 134])”. The promotion of traditional products works as a catalyst for many actors operating in rural areas: from tourist agents to agricultural operators, local authorities, trade associations and development agencies. In short, the valorisation of endogenous resources and thus of a territory presupposes the creation of what Murdoch [15] named horizontal networks.

4 A Case Study: The Costiera Amalfitana, in Italy The following case study is a valid example through which all the previous conceptualisations can be clarified providing guidelines for a simply model to be replicated elsewhere into the Mediterranean context. The selected case study is the Amalfi Coast, Costiera Amalfitana in Italian. It is a portion of coastline sited in the southern side of the Sorrentine Peninsula of Italy, covering 11,231 ha. It extends from Positano, in the west, to Vietri sul Mare, in the east (Photograph 1). Its natural boundary is the southern slope of the peninsula formed by the Lattari hills that, stretching from the Picentini hills to the Tyrrhenian Sea, separate the Gulf of Naples from the Gulf of Salerno. Indeed the Amalfi coast can be defined as an area of exceptional value resulting from the continuous work of both nature and man. In this area, nature is both well-preserved and harmoniously combined with the human activities. The landscape is shaped by rocks, wood and macchia mediterranea (maquis), but also by citrus groves and vineyards grown using the characteristic terraces (Photograph 2) that cover the steep slopes rising from the coast to the top of the mountains. In addition, the mountain areas are exploited for dairy farming, which represents an activity historically rooted here, based on sheep, goats and cattle breeding.

Photograph 1 Map of the Amalfi coast

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Photograph 2 Terraces of the Amalfi coast

In some parts of the Costiera, the natural landscape survives, preserving intact the traditional Mediterranean flora, which can withstand the windswept aridity of the area and a rich wildlife. The woods are populated by trees, such as oak and chestnut. The higher mountain areas are also characterised by mule tracks (mulattiere) which represent a notable feature of this landscape. Historically, these served as means for both communication among villages and for catching and channelling rainwater. Numerous are also the torrents, which produce impressive waterfalls. For all these reasons, this territory is listed by UNESCO as a World Cultural Heritage site. Particularly it has been selected on the basis of three of the ten selection criteria. Mainly, however, because it represents “an outstanding example of a Mediterranean landscape, with exceptional cultural and natural scenic values resulting from its dramatic topography and historical evolution (www.whc.unesco.org)”. As already mentioned, one of the main agricultural activities in this area is the cultivation of citrus, particularly lemons, from which originates the worldwide famous liqueur called Limoncello. Thanking for this process, in fact, as well as for both the peculiarity of the microclimatic conditions and the traditional variety, the local agricultural sector has overcome the high competitiveness of the global markets (mainly deriving from the South of America). As stated, then, this kind of cultivation actively contributes to the process of landscape making and preservation. The lemon trees, in fact, are cultivated in terraces still built with the traditional technique that protects soil, catches and channels waters. The safeguarding of this specific know how avoids also the abandonment of other traditional activities, such as the wood production. For instance, the chestnut wood used for the maintenance of the terraces is produced in the mountain part of the area. The system of terraces, then, has been perpetuated and nowadays constitutes the only landscape associated with this territory. Flagship of this area is, however, the Limoncello. The production of this spirit allows and starts a set of processes which make this area extremely competitive. As a traditional product, it requires “typicality” of both raw materials and technique of

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production. Furthermore, due to its strong linkage with the terroir and, particularly, with the landscape this product acquires also an esthetical value. By getting a bottle of Limoncello, consumers gain also “a piece of the landscape” and this becomes undoubtedly a valid strategy of territorial marketing. In short, this summarise what is known as the business of place or the power of provenance. In addition, using the Limoncello as an ingredient, the local gastronomy becomes a sort of cuisine de terroir, resulting, mainly into the tourists perspective, very fashionable. Yearly, this territory attracts millions of foreign visitors, who are hosted in the numerous hotels and restaurants, which are the core of the local economy.

5 Some Conclusions The presence in the Mediterranean context of numerous fragile territories threatened by degradation problems, such as the considered area, imposes the identification of strategies for halting these phenomena. Particularly, the analysis of the selected case study has had the specific objective to illustrate how a typical and traditional product contribute to maintaining and preserving a landscape, generating a virtuous circle of sustainable development in a area at high risk of degradation. After critically analysing the concepts of landscape, heritage and tradition, the role played by typical and traditional products in the process of landscape safeguarding has been clearly defined. The rediscovery and conservation of traditional knowledge permits a reconnection between human and nature. In other words, combining nature, identity, regional livelihood and a sense of well-being, traditional agri-food products encourage processes of both social and ecological reembeddedness. Moreover, the valorisation of these product has a multiplier effect on the whole local economy. Far from considering the Amalfi Coast as a model to simply imitate everywhere, the main idea in this paper has been to validate some general principles drawn from a successful case study that has shown an interesting working-effectiveness.

References 1. Antrop M (2006) Sustainable landscapes: contradiction, fiction or utopia? Landscape Urban Plan 75:187–197 2. Arriaza M, Cañas-Ortega JF, Cañas-Madueño JA, Ruiz-Aviles P (2004) Assessing the visual quality of rural landscapes. Landscape Urban Plan 69:115–125 3. Barham E (2003) Translating terroir: the global challenge of French AOC labelling. J Rural Stud 19:127–138 4. Bessière J (1998) Local development and heritage: traditional food and cuisine as tourist attractions in rural areas. Sociol Ruralis 38(1):21–34 5. Braudel F (2002) Il Mediterraneo. Lo spazio e la storia. Gli uomini e la tradizione, I volti della Storia. Newton & Compton Editori, Roma 6. Brunori G, Rossi A (2000) Synergy and coherence through collective action: some insights from wine routes in Tuscany. Sociol Ruralis 40(4):409–403

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7. Council of Europe (2000) European landscape convention. Firenze, 20 Oct 8. Fowler PJ (2003) World heritage cultural landscapes 1992–2002. World Heritage Paper 6, UNESCO World Heritage Centre, Paris 9. Giardiello A (1995) La valorizzazione dei prodotti agro-alimentari tipici. In: Giardiello A (ed) Prodotti tipici agro-alimentari tipici della Campania. Università degli studi di Napoli Federico II, Naples 10. Grove AT, Rackham O (2003) The nature of Mediterranean Europe. An ecological history. Yale University Press, New Haven, second printing 11. Hervieu–Léger D (1996) Tourisme, tradition et ethnologie. Source 27:55–86 12. Hinrichs CC (2000) Embeddedness and local food systems: notes on two types of direct agricultural market. J Rural Stud 16:295–303 13. Miele M, Murdoch J (2002) The practical aesthetics of traditional cuisines: slow food in Tuscany. Sociol Ruralis 42(4):312–328 14. Morgan K, Marsden T, Murdoch J (2006) Worlds of food. Place, power and provenance in the food chain. Oxford University Press, Oxford 15. Murdoch J (2000) Networks – a new paradigm of rural development? J Rural Stud 16:407–419 16. O’Neill P, Whatmore S (2000) The business of place: networks of property, partnership and procedure. Geoforum 31:121–136 17. Parrott N, Wilson N, Murdoch J (2002) Spatializing quality: regional protection and the alternative geography of food. Eur Urban Reg Stud 9(3):241–261 18. Penker M (2006) Mapping and measuring the ecological embeddedness of food supply chains. Geoforum 37:368–379 19. Pretty J (2002) Agri-culture. Reconnecting people, land and nature. Earthscan Publications Limited, London 20. Quaranta G, Salvia C (2003) Risorse agro-alimentari e degrado del territorio nel bacino del Mediterraneo. Il Diritto dell’agricoltura, Edizioni Scientifiche Italiane 21. Ray C (1998) Culture, intellectual property and territorial rural development. Sociol Ruralis 38(1):3–20 22. Sage C (2003) Social embeddedness and relations of regard: alternative ‘good food’ networks in south-west Ireland. J Rural Stud 19:47–60 23. Selman P (1996) Local sustainability. Managing and planning ecologically sound places. St Martin’s Press, New York 24. van der Ploeeg JD, Renting H (2004) Behind the ‘redux’: a rejoinder to David Goodman. Sociol Ruralis 44(2):233–242 25. Wilson JE (1998) Terroir: the role of geology, climate and culture in the making of French wines. University of California Press, Berkeley

Climate Change Critical to Cultural Heritage P. Brimblecombe, C.M. Grossi, and I. Harris

Abstract Although modellers have established the type of climate expected in Europe over the coming century, they have not been concerned with the combination of meteorological variables most important to building damage. We have identified the climatic parameters most likely to be critical for architectural surfaces and structures. They have been loosely grouped as: (1) Temperature derived parameters – range, freeze thaw, thermal shock (2) Water derived parameters – precipitation, humidity cycles, time of wetness (3) Wind derived parameters – wind, wind driven rain, sand and salt. We also looked at pollution derived parameters such as SO2 , NO2 , elemental carbon and pH, but neglect these in this analysis which focuses on a European situation with much reduced air pollution forecast for the future. As expected a future Europe will experience less frost damage to porous stone, although higher temperatures can enhance fungal growth on wood. Drier summers seem likely to increase structural problems from desiccated soils and salt weathering of porous stone. Our work hint at likely heritage management strategies for the future. Keywords Building · Climate Change · Damage · Heritage

1 Introduction Our built heritage is exposed to the atmosphere over long periods of time. This means that it is exposed to changes that occur on long timescales and accumulated damage from this exposure. The very choice of the term weathering to describe damage to buildings reflects the view that climate is a key factor in damage, despite the fact that the earliest uses of the word in the 1500s tend to reflect the positive benefits of exposure to weather or a sense of drying. However, architects and geologists, saw the more negative aspects of weathering in its ability to wear and disintegrate, P. Brimblecombe (B) School of Environmental Sciences, University of East Anglia, Norwich, UK e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_20,

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such that 300 years ago architects were convinced that buildings were destroyed by “time, smoke and weather” [3]. The blackening effect of air pollutants had long been known and the poet Horace was able to write in his Odes and Carmen Saeculare of the temples of Ancient Rome: “Your fathers’ guilt you still must pay, Till, Roman, you restore each shrine, Each temple, mouldering in decay, And smoke-grimed statue, scarce divine”

John Evelyn in 17th century London wrote in detail in his book Fumifugium (1661) of the damage that air pollution causes to our monumental heritage. The adoption of coal as a fuel led to increased concentrations of sulfur dioxide in urban atmospheres and from the 17th century there were complaints of the way this damaged stone buildings. Sir Christopher Wren claimed that the sulfate encrustations on London buildings were inches thick in places. Coal became widely adopted as the main fuel across Europe in the centuries that followed [2] such that these sulfate layers became ever more widespread. The 20th century saw a profound shift in the nature of urban air pollution. The adoption of the private automobile increased the concentration of volatile organic compounds in urban air and as coal was replaced by gas and electricity in cities its declined. Governments adopted increasingly well structured environmental regulations, perhaps beginning with the UK Clean Air Act (1956) through to the European Union’s Air Quality Monitoring and Management Directive (1996). Although this legislation derived from health concerns, there are doubtless benefits for building materials from the reduced pollution loads. The reduction in sulfur dioxide concentrations in urban air that paralleled the declining use of coal has reduced the damage from acid gases and the production of gypsum layers [3]. The urban fabric still shows dark damage layers, but these are increasingly the result of soot from diesel engines (see [1, 5]). These layers show the potential for a level of organic chemistry and biological activity that was not known in sulfur dioxide dominated atmospheres. Despite the potential for novel chemistry in dark crusts on buildings in the 21st century, the role of pollution in building damage is likely to be much reduced. There is evidence that erosion rates in the last decades of the 20th century in major cities such as London were much reduced [10]. Reduction in the damage from gaseous air pollutants and a decrease in some components within acid rain have meant that climate factors, which have hitherto been largely ignored, may become more important determinants of building damage. This is not to say that the potential impacts of frost, rain or wind have not been appreciated, but the changing balance of these factors as a result of climate change have largely been ignored. Buildings have to survive centuries such that they will confront increasing changes in climate. Historic buildings were designed to confront a climate very different from those in the future. Some of these problems have been of interest to a project Engineering Historic Futures coordinated by the University College London’s (UCL) Centre for Sustainable Heritage [4]. In the UCL project, the difficulties faced in managing historic buildings, archeological

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sites and parks and gardens. The report noted many different concerns although the increased frequency of heavy rain or flooding was a general worry. The European project NOAH’s ARK (http://noahsark.isac.cnr.it/) aims to assess the overall risk posed to monumental heritage by climate change. The project title alludes to the biblical story regarding the protection of what we value in times of great climatic stress. It is a broad project that intends to go beyond academic researchers to include practitioners and additionally the insurance industry, which has to confront the costs of climate in a very direct way. The project has excited considerable interest in the media because it seems to include threats that the public find real. This has ranged from worries about the effect of increased rainfall on the traditional English pub with its thatching and wattle and daub walls, through to concerns about climate impact on icons such as the Eiffel Tower in Paris or the Torre del Oro in Seville. As welcome as such media attention has been, the project has broad interests that go beyond concerns over individual monuments. This is because the project is concerned with the pressures on European monumental heritage as a whole. Table 1 The meteorological parameters thought critical in the NOAHs ARK project. Subdivided into groupings – in temperature, water, wind and pollution derived parameters Parameter

Definition and meteorological parameter

Temperature

(1) Range: max (T1 . . . Tn ) − min (T1 . . . Tn ); T = daily mean (2) Thermal shock: (Tmax − Tmin ) > X ◦ C; Counts for X = 7, 10, 15, 20 (3) Mean: mean (T1 . . . Tn ); T = daily mean (1) Number of freeze-thaw cycles: Cycle (1 cross) T (i) > 1∧ T (m) < −3∧ T (n) > 1 i,n,m are intervals of time (2) Frost damage: Crack length ∼ −0.14T 2 − 2.54T − 8, where ◦ C < T > −15◦ C and Fr Frost Index : T − 4 Ig = 0 360.30 T (−5) /30 (1) Mean: mean (S1 . . . Sn ), S = daily sun hours (1) Rainy days: Consecutive number of rainy days, (>0.1 mm): days of rain/time period (2) Extreme events: Z (mm/t) >200 mm/day (3) Sum of precipitation (1) Range RHmax − RHmin (2) Mean RH (1) Number of cycles crossing RH = 75% (2) Daily RH shocks (RH (n) − RH (n + 1) > 25% (1) Wind speed: mean (W1 . . . Wn ); W = daily mean (2) Win direction: Distribution of daily directions for 8 compass points (3) Extreme events: days v >7.5, 10, 15, 20 m/s (1) v.p; where v = wind speed; p = amount of precipitation (daily)

Freeze-thaw cycles

Sun hours Precipitation

Relative humidity Humidity cycles Wind

Wind driven rain Sea salt Gas (SO2 , NOx ), particulate pH precipitation

(1) Salt deposition inland wind speed (see wind) (1) Stone recession by dissolution of carbonate (2) Blackening of materials (3) Corrosion of metals (4) Influence on bio-colonization (1) Stone recession by dissolution of carbonate: Modified Lipfert function: Carbonate Stone = f(solubility of Calcite in equilibrium with [CO2 ], rain, [H+ ]

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Individual monuments are of course, exemplars of the processes that may be underway in the future, but these sites are not the focus of our study. The output from NOAH’s ARK will be a damage atlas for Europe, often couched in terms of risk to particular materials: stone, brick, clay rich materials, metals and wood. The changes examined in the project can in principle be subdivided into the following main categories (see Table 1): Temperature Derived Parameters: Range, freeze thaw, thermal shock. Water Derived Parameters: Precipitation, humidity cycles, time of wetness. Wind Derived Parameters: Wind, wind driven rain, wind driven sand, salt Pollution Derived Parameters: SO2 , NO2 , particulates and pH – largely neglected in this paper.

2 Modelling the Future Past climate change can be examined by looking at the long term records collected by meteorologists over the last three to four hundred years. We have drawn on a range of older data sets, although for convenience have used the daily records from central England [8] and Prague most closely. Estimates of future climate of the 21st century is increasing available from modelled output. This allows us to consider the changes in a wide range of meteorological parameters often on a daily basis. In the current study we have relied mostly on output from the Hadley model (HadCM3, a coupled ocean-atmosphere global circulation model from the UK Hadley Centre, see for example [7]). We have paid particular attention to the modelled grid cell that covers central England – stretching from the Welsh borders to the eastern coast of England and includes London. This was chosen to represent a maritime climate. Additionally we have looked in detail at a grid square in the Czech Republic, that includes Prague, and represents a more continental climate. The HadCM3 grid, typical of global models is coarse (2.5 × 3.75 degrees), so the grid squares examined here cover a large area. It is possible to examine the regional output from the HadRM3 model, but this covers a shorter time period (2070–2099) although at a finer spatial scale. The regional model output includes topography, increasing the validity of individual cell predictions. Most of the discussion here relates to the output from the global model. Our analysis of future trends has relied mostly on the A2 scenario (IPCC SRES Emissions Scenarios – Version 1.1 – July, 2000). This scenario describes a very heterogeneous world in which the underlying theme is that of strengthening regional cultural identities, with an emphasis on family values and local traditions, with high population growth. It gives pronounced changes in future climate, so should result in strong signals in terms of future pressures on architectural heritage, that allows us to consider problems likely to be most critical. The daily output from HadCM3 has been used here to calculate the specific values required to assess the potential for material damage in Europe.

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3 Temperature Derived Parameters Temperature is the most obvious parameter that will change in a world with greater greenhouse warming. Nevertheless temperature changes are often likely to be only a few degrees, so it is necessary to consider ways in which these relatively small changes are likely to affect building materials. One of the rather slow changes in temperature that has the potential to affect large buildings is the annual seasonal change. Such structures can change in response to this annual cycle as a kind of breathing of the building. We have examined the annual temperature range as shown in Fig. 1 for central England both from the period of historical instrumental measurements through to the modelled data that ends in 2099 AD. What we see from this figure is that although both summer and winter extremes in the monthly temperature increase in the future, the annual temperature range buildings experience remains fairly constant. Although our analysis is not complete for the rest of Europe, similar pictures of a relatively small change in the annual range over the next century becomes apparent. One should note the Hadley Model predictions for the minimum monthly temperature are rather lower than found in the overlapping historical record. This is probably the result of the warming effect of the North Sea not being well represented in the Hadley Model. Frost is an important source of damage to wet porous building stone. Freezing leads to substantial volume changes that induce mechanical stresses in the outer layers of the stone. There are a number of ways of estimating the potential for frost damage, but here we adopt a very simple one and suggest that the damage would be 30

Temperature/C

25 20 15 10 5 0 –5 1600

1700

1800

1900

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Year

Fig. 1 Long term monthly maximum and minimum temperature and annual temperature range in central England. The historical temperature range is marked by open squares and the range predicted from the Hadley model is in closed diamonds. The historical maximum and minimum values are shown as a smoothed line (11 year running mean). The Hadley model annual predicted values are shown by the jagged line

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Fig. 2 Number of freeze-thaw cycles each year as predicted for Hadley grid squares representing the Czech Republic and central England. The values displayed are decadal averages

related to the number of freeze-thaw cycles. These have been determined by examining the daily data from the Hadley Model output for points where the temperature ◦ crosses 0 C between 1 day and the next (see Fig. 2). More sophisticated approaches ◦ are possible. As seen in Table 1, we are interested in transitions between 1 and –3 C, but are also examining the particular temperatures reached and note in particular that ◦ crack propagation is especially important at about –10 C [11]. Figure 2 shows that the number of freeze-thaw cycles is likely to decrease in much of Europe in the future. It is also clear, the milder climate of England is subject to less freeze-thaw events throughout the period. In the far north, although there is a lower density of monuments, archeological sites are likely to experience an increase in the number of freeze thaw cycles. This is a potential problem as it can perturb middens. At Narssarssuaq in Greenland early calculations from the Hadley Model suggest a fourfold increase in the number of days above freezing. There is a very significant change in the number of freeze-thaw cycles during a period when the average temperature changes only slightly (just a few degrees). This emphasizes the way in which small changes in a meteorological parameter can be amplified and have large effects on materials. In a similar way crops can be very sensitive to temperature, such as the length of the growing season, and also the amount of freezing, so there are also biological mechanisms for amplification. Thus subtle changes of a few degrees increase in temperature or small percentages in precipitation might be able to affect buildings. Freezing and thawing is important because it represents a process where a phase change occurs at an exact temperature. Later we will see that phase changes induced by humidity can also be very sensitive to small shifts in climate. Overall Fig. 2 suggests that increasing winter temperatures may make frost damage less frequent in future mild climates such as that of Britain [3]. The temperature change on a greenhouse Earth might also be accompanied by an increase in solar irradiation. This may accelerate deterioration of organic materials such as paint coatings or materials used for consolidation of stone. Although

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the concentrations of “traditional” air pollutants have declined, changing climate could enhance their effects: e.g. changes in wetting and drying cycles on building surfaces alter the deposition rate of acidic gases, longer sunlight hours increase photochemical degradation of polymers (e.g. as restoration elements). The influence of temperature on the deterioration process for some materials, such as metals, is complicated. At low temperatures the deterioration rate increases with increasing temperature due to prolonged time of wetness. For some metals a maximum rate is followed by a decrease of the corrosion observed above about ◦ 9–11 C. However, this decrease is partly attributed to the faster evaporation of moisture layers after rain or dew periods. Additionally surface temperatures above ambient resulting from solar radiation reduce the time of wetness. It should however be mentioned that this phenomenon is not observed in marine locations where due to the presence of a surface moisture layer of hygroscopic chlorides. Here no maximum in the deterioration rate has been observed.

4 Water Derived Parameters As we have seen in the section above temperature can also influence some aspects of the water balance and humidity relations of outdoor materials. The hydro-meteorological parameters relevant to changing impacts on cultural heritage include: extreme precipitation events (a difficult parameter to predict, yet critically important in terms of predicting storm damage), saturation of soils and water loading on roofs and other architectural elements. For most materials an increasing relative humidity causes an increase in the deterioration due to a prolonged time of wetness, higher deposition rates of pollutants and more favorable conditions for microbiological activities. The Hadley model suggests rainfall in general is often likely to decrease slightly in Europe over the next century, particularly in the summer months. However, this potential for drier summers may be a little of an illusion in terms of cultural heritage. If we look at the predicted maximum daily rainfall we find the future looks as if it may have individual days that are much rainier. Figure 3 shows that number of days each year with large amounts of rain (>10 mm) is to increase. The frequency of very rainy days is predicted to increase over the next century. Predicted maximum daily rainfall amounts also increase, although these are not illustrated here as extreme events are more difficult to represent in the Hadley model. These heavy falls of rain in the future are likely to overload roofs and guttering and have the potential to cause local surface flooding. These represent an important threat to the built heritage in the future. It may be a particular problem for vernacular architecture constructed on unfired materials such as wattle and daub, adobe or cob. Precipitation can also affect the damage caused by wet deposition by dissolution of surface layers of materials. Erosion and delivery of acidity are important aspects of the role played by precipitation. Changes in the chemical composition and especially pH, can affect the deterioration rate of building material also.

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Events/year

25 20 15 10 5 0 1950

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Fig. 3 The number of heavy rain events (>10 mm) each year in the Czech Republic as predicted by HadCM3

We have already stressed that summers may have less precipitation. This also extends to relative humidity which is likely to be lower and changes the range of relative humidity cycles. Stone is especially vulnerable to relative humidity cycles. This arises because of damage caused by hygroscopic salts as they oscillate between high and low humidity. Lower humidity in the future means that the daily variations in humidity are more likely to cross critical values such as the 75.5% humidity where sodium chloride changes from a solution to a crystalline state. Figure 4 shows the number of times each year that humidity is likely to cross the critical 75.5% value that causes a phase change in sodium chloride in porous stone.

100 90 80 Cycles/year

70 60 50 40 30 20 10 0 1950

2000

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Fig. 4 The number times each year the relative humidity crosses the 75.5% value as predicted by HadCM3 for the Czech Republic

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This suggests a significant increase in these phase changes in the Czech Republic over the next century. The picture for central England is almost identical and these observations illustrate a potentially important and dramatic change in the rate of salt damage from sodium chloride. As with freezing we see once again that significant changes in damage to materials can be induced where there are phase changes. These occur at discrete values of temperature or relative humidity. Thus even slight changes in climate can allow these temperature or relative humidity values to be crossed more or less frequently. We saw earlier that the frequency of freezing is likely to decrease substantially in most places in Europe, even though the winter temperature change is only a few degrees. Similarly just small decreases in relative humidity can cause a large change in the number of time salts will crystallize or redissolve. However, drier summers might be favorable in reducing the time that building surfaces are wet, which could reduce the potential for pollution damage. Time of wetness has long been recognised as an important parameter in the action of pollutants such as sulfur dioxide. Humidity is also important in the degradation of organic materials, especially where biodeterioration is involved, with the Scheffer index- as a possible indicator of biological attack on organic materials [12]. The Scheffer index, which is the sum of the monthly temperature minus twice the number of wet days minus three, divided by an adjustment factor of 16.7 (i.e. (T−2)(Dw−3)/16.7). Figure 5 shows the change in the Scheffer Index for fungal attack for the Czech Republic and central England over the coming century. Increasing temperatures and lower rainfall rates in future summers imply increased evaporation and a reduction in soil moisture content. Drier conditions also suggest that the desiccation of unfired building materials could become an important concern. This may also have structural implications for building

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foundations and archaeological sites. Lower water tables are being noted by archaeologists [9]. When soils dry materials such as wood, which were waterlogged dry out and degrade very rapidly.

5 Wind Derived Parameters In gales stresses can cause elements of buildings to fail. Towers blow down and windows fall inwards. High winds blow rain almost horizontally and this wind driven rain can drive water deep into the fabric of buildings. In the same way close to the coast salt can be driven inland or in some areas abrasive sand can saltate and erode materials. These processes are complicated by the need to consider local winds, which are poorly predicted by existing large-scale models. Changes in winds also alter the eddies and flows around historical buildings and can increase the deposition rates of both gaseous and particulates pollutants. This when combined with rain can redistribute deposited diesel soot on facades and disfigure the building. Our initial analyses on a broad European scale have indicated only small changes in wind driven rain over the next century. However, it is likely that the relevant changes are being hidden by the coarse scale under consideration in HADCM3. One of the teams in the NOAHs ARK project is examining the effect of winds on towers, which may reveal the importance of changes in this parameter at a fine scale.

6 Conclusions The NOAHs ARK project assumed a decline for much of Europe in the concentrations of SO2 , NO2 , O3 , HNO3 and both primary and secondary particulates over the next century. A part of the project will test the validity of this assumption and see if the predicted pollutant concentrations will have effects under new climate regimes. In the early part of the project it became clear that temperature changes appeared not to have especially critical impacts on cultural heritage as even when temperature effects were amplified through freeze-thaw cycles these would be much reduced in the future. The early studies within the project have emphasized the importance of amplification mechanisms that allow quite small changes in temperature or relative humidity to significantly change the rate of damage to material. In particular we identified processes that are induced by phase change as important amplification mechanisms for heritage. The work draws also attention to the need for us to construct more sophisticated climate parameters. As an example we have been exploring the future frequency of what we have termed wet-frosts. A wet-frost occurs when porous stone is saturated by significant rainfall only to have a freezing event on the following day. Our early

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analysis suggests there are some regions of Europe, perhaps around the Black Sea where this may increase across the next century. Hydrometeorological parameters seemed likely to be more critical and we noted both increased heavy rainfall as critical for increased surface flooding and loading on roofs. Furthermore dry summers looked likely to increase the impact of humidity cycles (via salt crystallization) and potentially drying out unfired building materials and soils. So far our work has gathered modelled output that suggests changes in meteorological parameters that are of importance to cultural heritage. However, these changes need to be translated into rates of future material damage and then to risk if the work is to be useful to managers and policy makers. Furthermore the output needs to be displayed as user-friendly maps of future damage in Europe rather than analysis of individual grid squares from the Hadley Model that have been adopted here. Acknowledgements This work forms part of a eu Framework 6 project -ct-2003-501837NOAH’S ARK: Global Climate Change Impact on Built Heritage and Cultural Landscapes. We are also very grateful to the other teams of the Noah’s ark consortium for their contribution to developing this research.

References 1. Bonazza A, Brimblecombe P, Grossi CM, Cristina Sabbioni C (2007) Carbon in black layers at the tower of London. Environmental Science and Technology 4(12):4199–4204 2. Brimblecombe P (1999) History of urban air pollution. In: Fenger J, Hertel O, Palmgren F (eds) Urban air pollution – European aspects. Kluwer, Dordrecht, pp 7–20 3. Brimblecombe P (2000) Air pollution and architecture, past, present and future. J Archit Conserv 6:30–46 4. Cassar M (2005) Climate change and the historic environment. Centre for Sustainable Heritage UCL, London 5. Grossi CM, Brimblecombe P, Bonazza A, Sabbioni C, Zamagni J (2006) Carbon fluxes and transformation in black layers of historical buildings. In: Heritage weathering and conservation. Taylor and Francis, London, pp 441–446 6. García Fernández E (ed) (2001) Arquitectura solariega Asturiana. Gráficas Summa, Sedes, Llanera, Asturias 7. Johns TC, Gregory JM, Ingram WJ, Johnson CE, Jones A, Lowe JA, Mitchell JFB, Roberts DL, Sexton DMH, Stevenson DS, Tett SFB, Woodage MJ (2003) Anthropogenic climate change for 1860 to 2100 simulated with the HadCM3 model under updated emissions scenarios. Clim Dynam 20:583–612 8. Parker DE, Legg TP, Folland CK (1992) A new daily central England temperature series, 1772–1991. Int J Climatol 12:317–342 9. Sauer E (2005) Alchester – in search of Vespasian. Current Archeol 196:168–176 10. Trudgill ST, Viles H, Inkpen R, Moses C, Gosling W, Yates T, Collier P, Smith DI, Cooke RU (2001) Twenty-year weathering remeasurements at St Paul’s Cathedral, London. Earth Surf Proc Land 26:1129–1142 11. Walder J, Hallet B (1985) A theoretical model of the fracture of rock during freezing. Geol Soc Am Bull 96:336–346 12. Wilcox WW, Dietz M (1997) Fungi causing above-ground wood decay in structures in California. Wood Fiber Sci 29:291–298

Cultural Landscapes and Conservation Issues: Side Case Elmas Erdogan

Abstract Side which is one of the oldest settlements in the Mediterranean Region is a sub settlement located within the boundaries of the province of Antalya with the Taurus Mountains to the north, the Mediterranean to the south and the Manavgat River to the east which was known as Pamphylia in antiquity. The settlement was established on a peninsula about 1 km long in southeast direction having 350–400m wide. Due to its special location, Side was the only harbour city of Pamphylia region and became an important harbour and commercial centre in antiquity. Side which is 70 km from Antalya and 7 km from Manavgat town can be reached both by land, sea and air. In the ancient language of Side, “Side” meant pomegranate which was also the amblem of the city in ancient times. This fruit was depicted on the city coinage from about 500 BC till to Roman imperial times [8]. The historical background of the settlement dates back to the second half of the 7th century BC and according to Strabo, Side was founded by the inhabitants of Kyme – Aliaga, ˙Izmir. Side reached the climax of its glory in the 2nd century and the first half of the 3rd century AD. So, the most magnificent buildings in the settlement were erected during this phase of the Roman Era and Side became a metropolis. In the middle of the 4th century, an inner city wall was constructed across the narrowest part of the promontory which caused the abandonment of the north eastern part of the peninsula. During the 5th and 6th centuries, the settlement extended beyond its original limits. In the 7th century, Arab pirates began to damage the city and the settlement was destroyed in the 9th and 10th centuries resulted with the emigration of the inhabitants. So, by the 12th century, it was completely abandoned and ruined also as the result of several earthquakes. The Seljuks, dynasties and Ottomans were not inhabited Side so that no remains of these periods are to be found in the settlement. The buildings survived were covered by sand and weeds in time. In 1895, Turkish immigrants

E. Erdogan (B) Department of Landscape Architecture, Faculty of Agriculture, Ankara University, Di¸skapi Ankara 06110, Turkey e-mail: [email protected]

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from Crete established a small village spreading over the peninsula called Selimiye and integrated to the whole area. In recent years, along the coast, as a hot tourism spot, Side was noticable with its tourism potential and unhealthy construction activities giving harm to the existing rich urban pattern. Side is an impressive coastal settlement both reflecting the macroform of an antique settlement and Turkish vernacular architectural qualities forming a unique cultural landscape area with its flora and typical Mediterranean dune and maquis vegetation combined with the antique landscape of the peninsula. However, the quality of the townscape and the coastal landscape of the area is eroding rapidly day by day under the constraints of dense tourism activities and defective land uses. In this article, Side will be presented with its historical, archeological and natural qualities. The development of the settlement through history and changes in landscape will be given. Then, its problems and potentials defined by site analysis studies will be emphasized and conservation issues of cultural landscapes will be discussed both in general and in Side case. Keywords Conservation · Culture · Landscape

1 Introduction 1.1 Geographical Situation Side is an ancient settlement of Pamphylia region of Anatolia. Because of the fertelity of the land, the region was used as a settlement till prehistoric times (Fig. 1). Although the role of the Hittites lived in central Anatolian region was unknown, it was evident that the language that they spoke was also used in Pamphylia region. The coastal regions of Pamphylia were used as settlements by Aka civilizations during the 14th and 13th century BC. Then, the region was conquered by the Greeks in 12th century BC and the region was named as Pamphylia meaning the land of all civilizations [3]. The other cities of Pamphylia are Attelia (Antalya), Perge, Syllion, Aspendos, Side and Lybre (Seleukeia). Today, the town of Side consists the antique Side settlement and Selimiye village together. The name of “Side” derives from the name of promegranate is of Anatolian origin and was not associated with Greek or Phoenician. The symbol of blessing which can be seen on a number of artefacts and depicted on the city coinage from about 500 BC to Roman imperial times [2]. The colony was set up during the period of large scale emigration from the cities of western Asia Minor. It’s geographical siting on a peninsula is further indication that the colonists came from the western seaboard of Anatolia, where almost all cities were located on offshore islands or on narrow necks of land [1]. From 1947 to 1966, systematic excavations were carried out by professor Arif Mufit Mansel. After his death, the excavations were directed by professor Jale Inan. Important structures worth seing today are the tamples of Apollo and Athena, Side theater, city gates, acqueducts, the harbor of Side, the monumental fountains, Side bath and the traditional houses of Side built in the peninsula [7] (Fig. 2).

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Fig. 2 General views from Side

1.2 History According to Strabo, Side was founded by the inhabitants of Kyme, an Aeolian city located north of Smyrna. Soon after their arrival, the colonists from Kyme began to speak a barbaic dialect which was probably the original Anatolian tongue of Pamphylia. Greek became the official language in Side after its conquest by Alexander the Great, as is proved by inscriptions on stone dating back to 3rd century BC. The settlement dates back to the second half of the 7th century BC. Although Side was under Ptolemaic and the rivalry existing between the Hellenistic rulers Attolos II, the king of Pergamon (159–138 BC) founded Attelia (Antalya) to gain control of the southern coasts of Anatolia. Nevertheless, Side didn’t come under the sway of Pergamon at no time. On the contrary, in the 2nd and 1st century BC. Side enjoyed its firsy period of prosperity, continued good relations with Rome [1]. According to Akurgal [1], the wall marking the greatest extend of the city to the east must have been erected during this period. Side reached the height of its glory in the 2nd century and the first half of the 3rd century AD. The most magnificent of the city buildings were erected during this phase of the Roman era. In the middle of the 4th century, an inner city wall was constructed across the narrowest part of the promontory between the theater and the agora buildings thus reducing the city to half its former size so, the north-eastern part of the peninsula was abondened.

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The revival of the city has occured during the 5th and 6th centuries. After, it had become the centre of a diocese and during this period, the settlement extended beyond its original limits. In the 6th century BC, like the whole of Pamphylia, Side fell first under the domination of the Lydians and upon their collapse, of the Persians in 334 BC, the city surrended to Alexander the Great without any resistance and became the centre of one of his principal coin mints. After the death of Alexander, Side became the subject of struggles between the Hellenistic kingdoms. After 218 BC, the Seleucids dominated in the city and in 118 BC, Side was given to the kingdom of Pergamon and at that period, it developed commerce with eastern Mediterranean countries and became wealthy; the city was rebuilt and became the centre of science and culture. However, this was not of long duration. In the 1st century BC, pirates overran the area and gave harm so, in 78 BC, Side was included to the Roman empire. After the year 25 BC, the Pamphylia region became a seperate province of the empire. In the 2nd–3rd centuries AD. Side became a metropolis and began to live golden age with its great progress. Towards the end of the 3rd century AD, the tribes living in the northern region began to mander down the coastal regions. A newly constructed wall divided the city into two parts and the population moved to south. During the 5th–6th century AD, the city became the diocesan centre of eastern Pamphylia, and the walls built during the Hellenistic period were extended. In the 7th century, Arab pirates began damaging the most significant buildings and the people of Side gradually began to emigrate particularly to Antalya [3]. By the 12th century, Side was completely abandoned and ruined as the result of several earthquakes. The Seljuks having beaten the crussaders, took over the entire region in the 13th century; but, Ottomans held the region in 1391. However, neither the Seljukids nor the Ottomans ever inhabited in Side, therefore, no remains of these civilizations found in Side. The buildings ruined during the earthquakes were covered by sand and weeds. In 1895, Turkish immigrants from Crete founded a village on tip of the peninsula and settled there which is the core of the today’s village that spread over the entire peninsula and named as Selimiye. The ancient ruins and the village houses are forming the actual cultural landscape of the settlement. But, the settlement is and its natural qualities are deterioriating continiously under the pressure of tourism.

2 Cultural Values of Side 2.1 The City Plan Side has a memorial avenue (collonaded street) beginning at the city gate and passing through the whole city, reaching the seashore (Fig. 3). Almost a regular plan type was used. The main street starts from the main gate situated on the northeast side of the peninsula and passed near the theater. Then, after the second passage here continues diagonally towards the end of the peninsula in north-south direction. Both streets were collonaded and porticos took place on both sides of the road with rows

Fig. 3 Reconstruction drawing of Side antique settlement

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of shops behind. The part of the collonaded street between the main gate and the theater which remained today was used as the main road today and some columns and traces of the shops are existing. However, the remaining part of the collonaded street was destroyed during the Byzentine period and a great part of it is also under the sand dunes. Although the traces and ruins of some buildings are existing in the south section of the city, traditional houses were built through history combined with the antique site. Two collonaded streets built in 2nd century AD in corinthian order led into the city from the main gate. The one running to the south is now overgrown; the other one leading to the agora is still in use today connecting the parking lot to the city center and there is a building with a sacred fountain on this street dating back to 5th or 6th century AD. On the south side of this collonaded street there are the ruins of two peristyle plan type houses consisting courtyards surrounded with rooms. According to Akurgal [1], these houses were built in the 2nd and 1st century BC and they continued to be used in the Roman period also. They were restored and reinhabited in the 5th and 6th centuries. There are also the ruins and traces of the shops on the south side of the collonaded street. The city has a developed sewerage system whose remains can be seen today even in the narrowest roads. The water was supplied from the Manavgat River via holes carved into rocks, tunnels and acqueducts crossing over valleys which was 29 km in length.

2.2 Walls and Gates Side was surrounded by walls both from the land and seaward sides so that they were known as land or seaward walls. The walls have been largely destroyed especially on seaward side. These walls were built during the Hellenistic period but, reconstructed with reused material during the late Roman period. The inland walls dividing the peninsula are under sand. The gates were built on the inland walls. One of them is the great gate which is the main entrance gate of the city was damaged. The second largest gate was the east gate situated on the east side of the city. In the 4th century AD, when the city became impoverished and reduced in size, a wall was constructed of reused material across the narrowest part of the peninsula cutting the city in half [3]. City walls of Side were built of regular brick blocks in the 2nd century BC during the first period of prosperity of the city. The best preserved parts of the wall can be seen in the “main gate” section where it is reinforced by towers at irregular intervals and decorated by a cornice-moulding on the outer face. The section of the wall on the three seaward sides of the peninsula has undergone considerable modification and some parts were completely renovated during Roman and Byzentine periods. The part running across the neck of the peninsula was constructed in the 4th century AD [1]. Main city gate consists four small doors; two at each end of the semi-circular wall around the courtyard. City fountain/the nympheum opposite to

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the main gate is similar to that at Aspendos which gives clue about its construction date of the fountain.

2.3 The Acqueduct, Cistern and Fountains Water was supplied to Side from the Manavgat River by means of acqueducts built in 2nd century AD. The water was brought by tunnels dug through rocks and earth flowed along the two main collonaded streets in channels and distributed to baths and fountains. Besides, many wells were formed in houses and on street corners. Acqueduct, supplying water to the city from Manavgat River was probably built in the last years of the 2nd century AD. The sections of the acqueduct between the source and the city are still standing and are in good condition. A great part of the acqueduct was restored in the first quarter of the 3rd century AD. In the western front of the agora, there is a monumental gate and three fountains constructed in Roman period with decorative facades are forming an impressive passage with its water basins between four bases each supported an aedicula containing a statue. Besides, between this fountain and the eastern inner wall of the monumental gate lie the remains of semicircular building covered by a half dome and a cistern to the northwest of the mentioned fountain is dating back to Byzentine period. In this part between the theater building and the city walls, there is a monumental arched entrance gate giving access to the inner city in Roman times.

2.4 The Harbour As Side was a commercial center, the harbour dating back to Hellenistic era was an important part of the city constructed on the south eastern end of the peninsula. Actually, the harbour is largely buried on sand. In order to protect the harbour from the southwest waves a breakwater was constructed which its entrance is about 10 m wide and the city wall built in 2nd century AD was standing on the harbour in ancient times filled up with sand very frequently and had to be cleaned so, rather than cleaning this harbour they built a new one on the northeastern section of the old one.Three openings were left both for the passages of the skips and to drive out the sand. This section which is partly reinforced by the harbour is using by the inhabitants and fisherman today.

2.5 The Tamples The tample of Apollo and the Tample of Athena constructed in corinthian order were situated at the end of the collonaded street near the seashore are in ruins. Only the stylobates of the tamples and the ruins of the columns are existing. Tample of Apollo was partially restored to give an idea about the architectural character of a tample structure of thr period and contributing the quality of the cultural landscape

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of the settlement. On the other hand, a basilica was built on the foundations of these tamples during the Byzentine period but, ruined. 2.5.1 The Tample of Athena As mentioned in ancient documents, Athena was the main deity of Side. According to mythology, Athena was born from the head of Zeus and known as the protectress of young girls so that, the largest tample was built to her in Side (Fig. 4). The tample of Athena was erected on the eastern side of the harbour next to the end part of the collonaded street. The tample was built in corinthian order with a rectangular plan scheme surrounded with three steps mounting to the stylobate. Both in front and at the rear, there used to have 6 + 11 columns [3]. 2.5.2 The Tample of Apollo Near the tample of Athena, another tample was erected to Apollo; the god of light, knowledge and arts. The tample that built in 2nd century AD used to have 6 + 11 columns in the peripteros style but, damaged in time [3]. Today the tample of Apollo was restored and partially reconstructed. 2.5.3 The Tample of Men The semi-circular plan schemed tample dedicated to the moon god was built on the southern end of the square. There is a ceremonial stairway in front of the main sacred room (cella). Six columns between the cella and the platform carrying the upper structure with a pediment in front were mainly demolished in time. According to Atvur [3], the tample of Men was also built in the 2nd century AD. 2.5.4 The Tample of Dionysus The tample of Dionysus; a small scaled tample was built between the collonaded street and the theater building on the north side of the theater to the wine god

Fig. 4 Tample of Apollo, Side

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Fig. 5 Theater, Side

Dionysus. The tample was reached by a step stairway from the north direction. Four columns were built in front of the cella. Today, only the base/stylobate is existing (Fig. 5). The base of the Dionysus Tample is lying between the theater and the collonaded street continuing through the peninsula ending by the seashore. Along this collonaded street, on the east side of it the ruins of a basilica and in the inner settlement between the collonaded street and the seashore; the ruins of harbor baths are seen. 2.5.5 The Round Tample/Tholos Tample The round tample is situated on the agora facing the bath building with a single cella/cult room surrounded by 12 columned elevated portico. It was reached by means of steps. Only the stylobate of the tample is existing. According to Atvur [3], it was built in 2nd century AD and was dedicated to the goddess of good fortune.

2.6 The Theater Today, the theater is one of the two most impressive building of the ruins in Side peninsula on which the other one is the Tample of Apollo. Theater building is a Roman type theater dating back to the 2nd century AD built on a barrel vaulted substructure with superimposed arches on the facades. Side theater was built on the narrowest part of the peninsula in the middle of the settlement. Side theater is a unique example in Anatolia and even in the Mediterranean as far as construction technique is concerned. The second tier of

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Fig. 6 Bath building, Side

the structure stands entirely on vaults wheras the other theaters of the period were usually built on a natural slope (Fig. 6). The cavea consisting the seating area, the semi-circular orchestra and partially the scene portion of the theater building are existing. The cavea was two-tired and combined with a diazoma. The inner gallery containing the staircase leading to the upper tier is entirely in ruins wheras the outer gallery have 14 shops or stores and 5 entrances. In front of the orchestra, the scene building that used to be three storey was destroyed. Only first storey was existing and a passage way was constructed here to join the theater building to the agora. As the theater has a good acquistic quality, actually the theater is using for concerts, festival organisations, cultural and social activities.

2.7 The Agoras There were two big agora buildings in Side one in the northeastern side of the collonaded street adjacent to the theater and another built between the theater building and the palace buildings known as the state agora which is smaller in scale. Both agora buildings have square plan schemes with inner courtyards surrounded by stoa spaces or porticos on which shops were placed at the back parts. The agora situated

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on the east side of the theater was built in 2nd century AD [6]. This building which was the market place of the city has a central courtyard surrounded with collonades and shops behind them is now represented only by their foundations.

2.8 The Baths There were three bath buildings in Side namely the harbour baths, the great bath and the agora baths (using as museum today). The harbour baths were the oldest baths in Side built in 2nd century AD, built on the northeast end of the harbour. A great part of the building is still existing. Calidarium (hot bath), tepidarium (warm bath) and frigdarium (cold bath) sections of the bath building can be easily determined from the existing remains. The great bath is the largest one in Side built in the 3rd century AD. Also a great part of the bath building is existing. Apodyterium (dressing rooms), tapidarium (warm bath), frigdarium (cold bath), caldarium (hot bath), hot water basins and the palaestra (sports practicing area) are existing. Just on the opposite side of the agora; on the other side of the collonaded street are the ruins of the baths dating back to 5th century AD. According to Akurgal [1], it is now restored and serving as a museum exhibiting sculptures of Side antique site. The agora baths were built in the 5th century AD on the collonaded street facing the agora. This building is the most recent bath of Side which is used as a museum today (Fig. 7). The agora bath has five large sections formed of frigdarium with a round pool, laconium (dry air bath), caldarium (hot bath with two pools), tepidarium (warm bath) and the palaestra. Caldarium is the largest room of the bath and underneath the marble floor, there is the hypocastum used for the purpose of heating the bath. On the other hand, under the swimming pool built into massive walls are hot air pipes to keep water hot [3].

2.9 The Basilicas Three great basilicas were built in Side in the Byzentine period namely the South Basilica at the southern tip of the peninsula that was mainly destroyed, the Theater Basilica; located on the west side of the collonaded street near the theater, and the Archbishop’s Basilica that was built at the corner where the second collonaded street starting from the main gate and extending to the left meets the street commencing at the eastern gate.

2.10 The Monumental Fountain/Nympheum The monumental fountain/nympheum was situated opposite to the main gate outside the city walls. It was built in the mid 2nd century AD. The nympheum which had three tiers in original remained as two tiers. The water was conveyed by lead

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pipes from the acqueduct near the city wall to the fountain and than poured into the basin (Fig. 8). There is also another fountain next to the museum building near the formerly built agora baths. This fountain is also known as “triple basin fountain” decorated with marble statues. There was a fountain to the west of this one with a circular basin and a nische completed with a half dome. Facing these two fountains is a third one near the triumphal arch which was the city gate. A semi-circular nische with two pediments on each side of it is consists the Vespasianus Monument which was brought from another place and used in the construction of this fountain built in a later period.

2.11 The Houses The remains of the houses in Side were found 20–30 m north of the greater agora building. According to the excavations, the houses have collonaded inner/central stone paved courtyards and rooms around. The houses were mostly two storey houses with peristyle plan schemes. All the houses have sewerage systems, service spaces and rooms for various activities. And there are the ruins of Side baths and Byzentine houses on the east side of the collonaded street near the seashore. Side has been an important settlement especially during the Roman and Byzentine periods.

2.12 The Necropolis The necropolis area of the city is situated outside the inland walls occupying a large site between the eastern and western shores and consists graves belonging both Roman and Byzentine civilizations. Side’s prosperity was reflected in the necropolis due to the clues obtained from the remains of the monumental tombs and types of graves.

3 Cultural Landscapes and Conservation Issues/Conclusion Cultural landscape is a geographic area including both cultural and natural resources and wildlife therein associated with a historic event, activity or exhibiting other cultural or aesthetic values. Cultural landscapes can be classified into four main groups namely historic sites, historic designed landscapes, historical vernacular landscapes and ethnographic landscapes. The landscape quality of Side can be considered significant because character defining features such as the ruins of the antique settlement and plantation conveys its significance possess historic integrity. Location, setting, design quality, building material, construction technique determines the character of the Side cultural landscape with its historic integrity. Preservation planning for Side involves

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a broad array of dynamic variables. So, a comprehensive treatment and management plan with a preservation maintenance strategy should be prepared acknowledging cultural landscapes ever changing nature, management and maintenance. There is a balance between change and continuity in all cultural resources. Change is inherent in all cultural landscapes as a result of natural proceses and human activities [4]. The dynamic quality of cultural landscapes is balanced by the continuity of distinctive characteristics retained over time. Side is a cultural landscape consisting an archeological site; an urban pattern/settlement reflecting cultural traditions and the physical evidences of this civilizations. Side consisting an antique urban area, component landscapes and features contributing to its significance and historic character should be considered prior to treatment. The cultural landscape context of Side includes the overall pattern of an antique city, the ruins of buildings such as the tamples, theater, bath buildings, fountains, circulation networks, etc., views and vistas into and out of the landscape and natural features. Besides, Side has a historical vernacular landscape quality with its traditional houses built with stone and timber in the Selimiye Village combined with the antique settlement. Side not only has historical value, but can also reveal significant information about a cultural landscape. Cultural landscapes are composed of natural, historical and cultural features organized in space. They include small scale features as well as patterns of urban tissues, fields, forests which define the spatial character of the landscape. The individual features in the landscape should never be viewed in isolation, but in relationship to the landscape as a whole. The arrangement of the interrelationship of these character defining features as they existed during the period of significance that is most critical to consider prior to treatment. The modern concept of cultural heritage is related to the whole built environment and should be seen in ecological context of the world. The conservation of cultural heritage is a socio-cultural problem. Conservation involves making interventions at various scales determined by the physical conditions. Each case must be considered as a whole and individually taking all factors into account [5]. Since physical cultural heritage is one of the Turkey’s most important non-renewable resources, a special effort is needed to redress the imbalance between the needs of mankind and its protection. Cultural landscapes consists of different type of properties which relate to a variety of settings; they include not only important monuments and structures, historic areas and gardens, but also the man-made environment as a whole. Cultural heritage resources may be associated with different values depending on the context, thus their treatment differ from case to case. Combined works of nature and man and including archeological sites which are outstanding universal value from the historical, aesthetic, ethnological or anthropological points of view. The whole of archeological sites should thus not be considered only in relation to an architectural framework; it should also include the human value related to its social and economic context. These areas require particular study and consideration. Fragile features should be treated sensitively in rehabilitation. Every archeological site and its surroundings should be considered

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in their totality as a coherent whole with its specific nature, spatial organization and the surroundings. Authenticity is another curical aspect of the cultural landscapes/archeological sites in the assessment of heritage resources. Authenticity is ascribed to heritage that is metrially original or genuine and as it has aged in time. Authenticity in design, material, workmanship and in setting should be preserved/kept. Cultural values have identity value, relative artistic or technical value, rarity, economic, functional, educational, social and political values that should be considered as indicatives. Landscape features should always be assessed as they relate to the property as a whole. Thus, spatial organization and land patterns of Side are always taken into considerarion at first stage. In this respect, Side peninsula consisting an archeological settlement, vernacular houses and the Mediterranean plant species combined with the built environment should be conserved as it is. On the other hand, • the rhythym and the morphological pattern of the surrounding fabric, the relief of the area/site should be kept • artificial combinations should be avoided • mass balance of the cultural landscape must be conserved • silhouette reflecting the traditional lical character should be protected • traditional building material, the high quality in construction and design should be taken into consideration • factors related to townscape should be conserved as the parts of the landscape to transfer these environmental and cultural resources to future generations as the traces of past and present.

References 1. Akurgal E (1985) Ancient ruins of Turkey. From prehistoric times until the end of the roman empire. Turk Tarih Kurumu Basımevi, Ankara 2. Anonymous (2000) 2nd Side International Culture and Art Festival Book. Republic of Turkey, Ministry of Culture and Municipality of Side, Antalya 3. Atvur O, Atvur U (2000) Side. A guide to the ancient city and the museum. Secil Ofset, Istanbul 4. Bırnbaum CA, Madıgan KJ (1996) The secretary of the ınterior’s standarts for the treatment of historic properties with guidelines for the treatment of cultural landscapes. U.S. Department of the Interior, National Park Service, Heritage Preservation Services, Washington, DC 5. Fleıden BM, Jokıletho J (1993) Management guidelines for world cultural heritage sites. ICCROM, Rome, Italy 6. Mansel AM, Bosch E, Inan J (1951) Side Agorasi ve Civarındaki Binalar. TTK Basımevi, Ankara 7. Mansel AM (1978) Side. TTK Basımevi, Ankara 8. Yildizturan M (2003) Side. (Attelia-Perge-Silyon-Aspendos-Lyrbe, Manavgat, Köprülü Kanyon). T.C. Kültür ve Turizm Bakanligi, Kültür Varliklari ve Muzeler Genel Mudurlugu, Side Muzesi Yayinlari 1, Donmez Ofset Basimevi, Ankara

Survival of the Vernacular Environments in North Cyprus Through Sustainable Tourism Implementation Özlem Ogaç Türker

Abstract Today while the discussions are more concentrated on the reduction of environmental resources, the sustainability concept is gaining importance especially in today’s architectural developments. The acceleration in the building activities on North Cyprus creates the discussion of continuity in both natural resources and the cultural heritage of the island. Due to the lack of a conservation master plan, the traditional/vernacular environments of North Cyprus are under the threat of these rapid unplanned developments. Sustainable approaches include the adaptive re-use of existing building stock especially if this building stock is worth preserving since it is the reflection of a multi-cultural accumulation of different sovereignties1 through many centuries; and since it is the result of design principles that are evolved and developed through centuries, according to the environmental factors in addition to the cultural ones. The unique vernacular environment of the Island bears the potential to be learned from the tried, developed and evolved architectural solutions. For centuries, the Cypriots have benefited from both conscious and unconscious design criteria in shaping their living environments. Evaluating those decisions in the light of today’s discourse, sustainable identity of these environments can be emphasized in terms of locality, energy and resource efficiency of the building materials. In the light of right design decisions on location, orientation and formation; appropriateness to the natural and cultural environment has been achieved. The vernacular environments, as well as the previously untouched coastline of North Cyprus can be destroyed by the unplanned new constructions, causing demolishment in the vernacular environments as well as the flora and fauna of the island. As demand increases in the area, an interest in modernization, densification or reconstruction of existing traditional environments may come to a reversible level. In this study, it is aimed to

Ö.O. Türker (B) Department of Interior Architecture, Eastern Mediterranean University, Gazima˘gusa, Northern Cyprus e-mail: [email protected] 1 Throughout the history, Cyprus had been inhabited by the people from different cultural backgrounds ranging from Persians, Egyptians, Romans, Frankish, Venetians, British and the Ottomans [10].

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discuss the survival of these unique rural vernacular environments of North Cyprus through sustainable tourism implementations. Keywords North Cyprus · Sustainable tourism · Vernacular architecture

1 Introduction The island of Cyprus of which northern part is isolated geographically, socioeconomically as well as politically from the international arena, exhibits different dimensions and aspects of globalization. When the current living style, tastes and preferences of local people and the prevailing power of media upon them are considered, the recent building activities in Northern Cyprus could be explained in regards to erosion of “tradition”, mobility of “tradition” and adaptability of “tradition” [24]. Furthermore, the negotiation process on the Annan plan2 and the goal of EU membership of Cyprus have accelerated the construction sector and hence, foreign investors attacked to Northern Cyprus due to the cheap land and property prices compared to other European countries. This process, parallel to the general change in the residential environments, dictated by globalisation, deeply affected the tourism sector as well. Being the third largest island in the Mediterranean, Cyprus has the inherent Mediterranean attributes of climate and location. Hence the southern part of the island is a highly developed tourist destination. The high-density building and ribbon development in areas such as Larnaca and Paphos, have contributed to an over-supply of tourism facilities creating insensitive concrete masses. Other famous tourism centres of Southern Cyprus, such as Agia Napa and Protaras show the examples where tourism has negative effects on the locality. Originally being small traditional settlements, they have been converted to completely unfamiliar environments in the concept of entertainment. One can hardly notice local values as a reflection of the Cypriot culture [22] (Fig. 1). On the other hand, unlike other Mediterranean countries with such tourism resources, North Cyprus remained relatively undeveloped for tourism. The North

Fig. 1 Agia Napa & Protaras tourism developments [23]

2 Annan plan was the proposal which was generated by and named after the UN General Secretary, Kofi Annan, and consequently approved by the UN Security Council for the reunification of two societies in Cyprus Island.

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Cyprus constitutes 38% or 3,355 km2 of Cyprus, and it possesses many of the island’s best natural and cultural resources. In addition, it contains 55% of the island’s coastline; the spectacular Kyrenian Mountains with their associated rich natural history [25]; and the generous Turkish Cypriot hospitality. The valuable tourism assets such as the landscape aesthetics and ecological, wilderness and cultural indicators, contribute to the “unspoilt” product label given to the North Cyprus by tour companies in the UK and Germany. Up to recent years the indefinite political situation and the lack of economical welfare of the Northern Side was an advantage for the vernacular environments for preserving their originalities when compared with the Southern side. As stated by Sadler ([20], p. 147), this can be an advantage when applying alternative natural resource-based tourism objectives, provided that political and economic influences can favour sustainable planning. However the spread of mass-tourism accelerated building activities in North Cyprus as well, generating even holiday villages, recreation areas, a number of fivestar thematic hotels especially in Bafra region. As Feilden [9], mentions, five-star package travel clientele are the least sensitive to the local community as they wish to impose their own cultural standards. Five-star hotels depend on international finance so give little benefit and interest to the local community or the local environment. Hence the ongoing tourism developments in Bafra region in the north of Cyprus are standing at a very challenging position for the decision makers in terms of balancing the destructive and constructive impacts of tourism on rural vernacular environments of North Cyprus [23] (Fig. 2).

Fig. 2 Bafra tourism developments [21]

2 The Positive and Negative Effects of Tourism on the Vernacular Environments The positive effects of tourism are the development of cultures; and communication among different cultures; preservation and enhancement of cultural resources; providing labour possibilities by increasing employment; developing environmental

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quality by re-creative facilities and strong social relations [19, 13] (Kükrer, S., ¸ 1991, Tarihi Kentte Koruma ve Turizm Etkile¸simi ve Kaya Köy Örne˘gi, unpublished). Tourism is dynamic but if developed too quickly it can be destructive to the host community. Because of inadequate planning, wrong policies, and wrong administration, it destroys the resources and values which were what attracted visitors in the first instance. These negative impacts can include: • deterioration of the natural, cultural and architectural environment if they are not properly managed; • changes in the natural topography; flora and fauna; • environmental pollution types as air pollution, water pollution, rubbish, visual and noise pollution in natural environment; • depletion of social and cultural resources by the effect of acculturation in longterm cultural contact; • the hostility of residents; and social discrepancies; • inappropriate tourism development and overloaded tourist capacity that harm the unity; cause vandalism; and decrease in the picturesque values of old settlements and buildings; • increase in prices for housing and other commodities; and investment of public funds which often requires borrowing and servicing costs for police, fire, and sewage treatment; and traffic congestion (Kükrer, S., ¸ 1991, Tarihi Kentte Koruma ve Turizm Etkile¸simi ve Kaya Köy Örne˘gi, unpublished) [9, 13]. Consequently, the vernacular environments, as well as the previously untouched coastline of North Cyprus can be destroyed by the unplanned new constructions, causing demolishment in the vernacular environments as well as the flora and fauna of the island. As demand increases in the area, an interest in modernization, densification or reconstruction of existing vernacular environments may come to a reversible level unless a sustainable approach is implemented urgently.

3 The Reasons to Sustain the Vernacular Architecture of Cyprus Rural vernacular forms remained consistent with a response to agrarian way of life and natural environment of the island for ages; hence, the building form of the rural house is reflecting the geographical, topographical, climatic parameters and availability of building materials. The traditional house is a synthesis of different building traditions, which were engaged with adobe and masonry building techniques. The concept of development from the private interior (domestic core of the family) to semi-private defined yards to public exterior (public urban area) had been the fundamental formula controlling the spatial organisation of the vernacular settlements (Türker, Ö.O., 2002, A model for the conservation and continuity of a vernacular settlement: Kaplica village, North Cyprus, unpublished).

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In most of the houses, semi-open/semi-closed transitional space remained as the fundamental spatial component leading the space organisation both in rural vernacular settlements. These semi-open/semi-closed spaces served for transitions between indoor and outdoor, private and public, micro-climate and climate. In the absence of a semi-open/semi-closed transitional space, the defined courtyard took over this role. Besides spatial qualities in answering the functional needs, environmental consciousness is also noticeable in the vernacular houses of Cyprus. Cross ventilations of indoor spaces considering preferable summer breeze, shutters in the opening formations, upper ventilation holes for exhausting hot air, and forming physical barriers for preventing undesirable winds, especially during the winter periods, are the parameters which dominated the space formation. The traditional materials such as stone and earth in the construction of the load bearing walls provided appropriate micro climate for the human comfort inside the closed space, where the traditional thick walls, as well as the layered roofs acted as a natural heat barrier in the rural houses [16, 4] (Türker, Ö.O., 2002, A model for the conservation and continuity of a vernacular settlement: Kaplica village, North Cyprus, unpublished). On the other hand, modularity and modular organization gains much more significance in the development of rural house form as a fundamental design strategy. The linear modular combination of spaces expresses the development features of the rural house form [17, 5]. The modularity of the house ensures the flexibility as an answer to possible functional changes due to the family growth. The direct reflection of this modularity to the façade let the development of the most known image of the Cypriot house as the arcaded prism (Fig. 3). The deterioration of existing pattern, as well as the inappropriate developments, is expected to increase in the vernacular environments of North Cyprus, parallel to the growing tourism demands unless a strategic planning is envisioned (Türker, 2002, A model for the conservation and continuity of a vernacular settlement: Kaplica village, North Cyprus (unpublished)). In this respect, the revitalization of the vernacular environments with the adaptive re-use of their existing traditional dwelling stock can be an answer for the sustainability of cultural values instead of demolishing them under the threat of new insensitive concrete masses [2, 1]. Many scholars, like Echeverria [8], point out that tourism is virtually the only

Fig. 3 Modularity on plans and elevations of rural vernacular houses [6]

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resource that can be tapped to finance architectural conservation as a precaution to the deterioration of the historic environments. Instead of passive conservation, revitalisation by means of sustainable tourism implementations can be recommended for unique vernacular environments to be carried into future. By a conservation program including the revitalization and adaptive re-use of old building stock for sustainable tourism uses, the deterioration of the vernacular environments will be prevented; the destruction of local fabric will be exterminated and contemporary life conditions will be provided in addition to serving alternative tourism purposes.

4 Sustainable Tourism Developments in the World Communities, regions, and countries do benefit substantially from the proper planning of tourism and will do so more in the future. In an increasingly competitive tourism the world that is also concerned about maintaining the resources for tourism, the places with the best planned tourism development are likely to be the most successful tourist destination from the standpoint of both achieving high tourist satisfaction levels and bringing substantial benefits with minimal disruptions, to the local economy, environment, and society ([12], p. 17). Tourism can be sustainable as long as certain irreplaceable natural and cultural elements are protected by policies and legislations. At the roots of the concept of sustainable development is the notion of carrying capacity. This can be depicted as “the maximum number of people who can use a site without an unacceptable alteration in the physical environment and without an unacceptable decline in the quality of experience” ([14], p. 88). Sustainable tourism planning is complex and difficult because practically all natural resources in a given area are part of the product. Essentially, tourism planning is dynamic and the related processes and impacts are susceptible to change. Conversely, sustainable development implies a degree of stability and permanence. As stated by many authors as Echeverria [8], Feilden [9], Eber [7], some principal points about sustainable tourism development are: preservation of the natural resources; reduction of over consumption and waste; the need for need diversity; and the need for tourism development to be integrated with other economic and development activities. Eber [7], also mentions that tourism development should support local economic activities and take environmental and social costs and values into account, and contribution of local people to tourism experience itself. In this respect, when sustainable tourism is mentioned it includes conservation of natural and architectural environment, as well as the cultural identity and unity while providing economical benefits [8]. Many scholars especially Cuneo [3], Jamieson [13] and Feilden [9], emphasize the importance of the history and culture in the tourism developments. Tourism, like other activities cannot be restricted to simply visiting historical places and physical motion but has to include intellectual, cultural and spiritual experiences.

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Historical environment is accepted as a challenge tourist product. The essence of heritage tourism lies in recognizing an area’s unique qualities and making the best cultural and economic use of them. Establishing the broken continuities and bringing new life and new ways of existence into the cities or settlements; the general secretary of The Aga Khan Award for Architecture, mentions about a small selection of award winning projects. Each and every one of these projects has different approaches as well as different societal factors and all of them bring about a new solution which is pertinent to that society that is replicable under certain conditions [18]. Sidi Bou Saod, Tunis, Tunisia 1980: This is a model, more or less, to bring the affluent population or society to pay respect to their cultural heritage, so that the others would emulate or follow. Asilah, Morocco 1989: This is a primary example of an external factor, which was injected in the settlement for the purpose of renewal. Asilah is a traditional Moroccan town in a citadel. The Minister of Tourism, along with others, invented an occasion called an Asilah festival. It is the whole month of August every year that brings thousands of people here. Every year the local dwellers restore and pay more attention to their environment for thousands of guests next year. Conservation of Old Sana’a, Yemen 1995: In this case, UNESCO identified this place as a cultural heritage site and this of course had an international appeal. Many countries picked up different aspects, so it is a project that has local Yemeni input there, but it is the international community holding hands. Whatever could not be done together locally, Germans, Norwegians, French, Swiss and Italians made their contributions and added to the urban tissue. This motivated people to restore and establish the broken continuities with the past. One of the most significant cases in Turkey among the numerous applications is Cumalıkızık, Bursa 1998: The 700-year-old Ottoman village of Cumalıkızık is a unique village with the characteristic architectural structure and traditional life style, which has been able to preserve its structure physically against all the changes experienced. The Local Agenda 213 has been involved in implementing a project that aims to conserve and revitalize this unique heritage. The current planning efforts are directed towards achieving a sustainable tourism development that would preserve this authentic Ottoman village and the life style of its residents [17] (Fig. 4). The common success of the mentioned examples from the world comes from the contribution of local people. The main concern and understanding has to be among the local people. It rarely comes from the local or central governmental administrational level. Evaluating the local examples, Lefkara Village in the South Cyprus is a unique vernacular settlement of the island (Fig. 5) that is preserving its unity with some legislation limiting the building materials and heights of new constructions in the 3 Local Agenda 21, known as LA21 is a program that provides a framework for implementing sustainable development at the local level. LA21 aims to build upon existing local government strategies and resources (such as Corporate plans, vegetation management plans, and transport strategies) to better integrate environmental, economic and social goals [11].

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Fig. 4 Cumalıkızık, Bursa, Turkey [15]

Fig. 5 Lefkara village

village, hence creating harmony among the buildings as well as providing the continuity of the urban pattern (Fig. 5). The preserved settlement Karmi, in the North Cyprus which reflects the environmental consciousness between tourism and sense of place relations, preserves its unique architectural environment as a scenery however the life within is not Cypriot life any more. The houses are rented to foreigners by long term leasing and these new users are encouraged to restore and use them as houses and/or pensions. Although, all of the users are not natives, they express a respectful attitude in adapting to existing context and to preserve the authentic character. Instead of

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Fig. 6 Karmi

spending a few days for entertainment, the opportunities of having property in Karmi provide the foreigners to spend their most of times to experience the local context themselves. However the interaction between the foreigners and the locals is missing in this model (Fig. 6). It is a common view that the tourists prefer to experience the natural environment; the social and cultural life; the historical heritage of the region they are visiting. Hence it is obligatory to answer such needs of tourists for developing tourism activities. The Arched Houses, Dipkarpaz (Rizo Karpasso) North Cyprus, 2002: The only example of house renovation for tourism accommodations was applied to a group of houses limited by a single street in a traditional village. The project of Arched Houses avoided the deterioration process of almost ruined houses. The Arched Houses is an example for answering the needs of the sustainable tourism activities in North Cyprus. However it is still at a very small scale since the project is not distributed to the whole Dipkarpaz Village (Fig. 7).

Fig. 7 The arched houses

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Examining the basic process of strategic environmental assessment, and the potential organisation and implementation of the strategic environmental assessment process on the island, Sadler [20] mentions that an integrated strategic environmental assessment and strong tourism planning are urgently required to safeguard the future for tourism and the environment in the North Cyprus and he adds that the lack of a sustainable approach to alternative tourism is likely to lead to more environmental damage than mass tourism. Concentrated tourism activity in a resort may have less associated impacts than dispersed alternative tourists seeking new sites and experiences. Therefore, long-term competitiveness requires a sustainable approach to tourism. This requires planners to look beyond economic indicators and carrying capacity indicators and to adopt a more holistic approach [20].

5 Recommendations for Sustainable Tourism Implementations in Cypriot Vernacular Environments Development of travelling facilities and activities, the media and mass communication tools, and changing cultural structure by globalization generally end up with unhappy users that are not satisfied with their own houses any more. This leads to deterioration and decay in traditional environments due to abandonment and ignorance. The deterioration of existing pattern and inappropriate developments are expected to increase in the traditional environments of North Cyprus, parallel to the growing tourism demands unless a strategic planning is envisioned. What is more, generally in tourism applications the local culture is acculturated by the coming cultures hence a long-term cultural change can be observed in such cases. As mentioned before an important effect of tourism is the depletion of cultural resources if they are not properly managed. Instead of being abandoned and left to deteriorate, the traditional architectural heritage, that is the reflection of multi-cultural accumulations of the island and at the same time being in peace with the natural environment, can be sustained to the future through sustainable tourism implementations. What is more the existing building stock that is a well developed outcome of the tried and evolved design principles through centuries is a cultural and an economical welfare for tourism implementations. In the frame of sustainable tourism approach, the continuity of cultural heritage of unspoilt rural vernacular environments of North Cyprus is discussed in order to prevent the potential threats on the local architectural environments by the increasing demands of construction activities. Some recommendations for the sustainable planning of the vernacular environments are • Protecting natural resources including air, sun, climate, water, light and earth, in addition to the protection of the built environment including historical sites, settlements, archaeological and architectural remains; and protection of cultural resources including architectural pattern, cultural unity, values and activities;

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• Proposing a conservation program including the revitalisation, re-assessment and adaptive re-use of the abandoned and deteriorated traditional dwelling stock for tourism purposes; (While transforming the traditional houses into pensions it is important to preserve and encourage the continuity of the interactions among interior and exterior spaces; provide originality in interior spaces and preserve the identity of semi-closed and open spaces in the traditional houses as well as sustaining the close relations with the natural environment.) • Creation of financial, application, timing, and organisation models for the rehabilitation of sustainable physical environment; • Creating a pollution free environment both physical and visual; (These improved standards are very important in safeguarding the health of the local population who will also be serving in the new tourist facilities. The design of new buildings, sites and transport systems such as car park areas, public transportation, busstop, traffic sign systems, should minimize the potential harmful visual effects of tourism. Pollution controls should be built into all forms of infrastructure. Leaving some narrow streets for only pedestrians in order to prevent parked cars in front of the old buildings that will harm the picturesque value of these houses.) • Providing the necessary infrastructure for the considered life-style; (Improvements to street lighting and street furniture are needed, along with upgrading of the water supply, sanitation and solid waste collection.) The success of sustainable tourism implementations depends on taking parallel steps in different aspects of social, cultural, economical, physical, educational, administrational and managerial issues. It is also important that the revitalised values in the vernacular settlements should not be based on a culture that no longer exists, but a living and changing life-style should be reflected to the tourists. Revitalising the past is more like a theatrical scene that seems artificial but it is much more preferable for the tourist and the host communities to live together in the vernacular environments accompanied with contemporary services.

References 1. Aksugür N, Türker ÖO (2005) A model for the modernization of a vernacular settlement as a milieu for two different cultural backgrounds re-learning to live together. In Salman, Y and Do˘gu¸san N (eds) Proceedings of 5th International mAAN Conference, Re-thinking and Re-constructing Modern Asian Architecture, 27th–30th June 2005, Istanbul 2. Aksugür N, Türker ÖO (2004) Kültür Turizmi için bir Öneri, in Proceedings of the national symposium titled Alanya-Ma˘gusa Sempozyum Bildirileri: Do˘gal ve Kültürel De˘gerlerin Korunması Geli¸stirilmesi ve Turizmin Çe¸sitlenmdirilmesinde KKTC ve Alanya-Antalya ˙I¸sbirli˘gi, 15th–16th October 2004, K.T.M.M.O.B., pp 199–206 3. Cuneo P (1991) Cultural heritage and cultural tourism. In: Yenen Z (ed) The proceedings of international symposium on architecture of tourism in the Mediterranean, vol 2. Yıldız University Press, Istanbul, pp 233–238 4. Dinçyürek Ö (2001) The Mesaorian Rural Houses of Cyprus. A Typology, Open House International, 26:29–37

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5. Dinçyürek Ö and Türker ÖO (2007) Learning from traditional built environment of Cyprus: Re-interpretation of the contextual values. Building and Environment, 42(9):3384–3392 6. Dinçyürek Ö and Türker ÖO (2007) Sustainable tourism as an alternative to mass tourism developments of Bafra, North Cyprus. Open House International 32(4):107–118 7. Eber S (1994) Motivations for pilgrimage in the modern world. In: Twite R, Baskin G (eds) The conversion of dreams, the development of tourism in the middle east. IPCRI publications, Jerusalem, pp 29–39 8. Echeverria E (1993) Ilha de Mozambique – Preservation through tourism. In Proceedings of International Scientific Symposium, 10th General Assembly on Cultural Tourism, ICOMOS, Sri Lanka 9. Feilden BM (1993) Conservation and tourism. In Proceedings of International Scientific Symposium, 10th General Assembly on Cultural Tourism, ICOMOS, Sri Lanka 10. Hill SG (1972) A history of cyprus, vol I–IV. Cambridge University Press, Cambridge 11. http://www.deh.gov.au/esd/la21 12. Inskeep E (1991) Tourism planning: An integrated and sustainable development approach. Van Nostrand Reinhold, John Wiley & Sons New York 13. Jameison W (1993) Planning for small town cultural tourism. In Proceedings of International Scientific Symposium, 10th General Assembly on Cultural Tourism, ICOMOS, Sri Lanka 14. Mathieson A, Wall G (1982) Tourism: Economics, physical and social impacts. Prentice Hall, Englewood Cliffs, NJ 15. Municipality of Bursa, Bursa Yerel Gündem 21, Cumalıkızık Koruma – Ya¸satma Projesi, Municipality of Bursa, Turkey 16. Oliver P (ed) (1997) Encyclopedia of vernacular architecture of the world. Vol 1. Cambridge University Press, Cambridge, UK 17. Oren U, Woodcock DG, Var T (2001) Sustainable tourism development: A case of Cumalıkızık, Turkey. Tourism Anal 6(3/4):253–257 18. Özkan S (1999) The Aga Khan Award for Architecture, in Joannidu, SP (ed.) International conference on the Revitalisation of Historic cities, UNDP 20-22 May 1999, Nicosia, Cyprus, p 16–20 19. Russel AS, The role of tourism in urban conservation – The case of Singapore, Cities, August 1988, Butterworth 20. Sadler J (2004) Sustainable tourism planning in Northern Cyprus. In: Bramwell B (ed) Coastal mass tourism: Diversification and sustainable development in Southern Europe. Channel View Publications, Cromwell Press ltd. Great Britain 21. TRNC (2006) The poster of Bafra tourism area. Published by Tourism Planning Department of Turkish Republic of Northern Cyprus 22. Türker ÖO, Dinçyürek Ö (2004) Learning from traditional environments: Cyprus on the threshold of becoming a unified country and a member of European Union, XXXII. IAHS World Conference on Housing-Sustainability of the Housing Projects, Trento, September 21–25 (CD-ROM) 23. Türker ÖO, Dinçyürek Ö (2006) Continuity concerns for traditional settlements under the increasing demands of tourism developments: The case of Bafra Village, Cyprus, Proceedings of 34th IAHS World Congress, Naples, Italy, September 20th–23rd 2006 (CD-ROM) 24. Türker ÖO, Pulhan H (2006) Hyper-cypriot architecture: The transformation of local and global values. In: Nam S (ed) 2005–2006 Series of the traditional dwellings and settlements working paper series (WPS), vol 196. Global Transformations and Local Traditions, IASTE, University of California, Berkeley, pp 1532–1550 25. Viney DE (1994) An illustrated flora of North Cyprus, vol 1. Koeltz Scientific Books, Koenigstein, Germany

Environmental Basis of Sustainable Tourism Along Sensitive Coastal Areas – Principles and Applications D. Orhon, H. Gökçeku¸s, and Seval Sözen

Abstract Coastal zones are subject to both socio-economical concerns with respect to their tourist attraction, and also to environmental concerns since they are under the threat of water quality deterioration and water scarcity. This study overviews the environmental principles of sustainable tourism along sensitive coastal areas and its application to a small island is discussed through a detailed wastewater management study conducted in Turkish Republic of Northern Cyprus (TRNC). The study comes out with a proposed discharge limitation for the protection of sensitive areas involving nutrient restrictions and adapted wastewater characteristics from the values obtained in Turkey from previous research. Water consumption figures and pollution profiles from certain facilities are determined and specific pollution loads for tourism areas are assessed considering the occupancy rates. In the designation of suitable wastewater treatment technology emphasis is put on nutrient removal and also to advanced treatment technologies which will further enable wastewater recycle and reuse. Further concern is the monitoring of compliance along with legislation, administration and public awareness. Keywords Coastal areas · Islands · Sustainable tourism · Water scarcity · Wastewater management plan · Environmental management strategy

1 Introduction Coastal tourist resorts are increasingly threatened by economic and demographic pressure, and the marine ecosystems are in decline around the globe. From a wastewater management viewpoint, the developments should be evaluated within the context of maintaining the critical balance between tourist attractions and

S. Sözen (B) Civil Engineering Faculty, Department of Environmental Engineering, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey e-mail: [email protected]

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preserving water quality. In coastal tourist areas, quality of the receiving water is, on one hand, the prime concern for the value of the resort, and on the other hand, it is quite susceptible to pollution and especially to nutrients which are likely to create eutrophication problems. Tourism should contribute to sustainable development and be integrated with the natural, cultural and human environment. It should ensure an acceptable evolution as regards its influence on natural resources, biodiversity and the capacity for assimilation of any impacts and residues produced. Water scarcity is also the most crucial environmental problem in tourist resorts. It is exacerbated by the deteriorating quality of water resources due to population fluctuation and other activities. In view of water scarcity, coastal areas, especially islands suffering from water shortage, have to take measures to increase water use efficiency and stimulate greater conservation. This can only be achieved through a realistic environmental management strategy. Within this context, major issues necessary for the environmental basis of sustainable tourism have to be carefully considered and developed for the sustainability of tourism activities. This paper provides a critical overview of the basic environmental principles for sustainable tourism along sensitive coastal areas and discusses the application procedure in a small island by using the outcomes of an extensive study carried out on wastewater management in the Turkish Republic of Northern Cyprus. In this manner, expected water quality, wastewater characteristics and pollution profile, and appropriate treatment technologies are outlined and effective recommendations are offered for future activities.

2 Concept of Sustainable Tourism The concept of “sustainability”, launched in the 1970s in the industrial sector, has only been applied to tourism industry during the last decade, following the presentation in the World Conference in Lanzarote in 1995. This planning document highlighted not only the positive contribution of tourism in terms of socio-economic objectives, but also the detrimental effect it can have in terms of environmental deterioration. This initiated the understanding that, in the long run, tourism is to be considered both ecologically sustainable and economically beneficial, showing respect for local communities as well as for the environment. This concept was again undertaken at the International Conference on Sustainable Tourism in Rimini in 2001, and was reconfirmed in Johannesburg in 2002. These efforts lead to a change in the outlook, resulting in application of “good practices” capable of involving local policies, transport, urban planning, cultural activities, use of water, consumption, waste production and disposal. Sustainable tourism policy necessarily requires the support and promotion of environmentallycompatible tourism management systems, feasibility studies for the transformation of the sector, as well as the implementation of demonstration projects and development of international cooperation programmes.

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3 Characteristics of the Study Area The island of Cyprus, third largest island in the Mediterranean, is located in the Eastern Mediterranean. The Turkish Republic of Northern Cyprus (TRNC) is in the northern part of the island with a population of approximately 2,00,000 (1996). She has a surface area of 3,298 m2 , which almost covers 35% of the total island area [1]. TRNC is characterized by a heavy dependence on tourism on her coastal areas. Projections indicate that the population will be approximately doubled by 2015. Cyprus is announced among the countries, which will be added to scarcity category by 2025 if no measures will be taken [2]. Annual average rainfall of 440–450 mm at the beginning of the century fell down to 402 mm between 1941 and 1972 and further to 382.4 mm between 1975 and 1993 resulting in reduced capacity of water resources [3]. The water scarcity has given way to restriction of water quantity for irrigation, which resulted in limitation of irrigated regions [4]. Current status outlines that only 19% of the population (approximately 40,000) is connected to a sewer system and only 15% of the wastewater is discharged after being treated [1]. Therefore the need arises to protect the water resources within an integrated water and wastewater management concept. The integrated management of resources is directed towards supporting water resources planning, policy making and management through development of a strategy.

4 Management Approach For a sustainable tourism management system, first, an assessment of expected water quality or effluent limitation is necessary in terms of European Directives (Directive 91/271/EEC on Urban Waste Water Treatment; Directive 2000/60/EC on Water Framework Directive; Marine Strategy Directive COM/2005/505) achievable with feasible and economically applicable treatment technologies. Current application of discharge standards is limited with conventional parameters in TRNC. Protection of sensitive areas necessitates that the limitations include not only the conventional parameters, but also restrictions for nutrients. Table 1 outlines the proposed discharge limitations for sensitive zones [5]. This regulation proposes that Table 1 Proposed discharge limitations for sensitive zones [5] Parameter

Population > 10,000

Population < 10,000

BOD5 COD TSS Ammonia nitrogen Total nitrogen Total phosphorus pH

25 mg/l 125 mg/l 35 mg/l – 75% removal 80% removal 6–9

25 mg/l 150 mg/l 60 mg/l 2 mg/l (full nitrif.) 40% removal 80% removal 6–9

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all treatment plants have to remove the nutrients regardless of their population equivalent. The second important issue is the determination of wastewater characteristics. A detailed experimental survey on wastewater characteristics is not available for TRNC. For that reason the domestic wastewater characteristics have been adapted by using the results obtained from characterization studies carried out in Turkey (Table 2). The flowrate has been accepted as 90 l/capita.day for the year 2000, whereas it is extended to 120 l/capita.day for 2015 and 150 l/capita.day for 2030 [1]. The values in Table 2 indicate that the wastewater has a weaker nature compared to wastewaters generated in Istanbul [6, 7]. In addition to domestic wastewaters, discharges from different tourist activities will also contribute to pollution load. Applicable wastewater characteristics and pollution profiles are determined for different tourist facilities (Table 3). The table indicates that the wastewater quantity and quality are extensively affected by the facilities. The occupancy rate has also a vital effect on the wastewater generation in resort areas. In off seasons this rate fluctuates between 30 and 40%, whereas it increases up to 75–80% in high seasons. From engineering point of view, the characteristics outlined in Table 4 are assessed as the most applicable specific pollution loads for tourism areas after an intensive evaluation of all existing data [1]. The results of the study outlines that a domestic wastewater flow of 2,000 m3 /day will be generated additionally from tourism facilities. The amount of wastewater is estimated to be 3,200 m3 /day in 2015, in accordance with the expected increase in occupancy rate in resort areas.

Table 2 Characteristics of domestic wastewater for TRNC

Table 3 Water consumption-wastewater generation for different activities [1]

Parameter

Value (g/ca.day)

BOD5 COD TSS Total Kjehldahl nitrogen Total phosphorus

40 90 45 6.7 1.3

Activities Hotel Pension Daily stay Restaurant Entertainment center Settlement

Water consumption (l/bed.day)

Wastewater generation ratio (%)

BOD5 (g/ca.day)

1, 000 400 100 50 100

65 75 75 80 80

110 70 50 60 60

200

80

65

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Parameter

Value (g/ca.day)

BOD5 COD TSS Total Kjehldahl nitrogen Total phosphorus

100 200 120 8 2

Another important issue is the designation of appropriate wastewater treatment technology. In this manner, new treatment plants should be designed and constructed and the existing plants should be retrofitted for nutrient removal. Sequencing Batch Reactor, Step Feeding, Alternating Aerobic Anoxic Process, Moving Bed Biofilm Reactor are major technologies, requiring a minimum of maintenance, affordable in terms of installation and operation expenses and reliable in terms of process performance [8–11]. The use of advanced treatment technologies will also contribute to a large extent to the wastewater recycle and reuse for the compensation of water scarcity. Desalination systems have currently proven to be one of the best alternatives as a fresh water resource. The investment and operation costs of desalination systems are reduced with the new technological advances obtained in the last years, so that these systems can be considered as alternative solutions for water supply from sea water or brackish water. Following the assessment of the appropriate treatment technologies, compliance monitoring is to be established for a problem-oriented, cost-efficient, and sustainable management in the island. This approach could only be achieved with relevant legislative and administrative framework. Legislation should be amended to incorporate effluent standards compatible for the protection of sensitive zones. A monitoring program should be designed and enforced for the effective control of plants performance and coastal water quality. Institutional requirements for monitoring should be fulfilled in view of laboratory, trade man power and administrative aspects. Considering the significant issues, i.e. solid wastes, energy, transportation, interference with other beneficial uses, other than wastewater management within a comprehensive framework will ensure total quality management, that absolutely needs to be accompanied by raising public awareness.

5 Proposed Management Strategy The appropriate interaction between environmental protection and tourism planning and development has become a key concern for many institutions at the local, national and international levels. The trans-boundary characteristics and possible negative supra-regional effects of tourism industry require a unified approach and integrated planning and strategy, which has to be implemented or sustainability.

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In this respect, total quality management should be based on a platform for developing and promoting optimum efficiency of resource utilization, facility development and environmental management systems to achieve agreed benchmarks by ensuring a coherent sustainable tourism policy. In this framework the actions should be focus on; • continuous monitoring and management of negative impacts of tourist activities • assessing of priority issues for sustainable tourism policy • implementing a management strategy applicable Europe-wide in compliance with tourism standards • evaluating and improving, where necessary the relevant legislative and administrative framework, for sustainable tourism • developing guidance on technical issues • raising public awareness using media tools and information technologies • implementing training and education programs Sustainable development in tourist areas can only be ensured using the integrated concepts for the multi-purpose utilization of resources at economic, social and environmental levels for the mitigation of adverse effects influenced by human activities.

6 Conclusion Tourism is more sensitive to environmental degradation than other economic activities, as the environment is its primary resource. Clearly, tourism has a paramount economic role for coastal areas and, if planned and managed correctly, can significantly contribute to sustainable socio-economic development and environmental conservation. Fluctuations in water demand and wastewater generation in time, low population in off-seasons, water utilities with limited funding are actually the main characteristics differentiating the island from the urban examples. Without having an integrated water and wastewater management strategy, the required water quality and the essential tourism standards can not be achieved. In this respect, applicable discharge limitations, wastewater characterization and appropriate treatment technologies should not be avoided.

References 1. Orhon D, Tasli R, Turkoglu H, Gokcekus H, Gorgun E, Ovez S, Goksel C, Ozbasaran M, Bebek E (1999) Environmental master plan for Turkish Republic of Northern Cyprus. Report Ministry of Health and Environment for TRNC 2. Valls Xercavins J (1999) Carrying capacity in East Sub-Saharan Africa: A multilevel integrated assessment and a sustainable development approach. Ph-D Thesis, Universitat Politechnica de Catalunya

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3. Biyikoglu G (1995) Rainfall analysis in the Turkish Republic of Northern Cyprus. Proceedings of the Second Water Congress, Organized by the Cyprus Turkish Engineer and Architecture Chamber Association, North Cyprus, February 23–24, in Turkish 4. Biçak H, Özdemirag A (1997) Estimation of forecasting of water demand and supply in North Cyprus: The impact of various projects under various scenarios. Presented at the Seminar Series, Organized by the Department of Economics, Eastern Mediterranean University, Gazima˘gusa, North Cyprus 5. Orhon D, Tünay O, Germirli F, Artan N, Sözen S, Ta¸slı R, Çokgör Ubay E, Görgün E (1996) Appropriate wastewater treatment technologies and wastewater management. Report Turkish Foundation for Technology Development 6. WMT (1986) Istanbul sewerage project, stage 2 – feasibility study and preliminary engineering. Report, vol 1. Watson Motor & Temel, Istanbul, Turkey 7. Camp-Tekser (1975) Istanbul Sewerage project master plan revision, vol I. Istanbul Water and Sewerage Administration, Turkey 8. Artan N, Orhon D, Sözen S (1995) Conceptual basis of wastewater nitrogen removal in sensitive coastal areas. Water Sci Technol 32(11):77–84 9. Görgün E, Artan N, Orhon D, Tasli R (1995) The nitrogen removal potential of predenitrification systems in sensitive coastal areas. Water Sci Technol 32(7):135–142 10. Odegaard H, Rusten B, Westrum T (1994) A new moving bed biofilm reactor – applications and results. Water Sci Technol 29(10–11):157–165 11. Orhon D, Sözen S, Görgün E, Ubay Çokgör E, Artan N (1999) Technological aspects of wastewater management in coastal tourist areas. Water Sci Technol 39(8):177–184

Part III

Economics, Development, Sustainability and Risks

Medical Waste Survey in a University Hospital: Do Intern Doctors and Emergency Nurses Know and Pay Attention to Segregation of Wastes? ˙ F. Nur Aksakal, Evin Aras, Mustafa N. Ilhan, and Sefer Aycan

Abstract Medical wastes are of public health concern in both developed and developing countries being costly in disposal and carry risks of infection or physical injury and of exposure to potentially harmful pharmaceuticals. This study aimed to determine the knowledge and attitudes of intern doctors and emergency nurses in a university hospital and conducted in Gazi University Hospital in April 2006. One hundred and thirty one intern doctors and 27 emergency nurses are targeted to be reached for March–April 2006 period. A questionnaire form was filled out for each participant. Nurses have undergone training programs on medical wastes and waste segregation (50.0%) significantly more than the intern doctors (19.3%). The knowledge of the medical wastes that must be disposed in “red coloured plastic sacks” were known by almost all (98.6% of intern doctors, 100.0% of emergency nurses) participants (p > 0.05). Wastes which must be disposed in “blue coloured plastic sacks” and “black coloured plastic sacks” were known better by nurses (85.0 and 85.0%) than intern doctors (60.5 and 58.2%) (p < 0.05). Intern doctors and emergency nurses are found as a group of high risk and the appropriate training programs in terms of timing and content will be effective. Keywords Emergency Nurse · Medical Waste · Segregation

1 Introduction Medical wastes are of public health concern in both developed and developing countries being costly in disposal and carry risks of infection or physical injury and of exposure to potentially harmful pharmaceuticals although they constitute a relatively small percentage of all wastes [1, 2]. World Health Organization (WHO) supports clssification of the medical wastes in hospitals as special wastes, and United States Environmental Protection Agency F.N. Aksakal (B) Department of Public Health, Gazi University, Ankara, Turkey e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_24,

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(EPA) defines these wastes as hazardous [3]. For this reason; segregation, temporary storage, recycling, transportation and ultimate demolition require attention [4]. In Turkey, these applications are regulated by a legislation: Ordinance for Control of Medical Wastes dated 20 May 1993 and published in Official Gazette number 21586 [5]. This legislation was renewed and the new one is put inforce on 22 July 2005 [4]. In both of the ordinances, wastes in health facilities have been grouped into three as: domestic waste, recyclable waste and medical waste. Medical waste is defined as the infectious, pathological and sharp wastes generated trough the observational, diagnostic, research, therapeutic and rehabilitative services of medical establishments. Due to the older ordinance, domestic waste must be disposed in black and recyclable waste in blue plastic sacks whereas in the new ordinance the domestic waste, recyclable waste and medical wastes must be disposed in black, blue and red coloured plastic-sacks respectively for which the properties they must carry are described. Infected and pathological wastes must be collected in red plastics sacks and sharps must be collected in rigid bin made of either carton or plastic as before [4]. Health care facilities in which the medical wastes are generated are responsible for establishing a system to minimize the generation of these wastes and their demolition due to the ordinance. So, physicians, nurses, midwives, dentists, laboratory tecnicians and other staff involved in the observational, diagnostic, research, preventive, therapeutic or rehabilitative health care services are expected to segregate the wastes where they are generated [4]. Several studies have investigated the quantity and quality of hospital wastes, their transport and destruction [3, 6–10], but researches conducted among health-care personel are limited in number [11, 12]. University hospitals are large size health care facilities and classified as health facilities producing large quantity of medical wastes [4]. These facilities also serve for education and training purposes for medical faculties and schools for nurses and midwives. As in other medical faculties in Turkey, medical students rotate in different departments of hospitals for different time periods. Most of these departments are the wards and outpatient clinics in which a high quantity of medical wastes are generated. Although they are involved in many applications and interventions as injection, wound-care, blood collection etc. They do not have a detailed training about the medical wastes, their segregation and their risks in our university. The only source of information is the 5th year Public Health stage and health care workers with whom they work in wards or outpatient cinics. For the academical year of 2006–2007 a clinical skill laboratory has been scheduled for 1st year medical students which is conducted through an audiovisual training for 20 min. For intern doctors, when the shortness of the period they spent in each ward/outpatient clinic and diversity of the medical interventions they carry out are considered, they should be accepted as an important target group who may have a failure in waste segregation. In the emergency wards of hospitals, there is a intensive application of patients accompanied by an intense diagnostic interventions, and a need for quick and

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247

effective patient stabilization [13]. When the workload and work description is considered, emergency nurses may be concerned as another risk group who may fail to segregate wastes. For these reasons, this study aimed to determine the knowledge and attitudes of intern doctors and emergency nurses in a university hospital.

2 Materials and Methods This study is conducted among intern doctors and emergency nurses in Gazi University Hospital in April 2006. One hundred and thirty one intern doctors and 27 emergency nurses are targeted to be reached for March–April 2006 period. Seven nurses and 12 intern doctors could not be reached due to the maternity and annual leaves and rotational training in a maternity hospital respectively. As result, 119 (90.6%) intern doctors and 20 (574.1) nurses were included in the study. A questionnaire form including questions about some sociodemographical properties, knowledge and attitudes about medical wastes and their segregation was filled out by face-to-face interviewing technique for each participant. Plastic or laminated carton bins for sharps were defined as “safe disposal bins” while knowledge about medical wastes is evaluated. Answers as “safe disposal bins” for sharps, “red coloured plastic sacks” for other medical wastes, “blue coloured plastic sacks” for recyclable waste and “black coloured plastic sacks” for domestic wastes were regarded as correct. Data analysis was performed by SPSS 10.0 statistical package program. Descriptive statistics (median (min–max), percent distributions) are computed and Fischer’s exact chi-square test is performed. Probability values less than 0.05 is regarded as “statistically significant”.

3 Results A total of 139 (85.6% intern doctors, 14.4% nurses) participants were evaluated. Fifty six point one percent of them were female. Thirty seven percent of the intern doctors were practicing in clinical wards, 23.5% in outpatient clinics, 18.5% in emergency unit, 15.2% in public health department, 5.0% in intensive care units and 0.8% in operating theatres. Age, time spent in current position, daily and weekly working hours of the intern doctors and emergency nurses are shown in Table 1. Nurses have undergone training programs on medical wastes and waste segregation (50.0%) significantly more than the intern doctors (19.3%) (p < 0.05). The knowledge of the medical wastes that must be disposed in “red coloured plastic sacks” were known by almost all (98.6% of intern doctors, 100.0% of emergency nurses) participants (p > 0.05). Wastes which must be disposed in “blue coloured plastic sacks” and “black coloured plastic sacks” were known better by nurses (85.0 and 85.0%) than intern doctors (60.5 and 58.2%) (p < 0.05).

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Table 1 Age, time spent in current position, and daily and weekly working hours of the intern doctors and emergency nurses, Gazi University, Ankara, 2006

Age (year) Time spent in internship/profession (month) Time spent in current unit (month) Daily working hours Weekly working hours

Intern doctors

Emercency nurses

Median

(Min–max)

Median

(Min–max)

24 10 2 9 60

(23–33) (4–10) (1–2) (5–16) (25–99)

28 72 12.5 8 40

(23–33) (7–132) (2–132) (8–12) (40–48)

The knowledge of the participants about classification of different kinds of wastes and in which coloured sacks they must be disposed are shown in Table 2. There is no statistically significant difference between the level of knowledge of intern doctors and emercency nurses for the kinds of wastes to be disposed in red and blue coloured plastic sacks. Intravenous catheters are classified better by nurses than intern doctors (p < 0.05). Wastes which must be placed in black plastic sacks are better classified by nurses (p > 0.05). Reasons for failure to segregate the wastes declared by the participants are shown in Table 3. The most prevalent reason declared was “Not all colours of sacks are present in every room” by 49.6% of the participants. The second most prevalent reason was “Not enough time during intervention” (47.5%) and the third prevalent was “Usage of the sacks is not practicle”. The leading reason for failure was “Not all colours of sacks are present in every room” among intern doctors (54.4%), while it was “Not enough time during intervention” (85.0%) among emergency nurses. Presence of bins with coloured plastic sacks in the units in which the participants currently work are shown in Table 4. Fifty three point six percent of the participants declared that bins for medical waste disposal were not present in outpatient clinics. Hundred percent of the intern doctors declaring this reason were in internal medicine & cardiology, 50.0% of them in psychiatry and 50.0% of them in pediatrics. The utilization of bins for medical wastes and attituted towards notifying others for their use, are shown in Table 5. Twenty one percent of the intern doctors declared that they never used medical waste disposal bins. Fifty five percent of the emergency nurses declared that they use the medical waste disposal bins regulary, while only 16% of the intern doctors are regular users.

4 Discussion Healthcare establishments comprising observational, diagnostic, research, therapeutic and rehabilitative services are among the largest generators of solid waste on a per capita basis. A portion of their wastes are considered as potentially dangerous

a Percent

of right answers for each question.

Wastes that must be disposed in safe disposal bin Injectors IV catheters Sharps Wastes that must be disposed in red-coloured plastic sacks Urine bags and appendices Flacons Laboratory wastes Nasogastric catheter Surgical wound care wastes Patient care unit wastes Tracheostomia canule Foley catheter Blood and blood products Dialysis wastes Wastes that must be disposed in black-coloured plastic sacks Kitchen wastes Food and their packages Wastes that must be disposed in blue-coloured plastic sacks Office wastes 70.6 27.7 49.6

92.4 73.1 90.8 95.0 91.6 85.7 84.9 88.2 83.2 85.7

58.0 42.9

44.5

110 87 108 113 109 102 101 105 99 102

69 51

53

%a

84 33 59

No

Intern doctors (n = 119)

5

17 15

20 12 19 20 20 18 19 20 18 20

17 12 14

No.

25.0

85.0 75.0

100.0 60.0 95.0 100.0 100.0 90.0 95.0 100.0 90.0 100.0

85.0 60.0 70.0

%a

Emergency nurses (n = 20)

Knowledge about classification of different kinds of wastes

0.141

0.025 0.014

0.357 0.286 1.000 0.593 0.357 1.000 0.309 0.221 0.740 0.132

0.278 0.008 0.145

p

58

86 66

130 99 127 133 129 120 120 125 117 122

101 45 73

No.

41.7

61.9 47.5

93.5 71.2 91.4 95.7 92.8 86.3 86.3 89.9 84.2 87.8

72.7 32.4 52.5

%a

Total (n = 139)

Table 2 The knowledge about the classification of different kinds of wastes by intern doctors and emergency nurses, Gazi University Hospital, Ankara, 2006

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Table 3 Reasons for failure to segregate the wastes declared by the participants, Gazi University Hospital, Ankara 2006 Intern doctors (n = 119) Reasons for failure

No.

%a

Not all colours of plastic sacks are present in every room Not enough time during intervention Usage of the sacks is not practicle Usage of the sacks is not necessary Lack of training Not all colours of sacks are present in outpatient clinic Carelessness-tiredness

65

54.4

49 47 15 4 1 −

a Percent

Emergency nurses (n = 20)

Total (n = 139)

%a

No.

%a

4

20.0

69

49.6

40.0 39.4 12.5 3.4 0.8

17 6 2 − −

85.0 30.0 10.0 − −

66 53 17 4 1

47.5 38.0 12.2 2.9 0.7

−

1

5.0

1

0.7

No.

of declaration of each reason by the participants.

Table 4 Presence of waste bins with coloured plastic sacks in the units in which the participants currently work, Gazi University Hospital, Ankara 2006 Declaration about presence of bins for medical waste disposal (%)

Unita Out patient clinics (n = 28) Clinical wards (n = 44) Intensive care units (n = 6) Operating theatres (n = 1) Emergency (n = 42)

Absent

Sometimes Usually present present

Always present

No idea

53.6 – – – 2.4

14.3 15.9 – – 19.0

17.9 27.3 33.3 100.0 54.8

– 4.5 – – –

14.3 52.3 66.7 – 23.8

a Since 18 intern doctors in public health department are not involved in medical waste generation process during their rotational period, they are not involved in analysis.

because it may possess pathogenic agents and can cause undesirable effects on human health and environment [3]. The segregation process of the wastes is shown to be important to prevent the injuries and decrease the infection risk [14]. In the present study, knowledge and attitude of intern doctors and emergency nurses about medical wastes were evaluated in a university hospital. Half of the nurses have got a formal training about medical wastes while only one out of five intern doctors were trained. The content and frequency of the in-service training for nurses was not evaluated deeply but it is learned that the issue of waste segregation was being covered for a one hour course. For intern doctors there is no formal tarining but the topic is covered during fifth year public health stage as a one hour course. Emergency nurses knew the recent revisions in the ordinance significantly better than the intern doctors. This difference is attributed to the in-service trainings for the nurses. Likewise, in another study conducted by Dinç et al in hospitals in the center of Manisa province, it is reported that the trained nurses were more successful than the untrained ones [12].

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Table 5 The utilization of bins for medical wastes and attituted towards notifying others for their use, Gazi University Hospital, Ankara 2006 Intern doctors (n = 119)

Nurses (n = 20)

Total (n = 139)

No.

%

No.

%

No.

%

Frequency of usage of medical waste disposal bins Never Sometimes Frequently Always

25 18 57 19

21.0 15.1 47.9 16.0

– 1 8 11

– 5.0 40.0 55.0

25 19 65 30

18.0 13.7 46.8 21.6

Notification of others for usage of medical waste disposal bins Never Sometimes Frequently Always

40 43 25 11

33.6 36.1 21.0 9.2

1 6 6 7

5.0 30.0 30.0 35.0

41 49 31 18

29.5 35.3 22.3 12.9

% column percent.

In the present study, the utilization of the appropriate bins and sacks for medical waste disposal was found higher among nurses. As the level of knowledge for segregation, this is also attributed to the in-service training of the nurses. Nurses are also the group of personel who are somehow more stable in the current position and the ones leading the other staff about the segregation process [12]. The absence of the bins for medical wastes in outpatient clinics is one of the most common reasons declared by the intern doctors. This is an issue that must be addressed by the personel responsible for waste management process. The idea behind may be that there is not e need for their usage, but still,provision of them in every outpatient clinic may be encouraging and increase attention. The low level of knowledge of the intern doctors and attitudes towards not paying so much attention to segregation of wastes demonstrated that, this group should be considered as a risk group. In-service training programmes for this group before they are involved in medical waste generation process is essential. These training should be up to date. And also it will be very helpful if they are informed about the location of safe disposal bins, bins with different colours of plastic sacks during their first day in that specific ward or outpatient clinic. In conclusion, intern doctors and emergency nurses are found as a group of high risk and the appropriate training programs in terms of timing and content will be effective.

References 1. Medical Waste Committee, Air and Waste Management Association (1994) Medical waste disposal: Report of the medical waste committee (Wt-3), Technical Council. Air Waste 44:1176–1179

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2. Jang YC, Lee C, Yoon OS, Kim H (2006) Medical waste management in Korea. J Environ Manage 80:107–115 3. Bdour A, Altrabsheh B, Hadadin N, Al-Shareif M (2007) Assessment of medical wastes management practice: A case study of the northern part of Jordan. Waste Manag 27(6):746–759 4. Ordinance for Control of Medical Wastes (2005) Official Gazette number: 2158622, 22 July 2006 5. Ordinance for Control of Medical Wastes (1993) Official Gazette number: 21586, 20 May, 1993 6. Oweis R, Al-Widyan M, Al-Limoon O (2005) Medical waste management in Jordan: A study at the King Hussein Medical Center. Waste Manag 25:622–625 7. Bassey BE, Benka-Coker MO, Aluyi HS (2006) Characterization and management of solid medical wastes in the federal capital territory, Abuja Nigeria. Afr Health Sci 6(1):58–63 8. Askarian M, Vakili M, Kabir G (2004) Results of a hospital waste survey in private hospitals in Fars province, Iran. Waste Manag 24:347–352 9. Blenkharn JI (2006) Standards of clinical waste management in UK hospitals. J Hosp Infect 62:300–303 10. Blenkharn JI (2006) Medical wastes management in the south of Brazil. Waste Manag 26:315–317 11. Massrouje HT (2001) Medical waste and health workers in Gaza governorates. East Mediterr Health J 7(6):1017–1024 12. DinçG, Dallı D (1999) Practices about medical wastes in hospitals in Manisa city center and knowledge, attitude and behaviour of nurses working in these hospitals. Turkish J Infect 13(3):375–380 (in Turkish) 13. Ke¸saplı M, Çete Y, Kartal M (2004) Hand-washing behaviour and effective factors in emergency setting. Turkiye Klinikleri J Med Sci 24:235–242 14. Tulis J, Thomann W (1992) Medical waste management: Federal perspective and North Carolina Program. NC Med J 7:153

An Investigation of Appropriate Economic Instruments for Preventing the Negative Impacts of Construction Projects on the Environmental Utility Javad Jassbi, Fatemeh Razavian, and Hanieh Nikoomaram

Abstract Most large construction projects are accompanied with a plethora of impacts which either increase or reduce different utilities. A fall in the environmental utility, which is usually among the consequences of construction projects in the long run, arises from three different sources: mismanagement of projects, the nature of the development and lack of efficient methods for accurately measuring and estimating environmental externalities of projects. To compensate for such losses and to balance the total utility of the society, economic instruments can be used for the environmental management of projects. Developing countries’ governments are searching for sustainable development instruments. Such instruments, which are usually economic in nature, bring about a combination of economic and environmental policies. Economic instruments can be divided into the two distinct categories entitled Property Rights Approach (Coase Theory) and Government Policies, each having diversified approaches and instruments in their subcategories. The present study investigates the advantages and limitations of the above-mentioned instruments, thus allowing their appropriate applications. Based on such findings, the projects’ clients – usually the governments – would be able to select suitable economic instruments for preventing, mitigating and compensating for the fall in the environmental utility according to the type and nature of a given project. Keywords Construction projects · Environmental utility · Environmental externalities · Economic instruments · Sustainable development

F. Razavian (B) Department of Environmental Management, Graduate College of the Environment and Energy, Science and Research Campus, Islamic Azad University, Tehran, Iran e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_25,

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1 Introduction In general, the major goal pursued by implementing mega projects (usually construction projects) in most countries, particularly developing countries, is to achieve the economic development. On the other side, such a development comes with positive and negative social, cultural, political and environmental impacts and aspects. The environmental impacts arising from large projects in turn lead to a reduction in the environmental utility and ultimately to a fall in the total utility of the society in the long run. This runs counter to the objectives of sustainable development which stresses on the exploitation of natural resources on the condition of their protection for future generations. The different phases of projects (definition, design and engineering, implementation and operation) usually involve the demand side and the supply side. In mega projects, it is the government that mostly plays the role of the demand side (client) and the reasons behind this are the economic non-viability of private sector investments in such projects and that the environment – as a national asset – cannot be transferred to the private sector for its belonging to all of the individuals in the society. Clearly, each of the contracting sides pursues specific goals and has different approaches. The approach of the demand side (government) is to create or enhance the total utility in the society and when it comes to the implementation of a project, it tries, by employing economic policies and instruments, to act in such a way that the resulting positive impacts would ultimately surpass negative ones, or, put in other words, that the utility in the society would rise after the completion of the project. The level of the utility is the measure of satisfaction or happiness of every individual in a society over the existing economic, social, political, cultural and environmental state of affairs whereby, should any negative change emerge, the individual shall be prepared to pay parts of his/her income to restore the situation to its original state. As Eq. (1) shows the level of the utility for individuals in a society is a function of various utilities such as economic, social, political, cultural, environmental and . . . utility [2]. U = Ueconomic + Usocial + Upolitical + Ucultural + Uenvironmental + . . .

(1)

The numerous impacts and aspects arising from the implementation of a project serve as effective factors in a rise or fall in each of such utilities. As mentioned before, implementation of large construction projects is usually accompanied with a fall in the environmental utility. Such a decrease in the utility is ignored by both the demand and the supply sides at the feasibility studies and implementation phases of a project, mainly due to the following reasons: • the long-running nature of environmental consequences; • the inevitability of development owing to its role in increasing other utilities (such as economic, social, . . .); and

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• lack of appropriate and efficient procedures/instruments for appraisal and precise estimation of environmental expenses of projects. The purpose of this paper is to assist project managers and governments to prevent, minimize and compensate for any falls in the environmental utility by properly deploying economic policies and instruments based on the nature of projects, i.e. the positive impacts and aspects arising from a project, giving rise to an enhancement of the total utility, should be greater than the negative impacts which reduce the utility and in the worst-case scenario, the positive and negative impacts should neutralize each other [9]. Economic instruments for the environmental management of projects can encourage behavioral changes in exploiters and polluters of environmental resources or can provide a proper ground to compensate for environmental damages. The use of such instruments has become common in recent years. However, economic instruments have not been widely used in developing countries as yet. One of the factors that has prevented this from happening is the problem with transferring the experiences of developed countries in using such experiences to developing and economies-intransition countries. Furthermore, in many cases, developed countries have used such instruments to generate income instead of changing behaviors and thus, cannot serve as an appropriate model for other countries [3]. Search for instruments to be used for the environmental management in developing countries is itself a kind of search for instruments of sustainable development. Economic instruments such as charges, taxes, tradable permits and etc. have contributed to this search and are considered as the most important factors in the integration of environmental and economic policies [3]. The aim of using economic instruments for the environmental management is to assist project managers and governments to control pollution, preserve the environmental utility and achieve predefined objectives. However, based on the experiences of developing countries, some of the instruments are lacking in the required effectiveness to achieve such objectives. So they need some changes and modifications based on the internal conditions of each country and its other legal instruments [8]. Therefore, economic instruments constitute a major part of environmental policymaking instruments which stand alongside laws, regulations and other procedures. In brief, if such instruments are designed in such a way that would meet the specific requirements of developing countries, they can become powerful instruments for preventing any falls in the environmental utility and ultimately in the total utility in the long run. This paper proceeds as follows: Section 2 briefly states and delineates the problem in question. Section 3 investigates and explores different kinds of economic instruments along with the advantages and limitations of each as a tool for controlling pollution and compensating for intentional and unintentional damages arising from exploitation of environmental resources and implementation of projects. While classifying mega projects, Sect. 4 outlines the criteria for selecting appropriate instruments. Section 5 not only describes the achievement of the

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study, but also provides a suitable classification for appropriate applications of economic policies and instruments in the two phases of construction and operation based on the nature of projects. Finally, Sect. 6 incorporates the discussion and conclusion.

2 Problem Statement Environmental aspects and impacts of mega projects lead to a decline in the environmental utility and ultimately in the society’s total utility in the long term, which is mostly inevitable. In addition, preserving the environmental utility and preventing its reduction at the construction and operation phases of projects are difficult and cost-intensive tasks. For this reason, environmental externalities of projects are usually ignored, leading to irremediable environmental damages [5]. Despite the fact that there are numerous economic instruments for the environmental management of projects at different stages, a poor knowledge and understanding of such instruments and their improper applications not only do not help solve the above-mentioned problem, but also make the issue more complicated in some cases. As described in Sect. 1, ignorance of the fall in the environmental utility by both the supply and demand sides at different phases of projects arises mainly due to three reasons as follows: • the long-running nature of environmental impacts; • the inevitability of development owing to its role in increasing other utilities (such as economic, social, . . .); and • lack of appropriate and efficient procedures/instruments for appraisal and precise estimation of environmental expenses of projects. A fall in the environmental utility is caused for three reasons: (1) mismanagement of projects at different phases, leading to environmental damages, destruction and pollution; (2) the nature of projects, because with the implementation of each project, even if it is properly managed, a manmade resource replaces a natural resource, thus leading to changes in land use; (3) lack of efficient methods for accurately measuring and estimating environmental externalities of projects. Although a proper knowledge and an appropriate application of the policies and instruments, which makes up the objective of this study, can help resolve the mismanagement problem, there is a need for justifications to be made by the parties involved in the project and the affected society. These justifications should be made due to the intangibility and complexity of the problem relating to the nature of projects.

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3 Economic Instruments for Environmental Management of Projects: Types, Advantages and Limitations Two major approaches have been proposed for solving the problem of environmental pollution and destruction (Fig. 1). The first approach is known as the Market or Property Rights solution put forth by Ronald Coase. He believed that the open market system should be allowed to settle the problem through bargaining among stakeholders. The second approach is based on the government intervention. The pollution and resources destruction control policies adopted by the government are categorized into two major approaches known as the Command-and-Control Approach (CAC) and Market-based Instruments (MBI) [1]. The Command-and-Control Approach comprises the implementation of environmental standards (e.g. for air or water pollution) through legislation of laws, without seeking help from market-based motives. In contrast, the second approach incorporates market reform through centralized decision-making on the value of environmental services and guaranteeing that such values will be included in the prices of goods and services presented through the project implementation [7].

Economic Instruments for the environmental management of projects Property Rights (Coase Theory)

Market-based Instruments Charges Taxes

Government Policies Command & Control Approach Ambient Standards Emission Standards

Incentive Policies (such as subsidies) Tradable or Marketable Permits Deposit-Refund Schemes

Fig. 1 Economic instruments for the environmental management of projects

3.1 Property Rights Approach (Coase Theory) The Coase Theory (1960) stresses the significance of property rights and bargaining among the supply side (polluters) and the losing side (the society). Supposing the existence of an appropriate system based on property rights (whereby ownership of resources has been guaranteed through legal tools), Coase maintained that the

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polluter and the losing side should be left alone in an unconventional situation and free of any supervision and control, whereby the process of bargaining and reaching agreement would take shape automatically [7]. Some of the most important advantages and limitations of this approach are as follows: Advantages: – It adapts to changes and various conditions automatically. – It involves implementing costs due to non-intervention of the government. – This approach usually incorporates local and indigenous issues, owing to public participation. Limitations: – Great number of stakeholders (polluters and losing sides) makes negotiations and bargaining difficult. – In mega projects, it is usually difficult to recognize and determine the ownership of resources. – This approach provides more benefits for the stakeholder who holds the property right. – Although environmental resources belong to all generations, it is impossible to take consideration of all future generations in the bargaining process.

3.2 Government Policies Government policies are a set of policies employed by the government to achieve the intended goals (i.e. reducing and controlling environmental pollution and damages) [4]. As shown in Fig. 1, pollution control instruments used by the government are divided into the Command-and-Control Approach and Marketbased Instruments. Each of these will be elaborated on along the following lines. 3.2.1 Command-and-Control Approach (CAC) As the name suggests, this approach includes a kind of “command” based on which polluters and exploiters of resources should not exceed a specific limit (permitted level of pollution), i.e. a “control” that imposes and monitors such a permitted level. Such control is also referred to as formulation of standards or enactment of quantitative laws and regulations [1, 4]. Standards comprise the two categories of ambient and emission standards. Ambient standards determine the permitted level of exploitation of environmental resources (e.g. the permitted number of trees to be cut). Emission standards determine the authorized amounts of pollution (e.g. the level of CO2 emission

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from venting). Some of the most important advantages and limitations of the Command-and-Control Approach are as follows: Advantages: – Standards conform to the Precautionary Principle.1 – Standards are more practical and more socially acceptable in comparison with the Coase Theory. – In case of full conformity to the standards, the level of pollutants and resource destruction will be at the carrying capacity level of the environment. Limitations: – To set an optimum standard and suitable charges, the government should have knowledge about supply and demand curves (for further information, see Dehghanian [1]). – Under standard conditions and full enforcement of laws, project managers would have no economic incentives to reduce pollution or destruction beyond the standard level. – As external factors change, there is always a need for modification and improvement of standards. – Given the first limitations, it would be better to set the optimum standard and suitable charges locally, which is a time-taking, cost-intensive and sometimes impossible task. 3.2.2 Market-Based Instruments (MBI) Market-based Instruments function by means of economic incentives to encourage and persuade positive environmental behaviors [7]. As shown in Fig. 1, Marketbased Instruments consist of charges, taxes, incentive policies (such as subsidies), tradable or marketable permits and deposit-refund schemes, which are elaborated separately along the following lines. Charges This instrument is directly applied in the pricing of environmental utilization and is in fact a cost levied in proportion to the amount of environmental pollution or

1 The Precautionary Principle is based on the general idea that when there is an uncertainty regarding a potentially irreversible damage to the environment, it is better to deal with this issue proactively. In such cases, either the standard of pollutants is considered as zero or the emission of pollution should be controlled by means of the best technology.

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destruction. Such costs are actually charges that have to be paid in lieu of pollutants emission into air, discharge in water and dispose of in soil, destruction of biodiversity and vegetation, noise pollution, and other kinds of environmental pollution and destruction. The amounts of charges depend on the quantity and quality of the pollutant and the costs arising from the damages made to the environment [7]. Some of the most important advantages and limitations of charges are as follows: Advantages: – Charges serve as the simplest control instrument for the environmental management. – Contrary to standards which are uniformly applied to all sources of pollution, charges, as determined case by case, provide suitable incentives for further reduction of pollution or destruction, which itself results in the reduction of charges; however, their preventive aspect is weak. – They provide financial resources required for indemnifying environmental damages. Limitations: – As an offence needs to be proven for charges to be demanded and as environmental pollution is caused by various sources, it is difficult to prove the offence and identify the offender. – Project managers might destroy the environment and dispose of pollutants secretly in order to evade payment of charges. – Demanding charges on the disposal of hazardous wastes in the environment is not practical (it should preferably be prohibited). Taxes Tax is an instrument by which the level of pollution can be controlled through creation of economic incentives and adjustment of relative prices. Taxes can be levied on specific levels of projects’ inputs or specific levels of pollutants emission [4]. Some of the most important advantages and limitations of taxes are as follows: Advantages: – Environmental tax is demanded in proportion to the difference between the pollution level and the standard level, and since it is up to the polluter to decide whether to pay tax or reduce pollution, this instrument is more flexible from the project managers’ viewpoint.

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– As pollution taxes are levied within a governmental framework, they constitute further enforceability than the standards determined for pollution. – Levying taxes on existing pollutants might result in reduction of the pollution level of secondary and other associated pollutants. Limitations: – Rise in Injustice: Imposition of taxes causes project managers to either cut down their workforce or increase prices of services as means of reducing expenses. – As with charges, taxes are faced with such limitations as secret demolition and pollution of the environment and inefficiency in the disposal of hazardous wastes in the environment.

Incentive Policies (Such as Subsidies) An alternative to taxation is for the government to pay subsidy to the polluter on every unit of pollution reduction. In addition, subsidies can be awarded for purchase of pollution reduction equipment and technologies. Theoretically, both taxation and subsidization should lead to a similar optimum level of reduction in pollution [1]. Some of the most important advantages and limitations of subsidies are as follows: Advantages: – Subsidies serve as facilities for project managers to reduce environmental pollution and/or destruction. Limitations: – In case of there being no limitation on development, subsidies can lead to unrestrained construction, which in turn increases total pollution and destruction in the long term. – Reduction of pollution and destruction by payment of subsidies can be socially “unfair”, because it practically leads to the distribution of the government’s budget among project officials (owners of pollutant sources). Tradable or Marketable Permits This system functions on pollution credits or pollution allowances. Under pollution credits, the corporation receives credits on reducing pollution to a level lower than the standard, and such credits are tradable. Under pollution allowances, the

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corporation is allowed to emit a specific quantity of pollutants and corporations can trade their pollution allowances [1]. Some of the most important advantages and limitations of such permits are as follows: Advantages: – As such permits are tradable; they create motivation for corporations to reduce pollution. As a result such corporations can sale their own permits to others and earn an income. – They generate revenues for the government. – This instrument is capable of controlling the total quantity of pollution in a given area without there being any need for controlling each and every source of pollution separately. Limitations: – This system has high monitoring, administrative and implementing expenses, particularly in cases where there is a large number of pollution sources (e.g. industrial estates). – As such permits are issued in limited numbers by the government; they constitute risks of formation of a black market or a monopoly. – Initial grant of permits requires expertise and special attention. – Determining emission permits for the whole country simultaneously requires large amounts of time and money. If it is not done simultaneously, projects might rush towards areas for which the total emission levels have not been determined. Deposit-Refund Schemes Such schemes include the payment of deposits for products that are potentially pollutant. If the waste formed by the consumption of such products is returned to authorized collecting stations, the deposit will be refunded. Additionally, a deposit can be paid by corporations in lieu of using raw materials, thereby encouraging corporations to make more efficient use of raw materials during the manufacturing process [1, 7]. Some of the most important advantages and limitations of such schemes are as follows: Advantages: – As this is an optional and voluntary scheme, it involves lower monitoring and control expenses than other instruments. – It encourages recycling and efficient use of raw materials. – As it provides the possibility of safe and proper waste disposal or waste recycling, it leads to a reduction in adverse environmental impacts (particularly regarding the hazardous waste management).

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Limitations: – It requires a system to be organized for receiving and refunding deposits and also requires recycling facilities to be erected.

4 Criteria for Selecting Appropriate Instruments in Construction Projects As described in Sect. 3, there is a broad range of economic instruments for the environmental management of projects. Selecting and realizing such instruments are usually carried out by raising and answering the seven following questions, all of which are directly related to the specific conditions of every country [6]: 1. Environmental effectiveness: Does/do the intended instrument(s) meet the specified environmental goals within the given period? If so, to what extent can this be relied upon? 2. Economical aspect: Does/do the instrument(s) concerned satisfy the specified environmental goals at the lowest cost (for both the supply side and the demand side)? 3. Flexibility and predictability: Does/do the intended instrument(s) can predict technological changes, lack of resources and the market situation and be flexible enough so as to adapt to new conditions? 4. Dynamic output: Does/do the intended instrument(s) provide any incentive for development of new and effective technologies economically-wise and cleaner technologies environmentally-wise? 5. Justice: Are the costs and interests of the intended instrument(s) distributed fairly? 6. Convenience of supervision and law enforcement: Is/Are the intended instrument(s) congruent with the legal framework of the country? Is there any need for new legislations? Does the executive arm of the government have the required capacity to issue urgent regulations and manage the instruments? 7. Acceptability: Is/Are the intended instrument(s) comprehensible by the public, acceptable by parties involved in projects and enforceable politically? For a proper employment of economic policies and instruments based on the nature of construction projects, which serves as the objective of this paper, it is highly important to classify this group of projects into a suitable category. This classification can be conducted as follows: 1. 2. 3. 4.

Residential/Recreational Industrial/Commercial Service Infrastructural

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5 Results Given the discussions on the kinds of existing economic policies and instruments for the environmental management of projects as well as the advantages and limitations of each (Sect. 3), the types of mega projects and the criteria for selecting appropriate instruments (Sect. 4), for the purpose of preventing and mitigating any decline in the environmental utility arising from the implementation of projects, the following classification (Table 1) can be presented. This classification specifies the proper applications of instruments based on the nature of projects at the two major phases of construction and operation. Table 1 Proper applications of economic instruments based on the nature of projects Types of instruments Types of projects

DepositCoase CAC Tradable refund theory approach Charges Taxes Subsidies permits schemes

Residential/ recreational

Construction Operation

X

X X

X X

X X

Industrial/ commercial

Construction Operation

X

X X

X X

X X

Service

Construction Operation

X

X X

X X

X X

Infrastructural Construction Operation

X

X X

X X

X X

X

X X

6 Discussion and Conclusion Economic instruments for the environmental management of projects can be divided into the two distinct categories entitled Property Rights Approach (Coase Theory) and Government Policies, each having diversified approaches and instruments in their subcategories. The use of economic instruments for the environmental management of construction projects calls for an investigation of the advantages and limitations of such instruments. The purpose of this study was to explore and describe the advantages and limitations of the instruments concerned so as to make the most of them. After a precise study of the features of economic instruments, the advantages and limitations of each were delineated. According to the criteria for selecting appropriate instruments, classification of mega projects and the advantages and limitations, a proper classification was presented for allocation of economic policies and instruments based on the nature of projects at the two phases of construction and operation. The findings show that projects’ clients – usually the governments – particularly in developing countries, can select the most appropriate instruments from among

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economic instruments for preventing, minimizing and compensating for declines in the environmental utility at the two phases of construction and operation in view of the advantages and limitations concerned and the type and nature of projects, hence taking steps toward the sustainable development.

References 1. Dehghaniyan S, Farajzadeh Z (2002) Economy for economist and non-economist. Ferdosi University Publication, Mashhad 2. Layard RRG, Nickell SJ, Jackman R (1991) Unemployment: macroeconomic performance and the labour market, Oxford University Press, New York 3. Panayotou T (2002) Instrument of change: Motivating and financing sustainable development. Iran’s DOE Publication, Tehran 4. Perman R, Ma Y, McGilvray J and Common M (2003). Natural Resource and Environmental Economics. 3rd ed. Longman, Harlow 5. Soderholm P, Sundqvist T (2005) Pricing environmental externalities in the power sector: Ethical limits and implications for social choice. Ecol Econ 46:333–350 6. Storfner S (2004) Can market forces solve environmental problem? Neoclassical vs. Austrian analytics. University of Central England, Birmingham, UK 7. Turner RK, Pearce D and Bateman I (1993) Environmental economics: An elementary introduction. The Johns Hopkins University Press. Baltimore 8. Visvanathan C, Tiong TK (1999) Use of economic tools for Malaysian environmental management. J Strategic Environ Manag 1(4):333–350 9. Weiss J (2000) Some reflections on project economics and environmental issues: A development economist’s perspective. J Econ Stud 27(1/2):126–134

“Breaking Eco-limits” in Coal Mining in the Ústí Region in the Czech Republic: Possibilities, Decision-Making and Consequences Iva Ritschelová, Miroslav Farský, and Egor Sidorov

Abstract The possibility of cancellation of the territorial ecological limits for brown coal mining in North Bohemian Region (Podkrushnohori coal field) was a subject of wide speculation during the whole year 2005. The territorial ecological restrictions for individual mines and dumps determine the limits which should not be exceeded during strip mining and waste dumping activities. These limits are determined to protect the regional communities against the coalface front expansion and to respect the sanitary zones between the outskirts of the villages and the prospective utmost edges of the mine. These limits were established after the “Velvet Revolution” in the Czech Republic of 1991. Their aim was to prevent the further devastation of the landscape and exhaustion of the nonrenewable natural recourses in the region. The speculations about the cancellation of the limits arouse on the basis of refinement of the State Energy Policy of the Czech Republic. The discussion about the national fuel and energy balance, about the possibilities and hazards of the nuclear energy and renewable power sources use and about the power intensity of the Czech economy intensified at the same time. The authors of the paper discuss the possible environmental impacts of the cancellation of eco-limits, its influence on the economic situation in the Czech Republic and in the region itself, as well as social consequences of the respective decision. Keywords Coal Mining · Decision Making · Environment

1 Introduction During last year (2005), considerations of possible removal (“breaking”) of territorial ecological limits of brown coal mining in the Podkrušnohoˇrí coal basin area (Ore Mountains Foothills) attracted the attention of the public, particularly I. Ritschelová (B) University of Jan Evangelista Purkynˇe, 400 96 Ústí nad Labem, The Czech Republic e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_26,

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in the Ústí Region. These considerations originated in the context of the preparation of a more detailed State Energy Policy. They were accompanied by an intensified discussion about the fuel-energy balance from the point of view of national-economy policy, possibilities and risks of nuclear power engineering under our conditions, and about the energy demands of the Czech economy. The State Energy Concept [1] (of 2004) in its chosen and most probable so-called “green scenario” supposes the following coal mining:

Total coal quantity mined (in Mt)

2000

2005

2010

2015

2020

2025

2030

49.46

44.94

44.58

42.01

40.48

35.88

32.59

The basic precondition for this scenario is the growth of the installed capacity of the nuclear power engineering industry, which is not totally free of generally known environmental risks and problems. In this case, the adjective “green” is not used in the environmental meaning but symbolises a free way for the development of the power engineering sector. The chosen green scenario was evaluated [2] from the point of view of environmental impact according to Act no. 244/1922 Coll. The concept of power engineering should start from and be compatible with the raw material policy, whose updated and publicly accessible version it represents [3]. It says that the proposed development of brown coal-based power engineering is debatable because it has no sufficient raw material basis. We can quote: “The brown coal deposits being mined can provide approx. 1.25 billion tons of recoverable deposits that, with decreasing yearly extracted volumes, will ensure this raw material max. till the year 2035. In addition to that, in the areas located above the eco-limits declared by Czech Republic Government Decree no. 391, 444 and 490/1991, there is blocked another 0.97 billion tons of brown coal deposits that, in case they are used, could correspondingly prolong the life of this energy source. Nevertheless, this possible correction is conditioned by the corresponding general consensus in the region, which has to include mine-owners, concerned municipalities, public administration bodies, consent from the Ministry of the Environment, and change to the above-mentioned Government Decrees.” If such consensus is not reached, “. . .the deposits located outside the territorial eco-limits will be completely lost for mining or there will originate such mining conditions that deteriorate the economy of coal extraction and will not enable profitable mining in the future.” The following Table 1 presents basic data on the coal deposits on the Ústí Region territory in the sphere of mining activities and interests of the coal mining companies of Mostecká uhelná a.s. and Severoˇceské doly a.s. The table shows the situation as of 31st December 2003 as is registered in [4].

Source: [5]

Celkem

SD MUS

MUS SD MUS SD

938

x x

324 240 x x

Max. 27.5–32

x x

6.5–7.0 6.5–7.5 x x

10–12 4.5–5.5

2050–2053

x x

2050–2053 2035–2040 x x

2029–2034 2015–2018

356

x x

x 92 x x

x 264

12.5–13.5

x x

x 6.5–7.5 x x

x 6

x x

x 2047–2054 x x

x 2060

451

164 x

x x 163 124

x x

14

5 x

x x 5 4

x x

307 67

SD MUS

Libouš (13.6) ˇ armádyI+II Cs. et., (5.4) Vršany (11,1) Bílina (9.6) Bylany Podlesice -Velká Ves Zahoˇrany ˇ Armády Cs. III+IV et. (39.7 t/y)

Expected Recoverable mined coal per coal reserves Mt year Mt/y

Expected Recoverable mined coal per coal reserves Mt year Mt/y

Expected Recoverable- mined coal per year coal reserves Mt Mt/y

Opencast mine Joint stock (mined Mt in. 2003) company

Extended life till the year

Outside ecolimits

Outside ecolimits

Within the framework of ecolimits

Expected life till the year

Prognosed reserve areas

Active mining areas

Table 1 Coal reserves on the territory of the Ústí region

x x x x

x x

486

33 years x x 486

x x 33 years 31 years

x x

x 8

x x x x

x x

Expected Expected Recoverable mined coal per coal life till the year reserves Mt year Mt/y

Outside ecolimits

Post-prognosis areas

x 60 years

x x x x

x x

Expected life till the year

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2 What are Territorial Limits? The territorial ecological limits for individual mines and dumps determine borders that the open pit mining and its waste dumps should not exceed. The limits are set in a way protecting municipalities in the region against the progress of the working boundary, and they also respect protective hygiene zones between a village boundary and a future boundary of the open pit mine. These limits were set by three government decrees of the “Pithart Government” issued in autumn 1991 that gradually related to the municipality of Chabaˇrovice (no. 331/91), to the whole Podkrušnohoˇrí area (no. 444/91), and to the Sokolov area (no. 490/91). Events and facts that preceded the proclamation of these limits were discussed by I. Dejmal in the bulletin Zpravodaj MŽP 2005, no. 11, page 24–26 as well as in the document “Územní ekologické limity tˇežby in SHP” (Territorial Ecological Mining Limits in North Bohemian Brown Coal Basin prepared by the same author with co-workers, and disclosed in the Naturalists´ website (http://www.ochranciprirody.cz) including cartographic documentation. The above-mentioned decrees impose on corresponding bodies (ministries, district authorities, Czech Mining Office) the obligation to respect these limits and at the same time to modify already delimited mining areas of brown coal opencast mines by so-called writing off of deposits.1 This enables one either to totally remove the deposits from the records or to transfer them to the category of socalled non-balance deposits. In both cases their mining is excluded. Nevertheless, such writing off was applied only in the case of the Chabaˇrovice opencast mine. In practice, the write-off was not used in the Sokolov and Podkrušnohoˇrí area. The limits also restrict the advancement of mines in the Pudkrušnohoˇrí basin, and support pillar barriers protecting some larger towns, industrial premises and traffic corridors as determined by the CSSR Government as early as in 1963. Another pillar protects Jezeˇrí Palace and the adjacent arboretum. Map 1 shows the conditions of individual localities in the North Bohemian Brown Coal Basin and indicates areas to which the breaking of protective pillar barriers relates.

1 According to Act no. 44/1988 Coll. on the Protection and Use of Mineral Resources (The Mining Act), all kinds of coal belong to so-called dedicated minerals, whose volume of deposits and its changes must be recorded by the mining enterprises, and for individual minerals, there are set conditions for the recoverability of deposits that are a set of indicators of quantity and quality of minerals, geological indicators, as well as mining & technical and environmental indicators. Only “recorded deposits” marked as “balance deposits” can be extracted in an industrial way. The reported volume of balance deposits is falling not only because of the mining that has been carried out but also due to the change to the definition of their criteria.

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Map 1 neproduktivní a neefektivní oblasti, ochranné pilíˇre = non-productive and ineffective areas, protecting pillar barriers; oblasti definitivnˇe vyuhlené = definitely mined-out areas; rezervní lokalita = reserve locality; provozované a projektované lomy = operated and planned mines; oblasti výluˇcnˇe hlubiné tˇežby = exclusively deep mining areas

3 Current Positions and Attitudes After a certain lapse of time, the environmentally-orientated public considers the declaration of the limits as a certain compromise between the interests of mining enterprises and the interests and needs of municipalities in the sphere of environmental protection, and as a necessary starting point for the evaluation of the purposefulness of municipal investments. (E.g. the mine-owners can remove Faráˇrka Hill, which could otherwise form a natural protection barrier of the municipality of Droužkovice in the Chomutov district against noise and dust from the Libouš opencast mine, which is getting near to the municipality). In 2005, repeatedly expressed disagreement with the removal of the limits, shown particularly by the inhabitants of the most endangered municipalities – Horní Jiˇretín ˇ and Cernice – attracted considerable attention from the mass media. Nevertheless, it can be seen that part of the current population of the abovementioned municipalities would be willing to leave their place of residence if given sufficient financial compensation (Právo, 4. 4. 2006).

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As far as theoretical economists are concerned – J. Schwarz resolutely spoke out against ecological limits. He requires their removal and says that „it will create conditions for environmental enterprising, new jobs, growth of demand for additional goods and services offered by entrepreneurs from the region (demand for flats, transport and catering services, etc.), growth of income and therefore spending of the local population “(Hospodáˇrské noviny, 23. 6. 2005). The press interprets the attitude of the Ministry of Environment as not supporting „the breaking” of limits. Within the long-term perspective, the Ministry enforces larger use of gas for electric power. So far, this has not been changed – this policy is still followed, even after the “gas crisis” that occurred between Russia and Ukraine at the turn of 2005/2006. In fact, this view is also shared by Senator B. Moldan, who is against the limit removal, too. In his opinion, the threat that Russia could close the valves in gas pipelines can be eliminated by importing gas from various territories that, in addition to Norway, could also comprise the Middle East. (Hospodáˇrské noviny, 9. 1. 2006). According to the joint declaration of the prime minister and the minister of industry and trade of the Czech Republic of 4th January 2006,2 for the meantime, the government will not discuss any repeal of Government Decree no. 444/1991, and will respect the attitude of the representatives of the Ústí Region that will be based on public discussion on the region’s development plan “The government will respect this attitude. In case the Regional Referendum Act passes through the Parliament, this question will be decided directly by referendum.” In November 2005, the Regional Authority submitted for public discussion the “Development plan of the large territorial unit of Ústí Region (ÚP VÚC ÚK) – concept of solution”.3 This documentation considers two alternatives to the development of coal mining in the region: ˇ I. The ecological limits will also be respected in the future: Opencast mine CSA (Severoˇceské doly, a.s.) will terminate coal mining in 2017, and the opencast mine (Mostecká uhelná a.s.) will end mining in 2035. ˇ II. Ecological limits will be “broken”. The coal mining in opencast mine CSA (Mostecká uhelná a.s.) will stop at the line Litvínov-Janovice – Chemopetrol ˇ premises in 2060, and the towns of Horní Jiˇretín and Cernice will have to give way to the mining. The municipalities of Droužkovice fully and Spoˇrice and Bˇrezno partially should give way to the mining activities of Severoˇceské doly a.s. The public discussion about the draft of the development plan was administratively terminated by the Region on 9th February 2006. The date on which the Region representatives will formulate their opinion was not known when this article was prepared (May 2006). 2 See:

www.vláda.cz plan of the large territorial unit of Ústí Region (ÚP VÚC ÚK) – concept of solution. Prepared: April 2005; last update: 10th November 2005. http://www.kr-ustecky.cz/soubory/ 450018/vuc%5Fkolektiv.pdf 3 Development

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4 Impacts of “The Breaking” of Limits on the Environment Regarding the fact that one expects neither an increase in mined coal volume nor a decrease in the quality of mined material, the volume of emissions connected with mining should not exceed the current level (so-called gob-fires and spontaneous ignition). Subsequently, emissions from coal-burning power plants and thermal stations should not increase, on the assumption that general overhauls of current equipment units being at the end of their service life do not reduce efficiency of operation. Nevertheless, the “breaking” of the limits “will result in continued landscape devastation due to both transfer of mine stripping and coal substance mining as well as by origination of mine pits and external spoil banks”. As an illustration of the volume of mass to be handled, we present data taken from published company documentation. 2003 Company MU SD

2004 Coef.

Coal mined (Mt) Mine strippings (mil. m3 ) Coal mined (Mt) Mine strippings (mil. m3 )

16.5 29.6 23.4 91.1

1.8 3.9

Coef. 15.8 33.4 21.1 77.0

2.1 3.6

Coef. = m3 of mine strippings per 1 t of coal mined

5 Comments on Land Reclamation Works The opencast brown coal mining on the territory of Ústí Region from its beginning (as early as in 19th century) up to now has afflicted an area of 250 km2. From the 1960s about 116 villages and towns, including the historic centre of the town of Most, have been liquidated, and 90 thousand inhabitants have been moved out in connection with it. According to section 35 of Act no. 44/1988 Coll. on the Protection and Use of Mineral Resources (The Mining Act), the mine-owner is obliged to carry out complete treatment of areas and territorial structure affected by mining, i.e. land reclamation. Reclamation works are particularly focused on the area of spoil banks and other areas connected with coal mining, i.e. residual pits, mining (stripping and haulage levels) sides of former opencast pits, subsidence due to former underground mining areas indirectly affected by mining (former railway lines, areas of former buildings connected with mining activities), etc. Renewal of the function of disturbed landscape is, inter alia, supported by Government Decree no. 50/2002 and 272/2002 on the drawing of financial means intended for the removal of environmental damage that originated before the privatisation of brown coal mining companies in Ústí Region and Karlovy Vary Region

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defining the co-financing by the state. (According to the former Decree mentioned, it complies with the intention to gradually earmark CZK 15 billion from obtained privatisation yield, with the first drawing amounting to CZK 3 billion). The following Table 2 shows the registered area of land reclamation works in so-called coal basin districts of Ústí Region (Ústí n. L., Teplice, Most and Chomutov): (a) Works completed by 31st December 2003. (b) Works to be completed within the period 2004–2020 when respecting ecological limits. It is clear that even when the limits are adhered to, landscape devastation and subsequent land reclamation works will finally affect (at the level of the year 2020) at least 18% of the area of Most district, approx. 7% of the area of the districts of Teplice and Ústí nad Labem, and 3% of the area of Chomutov district. The data presented in Table 2 further show that the percentage of hydro reclamations is growing, while in the already completed land reclamations (ad a) this share amounts to 2.7%, and in the land reclamations that are to be completed by 2020 (ad b) it amounts to 8.3%. The percentage of hydro reclamations is also in good agreement with the water areas share (10.2%) of the total year-on-year increment of environmentally valuable water and forest areas in the nationwide balance for 2000– 2005 period as is documented by data in Table 3. (Another type of environmentally valuable land area, i.e. agricultural land, shows decrements in this period). One can say with certain simplification that this trend positively correlates with the original biotype of the landscape of the Ore Mountains Foothills. In prehistoric times, a large lake existed below the Ore Mountains but its area gradually shrank (first due to sedimentation and later as a result of human activity) and the area gradually divided into several smaller lakes. The largest was Komoˇranské Lake located to the northwest of the town of Most. This is described both in the monographs ˇ of exile P. Stránský (Ceský stát, 1634) and by B. Balbín, S. J. (Miscellanea historica Regni Bohemiae, 1679–1687). Another lake (called Bˇrvanské jezero) is known from other sources. All the lakes had to get out of the way for industrialisation and mining. The only reminder of the lakes is the German name of the municipality of Ervˇenice, “Seestadt” (i.e. town by the lake).

6 Economic Consequences of “The Breaking” of Coal Mining Limits One of the frequently used arguments in favour of “the breaking” is a supposed increase in the number of jobs and decrease in the unemployment rate in the region. Nevertheless, this is a debatable argument. In fact, coal mining will not increase, it will “only” be relocated, which means that a dramatic growth of new jobs cannot be expected, and it would be correct to speak rather about maintenance of employment.

572 1, 268 797 3, 834

469 467 935 x

a Existing ecological limits are adhered to Source: [5]

1, 197

404

Ústí nad Labem Teplice Most Chomutov Total

Agricultural

District area in km2

Territory of former districts

1, 085 2, 270 105 4, 073

613

Forest

90 121 21 252

20

Hydro

142 1, 094 58 1, 337

43

Other

1, 889 4, 753 981 9, 496

1, 873

Total

4.03 10.18 1.05 x

4.63

% of district area

340 568 801 1, 769

60

780 28 1, 468 411 800 0 3, 722 696

674 257

436 1, 311 256 2, 150

1, 584 3, 758 1, 857 8, 337

3.38 8.05 1.99 x

147 1, 138 2.82

Agricultural Forest Hydro Other Total

% of district area

Land reclamation completed as of 31st December 2003 (ha) Land reclamation to be completed in 2004–2020 (ha)a

Table 2 Land reclamation after brown coal mining Ustí region

7.41 18.23 3.04 x

7.45

Total % of district area

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Table 3 Recap of available and usable potential of renewable resources in the Czech Republic Technical potential Renewable resources Solar energy

Wind energy

Geothermal energy and energy of the environmentc Energy of water streams

Biomass

Total

Technology Solar liquid collectors Photovoltaics Wind-power plants >60 kW Hydrothermal >130◦ Ca Hydrothermal <130◦ C Heat pumps Large hydroelectric plants >10 MW Fuel Firewood and waste wood, otherb Cultivated biomass Biofuels and biomass

Available potential Current use

Electricity Heat Heat PJ GWh PJ

Electricity Electricity GWh Heat PJ GWh

25

–

17

–

0.4

–

–

23,000 16,000

– –

5,500 4,000

– –

0.03 4

–

35

–

3.5

0.2

–

< 0.1

–

< 0.1

–

< 0.1 –

– 13,100

< 0.1 –

– 1,165

–

1,850

– 78

–

– 45

1,115 –

– 22

705 420

275

–

136

–

–

.

33

–

16

1,200

2.5

214

12,984

25.1

–

2,979

a So-called hot dry rock heat; b other solid biofuels; c hot water taken from bore wells for water supply and spa purposes technical potential (theoretical potential) is technically available generation of energy regardless of other limitations; available potential (attainable potential) – technical potential limited only by known administrative, legislative, environmental and other limits that can be defined and determined Source: [7] according to association for the use of renewable energy resources and own calculations

Possible newly created jobs will have prevalently a manual work character, and due to the existing system of social insurance, they are difficult to fill from local labour resources. In many cases, the only labour available is from abroad. If long-term coal mining in the Czech Republic is in compliance with the State energy concept, further reduction in employment can be expected after 2020. This trend could be compensated by possible higher work intensiveness of coal mining due to more difficult mining conditions, which would probably be reflected in the price of coal, which may influence the demand for coal. A question that could be answered only after special research asks whether one could create more jobs in connection with land reclamation. An unofficial assessment of contributions from land reclamation financed by the National Property Fund

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that have been obtained so far nevertheless indicates that the promised increase in the local employment rate is usually not achieved.4 We assess any further use of reclaimed areas for economic activities in industrial zones, for building, transport, etc. in the future in a sober way. One identifies information that supports the statement saying that in the region, there exist sufficiently large and unused areas for the development of these activities within the framework of municipal industrial zones as well as in the Triangl zone (former military airport in the town of Louny area), where the Ústí Region is investing. The data on the volume of land reclamation in progress and on that planned for completion by 2020, as given in Table 3, respect the ecological limits. Their possible breaking would result in a marked increase in the volume of land reclamation works. A well known situation in Czech agriculture, particularly in the context of the EU agricultural policy, does not motivate agriculture to acquire new areas for growing traditional crops of this region. A certain possibility is agro-energy, particularly the growing of suitable crops for biomass production that could be added to solid fossil fuels burnt in power plants and thermal stations to decrease fossil fuel consumption. Vegetable oil produced from rapeseed can be used for methyl ester production, which can be added to diesel oil, which subsequently reduces petroleum imports. We also cannot a priori exclude the growing of such crops that could be processed by fermentation to provide ethanol for use as an additive to gasoline, which would again reduce petroleum import. The importance of biomass as one renewable energy source (RSE) is documented by the data in Table 3 that recaps the available and usable potential of renewable resources in the Czech Republic. The Ústí Region is a territory with good prospects for the practical application of agro-energy or phyto-energy. According to the EU criteria, this region is rated as LFA (Less Favourable Areas) for agriculture in spite of the relatively high share of agricultural lands, particularly meadows and pastures that are not used for agricultural production and are left fallow. At the Faculty of the Environment of J. E. Purkynˇe University in Ústí nad Labem, there was, within the framework of a research intention called “Research into Anthropogenic Loads in the North Bohemian Region,” solved a partial project, DÚ 1.3 “Possibilities of the Development of Agro-energy in North Bohemia”.Within this research, whose course, results, and publication output has been summarised in [6], there were recommended, inter alia, suitable plants and areas for their growing.

7 Conclusions The decision about the breaking of limits of coal mining should be preceded by a complex evaluation of the economic impacts of such decision, as well as the economic consequences of land reclamations that have been carried out so far. These aspects have been assessed nearly exclusively from the point of view of landscape 4 For

this, see for example:: Profit, 2004, no. 22–23, pp. 24–25, no. 26, pp. 20–21

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ecology (see e.g. [8, 9]). When choosing the optimum investment alternative, it is necessary to apply the method of Cost Benefit Analysis, which comprises not only financial cost and revenues for the investor but also associated induced cost and benefits in the sphere of public goods and services.

References ˇ 1. Státní energetická koncepce Ceské republiky (approved by Government Decree of the Czech Republic, no.211 of 10th March 2004) http://www.mpo.cz/xqw/webdav/-UTF8-/dms_mpo/ getFileinternet/10768/12925/SEK.doc 2. Posouzení vliv˚u SEK na životní prostˇredí (2004) Prepared by: Tebodin Czech Republic, s.r.o. http://www.mpo.cz/scripts/modules/dmsdoc/document.php?lid=1&dlid=1&id=10766 3. Surovinová politika v oblasti nerostných surovin. Editor: Ing. Lenka Benešová (2004) http:// www.mpo.cz/xqw/webdav/-UTF8-/dms_mpo/getFileinternet/10769/791/surpol.doc 4. Roˇcenka životního prostˇredí Ústeckého kraje 2003, Ústí n. L., KÚ 2005 5. Koncepce smˇer˚u rozvoje zemˇedˇelství a venkovských oblastí Ústeckého kraje (2005) Prepared by: ARR Euroregionu Labe, o.p.s., November 2005. http://rozvojkraje.kr-ustecky.cz/soubory/ 450018/koncepce%5Fsmeru%5Frozvoje%5Fzemedelstvi.pdf ˇ 6. Vráblíková J, Vráblík P (2006) Možnosti rozvoje agroenergetiky v severních Cechách. In Studia Oecologica. Ústí n. L. UJEP, being printed ˇ v kontextu státní energetické koncepce a 7. Beranovský J, Truxa J (2005) Plánování OZE v CR EU. Edited. http://www.energetika.cz/index.php?id=71&cl=12 8. Prach K (2006) Pˇríroda pracuje zadarmo. Vesmír 5:272–277 9. Šípek V (2006) Rekultivace – teˇcka za tˇežbou uhlí. Vesmír 5:304–305

Relationship Between Tourist Education and Development Perception About Environmental Impact of Tourism Development R. Shakeri and A. Barati

Abstract In this research the quantity of tourism information and acquaintance was studied for tourism development effects on different environmental parameters in Namak Abrood, a recreational area of Iran. Findings showed that the tourists had a variety of views about the tourism activities’ effects on environmental factors. Generally, they evaluated these effects with the low and medium quantities. Study of responders’ education degrees also showed that the different individuals, aside from their education degrees, had almost similar views. From the views of tourists, the relation between quantity of chargeability and the actions of different groups (tourists, managers and institutions of tourism development and local people) was considered insignificant in decreasing of environmental quality. According to their views, all involved groups in tourism development had the same share in the decrease of environmental quality. Results from this study showed a decrease in psychological expectation level of individuals using a limited area for recreation, and also showed an increase of tourism psychological carrying capacity. On this basis (63.4 ± 8.06) present of responders, suggested 5–20 family (20–80 person) for recreational use of land with an area of one hectare, that was very higher than the current standard psychological carrying capacity of Iran (7 persons, about 2 family per hectare). Keywords Tourism · Recreation · Environmental information · Psychological carrying capacity · Education

1 Introduction The quantity of acquaintance and information of persons who any way, involved in tourism development process (tourists, local people and managers of tourism development) is one of the important factors in tourism development discussions. R. Shakeri (B) Natural Resources Faculty, Chamran University, Ahvaz, Iran e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_27,

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Hillery et al. [2] studied the relation between environmental factors that affect the area and tourists’ conclusions from this at ten regions in central Australia. His results suggested that in spite of non significant environmental effects in these regions, tourism conclusion of tourism environmental effects was different. Even though the environment is considered as an raw material in tourism development [7], it is evident that the rate of tourism activities correlated to the environmental quality. Tourists tend to their use recreational area which have the highest environmental quality. If the environment quality does not provide the tourists expectation, some of them may change their travel paradigm [3]. Kaywood [5] stated that many of involved groups in tourism development such as tour managers or local people, and also tourists, agree that the tourism experience decreases and damages, with a resultant decrease of environmental quality, crowds, population etc. Tourism development is dependent on high environmental quality and is the best choice for long term benefits of tourism industry, growth and sustainable development control of this industry and also for evidence of these effects. For correct tourism management it is necessary to acquaintance from the ideas and views of tourists, local people and the persons who, anyway affected by tourism development, and also it is necessary to present intended information, programs, and limits to these people and to get their view and their suggestions. On this basis, an analytical assessment of tourists views, and their understanding level and interpretation of tourism environmental effects was done about tourists who has used Namak Abroud cable car facilities for a definite time period.

2 Materials and Methods 2.1 Studies Area Namak Abroud is a small tourism town that is located 12 km far from the west of Chalous, in north of Iran. This area is restricted from he north by Caspian Sea, from the south by Medoben mountain, a part of Alborz mountain range, and from the west by the farmlands. This small town is designed and constructed on a land with an area of 650 ha, with two main purposes: residency development (220 ha) and tourism development. Amusement park, cable car, artificial lake, athletic field, coastal recreational center, shopping center and services facilities are some recreational and tourism facilities that designed for tourism development in this area. Cable car is one of the important attraction of this area that is located on the south west of Namak Abroud and provide people for reaching to the beautiful peak of the Medoben mountain. At the top of the mountain a restricted land with an area of 2,975 m2 is allocated tourism use. The medium height of this area from the sea level is about 980 m. Prominent forest community in this area is the Fagetum. The most traditional use of this area also are picnic and forest sight seeing.

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According to the weather condition in different seasons and also according to the number and distribution of holidays the average of tourists differ through the year as at the holidays is between 2,500 and 3,500 (person per day) and at the other days differ from 700 to 1,000.

2.2 Methods This research was accomplished with survey method: A well recognized collection of data that provide with questionnaire method is the important feature of this method. Statistic community: Statistics community of this research is the people who had used the Namak Abroud cable car facilities as tourists during the sampling time.

2.3 Sampling Methods Studies individuals in this research were selected with random sampling method and for reaching to the best results, according to the increase of returning time, tried to diminish interfere variables, such as holidays.

2.4 Sample Volume According to the primary available and approximate estimation of the whole statistical community, and with the use of Cokran formula, 144 questionnaires were selected. n=

1+

t2 p.q 2 d2 t p.q 1 N d2

−1

As the sample volume following formula was used for calculating of up and down threshold of the parameters. %E =

pi .(1 − pi ).t2 .100 n

2.5 Definitions Tourist: In this research tourist is the person who comes from out to the studied area and use cable car facilities. Several suitable criteria (Table 1) were used for testing and measuring of tourist’s receptions and conclusions; and for each criterion, several indicators presented description statistics were used for analysis of data.

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Table 1 The criteria assumed for assessment of tourists conclusion about environmental effects of tourism development Criteria Tourism conclusion from environmental effects of tourism development

Indicators

Impact on economic condition of the area Impact on cultural condition of the area Impact on social condition of the area Impact on natural parameters

Air pollution Soil and water pollution Destruction of forest and plant vegetation Change of natural landscape Wildlife destruction

Effect rate of different person function on the destruction and decreasing of environmental quality

Function of local people Function of tourists Function of tourism development managers

Psychological carrying capacity

Suitable family number for recreation on a region with an area of one hectare

3 Results 3.1 Psychological Carrying Capacity from the View of Tourists Psychological carrying capacity as one of the different kinds of tourism carrying capacity means the number of individuals that can use a tourism area, without any disturbance and tension to each other. Psychological carrying capacity is completely depends on the level of tourists expectation and their ways of thinking. The question of (how many families (with 4 persons) can recreation on a land, with and area of one hectare) was suggested for awareness of tourist’s conclusion and the level of their expectation. The results of testing and majoring of these criteria is showed in Table 2.

Table 2 Psychological carrying capacity from the view of tourists

Suggested family number by tourists

Frequency

Percent

5–20 20–50 50–150 150–200 Sum

52 46 28 16 142

36.6 32.4 19.7 11.3 100

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According to these results, tourists have suggested 5–20 family for recreation on a land with and area of 1 ha. The results also show that from the view of (36.6 ± 8.088) percent of tourists, 5–20 family is suitable for this purpose.

3.2 The Effects of Tourism Activities on Economical, Social, and Cultural Condition of Destination Society On the base of findings evaluation of the most of tourists was positive about the effects of tourism development on economical and cultural conditions of the area (Table 3).

Table 3 Tourists estimations from the tourism development effects on economical, social and cultural conditions

Economic condition Cultural condition Social condition

Effective impact

Without impact

Negative impact

Number

Frequency

Percent

Frequency

Frequency

142

123

86.6

11

7.7

8

5.6

142

86

60.6

31

21.8

25

17.6

141

94

66.7

25

17.7

22

15.6

Percent

Percent

3.3 Effect of the Development of the Tourism Activities on Important Environmental Factor Studied Area Generally it seems that tourists are concern about the consequences, that decrease the possibility of use of recreational areas and they also concern about the remind thing from other tourists. Probably from the view of an ecologist these effects have low importance, because these effects are easily returnable and have little damage on functions of natural ecosystem. Thus for management and programming of tourism development it is necessary to consider test and compare of the conclusions and understanding of ecologists, tourists and managers of tourism development [6]. Some indicators were determined for testing and measuring of tourists ideas about this subject and for each indicator one spectrum with five sections was determined. On this basis the result of answers of each indicator is come in Table 4. Survey of tourists, about the amount of relationship between decrease of environmental quality and the effects of act’s of the groups that any way associated in tourism development process was considered as the other criteria in this research.

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Table 4 Tourists estimation from the effects of tourism development on environmental conditions of the studied area Tourist estimations from the effects of tourism development on each indicator and evaluation grade

Air pollution Soil & water pollution Forest & vegetation destruction Decrease of natural landscape Disturbance for wildlife Sum of rows Mean of effects percent

Very high (5)

High (4)

Medium Low (3) (2)

Very low (1)

Without impact (0)

Sum of columns Average

12.7 (17) 24.6 (33) 27.4 (37)

10.4 (14) 9.7 (14) 5.2 (7)

4.5 (6) 17.2 (23) 19.3 (26)

14.9 (20) 14.2 (19) 24.4 (33)

8.2 (11) 9.7 (13) 8.1 (11)

49.3 (66) 24.6 (33) 15.6 (21)

100 (134) 100 (134) 100 (135)

1.57 1

22.1 (29)

10.7 (14)

12.2 (16)

11.5 (15)

11.5 (15)

32.1 (42)

100 (131)

2.24 2

15.7 (21) 99.5 19.9

6 (8) 42 8.4

13.4 (18) 66.6 13.3

10.4 (8) 71 14.2

10.4 (14) 47.9 9.58

48.5 (65) 170.1 34.02

100 (134) 500 100

1.65 1

Table 5 Tourism conclusions about the effects of different group functions in decrease of environmental quality

Tourism conclusion about the function effect Local people Tourists Tourism development managers Sum

Frequency 50 45 49 144

2.51 3 2.73 3

10.7 2.14

Percent 34.7 31.3 34 100

Acquaintance from the way of thinking and conclusions of tourists is benefit for management and programming of tourism development. The results are in Table 5. The education degree of individuals can be considered as effective criteria in recognition and acquaintance of individual from environmental subjects. On this basis degree of education of persons who was studied, and their views about the environmental effects of tourism development is shown in Table 6. According to the chi-square test, the relation between degree of education and views 2 about the environmentaleffects of tourism development was not significant x = 5.545, df = 5, p = 0.353 .

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Table 6 Comparative table of tourism education degrees and the quality of conclusion above the environmental effects of tourism Kind of conclusion about the effect Degree of education Academic Below the academy Sum

Without impact

Very little

little

medium

much

Too much

sum

6 3

26 28

12 9

13 9

6 9

8 2

71 60

9

54

21

22

15

10

131

4 Discussion and Conclusion According to the results of this research, one of noticeable subjects is the decrease of psychological expectation level of people in use of a limited space or recreational purposes. 36.6 ± 8.08 percent of tourists who was studied in this research suggested 5–20 family (about 20–80 person) for the use of a land with an area of one hectare and from the view of 63.4 ± 8.08 percent. Suitable number of family for this purpose was very higher than standard psychological carrying capacity. Suitable number of family for this purpose was very higher than standard psychological capacity. Standard psychological carrying capacity for Iran is 7 persons (about 2 families per hectare). It seems that high requirement of people for recreation, and the deficiency of available facilities and services in this field cause the people to accept more people beside themselves in tourism areas and so the expectation level of people has noticeably decreased. The high percent of tourism is studied area and medium or good consent of many of them (%50.7 ± 8.39) approve our claim. Hadavi et al. [1] reached to the similar results in this subject. The rate of psychological carrying capacity that they reached from the view of local people in marginal recreational areas of Chalous road was about 110 user unit per hectare. According to the result, tourist conclusions about the effects of tourism development, activities, on environmental factors can be showed in different spectrum. It seems that, about the factors that have visible and evident effects, understanding of these effects and also the relation between tourism development and its effects on environmental quality is easier for tourist. On this basis and according to the tourist answers, the most impact of tourism development was in order on forest and vegetation destruction, soil and, soil and water pollution, and the change of natural landscapes.

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According to the results different effects of tourism development activities on quality of environmental factors generally was evaluate as low and medium, while study of different environmental parameters especially result from the study of soil and vegetation study [9] is represent the vast change of the factors, by tourism activity. Subjective change of some parameters such as plant vegetation, erosion, landscape change and etc. at the first, looks understandable for every person. Thus some false view of tourism about the degree of tourism activities effects on quality of environmental factors can be considered as an approval on lake of suitable environmental education and diversity of their information and acquaintance about the tourism effect on natural environments. According to the results from the view of 64.7 ± 7.9 percent of tourists, the most rate of effects on environment results from function of local people and tourism development managers, and only % 35.3 ± 7.96 considered more responsibly for function of tourists compare with two other groups. According to the result of chi-square test, relation between the effects of different group function in decrease 2 of environmental quality was non significant x = 0.292, df = 25, p = 0.864 . At a similar study about tourist’s ideas of responsibility rate of different group, including tourists, tourism development managers and local people in making destructive environmental effects in Mykonos, showed that from the view of tourists, managers and local people had the more share and according to the local studies in this area, native people had the most share in making the ecological effects to the others [4]. According to the different studies, because the different goals, expectation level and the way of thinking, important degree of different ecological effects and also recognition of this effects is completely differ between and in of different groups and many of tourists have little information about the ecological effects and some even is not able to recognize ecological effects [6]. Education system has an important role in directing to environmental interests and increase of people information and acquaintance about environmental subjects. Stockholm conference has imposed on the role of education system in giving awareness to people and acquaintance them with environmental subjects. Official education is one of the easiest ways to the main group of people. International conference of environmental education in Tefllis, in 1979 considered as the maximum point of education efforts for environment. The best achievement of this conference is the education manifest to of environment. the conference is regret for the lake of environmental education of specialist groups that caused them not to understand polymorphic characteristics of environmental problems and consider the education of person as the most important need of environment education in the world. Thus notice to the environment education in educational program of businessman who their activities and decisions are effective on environment is a critical subject [8]. The result of comparison between education degree of responders (tourists) and their view about the environmental effects of tourism development shows that

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different people and most of them estimated the effects of tourism development on environmental condition at low or very low rates. This issue in addition to the approval of previous findings of this research in environmental information deficiency of tourists, also emphasis to the necessity of more consideration to increase of people environmental acquaintance at different education levels of official education process.

References 1. Hadavi S et al (1994) Studying of psychology and ecological carrying capacity of chalous road. MSc Thesis, Natural Recourse Faculty of Tehran University, Iran 2. Hillery M et al (2001) Tourist perception of environmental impact. Ann Tourism Res 28(4):853–867 3. Inskeep E (1987) Environmental planning of tourism. Ann Tourism Res 14:118–135 4. Kavallinis I, Pizam A (1994) The environmental impacts of tourism whose responsibility is it anyway? The case study of Mykonos. J Travel Res 33(2):26–32 5. Kaywood M (1986) Can the tourist are a life cycle be made operational? Tourism Manag 7(3):154–167 6. Martin SR, Mecool SF (1989) Wilderness campsite impacts: Do managers and visitors see them the same? Environ Manag 13(5):623–629 7. Mlinari IB (1985) Tourism and the environment: A case for Mediterranean cooperation. Int J Environ Studies 25:239–245 8. Scientific Technical and Professional Part of UNESCO (1991) International teaching of environment. Translated by F. Borumand, 1991. National UNESCO Commission, Iran 9. Shakeri R (2004) Study and preparation of environmental impact assessment guidelines for developing tourism plans. MSc Thesis, Natural Recourse Faculty of Tarbiat Modarres University, Iran

Assessment of Dangerous Substances Release from Construction Products to Environment Nicoleta Schiopu, Emmanuel Jayr, Jacques Méhu, and Pierre Moszkowicz

Abstract In 2005 the European Commission mandate CEN to prepare test methods with which construction products can be tested with respect to the potential release of dangerous substances to water, soil and to indoor air. A horizontal approach is considered the best route for such test development. Horizontal approach means that it is product independent and consists of the development of a test method applicable for different products used in a certain scenario. This action will satisfy the needs resulting from Essential Requirement n◦ 3, on Hygiene, Health and Environment, as specified in the Construction Products Directive. In this context, the aim of the work presented here is to study the release mechanisms and the parameters which could influence the leaching of pollutants from construction products towards soil and water, in order to provide information for the development of a horizontal test. The research has been carried out on monolith products, based on three types of matrices: concrete, wood and metal (zinc). For the concrete products, one of the choice criteria was the presence of trace metals (e.g. chromium VI); the wood products are pertinent candidates for our study because of the preservation treatment, which by definition is toxic for some form of life (biocidal substances are used for the treatment); as for the zinc based products, research on contributions of the different sources of urban run-off pollution, showed a very high concentration of zinc (up to 6 mg/L in a catchment in Paris) in roof run-off. Also, this source represents a very high percentage among other urban run-off pollution sources (92% from roof vs. 8% from yard and street run-off). Keywords Dangerous substances · Construction products · Environmental assessment · Leaching behaviour

N. Schiopu (B) Sustainable Development Department, CSTB – Scientific and Technical Centre for the Building Industry, 24, rue Joseph Fourier, 38400 Saint Martin d’Hères, France; Laboratory of Environmental Assessment of Industrial Systems and Process (LAEPSI), INSA de Lyon – National Institute of Applied Sciences of Lyon, 9, Rue de la Physique, 69100 Villeurbanne, France e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_28,

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1 Introduction In 2005 the European Commission mandate CEN to prepare test methods with which construction products can be tested with respect to the potential release of dangerous substances to water, soil and to indoor air [8]. A horizontal approach is considered the best route for such test development. Horizontal approach means that it is product independent and consists of the development of a test method applicable for different products used in a certain scenario. This action will satisfy the needs resulting from Essential Requirement n◦ 3, on Hygiene, Health and Environment, as specified in the Construction Products Directive [7]. The most common tools for the environmental assessment of leaching behaviour are the leaching tests. Widely developed for waste (end-of-use phase of a product) [6, 1, 10], the existing leaching tests for the lifespan phase, are product specific and not scenario specific tests [4, 5]. Previous research on mineral materials showed that in addition to the intrinsic properties of the material (total content, porosity, etc.), parameters of the scenario conditions such as the leachant hydrodynamics (continuous or sequential renewal, liquid to solid ratio), leaching reactor type (closed, open) may also contribute to the release behaviour of the products’ constituents [12, 15]. The present research has been carried out on monolith products which were chosen by taking into account their (1) structural and physico – chemical characteristics: an inorganic (non – metallic) porous product, an organic porous product and a metallic non – porous product; (2) leaching mechanism: different dominant mechanism (diffusion, dissolution etc.); (3) representativeness on the market; (4) dangerous substances content: products which a priori could lead to some pollution problems. The three studied products are: the concrete paving slabs, the wood duckboards and the zinc gutters. Regarding the fourth choice criterion of the products to be studied (dangerous substances content), the concrete products were chosen because of the presence of trace metals (e.g. chromium, zinc, copper etc.). The wood products are pertinent candidates for our study because of the preservation treatment, which by definition is toxic for some form of life. Nowadays, the most widely available wood treatments are copper-based. Without the chromium and arsenic, as in the case of CCA preservatives, copper based compounds are seen as environmentally preferable to previous generation of preservatives. However, without chromium, which helps the copper bond tightly to wood, these types of preservatives are more subject to leaching [2]. We chose to study a wood product treated with a last generation preservative, based on copper-boron-propiconazole [13]. As for the metallic product, i.e. the zinc gutter, research on contributions of the different sources of urban run-off pollution, showed a very high concentration of zinc (up to 6 mg/L in a catchment in Paris) in roof run-off. Also, this source represents a very high percentage among other urban run-off pollution sources (92% from roof vs. 8% from yard and street run-off) [9]. The work presented here is a part of a larger research program and the methodology adopted for the overall research is presented elsewhere [14]. The aim of this part is to study the release mechanisms and the parameters which could influence the leaching of pollutants from construction products towards water. In order to achieve

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this objective, the experimental program was organised in two parts: (1) characterization of some intrinsic proprieties of the tested products, such as the porosity (for the porous matrices) and the composition of the pore water and (2) determination of the leachant hydrodynamics influence on the release (dynamic tests).

2 Materials and Methods The concrete paving slabs were manufactured by using a CEM I – based concrete, supplied by a concrete mixing plant (ready-mix concrete). The concrete was cast in rectangular moulds of 16 × 13 × 4 cm3 and cured in bulk form at room temperature in a humid environment for 28 days. The wood duckboards are a pine wood type (Pinus Sylvestris) industrially preservative treated for outdoor use in risk class IV (wood placed horizontally outside, wood in contact with fresh water etc.) [3], with some active substances based on boron-copper-propiconazole. The zinc gutters is made of a zinc alloy with 0.13% Cu and 0.05% Ti.

2.1 Physico-chemical Characterisation of Products A first characterisation of products (total content, acid/base neutralisation capacity (ANC/BNC), pH influence on release . . .) was carried out and reported in previous works [13, 14]. Here, are presented the Water Porosity Test (WPT) and Pore Water Test (PWT) carried out on the two porous products chosen for the research: the concrete slabs and the wood duckboards.

2.1.1 Water Porosity Test (WPT) The water porosity test was carried out in order to assess the “open water porosity” (i.e. volume of pores accessible to water: ε, %) of the porous products. The test is based on the determination of the water quantity absorbed by a sample of the product. In a close reactor, at room temperature and low pressure (∼10−3MPa), after a 4 h degassing phase, the sample was slowly immerged in demineralised water and maintained like that for 20 h. At the end of the test, the water saturated sample is weighted firstly immerged in water (hydrostatic balance method, mwater ) and than in the air (mair ). The mass of the dry (at 105◦C) sample was also measured (mdry). The “open water porosity” is given by the equation: ε = 100 · mair − mdry / (mair − mwater ).

2.1.2 Pore Water Test (PWT) The Pore Water Test objective is to estimate the initial composition of pore water. The test was carried out on crushed samples (≤1 mm), at natural own pH of the

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products (in demineralised water) and decreasing liquid to solid (L/S) ratio (which means the ratio between the volume of the leachant and the mass of the sample): 15, 10, 5, 1, 0.5 L/kg (in the case of wood sample a test at lower ratio than 5 L/kg wasn’t possible because of a too small quantity of “collectable” eluate). The leaching vessels were agitated by an end-over-end tumbler. The equilibrium conditions were reached before 48 h (in order to check the stationary state, some tests were conducted up to 10 days). At the end of the test, the pH, the conductivity and the potential redox of eluates were measured. After filtration (0.45 μm) the eluates composition was analysed by ICP-AES (Jobin Yvon ULTIMA 2): B (DL = 0.002 mg/L), Ca (DL = 0.001 mg/L), Cu (DL = 0.001 mg/L), K (DL = 0.072 mg/L), Na (DL = 0.009 mg/L), Zn (DL = 0.001 mg/L), by ion chromatography (Dionex IC 25): Cl− (DL = 0.5 mg/L), SO4 2− (DL = 0.5 mg/L), and by using a COT-meter 5000 A Shimadzu for the dissolved organic carbon: DOC (DL = 0.5 mg/L). The concentration errors were estimated to be up to 5%.

2.2 Dynamic Leaching Tests In order to study the leachant hydrodynamics influence on the release, two dynamic tests were carried out on the three products. 2.2.1 Continuous Monolithic Leaching Test (CMLT) The Continuous Monolithic Leaching Test is a dynamic test with continuous flow of the leachant, based on a protocol developed by Polden / Insavalor [11]. The monolithic sample(s) is (are) placed in a reactor (Fig. 1) and completely submerged in

Fig. 1 Experimental set-up for the CMLT (Continuous Monolithic Leaching Test)

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demineralised water (the leachant) all along the test period (64 days), at a L/A ratio of 5 cm3 /cm2 (the L/A ratio means the ratio between the volume of leachant and the geometric surface of the sample) and a renewal rate of 0.52 cm3 /cm2 /h (cumulative renewal rate about 800 cm3 /cm2 ). In the reactor, the local homogenization of the leachant is assured by an efficient stirring. This stirring was performed by a loop recirculation of the leachant with a peristaltic pump at a flow rate of 18 L/h. The eluate is collected in separate fractions after a fixed period of time: 2, 4, 8 h, 1, 2, 4, 9, 16, 36 and 64 days. Two types of eluate sampling were carried out: (1) a punctual sampling (beginning with the second day of leaching, a minimum quantity of eluate (∼25 mL, needed for analysis) collected at the end of the fixed periods of time) and (2) an average sampling (all eluate collected during the fixed period). The collected eluates were filtered through 0.45 μm pore size membranes. The eluate parameters (pH, conductivity, redox potential) and the concentration in the targets elements were monitored, following the same protocol as for the PWT.

2.2.2 MultiBatch Test (MBT) The MultiBatch Test is a dynamic test with sequential total renewal of leachant (Fig. 2). The protocol is based on the Dutch standard NEN 7345 [10]. As for the CMLT, the monolithic sample(s) is (are) placed in a reactor and completely submerged in demineralised water at a L/A ratio of 5 cm3 /cm2 but without any stirring. A total renewal of leachant is carried out at the same fixed period of time as for the CMLT sampling (2, 4, 8 h, 1, 2 etc. days). The cumulative renewal rate over the all period of test (64 days) was about 50 cm3 /cm2 . All the eluate is collected and analysed, at the end of each fixed period. The parameters of two dynamic tests (leachant nature, L/A ratio, sampling period. . .) are chosen as similar as possible, in order to make pertinent comparison of their results. The main protocol differences between CMLT and MBT consist in the reactor type (open – i.e. matter exchange with the exterior – or closed) and in the eluate hydrodynamics (sequential or continuous renewal).

Leaching reactor Monolithic sample

Fig. 2 Experimental set-up for the MBT (MultiBatch Test)

Sample supports

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3 Results and Discussion 3.1 Physico-chemical Characterisation of Products The main physico-chemical parameters of the products are listed in Table 1. The initial pore water composition was estimated by using the regression equation of the concentration vs. L/S ratio trendline (logarithmic scale). The concentration for the L/S ratio corresponding to the saturated open porosity was estimated by a backward forecast (Figs. 3 and 4). This L/S ratio (porosity L/S ratio) is estimated from the WPT (Table 1). The density and porosity values obtained for the two porous products are in agreement with literature data [16, 17]. The Figs. 3 and 4 show that a decrease in L/S ratio induces a slightly pH decrease (a 0.18 slope), in the case of the wood duckboards and a pH increase (a – 0.23 slope) in the case of the concrete slabs. The pH values of the concrete product are in agreement with the observed concentration of Na, K and Ca, which are higher in the pore solution. The low acidity of the wood product (pH in the pores water estimated at around 5) appears to be independent of the alkaline metals.

Table 1 Main physico-chemical parameters of the products Product Parameters Density (ρ), kg/m3 Humidity, % Open porosity (ε), % Porosity L/S ratio (ε/ρ), L/kg

Wood duckboards

Concrete slabs

410 ± 30 9.3 ± 0.1 71.7 ± 0.9 1.75

2420 ± 30 4.9 ± 0.2 14.7 ± 0.7 0.06

Zinc gutters 7143

Total content, mg/kg dry mat. [14] B Ca Cu K Na Zn

93 958 1244 754 863 20

24 230000 90 1613 562 94

Initial pore water estimated composition, mg/L B Ca Cu K Na Zn Cl− SO4 2− DOC

50 180 100 140 100 2.5 25 60 3140

– 19 – 8400 2710 2.5 52 450 23

1343

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Wood duckboards

DOC

4

R2 = 1,00 y = –1,06x + 2,51

Ca

3 Log (Conc., mg/L)

y = – 0,88x + 3,85

R2 = 1,00 y = –1,04x + 2,40

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2

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0

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–1

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Cl-

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0,8

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1,2

Zn

Log (L/S, L/kg)

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pH

R2 = 0,95

Fig. 3 Estimation (backward forecast) of the initial pore water composition of wood duckboards

Concrete slabs

K

4

Na

Log (Conc., mg/L)

3

y = – 0,83x + 2,91 R2 = 1,00

y = – 0,96x + 2,26 R2 = 0,97

2

2 Ca y = –0,71x2 + 0,16x + 2,53

1

2 SO4-- y = 0,72x – 0,54x + 0,92

R = 0,96

R2 = 0,89

0

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y = – 0,67x – 0,42 R2 = 0,92

Cl-

y = – 0,57x + 1,02 R2 = 0,96

DOC

y = – 0,45x + 0,82 R2 = 0,95

pH

y = – 0,23x + 12,42 R2 = 0,98

–1 –2 –1,2

–0,8

–0,4

0,0

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Log (L/S, L/kg)

Fig. 4 Estimation (backward forecast) of the initial pore water composition of concrete slabs

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In the case of both building products, the linear relationship in logarithmic scale between the Na & K concentration and the L/S ratios, with a ∼ (−1) slope, supports the hypothesis of the progressive dilution of their initial available quantity. This behaviour is a characteristic of the highly soluble constituents. In fact, in the case of the wood product, all the investigated constituents have a similar behaviour. This could be explained by the week buffering capacity of the wood matrix [13, 14]. For the concrete product, because of the matrix effect, the calcium concentration evolution vs. the L/S ratio is more complex and dependent of the pH, via the portlandite solubility dependence. The calcium concentration depends equally of the Na & K concentration, by a competition relationship between them. The Zn release is pH dependent and, as amphoteric metal in the pH range of concrete, it is more soluble at higher pH. The SO4 2− concentration is strongly Ca and pH dependent.

3.2 Dynamic Leaching Tests The results are expressed in two ways: I. the release behaviour observed in the CMLT is compared to the release observed in the MBT (Figs. 5 and 6). For both tests, (in dotted lines for the MBT and continuous lines for the CMLT), the results are expressed as a function of time (in hours): (1) in terms of pH and concentration (quantity of constituent released per litre of eluate, mg/L), in decimal scale, (2) in terms of surface-related cumulative release (quantity of constituent released cumulatively per surface unit of the product sample, mg/m2 ), in logarithmic scale, and (3) in terms of flux (quantity of constituent released per surface unit of the product sample and per time unit, mg/m2/day), in logarithmic scale. 14 12

pH

10 8 6 4 2 0 0

400

800

1200

1600

Time (hours)

Fig. 5 Eluates pH evolution

Concrete slabs MBT

Concrete slabs CMLT

Wood duckboards MBT

Wood duckboards CMLT

Zinc gutter MBT

Zinc gutter CMLT

Assessment of Dangerous Substances Release Concrete slabs MBT Concrete slabs CMLT Wood duckboards MBT Wood duckboards CMLT Zinc gutters MBT Zinc gutters CMLT

Zn MBT vs. CMLT

DOC MBT vs. CMLT

1 0,1 0,01 0,001

Concrete slabs MBT Concrete slabs CMLT Wood duckboards MBT Wood duckboards CMLT

100 Concentration (mg /L)

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10

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0,1

0,0001 400

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Concrete slabs MBT Concrete slabs CMLT Wood duckboards MBT Wood duckboards CMLT Zinc gutters MBT Zinc gutters CMLT

Zn MBT vs. CMLT

Cumulated release (mg/m2)

1000000 100000 10000 1000 100 10 1 0,1 0,01

1

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400

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Concrete slabs MBT Concrete slabs CMLT Wood duckboards MBT Wood duckboards CMLT

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100000 10000 1000 100 10

10000

Concrete slabs MBT Concrete slabs CMLT Wood duckboards MBT Wood duckboards CMLT Zinc gutters MBT Zinc gutters CMLT

Zn MBT vs. CMLT

0

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0

1

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100 1000 Time (hours)

10000

Concrete slabs MBT Concrete slabs CMLT Wood duckboards MBT Wood duckboards CMLT

DOC MBT vs. CMLT

1000 Flux (mg/m2/h)

Flux (mg/m2/h)

1000 100 10 1 0,1 0,01 0,001

100 10 1 0

0,0001

1

10

100

1000

10000

Time (hours)

1

10

100 1000 Time (hours)

10000

Fig. 6 Release behaviour in the two dynamic tests

II. the release behaviour observed in the two dynamic tests (CMLT and MBT) was compared with the results obtained form the PWT and from the Acid Neutralisation Capacity (ANC) test [6, 14], by plotting the eluate concentration in the target constituents against the pH (Fig. 7). The ANC test allows the determination of pH influence on constituents’ release and the acid/base neutralisation capacity (ANC/BNC) of the product. Figure 5 shows that the eluates pH remains quasi constant during the tests for the three products (∼11 for the concrete product, ∼6.5 for the metallic product and ∼ 6

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1000

CMLT ANC

MBT PWT

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MBT PWT

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pH

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MBT

ANC

PWT

DOC Wood duckboards

100000

100000 10000 1000 100 10 1 0,1 0,01 0,001 0,0001

CMLT ANC

MBT PWT

10000 1000 mg/L

mg/L

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MBT PWT

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Zn Zinc gutters

CMLT

MBT

ANC f

A

100

0,1

10 mg/L

mg/L

1000

1

0,01

1 0,1 0,01

0,001

0,001

0,0001 2

4

6

8 pH

10

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14

0,0001 0

2

4

6

8

12

10

14

pH

Fig. 7 Constituents release in CMLT and MBT compared with ANC and PWT

for the wood product), except for the concrete in the CMLT, when a decrease of 2 pH units is observed (from 11.2 the first day to 9.2 beginning with the 36th day of leaching and till the end of the test). The punctual sampling in the case of the CMLT allowed the determination of the eluate composition into the reactor at a given time. For wood and metallic product, the eluate pH evolution into the reactor is the same as for the collected eluate. Instead, for the concrete product, for the two last samplings (at 36, respectively 64 days) a higher pH is measured into the reactor (up to 0.8 unit of pH as shown in the Fig. 3 with the symbols). This could be explained by the exposure of the collected eluate to the air. Three types of release behaviour are observed: (1) elements for which the release is still under progress for the test duration (high slope of cumulated vs.

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Table 2 Type of release behaviour Release behaviour Test CMLT

MBT

Wood duckboards Concrete slabs Zinc gutters Wood duckboards Concrete slabs Zinc gutters

Depletion not reached during experiment

Depletion reached during experiment

Ca, K, Na, Zn, SO4 2−

B, Cu, DOC

Ca, K, Na, SO4 2− , DOC Zn

Zn B, Ca, Cu, K, Na, Zn, SO4 2− , DOC Ca, Cu, K, Na, Zn, SO4 2− , DOC Zn

< Detection Limit

B, Cu Cu

B Cu

time trendline); (2) elements for which a plateau is reached more or less rapidly (depletion reached during the experiment duration) and (3) elements for which the concentration were lower than the detection limit of the used for analysis. Table 2 summarizes the results in terms of release behaviour obtained from the cumulated release plotted against the time (examples given in the Fig. 6). In general, for the same element and product, in the CMLT, the cumulated release at the end of the test is higher compared with the MBT. As expected, for the zinc gutters, the cumulated release at the end of the test is very high in the case of the CMLT (∼83 g/m2 ) and the release is still under significant progress. Instead, a plateau is reached in the MBT and the cumulated release is two orders of magnitudes lower than in the CMLT. In the case of MultiBatch Test, for the target elements the depletion was reached during the experiment duration, in spite of the lower cumulated L/A ratio, compared with the CMLT (50 vs. 800 cm3 /cm2 ). This could be explained by the gradient effect which lessens during the MBT (the leachant is not continuous renewed). Some examples of the release behaviour observed in the two dynamic tests (CMLT and MBT) compared with the ANC test results and with the PWT results are shown in Fig. 7. In the case of highly soluble constituents (Na, K, Cl− ) but also pH dependent elements (Cu in wood product), the eluate concentrations are around one order of magnitude lower than in the ANC test and almost three orders of magnitude lower than the pore water concentration, thus the release is not limited by their solubility. Regarding the differences between the two dynamic tests, for the concrete slabs, no significant difference was noticed; in the case of wood duckboards, the CMLT gives higher amount of released constituent. In the case of the concrete product, the B and Cu concentrations in the eluates obtained from the dynamic tests are closed or lower than the detection limit, except for the Cu in MBT. In fact, for the elements release study from the construction products, this is one of the mean issues to deal with: the low (from analytical point of view) but yet significant (from environmental point of view) release concentration of the targets elements. Some constituents, such as

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Ca, Zn and SO4 2− in the case of concrete slabs and Zn in the case of wood duckboards, are controlled by the saturation of eluates (the eluates concentration from the dynamic tests are closed or even higher than the eluates concentrations from the ANC test). Moreover, for the concrete product, the calcium eluate concentration is higher than pore water concentration, which means that calcium release is due to the surface wash-off and matrix dissolution and not to the diffusion from the pore water. A similar mechanism is observed for the Dissolved Organic Carbon (DOC) release from wooden product in alkaline medium: the matrix dissolution is the main responsible for the release and not the diffusion phenomenon. In neutral medium, the DOC release is not solubility controlled (MBT & CMLT concentrations are more than one order of magnitude lower than in the ANC test) but the renewal type influence is high in controlling the release process: the concentrations in the case of continuous renewal (CMLT) are up to one order of magnitude higher than in the case of sequential renewal (MBT). In order to apply the horizontal concept (same tests for all the products), the same experimental protocol was performed for all the three products. Nevertheless, in the case of the metallic product, the results of the ANC test could not be considered as an acid neutralisation capacity, as for the porous products, because the matrix is the target element in itself: the dissolution of the matrix is the release mechanism. The main leaching mechanisms that can be identified for the three studied products are: (1) diffusion (from the pore solution to the leachant), (2) dissolution of constituents/solubility controlled release, (3) initial surface wash-off and (4) dissolution of the matrix.

4 Conclusions We can conclude that: – one of the mean issues to deal with in the case of the elements release study from the construction products is the low (from analytical point of view) but yet significant (from environmental point of view) release concentration of the targets elements. – the type of target constituents has a higher influence on release than the matrix of the product. Nevertheless, the matrix influence (type of the matrix (porous or not), acid neutralisation capacity etc.) must not be neglected in the tests choice and results interpretation. – it’s neither realistic nor useful to recreate in laboratory some exhaustively simulating tests of the real situations, in order to study the leaching phenomena. Nevertheless, because of the mass transfer parameters influence on the leaching behaviour, the exploitation of the laboratory tests results for the real scenarios requires a minimum of similitude between the tests and the reality, such as : the leachant type, the renewal type and rate (e.g. a very low renewal rate for a close to equilibrium situation; a high renewal rate for a scenario in which the leaching is independent of the already released elements), the value of the liquid (volume of leachant) to solid (mass or surface of the product) ratio, etc.

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References 1. AFNOR (2000) Standard XP X31-211 Déchets – Essai de lixiviation d’un déchet solide initialement massif ou généré par un procédé de solidification, Paris 2. California Department of Pesticide Regulation (2005) ACQ 2100. Registration Number: 010465-00037. Available on http://www.cdpr.ca.gov 3. CEN (1992) Standard EN 335 – Durability of wood and wood-based products. Hazard classes of wood and wood-based products against biological attack, Brussels 4. CEN (1994) Standard XP ENV 1250-2 – Wood preservatives – Methods for measuring losses of active ingredients and other preservative ingredients from treated timber – Part 2 : Laboratory method for obtaining samples for analysis to measure losses by leaching into water or synthetic sea water, Brussels 5. CEN (2002) Standard EN 1744 – 3. Tests for chemical properties of aggregates. Preparation of eluates by leaching of aggregates, Brussels 6. CEN (2004) Standard prCEN/TS 14429 – Characterisation of waste. Leaching behaviour test. Influence of pH on leaching with initial acid/base addition, Brussels 7. European Communities (1989) The Construction Products Directive n◦ . 89/106/EEC, on the approximation of laws, regulations and administrative provisions of the member states relating to construction products, Brussels 8. European Commission (1989) Mandate M/366. Horizontal complement to the mandates to CEN/CENELEC, concerning the execution of standardization work for the development of horizontal standardized assessment methods for harmonized approaches relating to dangerous substances under the Construction Products Directive (CPD). Emission to indoor air, soil, surface water and ground water, Brussels 9. Gromaire-Mertz MC, Garnaud S, Gonzalez A, Chebbo G (1999) Characterisation of urban runoff pollution in Paris. Water Sci Techn 39(2):1–8 10. NNI (1995) Dutch Standard NEN 7345. Leaching characteristics of building and solid waste materials. Leaching tests. Determination of the leaching behaviour of inorganic components from building materials, monolithic waste and stabilized waste materials, Delft 11. Polden/Insavalor (2005) Dynamic Monolithic Leaching Test. Research program n◦ 0372C0008/2005, financed by the French Agency for Environment and Energy Management (ADEME) 12. Réthy Z (2001) Etude du comportement à la lixiviation d’un matériau à base de liant hydraulique contenant des polluants solubles. Rôle des conditions de contact solide/liquide. PhD Thesis, National Institute of Applied Sciences, Lyon, France 13. Schiopu N, Barna L, Jayr E, Méhu J (2005) Caractérisation des émissions de substances des produits de construction à base de bois, en contact avec l’eau. ORGAGEC 05: Proceedings of the 2nd international conference on “Health and environmental risks of the organic materials for construction”. Nantes – France, 4–5 Oct 2005, pp 201–218 14. Schiopu N, Jayr E, Méhu J, Barna L, Moszkowicz P, (2006) Horizontal environmental assessment of building products in relation to the construction products directive (CPD). WASCON 2006: proceedings of the 6th international conference on “Science and Engineering of Recycling for Environmental Protection”. Belgrade – Serbia & Montenegro, May 30- June 2, 2006, pp 217–228, accepted for publication in Waste Manag J 15. Tiruta-Barna L, Barna R, Moszkowicz P (2001) Modelling of solid/liquid/gas mass transfer for environmental evaluation of cement-based solidified waste. Environ Sci Technol 35,2001:149–156 16. Usta I (2003) Comparative study of wood density by specific amount of void volume (porosity). Turk J Agric Forestry 27:1–6 17. Yang CC, Chob SW, Wang LC (2006) The relationship between pore structure and chloride diffusivity from ponding test in cement-based materials. Mater Chem Phys 100:203–210

Challenges of the Implementation of the WEEE Directive in the Danish Context Chiara Gobbi

Abstract Ecological and economic intentions often compete in today’s business world. So far, companies rarely accept the responsibility for external effects, i.e. the gap between ecological and economic costs. Although the European and National legislations are forcing the internalization of these costs (the recovery costs should be afforded by the original equipment manufacturers), the social responsibility of the enterprises and the environmental performances are also important issues, as well as to which extend governmental institutions and local municipalities should be involved in planning and performing the reverse process. The study considers the effects of the European Directives on electrical/electronic equipment waste and restriction of use of certain hazardous substances (WEEE – Directive 2002/96/EC of the European Parliament and of the Council of 27 January 2003 on waste electrical and electronic equipment and RoHS – Directive 2002/95/EC of the European Parliament and of the Council of 27 January 2003 on the restriction of the use of certain hazardous substances in electrical and electronic equipment), both influencing the electrical and electronic products market. It analyzes the impact of the recovery legislations on companies’ behaviour and end-oflife/end-of-use products disposal and it wants to stress the existing severe gap between the efforts made by producers in order to design and manufacture recyclable products and the existing recycling technologies. The analysis is based on considerations derived from interviews conducted in manufacturing companies operating in the medical devices, IT and mobile communications sectors, collective schemes agencies, governmental institutions, plastics producers and municipalities within Denmark. Keywords Reverse logistics · Product recovery · WEEE · RoHS Directives

C. Gobbi (B) Department of Industrial Management and Engineering, Technical University of Denmark, DTU Building 423, 2800 Lyngby, Denmark e-mail: [email protected]

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1 Introduction The reverse logistics drivers as well as recovery options are briefly described in order to set the framework in which the WEEE directive comes into place. The salient points of the Directive are then presented focusing on the concept of extended producers’ responsibility. The rest of the paper outlines how the WEEE Directive is shaping the flow undertaken by dismissed products in both the businessto-business (B2B) and business-to-consumers (B2C) markets: new actors, flow and processes configurations. Finally, some evaluations of the available recycling technologies in relation to product recovery are given.

1.1 Reverse Logistics Drivers Historically firms have concentrated on getting products and services to the market. Product returns and warranty program have existed for some time and in this sense, companies have been dealing with reverse logistics (RL) for a while. In evaluating the RL tasks, the focus has traditionally been in minimising costs ensuring a reasonable costumer service support, missing the possible significant returns on investment when considering different recovery options. Over time, the recognition of increasing value of products and technology created in the field at the end of the direct supply chain and the impact of the green laws, particularly in Europe, has moved companies’ focus to different types of recovery programs, not merely centred on customer service. Andel states: “. . .by ignoring the efficient return and refurbishment or disposal of product, many companies miss out a significant return on investment” [1]. Different reasons that can be grouped on economic, marketing and legislatives motives drive the developing of recovery programs and companies engagement in reverse logistics. Companies have become involved with reverse logistics, either because [4]: – of the economical and marketing benefits by improving company image on consumers mind; – “feel” moved to, as part of corporate citizenship and social responsibility; – due to regulations. Reverse logistics programs can bring direct gains to companies by reusing raw materials and components, reducing disposal costs, improving customers/suppliers relationship, reducing pollutions taxes, reducing energy consumption, improving marketing position, promoting the “green image”, etc. . . The growing environmental concern among both consumers and businesses is also a major reason to move towards reverse logistics programs in order to prove to the market that the firm operates according to a set of values and principles that consider social common interest. Finally, companies might have to enter RL programs in order to comply with state legislations. While few

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regulations specifically address reverse specific issues, a number of countries, states and municipalities have developed legislations relating to environmental issues, which can affect directly and indirectly RL. For example, the Directive on Packaging and Packaging Waste in Europe, based on the German “Green Dot” Law, has been the catalyst for the take-back legislation in more than 20 European countries, and several in Asia. The “White and Brown Goods Act” in the Netherlands obliged manufactures and importers of electronic appliances to take back their products after use and recover a certain minimum percentages [5]. During 1997, US States enacted about 80 recycling laws, bringing the total number of state recycling laws to approximately 500: 25 countries have “producer responsibility” laws for packaging and 13 countries require recovery of transport packaging [9]. The RoHS and WEEE directives have recently brought into force and they represent a full path to harmonisation and consensus among the European Member States along with the packaging regulation. As legal instrument, the material restrictions, the take-back and recycling obligations enacted through the RoHS and WEEE directives, respectively, strongly influences the end-of-life (EoL) and end-of-use (EoU) recovery policies (Nokia Environmental Report [7]).

1.2 Recovery Options The potential of the recovery process is variable and the process can include many different activities such as collection, transportation, inspection, handling, and redistribution. Different options span the product life: direct reuse (typically in the case of commercial returns without any major reprocessing), resale or transfer of ownership (sales on secondary markets), repair, refurbishing, remanufacturing, cannibalisation, recycling, until final disposition in the forms of incineration or landfill [6]. The selection of one of these options, but in most cases a combination of those, is one of the operations management problems. Furthermore, any option denotes different levels of product structure preservation until cannibalization and recycling where the product structure is completely lost and reusable parts or materials are recovered. Steven M. in his paper “Networks in Reverse Logistics” presents a hierarchy of product disposed treatment activities based on the priority given by the German Commercial and Industrial Waste Avoidance and Management Act. The highest priority is given to waste avoidance, therefore, reuse has the highest priority followed by remanufacturing, recycling, disposal with energy recovery and landfill [8]. Consequently, reuse is the option that should be preferred whenever possible since it implies the highest level of waste avoidance and the highest level of resources and energy savings. On the contrary, when the legislation triggers the reverse flow, the product has normally reached a stage equivalent to waste: the legislation generally affects only EoL and EoU products, which do not have any more market value (Fig. 1).

306 Fig. 1 Hierarchy of waste treatment activities [8]

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Reuse Remanufaturing Recycling Disposal with energy recovery Disposal in landfill

2 The European Directives 2.1 The RoHS Directive The RoHS Directive influences indirectly the recovery of electrical and electronic equipments, which is instead regulated by the WEEE. It sets restriction on the use of certain substances in plastic materials and therefore poses requirements in evaluating the possibility to recycle plastics. The Directive, which applies to electric and electronic equipment introduced in the market from 1 July 2006, bans the use of lead, cadmium, mercury, hexavalent chromium, and the brominated flame-retardants PBDE and PBB. In order to reach the target, major electrical and electronic producers started well ahead of legal deadlines to adopt the necessary measures. For instance, Nokia Corporation started early in advance to proactively working with its suppliers to comply with the materials restrictions. Bayer Group has also banned from all its products the use of the substances specified in the RoHS Directive long ago. However, historical waste will still carry the banned substances for a long while. This issue has to be properly considered when designing the process for recycling in order to avoid the dispersion of environmentally dangerous substances and ensure safe working conditions [11].

2.2 The WEEE Directive The WEEE Directive has been approved by the European Parliament on the 27 January 2003 and it came into force in Denmark the 1st of April 2006. By the 13th of August 2005, all producers affected by the WEEE Directive should have started to mark their products with the WEEE symbol. The Directive establishes the concept of producer responsibility and encourages the design and production of electrical and electronic equipment, which facilitate repair, possible upgrading, reuse, disassembly and recycling. By establishing the concept of extended producers’ responsibility, the Directive makes the producer accountable for financing the collection, treatment, and recovery of the dismissed

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products: the producer becomes the ultimate responsible for proper disposition, the owner of the recovery process in terms of costs, legal responsibility, and environmentally sound EoL management. Furthermore, the Directive sets recovery targets which vary from 50 to 80%, depending on 10 product categories. These targets should be met by the 31st December 2006 and reported by the producers to the local authorities by the end of year 2006. In Denmark a 3 months period has been given to the producers in order to archive these data starting from the 1st of January 2007. It has left the possibility to producers and importers to form and operate individual and collective take-back systems: industries/sector specific or generic collective schemes have been formed. By signing into a collective scheme, the company delegates the establishment and management of the recovery process previous payment of a fee calculated on the total sales in each member state [12]. For the national implementation, the Directive allows different configurations and operating systems to better adjust to the local needs and existing situation. This large degree of freedom has the downside that it creates diverging structural alternatives that are hardly comparable. For instance, the Danish legislation has decided that the collection of the WEEE waste is made by 5 fractions instead of the 10 product categories suggested by the Directive anyhow, the reporting system is due to give feedback to the European Commission on the base of the 10 categories [10].

3 The Impact of the European Directives on the Reverse Flow 3.1 Actors The number and type of actors involved are various and beside the traditional ones of the reverse flow, governmental agencies (local environmental protection agencies, EPAs), trade associations and collective schemes are involved with different levels of responsibility. The flow starts from the final user, which might be a commercial company or the end consumer. The WEEE information campaigns should specifically target those actors that initiate the reverse flow and they are crucial to get the process up running. After collection, the recovered products are transported to the waste management plants. Some kind of sorting and grouping might precede the arrival to the final treatment facilities. All these activities are performed by the collective schemes that coordinate all the intermediate stages before treatment handle the administrative tasks; manage the relations with national stakeholders (local WEEE system, EPA, Ministry of Environment), the members and all the contractors. Contractors are recyclers, third party logistics suppliers, other suppliers that might perform intermediate phases as maintenance of the collections sites, transportation, storage, consolidation, sorting, etc. . . The national organisms should supervise the process, adopt some sort of enforcement systems, and report to the national authorities and the European Union. In most of the member states, the enforcement program will act on the retail chain in order

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to assure that all products have the WEEE mark and the producer is registered in the local WEEE system.

3.2 Flow Direction and Characteristics If the legislative driver is the triggering factor, we claim that RL has some peculiar aspects and processes configuration, which tends to separate the forward and backwards flows in two different streams that rarely overlap. It is also relevant to underline that the term “reverse” appears quite inappropriate: the reverse flow tends to be a completely different flow from the forward one to the extreme that it can rarely be named “reverse”, else be considered a total different downstream flow [8] and generally outsourced (Fig. 2). The legislation norms those reverse logistics flows that deal with EoL and EoU products that do not represent a direct economical opportunity and require reprocessing in order to extract valuable parts, components or materials. Therefore, the flow requires processes and infrastructures that do not correspond to the ones deployed in the forward flow and that are normally part of the waste treatment process. Instead, when the returned product preserves market value, it is more likely that companies and dealers get the products back by using the original chain and infrastructures of the forward flow, optimising the transportation services (for instance the dismissed product is taken back when replaced by a new one). The more the product is in first phases of its using life cycle, the more probable is that the reverse chain overlaps the forward chain and companies take an active role on the reverse flow. Commercial returns is a clear case in which companies are directly involved since the returned product can be considered as new and after inspection and repackaging, it can be easily sold again in the original market place [2]. In addition, refurbishing

Dealer

Producer (manufacturer, importer, distributor)

Sold to raw materials market

Final disposal

End user (consumer or business)

Retailer

Recyling and reprocessing

Special processing and disposal

Sorting

Hazardous material

Collection and trasportation

End - of - life, End - of - use – WEEE delivered at the municipality collection stations

Fig. 2 Independent reverse flow of the WEEE stream in the B2C situation (adaptation from [3])

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Supplier

Producer (manufacturer, importer, distributor)

Dealer

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Retailer

Fig. 3 Relation between the using life cycle of a product and the reverse chain

and remanufacturing, if efficiently performed, can represent valuable opportunities for companies. In those cases, it is also more likely that the original forward chain is utilised for the reverse flow, at least to perform the initial steps (collection and inspection) and even if outsourced, there is a direct interest by the OEM to control the phases of the reverse chain (Fig. 3).

3.3 Actual Configuration Out of the 845 electrical and electronic Danish companies, both operating in B2B and B2C markets, 121 (14%) have decided to implement an “in-house” recovery program, but only one of them operates in the B2C market (Table 1). The other companies decided to participate into a collective scheme: – industry specific as in the case of LWF (The European Lighting Companies Federation - ELC, which groups 28 companies and importers of light sources, 8 of those are represented by major players) Table 1 Danish data on companies WEEE compliance

WEEE LWF NERA Elretur SUM

B2C

B2B

1

120

Unspecified

SUM

28 7 689

121 28 7 689 845

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– generic as in the case of Elretur which counts 689 members and NERA (The Nordic Electronic Recycling Association) which has been founded by some major companies as Sony, HP and Ingra Micro and groups also other minor vendors. Major players have formed specific schemes in order to afford common costs or because they might have a direct interest on the reverse chain outcome, for instance, they directly purchase the raw materials coming out from the recycling process: some members of the ELC scheme buy in directly from the recyclers the glass recovered from their recycled products. Both in the consumers and in business markets, the reverse chain operates independently of the forward chain. Since the one–to–many customers’ structure of the forward flow shifts to the collection many–to–one, it is in general economically inconvenient to implement its own recovery chain or use the forward chain in order to collect the disposed products. The market dispersion, the uncertainty related to quantity, quality, timing and variety of the recovered products make the reverse flow in most of the cases not profitable. Furthermore, some specific reasons derive from industry sectors requirements: – in the case of medical devices, “in-house” recovery programs would be unjustified because of the impossibility to reuse any of the components or materials due to additional legislations that impose products purity and sterility; – in the case of IT and mobile products, RoHS compliance. technology and materials obsolescence make impossible any economical gain. Therefore, given the lack of economic benefits and legal restrictions to disposal, companies tend for the larger part to take part to collective schemes and thereby delegate the recovery activities, sharing costs infrastructures, management and implementation. The collection of the EoL and EoU products happens nearby inhabited areas, at companies’ premises, and in some cases also adjacently to recyclers’ facilities. The collective schemes in collaboration with the local municipalities supply: – suitable containers for the waste collection placed in public receiving stations; – transportation of the filled containers to the recyclers’ premises; – correct treatment, recycling and landfill disposal. In order to assure the execution of all activities, collective schemes sign contracts with logistics service providers for the placing and transportation of the containers and with the recyclers in order to guarantee the necessary recycling capacity. In the B2B case, the situation differs (commercial collection sites): – the container is owned or rented out to the commercial customer while the recycling remains free of charge. It is not clear who gets to pay the collection and transportation costs, if the collective scheme or the commercial user;

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– participants to the collective scheme might have containers standing at their own premises; – the containers can also be placed at recyclers’ sites; – in case of assets protection, the commercial user assumes the producer responsibility during the buying process and therefore is responsible to discharge properly the product. The WEEE Directive imposes to recover EoL and EoU products. EoL is not synonym of EoU: a product that is disposed because considered EoU might still maintain intact its original functionality. Therefore, EoU products might not flow through the recovery process because better market options are available. This is the case of reuse or continues use or second hand markets that represent a grey area in terms of the WEEE dispositions. Reused products cannot be considered waste but will eventually become waste later on. In other terms, they represent a form of prolongation of the life cycle. In the mobile phones industry, there is a well-organised second hand market and, as long as the products move inside the European Community, the second hand market will only slightly compromise the balance of each country. However, most of the secondary used products do not end up in Europe. The Senior Environmental Manager and CMO Sales & Marketing Europe of Nokia Corporation states: “Second used products recovered by retailers reach Romania and Russia as closest markets, then Africa and the Far East. There is a huge, enormous fast growing demand of cheap phones in those countries”. In the automotive industry (especially for the high segment products), the second used market is so extended that problems arise in reaching proper, efficient recycling volumes. This phenomenon simply complies with normal market rules: whenever the products discharged still retain a market value, they can cover the needs of consumers in the emerging economies. The problem is that generally no infrastructures, environmental legislations, tracking systems are present in those countries; therefore, the WEEE philosophy is completely vanished.

3.4 Recovery Technology Both WEEE and RoHS Directives concern the environment protection and show the belief of the European Community that resources are limited and pollution creates problems to the human health and the environment itself. Anyhow, few considerations have been made on the recycling technology that should support the recovery process. Companies for decades have been developing, applying and improving sophisticated concepts, tools, and processes in order to deliver products and services to the market and major players have made evaluations of the possible environmental impact of their product along their total life cycle (life cycle assessment – LCA). If the production technology is stable and mature in some industries and in some others, it is subjected to continuous improvement and innovation, this is not true

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for the recycling technology, which in most of the cases is not developed enough, immature and using quite primitive means of materials separation. Only two industries have specific recycling technologies: the automotive that for a number of years has been dealing with the End of Life Vehicles Directive and the lighting products industry that counts already two different ways to separate and recycle materials. The others are left with recycling options that are not very efficient. Helena Castren from Nokia Corporation states: “We have done all the possible improvements already in the past 5 years in order to make our products recyclable. Now dismissed products should start to be collected so that recyclers start getting a stable products’ flow and consider improving their own processes because we can design and produce the most recyclable product but if the proper recycling technology has not been developed yet, all our efforts are in vain”. The recycling technology is a very poor technology, which did not get proper inputs to develop until now since the recycling demand has been relatively present if not completely absent in some countries and no recycling targets had been previously introduced. There is also a dispute in defining what is recycling: the incineration process produces energy and in that sense, it might be argued that it represents a form of recovery but not recycling; the WEEE Directive excludes energy recovery in the recycling computation and it indicates incineration as the latest possible option to be considered. Only recently we assist to specific investments on ODS (Optical Data Storage devices) recycling technologies and other specific techniques as air pressure, magnetic fields separation or material identification by a laser beam. In addition, some substances are simply not recyclable with the known technologies: for example plastic materials which varies according to industry specific composition requirements and properties, variety, colours, painted layers, etc. . . are simply be pulled together and grinded. This process is not very efficient in providing plastics that are reusable for specific industry purposes since the required properties are completely compromised. Small goods like mobile phones are not feasible for disassembly (which would be the most proper recycling option) due to their size and the size of their components which make timeless consuming trying to pull apart all the elements. Lars Buus Jensen, Design for Environment Specialist, Nokia Denmark, says: “We make sure we construct the phones in order to minimise landfill disposal, facilitate metals recover and make sure that no harmful substances end up in the environment. We calculated for each mobile phone model the amount of metals that will result in the recycling process and we strive to reach a level where at least 75% of our phones are recyclable. In addition, we design and produce the new models with fewer plastics and more metals in order to improve the recycling rate. We have covered all the recycling requirements that we could gather from the recycling industry early in advance WEEE Directive came into force”. Nevertheless, at this point of time, mobile phones, once the battery is removed, they are smashed. This gap between the efforts of the producers to design and manufacture recyclable products and the existing recycling technologies can be fulfilled only by making designers aware of the up-to-date available recycling technologies and by finding means to induce the recycling actors to invest in new recycling technologies and establish new recycling facilities. In addition, many different considerations

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should be made according to the product type. If the size is the primary characteristics that effects the recycling process, it seams not very valuable to produced sophisticated analysis that considers materials compositions and type, number of components, design for disassembly, hazardous substances, etc. . .: if the size is the driving parameter, the most reasonable analysis seams to be the one that strives at minimising materials variety.

4 Conclusions Environmental legislations are shaping a reverse flow that has some distinctive characteristics, configuration and issues that are not typical of other reverse flows and we should not neglect the fact that the WEEE and RoHS Directives norm the electronic and electrical recovery markets, other legislations would be needed for other products recovery programs. The WEEE and RoHS implementation process is currently undergoing and many problems are arising in terms of: – how to foresee the amount of incoming historical waste; – how to ensure that companies get an equal share on the required efforts; – how to ensure that products facing the decline of their life cycle if not of their existence (sawing machines is a typical example) do not load excessively the few manufactures left in the market; – how to control internet sales; – and beside all, how to harmonise the implementation within 25 different countries (different for traditions also in waste handling) in order to assure at least a minimum common efficiency and comparable standards. Finally, if the final user is not properly informed and motivated on the dispositions policies, all the resources used in the development and implementation of the WEEE and RoHS Directives will be lost. Acknowledgments I would like to thank the many people that contributed to the interviews, and in particular Helena Castren, Senior Environmental Manager, CMO Sales & Marketing Europe and Lars Buus Jensen, Design for Environment Specialist, from Nokia Corporation for their keen and thoughtful help. A special thank to Ulf Gilberg of Danish the WEEE-system for the enormous amount of hours he has taken to discuss the issue and in helping establishing the contacts with the major players in the WEEE arena.

References 1. Andel T (1997) Reverse logistics: A second chance to profit. Transportation Distrib 38(7): 61–66 2. Blackburn JD, Guide VDR Jr, Souza GC, Van Wassenhove LN (2004) Reverse supply chains for commercial returns. Calif Manag Rev 46(2):6–22 3. Blumberg DF (2004) Introduction to management of reverse logistics and closed loop supply chain processes, 1st edn. CRC Press, Boca Raton, FL

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4. De Brito MP, Dekker R (2004) A framework for reverse logistics. In: Dekker R et al (eds) Reverse logistics. 1st edn. Springer, Heidelberg, pp 3–27 5. Dutch Ministry of Housing Spatial Planning and the Environment VROM (2000) Dutch ministry of housing spatial planning and the environment VROM. VROM, The Netherlands 6. Fernandez I (2004) Reverse logistics implementation in manufacturing companies. University of Vaasa, Finland 7. Nokia Corporation (2004) Nokia environmental report. Espoo, Finland 8. Steven M (2004) Networks in revese logistics. In: Dyckhoff H, Lackes R, Reese J (eds) Supply chain management and reverse logistics. Springer, Heidelberg, pp 163–177 9. Stock JS (1998) Development and implementation of reverse logistics programs. Council of Logistics Management, University of South Florida, Oak Brook, IL 270p 10. The Commission (2005) Commission decision of 3 May 2005 laying down rules for monitoring compliance of member states and establishing data formats for the purposes of directive 2002/96/EC of the European parliament and of the council on waste electrical and electronic equipment. Off J Eur Community L 119/13 11. The European Parliament and the Council (2003a) Directive 2002/95/EC of the European parliament and of the council of the 27 January 2003 on the restriction of use of certain hazardous substances in electrical and electronic equipment. Off J Eur Community L 37/19 12. The European Parliament and the Council (2003b) Directive 2002/96/EC of the European parliament and of the council of the 27 January 2003 on waste electrical and electronic equipment (WEEE). Off J Eur Community L345:106

A Sustainable and Economically Recycling Real Estate Development Project: A Case Study for Istanbul Park H. Demir, F. Balik Sanli, M. Gur, and C. Goksel

Abstract Nowadays, together with the globalization fact, an effort is given to rebuild the environment. These models have been developed without taking natural and ecological corruption in to consideration. They just take into account the economical growth, leading to economical and cultural demolition. In order to balance economical development and ecology, a sustainable development must be reassured. If real estate development projects are investigated, one usually observes that the balance between urbanization and sustainability is not protected. Since the importance of land and land management has not been understood well, those implemented projects without required pre-evaluations have caused problems in terms of urbanization and urban economy. In this study, Formula One (F1) Istanbul Park Circuit real estate development project is evaluated considering relation of urbanization and sustainability. Evaluation of the project was made in terms of economy, changes in land use types, effects on real estate prices and contributions to the benefits of society. The changes of land use types were monitored using the time series of high-resolution satellite data, namely QUICKBIRD and IKONOS. Change detection methods were used for the analysis of ∼ 50 km2 area. Results show that 2,826 ha of the area, mainly having agricultural field land use types, appears to be open to urbanization. 1,268 ha area of green land including endemic vegetations is, under pressure of uncontrolled urbanization. Keywords Land use change · Sustainable Real Estate Development · Monitoring Urbanization · F1 Istanbul Park Circuit

H. Demir (B) Department of Geodesy and Photogrammetry Engineering, Yildiz Technical University, 34349-Besiktas Istanbul, Turkey e-mail: [email protected]

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1 Inroduction In conventional economical theories, the three main factors that create wealth are accepted as labor, capital and land. Land is the main production factor that causes the other production factors to continue their existence and impacts [3]. Land is environmentally and socially sensitive and a limited resource however economically it is a factor that creates wealth and attract investments. As of 1980s, with the policies of globalization/international unification the struggles for constituting a new world regime have been initiated. These efforts mainly enable free transfer of property, capital and services. The models primarily targeted economic growth without taking into account environmental quality and corruption in natural resources thus natural resources faced the threat of being demolished. Especially multi-national companies tend to develop business with countries that have not strict environmental laws in order to reduce additional financial burden. The system tried to find solutions with its own international institutions in order to prevent the environmental, economical, and cultural losses caused by the globalization. The report “our common future” written in 1987 by the World Environment and Development Commission on be half of United Nations General Assembly suggests that one needs to establish balance between ecological growth and economical development and the development, has to be sustainable. In that report, it was stated that current needs and expectations must be satisfied without making any concessions on the opportunities that will meet the expectations and needs of future generations. However if many real estate development projects that are implemented through globalization policies are examined, one will notice that the balance between the globalization and sustainability is not preserved. Real estate development project or the idea of the project is to create cost effective investments by unifying real estates, the capital and owners [16]. A real estate project is the unification of the factors of the area, project idea and capital that could be used in sustainable beneficiary. From the point of view of individual economy it should have the capacity of competition and creating and ensuring job opportunities. From the point of view of general economy it should create real estate objects that are compatible with the social situation and the environment [4]. From the point of view of project, development, a real estate should satisfy public needs, and as far as individual economy is concerned it should be in continuous beneficiary use. The success of real estate development projects is directly proportional to its productivity for the region and the nation. However in developing real estates, The projects that are competable with the environment and social conditions of the region, that take into account of the needs of the people, and following technological advances have greater chance in succeeding. The most useful way to preserve sustainable development is to detect changes. Determining land use types has great importance for both city planning and protecting the environment. If the change is monitored and maintained then the

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development is preserved. Land use types could be monitored using terrestrial methods that are impractical by the use of time and economy or with high resolution satellite imagery which is more cost and time effective. Using remote sensing techniques one also obtains the direction of the change and how rapid the variation occurring. Following technological advances, today one could obtain satellite images in a very high resolution, and very big areas could be viewed altogether and obtained with their past archives. With the time series obtained from past archives it is possible to monitor area changes and calculate the amount of the change. Making maps of residential areas in a quicker way, updating these maps and relating them with transformations are important tools for understanding social and economical ties. The socio-economic development of any country is based on land resources and water resources. Uncoordinated development can lead to undesirable environmental, social and economic conditions. Due to the increase in population these resources are in extensive use often leading to a decrease in resources. Remote Sensing (RS) and Geographic Information Systems (GIS) can be used affectively to monitor the changes in these resources that have vital importance. Following the developments in satellite technologies, RS experiments have been in use for more than three decades and they reached almost all sectors of Earth Science applications. RS techniques have become inevitable tool for resource inventory and environmental monitoring over regional and global scales. Since the derivative information can be obtained from RS data, remote sensing provides solution to facilitate sustainable development of natural resources and conservation of the environment. Recently this technology is used for doing both qualitative and quantitative estimates related to urban expansions. Therefore the use of remote sensing is very useful for monitoring land use/cover change, and the environmental sources can be maintained at a local level. Change detection is one of the most accepted methods of monitoring vast acreages in a very short time. It is the process of identifying differences in the state of an object or phenomenon by observing them in different times [15]. There are several algorithms applied widely for change detection, such as multidate composite image change detection [6, 5], image algebra change detection [8] using univariate image differencing, image regression, image rationing [9], vegetation index differencing [12] and manual on screen digitization of change [14], post classification comparison and change detection [10] Goksel and Turkoglu [7] and Musaoglu et al. [11] present case studies regarding to the northeastern part of Istanbul for identifying environmental impacts on land use changes. In addition Qi et al. [13] gives a good example on the use of RS and GIS for defining the impact of rapid land use changes on a river basin. The aim of the study is to determine land-use changes in the vicinity of F1 Istanbul Park using remote sensing data and GIS. Economic benefits of the project have been evaluated taking into consideration the opinion of Turkish Citizens up to date. In this study, it will be discussed if a balance was established between the environment and the economical developments. Also sustainable characteristics of F1 Istanbul Park Circuit Project have been studied.

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2 Study Area 2.1 Location and Physical Structure Study area is in the administrative zone of Akfirat town where the first settlement activities were started in 1978. Akfirat had the first planned neighborhood title in Turkey with an individual development plan completed in 1982. It became a village from neighborhood in 1987 and a town municipality dependent to Tuzla County in 1998. Its population is 12.370 according to last census in 2000 [17]. Akfirat town is a settlement that is located in the Asian side of Istanbul, the southeastern part of Omerli Water Basin Region across 5.900 ha area (Fig. 1). There are very important transportation facilities in the northern side; 5 km far from the junction of TEM Motorway, linking Istanbul to Ankara, and it is close to the newly constructed Sabiha Gokcen Istanbul Airport just 9 km apart. The structure of the ground is partly rough and covered with forests and scrub lands spanning 1,800 ha area mostly in the northern side of study field. The settlement and development (construction) area is 3,550 ha. F1 Istanbul Park Circuit was built in 221.5 ha area in the northern side of Akfirat town [17, 18]. The site surrounding F1 Istanbul Park Circuit is determined as a tourism center for cultural and touristic purposes in the environment formation plan of Istanbul, dated 2006 (Fig. 2). 3,000 ha area is reserved is military zone that will be planted with trees according to the same plan. There is also 240 ha land where ownership and usage conflicts exist (abbreviated as the 2B areas according to the Forestry Law). These places are registered as forest land and belong to the State, however current characteristic of these lands are not forest and they have been used for other purposes Also the legal judgment progress is still continuing. If the progress will be concluded in favor of persons who are using these problematic lands, they will obtain new title deeds and these places will open for construction. If not, these places will be covered with forest again.

Fig. 1 Omerli Water Basin

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Forest Military zone 2B Areas Preservation Zones Construction forbidden zones Tourism center

Fig. 2 Environment Formation Plan of Istanbul dated 2006

2.2 Natural and Ecological Structure The study area, F1 Istanbul Park vicinity, is located South of Omerli Water Basin, which provides 40% of the drinking water requirement of Istanbul. Ömerli Basin is not only an important fresh water resource, but also a natural habitat for rare plants and animal species and has a vital green zone for Istanbul citizens for outdoor activities. A wide range of habitat and species diversity exists in Omerli Basin. The basin contains forest, heath, and meadow, turbary and wetland habitats, having rare and endemic plant species. The largest undestroyed heaths of Turkey and Eastern Europe are located in the boundaries of Omerli Dam Water Basin and in the northern of the project area. More than 37 rare flowering plants and ferns species of Turkey grow in Omerli Basin. Approximately 10 of them are endemic for Turkey [19]. The endangered wild life environments in this area are heaths, blackpine forests and the mixture of oak-hornbeam forests which are indicated in the Bern Treaty. The initial studies of the Wildlife Conservation Organization identified 5 endangered plant species at global and national scales- 2 of which are endemic for Istanbul- in the vicinity of F1 Istanbul Park circuit that should be conserved in their natural environment in the context of the Bern Treaty (Table 1).

2.3 Economical Structure At first, evaluation of economical structure of the study area has to be divided into two parts as before and after F1 Istanbul Park Circuit. Some interesting results are obtained if the economical structure is investigated. There is no proper production sector in Akfirat main settlement unit as to locals work in close county centers and organized industry regions. Service sector is in a basic level. In Tepeoren neighborhood, which is the second settlement unit in the study

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H. Demir et al. Table 1 Endemic and rare plants in the vicinity of the Istanbul Park Circuit D [19]

Name

Species

Growth area

Risk Situation

Clovera

(Trifolium pachycalx)

Specific for Istanbul

............

(Circium polycephalum)

Specific for Istanbul

Delicate bitter crocusa

(Colchicum micranthum) Specific for Istanbul

...............

Crinitaria linosyris

North-west of Turkey

Thin-leaved fern

(Isoetes histrix & uriei)

In the wetlands

Endangered in the global scale Endangered in the global scale Endangered in the global scale Endangered in the national scale Endangered in the national scale

a Turkey

is obligated to conserve those plants in their natural environment as required by the Bern

Treaty

area dependent to Akfirat municipality, agriculture and livestock are main sectors and also there are some small scaled industry and workshops. High land profit (unearned income) and increasing temporary man power capacity caused by expensive luxury real estate investments, which are activated by F1 Istanbul Park, are new economical indicators after F1 in the study area. Improvement in service and tourism sectors should be maintained in close future.

3 Formula one Istanbul Park Circuit Istanbul park Circuit is one of the biggest investments approximately costed 160 million dollar with its additional investment [20]. Constructions of Istanbul Park started in 2003 and the first F1 race was run in 2005. The site of F1 Istanbul Park is declared as tourism center in the main development plan and environmental formation which are changed in 2006. The total area allocated for the race circuit is 221,5 ha and total building area that covers 3% of total project area is 66.900 m2 [18].

3.1 The Economic Benefits of Istanbul Park It is certain that F1 Istanbul Park circuit is very profitable for Turkey from the point of view of the economy. The income gained from people just coming to attend F1 races is about 120 million dollars. 2.2 million people attend F1 races and it is the most attractive sport event following Olympic Games. In this context, Istanbul Park Circuit has an important contribution to the advertisement of Turkey and development of tourism sector. The Circuit is also important for both motor sports and automotive sector [20]. The planned future investments in the concept

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of F1 Istanbul Park such as golf courses, hotels, residences, service depots, universities and etc, bring out development not only for Akfirat region but also for all country. The direct economic effect of F1 Istanbul Park at local levels has been observed on extra land price increases and construction sector. Over the 1 year period (2004–2005), a development plan was prepared, 1,023 villa type house construction licenses were given. The number of villas completed until the mid of 2006 is 2000, and estimated numbers for the next 10 and 20 year are 10,000 and 50.000 respectively. The average land prices was in a range of 5 to 10 US $ per square meter in 2002, and it has been increased to a range of 80–140 US $ recently [21].

3.2 Evaluating Istanbul Park Circuit from the Point of View of Sustainability The study area was declared as a forest area and the area to be afforested in 1/50.000 scaled master plan for Istanbul Metropolitan Area dated 1980. In September 2003, city development plans with a scale of 1/5,000 and 1/1,000 were reproduced not considering the requirements of the master plan. That area has been planned as the racing and sport area of Formula cars and the other motor vehicles in plans of the year 2003. In May 2004, a new master plan was produced according to the city development plans, and areas that were forest or afforestation were transferred to a tourism center in the new master plan. With these plan changes, the hierarchy relationship between scales was ignored. According to the principle decisions of ex-master plans, the expansion of Istanbul metropolitan area should be maintained towards east-west direction. However the new plans for the F1 region disagree with these principle decisions by demolishing the forest belt to the north of the city. The investment program is not only for the circuit for the races but also for forming a new urban zone. Other investments are also expected through the project or as a result of the motor races. These investments will be a centre for attraction creating smaller centers in the eastern part of the city, thus initiating linear development processes. City development/urbanization in Turkey is normally based on the developments through the construction of new highways. In addition to the uncontrolled urbanization along the highways of E-5 and TEM, F1 Istanbul Park Project will also create uncontrolled developments. This can cause the problem of unearned income from real estate properties and the loss of quality in historical, ecological, and cultural assets. Omerli Basin and the nearby ecology, which seems to be conserved by the treaty and the development plans, are actually under great threat through Istanbul Park applications due mainly to not obeying the existing laws. Although the authorities note that the project is environmentally conscious and necessary measures are taken, the environmental impact caused by the project is not limited with the borders of the project area, i.e. across 221.5 ha.

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4 Methodology This study is based on defining land use changes using multispectral and multitemporal high resolution satellite information covering the F1 Istanbul Park and its closer vicinity. The analysis carried out on the basis of defining urbanized areas and defining enlarged roads with the effect of F1 Istanbul Park area over a period of 3 years between 2002 and 2005. Visual classification of raster data applied through the images of each year. After classification of land use types, the results were overlaid in to a GIS environment together with city development plans to make further analyses.

4.1 Data and Data Processing In this study a variety of data including satellite images, city development plans, master plans, orthophoto maps, 1/5000 and 1/1000 standard topographic maps have been used. Satellite data of the study area were produced from Quickbird and Ikonos Images (Table 2). Quickbird and Ikonos images are provided as pansharpened data in order to utilize multispectral information and the high resolution feature of the panchromatic image. Spatial resolutions of multispectral and panchromatic data of Ikonos are 4 m and 1m respectively whereas they are 2.5 and 0.60 m for Quickbird. Visual and digital interpretation of satellite images was implemented mainly from Quickbird images for 2004 and Ikonos images for 2005. The complexity of physical environment cannot be acquired accurately by the airborne sensors due to the spatial, spectral and temporal radiometric constraints. Therefore it is inevitable to process remotely sensed data before making analyses on them. Beside applying the radiometric correction, the image data sets were rectified and geometrically corrected. Image rectification is designed to remove distortion from satellite images whereas geometric correction attempts to adjust for the effect of the Earth’s rotation on its axis during image acquisition and to register the image to a known co-ordinate system [2, 1]. The image data sets were rectified by using image to image registration method and they were geometrically corrected for the Universal Transverse Mercator (UTM) coordinate system. A first order polynomial transform was calculated to model geometric distortions in the satellite data. Geometric correction has been made using around 30 ground control points (GCPs) with total root means square (RMS) of less then 1 pixel (0.60 cm).

Table 2 The characteristics of satellite images Image

Data

Resolution

Number of bands

Quickbird Ikonos

June 2002/November 2004 June 2004/June 2005

0.60 m×0.60 m 1 m×1 m

4 4

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4.2 Visual Classification of Raster Data The most detailed data analyses were carried out for Istanbul park area and its vicinity for defining temporal changes by screen digitizing classification. To identify the differences between the years, digitally enhanced images were used. The classification process was carried out manually based on geo-referenced color composite images of Ikonos and Quickbird. Each changed land object was assigned to a class and the classification of entire area was determined by the vector GIS tool of PCI. Since one of the objective of this study is to monitor direction of urbanization and observe the contribution of F1 Istanbul Park to this expansion, mainly build up areas (Fig. 3) and newly constructed roads (Fig. 4) were classified. In Fig. 3a it is depicted that study area surrounded with blue solid line was a green area. In Fig. 3b the developments regarding the circuit are clearly seen. In Fig. 3c and Fig. 4, the circuit is almost located, and beside the expansion of roads newly built roads connecting the park to the city can easily be monitored. Based on the urban growth, to evaluate the rapid population growth and its expected effects, the densely built up areas were classified. It is observed the roads were constructed mainly between 2004 and 5005, some of which is not in the development plans for the year 2004 (Fig. 4).

2002

2004

2005

2002 2004 2005

Fig. 3 Urban expansions between 2002 and 2005

2002

2002

2005

Expanded roads

Fig. 4 Expanded and newly constructed roads according to years

New roads

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4.3 Overlay Analyses Overlay analyses were carried out using 1/1000 and 1/5000 scaled maps, city development plans and the master plan. The total land use change was calculated for the two settlements, namely Akfirat and Tepeoren, surrounding the F1 Istanbul Park (Fig. 5). According to city development plans, the areas of 2,362,8091 m2 and 837,8391 m2 for Akfirat and Tepeoren respectively will be open for building constructions (Fig. 6). The results show that there is still 28,260,521 m2 of the rural area that will be transformed to urban areas. Some figures regarding to this evaluation are given in Table 3. The table indicates that approximately 2,826 ha of the agricultural area have already been lost. Here one also may conclude that city plans will prevent unplanned and illegal urbanization which also gives harm to the environment. There is an unoccupied pasture area monitored from the satellite images covering about 1,268 ha of the research region, between the F1 circuit and Akfirat settlement (Fig. 5). This place is also in danger of a pressure for open construction, and for this

F1 Ist Park New road

Green area

Tepeören Akfırat Urban growth 2002 Urban growth 2004 Urban growth 2005 New roads-inetrcity

Fig. 5 Total land use change by the year 2005

City Development Plans Tepeoren Akfirat

Fig. 6 Overlaid city development Plans of Tepeoren and Akfirat towns

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Table 3 Total area of land use changes according to years

2002 2004 2005 City development plan Area to be urbanized

Urbanization (m2 )

New Road (m2 )

Akfirat

Tepeoren

Akfirat+Tepeoren

575,581 831,374 – 23,628,091 22,221,136

842,878 595,230 67,623 8,378,392 6,872,661

216,073 617,203 833,276

(m2 ) 1,418,459 1,642,677 684,826 32,006,483 28,260,521

area the communication of the biodiversity between the forest and the northern part has been intersected by the new wide surrounding roads. In the study region, a road enlargement construction which is harmful for the environment with its 60 m width is detected (Fig. 7).

2002 QB road width ≈ 3 m

2004QB_ road width ≈ 10 m

2005 ikonos ≈ 60 m

Fig. 7 Construction for the road enlargement

5 Conclusion A rapid and uncontrolled urbanization process which does not lake in to account wildlife, nature, and geologic and geographic structures has been carried out in Istanbul since 1970s. As a result of the construction of the new inner roads (intercity highways) and important punctuated public investments, unplanned settlements and industrial facilities had been built-up around these roads and areas without any control mechanism. In the ex-master plans, the west-east line was declared as the urbanization direction. Nowadays this urbanization line has been changed and redirected to the northern side of Istanbul where forests and water collecting basins are located. It is well known that these places are very important for wildlife, endangered plant species, habitats and vital fresh water. F1 Istanbul Park Circuit provides highly economical benefits in both local and national level. It is an environment friendly project but it creates a new attraction center for its vicinity. Only 4 years ago, Akfirat and Tepeoren towns were the settlements with rural characteristics and spanning 575,581 and 842,878 m2

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area respectively. However at present, according to our remote sensing analyses in comparison with 2004 city development plans, 2,826 ha of the area is still prone to new development for building construction. The city development plans of the study area also indicate, approximately 1,400 ha of the area was reserved for housing and density of the settlement, kept in the range of 30–58 people per ha. The west part of the new settlement area was very close to the basin boundary of 3rd order water collection. It is estimated that the total population of Akfirat and Tepeören will reach 60,000 in the following 10 years. There are still some potential dangers existing for this area such as; – The pressure of land spectaculars on pasture and forest lands – Uncertain economic structure especially for the ex-farmer who sold their lands for real estate projects – Losing flora and fauna due to over land use and construction works – Possible pollution of the water basin due to insufficient infrastructure – Uncontrollable and illegal house construction It’s very important to monitor this area using remote sensing and GIS techniques to control the developments as well as land use and environmental changes. To provide the sustainability, in addition to taking the advantage of technology, some social, economical and legal measures should be taken such as: – Creating new jobs and income opportunities for local people who lost their lands – Monitoring environmental changes and taking measures to improve the strategic planning concept – Establishing land markets to avoid land and real estate speculation and controlling the pressure on lands

References 1. Avery TE, Berlin GL (1992) Fundamentals of remote sensing and airphoto interpretation, Chapter 6, pp 109–115, 134–154, 5th Ed. Macmillian Publishing Company, NY 2. Campbell JB (1996) Introduction to remote sensing, 2nd edn. Taylor and Francis, London 3. Dale PF, Mc Laughlin JD (1999) Land administration, Oxford University Publications, ISBN 0-19-823390-6, New York, USA 4. Diederichs, CJ (1996). Grundkonzeption der Projektentwicklung. In: Schulte 1996: Handbuch Immobilien Projektentwicklung, Köln, 15–80 5. Eastment JR, Fulk M (1993) Long Sequence time series evaluation using standardised principal components. Photogramm Eng Remote Sens 59:1669–1694 6. Fung T, LeDrew E (1987) Application of principal components analyses for change detection. Photogramm Eng Remote Sens 53:1649–1658 7. Goksel Ç, Turkoglu H (2000) Integrating GIS and Remote Sensing for Evaluation and Monitoring of Omerli Region, Istanbul. XIXth ISPRS Congress. 16–23 July, Amsterdam, The Netherlands 8. Green K, Kempka D, Lackey L, (1994) Using remote sensing to detect and monitor the landcover and landuse change. Photo. Eng Remote Sens 60:331–337

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9. Howarth JP, Wickware GM, (1981) Procedure for change detection using Landsat digital data. Int J Remote Sens 2:227–291 10. Light D (1993) The national arial photography program as a geographic information system resource. Photogramm Eng Remote Sens 59:61–65 11. Musaoglu N, Tanik A, Kocabas V (2005) Identification of land-cover changes through image processing and associated impacts on water reservoir conditions. Environ Manag, 35(2): 220–230 12. Nelson RF, (1983) Detecting forest canopy change due to insect activity using landsat MSS. Photogramm Eng Remote Sens 49:1243–1314 13. Qi S, Luo F (2006) Land-use change and its environmental impact in the Heiche River Asin, arid northwestern China. Environ Geol, 50:535–540 14. Rutchey K, Velcheck L (1994) Developments of everglades vegetation map using a Spot image and the GPS. Photogramm Eng Remote Sens 60:767–775 15. Singh A (1989) Digital change detection techniques using remotely-sensed data. Int J Remote Sens 6:989–1003 16. Wiedeme JP (1994) Real estate investment. Regents/Prentice Hall, New Jersey 17. URL-1 Akfirat Municipilaty Legal web site www.akfirat.bel.tr 18. URL-2 F1 ˙Istanbul Park Legal web site http://www.formulal-istanbul.com 19. URL-3 Wildlife Conservation Organization www.dhkd.org 20. URL-4 Turkish Architectural http://www.arkitera.com 21. URL-5 Real Estate Services of Turkish Press; www.milliyetemlak.com.tr

Analysis of Land Use Changes in Nigeria: With Application of Integrated Bio-economic Spatial Model Igbekele A. Ajibefun

Abstract This paper presents results of analysis of land use changes in Nigeria, using the integrated bio-economic spatial model. Land use change is currently gaining global attention of researchers and policy makers, given the social, economic and environmental implications of land use and landscape changes. Understanding current land use situation and changes and projecting likely effects of current land use is important for sustainable development. Data for this study include social, economic, soil, crop production, vegetative and other relevant data. The data came from both primary and secondary sources. Data were also sourced from expert knowledge. Spatial maps of soil characteristics, land use patterns, vegetative cover, population density and rainfall patterns were produced. The maps show wide variations in spatial characteristics of the variables considered across the state. The results of gross margin analysis indicate that some particular crop combinations show better economic prospect than others. While the results from the study so far have been revealing, the analysis is still inconclusive, given that this is a progress report. The next phase of the study is to analyse the ecologic implications of current land use (or farming systems) in the study area and examine the trade-off between economic and ecologic factors.

1 Introduction and Problem Statement Agriculture is an important sector of Nigerian economy. It is not only the primary source of food, but also the principal means of livelihood for the majority of the population, with more than 70% of the people deriving their livelihoods from agriculture I.A. Ajibefun (B) Department of Agricultural Economics and Extension, Federal University of Technology, Akure, Nigeria e-mail: [email protected] A Paper prepared for Presentation at the “International Conference on Environment: Survival and Sustainability”, Nicosia-Northern Cyprus, 2007

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_31,

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and agricultural-related activities. Agriculture currently contributes about 45% to the Gross Domestic Product. With increasing population, which grows at about 3.0% per annum and rate of growth of food production of about 2.5% per annum, farmers must produce even more food than before. Given the challenges of meeting the increasing demand for food, as a result of rising population and rising income, farmers are being pushed to new and marginal lands. There are only two main ways to increasing natural food production in the country- increasing the land area planted to crops (extensive cultivation), or increasing yield per hectare of land under cultivation (intensive cultivation). Intensive and extensive agricultural production have negative implications on the environment, which include land degradation, large scale destruction of forests, and with them, wild life habitat and biodiversity. The challenge therefore, is to meet the rising demand for food while at the same time preserving the environment for current and future generations. Sustainable development aims at preserving private and public goods to secure current and future survival of mankind with high probability. It is assumed that the natural environment, as a future means of production, has to be preserved as healthy as possible. This requires knowledge of the processes involved in land use and land use changes and the effects of such changes on social, economic and ecological factors. A good understanding of such processes will involve integration of ecological objectives into economic activities. Given these scenarios, Nigerian government has recognised the need for policy on agricultural land use and planning. However, the policy will have to be based on sound empirical findings from integrated land use studies. While much research studies have been conducted on sustainable land use options in the developed countries in Europe, USA and parts of Asia, available literature indicates that much has not been done on research relating to land use and land use changes in Africa in general and in Nigeria in particular. It is also important to state that while most land use studies are either based solely on economic models or solely on ecologic models, only few attempts have been made to integrate ecologic and economic variables in models to study land use and landscape changes. Land, water and forest resources are part of basic inputs and dominant factors for national development to be used and managed within the nation. Nigeria with a total land area of 92.4 million hectares (or 923.773 km2 ) is now facing a serious challenge of how to use the land resources in a sustainable way so as to preserve it for future generations. The FAO estimates of Nigeria’s arable land and forests and woodlands indicate that the forest and woodlands are declining rapidly. The rapidly declining forest and woodland has serious implications on the conservation of environmental resources for future use and sustainable development.

2 Research Questions and Study Objectives One policy goal of Nigerian agriculture is the attainment of food security through increased food production. Achieving food security would imply drastic increase in the current level of agricultural production by extensive farming or intensive

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farming, with the associated environmental implications. It is also important to note that farm and farming situations in Nigeria in general and in Ondo state in particular are fast changing, due to rapid population growth as well as changes in social and economic realities. The questions that readily come to mind are: What have been the patterns of land use in Ondo state, given the population pressure on available land and given the changes in social, economic and farming situations? What are the consequences of current land use patterns and intensity as well as land use changes on sustainable farming? What are the income effects of different land use options for agricultural production? What are the economic consequences that are expected of land use change for the farmers? What is the best alternative for land use in order to attain sustainable food production, while ensuring protection of the environment? What are the economic and environmental quality trade-offs associated with agricultural land uses of various magnitudes? The above questions form the basis for the objectives of this study. Given these questions, the study has the following specific objectives. (i) To generate the spatial map of the soil, land use patterns, rainfall and vegetation a distribution patterns of Ondo state. (ii) To develop methods to link geo-referenced databases to integrated ecologiceconomic models. (iii) To quantify the trade-offs among economic, agronomic and environmental objectives, so as to determine the best alternative land use options. While it is acknowledged that several studies have been carried out on land use and landscape changes, especially in the developed countries [10, 6, 7, 3, 4, 5, 14, 1, 11, 8, 12, 13], there is increasing need to develop new models and techniques of analysis to take care of complex interactions between agricultural production, environmental and economic factors. Whereas land use studies received much attention in the literature, the issue of how to formalise quantification of land use systems and integration of ecologic-economic variables into the models has only been addressed to a limited extent. Understanding the dynamics of land use change is a scientific challenge of considerable importance to humanity. The demands for improved knowledge of environmental processes and the impacts of policy on their dynamics must increase, as population pressures on food supplies and natural resources mount and publicly held perception of preserving environmental diversity and amenity strengthens. Some of the most profound changes in the landscape have arisen from direct decisions by man concerning land use: from changes in cropping patterns, afforestation and deforestation to modification of water courses [9]. These in turn have affected both the quality of environmental resources and the sustainability of a lasting and diversified food chain. Given the above considerations, this study is therefore important in developing integrated bio-economic models to simulate complex economic and ecologic impacts of land use and landscape changes as well as effects of policy changes on land use in Nigeria.

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3 Research Methodology 3.1 Area of Study This study is being conducted in Ondo State, which is one of the 36 states of Nigeria and is located in the Southwestern part of Nigeria. The State lies within latitudes ◦ ◦ ◦ ◦ 5 45 and 8 15 North and longitudes 4 45 and 6 East. The Southern coastline of the state rests on the Atlantic Ocean with considerable territorial waters offshore rich in aquatic and mineral resources of significant importance. The relative position of Ondo State in Nigeria is shown in Fig. 1 in the appendix. Spatial Model

Economic Model Ecologic Model

Simulation

Ecologic output

Economic output

Fig. 1 Integrated ecologic-economic

3.2 Data Requirement and Collection For this study, geo-reference data, as well as primary and secondary data are involved. Data include digitized thematic maps, consisting of soil map, land use map, rainfall map, vegetation, yield data, soil nutrient balance data, hydrological data, climatic data, including rainfall and temperature, as well as other relevant social and economic data.

3.3 The Integrated Model The purpose of the integrated bio-economic modelling approach is to couple ecologic, spatial and economic parameters that influence landscape and land use changes in a single integrated model. The integrated model is in the form of module.

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The different modules include (i) the economic model, which uses socio-economic data, production data and price data (ii) the ecologic model, which involves modeling the physical environment of agricultural production activities (iii) the spatial model, which consists of spatial data and makes use of digital elevation model (Fig. 1). The output from the ecologic, economic and spatial models can then be coupled and simulated in a GIS environment. Figure 1 presents a diagrammatic representation of the integrated model. Economic module: The economic module consists of models that maximizes the objective function of production [2], which is generally assumed to be income maximization. In this sense, it is assumed that farmers tend to maximize gross margins from different farm enterprises. The gross margins, together with production inputs and constraints are then fed to the linear programming models for optimization processes. The linear programming (LP) model makes use of economic data from the database, with capability for different land use scenarios. The economic model describes the economic behaviour of farmers. Ecologic model: The ecologic component of the integrated model consists of soil erosion model, which include soil loss equation and the degree of crop coverage function. The soil erosion model is based on the Universal Soil Loss Equation (USLE). The parameters for deriving USLE include rainfall erosivity factor (R-factor), soil erodibility factor (K-factor), slope and slope length factor (LS-factor), vegetative cover factor (C-factor) and conservation practice factor (P-factor). Spatial model: This consists of the spatial soil map, land use patterns map, vegetative cover map, rainfall distribution map, relief map and population density map.

3.4 Model Specification and Implementation The integrated bio-economic models will combine economic optimization model (Linear programming model) with ecologic and spatial models. Within the integrated model, different land use scenarios and policy scenarios will be implemented in the optimization model to produce different gross margins, given the scenario assumption.

4 Results and Discussion The results cover, the spatial maps of the soil, rainfall and land use patterns. Results from economic models showing gross margins from different farming systems and land use options are also provided.

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4.1 Spatial Soil and Rainfall Maps of Ondo State Soil types, their fertility, and present and potential productivity as well as rainfall distribution patterns exert considerable influence on agricultural production in the state as in the rest of Nigeria. Regional variations in soil types which account for variations in the types of agricultural practices in any environment are also evident in Ondo State. The major soil types found in Ondo State are (i) alluvial, (ii) ferralsols, and (iii) ferruginous tropical soils. The alluvial soil types, which characterize the coastal LGAs of Ilaje and Ese-Odo, are not very important agriculturally. This is due to the sandy and acidic nature of such soils. The soils there are generally associated with areas of sedimentary rocks. They are intensively leached and contain limited reserves of weatherable minerals. Although a number of crops are grown on such soils, they are considered to be of low fertility and of low agricultural value. Areas with ferruginous soils are particularly suitable for cocoa production as evident in the long history of significant cocoa production in Ondo State, chiefly in Ondowest, Ondo-east, Idanre, Ile-Oluji/Okeigbo and Akure-south LGAs. The soils have an exceptional clayey texture, but combine good drainage and aeration with good properties of moisture and nutrient retention. In terms of productivity and potentialities of Ondo State soil, the coastal alluvial soils of Ilaje and Ese-Odo LGA are low. The remaining soils of the State are of medium to high productivity with medium to good potentialities for both food and non-food agricultural production. The main characteristics of soils in Ondo State are shown in Fig. 2. The climatic condition in Ondo State follows the pattern of southwestern Nigeria where the climate is influenced mainly by the rain-bearing southwest monsoon winds from the ocean and the dry northwest winds from the Sahara Desert. High temperatures and high humidity also characterise the climate, which facilitate the

N W S

Fig. 2 Soil distribution patterns in Ondo state

Soil E

Clayey Loamy No Data Sandy

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Ife dore Ile – Oujji – Akure Nouth Oke – IgboAkure South Ondo – East Owo Ondo – west Idanre

Akoko NW Akoko NE Akoko SE Akoko SW

Ose

Odigbo

Okitipupa

Irele

N W

E S

Ilaje Ese – Odo

Rainfall Pattern 1270–1524 mm. 1524–2032 mm. 2032–2540 mm. 2540–3048 mm.

Fig. 3 Present rainfall pattern for the state

growth of tropical crops and high forest. There are two distinct seasons, the rainy and dry seasons. The rainy season lasts for about 7 months April to October, and the dry season lasts generally from October to March. The rainfall amount and pattern of rainfall remain the most important climatic factor in agricultural production possibilities in Ondo State. The rainfall pattern is showing in the spatial map in Fig. 3.

4.2 Spatial Map of Vegetation and Land Use Patterns Most part of the state is under forest vegetation, given high amount of rainfall and ◦ atmospheric temperature ranging between 28 and 31 c and a mean annual relative humidity of about 80%. Figure 4 shows the spatial map of the vegetation distribution of the State. This consists of coastal forest and mangrove; swamp forest; the most lowland forest; and the forest savannah mosaic. The total agricultural area of Ondo State is about 1.3 million hectares of which over 859.230 is under smallholder rain fed production, 27,633 is under tree crop plantations and 350,733 is under high forest cover. The satellite photography of land use pattern is shown in Fig. 5. The Guinea Savannah zone is covered mainly by grassland and suitable for livestock production particularly the husbandry of large and small ruminants.

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Akoko NW Akoko SE Akoko SW Akoko SE

Ifedore Ile – Ouji – Oke – Igbo

Ondo – East Ondo–west

Akure Nouth Akure South

Owo

Ose

Idanre

Odigbo Okitipupa Iele

N W

E S

Ese – Odot

Vegetation Derived Savanna Freshwater Swamp Forest Lowland Rainforest – Dry Lowland Rainforest – Moist Mangrove Forestand Coastal Vegetation

Ilaje

Fig. 4 Pattern of vegetation cover

Fig. 5 Land use patterns

4.3 Gross Margin Analysis The notion of economic sustainability focuses on the profitability of specific technical choices. They include margins analysis and income generation as a function of a specific activity. Faced with market uncertainties, price volatility and climatic

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hazards, most tree-crop farmers in the study area have developed diversification strategies, in which different crops are grown to mitigate the problem of risks involved in agriculture. This involves growing different crops simultaneously with cocoa. It is therefore important to analyse economic viability of these different diversification options or farming systems. An analysis of the gross margin from different farming systems will provide a better knowledge of economic consequences of various farming systems and practices in terms of gross margin. The current practices of farmers in the study area involve inter-planting of cocoa with different crops. Such inter-planted crops include plantain/banana, kola, palm oil, vegetables and oranges. Table 1 below provides information about farming system adopted by farmers in the study area, showing different crops that are grown together. Farmers in the study area go into diversification for economic reasons. Crop diversification shows the attitude of farmers to engage in production of different agricultural products simultaneously. Farmers go into crop diversification mainly to offset or reduce the level of risk involved in agricultural production. Figure 6 presents gross margin from different crop combination. The figure indicates that the highest gross margin is from crop combination comprising cocoa, oil-palm, cocoyam and vegetables while the least gross margin came from combination ococoa, plantain, cassava and banana. A simulation analysis of the variation in gross margin for the next 10 years on the basis of different crop combinations was carried. The results show different patterns of gross margin for the different crop combinations over the 10-year period. The results of the simulation (Fig. 7) show that farming systems with more crop diversification have higher projected stream of income over the 10 year period. The results have shown that apart from cocoa production, arable crops are important in the production programme of the farmers, with most of the farmers growing two or more arable crops, in addition to cocoa. Smallholders developed diversification strategies while maintaining traditional practices. The persistence of traditional practices demonstrates the attachment people have to traditions and social standards, and consequently to cohesion and social structure, at least at the community level. Indeed, the whole process of social organization is concerned with the maintenance of these practices. Diversification strategies are developed to obtain a more even distribution of income throughout the year, to

Table 1 Farming systems in the study area

S/N

General farming systems among cocoa farmers

1 2 3 4 5 6 7

Cocoa with plantain, oranges and economic trees Cocoa with plantain, banana and Maize Cocoa with yam, cocoyam and plantain Cocoa with cocoyam and plantain Cocoa with oil palm, cocoyam and vegetables Cocoa with plantain Cocoa with plantain, cassava and banana

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120,000

100,000

GM/ha

80,000

60,000

40,000

20,000

0 CA+OR+TR

CA+PL+BA+MZ CA+YA+CO+PL

CA+CO+PL

CA+OP+CO+VE

CA+PL

CA+PL+CV+BA

Farming Systems

Fig. 6 Gross margin from different crop combinations Note: CA = cocoa; CO = cocoyam; OR = oranges; oil palm; TR = economic tree; PL = plantain; BA = banana; MZ = maize; YA = yam; Ve = vegetables

profit from potential opportunities by being less dependant on a single commodity, and to increase knowledge, and technical know-how in order to be in a better position to innovate. While the results have indicated different economic implications for different crop combinations, it is important to state that such crop combinations are also bound to have varying ecological implications. Hence, there is need to carry out trade-off analysis between economic and ecologic implications. This is the next phase of this research.

4.4 Summary and Conclusion The aim of this research is to carry out bio-economic analysis of land use change, given different farming systems in Ondo State, Nigeria. The results of spatial maps have indicated varying soil characteristics, land use patterns, population distribution, rainfall patterns and vegetative covers across the state. The study also shows different gross margin implications for different crop combinations. While the results

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400,000

350,000

Farm Income

300,000

250,000 Cocoa+Plantain sole Cocoa+Kola Cocoa+Plantain+Kola

200,000

Cocoa+Plantain +10% Cocoa+Kola+10% Cocoa+Plantain+Kola+10%

150,000

100,000

50,000

0 2004

2006

2008

2010

2012

2014

2016

Year

Fig. 7 Simulation of gross margin for different crop combinations

so far have been revealing, it is inconclusive as further analysis will be conducted on trade-off between economic and ecologic factors and their implications on sustainability of the environment. Acknowledgement Thanks are due to the Alexander von Humboldt Foundation of Germany for providing funding for this research under the “Return Fellowship Programme”.

References 1. Ajibefun IA, Wenkel K-O, Wieland R, Mirschel W (2004) Modelling of landscape and land use changes: with application of spatial analysis modelling tool to quillow region of north east Germany. Int J Food, Agric Environ Finland 2(2):364–368 2. Anderson JR, Dillon JL, Hardaker JB (1977) Agricultural decision analysis. Iowa State University Press, Ames 3. Armstrong AC, Legros JP, Voltz M (1996) A detailed model for crop growth and water condition. Int Agrophys (10):171–184 4. Bouman BAM, Nieuwenhuyse A, Hengsdijk H, (1998) PASTOR: A technical coefficient generator for pasture and livestock systems in the humid tropics. Version 2.0. A users guide. Quantitative approaches in systems analysis, No. 18. AB-DLO-PE, Wageningen, The Netherlands

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5. Hengsdijk H, Nieuwenhuyse A, Bouman BAM (1998) LUCTOR: Land use crop technical coefficient generator. A model to quantify cropping systems in the Northern Atlantic Zone of Costa Rica, Version 2.0. QUASA series no. 17, ABDLO/PEW, Wageningen, The Netherlands 6. Krugman P (1995) Development, Geography and Economic theory. MIT Press, Cambridge, MA 7. Loveland PJ, Rounse vell MDA, Mayr TR, Legros JP, Voltz M, de la Rosa D, Armstrong AC (1993) Agroclimatic Change and European Soil Suitability- a spatially distributed model. In: Troen I (ed) Climate change and impacts. European Union publication 15921 EN, pp 215–228 Copenhagen, Denmark 8. Mirschel W, Wieland R, Voss M, Ajibefun I, Deumlich D (2006) Spatial analysis and modelling tool (SAMT) 2: Applications. Ecological informatics, vol. 1. Elsevier Science, United Kingdom, pp 77–85 9. Rounsevell MDA, Evans SP, Mayr TR, Andsley E (2001) Integrating biophysical and socioeconomic model for land use studies soil survey and land research centre. Cranfield University Silsoe 10. Van Keulen H, Veeneklaas FR (1993) Options for Agricultural development: A case study of Mali’s fifth region. In: Penning de vries FWT, Teng P, Metselaar K (eds), System approaches for agricultural development. Proceedings of the International Symposium on Systems Approaches for Agricultural Development, Bangkok, Thailand. Kluwer Academic Publishers, Dordrecht, Netherlands, pp 369–382 11. Wieland R, Voss M, Holtman X, Mirschel W, Ajibefun I (2006) Spatial analysis and modelling tool (SAMT) 1: Structure and possibilities. Ecological informatics, vol 1. Elsevier Science, United Kingdom, pp 67–76 12. Wieland R, Mirschel W, Wenkel K-O, Ajibefun I (2004) Spatial simulation with SAMT. In: Wittmann J, Wieland R (eds) Simulation in environment and geosciences. Shaker Verlag, Aachen, Germany, pp 161–181 13. Wischmeier W, Smith DD (1978) Predicting rainfall erosion losses: A guide to conservation planing. Agricultural handbook No 537. Washington, DC, USDA 14. Zander P (2003) Agricultural land use and conservation options: A modelling approach, Thesis Landbouwuniversiteit Wageningen, 222pp

Green Marketing Willingness of Bulgarian Market: Comparison with Italy Teodoro Gallucci, Giovanni Lagioia, Julia Uzunova, and Vesselina Dimitrova

Abstract The concept of green marketing is wide covering different aspects of business strategy and policy making. Green marketing puts together issues of sustainable development, such as recycling concerns, material re-use or eco-efficiency with the promotion of products by the conventional marketing policy. The purpose of this paper is to establish how the adoption of green marketing could be an effective tool for improving the market share in Bulgaria following the example of the Italian case. The adoption of eco-label brand or the fulfilling of other environmental certifications could enable to the small medium enterprises (SMEs) to become more competitive in the EU market. We try to explain how a changing view about the environmental aspect could represent an opportunity to snap it up in shorter-medium time. Keywords Green marketing · Eco-label · Benchmarking dimensions

1 Introduction The promotion of the green marketing started in Europe in the early 1980s when were discovered different commodities of chemical production capable of damaging environment and human’s health. As a result, new “green” approach was introduced with the aim to promote ecologically aspect of products [1]. For this reason, nowadays, labels report some indications in order to inform consumers about several characteristics of the products. A better knowledge about environmental aspects of products, such as recycling and biodegradability of packaging, energy or water consumption or other ethical and social indications, cause changes of habits and behaviour. This information has made consumers more conscious V. Dimitrova (B) Department of International Economic Relations, University of Economics Varna, 77, Kniaz Boris I blv., Varna 9002, Bulgaria e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_32,

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of the environmental limits on the light of sustainable, “green” purchasing. As consequence “Green marketing” is evaluated as very intensive research topic and has becoming important for the business due to the environmental aspect enclosed in the label. This qualitative policy is not a question of fashion but a real necessity that could improve a market share, especially on export markets. In fact in all Europe, associations of consumers are forcing the enterprises to develop an appropriate marketing strategy concerning the presentation of more green labels, such as the Eco-label. The enterprises understood that fulfilling green marketing strategies could be convenient to be more competitive. The appellation “green enterprise” encourages more consumers to give trust on these environmentalfriendly products. Despite the huge economic investments, necessary for adopting the policy of green marketing, the efforts of the firms could turn into a net turnover for the nearest future. A study carried out by IEFE Bocconi University of Milan (Italy) is concerning the capacity to increase the turnover of eco-labelling enterprises.1 This increase is estimated more than 50% [2]. Other studies have shown how eco-label could affect the demands on suppliers and on retails sector [3]. European companies develop their production methods and image-building thanks to the eco-labelling. Bulgaria as a new member of EU since January 2007 needs to involve its industrial policy to eco-labelling and to benefit from green certification. The example of leading EU country as Italy for the environmentallyprotected and sustainable products is very important, because encourages an innovative ecological responsability in EU market. The purpose of this paper is to establish how the green marketing could be an effective tool for improving the market share in Bulgaria following the example of the Italian case. The analytic framework includes the comparison of the eco-label policy and the relative legislation in the both markets. We choose a benchmarking approach in order to make better assessment of Bulgarian green policy. The whole paper is organized into four sections. Section 1 presents the nature of the green marketing. Section 2 is a brief overview for the modern tendencies in European eco-label practice and the challenges for the East part of the continent. Section 3 discusses the eco-label instruments and the relative legislation in Italy and Bulgaria in the framework of EU. Section 4 summarizes our findings for the green marketing willingness of Bulgarian market.

2 Theoretical Background “Greenness” has become a code-word for a range of environmental concerns, and it is usually considered positively. The development of green power determinants is important because provides a stream for additional ecological and renewable sources. Green power is an international activity and determines structures, strategies and concepts in different levels- marketing, management and logistics. The 1 The

eco-label logo is a flower.

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most general concept of green marketing, which refers to the promotion or advertising of products with environmental characteristics has searching the necessary modifications in traditional marketing practices. Green marketing is defined as an opportunity to take advantage of customers’ willingness to purchase, and sometimes pay a premium for, products that provide private benefits as well as public environmental and other, less tangible, benefits [4]. One typical definition describes “green marketing” as the practice of “. . . adopting resource conserving and environmentally-friendly strategies in all stages of the value chain. . .” [5]. According to B. Paulos [6] the green marketing learns to eight principal lessons each competitive enterprise: (1) what is “green”; (2) how to interpreting green willingness; (3) how to understand green pricing; (4) who will buy green power products and services; (5) how important is green marketing performance; (6) why to initiate eco-label and certification; (7) if it is necessary to accept private eco-label programs; (8) what is the importance of release green marketing regulations [6]. Green marketing aims necessary standards as green certification or eco-label. Eco-labelling is a voluntary certification used as an insurance against several logos, trade marks and labels. The purpose of the eco-label is to facilitate the transfer of ecologically relative information toward the customers for the products and services; to help business and supply chain management of the firms to change and to adapt new internal and external challenges concerning productivity, revenues and protections [7]. Green concept is strongly used in European countries and connected with purchasing, pricing and consumption processes. The first attempts for green practices are in UK, Switzerland, Germany, Finland, Netherlands, Sweden and Denmark. Especially large –sized companies are remarked with green marketing status. These enterprises win more competitiveness and make better emerging of green activity. In the United States of America, an estimated 75% of consumers claim that their purchasing decisions are influenced by a company’s environmental reputation, and 80% would be willing to pay more for environmentally friendly goods [8]. On the other hand according to a study of O’Rourke in 2005 only 10–12% of consumers buy regularly products considered “green”. This significant difference is due to a lacking of information about the products at low environmental impact [9]. On a worldwide level, a recent 22-country survey of environmental attitudes found that citizens avoid products that are harmful to the environment [10].

3 Challenges for the Eco-label Policy in East-European Countries The EU Eco-label is administered by the European Eco-labelling Board (EUEB). The Eco-label receives the support of the European Commission, all Member States of the European Union and the European Economic Area (EEA). The Eco-labelling Board includes representatives such as industry, environment protection groups and consumer organisations.

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The Eco-label is the European brand of certification for products and services. It was created in 1992 with the adoption of the European Regulations 880/92, and successively updated with the new Regulations 1980 of the 17 July 2000. It is a voluntary tool of environmental policy and represents a selective one, based on environmental and quality performances related to the life cycle of products, raw materials used for manufacturing and recycling processes. The better comprehension of production cycle needs a detailed Material Flow Analysis (MFA) to gather data about material circulation into the economic system. This approach associated to input output analysis, more and more cutting edge, is also capable of illustrating inter-linkages between economic system and the environment. For obtaining the European eco-label each enterprise shall interact with the competent authority of its own country. The criteria have standardised and harmonised rules in order to make lighten the procedure. This criteria are submitted to the European Committee Awards (CUEME) that it is composed by different competent organisms of each members state (such as delegate of the ONG environmentalist, associations of consumers and industry, and also delegates of SMEs) and are periodically reviewed, in order to favour the improvement of the quality of products and services. At regional level other eco-labels are well-known as Nordic Environmental label (Sweden, Norway, Finland and Ireland), Blaue Engel (Germany) etc.2 As above stressed for the eco-label is necessary to follow a procedure of accreditation and to invest money. Normally the preliminary documentation for obtaining the eco-label has a cost between 300 and 1,300 euros. Expenditures for the copyright to use the eco-label represent 0.15% of the annual volume of sales. But there are some shrinking for the enterprises: 25% for small medium enterprises (SMEs); 15% for enterprises with the certification EMAS or ISO 14001; 20% for “first movers” that are the first three enterprises that require the certification for each groups of product; 30% in the case that the enterprise had another certification that satisfy the norm ISO 14024. Reduction can’t exceed in total the 50%. In Fig. 1 are shown the percentage of the companies in EU by country that decided to proceed with the eco-label accreditation. At December 2005 Italy is the 90 80 70 60 50 40 30 20 10 0 AT

BE

CZ

DE

DK

EL

ES

FI

FR

HU

IT

NL

Fig. 1 Companies with eco-label by country (2005). Source: [12] 2 The

eco-label in USA and Canada is “Green Seal”.

NO

PL

PT

SE

UK

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leader country with 84 eco-labelled companies. It is followed by Denmark with 53, France with 45, Spain with 19, Sweden with 15 and Germany with 11. As emerges from the Fig. 1 almost all Western area of Europe decided to invest in ecolabel certification. In comparison, the East part of EU countries (Czech Republic, Hungary, Poland) is still missed the opportunity to develop the green certification as a guarantee for efficient sales and higher product price. In the East part the companies meet some constraints for adopting the ecolabel above all for two reasons: First, the costs for obtaining the label. Some small companies, above all in East part of EU find expensive to start the procedure for accreditation (initial cost for application, internal preparatory efforts and costs, costs of testing, costs for marketing and etc.). Second, difficulty to involve their suppliers in the concept of “green purchasing”, because there is a low awareness of the benefits for the environment and for the health [11]. Thus, a campaign of information at domestic level becomes significant to boost the eco-label meaning, characteristics and advantages. On the contrary in the West part the companies having less problems from economic point of view, have benefited by becoming the “first movers” in this sector. They have invested in their image in front of their consumers and this have repaid with a better customer satisfaction, giving more credibility to the products in a context that has becoming more competitive and globally integrated. Guided by the logo the customer is sure that a certified business or product meets a certain standard. For this reason, a better knowledge of the meaning and the characteristics of eco-label logo are essential. In summary, the development of environmental alternatives of production processes really has been convenient both to motivate the customers and addressing their choice to eco-labelled products. In Fig. 2 are reported the eco-label by product group. In EU it is possible to require eco-label brand for 27 groups of products, identified by a study of feasibility, but as above stressed, periodically the members EU Commission can take into consideration different product to review. At December 2005, 284 licenses have been awarded of which 64 in the textile sector, 46 in paints/varnishes, 40 in tourism accommodation, 25 sanitary cleanings, while 20 in the fertilizers and 15 tissue paper sectors.

fri

pa

re

di

sh

w as he g s in e ts re /v to ar rs ni s fe he r t tis iliz s di s er sh c u w op e p s as yi ap hi ng er n la g d pa p un dr ete er r y de gen te t r te lig gen xt ht t ile bu s pr lbs o fo duc ot t b sa ed we ha nita ma ar nd ry tre di cle ss sh a de ner te s rg to ur flo tele en is or v t m in is ac g c ion co ov m er o s ca lu dat m br ion pi ific ng a se nts rv ic es

70 60 50 40 30 20 10 0

Fig. 2 Companies in EU with ecolabel by prouduct group (2005). Source: [12]

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4 Benchmarking and Eco-labelling 4.1 Italian Example As above stressed, enterprises shall interact with the competent body of its own country. The authors have chosen Italian example because it is leader in the accreditation label and could represent a pattern to imitate for incentive the adoption of this approach. In Italy the competent authority for awarding the eco-label is APAT (National Agency Protection of Environment and technical services) that interacts with European Committee Awards for all the criteria development and revision. Figure 3, illustrates the diagram flow of the procedure. The documentation required consists in different steps: application format for awarding the certificate, receipt payment of preliminary application fees (between 300 and 1,300 euros); technical format; copy of accreditation of the laboratory; copy of further environmental certification e.g. EMAS and so on; declaration of conformity. In Italy industrial districts provide an interesting example of local production systems able to face global competition. They are characterized by the development of strategies to change consumption patterns and recycling, require data on the firm material and energy use in physical terms [13]. Firms in developed countries like Italy consider that the ability to enhance raw material and product design from the beginning, to mitigate the environmental impact, and to rationalize and comply with environmental regulations to improve corporate image will pressure more European firms to adopt an EMS system. On the whole, the incorporation of green purchasing into an environmental management system can encourage all businesses and administrative agencies to think over the whole range of production systems from material supplies to waste treatments. It can also lead to homogeneity in management processes and an improvement in administrative efficiency, in addition to cuts in costs, which consequently help expand a firm’s environmental and financial performance [14].

The applicant

Committee eco-label

Fig. 3 Diagram flow of procedure accreditation eco-label in Italy

The committee awars the Ecolabel (30 days)

Apat examines the dossier (60 days)

European Commission

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4.2 Bulgarian Example Until 2005, EU includes 27 product groups with their green criteria. Since May 2005, in Bulgaria have been approved only 17 of these 27 product groups as enough green, with environmentally-aware references. They are: shoes, textile products, hard floor covering, printed paper, matrax, indoor paints and varnishes, vacuum cleaner, TV set, ice and meat safe boxes and hotel nights’ accomodation. This implies that these products could receive their eco-label not later than 2 months after the correct notification of the presented preliminary documentation. The whole procedure is under the National Regulation 3/15 May 2003 about the eco-label of the Bulgarian products, elaborated by the Ministry of Ecology and Waters. The issue of the preliminary documentation costs between 75 and 100 EUR and for enterprises with managerial system for ecological certification (ISO 14 000, ISO 9001) the price is only 25 EUR. The validation of the eco-label is 3 years. During this period, the certificated product is included in the Ecological Register of the Ministry of Ecology and Water as safe and guaranteed [15]. In Bulgaria, there is a crucial and potentially positive link between economic development and the environment. The SWOT analysis of Bulgarian eco-market shows the dominations of more negative features in comparison with the benefits from the impact of “new environmentalism” in EU countries [16] (see Table 1). The existing ecological problems in Bulgarian enterprises couldn’t be resolved with a simple participation in the large EU market. European institutions indicate the right direction for green marketing activities, but the way to promote this policy is in the hands of the Bulgarian institutions. Environmental organizations in Bulgaria (like the Union of the Customers, Bulgarian Association for recycling etc.) need to play key roles for the informational dissemination of green priorities between the business and the customers. They need to be able to communicate systematically in vertical, horizontal or crossed way with the customers about the importance of eco-labeling. The effective feedback is a principal criteria for the ecological control in the country. For comparison, eco-labelling has dramatically affected EU market, because the green certification means quality and production in an environmentally sound way [18]. Until now, only some tourism agencies and enterprises in textile and equipment sectors in Bulgaria could establish ecological prevention and control for their products.3 According to EU Eco-label data 2005, the eco-label is well-known in Bulgaria, launched especially by original Italian, Greek and Spanish products and services, but also from Czech Republic and New Zealand. The proposed ecocategories are: hard floor covering, paints and varnished textile (wool) products for bed and tables, dishwashers. These are the same categories which Bulgarian manufacturers, retailers and service providers aim to be competitive and to satisfy domestic and international market requirements. The principal problem of Bulgarian

3 In Bulgaria the eco-label is not necessary for drugs, foods, beverage and toxic chemical substances.

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T. Gallucci et al. Table 1 SWOT analysis of Bulgarian eco-market

Strengths

Opportunities

Low level of soil, air and water pollution of the Better EU project involvement and use of EU territory; financial tools (ISPA, SAPARD, PHARE); Possession of the one of the richest Supporting more green initiatives of EU for bio-diversity in Europe and large clean restructuring energy sector and tourism territories; industry. Implementation of green activities JIT. Strong regulatory response and adopted legislative response in the respect to the environment; Well-developed systems for eco-monitoring from EU institutions; High percentage of nuclear power generation in the power generation structure. Treats

Weakness

Enourmous expenditires for synchronizing Bulgarian ecological legislation with European legislation; Impact of global climate changes. Bulgaria is a droughty zone with a continious process of delioration of forests; Out-dated technologies used in the eco-industry and energy sector; Obscurely reglamentation for the monitoring of liquidated coal mines;

Shortage of funding opportunities-high external debt, relatively poor population; Lack of sufficient quatity of water resources and inefficient use of existing resources; High level of noise urban pollution;

Low quality of liquid fuels and considerable pollution from transport sources in large cities; Lack of ratifies intergovernamental agreements Lack of administrative capacity for the implementation of the new legal between the neibouring countries in the field documentation. This way, the respective of transboundary pollution in Danube and funds and environmental management Black sea littoral. experience of EU countries need to be used. Source: [17]

products is the lack of environmental competitiveness. The products need to adduce positive proof of green production, according to EU criteria and quality documentation (equipment inspection against ecological pollution, energy use, eco-toxicity, hydrological management etc.).4 The enterprises need to dispose installations, laboratories, equipment and human resources to control the content of waste and beneficial substances in the supplying materials. The durability and safety of the products require a huge investment, which is an obstacle for the business activity of the majority of enterprises in Bulgaria- SMEs. To a certain extent, the environmental plans of Bulgarian SMEs are based only to ISO regulations (ISO 9001, ISO

4 The period for investigation and verification of the eco-labeling documentation in Bulgaria by the Ministry is around 1 month.

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14 001, OHSAS 18001 etc) which is a positive sign. Higher percent of certificated SMEs could be pointed as a good possibility for training a staff and creating tangible effects for inflow investments by technological transfer and value-added. The quality systems explain a better competitiveness of the product or services and a better satisfaction of the customers [19]. With regard to these problems, Bulgarian SMEs couldn’t point out the life-cycle approach as the principal approach for the eco-labeling in EU. Longer is the life-cycle of equipment production higher would be the level of energy used for the recycling process. Finally more are the ecological losses for the enterprises and the state. However, the problem of recycling (it is also named “reverse logistics”) is under resolution in Europe. Until 2003 according the Report of European Commission high level of packaging recycled have only Belgium, UK, France, Netherlands and Luxembourg (see Fig. 4) Life-cycle assessment or Material Flow analysis as a scientifically-based indicator is not still adopted in Bulgarian eco-label policy. Most of the Bulgarian industrial products suffer from out-dated technologies which propose low quality and worse pollution. In Table 2 we present a comparison between benchmarking dimensions, developed in the European green practice and the example of Bulgaria. The current green marketing philosophy in Bulgaria concerns some of the primary characteristics of the evolution of environmental management, corresponding to the USA and West Europe ecological practices for the period 1970’s- mid 1980’s. The focus of life-cycle environmental effects of processes and products (corresponding to the mid 1990s in developed countries) will be implemented in the future. The principal factors for this performance could be the flexibility of environmental choice of Bulgarian enterprises toward sustainable business practices through continual system auditing; reducing of costs and improving the efficiency of green marketing efforts by extensive international deal that could remove existing trade barriers for present eco-labeling products in EU.

Fig. 4 Levels of recycling the packaging waste, in percent (2001–2003). Source: [20]

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T. Gallucci et al. Table 2 Benchmarking dimensions of green marketing

Traditional dimensions5

Modern dimensions

Resources conservation and pollution control;

Involvement in green power programs (global green integration); Green sales and managing eco-efficiency; Customer partnership; Including third-party marketers with long-term contracts (at least 3–5 years); Product design criteria and eco-branding6 ; Systematic product and process management to maximize profitability and ensure environmental quality.

Waste management; New environmental legislation; Process improvement to reduce material use and improve efficiency.

5 The Future of the Green Marketing in Bulgaria Consumers’ organisations in all Europe are pushing the enterprises to develop an appropriate marketing strategy concerning green labels, such as the Eco-label. The use of this brand, in fact, gives better market visibility thanks to products recognised, advertised and sold in all Europe. This could represent strategic choice of differentiation of the products or services offered in order to win customers sensible to environmental aspect. This become crucial because allows to identify and to find solution for reduction of wastes as, for instance, energetic supplying from renewable source. This kind of policy is adopted in Italy, but in Bulgaria although the eco-label is a voluntary procedure for each enterprise, Bulgarian firms don’t follow the criteria for eco-labelled their products. Eco-label is also still not enough necessary in comparison with the Italian clients for the Bulgarian customers to change their perceptions, traditions, values toward European green taste. They have yet the appropriate marketing culture and strategic customer behaviour. As a consequence, Bulgarian business requires more and more eco-labelling procedure with the necessity to break immediately into EU market. Bulgaria still has a lot of environmental problems in comparison with Italy that differ from sector to sector. Bulgarian government needs to develop more sophisticated and better applied policy to reduce the negative-side effects of the intensive production methods specific of the Bulgarian industry. There are some efforts for trying to convince the small and medium enterprise in Bulgaria to adopt eco-label procedure. Some enterprises think this marketing

5 The above-cited indicators are included in Bulgarian Regulation 3/ 2003 as priority aspects to assess the eco-label of Bulgarian goods and services. 6 Although use of multiple brands and logos could create difficulties in preparing marketing materials, eco-branding is identified as a preferred approach in order to avoid confusion among customers [21].

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strategy as a problem and not as an opportunity. For this reason become significant to undertake an important campaign of information about the potentiality of environmental friendly technology and green action for the market share. An innovative approach of marketing and benchmarking dimensions could be effective in addressing the purchasing of Bulgarian consumers in eco-labelled products. The best parameters to take into consideration for influencing the consumer’s choices are the quality, the function and the very fashion design. An adequate green policy at domestic level would make more visible the green brand in way to convince both the people about a responsible purchase and enterprises to understand the economic advantages. It is important to look beyond and don’t miss the opportunity of environmental performance in way to compete in the future with their products in EU affecting by green thought. Strongly precise and subordinated to the monitoring of European Commission of Environment, Italy benefits from faster and adequate implementation of EU ecological rules. The benefits would be to develop more green benchmarks in Bulgaria as innovative initiatives. These are environmental audits, environmental friendly technology and green action plans in order to attract potential clients. For the future, not only the Environmental Management Systems of ISO 14001 (International Organization for the Standardization), but also the Eco-Management and Audit Scheme Directive (EMAS) of the EU should provide the legal basis for eco-label in Bulgaria. In these systems firms receive certification on the basis of establishing an environmental quality control tailored to that firm, and the setting up of environmental monitoring and accounting procedures. Obtaining certification is seen as evidence of the firm’s commitment to the environment, and is frequently used as a public relations, marketing, and government relations advantage [22]. This represents a fundamental commitment of Bulgarian enterprises to engage in environmental assessment and audit that represent a significant modification of traditional practices, in which efficiency, quality and cost evaluations prevailed. Eco-labeling could give an impetus developement of sustainable production for SMEs in Bulgaria. If eco-labels are to become manageable and effective instrument as in the business activity of Italy, the further result for Bulgaria is to decrease the expenditures and to increase the productivity and supply chain optimization.

6 Contributions Each author is contributed in the present paper as follow: G. Lagioia § Introduction; T. Gallucci § 2., § 3.1; J. Uzunova- §.4.; V. Dimitrova- § 1., § 3.2

References 1. Fischer H (1995) Chimica pulita Per un uso intelligente delle materie prime. Laterza, Milano 2. IEFE Bocconi (2003) Diffusione, utilizzo ed efficacia competitiva dell’Ecolabel Europeo in Italia. Quaderni Università Bocconi, Milano

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3. Cadman J, Dooley P (2004) The Direct and indirect benefits of the European eco-label – final report, London 4. Wiser RH (1998) Green power marketing: Increasing customer demand for renewable energy. Utilities Policy 7:107–119 5. Johri LM, Sahasakmontri K (1998) Green marketing of cosmetics and toiletries in Thailand. J Consumer Marketing 15(3):265 6. Paulos B (1998) Green power in perspective: Lessons from green marketing of consumer goods, Electricity J Jan/Feb:46–55 7. Mouritsen J, Ernst J, Jorgensen AM (2000) ‘Green’ certification as a managerial technology. Scand J Manag 16:167–187 8. Lamming R, Hampson J (1998) The environment as a supply chain issue. Br J Manag 7:45–62 9. O’Rourke D (2005) Market movements. J Ind Ecol 9(1–2):115–128 10. Elkington J (1999) Toward the sustainable corporation: Win-Win business strategies for sustainable development. Calif Manag Rev 36(2):90–100 11. Interim report ever study (2005) available at http://ec.europa.eu/environment/ecolabel/pdf/ news/ever_interimreport.pdf, last accessed October 2006 12. EU Commission, Eco-label statistics (2005) available at http://ec.europa.eu/environment/ e-colabel/marketing/statistics_en.htm, last accessed October 2006 13. Albino V, Kühtz S (2004) Enterprise input-output model for local sustainable development-the case of a tiles manufacturer in Italy. Resour Conserv Recy 41:165–176 14. Chen C-C (2005) Incorporating green purchasing into the frame of ISO 14 000. J Cleaner Prod 13:927–933 15. Ministry of Ecology and Water of Bulgaria (2003) Regulation for national schema for ecolabel Ministry of Ecology and Water of Bulgaria, Bulgaria 16. Steer A (1996) Ten principales of the new environmentalism. Finance Dev Dec:4–7 17. National Strategy for environmental and Action Plan 2000–2006 under the Sub- project 1 of PHARE Twinning Project BG98/IB-EN-01/01 (2001) Bulgarian Ministry of Ecology and Water, Sofia 18. de Snoo G-R, Van de Ven GWJ (1999) Environmental themes on ecolabels. Landsc Urban Plann 46:179–184 19. Dimitrova V (2006) Perspectives for logistics management in the subsidiaries of transnational corporations (TNCs) in Bulgaria, Chapter 10, Supply chain management and information systems handbook: Supply chain management and Logistics in South East Europe. SEERC 156–175 20. European Commission- Sector Environment (2003) Regular report of EU-15, directive 97/138/ES i 2005/270/EC 21. Bird LA, Brown ES (2006) Utility-marketer partnerships: An effective strategy for marketing green power. Technical report NREL/TR 620-39730, Apr:1–40 22. Brewer AM, Button KJ, Hensher DA (2001) Green logistics (The Paradoxes of), Handbook of logistics and supply chain management. Pergamon/Elsevier, London, pp 1–11

The Distribution of Carcinogenic Heavy Metals in Cyprus Soil M. Ertan Akun, Rezan Fahrio˘glu Yamacı, Christophoros Charalambous, Savvas Lechtvich, and Mustafa B.A. Djamgoz

Abstract The number of cancer cases has been deliberately increasing both in Turkish and Greek Cypriot communities in Cyprus. The presence of various carcinogens in the environment is suspected to be the major cause of this increase. The main aim of this study was to identify the heavy metal contamination in Cyprus soil, mainly lead, cadmium and arsenic that are involved in cancer development. The collaborative investigations were accomplished by Cancer Research Fund (CRF) in North Cyprus (NC) and Frederick Institute of Technology in South Cyprus (SC). To achieve an analytical distribution, 260 composite soil samples (140 from NC and 120 from SC) were investigated for the presence of heavy metal contamination. The soil samples were obtained from Güzelyurt Bostancı, Yuvacık, Lefko¸sa, Karpaz, Alevkayası, Kırnı and Mesarya in NC and from Dhali, Sotira, Omodos, Acheilia, Polis and Evrychu in SC. The results showed that the amount of lead in the mentioned areas was within the range of 5.7–224.9 ppm in NC and 4.7–121.7 ppm in SC. The cadmium content ranged between 0.2–1.89 ppm in NC and 0.2–0.59 ppm in SC. Arsenic was measured to be between 0.2–18.5 ppm in NC and 2.8–22.5 in SC. Since the limit of lead contamination in soil is determined to be 400 ppm by EPA, all the analyzed areas in Cyprus can be said to be safe and fit for agriculture. However, compared to SC higher concentrations were found in NC that may be due to the use of leaded petrol. Arsenic is another carcinogen that is implicated in cancers of skin, bladder, liver, lung, and prostate and diseases of heart and brain. Because of its various disease causing effects, the widely adopted limit of arsenic contamination is determined to be 10 ppm. The results of soil investigation indicate presence of high arsenic concentrations in majority of the samples showing contamination in the entire island. Cadmium is well known to have a triggering effect on the development of breast cancer. Since the contaminating concentration for cadmium was determined to be 1 ppm (EPA), the analyses imply a threat for NC only. The current study presents the results of heavy metal analyses in Cyprus soil and M.E. Akun (B) Chairman, Department of Industrial Engineering, Cyprus International University, Haspolat, North Cyprus e-mail: [email protected]

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illustrates the areas with lead, cadmium and arsenic contaminations in the island. These data will enlighten the farmers for choosing the right place for agriculture. In addition to this, it will alert the related official authorities to take precautions for the removal of the contaminants and prohibit the use of agents that cause the respective contamination. In the long run, these will help increasing the health conditions of the both communities living in the island. Keywords Cancer · Lead · Cadmium · Arsenic · Soil · Cyprus

1 Introduction Heavy metal contamination of the environment has been a big deal since the time of civilization. Uncontrolled release of metals, specially in developing countries like Cyprus, causes pollution in soil, water and air. Since these metals are absorbed by plants and cannot be removed easily, they eventually enter the human body through food chain. Lead has been used since the beginning of civilization being widely spread to the environment. Areas of lead application are refining, brass/bronze foundries, rubber production and plastic industry, soldering, steel welding/cutting, battery manufacturing, pottery/ceramics industry, paints, insecticides, gasoline and lead cable, pipe manufacturing [1]. Exposure to lead is mainly through ingestion or inhalation. The combustion of leaded gasoline generated approximately 90% of all lead emissions in early 1980s. Therefore EPA banned the use of leaded gasoline in USA in 1996. Whereas in Cyprus and other developing countries, the continuous use of leaded gasoline poses a major public health. Lead used in paints causes soil contamination allowing its entry to human body through hand-to-mouth activity and inhalation [1]. It is a highly neurotoxic heavy metal [9] and when absorbed lead is retained in blood, soft tissue (liver, kidney, lung, brain, spleen, muscle and heart) and mineralizing tissues (bone and teeth). The negative effects of lead on children are higher than that of adults; specially very harmful for children, causing decrease in intelligence, impaired behavioral development and hearing defects [17]. It is harmful to developing nervous system of fetus and young children where high doses cause neurologic problems e.g. seizure, coma and death. Arsenic is estimated to comprise 1.5–5 × 10−4 percent of the earth’s crust. It is a component of sedimentary and igneous rocks, some coals, and peat as well as most sediments [19, 20, 15]. Arsenic is biologically toxic and is a threat to human health causing different types of cancers like bladder and lung [16, 3, 2]. It is extensively used as wood preservatives, in alloys, glass manufacturers, semiconductor material, feed additives, herbicides, insecticides, hematosis additives and veterinary chemicals [12]. Arsenic enters the environment through smelting of lead, copper and nickel ores and combustion of fossil fuels and excessive or improper use of pesticides containing arsenic [10]. Exposure to arsenic can be due to arsenic contamination in soil that would enter the human body through soil ingestion and the food chain [13].

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Cadmium, lead and arsenic are the major worldwide metal contamination. Cadmium is a naturally occurring metal, found in soil, rocks, and water. It is the second toxic element, in the Environmental Protection Agency (EPA)’s priority pollutant list [5] and accepted as Category I carcinogen by International Agency for Research in Cancer [8]. Studies have shown the correlation of cadmium exposure and cancers of breast, lung, prostate and testis [6, 3, 2, 18, 14, 8, 7, 11]. Cadmium is used to galvanize pipes causing pollution of water by corrosion of pipes or improper waste disposal. Also erosion of natural deposits, discharge from metal refineries, runoff from waste batteries and paints are the major sources of cadmium pollution. Since it is also used in fungicide and insecticides soil and plants are also contaminated. Human beings are exposed to cadmium by eating food grown in contaminated soil or fish from tainted water, but more extreme exposure comes from smoking or interaction with smelting, welding or shipbuilding. Smoking doubles the average daily intake of cadmium [4]. Organic agriculture that is highly important in the production of crops and vegetables free from contaminating toxic elements requires the identification of non-contaminated soil. This study aims to determine the regions safe for organic agriculture and regions that require removal of contaminants. In the future, these data will enable the decrease in the uptake of toxic metals by plants thus their concentration in the food chain of human beings. Therefore this can be related to a decrease in the uptake of carcinogens by the Cypriot community.

2 Methodology The methodology adopted was to collect samples at pre-defined locations of agricultural activities, especially related to vegetables and crops under investigation. The samples of soil were collected by using hand augers, so as to retrieve soil at a depth of 20–40 cm. This is in fact the depth at which the root hairs of the plants under investigation lies, which are capable of extracting contaminating elements from the soil within which they occur. Since the downward motion of water during rainy seasons can lead to the leaching of the elements in the soil which travel deeper, the sample collection was carried out twice; one during the dry season and the other during the rainy season. The concentration of heavy metals in soil was analyzed in Frederick Institute of Technology and confirmed in Imperial College using specific techniques.

3 Results of Field Studies Within the scope of an international project, Lead (Pb), Arsenic (As) and Cadmium (Cd), as the major sources of soil contamination were searched in Cyprus soils. Being absorbed by plants and entering human body via the food chain, the aim of the study was to designate their distribution in soils and recommend remedies as

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well as to determine safe areas for organic agriculture. In addition to this, the aim was to indicate the presence of carcinogenic metals in specific areas that can be related to increased cancer incidence in further studies. The tolerable limits of the mentioned heavy metals in the soils (approved by EPA) are given below in Table 1. The average concentrations of Pb, As and Cd in Northern Regions of Cyprus were found as given in Table 2, following the collection of soil samples at different areas. The same type of study was accomplished at the Southern Regions of Cyprus as well and similar results were obtained, as presented in Table 3 below. Table 1 Tolerable limits of Pb, As and Cd (EPA)

Table 2 Average concentrations of Pb, As and Cd in Northern Regions of Cyprus

Table 3 Average concentrations of Pb, As and Cd in Southern Regions of Cyprus

Heavy metal

Max limit (ppm)

Lead Arsenic Cadmium

400 10 1

Area

Pb (ppm)

As (ppm)

Cd (ppm)

Alevga Nicosia Kyr. – Krini M. Kyra M. Zodhia Messaoria Karpasia

32.58 44.29 40.51 32.42 8.02 12.6 17.19

11.25 11.87 14.63 8.98 9.47 11.09 13.56

0.34 0.69 0.47 0.34 0.2 0.33 0.3

Area

Pb

As

Cd

Dhali Sotira Omodos Achelia Evrycheu Polis

10.25 14.02 6.81 20.58 52.39 13.59

7.17 11.68 6.37 10.06 18.30 12.43

0.39 0.26 0.20 0.35 0.26 0.23

4 Discussion After collecting the soil specimens and analyzing them in accredited laboratories, the results were investigated in accordance with the EPA (Environmental Pollution Agency) standards. First, the general situation and distribution of lead in the entire island was evaluated. The distribution is given below in Fig. 1. According to Fig. 1, it is observed that maximum lead concentrations are around Everychu and Nicosia,

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Average Pb distribution in Cyprus Average Pb content, mg/kg

70 60 50 40 30 20 10 0 –10 Alevga

Nicosia

Kyrenia- Morphou Morphou Messaoria Karpasso Krini Kyra Zodhia

Dhali

Omodos

Sotira

Achelia

Everychu Polis

Area

Fig. 1 The distribution of Lead in Cyprus soil. The analyses of samples indicate highest levels of Pb in Everychu followed by Nicosia. Other areas are free from threat

and that the other areas seem to be free of threat. However higher Pb concentrations were determined in the North when compared South Cyprus. This may indicate the results of extensive leaded petrol use in the North Cyprus. Secondly, the general situation and distribution of arsenic in the entire island was evaluated. The distribution is given below in Fig. 2. According to Fig. 2, it is observed that arsenic is indeed a threat all over the island. This also implies the need for further investigations in more detail and necessitates the elaboration of a plan to neutralize the threat. Finally, the general situation and distribution of cadmium in the entire island was evaluated. The distribution is given below in Fig. 3. According to Fig. 3, the maximum amount of concentration is observed to be at Nicosia and is regarded that it might become a threat. The other areas seem to be free of threat. Average As distribution in Cyprus Average As content mn /kg

25

20

15

10

5

0 Alevga

Nicosia

Kyrenia- Morphou Morphou Messaoria Karpasso Krini Kyra Zodhia

Dhali

Omodos

Sotira

Achelia

Everychu

Polis

Area

Fig. 2 The distribution of Arsenic in Cyprus soil. Except for Morphu, Dhali and Omodos all the investigated areas are under a big thread of As contamination

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Average Cd content, mg /kg

0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 Alevga

Nicosia

Kyrenia- Morphou Morphou Messaoria Karpasso Krini Kyra Zodhia

Dhali

Omodos

Sotira

Achelia

Everychu

Polis

Area

Fig. 3 The distribution of Cadmium in Cyprus soil. The results show that Nicosia is under the risk of Cd contamination and the rest of island is free of this risk

5 Conclusion and Recommendations Following the field studies and the laboratory analysis, the degree of threat imposed by the concentrations of the heavy metals in question are evaluated in detail, with the EPA standards. According to this, the following recommendations are forwarded: • Lead seems to be a potential danger in only a few areas. To eliminate this danger, unleaded petrol usage must be rendered obligatory all over the island. In addition, ceramic industry, paints and insecticides should be monitored. • Cadmium threat requires preventive measures, especially in waste disposal methods, use of fungicides and insecticides, as well as in relation to pipes where Cd is used for galvanization. • Arsenic is a major threat all over the island. Although it is naturally present in nature in sedimentary and igneous rocks, it is also introduced into soils via herbicides and insecticides. Therefore use of As containing pesticides should be under strict control. • Contamination is a serious issue: for farmers, policy makers and PUBLIC, who need to be informed about environmental dangers they face. • Organic farming can help mitigate the input of heavy metals into the soil and must therefore be encouraged. • The intake of heavy metals to the human body through soil is well known to cause cancer. One of the reasons of increased cancer incidence in Cyprus may depend on the presence of these metals. Therefore a prevention strategy should be established and applied immediately. • Further investigations will be performed to prove the relation between heavy metal contamination in Cyprus soil and cancer.

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References 1. Agency for Toxic Substances and Disease Registry (1999) Toxicological profile for lead. US Department of Health and Human Services, Atlanta 2. Bates MN, Rey OA, Biggs ML (2004) Case–control study of bladder cancer and exposure to arsenic in Argentina. Am J Epidemiol 159:381–389 3. Chen Y, Ahsan H (2004) Cancer burden from arsenic in drinking water in Bangladesh. Am J Public Health 94:741–744 4. Cox LA Jr (2006) Quantifying potential health impacts of cadmium in cigarettes on smoker risk of lung cancer: A portfolio-of-mechanisms approach. Risk Anal 26(6):1581–1599 5. Davis, ML Cornwell, DA (1998). Introduction to Environmental Engineering: McGrawHill Series in Water Resources and Environmental Engineering. WCB/McGraw-Hill; Third Edition New York 6. Ferreccio C, Gonzalez PC, Milosavjlevic SV, Marshall GG, Sancha AM, Smith AH (2000) Lung cancer and arsenic concentrations in drinking water in Chile. Epidemiology 1:673–679 7. Gover, RA Liu, J Waalke, MP (2004) Cadmium and cancer of prostate and testis. Biometals.17(5):555–558 8. Goyer RA, Liu J, Waalkes MP (2004) Cadmium and cancer of prostate and testis. Biometals 17:555–558 9. Grandjean P, Landrigan PJ (2006) Developmental neurotoxicity of industrial chemicals. Lancet 16;368(9553):2167–2178 10. Hinck JE, Schmitt CJ, Echols KR, May TW, Orazio CE, Tillitt DE (2006) Environmental contaminants in fish and their associated risk to piscivorous wildlife in the Yukon River Basin, Alaska. Arch Environ Contam Toxicol Nov;51(4):661–672 11. Johnson MD, Kenney N, Stoica A, Hilakivi-Clarke L, Singh B, Chepko G, Clarke R, Sholler PF, Lirio AA, Foss C, Reiter R, Trock B, Paik S, Martin MB (2003) Cadmium mimics the in vivo effects of estrogen in the uterus and mammary gland. Nat Med 8:1081–1084 12. Kumaresan M, Riyazuddin P (2001) Overview of speciation chemistry of arsenic. Curr Sci 80(7):837–846 13. Mandal BK, Suzuki KT (2002) Arsenic round the world: A review. Talanta 58:201–235 14. Michaud DS, Wright ME, Cantor KP, Taylor PR, Virtamo J, Albanes D (2004) Arsenic concentrations in prediagnostic toenails and the risk of bladder cancer in a cohort of male smokers, Am J Epidemiol 160:835–859 15. National Research Council (1977) Medical and biologic effects of environmental pollutants: Arsenic. National Academy of Sciences, Washington 16. Office of Environmental Health Hazard Assessment (2004) Public health goal for arsenic in drinking water. California Environmental Protection Agency, California 17. Rajkumar WS, Manohar J, Doon R, Siung-Chang A, Chang-Yen I, Monteil M (2006) Blood lead levels in primary school children in Trinidad and Tobago. Sci Total Environ 361(1–3): 81–87 18. Steinmaus C, Yuan Y, Bates MN, Smith AH (2003) Case–control study of bladder cancer and drinking water arsenic in the western USA. Am J Epidemiol 158:1193–1201 19. Tamaki S, Frankenberger WT Jr (1992) Environmental biochemistry of arsenic. Rev Environ Contamin Toxicol 124:79–110 20. Waugh JLT (1982) Arsenic. In: Parker SP, Weil J, Richman B (eds), McGraw-Hill encyclopedia of science and technology, 5th edn, vol. 1. McGraw-Hill, New York, pp 715–718

Biotechnology: A Powerful Tool for Human Survival and Sustainability Anwar Nasim

Abstract The concept of sustainable development for a meaningful human survival is now well documented. Among a large number of different components that can help achieve this highly desirable goal is the pivotal role that “Science and Technology” will play in our future. Among different disciplines of science which in recent times have achieved revolutionary breakthrough “Biotechnology” clearly is one. The multiple applications of “Biotechnology” include “Environment” as one area that constitutes an aspect that merits special attention. The newly acquired techniques involving use of microorganisms, manipulation of genetic material and bioremediation are closely related to the sustainable development. The examples of developing countries with special focus on Pakistan will be given to list the future challenges and possible solutions for achieving the well defined goals of human survival and sustainability. An attempt will be made to discuss the importance of both physical and biological environment as these relate to future human survival. Keywords Biotechnology · Environment · Bioremediation · Sustainability · Survival For survival of human beings, easy and sustainable availability of basic human needs like food security, clean environment, proper health care, education facilities and economic prosperity are all crucial. Unless a society has these basic needs human survival will remain under continuing threat. We can come to this conclusion by comparing life expectancy in societies from the developed and underdeveloped world. The life expectancy of Norway a country that tops HDI rank list is 79 years compared to Niger that is at the bottom of HDI rank is 44 years. This is the result of non-availability of basic human needs mentioned above. For bridging the gap between these two extremes we have to strive for sustainable development through recognizing the role of science and technology for the development of societies [4, 5]. A. Nasim (B) COMSTECH Secretariat, 33-Constitution Avenue, G-5/2, Islamabad, Pakistan e-mail: [email protected]

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Role of science and technology for the socio-economic development is crucial. One can ascertain the role of science and technology for development by using the example of countries rich in natural resources but poor in science and technology which are in the list of developing countries. On the other hand one can find some developed countries with poor natural resources but they are strong in science and technology. Following table shows Human Development Index (HDI) rank.

HDI rank 9 11 14 16 18 20

Industrialized countries Belgium Japan Denmark France Italy Germany

HDI rank 40 41 44 58 75 77 99

Oil exporting countries Qatar UAE Kuwait Libya Venezuela Saudi Arabia Iran

Economic prosperity, development and more so sustainable development are complex issues which are the final end result of a whole set of interacting factors [10, 12, 13]. The concept of sustainable development was launched by the World Commission on environment and Development in the report “Our Common future” in 1987. The report says “Humanity has the ability to make development sustainable – to ensure that it meets the needs of the present without compromising the ability of future generations to meet their own needs”. This concept of sustainable development was reinforced by the UN Earth Summit in Rio de Janeiro in 1992. The concept of sustainable development is based on the conviction that it should be possible to increase the basic standard of living of the world’s growing population, without unnecessarily depleting our finite natural resources and further degrading the environment in which we live [1, 3]. The world of science has grown and changed beyond all expectations. This knowledge growth has brought new term “knowledge-based economy” which refers to the use of knowledge to produce economic benefits. Today, a revolution is taking place in the biological sciences. It is fueled by the groundbreaking work in modern molecular genetics, the enormous advances in bioinformatics and computing, and the enormous sums being invested in biotechnology research. It is truly an exhilarating time for the biological sciences; similar to what physics experienced in the glorious 40 years between 1905 and 1945, when all the concepts were changed, from cosmology to quantum physics, from relativity to the structure of atoms. We are decoding the very blueprints of life; we are learning to manage the deployment

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and expression of genes. So we live in a time unmatched for the opportunities that science provides. We can dream of new scientific breakthroughs and new products that can help humanity as never before: New higher yielding plants that are more environment friendly, new remedies for killer diseases, edible vaccines, single cell proteins to feed cattle and clean wastes, hyper-accumulating plants to take toxins out of the soil, expanding forests and habitats where more species thrive, and so much more. We can dream of a future of sustainable development where humans thrive in harmony with each other and with the environment. These opportunities are a necessary focus of interest among all of us who believe that the full potential of science has yet to be realized in our continuing efforts to fight poverty, end hunger, and protect the environment [2]. For thousands of years, people have used biotechnology to produce foods such as cheese and bread with bacteria and yeast. The genetic manipulation of both animals and plants started in prehistoric time. Archaeological findings and suggestions from ancient writings support the view that there were rudimentary agricultural crops at least some 7,000–9,000 years ago, in the hills between Iran and north-western Iraq, from where they spread to the valleys between the Tigris and Euphrates. In fact, all the plants now grown had started from ancient wild relatives. Similarly, all the domesticated animals came from the genetic modification of their wild ancestors. A very large amount of plant science data reveals natural crossings between species and even spontaneous mutations. It is also known that new species arise from these natural hybridizations and mutations. One of the more recent example of revolutionary breakthroughs in science is the new biotechnology that includes recombinant DNA and Genetic Engineering. Since the discovery of DNA in 1953 the other most important advance in genetics has been the discovery of the restriction enzymes in 1972, which allowed DNA to be cut at specific sites and then put back together. Next came the discovery of polymerase chain reaction (PCR), which allowed fragments of DNA to multiply. The identification for specific DNA genes for desirable traits, and the transfer of those genes into another organism constitute genetic engineering. The gene transfer involves the use of a vector carrier, which can be a plasmid or a virus. The full potential of genetic engineering is still unknown and the results so far achieved are only the beginning. Such breeding methods largely accounted for the phenomenal gains in productivity during the 20th century. Karl Ereky coined the term biotechnology in 1919. One of the several proposed definitions of Biotechnology is the application of science and engineering to the direct or indirect use of living organisms, or parts or products of living organisms, in their natural or modified forms. It can offer enormous benefits to mankind, from an improved environment to better crop yields and from better health to more effective healthcare. The development and dependence on Biotechnology has largely increased in countries all over the world in the last few years. The human genome project, production of antibiotics and improvement of crops by agricultural biotechnology are some of the major breakthroughs provided by this technology.

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Emerging biotechnologies, based on new scientific discoveries, offer novel approaches for striking a balance between developmental needs and environmental conservation [6, 7, 9]. A wider diffusion of the technology is thus seen as the key to directing its positive impacts onto the world’s society as a whole. Biotechnology is continuously and rapidly developing in an increasing number of sectors that improve the effectiveness for the way in which products and services are provided. In 1953, James Watson and Francis Crick revealed three dimensional double helical structure of DNA which ushered biotechnology into a new era. New techniques for manipulation of DNA were developed that enable human beings to make desired changes in the DNA. This new invention changed the phenomenon altogether. High yield of crops became possible, transgenic crops were designed. This technology not only brought revolution in agriculture but also brought remarkable changes in Industry, Environment and Health as well.

The latest biotechnology revolution began in the 1970s with the arrival of Applied Genetics and Recombinant DNA technology. This genetic engineering had a profound impact on almost all areas of traditional biotechnology and further led to breakthroughs. During these last three decades a large number of powerful techniques to manipulate DNA the magic molecule that governs the development of living organisms have been developed (Fig. 1). The major strength of biotechnology is its multidisciplinary nature and the extremely broad range of scientific approaches and economic applications that it encompasses. This is graphically represented below Fig. 2: The same is true for the very large number of products that biotechnology can provide shown below Fig. 3: The above figures showing multidisciplinary approach of biotechnology and its products clearly indicate that how biotechnology can be beneficial for human survival. Proper applications of biotechnology in agriculture help us to grow as much food as we need with improved nutritional value. Biotechnology plays crucial role

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to achieve clean environment, decrease water [8] and air pollution, diagnose disease, produce vaccines and medicine and develop biodegradable plastics. Following graph shows biotech market capitalization.

Biotechnology has become a pivotal tool for sustainable development in such diverse areas as Agriculture, Environment, Industry and Human Health. Biotechnology, the application of an explosion of biological knowledge, gives humankind the ability to alter the structure of life itself. Whether biotechnology

AT

Restriction Enzymes (cutting) Gene Amplification (PCR)

Ligation (joining) cDNA Libraries

TA CT

Cloning

GC

Hybridisation using probes

Sequencing Gene Synthesis

AT TA

Mutations

CT

GC

Fig. 1 DNA manipulations

Site Directed Mutagenesis

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Molecular Biology

Cell Biology

Biochemistry

Genetics

China Egypt Conventional Biotechnology Modern Genetic Engineering

Fermentation Technology

Chemical Engineering

Microbiology

Pharmacogenetics

Fig. 2 Multidisciplinary nature of biotechnology

Transgenic Animals

Diagnostics

Vaccines

Insulin, Interferon Parmaceuticals

Biotechnology Products

Transgenic Crops

Growth Hormones

Fig. 3 Biotechnology products

proves to be a miracle or a menace depends on how it is used and controlled. Biotechnology has made it possible to achieve the following: 1. 2. 3. 4. 5. 6. 7. 8.

Produce new and safer vaccines Treat genetic diseases Provide new and better medicines Increase crop-yields and decrease production-costs Improve food nutritional value Increase livestock productivity Develop biodegradable plastics Decrease water and air pollution

Commercial biotechnology consists of an expanding range of interrelated techniques, procedures and processes for practical applications in the health care, agriculture, industrial and environment sectors. Commercialization of biotechnology ranges from research to products and services. These are powerful technologies, supported by complementary bioprocess-engineering, to help translate new discoveries of life-sciences into practical products and services. As such, biotechnology should also be seen as an integration of the new techniques emerging from modern

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biotechnology with the well-established approaches of traditional biotechnology, such as plant breeding, food fermentation and compositing. Biotechnology-derived applications must be economically feasible and socially responsible in addition to being environmentally friendly – they must present a cost advantage, monetary or otherwise, before they may be accepted by industry. Even though biotechnology-derived applications may reduce manufacturing costs and improve profitability, there are many companies that rely instead upon traditional production methods, be it because they are unaware of biotechnology’s industrial applications, or because they remain cautious of biotechnology use in industry. Biotechnology-derived applications are generally more environmentally friendly than existing industrial methods. They can also reduce production costs, promote production efficiency, and improve product quality. In industry, biotechnology derived applications accomplish thee goals through the following methods: • Replacing non-renewable resources with renewable ones; • Replacing harsh chemicals with biological organisms; and • Developing more efficient and effective technologies. The rate at which information is being generated has indeed no parallel in earlier human history. The ease with which one can access available information is just as impressive. It has been estimated that, whereas the total knowledge-pool will double in 6–7 years, for life sciences such doubling time is estimated to be nearly 3 years. This new scenario provides an extremely rich and almost unmanageable store of data, but also poses the serious challenge for an effective and meaningful approach towards a focused discussion. Thus for scientists, academicians and policy makers there is a dire need to realise that computers and other highly sophisticated devices have dramatically changed our ability to acquire, store and retrieve information. So how do we cope with this knowledge explosion? Internet, ISP’s enable us to download enormous amount of data in no time – that fact alone poses a serious challenge of how to manage, coordinate, analyse, draw conclusions, develop guidelines and then formulate effective strategies to cope with future challenges [1]. To formulate an effective strategy to get benefit from latest technologies like biotechnology one can easily get examples from other countries that already have formulated effective strategies. What is needed to be done is to reformulate it according to the country specific needs. Here I would like to give an example of Canadian biotech development strategy. Although wide-spread interest in biotechnology issues is a recent phenomenon, the Government of Canada first identified biotechnology as an important economic sector and a key enabling technology to support economic growth and international competitiveness in the 1970s. The Government of Canada adopted the first National Biotechnology Strategy in 1983. It refocused its policies in 1993, with a revised Federal Regulatory Framework for Biotechnology. Now the Government’s approach has been redefined once more to address a much broader range of emerging issues in a new Canadian

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Biotechnology Strategy (CBS). Following policy documents have been prepared for the Government of Canada. 1. The 1998 Canadian Biotechnology Strategy: An ongoing Renewal Process 2. Canadian biotechnology Strategy overall performance report 1999–2002 3. Canadian Biotechnology Advisory Committee: many perspectives, one source. Annual Report 2005. 4. BioPromise? Biotechnology, Sustainable Development and Canada’s Future economy. Technical Report to CBAC, 2006. 5. Toward a Canadian Action Agenda for biotechnology: A report from the Canadian Biotechnology Advisory Committee, 2006. Above listed documents are available online on the following website: www. cbac-cccb.ca Like many countries that began investing in biotechnology research in the 1980s, Canada can now build on its strengths. But worldwide investment in biotechnology is growing rapidly and the pace of development is accelerating. The faster pace of change has also brought many ethical, social and environmental issues to the forefront. Canadians want to realise the potential benefits from biotechnology, especially in the areas of personal health, quality of life, and the promotion of a sustainable environment. The Government of Canada wants to ensure that this new strategy reflects Canadian values and Canadian standards. In addition to the promise of advances in the areas of health care and the environment, biotechnology offers economic opportunities. The Canadian biotechnology industry today generates almost $2 billion a year in revenues, including $750 million in exports. With over 500 firms, most of which are small companies, Canada has generated more biotechnology companies per capita than any other country. Every region of Canada shares in the growth of the biotechnology industry, which employs 25,000 people, typically in high-quality jobs. About 60% of Canadian firms are in the area of healthcare with most of the remaining activity in agriculture. Canada ranks third in the world after the United States and the United Kingdom in a $20 billion industry that is expected to grow to $50 billion by 2005. The Government of Canada has consistently made biotechnology a priority, in the Science and Technology Strategy, the Jobs and Growth Strategy, and, most recently, in the 1997 Speech from the Throne [17]. India, China, Cuba and Brazil have also made progress in the field of biotechnology [11]. This rich pool of available information provides a unique opportunity for the developing countries to benefit from the data, analysis, reports and strategies that have been developed in other nations. There is no denying the fact that all such policies and strategies have to be “country specific”. So the approach is to carefully define the specific national priorities and then see which of the proposed strategies can be applied to the specific needs of any given country [14, 15, 16]. For purpose of comparison one can use the example of Pakistan from the developing world. We in Pakistan have tried to come up with national action plan in biotechnology. In view of my close personal involvement in the development of biotechnology in Pakistan I would attempt to outline this scenario.

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The importance of vast potential of biotechnology was formally recognized in 1981 when first course on recombinant DNA technology was organized by Nuclear Institute for Agriculture and Biology (NIAB), Faisalabad, one of three agriculture centres of Pakistan Atomic Energy Commission. The first course was organized by Dr. Sheikh Riazuddin and was conducted by Late Dr. I.A. Bukhari of Cold Spring Harbor, New York, USA and Dr. Anwar Nasim Adviser Science COMSTECH (then at NRC, Ottawa, Canada). The workshop among other recommendations specifically asked Govt. of Pakistan to develop an exclusive national centre of Biotechnology and Genetic Engineering [18]. Thus ministry of education approved Centre of Excellence in Molecular Biology (CEMB) to be built in the campus of Punjab University. Taking start with specialized restriction enzymes, CEMB expanded gradually into Agriculture Biotechnology which at present is the main interest area of this elite centre. Consultation, planning and paper work on National Institute for Biotechnology and Genetic Engineering (NIBGE) was started in 1983. The institute was established under the provisions of the 1984 Science policy was approved in 1986. The project aims to develop/adopt/apply innovative and modern research in agriculture, industry, health and environment. It is a federal research institute which is being run under the auspicious of Pakistan Atomic Energy Commission. The centre was formally inaugurated by the President of Pakistan in 1994 [19]. National Commission on biotechnology (NCB) was established in 2001 with the purpose of promotion of biotechnology research in Pakistan and preparation of biotechnology action plan. The commission comprises of 15 eminent scientists in the field of biotechnology. NCB is an advisory body to the ministry of science and technology to monitor new developments in the field of biotechnology at National and International levels, and to recommend appropriate measures for sustainable economic growth of the country. For further information on NCB activities one can visit following NCB website http://www.ncb.gov.pk In conclusion it is important to emphasize that for an optimal utilization of biotechnology as a tool for human survival and sustainability the developing countries need to carefully and critically examine the strategies used by the developed nations. With this background in view one needs to develop country specific action plans for any given nation. To illustrate this approach the examples of Canada and Pakistan have been discussed in the present manuscript. There is certainly no denying the fact that among the new and emerging technologies of the modern times biotechnology is a leading technology. It is here to stay and should be given the highest priority by policy makers trying to plan the future economic development.

References 1. Nasim A (2001) Biotechnology for sustainable development. Sci Vis Q 7(1–2), JulyDecember 2001. Commission on Science and Technology for Sustainable Development in the South (COMSATS), Islamabad, Pakistan

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2. Serageldin I (1999) The challenge of poverty in the 21st century: the role of science, agricultural biotechnology and the poor. In: Persley GJ, Lantin MM (eds) An international conference on biotechnology, convened by consultative group on international agricultural research and US national academy of sciences, pp 25–31 3. Our Common Future (1987) The world commission on environment and development. Palais Wislon, 52 rue des Paquis 1201, Geneva, Switzerland 4. An Assault on Poverty: Basic Human Needs, Science, and Technology (1997) Jointly published by: International Development Research Centre, Ottawa, Canada & United Nations conference on trade and development, Palais des Nations, Geneva, Switzerland 5. Meadows DH, Meadows DL, Randers J, Behrens WW III (1972) The limits to growth: a report for the club of Rome’s project on the predicament of mankind. Universe Books, New York 6. Khan HA (2005) Scientific and technological research for development. Islamic Educational, Scientific and Cultural Organization (ISESCO). Rabat, Morocco 7. Khan HA (2004) Education, science and technology in developing countries: some thoughts and recollections. Commission on Science and Technology for Sustainable Development in the South (COMSATS). Islamabad, Pakistan 8. Ahmad I (2002) Water and new technologies. Global Change Impact Studies Centre, Islamabad, Pakistan 9. Khan HA, Qurashi MM, Hussain T, Hayee I (2005) Renewable-energy technologies and sustainable development. Commission on Science and Technology for Sustainable Development in the South (COMSATS). Islamabad, Pakistan 10. Gordon Conway (1997) The doubly green revolution: food for all in the 21st century. Penguin Books, New York 11. Tzotzos GT, Skryabin KG (2000) Biotechnology in the developing world and countries in economic transition. CABI Publishing, Wallingford, UK 12. Agricultural biotechnology, poverty reduction and food security. A working paper (2001) Asian Development Bank 13. Atlas of the Sustainability of Food Security (2004) M.S. Swaminathan Research Foundation, Centre for Research on Sustainable Agricultural and Rural Development 14. Majali AS, Ergin M, Zou’bi MR (2001) Biotechnology and genetic engineering for development in the Islamic world. Islamic Academy of Sciences, Amman, Jordan 15. Strategies for the development and application of biotechnology for economic growth. Expert Group Meeting Proceedings. Pakistan Council for Science and Technology. Islamabad, Pakistan 16. Malik KA, (2004) Strategy for development of biotechnology in the Islamic countries. COMSTECH, Islamabad, Pakistan 17. www.biostrategy.gc.ca 18. Masood A (The Muslim 7th March 1981). Sponsoring of Genetic Engg. Institute offered. Islamabad, Pakistan 19. Anees MA (1985). Cloning Better Futures. Inquiry, 2(5): 48–51

Ecotourism – Environment Relationship in Contemporary Eastern Europe Countries. Its Facts, Myths and Challenges. The Case of Albania and Macedonia Liljana Elmazi and Jovan Stojanoski

Abstract The purpose of this paper is to critically evaluate the perceptions and intended applications of ecotourism in Eastern Europe. This is placed within the context of past tourism patterns under state socialism, current issues of the transition and restructuring and likely future trends in the region for the tourism generally and environmentally sensitive tourism development in particular. The political and economic changes which have characterized Eastern Europe in generally and Albania and Macedonia in particularly, since 1989 have exerted a number of influences on patterns of international tourism to, within and from the region. Sustainable forms of tourism are a relatively new concept for these countries, although past practices did see the restriction of tourists’ mobility, albeit not necessarily for environmental reasons. These countries are vulnerable to tourism fashion changes, which are themselves sensitive to the instability and myriad problems besetting the region. In spite of this, the region’s cultural and environmental diversity provides the potential for substantial market segmentation. Targeting niche markets- ideally high spending groups with minimal adverse impacts and season- extending activities – should emphasise the significance of “green” forms of tourism. The region’s substantial heritage potential and natural protected areas can be used to considerable educational as well as economic advantage to the region. Keywords Ecotourism · Environment · Sustainability

1 Introduction Environmentally sensitive tourism must involve the local population in decisionmaking as well as participation in accommodation provision, conservation and education. In these countries domestic recreational demands are likely to increase considerably in the longer term with rising consumerism, and environmental impact

L. Elmazi (B) Faculty of Economics and Business, University of Tirana, Tirana, Albania e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_35,

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of this grossly underenumerated activity may be substantial. Local cross- border movement between neighbouring countries for petty trading purposes has grown to considerable proportions in recent years, swelling international arrivals figures and complicating analyses of the scale of international tourism in the region [2].

2 Ecotourism as a Tool for Sustainable Development Although the first mention of the word ecotourism is set around the late 70s and the early 80s, its main components are rooted in history. Some components of ecotourism (as seen below) can be found in many previous forms and philosophies of tourism [4]. Components of Ecotourism • • • • • • •

Contributes to conservation of biodiversity Sustains the well being of local people Includes an interpretation/learning experience Involves responsible action on the part of tourists Is delivered to small groups by small-scale businesses Requires lowest possible consumption of non-renewable resources Stresses local ownership and business opportunities, particularly for rural people

Ecotourism, is to be taken within the broader framework of sustainable development of tourism overall, with four main motivations: • Sustainable use of biodiversity and natural resources • Impact minimization, especially in terms of climate change and energy consumption • Empowerment and fully informed participation of local stakeholders, particularly local communities and indigenous peoples • Awareness raising and environmental education of travelers and hosts Ecotourism may be said to have three aspects: • a concept. Based on a set of so-called aspirational principles, it sets out an ideal to be targeted at. As such, it’s very useful as a goal to be targeted. • a market segment. Linked to nature and adventure tourism, it’s a relatively small niche market, mostly for small-and medium-sized companies and for small groups of discriminating tourists. As such, it can be studied and analyzed, although little statistical investigation has been made. In spite of the high goals set up its aspirational aspect, colourist cannot help being part of a global economic and political system which has very often led to income and capacity gaps and divides, and many actual colourist products do not fulfill the principles set up above.

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• a practical laboratory for pioneering ideas and practices potentially applicable in mainstream tourism. In the 80’s, some ecolodges in Costa Rica and in Africa started setting aside private reserves for their guests’ enjoyment. Today, the 200room Punta Cana Beach and Golf resort in the Dominican Republic has a 150 hectare rainforest reserve, managed by an Ecological Foundation. Based on ecotourism experiences, cruise tourists are being sold ecotours in Saint Lucia, theme parks in the US attempt to replicate nature experiences, and zoos make visitors feel they are part of the animal’s environment. • Canopy walkways, used first for scientific purpose, are now widely used as ecotourism attractions, and receive hundreds of thousands of visitors yearly all over the world. Over the years, as the concept has been applied under very different circumstances, some regional differences can be perceived. Several stereotypical “schools of thought”, based on different cultural and historical circumstances, could be proposed in a global overview: • From North America, backed by a philosophy of admiration for nature as ultimate perfection (Thoreau and others), comes the idea of visitation to parks totally undisturbed by human settlements. In some cases, the notion of nature as a standalone balance that should be protected from any human interference has led to systems that propose to relocate residents. As a haven against the kind of uncontrolled development reigning in most other places, parks are seen as carefully managed areas where limited exposure to nature can be offered to the educated public under more or less strict management rules-in fact, management systems found in the US and Canada are well tested, and have been used as references for many other national systems. Also, in the US, given the unparalleled advance of the paradigm of the State more as a regulator than an agent, many effective models of public/private partnerships to manage protected areas-concessions, land leases, opportunities for entrepreneurs-can be found. The concept of nature interpretation (Tilden), where the most essential environmental messages are communicated emotionally as well as through information, by a variety of means including, as far as possible, an interactive participation of the visitor, has been developed mostly in the US, and some of the most advance technology as well leading experts are there. • In Europe, the natural landscape has been managed with human interference for ages, and ecotourism relates closely to rural tourism. Natural settings always have had local culture and inhabitants as components of the landscape. As the models of agricultural production change over time, and the subsidies set up to help European agriculture remain competitive prove to be very expensive, the need for supplementary income sources has paved the way for opening remote homes and farms to urban visitation, with positive results especially in economically depressed areas. Also, the experience of associating the image and the actual experience of a place to the products originating from it (the notion of the French “terroir”, or the ecolabels for water, handicraft, wine and food from certain natural areas) has helped to add value and shorten distribution channels. This has been very successful by promoting local Small and Medium Enterprises, the core of any sustainable tourism policy. Successes with Bed & Breakfast reservation

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systems, or with the Gites de France mechanism, can be immediately related to ecotourism. With most of its areas inhabited by diverse social groups, Europe also had great experience in participative land use planning (regional parks), and multi-stakeholder management systems. In a recent research by UNEP, most of the municipal destinations using Local Agenda 21 systems for tourism were to be found here. The notion of “fair” and “pro-poor” tourism also is stronger with European outbound tourism actors than elsewhere, and indeed the first critiques about the negative social and environmental impacts of tourism have originated here in the 70s. The continent also benefits from having the largest proportion of potential outbound travelers close to rural/natural areas, therefore increasing so-called ecotourism FITs (frequent independent travelers) and allowing value-added distribution chains. Ecotourism is therefore an extremely useful and important concept in the European context. • In Southeast Asia, Africa and Latin America, apart from the obvious attractiveness of destinations, the many problems associated with unequal development and control of capital development become very significant. In regions where pronounced poverty coexists with quick and strong development, issue such as indigenous land rights, informed participation of local communities in ecotourism ventures, and the serious risks of “green-washing” ecotourism come up strongly. • Many grass roots NGOs particularly in Southeast Asia associate ecotourism to alienation of the rights to the use of land and natural resources in benefit of major economic and political groups. This also happens as indigenous and local communities in some destinations are poorly empowered, and often don’t participate in policy decision-making. Centrally planned, low-participation ecotourism projects can become examples of unsustainable development and may stir serious social and environmental problems. In many places, indigenous communities have only recently been accepted as an integral part of any ecosystem, and conflicts are still common. On the other hand, ecotourism in developing countries has also been relatively successful in ensuring political and financial support to the conservation of certain “charismatic” and accessible ecosystems and fauna, by offering steward communities and protected area managers an alternative (or sometimes exclusive) economic mechanism. In some cases, ecotourism projects have improved the community’s sense of self-respect and the value of traditional cultural practices-in Cape Coast, Ghana, a traditional dance has been revitalized by a community due to the interest and financial support of visitors.

3 Facts, Myths and Challenges of Ecotourism 3.1 Facts • To developing countries, one of the most important drivers for ecotourism is the generation of less-destructive and consumptive livelihood and employment for local residents, and financial means for the management of protected areas.

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Resource-poor governmental park management agencies find in ecotourism a much-needed source of income, either through direct management or via concessions to third parties, to the extent that in some cases they become tour operators or auction off parks to NGOs. Overall, though, under the right circumstances, ecotourism has proven to be one of the most effective means to finance conservation (the Kenyan “it stays because it pays”, the Rwandan Mountain gorillas, land concessions to operators in Zimbabwe and Botswana, Costa Rica’s park system, the Philippines’ Olango Bay project). In most rich biodiversity areas, actual revenue flows for ecotourism are better than non-timber forest products and bio pharmacy, and comparable only to agro forestry. Also, in some cases, ecotourism can provide much needed business and income opportunities for steward communities, and the negative effects of its implementation very often compare favorably to other alternatives. The creation and maintenance of hundreds of public, community-managed and private parks in developing countries can ultimately be linked to visitation revenues. • Some countries (among them Costa Rica, Australia, Brazil, the Philippines, Dominica and Canada) are using their biological and cultural diversity as an important tourism asset, and ecotourism policy is a growth field. A recent report from the Organization of American States found that most of its member governments have only very basic ecotourism policies if at all, developed with relatively little consultation and with low levels of implementation. Similarly, many multilateral and bilateral development agencies have incorporated ecotourism as a tool, mostly within conservation and development investment pipelines, but a coherent system of exchanging lessons learned is still largely lacking. Weak or inconsistent policies can lead to inadequate application of the principles of ecotourism. • In many cases, the concept of ecotourism can be misused by developers (public, nongovernmental or private) to advance particular agendas without full consideration of its principles, in what is called “green-washing”. • Examples can include unregulated development of relatively undisturbed areas, subsidized loans or infrastructure development, appropriation of ancestral land domains, or just applying traditional tourism development models under the name of ecotourism (such as an 200-room ecolodge in the Brazilian Amazon with no sewage treatment, no involvement of traditional communities, and no effort at lowering any social or environmental impacts).

3.2 Myths • Ecotourism is not particularly profitable, and this might nor change soon. In a recent research, the International Ecotourism Society has found that only a third of the 350 ecolodges surveyed are making any return on investments-a proportion very similar to most SMEs globally. It certainly does not compete with other tourism markets, such as the Meetings, Incentives, Congresses and Exhibitions, the theme parks and the cruise ship segments, also not hampered by high the expectations of ecotourism.

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• For these and other reasons, major global corporations are NOT yet interested in significant investments in ecotourism. The more professional ecotourism developers, involving some medium-sized chains and ethically committed investment groups, are still finding ways to cope with investment guarantees, widely differing management standards and the absence of consistent statistics and sufficient professional capacity in the area. • There is no immediate risk of a global stampede of ecotourists worldwide. Ninety percent of UNESCO’s 250 natural World Heritage sites are used well below their carrying capacity. The overwhelming majority of tourists are ambiguous about their commitment to conservation (like the idea, but are not willing to pay more for it) and their attitude towards any risk or discomfort on their vacation (like the perception of “roughing it” and risk in nature, but shy away from any real lack of comfort or uncertainties-the most frequent complaint of ecotourists in lodges in the Peruvian steaming hot Amazon is the absence of hot water!). Projections of a yearly increase of 20% on a market supposed to mean 3–5% of the overall tourism trade have not yet materialized (a good thing as it would mean 25% of global tourism in 2,011 or 165 million international ecotourists), and probably won’t. Of course, there is some risk in certain fragile destinations-tourism tends to focus on the tried and tested models, such as the Hollywood movie industry [1].

3.3 Challenges Most of the issues listed below, as well as the management systems that should be set up to advance them, could be addressed by a sound request from various stakeholders: the creation of an International Commission on Ecotourism, with representatives from various interest groups, broadly based on the model of the World Commission on Large Dams. For UNEP, the Year and the various events being organized could be the process to bring such a commission into existence. • Financing the transference of the technology gained by North America and Europe in ecotourism (mobility, incubating SMEs, private/public partnerships such as concessions, protected area visitor management, multistakeholder planning, marketing) to developing destinations. • Mainstreaming community-based ecotourism through efficient marketing and reservation systems, and increasing customer acceptance of products with basic quality standards. Beneficial effects are still too small to make a difference! • Coordinate various donor investments in ecotourism, and produce guidelines for projects to avoid common problems (business feasibility, marketing research, entrepreneurial capacity, and private sector matching funds). Although a number of donors have incorporated ecotourism components in their project portfolios, little inter-institutional exchange is promoted.

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• Creating and implementing common quality and operational standards, leading to certification and accreditation (avoid green-washing!). • Disseminating best practices in community land-use rights, and planning/development control mechanisms for steward (including indigenous) communities. Some good examples can be found in Africa (land concessions in Namibia and Botswana), Europe (with Pan Parks and the Europarc Foundation) • Improve local revenue retention through capacity building and value-added supply chain management. • Convince pioneers to become professional. Specifically for Europe, the International Year of Ecotourism could be used to propose an action plan to include [5]: • Generation of European standards for ecotourism products, leading to certification and even accreditation-in order to ultimate increase potential market shares. • An increased independence of initially subsidized projects, such as rural tourism lodging and reservation systems-ironically, this might be more difficult in developed countries, where the State is well structure and can offer some welfare support, and motivation for entrepreneurship may be lower. • Increased dissemination of successful components of existent projects, to support the transfer of technology, especially to Central and Eastern Europe.

4 Past Tourism Patterns in Eastern Europe 4.1 Tourism Resources The region’s tourism resources may conveniently be divided into five categories: 1. Sand, surf and sun- from Poland’s short- season Baltic coast to Albania’s still largely unspoilt Ionian littoral. Marine pollution problems, arising both from the pressure of tourism itself and from other sources, are increasingly posing environmental challenges. 2. Heritage – the long and complicated history of the region is selectively represented in museums, exhibitions, statues, architecture, domestic artifacts, artisan crafts, music, song, dance and costume. 3. Spas- mineral springs and curative treatments have served a wealthy, often foreign clientele, since classical times. 4. Winter sports – these now attract large numbers of Western tourists and major land use conflicts have arisen.

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5 Problems of Ecotourism Development in Contemporary Eastern Europe 5.1 Adoption of “Ecotourism” The often poor environmental image of the region, coupled with the existing and potential environmental impacts of tourism activities, have seen a post- communist reappraisal of tourism and conservation strategies in the region. Recognition is now being extended to the need for “sustainable”, “green” and “eco” tourism, as, for example, stated in the Romanian , Macedonian and Albanian national tourism programmes and in the objectives of a number of environmental NGOs attempting to influence policy both in the region’s governments and in the major Western funding agencies. Indeed, at a general level, as “ecotourism” implicitly requires management, control and proscription, there will be inevitable reaction within the region, particularly from the newly privatized sectors against any policies echoing aspects of the old communist regimes’ practices [3].

5.2 Local Participation The encouragement of active participation by the local population in the conservation and education dimensions of the tourism development process is an essential element of ecotourism. In Eastern Europe, however, attempts to involve local communities have been inhibited both by the lack of experience of bottomup development from which citizens can draw, and the often dismissive or ate best patronizing attitude taken by some officials towards local populations, particularly in rural and more remote areas. Local citizen participation is often seen as a threat to power structure of both local and central bureaucracies and to the very valuable perks which accompany the membership of such structures.

5.3 Support Requirements Inventories of natural and human resources, entailing data collection and collation, processing, analyzing and representation are still required in much of the region. Particularly, in the Balkans, shortages of often basic equipment and access to literature are commonplace and constrain implementation. Linking mechanisms to ensure essential cooperation and rationalization of effort, resources, skills and experience are often lacking [7]. Appropriate legal and administrative frameworks may still need to be established in some countries to clarify land and property rights, control transport and accommodation and establish insurance guarantees and tax regimes. These should also include codes of tourist conduct in protected areas updated to meet new conditions.

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5.4 Information/Education Requirements Clear statements of the nature and aims of ecotourism need to be incorporated into literature and publicity material to educate and encourage active participation by interested parties (local populations, tourism organizations, local and national state bodies and individuals), as well as for potential tourists themselves. Education and information programmes on environmental protection amongst the local population must be effective, especially through the medium of schools, and put into practice, recruiting locals as wardens and deploying them on financially beneficial training courses to strengthen tourist control mechanisms [6]. The interest, support and participation of the local community is vital, especially where ecotourism strategies are perceived as threatening its economic interests. Bottom – up information flows may not be easy to stimulate in the short term given the nature of past decision- making practices in the region. Similarly, it will be difficult to successfully undertake social surveys, given the understandable suspicion and hostility with which previous official prying into domestic affairs was viewed.

5.5 Strategy Formulation There appear to be six types of action study required for an ecotourism strategy plan: 1. A strategy for assessing tourism demand and targeting specialist market/niche groups; 2. An interim plan for matching different tourism activities/types of tourists, their likely environmental impacts and economic benefits; 3. The establishment of a working formula for assessing tourism carrying capacities; 4. An interim plan for a system of prescribed routeways and transport forms appropriate for different ecological conditions within and adjacent to the designated area 5. An interim plan for prescribed infrastructure and services, accommodation and activity areas, their access and seasonality; and 6. A longer term plan for the nature and location of information/education centres, coordinated with the local educational programs for “gateways” into, and at, “honeypots” on the periphery of protected areas. These would also act as “tax” collection points, permit issue centres and questionnaire survey points. Production of a final composite plan/strategy should insure its complementary and integration with local, regional and national environmental, tourism planning strategies in Albania and Macedonia.

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6 Conclusions Sustainable forms of tourism are a relatively new concept for Eastern Europe in generally, and for Albania and Macedonia especially, although past practices did see the restriction of “tourists” mobility, albeit not necessarily for environmental reasons. Albania and Macedonia as Eastern Europe countries are vulnerable to tourism fashion changes, which are themselves sensitive to the instability and myriad problems besetting the region. In spite of this, the region’s cultural and environmental diversity provides the potential for substantial market segmentation. Targeting niche markets – ideally high spending with minimal adverse impacts and season- extending activities – should emphasise the significance of “green” forms of tourism [7]. The region’s substantial heritage potential and natural protected areas in Albania and Macedonia can be used to considerable educational as well as economic advantage to the region. However, there are very real dangers of ecotourism being cynically taken up as a development objective simply because of: • The fashionability of the concept; • The propaganda value for Albanian and Macedonia governments and agencies of being seen to be “greening” development and particularly tourism development; and • Its role as a means of gaining access to development aid funds from the other West Europe countries. Also, it appears that too many projects are being developed based on Western European experience, despite the cultural and environmental circumstances and nature of consequent pressures being very particular to the region itself. Indeed, there may be better lessons to be learned from the experience of the developing world than from the developed. In short, there is more than a slight danger of eco- ethnocentrism being superimposed on the application of ecotourism in Eastern Europe countries, such that Albania and Macedonia [8]. For tourism development to be successful and acceptable, sensitivity of implementation and sustainability and local participation must be more than just cliches in our national or corporate plans. Most importantly, local populations must be involved and shown that conservation and tourism can complement each other to the economic advantage of the local community. Unless this is successfully achieved, longer term tourism development in Eastern Europe countries, also in Albania and Macedonia is likely to pose far more problems than it solves.

References 1. Albrecht C (1987) Environmental policies and politics in contemporary Slovakia. Stud Comp Communism 2(3–4):291–302 2. Allcock J (1999) Tourism and economic development in Eastern Europe and the Soviet Union. Belhaven Press, London, New York, pp 236–258

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3. Boo E (1998) Ecotourism: potentials and pitfalls, vol 2. World Wildlife Fund, Washington 4. Boo E (1992) The ecotourism boom, planning for development and management. World Wildlife Fund, Washington 5. Hall DR (1991) The ecotourism and economic development in eastern Europe. Belhaven Press, London, New York 6. Ostrowski S (1996) Ethnic tourism – focus on Poland. Tourism Manag 12:125–131 7. Pearce F (1998) The wild east, BBC Wildlife, April, 40–47 8. Spaho E (1998) Tourism: promising contracts. Albanian Econ Tribune 6(10):17–21

Earthquake is Manmade Catastrophe Rather than a Natural Disaster: Turkey Özgür Yilmazer, Özlem Yilmazer, Ali Özvan, Yasemin Leventeli, and Ilays Yilmazer

Abstract Soil grounds are several billion times more susceptible to earthquake disaster than rocky grounds. The probability of any soil to be liquefied is several billion times greater than that of even an extremely weak rock in case of fully saturated. Any rock, ranging from extremely weak to strong rock, is not susceptible to liquefaction even at submerged state. Shear strength of a saturated soil under dynamic condition approaches zero whereas the reduction in strength of the saturated rock is practically negligible. In another saying, the ratio of shear strengths [τ = c+σn tan φ] of saturated rock over soil goes to infinite. Similarly, the ratio of modulus of elasticily [E, kPa] of saturated rock over soil tends to go infinite too. Turkey is a country over which many micro plates are moving relative to each other. The North Anatolian (NAF), East Anatolian (EAF), and Ecemi¸s fault (EF) are the three major strike-slip faults that cause destructive earthquakes only in soil grounds. The fourth distinct one is the gravity fault (graben) system prevailing in the Aegean region, which is less destructive due to lower energy storage capacity. All of the active fault systems comprise fertile farm fields and extend their limits with time. Such soil grounds form lowlands rich in groundwater and mineral. However, such soil lands are exposed to earthquake catastrophe. Furthermore, the lowlands are not good human health. Most of the viruses and bacteria can grow up. That is the main reason why such lands have to be preserved for farming and should be closed to settlement. The strike slip faults are, in general, coincident with the former suture zones bearing numerous polished sub-vertical discontinuities. These planes have great potential to act as a strike slip fault plane. San Andreas Fault in USA, Kobe Fault in Japan, and Dead Sea Fault extending from Jordan to Turkey are the typical examples. The recurrences of earthquakes create fertile low lands with shallow groundwater table. Such medium favors liquefaction, plastic deformation, rupture, sand ridges and cones, and magnification of the amplitude. An earthquake becomes more destructive in the cases of shallower groundwater table (z < 20 m) and thicker

Ö. Yilmazer (B) Yilmazer Education, 8. Cd., 89. Sk., 9/8, 06460 A.Ovecler, Ankara-Turkey e-mail: [email protected]

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soil mantle (t > 20 m). Hence, one may conclude that rocky grounds are favorable for construction whereas soil grounds should be reserved for agricultural activities. Keywords Geotechnics · Rock-soil grounds · Earthquake · Catastrophe · Land-use

1 Introduction Saturated thick (t > 20 m) soil grounds are billion times more susceptible earthquake than saturated rocks. All earthquakes prove that only the structures in the fertile soil grounds suffer from earthquakes. The last major earthquakes that occurred on 17th of August and 12th of September 1999, 6.6.2000, 27.5.2001, 10.07.2001, and 3.02.2002 in Turkey have once more indicated that the deformation boundary coincides with the boundary of the fertile plains [11, 12]. This is due to the lower values of frequency, shear strength, and elastic modulus [1] in soil grounds. Furthermore, the thick (t > 20 m) soil mantle, and shallow (d < 20 m) groundwater table amplify the risk of earthquake. The buildings on rocky formations, although they are adjacent to the epicenter, preserved their original identities whereas noticeable destruction happened in Porsuk and Bolu plains which are more than 120 km far from the epicenter of Marmora Earthquakes hit in 1999. It is explicit that the fertile low lands are hazardous grounds in regards to earthquakes, floods, and healthy living environment. In spite of this fact, most of the international engineering projects, including motorway and industrial plants, are located in fertile lands accompanied with fault zones in Turkey since 1943 [13–16].

2 Earthquake Destruction Occurs Only in Soil Ground The Kobe earthquake (January 17, 1995) with a middle magnitude (M = 6.9) has caused 6,500 dead and lost of 150 billion dollars of infrastructures owned by government. This is purely due to that the city Kobe was settled and invaded large soil grounds of deltaic deposits (Fig. 1). On the other hand, the Tokachi-oki Earthquake (September 26, 2003) with a magnitude 8.0 did caused any live lost. The reason was that the nearest settlement area in/on fertile lowlands of soil is about 200 km far from the epicenter. However, the city Kobe was 65 km far from the epicenter of 1995 earthquake. Recent tectonic activities in Turkey have been controlled by northward movement of Arabian plate that pushes on Eastern Anatolia (Fig. 2). Consequently, the following geological and geotectonic features and related activities have occurred Eastern Anatolian Fault (EAF): It is a northward extension of Dead Sea fault. Ecemis fault (EF): It is a left-strike slip fault. It bears about 5% of the fertile lands of Turkey.

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Fig. 1 The 1995 Kobe catastrophe was due to being settled in fertile deltaic soils

Fig. 2 Tectonic outline of the Anatolia

North Anatolian Fault (NAF): It has formed in the suture zone of the NeoTethys Ocean closure. About 20% of the fertile lands of Turkey formed along the NAF. Western Anatolian graben fault system (WAF): It has formed due to barrier effect of Rhodes-Greek (Aegean) plate against the western movement of Anatolian plate. Thus, north-south extensional tectonic regime has been created over Western Anatolian Region. However fertile farm lands, high geothermal gradients, geothermal energy resources, and hot springs are pertinent to these fault zones. All are natural

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Ö. Yilmazer et al. Table 1 Recent destructive earthquakes in Turkey

Date

Depth, km

Magnitude

Num. of deaths

Witnessed Heavy Damage over Lowlands of: about . . . %

5.7.1983; 12. 30.10.1983; 4. 18.9.1984; 13. 5.5.1986; 3. 13..3.1992; 17. 1.10.1995; 15. 27.6.1998; 13. 17.8.1999; 00.

10 33 10 4 27 33 33 17

6.1 6.9 5.4 5.9 6.9 6.1 6.2 7.8

5 1,400 3 15 498 101 145 15,637

5.8 7.5 6.1 5.8 6.1

7 834 2 6 42

Biga, Erdek, and Istanbul: 98 Pasinler and Erzurum: 98 Erzurn, Pasinler and Kars: 98 Gölpasi – Dogansehir: 99 Erzincan: 98 Dinar – Evciler: 100 Ceyhan – Adana: 100 Kocaeli, Sakarya, Bolu, Eskisehir, Istanbul, Bursa, Zonguldak, Tekirdag: 99 Sakarya and Kocaeli: 100 Düzce, Sakarya, and Bolu: 100 Orta-Anakra-Cankiri: 100 Aksehir, Konya, and Afyon: 100 Cay, Eber. Sultandagi, Bolvadin, and Afyon: 100

13.9.1999; 11. 12.11.1999; 16. 6.6.2000; 2. 15.12.2000; 16. 03.02.2002; 09.

13 10 10 10 5

resources. The earthquake inventory in hand indicates that any considerable disaster happened 10 engineering structures on rocky grounds. On The other hand, most of the structures built in the fertile lowland where no rocky formation is reached at their foundation, were severely damaged or completely collapsed (Table 1).

Table 2 Superiority of rocks to the saturated thick soil mantle Approximate Values Rock

Soil

Superiority of rocky grounds Remarks

Elastic modulus (E), kN/m2 Cohesion (c), kN/m2 Tangent of friction angle (tan φ),

106

102

104

104

101

103

100

10–2

102

Seismic value (v), m/s Probability of liquefaction, Oscillation (10 Story building), Faulting (strike slip fault),

103

102

10

Parameters and features

X/10∞ X

∞

Y/1010 Y

1010

Z/1010 Z

1010

As the figures on the left indicate, rocky grounds are billion times superior to soil grounds. Soil grounds are proper for farming. Hence, constitutional laws of almost all countries conserve soil grounds for agricultural activities. However all structures have to be constructed according to the international building codes. The risk increases with the soil mantle thickness (t > 20 m) and decreasing depth to the water table (d <20 m). This is a very simple and every body can observe after any earthquake in her/his region.

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All earthquake scientists who study actual earthquake events agree that liquefaction only occurs in saturated soil, its effects are most commonly observed in low-lying areas near bodies of water such as rivers, lakes, bays, and oceans [2, 7, 9, 10]. There are numerous online references supporting this reality. Four of them are cited under the section references. The phenomena behind the susceptibility of soil grounds to earthquake are summarized in Table 2.

3 Discussions and Results Almost, all of the lowlands bear shallow (d < 20 m) water table and thick (t > 20) layers of soil. Shallow water table condition and the comparatively very poor engineering properties of soil escalate earthquake disaster. Most of the fertile lands associated with the fault zones are actually found in conjunction with more mineralized and aerated farm soils. This situation enhances farmers to raise crops in these fertile lowlands throughout a year. They, therefore, are high quality agricultural fields which should be restricted for construction and utilized for farming. This is actually an important consideration in land-use planning study. The constitutional law almost all countries bears articles stating that soil grounds have to be preserved for farming. The articles 43–46 of the Turkish Constitutional Law state that the soil can not be used for any purpose other than farming and if such lands occupied before they have to be nationalized and back to be used for farming. Rocky land good for settlement is 57 times larger than the need. There is no reason to use soil grounds for settlement. Then, earthquake disaster will naturally finish. It is easy to find numerous international engineering projects which disregard this fact. Dams with wide reservoirs, highways, organized industrial districts, city settlement are a few of these projects erected within the heart of lowlands of soils. It is strictly recommended to take the fact that the fertile lowlands are hazardous grounds in regards with earthquake and flooding. They are not healthy environment to live either. In spite of them, they are favorable for agriculture and recreational activities into consideration. Kramer [8] suggested the following criteria to reveal the phenomenon liquefaction. (1) Historical criteria: Soils that have liquefied in the past can liquefy again in future earthquakes. (2) Geological criteria: Saturated soil deposits that have been created by sedimentation in rivers and lakes, deposition of debris or eroded material, or deposits formed by wind action can be very liquefaction susceptible [3–6]. (3) Compositional criteria: Liquefaction susceptibility depends on the soil type. Soils composed of particles that are all about the same size are more susceptible to liquefaction than soils with a wide range of particle sizes.

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(4) State criteria: At a given effective stress level, looser soils are more susceptible to liquefaction than dense soils. For a given density, soils at high effective stresses are generally more susceptible to liquefaction than soils at low effective stresses. There is no obligation to invade saturated soil grounds. Earthquake engineers who neglect this reality do not help people to protect themselves from earthquake disaster (see Fig. 1).

4 Conclusions and Recommendations Earthquakes created by strike-slip faults and reverse faults are more destructive than that of gravity faults. Strike slip and gravity faults could easily be detected by surface inspection and seismically induced stress measurements. They can easily be monitored to predict an earthquake in strike slip and gravity fault zones by overeating method and the other in-situ stress versus time measurement methods. Strike-slip faults create wider fertile lands in weaker rocks. which are proper for farming. Particularly tall buildings on rocky formation, even adjacent to a fault zone could not suffer from earthquakes because of the; • • • • • •

higher elastic properties, allowance to higher seismic velocity (higher frequency and shorter wave length), lower porosity, higher shear strength, higher capacity to attenuate earthquake energy, deeper water table condition, and grains are cemented hence, inhibiting liquefaction, subsidence, rupture, and similar ground instabilities.

References 1. Bell GF (1980) Engineering geology and geotechnics. Butterworth & Co Ltd., London p 497 2. Berrill JB, Davis RO (1985) Energy dissipation and seismic liquefaction of sands: revised model. Soils and foundations, Jap Soc Soil Mech Found Engrg 25(2): 106–118 3. Georgia Institute of Technology, Liquefaction research, http://geosystems.gatech.edu/ Research/gpr.html 4. United States Geological Survey Earthquake Information, http://quake.wr.usgs.gov 5. Canadian Liquefaction Experiment, CANLEX, http://www.civil.ualberta.ca/geot/document/ canlex.htm 6. Earthquake Engineering Research Center, http://www.eerc.berkeley.edu 7. Kerwin ST, Stone JJ (1997) Liquefaction failure and remediation: King Harbor Redondo Beach, Calif J Geotec Geoenvironmental Eng ASCE 123(8): 760–769 8. Kramer SL (1996) Geotechnical earthquake engineering. Prentice Hall, Englewood cliffs, NJ 9. Todorovska MI, Trifunac MD (1997) Distribution of pseudo spectral velocity during the Northridge, California, earthquake of 17 January, 1994. Soil Dynam Earthquake Eng 16(3): 173–192

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10. Trifunac MD (1998) Seismic microzonation mapping via uniform risk spectra. Proceedings of the 9th world conference on Earthquake Engineering, Tokyo-Kyoto, Japan, vol. VII, pp 75–80 11. Yilmazer ˙I (2002) A permanent solution to earthquake disaster (in Turkish). Kaynak Publishing Co., Istanbul, P 104 12. Yilmazer ˙I (2002) A permanent solution to flood disaster (in Turkish). Kaynak Publishing Co., Istanbul, P 72 13. Yilmazer ˙I, Yilmazer Ö, Gökçeku¸s H (1999a) Practical engineering approaches to mitigate earthquake disasters. The International Conference on Earthquake Hazard and Risk in the Mediterranean Region, organized by Near East University, Nicosia, North Cyprus 14. Yilmazer ˙I, Yilmazer Ö, Gökçeku¸s H (1999b) Tensional tectonic regimes and engineering works: interactions and mitigation measures. The International Conference on Earthquake Hazard and Risk in the Mediterranean Region, organized by Near East University, Nicosia, North Cyprus 15. Yilmazer ˙I, Yilmazer Ö, Özkök D (2000) Geotechnical design of the Ercan Airport motorway and the Nicosia – Magusa motorway. Unpublished report, p 130, State Highway archives, Ankara-Turkey 16. Yilmazer ˙I, Yilmazer O, Özvan A, Biçek C (2004) Why the earthquake disasters occur only in fertile soil grounds? Turkey. Proceedings of the 5th international symposium on eastern mediterranean geology, vol 2, pp 667–669, Thessaloniki, Greece, 14–20 April 2004

Mitigation of Seismic Risk on Earthen Buildings Marcial Blondet

Abstract Earthen buildings are highly vulnerable to the destructive action of earthquakes, as is tragically revealed by the considerable damage and loss of life that takes place during earthquakes occurring in areas where construction with earth is prevalent. Although many historical earthen monuments have survived strong earthquakes, contemporary vernacular dwellings built with earth have shown extremely poor response in recent earthquakes. Many persons, most of them very poor, have lost their lives due to the collapse of their weak and fragile houses. It is urgent, therefore, to find simple technical solutions to improve the seismic performance of earthen buildings. This paper first describes the seismic response of traditional, unreinforced earthen buildings. It then presents some of the reinforcement techniques developed over more than 35 years of research carried out by the Catholic University of Peru. Finally, it briefly outlines the challenges involved in the dissemination of economical and safe construction techniques, in order to mitigate the risk of earthen buildings in seismic areas. Keywords Adobe · Construction · Earthen · Earthquake · Reinforcement

1 Earthen Buildings in Seismic Areas Men have used soil to build their homes and monuments since the beginning of civilization. In many developing countries soil is still a widely used construction material because it is readily available at little or no cost. Most underprivileged people in these countries, therefore, have no alternative but to build with soil, because the cost of manufactured or industrial materials such as wood, fired clay bricks, cement, or reinforcing steel is completely beyond their economic possibilities. Many construction techniques using earth as the main material are employed throughout the world; the most common are adobe and rammed earth. Because M. Blondet (B) Catholic University of Peru, Lima, Peru e-mail: [email protected]

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Fig. 1 Earthen construction and high seismic risk areas in the world

building with earth is relatively simple, it is usually performed by the residents themselves, without technical assistance or quality control. Reasonably well built earthen houses are, in fact, very comfortable because the walls have excellent thermal and acoustic characteristics. Many countries with a long tradition in the use of soil as a building material are located in areas of high seismic hazard, as can be seen in Fig. 1 [5]. This is unfortunate, because the seismic performance of vernacular, unreinforced earthen buildings is extremely poor. Every significant earthquake that has occurred in regions where earthen construction is common has produced tragic loss of life and considerable material damage. The high seismic vulnerability of earthen buildings is due to a perverse combination of the mechanical properties of their walls: earthen walls are dense and heavy, have extremely low tensile strength and they fail in a brittle fashion, without warning. During seismic motions, heavy walls develop large inertia forces, which they are unable to resist because of their low strength, and thus they suddenly fracture and many times collapse, preventing evacuation and causing death and material loss (Fig. 2). In Peru, several historical earthen constructions have been able to withstand severe earthquakes because of their massiveness and regular configuration. For example, the Chan-Chan archeological site (1200 CE), located on the coast of Peru,

Fig. 2 Adobe houses in seismic areas: (a) Huaraz, Peru 1970 (Photo courtesy of NISEE); (b) El Salvador 2001 (Photo courtesy of D. Dowling)

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Fig. 3 Ancient earthen citadels of Chan-Chan and Arg-e Bam (Photo: Cultural Heritage News)

is considered to be one of the world’s largest mud citadels, and has survived many severe earthquakes during the past 600 years. Decorated boundary earthen walls, some of them up to 9 m tall and 3 m wide at the base, can be found in the citadel. Many long and slender walls without buttresses are still standing (Fig. 3, left). On the other hand, the 2003 Bam earthquake in Iran has destroyed not only several thousands of poorly made adobe houses, but also important ancient historical monuments such as the earthen citadel of Arg-e Bam (500 BCE, Fig. 3, right). This seriously undermines the argument of massiveness as a guarantee for earthquake endurance. The architectural design of the Bam citadel and surroundings includes upper thin walls standing over thick base walls, irregular plan configurations, and high wall densification. It seems that slender walls have collapsed, impacting adjacent walls and constructions, causing total destruction of the site, in spite of its massiveness. Most vernacular earthen houses are built without professional intervention, and thus with poor construction quality. Furthermore, they tend to imitate the architectural features of clay masonry houses. Therefore, most present-day earthen houses are built without any structural reinforcement, with several stories, thin walls, large window and door openings and irregular plan and elevation configurations (Fig. 4).

Fig. 4 “Modern” adobe houses in Cusco, Peru

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These buildings are extremely vulnerable to earthquakes. When an earthquake occurs, the out-of-plane seismic forces produce large vertical cracks at the corners, and the in-plane shear forces produce diagonal cracks in the walls. The walls are thus broken in large independent pieces, which fall down, causing in turn the collapse of the roof.

2 Reinforcement Techniques for Earthen Buildings During the last three decades, researchers at the Catholic University of Peru (PUCP) have attempted to find solutions for improving the seismic performance of earthen buildings [9]. Several related publications can be found in http://www.pucp.edu.pe/ secc/civil/publicaciones.php. Some of the reinforcement systems studied are based on natural materials such as wood and cane. Figure 5, left, shows an internal cane mesh that has demonstrated excellent seismic response in full-scale shaking table tests [1]. The internal reinforcement, which should be tied together by a crown wooden beam, must be provided on all walls. The main limitation of cane reinforcement is the fact that it is not available in all regions. Moreover, even in areas where cane is produced, it is practically impossible to obtain the required quantity for a massive construction or reconstruction program. An external reinforcement consisting of strips of wire mesh covered with cement mortar, shown in Fig. 5, right, has also demonstrated good response under earthquake simulation tests, and in the field during a moderate earthquake [10, 11]. However, wire mesh and cement are prohibitively expensive for the inhabitants of earthen houses in developing countries. External reinforcement with welded mesh could cost up to US $200 for a typical one floor, two room adobe house. This amount exceeds the economic capacity of most Peruvian adobe users. These reinforcement systems, therefore, although technically efficient for earthquake endurance, are still far from being real alternatives to improve the seismic behavior of adobe houses. It seemed imperative to continue research to develop

Fig. 5 Reinforcement of adobe buildings. (a) Internal cane mesh; (b) external wire mesh covered with cement mortar

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Table 1 Properties of adobe models Model number 1 2 3 4 5

Model ID

Reinforcement amount

M000 M100-T12 M075-T11 M050-T11 M080-E

None Full (100%) Partial (75%) Partial (50%) Partial (80%)

Mesh type

Mesh strength (kN/m)

Mesh cost (US$/m2 )

Model reinf. cost (US$/m2 )

– Tensar BX1200 Tensar BX1100 Tensar BX1100 Soft plastic fence

– 9.0 6.6 6.6 1.4

0.00 2.00 1.50 1.50 0.50

0.00 19.00 9.00 6.00 4.00

reinforcement systems that use industrially produced materials, which would be acceptable to earthen house dwellers because of their low cost and simplicity of application. A recent study has been performed at PUCP to evaluate the possibility of using polymer mesh to reinforce earthen buildings [3]. Five similar full-scale adobe housing models were tested on the unidirectional PUCP shaking table. The earthen models were reinforced with different amounts and types of polymer mesh, as summarized in Table 1 below. Each model was subjected to a sequence of shaking tests of increasing intensity. The first model was tested without reinforcement, and represented a typical adobe house (Fig. 6, left). This model also served as baseline for evaluation of the degree of improvement on the seismic response obtained with each reinforcement system. As expected, its high seismic vulnerability was evident: both transverse walls (without windows) collapsed suddenly during moderate shaking. Model 2 was fully reinforced by completely wrapping all walls, both inside and outside, with a geogrid. One side of the model was left without mud plaster, in order to observe the mesh response after each shaking test (Fig. 6, right). This model proved to be overreinforced, as it slid over its concrete base during a strong shaking test. Although the walls suffered little damage, it was interesting to note that the walls with mud plaster showed significant less damage than those left unplastered.

Fig. 6 Models 1 (M000, unreinforced) and 2 (M100-T12, fully reinforced with geogrid)

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This means that mud plaster has a beneficial effect by providing extra resisting material and by confining the plastic mesh. The following three models were reinforced with different amounts of a slightly lighter and cheaper geogrid. The amount and location of the reinforcement was selected according to the stability-based criterion used in the Getty Seismic Adobe Project (GSAP) [8]. Which attempts to predict the crack patterns of the earthen walls and then provides the minimum amount of reinforcement required to control these cracks and therefore to avoid significant damage. All the models showed very good dynamic response during the earthquake simulation tests: although the adobe walls suffered some damage, collapse was avoided. As expected, however, the amount and spread of damage on the adobe walls increased as the quantity of polymer mesh reinforcement decreased. Since geogrid polymer mesh is quite expensive in Peru, it was decided to study the use of a cheaper plastic mesh, usually employed as a soft safety fence in construction sites. The fifth adobe model, shown in Fig. 7 below, was reinforced with bands of plastic mesh located in the regions where most damage was expected on the adobe walls. The photo at the left shows the plastic mesh bands, which were tied to the walls with plastic string placed across the walls during construction. The photo at the right shows the state of the housing model after a strong shaking test. The adobe walls were broken into several large pieces, which were held together by the plastic mesh. The mesh was deformed and broken in several places, indicating that the amount provided was barely adequate. It is clear, however, that although the building suffered significant damage, collapse was averted. This research project has demonstrated that moderate amounts of strategically placed polymer mesh reinforcement can be used to prevent the collapse of adobe buildings, even during severe earthquakes. However, the optimal amount and placement of polymer mesh needs to be investigated, and simple reinforcement design procedures and construction recommendations need to be developed, in order to provide the professional community with tools to design and build economical and safe earthen houses in seismic areas.

Fig. 7 Reinforcement arrangement and finished model M080-E

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3 Main Challenges (and Possible Solutions) The reinforcement systems studied at PUCP have proved to be adequate for the seismic protection of earthen houses. This might suggest that the problem of constructing earthquake resistant earthen buildings has been solved. Indeed, the application of these technical solutions would provide a sufficient degree of safety to these buildings to prevent their collapse and therefore to avoid personal injuries and loss of life. The availability of technical solutions, unfortunately, is not sufficient to solve the real problem of the unacceptable seismic risk for the millions of earthen house dwellers. This problem has important social dimensions that need to be addressed, because in many cases significant cultural transformations are required to change the way people build their dwellings. Many people who have traditionally used soil as a construction material are reticent to change the way they build. In many cases it is because the communities have an adverse reaction to interference in their traditional way of life from persons extraneous to the community. Another very important reason for the rejection of new construction techniques is certainly economical, because these techniques necessarily imply a higher cost, either in money to buy extra reinforcing materials, or in time because training is required or the new building process is more elaborate. Another problem is the short seismic memory of the population. Awareness of seismic hazard is only high after an earthquake, and fades away in a matter of a few years. If earthquakes are not perceived as an immediate danger, there does not seem to be a need to spend for seismic prevention scarce resources which are required for daily subsistence. Furthermore, in many places there is a social stigma attached to earthen houses. In Peru, for instance, masonry brick houses are regarded as a status symbol of progress, especially in urban areas. Thus, urban dwellers consider adobe houses only as temporary solutions, not worthy of any special additional construction effort. Mitigation of seismic risk will therefore be possible only when the users themselves adopt improved earthen construction systems as part of their own culture. A possible set of actions to achieve this transformation is suggested below. Several of them can be performed simultaneously. • Development of simple and cheap reinforcement methods. Although technical solutions to improve the seismic safety of earthen buildings are available, they are still expensive and require relatively high technical skills. It is necessary to optimize the existing solutions and find new ones, using cheaper materials. • Development and implementation of national seismic design codes. Design codes are official documents which contains technical specifications for the structural design and construction of buildings. The seismic design philosophy of earthen buildings should recognize that the material is heavy, weak and brittle. It must be accepted, therefore, that significant cracking may occur even during moderate earthquakes. However, brittle collapse during moderate and severe earthquakes should always be avoided by placing the necessary reinforcement, in order to

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•

•

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prevent the loss of life. Several countries, such as Peru, have already developed design codes for earthen buildings [7]. There are also a number of published documents which could serve as guidelines for the development of codes in countries where these do not exist [4, 6]. It is important to take into account, however, that the code provisions are addressed to professionals who rarely live in vernacular earthen houses and that most of the people that build and live in earthen houses do not know or use the design codes. Therefore, most codes for design of earthen buildings do not fulfill their aim, because they do not reach the users whom it should benefit. Development and dissemination of educational materials for the safe construction with earth. The knowledge required for guaranteeing safe and economical earthen construction must be disseminated to the stakeholders at all levels: engineers, architects, masons, construction workers, government officials, dwellers. It is clear that each group requires the information in a different technical level and format. Therefore, efforts should be made to publish analysis and design books and technical papers, design codes, technical specifications, construction manuals, construction booklets, and educational materials for children. An important dissemination tool for professionals and builders is the internet. There is a wealth of material already published there, such as the EERI/IAEE World Housing Encyclopedia (www.world-housing.net), which contains a tutorial on adobe building in Spanish and English available for download [2]. Development and implementation of seismic risk awareness campaigns. It is indispensable to find ways to reach the communities who build with earth in regions with high seismic hazard in order to persuade them that the danger is real: earthquakes will happen again and again, to remind them that their earthen houses are vulnerable and will collapse or suffer devastating damage, and to convince them that with simple technical improvements it will be possible to build earthquake-resistant houses and thus to protect their own lives. This communication effort is complex and multidimensional. It cannot (and should not) be performed by the academic community alone. It must involve the contribution of the government, at central, regional, and local levels; of NGOs involved with urban and rural development; of the professional communities of engineers, architects, social scientists, and communicators; the educational system starting in elementary school; and the media in all its forms. Development and implementation of community training programs. Educational campaigns should be designed and implemented through popular organizations and local governments to train the community builders and the inhabitants on the basic concepts of earthquake-resistant construction with earth. This effort should be guided by social scientists and communicators. The professional community has the responsibility of disseminating the technical knowledge required to mitigate the risk of earthen houses in seismic areas, which today has reached unacceptable levels. Development and implementation of massive programs for construction of new earthen houses and retrofit of existing houses. Ideally, all existing vulnerable

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earthen houses should be retrofitted and every new earthen house should incorporate adequate seismic reinforcement. This can be achieved only through massive construction and retrofit programs, which could be sponsored by the central government and partially financed by private investors.

4 Conclusions Vernacular earthen houses located in seismic areas are at risk because of their inherent structural vulnerability. However, and due mainly to economic reasons, earth is the only available building material for many communities in developing countries. It is urgent therefore to take action in order to mitigate this unacceptable risk. Experimental research has shown that it is possible to improve the structural performance of earthen buildings during earthquakes, by preventing their collapse. Seismic design codes are effective tools, but they reach only the professionals and not the actual users. Builders in developing countries must be reached and trained to build safe and economic earthen dwellings. The challenges to be undertaken would involve obtaining acceptable technical solutions, educational campaigns to reach awareness of the seismic risk, cultural transformations to adopt safe construction techniques with earth, and massive construction programs. These steps will contribute to solve in a safe and economical way the housing deficit in the most impoverished third world countries. Acknowledgements This article summarizes results obtained through several projects developed by the earthen construction research team at PUCP’s Department of Engineering. The contribution of Julio Vargas, Daniel Torrealva, Francisco Ginocchio, and Gladys Villa-Garcia towards the successful completion of these projects has been invaluable. Mary Hardy and Claudia Cancino, from the Getty Conservation Institute, actively participated in some of the projects described in the paper. Most of the work described here was financed, and thus made possible through grants of PUCP’s Research Office. All the experimental work was performed at the PUCP Structural Lab, and the support of its technical staff is gratefully acknowledged. Last but not least, many students worked hard for many hours to make these projects a reality. These students are Nicola Tarque, Jose Velasquez, Ivonne Madueño, Rafael Aguilar, Maria Angela Astorga, Carlos Iwaki, and Kathya Morales.

References 1. Blondet M, Ginocchio F, Marsh C, Ottazzi G, Villa Garcia G, Yep J (1988) Shaking table test of improved adobe masonry houses. 9th world conference on earthquake engineering, Tokyo-Kyoto, Japan 2. Blondet M, Villa-Garcia G, Brzev S (2003) Earthquake-resistant construction of adobe buildings: a tutorial. Published as a contribution to the EERI/IAEE World Housing Encyclopedia. http://www.world-housing.net 3. Blondet M, Torrealva D, Vargas J, Velasquez J, Tarque N (2006) Seismic reinforcement of adobe houses using external polymer mesh. First European conference on earthquake engineering and seismology, Geneva, Switzerland

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4. CYTED (Programa Iberoamericano de Ciencia y tecnología para el Desarrollo) (1995) Recommendations for the development of technical regulations for adobe, rammed earth, blocks and soil-cement buildings. In: Spanish. Red Temática XIV.A: HABITERRA. La Paz, Bolivia 5. De Sensi B (2003) Terracruda: the dissemination of earthen architecture. In Italian. http:// www.terracruda.com/architetturadiffusione.htm 6. IAEE (International Association of Earthquake Engineering) (1986) Guidelines for earthquake-resistant non-engineered construction, Tokyo, Japan 7. MTC (Ministerio de Transportes y Comunicaciones) (2000) Nacional construction code: adobe. Building technical regulation E-080. In Spanish. MTC/SENCICO. Lima, Perú 8. Tolles L, Kimbro E, Webster F, Ginell F (2000) Seismic stabilization of historic adobe structures: final report of the Getty Seismic Adobe Project, GSAP. The Getty Conservation Institute, Los Angeles 9. Vargas J, Blondet M, Ginocchio F, Villa-Garcia G (2005) 35 Years of research on SismoAdobe. In Spanish. Internacional seminar on architecture, construction and conservation of earthen buildings in seismic areas, SismoAdobe2005. PUCP. Lima. Peru 10. Zegarra L, Quiun D, San Bartolome A, Giesecke A (1997) Reinforcement of existing adobe dwellings 2nd part: seismic test of modules. In Spanish. XI national congress on civil engineering, Trujillo, Peru 11. Zegarra L, Quiun D, San Bartolome A, Giesecke A (2001) Behavior of reinforced adobe houses in Moquegua, Tacna and Arica during the June 23, 2001 earthquake. In Spanish. XIII national congress on civil engineering, Puno, Peru

Land Use Conversion and Agricultural Intensification in Tropical Hill Slopes: A Geographical Approach David Lopez Cornelio

Abstract Three major types of land use in Huanuco (central province in Peru) are discussed on the basis of cartographical and socioeconomical data, document reviews, and field surveys. This traditional agricultural region has critical importance for being the gateway for timber transportation from the eastern mountainous tropical forests where also extensive coca plantations forced human emigration, land abandonment, and deforestation. An optimal land use map was built by overlaying four maps of biophysical characteristics and delineated cultivated areas from a Landsat TM image using ILWIS gis software. In Peru, ancient agricultural systems still coexist with the intensification of commerce. Property types, rates of land use changes, as well as the use of and the number of farms, are discussed. The type of land use varies periodically among each district within the province. State policies not fully structured indicate a poor understanding of the real needs of the Andean society. From now on they must combine elements of tradition, central planning, and markets. Keywords Andes · Land use change · Land reform · Property rights · Traditional systems

1 Introduction The Andes is a mosaic of local habitats with broad tolerant crops overlapping, high elevations, mostly arid, and high eco climatic heterogeneity per area unit [5]. PreColumbian intensive cultivation supported dense and complex states, but since the conquest it became wasteful of land and labor [19], in contrast with the shift from quantity to quality in food production of European countries [9]. Other countries intend to make compatible communal/traditional land tenure systems with structural adjustment and economic reform [30]. D.L. Cornelio (B) Correo central de Huanuco, Huanuco, Peru e-mail: [email protected]; [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_38,

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The effects of population growth are uncertain [32], with the cost of land relative to labor increasing as people change their practices to offset declines in productivity due to intensification. Land degradation and intensification occur simultaneously and incomes may increase during degradation [1]. In Peru, the costs of soil erosion in Peru (in 73% of its area) are between 5 and 10% of the agricultural sector production [37], affecting the people through reduced food supplies, lower income and increased landlessness. Inadequate institutions can be a main factor for land degradation [33] but also adjustments through them positively affect the environment [24]. The study describes main land use of a representative province in the central Andes of Peru. Even though the patterns of land use reflect the current economic model [34] and are bound to the local development processes, the paper focuses on the actual physical condition of land use in the ten districts of the province. The hypothesis is that the prevalent conditions of land use in the province are able to support economic growth with reduced land degradation within the framework of globalization, which currently tend to widen inequality in developing countries [36]. Although a successful combination of local and global know-how is a precondition for development, neo liberal policies in the Andes must be carefully monitored; the irony is that their leading proponents are from countries that heavily subsidize their own agricultural sectors.

2 Materials and Methods 2.1 Location The province of Huanuco is located in the central Andes (Fig. 1) at 08◦ 44 55 – 10◦ 20 21 south latitude, and 74◦ 39 00 –77◦30 00 west longitude, it has 10 districts with a total area of 409,171 ha. The landscape comprehends three main watersheds with semiarid mountains, except the humid tropical conditions of Huallaga valley. In this last, 7,217 ha [18] are planted with coca (Erythroxylum coca) with revenues around 4,000$/ha/year [35], double that is realizable from the cultivation of legal crops [14]. Because of immigration, shantytowns around Huanuco city proliferated. Policies failed to treat land as natural capital that progressively increases its value [34], but property rights policies alone cannot reduce environmental impacts [20]. The population is not equally distributed. Huanuco district has 74,676 habitants, even though covers 4.27% of the provincial area, the same case in Amarilis (3.38% of the total area) with 60,762 habitants, while Chinchao district (44.5% of the total area) has only 22,011 habitants (Table 1). However, the rates of areas suitable for agriculture are relatively high in Huanuco, Amarilis, Chinchao and Santa Maria del Valle (SMValle) (Fig. 8).

Land Use Conversion and Agricultural Intensification in Tropical Hill Slopes

Fig. 1 Location of Huanuco province with delimitation of districts

Table 1 Contents of questionnaire for field interviews (adapted from [21]) The crops ∗ Crops raised and purpose. ∗ Agricultural cycle organization ∗ Main constraints for yields improvement The livestock ∗ Type of livestock and purpose ∗ Grazing organization Natural vegetation and trees ∗ Availability of natural/planted forests. Uses. ∗ Rights on forest resources. Potential problems. ∗ Potential multiple use of trees on farms ∗ Constraints to establish forest plantations.

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2.2 Methods Official statistical data, based on the agricultural unit (AU) from the last two provincial agricultural censuses (1986 and 1996), were analyzed. An agricultural unit is an extension that may comprehend many patches at different altitudes with a unique owner and in the same district. Field visits were carried out from OctoberDecember 2000 in 4 districts on farming methods and land management according to a questionnaire (Table 1). The results are discussed in the following subtitles. The methodology considers that the results could be put into a wider context using census and household data in which an important milestone is the land reform of the early 1970s [3]. A map of land use suitability for a central Andean province was built by overlaying 4 land type maps of 1985 (forests, ecological zones, climatic and soils) at a scale of 1/250,000. In the overlaying operation, made by pairs of raster maps, pixels on the same positions in both maps are compared and the occurring combinations of identifiers or values of pixels are stored. These combinations give an output cross map and a cross table. The cross table includes the combinations of input values or IDs, the number of pixels and the area for each combination [15]. The selected descriptor of each polygon in the resultant map (Fig. 6) is the most concurrent among the four descriptors of each land type map for that polygon (Table 2). The result is a map of optimal land use (ideal map) suitable to the biophysical characteristics of each site, on which the extent of cultivated areas (from a Landsat TM image) was overlaid to get the extension of cropped areas per district. The correlation between the actual (regional census) and ideal distribution of land areas per type was measured by the Spearman’s rank correlation coefficient (the population of both variables in the bivariate analysis are not normally distributed). To determine the rate of land use conversion around the city of Huanuco, polygons demarking urban sprawl drawn on aerial photographs with 33 years of time difference were compared. Table 2 Weights assignment table per types of each map. Ranks 0 and 3 indicate the lowest and highest priorities for land use respectively, chosen according to the description. Final classes after overlaying are denoted as a (agriculture), f (forestry), g (grazing) and c (conservation) RANKING MAP

TYPES

DESCRIPTION

0 1 2 3

Climatic

A(r)A’H4 A (r)B’2H3 B (i)B’1H3 B (o,i) B’3H3

Hot weather, yearlong rainy, very humid. Warm weather, yearlong rainy, humid. Weather semicalid, scarce rains on winter, humid. Semicold weather, scarce rains on winter and autumn, humid. Cold weather, rainy, scarce rains on winter and autumn, humid. Semidry weather, cold, scarce rains on winter, humid.

a c c g

B (0,I)C’H3 C (I)C’H3

g a g a

f g a f

c f f c

a g f c

Land Use Conversion and Agricultural Intensification in Tropical Hill Slopes

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Table 2 (continued) RANKING MAP

TYPES

DESCRIPTION

0 1 2 3

Forests

Bh mo

Mountainous environment, shallow soils, exhuberant vegetation. In Andean highlands above 3,800 masl, cold, variety of grasses, extensive grazing. Mainly located at the lower levels of mountaineous forests. Deforested areas occupied by secondary vegetation on different stages of development. Shrublands(perennial and decidual), average temperature: 9-18 Andean graaslands of hard leaves. Above 3800 masl.

a g f c

Cp Df

Msh Pj Soils

A2s (r) A3c-P1c

F3c-P2e-A2sc

P1c-X

P2e-X X-F2e

X-F3e

X

Ecological bh-PT zones bp-PT

bs-PT

a g f c a c g f

a g c f a f c g

In andean valleys, suitable for annual crops. Conformed by two groups of soil use capacity: (1) with agricultural vocation and weather deficiencies and (mainly tubers on slopes lower than 15%) (2) with pastures vocation, also with weather limitants (on slopes over 20%). With vocation for reforestation on areas with low soil quality (40% of the asociation total extension), with vocation for pastures on soils with medium quality (30%) and protected areas on soils with severe restrictions. Located on high Andean plains, suitable for pastures on low slopes and deep soils, superficial soils on slopes over 75% are denominated of protection. Steepy phisiography, mainly of protection. Pastures can be produced with suitable practices. Distributed on mountaineous tropical forests, because of the topography (slopes over 75%) only 30% of its total extension can be used in forestry. Distributed on mountaineous tropical forests, because of the topography forestry use can be done on slopes less than 50% with careful harvesting systems. Because of topographical and soil limitations cannot be used for forestry, pastures or agricultural activities. Have value for minning, ecotourism and hydrologic cycle maintenance.

c f g a c f g a

Humid forest premountaineous tropical. Total Precipitation/year: 1000–2000 mm Annual biotemperature(average): 16–24C Pluvial forest premountaineous tropical. Total Precipitation/year: 4000-8000 mm Annual biotemperature(average): 16–24C Dry forest premountaineous tropical. Total Precipitation/year: 500-1000 mm Annual biotemperature(average): 16–24C

c f a g

a c g f

a g f c

a f g c a g f c

a g f c

a g f c

a g f c

c g f a

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D.L. Cornelio Table 2 (continued) RANKING

MAP

TYPES

DESCRIPTION

0 1 2 3

bs-MBT

Dry forest low mountaineous tropical. Total Precipitation/year: 500-1000 mm Annual biotemperature(average): 12-16C Very humid forest mountaineous tropical. Total Precipitation/year: 1000-2000 mm Annual biotemperature(average): 6-12C Pluvial forest mountaineous tropical. Total Precipitation/year: 4000-8000 mm Annual biotemperature (average): 6-12C Pluvial param tropical subalpine

c g f a

bmh-MT

bp-MT

pp-Sat

a g f c

a g f c

3 Results 3.1 Land Reform The central government has tried to formalize property rights 22 times since colonial times [6]. The land legislation laws of 1849, 1853 and 1909, established various means of access to land in the Amazonian region: land could be bought, received as a temporary or permanent concession, appropriated at no cost, or granted under colonization contract [31]. The agrarian reform initiated in 1969–1980, the most striking in Latin America [19], changed the land structure in social terms, but not the land concentration and agricultural output. The argument was that redistributing land was better than costly investments in modern technology, which may also displace labor, and could increase land productivity more easily. At that time, 0.3% of the agricultural units (AU) owned 66% of the agricultural land, while 50% of the smaller AU owned only 2.2% of the land [3]. The enforcement of a development model by the central government intended to gain popular support, destroy oligarchic domination, control conflict and rural discontent, improve income distribution, stop massive migration to the cities, and create a stable sector for an expanding internal market. The designed system of price controls and monopoly forced the country to spend 25% of its annual budget on food imports [14] and land rents fell from 20 to 2–3% of total household incomes [36]. The reform was applied by regions and not by agricultural units to gain time and broader coberture [22], moreover, it largely excluded the mass of small holders (the most vulnerable to temporal unemployment) introducing new factors of social differentiation. The probe is that after a decade of land redistribution, peasants which grouped into the National Confederation of Agriculture (CAN) and the Peasants Confederation of Peru (CCP) forcefully occupied land that was assigned to the created cooperatives and agricultural societies [22].

Land Use Conversion and Agricultural Intensification in Tropical Hill Slopes

407

x 1000 ha

The cooperatives seldom succeeded, few of them were able to repay their accumulated debts, and the majority was converted into communities during the 1980s. Their number reached an all-time high of 5,680 in 1994 [14]. The conversions were authorized by changes in the basic land reform legislation, and were put into effect after majority votes of the cooperative members in each case. Preferences of the people involved were contrary to the original intention. The main changes in the agrarian structure were: (1) Land owned by rich landlords passed to the workers, (2) the quantity and the quality of land received was variable and unequal, (3) the reform modified the worker status, from salaried to cooperative-salaried, (4) the land received in marginal areas consolidated the traditional production systems, and (5) the land reform affected only 36.7% of AU in the Andes (in contrast with 64.5% of AU affected in the coastal region). After 1980, privatization returned the structure of the AU distribution to near that of the 1960s trend. Figure 2 shows the evolution of the agricultural unit dimension (changes in percentage from 1961 to 1985) [11]. The total area of AU of 5–10 ha increased 4.1%, AU of 1–2 ha and AU of 10–20 ha increased only 1.3 and 1.4% respectively. The total area of farms within 2–5 ha and larger than 100 ha decreased 3 and 2.8% respectively. Globally, from the 30.6 million ha of agricultural and grazing farms in the country, 10 million were affected by the reform, 11 million (mostly grazing farms) came under common property and 10 million are small and medium private holdings. The total agricultural land affected by the reform (43.9% irrigated and 23.5% rain fed) contrast with the grazing areas transferred (23.4%) [22]. The next period of rural development (1980–1985) followed a worldwide trend and included the dismantling of associative enterprises. Traditional communal rights of peasant communities were made more “flexible”, land could be sold or mortgaged. This benefited the richer peasants within the peasant communities and alienated those who did not have the resources to purchase land. The divergent period inaugurated with presidents Alan Garcia (1985–1990) and Alberto Fujimori (1990–2000) witnessed the intensification of the privatization process. Garcia’s plan included a new land-distribution program, particularly for peasant communities, and economic policies (price controls, state subsidies, credits, and privileged exchange rates to favor the purchase of goods) designed to strengthen small-scale 900 800 700 600 500 400 300 200 100 0

<1ha

1..2

2..5 1961

5..10 1979

Fig. 2 Evolution of the agrarian structure in Peru [11]

10..20 1985

20..100 >100ha

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D.L. Cornelio

producers. Initially associative enterprises were promoted, but turned to privatization. Fujimori’s neo liberal program, confronted with hyperinflation and terrorism, could not thoroughly plan rural development [14]. Two important steps were the enactment of the Agricultural Law of Promotion and Investments in 1998 (DL 26505) ended the restrictions on private ownerships imposed by the agrarian reform. A subsequent special project of land entitlement and cadastre (DS 006-98-AG) regulates the land tenure, legally and physically amending the properties affected by the agrarian reform. Currently, 73% of the peasant communities and 47% of the private small holders have been registered and entitled [29].

3.2 Agricultural and Grazing Systems Rental contracts such as sharecropping allow for mitigating the capital and risk market failures [7]. Sharecropping mechanisms and reciprocal exchanges of labor, oxen, and dung between households alleviate inequalities in land distribution. On fields not used for maize cultivation, the peasant rotates barley, wheat, and beans, followed by a period of fallow, alfalfa, and potatoes, at which point the cycle begins again. Because of modernization, the rate of land under fallow in the Andes decreased from 41% in 1964 to 33% in 1971 [3]. The effects of fallow decrements are not fully perceptible, and areas that seem under fallow may actually loss its fertility since the 18% of usable land has been degraded at different degrees [37]. Although agricultural production is much more labor intensive and specialized than herding, this last is an important non-technified economic activity that relies on natural grasses and post harvest residues. Livestock serves multiple objectives (quasi money, animal traction, provision of derivate products, purchase of human labor, provision of fertilizer). Natural grasslands predominate in all districts, ranging from 22.09% (Chinchao) to 76.79% (SMValle) (Fig. 3). Communal pastures shrunk because of privatization and families strive to have high and low altitude grasslands to seasonally move the animals. Grazing is a main economic activity in Amarilis, Chaulan, SMValle and Margos districts, although is complemented with agriculture since do not constitute a constant flow of incomes. Soil erosion in abandoned/fallow fields is due to the unregulated grazing [13]. Cattle management rather than the elimination of pastoralism is essential. Table 3 shows the livestock totals per type and they range from 2,133 (Yarumayo) to 7,833 (Margos). The activity is especially important in Amarilis, Margos, Chaulan and SMValle districts.

3.3 Forest Condition Forestry development is still insufficient, contrastingly with the intensive use of forests in the Himalayas [18]. Deforestation is consequence of the skewed

Land Use Conversion and Agricultural Intensification in Tropical Hill Slopes

409

40

Thousands of ha

35 30 25 20 15 10 5

Grassland

Forests

Irrigated

lle Ya ru m ay o

SM Va

ha ul an C

i

C ay ra n

Q ui sq u

M ar go s

Am ar ilis C hi nc ha o C hu ru ba m ba

H ua nu co

0

Non Irrigated

Fig. 3 Land use type (ha) per district [16]

distribution of arable lands, chronic landlessness and the macroeconomic stresses of the 1980s [20]. According to Fig. 3, forested areas range from 0.315% (Margos) and 0.54% (Cayran) to 50.08% (Chinchao, mostly tropical secondary forests) and 25.89% (Yarumayo, mostly eucalyptus plantations). The National Program for Soil and Water Conservation (Pronamachcs) directs the reforestation projects in the highlands, and the Reforestation Committee in the Amazonian basin. Pronamachcs administrates eleven tree-breeding centers in the province with an annual production of 147,500–394,000 seedlings [28]. Although 8,267 ha have been reforested until 1991, the 24.2% of the province had been deforested [17], especially in Chinchao district, where for every 4 ha that are deforested, 1 is under actual cultivation and 3 are abandoned [33]. In the highlands, woods are used for firewood (90%), construction (5%) and carpentry (5%) [8]. To satisfy energy requirements, a family needs two poles of eucalyptus (50 cm dbh) per year. Income from wood is complementary, confined to early stages of agricultural frontier expansion, and tends to be reinvested in agriculture and cattle ranching. Shrub and grasslands can be converted to more productive categories of forestland. Steep regions supporting woodlands are an invested capital that farmers can use at the most convenient time or give to the inherited. Trees also protect and nurture agricultural lands. They would neutralize the inevitable environmental consequences of overgrazing and continuous cropping. Reforestation costs per ha range between $100 and $800 [25], unavailable for most of local farmers. Eco-tourism, as well, would add value to unutilized highlands where most of the archeological sites are located. However, lack of funds is not always the problem but that loan conditions are inappropriate for investments in the sector [26]. The government commonly funds reforestation [20].

1858–3500 1900–3800 2060–3800 3260–4800 2800–4185 1865–4400 2000–4000 1835–3800 2450–4170 2600–3910

Area ha (%) 17458 (4.27) 13815 (3.38) 9942 (2.43) 28921 (7.07) 28101 (6.07) 49565 (12.11) 182307 (44.5) 56267 (13.75) 16294 (3.98) 6411 (1.57)

Latitude 9.55 40" 9.57 45" 9.59 45" 10.01 05" 10.03 07" 9.51 45" 9.46 15" 9.46 20" 9.54 06" 9.55 45"

(t) dispersed households (s) communities (c) (s) cows (c) goats (g)

** sheep

* towns

Huanuco Amarilis Cayran Margos Chaulan SMValle Chinchao Churubamba Quisqui Yarumayo

Alt.(masl) 74676 60762 3940 16570 5404 17965 22011 16570 5607 2582

Tot. hab

Table 3 Characteristics of districts

32s 05c 17t 03c 01t 18s 02c 22t 06s 02c 10t 07s 01c 04t 30s 12c 03t 32s 02c 04t 30s 07c 11t 06c 04t 05s 02c

Settlement type*

5000s 1000c 800 g 10000s 3000c 1500 g 8000s 300c 500 g 20000s 2000c 1500 g 15000s 1000c 1500 g 15000s 1000c 2500 g 1000s 4000c 1800 g 8000s 2500c 1000 g 5000s 1500c 1000 g 5000s 600c 800 g

Livestock**

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411

3.4 Measures of Stratification and Inequality While poverty and inequality in rural areas still depend on access to land, the contribution of land concentration to the explanation of total income inequality has declined over time. Income inequalities within communities are higher than resource inequalities [11]. Average family incomes in a modern region can be four to five times higher than those in a traditional region [3] and educational achievement is the most important source of income differences [36]. Modern holdings (private ownership, artificial irrigation, mechanization, and use of chemicals) are commonly located in the lowlands; they influence and coexist with the highland traditional ones (common property, native crops, rotation, and long fallows). Their integration through flows of energy, materials and investment is asymmetric. Highland communities give more importance to landholding conflicts, whereas middle and lowland communities give more importance to difficulties in acquiring chemicals (fertilizers and pesticides). A source of inequality in farm size is demographic differentiation. As households begin, grow, and mature over the course of their life cycles, changes in land holding reflect fluctuations in the demand for land associated with each stage [4]. A young household forms and expands, acquiring land to meet its growing needs. Later, as children mature and leave the household, pressures decline and land holdings may contract. Increasing population, combined with bilateral inheritance, results in successive subdivision of land at the death of the owner. Extreme fragmentation creates difficulties for technological innovation since many of their packages are inadequate in small properties. Technological change facilitates the evolution of land use systems and at the same time, this evolution facilitates the diffusion of technical change. Since AU with less than 2 ha cannot sustain a family with 5–6 members, peasants approach the use of resources through cooperation. Interviews with 44 family heads and 11 groups of farmers showed that a common concern is the decrease of land productivity and availability. Farmers recognize that a plot that produced around 20 bags of potatoes actually only yields four. However, that perception is not as acute as chronic cash shortages [23]. The cost of soil recovery ranges from US$ 777–962 /ha/year [31].

3.5 Land Use Systems Land, water, grazing territories, and labor were neither bought nor sold in preColumbian times [23]. Changes in field systems reflected adaptations to changing environments and socio economic demographic conditions, based either on innovation or diffusion [5]. Peasants still manage multiple farms at the same time to maximize human labor and get advantage from the ecological variability. In a dual decision making system, the household is the producing unit, while at a higher level the community administers a vast territory. The difficulties of supplying and scheduling labor limit the total size that a family can farm.

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The land can be divided into three concentric circles around each town. The nearest one is under intensive use, privatized, and generally irrigated. The parcels located in the outer circle are of common use, mainly for grass, and are located above 4,000 m asl, or are areas without drainage. In “modern” communities, communal rotation has disappeared, and the privatization of land has expanded. This process is faster in communities situated at low and intermediate altitudes [5]. The system of cropping and the property rights are different in each circle. Within the agricultural belt, abandoned fields and non-cultivatable land are referred to as tierra eriaza; which are not irrigated and are communally controlled and open to residents of the village for grazing and the collection of herbs and firewood. The most common form of access to land is inheritance [12], followed by purchase, sharecropping, and to a lesser extent, renting and acquisition of land as collateral for a loan (anticresis). Agricultural plots are the basis of a land market in which prices are regulated by supply and demand, and there are no restrictions on sales to outsiders (forasteros).

3.6 Factors Interrelation and Statistics of Land Use per District The correlation between the total AU and entitled AU with district area are positive (R = 0.64 and 0.61 respectively), irrigated area and population (R = 0.51), total and entitled AU (R = 0.78), and altitude and AU under common property (R = 0.91). Variables with non significant correlation are the total of AU with the number of AU under common property (R = 0.04), the area of grasslands with the number of AU under common property (R = –0.04), population and total of AU (R = –0.08), irrigated and forested areas (R = –0.02) and irrigated and grassland areas (R = –0.07) (Table 4). Santos-Granero and Barclay [31] add that the length of occupation is correlated with greater land fragmentation and that the relation between the proportion of perennial crops and the proportion of fallow land is negative. While in Amarilis, Cayran and Yarumayo the rates of irrigated fields are 97, 86 and 65%; in Chaulan, Quisquis, Chinchao and Margos they are 39, 38, is 29 and 10% respectively (Fig. 3), meaning that in the last four districts more than half of fields depend on rains. Accessibility is a main factor to access irrigation infrastructure; Amarilis and Cayran are next to the city of Huanuco. The 32,723.3 ha of irrigated plots in Amarilis constitute 58% of the total irrigated area in the province. The distribution of irrigated areas in the province is heterogeneous. Irrigation influences the crop structure, the type of tillage, and the level of fragmentation of the agricultural unit [10]. The irrigation canals are built by communal labor, anyone wishing to have land allotted in the new area must participate in their construction. Margos has two communities and 8,538 AU under common use (Table 3, Fig. 5) while in Churubamba there are seven peasant communities and only 1,119 AU under common use. Production zones with higher productivity (lowlands) accelerate the degree of privatization [23]. Effectively, in Churubamba half of the total AU has only one patch while in Margos only 17% (Fig. 4). Communities do not necessarily control common land, individual herders can share common grasslands. There

A. Area (%) B. Population C. Altitude (masl) D. Agric. Land (ha) E. Irrigated area (ha) F. Grassland (ha) G. Forest land (ha) H. Total AU I. Entitled Properties J. Common Properties

1.00 −0.04 −0.13 −0.35 −0.22 −0.17 −0.24 0.64 0.61 0.00

A

C −0.13 −0.51 1.00 −0.17 −0.21 0.25 −0.14 −0.16 −0.56 0.91

B

−0.04 1.00 −0.51 0.33 0.51 −0.39 −0.30 −0.08 0.25 −0.27

−0.35 0.33 −0.17 1.00 0.92 0.07 0.31 −0.39 −0.23 −0.12

D −0.22 0.51 −0.21 0.92 1.00 −0.07 −0.02 −0.20 −0.07 −0.13

E −0.17 −0.39 0.25 0.07 −0.07 1.00 0.27 −0.29 −0.32 −0.04

F −0.24 −0.30 −0.14 0.31 −0.02 0.27 1.00 −0.30 −0.23 −0.18

G

Table 4 Correlation matrix between main parameters (total of districts)

0.64 −0.08 −0.16 −0.39 −0.20 −0.29 −0.30 1.00 0.78 0.04

H

0.61 0.25 −0.56 −0.23 −0.07 −0.32 −0.23 0.78 1.00 −0.33

I

0.00 −0.27 0.91 −0.12 −0.13 −0.04 −0.18 0.04 −0.33 1.00

J

Land Use Conversion and Agricultural Intensification in Tropical Hill Slopes 413

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Number of patches

4000 3000

2..5

>6

1

2000 1000

H ua nu co Am ar ilis C hi nc ha C hu o ru ba m ba M ar go s Q ui sq iu C ay ra n C ha ul an SM Va lle Ya ru m ay o

0

Fig. 4 Number of patches per agricultural unit [16] entitled registered common

10000

without entitling total

Number of AU

8000 6000 4000 2000

o ay

lle

m ru

an ul

Va Ya

SM

n ha C

ay

ra

iu C

sq ui Q

M

ar

go

s

ba

o C

hu r

hi

ub

nc

am

ha

ilis ar C

Am

H

ua

nu

co

0

Fig. 5 Land tenure condition per district (status of agricultural units per district) [16]

are more patches per AU in highland than lowland areas (parallel use of diverse production zones). In Churubamba 122 AU comprise between 11 and 15 patches of land. In Chaulan it is 35, and in Yarumayo it is 65. In Margos, 5 patches compose 223 AU and 318 AU by 6–10 dispersed patches, the higher values for those ranked. The proportion of AU with only one patch ranks from 14% (Chaulan) and 16% (Margos) to 54% (Huanuco) and 67% (Chinchao). In half of the total districts, more than half of AU posses only one patch (Huanuco, Amarilis, Chinchao, Churubamba, and Yarumayo) (Fig. 4). The number of entitlements in each district depends on its accessibility and distance to the capital. In Margos and Yarumayo it is less than 1%, while in the Huanuco district it is 39%. The proportion of AU under common property in each

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district is 100% in Margos, 98% in Chaulan, and 100% in Yarumayo (Fig. 5); in contrast, there is 23% in Huanuco and 17% in Churubamba (their territory extends from lowlands to highlands). An owner is recognized as one who is holding a land title even though it is still not registered in the official records; an owner without a title is simply denominated “land holder”.

3.7 Change in Land Use The comparison of aerial photographs from 1962 to 1995 in an area of 7.30 km2 enclosing the 4/5 of Huanuco city, indicates that croplands converted to urban areas at a rate of 2.6% per year. As there are no easy routes to change the status of land tenure, farmers in state cooperatives and other agricultural societies illegally subdivide the common land into private plots, and few have valid titles over them [6]. In 10 observations, a higher correlation exists between the forest areas of the real and ideal condition maps (R = 0.6364) than in the case of agriculture (R = 0.463) or grassland areas (R = 0.2242), explained by the overlapping in time and space of grazing and agricultural areas. In the real situation, there is no conservation or protection class as such; it is intermingled within the forest and grassland classes. Moreover, the regional census did not consider that land category. Data for the ideal condition was obtained according to the methodology; since they are types of physiographical characteristics at small scale, it is assumed that will not change substantially over time.

Fig. 6 Map of suitable land use with demarcation of cultivated areas

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D.L. Cornelio

conservation

forests

agriculture

grassland

Yarumayo SMValle Quisquis Margos Huanuco Churubamba Chinchao Chaulan Cayran Amarilis 0%

10%

20%

30%

40%

50%

60%

70%

80%

90% 100%

Fig. 7 Rates of crop areas established on areas with other suitability (current situation)

The extent of farms established in areas with other suitability was delineated on the ideal map (Fig. 6) The total of pixels (smallest units on the map) for each case were converted to percentage of ground area considering that 1 pixel equals 0.704 km2 . In the current situation (Fig. 7) agriculture occupies over 50% of the total area in most of the districts, while in an optimal situation (Fig. 8) it is restricted to some areas and land dedicated to other uses are better distributed. The results are shown in Figs. 7 and 8. The cropped areas in Amarilis, Churubamba, Huanuco,

conservation

forests

agriculture

grassland

Yarumayo SMValle Quisqui Margos Huanuco Churubamba Chinchao Chaulan Cayran Amarilis 0%

10%

20% 30%

40% 50%

60% 70%

Fig. 8 Area rates per category of land use in an ideal condition

80% 90% 100%

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and SMValle are properly located (78.6, 80.5, 64.7, and 77.1%, respectively, of the total area cultivated in each district). However, in the same districts, the proportion of cropped areas suitable for forestry are 21.4, 19.5, 35.3, and 18.3%, respectively. In Quisqui this use reaches 72.3%. In Chinchao, primarily, and in Quisqui, Margos, and Chaulan, the proportion of cultivated plots to areas suitable for only conservation are 34.3, 10.7, 7.57, and 3.6%. The rates of cropped plots on areas suitable for grazing are high in Yarumayo (76.2%), Chaulan (63.6%), Cayran (59.74%), and Margos (45.2%). It is notable the overuse of land for agriculture in Amarilis (31,291.7 ha) and Margos (8,118.8 ha), for grasslands in Chinchao (8,320.8 ha), Quisquis (5,538.5 ha) and SMValle (29,971.5 ha) and the sub use of areas suitable for forests in Chinchao (14,762.52 ha), Quisquis (5,670.7 ha) and SMValle (9,822.5 ha). Figure 9 is a proposed scheme to achieve a sustainable use of land in the central Andes of Peru. Common natural grasslands and agricultural holdings in marginal lands comprehend the majority of area under use; their progressive conversion to widespread recommended measures (encircled) with permanent and higher output values can be achieved through the actions described in the right box, failure in any of them will not assure success. Local institutions (diverse systems of cooperative work, sharecropping, regulated use of productive resources and control of diverse production zones at different altitudes) and incentive alternatives should be negotiated with the local communities. Technical assistance and training might enhance the managerial skills of the locals, adapt new methods of land use and reconsider good practices of traditional knowledge.

Fig. 9 Proposed scheme to increase land value

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4 Discussion and Conclusions Areas under agricultural, grazing, and forest use changed broadly from 1972 to 1996 in all districts, and are far from matching the most suitable land use. A farmer changes cultivation practices both from year to year and from field to field for reasons that may be spatial, environmental, economic, informational, demographic or idiosyncratic. Land use is heterogeneous among the districts. Pressure on land varies from district to district and is the main force that conduces to institutional change. Policy shifts from collectivism to market oriented solutions and back to heterodoxy created uncertainties and deepened rural divisions. Although the paradox of an ideology of egalitarian resource distribution alongside differentiation continues to provoke tensions in Andean communities [13]. Land reforms as were traditionally conceived are no longer needed since do not solve social infrastructural problems. Even though management systems are similar, there are differences regarding intensity, areas, and type of land use. The average patch area/owner is 5 ha, with exceptions in Chinchao (less than 0.5 ha) and Churubamba (10 ha). This can hinder technological innovation since studies in other realms confirm that larger farms are more open to it [27]; and that households with more land have higher levels of income from non agricultural employment [7]. Inequality has to be confronted by reducing economic instability and through programs that improve the access by the poor to productive assets. The number of patch/owner is inversely proportional to the patch size in all cases, meaning that while large holders are prone to technological change, smallholders diversify their production in multiple cycles to divert risk. Accessibility is a main factor for the diffusion of infrastructure and property formalization. Development policies for each district will differ. In Chinchao rehabilitation measures have to focus on forest resources while in SMValle on grasslands management. In Huanuco and Churubamba the main actors are small holders while in Chaulan and Yarumayo most of the productive resources are under common use. The local social institutions have the potentiality to enable a sustainable use of land if they are duly recognized by state policies and receive an external stimulus from agencies of development. The success of this effort will depend on action within the sector (institutions, policy, technology) as well as outside the sector (economical and political stability, education, transportation, communication). Traditional land tenure in the Andes is not well described by artificial categories such as private or communal, both are complementary and intermingled. The point is not who has the right over land, but who has the right to use determined area for a specific purpose. Although the existence of production zones as a production system is not exclusive [23], the inclusion of people and institutions with different objectives and interests but with the ability to cooperate in the coordination, creation and exploitation of them which is exceptional in the Andes; and forms the basis on which of land use policy must rely. Agriculture in steep areas suitable for other uses has been traditionally inherited but the customary institutions that regulated land use are diminishing because of modernization. The environmental consequences can be unexpected since peasant communities control more than 30% of the fragile lands [3]. The evidence that privatizing cooperative property does not automatically led

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to sustainable investment must be pondered; it is of interest only if individual management is highly profited [30]. Agricultural output would rise, but the impact on employment will depend on the technologies used on the new consolidation holdings. A policy risk is that smallholders who sell their lands may move to the forested areas. Moreover, given the high ecological diversity in the Andes, it is unlikely that a land market is going to develop for second or third quality land. Andean genetic diversity is a case where common access leads to an increase in biological diversity rather than a reduction [23]. People self organize in response to change [34], creating new instruments and institutional forms capable of responding to restructuring pressures [27]. They spontaneously organize into extralegal independent groups until the government is able to create a unique system of legal property. Entitling farmers and deregulating agricultural prices can slow emigration. If the farmer has a legal right to his land, he will also invest more in its conservation. Together with a well-designed land information system it would create the needed social capital for sustainable land use. The emergence, implementation and effectiveness of local policies depend upon the complex of economic, social and political conditions found within and beyond the locality. The changes are slow and continuous, a “green revolution” has not occurred. The growing tendency towards external linkages offers new potentialities, but also new risks for the local people. Markets tend to reinforce the extractive activities, conduces resources outside the rural realm and is indifferent to processes of environmental degradation [27]. Acknowledgements The author wishes to acknowledge the valuable insights of Mr. Ebenezer Annan Afful and give special thanks to Mr. Scott Menking for proofreading the final manuscript. Any mistakes that remain are the author’s responsibility. The Japanese Ministry of Education provided funding for this study.

References 1. Birch-Thomsen T, Frederiksen P, Sano H (2001) A livelihood perspective on natural resource management and environmental change in semiarid Tanzania. Econ Geogr 77:41–66 2. Bussink C, Hijmans R (2000) Land use change in the Cajamarca basin, Peru, 1975–1996. CIP Program report 1999–2000, Lima, pp 421–428 3. Cotlear D (1989) Desarrollo campesino en los Andes. Instituto de Estudios Peruanos, Lima, 325 pp 4. Chayanov A (1996) The theory of peasant economy. Manchester University Press, Manchester, 316 pp 5. Denevan W (2000) Cultivated landscapes of native Amazonia and the Andes, Oxford geographical and environmental studies. Oxford University Press, Oxford, 396 pp 6. De Soto H (2000) El misterio del capital – porque el capitalismo triunfa en occidente y fracasa en el resto del mundo, edit. El Comercio, Lima, 287 pp 7. Echevarria R (2001) Development of rural economies. Inter-American Development Bank, Washington, DC, 224 pp 8. Espinel L (1996) Propuesta para la introduccion de especies forestales a sistemas de produccion agropecuaria en Obas – Huanuco, forest engineer thesis. UNALM, Lima, 81 pp 9. Evans N, Morris C, Winter M (2002) Conceptualizing agriculture: a critique of postproductivism as the new orthodoxy. Prog Hum Geogr 26(3):313–332

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10. Gonzales de Olarte E, Hiopkins R, Kervyn B, Alvarado J, Barrantes R (1987) La lenta modernizacion de la economia campesina. IEP, Lima, 233 pp 11. Gonzales de Olarte E (1994) En las fronteras del mercado – economia politica del campesinado del Peru. IEP, Lima, 370 pp 12. Guillet D (1995) Covering ground–communal water management and the state in the Peruvian Highlands. The University of Michigan Press, Ann Arbor, MI, 250 pp 13. Harden C (1996) Interrelationships between land abandonment and land degradation: a case from the Ecuadorian Andes. Mt Res Dev 16(3):274–280 14. Hunefeldt C (1997) The rural landscape and changing political awareness: enterprises, agrarian producers, and peasant communities, 1969–1994, In the Peruvian labyrinth – polity, society, economy. The Pennsylvania State University Press, University Park, PA, pp 107–133 15. ILWIS (2003) Online GIS tutorial. Downloaded from www.itc.nl/ilwis 16. INEI III (1996) Censo nacional agropecuario Ministerio de Agricultura, Lima, 4 volumes 17. INRENA (1994) Compendio estadistico de la actividad forestal y fauna 1980–1991. Ministerio de Agricultura, Lima, 120 pp 18. Ives J, Messerly B (1999) The Himalayan dilemma. The UNU press, London, 324 pp 19. Kay C (1998) Latin America’s agrarian reform: lights and shadows, Land Reform Journal, Institute of social studies, (2)8–32 The Hague, The Netherlands 20. Keipi K (1999) Forest resource policy in Latin America. Inter America Development Bank, Washington, DC, 280 pp 21. Mantang C, Shaofang H (1995) National training workshop on identification of tools for degraded land management in rural areas with emphasis in wood energy problems, training materials, Research Institute of Tropical Forestry, Guangzhou 11–16 December, P. R. China, 84 pp 22. Matos J, Mejia J (1984) Reforma agraria: Logros y contradicciones 1969–1979. IEP, Lima, 138 pp 23. Mayer E (2002) The articulated peasant: household economies in the Andes. Westview Press, Oxford, 390 pp 24. Mazzucato V, Niemeijer D (2002) Population growth and the environment in Africa: local informal institutions, the missing link. Economic Geography 78(2): 171–193 25. McGaughey S, Gregersen H (1983) Forest based development in Latin America. InterAmerican Development Bank, Washington, DC, 215 pp 26. McGaughey S, Gregersen H (1988) Investment policies and financing mechanisms for sustainable forestry development. Inter-American Development Bank, Washington, DC, 126 pp 27. Neil C, Tykkylainen M (1998) Local economic development: a geographical comparison of rural community restructuring. United Nations University Press, Tokyo, 365 pp 28. OIA (2000) Sintesis agrario No. 6, 7, 8. Oficina de informacion agraria del ministerio de agricultura, Huanuco, Peru 29. PETT (2002) Proyecto especial de titulacion de tierras y catastro rural, Ministerio de Agricultura. Downloaded from www.minag.gob.pe 30. Ridell J (2000) Emerging trends in land tenure reform: progress towards a unified theory. FAO Sustainable Development Department, Rome 31. Santos-Granero F, Barclay F (1998) Selva central, history, economy and land use in Peruvian Amazonia. Smithsonian Institution Press, Washington, DC, 351 pp 32. Scherr S (1999) Poverty-environment interactions in agriculture: key factors and policy implications. Paper prepared for the UNDP and the EC expert workshop on poverty and the environment. Brussels, Belgium 33. Schweik C, Adhikari K, Nidhi K (1997) Land-cover change and forest institutions: a comparison of two sub-basins in the southern Siwalik Hills of Nepal. Mt Res Dev 17(2):99–116 34. Silberstein J, Maser C (2000) Land use planning for sustainable development. Lewis Publishers, Boca Raton, FL, 203 pp

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35. Tammen M (1991) The drug war vs. land reform in Peru, in Policy Analysis No 56, Cato Institute. Downloaded from www.cato.org/pubs/pas/pa-156.html 36. Van Ginkel H, Barrett B, Velasquez J (2002) Human development and the environment – challenges for the United Nations in the new millennium. The United Nation University Press, Tokyo, 313 pp 37. Young A (1998) Land resources, now and the future. Cambridge University Press, Cambridge, 319 pp

Part IV

Energy and Development: New and Renewable Energy

Role of Renewable Energy in Development of Self Sufficient Housing in Developing Countries Debashis Sanyal

Abstract Energy is a burning problem of present era. The conventional centralized energy distribution network accounts for high transmission losses (ranging from 9 to 20% at times). The energy consumption in residential structures accounts considerably high than other buildings, also it is a recurring ever cost increasing phenomena. It is very difficult to remain in the city and save energy beyond a certain limit without compromising the present day materialistic lifestyle by the city dweller households. Also the factor of polluting the environment by using conventional fossil fuels for energy generation accounts for a disastrous future. The concept of ‘self sufficient housing’ is to develop a self-contained commune with a building unit designed to cater the needs of approximately 15–20 families. The provisions will be made in these housing to enable the inhabitants to produce their own energy, grow their own agricultural produces for food, recycle all the resources/waste. These units will be essentially located in rural/countryside areas. The building will be planned in such a way that it will use non-conventional/renewal energy sources totally and will not use any form of external energy source. The building will be planned in such a way that it will use non-conventional & renewal energy sources totally and will not use any form of external energy source like electrical grid network or fossil fuels, etc. The main objective of this research is to develop suitable architectural designs for selfsufficient housing units incorporating the necessary infrastructures, like equipment of energy generation. Keywords Architectural design · Self-sufficient housing

1 The Scene With its present growth rate (about 150 persons/min) the world population will be crossing 8.5 billion by the end of the year 2025. As per the projections made, 57% D. Sanyal (B) Department of Architecture, National Institute of Technology Raipur, P.O. Ravishankar University, Raipur Chhattisgarh 492010, India e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_39,

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of this population will be urban, out of which 95% contribution will be due to the developing countries. As a result, the population of many cities in developing countries will cross the figure of 20 million by the year 2015. Based on projections made by UNCHS, 17 of the 21-mega cities will be in the developing countries. Existing mega cities (2006) Beijing, Buenos Aires, Cairo, Dacca, Delhi, Jakarta, Karachi, Kolkata, Lagos, Los Angeles, Manila, Mexico City, Mumbai, New York, Osaka, Rio de Janeiro, Sao Paulo, Seoul, Shanghai, Tianjin, Tokyo Projected list of mega cities of future (2015) Chennai, Hyderabad, Istanbul, Kinhasa, Lahore, Lima, Moscow, Paris, Teheran

Based on above projections, it is quite easy to predict the future housing needs. Already there is a global shortage of housing for 2 billion people. This shortage will be becoming more and more acute if no immediate actions/measures are taken. This definitely advocates the need of development of mass housing projects. This shortage will further increase by the year 2025, when the world population will be around 8.5 billion. But what about the tremendous impact on the field of energy usage of these future developmental projects of mass housing? A study of present processes of development with associated energy usage will help architects in designing mass housing with less energy consumption, leading ultimately to conservation of natural resources and less polluted urban environment.

2 The Pressure It is necessary here, to identify various major pressures, which are generally put on the urban areas by building more mass housing units:

2.1 Land As of today the land in the urban metro cities has become very dear & costly; also it is difficult to find new land suitable for mass housing. The alternative of housing in high-rise apartments is leading these urban areas towards chaotic development. They also pose greater pressure on parking and transportation system network.

2.2 Energy This is a burning problem of present era. The present unplanned and uncontrolled growth of housing cares little about energy conservation aspects. Sometimes even providing minimum energy to all households is not becoming possible by the local authorities. Studies reveal that around 18% of total energy consumption of mankind is in housing sector. It is necessary to consider energy conservation techniques

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before, during and after construction; as energy can be saved considerably in each stage. Over 80% of the embodied energy in mass housing is the energy required to manufacture the materials. Most of this energy usage is for manufacturing only a small number of the (high-energy) materials used in construction of housing units, principally steel products, cement, concrete products, bricks and ceramic materials. This embodied energy amounts to several times the annual energy consumption of that same housing in use. Energy is used wastefully in heat recovery processes, insulation techniques, simple orientation concerns. Architectural lighting & space heating/cooling are also two of the largest and most visible consumers of energy. A properly designed energy efficient housing will have a lower initial cost than one planned disregarding energy consequences. This cost advantage derives mainly from smaller building volume & lower energy demands. The conventional centralized energy distribution network accounts for high transmission losses (ranging from 9 to 20% at times). The energy consumption in residential structures accounts considerably high than other buildings, also it is a recurring ever cost increasing phenomena. It is very difficult to remain in the city and save energy beyond a certain limit without compromising the present day materialistic lifestyle by the city dweller households.

2.3 Utilities The present day big cities are growing in a faster speed; the utilities & the city of basic amenities to urban population is becoming increasingly difficult day-by-day. It is a very complex situation and a major multifaceted problem to cope up with such a huge demand. Lack of finance/civic sense resources are further adding to this precarious condition.

2.4 Environment The present day pollution & lack of basic amenities are proving detrimental to future growth of residential nature in metro city areas. The polluted air and water, the toxic wastes, the dangerous fuel emissions from vehicles, are further aggravating this situation. The decreasing green areas are bringing changes in the microclimate in of these cities, making it more and more uncomfortable for living.

2.5 Transportation The public transport systems of almost all these urban conglomerations are running at a loss and it has become increasingly difficult to maintain their effectiveness cleanliness and punctuality, because of overcrowding and pressure of daily commuting population.

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3 Energy Efficiency to Sufficiency It had already been established in 1970 that there is no inexhaustible supply of cheap conventional energy sources, available in world & therefore serious efforts should be aimed at identifying energy conservation methods and a lot of research is being done to effectively use the available non-conventional & renewable energy sources. The future of housing design should rely on not only energy efficiency but towards energy sufficiency. For effectively using these concepts, simultaneous use of various non-conventional energy sources is necessary, which will cover the lean period of generation of energy by one source and will provide designed uninterrupted quantity of energy all the time. UNCHS recommends, ‘Housing should be designed with the application of bio-climatic design principle & employment of energy conservation measures will reduce 60% energy consumption in heating/cooling of buildings.’

4 The New Concept The concept of ‘self sufficient housing’ is to minimize the pressures on cities in terms of space, energy, traffic, population, etc. This housing will be in a self-contained commune with a building unit designed to cater the needs of approximately 15–20 families [1]. They will produce their own energy for domestic use; grow their own agricultural produces for food, thereby limiting their visits to urban areas for such tasks and products, which are not feasible in this commune. They will be sited in economical rural spaces/natural surroundings [2]. A self sufficient home is a structure that is designed, built, renovated, operated, or reused in an ecological and resource-efficient manner. These homes are designed to meet certain objectives such as protecting health; using energy, water, and other resources more efficiently; and reducing the overall impact on the environment.

5 The Advantage 5.1 Location and Siting These units will be located in rural/country areas & they will be well connected with the possible work centers. The rural natural fresh & unpolluted environment and low cost of land will be the first positive aspect of siting such dwelling units. Protect and retain existing landscaping and natural features. Select plants that have low water and pesticide needs, and generate minimum plant trimmings. Use compost and mulches. This will save water and time [4]. Recycled content paving materials, furnishings, and mulches help close the recycling loop.

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5.2 Energy Sufficiency The building will be planned in such a way that it will use non-conventional & renewal energy sources totally and will not use any form of external energy source like electrical grid network or fossil fuels, etc. • Develop strategies to provide natural lighting. Studies have shown that it has a positive impact well being. • Task lighting reduces general overhead light levels. • Use a properly sized and energy-efficient heat/cooling system in conjunction with thermally efficient walls, roofs and floors. • Maximize light colors for roofing and wall finish materials; install high R-value wall and ceiling insulation; and use minimal glass on undesired sun exposures. • Consider alternative and renewable energy sources. • Passive design strategies can dramatically affect a homes energy performance. These measures include home shape and orientation, passive solar design, and the use of natural lighting.

5.3 Materials Efficiency Select sustainable construction materials and products by evaluating several characteristics such as reused and recycled content, zero or low off gassing of harmful air emissions, zero or low toxicity, sustainably harvested materials, high recyclables, durability, longevity, and local production. Such products promote resource conservation and efficiency. Reuse and recycle construction and demolition materials.

5.4 Recycling The concept of recycling of waste/water/garbage will be applied in such a way that it fulfils the need of dwellers without tapping any external services or utility networks. The garbage will be recycled to produce energy through non-conventional methods & end product will become manure for crops. One example of recycling can be using wastewater from washing in fishponds and from there it can be used in fields/vegetable farms [3]. Some other measures which will definitely improve water efficiency can be: • Design for dual plumbing to use recycled water for toilet flushing or a gray water system that recovers rainwater or other nonpotable water for site irrigation. • Minimize wastewater by using ultra low-flush toilets, low-flow showerheads, and other water conserving fixtures.

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• Use recirculating systems for centralized hot water distribution. • Install point-of-use tank less hot water heating systems. • Use micro-irrigation (which excludes sprinklers and high-pressure sprayers) to supply water in non-turf areas. • Use state-of-the-art irrigation controllers and self-closing nozzles on hoses.

5.5 Space Economy This building will be providing minimum adequate living space for 15–20 families in an economical rural/countryside site. This number of dwellers will depend upon local conditions, extent of the problem and energy sufficiency parameters along with other factors.

5.6 Environment Friendly The main aim of these self sufficient housing units is to develop such a housing system in which there will be no generation of pollution by any means. Besides being sited in a rural environment these houses will be using recycling of water and all the waste materials. Thus a nature friendly & ecologically balanced surrounding will be created by these dwellers through these housing systems.

5.7 Employment Generating The commune development activities and maintenance of various energy generation equipments will also generate employment for the dwellers & only a handful (one person per family) may have to go to city areas for sophisticated jobs etc. As this concept provides partial food growing facility/zero energy bill along with Other economical advantages; there will be less necessity of a job, and dwellers can engage themselves in a occupation/vocation of their own choice for better income, while living in the commune.

5.8 Minimizing Transportation The dwellers require minimum transportation. As only periodical shopping of merchandise & some other works may require traveling to other areas which are not possible within this commune. Though through scientific application of knowledge of farming will reduce this need to travel. This in turn will decrease the overall stress on existing transportation systems.

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6 The Process 1. Selection of a target group representing largest portion of such migratory population. This selection must be made at local level considering the nearness of urban areas. 2. Determination of a feasible size of commune by considering local problems of Siting. Though preliminary studies suggest about 250 families can be a manageable size for Indian conditions, having a maximum of 5 persons per family. 3. Proposing living space. For 15–20 families in one building, by undertaking anthropometrical studies and deciding space standards, taking along with the study of economical feasibility of the target group. The minimum proposed enclosed spaces required for a family should be: • Habitable space: bedroom/living room; utilities: kitchen/toilet/bathroom/ store, etc. In addition to these some common spaces are necessary for community living, which may be: • Services/electric room/garbage collection room, Kitchen garden/open garden/terrace garden, farming, fishpond, poultry etc. These spaces can be created in common spaces left between the units. 4. Estimating space requirements. For energy production by renewable or nonconventional energy sources: Biogas/biomass plant, wind energy, solar energy. Where feasible tidal energy can be also used. 5. Earmarking spaces. Necessary to produce agricultural products for food, i.e. Terrace gardens/Semi built up spaces; these spaces can be integrated with the building design, whereas some open plot can be attached to the commune for collective/family-wise farming. 6. Deciding Building fabric and enclosure spaces (including structural considerations). Here due attention must be paid to achieve a structurally safe & maintenance free construction. 7. Earmarking Spaces for recycling plants. For water/garbage/sewerage for energy and manure production. These spaces should be designed with optimum space utilization concept, though importance of these cannot be ignored due to their necessity in keeping the pollution level low. Care must be taken to adapt foolproof recycling systems. 8. Providing community spaces & common spaces for recreation and other utilities. Park/school/primary health center/recreation center, roads/pathways, etc. 9. Calculating the energy demands of the unit and proposing energy sufficiency by tapping non-conventional energy sources. Some of such energy sources under consideration are: Solar (photo-voltaic), Biomass, Wind, Tidal, etc. It may be necessary to install a combination of these energy sources to get desired result all the year round.

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10. Estimating the necessity of other resources, like water, etc., & proposing their procurement from locally available natural sources. Rainwater must be compulsorily collected & underground water level must be allowed to charge through natural means. 11. Deciding the size of one building unit with cross checking each of the above mentioned spaces as per their feasibility and sustainability with respect to number of dwellers and self-sufficiency parameters. 12. Arriving at a suitable size as per local conditions/resources availability/willing population. 13. Determining the social acceptability of these relatively new housing systems, through preliminary survey of various shelter less people, or people suffering from overcrowding in conventional housing.

7 Architectural Design of Housing The housing design should incorporate energy saving techniques by reducing the energy demands & some major recommendations are: 1. Proper site selection & orientation. 2. Use of shady trees to control radiation reaching unwanted places of building envelope. 3. Maximum window placement on the side of least sun exposure. 4. Minimize exposed surface area for reducing heat transmission.

8 The Materials Over 80% of the embodied energy in housing is the energy required to manufacture the building materials. It has been established that most of this energy is used in only a small number of materials, principally, iron/steel products, cement/concrete products, bricks/ceramic materials. The embodied energy in a housing unit amounts to several times the annual energy consumption of that same housing in use [6] (Table 1).

Table 1 Ratio of embodied energy to annual energy for houses in different locations Location

Embodied energy (GJ)

Annual: energy (GJ)

Ratio

UK, 1975 USA, 1981 Switzerland, 1987 (SQ.M.) Pakistan, 1986

140 (average) 190 4.6 20–100

71 (average) 119 0.8 2

2 1.6 2.99 3–14

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So, architects of self-sufficient housing have the opportunity to make a major contribution to the reduction of total energy use in built environment through some of the strategies enlisted here: 1. Maximum use of low energy materials. 2. Selection of lower-energy structural systems, such as load bearing masonry in place of RCC/steel frames. 3. Selection of waste/recycled materials, or manufactured materials, which incorporate these. 4. Use local materials, involving less transportation. 5. Use more functional windows (designed as passive solar collectors). Optionally smart windows can be also used, which use anti reflection layers, low emission coatings and switch able films.

9 The Construction During construction process, materials are combined in composite building components such as walls, floors and roofs. Based on the energy intensity of the materials and the quantities used, it is possible to calculate the energy insensitivity of various types of building materials and construction methods (Table 2). Table 2 Energy requirements for typical housing components Components

Energy (MJ/Sq.m)

Floors:

Suspended timber Concrete slab on ground

733 1014

Walls:

Timber frame, weatherboard cladding Timber frame, brick-veneer cladding Concrete block

198 1284 755

Roofs:

Galvanized Steel Concrete tile

508 176

Similarly, the energy intensity of various house designs can be calculated and compared. It is notable that structures can vary up to 60% in capital energy requirement, as a result of architect’s choice of materials [5].

10 The Intelligence In developing self-sufficient housing the concept of intelligent/smart buildings adds quite a lot. The continuous monitoring of energy requirement levels, the automatic provisions of reducing wasteful energy demands will add to this novel concept. Intelligent buildings effectively use energy conservation methods and maintain the optimum energy usage level all the time. The energy production cost is higher in developing countries; the reduction of unnecessary wastage of household energy

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will be very advantageous. Reduction in energy consumption derives from strategies, in the form of intelligence, for manipulating the HVAC and electrical systems. These strategies are complex, because energy optimization schemes have an impact on many different functional aspects simultaneously; consequently, they can be effectively followed by intelligent system only. It has been already experienced that using intelligent software that reacts to the electrical demand approaching a new monthly peak value can reduce electrical power costs, and then recommends shedding, of certain building electrical loads in accordance with a priority schedule. Computer monitors the relative heat of the outdoor air and the return air in the building, and then controls the optimum use of either to reduce the energy consumed by the air-supply systems.

11 Advantages of Self Sufficient Housing A Self Sufficient home may cost more up front, but saves through lower operating costs over the life of the home. These homes require fewer trips to the doctor’s office. This approach applies a life cycle cost analysis for determining the appropriate up-front cost. This analytical method calculates costs over the useful life of the home. These cost-savings can only be fully realized when they are incorporated at the project’s conceptual design phase with the assistance of an integrated team of professionals. The integrated systems approach ensures that the home is designed as one system rather than a collection of stand-alone systems. Some benefits, such as improving health and comfort, reducing pollution and landfill waste are not easily quantified. Consequently, they are not adequately considered in a cost analysis. For this reason, consider setting aside a small portion of the building budget to cover differential costs associated with less tangible benefits or to cover the cost of researching and analyzing Self Sufficient housing options. This development may lead to a school of thought in the inhabitants and they will thrive to become self-sufficient.

References 1. Sanyal D (1995) Self sufficient housing: searching of parameters. Architects India, Bombay 7(6):26–27 2. Sanyal D (1997) Development of self sufficient housing using intelligent buildings in Indian context. New methods and technologies in planning and construction of ıntelligent buildings II. Proceedings of IB/IC ıntelligent buildings congress. Tel Aviv, pp 88–97 3. Sanyal D (1999) Self-sufficient housing for urban India: a study of architectural considerations. Proceedings of national seminar on advances in energy efficient construction systems, Gorakhpur, pp 25–35 4. Sanyal D (2000) Exploration of architectural design aspects for intelligent self sufficient housing: a study. Proceedings of world conference on green design, world congress on environmental design for the new millennium Seoul, pp 375–385, 5. UNCHS (Habitat) (1991) Energy efficiency in housing construction and domestic use in developing countries. Nairobi (HS/218/91/E), p 8 6. UNCHS (Habitat) (1991) Energy for buildings. Nairobi (HS/250/91/E), p 88

Energy and Environmental Significance of an Alternative Fuels Utilization Produced with to Liquid Technology Nenad Kukulj and Tomislav Kurevija

Abstract Higher costs of crude oil on world market, as well as awareness about negative environmental impact related to conventional diesel fuel utilization, are creating favourable economic conditions for production expansion and greater application of alternative fuels. Natural gas could be converted through FischerTropsch synthesis technology process, dating from the beginning of the last century, to alternative form of fuel named Gas to Liquid (GTL) which can be utilized in all recent diesel engines. GTL has lower emissions in comparison to fossil diesel and it is characterized with higher cetane number which is measurement of the fuel ignition quality. Furthermore, additional advantage is that the existing infrastructure for fuel transportation and distribution could be used without any significant changes, either for pure GTL or blend with diesel. In compliance with present and future EU directives, concerning greenhouse gases reduction and decrement of imported crude oil dependence, Gas to Liquid technology imposes as one of the alternative fuels for utilization in transportation sector. Keywords Gas · Liquid · Alternative fuels

1 Introduction Today world production of crude oil is just below 80 million barrels per day and such large emissions of GHG and harmful gasses into the atmosphere, caused by oil utilization, have led to increased introduction of alternative fuels because of rigorous air quality regulations regarding climate change fears. Many oil companies believe that the world’s oil producing regions have reached sustainable production limit and the natural gas must be exploited to produce transportation fuels. Increased demand from China and India will soon influence the world’s ability to supply crude N. Kukulj (B) Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Pierottijeva 6, Zagreb, Croatia e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_40,

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oil-based products which will increase crude oil prices. In 2003, the transport sector consumed 1,500 Mtoe [2] worldwide and over the next 30 years, the most fastest increase in energy demand is expected to come from this sector (+2.1%/yr versus 1.7%/yr for total demand). Today, transport relies almost entirely on petroleum products, which causes rise in dependence upon oil import and increase in emissions of harmful and greenhouse gases. Alternative motor fuels such as natural gas for vehicles (NGV), liquefied petroleum gas (LPG) and biofuels, represent about 40 Mtoe which is less than 3% of the total fuel consumption. In the early 20th century Germany started to develop process known as FischerTropsch (F-T) which produced transport fuels from coal, resulting in numerous large scale plants built during the 1938–1943 era. Afterwards, the conversion process has improved in South Africa which has plentiful coal and low domestic oil and natural gas resources. The key drivers for implementation of alternative fuels are environmental regulations concerning fossil diesel and the fact that supply cannot meet present demand especially in EU countries with negligible oil resources. Beside present alternative fuels, Gas to Liquid synthetic fuels derived from wide variety of carbon-based feedstock, such as natural gas, coal, biomass and oil sands can reduce petroleum dependency, ensuring security of energy supply and improving air quality. In last 5 years oil price has become quiet politically influenced that caused the highest world market price per barrel ever. Due to political world instability it is predicted that oil price will never reach a 20th century level again. Therefore, most of major oil companies have started further R&D of Fischer-Tropsch fuel conversion technology and construction of GTL production facilities.

2 Conversion Process of Carbon-Based Feedstock into Synthetic Hydrocarbon Liquid Fischer-Tropsch is the process of chemical converting natural gas into liquids (GTL), coal to liquids (CTL), biomass to liquids (BTL) or bitumen from oil sands to liquids (OTL). All four processes, usually known as Gas-to-Liquids, consist of three technological separate sections. In the first step carbon feedstock is reacting with oxygen and steam inside of gasifier/reformer generating mixture of hydrogen and carbon monoxide (H2 + CO) called syngas. This syngas generation can be used in many processes like fertilizer, methanol and specialty chemical production. In addition, generated waste heat could produce steam-derived electricity in IGCC power plants as side-product of the GTL process that could increase the overall energy efficiency, thereby helping to offset the large cost of the equipment. After that, syngas undergoes high pressure with presence of a catalyst inside F-T synthesis reactor and forms long chain carbon-hydrogen molecules, named F-T wax or paraffin. In the third step these long chain molecules are splitted into shorter-length hydrocarbon molecules (diesel, naphtha, kerosene, LPG) in a hydrocracking stage that is almost

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Fig. 1 Gas to liquid technological process with Fischer-Tropsch synthesis reactor

identical to crude oil refining. The F-T process offers the potential to produce variety range of products such as middle distillates fuels, as well as lubricants and waxes. The complete Fischer-Tropsch input and output process is illustrated in Fig. 1. F-T synthetic fuels are made from natural gas, coal, bitumen or biomass through a chemical process. Due to that, they have none of the impurities as crude oil derived products such as sulphur, heavy metals and carcinogenic compounds as benzene. During Gas to Liquid technological process CO2 becomes significantly problematic as by-product. However, CO2 gas is in a concentrated stream and therefore it is easily sequestered as long as there is a disposal or utilization possibility near the GTL production site. Biomass synthetic fuel (BTL) is considered as CO2 neutral transport fuel when it is evaluated on a full life cycle basis that could contribute to greenhouse gasses (GHG) emissions reducement. The efficient combination of all this three steps and integration process is a major challenge for F-T technology developers. Advances and improvements in the first two steps will cause lower production costs due to enhanced carbon conversion, thermal and process efficiencies. The plant economy strongly depends upon the chosen feedstock as carbon source. The choice whether GTL plant will use natural gas, coal or biomass in conversion process also depends on feedstock availability for specific region. Many projects with natural gas based GTL plant are planned in Middle East region because of numerous gas and oil fields as well as stranded gas resources.

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In North America has large conventional fuel consumption, dependence upon imported oil and natural gas, substantial domestic coal resources and due to that few large-scale production projects are considered, regarding coal and biomass feedstock. The infrastructure of GTL plant should be properly sized because of different feedstock properties as carbon content and specific calorific value, concerning feedstock quantity transportation needed for designed fuel plant output. If coal is considered as feedstock for production for GTL fuel (CTL) it should be taking into account widespread calorific value for different sorts of coal (coal, coke, charcoal and carbon) which varies approximately from 10 to 30 MJ/kg. For example, assuming conversion process gross plant energy efficiency of 45% [3], the amount of coal feedstock needed could be calculated as follows: f =

Efuel (Hd )feedstock · η

where is: f – feedstock needed for production of 1 bbl CTL, kg Efuel – calorific value of 1 bbl CTL (5331 MJ) (Hd )feedstock – lower calorific value of coal (10–30), MJ/kg η – gross plant energy efficiency (45%) For production of 1 bbl CTL and 20 MJ/kg coal calorific value it is needed: fcoal =

5331 ECTL = ≈ 590 kg (Hd )coal η 20 × 0.45

Analogue to that, if biomass as feedstock is considered (≈15 MJ/kg), for production of 1 bbl BTL it is needed: fbiomass =

5331 EBTL = ≈ 790 kg (Hd )biomass η 15 × 0.45

Natural gas is the most available and economically favourable of all of these three investigated feedstock. Although, there were some investigations made concerning underground coal gasification which significantly reduces capital and operative costs, natural gas is still primarily used in worldwide existing production facilities. In GTL refinery, for production of 1 bbl GTL and average natural gas calorific value of 33 MJ/m3 , it is needed: fnatural gas =

EGTL (Hd )natural gas η

=

5331 ≈ 360 m3 33 × 0.45

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3 World Gas to Liquid Production Activities and Future Prospects Total world gas reserves are estimated to be 176 billions m3 , equivalent to 1.10 BOE (148.7 million m3 oe) which is almost equal to the proven world oil reserves of 1.15 billion barrels (155.4 m3 oe) [9]. Most of the natural gas world reserves are located in Former Soviet Union (32.1%) while in the Middle East natural gas reserves accounted for 40.8% and crude oil reserves of 63.3%. Initial development and future activities regarding construction of the GTL facilities are related to locations of hydrocarbons reserves in the world. Exception is South Africa’s coal based GTL plant which was built due to oil embargo. Today there are totally five synthetic fuel production plants, of which two are pilot-plants, located in Japan (GTL) and Germany (BTL). Commercial sized plants that are in operational stage have been developed on coal based feedstock (South Africa) and natural gas (Qatar, Malaysia). All production and proposed synthetic fuel projects are shown in Fig. 2 in view of proven natural gas reserves and project characteristics are presented in Table 1. The main companies started to develop GTL plant projects near the large natural gas and oil fields, mainly in Russia, Qatar, Iran and the FSU. There are two main reasons; GTL processes are using natural gas as the feedstock and in this locations they could be commercialized at large production scales projects (>100.000 barrels/d), especially where natural gas is abundant or gas flared associated with oil production. Gas flaring is estimated at 108 billion cubic meters per year what is equivalent of approximately 700 million barrels of oil (BOE) per year [7]. In some countries, particularly Nigeria, flaring will bring economic penalties such that the natural gas resource will have negative values, what improves the economics of

Fig. 2 World wide synthetic fuel projects in view of proven natural gas reserves [6]

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N. Kukulj and T. Kurevija Table 1 Worldwide GTL production facilities and future prospects [1, 8]

Facilities

Investor

Production capacity (103 bbl/d)

Production start-up

Existing Sasol II & III Mossel Bay, South Africa Bintulu, Malaysia Ras Laffan, Oryx I, Qatar

Sasol PetroSA Shell Sasol, QP

150.0 22.5 12.5 34.0

1974/1979 1992 1993 2006

Under construction Escavros, Nigeria

Chevron, NNPC

34.0

2008

Planned Ras Laffan, OryxII, Qatar Ras Laffan, Qatar Qatar Qatar Qatar Australia Arzew, Alger

Sasol, QP Shell, QP ExxonMobil, QP Sasol, QP ConocoPhillips, QP Sasol Chevron Shell, Statoil,PetroSA

32.0 70.0 + 70.0 166.0 130.0 80.0 + 80.0 45.0 36.0

2009 + 2010 + 2010 + 2010 + 2010 + 2012 + 2010 +

Project proposal USA, China, Russia, Iran, Venezuela, Argentina, Bolivia, Angola, Trinidad & Tobago

most GTL projects. The second reason is associated with production of CO2 as GTL technological process by-product. Sequestration of carbon dioxide could be utilized in view of enhanced oil recovery projects which offer further GTL production cost effectiveness and increased oil yield.

4 Energy and Environmental Advantages of Gtl Fuel over Conventional Fossil Diesel The trend of world growth in diesel consumption will continue in the future, what is caused by increment in number of diesel engine vehicles from 750 million in 2005 to predicted 1.10 billion in 2020. Such growth represents a major problem of ecologically sustainable development (Fig. 3). Today, various transport fuels are taking into consideration as one of the alternatives to the conventional fossil fuels. GTL seems to be available in significant quantities in the near future what could lead to the further reduction of emissions into the atmosphere, necessary to meet future air-quality regulations. The influence of GTL fuel and GTL blends on emissions and engine performance has been researched by numerous oil companies. GTL is extremely clean fuel with low sulphur and aromatics content and has cetane number larger than 70, what is advantageous during cold start and low temperature engine operation, as seen on Table 2. Higher cetane number yields in

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Fig. 3 Diesel fuel consumption growth by world regions and future predictions [7]

Table 2 Comparative of GTL fuel properties with conventional diesel and biodiesel [6, 4] Low sulphur EU Biodiesel 2005 Diesel (RME)

Blend 60% DF 20% GTL 20% RME

Blend 95%GTL 5%RME

Fuel properties

GTL

Lower calorific value, MJ/kg (MJ/L) Density, kg/dm3 Cetane number Kinematic viscosity, cSt (mm2 /s) Total sulphur, ppm GHG emission due to production process, kg eq.CO2 /MJ GHG emission due to combustion process, kg eq.CO2 /MJ Total life cycle GHG emission, kg eq. CO2 /MJ)

43.8 (33.53) 42.7 (35.44) 37.8 (33.3) 41.94 (34.68)

43.5 (33.52)

0.765 ≈ 70 ≈ 2.0

0.83 45–50 2.5–4.0

0.88 50–60 ≈ 7.0

0.827 53 3.75

0.771 69 2.25

< 1.0 0.0336

8.0 0.0191

0 0.0240

5 0.0230

0.95 0.0331

0.0667

0.0639

0

0.0517

0.0634

0.1003

0.0830

0.0240

0.0747

0.0965

reduced ignition delay and reduced fuel evaporation before ignition. Furthermore, GTL demonstrated a slightly longer combustion duration and more uniform heat release rate than the fossil diesel. Density is 8% lower than conventional diesel, but with 1.8% larger heating value and the properties of the blends change roughly proportionally to the blending ratio. Only disadvantage in physical-chemical properties of GTL fuel is that the total GHG emission during combustion, when observing complete life cycle of the fuel, is higher as much as 15% than those for conventional technologies.

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Fig. 4 Comparison of GTL emissions with various types [5, 7]

Compared to regular diesel fuels over various conditions tested taking into account both heavy-duty and light-duty vehicles, FT fuel reduce particulate emissions substantially around 20% and HC 10%. NOx emission reduction using the FT fuel is approximately 20% while carbon monoxide CO emission is reduced for 10%. Average savings in harmful exhaust emission for various blends of GTL and biodiesel is shown on Fig. 4.

5 Gas to Liquid Production Economy Major OPEC exporters willing to sustain and support crude prices certainly in the $40/bbl–$60/bbl range. The tendency in the GTL industry is to improve plant economics and reduce operating costs. As plant size increases, natural gas feedstock required to support the operation increase with total costs of the complex (from small scale of $2 million to large facilities of $5 billion investment), eliminating all but the largest oil companies and State-run oil companies from developing new projects. Today, majority of technological R&D advances are directed to the largescale GTL projects. The economics of modern F-T plants is determined with six individual factors; the cost of capital investments, construction costs; feedstock costs (coal, natural gas or biomass); the gross conversion/thermal plant efficiency; operating costs and the value of the finished products. Plant capital expenses various from $30.000/bbl/d to $60.000/bbl/d, depending upon location and type of plant, feedstock and output fuel transportation infrastructure and energy efficiency of the plant [2]. The future intention is to reach $15.000/bbl/d threshold with implementation of next generation reactor where GTL projects could compete with new crude-oil

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Fig. 5 Total investment cost depending upon operational capacity of GTL refinery

refineries. Figure 5 presents production capacity unit costs trend line and future cost index with share of investments in overall GTL production refinery. Typically F-T fuel plants require big investments in utility and offsite support systems which can account for 40–50% of the total cost of a plant. These costs are usually included in each of three basic F-T steps; synthetic gas generation, F-T wax conversion and product workup. Typical cost allocation is 50–55% of the total cost for syngas generation, 25–30% to the F-T conversion and 15–25% to product upgrading. Technologies for a large scale F-T plant have a common infrastructure requirement which includes need for large amount of energy for air separation processes, the pre-heater for the syngas generation step, waste heat recovery from syngas and its effective utilization, medium/low grade heat generation by the FT process, hydrogen provision for the hydrocracker and optimum product recovery. GTL projects are around 60% thermal efficient, with around 45% of gross plant efficiency, resulting in around 40% heat rejection [3]. Research in this sector will provide greater utilization of this latent heat on economical basis. The element of market risk is particularly significant due to the massive scale at which the refineries are planned. With expected cash flows of over $1 billion per year from the sale of products, unexpected down time can doom a project. On a smaller scale, installation costs of GTL/CTL/BTL F-T plants rise rapidly, soon exceeding $80,000 per daily barrel of capacity. Most major F-T technology companies are seeking large gas fields to support large-scale projects. As seen on Table 3 GTL fuel has greater costs than CTL fuel production technology. Nevertheless, natural gas is often flared during oil production because of lack in transportation and utilization infrastructure grid which results in CO2 emissions penalties. Oil produced from such reservoirs, especially Nigeria and Middle East, could have poor economical balance. Possibility of the GTL projects development near such fields would have economical advantage and environmental significance over similar projects. CTL projects are of special

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Table 3 Synthetic fuel production costs from the different carbon source types for power plant’s gross energy efficiency of 45% Production costs

Biomass (MJ/kg)

Crude oil (MJ/kg)

Coal (MJ/kg)

Natural gas (MJ/m3 )

Lower calorific value Feedstock price, $/GJ (2006) Fuel price, $/GJ Fuel logistics, $/GJ Production syngas from fuel, $/GJ Production diesel from syngas, $/GJ Diesel total costs, $/GJ Diesel total costs, $/GJ

15 4.0 8.0 3.0 3.8 1.8 16.60 0.56

42 9.4 (60$/bbl) – – – – 11.85 0.42

20 3.0(60$/ton) 6.66 1.0 3.8 1.8 13.26 0.44

33 3.46 7.70 1.0 3.5 1.8 14.00 0.47

interest for countries that poses significant coal deposits. World coal reserves, which can ensure production for more than 200 years at the present rate of utilization, are mainly concentrated in countries like China and India. High world oil prices and traditionally low-cost coal mined in these regions, assure economical competitiveness of future CTL projects. As seen on Table 3 BTL synthetic fuel has the greatest production costs and future prospects are related only as fuel extender (adding coal to biomass feedstock) [9]. Table values have been derived according to calorific value for each feedstock, taking into account assumed power plant’s gross energy efficiency of 45% and uptodate feedstock world market prices (September 2006).

6 Conclusion In the time of high oil prices and their instability on world market there is a trend of increased research and development in the field of alternative fuels. Aside that, drivers that contributed to greater implementation of alternative sources of energy, are high level of harmful and greenhouse gasses emissions into the atmosphere, especially in highly populated regions, strong global demand for liquid fuel supply, geopolitical uncertainty of oil supply and principles of sustainable development. Due to life standard increment, especially in developing countries, there is accretion in demand for transportation fuel what will soon lead to problems in supply chain. Gas to liquid technology could supplement share of conventional fossil fuels, resulting in that way with lower dependency upon oil, as well as some ecological and energetic advantages. Transportation and distribution of synthetic fuels could be carried out without significant investments, using existing infrastructure. Future GTL projects are planned near large oil and gas fields, as well as substantial coal deposits, making in that way projects more economically feasible. Regarding existence of CO2 as by-product of the F-T production process, sequestration could be accomplished by injection of carbon dioxide into the oil reservoirs as part of tertiary methods of recovery. In this way GTL fuel could lower overall greenhouse

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gasses emissions, as well as make economic benefits to oil production. Moreover, locations of special interest for GTL projects could be oil fields without natural gas transportation grid, where gas is flared making in that way production of oil economically burdened because of enormous CO2 emissions. Further research of synthetic fuel production technologies will lower investment costs, making it in that way more economically competitive with conventional fuels. On EU example, continued world GTL technology development would not be dependent upon world oil market price because of directives and regulations concerning ecology, implementation of alternative sources of energy and diversification of fuel supply.

References 1. California Energy Commission (2004) GTL Working Group Analysis. Sacramento, CA, USA, October 2004, p 21 2. Cornitius T (2006) The impact of synfuels (GTL,CTL,BTL,OTL) on world petroleum supply. Zeus Development Co, 14th Annual EIA Energy Outlook and Modeling Conference, March 2006, p 16 3. Department of Energy National Energy Technology Laboratory (2004) Gilberton coal-to-clean fuels and power co-product project. Pittsburgh PA DOE, p 2 4. Fiato R, Sibal P (2005) ExxonMobil’s advanced gas-to-liquids technology – AGC21. Presentation at the 2005 middle east oil & gas show and conference, March 2005, Kingdom of Bahrain. p 16 5. Munack A, Schröder O, Ruschel Y, Herbst L, Kaufmann A (2006) Comparison of shell middle distillate, premium diesel fuel and fossil diesel fuel with rapeseed oil methyl ester. Institute of Technology and Biosystems Engineering. April 2006, p 43 6. Schaberg P, Botha J, Schnell M, Maly R, Pelz N, Herrmann H (2004) Effect of GTL diesel fuels on emissions and engine performance. Proceedings of the 2004 DEER conference: 2004 diesel engine emission reduction, Coronado, USA, August 2004, p 5 7. Shell International Gas Limited Technical Report (2003) Shell Middle Distillate Synthesis (SMDS) Update of a life cycle approach to assess the environmental inputs and outputs, and associated environmental impacts, of production and use of distillates from a complex refinery and SMDS route. PricewaterhouseCoopers Co., New York, May 2003, p 171 8. Sichinga J, Jordaan N, Govender M, Van de Venter E (2005) Sasol coal-to-liquids developments. Presentation to the gasification technologies council conference,10–12 October 2005, San Francisco, USA, p 43 9. Van Ree R, Van der Drift B, Zwart R, Boerrigter H (2005) Market competitive Fischer-Tropsch diesel production. 1st International biorefinery workshop, 20–21 July 2005, Washington, p 22

Sustainability Concept for Energy, Water and Environment Systems Naim Hamdia Afgan

Abstract This review is aimed to introduce historical background for the sustainability concept development for energy, water and environment systems. In the assessment of global energy and water resources attention is focussed in on the resource consumption and its relevancy to the future demand. In the review of sustainability concept development special emphasize is devoted to the definition of sustainability and its relevancy to the historical background of the sustainability idea. In order to introduce the sustainability measurement the attention is devoted to the definition of respective criteria. There have been a number of attempts to define the criterions for the assessment of the sustainability of the market products. Having those criterions as bases, it was introduced a specific application in the energy system design. Demonstration of the multi-criteria sustainability measurement of the energy system options based on the selected number indicators, namely: efficiency, economic, environmental and social indicators. Keywords Sustainability · Energy · Water and environment system · Resources · Limits

1 Introduction Our civilisation through the history has been under constrains which has encompasses economic, social and ecological perspective in its development. Since the beginning of industrial revolution it was recognised the need for the harmonised development of different commodities leading to the better life. In this respect, economic and social developments have been based on the natural capital available at the respective level of technology development. N.H. Afgan (B) Instituto Superior Tecnico, Lisbon, Portugal e-mail: [email protected] Naim Hamdia Afgan is a Member of Academy of Sciences and Arts of Bosnia and Herzegovina, Sarajevo

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It should be notice that through the history of human society the changes in the pattern of the social structures have been linked to the cyclic development of the human structure. These changes are result of the critical state, which have been achieved at the specific period of time reflecting the need for the addition of a new complexity in human society. In this respect the industrial revolution has introduced commodities to our society, which by itself contributes to the increase of the complexity. Nearing to the end of the industrial revolution, it has become evident that the complexity indicators as population, economics, material resources, social structure and religious devotion have reached the state, which requires our special attention. Sustainable development encompasses economic, social, and ecological perspectives of conservation and change. In correspondence with the WCED, it is generally defined as “development that meets the needs of the present without compromising the ability of future generations to meet their own needs.” This definition is based on ethical imperative of equity within and between generations. Moreover, apart from meeting; basic needs of all; sustainable development implies sustaining the natural life-support systems on Earth, and extending to all the opportunity to satisfy their aspirations for a better life. Hence, sustainable development is more precisely defined as ‘a process of change in which the exploitation of resources, the direction of investments, the orientation of technological development, and institutional change’ are all harmony and enhance both current and future potential to meet human needs and aspiration. Complexity is the property which describes the state of complex system [1, 2]. It is multi-criteria indicator which comprises all individual characteristics of the system. Complex system is entity which characterizes the structure with a large number of elements interacting among themselves. There is different structure of elements. Elements in biology are structured to perform specific function. Typical example is DNK molecule, comprising large number of elements interacting among themselves. In the information theory the structure of elements is described as the internet network with large number of nodes for information exchange. In energy system we can describe complex system as the system which produces, transport and utilize different energy sources. The complexity of these systems is the internal property of the system expressed as the wholeness property. This imply that the complexity describe the essential characteristic of the system. If the complexity is described in thermodynamic words, it represents the internal parameter of the system expressed by agglomerated indicators describing specific property of the system. If we take into a consideration only material system, we can take the entropy of the system as the macroscopic property of the system. These can be applied to chemically bounded molecules. Prigogine [3, 4] has determined the characteristic property of these systems as the entropy generation. This means that every interaction between elements accompanying with mass, momentum and energy exchange ultimately is connected and contribute to the entropy generation in the system. It should be taken into a consideration that the entropy generation is defined per unit mass of the system and represent specific property of the system. So the entropy generation represents the complexity property of the system.

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If we take into a consideration non-material system where complex properties include entities which are not defined per unit mass of the system, we have to introduce notion which represents wholeness of the system. Good example for this type of complex system Internet system. Large numbers of nodes are connected in large net serving to transfer information among nodes. If we assume that transfer of information contribute to the increase of informativity of the system, we can see that the increase of informatively is equivalent to the increase of the complexity of the system. In this respect the informativity is equivalent to complexity. It is of the paramount importance to develop a notion based on the modern scientific knowledge which will help us to understand a basic concept of sustainability. In this respect sustainable science as defined in [5] is challenging attempt to focus attention of scientific community in large, to dwell into a basic knowledge in different fields and emulate them by the respective complexity in order to reveal a new understanding of the future of our planet (Fig. 1). Globalisation

Fig. 1 Schematic presentation of interaction. Sustainability – globalisation – democratisation – decentralisation Decentralisation

Sustainability

Democratisation

1.1 Globalisation In the complexity definition of the sustainability concept there are three clusters of indicators, which are in use to describe the state of global system. There are: resource, environment and social cluster of indicators. There are three processes that are immanent to the development of our planet, namely, globalisation, democratisation and decentralisation [6]. Even, there are in many cases, where these processes are in conflict, the effects of these processes across the full range of scale is of fundamental importance for the understanding issues as the behaviour of complex systems. Recently, it has become evident that economic forces are driving forces that are transferring capital, material, resources and manpower through the global space without obstacles posed by the local, state and regional boundaries. The process of economic reform is named globalisation. The contemporary revival of interest in the field of international political economy has coincided with the appropriately unprecedented restructuring of the world economy to be labelled as globalisation. The forces of changes associated with globalisation have been felt through statesocieties to such an extent that it has become the focus for a large amount of

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research undertaken across the social sciences. The comprehension of globalisation will require substantial contribution in order to become firmly recognised as a field of interest for social science.

1.2 Democratisation Democracy is the principles of equity of right, opportunity and treatment [7]. The process leading to the establishment of social organisation based on the democracy principles is democratisation. So, the democratisation process can be defined within the different boundaries including local, regional and global environment. The intensity of democratisation process is depending on the number of attributes reflecting ethnic, religious, cultural and educational environment. For every social structured system the respective indicators reflecting different aspect of the democratisation process can define the intensity of democratisation process. Individual parameters defining specific characteristics of democratisation can be used to measure intensity of the democratisation process. Among those are: Equity of right, job opportunity and treatment. Each of the parameters can be defined as the specific value of internal parameter of the system under consideration. As the internal parameters of the respective parameter the indicators of democratisation process can be defined as: specific number citizens participation in voting system, specific number of job opportunity in the system and many other. Since the democratisation process is also defined by the respective indicators cluster, it is of interest to make the assessment with reference to effect of the social parameters defined by the democratisation on the observed system. Again, we have to form respective aggregation function which will describe the state of the system. In this respect the sustainability assessment can be used as the decision making paradigm for the system assessment.

1.3 Decentralisation It has been proved that the large energy and water systems are economically better justified then small systems. In the past, a driving force in decision making process under economic constrain has been to build the large systems. With a new wave of miniaturisation, it has become evident that in the complex system assessment the priority may be given to the smaller system [8]. In this respect recently developed governing system is seeing more support for the local government. The same can be applied to the development of energy, water and environment systems. Smaller cogeneration units have become attractive solution in many areas, leading to the better economic, environmental and social values in the use of available resources. The modern micro gas turbine with respective cogeneration unit has proved to be justified by the complex assessment method. The goal of the network system is therefore to investigate options and pathways for an accelerated transition towards sustainable energy technologies and systems. In this respect, the appropriate selection of

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the criteria and respective indicators with corresponding decision making procedure will lead to the priority of decentralised systems. The aggregation function for the decentralisation assessment should include all parameters which are of the importance the assessment of the system. Adoption of this procedure which will lead to the formation of clusters of indicators represented by the respective sustainability indicator will unable us to defined appropriate sustainability index which represent the quality of the system.

2 Limits Energy, water and environment are essential commodities, which are needed for the human life on our planet. In the development of our civilisation these three commodities have served as the fundamental resources for the economic, social and cultural development. In early days of human history it was believed that there are abundant resources of these commodities. With industrial revolution use of the resources has become the essential driving force for the economic and social development. With the increase of population and respective increase of the standard of living, the natural resources have become scarcity in some specific regions. With the further increase on the demand it has become evident that the scarcity of the natural resources may lead to the global dimension and effect human life on our planet. The Club of Rome was among the first to draw the world scale attention to the potential limits in availability of the natural capital on our planet. Energy crises in 1972 and 1978 have focussed attention of our community in large to investigate the limits in energy resources [9]. This was a moment when our society through the different institutions has launched programs aimed to investigate global scarcity of natural resources on our planet. It has become obvious that modern society has to adapt a new philosophy in its development, which has to be based on the limited natural resources.

2.1 Energy Boltzman [10] one of the Father of modern physical chemistry, wrote, in 1886, that the struggle for life is not a struggle for basic elements or energy, but a struggle for the availability of negative entropy in energy transfer from the hot Sun to the cold Earth. In fact, life on the Earth requires a continuous flux of negative entropy as the result of the solar energy captured by photosynthesis [11]. The Sun is an enormous machine that produces energy by nuclear fusion and offers planet Earth the possibility of receiving large quantities of negative entropy. Every year the Sun sends 5.6 × 1024 J of energy to the Earth and produces 2 × 1011 tons of organic material by photosynthesis. This is equivalent to 3 × 1021 J/yr. Through the billions of years since the creation of the planet Earth this process has led to the accumulation of an enormous energy in form of different hydrocarbons. Most of the fossil fuels belong

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N.H. Afgan Table 1 Assessed energy resources

Oil Gas Coal

Total 109 toe

CPE (%)

North America (%)

Latin America (%)

West Europe (%)

Africa (%)

AsiaPacific (%)

Middle East (%)

95 85 530

11.5 41.5 46.6

4.9 8.3 26.6

13.5 3.7 0.6

3.2 3.5 9.8

7.9 6.1 7.5

2.7 6.2 8.9

56.3 26.7 0.00

to the type of material where molecular binding is due to Van der Waals potential between every two molecules of the same material. Mankind’s energy resources rely heavily on the chemical energy stored in the fossil fuel. Table 1 shows assessed energy resources [12, 13]. Energy and matter constitute the earth’s natural capital that is essential for human activities such as industry, amenities and services in our natural capital as the inhabitants of the planet earth may be classified as: • Solar capital (provides 99% of the energy used on the Earth) • Earth capital (life support resources and processes including human resources) These, and other, natural resources and processes comprise what has become known as ‘natural capital’ and ‘it is this natural capital that many suggest is being rapidly degraded at this time’. Many also suggest that contemporary economic theory does not appreciate the significance of natural capital in techno-economic production. All natural resources are, in theory, renewable but over widely different time scales. If the time period for renewal is small, they are said to be renewable. If the renewal takes place over a somewhat longer period of time that falls within the time frame of our lives, they are said to be potentially renewable. Since renewal of certain natural resources is only possible due to geological processes, which take place on such a long time scale that for all our practical purposes, we should regard them as non-renewable. Our use of natural material resources is associated with no loss of matter as such. Basically all earth matter remains with the earth but in a form in which it cannot be used easily. The quality or useful part of a given amount of energy is degraded invariably due to use and we say that entropy is increased. The abundant energy resources at the early days of the industrial development of the modern society have imposed the development strategy of our civilization to be based on the anticipated thinking that energy resources are unlimited and there are no other limitations, which might affect human welfare development. It has been recognized that the pattern of the energy resource use has been strongly dependent on the technology development. In this respect it is instructive to observe the change in the consumption of different resources through the history of energy consumption. Worldwide use of primary energy sources since 1850 is shown in Fig. 2 [14, 15].

Sustainability Concept for Energy, Water and Environment Systems

Evolution of market share (log F/1-F)

10

453

2

10

1

Natural gas

Coal

Nuclear energy

Wood

10

0

Solar or fusion

–1 10 Oil –2 10 1850

1900

1950

2000

2050

2100

Year

Fig. 2 Market penetration of primary energy sources

F is the fraction of the market taken by each primary-energy source at a given time. It could be noticed that two factors are affecting the energy pattern in the history. The first is related to the technology development and, the second, to availability of the respective energy resources. Obviously, this pattern of energy source use is developed under constraint immanent to the total level of energy resources consumption and reflects the existing social structure both in numbers and diversity [16–18]. The world energy consumption is shown in Fig. 3.

Fig. 3 World energy consumption

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Looking at the present energy sources consumption pattern, it can be noticed that oil is a major contender, supplying about 40% of energy. Next, coal supply is around 30%, natural gas 20% and nuclear energy 6.5%. This means that current fossil fuel supply is 90% of the present energy use. In the last several decades our civilization has witnessed changes, which are questioning our long-term prospect. Fossil fuel, non-recyclable is an exhaustible natural resource that will be no more available 1 day. In this respect it is of common interest to learn how long fossil fuel resources will be available, as they are the main source of energy for our civilization. This question has attracted the attention of a number of distinguished authorities, trying to forecast the energy future of our planet. The Report of the Club of Rome “Limits to Growth”, published in 1972 was among the first ones, which pointed to the finite nature of fossil fuel. After the first and second energy crisis the community at large has become aware of the possible the physical exhaustion of fossil fuels. The amount of fuel available is dependent on the cost involved. For oil it was estimated that proved amount of reserves has, over past 20 years, levelled off at 2.2 trillion of barrels produced under $ 20 per barrel. Over the last 150 years we have already used up one-third of that amount, or about 700 billion of barrels, which leaves only a remaining of 1.5 trillion of barrels. If compared with the present consumption, it means that oil is available only for the next 40 years. Figure 4 shows the ratio of the discovered resources to the yearly consumption for the fossil fuels. From this figure it can be noticed that coal is available for the next 250 years and gas for the next 50 years. Also, it is evident that as much as the fuel consumption is increasing, new technologies aimed to the discovery of new resources are becoming available, leading to a slow increase of the time period for the exhausting of the available energy sources.

230

Coal

220 Natural Gas

Years

60 50 40

Oil

30 20

Fig. 4 Residual life forecast of energy resources

0 1945

1955

1965

1975 Year

1985

1990

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Nevertheless, whatever is the accuracy of our prediction methods and models, it is obvious that any inaccuracy in our calculation may affect only the time scale but not the essential understanding that the energy resources depletion process has begun and requires the human action before adverse effects may irreversibly enforce [20].

2.2 Environment It can be noticed that each one of the energy resources has become significantly scarcer during the decade of the 1970s. The situation reversed itself during the 1980s. The change, that took place, has implications for the future economic growth to the extent resources scarcity and economic growth are interrelated, even if it was not proved that short term energy resources scarcity fluctuation has substantial implication on the long term economic growth. It has become obvious the need for an active involvement in allocating scarce, non-renewable energy resources and its potential effect on the economic growth. Primary energy resources use is a major source of emissions [21–24]. Since fossil fuels have demonstrated their economic superiority, more than 88% of primary energy in the world in recent years has been generated from fossil fuels. However, the exhaust gases from combusted fuels have accumulated to an extent where a serious damage is being done to the world global environment. The accumulated amount of CO2 in atmosphere is estimated at about 2.75 × 1012 ton. The global warming trend from 1900 to 1997 is shown in Fig. 5 [25]. The future trend of the carbon dioxide concentration in the atmosphere can be seen from the Fig. 6. It is rather obvious that the further increase of the CO2 will lead to disastrous effects to the environment. Also, the emission of SO2 , NOx and suspended

Temperature deviation From 1950 - 1990 mean

0.6 0.4 0.2 0 –0.2 –0.4 –0.6 –0.8 1850

1870

1890

Fig. 5 Global warming trend 1900–1990

1910

1930

1950

1970

1990

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N.H. Afgan

20.000 18.000

Developing Countries

16.000

CHINA

14.000

INDIA USA

12.000

JAPAN

10.000

NIS

8.000

Eastern Europe

6.000

EU

4.000 2.000 0 1990

2005

2030

2050

Fig. 6 Forecast for CO2 emission

particulate matters will substantially contribute to exasperate the effect on the environment. In a world scale, coal will continue to be a major source of fuel for the electric power generation. Many developing countries, such as China and India, will continue to use inexpensive, abundant, indigenous coal to meet growing domestic needs. This trend greatly increases the use of coal worldwide as economy in the other developing countries, continues to expand. In this respect the major long-term environmental concern about coal use has changed from acid rain to greenhouse gas emissions – primarily carbon dioxide from combustion. It is expected that coal will continue to dominate China’s energy picture in the future. The share of coal, in primary energy consumption is forecast to be no less than 70% during the period 1995–2010. In 1993 China has produced a total of 1.114 billion tons of coal, in 2000 it is planned 1.5 trillion and in 2010 it will be 2.0. Since China is the third largest energy producer in world, after USA and Russia its contribution to the global accumulation of the CO2 will be substantial if the respective mitigation strategies will not be adopted. The example of China is instructive in the assessment of the future development of developing countries and their need for accelerated economic development.

2.3 Water In this part sustainability of desalination systems, essential component of humanmade or built capital is discussed with respect to its important contribution to life support systems. Figure 7 shows the distribution of the global stock of water [26, 27].

Sustainability Concept for Energy, Water and Environment Systems Fig. 7 Global stock of water

457

EARTH'S TOTAL STOCK OF WATER Fresh water (2.5%)

Polar ice caps (70%)

On and under the earth's surface (30%)

Less than 1% of the world's fresh water (about 0.007% of the total water stock of the earth) is accessible for direct human use. (Lakes, rivers, reservoirs, and accessible shallow underground sources) Fresh water lakes 0.009%

Saline lakes and inland seas 0.008%

Soil water 0.005 %

Atmosphere 0.001%

Stream channels 0.0001%

Ninety-seven point-five percent of the total global stock of water is saline and only 2.5% is fresh water. Approximately 70% of this global freshwater stock is locked up in polar icecaps and a major part of the remaining 30% lies in remote underground aquifers. In effect, only a miniscule fraction of the freshwater available (less than 1% of total freshwater, or 0.007% of the total global water stock) in rivers, lakes and reservoirs is readily accessible for direct human use. Furthermore, the spatial and temporal distribution of the freshwater stocks and flows is hugely uneven. Hydrologists estimate the average annual flow of all the World’s rivers to be about 41,000 km3 /yr. less than a third of this potential resource can be harnessed for human needs. This is further reduced by pollution such as discharges from industrial processes, drainage from mines and leaching of the residues of fertilizers and pesticides used in agriculture. The World Health Organization (WHO) has estimated that 1,000 m3 per person per year is the benchmark level below which chronic water scarcity is considered to impede development and harm human health. Several countries are technically in a situation of water scarcity, i.e. with less than 1,000 m3 of renewable water per year per head of population. Water shortage is predicted to increase significantly, mainly as a result of increase in population. The Dublin Statement of January 1992 on Water and Sustainable Development and the subsequent Rio Earth Summit Agenda 21, Chap. 18, Protection of the quality and supply of freshwater resources, are closest to the present context since desalination augments fresh water resources. Chapter 30 of Agenda 21 is also important in the context of desalination since it draws the attention of leaders of business and industry including transnational corporations, and their representative organizations in general, to their critical role in helping the world achieve the goals for sustainable development. Desalination systems are of paramount importance in the process of augmenting fresh water resources and happen to be the main life support systems in many arid

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regions of the world. The world has seen a 22-fold increase in desalination capacity since 1972 and the figure continues to rise. In 1997 the total desalination capacity, was 22,730,000 m3 of fresh water per day. That represents a doubling in global capacity over 10 years and a 22-fold increase over 25 years. Yet, desalinated seawater is only about one thousandth of the fresh water used worldwide. Desalinated water costs several times more than the water supplied by conventional means. The countries in the Arabian Gulf Region heavily subsidize the costs to render it affordable. In some of these countries, water is subsidized so heavily that users make little effort to curb their use. Water consumption would be greatly reduced if the price were closer to the true cost of production.

3 Sustainability Definitions Lately, in a number of years “sustainability” has become a popular buzzword in the discussion of the resources use and environment policy. Before any further discussion of the subject, it is necessary to define and properly assess the term we are going to use. So, what is sustainability? Among the terms most often adapted are the following. (a) for the World Commission on Environment and Development (Brundtland Commission) [28] “Development that meets the needs of the present without compromising the ability of future generation to meet their own needs” (b) for the Agenda 21, Chap. 35 [29] “Development requires taking long-term perspectives, integrating local and regional effects of global change into the development process, and using the best scientific and traditional knowledge available” (c) for the Council of Academies of Engineering and Technological Sciences [30] “It means the balancing of economic, social, environmental and technological consideration, as well as the incorporation of a set of ethic values” (d) for the Earth Chapter [31] “The protection of the environment is essential for human well-being and the enjoyment of fundamental rights, and as such requires the exercise of corresponding fundamental duties” (e) Thomas Jefferson, Sept. 6 1889 [32] “Then I say the earth belongs to each generation during its course, fully and in its right no generation can contract debts greater than may be paid during the course of its existence” All five definitions stand for the emphasis of specific aspect of sustainability. Definition (a) and (e) implies that each generation must bequeath enough natural capital to permit future generations to satisfy their needs. Even if there is some ambiguity in this definition, it is meant that we should leave our descendants the ability to survive and meet their own needs. Also, there is no specification in what form resources are to be left and how much is needed for the future generation, because it is difficulty to anticipate the future scenarios.

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Definitions (b) and (c) are more politic ply for the actions to be taken at global, regional and local levels in order to stimulate United Nation, Government and Local Authorities to plan development programs in accordance with the scientific and technological knowledge. In particular it should be noticed in definition (c) the ethic aspect of the future development actions to be taken to meet sustainable development. Definition (d) is based on the religious believes playing the responsibility and duties toward the nature and Earth. In this respect it is of interest to enlighten that the Old Testimony in which the story of creation is told is a fundamental basis for Hebrew and Christian doctrine of the environment. In the world of Islam, nature is the basis for human consciousness. According to the Koran, while humankind is God’s vice-regent on Earth, God is the Creator and Owner of nature. But human beings are his trusted administrators, they ought to follow God instructions, that is, acquiesce to authority of Prophet and to the Koran regarding nature and natural resources.

4 Sustainability Concept Definition Sustainable development encompasses economic, social, and ecological perspectives of conservation and change. In correspondence with the WCED, it is generally defined as “development that meets the needs of the present without compromising the ability of future generations to meet their own needs.” This definition is based on ethical imperative of equity within and between generations. Moreover, apart from meeting; basic needs of all; sustainable development implies sustaining the natural life-support systems on Earth, and extending to all the opportunity to satisfy their aspirations for a better life. Hence, sustainable development is more precisely defined as ‘a process of change in which the exploitation of resources, the direction of investments, the orientation of technological development, and institutional change’ are all harmony and enhance both current and future potential to meet human needs and aspiration [33, 34]. This definition involves an important transformation and extension of the ecologically based concept of physical sustainability to the social and economic context of development. Thus, terms of sustainability cannot exclusively be defined from an environmental point of view or basis of attitudes. Rather, the challenge is to define operational and consistent terms of sustainability from an integrated social, ecological, and economic system perspective. The main issue deals with the positive aspect of sustainable development; that is, the feasibility problem of “what can be sustained” and “what kind of system we can get”. It requires one to understand how the different systems interact and evolve, and how they could be managed. Formally, this can be represented in a dynamic model by a set of differential equations and additional constraints. The entire set of feasible combinations of social, economic and ecological states describes the inter-temporal transformation space of the economy in the broadest sense [35–37].

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5 Sustainability Measurement Measuring sustainability is a major issue as well as a driving force of the discussion on sustainability development. The tool development that reliable measure sustainability is a prerequisite for identifying non-sustainable processes informing design-makers of the quality of products and monitoring impacts to the social environment. The multiplicity of indicators and measuring tools being developed in this fast growing field shows the importance of the conceptual and methodological work in this area. The development and selection of indicators require parameters related to the reliability, appropriateness, practicality and limitations of measurement [38–42]. In order to cope the complexity of sustainability related issues for different systems the indicators have to reflect the wholeness of the system as well as the interaction of its subsystems. Consequently, indicators have to measure intensity of the interactions among elements of the systems and system and its environment. In this view, there is a need for the indicator sets related to the interaction processes that allow an assessment of the complex relationship of every system and its environment.

5.1 Characteristics of Effective Indicators Indicators can be useful as proxies or substitutes for measuring conditions that are so complex that there is no direct measurement. For instance, it is hard to measure the “quality of life in my town” because there are many different things that make up quality of life and people may have different opinions on which conditions count most. A very simple substitute indicator is “Number of people moving into the town compared to the number moving out.” Sustainability can be presented in the form of triangle pyramid, where every corner on bases represents one of efficiencies to be included in the assessment of any system. Fourth corner representing Sustainability Index. Figure 8 shows the three efficiency indicators of sustainability as three corners of a triangle and Sustainability

General Index of Sustainability

Eco-efficiency

Fig. 8 General index of sustainability

Socio-efficiency

Economic-efficiency

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Index. The Sustainability Index is obtained when a balance is found between the issues of all three efficiencies reflecting imposed constrains. In order to obtain Sustainability Index for the option under consideration the weighting coefficient for the efficiencies has to be determined. The decision-making theory is used to calculate weighting coefficients. In particular non-numerical constrains are generated to represent constrains between the criteria. The interactions between the three aspects of sustainability emphasise that sustainable development is not a static concept, which can be easily translated and quantified. It is a dynamic concept that is the result of a process of social learning involving many actors. For instance, in order to know what system is more sustained it is necessary to formulate and share visions about the value of non-economic elements like biodiversity or cultural heritage. And because visions and the underlying eco and social values change over time, it is imperative to take all three aspect of the sustainability including the process of social learning and the environment global change to be a continuous process. For the assessment of system the attention will be focused on following three efficiency definitions:

5.2 Economic Efficiency The traditional method for the assessment of systems is based on the econometric justification of the use of capital needed for unit production. This method has been essential basis for the decision-making procedure in selection of systems. It has proved to be a driving force for the development of economic welfare in the industrial society. One of the basic assumptions in this procedure was assumption of the abundant resource. With the development notion that the scarcity of resources is imposing limits to the use of resources it has been realised that beside the resources limits there are also other limits which play important role in the decision making process. Indicators for the economic efficiency assessment are: investment cost including material cost, fuel cost, thermal efficiency and operation and maintenance cost. These indicators are result of the optimisation procedure adopted for the with respective optimisation function and respective design parameter of the system.

5.3 Ecological Efficiency Following recognition of the effect of combustion products on the environment, it has been introduced a new indicators in the decision making procedure for the selection of the system. In this respect Kyoto Protocol has imposed local, regional and global limits of CO2 , which are to be followed in the design, operation and selection of new energy systems. This has lead to the development and introduction

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of indicator, which are of importance for the ecological aspects of the respective energy system. Indicators for the ecological efficiency assessment are concentration of the product species, which are, suppose to have adverse effect to the local, regional and global environment. The monitoring and assessment of those indicators, which are contribution to the general quality of the environment, can evaluate ecologic efficiency.

5.4 Social Efficiency Social aspect of any human endeavour is of paramount importance for the successful selection of possible options. Lately it has become evident that social aspect of any engineering system has become important part of the total quality of the system. In this respect criteria, which are designed to present assessment of social aspect of the system, are of the same importance as the economic and environment criteria. For the formulation of social criteria it is necessary to create a system of indicators of sustainable development, which provide reference for the respective type of the system and may be used in the numerical evaluation of the system. In order to meet this requirement, it is necessary to develop specific techniques for calculation of indicators, which are aimed to reflect social merits of the energy system. Indicators for the social efficiency assessment are: job opportunity, diversification of qualification, community benefits and local safety consequence. Job opportunity indicator is designed to take into a consideration number of job created by the respective system.

6 Sustainability Index Definition The decision making procedure comprise several steps in order to obtain mathematical tool for the assessment of the rating among the options under consideration [43–47]. The next step in the preparation of data for the multi-criteria sustainability assessment is aritimetization of the date. This step consists in the formation of particular membership functions q1 (x1 ), ..., qm(xm ). For every Indicator xi we have: (1) to fix two values MIN(i), MAX(i); (2) to indicate is the function qi (xi ) decreasing or increasing with argument xi increasing; (3) to choice the exponent’s value λ in the formula

qi (xi ) =

⎧ ⎪ ⎪ ⎨

⎪ ⎪ ⎩

0, if xi ≤ MIN(i), λ xi − MIN(i) , if MIN(i) < xi ≤ MAX(i), MAX(i) − MIN(i) 1, if xi > MAX(i)

for the increasing function qi (xi ).

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The functions q1 (x1 ) , . . . , qm (xm ) formation process being finished with a (j) (j) matrix qi , i = 1, . . . , m, j = 1, . . . , k, where an element qi is a value of ith particular criterion for jth option. In this analysis it assumed that the linear functions q1 (x1 ) , . . . , qm (xm ) are used. For q1 , q2 and q4 membership function the decreasing function are adapted. General indices method comprise formation of an aggregative function with the weighted arithmetic mean as the synthesizing function defined as Q (q; w) =

m

wi qi

i=1

where wi – weight-coefficients elements of vector w qi – indicators of specific criteria In order to define weight-coefficient vector the randomization of uncertainty is introduced. Randomization produces stochastic with realizations from corresponding sets of functions and a random weight-vector. It is assumed that the measurement of the weight coefficients is accurate to within a steps h = 1/n, with n a positive integer. In this case the infinite set of all possible vectors may be approximated by the finite set W(m, n) of all possible weight vectors with discrete components. For nonnumeric, inexact and incomplete information I = OI U II used for the reduction of the set W(m, n) of all possible vectors w to obtain the discrete components set W(I; n, m) is defined a number of constrain reflecting nonnumeric information about mutual relation among the criteria under consideration.

6.1 Multi-criteria Assessment of Energy Systems As the non-numerical information we will impose condition which will define mutual relation of the individual criteria This will give us possibility to introduce a qualitative measure between the criteria. As the example for the multi-criteria assessment of energy system we will take number of energy system options with respective values for the five indicators including economic, environment and social indices [46]. As constrain in this assessment several grope are formed giving priority to the specific indicator (Table 2). The group of cases are designed to give priority to the single indicator with other indicators having the same values. Each Case will represent a different set of the priority of criteria as they are used in the definition General Index of Sustainability. Among the Cases which are designed with the preference of single options are:

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N.H. Afgan Table 2 Energy system indicators

Coal Solar thermal Geothermal Biomass Nuclear PV solar Wind Ocean Hidro Gas

Efficiency (%)

Instalation (USD/kW)

Elect.cost (c/kWh)

CO2 (kgCO2 /kWh)

Area(km2 /kW)

43 15 8 1 33 10 28 3 80 38

1,000 3,500 2,500 2,500 2,300 4,500 1,100 10,000 2,000 650

5,4 17 8 14 4 75 7 25 8 4

0.82 0.1 0.06 1.18 0.025 0.1 0.02 0.02 0.04 0.38

0.04 0.08 0.03 5.2 0.01 0.12 0.79 0.28 0.13 0.04

6.1.1 Case 1 Efficiency > Investment = Elect. Cost > CO2 = Area This case reflects the priority given to the energy system efficiency criteria. As it is shown, the efficiency of systems with the different basic principles is not very realistic indicator to be used for the comparison of the system. This suggests that in the evaluation of efficiency criteria it would be better to use the relative value of the efficiency for each system. For example, for the heat conversion system the Carnot efficiency should be used as the absolute efficiency. Figure 9 presents Sustainable Index and Weighting Coefficient for the Case 1.

Weighting Coefficients

Fig. 9 CASE 1 sustainability index and weighting coefficients

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6.1.2 Case 2 Investment > Efficiency = Elect. Cost > CO2 = Area The change in priority from the efficiency criteria to the investment cost criteria has lead to the drastic change in the priority list. Gas, Wind and Coal energy systems form a single group with the General Index of Sustainability being marginally different among themselves. It is of interest to notice that the effect of single criteria can be so strong to bring into the picture different priority list. From the values for probability of dominance in this case it is visible that this case do not have high certainty. Figure 10 presents Sustainable Index and Weighting Coefficient for the Case 2.

Weighting Coefficients

Fig. 10 CASE 2 sustainability index and weighting coefficients

6.1.3 Case 3 Elect. Cost > Efficiency = Investment = CO2 = Area With priority given to the Electricity cost criteria we will obtain two groups of options. Namely, Gas, Wind, Coal, Hidro and Nuclear group. Geothermal, Solar Thermal, Biomass, PV solar and Ocean power plants make second group. Figure 11 presents Sustainable Index and Weighting Coefficient for the Case 3. 6.1.4 Case 4 CO2 > Efficiency = Investment = Elect. Cost = Area Environment criteria measured by CO2 is effecting only Coal and Biomass options. All other options are presented in the single group with marginal

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Weighting Coefficients

Fig. 11 CASE 3 sustainability index and weighting coefficients

differences. Figure 12 presents Sustainable Index and Weighting Coefficient for the Case 4 Even this analysis is based on limited number of cases taken into a consideration, it can be noticed that the priority on rating list is result of the respective relation among the criteria under consideration. It can be noticed that the option which is the first on the rating list is closely related to the respective indicator priority and its Weighting Coefficients

Fig. 12 CASE 4 sustainability index and weighting coefficients

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value. In the group of cases, it can be noticed that if the priority is given to the single criteria with the other criteria having respective value of indicators for individual option, it may effect the rating list of the options. If the efficiency criteria has been given priority there is changes in the rating list. In comparison to the single criteria rating and priority is obtained for Hidro, Coa, and Gas options. The same can be noticed with if priority is given to the other indicators. For the case if Investment Indicator has priority the Gas, Wind and Coal power plants are the first on the rating list of the options under consideration. For the case with Electricity cost indicator priority the first places on the priority list is obtained by Gas and Nuclear options. Also, if CO2 Production Indicator and Area Indicator, the gas and Nuclear power plants are rated on the first place in the rating list of options. Special Case is designed with criteria conduction defined introducing relation among individual Indicators Beside the changes on the first place on the rating list, it can be noticed that there are changes in the rating among options. Options with renewable energy power plants have gained higher place on the rating list in comparison with the case with equal weighting factor for all indicators.

7 Conclusions Sustainability assessment of power plants is immanent goal for the development of the future energy strategy. It imply the need to verify multi criteria analysis of potential options. In this respect it is of interest to introduce a new methodology for the evaluation power plant options taken into a consideration. The lecture was aimed to reveal potential possibility of the sustainability notion in meeting the present need of modern society. Starting from the present definition of the sustainability and showing their close relation to the historically old definition, it was proved that our human society has beard in mind the need for preservation of the commodity given to for the future generation to come. Sustainability is introduced as complex system property. With its multi dimension scope it require a new method for the evaluation of complex system. Energy system is typical example of complex system with multi-criteria assessment. In this respect the need for the respective methodology is visualised and introduced in this lecture. Demonstration of the method is presented for the specific number of energy system taking into a consideration number of criteria with respective indicators.

References 1. Kates RW et al (2001) Sustainability science. Science 292:641–642 2. Ravetz J (1996) Gallimard, scientific knowledge and its social problems. Transaction, New Jersey 3. Nicolis G, Prigogine I (1977) Self-organisation in non-equilibrium systems: from dissipative structure to order through fluctuation. John Wiley & Sons, New York

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4. Progogine I, Stengers I (1979) La novelle alliance, metamorphse la science. Gallimard, Paris 5. van Kruoonenberg HH (1994) Energy for sustainable development: post Rio challenges and Dutch response. Resour Conserv Recycl 12 (1–2):vii–ix 6. Foreign Policy (2004) Managing Globalisation, Foreign Policy Magazine, March, 2004 7. Fukuda S et al (2002) A democratisation 21th century. Courier ACP-EU, No. 194, Sep–Oct, 2002 8. Decentralisation, http://www.fact/index.com 9. Medows D, Meadows H, Randers DL, Behrens J (1972) The limits of growth. Universe Book, New York 10. Botzman L (1896) Vorlesung uber Gas Theorie, vol 1. Johann Ambrosius Barth, Leipzig 11. Ohta T (1994) Energy technology. Elsevier Science, Oxford 12. Marchetti C (1979) Check on the earth – capacity for man. Energy 4:1107–1117 13. Master CD (1987) World resources of crude oil, natural gas, Bitumen’s and shale oil. Topic 25. World Petroleum Congress Publ., Houston 14. Marchetti C (1991) The “historical instant” of fossil fuel, symptom of sick world. Int J Hydrogen Energy 16:563–575 15. Marchetti C (1980) Society as learning system. Techno Forecast Soc Changes 18:267–282 16. Arnold MStJ, Kersall GJ, Nelson DM (1997) Clean efficient electric generation for the next century: British coal toping cycle.. In: Carvalho MG, Fineland WA, Lockwood FC Papaloupolos Ch (ed.) Combustion technology for clean environment 17. Mazzuracchio P, Raggi A, Barbiri G (1996) New method for assessment the global quality of energy system. Appl Energy 53:315–324 18. Noel D (1995) A recommendation of effect of energy scarcity on economic growth. Energy 2:1–12 19. Farinelli U (1994) Alternative energy sources for the third world: perspective, barriers, opportunity, pontifical academy of science. Plenary Session 25–29 October 20. Keatiny M (1993) Agenda for change. Center for Our Common Future, Geneva 21. Mackey RM, Probert SD (1995) National policy for achieving thrift, environmental protection, improved quality of life and sustainability. Appl Energy 51:243–367 22. Price T, Probert SD (1995) An energy and environmental strategy for the Rhymney value, south walls. Appl Energy 51:139–195 23. Mackey RM, Probert SD (1995) NAFTA countries energy and environmental interdependence. Appl Energy 52:1–33 24. Mackey RM, Probert SD (1995) Energy and environmental policies of the developed and developing countries within the evolving Oceania and south-east Asian trading block. Appl Energy 51:369–406 25. Hought RA, Woodwell GM (1989) Global climatic change. Sci Ame 260:36–44 26. Al Gobaisi D (2000) Sustainability of desalination systems. EURO Course on Sustainability Assessment of Desalination Plants, Vilamore 27. Al Gobaisi D (1998) Sustainable use of our planetary natural capital for life support on the earth. IEEE systems, man and cybernetics conference, Tunisia, 1998 28. Report of the United Nation Conference on Environment and Development (1992), Vol. 1, Chapter 7. June, 1992 29. UN (1992) Agenda 21, Chapter 35, Science for Sustainable Development, United Nations Conference on Environment and Development, Rio de Janeiro 30. Council of Academies of Engineering and Technological Sciences (2005) CAETS Statement: oceans and the world’s future. Cairns Austrila 31. The Earth Chapter: a contribution toward its realization, Franciscan Centre of Environment Studies, Roma, 1995 32. Jenkinson CS The quality of Thomas Jefferson’s soul. White House Library USA 33. Annan KA (2000) We, the peoples of United Nations in the 21st Century. United Nations, New York 34. Kates RW et al (2001) Sustainability science. Science 292:641–642, 27 April

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35. National Research Council, Board on Sustainable Development (1999) Our common journey: transition toward sustainability. National Academic Press, Washington, DC 36. Watson R et al (1998) Protecting our planet, securing our future. United Nations Environmental Programme, Nairobi 37. Hammond GF (July 2000) Energy, environment and sustainable development: A UK perspective. Trans ICHemE B 78:304–323 38. Binswangen M (2001) Technological progress and sustainability development: what about the rebound. Ecol Econ 36:119–132 39. Pemberton M, Ulph D (2001) Measuring income and measuring sustainability. Scand J Econ 10(1):25–40 40. Indicators of Sustainable Engineering, Physical Sciences Research Council, Dec 1996 41. D’Angelo E. Perrella G. Bianco R. Energy efficiency indicators of Italy. ENEA Centro Ricerche Casaccia, Roma, RT/ERG/96/3 42. Cafier G, Conte G (1995) Rome as a sustainable city. Agency for a Sustainable Mediterranean Development 43. Afgan NH, Carvalho MG (2000) Sustainability assessment method for energy systems. Kluwer Academic Publisher, New York 44. Afgan NH, Al Gobaisi D, Carvalho MG, Cumo M (1998) Energy sustainable development. Renewable Sustain Energy Rev, 2:235–286 45. Afgan NH, Carvalho MG, Hovanov AN (2000) Energy system assessment with sustainability indicators. Energy Policy 28:603–612 46. Afgan N, Carvalho MG (2002) Multi-criteria assessment of new and renewable energy power plants. Int J Energy 27:739– 755 47. Afgan HN, Carvalho GM (2006) Quality, sustainability, indicators of energy systems. Begell House Publisher, New York

Energy and Sustainable Development: Environmental Impacts of Energy Use in Africa Muawya Ahmed Hussein

Abstract More than half of the world’s population relies on dung, wood, crop waste or coal to meet their most basic energy needs [15]. In 1992, 24 million tones of charcoal were consumed worldwide. Developing countries account for nearly all of this consumption, and Africa alone consumes about half of the world’s production. Charcoal production has increased by about a third from 1981 to 1992, and is expected to increase with the rapidly growing population in the developing world. Despite the cooking advantages of charcoal and charcoal’s ranking on the cooking ladder, this preliminary review suggests that charcoal may be far more damaging to the environment than the less preferable biomass fuels, biomass residues and fuelwood [3]. This study indicates that charcoal is problematic from energy, environmental and social perspective and is likely to be used as long as the feedstock supply and the demand from impoverished people in the developing world exist. The potential environmental problems associated with charcoal use are exposure of users to high carbon monoxide concentration levels during cooking and emission of relatively large quantities of nitrogen oxides. As a consequence of the fastgrowing energy requirements and the increasing use of low-grade domestic fuels, air pollution has increased considerably in recent years in Africa [14]. Keywords Africa · Coal energy · Consumption · Energy · Production

1 Introduction The African continent depends on wood and charcoal for cooking and heating homes. In 2000, nearly 470 million tons of wood were consumed in homes in sub-Saharan Africa in the form of firewood and charcoal, more wood per capita than any other region in the world. More than 1.6 million people, primarily women and children, die prematurely each year worldwide (400,000 in sub-Saharan Africa) M.A. Hussein (B) University of Dhofar, Salalah, Oman e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_42,

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from respiratory diseases caused by the pollution from such fires [11, 12]. The study finds that smoke from wood fires used for cooking will cause an estimated 10 million premature deaths among women and children by 2030 in Africa and release about 7 billion tons of carbon in the form of greenhouse gases to the environment by 2050, about 6% of the total expected greenhouse gases from the continent. Precise statistics are very difficult to obtain for traditional energy production and use, as they take place largely outside the formal commercial economy. One of the challenges many African countries face is to develop more reliable energy data to serve as a basis for policy formulation and investment, a challenge being taken up by the recently formed African Energy Commission. The problem is made particularly acute where dependence on traditional fuels is high and commercial energy use correspondingly low. Other problems associated with traditional fuels are their health impacts (particularly for women) [1], environmental degradation and the time unavailable for more productive activities because of the long hours involved in collection. Africa’s relatively low use of commercial energy is not a consequence, however, of poor endowment with energy resources. While Africa’s energy resources may not be dominant on a world-scale, they are physically more than adequate to meet near and even medium-term needs.

1.1 Energy and Environment in Africa Most social and economic activities require the use of energy in various forms and quantities. Energy is as important to households for basic uses, such as cooking, heating and lighting as it is to large industries for production of heavy goods or to fuel automobiles. The world consumed, in 2002, a staggering amount of 7,095 million tons of Oil Equivalent (MTOE) in the form of oil, natural gas, coal, electricity and combustible renewables and waste. For its development, the world thirst for energy is growing at a faster rate than ever. According to recent BP statistics, energy consumption grew by 4.3% between 2003 and 2004. In countries, mostly in the developing world, where the availability of energy is limited or where energy is economically unaffordable to most households or the society in general, development is seriously impaired, and growth limited. Energy is thus an essential ingredient for socioeconomic development. Rightfully then, issues of energy supply, access and security, as well as issues related to the impact of the consumption and production patterns of energy on the world sustainability, have been at the core of the world attention for decades.

2 Statistical Overview of Energy Resources in Africa Africa is relatively well endowed with energy resources. In 2004, its proved oil, gas and coal reserves were 9.4, 7.9 and 5.54% respectively of the world total, compared to 8.5, 4 and 2.19% respectively for South and Central America, taken

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Table 1 Primary energy supply by fuel in Africa in 2002 Fuel share of total primary energy supply (Total 539.846 MTOE)-2002 Kind of fuel energy

Share (%)

Combustibles renewable and waste Coal Crude oil Gas Hydro Nuclear Geothermal solar

47 16.46 24.28 10.40 1.30 0.56 0

together. The hydropower potential of the continent amounts to 13% of the world. In Africa, energy is produced mainly from biomass (47%), oil (24.28%), coal (16.5%), gas (10.4%), and other renewable sources, such as large and small hydro damps, solar, and geothermal sources (1.3%) (Table 1). However, Africa is a vast continent with 53 countries and energy resources are unevenly regionally located. Most of the hydropower potential lies in central and western Africa, oil and gas resources are located in the western and northern parts of the continent, coal reserves are concentrated almost exclusively in Southern Africa, and geothermal is only being developed in eastern Africa. It is apparent from Figs. 1 and 2 that 68% of all proved natural gas reserves of the continent is located in two countries (Nigeria and Algeria), while more than 74% of proved oil reserves is found in Nigeria and Libya. These three countries hold the large majority oil and natural gas reserves of the continent. Because of its geographical location across the equator, Africa has abundant solar irradiation ranging from 5 to 7 kWh/m2 , all year round, and it enjoys a relatively strong wind power potential in Northern, Southern and Eastern Africa. Finally, the continent has an estimated geothermal energy potential of 9,000 MW

Fig. 1 Proved Natural Gas Reserves in Africa, in 2004

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Fig. 2 Proved Oil Reserves in Africa, 2005

in the Rift Valley area in East Africa. Based on these potential and reserves, it could have been possible to achieve a well-balanced energy generation mix on the continent. However, due to numerous barriers this is not currently the case [5].

3 Statistical Overview of the Energy Consumption and Production Africa exports more of its energy than it consumes. In the last decade, oil, natural gas, and electricity production have increased by 48.1, 24.3 and 32.8% respectively, while coal production increased much less. In absolute terms, oil remains the largest source of modern energy in Africa, with production reaching 441 MTOE in 2004, which represents 11.4% of the world total. In Southern Africa, efforts for improving the energy resource mix through more import of electricity within the Southern African Power Pool, led to a slower increase in coal production. Despite its relatively important energy resources, Africa generates only 3.1% of the world electricity, less than any other region of the world. This share has not changed for the last 10 years and most analysts forecast that it will remain the case for the next 15 years, though production of fuels used for electricity will continue to grow steadily. Electricity is generated mainly from coal (46%), gas (23%), hydro (18%), oil (11%) and nuclear (2%) (Table 2). Other renewable sources such as solar, Table 2 Electricity generation in Africa by fuel, 2002

Kind of source

Percentage

Coal Gas Hydro Oil Nuclear

46 23 18 11 2

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geothermal, wind, etc. play an insignificant role despite some noteworthy initiatives such as the 140 MW wind farms in Egypt. On the continent there are strong disparities among countries: South Africa alone generates close to half of the total African electricity. Many African countries, mostly in SSA with the exception of South Africa, rely heavily on hydropower (70–80%) for their electricity generation. With 13.1% of the world’s total population, Africa consumes only 5.5% of the world energy. The per capita energy consumption of 0.5 TOE, far lower than the world average of 1.2 TOE per capita, makes the continent lag behind all the others in energy use. Energy consumption in Africa is largely dominated by combustible renewable resources (biomass, animal wastes, municipal and industrial wastes). Energy from biomass accounts for more than 30% of the energy consumed in Africa and more than 80% in some countries such as Burundi (91%), Rwanda and Central Africa Republic (90%), Mozambique (89%), Burkina Faso (87%), Benin (86%), Madagascar and Niger (85%). Biomass constitutes the main energy resource for the large majority of African households for cooking, drying and space heating. Several million people are involved in the production, distribution and sale of fuelwood and charcoal. From 1994 to 2004, primary energy consumption increased by 24% . All African countries consume some oil mainly for transportation, electricity generation and industries regardless of whether they have refinery capacities or not. Gas consumption, however, is limited mostly to the few countries that produce it, such as Algeria, Libya, Egypt, Tunisia, Nigeria, Cote d’Ivoire, or those that are located in close proximity with them. This is explained by the lack of transboundary pipeline infrastructure for the transportation of natural gas. South Africa, with its large reserve of coal, is the only country with a significant use of coal. In 2002, the continent electricity consumption was only 514 kWh per capita, lowest of all other world regions. The very limited availability of electricity combined with affordability issues to electricity services in most countries in Africa, have made access to electricity by most Africans very elusive. While electricity access data varies widely depending on the reporting sources, IEA data reports rates ranging from 70% to over 94% in Northern Africa, and an average of 23% in subSaharan Africa, in 2002. These numbers do not reflect the large disparities between countries (for instance less than 4% in Uganda compared to 66% in South Africa or 100% in Mauritius), and between urban and rural areas, where in the latter, rates can be as low as 1%.

4 Environmental Impact of Energy Use Environmental problems associated with oil-related activities are numerous. For example, in shipping ports, where the transshipment of oil takes place, the chronic release of oil into the water through ship leakage, ship maintenance or mishandling is a continuing dilemma. This problem is often ignored, despite the fact that its cumulative effects may have significant effects on the surrounding ecosystem [9]. Natural habitats, such as seabeds, wetlands and mudlands, which are increasingly

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recognized as fundamental elements of a country’s natural environment and economic resource base, are often located near or in maritime port locations. As world oil demand increases, oil-producing countries in sub-Saharan Africa are increasing their production and export capacities, leading to an increasing volume of oil being shipped through pipelines and via tankers. As shipping lanes become more congested, the chances of spills and accidents increase, putting the environment at greater risk. A recent example of growing global awareness towards the environmental impacts associated with oil exploration and development was the controversy surrounding the World Bank’s approval of the Chad-Cameroon Pipeline Project in June 2000. The project, led by ExxonMobil Corp., is one of the largest construction ventures in sub-Saharan Africa ever ($3.7 billion), and is expected to bring Chad $80–$100 million a year (about half of Chad’s budget) and Cameroon $20 million a year. Plans for the Chad-Cameroon Pipeline Project include development of Chad’s Doba oil fields, construction of a 673-mile pipeline from the Doba oil fields to Cameroon’s Atlantic coast at Kribi, installation of an offshore floating storage and offloading vessel, and a submarine pipeline from the Atlantic coast to the vessel [10]. Construction on the pipeline began in 2000 and the first barrels of oil were pumped through in July 2003. Despite its recent success, the project has been the target of vehement protests from environmental and human rights groups, which argue that the project would harm wildlife (black rhinos, chimpanzees, gorillas and elephants) in the rainforests which the pipeline would pass through, dislocate inhabitants along the pipeline route, and further increase civil strife through profiteering by local officials.

5 Energy Use and Carbon Emissions Energy consumption in sub-Saharan Africa varies dramatically with noncommercial fuels, such as wood and animal waste, dominating fuel consumption. The use of wood for fuel is predominant in both rural and urban locations – accounting for approximately 70% of total energy use and 90% of household energy use in subSaharan Africa. Africa is the world’s largest consumer of biomass energy (firewood, agricultural residues, animal wastes, and charcoal), calculated as a percentage of overall energy consumption. In 2001, total commercial energy consumption in subSaharan Africa measured 2.90 quadrillion British thermal units (Btu). Nigeria consistently leads sub-Saharan Africa in commercial energy consumption. In 2001, Nigeria consumed 0.92 quadrillion Btu (quads), 32% of all energy consumed in the region. Of the remaining countries, Zimbabwe registered the next highest level with 0.24 quads of energy consumed. Ghana followed close behind with consumption of 0.17 quads. These numbers are generally higher than in most of sub-Saharan Africa, which averaged a low 0.06 quads in 2001. Although domestic demand for energy consumption in sub-Saharan Africa is growing rapidly, consumption levels remain well below world averages.

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Per capita energy-related carbon emissions in sub-Saharan Africa countries vary greatly, in part because certain countries tend to consume more carbon intensive fuels than others. For example, in 2001 Botswana emitted 0.79 metric tons of energy-related carbon per person, more than five times the sub-Saharan per capita rate. Botswana has relatively abundant sources of cheap coal and therefore burns more coal for energy use than most other sub-Saharan nations. The carbon content of coal is much higher than other fossil fuels such as oil and natural gas, and is therefore responsible for the higher rates of carbon emissions among coal-burning countries [6]. Although the average level of per capita energy-related carbon emissions in sub-Saharan Africa (0.09 metric tons) is expected to increase as a result of economic and urban expansion in coming years, per capita energy-related carbon emission levels are expected to continue to remain well below the world average of 4 metric tons per person.The flaring of natural gas in Nigeria, Angola, Cameroon, and Gabon has proven to be a significant source of carbon emissions in sub-Saharan Africa. In the process of oil production, natural gas is released. Because gas infrastructure in sub-Saharan Africa is extremely limited, this “associated” gas is often burned off, or “flared,” rather than captured for use. Not only does this waste a potentially valuable energy source (the World Bank estimates that every day Africa flares gas equivalent to 12 times the energy that the continent uses), but it releases carbon dioxide directly into the atmosphere. Nigeria is working on developing a gasto-liquids industry and expanding their liquefied natural gas trade to reduce flaring. The government has set a deadline of 2008 for the termination of all gas flaring, with heavy fines for companies that do not comply.

6 Deforestation and Desertification Central Africa is home to one of the world’s largest rain forests, and serves as one of the world’s most important carbon sinks. Carbon sinks capture carbon dioxide from the atmosphere, thus reducing global carbon dioxide levels. Deforestation is one of the most pressing environmental problems faced by almost all sub-Saharan African nations, with one of the primary causes of deforestation being wood utilization for fuel. Many sub-Saharan countries have had over three quarters of their forest cover depleted, and it is estimated that if current trends continue, many areas, especially that of the Sudano-Sahelian belt, will experience a severe shortage of fuelwood by 2025. Deforestation also has negative implications for the local environment (increased erosion and loss of biodiversity) [4]. The highest rates of deforestation occur in areas with large growing populations such as the East African Highlands and the Sahel. The harvesting of wood for use as fuel also has contributed to the problem of desertification. Desertification is the term used to describe the loss of soil fertility and structure to the extent that its ability to support plant life is severely compromised. In sub-Saharan Africa, where desertification has its greatest impact, forest areas are often cleared in order to harvest fuelwood and for agricultural use.

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Traditional farming practices, which tend to be inefficient and land-intensive, significantly degrade scarce arable land – the single most important natural resource in sub-Saharan Africa. Desertification can lead to downstream flooding, reduced water quality and sedimentation in rivers and lakes. It also can lead to dust storms, air pollution and health problems such as respiratory illnesses and allergies. All 47 countries which comprise sub-Saharan Africa have signed and ratified the Convention to Combat Desertification, which entered into force in 1997.

7 Hydropower and Other Renewable Energy Hydropower currently is experiencing a renaissance in many sub-Saharan countries especially given rising oil prices. Hydroelectric power is the only significant grid-connected renewable energy source in sub-Saharan Africa, and in several of the region’s countries, hydroelectricity’s share of total installed electric capacity is quite high [8]. In Ivory Coast, the Democratic Republic of Congo, Ethiopia, Mozambique, and Zambia, the vast majority of on-grid electricity generation comes from hydropower. Many new projects are planned or are under construction in main hydro areas such as the Congo River, the Nile River, and the Zambezi River. Many argue that because large portions of rural populations often are not hooked up to the energy grid (95% of the population in Uganda, for example), large and expensive projects do not solve these countries’ energy problems. Many believe that alternative energy sources such as wind, geothermal, and solar power are the key to solving the massive energy deficits in sub-Saharan Africa. Several countries in the region have made considerable advances in the use of photovoltaic (PV), or solar power. Zimbabwe plans to utilize solar power to electrify over 500 districts and rural service points. Each site would receive solar systems with generation capacity of either 100 kW or 500 kW These solar systems can also be used for small scale projects such as milling grain, pumping water, and operating cookstoves. Zambia also is developing a program of electrification by solar energy in order to accelerate its rural electrification program. In Kenya, a series of similar programs has resulted in the installation of more than 20,000 small-scale PV systems since 1986. These PV systems now play a prominent role in decentralized, sustainable electrification.

8 Conclusion In Africa, environmental concerns are strongly tied to human and economic development issues. The continent will likely continue to face pressure to fully address energy-related environmental issues, including access to clean drinking water, safe food and improved air quality, while trying to promote growth. Successful implementation of national environmental policy and enforcement of the corresponding laws is critical in reversing energy production and consumption trends that have a deleterious effect on human health and the environment. Much of the challenge lies

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in adopting viable pollution control schemes that will not preclude development of energy infrastructure throughout the continent [13]. The achievement of this goal lies much in Africa’s ability to reduce dependency on outmoded coal technologies for electricity generation, despite the fact that many alternative technologies are yet to be proven economically viable.

References 1. Armstrong J, Menon R (1998) Mining and quarrying. In: Stellman JM (ed) Encyclopaedia of occupational health and safety, 4th edn. International Labour Organization, Geneva 2. Carpenter L et al (1990) Health related selection and death rates in the United Kingdom atomic energy authority workforce. Br J Ind Med 47(4):248–258 3. Dvorak AJ, Lewis BG (1978) Impacts of coal-fired power plantson fish, wildlife, and their habitats. Argonne National Laboratory, Division of Environmental Impact Studies, Ann Arbor, MI 4. Environment Canada (1999) A primer on environmental citizenship. http://www.ns.ec.gc.ca/ aeb/ssd/acid/acidfaq.html 5. Faaij A et al (1998) Externalities of biomass based electricity production compared with power generation from coal in the Netherlands. Biomass Bioenergy 14(2):125–147 6. Gagnon L (1998) Greenhouse gas emissions from hydro reservoirs: the level of scientific uncertainty in 1998. Hydro-Quebec, Montreal 7. Jenkins SA et al The impacts of dam building on the California coastal zone. California Waterfront Age, September 8. Rudd J et al (1993) Are hydroelectric reservoirs significant sources of greenhouse gases? Ambio 22(4):246–248 9. Saez RM et al (1998) Assessment of the externalities of biomass energy, and a comparison of its full costs with coal. Biomass Bioenergy 14(5/6):469–478 10. Smith KR et al (2000a) Greenhouse gases from small-scale combustion devices in developing countries Phase IIa: Household stoves in India. Technical report no EPA-600/R-30-052 11. UNEP and WHO (United Nations Environment Programme and World Health Organization) (1992) Urban air pollution in megacities of the world. Blackwell Publishers, Oxford 12. UNECE (United Nations Economic Commission for Europe) (1996) The state of transboundary air pollution. Air Pollution Studies 12. Geneva 13. UNEP (United Nations Environment Programme) (1998) Protecting our planet, securing our future. United Nations Environment Programme, U.S. National Aeronautics and Space Administration, and World Bank 14. UNEP and WHO (United Nations Environment Programme and World Health Organization) (1992) Urban air pollution in megacities of the world. Blackwell Publishers, Oxford 15. WHO (World Health Organisation) (2005). Fact sheet No 292

Economizing the Energy Consumption in Circular Surface Aerator Achanta Ramakrishna Rao and Bimlesh Kumar

Abstract Oxygen transfer and power requirement with rotor speed has always been a central topic for design and scale-up of surface aerators. Present study develops design curves correlating the oxygen transfer coefficient, power per unit volume and rotor speed. Based on the design curves, energy conservation by using right sized circular tank surface aerators has been discussed and demonstrated that it is economical to use a big sized circular tank surface aerator rather than using multiple numbers of smaller sized circular tank to aerate the same volume of water. Keywords Energy consumption · Surface aerators

1 Introduction Oxygen transfer, the process by which oxygen is transferred from the gaseous to liquid phase, is a vital part of the wastewater treatment process [7]. Because of low solubility of oxygen and consequent low rate of oxygen transfer, sufficient oxygen to meet the requirements of aerobic waste does not enter through normal surface air-water interfaces. To transfer the large quantities of oxygen that are needed, additional interfaces are created by employing aeration process. The creation of additional interfaces enhance the rate of oxygen transfer so that the dissolved oxygen (DO) level gets raised to allow aerobic bacteria to reduce biochemical oxygen demand (BOD) of the effluent. To provide the required amount of oxygen, an aeration system is always needed. The two basic and widely used methods of aerating wastewater are: (1) to introduce air or pure oxygen into the wastewater body with diffusers generally called as bubble or diffused aerators and (2) to agitate the wastewater mechanically so as to promote the mass transfer of air from the atmosphere into the wastewater body, which is generally achieved by surface aerators. Aeration is usually the single largest cost in a wastewater treatment system comprising as much as 50–90% of the total energy requirements of a wastewater treatment B. Kumar (B) Department of Civil Engineering, Indian Institute of Science, Bangalore, India e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_43,

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plant [13]. Due to the energy crisis and the continuing trend in higher energy costs, development of appropriate technologies towards increasing aeration efficiency in wastewater treatment plants has become very important for municipalities. To design surface aerators in geometrically similar systems, one may require three basic parameters- oxygen transfer rates, rotor speed and input power. Present study aims in developing the design curves correlating all the three basic parameters of geometrically similar circular surface aerators. Based on the design curves developed in the study, the issue of economizing power by using right sized circular surface aerators is evaluated.

2 Surface Aerators A typical surface aerator is shown in Fig. 1. The various geometric dimensions of the aerator are: A, the cross-sectional area; H, the water depth; h, the distance between the horizontal bottom of the tank and the top of the blades and D, the diameter of the rotor. The rotor is fitted with six flat blades in symmetrical and evenly manner such that b and l are their linear dimensions. Rotor shaft is connected to a DC motor to rotate the rotor at desired speed. The rotor is rotated to create turbulence in the water body so that aeration takes place through the interface of atmospheric air and water surface. The rate of oxygen transfer depends on a number of factors like intensity of turbulence which in turn, depends on the speed of rotation, size, shape and number of blades, diameter and immersion depth of the rotor, and size and shape of aeration tank, as well as on the physical, chemical and biological characteristics of water [8]. The aeration process generally depends on three types of variables namely geometric, physical and dynamic variables. Functions relating the oxygen transfer rates and these three types of the variables may be given by the following equations [8, 9]: k=f

√ A/D, H/D, h/D, l/D, b/D, X

(1)

DC Motor Flange

N

Shaft b H

Fig. 1 Schematic diagram of a surface aerator

Rotor blades

l h

D

d

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1/3 Where k = KL a20 v/g2 is the non-dimensional oxygen transfer parameter and KL a20 is the oxygen transfer coefficient at 20◦ C and the dynamic variables X = F 4/3 R1/3 is the parameter in which F = N 2 D/g is the Froude number, and R = ND2 /ν is the Reynolds number. It may be noted that from basic hydrodynamics principles X can be derived as parameter governing the theoretical power per unit volume. The intensity of turbulence and wave action on the water are the major sources normally associated with surface aeration. Turbulence and viscous effects are generally described by the Reynolds number (R), whereas the surface wave action is described by the Froude number (F). The first five non-dimensional parameters represent the “geometric similarity” of the system and the last parameter represents the “dynamic similarity”. When the geometric similarity conditions are maintained, the functional relationship represented by Eq. (1) is reduced to a function of dynamic similarity [8] for any shape of aeration tank. k = f (X)

(2)

Several investigators Horvath [2], Udaya et al. [11], Rao [8] and Rao et al. [9] stated that if power demand (P) per unit volume (V) remains constant then there would be a similarity in oxygen transfer between geometrically similar systems. Therefore one may expect a correlation between the effective (actual or measured) power per unit volume (P/V) and X. Furthermore the oxygen transfer coefficient (k) is a function of P/V because k = f (X) and P/V and X are directly related. In this functional relationship P/V can be expressed as non dimensional form PV = P/ Vγ (gυ)1/3 . Hence the relationship between k and P/V can be expressed as, k = f (PV )

(3)

3 Experimentation Experimental data obtained from our earlier studies [9] under geometrically similar conditions on circular surface aerators and in additions to this r data; some more experiments were conducted in circular surface aerators to provide a sufficient number of data for the development of the design curves. The cross-sectional area of circular tank tested√are A = 1 m2 , 0.5184 m2 and 0.1681 m2 . Conditions of geometric similarity i.e., A/D = 2.88, H/D = 1.0, l/D = 0.3, b/D = 0.24 and h/H = 0.94: as suggested by Udaya et al. [11] were maintained in all the surface aerators.

3.1 Determination of KL a20 ◦

According to two-film theory [6], the oxygen transfer coefficient at T C, KL aT may be expressed as follows.

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KL aT = [ln (Cs − C0 ) − ln (Cs − Ct )] /t

(4)

Where, ln represents natural logarithm and the concentrations Cs, C0 and Ct are dissolved oxygen (DO) concentrations in parts per million (ppm), Cs = the saturation DO concentration at time tending to very large values, C0 is at t = 0 and Ct is at time t = t. The value of KL aT can be obtained as slope of the linear plot between ln(Cs –Ct ) and time t. The value of KL aT can be corrected for a temperature other than the standard temperature of 20◦ C as KL a20, using the Vant- Hoff Arrhenins equation [12]: KL aT = KL a20 θ (T−20)

(5)

Where θ is the temperature coefficient 1.024 for pure water. The known values of DO measurements in terms of Ct at regular intervals of time t (including the known value of C0 at t = 0) a line is fitted, by linear regression analysis of Eq. (4), between the logarithm of (Cs –Ct ) and t, by assuming different but appropriate values of Cs such that the regression that gives the minimum “standard error of estimate” is taken and thus the values of KL aT and Cs were obtained simultaneously. The values KL a20 are computed using Eq. (5) with θ = 1.024 as per the standards for pure water [12]. Thus the values of KL a20 were determined for different rotational rotor speeds N in all of the geometrically similar tanks.

3.2 Determination of Power Availability to the Shaft The power available at the shaft was calculated as follows [1]. From the measurement of no load current (I1 ) and voltage (V1 ) the iron loss was calculated by IL = I1 V1 − I12 Ra

(6)

Where, Ra = armature resistance of the DC motor and I1 2 Ra is no load copper loss. From the measured loaded condition current (I2 ), and voltage (V2 ) the copper loss was calculated by CL = I22 Ra

(7)

Total loss occurring in DC motor, TL = IL + CL

(8)

Pi = I 2 V2

(9)

Incoming power to DC Motor

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The power available at the shaft, P = Pi − TL = I2 V2 − I1 V1 − Ra I22 − I12

(10)

4 Results and Discussion The experimental data expressed in terms of X = N 3 D2 /g4/3 ν 1/3 and k = 1/3 KL a20 ν/g2 are plotted in Fig. 2. It is quite interesting to note that the each set of data points pertaining to the given size of the tank fall very uniquely on a simulation equation given by Rao et al. [9]. The equation developed earlier by Rao et al. [9] for circular tanks is presented below: k = 10.45 exp −4.5/X + 2.45 − 0.7 exp −5 (X − 0.35)2 10−6X 0.5 (11) As reported in literature [5, 4, 3], the rates of oxygen transfer can be correlated with effective power consumption per unit volume. Figure 3 shows the behavior of oxygen transfer coefficient with input power per unit volume of circular tanks. It is quite interesting to observe that data of an individual size of an aerator falls on a unique curve, suggesting that the oxygen transfer rates can be simulated with the effective power per unit volume. The following equation is developed [10] after doing statistical analysis of the data as shown in Fig. 3.

10

1 )

105k

04

o

et

al

0 (2

Ra

0.1 Circular tank, A = 0.168m2 Circular tank, A = 0.5184 m2 Circular tank, A = 1 m2 0.01 0.01

0.1

1

10

100

X

Fig. 2 Simulation of oxygen transfer coefficient with theoretical power per unit volume

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Fig. 3 Simulation of oxygen transfer coefficient with actual power per unit volume

105kc

1

0.1

Circular Tank, A = 0.168 m2 Circular Tank, A = 0.5184 m2 Circular Tank, A = 1 m2 0.01 0.1

0.01

1

PV

105 k = 7.38 PV exp (−0.189/PV ) + 0.33 (PV )0.5

(12)

Energy requirements of surface aerators are of paramount importance while choosing and designing particular types of aerator to meet the demand. The energy can be computed as the product of power and time required to achieve a desired level of DO concentration. As KL a20 has the units of inverse of time, one may express characteristically the energy by a parameter P/KL a20 . As k is a non-dimensional form of KL a20 and PV is the non dimensional form of P/V, the energy (parameter)

10

b.

Circular Tank

ε x 105

A = 0.1684 m2 A = 0.5184 m2 A = 1 m2

1

0.1 0.01

0.1

1 X

Fig. 4 Energy characteristics of circular surface aerators

10

100

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per unit volume (ε) may be defined as, ε = PV /k, and it is plotted with X for circular surface aerators in Fig. 4.

5 Application of the Results In order to demonstrate the application of results, a volume of 1 m3 is considered for reaeration. Analysis has been done by dividing this volume into different volumes say 1 , 0.5, 0.25 and 0.1 m3 i.e. the number of aerators to aerate 1 m3 of water are : n = 1, 2, 4 and 10 respectively. Rotor diameter and other geometrical configurations have been derived by the geometrical similar condition given by Udaya et al. [11]. Energy of the each size surface aeration tanks with rotor speed is plotted in Fig. 5a and their comparison in Fig. 5b by using Eqs. (12) and (13). As shown in Fig. 5a, b, it can be stated that smaller tanks are taking more energy to aerate the same volume of water. It can be noticed from Fig. 5b that, for example, while using ten smaller tanks the energy consumed can be as high as about 16 times when compared to a single size big tank. Hence it can be concluded that while aerating the same volume of water smaller size tanks are not economical in saving energy consumption whereas a single largest tank is the best choice to minimize the energy requirements. Such analyses have been done in square surface aerators with the help of earlier published simulation equation [8] and comparisons are made for each size between square and circular surface aerators to ascertain their energy efficiency. Such comparison is shown in Fig. 6. It can be seen from Fig. 6 that except in very narrow range and that to in the smallest configuration, circular tank surface aerators are more energy efficient than the square tank surface aerators.

10

20

Volume of water to be aerated=1m3

na = Number of Circular Surface Aerators of equal volume

(a)

5

ε x 10

1

D = 311 mm,na = 4

(b)

15

D = 229 mm,na = 10

na = 10

εMultiple-εSingle ----------------εSingle 10

D = 392 mm,na = 2 D = 494 mm,na = 1

5

na = 4 na = 2

0.1 10

100

1000

Speed (RPM)

na = 1

0 1

10

100

Speed (RPM)

Fig. 5 Energy economics of using smaller aerators

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0.2

Comparison of Square and Circular Tank of same volume

0.0

– 0.2

εCircular - εSquare ------------------ – 0.4 εSquare – 0.6 D = 494 mm D = 392 mm D = 311 mm D = 229 mm

– 0.8

– 1.0 1

10

100

1000

Speed (RPM)

Fig. 6 Comparison of square and circular surface aerators

6 Conclusion Design curves for designing geometrical similar circular tank surface aerators are presented in this paper. Based on the analysis conducted in this study, the following conclusion can be made. • Simulation equation developed earlier for circular tank correlating the oxygen transfer coefficient (k) with theoretical power per unit volume (X) was confirmed and more generalized through experiments. (Fig. 2 and Eq. (11)) • It has been established that k can be simulated also with the effective power per unit volume (PV ) for the circular tank. Simulation equation governing k and PV is developed for the circular surface aerators. (Fig. 3 and Eq. (12)) • By using the design curves presented in this paper, one can easily design the circular surface aerators under the geometrical similarity conditions. • Based on the analyses, it can be concluded that single and big size surface aerators are more energy efficient than a number of small size aerator to aerate the same volume of water. • It has been also shown that circular tank surface aerators are more energy efficient than square shaped surface aerators.

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References 1. Cook AL, Carr CC (1947) Elements of Electrical engineering, 5th edn. Wiley, New York 2. Horvath I (1984) Modeling in the technology of wastewater treatment. Pergamon, Tarrytown, NY 3. Hsieh C-C (1991) Estimating volatilization rates and gas/liquidmass transfer coefficients in aeration systems, PhD thesis, Department of Civil Engineering, University of California, Los Angeles, USA 4. Hwang HJ (1983) Comprehensive Studies of Oxygen Transfer under Nonideal Conditions, Ph.D. thesis, Department of Civil Engineering, University of California, Los Angeles, USA 5. Kozinski AA, King CJ (1966). The influence of diffusivity on liquid phase mass transfer to the free surface in a stirred vessel. AIChE J 12:109–116 6. Lewis WK, Whitman WG (1924) Principles of gas absorption. Ind Eng Chem Res 16(12):1215–1220 7. Metcalf & Eddy Inc. (2004) Waste water engineering: Treatment disposal and reuse. Tata McGraw-Hill, New Delhi 8. Rao ARK (1999) Prediction of reaeration rates in circular, stirred tanks. J Environ Eng, ASCE 125(3):215–233 9. Rao ARK, Laxmi BVB, Narasiah KS (2004) Simulation of Oxygen transfer rates in circular aeration tanks. Water Qual Res J Can 39(3):237–244 10. Rao ARK, Kumar B, Patel AK (2007) Relative performance of different shaped surface aeration tanks- Water Qual Res J, Canada 42(1):26–40 11. Udaya SL, Shrma KVNS, Rao ARK (1991) Effect of geometrical parameters for overall Oxygen transfer coefficient. Proceedings of the Symposium on Environmental Hydraulics, University of Honkong, pp 1577–1581 12. WEF and ASCE Manual of practice for water pollution control (1988) Aeration a waste water treatment process. Water Environment Federation, Alexandria, Va., and ASCE, New York 13. Wesner GM, Ewing LJ, Lineck TS Jr, Hinrichs DJ (1977), Energy conservation in municipal wastewater treatment. EPA-430/9-77-01 1, NTIS No. PB81-165391, US EPA Report, Washington, DC

Sewage Biogas Conversion into Electricity by Using Small Systems Suani Teixeira Coelho, Sílvia Maria Stortini González Velázquez, Osvaldo Stella Martins, and Fernando Castro de Abreu

Abstract This article intends to present some considerations about electricity generation with 30 kW (ISO) microturbines, using biogas generated by a sewage treatment process at SABESP (Basic Sanitation Company of São Paulo State), located in Barueri, Brazil. This project, pioneer in Latin America, is being accomplished together with BUN – Biomass Users Network of Brazil (proponent), in association with CENBIO – Brazilian Reference Center on Biomass (executer), with patronage of FINEP/CT-ENERG (financial backer), by means of CONVENTION No: 23.01.0653.00, regarding to ENERG-BIOG Project – “Installation and Tests of an Electric Energy Generation Demonstration Unit from Biogas Sewage Treatment”. The study is being held at Barueri Sewage Treatment Plant. This plant operates with anaerobic digestion process, which has as mainly products biogas (composed mainly by methane) and sludge. Currently, part of the methane produced is burnt in a boiler being used to increase the digesters temperature and so, the process efficiency. The methane remnant is burnt in flare to reduce the impacts caused by gases emissions. An alternative to burn it in flare is the biogas conversion into electricity through engines or microturbines. This paper describes the proposed system to convert biogas in electricity and heat using microturbine. Thus, this article presents some technical, financial and environmental project results, related to the exploitation of sewer biogas for power generation, as well as more details about purification, compression and electricity generation systems (biogas microturbine), used in the facility. It is possible to conclude that the purification system projected takes care of the fuel specifications, demanded by the microturbine, but the costs analysis on using microturbines are not positive when compared with a conventional generator

S.T. Coelho (B) CENBIO – Brazilian Reference Center on Biomass, IEE – Institute of Electrotechnics and Energy, USP – University of São Paulo, Av. Prof. Luciano Gualberto, 1289 CEP 05508-010, São Paulo, Brazil e-mail: [email protected]

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of equal power. Until the present moment, the data obtained will serve to baseline for the accomplishment of future environmental impact comparative studies, between engines (Otto – Cycle) and microturbines. Keywords Biogas · Biodigestor · Renewable source · Turbine and generating group

1 Introduction The ENERG-BIOG Project aims to analyze the use of sewer biogas to electricity production in Brazil. The study in being done in a sewer treatment plant located in Barueri, State of São Paulo. This plant operates with anaerobic digestion process, which has as mainly products biogas (composed mainly by methane) and sludge. The main advantage in using anaerobic digestion process is that the sludge treatment process is followed by energy production as biogas. Currently, part of the methane produced is burnt in a boiler being used to increase digestors temperature and so, the process efficiency. The methane reminiscent is burnt in flare to reduce the impacts caused by gases emissions. An alternative to burn it in flare is the biogas conversion into electricity through engines or microturbines. This paper describes the proposed system to convert biogas in electricity and heat using microturbine.

2 Biogas Production in Sewage Treatment Systems Biogas is a gas combustible mixture produced during the organic matter anaerobic digestion, sludge, in the sewage treatment. The amount of each gas in the mixture depends on many factors as the type of digestor and the kind of organic matter. In any way this mixture is basically made of methane (CH4 ) and carbon dioxide (CO2 ), and its heating value is straightly linked to the methane content. The pilot project located at SABESP, in Barueri/SP, the largest sewage treatment station (STS) of Latin America, is in test phase, aiming to analyze the potential for biogas use as fuel for the electric energy generation. The first survey indicated an average production of 24,000 m3 (secondary treatment) per day of biogas (reaching 28,000 m3 /dia in some periods), with a LHV (lower heat value) of 5,300 kcal/Nm3

Table 1 Biomass measure composition in % of SABESP STS at Barueri (CENBIO [1]) Gas mixture measure composition Methane (CH4 ) Carbon dioxide (CO2 ) Oxygen (O2 ) + nitrogen (N2 ) Humidity (H2 O)

66.5% 30.5% 0.5% 2.5%

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Table 2 Others characteristics (CENBIO [1] e SABESP [3]) Others characteristics Sulfuric acid (H2 S) LHV Relative density Pressure Produced volume

134 ppm or 0.01% 5,300 kcal/m3 or 22,195 kJ/m3 0.86 a 15◦ C 101.325 kPa 250 mm c.a. (gas tank measure) 24,000 m3 /dia (approximately)

Fig. 1 Barueri sewage treatment station (SABESP [3])

(22.2 MJ/Nm3 ), whose composition (%) are presented in Table 1 and other biogas characteristics are presented in Table 2 (Fig. 1).

3 Some Technologies for Biogas Conversion There are different kinds of technology to convert the chemical energy in the biogas into electricity. Energy conversion mean a process where one type of energy is converted to other one. In biogas conversion the chemical energy in the molecules is converted to mechanical energy in a controlled combustion system, then, this mechanical energy activates a generator producing electrical power. The gas turbines and the internal combustion engines are the most common technologies used to this kind of energy conversion. Even so, in general, engines are more efficient turbines may be more efficient when operating in a cogeneration cycle producing heat and electricity (COSTA et al. [2]). Aiming to evaluate technologies efficiency, a 30 kW (electric) Capstone microturbine (ISO) with a biogas cleaning system was installed for tests in December 2002. The results will be compared with the engines performance, in technical, economic and environmental terms. The test’s objective is to evaluate the possibility of using microturbines in small scale sewage treatment plants for energy generation.

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4 Biogas Cleaning The presence of non-burnable substances in the biogas, like water and carbon dioxide, reduces the conversion efficiency. Incomplete combustion can occur, causing power reduction and corrosion, due to H2 S presence. Most anaerobic digesters produce a biogas with 0.3–2% H2 S and significant amounts of nitrogen and hydrogen. The biogas generated in SABESP’s sewage treatment station in Barueri contains impurities that can compromise the operation of the installation, damaging the cleaning system, the compression system and the electric energy generation system (microturbine). The most common impurities in biogas are: • Humidity: it can compromise the operation of microturbine’s internal parts (injector, combustion chamber, turbine rotor), besides reducing the biogas heating value; • H2 S: it can damage drier’s internal parts, as well as the compressor and the microturbine, because H2 S is corrodible; • Air presence into the pipeline: reduces the biogas heating value; • CO2 : inert gas that also reduces the biogas heating value; however, the microturbine was projected to operate with CO2 levels between 30 and 50%. So, the withdrawal of this element did not become necessary. For the humidity withdrawal present on the biogas, coalescent filters were used on the line and two refrigerated driers, one before and another after the compressor. To deal with the H2 S gas removal, a carbon filter was used, operating by absorption principle. For the H2 S in water solution were used refrigeration drier and coalescent filters. The purification system used in this project, also the first one in Latin America, was designed to guarantee that the biogas characteristics would accomplish to the microturbine specifications, what happened indeed. The gas analysis results (Table 3) shows that the gas cleaning system used fulfills the turbine requirements. The microturbine consumes an average of 20 m3 /h or 480 m3 /dia. Figure 2 shows the microturbine installed in Barueri. Table 3 Comparison of biogas analyses results with the capstone specifications (CENBIO [1]) Variant

Unit

Capstone

Barueri

Notes

O2 N2 CO2 CH4 H2 S H2 O (D.P.) L.H.V.

% Vol. % Vol. % Vol. % Vol. ppm-vol % Vol. kJ/m3

0–10 0–50 0–50 30–100 0–70.000 0–5 13.800–27.605

0.00–6.30 0.22–23,8 25.0–30,8 44.1–69.9 0.08–230 0.1–2.8 14.715–23.852

Approved Approved Approved Approved Approved Approved Approved

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Fig. 2 Project facility photo (CENBIO [1])

5 Conclusions The energetic use of biogas causes different environmental and economical impacts depending on witch system is used. The electricity generation using biogas in landfills fulfills the electricity requirements of the plant and a surplus of energy can be delivered to the grid. In the agricultural sector the biogas produced, mainly in anaerobic digestors feed by manure residues, can provide energy surplus to, depending one the number of animals and the technology used to treat their residues. In sewage treatment plants the biogas use to electricity production allows a reduction of 20% in electricity consumption. This relation between the electricity production and consumption don’t change due the size of the facilities. Even so, the microtubine electricity cost is higher then the electricity produced in conventional generators the emissions, mainly NOx, are significantly lower (Table 4). Table 4 Comparison between installations costs relations for both technologies (Capstone microturbine and trigas generation group) (CENBIO [1])

Relation between initial investment and installed power Relation between initial investment and liquid installed power Relation between operation and maintenance costs by the electric energy production Relation between total costs by the electric energy production

Capstone microturbine

Trigas Generation Group

R1 = 2,195.28 US$/kW R1 ’ = 3,377.36 US$/kW R3 = 0.0989 US$/kWh R5 = 0.2045 US$/kWh

R2 = 358.69 US$/kW R2 ’ = 430.43 US$/kW R4 = 0.0148 US$/kWh R6 = 0.1224 US$/kWh

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O2 (% vol.) CO2 (% vol.) CO (ppm) SO2 (ppm) NO (ppm) NOx (ppm) THC (ppm)

Minimum

Maximum

Average

18.0 2.1 10.0 0.001 0.014 0.162 42.0

18.5 2.1 145.0 2.900 0.037 0.640 51.0

18.2 2.1 80.8 1.800 0.029 0.412 46.0

The exhaustion gases analysis (Table 5) showed NOx emissions of less then 1 ppm (parts per million). Then the large advantage of using this technology is directly tied with the environmental benefits, when these emissions are compared with the internal combustion engines ones, approximately 3,000 ppm NOx. It is necessary to consider in this scenario the potential of emissions reductions and the carbon credits in a Kyoto Protocol CDM (Clean Development Mechanism) project where each kWh produced using biogas, in Brazilian conditions, avoids emissions of 0.5 tC. Acknowledgments Alves JWS (2000) Diagnóstico Técnico Institucional da Recuperação e Uso Energético do Biogás Gerado pela Digestão Anaeróbica de Resíduos. Dissertação de Mestrado, PIPGE/USP, São Paulo Campos JR et al (1999) Tratamento de Esgotos Sanitários por Processo Anaeróbio e Disposição Controlada no Solo. PROSAB, Abes, Rio de Janeiro, p 435 Capstone (2001) Authorized service provider training manual. Capstone Turbine Corporation, Los Angeles Cenbio (2000) Medidas Mitigadoras para a Redução de Emissões de Gases de Efeito Estufa na Geração Termelétrica. Brasília, 222p Cenbio (2001) Nota Técnica VII – Geração de Energia a Partir do Biogás Gerado por Resíduos Urbanos e Rurais. São Paulo EPA (2001) Case Studies in Residual Use and Energy Conservation at Wastewater Treatment Plants. Washington IBGE (2000) Instituto Brasileiro de Geografia e Estatística. Brasil IPT (2001) Instituto de Pesquisas Tecnológicas. São Paulo Miller W (1994) Energy Audit: Buffalo Creek Wastewater Treatment Facility. City of Sanford Parks B (2000) Gas Turbines for Power Generation: A.U.S. DOE Perspectives. EUA Sayed SKI (1987) Anaerobic Treatment of Slaughterhouse Wastewater Maing the UASB Process. University de Wageningen, Wageningen, Holanda van Haandel AC, Lettinger G (1994) Tratamento Anaeróbio de Esgotos: Um Manual para Regiões de Clima Quente. Epgraf, Campina Grande, 240p van Wylen G (1995) Fundamentos da Termodinâmica Clássica. Tradução da 4ª edição americana von Sperling M (1996) Princípios Básicos do Tratamento de Esgotos. DESA-UFMG, Belo Horizonte, 210p

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References 1. CENBIO (2002–2004) Relatórios de Atividades – Projeto ENERG-BIOG, São Paulo 2. COSTA et al (2001) Produção de Energia Elétrica a partir de Resíduos Sólidos Urbanos. Trabalho de Graduação Interdisciplinar/FAAP, São Paulo 3. SABESP (2001) Companhia e Saneamento Básico do Estado de São Paulo

Algae Biofuels as a Possible Alternative to Environmentally Doubtful Conventional Methods of Biodiesel Production Tomislav Kurevija and Nenad Kukulj

Abstract In last 10 years there was significant rise in transportation fuel consumption in Europe from 180 Mt in 1985. to 270 Mt in 2004., with gasoline representing 40% and diesel 60%. To decrease dependence upon imported fossil fuels, EU aim is to introduce biodiesel in share of 5.75% in transportation sector until 2010. and finally 8% until 2020. Because of limited production potential from some EU countries, today and in near future, large quotas of import would be required. Biodiesel is often called clean, ecological and renewable alternative fuel, but with present land-intensive methods of production it could easily be named as one of the most dangerous sources of energy for Earth’s ecosystem. Main threat from large scale biofuels utilization comes from deforestation of land that is needed for cultivation of crops. Every year large areas of rainforests in South East Asia and South America are irretrievably lost due to increasing demand. Combustion of wood and oxidation of peat during drying emits enormous quantities of CO2 into the atmosphere which is contrary to biodiesel appellation as “CO2 balanced fuel”. Unlike conventional crops that are used for production of biodiesel (rapeseed, soybean, palm etc.), possible production from algae would significantly lower unit of land needed for biofuel production. Contemporary researches give some estimation of about 25 times greater yield than palm plantation and 100 times over rapeseed, which is common biodiesel production crop in EU. Regarding lately high world oil prices, greater investment in researches upon algae, as a new source of biofuel, are bringing technological solutions for economically production start-up. Keywords Biofuel · Conventional · Microalgea

T. Kurevija (B) Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Pierottijeva 6, Zagreb, Croatia e-mail: [email protected]

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1 Introduction The European Union is heavily dependent upon energy imports and particularly to oil imports, which leads to large emissions of greenhouse gases (GHG) and contributes to global warming and climate changes. In an effort to slow down this increase, most industrialized countries have joined in to Kyoto protocol policy to hold carbon dioxide emissions in the year 2000 to 1990 levels. Transport is a main oil consuming and GHG generating sector in the EU, and therefore the reduction of energy consumption and emissions from the road transport will be an important step on the way of reaching these EU policy objectives. Although the importance of the biofuels use in transport has already been stressed in the EU White Paper on renewable sources of energy (1997) and the Green Paper on a European strategy for the security of energy supply (2000), this has not led to the development of specific biofuel national policies in many EU Member States. Some countries support the use of biodiesel by exempting them from excise duties or environmental taxes and in June 2001 two EU Directive proposals passed, concerning the promotion of biofuels. The first draft Directive obligates the EU Member States to sell a certain amount of biofuels on their national markets in the period 2005–2010. In order to support this, the second draft Directive provides the opportunity to the Member States to adjust their national excise duty systems for automotive fuels in favour of biofuels. EU directive proposal also obligates the Member States to establish a minimum percentage of 2% of biodiesel share in the total transport fuel consumption till 31 December 2005. This amount must be increased every year by 0.75–5.75% by the 2010 and 8% by the end of 2020 [3]. Biodiesel is cleaner than gasoline and diesel and it is virtually sulphur free. Hydrocarbons and carbon monoxide emissions and particles during combustion process are also significantly reduced but with slight increase in nitrogen oxides emissions. Another advantage is that biodiesel blends may potentially be utilized in a standard, unmodified diesel engine. While positive impacts such as reduction in CO2 emissions at the combustion stage are evident, the indirect impacts such as deforestation, the danger of reducing biodiversity, competition for land with food production sector, contamination of land and water with nitrates, phosphates and pesticides are more complex and have global impact on environment as well. Opposite to terrestrial plants which are favourable for production of biodiesel, microalgae have the advantages of greater efficient photosynthesis, fast proliferation rates, wide tolerance to extreme environments, potential for intensive cultures and lesser land area requirement. These advantages promise the reduction of carbon dioxide if microalgae production ponds would be build near fossil fired power plants. Exhaust gases from heavy industries commonly contain carbon dioxide levels significantly higher than that found in the atmosphere, 10–20% for coal plants and around 4% for natural gas [4] what could be use for growing of microalgae cultures and sequestration of CO2 at the same time. Once the lipids are extracted from the harvest algae, potential use for the microalgae residue include fodder for livestock, food and chemicals, colorants, perfumes, and vitamins, which leads to greater economically feasibility of the project.

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2 Status of World Biodiesel Production At present, the biofuel producing countries in the European Union only have a small share in global production of biofuels, namely a little less than 6%. Most of the global biofuel production consists of ethanol and the main producers are the USA and Brazil, whereas the share of Europe is rather small. However, Europe is the most important producer of biodiesel on the global market. From 1993, the European production level has increased by almost 40 times, from 80.000 tons in 1993 to 780.000 tons in 2001, and finally to 3.184.000 tons in 2005 [3] (Fig. 1). Germany is the leading European producer, followed by France, Italy and Czech Republic. Throughout the European Union, biodiesel is applied in automotive engines in various blends with regular diesel. In Germany, Austria and Sweden, it is used in pure form in adapted captive fleet vehicles. Currently, only biodiesel (mainly Rapeseed Methyl Ester, RME) and ethanol (and its derivative ETBE) produced from food crops are applied on a commercial basis on the European market. Around 12% of total biodiesel volume, EU is importing from East Asia (Malaysia and Indonesia) in form of crude palm oil. Biodiesel production currently uses around 1.4 million hectares of arable land in the EU and today there are approximately 40 plants in the EU producing up to 3.184.000 tonnes of biodiesel annually. These plants are mainly located in Germany, Italy, Austria, France and Sweden. In the USA, the most common crop for producing biodiesel is soy while in East Asia (Malaysia and Indonesia) biodiesel is mainly produced from crude palm oil. As the demand for biodiesel in EU rises, there is a problem of meeting consumption by domestic production of rapeseed oil. It is estimated that until 2010, 20% of total biodiesel on EU market will come from SE Asia in form of crude palm oil [3]. This share could go even bigger taking into account that palm oil is more economically favourable than rapeseed (Table 1).

Fig. 1 World production of biodiesel from 1991 till 2003 [3]

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Country

Production of biodiesel in 2005(×1000 tonnes)

Production capacity in 2005(×1000 tonnes)

Share of biodiesel in diesel consumption in 2005 (%)

Germany France Italy Czech Republic Poland Austria Slovakia Spain Denmark UK Slovenia Estonia Lithuania Latvia Other EU states

1669 492 396 133 100 85 78 73 71 51 8 7 7 5 9

2681 775 857 203 150 134 89 224 81 445 17 20 10 8 375

2.00 2.00 2.00 3.03 – 2.50 2.00 2.00 0.00 0.30

TOTAL

3184

6069

1.50

–

–

Imports of palm oil from East Asia for biodiesesel purposes

≈ 500

0.00 2.00 2.00 –

3 Research and Development of Microalgae Based Biodiesel Currently most research into efficient algal-oil production for biodiesel purposes is being done in the private sector in the view of small scale pilot-projects. Mass-production of oil is mainly focused on microalgae, organisms capable of photosynthesis that are less than 2 mm in diameter, including the diatoms and cyanobacteria. This preference towards microalgae is due to its less complex structure, fast growth rate, and high oil content for some species (as many as 70% in favourable conditions). Commercial microalgal culture in a food sector today is a well established industry and much of the early work on microalgae oil production focused on closed culture systems (photobioreactors). A photobioreactor is basically a bioreactor which incorporates some type of light source and because these systems are closed, everything that the algae need to grow (carbon dioxide, nutrient-rich water and light) must be introduced into the system. Large commercial systems that are used today are almost always open-air systems design types, due to economical reason. Closed culture systems are very expensive and many of them are difficult to scale up. Furthermore, most closed systems are operated indoors with artificial lighting and this result in high energy costs (Table 2). However, the number of species that has been successfully cultivated for a given purpose (for the production of biodiesel and as food source) in an outdoor system is relatively small. In open systems there is no control over water temperature

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Table 2 Comparison of microalgae bio-oil yield and common cultures for biodiesel production [1] Plant Yield of bio-oil

m3 /km2 /year bbl/acres/year GJ/km2 /year

Microalgae

Soybean

Rapeseed

Jatropha

Palm

>15,000 >380 >500,000

35–45 0.90–1.15 1165–1500

100–130 2.55–3.30 3330–4330

160 4.10 5330

580 14.80 19,315

and lighting conditions and due to the fact that these systems are atmospherically open, they are much more vulnerable to be invaded by other algal species and bacteria. The growing season is largely dependent on location and apart from tropical areas it is limited to the warmer months with productivity achieved lesser than it is theoretically possible. The pond depth is often compromised between the need of providing adequate light to the algal cells (the shallower it is, the more light is available to the cells) and the need of maintaining an adequate water depth for mixing, regarding large changes in ionic composition due to evaporation. Algae only need about 1/10th of the light amount they receive from direct sunlight [5]. In order to have ponds that are deeper than 4 in., various methods of water agitation in ponds need to be used, exposing the algae below to light and keeping algae on the surface from being over-exposed. Paddle wheels can be used to circulate the water in a pond and compressed air can be introduced into the bottom of a pond to agitate the water, bringing algae from the lower levels upwards. Aside from agitation, light algae supply could be done by introducing the light into the system by using glow plates, submerging them into the water, providing in that way light directly to the algae at the right concentration. Algae can be harvested using microscreens, by centrifugation, or by flocculation methods. Microalgae have much faster growth-rates than terrestrial crops. The yield of oil from algae as seen from Table 2 is estimated to be between 5000 and 15.000 m3 /km2 /year which is around 8–25 times greater than the next best crop, palm oil [6]. In order to obtain high algal production rates, many of pilot projects harvested the biomass daily. If unharvested, production rates will reach a peak and then decline with increasing biomass concentration because of reduced available light (mutual shading) and depletion of nutrients. Therefore, harvesting is an essential part of maintaining high microalgal productivity rates. Algal-oil is transformed into biodiesel as easily as oil derived from land-based crops and the difficulties in the efficient biodiesel production from algae lie not in the extraction of the oil, but in finding an algal strain with a high lipid content and fast growth rate that is not too difficult to harvest, and a cost-effective cultivation system that is best suited to that strain. The knowledge of the biochemistry and physiology of lipid synthesis, combined with basic studies on microalgal molecular biology and genetic engineering to develop algae strains with optimal properties of growth and lipid production, may lead to great improvement and enhance the commercial viability of this alga as an optimum hydrocarbon source.

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4 Possibility of Co2 Sequestration in the Algae Culture Plants Much of the carbon dioxide that is released into the atmosphere is from the burning of fossil fuels for the production of energy (coal power plants are especially major source of carbon dioxide emissions) or in the heavy industry. Regarding global warming effect, new methods for the thorough and efficient sequestration of CO2 are being sought out and selection of the most appropriate technology to limit the amount of carbon dioxide entering the atmosphere is the major focus of research. Carbon dioxide could be captured and sequestrated into the aquifers or depleted oil and gas wells. This is an expensive option (potentially more than doubling the cost of electrical generation via fossil fuels) with no opportunity for profit to displace the cost, except if the CO2 is used as part of tertiary methods of oil recovery. Biofixation of carbon dioxide using microalgae has emerged as a potential option. Commercial interests into large scale algal-cultivation systems could be obtained by placing algae plants near coal power plants, sewage treatment facilities or any industry that emit large quantities of carbon-dioxide into the atmosphere. This approach not only provides the raw materials for the system, such as CO2 and nutrients making in that way greater yield of biodiesel, but it changes those wastes into resources (Fig. 2). Much work has been done on the effect of different flue gas constituents on microalgal growth rates and carbon dioxide fixation. Typical coal power plant flue gases have carbon dioxide levels ranging from 10 to 15% (4% for natural gas fired ones). At the typical carbon dioxide percentages in the atmosphere of 0.036%, microalgae show no signs of significant growth inhibition. Furthermore, various studies have shown that microalgae respond better to increased carbon dioxide concentrations, outgrowing (on a biomass basis) microalgae exposed only to ambient air (Table 3). Sulfur oxides, particularly SO2 , can have a significant effect on the growth rates and health of the microalgae, especially effect that SO2 has on the pH of the microalgal growth. When the SO2 concentration reaches 400 ppm, the pH of the pond water can become as lower as 4, which significantly affects the productivity of the microalgae [5]. However, if the pH is maintained at 8 using NaOH, the productivity does not decrease [4]. Nitrogen oxides also comprise a significant portion of power plant flue gas. As with the sulphur oxides, nitrogen oxides can affect the pH of the algal medium, but to a lesser degree. Microalgae have been shown to tolerate and grow in a medium containing as many as 240 ppm of NOx, with pH adjustment. The effect of soot dust and ash containing heavy metals has limited attention. When soot dust concentration is greater than 200.000 mg/m3, algal productivity is influenced [4]. It is rare for the soot dust concentration to reach such a value. Higher concentrations of heavy metals in gas flue can affect algal productivity, but only in rare situations will the concentrations exceed those that will result in a significant impact. Another concern with the flue gas is the elevated temperatures. In a commercial application, flue gas from the desulfurization scrubbers would be sent to the CO2 sequestration ponds for treatment. Temperatures exiting the scrubbers are usually around 60◦ C.

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Fig. 2 Simplified schematic of the algae biodiesel production with introduction of CO2 from fossil fuel fired power plant

Table 3 Example of typical flue gas composition from coal fired power plant [4] Component

N2

CO2

O2

SO2

NOx

Soot dust

Concentration 82% 12% 5.5% 400 ppm 120 ppm 50 mg/m3

Therefore, microalgae would need to exhibit tolerances at temperatures of this magnitude. Although most organisms cannot survive at these higher temperatures, some cyanophycean algae have been shown to grow at 80◦ C. Some investigations showed carbon fixation rate of 14.6 g C/m2 (basal area) per day at a growth rate of 30.2 g dry wt/m2 /day [7]. as well as range of 0.65–4.0 g CO2 /L/day at growth rates of 0.4–2.5 g dry wt/L/day [6]. Results were corroborated using direct measurements of the inlet and outlet gas streams and indirectly estimated from the carbon content of the cell and the cell growth rate. The capture of carbon dioxide by large pond-type systems when operating under optimum conditions has been shown to be as high as 99% [4]. Pond sizes should not exceed 20 ha each (a larger pond would be difficult to operate). It is estimated that for a 500-MW power plant open pond surface area of 14.000 ha is needed [4]. These results show the potential for using microalgae for carbon dioxide fixation, especially because of large investment costs in alone standing algae plants. By introduction of CO2

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source and construction of algae plants near fossil power plants projects are becoming more economically feasible concerning sequestration of carbon-dioxide and, in that way, contributing to global warming effect decrease. There are some estimation of $80.000 per hectare for the construction costs of algae ponds and $12.000 per hectare for operating costs (including power consumption, labour, chemicals, and fixed capital costs) [4]. With further research and development, as well as high oil prices, this method of biodiesel production could be very interesting in future.

5 Environmental Issues Concerning Conventional Biodiesel Production As world population is continuously increasing and consequently energy demand as well, especially in the transport sector, there is lesser arable land needed for growing food crops and energy interesting crops for production of biodiesel. To satisfy biodiesel demand, especially from EU which has limited arable area for reaching 8% of biodiesel share in 2020, production is moved from EU to the other continents, especially SE Asia. Because EU is currently short of biodiesel, as some Member States have underinvested in refinery production in recent decades experts estimates that palm oil bio-diesel in a few years could account as much as 20% of Europe’s biodiesel consumption and cause the destruction of some of the most valuable forests of the world because of the land clearance (Fig. 3). Reason of increased share of palm-oil in total EU biodiesel consumption lies in greater yield per area of palm plantation over rapeseed and lower cost production which influences final purchase price. Until today, rapeseed is still dominant source for biodiesel in EU with share of some 80% but competition with food sector has driven its price to somewhat 600 C per ton in 2005. At the same time, price of crude palm-oil was around 33% cheaper, making it about 400 C per ton [2]. The main world producers of crude palm oil are Indonesia and Malaysia. Between 1989 and 2000, the area of oil palm harvested in Indonesia more than tripled. In 2003, 75% of Indonesia’s 5.2 million hectares of oil-palm plantations were located in Sumatra, with a further 18% in Kalimantan [2]. It is expected that this total will more than triple to approximately 20 million hectares in Indonesia and 10 million hectares in Malaysia by 2020. Between 1985 and 2000 the development of oil-palm plantations was responsible for an estimated 87% of deforestation in Malaysia, and an estimated 66% of Indonesia’s plantations have involved forest conversion [10]. By the beginning of 2004, there were 6.5 million hectares of oil-palm plantations across Sumatra and Borneo [2]. Of this total area, almost 4 million hectares had previously been forested. Currently, every year about 2 million hectares of Indonesian virgin forest, a total area half the size of Belgium, are turned over to palm oil production (Fig. 4). The palm-oil business is often advertised by governments and companies as making an important economic contribution to development. However, this analysis is

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507

Fig. 3 Necessary total arable area for EU goal of 8% biodiesel share in comparison to 100% biodiesel share in total diesel consumption, according to rapeseed yield

often one-sided, and fails to take into account the substantial social and environmental costs. These include the ecological price of removing rainforest such, as well as pollution and damage to water and air that are rarely taken into account. However, the area released for conversion does not necessarily reflect the real area planted, and the palm-oil industry is habitually associated with deforestation beyond establishing

Fig. 4 Example of Indonesia’s rainforest destruction due to palm-oil production expansion [2]

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oil-palm estates on previously forested land. The amount of forest removed under the plantation development, regardless of whether palms have ever been planted, may be as much as 10 million hectares [10]. Around 40% of Indonesia’s legal timber supply results from land clearance for conversion to plantations. In the past, if the remaining timber stands are not commercially valuable, burning has been a widely-used method of land clearance. The forest fires of 1997/1998 were responsible for the devastation of over 5 million hectares of forest and often the major fires are in oil-palm plantations [8]. Peat-swamp forests, including those in Tripa, Singkil, and Kluet in Sumatra, and Sebangau, Mawas, and Tanjung Puting in Borneo, play a major role in carbon sequestration and biodiversity. This forest type is being promoted as a carbon sink and used in international carbon offset agreements, while palm oil is concurrently publicised as a carbon emission-reducing fuel. Peat-swamp forests, however, are increasingly becoming prime targets for oil-palm expansion, despite regulations against the development of deep peats and lower productivity relative to other soils. It is crucial that the expansion of oil-palm plantations does not lead to the clearance of forests and, in particular, peat forests. It is difficult to cultivate oil palms on peat land greater than 1 m thick [9], and the costs of establishing a plantation on this soil type tend to be 40%higher than on dry land but nevertheless, numerous companies continue to apply for licences to allow the conversion of deep peat land (Table 4). If the palm-oil plantation is planned on peat swamp tropical forest, which is promoted as large carbon sink, forest fires necessary for land clearance would emit approximately 8000 tons of GHG per km2, drained peat-swamp land will additionally release about 1000 tons/km2/year of GHG emissions, mostly CO2 , for period of 5 years needed for complete drainage. It is estimated that in the whole of SE Asia about 7 million hectares of peat lands are drained now, mainly for palm-oil cultivation purposes. In that case the drained peat lands used for agriculture in SE Asia will contribute to about 0.35–0.7 gigaton CO2 /year, or about 5–10% of the total yearly worldwide CO2 emissions [9]. As oppose to this problems with land clearance and competition of conventional biodiesel crops with food sector, algae cultures could be grown even in desert regions and some brackish waters locations, as well as at the sea near the cost. All of these projects would be placed aside the existing industry because of necessary Table 4 Plantation area and estimated forest area cleared based on industry estimates (million hectares) [9]

Country

Oil palm plantation area (2002)

Share of oil palm plantations involving forest conversion (%)

Forest area cleared for oil palm (end of 2002)

Total oil palm area target/ allocation (2003)

Additional area to be established (after 2004)

Additional forest to be cleared (after 2004)

Malaysia Indonesia Total

3.67 3.10 6.77

33 66 48

1.21 2.05 3.26

3.74 9.13 12.87

0.07 6.03 6.10

0.02 3.98 4.00

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CO2 input from power plants. Aside that, algae cultures have significantly greater yield than terrestrial crops making in that way lesser arable land needed for the same amount of biodiesel produced.

6 Conclusion In the global trend of increased primary energy consumption and large carbon dioxide emission into the atmosphere, it is necessary to raise production of energy from renewable resources, as well as promote cleaner alternative fuels than oil refined products. Due to EU Directive of 5.75% biodiesel share aim until 2010, in total diesel market, EU Member States are facing difficulties to fulfil these obligation because of insufficient arable area needed for crop cultivation, especially for states which are populous or have unfavourable climatic conditions. It is certain that goal of 5.75% until 2010. And finally 8% till 2020 would not be possible just relaying on domestic rapeseed production which will result in increased import of bio-oil, especially palm crude oil from SE Asia. Some estimations give share of at least 20% until 2010 or even more, regarding lower market price of palm oil than rapeseed. Production of palm oil is related with deforestation and peat drying which emit large quantities of carbon dioxide into the atmosphere which is contrary to biodiesel appellation as CO2 balanced fuel. Unlike biodiesel produced from terrestrial crops, microalgae have greater yield per area for the same amount of energy produced. Moreover, they can be even cultivated in arid and warm regions where there is no huge impact on environment or competition with food sector for arable area. Likewise, to produce algae biodiesel, on economically favourable conditions, it is needed that outside CO2 source is introduced into the system. Algae production plants should be placed near large fossil fired power plants or any other industry that emits carbon dioxide. In this way, not only that alternative clean transport fuel is produced, but CO2 is permanently sequestrated by means of biofixation.

References 1. Borowitzka M (1999) Commercial production of microalgae: ponds, tanks, tubes and fermenters. J Biotechnol 70:313–321 2. Buckland H (2005) The oil for ape scandal: How palm oil is threatening orang-utan survival. Research report for friends of the earth society, London, Sep, p 50, http://www.foe.co.uk/ resource/reports/oil_for_ape_full.pdf 3. Commission of the European Communities (2006) An EU Strategy for Biofuels, Communication from the Commision, COM(2006)34 final, SEC(2006)142, Brussels, http://ec.europa. eu/energy/res/biomass_action_plan/doc/2006_02_08_comm_eu_strategy_en.pdf 4. Kadam K (2001) Microalgae production from power plant flue gas: environmental implications on a life cycle basis. National Renewable Energy Laboratory, NREL/TP-510-29417, p 63 5. Qin J (2005) Bio-hydrocarbons from Algae-impacts of temperature, light and salinity on algae growth. A report for the rural industries research and development corporation, RIRDC Publication No 05/025, RIRDC Project No SQC-1A, p 26

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6. Sheehan J, Dunahay T, Benemann J, Roessler P (1998) A look back at the US department of energy’s aquatic species program: Biodiesel from algae, US department of energy’s office of fuels development, Prepared by the National Renewable Energy Laboratory, USA, p 328 7. Stepan D, Shockey R, Moe T, Dorn R, (2002) Carbon dioxide sequestering using microalgal systems. US Department of Energy, National Energy Technology Laboratory, p 32 8. UNEP (1999) Levine JS, Bobbe T, Ray N, Singh A, Witt RG. Wildland fires and the environment: A global synthesis. UNEP/DEIAEW/TR.99-1. Division of Environmental Information, Assessment and Early Warning (DEIA&EW) United Nations Environment Programme (UNEP), p 52 9. Van den Eelaart, A. (2006) Ombrogenous peat swamps and recommended uses in tropical areas, A Web site by Adriaan van den Eelaart in support of ISDP (Integrated Swamp Development Project) IBRD Loan 3755-IND, http://www.eelaart.com/, p 8 10. Wakker E (2004) Greasy palms: The social and ecological impacts of large-scale oil palm plantation development in Southeast Asia. Research for friends of the earth society, London, Mar, p 49, www.foe.co.uk/resource/reports/greasy_palms_impacts.pdf

Investigation of Combustion Kinetics of Five Waste Wood Samples with Thermogravimetric Analysis Sema Yurdakul Yorulmaz and Aysel Atimtay

Abstract In the present study, combustion mechanisms, thermal kinetics, and phases of combustion were investigated for untreated pine and treated MDF, plywood and particleboard samples. Waste wood samples were combusted in air at ◦ 10, 20 and 30 C/min heating rates in TGA. As a result of TG analysis, thermal decomposition of treated samples was observed at lower temperatures as compared to the untreated pine sample because of the catalyzing effects of the chemicals in the samples. Therefore, there were less flammable products, lower weight losses in the main oxidation region, decrease in the max. weight loss temperatures and formation of more char for treated samples as compared to untreated pine sample. In other words, chemicals used during production of these samples lead to decrease in the combustibility of the treated samples. Thermal kinetic constants for the samples were calculated by using Coats Redfern and Broido Methods. In order to find out the mechanisms responsible for the oxidation of the waste wood samples, six solid state mechanisms of Coats Redfern Method were tested. Keywords Wood and waste · Pine · MDF · Plywood · Particleboard · TGA · Activation energy Öz Bu çalı¸smada, kimyasal i¸slem görmemi¸s çam örne˘gi ve i¸slem görmü¸s, yani bazı kimyasallar ve katkı maddeleri içeren MDF, kontraplak ve sunta gibi maddelerin yanma mekanizmaları, ısıl kinetikleri ve yanma a¸samaları incelenmi¸stir. ◦ Atık odun örnekleri hava ortamında 10, 20 and 30 C/dak ısıtma hızlarında TGA cihazında yakılmı¸stır. TG analizleri sonunda, i¸slem görmü¸s örneklerde ısıl bozulmanın, i¸slem görmemi¸slere göre daha dü¸sük sıcaklıklarda olu¸stu˘gu gözlenmi¸stir. Bunun, içeri˘gindeki kimyasallara ba˘glı oldu˘gu dü¸sünülmü¸stür. Dolayısıyla, i¸slem görmü¸s örneklerde çam gibi i¸slem görmemi¸s örne˘ge göre daha az yanabilir ürünler, ana oksidasyon bölgesinde daha az a˘gırlık kayıpları ve daha fazla kok (char) olu¸sumu meydana gelmi¸stir. Ba¸ska bir deyi¸sle, bu örneklerin üretimi esnasında S.Y. Yorulmaz (B) Environmental Engineering Department, METU, 06531 Ankara, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_46,

511

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kullanılan kimyasallar, i¸slem görmü¸s örneklerin yanabilirli˘ginde azalmaya neden olmaktadır. ˙Incelenen örneklerin yanma kinetik sabitleri Coats Redfern ve Broido Yöntemleri kullanılarak hesaplanmı¸stır. Atık odun örneklerinin de˘gi¸sik bölgelerdeki oksitlenme mekanizmalarını incelemek üzere Coats Redfern metodundaki 6 de˘gi¸sik mekanizma denenmi¸stir. Anahtar kelimeler Aktivasyon enerjisi

Odun ve atık · Çam · MDF · Sunta · Kontrplak · TGA ·

1 Introduction During the production of wood based products or after the service life of these products, great amounts of waste wood are generated as by products. Depending on the production processes or usage purpose, these wastes can have different kinds of contaminants. Therefore, disposal of waste wood has great importance for elimination of these types of wastes with appropriate methods and technologies. Analysis and modeling of combustion in stoves, furnaces, boilers and industrial processes require adequate knowledge of wood properties [16]. Consequently, knowledge of the thermal kinetics and properties of the wood is essential for the designs and operations of the thermal processes. In the present study, combustion mechanisms, activation energy and preexponential constants, and phases of combustion were investigated for natural pine, MDF, particleboard and plywood samples in air environment at 10, 20 and ◦ 30 C/min. heating rates by means of Thermo Gravimetric Analysis (TGA).

2 Material and Methods About 5 mg sample (air dried, milled and sieved to 300–850 μm) was used for the experiments. Experiments were performed in TGA at 20 ml/min air flow rate ◦ and in a temperature range of 30–900 C. Three heating rates, namely 10, 20 and ◦ 30 C/min were used to understand the effect of heating rate on thermal kinetics, and emissions of the waste wood samples. For each experiment, weight loss of the samples was determined as a function of temperature. The output of the instrument gives the TG (Thermo gravimetric) curves as well as the derivative curves (DTG) of the sample. Elemental and proximate analyses results of the pine and MDF sample are given in Tables 1 and 2. In this study for the calculation of the thermal kinetics; activation energy and preexponential constant, Coats Redfern Method which is given in Eq. (2.1) was used.

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Table 1 Elemental composition of all samples (on dry, ash free basis) Sample

C (% by wt)

H (% by wt)

N (% by wt)

O (% by wt)

S (% by wt)

Pine MDF Particleboard Plywood

53.28 49.57 46.26 47.12

6.35 6.33 5.83 5.92

0.16 4.44 2.36 1.19

40.21 39.66 45.51 45.72

– – 0.04 0.05

Table 2 Proximate analysis and calorific values of all samples (on dry basis) Sample

Volatile matter (% by wt)

Ash (% by wt)

Fixed carbon (% by wt)

Calorific value (MJ/kg)

Pine MDF Particleboard Plywood

88.02 86.68 83.82 85.79

0.62 2.29 1.22 0.80

11.29 11.06 14.38 13.40

19.72 19.31 17.51 18.64

ln

E g(α) AR − = ln 2 T βE RT

(2.1)

α = (m0 − mt )/(m0 − m∞ )

(2.2)

where; m0 – initial weight of the reactant, mt – weight at time t, m∞ – weight at equilibrium. A is the pre-exponential factor, E is the activation energy, T is the absolute temperature, and R is the gas constant. According to the Eq. (2.1), a plot of ln[g(α)/T2 ] against reciprocal of temperature should give in a straight line with a slope equal to –E/R. Where g(α) is the integral function of conversion [1]. Table 3 shows different expressions of g(α) for the six different solid state mechanisms which were used in this study for the estimation of reaction mechanisms from dynamic TG curves by using Coats Redfern method. If the correct g(α) is used, the plot of ln[g(α)/T2] against 1/T should give a straight line with high correlation Table 3 Coats and Redfern Mechanisms used for the calculation of thermal kinetics in this study [7] Mechanism

g(α)

Symbol

Diffusion mechanism One-way transport Two-way transport Three-way transport Ginstling-Brounshtein equation

α2 α + (1 + α) ln (1 − α) 2 (1 − α)1/3 1 − 2 α/3 − (1 − α)2/3

D1 D2 D3 D4

1 − (1 − α)1/3

R3

− ln (1 − α)

F1

Limiting surface reactions both phases Three dimensions Chemical reaction First order

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coefficient of linear regression analysis, from which the values of E and A can be derived, therefore; the slope of the linear function will give the activation energy, E, and the intercept of the line will give the pre-exponential constant, A [2]. In this study Broido method was also used for the calculation of thermal constants. For Broido method Eq. (2.3) was used.. 2 Ln ln (1/y) = −E/RT + ln RATmax /Eβ

(2.3)

In this equation y is the mass fraction of initial sample that has not been decomposed, Tmax is the temperature of maximum reaction velocity, β is the rate of heating (Kmin−1 ), A is the pre-exponential constant, E is the activation energy and R is the gas constant equal to 8.314 Jmol−1 K−1 . From the above derivation, it can be concluded that the Broido method is in fact based on the assumption that the order of reaction is unity [15]. By using the Broido method, the activation energy of the reaction can be determined from the slope of the plot ln(ln1/y) versus 1/T [14].

3 Thermal Kinetic Results of the Samples According to TGA analysis results four regions were determined on thermographs. These regions were determined according to the approximate start and end points of the Derivative Thermogravimetry (DTG) curve which shows thermal breakdown of the organic matters and volatiles in the samples [3]. The first region on the DTG curve was due to the moisture in the sample. The second region, where elimination of the moisture finished and main oxidation did not start precisely, was due to very volatile matters. The third region where the main weight loss occurred was due to oxidation and removal of the volatile matters of the sample. The last region was due to oxidation of the char remaining after the volatiles were removed from the sample. Thermal kinetics of the first region which was due to moisture was not calculated. Duplicate experiments were done in order to observe reproducibility. Weight losses of the samples as compared to the regions are given in Table 4. As can be seen from Table 4, the largest weight loss was detected in the third region for pine samples (average 63%) among the investigated waste wood samples. For the treated Table 4 Weight loss of all samples for different regions Weight loss of samples, % by weight Region

P-10 P-20 P-30 M-10 M-20 M-30 PL-10 PL-20 PL-30 PB-10 PB-20 PB-30

1 2 3 4

4.7 4.3 65 26

5.9 4.7 63.4 26

5.4 5.6 63 26 ◦

4.5 7.7 52.2 35.6

4.6 9.1 52.8 33.5

5.16 7.95 53.7 33.19

6.1 5 55.4 33.5

7.8 2.13 61 29

4 2 61 33

7 8 54 31

8.5 5.5 51.6 33.4

4.41 3.58 59.83 32.18

P-10 = Pine sample at 10 C/min heating rate, M = MDF, PL = Plywood, PB = Particleboard

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Temperature (°C)

samples, smaller weight losses were observed in this region. However, for the fourth regions, the largest weight losses were seen for the treated waste wood samples. Owing to chemical treatment, probably lower percentages of volatile matters were released during the main oxidation region and this increased the amount of char in the treated wood samples. This indicated the catalytic effect of adsorbed chemicals in the treated samples on the oxidation behavior of the samples [5, 8, 4]. When the heating rate was increased, weight loss of the samples also increased. As heating rate was increased, higher temperatures were detected for the same weight loss for all samples, namely the highest temperatures were detected at ◦ ◦ 30 C/min heating rates, and the lowest temperatures were observed at 10 /min for the same weight loss. As can be seen from the Fig. 1, for the 60% weight loss, higher temperatures were observed for P-30 sample as compared to other samples, but after the 60% weight loss, the higher temperatures were observed for treated samples because of some chemicals used. Parallel weight losses were observed for other waste wood samples, especially PB and PL samples. The temperature of the peaks in the DTG curves depends on the heating regime [2]. Peak temperature (PT) and Burnout temperature (BT) are the main characteristic temperatures for the DTG curves. The peak temperature represents the place where the rate of weight loss is at maximum. This parameter is used mainly in the assessment of combustibility. Lower temperature shows the easily ignition. The burnout temperature shows the temperature where sample oxidation is completed [3]. The characteristic peak and burnout temperatures of all waste wood samples for the present study are given in Table 5. As can be seen from the table, generally speaking, when the heating rate was increased, peak and burnout temperatures also increased. Hence, when heating rate increased, ignitions of the samples were

P-10

600 550 500 450 400 350 300 250 200 150 100

P-20 P-30 M-20 M-30 PB-10 PB-20 PB-30 PL-10 0

10

20

30

40

50

60

70

80

90

Weight loss (%)

100

PL-20 PL-30 M-10

Fig. 1 Temperature vs. weight losses of all samples at different heating rates

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S.Y. Yorulmaz and A. Atimtay Table 5 Peak and burnout temperatures of the samples Peak temperatures (o C) Sample

In third region

In fourth region

Burnout temperatures (o C)

P-10 P-20 P-30 M-10 M-20 M-30 PL-10 PL-20 PL-30 PB-10 PB-20 PB-30

358 366 371 341 346 352 326 324 374 321 332 362

510 523 520 509 514 537 464 448 554 466 483 550

553 555 575 567 570 583 500 500 620 510 520 610

difficult. Among all samples, pine samples had also the highest peak temperatures; therefore, pine samples could not be ignited easily among the other samples. For the thermal decomposition of the waste wood samples, the third region, where the highest and rapid weight loss occurred, played important role for the combustibility of the samples. For treated samples; MDF, particleboard and plywood, the third stage of thermal decomposition was observed at lower temperatures as compared to pine sample which is an untreated sample, because chemicals in the treated samples might catalyzed the decomposition of the cellulose which makes the whole oxidative decomposition of the wood occur at lower temperatures [5]. As a result of this, less flammable products were emitted and more char was observed from these treated samples [6]. However, in the present study char yields of the treated samples were found a little lower than the char yield in the literature as 11.1–17.7% [13]. This may be due to the different samples used in the literature. Low char yields of the treated flame retardancy is poor. When thermal kinetic results of all samples were examined by using Coats Redfern Method, for all heating rates, it can be seen that in the second regions, D1 mechanism in the third regions, D4 mechanism and in the fourth regions, D1 and D2 mechanisms were found as an effective solid state mechanisms for the oxidation process for untreated pine samples. For the treated samples such as MDF, plywood, particleboard samples, in second and fourth regions of these samples diffusion mechanisms; in the third region of the samples F1 mechanism was assumed as the main mechanism which is responsible for the oxidation of these samples. Therefore, for the thermal oxidation of the waste wood composites, in the main oxidation region F1 mechanism seems to be responsible mechanism; however for untreated samples D4 mechanism was found as an effective mechanism. As a conclusion, treatment of the wood with different additives and glues altered the thermal oxidation process and changed the effective mechanism.

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With Broido Method, good correlation coefficients were obtained for pine samples, except the third region. In the second region, higher correlation coefficients were found as compared to Coats Redfern Method. On the other hand, when activation energies and pre-exponential constants found with Broido Method were compared with that of Coats Redfern Method, dissimilar results were obtained especially in the third regions of the pine sample. However, in our study for treated samples, higher correlation coefficients were found in the main oxidation region as compared to untreated samples with Broido Method. It can be seen that such agreements are not surprising, because for the treated samples first order reaction was found as a responsible mechanism. Therefore, since Broido method was based on the first order reaction, good correlation coefficients were obtained. However, for the untreated samples lower correlation coefficients were found with Broido method as compared to treated samples in the main oxidation region, because for untreated samples D4 mechanism was found as a responsible mechanism and it is different than the first order models. In conclusion, it can be said that for the calculation of the kinetic constants in the main oxidation region for the treated samples Broido method is satisfactory. For the untreated samples the Coats Redfern Method can be preferred for the calculation of kinetic constants due to good correlation coefficients obtained and also due to the agreement of the results with literature. Comparison of the activation energies found in the present study and other studies in the literature are given in Table 6. For pine samples (i.e., untreated), the activation energy values and pre-exponential constant values of the samples were compared with treated samples (MDF, plywood, particleboard) higher activation energies were found for the main oxidation region. The presence of the inorganic materials influences the thermal degradation of the lignocellulosic materials and may act as a flame retardant by lowering the activation energy of the thermal reaction [4]. This also indicate that the chemicals in the waste wood samples change the mechanism of thermal decomposition in such a way as to reduce the decomposition temperatures of wood, which can lead to less flammable volatile products and more char [6]. When activation energies of the treated waste wood samples (MDF, particleboard and plywood samples) were compared with each other (Table 6), closer values were found because of the similar production techniques and chemicals. Consequently, it must be stated that the chemical composition of each type of wood together with the chemicals added to the wood for each application, have a very important function in the kinetic behavior of the thermal decomposition of the wood [9]. For all samples, activation energy and pre-exponential constant values were also affected by the heating rate because the temperature of the peaks in the DTG curves depends on the heating regime. Consequently, the kinetic parameters characterizing the different processes were anticipated to be different [2]. Especially in the third region of the samples, this effect was observed clearly, because activation energy and pre-exponential constant values were got higher with increasing heating rate. The highest activation energies and pre-exponential constant values were found in the third regions of all samples due to high volatile released in this region [2].

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Table 6 Comparison of the activation energies found in the present study with that of literature for the main oxidation, second and fourth region Ea (kJ/mole) in air atmosphere

Literature

Sample

Ea (kJ/mole) in nitrogen Third atmosphere region

Present study

Pine

–

123–136a (62–74)b

Second and fourth regions Second region Fourth region

MDF

–

45–50 (54–59)

Second region Fourth region

Particleboard

–

54–59 (63–69)

Second region Fourth region

Plywood

–

52–72 (62–82)

Second region Fourth region

Gao [5] ◦ (@ 10 C/min)c

Antal et al. [17] Reina et al. [9] ◦ (@ 5 C/min) Deka et al. [10] ◦ (@ 20◦ C/min) (@ 30 C/min) Zakrewski [12] (@ 5 o C/min) Schniewind [11]

Untreated wood

–

126

MF treated wood

–

95

MFP treated wood UDFP treated wood Wood Furniture Forest Pellet Untreated wood Treated wood Untreated wood Treated wood Pine wood

–

74

–

80

109–138 129.36 136.18 127.61 112 132–138 119 130–134 85.6–168.3

– – – – – – – – –

63–139

96–147

◦

Wood (T<300 C)

First region Third region First region Third region First region Third region First region Third region

23–28a (16–19)b 15–18a (35–40) 23–26 (16–17) 10–11 (35–38) 21–25 (15–17) 8–10 (27–35) 24–61 (17–36) 11–24 (31–45) 68 18 29 17 50 15 57 13

a Result

of the Coats Redfern Method for the highest correlation in the given regions show the results of the Broido method in the given regions c Results of the main oxidation region of the samples b Parenthesis

For all samples, the lowest activation energies for the Coats Redfern method were found in the last region due to lower content of the volatile matters in the samples (Table 6). This situation was also observed by Gao [5], however for the second region values of the activation energies were found lower than the results of the Gao,

Investigation of Combustion Kinetics of Five Waste Wood Samples with TGA

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this was probably caused different reasons, mainly due to selection of the regions, difference between the heating rate, flow rate, operational conditions, sample size and amount and the other conditions. In addition to the operational conditions, sample type mainly affects the thermal constants, in the present study composite waste wood samples which were formed wood particles were used directly; however, Gao used the wood samples for the chemical treatment; therefore, for only one chemical type was studied, but in the present study different chemical and additives could be used for the production of the waste wood samples.

4 Conclusion • The TG curves for waste wood samples investigated in this study show four regions of thermal degradation in air. The first region on the DTG curve was due to the moisture in the sample. The second region was due to very volatile matters. The third region where the main weight loss occurred was due to the oxidation and removal of the volatile matters of the sample. The last region was due to the oxidation of the char remaining after the volatiles were removed from the sample. • Addition of the chemicals to the wood improved the fire retardancy of wood by lowering its weight loss rate, lowering peak temperatures for decomposition and by decreasing the formation of volatile combustibles through promotion of higher char yield as compared to the untreated sample. • When thermal kinetic results of pine samples were examined by using Coats Redfern Method, diffusion mechanisms were found to be an effective mechanism for all regions. For the main oxidation region, D4 mechanism (GinstlingBrounshtein equation) was found as the main diffusion mechanism for pine sample. • For the treated samples such as MDF, plywood and particleboard, diffusion mechanisms in the second and the fourth regions of these samples were found to be effective mechanisms. However, for the main oxidation region of these samples F1 mechanism (First order reaction) was assumed as main mechanism. Accordingly, treatment of the wood with different additives and glues seemed to alter the thermal oxidation process and change the effective mechanisms. • When activation energies are compared by using the Broido Method and the Coats Redfern Method, dissimilar results were obtained especially in the third region of the pine samples, but for the MDF, particleboard and plywood samples more similar results were found. • For treated samples (MDF, plywood and particleboard), lower activation energies were found for the main oxidation region because of the chemicals which may act as catalysts by lowering the activation energy of the thermal reaction. Consequently, chemicals added to wood for different purposes, have a very important role in the kinetic behavior of the thermal decomposition of the wood.

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References 1. Minying L, Lijun G et al (2003) Thermal degradation process and kinetics of poly (dodecamethyleneisophthalamide). CJI 5(6):43 2. Vlaev LT, Markovska IG, Lyubchev LA (2003) Thermochemica Acta 406:1–7 3. Sonibare OO, Ehinola OA, Egashira R, KeanGiap L (2005) An investigation into the thermal decomposition of Nigerian Coal. J Appl Sci 5:104–107 4. Nassar MM (2004) Kinetic and thermodynamic parameters during thermal decomposition of dye adsorbent bagasse. Energy Sour 26:1357–1362 5. Gao M (2004) Thermal degradation of wood in air and nitrogen treated with basic nitrogen compounds and phosphoric acid. Combustion Sci Technol 176:2057–2070 6. Gao M, Pan DX (2003) Study on the thermal degradation of wood treated with amino resin and amino resin modified with phosphoric acid. J Fire Sci 21:189–201 7. Sun JT, Huang YD et al (2006) Thermal degradation kinetics of poly(methylphenylsiloxane) containing methacryloyl groups. Polym Degrad Stab 91:339–346 8. Getto H, Ishihara S (1998) The functional gradient of fire resistance laminated board. Fire Mater 22:89–94 9. Reina J, Velo E, Puigjaner L (1998) Thermogravimetric study of the pyrolysis of waste wood. Thermochimica Acta 320:161–167 10. Deka M, Saikia CN, Baruah KK (2002) Studies on thermal degradation and termite resistant properties of chemically modified wood. Bioresorce Technol 84:151–157 11. Schniewind AP (1989) Concise encyclopedia of wood and wood based materials, 1st edn. Pergamon Press, Elmsford, pp 271–273 12. Zakrzewski R (2003) Pyrolysis kinetics of wood comparison of iso and polythermal thermogravimetric methods. Electr J Polish Agric Univ 6:2 13. Lee HL, Chen GC, Rowell RM (2004) Thermal properties of wood reacted with a phosphate pentoxide amine system. J Appl Polym Sci 91:2465–2481 14. Jianzhong X, Xiaolong Z, Hongqiang Q (2004) Study on the thermal stability of flame retardant wools. CJI 6(10):74 15. Liu NA, Fan WC (1998) The kinetic methods for which no assumption about the order of reaction is needed. Fire Mater 22:219–220 16. Ragland KW, Aerts DJ, Baker AJ (1991) Properties of Wood for Combustion Analysis. Bioresource Technology 37:161–168 17. Antal MJ, Gronli M (2003) The art, science and technology of charcoal production. Ind. Engin. Chem. Res. 42: 1619–1640

On Integration of Mirror Collector and Stirling Engine for Solar Power System B.F. Yousif, Ammar Al-Shalabi, and Dirk G. Rilling

Abstract In the current work, several types of solar collectors, i.e. parabolic, cylindrical, and mirrors, were designed and fabricated. The aim of this study is to integrate the optimum collector with Stirling engine in Malacca city, Malaysia. Stirling engine was designed using CATIA software. The solar collectors were tested for several sunny days and the temperature in the focus point was measured. Comparing the experiment results shows that mirror solar collector introduces ◦ highest temperature among others, which was about 190 C. According to that temperature, the Stirling engine has been designed in bore piston dimension of 50 mm. Alpha Stirling engine type was selected for this purpose, which may run in this range of temperature. Keywords Solar power · Collector · Stirling engine · Solar energy

1 Introduction Nowadays, need of energy and increasing environmental awareness, alternatives to fossil fuels are being of high concern to many engineers. One of the alternative resources is solar energy, which are free, clean and free of environmental pollution [10, 11]. Solar energy is simply the energy which is produced directly from the sun light. There are many reported methods to implement the solar energy for useful life applications, such as solar water heater system [7], solar dryer system [7], and solar power generator [7, 15, 9, 2, 12]. In the last decades, there have been many research attempts to run the external combustion engines, such as Stirling engine, using solar energy [3], it has been reported by Abdullah et al. [2] that the maximum temperature gain is about B.F. Yousif (B) Faculty of Engineering and Technology, Malacca Campus, Multimedia University, 75450 MMU, Malacca, Malaysia e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_47,

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◦

70 C. Using hot water as a heat resource [2]. Meanwhile, in using mirror collectors, high temperature may be obtained [7, 12]. Currently, Stirling engine is one of the most efficient devices for converting solar heat into mechanical work and an ideal candidate for harvesting the power from the sun [15]. Integrating Stirling engine with high temperature solar collector is carried out in Malacca city in Malaysia where there is only one season which is always hot. In the present work, several types of solar collectors (mirror collector, parabolic, and cylindrical trough) are designed, fabricated and tested. Mirror collector is selected as the best to be integrated with the proposed Stirling engine.

2 Solar Collector Design Generally, there are two main parts of concentrating collector, concentrator and receiver. Concentrator can be cylindrical or parabolic, continuous or segmented. Receiver can be convex, flat, cylindrical or concave, and can be covered with glazing or uncovered. Some important parameters are to be considered in the design of concentrating collector such as concentrating ratio, rim angle, reflective surface, receiver material, collector orientation and mode of tracking. Concentrating ratio is the ratio of aperture area (opening area of solar collector) to receiver area; it can vary over several orders of magnitude. An increased concentrating ratio corresponds to increased temperature at which energy can be delivered but this increases the requirement for precision in concentrator quality and positioning of the concentrator [6]. Rim angle is defined as the angle between the incident ray and the reflected ray. Materials used in the collector affect its performance. For concentrator, material with better reflectance is preferred since it needs to reflect as much solar radiation as possible. And, it must have long life and low cost because the reflecting surface may deteriorate when exposed to weather. The common materials used are, for instance, polished aluminum surface and iron glass mirror. The essential task of a receiver is to absorb maximum amount of reflected solar energy and transfer it to heat with minimum losses to the surrounding. The commonly used materials are copper and brass. Concentrating collector can be orientated east-west tracking north-south or orientated north-south tracking east-west [11].

2.1 Parabolic Trough Collector The scale model of this collector (Fig. 1) uses a piece of shining aluminum shield as a concentrator (reflective surface) while a solid brass rod as the receiver. These two materials are selected due to their low cost and availability. Aluminum shield is easy to fabricate and form into parabolic shape to develop the parabolic trough. Both materials have been cleaned before put into use. The trough is made base on a parabola function,

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Fig. 1 Scale model of parabolic trough collector in 3-D view in catia. 1. Polystyrene, 2. Aluminum shield, 3. Brass rod

y=

x2 4f

where y and x are the coordinates of trough and f is its focal point location from the vertex of the parabolic trough. This function is used to calculate the size of the trough when the focal point location is selected [4]. A focal point of 5.08 cm from vertex is selected. The receiver (brass rod) is placed at this position, creating a focal line. At this position, it is near to the trough’s surface, thus reducing the heat convection loss between them since the gap is small. To reduce heat conduction loss from the receiver, a brass rod of less surface area is selected. By reducing overall heat loss, a higher temperature can be obtained at the receiver. The frame and support of the parabolic trough are made of polystyrene due to its low cost, light weight, and moreover it is easy to fabricate. In order to obtain maximum possible temperature and to save cost, the parabolic trough is manually adjustable to track the sun motion for sharp focal on the receiver. The designed collector is a single axis tracking type. Thus, the scale model of this collector is orientated north-south tracking east-west. The dimension of aluminum shield and solid brass rod are shown in Table 1 and the parameter of parabolic trough collector is shown in Table 2. Table 1 Dimension of aluminum shield and solid brass rod Part

Diameter (cm)

Length (cm)

Width (cm)

Aluminum shield Solid brass rod

– 0.8

38.1 81.3

60.96 –

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Table 2 Parameter of parabolic trough collector

Parameter

Unit

Rim angle Aperture area Concentration ratio

127◦ 1548.38 cm2 16:1

2.2 Iron Glass Mirror Collector The glass collector (Fig. 2) uses 81 pieces of iron glass mirror as a concentrator. The concentrator is a point focusing type. A copper plate is used as receiver. The dimension of iron glass mirror and copper plate is shown in Table 3 and the parameter of parabolic trough collector is shown in Table 4. The mirrors are used to stimulate the paraboloid shape to focus the reflected ray to receiver as one focal point according to the law of reflection. Figure 3 explains that the angle of incidence at which a ray intersects a reflective plane is equal to the

Fig. 2 Iron glass mirror collector. 1. Concentrator frame in paraboloid shape to attach 81 pieces iron glass mirrors, 2. Support plate

Table 3 Dimension of iron glass mirror and copper plate Part

Length (cm)

Width (cm)

Quantity (pcs)

Iron glass mirror Copper plate

14 14

10 10

20 1

On Integration of Mirror Collector and Stirling Engine for Solar Power System Table 4 Parameter of parabolic trough collector

525

Parameter

Unit

Rim angle Aperture area Concentration ratio

37◦ 2800 cm2 20:1

n

Fig. 3 Law of reflection

Reflected ray

Incident ray

i

r

Reflective surface

Angle i = Angle r

Fig. 4 Reflection of incident ray from iron glass mirror to focal point

f i r Iron glass mirror

y

x

angle of reflection at which the ray is reflected [5]. Figure 4 shows the reflection of incident ray from iron glass mirror to focal point. To simulate the paraboloid shape, each mirror is arranged by having five mirrors in a row and each row is stacked above one another, giving a total of four rows. A manually adjustable support behind each mirror allows the mirrors to focus the sun ray on the receiver according to sun motion. A parabola function is used to calculate the exact position of each mirror to be attached to a frame by setting fixed value for coordinate x and focus point f [4].

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3 Stirling Engine Commonly, solar powered Stirling engines are classified according to the operating temperature difference, regardless of kinematics or “free piston”, non physical linkage; High Differential Temperature Stirling Engine (HDTS) and Low Differential Temperature Stirling Engine (LDTS) [1]. These engines are used to power application like water pump, electricity generator or even refrigeration cooler [8]. In this paper, an alpha-type engine is suggested. A simple thermodynamic model is set up to obtain the necessary basic design parameters for the Stirling engine. Although Stirling engine operates in a close cycle with consistent gas composition, it is still very difficult to simulate the actual process as the working fluid travels across different chambers and has varying heat transfer rate; therefore a standard ideal gas cycle is considered as an approximate substitute to the real cycle [17]. Figure 5 is used to develop the energy equation and subsequently the thermodynamic model. The separated expansion cylinder is the sole power provider for the focus of analysis, thus simplifying the task. The energy equation can be simplified as the gross heat input. The QH and QL describe the heat flux entering and leaving the thermal engine. Energy equation: Qin = QH − QL The working gas of the engine is atmospheric air (treated as ideal gas), and assumed to be working under normal atmospheric pressure of one bar. The heat transfer and the working gas flow friction losses in the engine are insignificant, and should be ignored; but those losses will be taken into account in the later stages. The classical Schmidt analysis has been the simplest and most widely used method in Stirling engine design. Although subjected to limitations [1], the analysis is still able to provide a lot of useful information. Due to the fact that the working concept is based on an ideal isothermal model; the thermal efficiency should be reduced to the simple Carnot Efficiency [14]. Consequently, it is possible and much more convenient to start the engine design with a classical Carnot Cycle [19] without much error.

Ideal thermal efficiency: (η)Stirling = 1 −

Q Fig. 5 Stirling engine schematic model

Expansion Chamber

TLow THigh

Piston

Working Gas

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However in actual situation, the maximum achievable efficiency may only reach about 50% of the theoretical ideal Carnot value [16]. In short, the engine suggested for this paper must produce at least as twice as much power in the analysis of the desired load required. By substituting a coefficient, the losses will be more or less compensated. Then, multiplying the equation with heat input which will yield the estimated actual work produce: WStirling

1 TLow = Qin 1 − 2 THigh

From the equation, the temperature difference is directly proportional to the engine performance. Therefore, the solar collector is designed to achieve the highest temperature difference possible. In the design, the engine needs to cater power requirement to run the desired application and compensate all loses in the system. Therefore, the gross indicated power can be generalized as shown. (W)Indicated = (W)Brake + (W)Losses,System After the initial design, all the parameters will be optimized to maximize thermal efficiency and avoid lose to produce the highest output possible.

4 Results and Discussion 4.1 Solar Collector The temperature achieved by the solar collector is measured at its receiver when exposed to solar radiation. A parabolic trough with the entire parallel ray from sunlight reflected to a focal line which is formed along the brass rod (receiver). A parabolic trough is not symmetrical to rotation about its focal point. Thus, if the incident beam of parallel rays (solar radiation) is even slightly off normal to the trough aperture, beam dispersion occurs, resulting in spreading of the image at the focal line [18]. Since the trough is manually adjusted, there is always some beam dispersion, which reduces the possible maximum temperature. The temperature achieved by the collector is shown in Fig. 6. It is obvious that there is fluctuation in the temperature. The fluctuation is caused by the blocking of sun by moving cloud and wind blow. The sun’s intensity is reduced when blocked, causing the decrease in temperature. The temperature also drops when there is light wind blow due to greater degree of convective heat loss of the receiver to the surrounding. For this collector, the sun ray is reflected to a focal point (copper plate). In order to obtain maximal temperature, each mirror is manually adjusted every 15 minutes to track the sun motion. From Fig. 7, it is noticed that the temperature obtained is not

528 160 140 Temperature oC

Fig. 6 Temperature measurement of parabolic trough collector, 2005

B.F. Yousif et al.

136.5

120

117.7

100

97.3

80

76.9

105.5

118.6

101.6 89.9 78.2

84.6 63.7

100.6

60 40

temperature max temperature average temperature min

20 0 31/8

4/9

2/9

5/9

Fig. 7 Temperature measurement of iron glass mirror collector, 2005

Temperature °C

Date

200 180 160 140 120 100 80 60 40 20 0

184.8

162.9

189.9 160.1

141.45

145.3

120

123.85

144.7

130.3

104.6

102.4

temperature max temperature average temperature min 31/8

2/9

4/9

5/9

Date

constant due to cloudy weather and wind blow. Overall temperature also decreases at late evening because the collector has already reached the maximum adjustable angle. Basically, the common features between the two collectors are using parabola as its concentrator and they are categorized as concentrating collector which track the sun motion. However, there are few differences between them. Firstly, the reflective material used for the parabolic trough collector is continuous shining aluminum shield and the other one made used of segmented iron glass mirror which form the parabolic shape. And, the reflectance of the shining aluminum shield surface is in the range of 0.8–0.9. The reflectance of the iron glass mirror is above 0.9 which gives better temperature reading as compare with parabolic trough collector [13].

4.2 Stirling Engine Design Initial design of the engine is started with bore dimension of 50 and 100 mm stroke according to the estimated maximum temperature from the solar collectors. Figures 8 and 9 show the first design drafting for the engine.

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Fig. 8 Two dimensional drawing of stirling engine design in catia

Fig. 9 Three dimensional model of stirling engine in catia. 1. Expansion Cylinder with integrated heater, 2. Compression Cylinder, 3. Piston, 4. Connecting Rod, 5. Fly Wheel, 6. Support Stand

Alpha-type engine was opted for several reasons. Firstly, the simplicity of construction; components are easily fabricated from items available in market and it can be modified easily. The drive mechanism is simple. Integrated heater with expansion cylinder eliminates the need to heat regenerator and minimizes dead volume in the system. Besides that, it is far away from the compression cylinder.

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The engine parameters will be optimized in a series of iteration process to acquired the best performance in between the trade offs.

5 Conclusion Generally, the iron glass mirror collector shows the highest temperature as compared to parabolic trough collector. The highest temperature obtained by iron glass mirror and parabolic trough collector is 189.9 and 136.5◦C respectively. This is because the reflectance of mirror is higher than aluminum shield and the iron glass mirror collector has greater concentration ratio. As explained earlier, higher concentration ratio corrresponds to higher maximum temperature. The configuration of the scale model for both collectors is still in testing stage. There are more corrections need to be done to improve the performance. The engine design is still in the initial stage, all the details are merely for demonstration purpose only. More work will be following to complete the design.

References 1. Abdullah S, Sopian K, Ali Y (2000) Design of an environment friendly solar water pumping system using the stirling engine. Proc. Reg. Conf. Energy Envionment, Malayisa, Universiti Tenaga Nasional, Malaysia 2. Abdullah S, Yousif BF, Sopian K (2005), Design consideration of low temperature differential double-acting Stirling engine for solar application. Renewable Energy 30(12);Oct 2005: 1923–1941 3. Bancha K, Somchai W (2005) Optimum absorber temperature of a once-reflecting full conical concentrator of a low temperature differential Stirling engine. Renewable Energy 30(11);Sept 2005:1671–1687 4. Dendane A.(2007) Find the focus of parabolic dish antennas;5. Future Scientists and Engineering of America, FSEA Project Plan (1999). Retrieved November 15, 2009 from http://www.analyzemath.com/parabola/parabola_focus.html. 5. Future Scientists and Engineering of America, FSEA Project Plan (1999) 6. Kreith F, Kreider JF (1978) Principle of solar engineering. McGraw Hill, New York 7. Mills D (2004) Advances in solar thermal electricity technology. Solar Energy 76(1–3); Jan-Mar 2004:19–31 8. Organ AJ (1997) The regenerator and the stirling engine. MEP, London 9. Pongsakorn K, Maung M, Sombat T, Jongjit H, Joseph K, Belkacem Z (2005) Development of a new solar thermal engine system for circulating water for aeration. Solar Energy 78(4); Apr 2005:518–527 10. Senft JR (1993) General analysis of the mechanical efficiency of reciprocating heat engines. J Franklin Inst 330(5); Sept 1993:967–984 11. Kalogirou SA (2004) Solar thermal collectors and application, Department of Mechanical Engineering, Higher Technical Institute, Cyprus 12. Theocharis T, Vasilis G, Katerina M (2003) Technical and economical evaluation of solar thermal power generation. Renewable Energy 28(6);May 2003:873–886 13. Tripanagnostopoulos Y, Yianoulis P, Papaefthimiou S, Zafeiratos S (2000) CPC solar collectors with flat bifacial absorbers. Solar Energy, 69: 171–203 14. Urieli I, Berchowitz D (1984) Stirling cycle engine analysis. Adam Hilger Ltd., Bristol

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15. Valdès C (2004) Competitive solar heat engines. Renewable Energy 29(11);Sept 2004: 1825–1842 16. Walker G (1980) Stirling engine. Claredon Press, Oxford 17. Willard WP (1997) Engine cycles, engineering fundamentals of the internal combustion engine (International edn). Pearson Prentice Hall, London 18. Stine WB, Geyer M (2001) Power from the sun. http://www.powerfromthesun.net 19. Yunus AC, Boles MA (2002) Thermodynamics, an engineering approach, 4th edn. McGraw Hill, New York

Part V

Environment and Health

Antioxidant Activities of Molokhia (Corchorus olitorius L.) Extracts Nilgün Öztürk and Filiz Savaro˘glu

Abstract Corchorus olitorius L. (Molokhia) (Tiliaceae), collected from the Do˘ganci, Güzelyurt, Northern Cyprus, infusion and extracts with different polarities have been studied for their polyphenolic contents and antioxidant activities. Total phenolic content was determined spectrometrically according to the Folin-Ciocalteu method and calculated as gallic acid equivalents (GAE). Antioxidant activitiy was studied in an aqueous emulsion system of β-carotene and linoleic acid by measuring the absorbance of the samples. The free radical-scavenging properties were also evaluated against 2,2-diphenyl-1-picryhydrazyl radical (DPPH• ). Results were compared those of an synthetic antioxidant, BHT. Antioxidant effects were correlated with the total amount of phenolic compounds contained in the extracts. In all these cases higher antioxidant activity was seen in the samples with higher phenolic content. Keywords Corchorus olitorius L · Molokhia · Antioxidant activity · Antiradical activity

1 Introduction Fruits and vegetables have a regular place in traditional vegetarian cuisine. Green leafy vegetables are more common in daily diet than other vegetables. These vegetables are rich in potassium, calcium, magnesium and phosphorus, vitamins C, E, K and carotenoids. The protective action of vegetables has been attributed to the presence of antioxidants, especially antioxidant vitamins including ascorbic acid, α-tocopherol and β-carotene [1].

N. Öztürk (B) Department of Pharmacognosy, Faculty of Pharmacy, University of Anadolu Tepebasi, 26470 Eskisehir, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_48,

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However numerous studies have conclusively shown that the majority of the antioxidant activity may be from compounds such as flavonoids, isoflavone, flavones, anthocyanin, catechin and isocatechin rather than from Vitamin C, E and β-carotene. They retard oxidative degradation of lipids and there by improve the quality and nutritional value of food [2]. In addition; epidemiological studies have shown that consumption of food rich in phenolic content can reduce the risk of heart disease by slowing the progression of atherosclerosis by acting as anti-oxidants towards low-density lipo- protein (LDL) [3]. Considering the chemical diversity of the antioxidant compounds present in foods and the interaction occurring among those different molecules, the evaluation of the total antioxidant capacity of foods seems to be a more useful marker than the evaluation of single compound. However, no single method to test the total antioxidant capacity of foods fully consider, at the same time, the activity of all the antioxidant compounds [4–5]. The genus Corchorus comprises certain herbs and shrubs. It contains about 100 species which are distributed in the tropics and subtropics, chiefly South-East Asia and South America. Corchorus olitorius Linn., commonly known as jute, belongs to the botanical family Tiliaceae. It is also known as Moroheiya in Japan, Molehiya in Cyprus and Philippines. Jute is an annual herb with slender stems and an important green leafy vegetable in many tropical areas including Egypt, Sudan, India, Bangladesh, tropical Asia such as the Philippines and Malaysia, tropical Africa, Japan, South America, the Caribbean and Cyprus. In West African countries particularly Ghana, Nigeria and Sierra Leone, where staple diets consist of starchy food-stuffs like rice, cassava, maize and yams, leafy vegetables are used to complement such staple foods [6]. C. olitorius, which is cultivated to provide bark for the production of fibres (Jute) and mucilaginous leaves for using in food as a vegetable [7–8], is extensively consumed as a “health vegetable” in Japan, because it contains abundant carotenoids, vitamin A, B1 , B2 , C and E, minerals including calcium and iron and other micronutrients and high levels of all essential amino acids except methionine [9]. It has high protein and is, along with other leafy species, the main source of dietary protein in many tropical countries [6]. The seeds are used as purgative and antibacterial [10], and they are contain cardenolide glycosides [11–12]. The leaves are used as demulscent, diuretic, febrifuge (infusion) and in chronic cystitis and dysuria. The aqueous solution of the leaves was found to decrease hyperglycaemea in mice, guinea-pigs and rabbits. it promoted the degradation of glucose [8]. In addition, the antioxidative activity of C. olitorius leaves was assayed by using a linoleic acid system, was reported six phenolic antioxidative compounds (5-caffeoylquinic acid (chlorogenic acid), 3,5-dicaffeoylquinic acid, quercetin 3-galactoside, quercetin 3-glucoside, quercetin 3-(6-malonylglucoside), and quercetin 3-(6-malonylgalactoside)) [13]. In this study, we examined the antioxidant activity of molokhia (C. olitorius), employing various in vitro assay systems, such as the β-carotene linoleate model system, DPPH radical scavenging, in order to understand the usefulness of this plant as a foodstuff. as well as in medicine. The results were related to the total phenolic content determined by the Folin–Ciocalteu method, and were compared with those exhibited by a reference substance, butylated hydroxytoluol (BHT).

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2 Materials and Methods 2.1 Plant Materials Corchorus olitorius L. (Molokhia) (Tiliaceae), collected from the Do˘ganci, Güzelyurt, in Northern Cyprus. The voucher specimens were deposited in the Herbarium of the Faculty of Science and Arts, Eski¸sehir Osmangazi University, Eski¸sehir-Turkey (ESOGU).

2.2 Chemicals BHT and Folin Ciocalteu’s phenol reagent, β-caroten, linoleic acid and Tween 80 were purchased from Sigma Chemical Co. (St. Louis, MO), 2,2-diphenyl-1picrylhydrazyl radical (DPPH. ) and all solvents were from Aldrich Chemical Co. (Milwaukee, WI). All solvents used were of analytical grade.

2.3 Preparation of the Extracts Dried and powdered C. olitorius leaves were extracted with petroleum ether to remove fats and chlorophyl. Fat-free air dried material was extracted with aqueous methanol (70%) at 40◦ C water bath 30 s (4×). MeOH was removed under reduced pressure by a rotary evaporator and the remaining aqueous solution was lyophilizied (MF). This extraction process was repeated and aqueous methanol extraction was partitioned with ethylacetate, in order to obtain compounds in different polarity. After concentration under reduced pressure a dark green ethyl acetate fraction was obtained (EF). The remaining water fraction was freeze dried (WF). In addition, 2% infusion (in water) was prepared from C. olitorius leavesand after the water fraction was freeze dried (Cinf). All fractions (MF, EF and WF) and infusion (Cinf) obtained were weighed to determine the yields of soluble constituents, total phenolic content and their antioxidant activity.

2.4 Total Phenolics Determination Antioxidant compounds generally contains phenolic group(s). Because of this, amounts of phenolic compounds in each of the fractions were compared to obtain more information about the fraction(s) which posses(s) antioxidant potential. The total phenolics were determined by the Folin-Ciocaltaeu colorimetric method [14] as follows: Samples (0.5 ml) were introduced into test tubes; 2.5 ml of Folin Ciocalteu (10% in water) reagent solution and 7.5 ml of Na2 CO3 (20% in water) solution were added. The tubes were mixed and allowed to stand at room temperature in the dark

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for 2 h. Absorption at 750 nm was measured. A standard curve was prepared with gallic acid of known concentrations. Total phenolic content was expressed as gallic acid equivalents (GAE) in mg/g dry material. The results are expressed as average of three measurements.

2.5 Antioxidant Activity Evaluation 2.5.1 Free Radical Scavenging Activity on DPPH The DPPH method is representative of the methods employing model radicals in the evaluation of radical scavengers; such methods have gained high popularity over the last decade because of their rapidity and sensitivity. Free radical scavenging effects of the fractions on DPPH were estimated according to the method of Sanchez-Moreno [15] with some modification. An aliquot of methanol (0.3 ml), solution containing different sample concentrations (3 μg/ml)) was added to 3 ml of 0.05 mM 2,2-diphenyl-1-picrylhydrazyl radical (DPPH. ) in methanol prepared daily. The mixture was shaken vigorously and left standing at room temperature for 30 min; absorbance of the resulting solution was then measured spectrophotometrically at 517 nm. Decreasing of the DPPH solution absorbance indicates an increase of the DPPH radical-scavenging activity. The radical scavenging activity of the tested samples, expressed as percentage inhibition against DPPH, was calculated as follows: Inhibition (% ) = [(Acontrol - Asample)/Acontrol] × 100. Free radical scavenging activity determination was repeated four times for each sample and the means are reported. The DPPH solution without sample solution was used as control.

2.6 β-Caroten Bleaching System (BCB) The antioxidative activity of extracts was evaluated using the β-carotene-linoleic acid model system as described by Maure [16]. Briefly, 10 mg β-carotene was dissolved in 3 ml of chloroform. The solution was added to 40 mg linoleic acid and 400 mg Tween 80. After removing the chloroform using a rotary evaporator at 40◦ C, oxygenated distilled water (100 ml) was added to the β-carotene-linoleic acid emulsion with vigorously shaking. 3 ml of this solution were mixed with 200 μl extract prepared at 0.2 mg/ml concentration. After incubation at 50◦ C for 180 min, absorbance of each sample at 470 nm was monitored at time intervals of 15 min during 180 min. Antioxidant activities of extracts were compared with those of BHT at the same concentration and blank consisting of 0.2 ml of methanol. The antioxidant activity (AA) was calculated from the following equation:

Antioxidant Activities of Molokhia (Corchorus olitorius L.) Extracts

AA =

539

A s − Ac × 100 A0 − Ac

where, As and Ac are absorbances of sample and control, respectively at 180 min; A0 is absorbance at 470 nm of sample at the start of test.

3 Results 3.1 Total Phenolics Content Table 1 shows an overview of jute leaves, as well as the extraction yields expressed as percentage of dry matter and total phenols, for the extracts and infusion. The extraction yields range from 2.91% plant material for CEE to 28.03% plant material for CME. Table 1 Total phenolics contents and yields of extracts obtained from jute leaves Extracts

Extraction yield (%)a

Total phenolic contentb,c

C. olitorius-methanol (CME) C. olitorius-ethylacetate (CEE) C. olitorius-water (CWE) C. olitorius-infusion (Cinf)

28.03 2.91 21.91 21.27

42.50 ± 1.39 137.42 ± 1.09 20.46 ± 1.71 25.05 ± 1.07

w/w on dry weight basis, b mg GAE∗ /g extract, c results are represented as means ± standard deviation (n = 3) a %,

Phenolic substances have been shown to be responsible for the antioxidant activity of plant materials. Therefore, the amount of total phenols in the extracts was investigated by the Folin- Ciocalteu method. The content of total phenols is expressed as gallic acid equivalents (mg gallic acid/g extract). The highest total phenolic contents were detected for ethyl-acetate extracts, the lowest total phenolic contents were detected for water extracts. Total phenols in all fractions varied from 20.46 mg/g extract of GAE in C. olitorius-water extract (CWF) to 137.42 mg/g extract of GAE in C. olitorius-ethylacetate extract(CEF).

3.2 Evaluation of Antioxidant Activity The presence of different anti-oxidant components in plant tissues especially fruits and vegetables make it relatively difficult to measure each anti- oxidant component separately. Therefore several methods have been developed in recent years to calculate the total anti-oxidant activity of biological samples.

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3.3 Antiradical Activity The DPPH. free radical method determines the antiradical power of antioxidants [15]. DPPH radical-scavenging activities of each of fractions (1.6 μg/ml) were measured. Figure 1 shows the effect of the fractions obtained from C. olitorius on the reduction of DPPH. As shown in Fig. 1, there were big differences in antiradical activities between the investigated C. olitorius fractions. Ethyl-acetate fractions were found to effectively scavenge free radicals generated by DPPH. The lowest activity was shown water fractions. Among the investigated fractions; the CEF (34.97%, value of inhibition %) showed the highest DPPH radical-scavenging activity and amount of total phenolic compounds. However, the antioxidant activities of extracts and fractions were lower than that of synthetic antioxidant, BHT (60.04%, value of inhibition %). 70,00

Fig. 1 The antiradical activities of C. olitorius extracts and infusions Inhibition (%)

60,00 50,00 40,00 30,00 20,00 10,00 0,00 CME

CEA

CWE samples

Cinf

BHT

3.4 β-Caroten Bleaching System (BCB) The method is based on the loss of the yellow colour of β-carotene due to its reaction with radicals which are formed by linoleic acid oxidation in an emulsion. β-Carotene bleaching, measured by the decrease in the initial absorbance at 470 nm, is slowed down in the presence of antioxidants. The method is widely used in the AOA evaluation of different types of samples [17]. The decrease in absorbance of β-carotene in the presence of different extracts with the oxidation of β-carotene and linoleic acid is shown in Fig. 2. For easier comparison the antioxidant activities of the extracts, the data calculated at 180 min are additionally presented in the form of values collected in Fig. 2. The antioxidant activity of extracts ranged from 12.5 to 27.25%. As results from Table 2, ethylacetate fraction exhibited significantly neutralizing activity (27.25%) of free radicals. However, activity of fractions was not comparable with the activity of BHT. In this work, the highest antioxidant activity found was from the synthetic antioxidant (i.e. BHT).

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absorbance (at 470 nm)

0,6 0,5 0,4 0,3 0,2 0,1 0

0'

15' 30' 45' 60' 75' 90' 105' 120' 135' 150' 165' 180 time (sec)

BHT

C-inf

C-EA

C-ME

C-W

control

Fig. 2 Anti-oxidant activity measured by bleaching of linoleic acid–β-carotene emulsion

Table 2 Percentage of inhibition estimated by means of antiradical activity (on DPPH) and β-carotene bleaching methods of C. olitorius leaves extracts Extracts

Total phenolic content

Inhibition (%)a

Antioxidant ındexb

C. olitorius-methanol (CME) C. olitorius-ethylacetate (CEE) C. olitorius-water (CWE) C.olitorius-infusion (Cinf) BHT

42.50 ± 1.39 137.42 ± 1.09 20.46 ± 1.71 25.05 ± 1.07

25.68 ± 0.78 34.97 ± 0.85 26.78 ± 0.73 9.08 ± 0.97 60.04 ± 1.02

18.00 ± 0.83 27.25 ± 0.94 12.5 ± 0.85 18.25 ± 0.09 82.64 ± 1.02

a Inhibition

(%) value estimated by DPPH, b antioxidant Index estimated by BCB method

4 Conclusion The study clearly indicates that it is important to measure the antioxidant activity using various radicals and oxidation systems and to take both phenolic content and antioxidant activity into account while evaluating the antioxidant potential of plant extracts. As previously described [18] the use of different methods is necessary in antioxidant activity assessment. The presented study shows that no single testing method is sufficient to estimate the antioxidant activity of a studied sample. The BCB method can be helpful especially for investigations of lipophilic antioxidants. On the other hand, if polar compounds (ascorbic acid, rosmarinic acid, caffeic acid etc.) are tested only by the BCB method they would be considered as weak antioxidants [16]. The DPPH method is faster than BCB method and it can be helpful in investigation of novel antioxidants for a rapid estimation and preliminary information of radical scavenging abilities. The method is sensitive and requires small sample amounts. DPPH allow testing of both lipophilic and hydrophilic substances [15].

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In this study, we present results on the antioxidant activity of extracts obtained from C. olitorius leaves. At only specific data on the antioxidative properties of C. olitorius leaves, the acidic n-BuOH fraction of MeOH extract, was relatively high antioxidative activity was also found in the neutral aqueous fraction of the MeOH extract of C. olitorius leaves [13]. The antioxidant activity of this fraction was measured using the radical generator-initiated peroxidation of linoleic acid. Similarly, in our study, the ethyl acetate extract, the highest total phenolic contents, found to have the highest antioxidant activity in the assays (Figs. 1, 2, Table 2). The weakest antiradical activity was shown at Cinf and the weakest antioxidant activity was also shown at CWE. Green leafy vegetables are rich sources of antioxidant micronutrients and should be included in diets as promising means to exert protective effects. Creating awareness about these aspects could provide health benefits to the consumer. This would enable an increase the quality of life, especially among the elderly population, which is more vulnerable to micronutrient deficiencies and to oxidative stress related health disorders. Acknowledgment Authors acknowledge to the Research Foundation of University of Anadolu (Project No: 30353) and of Plant, Drug and Scientific Research Centre of Anadolu Univercity (AUBIBAM) for their kindly support of this study.

References 1. Hasler CM (1998) Functional foods: Their role in disease prevention and health promotion. Food Tech 52:63–70 2. Kahkonen MP, Hopia AI, Vuorela HJ (1999) Antioxidant activity of plant extracts containing phenolic compounds. J Agric Food Chem 47:3954–3962 3. Frankel EN, Waterhouse AL, Teissedre PL (1995) Principal phenolic phytochemicals in selected California wines and their antioxidant activity in inhibiting oxidation of human low-density lipoprotins. J Agric Food Chem 43:890–894 4. Antolovich M, Prenzler PD, Patsalides E, McDonald S, Robards K (2002) Methods for testing antioxidant activity. Analyst 127:183–198 5. Shahidi F, Wanasundara PKJ (1992) Phenolic antioxidants. Crit Rev Food Sci Nutr 32:67–103 6. Tulio JAZ, Ose K, Chachin K, Ueda Y (2002) Effects of storage temperatures on the postharvest quality of jute leaves (Corchorus olitorius L.). Postharvest Biol Technol 26:329–338 7. Meikle, RD (1977) Flora of Cyprus, vol. 1, Published by The Bentham,– Moxon Trust Royal Gardens, Kew 8. Abou Zeid AHS (2002) Stress metabolites from Corchorus olitorius L. leaves in response to certain stress agents. Food Chem 76:187–195 9. Matsufuji H, Sakai S, Chino M, Goda Y, Toyoda M, Takeda M (2001) Relationship between cardiac glycoside contents and color of Corchorus olitorius seeds. J Health Sci 47:89–93 10. Pal DK, Mandal M, Senthilkumar GP, Padhiari A (2006) Antibacterial activity of Cuscuta reflexa stem and Corchorus olitorius seed. Fitoterapia 77(7–8):589–591 11. Nakamura T, Goda Y, Sakai S, Kondo K, Akiyama H, Toyoda M (1998) Cardenolide glycosides from seeds of Corchorus olitorius. Phytochem 49:2097–2101 12. Gupta M, Mazumder UK, Pal DK, Bhattacharya S (2003) Onset of puberty and ovarian steroidogenesis following adminstration of methanolic extract of Cuscuta reflexa Roxb. stem and Corchorus olitorius Linn. seed in mice. J Ethnopharmacol 89:55–59 13. Azuma K, Nakayama M, Koshioka M, Ippoushi K, Yamaguchi Y, Kohata K, Yamauchi Y, Ito H, Higashio H (1999) Phenolic antioxidants from the leaves of Corchorus olitorius L. J Agric Food Chem 47:3963–3966

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14. Hoff J-F, Singleton T-J (1977) A method for determination of tannin in foods by means of immobilized enzymes. J Food Sci 42:1956 15. Sanchez-Moreno C, Larrauri JA, Saura-Calixto F (1998) A procedure to measure the antiradical efficiency of phenols. J Food Sci 76:270–76 16. Maure A, Cruz JM, Franco D, Dominquez JM, Sineiro J, Dominquez H, Jose Ninez M, Parajo C (2001) Natural antioxidants from residual sources. Food Chem 72(2):145–171 17. Roginsky V, Lissi EA (2005) Review of methods to determine chain-breaking antioxidant activity in food. Food Chem 92(2):235–254 18. Koleva II, Van Beek TA, Linssen JPH, De Groot A, Evstatieva LN (2002) Screening of plant extracts for antioxidant activity: a comparative study on three testing methods. Phytochem Anal 13:8–17

Solid Medical Waste Management in Healthcare Centers in Palestine Issam A. Al-Khatib, Mohamed Abu-Dayah, Hussein Hajjeh, and Tayseer Al-Shanbleh

Abstract This chapter discusses the current situation of solid waste management in healthcare centers in Palestine. The monthly estimated quantity of solid waste produced by the healthcare centers in Palestine was 472.9 tons. There is very little separation of solid waste in primary healthcare centers (38.1%) as compared to secondary healthcare centers (71%). Only 17.3% of the healthcare centers in Palestine perform treatment of their solid waste. The place of final disposal of healthcare waste is an unsanitary dumping site owned by the local authority, and is used by 87.2% of the healthcare centers. Collection, storage and disposal of healthcare waste constitutes an environmental problem that poses an important health risk and calls for immediate attention and intervention. Healthcare centers have inadequate refuse collection services, lack of storage and disposal facilities. Special efforts should be made to improve the healthcare management in an effective and integrated manner. Keywords Palestine · Healthcare solid waste · Management · Health effects

1 Introduction The term waste refers to discarded or unwanted materials. Healthcare facilities are one of the major producers of solid wastes in nature. Healthcare solid waste includes both non-hazardous and hazardous waste constituents. According to WHO [15], almost 80% of healthcare wastes are benign and comparable to domestic waste while the remaining approximately 20% are considered hazardous, as it may be infectious, toxic and/or radioactive [14]. The non-hazardous waste includes wool,

I.A. Al-Khatib (B) Institute of Community and Public Health and Faculty of Engineering, Birzeit University, Ramallah, Palestine e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_49,

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kitchen wastes, etc. that do not constitute any special handling problem, risk to health or to the environment. The hazardous waste includes pathological, infectious, sharps and chemical wastes [7]. Improper management of wastes generated in healthcare facilities causes direct health impacts on the community, the personnel working in healthcare facilities, and on the environment. Lack of adherence to standards for the disposal of waste not only reduces the quality of health and welfare of the entire society but also increases the workload of health services, which both obstruct health management policies and affect the national economy [3]. The characteristics of waste from healthcare centers are similar in all countries except for amounts generated due to standard procedures executed in the healthcare field. The quantities of waste generated from healthcare services among other factors depend on the status of the healthcare center, level of instrumentation, and sometimes location of the healthcare facility. Legislation on the safe disposal of healthcare wastes may vary from one country to another [5]. Healthcare centers often generate significant quantities of wastes containing materials of biological origin. These biological wastes may be subject to special management requirements because they contain: (a) biohazardous (infectious) agents; (b) blood or other body fluids; (c) toxins; (d) pathological wastes, solid human or animal tissues; and (e) needles, scalpels, syringes, and other sharp objects that form physical hazards and may be contaminated with biohazardous agents [8]. Poor management of healthcare waste can cause serious diseases to healthcare personnel, waste workers, patients, and to the general public. The greatest risk posed by infectious waste is accidental needle stick injuries and the reuse of syringes. WHO estimated that in 2000, worldwide, injections undertaken with contaminated syringes caused about 23 million infections of hepatitis B, Hepatitis A, and AIDS infections, in addition to other diseases. During the handling of wastes, injuries occur when needles or other sharps have not been collected properly in rigid containers. Conditions such as inappropriate design of waste collection, overflow of existing sharp containers, unprotected pits, improper dumping, and easy public access to healthcare wastes are risk factors increasing the public risk exposure to needle stick injuries. Children are particularly at risk to exposure to healthcare wastes [15]. In addition to health risk derived from direct contact, healthcare waste can adversely impact human health by contaminating water bodies and polluting the air during waste management [13]. Segregation of wastes is in some way a minimization of wastes by the separation of wastes. For healthcare wastes, the main aim of treatment is to disinfect infectious waste, to destroy disposable healthcare devices which should not be used [6]. The aim of this research was to assess health care waste (HCW) management practices in the Palestinian territory including segregation, collection, storage, transport, treatment and final disposal, in addition to identifying quantities of solid wastes generated by healthcare centers.

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2 Methodology The target population of this survey are all healthcare centers in the Palestinian Territory. The sample size included all governmental and non-governmental healthcare centers, totaling 663 (adding up 116 centers of hospitals, 420 centers of healthcare and dental practices, 127 centers of other human health activities. The sample of the survey is a single-stage stratified cluster random sample. The data was collected from two sources, and each one of these followed a particular method: (1) the data obtained from administrative record sources (governmental and non-governmental healthcare centers), where they apportion the questionnaires to the respondents who fill them by themselves; (2) the data obtained from the private healthcare sector that was collected by well trained field workers. The tool of data collection was a questionnaire. The questionnaire included questions about (1) the amounts of HCW collected, (2) HCW collection service availability, (3) frequency of HCW collection, (4) HCW collection equipment and vehicles, (5) HCW treatment, (5) HCW final disposal methods, and others. All questionnaires were edited both in the field and in the office. Data were entered into the computer, using Microsoft Access, and analyzed using other statistical analytical system SPSS version 12.0.

3 Results The results of the environmental survey of healthcare centers conducted by the Palestinian Central Bureau of Statistics [11] were utilized, analyzed and conclusions and recommendations were derived.

3.1 Quantity The monthly estimated quantities produced by the healthcare centers in the Palestinian Territory were about 472.9 tons including 374.9 tons in the West Bank and 98.0 tons in Gaza Strip. Out of the total, the estimated quantities produced by the secondary healthcare centers in the Palestinian Territory were about 198.2 tons, as shown in Fig. 1.

3.2 Separation Only 34.1% of the healthcare centers in the Palestinian Territory perform separation of healthcare waste components, as shown in Table 1. Out of the centers that separate healthcare waste, 70.1% of them partially separate the waste, while 29.9% of them completely separate the waste into its components.

I.A. Al-Khatib et al.

Fig. 1 Estimated quantities of produced solid waste from healthcare centers estimated by tons/month

Quantity by Ton/month

548 250 200 150 100 50 0 Palestinian Territory

West bank

Gaza strip

secondary health care centers primary health care centers

Table 1 Percentage distribution of healthcare centers in the Palestinian Territory by existence of solid waste separation and type of separation and region Region and type of healthcare center

Existence of separation

Palestinian territory Secondary Primary Other West bank Gaza strip

34.1 71.3 34.5 19.0 37.8 25.1

Types of separation Partial

Completely

Total

70.1 62.2 73.3 25.9 66.3 84.4

29.9 37.8 26.7 74.1 33.7 15.6

100 100 100 100 100 100

3.3 Transportation The transportation in the healthcare centers in the Palestinian Territory that perform separation of solid waste into its different components is done manually in 90.2, 94.3, and 97.0% of the healthcare centers for general waste, infectious waste, and sharp waste respectively, as shown in Table 2. Special carriages used for the transportation of the different components of separated solid wastes are found in low percentages. The periodicity of collecting general, infectious and sharp healthcare wastes of more than 6 times per week was 15.4, 31.2, and 7.8% respectively in the healthcare centers of the Palestinian Territory as shown in Table 3.

3.4 Treatment The percentage of the healthcare centers in the Palestinian Territory that do perform treatment of healthcare waste is about 17.3%, of which 32.9% in secondary healthcare centers, 16.7% in primary healthcare centers and 17.7% in the other human health activities as shown in Table 4.

Manual

90.2 83.4 89.9 100.0 88.5 97.6

Region and type of healthcare center

Palestinian territory Secondary Primary Others West bank Gaza strip

1.9 8.3 1.6 0.0 2.1 1.2

Special carriage

General waste

7.9 8.3 8.5 0.0 9.4 1.2

Both methods 100 100 100 100 100 100

Total

Types of waste and transportation method

94.3 84.2 95.7 100.0 94.4 93.9

Manual 2.1 2.0 2.2 0.0 2.5 1.0

Special carriage

Infectious waste

3.6 13.8 2.1 0.0 3.1 5.1

Both methods 100 100 100 100 100 100

Total

97.0 6.6 1.1 0.0 96.9 97.2

Manual

1.6 3.3 1.5 0.0 1.7 1.1

Special carriage

Sharp waste

1.4 90.1 97.4 100 1.4 1.7

Both methods

Table 2 Percentage distribution of healthcare centers in palestinian territories by the solid healthcare waste transportation method

100 100 100 100 100 100

Total

Solid Medical Waste Management in Healthcare Centers in Palestine 549

36.9 4.5 38.7 41.7 45.8 0.7

100 100 100 100 100 100

15.4 78.5 11.5 11.5 16.1 12.4

Palestinian territory Secondary Primary Others West bank Gaza strip

47.7 17.0 49.8 46.8 38.1 86.9

More than 6 times 4–6 times 1–3 times total

Region and type of healthcare center

General waste

31.2 62.4 26.2 28.3 25.6 46.5

29.3 13.3 32.5 15.2 23.6 44.7

39.5 24.3 41.3 56.5 50.8 8.8

100 100 100 100 100 100

More than 6 times 4–6 times 1–3 times total

Infectious waste

Types of waste and weekly periodicity of collection

7.8 37.9 5.3 28.9 7.8 8.2

22.9 14.9 23.7 16.0 20.1 33.7

69.3 47.2 71.0 55.1 72.1 58.1

100 100 100 100 100 100

More than 6times 4–6 times 1–3 times total

Sharp waste

Table 3 Percentage of healthcare centers by weekly periodicity of general waste, infectious waste, and sharp waste collection, by region and types of healthcare centers that separate the healthcare waste

550 I.A. Al-Khatib et al.

17.3 32.9 16.7 17.7 20.7 9.0

Palestinian territory Secondary Primary Others West bank Gaza strip

4.1 0.0 0.5 37.8 4.5 1.3

Disposed Existence in the sink of treatment With water

Region and type of healthcare center 5.2 18.7 4.8 0.0 3.9 12.5

5.1 0.0 6.0 0.0 0.0 33.8

Incineration Insulation

Types of treatment

0.4 0.0 0.2 2.8 0.3 1.8

0.2 0.0 0.3 0.0 0.3 0.0

Mechanical Radiation treatment disinfections 11.3 22.8 7.9 34.3 6.5 38.4

Thermal disinfections

17.2 21.6 18.8 0.0 19.3 4.9

Chemical disinfections

Table 4 Percentage of healthcare centers that treat waste by region, type of treatment and type of healthcare center

56.5 36.9 61.5 25.0 65.2 7.3

Open burning

100 100 100 100 100 100

total

Solid Medical Waste Management in Healthcare Centers in Palestine 551

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For those healthcare centers that perform treatment, the most common treatment methods are open burning, chemical disinfections, and thermal disinfections with percentages of 56.5, 17.2 and 11.3% respectively.

3.5 Disposal The generated waste from healthcare centers is compiled in a certain place, and then transferred to a place of final disposal: 69.4% of the healthcare centers compile waste in a local authority open container, 12.7% of the healthcare centers compile waste in local authority provided closed containers, and 3.4% of the healthcare centers compile waste in an open container of the center, while 5.2% of the healthcare centers compile waste in a closed container of the center, and 9.3% of the healthcare centers do not use a container as shown in Table 5. The place of final disposal was a dumping site owned by the local authority for 87.2% of the healthcare centers in the Palestinian Territory as shown in Table 6. Table 5 Percentage distribution of healthcare centers in thePalestinian Territory by the solid waste collection mean inside the healthcare center and region Collection mean Region and type of healthcare center Palestinian territory Secondary Primary Others West bank Gaza strip

Without container

Healthcare Healthcare center closed center open container container

Local authority closed container

Local authority open container

Total

9.3

5.2

3.4

12.7

69.4

100

1.4 9.6 9.2 9.1 9.7

17.4 4.4 8.1 5.9 3.3

2.6 3.4 3.8 3.3 3.8

36.9 12.9 2.7 16.3 3.8

41.7 69.7 76.2 65.4 79.4

100 100 100 100 100

Table 6 Percentage distribution of healthcare centers in the Palestinian Territory by the waste final disposal place and region Waste final disposal place Region and type of healthcare center

Disposed randomly

Private dumping site

Local authority dumping site

Others

Total

Palestinian territory Secondary Primary Others West bank Gaza strip

0.1 0.0 0.1 0.0 0.1 0.0

10.1 18.4 7.9 28.1 10.5 9.0

87.2 80.7 90.0 63.4 85.9 90.4

2.6 0.9 2.9 8.5 3.5 0.6

100 100 100 100 100 100

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4 Discussion As demonstrated in Fig. 1, the monthly estimated quantity of solid waste produced by primary healthcare centers in West Bank (147.3 tons) is significantly higher than in Gaza strip (60.4 tons). This difference can be attributed to the higher number of primary healthcare centers (PHCC) in West Bank (606 PHCC) than in the Gaza strip (125 PHCC) at year 2004 [9]. The low percentage (34.1%) of solid healthcare waste separation in Palestinian Territory as shown in Table 1 may be related to the high prevalence of hepatitis B in Palestine, estimated at (3.4%), due to higher risk of exposure to contaminated solid healthcare waste [10, 4]. Moreover, there is significantly less separation of solid healthcare waste in primary healthcare centers (38.1%), which are mainly concentrated in the rural areas, than in secondary healthcare centers (71%), which are mainly available in urban areas. This difference can also explain the higher prevalence of Hepatitis B and other infectious diseases among the rural population compared to the urban population. The currently prevailing separation practice is not sufficient to assure enough safety and avoid community and environmental hazards. The appropriate separation of healthcare solid wastes is necessary for the safeguard of waste handlers inside and outside the healthcare centers against the risk of injuries by sharp instruments and contamination from pathological wastes in addition to the environmental concerns. The low proportion of healthcare waste separation can contribute to higher environmental irradiation pollution. This exposes the health workers and the community to more risk of irradiation pollution with higher rates of cancers. Cancer is becoming an increasingly important factor in the global burden of disease for the future. The estimated number of new cancer cases in the year 2000 was 10 million, and some 60% of those occur in the less developed part of the world. Most of these cases are related to different types of environmental pollution [2]. In Palestine, malignant neoplasms constituted 9.3% of the death causes among the population in the year 2000. Among neoplasms, Limphomas, which are closely related to high environmental irradiation pollution, constitute the second leading cause of cancer morbidity in the general male population, with the highest percentage (35.2%) among the active age group of 25–29 years [2]. Healthcare wastes should be collected every day due to their hazardous nature. More than 7 times weekly waste collection practiced in only 11.5% of the primary healthcare centers in Palestine. This can be attributed to the lack of specialized waste collection teams in the primary healthcare centers compared to secondary services. Usually, health workers in the primary healthcare centers carry out this work themselves, while in most secondary healthcare centers there are specialized waste collection teams. It is known that less frequent solid healthcare waste collection can lead to more exposure of the health staff and the patients to hazardous risks such as injuries, infections and chemical harm. The predominant method of waste transportation by healthcare centers in the Palestinian Territory is manual, as 90.2, 94.3, and 97.0% of the healthcare centers that separate healthcare waste collect general waste, infectious waste and sharp waste, respectively (Table 3) This may indicate a significant lack of transport

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facilities probably due to financial reasons, concerns of the waste collection teams, and lack of compliance. The absence of specialized collection and transportation teams leads to inappropriate healthcare waste handling due to the lack of knowledge of the hazardous effects of these wastes on human health and on the whole environment. The percentage of the healthcare centers in the Palestinian Territory that do perform treatment of healthcare waste is only about 17.3%. This low percentage of healthcare waste treatment can expose the Palestinian people to hazards, as about 10–25% of healthcare waste is regarded as hazardous if it: it may contains infectious agents, sharps, toxic or hazardous chemicals or if it is radioactive. Infectious health-care waste, particularly sharps, has been responsible for most of the accidents reported in the literature [4]. Open burning is the most popular treatment method as it is used by 56.5% of the healthcare centers that treat their waste. This method of treatment is not a proper method because it causes pollution of the surrounding environment with toxic agents such as dioxin and furans [12, 1]. More than 82% of healthcare centers compile waste in an open container or do not even have a container, as shown in Table 5. This means that the healthcare waste is exposed to contact with insects, flies, rodents and other intermediate vectors that may transmit different types of dangerous diseases. The most common method used for healthcare waste final disposal was open dumping (97.3%). Dumping without treatment, uncontrolled incineration and open burning can cause environmental pollution and public health problems, as solid healthcare wastes are considered hazardous and require special treatment, sanitary landfills or hazardous waste landfills for safe final disposal. The existing practices pose potential risks of contamination with tetanus, AIDS, typhoid, hepatitis, and other diseases to scavengers, dump site operators, as well as the general public.

5 Conclusions and Recommendations The existing system of healthcare waste management in the Palestinian Territory is not operated properly and exposes the environment to pollution and the public to many health risks. There is a lack of necessary supplies and facilities, a lack of knowledge among health workers and a lack of coordination among different related ministries and authorities. In order to enhance healthcare management more adequately and effectively, the following general recommendations are proposed: • The Environmental Health Department at the Ministry of Health (MoH) should be activated in coordination with the other related departments, the Ministry of Local Government and the Environment Quality Authority, to work closely with the healthcare centers through supervising, monitoring, and forcing them to implement an appropriate system for healthcare waste management.

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• Creation of legislations and national standards to organize and control healthcare waste management. • Adequate supplies and facilities needed for healthcare waste management (such as receptacles, special areas for final disposal of healthcare wastes, and proper and effective protective gear) should be available inside and outside the healthcare centers wherever necessary. • Health education and awareness should be provided for health workers as well as for the community, about the hazards of healthcare waste and how to minimize them.

References 1. Al-Khatib IA, Alshanableh TAM (2000) Healthcare waste management in the Turkish Republic of Northern Cyprus (TRNC), a case study: Dr. Burhan Nalbantoglu governmental hospital. Proceedings of the Third International Congress for Cyprus Studies, Eastern Mediterranean University, Famagosta, TRNC, 13–17 Nov 2000 2. Al-Najar K, Awad R (2002) Cancer 1995–2000. Ministry of health, Ramallah, Palestine 3. Askarian M, Vakilli M, Kabir G (2004) Hospital waste management status in university hospitals of the Fars province, Iran. Int J Environ Health Res 14(4):295–305 4. Carvalho SML, Silva MGC (2002) Preliminary risk analysis applied to the handling of healthcare waste. Braz J Chem Eng 19(4):377–381 5. Hagen DL, Al-Humaidi F, Blake MA (2001) Infectious waste surveys in a Saudi Arabian hospital: an important quality improvement tool. Am J Infect Control 29(3):198–202 6. Massrouji HT (2001) Healthcare waste and health workers in Gaza governates. East Mediterr Health J 7(6):1017–1024 7. Mato RRAM, Kasenga GR (1997) A study on problems of management of healthcare solid wastes in Dar es Salaam and their remedial measures. Resour Conserv Recy 21:1–16 8. Mato RR, Kaseva ME (1999) Critical review of industrial and healthcare waste practices in Dar es Salaam city. Resour Conserv Recy 25:271–287 9. Ministry of Health (MoH) (2005a) Health status in Palestine, annual report. Gaza, Palestine 10. Ministry of Health (MoH) (2005b) Sero-survey for measles, rubella and hepatitis B. Ramallah, Palestine 11. Palestinian Central Bureau of Statistics (PCBS) (2005) Environmental survey for healthcare centers, 2005: Main findings. Ramallah, Palestine 12. Prüss EG, Rushbrook P (1999) Safe management of wastes from healthcare activities. World Health Organization, Geneva 13. Rau HE, Alaimo RJ, Ashbrook PC (2000) Minimization and management of wastes from biohealthcare research. J Environ Health Perspect 108(56):953–977 14. Subratty AH, Hassed NME (2005) A survey on home generated healthcare waste in Mauritius. Int J Environ Health Res 15(1):45–52 15. World Health Organization (WHO) (2005) Management of solid healthcare waste at primary healthcare centers: A decision making guide. WHO, Geneva, Switzerland

Sustainable Indoor Air Quality (IAQ) in Hospital Buildings Çi˘gdem Belgin Dikmen and Arzuhan Burcu Gültekin

Abstract In the past decade, a growing interest of scientific researches has indicated that the air within the buildings can be more seriously polluted than the outdoor air. Indoor pollution has increased due to variety of factors including the construction of more tightly sealed buildings, the use of synthetic finishes and furnishings, and the use of chemically formulated personel care products. The presence of the sources that release gases or particles into the air are the main causes of indoor pollution in buildings, and in this context in hospital buildings. The indoor pollution bounds the indoor air quality (IAQ). To identify sustainable IAQ of the hospitals, the determinants of IAQ such as “indoor pollutants”, “indoor pollutant sources”, “indoor pollutant removal mechanisms”, and “the health effects of indoor pollutants” are discussed within the context of indoor pollution in the current paper. Furthermore, a comprehensive approach to hospital building design dealing with the sustainability criteria from cradle to grave process is presented. Keywords Sustainable design · Hospital buildings · Indoor air quality · Indoor air pollution · Pollutants · Health effects

1 Introduction In the past decade, most of the building designers are involved in “sustainable building design” in response to user requirements. Some designers initiate “sustainable designs” based on their own recognition of the need for reducing human impacts on the local and global environment. Designing buildings with low environmental impacts are both a necessary and a challenging part of building designers work nowadays. The challenging opportunity facing designers today is to implement the

Ç.B. Dikmen (B) Engineering and Architecture Faculty, Bozok University, Yozgat, Turkey e-mail: [email protected]

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measures in the context of a “sustainable building design” [1]. The goal of sustainable building design is to find architectural solutions [2, 3] which prevent the building related environmental impacts listed in the following [4]: • • • • • • • • • • • •

Global warming Stratospheric ozone depletion Acidification Nutrification Human toxicity Eco-toxicity Depletion of sources Photochemical oxide formation Habitat deterioration Water pollution Soil pollution Air pollution (Indoor/outdoor)

One of the architectural solutions in order to remove building related environmental impacts listed above is to prevent indoor air pollution in all types of buildings by sustainable design criteria. Indoor air pollution is one of the risks to our health as we go about our day-to-day lives. In the last several years, scientific researches have indicated that the air within the buildings can be more seriously polluted than the outdoor air in even the largest and most industrialized cities. The researchers indicate that people spend approximately 90% of their time indoors [5, 6]. Thus, for many people, the risks to health may be greater due to exposure to air pollution indoors than outdoors. Over the past several decades, exposure to indoor air pollution has increased due to variety of factors, including the construction of more tightly sealed buildings, the use of synthetic finishes and furnishings, and the use of chemically formulated personnel care products [7]. In order to decrease these factors, it is important to determine the design consideration of indoor air quality (IAQ) within the context of sustainability.

2 Sustainable Indoor Air Quality Good indoor air quality (IAQ) enhances occupant health, comfort and workplace productivity [8]. According to sustainable design criteria, the designers should undertake overall design consideration of IAQ from cradle to grave [9–11] process with the function of spaces, finishes and furnishings, building equipment (machines and appliances), occupants, and occupant activities, and maintenance in buildings. This process consists of three phases: before usage, usage, and after usage. One of the major causes of IAQ problems is pre-occupancy of buildings “before usage phase [12]”. Buildings are occupied before construction is complete, related to installation of finishes and furnishings, or testing and adjusting of heating,

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ventilation, and air conditioning (HVAC) systems [13] of the building. The IAQ problems which may occur during the curing of new products and the verification of a properly functioning ventilation system should be avoided. The building designers must document the operating procedures by preparing operational schedules about the use of the building for the operators of the building in the “usage phase [14]”. These schedules must be adequate not only to control thermal conditions but also to remove pollutants accumulated during the usage of the building. The buildings require maintenance periodically in order to remove pollutants. Neglected or deferred maintenance is often the source of IAQ problems. Maintenance consists of inspection, repair and cleaning processes. The building design should provide access to all components of HVAC systems for these processes. Cleaning of surfaces, especially periodic control of accumulated dust from concealed surfaces above a suspended ceiling is essential. In order to remove the accumulated emissions, the maintenance involves the application of chemicals such as cleansers, waxes, disinfectants, air fresheners, adhesives, drain cleaners, vacuuming, paints and coatings, solvents, pesticides, or lubricants. Vertical fabric covered surfaces such as walls or panels should be vacuumed since small, concentrating dust of particles deposit as easily on vertical as on horizontal surfaces. Construction dust, fumes, and vapors must be contained and not allowed to contaminant building surfaces or the air in occupied spaces during construction “after usage phase [15]”. Temporary ventilation and isolation barriers should be employed. When the use of a space or building is significantly changed, it is essential to determine whether the building can support the new activities and occupancy loads. This can be done by reviewing operational schedules, record drawings, and other related documents. If such documents are not available, an engineering assessment should be conducted. It is also essential to take care to avoid contamination of occupied spaces or of surfaces that will remain in use or be reused during demolition when buildings or portions of buildings will be demounted and replaced [1]. As the IAQ is mentioned from cradle to grave process, this point of view should be acceptable in any type of buildings. In this context the aim of the paper is to provide to better understand indoor air pollution, and to reduce human’s exposure to air pollutants in hospital buildings where people go for medical treatment, visit and work. Hospital buildings are complex environments that require specialized pollutant removal mechanisms for the comfort of occupants (patients, visitors, administrative staff, and health staff) to control hazardous emissions [16]. People generally go to hospitals for medical treatment in the cases of minor/serious illnesses. However, a life-threatening infection could be acquired in hospital buildings that would contradict the purpose of their visits and cause great concern to everyone. In addition, given the appropriate set of circumstances, any patient could acquire an infection, as could hospital visitors or administrative and health staff [17]. In this case, some prevention ways of indoor air pollution should be found. In order to prevent indoor air pollution, and improve IAQ in hospital buildings the determinants of indoor air quality such as indoor pollutants, pollutant sources, pollutant removal mechanisms and health effects of indoor pollution should be identified first.

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3 Determinants of Indoor Air Quality in Hospital Buildings The indicators of indoor air pollution are the indoor pollutants. For removal of these pollutants, the sources of them must be determined first. The presence of indoor air pollution sources that release gases or particles into the air are the primary causes of IAQ problems in hospital buildings. While pollutant levels from individual sources may not pose a significant health risk by themselves, most hospitals have more than one source that contributes to indoor air pollution. The relative importance of any single source depends on how much pollutant it emits and how hazardous those emissions are [18]. In this case it is important to identify the determinants of IAQ which might be listed as indoor pollutants, indoor pollutant sources, indoor pollutant removal mechanisms, and health effects of indoor pollutants.

3.1 Indoor Pollutants The provision of thermally comfortable indoor environment for the occupants is only one aspect in achieving better indoor air quality. However, indoor pollutants are other factors that have impact on the quality of indoor air [8]. They are the indicators of indoor air pollution, and one of the determining factors of IAQ. These pollutants are combustion pollutants, biological pollutants, microbial pollutants (fungi, bacteria, viruses), volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs), formaldehyde, soil gases (radon, sewer gas, methane), pesticides, particles, fibers, asbestos, carbon monoxide, formaldehyde, radon, pesticides, and molds [19–21].

3.2 Indoor Pollutant Sources The most effective strategy for achieving good IAQ is the source control. The major indoor pollutant sources include function of spaces, finishes and furnishings, building equipment (machines and appliances), occupants and occupant activities, and maintenance. In this context, the indoor pollutant sources commonly found in hospital buildings are identified, and some measures for controlling these sources are offered in Table 1.

3.3 Indoor Pollutant Removal Mechanisms There are some mechanisms in order to prevent indoor pollutants and new indoor air quality problems. These are the removal mechanisms of pollutants such as heating, ventilating and air conditioning. Indoor thermal conditions may be controlled and removed by the heating, ventilating, and air conditioning (HVAC) systems.

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Table 1 Indoor pollutant sources and measures for indoor pollutant control Indoor pollutant sources

Measures for pollutant control [22]

Function of spaces in hospital buildings • Print/photocopy shop • Dry cleaning • Science laboratory • Medical office • Cafeteria • Underground/attached garage

• Using exhaust ventilation and pressure control • Using exhaust hoods where appropriate • Checking hood airflows • Maintaining garage under negative pressure relative to the building • Checking air flow patterns frequently • Monitoring

Finishes and furnishings in hospital buildings • Plywood/compressed wood • Construction adhesives • Asbestos products • Insulation • Wall/floor coverings (vinyl/plastic) • Carpets/carpet adhesives • Wet building products • Transformers • Upholstered furniture • Renovation/remodeling

• Using low emitting products • Airing out in an open/ventilated area before installing • Increasing ventilation rates during installing and after installing • Keeping materials dry prior to enclosing

Building equipment (machines and appliances) in hospital buildings • Polluted filters • Polluted duct lining • Dirty drain pans • Humidifiers • Lubricants • Refrigerants • Mechanical room • Maintenance activities • Combustion appliances (boilers/furnaces, generators, stoves)

• Cleaning drain pans; proper slope and drainage • Using potable water for steam humidification • Keeping duct lining dry; moving lining outside of duct • Fixing leaks/cleaning spills • Maintaining spotless mechanical room • Checking/maintaining flues from boiler to outside • Keeping combustion appliances properly tuned • Disallowing unvented combustion appliances • Performing polluting activities during unoccupied hours

Occupants and occupant activities in hospital buildings • Tobacco products • Office equipment (printers, copiers) • Cooking/microwave • Art supplies • Marking pens • Paper products • Personal care products (e.g. perfume)

• Using exhaust ventilation with pressure control for major local sources • Lowering emitting art supplies/marking pens • Avoiding paper clutter • Training occupants and staff

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Indoor pollutant sources

Measures for pollutant control [22]

Maintenance in hospital buildings • Cleansers • Waxes • Disinfectants • Air fresheners • Adhesives • Janitor’s/storage closets • Wet mops • Drain cleaners • Vacuuming • Paints and coatings • Solvents • Pesticides • Lubricants

• Using low emitting products • Avoiding aerosols and sprays • Diluting to proper strength (manufacturer’s instructions) • Using during unoccupied hours (not overusing) • Using proper procedures when diluting and mixing • Storing properly with containers closed and lid tight • Using exhaust ventilation for storage spaces (eliminating return air) • Cleaning mops • Storing mops dry • Avoiding air fresheners (cleaning and exhausting instead) • Using high efficiency vacuum bags/filters

How well the thermal environment is controlled depends on the design and operating parameters of the HVAC system, and on the heat gains and losses in the space being controlled. These gains and losses are principally determined by indoor sources of heat, the heat gains from sunlight, the heat exchange through the thermal envelope, the outdoor conditions and the outdoor air ventilation rates [23]. Mechanical ventilation systems in hospital buildings are designed and operated not only to heat and cool the air, but also to draw in and circulate outdoor air. However these systems can contribute to indoor air problems in several ways if they are poorly designed, operated, or maintained. Ventilation systems can be a source of indoor pollution themselves by spreading biological contaminants that have multiplied in cooling towers, humidifiers, dehumidifiers, air conditioners, or the inside surfaces of ventilation duct work [18] which necessitates appropriate maintenance.

3.4 Health Effects of Indoor Pollutants As mentioned in Sect. 3.1, the common indoor pollutants in hospitals are environmental tobacco smoke, combustion pollutants, biological pollutants, microbial pollutants (fungi, bacteria, viruses), volatile organic compounds (VOCs), environmental tobacco smoke, combustion pollutants, biological pollutants, volatile organic compounds (VOCs) semi-volatile organic compounds (SVOCs), formaldehyde, soil gases (radon, sewer gas, methane), pesticides, particles and fibers, asbestos, carbon monoxide, formaldehyde, radon, pesticides, and molds [19–22]. These pollutants are abundant in most indoor air, although the concentrations are generally far lower than known thresholds for health effects [1]. Nevertheless, the huge number of pollutant sources may cause serious health effects. These effects can range from irritation and discomfort to disability or life threatening diseases which may be listed as in Table 2.

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Table 2 Health effects of indoor pollutants (http://www.montana.edu/wwwcxair/health_effects. htm) [18, 24–26] Eye Findings Ear Findings Nasal Manifestations

Respiratory Manifestations

Oropharyngeal Manifestations Lung Cancer General Symptoms

Skin Manifestations Mental Manifestations Sick Building Syndrome – SBS [24, 25] Building Related Illness – BRI [25] Multiple Chemical Sensitivity [25, 26]

Irritant or allergic conjunctivitis (burning, sensation of dryness, redness) Ear infection, fluid in the middle ear Rhinorrhea, nasal obstruction Irritant rhinitis Allergic rhinitis, chronic sinusitis Chest tightness, cough +/− fever, shortness of breath with exertion Nonspecific abnormalities Asthma Hypersensitivity pneumonitis Infectious pneumonia – Legionella pneumonia – Aspergillus pneumonia (inimmunosuppressed persons) – Tuberculosis – Others (most common inimmunosuppressed persons) Dryness, irritation of the throat Headaches, lethargy, fatigue, dizziness, weakness, poor concentration Non-specific complaints Systemic effects of hypersensitivity pneumonitis Variant of organic dust toxic syndrome (humidifier fever) Carbon monoxide poisoning Nausea, tingling sensation, muscle twitching Dryness, irritation, rash Coma

4 Conclusion One of the architectural solutions in order to remove building related environmental impacts in hospital buildings, where people go for medical treatment, visit and work, is to prevent indoor air pollution, and improve IAQ by sustainable design criteria. Hospitals are complex buildings that require specialized pollutant removal mechanisms to control hazardous emissions for the comfort of patients, visitors, administrative staff, and health staff. Besides, hospital building design and IAQ issues must be considered from cradle to grave process. The measures for controlling indoor pollutants should be cared in all phases of this process. In this context the aim of the paper is to provide to better understand indoor air pollution, and to reduce human’s exposure to air pollutants in hospital buildings where people go for medical treatment, visit and work. In further scientific researches, these issues should again be addressed by solutions in order to reduce the risks to occupant’s health.

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References 1. Levin H (2006) Ten basic concepts for architects and other building designers: Best sustainable indoor air quality practices in commercial buildings. Santa Cruz, USA http:// www.buildinggreen.com/elists/halpaper.cfm 2. Çelebi G, Aydın AB (2001) Architectural responsibilities within the context of sustainability. Livenarch 2001, Livable Environments and Architecture International Congress Proceedings, Karadeniz Technical University, Department of Architecture, Trabzon, Turkey, 4–7 July, 2001, pp 140–146 3. Andrew SJ (1992) Sourcebook of sustainable design. Wiley, New York 4. International Organization of Standardization (ISO) (2003) Environmental management – life cycle impact assessment – examples of application of ISO 14042, ISO/TR 14047: 2003(E). Geneva 5. National Safety Council (2004) http://www.nsc.org/ehc/indoor/iaqfaqs.htm 6. Metropolitan Washington Council of Governments – Metropolitan Washington Air Quality Committee (MWAQC) http://www.mwcog.org/environment/air/indoor/ 7. US Environmental Protection of Agency (2006) http://www.epa.gov/iaq/ 8. Cheong KW, Chong KY (2006) Development and application of an indoor air quality audit to an air-conditioned building in Singapore. Build Environ 36(2):181–188 9. Jonsson A (2000) Is it feasible to address indoor climate issues in LCA?. Environ Impact Assess Rev 20(2):241–259 10. Erlandsson M, Borg M (2003) Generic LCA – methodology applicable for buildings, constructions and operation services-today practice and development needs. Build Environ 38(7):919–938 11. Zhang Z, Wu X, Yang X, Zhu Y (2006) BEPAS - a life cycle building environmental performance assessment model. Build Environ 41(5):669–675 12. Pastuszka JS, Marchwinska-Wyrwal E, Wlazlo A (2005) bacterial aerosol in silesian hospitals: Preliminary results. Polish J Environ Stud 14(6):883–890 13. Leyten JL, Kurvers SR (2006) Robustness of buildings and HVAC systems as a hypothetical construct explaining differences in building related health and comfort symptoms and complaint rates. Energy Build 38(6):701–707 14. Paulsen J (2001) Life cycle assessment for building products – the significance of the usage phase. Ph.D Thesis, Kungliga Tekniska Hogskolan, Stockholm, Sweden 15. Bouza E, Pelaez T, Perez-Molina J, et al (2002) Demolition of a hospital building by controlled explosion: the impact on filamentous fungal load in internal and external air. J Hosp Infect 52(4):234–242 16. Holcatova I, Benesova V, Hartlova D (2003) Comparison of the environment in operating theatres in two hospitals. Indoor Built Environ 12(1–2):121–124 17. Mills F. Indoor air quality standards in hospitals. Construction and Building Services Group, Institute of Mechanical Engineers (IMechE) http://www.touchbriefings.com/pdf/ 13/hosp031_p_MILLS.PDF 18. EPA document # 402-K-93-007: A guide to indoor air quality’, United States Environmental Protection Agency and the United States Consumer Product Safety Commission Office of Radiation and Indoor Air (6604 J), 1995 19. Department of Health Service (1996) Reducing occupant exposure to volatile organic compounds (VOCs) from office building construction materials: Non-binding guidelines, USA 20. Nazaroff WW, Weschler CJ (2004) Cleaning products and air fresheners: exposure to primary and secondary air pollutants. Atmosp Environ 38(18):2841–2865 21. Shilton V, Giess P, Mitchell D, et al (2002) The relationships between indoor and outdoor respirable particulate matter: Meteorology, chemistry and personal exposure. Indoor Built Environ 11(5):266–274 22. Nordstrom K, Norback D, Wieslander G (1999) Subjective indoor air quality in geriatric hospitals. Indoor Built Environ 8(1):49–57

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23. US Environmental Protection of Agency (2006) http://www.epa.gov/iaq/largebldgs/i-beam_ html/ch1-fund.htm 24. Heimlich JE. Sick building syndrome. Ohio State University; http://ohioline.osu.edu/cdfact/0194.html 25. Kipen HM, Fiedler N (2002) Environmental factors in medically unexplained symptoms and related syndromes: the evidence and the challenge. Environ Health Perspect 110:597–599 26. Eberlein-Konig B, Przybilla B, Kuhnl P, et al (2002) Multiple chemical sensitivity (MCS) and others: allergological, environmental and psychological investigations in individuals with indoor air related complaints. Int J Hyg Environ Health 205(3):213–220

The Regional Level of Microelements in the Food Materials Aida Sahmurova, Gunay (Yildiz) Tore, Atakan Ongen, and Suna Ozden Celik

Abstract The basic resources of microelements that are essential for human life are food materials. However, in larger or lower amounts, they may become more important and critical. They may be accumulated in biological systems and become a significant health hazard. Biochemical and physical adaptation of microorganisms are related to geophysical properties and the environmental factors in the habitat around. Therefore many research activities have been done about microelements and their effect on ecosystem. In the Republic of Azerbaijan specialized research activities have been carried out since 1950s. This study was carried out in the Kuba – Khachmas and Sheki – Zaqatala regions where endemic goiter is a critical health disease. In order to compare the effect of microelements, their level in a blank region, Apsheron peninsula, was also investigated. 160 samples of consumed food materials in the regions were collected from farms, factory and household meal and nursery schools. Iodine, fluorine, copper, cobalt, manganese, zinc and Molybdenum levels were determined for each samples. Although a large range between minimum and maximum levels for almost each microelement were observed, the results showed that the soil character in the studied areas had microelement levels below required amount for vital activities. Keywords Microelement · Endemic goiter · Food materials · Environmental factors

1 Introduction 1.1 Introduction of Research Area Apsheron is a peninsula where Baku, the capital city of the Republic of the Azerbaijan was founded. One of the biggest industrial zones, Sumkayıt, is also located in the peninsula. The surface area of the peninsula is around 4,365 m2 that A. Sahmurova (B) Engineering Faculty, Department of Environmental Engineering, Istanbul University, 34320 Avcilar, Istanbul e-mail: [email protected]

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Fig. 1 Sampling sites

is equal to 4.5% of total surface area of the republic. The region is reach in natural sources such as patrol and natural gas reserves. Clay is the dominant soil form in peninsula and agricultural activities are wide-spread and it has economical value for people. Sheki – Zaqatala region is located in northwest of the Republic and southwest of Kafkas mountains. The surface area is 8,227 m2 . Natural environment has a characteristic property depending on regional climatic conditions. Agriculture is an important activity for local people. Walnut, hazelnut and fruit cultivation is widespread and has economical value. Stockbreeding is also an important activity in the lands of Sheki – Zaqatala. Kuba – Khachmas region is located in the northwest side of the Azerbaijan. The surface area is about 8,500 m2 . Climate has an unstable characteristic in the region. Region is rich in surface water resources that agriculture is also wide-spread. Soil has different structures. It changes depending on the distance to the coastal zone. Sand and clay are the dominant soil form in the region. Figure 1 illustrated the study area.

1.2 Microelements and Their Adequate Daily Amount in Food Materials Consumed by Adults and Children Food materials are one of the most important resources for beneficial microelements that are essential for human and animal. Biochemical and physical adaptation

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of organisms are dependent to the geophysical properties of the surrounding environment. Therefore, numerous studies have been conducted on this subject [4, 2, 3]. Vegetal food materials are the main resources for microelements that are inevitable for human. Biological characteristics of plants, type and amount microelement are important factors of transportation of microelements from soil to plant [10, 11]. In this case, food type consumed, age of animal and class of food materials are important as well as taxonomy of microelements for each specific organism [9]. The level of daily microelement (iodine, phosphorus, manganese, cobalt, copper, zinc, molybdenum) requirement of an adult is much higher when compared to the microelement level that animal and vegetal based food materials contain. Russian scientist took along away by their researches about microelements and their accumulation in the region. In a previous study, scientist determined the copper and zinc level in the food materials that were consumed by children and adults in Baku. The main object of this study was to determine daily levels of microelements in food materials consumed by children and adults, in different regions with different characteristics in the Azerbaijan Republic. In the literature, regional studies on microelements and their contents in the different varieties of food materials are limited. Therefore Kuba – Khachmas and Sheki – Zaqatala regions, where goiter is an endemic disease, were the main areas where this study was carried out. In order to compare the results a controlling region was also taken into consideration. Apsheron was selected as blank area where goiter is not an endemic disease. The data related to the health diseases were taken from regional health institutions. Some specific primary schools, universities and day nurseries were selected as sampling sites. In the samples taken from selected sites microelements such as, iodine, phosphorus, manganese, cobalt, copper, zinc, molybdenum, were analyzed. 24 composite samples were derived from 160 samples and analyses were carried. Microelement levels were determined for each sample. Tables 1, 2 and 3 show the analyzed values for the samples.

2 Materials and Methods In the study, microelement contents of both regions with endemic goiter disease and region without endemic disease were determined and the results were compared in order to reveal a clear and understandable data background for present situation in the Apsheron peninsula. For this purpose sampling sites such as agricultural lands, factories, bakeries, educational institutes and residences, were selected. Samples for determination of contents in daily food materials were collected from primary schools, universities and day nurseries in Sheki, Kuba and Baku provinces. Iodine, fluorine, manganese, cobalt, zinc, copper and molybdenum were analyzed in 24 composite samples.

50.7 33.8 35.9 63.4 63.4 44.0 64.9 219.9 215.7 261.0 182.9 169.1 29.4 8.4 4.9 7.7 4.2 73.3 109.0 28.3 42.3 4.4 52.8 22.7 52.8

1. Wheat flour (quality 1) 2. Wheat Flour (quality 2) 3. Macaroni types 4. Pounded wheat 5. Dark pounded wheat 6. Bread 7. Dark bread 8. Pakistan rice 9. Rice (Lenkaran) 10. Kidney bean (Lenkaran) 11. Haricot bean 12. Pea 13. Potatoes 14. Tomatoes 15. Aubergine 16. Bulgarian pepper 17. Green pepper 18. Green onion 19. Green leaf plants 20. Cabbage 21. Carrots 22. Cow milk 23. Milk powder 24. Veal 25. Lamb

15.0 82.5 104.2 15.0 157.5 86.0 292.0 621.0 22.5 1, 275 195 320 21.4 − − 0.9 − 182.5 18.0 − − 3.8 45.6 53.4 42.8

μg/kg or μg/l (for liquids)

Fluorine

Food type

Iodine

720.0 1, 200.0 860.0 940.0 1, 300.0 920.0 2, 010.0 1, 700.0 1, 888.0 1, 940.0 2, 200.0 2, 960.0 278.6 − 913.0 746.0 1, 976.0 1, 108.0 2, 120.0 − 1, 302.0 17.0 35.5 13.0 27.0

Manganese

13.0 16.0 16.0 17.0 16.0 9.0 9.65 8.0 7.0 14.0 9.0 41.5 7.6 2.4 17.0 16.5 18.0 12.1 19.0 − 6.8 0.45 2.25 6.0 16.0

Cobalt

160.0 360.0 240.0 200.0 280.0 800.0 580 400.0 480.0 480.0 720.0 720.0 131.6 7.0 5.2 41.0 23.0 80.0 27.0 − 171.0 1.3 9.1 80.0 40.0

Copper

Table 1 Microelement content in food materials in Apsheron (average)

480.0 360.0 324.0 192.0 240.0 4, 320.0 1, 760 1, 000.0 6, 600.0 1, 800.0 6, 480.0 4, 800.0 527.0 82.0 703.0 498.0 558.0 1, 613.3 1, 730.0 − 2, 440.0 160.0 − 160.0 160.0

Zinc

5.3 5.3 5.3 4.0 4.0 28.0 32 24.0 48.0 640.0 536.0 80.0 5.7 0.8 10.3 16.5 32.0 15.1 33.0 − 4.2 0.9 3.6 13.0 27.0

Molybdenum

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Table 2 Microelement content in food materials in Kuba- Khachmas (Average) Iodine

Fluorine Manganese Cobalt

Food type

μg/kg or μg/l

1. Wheat 2. Bread 3. Tomatoes 4. Onion 5. Cabbage 6. Potatoes 7. Red beet 8. Apple 9. Pear 10. Plum 11. Lamb 12. White cheese 13. Milk 14. Egg

67.4 33.8 7.3 22.2 28.3 71.8 63.1 25.2 16.9 17.2 14.8 8.8 6.65 64.0

157.2 − − 121.3 70.7 67.3 149.1 37.2 48.3 − − 131.0 4.25 139.2

3, 400.0 2, 250.0 313.7 1, 318.0 1, 418.0 1, 137.0 1, 710.0 1, 313.2 980.0 867.0 1, 390.0 28.0 44.0 64.0

3.38 3.75 0.9 1.4 1.7 3.25 2.15 1.45 1.0 2.1 2.6 1.3 0.4

Copper Zinc

24.0 35.0 195.0 29.8 13.0 90.5 124.0 37.6 151.5 33.0 8.0 4.0 3.0 120.0

4, 200.0 1, 980.0 923.7 546.2 1, 215.0 756.2 1, 330.0 1, 069.5 1, 313.2 153.0 1, 408.0 624.0 384.0 760.0

Molybdenum

22.0 17.5 3.1 5.9 5.5 6.7 6.6 12.1 8.8 2.0 2.1 1.9 1.0 6.3

Table 3 Microelement content in food materials in Sheki – Zaqatala (average) Iodine

Fluorine Manganese Cobalt

Copper Zinc

Molybdenum

Iodine

μg/kg or μg/l

1. Bread 2. Kidney bean 3. Rice 4. Cabbage 5. Potatoes 6. Carrots 7. Onion 8. Green leaf plants 9. Milk 10. White cheese 11. Veal 12. Lamb 13. Egg 14. Yolk 15. The white of an egg 16. Walnut 17. Hazelnut

25.5 44.4 80.3 30.4 8.88 5.17 5.45 71.5

53.0 247.5 172.5 15.8 13.5 17.5 33.0 381.9

224.5 − − 104.0 100.0 147.0 80.0 268.9

4.0 8.0 6.0 2.56 2.0 9.2 2.0 7.8

19.7 40.0 200.0 5.8 4.0 7.4 4.0 37.1

410.6 2, 600.0 720.0 166.4 160.0 370.0 240.0 2, 156.0

3.3 40.0 8.0 5.48 4.2 5.0 2.4 72.6

6.24 11.4 12.3 0.88 39.3 28.4 10.8

3.7 136.5 − 72.0 143.3 100.0 51.7

40.0 84.0 − − − − −

1.0 2.0 1.8 1.6 2.80 1.8 0.36

4.3 425.0 4.0 16.0 95.0 46.0 18.0

200.0 1, 240.0 260.0 528.0 763.0 443.0 146.0

0.8 5.2 1.6 0.8 7.4 5.4 5.4

68.9 69.0

45.0 195.0

416.0 720.0

48.0 88.0

1, 280.0 1, 920.0

9.0 9.0

8.0 12.8

Samples were prepared for colorimetric analyses. Elemental analyses were carried out according to the Standard Methods in the Laboratories of National Medical Research Institute.

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2.1 Results of Experimental Studies Results were obtained from experimental analyses and were evaluated by sub-titles.

2.1.1 Iodine Gaitan [5] reported that in the regions with endemic goiter iodine content of soil was determined below the essential level. Therefore, food materials also contain insufficient amounts of iodine. Kuba – Khachmas, Sheki – Zaqatala and Apsheron region had different soil structures with respect to iodine content. The results confirmed that in the blank region iodine determined much higher than other two sampling sites did. Iodine values were found very high as 215–220 μg/kg in rice samples in Apsheron. In addition, in the region iodine contents of kidney bean and bean were determined as 183–261 μg/kg, for pea it was 169 μg/kg, for green leaf vegetables the value was 109 μg/kg. Sheki – Zaqatala showed lower iodine composure. Iodine content of rice was determined as 80 μg/kg, for bean 44 μg/kg and it was 72 μg/kg for green leaf vegetables in the region. The lowest iodine level was analyzed in onion samples as 5.5 μg/kg. Content of iodine in carrot samples was found as 5.17 μg/kg in Sheki – Zaqatala as it was 42.3 μg/kg in Apsheron. In the same period of time samples taken in Kuba – Khachmas were also analyzed. Iodine values were found as 22 μg/kg in onion as it was 73 μg/kg in Apsheron. Animal food materials also showed different iodine content variations when compared to each other. Iodine in veal samples were determined as 22.73 μg/kg in Apsheron, 12.3 μg/kg in Sheki – Zaqatala. In lamb samples the level was 53 μg/kg in Apsheron, 15 μg/kg in Sheki – Zaqatala and 0.88 μg/kg in Kuba – Khachmas. 1967’de V.A. Fluorineinski ile 1968’de Barannik reported that meat samples taken from the areas where goiter was not endemic had iodine amount >80 μg/kg. M. Kirhesneper also made a research about iodine in cow milk ˙In the Republic of Azerbaijan. It was found between 4.4–6.65 μg/kg as it had to be about 100 μg/kg as mentioned in literature. When it comes to wheat samples, in Kuba – Khachmas iodine level in wheat samples were found in a large range as 21–192 μg/kg. In Khachmas the values were between 21–46.5 μg/kg, in Kusar 107.8–192.4 μg/kg and in Kuba it was 23.2–91 μg/kg. Depending on both previous regional studies and this study it was observed that iodine in food materials was below the desired levels in the regions with endemic goiter.

2.1.2 Fluorine In the Republic fluorine level varied in a large range. For instance, in Khachmas fluorine in wheat samples varied in the range of 127–170 μg/kg with average value

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of 157.2 μg/kg. Fluorine amount in bread was found as 53 and 86 μg/kg in Sheki – Zaqatala and Apsheron, respectively. Leguminosae was known to be a good fluorine accumulator. Iodine level was determined between 127.5–320 μg/kg in Apsheron and was found as 247.5 μg/kg in Sheki – Zaqatala. The highest value was determined in Pakistan price with 621 μg/kg. Native price samples contained fluorine in the range of 22.5–172.5 in Lenkaran, Apsheron, Sheki – Zaqatala regions. Experiments revealed that fluorine content of potatoes in 3 regions was almost similar. The range was determined as 21.4–67.3 μg/kg. Apple, pear and grape samples had a low amount of fluorine. Previous studies reported that fluorine content in cow milk was dependent to fluorine amount in the cow feeding materials and water they consumed. In this study, fluorine amount in cow milk was found as 3.7, 3.0 and 4.25 μg/kg in Sheki, Apsheron and Kuba, respectively. In milk powder and milk produced in factory fluorine was determined 10–12 times higher than the amounts in milk produced by domestic way. Fluorine in egg samples was around 139.2–143.3 μg/kg as yolk contained 100 μg/kg fluorine. Fluorine content of cow meat and lamb samples varied in the range of 42.8–72 μg/kg. Experimental results among 3 sites showed no significant differences. 2.1.3 Manganese Manganese amount was determined in the vegetal food materials in the range of 720–2,960 μg/kg. In the Apsheron peninsula, green leaf vegetables, green onion, pepper and carrot samples contained 2,120, 1,108, 1,976 and 1,302 μg/kg fluorine, respectively. In Sheki – Zaqatala, the manganese values in green leaf vegetables and carrots were around 268.3 and147 μg/kg. In the same region hazelnut and walnut samples contained relatively higher amounts, 416 and 720 μg/kg. In Kuba – Khachmas region manganese in apple, grape and pear samples was determined in a range between 867–1,313 μg/kg. The manganese amount in animal based food materials was found relatively low during elemental analyses. Manganese in milk was 17 μg/kg in Apsheron, 44 μg/kg in Kuba – Khachmas and 40 μg/kg in Sheki – Zaqatala. When it comes to milk samples, manganese level was around 13–28 μg/kg. Evaluation of experimental data showed that except some vegetables there was not significant manganese variation among the samples. 2.1.4 Cobalt In the literature high cobalt values was reported in leguminosae, chickpea and cereals. In Kuba – Khachmas, chickpea and leguminosae cobalt content was found as 41.5 and 13–17 μg/kg, respectively. Cobalt content in aubergine samples was 17 μg/kg and in pepper 16–18 μg/kg, in green leaf vegetables 8–19 μg/kg and in walnut samples 8–12 μg/kg.

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In the cabbage, potatoes, tomatoes and onion samples taken from area with endemic goiter cobalt was determined relatively low when compared to blank site cobalt levels. In Kuba – Khachmas cobalt in tomatoes was found around 0.9 μg/kg as it was 2.4 μg/kg in Apsheron. Cobalt in cabbage, potatoes and onion samples was 1.7–2.56 μg/kg, 2–3.5 μg/kg and 1.4–2 μg/kg in Kuba – Khachmas and in Sheki – Zaqatala, respectively. For animal food materials cobalt levels were determined relatively low. For cow milk cobalt was found as 1.1–1.3 μg/kg in Apsheron and around 0.45 μg/kg for both Kuba and Sheki. 2.25 μg/kg cobalt was determined in milk powder samples. In Kuba – Khachmas and Sheki-Zaqatala, meat and meat products cobalt content was around 1.6–2.1 μg/kg as it was 6–8 μg/kg in Apsheron. When compared to related literature in some sort of food materials, cobalt values were less than required levels. 2.1.5 Copper Generally, average amount for copper in vegetal food materials is around 1 mg/kg. as mentioned in literature. Copper in hazelnut and walnut samples in Sheki – Zaqatala region was determined as 1,280–1,920 μg/kg. Copper content in cereals and cereals products was around160–180 μg/kg. Leguminosae and rice copper values were relatively high as 480–720 μg/kg. In Sheki – Zaqatala cooper content in kidney bean and rice was found as 40 μg/kg and 100 μg/kg, respectively. Copper values was analyzed 13–4.3 μg/kg in milk samples. The lowest values were analyzed in Apsheron. In milk powder this value was determined as 9.1 μg/kg. In the same region meat products had 40–80 μg/kg copper. In the same period, in Kuba – Khachmas and Sheki – Zaqatala, values for meat and meat products varied in the range of 4–16 μg/kg. Egg samples contained 120 and 95 μg/kg in Kuba – Khachmas and Sheki – Zaqatala regions, respectively. Reported copper values in national research activities in The Republic and the results in present study almost similar. 2.1.6 Zinc In the literature, especially leguminosae family was known to be high zinc accumulator with around 6,500 μg/kg detected amount. In Lenkaran zinc content in Pakistan rice was 1,000 μg/kg and in pepper and aubergine samples it was found as 1,730–2,156 μg/kg and in carrots it was in the range of 370–2,440 μg/kg. When compared to other microelements, animal food materials accumulated zinc much higher. According to the data obtained in this study, zinc content in chicken egg and cow meat samples were found around 765 μg/kg and 160 μg/kg, respectively. In Sheki – Zaqatala zinc content in cow milk was around 260 μg/kg. Zinc content in lamb was relatively high both for Sheki – Zaqatala and Kuba – Khachmas regions with average value of 528–1,408 μg/kg. In the same region 160–384 μg/kg zinc content

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was determined in cow milk samples and it was 624–1,240 μg/kg in cheese samples. During analyses significant critical values was not determined in the samples. 2.1.7 Molybdenum In the previous studies average amount of molybdenum in food materials was determined in the range of 0.0004–3.5 μg/kg. These studies also reported that the highest molybdenum values were determined in leguminosae, especially in Apsheron with 536–640 μg/kg molybdenum. Molybdenum content in chickpea in the same region was 80 μg/kg. 4.2–6.7 μg/kg molybdenum was analyzed in potatoes samples in Sheki – Zaqatala as it was 2.4 μg/kg in onion samples. Meanwhile, 15.1 in Apsheron and 519 μg/kg in Kuba – Khachmas for same food materials, respectively. Cabbage and carrots samples did not exceed the value of 5.5 μg/kg in the region. In milk samples molybdenum content was around 0.8–1 μg as it was much higher, 3.6 μg/kg, in milk powder samples. Lamb samples contained 0.8 μg/kg, 2.1 μg/kg and 27 μg/kg molybdenum in Sheki – Zaqatala, Kuba – Khachmas and Apsheron, respectively. High amount of molybdenum level was determined in chicken eggs. The range was between 6.3–7.4 μg/kg. The white of an egg an yolk samples contained almost similar amount, 5.4 μg/kg. 9, 8.8 and 12.2 μg/kg molybdenum was reported in walnut, pear and apple samples, respectively. Significant differences among endemic and blank sites were not determined during experimental analyses.

3 Results and Discussions Microelement content in animal and vegetal food materials were analyzed and relation among soil structure, food material and endemic goiter were evaluated depending on the experimental data in the Republic of Azerbaijan. Results showed that plant food material type, its accumulation potential and its existence in soil structure are dependent to each other. Especially, it was observed that leguminosae and cereals are the richest products in element accumulation. Meanwhile, animal food products have less potential to accumulate microelements. Experiments and analyses claimed that there was a great relation between goiter and iodine deficiency. Not only iodine deficiency but also existence of other microelements in soil had a significant affect on accumulation properties. Data obtained from this study and experimental analyses were given in Tables 4, 5, 6 and 7. Statistical approach was also used in order to make a reliable evaluation of the results. Cooking and keeping methods that resulted in microelement loss in food materials were not considered in this statistical approach. Values in the tables above revealed the iodine amount that was included in the food materials consumed by children in studied regions. Average values were determined as 275.2, 172 μg and in the range of 137–171 μg in Baku, Kuba and Sheki, respectively.

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Table 4 Determination of microelement content in food materials consumed by children (Baku, Suvelan Small town, Boarding school) Iodine

Fluorine

Manganese

Cobalt

Copper

Zinc

Molybdenum

No p/p

μg/portion

1 2 3 4 5 Average (M ) δ m+

260.1 269.3 179.8 412.0 254.9

2, 741.2 5, 569.2 3, 925.0 4, 970.7 4, 244.4

1, 410.0 2, 120.0 2, 000.0 2, 100.0 1, 640.0

70.0 127.0 53.0 210.0 52.0

88.0 106.0 100.0 158.0 104.0

31, 610.0 38, 200.0 5, 400.0 12, 620.0 2, 510.0

140.0 127.0 60.0 63.0 84.0

275.2 84.4 37.7

4, 290.1 1, 074.7 480.6

1, 854.0 314.5 140.6

102.4 67.5 30.2

111.2 27.1 12.1

18, 068.0 15, 976.0 7, 144.7

94.8 36.8 16.5

Table 5 Determination of microelement content in food materials consumed by children (Kuba, Boarding school) Iodine

Fluorine

Manganese

Cobalt

Copper

Zinc

Molybdenum

No p/p

μg/portion

1 2 3 4 5 6 Average (M) δ m+

177.6 160.7 152.2 179.8 186.0 175.0

2, 447.0 2, 021.2 2, 021.2 2, 447.0 2, 021.2 2, 447.0

4, 960.0 3, 490.0 3, 740.0 5, 200.0 3, 680.0 3, 710.0

64.0 40.0 57.0 52.0 40.0 5,102

40.0 38.0 108.0 42.0 120.0 64.0

7, 200.0 2, 740.0 2, 070.0 2, 690.0 2, 560.0 1, 820.0

40.0 38.0 21.0 25.0 44.0 19.0

172.0 12.84 5.2

2, 234.0 233.2 95.2

4, 130.0 744.9 304.1

50.7 9.46 3.9

68.7 36.5 14.9

3, 180.0 2, 003.0 817.7

31.2 10.8 4.4

In the literature iodine level for an adult was reported to be 200–220 μg. Depending on this reality, food material in Baku requires adequate level of iodine for children in the region. However, in Sheki and Kuba iodine deficiency was observed in the samples taken from day nurseries. This case resulted in lower uptake of iodine for children in these regions. The iodine in food materials supplied only 62–78% of total requirement of daily uptake. The fact that there was a great relation between fluorine uptake and fluorine content water and food materials was considered during this study. High fluorine detection in Baku was directly related to this case. 4,290 μg fluorine was determined in Baku, 2,334 μg in Kuba and 930–1,230 μg in Sheki as daily uptake for children from food materials they consumed. For instance, fluorine content of water supply resources in Suvelen was between 2.9–3.2 mg/l. The value was 0.4–0.6 mg/l in Kuba. This difference resulted in lower

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Table 6 Determination of microelement content in food materials consumed by children (Sheki, Boarding school) Iodine

Fluorine

Manganese

Cobalt

Copper

Zinc

Molybdenum

No p/p

μg/portion

1 2 3 4 5 6 7 8 9 10 Average (M) δ m+

186.2 189.2 198.2 144.2 151.1 124.4 198.0 188.0 165.2 169.3

1, 214.5 1, 086.3 1, 240.0 985.5 1, 190.0 1, 260.0 1, 188.0 1, 188.0 1, 503.6 1, 498.0

1, 704.0 2, 130.0 3, 919.0 3, 919.0 3, 260.0 2, 100.0 2, 475.0 2, 475.0 3, 178.0 2, 360.0

34.1 16.0 16.0 16.0 25.0 21.0 25.0 19.8 9.1 36.0

298.0 170.4 426.0 384.0 462.0 495.0 227.0 272.0 210.0 200.0

5, 110.0 8, 180.0 8, 520.0 5, 340.0 5, 390.0 6, 720.0 7, 130.0 5, 690.0 4, 630.0 5, 450.0

34.0 29.0 42.0 26.0 16.8 33.6 29.7 39.6 27.0 27.0

171.4 25.1 7.9

1, 229.4 205.9 65.1

2, 752.1 773.1 244.5

21.8 8.43 2.7

314.4 118.5 37.5

6, 216.0 1, 346.0 425.7

30.4 7.1 2.3

Table 7 Determination of microelement content in food materials consumed by children (Sheki, day nursery) Iodine

Fluorine

Manganese

Cobalt

Copper

Zinc

Molybdenum

No p/p

μg/portion

1 2 3 Average (M) δ m+

167.2 124.7 121.2

967.5 976.5 846.0

750.0 671.0 800.0

9.4 26.0 26.0

38.0 52.0 210.0

1, 320.0 2, 490.0 730.0

15.0 20.0 20.0

137.7 25.6 14.8

930.0 72.9 42.1

740.0 65.6 37.9

20.4 9.5 5.5

100.0 95.5 55.2

1, 513.0 895.9 517.2

18.4 2.6 1.5

uptake level in Kuba. Fluorine content in Baku resources was around 0.08–0.2 mg/l. Related to this result daily uptake in the region was also relatively low. In Ukraine daily uptake of fluorine by food materials was reported to be 0.54–1.6 ml [6, 7]. In Moscow this level was reported to be 0.8–1.1 mg (M.I. Krılova) and 1.18 mg in Irkutsk by T.N. Rujnikova. Some other local studies reported that change in fluorine level in drinking water resulted in change in fluorine uptake level in Irkutsk. Fluorine level was 0.76, 2, 3.4, 6.2 and 7.6 mg when water analyze results were 0.114, 1, 2, 4 and 5 mg/l. It was reported that physiological fluorine need for children in the age of 7–16 was 0.5–1.8 mg/day in the literature. For this reason, in Kuba and Sheki fluorine uptake by food materials and water resources was not adequate.

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A.O. Voyner reported that manganese daily requirement for children were at least 3 times higher than an adult needed. 7–8 mg/day manganese was reported to be the sufficient level for children. When experimental data was evaluated it was observed that in Baku (1,854 μg), in Kuba 4,130 μg) and in Sheki (740–2,752 μg) determined values were below the literature data of 7–8 mg. Manganese content of food materials for children in day nurseries also showed a large variation between 2.3 and 9.8 mg. Generally, intensive consumption of vegetal food materials was assumed to be the one of the reasons for low manganese uptake in the republic. It was also reported that daily uptake for a person by usual nourishment habits was 5–8 mg [1, 8]. In this study 102.4, 50.7 and 20 μg cobalt was determined in the samples collected in Baku, Kuba and Sheki, respectively. In Apsheron optimum uptake levels were observed. Copper values were also relatively low in the Republic of Azerbaijan. In Baku, daily copper deficiency in food materials for children in winter season was reported to be 32–53%, and in summer 19–44%. Copper deficiency was also observed in Kuba and Sheki. Previous studies reported that an adult needed 10–16 mg zinc per day. Zinc requirement for a growing children was 0.3–0.6 mg/kg. With respect to this information, in Baku daily zinc uptake of 18,068 μg for children by food materials was accepted to be adequate. In Sheki and Kuba zinc amount in food materials and uptake level were not adequate for a children. 6,216 and 2,752 μg zinc was determined in food materials, respectively. In the literature there are a lot of reports related to molybdenum and its adequate uptake amount. Reported values were 75 μg in minimum and 100 μg in maximum. In Baku observed values were around 95 μg/day. Daily uptake level for children in research areas was relatively low. 31.1, 18–31 μg molybdenum levels were analyzed in the samples collected from day nurseries in Kuba and Sheki, respectively. Statistical analyses for data obtained during this study was made and given in Table 8. Iodine deficiency was observed in the republic of Azerbaijan. Not only iodine but olsa other microelement uptakes by food materials and drinking water were also reported to be below the required values in the literature and previous studies. Especially, iodine deficiency and regions with endemic goiter showed a strong relation. Additional iodine reinforcement was needed in the endemic regions. Interaction among the microelements in the soil structure was another important point to be considered. Not only for the Republic of Azerbaijan but also for each country monitoring the relation among soil structure, food materials and microelement uptake by food materials, such as animal and vegetal products, will be inevitable in order to evaluate the adverse affects of rapid industrialization and uncontrolled agricultural activities. Undesired affects of uncontrolled human activities may result irreversible health diseases.

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Table 8 Statistical evaluation of the results of microelement analyses in Baku, Kuba ve Sheki (Boarding school samples) Parameters Provinces

M

m+

t

p

Microelements

1

2

3

4

5

Iodine

Baku Kuba Sheki Baku Kuba Sheki Baku Kuba Sheki Baku Kuba Sheki Baku Kuba Sheki Baku Kuba Sheki Baku Kuba Sheki

275.2 171.9 171.4 4,290.1 2,234.1 1,229.1 1,854.1 4,130.0 2,752.1 102.4 50.7 21.8 111.2 68.7 314.4 18,068.0 68.7 6,216.0 94.8 31.2 30.5

37.7 5.3 7.9 480.6 95.1 65.1 140.6 304.1 244.5 30.2 3.86 2.7 12.1 14.9 37.5 7, 144.7 14.9 425.7 16.5 4.4 2.3

Control 2.71 2.69 Control 4.2 6.31 Control 6.8 6.3 Control 1.7 2.7 Control 2.2 5.2 Control 2.1 1.7 Control 3.7 3.9

Fluorine

Manganese

Cobalt

Copper

Zinc

Molybdenum

0.05 0.02 0.01 0.0001 0.0001 0.01 0.2 0.02 0.1 0.001 0.1 0.2 0.01 0.002

M: Average value of repeated analyses; +m: Values higher than M; –m: Values lower than M; T: Mathematical average; P: Probability (t and p real mathematical values of study results); Control: Blank (Comparison-area with endemic goiter and area where goiter is not endemic disease)

References 1. Belz R (1960) The amounts of iron, copper, manganese and cobalt in average diets of various age groups in the Netherlands. Voeding 21:236–251 2. Coni E, Bocca A, lanni D, Caroli S (1995) Preliminary evaluation of the factors influencing the trace element content of milk and dairy products. Food Chem 52:123–130 3. Coni E, Bocca A, Coppolelli P, Caroli S, Cavallucci C, Trabalza Marinucci M (1996) Minor and trace element content in sheep and goat milk and dairy products. Food Chem 57:253–260 4. Coni E, Caroli S, Lanni D, Bocca A (1994) A methodological approach to the assessment of trace elements in milk and dairy products. Food Chem 50:203–210 5. Gaitan E, Dunn JT (1992) Epidemiology of iodine deficiency. Trends Endocrinol Metabol 3(5):170–175 6. Gabovich RD (1957) Fluorine and its hygienic importance. Kazan, USSR (in Russian) 7. Gabovich RD, Ovrutskiy CD (1969) Fluorine in stomatology and hygiene, Bethesda, Maryland, US Department of Health and Welfare, 1028 pp. (DHEW Publication No. (NIH) 78–785, 1977.) 8. Harp MJ, Scoular FI (1952) Cobalt metabolism of young college women on self-selected diets. J. Nutr. 47:67–72

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9. Moreno-Rojas R, Amaro-Lopez MA, Garcia-Gimeno RH, Zurera-Cosano G (1995) Effect of Manchego-type cheese-making process on contents of mineral elements. Food Chem 53: 435–439 10. World Health Organisation (1993) Global prevalence of iodine deficiency disorders. UNICEF International Council for the Control of Iodine Deficiency Disorders, WHO, Geneva 11. World Health Organisation (1996) Trace elements in human nutrition and health. World Health Organisation, Geneva

Microbiological Pollution Levels of Some Vegetable Specimens Taken From Public Markets of Three Central Towns of Konya-Turkey K. Gur, H.N. Uçan, and S. ¸ Dursun

Abstract Konya Province has the largest agricultural lands among the other provinces in Turkey and thus it has been named “food store of Anatolia” as far as agricultural production is concerned. However, the climate around Konya Province is semi-arid and thus irrigation of the agricultural lands is not usually adequate. In other words, many towns around Konya have to draw waters, for irrigation, from lower quality sources including municipal wastewaters. With the application to land of large volumes of minimally pretreated wastewater, it is evident that considerable potential for adverse health effects exists. Microbiological pollution could occur from food crop contamination, pathogen-laden aerosols [2], ground water pollution or surface water pollution. A case study was carried out with the principal objective to investigate entrobacteria as an indicator of microbiological pollution in vegetables collected from public markets of three central towns in the province of Konya. The work was conducted upon 20 specimens representing 10 different varieties of vegetable samples taken from the main public markets of Konya city. The results were summarized as follows: (1) The distribution of total coliform bacteria on the vegetable specimens ranged from 12 to 50%. (2) The highest incidence of coliform bacterial pollution was found with parsley (approx. 100%) and it was followed by watercress, lettuce, radishes, green onions, carrots, cabbage, cucumber skin, tomatoes and green pepper (33–39%) specimens, respectively. (3) Among the markets from which the vegetable samples were collected, the highest incidence of the microbiological pollution in terms of the coliform distributions was detected with the Ilgın market and it was followed by the Beysehir and Do˘ganhisar markets respectively. (4) The incidences of the pathogenic bacterial pollution found with the vegetable specimens were generally very low when compared to coliform bacterial distribution detected from the specimens, and the genera of the pathogenic bacteria isolated from the vegetables were as follows: Proteus sp., Salmonella sp. and Shigella sp. (5) The findings indicated that the presence of fecal pollution of the vegetables which were supposed to be eaten fresh in the region. (6) The “scalding” K. Gur (B) Environmental Engineering Department, Selcuk University, Konya, Turkey e-mail: [email protected]

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was found to be the most effective method to disinfect the vegetables studied among the four treatments tested then it was followed by the treatments of “washing with a bactericide” and “washing with a detergent” respectively [1–9]. Keywords Microbiological pollution · Vegetables · Disinfection · Pathogens · Fecal coliform

1 Introduction Contaminants of domestic wastewater may be categorized into: (a) disease causing microorganisms, (b) essential plant nutrient elements, (c) dissolved minerals, (d) toxic chemicals and (e) biodegradable organic matter. Since advent of community wastewater treatment systems, the attention of land disposal of wastewater has invariably been focused on pathogenic organisms. On the other hand, once deposited on the ground, the feces, with their high bacterial content, are carried along by rain water and in combination with normal sewage discharges make up the water which is used for agricultural irrigation. In addition, the soil, with its high content of pollutants from both human and animal fecal materials, is also a contamination source for fruits and vegetables at various stages of production from the very beginning of cultivation, there are obviously many such contacts and again at harvest as well as when the produce is packed and distributed to the public. This does not take into account the damage by bad handling which causes knocks and bruises. Meanwhile, it might be needed to summarize a few points of bacterial terminology. The term “enteric bacteria” includes all those bacteria whose natural habitat is the intestinal tract of humans and animals, including members of several families, particularly Enterobacteriaceae and Pseudomonadaceae. They are all aerobic, gram-negative, nonspore-forming rods. The family Enterobacteriaceae includes the following tribes and genera respectively. (a) Esherichieae: Esherichia, (b) Klebsielleae: Klebsiella, Enterobacter, (c) Proteaeceae: Proteus, (d) Yersinieae: Yersinia and (e) Erwinieae: Erwinia. On the other hand, the terms “total coliform” and “fecal coliform” are operationally-defined entities used for indicator purposes. Their taxonomic composition is variable, but all are members of the Enterobacteriacea. A recent study of fecally-contaminated drinking water found the following composition: (a) Total Coliform Species: 46% Citrobacter freundii, 18% Klebsiella pneumoniae, 14% Escherichia coli, 12% Enterobacter agglomerans, 4% E. cloacae, 3% E. hafniae and 1% Serratialiqufeciens, and (b) Fecal Coliform Species: 73% E. coli, 18% Serretia liqufaciens, and 9% C. freundii. Most bacteria of concern in wastewater get there from human faces although such as Leptospira enter through urine. The most prominent bacteria of human origin in raw municipal wastewater are Proteus Enterobacteria (105 mL−1 ), Fecal Streptococcus (103–104 mL−1 ) and Clostridium (102–103 mL−1 ). Less prominent bacteria include Salmonella and Mycobacterium tuberculosis. The total bacterial

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content of raw wastewater, as recovered on standard media at 20◦C is about 106 –107 mL−1 organisms. The presence and levels in wastewater of any of the pathogens given depend, of course, on the levels of infection in the contributing population [11]. The survival of bacteria on plants, particularly crops, is especially important since they may be eaten raw by animals or humans, may contaminate hands of workers touching them, or may contaminate equipment contacting them. Such ingestion or contact would probably not result in an infective dose of a bacterial pathogen, but if contaminated crops are brought into the kitchen in an unprocessed state, they could result in the regrowth of pathogenic bacteria, e.g., Salmonella, in a food material affording suitable moisture, nutrients, and temperature. Pathogens do not penetrate into vegetables or fruits unless their skin is broken, and many of the same factors affect bacterial survival or plants as those in soil, particularly sunlight and desiccation. Microbiological pollution may arise quite easily by ingestion of food contaminated with fecal material following the deposition of feces on the ground. The food, fruit and garden produce prepared for sale by personal handling most easily encounters countless numbers of biological or biotic agents. These come directly from the soil and water used for cultivation or irrigation. As wastewater is more and more frequently used, special cause must be exercised because it contains various biotic agents such as viruses, fungi, bacteria and protozoa. Pathogens in domestic wastewaters are subject to adverse environmental conditions once they are introduced into the soil. As stated in the literature, microbiological quality of reclaimed wastewater is very important for any reuse in order to assure health protection preventing environmental degradation and avoiding public nuisance. Epidemiological investigations on reuse of raw or minimally-treated wastewater for food crop irrigation provided evidence of infectious diseases transmission. A case study was undertaken to investigate entrobacteria as an indicator of microbiological pollution in vegetables sold at three public markets in Konya Province.

2 Material and Method 2.1 Description of the Area and the Market Places The area under examination, i.e. Konya Province, is located on a large plateau that is known “The Great Konya Basin” in the central part of Anatolia. The Province is situated at 36◦ 51 −39◦ 29 Northern latitude and 31◦ 36 −34◦ 52 Eastern longitude and the surface area of the Basin is nearly 5.4 million hectares that makes up nearly 7% of land surface of Turkey. The vegetable specimens, as experimental material were acquired of the three main markets in Konya Province: Beysehir, Do˘ganhisar and Ilgın towns which are subprovinces of Konya Province, in 2002 (Fig. 1).

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Fig. 1 Description of the Konya province and its subprovinces from which the vegetable specimens have been collected

2.2 Collection and Preparation of the Experimental Specimens The following vegetable varieties were studied: green (fresh) onion, tomatoes, cabbage, parsley, watercress, radishes, carrots, cucumber skin, lettuce, green (fresh) pepper. A total 20 specimens were taken of each product in each market. All specimens of the vegetables were raw and fresh when they were brought to the laboratory for the work. Four different disinfection treatments were used for the vegetable specimens studied. Some kind of hydroclonazone tablets were used to disinfect the specimens. The tablets were composed of chloramines. The specimens were also immersed in two different solutions containing 0.32 colloidal silver and chlorine salts respectively. The specimens were also washed with detergent and scalded with hot water in the laboratory. Five replications were used for each treatment applied in the study.

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After obtaining the vegetable specimens from the markets, 20 g of each were weighed out. For each of these aliquots, one of the following treatments was chosen at random: (a) washed with detergent and ordinary water, (b) treated with a commercial bactericide, (c) scalded at 70◦ C for 60 s, (d) washed with running tap water, or (e) the unwashed vegetable was taken with no treatment. After the foregoing treatment mentioned above, each specimens was liquefied in a blender with 200 mL of sterile water. They were then filtered through five layers of sterile gauze and the filtrate was collected in glass containers. Subsamples of 10 mL were added to 90 mL sterile physiological saline (0.85%) water. After vigorous shaking the following microbiological analyses were performed by the membrane filtration technique. The diluted filtrates were immediately streaked on selected culture media such as EMB, Mac Conkey, and/or agar containing lactose. These were incubated 37◦C for 24 h. Typical coliform and the suspected enterobacteria colonies were identified by their colonial morphology and smears which were stained with Gram’s stain. Colonies suspected of being pathogenic were streaked on brilliant green agar, S/S agar and/or deoxicholated citrate agar. These were all incubated under the same conditions; and differential media such as the Kligler’s iron agar, Sim’s agar, and/or surraco medium were used to identify the genus. Besides, total bacterial counts were executed on Plate Count Agar (OXOID) by pour plate techniques with an incubation of 15 days at 18◦ C [3, 5, 8, 10]. All platings were done in triplicate.

3 Results and Discussion All the microbiological data, obtained during this study, were summarized in Tables 1, 2 and 3. The values in the Tables 1 and 2 represent the distribution patterns of the total coliforms and pathogenic microorganisms i.e. Proteus sp., Salmonella sp. and Shigella sp. respectively. The results obtained from the tables can be summarized as follows: – The distribution of the total coliform bacteria on the vegetable specimens ranged from 24 to 100% (Table 1). – The highest incidence of coliform contamination (approximately 50%) was found with parsely specimens among all the vegetable specimens studied and it was followed by watercress (48–49%), lettuce (48–50%), radishes (46–48%), green onions (46–48%), carrots (39–49%), cabbage (37–43%), cucumber skin (36–41%), tomatoes (36–39%) and green pepper specimens (33–39%) respectively. So that the lowest figures related to green pepper specimens (Table 2).

20 20 20 20 20 20 20 20 20 20

Vegetable varieties

Green (fresh) pepper Lettuce Cucumber (skin) Carrots Radishes Watercress Parsley Cabbage Tomatoes Green onions

IL

BS¸

DH

Treated by scalding IL

BS¸

DH

IL

Washed with a bacteriocide

BS¸

DH

IL

Washed with a detergent

------------------------------------%-----------------------------------33 38 39 32 34 37 14 18 26 20 27 32 25 28 31 48 49 50 47 49 49 34 35 36 35 38 39 41 45 47 36 38 41 35 37 40 13 19 35 33 29 31 35 37 39 39 45 49 38 42 45 19 23 23 32 37 34 36 39 41 46 47 48 45 46 42 32 34 40 38 39 40 46 47 50 48 49 50 47 49 50 33 35 36 43 44 48 49 50 48 50 50 50 47 49 50 33 35 36 44 46 47 47 49 48 37 42 43 32 42 44 12 16 23 23 29 34 26 34 37 36 37 39 35 37 38 17 19 28 35 36 38 38 39 40 46 46 48 45 46 47 34 39 38 40 43 45 40 45 46

DH

BS¸

IL

BS¸

DH

Washed with water

No treatment

BS: Beysehir market place; DH: Do˘ganhisar market place; IL: Ilgın market place

Number of specimens

The treatments used

Table 1 Percent of vegetables collected from Beysehir, Do˘ganhisar and Ilgın markets in Konya province that gave positive responses for coliform bacteria (%) (n = 5)

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20 20 20 20 20 20 20 20 20 20

Vegetable varieties

Green (fresh) pepper Lettuce Cucumber (skin) Carrots Radishes Watercress Parsely Cabbage Tomatoes Green onions

IL

BS¸

DH

Treated by scalding IL

BS¸

DH

IL

Washed with a bacteriocide

BS¸

DH

IL

Washed with a detergent

------------------------------------%-----------------------------------2 0 0 1p 0 2s 2sh 0 1p 3 0 1s 2p 0 1s 6p 4s 3sh 7p 5s 9p 3p 5s 6sh 6p 5s 7sh 2 5s 6sh 0 1s 2p 0 0 0 0 0 0 0 0 1p 0 3p 4p 0 0 1p 0 2p 2p 0 2p 4p 0 3p 2p 0 2p 2p 0 2p 1p 9p 2s 1p 0 2p 2p 0 2p 3p 0 0 0 5s 3p 9p 10p 13p 1 4p 5p 5p 8s 4sh 5p 5s 4sh 8p 9p 4s 2p 9p 11p 8p 0 4p 5p 4p 6s 5sh 5p 2s 2sh p sh p p p p p sh p p 0 2 3 0 1 3 2 2 2 0 0 2 2 2 2sh 0 1p 2sh 0 3p 3p 0 0 0 2p 2p 2p 0 4p 0 2p 4sh 0 4p 4p 0 0 4p 0 0 4p 0 0 0 1p

DH

BS¸

IL

BS¸

DH

Washed with water

No treatment

p: Proteus spp., s: Salmonella spp., sh: Shigella spp; BS: Bey¸sehir market place, DH; Do˘ganhisar market place, IL; Ilgın market place

Number of specimens

The treatments used

Table 2 Percent of vegetables collected from Beysehir, Do˘ganhisar and Ilgın markets in Konya Province that gave positive responses for pathogenic microorganisms (%) (n = 5)

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Green onion

3 10.5 16 10.5 18 11.6

Microorganisms

Shigella spp Salmonella spp Proteus spp Escherichia coli Coliform Mean

2.5 4 14 4 15 7.9

Tomatoes

Vegetable varieties

4 3 11 6 14 7.6

Cabbage 3 16 17.5 9.5 20 10.4

Parsely 5 14 16 10 20 12.9

Watercress 2 3.5 11 5 13 6.9

Radish 3 6 9 3 12 6.6

Carrots 2.5 5 13 3 15 7.7

Cucumber (skin)

6 15 19 10 19.5 13.7

Lettuce

2 5 8.5 2 10 5.5

Green pepper

3.3 8.2 13.45 6.3 15.55

Mean

Table 3 Survival periods (days) of microorganisms on the vegetable specimens collected from Beysehir, Do˘ganhisar and Ilgın markets in Konya province (n = 5)

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• When the market places were compared to each other, in terms of the distribution of the microbiological pollution, the highest incidence of coliform contamination (39–50%) with the Ilgın Market and it was followed by the Do˘ganhisar (37–50%) and Beysehir (36–50%) market places, respectively (Table 1). These findings were coincided with the observations stated above that the hygiene precautions taken were found to be very deficient in the Ilgın Market and the sanitary conditions in the Do˘ganhisar Market were in sufficient. Whereas, the Main Market Place of Konya city has been supposed to have higher levels of hygiene then the other two markets. • As far as the pathogenic bacterial pollution was concerned, only three pathogenic genera were isolated from the vegetable specimens studied, and they were Proteus sp., Salmonella sp. and Shigella sp. The highest incidence of pathogenic pollution was found to be related to the genus of Proteus and it was followed by the genera of Salmonella and Shigella spp. respectively. On the other hand, the microbiological pollution of the pathogenic microorganisms given above showed nearly similar distribution patterns among both the vegetable specimens and the market places studied to those in the case of coliform contamination as shown in the Tables 1 and 2. • The results stated above could indicate high percentages of coliforms but low percentages of pathogenic microorganisms and thus fecal pollution of vegetables which are eaten fresh. • It was found that the bacterial coliforms most frequently encountered were E. coli and Enterobacter aerogene. Whereas, with respect to potential pathogens, microorganisms of the genera of Proteus, Salmonella and Shigella were detected. • When the treatment methods tested, were compared to each other, it was found that the “scalding” was the most effective method to disinfect the vegetable samples studied among the four treatment methods tested and then it was followed by the treatment methods of “washing with a bacteriocide” and “washing with a detergent” respectively. On the other hand, the treatment method of “washing with water” was found to have not any significant effect upon the disinfection of the vegetable samples studied comparing to the treatment method of “No Treatment”, in the experiment. • The longest survival period on the vegetable samples examined, was observed with the bacteria of coliform (mean: 15 days) and then it was followed by Proteus spp (13 days), Salmonella spp (8 days), E. coli (8 days) and Shigella spp (3 days) respectively. On the other hand, it was found that the microorganisms had a general tendency to have the longest survival time with the samples of lettuce plant (mean: 13 days) and then it was followed by the watercress (13 days), green onion (11 days), parsley (10 days), tomatoes (8 days), cucumber skin and cabbage (7 days), radish (7 days), carrots (7 days) and green pepper (5 days) vegetable samples, respectively (Table 3). These findings were supported by the results of Larkin et al. [12] and Rudolfs et al. [13] who have carried out several field experiments with vegetables irrigated with municipal wastewaters and thus, suggested that the leafy vegetables had a general

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tendency to have larger spaces to host higher number of microorganisms on their surfaces. • The results obtained from this study were generally supported by various works given in the literature.

References 1. Aydin ME, Gür K (2002) Using reclaimed municipal wastewater for irrigation. EPMR-2002 International Conference, Environmental Problems of the Mediterranean Region, 12–15 April 2002, NEU Nicosia-Northern Cyprus (in English with Turkish summary) organized by Near East University of Turkish Republic of Northern Cyprus 2. Carnow B, Northrop R, Wadden R, Rosenberg S, Holden J, Neal A, Scheaff L, Scheff P, Meyer S (1979) Health effects of aerosols emitted from an activated sludge plant. EPA 600/1-79019. Health Effects Research Laboratory, US Environmental Protection Agency, Cincinnati, OH, 45268, 214 pp 3. Clesseri LS, Eaton AD (1992) Standard methods for the examination of water and wastewater (Vol. II, for microbiological examinations). American Public Health Association, American Water Works Association and American Water Environment Federation, 1015 Fifteenth Street New York, Washington 4. Gür K, Özcan S (2002) A case study upon the distributions of some pathogenic microorganisms on the used banknotes, playing cards and telephone receivers in Konya. I. National symposium on the environmental problems in Turkey (16–18 October, 2002), Organized by Atatürk University, Erzurum (in Turkish with English summary) 5. Gür K, Özcan S (2002) Microbiological pollution of beach waters around Icel Province located at the North-Eastern Coast of the Mediterranean Sea, Turkiye. 2nd international conference on marine wastewater discharges MWWD 2002-Istanbul, 16–20 September 6. Gür K (2000) Introduction to environmental microbiology. Selcuk University, Faculty of Engineering and Architecture, Department of Environmental Engineering, Campus- Konya, Turkiye (in Turkish with English summary) 7. Gür K (1987) Environmental problems caused by the using the municipal wastewaters to irrigate agricultural lands: II. Microbiological pollution. J Agricult Harvest, Istanbul, Turkey, pp 30–32 (in Turkish with English summary) 8. Gür K (1986) A case study on the effects of bacterial leaching upon the minimizing the heavy metal contents of the sewage-sludge used in agriculture. The Symposium on the Environmental Pollution, Izmir, Turkey, 2–5 June 1986 (in Turkish with English summary) 9. Gür K (1984) Microbiological pollution in the agricultural lands irrigated with the municipal wastewaters. The symposium on the environmental problems, Erzurum, Turkiye, 12–15 November 1984 (in Turkish with English summary) 10. Kowal NE, Pahren HR, Akin EW (1981) Microbiological health effects associated with the use of municipal wastewater for irrigation. In: Municipal wastewater in agriculture. Academic Press, New York, ISBN 0-12-214880-0, pp 271–343 11. Lamka KG, Lechevallier MW, Seidler RJ (1980) Bacterial contamination of drinking water supplies in a modern rural neighborhood. App Environ Microbiol 39(4):734–738 12. Larkin EP, Tierney JT, Lowett J, Dunsel DV, Francis DW (1978) Land application of sewage wastes: potential for contamination of foodstuffs and agricultural soils by viruses and bacterial pathogens. In: Sagile BP, Sober CA (eds) Risk assessment and health effects of land application of municipal wastewaters and sludges. University of Texas at San Antonio, San Antonia, TX 78285, pp 102–115 13. Rudolfs W, Falle LL, Rogotzkie RA (1951) Contamination of vegetables in polluted soils I., bacterial contamination. Sewage Ind Wastes 23:253–268

Assessment of Metal Pollution Based on Multivariate Statistical Modelling of Soils from Gediz and Buyuk Menderes Rivers M. Bakaç and M.N. Kumru

Abstract In this study, two economically important rivers of Turkey, Gediz and Buyuk Menderes are studied to determine their environmental pollution levels. Soil samples are analysed using graphic-furnace atomic absorption spectroscopy for the trace metals Cu, Co, Cr, Mn, Zn, Pb and Ni. The results show that the pollution levels are significant especially for Pb, Cr, Ni in the Gediz River and Cr, Zn, Co in the Buyuk Menderes river. Factor analysis technique, which is some of the statistical analyses, was used in order to explain relation between the elements. Keywords Trace metals · River pollution · Environment · Factor analysis · Turkey

1 Introduction Element concentrations in soils are mainly related to the chemical composition of parent materials and to changes due to weathering which differ for various climatic environments [16]. Chemical composition of soil, particularly its metal content, is environmentally important, because depending on their concentrations, levels of toxic elements can reduce soil fertility, can increase input to food chain, which leads to accumulate toxic metals in foodstuffs, and ultimately can endanger human health. For this, heavy metals-especially toxically- have special importance in environmental samples [12]. Trace elements are introduced into soil from both natural and anthropogenic sources. Major, minor and trace elements in parent rocks eventually is included in the formed soil fractions. Most contaminants discharged into river waters rapidly become associated with stream particulate matter and incorporated in sediments. Unfortunately, industrial and household waste discharges-directly or

M. Bakaç (B) Buca Faculty of Education, Department of Physics, Dokuz Eylul University, Buca – Izmir, Turkey e-mail: [email protected]

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indirectly, through leakages in the sewage systems- into water sources cause excessive pollution of surface and underground water. Consequently, water quality and irrigation value are lost. A number of studies on the metal distribution in river soils, sediments and suspended particles, and on speciation of metals have been performed [3, 4, 9, 6]. Multivariate statistical analyses studies are especially useful for assessing and depicting multiple chemical and physical variables. Factor analysis has been widely successful for the interpretation of geochemical and lithogeochemical affinities for elements and materials for sediments, soils and waters [15, 2, 8, 13]. In this work, two economically important rivers of Turkey, Gediz and Buyuk Menderes, are studied by the method of factor analysis to establish their environmental pollution levels for some major trace elements.

2 Materials and Methods 2.1 Site Study and Geology Setting The Gediz and Buyuk Menderes Rivers are known to be under contamination menace by wastes derived from industrial sources (industrial operations represent approximately 1/5 of the total industry activity in Turkey), sewage (there are four big cities discharges) and agricultural activities which correspond in these regions to 35% of the total in Turkey [10, 3]. The Gediz River originates in the vicinity of Gediz near Kütahya and flows into the Aegean Sea near the Menemen plain. It has about 401 km long and stands between 38◦04 −39◦13 north latitudes and 27◦ 48 −28◦ 04 east longitudes. The bedrock structure is a composite mainly of metamorphic and volcanic rocks of Palaeozoic, Mesozoic and Neogene ages. A geological map of Gediz River and the sampling points are given in Fig. 1. The Büyük Menderes River is located in the Menderes Massif which covers a large area starting from the Aegean Sea in the south of ˙Izmir, West Anatolia, Turkey, to Mu˘gla in the south, to Afyon, in the east and Kütahya via Demirci in the northeast. The river originates in the vicinity of Dinar near Afyon and reaches to the Aegean Sea near Söke plain. It is about 500 km long and the bedrock structure of the river is composed mainly of metamorphic rocks [5]. A geological map of Buyuk Menderes River and the sampling points are given in Fig. 2.

2.2 Area Work During expeditions between 1995 and 1997, a total of 73 soil samples are collected from various part of the Buyuk Menderes and Gediz Rivers. Every sample consists of approximately 2 kg of surface layer soil (0−5 cm) without plants and stones. Polyethylene scoops and cans are used exclusively for sampling and storage.

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Fig. 1 A map of the study area showing sampling sites for Gediz River

Fig. 2 A map of the study area showing sampling sites for Buyuk Menderes River

Samples were dried and thoroughly homogenised and sieved separately to obtain the fine fraction for analysis. The samples are put in ice bags during the transportation to the laboratory and stored in a deepfreeze unit until the drying procedure.

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2.3 Laboratory Work All devices are cleaned by rinsing with pure water and kept in 0.1 M HNO3 for several days before sampling. Taking a 50 g of each of samples, they are dried in an oven at 55◦ C for 2 days. In order to normalise the variations in grain size distributions, the dried soil samples are sieved through a 270 mesh screen for the analysis. Cu, Co, Mn, Cr, Zn, Pb and Ni were determined by atomic absorption spectrometry method, including background correction for Pb, Ni and Co, PERKIN ELMER, Model AA 100/200 using an air/C2 H2 and N2 O/C2 H2 flames, respectively. Samples were digested using hot acid mixture. The procedure is as follows: A 0.50 g sample of prepared soil sample material was digested in a teflon beaker with 8 ml of %50 HF, 2 ml conc. H2 O2 and 1 ml conc. HNO3 . This was taken to dryness and a mixture of 5 ml conc. HNO3 -2 ml HClO4 was added and evaporated until fumes of HClO4 were produced. The resulting material was then taken up in 20 ml of 1 M HCl. The resulting solution was filtered and diluted with deionised water to a final volume of 100 ml and then the concentrations of the element were determined. Laboratory blanks were routinely prepared and analysed (one blank for every 5 samples) to monitor the possibility of sample contamination during digestion and subsequent analysis. Accuracy of AAS measurements were checked by regular analysis of standard reference material NIST, RM-8704, SRM 2704 (Buffolo River Sediment). Results are presented in Table 1. Table 1 Results of reference materials analysis (in ppm)

RM-8704 Element

Certified

Measured

Co Cr Cu Mn Ni Pb Zn

13.57 ± 0.43 121.9 ± 3.8 98.6a 544 ± 21 42.9 ± 3.7 150 ± 17 408 ± 15

13.12 123.0 101 557 40.4 156 404

a SRM

2704

2.4 Statistical Analysis Factor analysis, a widely used multivariate statistical method, was employed to interpret data. This technique reveals the correlation structure of the environmental and geochemical variables allowing the identification of affinity groups of elements and samples. The purpose of the factor analysis (FA) is the description of the observed variables in complex environmental compartments by finding summarising factors, which are often causally explainable. The extracted factors

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reflect the main part of information of the data set. For a detailed description of the mathematical principles see for instance [11]. The statistical analyses of the data were performed using the SPSS Program for Windows (Version 11.0).

3 Results and Discussion Summary statistics of elemental concentrations (range and mean) and the limit values in the Turkish soils [7] for the element analysed in this work are presented in Table 2. A comparison of the mean element concentrations of soils in the Upper Continental Core (UCC) from Taylor and McLeannan [14] is also presented in Table 2. Compared with the mean chemical composition of the lithosphere the obtained results revealed that the experimental maxima of nickel are ten times and four times and those of chromium nine times and two times as high as those of the Upper Continental Crust and allowed concentrations in Turkish soils, respectively. The present study, performed on 7 data sets at 33 and 40 sampling points on the basin in Gediz and Buyuk Menderes Rivers, respectively, was undertaken in an effort to evaluate factor analysis more completely with respect to agricultural, municipalities and industrial features. The initial step in the analysis was to find the matrix showing the correlations among the elements. This matrix of simple correlation coefficient was first computed from the normalised variables. In the second step, statistically significant principal components were extracted from the correlation matrix. The method of principal component analysis provides a unique solution, so that the original data can be reconstructed from the results. In the third step, the varimax rotated factor loading matrix was preferred. It is given in Table 3. All factors loading in the matrix were considered to be significant and the elements were accordingly grouped under the respective factors for floodplain soils. There are two factors in the analysis and they account for about 78% and 84% of the total variance of the data for Gediz and Buyuk Menderes Rivers, respectively. Factor 1, which is described as 42% and 46% of the variances, is the most important one loading for the elements Co, Cr, Ni and Zn. Factor 2, which is described as 46% and 38% of the variances, is the one loading for the elements Cu, Mn and Pb. Table 2 Summary statistics for soil data (values in ppm) River Gediz

Co

Cr

Cu

Mn

Ni

Pb

Zn

Min Max Mean Buyuk Menderes Min Max Mean Worldwide Conc. (UCC) Turkish soil guidelines

8 40 16 – 7 35 13 10 31

22 217 110 – 30 205 160 35 100

23 120 41 – 19 136 51 25 100

230 630 390 – 220 680 410 600 800

44 826 234 – 50 924 236 20 50

2 46 9 – 4 50 42 20 100

45 530 112 – 54 548 146 71 300

596

M. Bakaç and M.N. Kumru Table 3 Varimax factor matrix, eigenvalues, variances

Factors

Co

Cr

Ni

Zn

Cu

Mn

Pb

Eigenvalue

%Var. expl.

Cum. %var

Gediz River Factor 1 Factor 2 Communality

– 0.92 – 0.84

– 0.90 – 0.60

– 0.84 – 0.77

– 0.82 – 0.67

– – 0.78 0.56

– – 0.69 0.67

– – 0.66 0.74

– 3.26 2.18 –

– 42 36 –

– 78

Buyuk M. River Factor 1 Factor 2 Communality

– 0.86 – 0.82

– 0.84 – 0.76

– 0.76 – 0.72

– 0.70 – 0.74

– – 0.74 0.66

– – 0.68 0.70

– – 0.62 0.78

– 3.44 2.68 –

– 46 38 –

– 84

–

–

The first factor loaded by Cr, Co, Ni and Zn for both of rivers is effective in the middle part of the basin along the river. These sectors are places where the industry becomes dense. Then, this factor, which is highly loaded by heavy metals, indicates the influence of the wastewater discharged by big chemical plants in the Gediz and Buyuk Menderes Basins. Chromium, which is one of the elements in this group, is used in most industry branches like tanning, leather industry and processing surface of metals. Big and small plants, which are located here, discharge their wastewater into the river directly without refining it. Thus, they pollute the river water and the basin soil. The reason why these elements have high values in the middle part of the Gediz Basin is related to the big leather plants in Salihli and Usak cities [1]. The plants in the above cities above discharge their wastewater into the Gediz River. Then, this water reaches the soil of the basin due to overflowing and by means of using in the agricultural fields. Additionally, it is expected that Nif Stream, which flows into the Gediz River by passing a lot of chemical and leather industries in Turgutlu, would be effective in finding the high values in Manisa for Gediz River. For Buyuk Menderes River, the elements Cr and Ni in this group show that streams, which join the river, have a role in the pollution of Büyük Menderes River soils. There are, that is, industrial branches discharging these elements in the central Aydın and its surroundings. Chromium, especially, points out that wastewaters from the leather trade on the Aydın and Denizli basin, which is located up to river run into the river. Particularly, small and large leather plants are situated in the centre of Denizli in the middle of the river. This is a factor in connection with the industrial activities (tanning, leather and chemical plants). This points out that the pollution arising from industry is collected in river sediment and basin soil. So, this factor is directly named as an industrial one. In a work carried out by Akcay et al. [3] between 1996 and 1998, the water and sediments samples were collected from a number of points from the Gediz and Buyuk Menderes Rivers and the concentrations of Cr, Mn, Fe, Co, Cu, Ni and Pb were measured. And then, it was announced that heavy metal pollution of the environment of the Gediz River was gradually increasing due to urbanisation, industrial and agricultural activities. This result shows that the variations in the element concentrations in the Gediz Basin have both industrial and anthropogenic origin.

Assessment of Metal Pollution

597

The second factor highly loaded by Cu, Mn and Pb has showed its highest values in the middle parts of the basin. The reason for these elements grouping on the same factor points out that their sources are different from each other. That is to say, the source of this factor can be widespread since the Middle Gediz catchments basin is very important as fruit farming and industrial (tanning and electroplating) activities. The manganese in this factor has been definitely deposited on alluvial soils through water chemistry because of high potassium in soil. Furthermore, it is well known that manganese salt is used as an ingredient of the fertilizer. In addition to these, one reason for the higher concentration of copper in soils between river-km 61 and 81 can also be agricultural activities as the copper is used as pesticides on the peach trees. In short, agricultural activities in Manisa and Salihli for Gediz and in Aydin, Soke and Nazilli for Buyuk Menderes can constitute the reason for this factor. In addition, in order to be able to explain a cause of a number of effects on the second factor arising at the same time, it would also be important to consider the actual concentrations of the elements in soil along the entire basin to be able to distinguish additions due to human activities. Some papers were published on the trace metal levels in the waters of the Gediz River region. One of these researches is to be carried out by ˙Izmir Foundation of Environment Authority [7]. In that study which was carried out in the year of 1997, the water samples were collected from a number of points from the river and the concentrations of Cr, Mn, Fe, Cd and Pb were measured. And then, it was announced that heavy metal pollution of the environment of the Gediz River was gradually increasing due to urbanization, industrial and agricultural activities. This result shows that the variations in the element concentrations in the Gediz Basin have both industrial and anthropogenic origin.

4 Conclusion In natural media, trace metals undergo numerous changes during their transport due to dissolution, precipitation and sorption phenomena. Trace element concentrations of river basins depend on not only industrial, agricultural and household waste inputs but also on the geochemical composition of the area. High concentrations of Cr, Mn, Cu and Zn are thought to have resulted from anthropogenic influences, practically from industry and pesticides used in agriculture, and are found to present a pollution risk. The Cu content of Buyuk Menderes River is higher than Gediz River’ ones, especially in Soke-Aydin region and this is a potential pollution risk for this region. Cr analyses indicate the pollution presence in Gediz and Buyuk Menderes Rivers. Especially, high values at some points confirm that the pollution originated from industrial activities is crucial. Mn pollution might be originated from a kind of pesticide, which contains Mn and is used widely in this region. Co values suggest a weak pollution risk in both rivers.

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References 1. Altınbas U, Hakerlerler H, Anac D, Tuncay H, Okur B (1994) Heavy metal contamination in Gediz Valley irregatable land and its causes. Research Report. Ege University Research Fund, Turkey, 65 pp (in Turkish with English abstract) 2. Ahmed SM, Hussain M, Abderrahman W (2005) Using multivariate factor analysis to assess surface/logged water quality and source of contamination at a large irrigation project at Al-Fadhli, Eastern Province, Saudi Arabia. Bull Eng Geol Environ 64:319–327 3. Akcay H, Oguz A, Karapire C (2003) Study of heavy metal pollution and speciation in Buyuk Menderes and Gediz river sediments. Water Res 37:813–822 4. Chen MH, Wu HT (1995) Copper, cadmium, and lead in sediments from the Kauhsiung River and its harbour area. Mar Pollut Bull 12:879–884 5. Dora OÖ, Candan O, Dürr St, Oberhänsli R (1995) New evidence on the geotectonic evolution of the Menderes Massif. International Earth Sciences Colloquium on the Aegean Region, ˙Izmir/Güllük-Turkey, 53–69 6. Ivorra N, Hettelaar J, Tubbing GMJ, Kraak MHS, Sabater S, Admiraal W (1999) Translocation of microbenthic algal assemblages used for in situ analysis of metal pollution in rivers. Arch Environ Contam Toxicol 37:19–28 7. ˙Izmir Foundation of Environment Authors (1997) Gediz Havzası Çalı¸smaları. Izmir Society of Environment, Izmir, 25 pp (in Turkish) 8. Korfali SI, Davies BE (2004) Speciation of metals in sediment and water in a river underlain by limestone: role of carbonate species for purification capacity of rivers. Adv Environ Res 8:599–612 9. Leivuori M, Joksas K, Seisuma Z, Kulikova I, Petersell V, Larsen B, Pedersen B, Floderus S (2000) Distribution of heavy metals in sediments of the Gulf of Riga, Baltic Sea. Boreal Environ Res 5:165–185 10. Mineral Resource and Exploration Institute Authority (1974) Gediz Basin’s Soils, Mineral Resource and Exploration Institute, Ankara-Turkey, 101 pp (in Turkish) 11. Nie NH, Hull CH, Jenkins JG, Steinbrenner K, Bent DH (1975) Statistical package for the social sciences. McGraw-Hill, New York 12. Novotry K, Turzikova A, Komarek J (2000) Speciation of copper, lead and cadmium in aquatic systems by circulating dialysis combined with flame AAS. Fresenius J Anal Chem 366: 209–212 13. Pardo R, Barrado R, Castrillejo Y, Velasco MA, Vega M (1993) Study of the contents end speciation of heavy metals in river sediments by factor analysis. Anal Lett 26:1719–1739 14. Taylor SR, McLeannan SM (1895) In the continental crust: its composition, evolution. Blackwell, Oxford, 600 pp 15. Thanachit S, Suddhiprakarn A, Kheoruenromne I, Gilkes RJ (2006) The geochemistry of soils on a catena on sedimentary rock at Nam Phong, north-east Thailand. Aust J Soil Res 44:143–154 16. Topp SE, Salbu B, Roaldset E, Jorgensen P (1984) Vertical distribution of trace elements in lateritic soil (Suriname). Cheml Geol 47:159–174

A Commonly Used Pesticide Endosulfan in Diet Could Cause Hepatomegaly and Kidney Tumor When Combined with Nitrosamines Recai Ogur and Omer Faruk Tekbas

Abstract Pesticides and nitrites which could be available in foods are generally investigated individually, although they could be found in foods together and exhibit combined health effects. In this study we aimed to determine the combined effects of endosulfan which is a commonly used pesticide and N-nitroso-N-methylurea (NMU) which is a prototype for mammary tumor development in Sprague Dawley rats and could be formed in brine foods or also in body from nitrites which is commonly used in meat. Ninety female Sprague Dawley rats had been used. Animals were divided three groups which consisted 30 animals. The first group took a single dose endosulfan intraperitoneal (ip) on 19th day and a single dose NMU ip on 21 day, the second group took endosulfan by their drinking waters for the first 60 days of their life and a single dose NMU ip on 21 day, and the third group took only a single dose NMU ip on 21 day. Animals were controlled for their general health status, mammary mass develeopment, daily water consumption and weekly weight gain. At the end of the study rats were examinated carefully under anesthesia, and tissue samples were prepared from their mammary glands and intraabdominal organs. Tissue samples taken from mammary glands, liver and kidneys were histopathalogically examined. It was determined a statistically significant hepatomegally in the second group when we compared to other groups (p < 0.05). No animals developed mammary tumors. On the macroscopic examination and manual palpation of intraabdominal region, it was showed that solid tumors in kidneys as a ratio of 76.7% of the animals in the second group (bilateral in 1,3% of them, the others are unilaterally and 70% of the unilateral tumors are in the left kidneys while the rest of them are right localized). Also it was found that in the first group, 13.4% of the animals developed unilateral kidney tumors.

R. Ogur (B) Department of Environmental Health, Gulhane Military Medical Faculty, Ankara, Turkey; GATA Halk Sagligi AD, 06018, Etlik, Ankara, Turkey e-mail: [email protected]; [email protected]

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The third group which had been applied only NMU developed no kidney or liver pathalogy macroscopically. As a result it was considered that a diversity which is named as “genetic shift” could be developed in our animal research center and because of this shift we could not developed NMU induced mammary tumors in our Sprague Dawley rats. But it has been showed that long term endosulfan expose has resulted in kidney tumor development for the first time. Because of the genetic shifting mentioned above, it should be tested whether this experimental animal cancer model is limited for our research center or not by obtaining sprague dawley animals from different centers. Interactions of living style, environmental factors and genetic properties in the development of cancer and its necessary to control all of three factors in order to reduce cancer frequency in public showed that the importance of interdiciplinary collaboration and public education. Consumers and appliers should be educated about using pestices, and healthy and safety food production and concumption should be considered as one of the primary subjects in public health studies. Keywords Endosulfan · N-methyl-N-nitorsourea · NMU · Kidney cancer · Pesticides

1 Introduction Pesticides are toxic substances commonly used in order to eliminate harmfull effects of animals or plants in agriculture or daily public life. Pesticides are generally toxic to more than one species, and could be detrimental to humans as well as to wildlife [1–4]. Although they are used widely, there are efforts to limit their use. Pesticide residues on the crops could be considered as external toxic chemicals contaminants. Endosulfan is one of the commonly used pesticides in the agriculture, and also it was found in water sources, fish products, meat products, milk, air and falling as well as vegetables and fruits because of contamination [5–10]. Beside pesticides, there are a lot of chemicals which we add to foods through food processing and manufacturing. They have to be healthy for human and there are some regulations about these food additives. Nitrates and nitrites are the food additives which have special interest [11]. Because they are known as toxic for human, but they are superior to the other preservatives for meat and meat products [12]. There are some studies about the production of cancerogenic nitoroso compounds in meat products which have contain nitrate/nitrite [12–14]. Pesticides and nitrites which could be available in foods are generally investigated individually, although they could be found in foods together and exhibit combined health effects. In this study we aimed to determine the combined effects of endosulfan which is a commonly used pesticide and N-nitroso-N-methylurea (NMU) which is a prototype for mammary tumor development in Sprague Dawley rats and could be formed in brine foods or also in body from nitrites which is commonly used in meat [15, 16].

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2 Material and Method Ninety female Sprague Dawley rats had been used. All studies on rats conformed to the principles of the Care and Use of Laboratory Animals (Institute of Laboratory Animal Resources) [17]. The laboratory animals used in the Study were provided by the Gulhane Medical Academy. Sprague Dawley rats were divided three groups which consisted 30 animals. The first group took a single dose (2 mg/kg) endosulfan (Dr. Ehrenstorfer GmbH, Germany, Catalog No: 13120000) intraperitoneal (ip) on 19th day and a single dose (75 mg/kg) N-Nitroso-N-methylurea (NMU) (Sigma No: N1517, Sigma, Germany) ip on 21 day, the second group took endosulfan by their drinking waters for the first 60 days of their life (3 mg/kg/day) and a single dose (75 mg/kg) NMU ip on 21 day, and the third group took only a single dose NMU ip on 21 day. Animals were controlled for their general health status, mammary mass develeopment, daily water consumption and weekly weight gain for 90 days. At the end of the study rats were examinated carefully under anesthesia (ip ketamine (50 mg/kg) and dehydrobenzoperidol (2 mg/kg)), and tissue samples were prepared from their mammary glands and intraabdominal organs. Tissue samples taken from mammary glands, liver and kidneys were histopathalogically examined. Sections taken from the samples fixed in formalin were stained with Hematoxylin and Eosin for examination. All the obtained data were transferred to the computer and analyzed statistically with the SPSS for Windows 11.0 software. The data have been presented as mean ± standard deviation (SD). By using frequency distribution graphs, and skewness and kurtosis statistics which describe the shape and symmetry of the distribution, it was decided that our data were parametric. So, parametric tests (ANOVA and chi-square tests) were used to compare the groups.

3 Results During the study no animal was died for any reason and the study was ended with 90 female Sprague Dawley rats. Anesthesia was applied before obtaining tissue specimens and the abdomen was examined with detail. Among the animals in second group exposed to NMU plus endosulfan in top water during 60 days, 76.7% of female SD rats were encountered renal tumor (1.3% bilaterally, others single side, among the single side ones %70 on left, 30% on right) when examined via palpation and macroscopically. When examined macroscopically and via palpation, the first group those took single dose endosulfan together with single dose NMU, single side renal tumor was encountered 13.4% of the animals. Although second group animals had severe hepotamegalia, animals in first group have also been observed to have relatively bigger liver. Group 3, exposed NMU only, had normal liver and kidney when examined macroscopically and via palpation. Daily water consuption of rats were followed and changes in daily water consupmtion depending on the endosulfan in top water or chemicals exposured to

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animals were examined closely. Although, water consumption according to groups varied between 42.7 ± 4.8 and 46.3 ± 5.6 ml/day there was no statistical significance for water consumption among groups (p > 0.05). Gaining weight ratio among groups was statistically insignificant (p > 0.05) although the group taken endosulfan with top water was less (Figs. 1 and 2). All rats’ livers were weighted after removal and liver/body weight ratios were obtained. Diffuse hepatomegalia was encountered the groups first and second those exposed to endosulfan. Animals in groups those took endosulfan during 60 days had higher liver/body weight ratios than others and statistically significant differance was observed (p < 0.05) (Table 1). In group 1 and group 2 liver specimens, observation of sinusoidal widening were supported the hepatomegalia when examined histologically. Among animals those took endosulfan with top water and single dose NMU, sinusoidal widening of 2nd group animals were larger than those group 1st animals and hepatomegalia of this group was more severe (Table 1) (Fig. 3).

Fig. 1 Kidney with tumor from intra abdominal view

Fig. 2 Kidney with tumor after excision from abdominal wall

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Table 1 Female SD rats liver/body weight ratios according to groups

Liver/body weight ratio

Group 1

Group 2

Group 3

0.0165 ± 0.0017

0.0191 ± 0.0023∗

0.0125 ± 0.0031

∗ statistically singificant differance had been encountered in 2nd group as compared with others (p < 0.05)

Fig. 3 A microscopic liver specimen view belonged to animals those took endosulfan during 60 days and single dose NMU at day 21st (2nd group). Portal vein at center and sinusoids widening were more pronounced than those first group liver exposed to single dose i.p.endosulfan at day 19th plus single dose NMU at day 21st (H&E 100x)

Infiltrative tumor had been established after histopathologic examination of the specimens of animals those had renal tumor. The tumors had been observed to have relatively higher mitotic frequency and infiltrated the normal glomerulus and renal tubuli. No pathology had been observed in animals those took single dose NMU when examined both macroscopically and microscopically (Fig. 4).

Fig. 4 Infiltrative tumors (right side of picture with arrows) together with normal renal tubuli. Renal tumors infiltrating normal glomerulus (short arrow) and normal renal tubuli (long arrows) could be seen (H&E, 50x)

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No tumor or growing breast had been encountered when breasts of female Sprague Dawley rats had been examined weekly and end of the study. However, breast tissue specimens were taken and examined microscopically. Breast tissues taken from animals had been accepted normal after specimens examined histopathologically, no fibrocystic changes or atypic characteristic related to carcinogenic improvement had been encountered. No calcification had been encountered in any specimens. Because of the possibility of histologic differences between human and Sprague Dawley rats breast tissues, related references were used for making true histopathologic examinations during evaluation [16, 18, 19].

4 Discussion Although developing of NMU induced mammary tumors would be expected in Sprague Dawley rats, we could not detect any mammary tumors [16, 17, 20, 21]. It was considered that a diversity named as “genetic shift” could be developed in our animal research center and because of this shift we could not developed NMU induced mammary tumors in our Sprague Dawley rats [22, 23]. But it has been showed that long term endosulfan expose has resulted in kidney tumor development for the first time. Because of the genetic shifting mentioned above, it should be tested whether this experimental animal cancer model is limited for our research center or not by obtaining sprague dawley animals from different centers. Because there are no scientific documentation about kidney tumor development in rats resulting from endosulfan, new studies should be planned to explain mechanism of kidney tumor development. And also it should be well documented whether there is an interaction between endosulfan and NMU. Interactions of living style, environmental factors and genetic properties in the development of cancer and its necessary to control all of three factors in order to reduce cancer frequency in public showed that the importance of interdiciplinary collaboration and public education [11, 24]. Consumers and appliers should be educated about using pestices, and healthy and safety food production and concumption should be considered as one of the primary subjects in public health studies.

References 1. Abelsohn A, Gibson BL, Sanborn MD, Weir E (2002) Identifying and managing adverse environmental health effects: 5. Persistent organic pollutants. Can Med Assoc J 166(12):1549– 1554 2. Adeoya-Osiguwa SA, Markoulaki S, Pocock V, Milligan SR, Fraser LR (2003) 17betaestradiol and environmental estrogens significantly affect mammalian sperm function. Hum Reprod 18(1):100–107 3. Ahlbom J, Fredriksson A, Eriksson P (1995) Exposure to an organophosphate (DFP) during a defined period in neonatal life induces permanent changes in brain muscarinic receptors and behavior in adult mice. Brain Res 677:13–19

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4. Carpy SA, Kobel W, Doe J (2000) Health risk of low-dose pesticides mixtures: A review of the 1985–1998 literature on combination toxicology and health risk assessment. J Toxicol Environ Health Part B, Crit Rev 3(1):1–25 5. Aguilera-Del AR, Valverde-Garcia A, Fernandez-Alba AR, Camacho-Ferre F (1997) Behaviour of endosulfan residues in peppers, cucumbers and cherry tomatoes grown in greenhouse: Evaluation of decline curves. Pest Sci 51:194–200 6. Amaraneni SR (2002) Persistence of pesticides in water, sediment and fish from fish farms in Kolleru Lake, India. J Sci Food Agric 82(8):918–923 7. Archibeque-Engle SL, Tessari JD, Winn DT, Kefe TJ, Nett TM, Zheng T (1997) Comparison of organochlorine pesticide and polychlorinated biphenyl residues in human breast adipose tissue and serum. J Toxicol Environ Health 52:285–293 8. Arrebola FJ, Egea-Gonzalez FJ, Moreno M, Fernandez-Gutierrez A, Hernandez-Torres ME, Martinez-Vidal JL (2001) Evaluation of endosulfan residues in vegetables grown in greenhouses. Pest Manage Sci 57(7):645–652 9. Cerrillo I, Granada A, Lopez-Espinosa MJ, Olmos B, Jimenez M, Cano A, Olea N, OleaSerrano MF (2005) Endosulfan and its metabolites in fertile women, placenta, cord blood, and human milk. Environ Res 98(2):233–239 10. Safi JM, Abou-Foul NS, el-Nahhal YZ, el-Sebae AH (2002) Monitoring of pesticide residues on cucumber, tomatoes and strawberries in Gaza Governorates, Palestine. Nahrung 46(1): 34–39 11. Barnard RJ (2004) Prevention of cancer through lifestyle changes. Evidence Based Complement Altern Med 1(3):233–239 12. Aklın E (2005) Et Ürünlerinde Nitrat, Nitrit ve Nitrozaminler. ˙Izmir Veteriner Hekimler Odası. http://izmir-vho.org/izmir-vho/kutuphane.asp?talep=konu&id=129&g=3 (Eri¸simtarihi: 20.04.2005) 13. Calle EE, Frumkin H, Henley SJ, Savitz DA, Thun MJ (2002) Organochlorines and breast cancer risk. CA Cancer J Clin 52(5):301–309 14. Johnson FM (2002) How many food additives are rodent carcinogens? Environ Mol Mutagen 39(1):69–80 15. Macejova D, Brtko J (2001) Chemically induced carcinogenesis: a comparison of 1-methyl1-nitrosourea, 7,12-dimethylbenzanthracene,diethylnitroso-amine and azoxymethan models (minireview). Endocr Regul 35(1):53–59 16. McCormick DL, Adamowski CB, Fiks A, Moon RC (1981) Lifetime dose-response relationships for mammary tumor induction by a single administration of N-methyl-N-nitrosourea. Cancer Res 41(5):1690–1694 17. Festing MFW, Altman DG (2002) Guidelines for the design and statistical analysis of experiments using laboratory animals. ILAR J 43(4):244–258 18. Masso-Welch PA, Darcy KM, Stangle-Castor NC, Ip MM (2000) A developmental atlas of rat mammary gland histology. J Mammary Gland Biol Neoplasia 5(2):165–185 19. Russo J, Russo IH (2000) Atlas and histologic classification of tumors of the rat mammary gland. J Mammary Gland Biol Neoplasia 5(2):187–200 20. Chou YC, Guzman RC, Swanson SM, Yang J, Lui HM, Wu V, Nandi S (1999) Induction of mammary carcinomas by N-methyl-N-nitrosourea in ovariectomized rats treated with epidermal growth factor. Carcinogenesis 20(4):677–684 21. Hu L, Lin L, Crist KA, Kelloff GJ, Steele VE, Lubet RA, You M, Wang Y (1997) Detection of differentially expressed genes in methylnitrosourea-induced rat mammary adenocarcinomas. J Cell Biochem Suppl 28–29:117–124 22. Bailey DW (1977) Genetic drift: the problem and its possible solution by frozen-embryo storage. Ciba Found Symp 291–303 23. Bailey DW (1982) How pure are inbred strains of mice? Immunol Today 3:210–214 24. Ames BN, Gold LS (1998) The causes and prevention of cancer: the role of environment. Biotherapy 11(2–3):205–220

Effect of Different Time and Temperature of Various Cooking Methods on Sulfonamide Residues in Chicken Balls M.R. Ismail-Fitry, S. Jinap, B. Jamilah, and A.A. Saleha

Abstract Sulfonamide residues are proven to be reduced in raw chicken meat after heat treatment but in processed chicken balls it is yet to be done. The objective of the study was to determine the optimum heat treatment condition for the reduction of sulfonamide residues in production of acceptable quality chicken balls. Three heat treatment processes; boiling, deep-frying and microwaving were consecutively applied on chicken balls pre-fortified at raw stage with four types of sulfonamides (SAs) namely sulfadiazine (SDZ), sulfamethazine (SMZ), sulfamethoxazole (SMX) and sulfaquinoxaline (SQX). Boiling process was carried out at 3, 6 and 9 min with ◦ ◦ temperature of 80, 90 and 100 C. Boiling of chicken balls at 100 C for 6 min was found to be the most acceptable in appearance and were brought to deep frying ◦ process with temperature of 170, 180, and 190 C and time of 3, 6, and 9 min. ◦ For deep-fried chicken balls, temperature of 180 C for 6 min was found to be the most acceptable in appearance and was used for microwaving process at power of 100, 250, and 440 W for 20, 40, and 60 s. For boiling, both factors (time and temperature) had significant reduction for all SAs (p < 0.05). The same went for deep-frying process; time and temperature had caused significant reduction for all SAs (p < 0.05). For microwave process, both factors (time and power) also showed significant reduction for all SAs (p < 0.05). SDZ was reduced up to 62% after application of the three cooking methods continuously. For SMZ the reduction was 52%. Meanwhile, 62% and 55% of reduction were observed for SMX and SQX respectively. The sequence of reduction on SAs residues for all cooking methods was deep-frying > boiling > microwave. The results would be guidance for industries and consumers to reduce risk of sulfonamide residues by heat treatments.

1 Introduction The practice of sulfonamide in animal husbandry is purposely to prevent diseases caused by both gram-positive and gram-negative bacteria, as well as some protozoa M.R. Ismail-Fitry (B) Faculty of Food Science and Technology, University of Putra Malaysia e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_55,

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(Sulfonamides Veterinary-Systemic, 2000). At the same time, sulfonamide also can act as growth promoter for the animal [3]. Due to the harmful effect to human, residues of sulfonamide have been restricted to 100 μg/kg of food producing animal [1]. Even though the Maximum Residue Limit (MRL) has been enforced, some farmers still violating the law by providing over dosage of sulfonamide or/and slaughtering before withdrawal period to increase their profits. It has been an issue of food safety when consumers were exposed to the residues without knowing it. Monitoring has been done frequently to control the over limit of sulfonamide residues in chicken meat but possibilities of undetected still exist because of too many samples and limited ability of detections. Furthermore, long time effect of sulfonamide residues due to accumulation in human body is still concerning the consumers. Cooking is proven to reduce sulfonamide residues in animal meat [5]. To what extend of the effect is depending on the type of cooking, temperature and time used. Most foods need to be applied heat treatment before human can eat them. This is related to the safety and quality of the food, where heat will reduce or inhibit microbial in food thus make sure the food will not cause harm to human. Foods also need heat treatment in form of cooking to maintain the quality especially for the sensory. Several studies have been done to study the effect of heat treatment to antibiotics in meat. Sulfonamide residues have been examined by several researchers related to effect of heat treatment. Sulfadimethoxine was used by Xu et al. [8] as antibiotic in muscle of channel catfish to determine the effect of cooking on the residues and cooking caused an average 46.1% reduction of sulfadimethoxine from raw fillet of fish. Meanwhile, Lan et al. [4] used sulfamethazine in their research on tilapia meat with microwave treatment reduced up to 90% and roast treatment reduced up to 85% of sulfamethazine in the fish. Furusawa and Hanabusa [2] did the experiment with chicken thigh muscle using sulfadiazine, sulfamethoxazole, sulfamonomethoxine and sulfaquinoxaline. The results were 45–61% reduction of boiling, 38–40% reduction of roasting except for sulfadiazine, and 35–41% reduction of microwaving to all the four sulfonamides. Among all the studies, none was on process product. So the objective of the study was to determine the effect of heat treatment on sulfonamide residues in production of acceptable quality chicken balls. Furthermore, the chicken balls were cooked with three different cooking methods consecutively to determine the reduction of the sulfonamide residues that might occur along the processing chain.

2 Experimental 2.1 Equipment For processing of chicken balls, bowl cutter/mixer (ADE SL-18), deep fryer (Philips Cucina) and microwave oven (National) were used. For sample preparation homogenizer Ultra Turrax basic (IKA LABORTECHNIK), Centrifuge Mettler PM34 Delta

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Range, Sonicator ULTRASONIK 104X (NEYTECH USA), Rotary evaporator and aspirator pump (EYELA), Nitrogen – PIERCE, Reacti – Therm, Heating/Stirring Module, Vortex (Stuart Autovortex mixer), and Microcentrifuge (EBA 12 – Hettich with rotor) were used. The following equipment were used for HPLC analysis: Photo diode array detector – Waters Associate 996, HPLC autosampler – Waters 717 PLUS, Pump – Waters model 510, Waters pump programmable 590, Symmetry C18 5 μm 3.9X150 mm, Waters.

2.2 Chemicals Acetonitrile, acetone, methanol, and N-hexane were from Fischer. Dichloromethane was from Merck. Sulfadiazine (SDZ), Sulfamethazine (SMZ), Sulfmethoxazole (SMX), and Sulfaquinoxaline (SQX) were from Sigma.

2.3 Standard Solutions Stock standard solution was prepared by dissolving 0.1 g of standard with 10 ml 90% acetonitrile (N-hexane saturated) separately. Intermediate standard solution was prepared by diluting an aliquot from the stock solution with 50% methanol. Working solution was prepared daily by diluting from intermediate standard prior the analysis.

2.4 Chicken Ball Production Chickens were bought from Nutriplus – Free Antibiotic Chicken type. Only the breast parts of the chicken were used for processing. The meat was ground and fortified with sulfonamide standards. Then the ground meat was left for one hour ◦ at chilling temperature (0–4 C). After that, corn starch, Sodium Triphosphate, black pepper, sugar, salt and garlic were added as ingredients. Bowl mixer 1 kg was used to grind and mix all the ingredients. Ice cubes were added while processing to control the temperature. The mixed dough was made into portion of 10 g separately. All the portions then were formed into ‘balls’ and flashed dip into 1,000 ml beaker containing distilled water and ice. The chicken balls then were taken out and put ◦ into plastic container and stored under –20 C before cooking process.

2.5 Cooking Processes Three type of cooking methods were applied consecutively on a batch of chicken balls pre-fortified with sulfonamides. Each cooking method was carried out at various time and temperature.

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Boiling processes were done at the temperature of 80, 90 and 100 C for 3, 6 and 9 min. From the boiling process, a batch of boiled chicken balls was brought to deep-frying processes. The frying processes were carried out at the temperature of ◦ 170, 180 and 190 C for 3, 6 and 9 min. After that a batch of fried chicken balls were brought to microwaving processes. The processes were carried out at the power of 100, 250 and 440 W for 20, 40 and 60 s.

2.6 Sample Extraction and Clean-Up Method of extraction used was by Furusawa and Hanabusa [2] with several modifications. 10 g sample was weighed in glass centrifuge tube and 30 ml 90% acetonitrile (N-hexane saturated) was added. The sample was homogenized for 1 min with Ultra Turrax Homogenizer. The solution was centrifuged for 10 min at 35,000 rpm. The supernatant was transferred into pear-shaped flask. 20 ml acetone was added to the sediment and sonicated for 10 min. Centrifuged and the super◦ natant is added into the pear-shaped flask. The solution was evaporated at 70 C until only water left. 5 ml methylene chloride was added and vortexed. The methylene chloride solution was transferred to test tube (repeated 3 times). The methylene ◦ chloride was dried under nitrogen at 50 C. The residue was reconstituted with 1 ml 50% methanol in acetate buffer and vortexed. 2 ml N-hexane is added for clean up. The cleaned portion was injected into HPLC system.

3 Results and Discussion Figure 1 shows the chromatogram of the SAs residues in chicken ball. The first peak to elute is SDZ at 8th minute. It is followed by SMZ at 12th minute. SMX and SQX are eluted at 16th and 19th minute respectively. All the peaks have been well separated. The effect of boiling on sulfonamide residues (SAs) in chicken balls is shown in bar chart (Fig. 2). Both factors, which are temperature and time have significant effect in the reduction of all the SAs with p < 0.05. Even though it has been ◦ reported by Rose et al. [6] that sulfamethazine was stable at temperature of 100 C, the reduction occurred was probably due to protein denaturation of the sample [5]. In Table 1 all the SAs except SDZ were reduced less than 10%. SDZ was reduced up to 22% considering that the SDZ has higher polarity compared to other SAs. This will probably increase the solubility of the SDZ compound in water. Figure 3 shows the bar chart of the deep-frying effect on SAs residues in pre◦ boiled chicken balls (100 C, 6 min). Temperature of deep-frying and time used have shown significant reduction (p < 0.05) on the SAs residues. The replacement of water in chicken balls with frying oil during deep-frying might be the main factor of the reduction on SAs residues. From the Table 1, it shows that after deep-frying, only 44–66% of SAs residues left compared to the raw chicken balls.

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Fig. 1 Chromatogram of SAs residues in chicken ball

Concentration (ppm)

BOILING 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0

SDZ SMZ SMX SQX

B0

B1

B2

B3

B4

B5

B6

B7

B8

B9

Treatment

B0

Control

B1

80°C 3min

B2

80°C 6min

B3

80°C 9min

B4

90°C 3min

B5

90°C 6min

B6

90°C 9min

B7

100°C 3min

B8

100°C 6min

B9

100°C 9min

Fig. 2 Effect of boiling in SAs residues

Table 1 Effect of different cooking methods consecutively on SAs residues in chicken balls Cooking process

Temperature/ power, time

SDZ left (%)

SMZ left (%)

SMX left (%)

SQX left (%)

Raw Boiling Deep-frying Microwaving

Control ◦ 100 C, 6 min ◦ 180 C, 6 min 440 W, 60 s

100a 77.58b 44.25 38.29

100a 90.92b 65.89 48.17

100a 94.49b 58.35 38.09

100a 91.53b 66.49 45.23

Values with different letters (a–b) within the same column reduce significantly (p < 0.05)

Concentration (ppm)

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DEEP-FRYING

0.35 0.3 0.25

SDZ SMZ SMX SQX

0.2 0.15 0.1 0.05 0 F0

F1

F2

F3

F4

F5

F6

F7

F8

F9

Treatment

F0

Control

F1

170°C 3min

F2

170°C 6min

F3

170°C 9min

F4

180°C 3min

F5

180°C 6min

F6

180°C 9min

F7

190°C 3min

F8

190°C 6min

F9

190°C 9min

Fig. 3 Effect of deep-frying in SAs residues

Concentration (ppm)

MICROWAVING

M0

Control

M1

100W 20s

M2

100W 40s

M3

100W 60s

0.25 0.2 SDZ SMZ SMX SQX

0.15 0.1

M4

250W 20s

M5

250W 40s

0.05

M6

250W 60s

0

M7

440W 20s

M8

440W 40s

M9

440W 60s

M0

M1

M2

M3

M4

M5

M6

Treatment

M7

M8

M9

Fig. 4 Effect of microwaving in SAs residues

The bar chart from Fig. 4 shows the effect of microwaving on the SAs residues ◦ in pre-fried chicken balls (180 C, 6 min). Significant reductions with p < 0.05 were observed for both power (W) and time (s) on SAs residues after microwaving processes. Table 1 shows that by microwaving pre-fried chicken balls, the residues left are from 38 to 45%. In microwave treatment, the reduction of SAs residues might be due to migration of juice out of the chicken balls. Table 1 shows that SDZ was reduced up to 62% after application of the three cooking methods consecutively. For SMZ the reduction was 52%. Meanwhile, 62 and 55% of reduction were observed for SMX and SQX respectively. The percentage of reduction for all SAs residues were different compared to previous studies because the sample itself and the cooking treatments were done consecutively.

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4 Conclusions As time and temperature increased, sulfonamide residues decreased; as such, texture and taste of the chicken balls might be affected. Both parameters were considered in selection of best time and temperature. Sulfonamide reduction during boiling and deep frying was due its migration from chicken balls to cooking medium (water and oil); during microwave process, it was due to juice exude out from chicken balls. The loss of sulfonamide residues was due to denaturation of protein-sulfonamide compounds. The sequence of reduction on SAs residues for all cooking methods was deep-frying > boiling > microwave.

References 1. Food Act 1983 (Act 281) & Regulations (2000) International law book services, p 198 2. Furusawa N, Hanabusa R (2002) Cooking effects on sulfonamide residues in chicken thigh muscle. Food Res Int 35:37–42 3. Kishida K, Furusawa N (2001) Matrix solid-phase dispersion extraction and high-performance liquid chromatographic determination of residual sulfonamides in chicken. J Chromatogr A 937:49–55 4. Lan CC, Hwang BS, Tu MF (2001) Effect of microwave and roast treatment on the degradation of sulfamethazine residue in tilapia meat. J Food Drug Anal 9(2):102–106 5. Papapanagiotou EP, Fletouris DJ, Psomas EI (2005) Effect of various heat treatments and cold storage on sulphamethazine residues stability in incurred piglet muscle and cow milk samples. Anal Chim Acta 529:305–309 6. Rose MD, Farrington WHH, Shearer G (1995) The effect of cooking on veterinary drug residues in food: III. Sulphamethazine (sulphdimidine) Food Addit. Contam. 12:739–750 7. Sulfonamides Veterinary–Systemic (2000) Drugs for animal use. http://www.usp.org/pdf/ veterinary/sulfonamides.pdf 8. Xu D, Grizzle JM, Rogers WA, Santerre CR (1996) Effect of cooking on residues of ormetoprim and sulfadimethoxine in the muscle of channel catfish. Food Research International 29(3–4):339–344

Reassessment of Tritium Dose Coefficients A. Melintescu, D. Galeriu, and H. Takeda

Abstract Concerns of increased risk from tritium intakes by humans have been claimed in the past years. The arguments concerning radiobiological efficiency assessment, longer retention in human body, and the DNA’s hydration shell are analysed in this paper. A biokinetic model for tritiated water and organically bound tritium retention in human body is used, based on a common approach for mammals using energy and hydrogen metabolism and tested separately with animal experiments. Extension to humans considers the increased role of brain, food quality and unique growth patterns of humans. Various ages and genders for Caucasians are considered. For an intake of tritium in organic forms in the diet, the retention for the female of about a factor 2 compared with ICRP recommendations. Effective dose coefficients are determined to be about a factor of 2–3 higher than those of the ICRP.

1 Introduction Tritium environmental behaviour and biological effects are of special relevance for the public around some nuclear facilities and for the future International Thermonuclear Experimental Reactor (ITER). Since 2003 International Atomic Energy Agency has conducted a special programme on Environmental Modelling for Radiation Safety (EMRAS) which has been running with a working group for tritium and 14 C (EMRAS T&C). In parallel, the International Commission for Radiological Protection is leading in the development of robust, physiologically based, compartmental, bio kinetic models for the radionuclide transfer into humans, with focus on the dose coefficients. Such a model is missing for tritium and the current ICRP model is under scrutiny [1]. Tritium, an internal emitter, can be A. Melintescu (B) Department of Life and Environmental Sciences, Horia Hulubei National Institute of R&D for Physics and Nuclear Engineering, 407 Atomistilor St., PO Box MG-6, RO-077125 Bucharest – Magurele, Romania e-mail: [email protected]

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ingested by public in two forms: tritiated water (HTO) or organically bound tritium (OBT). When tritium replaces hydrogen in a carbon-hydrogen bond, it is difficult to remove and is referred to as non exchangeable OBT. Tritium attached to oxygen, sulphur, nitrogen or phosphorus is in general readily exchangeable with the hydrogen of the body water pool and can be easy separated. In living organisms, protein biomolecules are surrounded by a hydration shell, a few layers of water molecules strongly bonded to the biomolecule and hydrogen (or tritium) is not exchangeable; tritium is buried in the hydration layer. The effect is strong in the case of DNA. Consequently the EMRAS T&C working group has adopted and expanded a definition of OBT in which included buried tritium in hydration shell and tritium bond to carbon. In the following we will refer only to this form of OBT, as ingested by humans in the diet. The dose coefficients actually recommended by ICRP [2] are based on a single (whole body) compartment for OBT with simple rules for the biokinetic parameters and assuming that the tritium radiobiological efficiency (RBE) is 1. In the past, parameter uncertainty for the ICRP model [2] was analysed for HTO intake [3] and for both forms [4], including RBE and an increase of a factor 2 was recommended, due to increased RBE. Much higher dose coefficients were claimed [1], up to a factor 15 for HTO and much more for OBT, due to hydration shell, RBE and increased retention of OBT. Uncertainties in model predictions come from uncertainties in model parameters, inability to account for natural variability of processes and model uncertainties themselves [5]. In the present paper each source of uncertainty is analysed and an alternative model for the dynamics of tritium in the human body is used, developed for mammals and based on general principles and links between bio matter turnover and energy fluxes [6, 7]. The model was favourably tested with farm and laboratory animal data, without calibration [8].

2 Uncerntainties Due to Hydration Shell (Buried Tritium) Buried tritium, included in our definition of OBT, is due to strong binding of tritium in the hydration shell (mostly in DNA). After extraction of exchangeable OBT, samples of aquatic plants and fish have been denatured with strong reagents in order to extract the buried tritium [9]. Buried tritium only contributed 5% in plants and less than 20% in fish. By consideration of binding propriety of hydrogen and stoichiometry, an upper limit of 25% was assessed (F. Baumgartner, 2006, personal communication) . Due to its low contribution we concluded that buried tritium is not a special problem in analytical technique of current transfer modelling approach, at the level of today requirements in accuracy. As for dose consequences, the increased health effects due to local increased concentration of tritium in DNA are included in the assessment of RBE by direct experiments or microdosimetry and it cannot count twice. The buried tritium, considered in the definition of OBT, is not changing the present dose assessment procedures [10].

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3 Uncerntainties Due to RBE ICRP [2] considers the RBE for tritium to have a value of 1, although there is much experimental evidence of higher values [4]. The RBE for tritium is 2 times greater if based on gamma rays rather than on X rays. Hamby [3] considered the two cases separately; Harrison [4] used a single distribution but limited to a value of 2.5 (less than maximum value if based on gamma rays). In absence of agreement on a unique, standardised reference radiation, it is better to consider the ensemble of values, disregarding the standard used in each experiment. Experimental values of RBE have been obtained at high dose or dose rate. In practice people around nuclear facilities encounter low doses. In hypothetical accidents it is expected a maximum dose less than 100 m Sv for a release of 10 g of T as HTO (EMRAS T&C current work). There are no direct data on tritium RBE in this low dose and the precautionary principle is applied. The probability distribution of tritium RBE is taken up to higher values measured at relatively high dose (Table 1). It is assumed a lognormal distribution with mean around 1.8 for HTO and 2 for OBT. There is no clear evidence of deterministic health effects from exposure to tritium in long-term studies of workers or members of the public, up to now, and at low dose carcinogenesis is more important. It is possible that RBE is lower than the upper range considered in this paper. Table 1 Distributed model parameters Variable

Distribution

Range

Comment

RBE HTO RBE HTO Metabolisable fraction of the diet

Lognormal Lognormal Uniform

1–3.3 (mean 1.8) 1– 4 (mean 2) 0.9–1

Non exchangeable fraction

Uniform

0.4–0.75

Bound H from free H

Uniform

0.25–0.35

Diet composition (kg OH/MJ) Water intake

Uniform

0.00325–0.00354

All values for X and γ ray All values for X and γ ray Equivalent with fraction transferred to blood in other models From organic tritium in the diet, transferred to body OBT after digestion Fraction of OBH in the body, at equilibrium, coming from free H in body water OH in diet per MJ of diet energy

Lognormal

Depends on case

Adapted from USA and Canada water intake distributions.

4 Retention of Tritium in Humans The dynamic model for the transfer of tritium and radiocarbon in mammals is based on some assumptions [8] as follows: 1. Net needs of nutrients and energy for maintenance, thermo genesis and activity are of first concern in all mammals; mammals adapted the gastrointestinal tract

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for digestion of available nutrients in order to satisfy net needs. The model is only for post weaning period. The model considers only normal balanced diet (not limited in energy and protein) with specific activity of protein, carbohydrates and lipids relatively close. A single rate of respiration (CO2 exhaled or H2 O to body water) is used. Biokinetic rate of organics from organs to blood plasma are assessed using the organs energy turnover rate. Other transfer rates are assessed by a balance of stable hydrogen (free or organically bounded). Empty body mass (mass of the living animal minus GIT and urinary bladder content) is divided into tissues with high metabolic rate – visceral organs (portal drained viscera, liver, kidney and heart), adipose tissue, muscle, blood plasma, red blood cells, and the remainder (mostly brain, bone, cartilage, red bone marrow, skin etc).

Despite simplifying assumptions, the model gives satisfactory predictions and is able to reproduce time-integrated concentrations in whole body and milk in tested animals [8]. Humans are the top primates and compared with other mammals take longer to mature, have a much higher brain and require better food quality [11]. For humans the net energy needs are 90% from daily energy intake [12]. Average reference human characteristics have been defined for healthy persons of various ages, gender, body mass, height, organ mass, basal metabolic rate and daily energy expenditure [13]. Organ compositions were taken from the literature [14]. Values of the specific metabolic rate (SMRo) for many organs in adults are known [11, 15]. Resting (basal) metabolic rate can be reconstructed from organ mass and SMRo. For a child an increased metabolic activity in brain were considered. The reconstructed basal metabolic rates are closed to recommended values [13]. The partition of net maintenance energy for model compartments (active humans) considers the increased contribution of muscle and a 20% increase in viscera metabolism. For reference humans, with fixed body composition, basal and daily energy expenditure, only few model parameters have variability (Table 1). The metabolisable fraction in the diet (fraction absorbed from the intestine) and the non exchangeable fraction after digestion (transferred as OBT to blood from the OBT absorbed) have uniform distributions close to similar parameters in literature [4]. The fraction, at equilibrium, of OBT in the body metabolised from free tritium is assessed with uniform distribution having the same range as experiments with small laboratory mammals. Water intake is supposed lognormal distributed with ranges close to statistics in USA and Canada [16]. Latin Hypercube Sampling was used with 500 trials in each case and the model was solved with ODEPACK routines (public domain). We first consider the case of equivalent dose, with RBE = 1, in order to compare directly with ICRP [2] and have a direct estimate of the increase of tritium retention in the present model. Final dose assessment considers RBE probability distribution, non uniform distribution of OBT and effective committed dose. Tissue weighting factors were combined to obtain the compartment weighting factors (0.008 for adipose tissue and muscle, 0.45 for viscera and 0.53 for remainder). For child, it has

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been considered the growth dynamics, imposing the trend from the reference value at various ages [13].

5 Results The equivalent doses (RBE = 1, uniform tritium distribution) obtained with the model are compared with ICRP [2] values in Table 2. The contribution of OBT to total tritium integrated activity is 14% for HTO intake (range 11–16%) and 75% for OBT intake (range 66–85%), closed to ICRP [2] and experimental data after HTO intake. For HTO intake the 50% prediction is slightly higher than ICRP [2] for children and women due to different assumptions about water intake. For OBT intake the retention is increased significantly only for female (factor near 2–2.4) as expected from the higher adipose mass [4]. The proposed model takes into consideration the non uniform distribution of tritium into the body. For example in the case of an adult female about 70% of the integrated OBT activity after OBT intake is in adipose tissue while its mass contribution is only 31%. Consequently, for the final assessment it is considered the committed effective doses, given in Table 2 including the consideration of RBE probability distribution. Considering the best estimate (50% percentile in the dose distribution) the largest difference compared with ICRP [2] is for a female of 15 years, with a factor three for HTO and OBT intake. From Table 2, the dose after OBT intake is 2.5–2.9 times higher than after HTO intake. At 95% percentile (upper safe estimate) the increase in dose is between 2.8 for adult male and 5 for a 15 years

Table 2 Dose coefficients (Sv × 10−11 Bq−1 ); H (RBE = 1; uniforme distribution) and effective dose E HTO

OBT

H (RBE = 1, ICRP unif.)

H (RBE = 1, ICRP unif.)

E

Case

–

5%

50% 95% 5%

50% 95% –

1y 5y 10 y 15 yf 15 ym Ad. F Ad. M Ad. Ob Ad. Ath Ad [4]

4.8 3 2.3 1.8 1.8 1.8 1.8 1.8

2.9 2.3 1.8 1.7 1.2 1.26 1 1

4.6 3.5 3.1 3 2.4 2.4 1.8 1.7

6.6 5.1 4.8 4.8 3.9 3.9 2.9 2.7

4.9 3.8 3.1 2.8 1.8 2 1.5 1.6

8.6 6.6 5.8 5.4 3.8 4.2 3. 3.2

1.8

1

1.7

2.7

1.5

2.8

4.7

–

–

–

–

2.1

3.9

6.6 –

5%

50% 95% 5%

13.3 12 14.3 16 10.2 7.3 8.4 9.6 9.5 5.7 8.3 9.5 9. 4.2 8.2 9.5 6.6 4.2 5.5 6.5 7.3 4.2 9.1 10.2 5.1 4.2 5. 5.8 5.4 4.2 7.3 8.1 4.2

2.5 –

E

18 10.9 10.9 11 7.8 11.5 6.7 9

16.3 10 10 8.2 5.9 7.5 5. 5.2

25 15.7 15.2 13. 9.5 11.8 7.8 8.2

36. 22.7 22.2 19. 14. 17 11.3 12

4.1

3.7

6

8.8

3.9

8.7

3.2 –

50% 95%

–

20

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female. The dose distribution for OBT intake is dominated by the contribution of RBE uncertainty while for HTO intake, the probabilistic effective dose depends also on assumed water intake distribution.

6 Discussion and Conclusions In this contribution it was attempted a reassessment of tritium human dosimetry starting with an analysis of the effects of buried tritium, precautionary approach for RBE and using a distinct transfer model for tritium in humans, giving details on OBT distribution in human body. The final results, in terms of effective dose, assess the potential dose increase from past deterministic recommendation of ICRP [2] with an upper, conservative, safe limit of 5 and a best estimate of 3. In practice, considering the low dose encountered and lower RBE for carcinogenic effects, an increase in dose with a factor about 2–3 from actual ICRP recommendation, suffices for prospective dose assessment. Comparing with the parameter uncertainty estimates of ICRP model [4], for adults (last row in Table 2), the estimates are apparently very close. The present approach considers a larger range for RBE and it assesses effective dose and not the equivalent dose for uniform tritium distribution in the body. Also, it demonstrates a strong gender effect. The present estimates of the range of biokinetic rate for HTO are closed to previous assessment [4] but for OBT, the biokinetic rate for references human are fixed in the model. A first attempt to see the variability due to habits and body mass for male adults was done considering an obese sedentary and an athlete (Ad. ob. and Ad. ath in Table 2). For the effective dose the variability is quite low. The model presented can be developed and applied for retrospective dosimetry, if needed. A consensus on a single reference radiation and further progresses in clarifying RBE for tritium at low dose are desirable in order to decrease the uncertainty.

References 1. CERRIE (2004) Report of the Committee Examining Radiation Risks of Internal Emitters (CERRIE). ISBN 0-85951-545-1. www.cerrie.org 2. ICRP (1993) Age-dependent doses to members of the public from intakes of radionuclides: Part 2 Ingestion Dose Coefficients. Publication 67. Ann ICRP 23(3/4). Pergamon Press, Oxford 3. Hamby DM (1999) Uncertainty of the tritium dose conversion factor. Health Phys 77(3):291–297 4. Harrison JD, Khursheed A, Lambert ABE (2002) Uncertainties in dose coefficients for intakes of tritiated water and organically bound forms of tritium by members of the public. Radiat Prot Dosim 98:299–311 5. NCRP Commentary No. 14 (1996). A guide for uncertainty analysis in dose and risk assessments related to environmental contamination, Bethesda, MD 6. Galeriu D, Melintescu A, Beresford NA, Crout NMJ, Takeda H (2005) 14 C and tritium dynamics in wild mammals: A metabolic model. Radioprotection 40(1):S351–S357

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7. Galeriu D, Takeda H, Melintescu A, Trivedi A (2005) Energy metabolism and human dosimetry of tritium. Fusion Sci Technol 48(1):795–798 8. Galeriu D, Melintescu A, Beresford NA, Takeda H, Crout NMJ (2009) The dynamic transfer of 3 H and 14 C in mammals – A proposed generic model. Radiat Environ Biophys 48:29–45 9. Kim SB, Workman WJG, Davies PA (2008) Experimental Investigation of Buried Tritium in Plant and Animal Tissues. Fusion Sci Technol 54(1):257–260 10. Baumgartner F, Donhaerl W (2004) Non-exchangeable organically bound tritium (OBT): its real nature. Anal Bioanal Chem 379:204–209 11. Aiello LC (1997) Brains and guts in human evolution: The expensive tissue hypothesis. Braz J Genet 20(1) 12. NAP (National Academy Press) 2005 Dietary reference intakes for energy, carbohydrate, fibre, fat, fatty acids, cholesterol, protein, and amino acids (macronutrients) Food and Nutrition Board (Institute of Medicine of the National Academies, The National Academies Press, Washington D.C., USA) ISBN: 0-309-65520-X 13. ICRP (2002) Basic anatomical and physiological data for use in radiological protection. ICRP Publication 89. Ann ICRP 32. Elsevier Science Ltd, Oxford 14. Richardson RB, Dunford DW (2003) A biochemical- based model for the dosimetry of dietary organically bound tritium. Health Phys 85:523–539 15. Gallagher D, Elia M (2005) Body composition, organ mass, and energy expenditure. In: Heymsfield SB, Lohman TG, Wang ZM, Going SB (eds). Human body composition, 2nd edn. Human kinetics, Champaign, IL 16. NAP (National Academy Press) 2005 Dietary reference intakes for water, potassium, sodium, chloride, and sulphate 2005 Food and Nutrition Board (Institute of Medicine of the National Academies, The National Academies Press, Washington, D.C., USA) ISBN: 0-309-53049-0

Approaches on H5N1 Avian Influenza Spreading in Relation with Human Health Risk Monica Popa, Daniela Cur¸seu, Dana Sîrbu, Ioan Stoian, and Adriana Manciu

Abstract Recent experiences with highly pathogenic H5N1 avian influenza have given the world its first advance warning that another influenza pandemic may be imminent. Given the serious consequences of past pandemics, this advance warning has stimulated a search for ways to prevent such an event from occurring through preparedness, rapid response and containment. The rapid response and containment strategy aims to stop, or at least slow the spread of pandemic influenza at the source of its emergence in order to minimize global morbidity and mortality. Keywords Epidemiological · H5N1 · Influenza

1 Introduction Influenza is one of the most spread and studied disease in the world, mentioned by Hippocrate in 412 bc., the first attested epidemic being documented in 1580. Since then, 31 pandemics were counted, of which three in the last century: 1918 (Spanish flu), 1957 (Asian flu) and 1968 (Hong Kong flu). Spanish flu was the most virulent, decimating the population at the end of First World War. There are detailed descriptions of three centers of contagion: Brest (France), Boston (USA) and Freetown (Sierra Leone). If the number of deaths in the period 1918–1919 exceeded twenty millions, it is estimated that a new imminent pandemic will sick 30% of the world population, determining between 20 and 100 millions of deaths [1]. The concern to avoid this calamity is coordinated by international organizations as WHO, FAO, EIO. At European level this concern was emphasized by preparing national preventing plans for the potential pandemic in 18 of the 25 European Union countries. These plans consist of programs of rapid preparation for efficient vaccines and the M. Popa (B) Department of Environmental Health, University of Medicine and Pharmacy Cluj-Napoca, Cluj-Napoca, Romania e-mail: [email protected]

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assurance of safety stocks for anti-flu medicines. Totally, 24 European countries including Romania, have achieved such plans at the end of 2005, countering more than 30 measures, which fast implemented in case of pandemic, will minimize the its impact. A flu pandemic starts in one country (usually in the South-East of Asia) and spreads rapidly worldwide (in 2–4 weeks) [2]. The pandemics of 20th century were developed 2–3 years with secondary/tertiary peaks till the immunization of the susceptible population, with notable differences between pandemic and inter-pandemic periods. Flu is a problem of public health even in the inter-pandemic periods, each season of fall-winter determining an excess of hospitalization due to pneumonia and other acute respiratory infections. Although the flu etiology isn’t always confirmed, its prevalence is considerable in extreme ages: children under 3 year old and people beyond 65 year old. During epidemic periods, happening once in 3–4 years due to antigenic shifting, the mortality in aged people increases 3–5 times. At present, the circulating human stems are A H1N1, A H3N2 and B. The pandemic stems appear due to recombining among human and aquatic birds stems. This recombining type appears frequently in the South-East of Asia due to the proximity of man-birds and density of population [3]. In this area there is no flu-seasonality and the surveillance must be extended the whole year. Other scenarios for the emergence of pandemic types confer a role to the direct human transmission of avian stems which acquire human tropism, leading to man to man transmission. This possibility is carefully investigated for avian types A H5N1, circulating from some years in the South-East of Asia. It was suggested also, the possibility of recycling old pandemic types, remained latent in an animal reservoir which could be transmitted to young generations, highly susceptible from the immunologic point of view [4]. This scenario explained the re-apparition of H1N1 type in 1977–1978 (Table 1). Epidemiological signals are likely to be the most sensitive and reliable indicators of a transition from inefficient, non-sustained human-to-human transmission of the virus to efficient and sustained transmission [5]. The detection of clusters of cases, closely related in time and place, is likely to be the most important epidemiological signal of such transition [6]. An epidemiological signal may manifest itself as an

Table 1 The flu pandemics of 20th century Period

Type

Attack rate

Mortality Comments

1918–1919

H1N1

40%

20%

1957–1958 1967–1968

H2N2 H3N2

< 10% < 10%

2% 1%

1977

H1N1 H3N2

20%

2%

Mortality in all groups of age by haemorragic pneumonia Mortality in extreme ages Crossed immunity due to the maintain of NA Mortality only in persons born after 1956

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increase in the number of persons with unexplained respiratory illness in a defined area over a short period of time. This pattern of unexplained respiratory illness should be different from that usually seen in the area. Observations with H5N1 infections to date suggest that a cluster of five closely related cases (including the index case) in which human-to-human transmission is suspected would constitute a signal [7]. To date, cases of human infection with the H5N1 virus have been sporadic and rare events, even in areas where the virus is widespread in poultry. Any transition in the behaviour and epidemiology of the virus indicating improved human-to-human transmissibility will most likely result in a visible event sufficiently “unusual” to be picked up by alert clinicians or the public health system.

2 The Surveillance of H5N1 Avian Influenza Virus Dissemination The dates from the first half of 2005 resulted from the surveillance of H5N1 dissemination suggest that: – The host spectrum of H5N1 was extended from chicken to other bird species; – Recent epidemics in aquatic/terrestrial birds lead to a broad area of spreading for avian influenza; – Different isolated H5N1 may be grouped in distinct genotypes with distinctive pathogenic and epidemic potential; – The transmission of H5N1 from birds to man is certain and several control measures are imposed in subjects with professional risk; – The early diagnose of human avian flu cases is difficult and this alternative must be carefully assessed; – The experimental tests of anti-H5N1 vaccines in humans should be accelerated. The flu virus H5N1 continues its evolution both as host spectrum and as virulence. In 2002, major epidemics in aquatic and terrestrial wild birds (Ardeidae sp, Falcon sp.) were noticed. Wild ducks and gooses (Anatidae sp, Anser sp) represent the natural reservoir and the source of flu viruses type A, for all the other mammalian and bird species. Usually, the virus H5N1 doesn’t produce the illness in aquatic birds, but the high mortality in some Chinese lakes indicates the selection of some virulent types [8]. The study of H5N1 types emphasized the separation of two clusters corresponding to the geographic migration route of birds (Eurasiatic and American): highly pathogenic avian influenza (HPAI) and low pathogenic avian influenza (LPAI) (Table 2). The pathogenity isn’t determined by the geographical distribution, anywhere being possible the appearance of highly pathogenic types. Without exception, the very pathogenic types belong to sub-types H5 and H7, the neuraminidase not being essential for the virulence [9]. The highly pathogen viruses in some bird species may act as opportunistic in other species. Among domestic species, the chickens and the

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M. Popa et al. Table 2 The morphological and clinical differences in avian flu infections

Type

Replication site

Infection

Simptomatology

LPAI HPAI

Respiratory/digestive tract Respiratory/digestive tract; Vascular endothelium

Local Systemic

Absent/moderate Severe/lethal

Table 3 Structural differences among HA of H5N1 types Types

Cleavage sites HA

Cleavage enzymes

Aminoacides at cleavage sites

LPAI HPAI

Unique Multiple

Bacterial proteases Viral and ubiquitor proteases

Arginine Different basic amino acids

turkeys are highly susceptible to HPAI types, while the ducks and the gooses are resistant. The transmission route for all avian flu viruses is fecal-oral (especially in aquatic birds) and by air (especially in domestic birds living in high density).The post-proteolytic activation of H5N1 hemagglutinin (HA) is essential for the infective power, dissemination-excretion and virulence (Table 3). The viruses LPAI are activated by enzymes acting in blood coagulation, or by bacterial proteases present in normal conditions, in different bird species [10, 11]. The acquisition of new cleavage sites in flu HA sequences is determinant for the conversion of non-virulent stems in virulent ones and for the host spectrum change [12]. In last 5 years, 4 new types of flu viruses type A have appeared: H1N1 and H2N7 (in USA), H9N2 in Holland and H5N1 in South-East of Asia and even in Siberia and Kazahstan. It is difficult to predict the pandemic potential of these stems but it is obvious that H5N1 evolution imposes a high alert level. The A viruses type H7N7 and H3N8 were isolated in Europe in horses. At present, three A viruses are circulating in Europe, being found in pigs: H1N1 (with an avian variant), H1N2 and H3N2 [13]. The H1 hemagglutinin from pigs is similar with the human H1 in proportion of 80%, and pigs represent a potential reservoir for the appearance of avian/human recombining.

3 The Possibility of Human Transmission for H5N1 Avian Influenza Generally, the avian viruses aren’t capable to be directly transferred in humans. The communicated cases starting from 1997, when an 3 year old boy died due a pneumonia complicated with a Reye syndrome and a H5N1 virus was isolated from him, resulted from infections with extremely concentrated doses of virus in immunodepresive persons. In 1997 in Hong-Kong 18 cases of H5N1 avian flu with 6 deaths were reported. These cases didn’t confirm the possibility of inter-human transmission, but the fact that the avian viruses are not replicative in humans [14]. The extreme measure of bird sacrificing was selected as the only measure to avoid

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Table 4 Significant events in the evolution of H5N1 types Year

Clinical/epidemiological event

2002 2003 2003–2004

The appearance of HPAI types in ducks and other aquatic birds in China Familial focus of human avian flu with two deaths in Hong Kong Extended H5N1 epidemics in birds, HPAI types in domestic birds isolated in 9 countries from Asiaa Isolation of virulent genotype Z+ in birds Notification of HPAI types dissemination through Siberia New human cases in Vietman (37 deaths at 76 cases), Thailand (12/17) and Cambodia (4/4) The first cases of inter-human transmission The cytokine balance – pathogenic element in human infection Other susceptible species (felines) possible vectors of avian flu Infections H5N1in pigs – hosts generating recombining with human tropism

2004 2004 2004 2004 2005 2005 2005 a Vietnam,

Thailand, Indonesia, Cambodia, Laos, Korea, Japan, Malaysia, China

Table 5 Genomic determinants of human tropism and virulence for H5N1 types Involved gene

Molecular transformation

Result

HA PB2 NS1 NA

New cleavage sites Glu 627→Lys 627 Only for HPAI types Depletion of 19 aminoacids

Enlargement of host spectrum Human virulence IFN antagonist Higher pathogenesis, resistance to Oseltamivir

a pandemy. In the following years, the permanent circulation of H5N1 viruses has determined the extent of host spectrum and the increase of human pathogen potential (Table 4). The possibility of man to man transmission of H5N1 avian influenza is the critical point in the initiation of a new pandemic. This viral characteristic becomes consistent in case of highly pathogenic viral isolates (HPAI) characterized during 2004–2005 (Table 5). The old isolates were less pathogenic in birds and mammalians. However, in rare cases (healthcare workers carrying for patients with avian flu) the H5N1 serum conversion was noticed, although the respiratory symptoms were missing.

4 Aspects of Public Health Influenza is the most frequent infection of the upper respiratory airways. It is estimated that in every season, between November and March, 10–20% of the population get one flu episode, at least. Children are 2–3 times more susceptible than adults. In Romania, every year approx. 20,000 cases need hospitalization and more than 2,000 deaths are set down to flu, especially in ages upon 65 years. and chronic cardio-respiratory illnesses. The previous dates are 3–5 times multiplied during flu epidemics. The schoolchildren have a major contribution to the

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disease dissemination. The families with schoolchildren aged 6–14 years are much more exposed, influenza affecting half or even more of their members. Influenza is transmitted not only by air, but through contaminated objects also, for example a door handle, a telephone receiver. The simptomatology represents the most used criteria for diagnostic. The general symptoms (fever, chills, muscle pains, headache) prevail upon respiratory symptoms (dry cough, obstructed nose). The symptoms start in 1–2 days from the infective contact, last 4–5 days, followed by the convalescence with or without complications. The incubation period is 1–3 days, the virus excretion precedes the disease beginning and continues more 3–5 days. The transmission route is by air or by contact. The children have a larger period of viral excretion and a higher attack rate (especially schoolchildren represents the main vector in flu dissemination in collectivities). The acute debut consists of fever, muscle pain, nasal congestion, dry cough. The symptoms last 3–7 days, which make that flu not to differentiate from other acute respiratory infections (Table 6). The most frequent complications are: pulmonary (primary viral/secondary bacterial pneumonia), renal and cardiac impairment, encephalitis, Reye syndrome (hepatic failure and encephalopathy).

Table 6 Clinical and laboratory data for a severe prognostic Clinical data

Laboratory data

Respiratory frequency > 30/min Dyastolic blood pressure < 60 mmHg Age > 65 years Atrial fibrillation Associated severe chronic diseases Drowsiness, confussion

Urea > 7 mmol/l Albumine < 35 g/l Hipooxemie pO2 < 8 kPa Leucocytes < 4,000 Leucocytes > 20,000 Positive hemoculture

5 Risk Assessment If this assessment based on relevant information concludes that the signal requires further investigation, several activities should follow immediately.

5.1 Diagnostic Confirmation Laboratory specimens should be sent to a WHO H5 reference laboratory for identification, verification and confirmation of the causative agent, even when prior cases have been confirmed in the affected country.

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5.2 Burden Assessment The available data generated during the signal investigation will be used to characterize the disease pattern, determine the population at risk, and identify factors affecting transmission pattern and control activities (such as geographical location of outbreak, movements in an out of the area). Where feasible, modelling should be undertaken to help predict spread, and anthropological investigation should be undertaken to examine socio-cultural factors that may have implications for control interventions.

5.3 Needs Assessment Based on the analysis of the burden and the available national resources for rapid response and containment, the need for additional support will be assessed, which may include personnel (such as epidemiologists, clinicians, logisticians, laboratory experts, experts in communications and social mobilization), supplies (such as personal protective equipment and antiviral drugs).

5.4 Request for Antiviral Should the assessment establish a need to deploy a portion of the antiviral drug (Oseltamivir) from the global stockpile.

5.5 Outbreak Communications A communication plan will be formulated to ensure that all information relevant to outbreak assessment and response is communicated to the general public, international community and partners. Risk communication, including key messages to the public, will be disseminated swiftly.

6 Immediate Control Measures Routine control measures aimed at reducing opportunities for further transmission to occur should be initiated as soon as preliminary investigations of the detected clusters of cases confirm an existing epidemic. These measures should be strengthened and intensified concurrently as the risk assessment is being conducted in order not to loose time. Recommended measures include traditional, standard interventions used during outbreak control. At present, many of these measures are being applied routinely in H5N1 outbreaks characterized by sporadic human cases with no evidence

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of efficient human-to-human transmission. These measures should be introduced immediately and should not await laboratory confirmation of the causative agent. Immediate measures include: – Isolation of clinical cases of moderate-to-severe respiratory disease in respiratory isolation rooms or single rooms; – Identification and voluntary home quarantine of persons who have had close contact with a case, and their daily monitoring for symptom onset; – Antiviral drugs for the treatment of cases and for the targeted prophylaxis of close contacts; – Strict infection control and the use of personal protective equipment during the delivery of health care in health care facilities. – Intensive promotion of hand and cough hygiene. – Domestic cleaning, using household cleaning products, to reduce transmission via fomites and from infectious respiratory secretions on surfaces. – Appropriate waste management and disposal. – Informing the public of the outbreak and initiating social mobilization measures.

7 A Two-Phased Containment Strategy The rapid containment strategy is implemented in two phases: 1. Immediate implementation of standard measures aimed at reducing further transmission. In this phase, isolation of cases, active case finding and contact tracing are undertaken and antiviral drugs are administered, in a targeted way, to persons identified during these activities. 2. Implementation of exceptional measures, including wider prophylactic administration of antiviral drugs, quarantine, and the introduction of social distancing measures. During both phases, surveillance activities should be intensified in the outbreak zone and the surrounding areas to guide the continued implementation of public health measures and monitor their impact. Geographically surrounding countries, or those that are linked through communication routes, may need to be on the alert for possible introduction of potential cases.

7.1 Phase One: Standard Measures to Reduce Transmission Activities in this phase are based on the assumption that an emerging pandemic virus will not immediately cause the explosive increase in the number of cases seen during a full-fledged pandemic. Assuming that the number of new cases is still manageable,

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activities should concentrate on investigation and laboratory confirmation of cases, appropriate management of cases in a safe environment, implementation of infection control measures within the health care setting, contact tracing and monitoring, use of antiviral drugs for the treatment of cases and targeted prophylaxis, intensified surveillance and the real-time reporting of data. The interventions at this phase aim to reduce opportunities for further transmission to occur and thus, ideally, prevent the virus from becoming well adapted to humans. 7.1.1 Case Management In the initial phase, when a manageable number of cases is assumed, clinical cases should be hospitalized and managed in single rooms if possible. Once laboratory confirmation of infection is available, and the number of cases exceeds the available number of single rooms, patients may be hospitalized in group isolation rooms adapted to negative pressure facilities. Patients should be transported to these facilities by trained staff wearing appropriate personal protective equipment and using designated vehicles. To minimize the risk of nosocomial transmission, persons showing signs of mild, moderate or severe respiratory illness must be assessed in premises separated from those where confirmed cases are being managed. Options for doing so include the establishment of fever clinics, home visits by medical staff, drive-through consultation services, and other methods of triage and diagnosis that limit opportunities for exposure. 7.1.2 Antiviral Treatment and Targeted Prophylaxis In the containment zone, antiviral drugs should be administered to cases of moderate-to-severe respiratory illness to reduce morbidity and mortality, and to their contacts to reduce ongoing spread. Priority access to antiviral drugs and other medical interventions is expected to work as an incentive that increases the willingness of patients and their contacts to comply with recommended public health measures under what are likely to be stressful and demanding conditions. Local and national authorities will define jointly (within the outbreak zone) the households, schools, workplaces, health facilities or other settings where the delivery of antiviral drugs, personal protective equipment, and other medical supplies should be targeted. 7.1.3 Intensified Surveillance Once the reported signal is confirmed to be an influenza alert requiring immediate intervention, surveillance activities should be intensified immediately within the initial outbreak zone. The surrounding area, and the geographically “at risk” areas, should also intensify their surveillance and remain on alert for possible introduction of the virus. Within the outbreak zone, enhanced detection and reporting

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of individual cases and clusters of human-to-human transmission can be achieved through institution of active surveillance to identify all potential cases, and increased diagnostic suspicion.

7.1.4 Contact Tracing During investigation and response, contact tracing must be implemented to include the identification of extended social networks and the travel history of all cases and contacts during the preceding 14 days. Contacts of cases should be traced and followed up for evidence of respiratory illness for at least 7 days after last contact. If the number of contacts requiring investigation is large, follow up should be prioritized based on: – Heightened probability of infection, such as contact with a laboratoryconfirmed case – Duration and closeness of this contact – A high-risk exposure, such as unprotected patient care – Exposure in settings that could accelerate spread to large numbers of contacts, such as when a confirmed case worked in a school or attended a large gathering. Whenever possible, cases should be isolated in health care facilities to maintain strict infection control. Contacts should be advised to remain at home (voluntary home quarantine) for at least 7 days after the last contact with a person under investigation.

7.1.5 Monitoring Contacts for Signs of Illness The public should be informed of the most common symptoms which are fever and/or cough. They should receive instructions on how to self-monitor for fever post exposure, which should be performed for at least 7 days following the last contact with a possible case of influenza. People should immediately report the onset of fever and other symptoms to the health authorities and remain in voluntary home quarantine during the duration of self monitoring.

7.2 Phase Two: Exceptional Measures, Including Use of the Antiviral Stockpile 7.2.1 Voluntary Quarantine Experience during the SARS outbreak suggests that quarantine, applied on a voluntary basis, may be as effective as enforced quarantine. However, for voluntary quarantine to succeed, the public will need to be informed and sensitized on benefits.

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Local authorities should apply quarantine in the following situations: – Exposure has occurred in a defined group of persons as, for example, in a household setting, at the workplace or school, or at a well-defined and circumscribed public gathering – Exposure has occurred in a defined site or building (such as a hospital or an apartment building) Quarantine may involve confinement at home or in a designed facility with appropriate equipment. Persons in home quarantine may need to be provided with food, access to communications, psychosocial support, and supplies of their usual medications, especially for chronic conditions.

References 1. World Health Organization (2004) Avian influenza A (H5N1). Weekly Epidemiol 79:65–70 2. Li KS, Guan Y, Wang J, et al (2004) Genesis of a highly pathogenic and potentially pandemic H5N1 influenza virus in Eastern Asia. Nature 430:209–213 3. Claas ECJ (1998) Human influenza A H5N1 virus related to a highly pathogenic avian influenza virus. Lancet 351:472–477 4. Webster RG, Bean WT, Gorman OT, Chambers TM, Kawaoka Y (2003) Evolution and ecology of influenza A viruses. Microbiol Rev 56:152–179 5. Guan Y, et al (2004) H5N1 Influenza: A protean pandemic threat. Proc Natl Acad Sci USA, 101:8156–8161 6. Guan Y, Shortridge KF, Krauss S, Webster RG (1999) Molecular characterization of H9N2 influenza viruses: were they the donors of the internal genes of H5N1 viruses in Hong-Kong? Proc Natl Acad Sci USA 96:9363–9367 7. Hien TT, et al (2004) Avian influenza A (H5N1) in ten patients in Vietnam. N Engl J Med 350:1179–1188 8. Li KS, et al (2003) Characterization of H9 subtype influenza viruses from the ducks of southern China: a candidate for the next influenza pandemic in humans? J Virol 77:6988–6994 9. Xu X, Subbarao K, Cox NJ, Guo Y (1999) Genetic characterization of the pathogenic influenza A: similarity of its hemagglutinin gene to those of H5N1 viruses from the 1997 outbreaks in Hong-Kong. Virology 261:15–19 10. Thomas JM, Stevens MP, Percy N, Barclay WS (1998) Phosphorylation of the M2 protein of influenza A virus is not essentially for virus viability. Virology 252:54–64 11. Holsinger LJ, Shaughnessy MA, Micko A, Pinto LH, Lamb RA (1995) Analysis of the posttranslational modifications of the influenza virus M2 protein. J Virol 69:1219–1225 12. Matrosovich M, Zhou NN, Kawaoka Y, Webster RG (2003) The surface glycoproteins of H5N1 influenza viruses isolated from humans, chickens and wild aquatic birds have distinguishable properties. J Virol 77:6988–6994 13. Ha Y, Stevens DJ, Skehel JJ, Wiley DC (2001) X-ray structures of H5 avian and H9 swine influenza virus hemagglutinins bound to avian and human receptor analogs. Proc Natl Acad Sci USA 98:11181–11186 14. Shortridge KF, et al (1998) Characterization of avian H5N1 influenza viruses from poultry in Hong-Kong. Virology 252:331–342

The Relationship Between Infant Methemoglobinemia and Environmental Exposure to Nitrates Daniela Cur¸seu, Dana Sîrbu, Monica Popa, and Alina Ionutas

Abstract In the framework of the paper the incidence of infant methemoglobinemia in Cluj county, Romania was evaluated from medical records. The incidence rate ranged from 42 to 239 per 100,000 live births between 2000 and 2004. Bottle-babies less than 4 months are the age group most at risk of acquired methemoglobinemia. Well water was the main source of nitrate, though early incorporation of vegetable juices and table food into infant diet were also incriminated. Some recommendations for the management of methemoglobinemia in this area are described: introduce a low nitrate water supply scheme specially for infant feeding, education program for mothers to increase duration of breast feeding, further studies on long-term development effects on infants. Keywords Nitrates · Methemoglobinemia · Environment · Water pollution

1 Introduction Nitrate is a naturally occurring ion, which makes up part of the nitrogen cycle. The nitrate ion (NO3 − ) is the stable form of combined nitrogen for oxygenated systems. Although it is chemically unreactive, it can be microbially reduced to the reactive nitrite ion. Nitrite converts oxygen-carrying hemoglobin to methemoglobin, which cannot bind oxygen, by oxidizing the Fe2+ in heme to Fe3+ . The condition of methemoglobinemia is characterized by cyanosis, stupor, and cerebral anoxia [5]. Naturally, 0.53–3.0% of the total hemoglobin (Hb) circulates as methemoglobin (MetHb). Generally, detectable clinical signs of methemoglobinemia appear at 10% MetHb or more [7, 9]. Symptoms include an unusual bluish gray or brownish gray skin color, irritability, and excessive crying in children with moderate MetHb levels

D. Cur¸seu (B) Environmental Health Department, University of Medicine and Pharmacy, Cluj Napoca, Romania e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_58,

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and drowsiness and lethargy at higher levels. Diagnosis is through the observation of chocolate-colored blood or a laboratory test showing the presence of elevated MetHb levels [2]. Hunter Comly in the United States first linked infant methemoglobinemia to nitrates in drinking water in 1945. He reported on two cases and concluded that methemoglobinemia may occur in an infant after ingestion of water high in nitrates, especially if the infant was suffering from a gastrointestinal disturbance [4]. Guidelines and regulatory limits relating to the amount of nitrate in drinking water, of 10 mg/L nitrate–nitrogen (NO3 –N) and 50 mg/L nitrate [nitrate concentrations are typically expressed either as mg/L NO3 –N or nitrate (NO3 ); 50 mg/L NO3 is equivalent to 11.3 NO3 –N], were established to prevent infantile methemoglobinemia [11]. High-nitrate drinking water is most often associated with privately owned wells, especially with shallow wells with depths <15 m in regions with permeable soils [5]. Beside methemoglobinemia, high nitrate consumption has been implicated in other health effects, such as gastric cancer, hypertension, increased infant mortality, central nervous system birth defects, diabetes, spontaneous abortions, respiratory tract infections, and changes to the immune system [3]. The aim of this study is to evaluate reported cases of infant methemoglobinemia and to assess the priorities for the risk management in Cluj county, Romania.

2 Methods To satisfy our objectives, infants diagnosed with methemoglobinemia in Cluj county were identified. Field visits were undertaken to examine medical records, review hospital/clinic conditions relative to diagnosis of methemoglobinemia, observe household environmental conditions (including well location and condition), and measure nitrate/nitrite level in water source and vegetables cultivated in individual farms and used for infant feeding. We analyzed 58 well water samples taken twice a year (in spring and in autumn) and 121 fruit and vegetables samples; the nitrates/nitrites concentration was measured using the phenol-disulphonic acid method, respectively the sulphanilic acid and α-naphtylamine hydrochlorate method.

3 Results and Discussion During 2000–2004 in Cluj county 28 methemoglobinemia cases (42.9% boys and 57.1% girls) have been recorded (Table 1). Annual data for live births in Cluj county were also available, so we were able to calculate the incidence rate of methemoglobinemia based on clinically reported cases. The annual estimated incidence of methemoglobinemia in the county ranged from 42 to 239 per 100,000 live births during the study period, with a mean of 118/100,000 over the 5 year period, but

Infant Methemoglobinemia and Environmental Exposure to Nitrates Table 1 Incidence of methemoglobinemia in Cluj county

Incidence ratea

Year

Cases

2000 2001 2002 2003 2004

12 2 3 6 5

5, 021 4, 890 4, 795 4, 673 4, 334

239 42 63 128 115

Total

28

23, 713

118

a Number

Table 2 Selected clinical data for infants hospitalized with methemoglobinemia

637

of methemoglobinemia cases per 100,000 live births

Birthweight (g) Weight at admission (g) Breastfeeding (days) Hemoglobin (%) aN

Live births

Mean (range)a

Romaniab (range)

2,921 (2,100–4,150) 4,020 (2,800– 6,750)

3,465 4,980

28 (10–45)

–

11.2 (6.8–13.1)

13.3 (10.8–18.0)

= 28 cases National Average

b Romanian

it is not known how many additional cases go unreported. Thirty-one percent of the infants reporting with methemoglobinemia had symptoms of diarrhea on initial diagnosis, and all cases presented cyanosis. These cases (28 records) are not intended to be representative of the entire population of Romania. However, the samples provide useful information for designing further studies for region of Transylvania. A summary of selected clinical data is presented in Table 2. The average birth weight of infants who developed methemoglobinemia was 2,921 ± 422 g, which is above the 2,500 g internationally acceptable definition of low birthweight [10], but statistically (p < 0.001) lower than the Romanian national average of 3,465 ± 365 g. The average weight of infants at the time of diagnosis with methemoglobinemia is 4,020 ± 450 g, significantly lower than comparable age group infants (4,020 g vs. 4,980 g). Breastfeeding data indicate that about 74% of infants had been breast fed for at least one week postpartum. The duration of breastfeeding were generally less than one month. No infant was diagnosed with methemoglobinemia while being breast-fed. Medical examination revealed a high incidence of anemia in infants reported with methemoglobinemia. The hemoglobin of infants averaged 11.2% for all ages, which is within the normal range of Romanian national hemoglobin values of 10.8–18.0, with a mean of 13.3%. However, when compared to national average data according to age distribution, 39.2% of the infants were classified as anemic (Table 3). As Fig. 1, the overwhelming majority of cases were under 4 month. The average age at which infants reported with methemoglobinemia was 45 days, with a range of 12 days to 6.5 months.

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D. Curseu et al. Table 3 Comparison of infant hemoglobin levels

Age (month) under one month 1–4 month Over 4 month

Anemia cases

MetHba cases Hb (%)

Romanianb average Hb (%)

N 2 8 1

Mean (range)1 11.3 (11.1–11.7) 11.0 (7.5–12.5) 11.2 (9.6–14.7)

Romania2 (range) 16.6 (13.2–23.0) 13.3 (10.8–18.0) 12.4 (10.2–15.0)

a Methemoglobinemia b Romanian

national values

Fig. 1 Age distribution of cases with methemoglobinemia

18%

21%

under one month 1–4 months over 4 months 61%

Geographically, all infants hospitalized with acute methemoglobinemia lived in rural. The infants were weaned after a short breastfeeding period to cow milk diluted (1:1) with boiled water. All mothers interviewed routinely boiled water to kill any pathogenic microorganisms in well water before use for infant feeding. However, this practice actually increases nitrate concentration. Most communities where methemoglobinemia was reported had water nitrate levels in excess of 100 mg/L. The highest recorded concentration was 265 mg/L. No reported episodes of methemoglobinemia occurred within the rural communities with normal nitrate well water levels or in urban population supplied with treated piped water. Breastfeeding infants are not at risk of methemoglobinemia even when mothers ingest water with very high concentrations of nitrate (>100 mg/L). According to the well water nitrates concentration, we categorized two group of risk of methemoglobinemia: – moderate risk – with well water pollution between 50 and 100 mg/L; – high risk – with well water pollution over 100 mg/L. A significantly higher mean value of methemoglobin was found when nitrate concentration in well water exceeded 100 mg/L (Table 4). Table 4 The average values of methemoglobinemia in relation with nitrate levels in well water Nitrate conc. in well water

50–100 mg/L

>100 mg/L

Values of MetHb (%)

N Mean ± SD 10 6.1 ± 1.47 t = 4.159 (p = 0.0003)

N 18

t-test (p-value)

Mean 10.20

± SD ± 2.9

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Nitrites were detected in concentration up to 0.75 mg/L in all samples of well water. The wells were dug outs of less than 8 m, with some as shallow as 3–4 m without casing and no protective cover over the wellhead. The growth of algae was common on the inside walls, and most wells were located very close to human traffic areas and livestock rearing facilities. Nitrate contamination from agricultural use of fertilizers and animal manure may occur, but the most likely source of nitrate for the wells observed in this study is local human and animal waste. Well construction methods, placement, and general hygiene are the primary causes of poor well water quality and high nitrate level. Household laundry and washing of utensils is done around the open shallow wellhead. The nitrate concentration of water in most of the wells used for infant feeding exceeds the maximum contaminant limit of 50 mg/L. In one multiple episode of methemoglobinemia reported, the first episode occurred when the infant’s feed included spinach, carrot juice, apple juice (which are naturally high in nitrate). They are given to supplement the infant’s diet of diluted cow milk or formula. Frequently the fruits and the vegetable cultivated in individual farms constitute an additional source of nitrates. Table 5 shows the nitrates and nitrites average concentrations in vegetables comparing to maximum acceptable level (MAL) according to Direction 975/1998 of the Ministry of Health. It has to be noted the over limit nitrates concentrations in potatoes and carrots samples. Many studies [5] associate methemoglobinemia with infantile cases of severe diarrhea, when nitrite is formed in stomach from the endogenous bacterial conversion of nitrate. This observation is important because carrot soup is recommended especially if the infant is suffering from a gastrointestinal disturbance, so the high nitrate level in carrots and gastrointestinal illness often go “hand in hand”. Also, others authors [8] suggested that it is possible that bacterial growth within the bottle or stored soup and exogenous conversion of nitrate to nitrite is the source of the problem. Table 5 The nitrates and nitrites average concentrations in vegetables Nitrates concentration (mg/kg)

Nitrites concentration (mg/kg)

Species

Mean ± SD

MAL

Mean ± SD

Carrots Potatoes Spinach Apples

395.9 ±23.3 311.3 ± 37.01 291.7 ± 69.4 48.5 ± 11

400 300 2, 000 60

0.45 ± 0.09 0.78 ± 0.27 0.58 ± 0.12 0.32 ± 0.05

4 Conclusions 1. The annual incidence of methemoglobinemia in the study area from Romania ranged between 42 and 239 per 100,000 live births. These rates are considerably below the previously reported levels of 13,000/100,000 live births or 13% [6],

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but are in accordance with rates reported by Ayebo et al. [1] in contiguous areas from Transylvania. 2. Weaned infants less than 4 months are the most susceptible group. Breastfeeding is a very effective dietary method of preventing infant methemoglobinemia, because no infants being breast-fed were diagnosed. 3. Contaminated well water was the major source of nitrate in the cases reviewed. In addition, feeding practices included early incorporation of vegetable juices and table food into infant diets. All cases of methemoglobinemia examined involved ingestion of water with high nitrate concentration. 4. This study suggests in consequence some recommendations for the management of methemoglobinemia in this area: introduce a low nitrate water supply scheme specially for infant feeding, education program for mothers to increase duration of breast feeding, further studies on long-term development effects on infants.

References 1. Ayebo A, Kross B, Vlad M, Sinca A (1997) Infant methemoglobinemia in the transylvania region of Romania. Int J Occup Environ Health 3(1):20–29 2. Brunning-Fann CS, Kaneene JB (1993) The effects of nitrate, nitrite and N-nitroso compounds on human health: a review. Vet Hum Toxicol 35(6):521–538 3. CDC (Centers for Disease Control and Prevention) (1996) Spontaneous abortions possibly related to ingestion of nitrate-contaminated well water—LaGrange County, Indiana, 1991–1994. Morb Mortal Wkly Rep 45(26):569–572 4. Comly HH (1945) Cyanosis in infants caused by nitrates in well-water. JAMA 129:112–116. Reprinted in 1987. JAMA 257(20):2788–2792 5. Fan AM, Willhite CC, Book SA (1987) Evaluation of the nitrate drinking water standard with reference to infant methemoglobinemia and potential reproductive toxicology. Regul Toxicol Pharmacol 7(2):135–148 6. Fewtrell L (2004) Drinking-water nitrate, methemoglobinemia, and global burden of disease: A disscussion. Environ Health Perspect 112(14):1371–1374 7. Kross BC, Ayebo AD, Fuortes LJ (1992) Methemoglobinemia: nitrate toxicity in rural America. Am Fam Physician 46(1):183–188 8. L’hirondel J, L’hirondel J-L (2002) Nitrate and man. Toxic, harmless or beneficial? CABI Publishing. CABI Publishing, Wallingford, UK 9. NAS (1981) The health effects of nitrate, nitrite and N-nitroso compounds. National Academy of Science, Washington, DC 10. Office of Technology Assessment (1993) Infant mortality. In International health statistics: what the number mean for United States-background paper, US Congress, Office of Technology Assessment, Government Printing Office, Washington, DC, OTA-BP-H-116 4, p 29 11. WHO (1996) Guidelines for drinking-water quality. Health criteria and other supporting information, 2nd edn, Vol. 2. World Health Organization, Geneva

West Nile Virus: Risk Factors of Spreading, Prevention and Control Measures Dana Sîrbu, Monica Popa, Daniela Cur¸seu, Ovidiu Ghiran, and Adriana Manciu

Abstract West Nile is an insect-borne flavivirus which can cause serious, lifealtering and even fatal diseases. It has been detected in at least 48 species of mosquitoes, over 250 species of birds, and at 18 mammalian species, including humans. The most serious manifestation of West Nile Virus (WNV) infection is fatal encephalitis in humans and horses, as well as mortality in certain domestic and wild birds. Approximately one in 150 infections results in severe neurological illness. Given our incomplete and evolving knowledge of the ecology and public health impact of WN virus, as well as the efficacy of control efforts, the virus will remain an important public health challenge in the next years all round the world. The purpose of this study is to understanding how and why the WNV epidemics occurred, by the evaluation of epidemiological, ecological, clinical and potential risk factors that can lead to epidemic manifestation. This information will be both interesting and useful in order to developing a global surveillance and effective control strategies for preventing the spread of WNV. Keywords Arboviruses · Control · Neurology · Risk

1 Introduction West Nile virus is an “arboviruses” (arbo from arthropod-borne) 50 nm enveloped RNA virus belonging to the Flaviviridae family, first isolated in 1937 from a human patient in the West Nile region of Uganda [6]. WNV have been currently distributed over a wide area encompassing Africa, Europe, the Middle East, Central Asia, West Asia—its east-west range in the Old World is from India to Portugal; the northsouth range is from South Africa to middle European latitudes (France, Ukraine, Belarus)—and North America (Fig. 1). D. Sîrbu (B) Department of Environmental Health, Iuliu Hatieganu University of Medicine and Pharmacy, Cluj-Napoca, Romania e-mail: [email protected]

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Fig. 1 Distribution of the West Nile virus, Source: Information on infectious diseases overseas, Quarantine station, Ministry of health, labour and welfare

2 History Since the original isolation of WNV, outbreaks have occurred infrequently in humans, those in Israel (1951–1954 and 1957) and South Africa with 3,000 clinical cases (1974) being most notable. Since the mid-1990s, the frequency and apparent clinical severity of West Nile virus outbreaks have increased. Human and equine West Nile virus sporadic outbreaks have occurred in Europe for many years. In the Mediterranean area, the virus is endemic in Israel and human outbreaks have occurred within the past 15 years in Algeria and Tunisia. The three most notable European outbreaks which involved hundreds of persons with severe neurologic disease include: Romania in 1996 involving 393 laboratory-diagnosed cases including 17 deaths, Southern Russia in 1999 involving 826 clinical cases including 40 deaths of which 183 were serologically confirmed and Israel in 2000, when 417 confirmed cases including 35 deaths were reported [20, 18, 4]. In 2004 a cluster of equine cases was identified in the Camargue area of France and two human cases, thought to have been acquired in Portugal, were reported from the Republic of Ireland. Other countries outside Europe where human infections have been serologically confirmed include Algeria, Azerbaijan, Central African Republic, Democratic Republic of the Congo, Egypt, Ethiopia, India, Madagascar, Nigeria, Pakistan, Senegal, South Africa, and Uganda [13]. In 1999, the virus appeared in New York and has since spread rapidly throughout North America, and later to Canada, Mexico, Central America, and the West Indies. Between 1999 and 2003 the United States reported annual increases in West Nile Virus activity (Table 1). These increases were in terms of the annual case count, geographical spread, and extension of the transmission period. Although geographical spread continued in 2004–2006 there was a substantial decrease in the number of reported human cases compared to 9862 cases in 2003 [2].

West Nile Virus: Risk Factors of Spreading, Prevention and Control Measures Table 1 Outbreaks in USA (CDC)

Year

Number of human cases of WNV reported

1999 2000 2001 2002 2003 2004 2005 2006

62 21 66 4, 156 9, 862 2, 539 3, 000 3, 135

643

Number of death 7 2 9 284 264 100 119

Since the mid-1990s, three disturbing epidemiologic trends for WN virus have emerged: – increase in frequency of outbreaks in humans and horses – apparent increase in severe human disease (confirmed human infections in recent outbreaks: Romania, 393 cases; Russia 826 cases; United States, 62 cases in 1999 and 9862 in 2003; Israel, 2 cases in 1999 and 417 in 2000); and – high avian death rates accompanying the human outbreaks, in outbreaks in Israel and the United States [15].

3 Routes of Transmission The West Nile virus is primarily carried by birds, and is maintained in a transmission cycle between birds and mosquitoes, while humans are incidental hosts. Incidental infection may also occur in other mammals including horses, cats, and domestic mammals (Fig. 2).

Fig. 2 Transmission cycle of West Nile virus [10]

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3.1 Birds Birds are the natural host for the virus, the infection being fatal to many native and exotic bird species. The most important birds involved in virus amplification have not been identified, although recent studies have demonstrated that crows, perching birds (Passeriformes), certain gulls (Charadriiformes), and two birds of prey species (Falconiformes and Strigiformes) had a greater ability to pass on the virus to a mosquito host than other bird groups tested. Migratory birds have long been suspected as the principal introductory hosts of West Nile virus into new regions for the following reasons [14]: – outbreaks of the virus in temperate regions generally occur during late summer or early fall, coinciding with the arrival of large concentrations of migratory birds (and mosquitoes) – these outbreaks often occur among humans living in or near wetlands where high concentrations of birds come into contact with large numbers of ornithophilic mosquitoes the principal vectors from which the virus has been isolated – antibodies to the virus have been found in the blood of many migratory bird species in Eurasia – migratory birds have been linked with transporting related viruses in the Western Hemisphere – West Nile virus has been isolated from some species of actively migrating birds (e.g., the Barred Warbler (Sylvia risoria) in Cyprus and the Turtle Dove (Streptopelia turtur) in Slovakia – viremia sufficiently long-term to infect vector mosquitoes has been documented in several bird species and – migration places substantial physiologic stress on birds. It is very probable that WNV are transported between sub-Saharan Africa and Europe by migratory birds [13, 12].

3.2 Mosquitoes Several species of mosquitoes (at least 48 species), and of ticks, are known to become infected with WN and to transmit the virus to vertebrate hosts. The virus is most commonly transmitted by mosquitoes of the genus Culex. In South Africa, Egypt and Israel, the mosquito Culex univittatus appears to be the most important arthropod host, with 0.5–2 infected individuals found per 1,000 females tested. Soft ticks of the genera Ornithodorus and Argas collected at colony sites of colonial water birds also have been found to be infected, and these ticks may be part of natural cycles of the virus in some instances. The European and American outbreaks were associated with high populations of mosquitoes especially Culex spp. caused by flooding and subsequent dry and warm weather, or formation of suitable larval

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breeding habitats. Culex pipiens is the most common mosquito found around the world. It occurs on every continent except Antarctica and is usually the most common pest mosquito in urban and suburban settings. C. pipiens is a serious pest, called the “house mosquito” becaues it commonly develops in small containers around the home. It shows great skill in finding ways to get into the house where it feeds on the occupants at night. It also occurs in containers and sumps on farms and industrial plants, in polluted waters, and will feed out-of-doors at night. It is an indicator of polluted water in the immediate vicinity [17, 5].

3.3 Human Human infection is through the bite of an infected mosquito. Human-to-human transmission (direct oral contact, droplet spread, or airborne transmission), human-to-mosquito-to-human transmission and bird-to-human transmission are not possible. In rare cases, it’s possible for West Nile virus to spread through other routes, including transmission via blood transfusion [6], organ transplantation, breast milk (experts at the CDC say that such cases are extremely rare) and laboratory acquisition (some laboratory workers involved in West Nile surveillance and research have contracted the disease from infected animals) [2, 7]. West Nile virus infection appears to be equally distributed among all age groups and in both sexes. However, the incidence of encephalitis and death increases 20fold among persons 50 years of age and older.

4 Risk Factors Risk factors associated with West Nile virus infection are: • Time of year: in temperate regions, West Nile virus follows a seasonal pattern that begins in late spring, with the peak time for infection occurring in late summer and early fall—usually August and September. People living in southern climates may run the risk of infection year-round. • Geographic region: visiting or living in areas of the country where mosquitoborne viruses are common—especially in Africa, Europe, the Middle East, Central Asia, West Asia and North America—increases the risk of West Nile virus. • Occupation: if someone works outdoors, have a greater chance of being bitten by an infected mosquito. • In recent urban epidemics, risk factors included length of time spent outdoors, failure to apply mosquito repellent regularly, living in a building with a flooded basement, and presence of mosquitoes in the home [11]. • Major global demographic and societal changes (e.g., population growth, urbanization, environmental pollution and modern agricultural practices) have directly

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affected the resurgence of mosquito- and tick-borne infections. Modes of transportation, such as air travel, have facilitated the transportation of pathogens among areas of dense population, enabling arboviruses to travel large distances in a short amount of time. • Environmental factors, including human activities that enhance vector population densities (irrigation, heavy rains followed by floods, higher than usual temperatures, and formation of ecologic niches enabling the mass breeding of mosquitoes) allow the reemergence of this mosquito-borne disease. For instance, global warming scenarios hypothesize warmer, more humid weather that may produce an increase in the distribution and abundance of mosquito vectors and mosquito-borne diseases. Elementary models suggest that higher global temperatures will enhance their transmission rates and extend their geographic ranges [19].

The risk populations to develop severe or fatal infections are: older adults, the advanced age being the greatest risk factor for severe neurological disease, longterm sequelae, and death; people with immune systems weakened by HIV/AIDS, long-term steroid use, chemotherapy drugs or anti-rejection drugs following transplant surgery; pregnant women; people with certain genetic mutations and workers those working outdoors. Outdoor workers at risk include farmers, foresters, landscapers, groundskeepers and gardeners, painters, roofers, pavers, construction workers, laborers, mechanics, and other outdoor workers. Entomologists and other field workers are also at risk while conducting surveillance and other research outdoors.

5 Clinical Features After being bitten by an infected female mosquito, the virus spreads throughout the body of the human host. The incubation period of West Nile virus, although not precisely known, probably ranges from 3 to 14 days. Many persons remain asymptomatic. West Nile fever in humans usually is a febrile, influenza like illness, characterized by an abrupt onset of moderate to high fever (3–5 days, infrequently biphasic, sometimes with chills), headache (often frontal), sore throat, backache, myalgia, arthralgia, fatigue, conjunctivitis, retrobulbar pain, maculopapular or roseolar rash (in approximately half the cases, spreading from the trunk to the extremities and head), lymphadenopathy, anorexia, nausea, abdominal pain, diarrhea, and respiratory symptoms. Occasionally (<15% of cases), acute aseptic meningitis or encephalitis (associated with neck stiffness, vomiting, confusion, disturbed consciousness, somnolence, tremor of extremities, abnormal reflexes, convulsions, pareses, and coma), anterior myelitis, hepatosplenomegaly, hepatitis, pancreatitis, and myocarditis occur. Most fatal cases have been recorded in patients older than 50 years [2, 4, 16].

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6 Characteristics of the Outbreak in Romania In temperate regions, outbreaks of the virus normally occur during the period of maximum annual activity of mosquito vectors, from the latter half of summer to early autumn (July–September). One of the last major European epidemic occurred in Romania. Between 15 July and 12 October 1996, 393 cases of laboratory-confirmed WNV meningoencephalitis appear in southeastern Romania, of which 286 (73%) in the capital city of Bucharest with the highest attack and fatality rates occurred among the elderly [9]. This was the largest epidemic of WNV-associated neurological disease ever reported, the first to occur predominantly in an urban setting, and only the second to occur in Europe [20]. Contributing factors included a susceptible avian population and urban/suburban infrastructural conditions that favored the production of large numbers of C. pipiens. Most human infections were not clinically apparent. If symptoms appear they are typically an acute, usually mild febrile disease often accompanied by malaise, anorexia, nausea, vomiting, and headache (Table 2). Transient meningeal involvement may occur at this time. Fatal cases associated with severe neurological manifestations have been seen in the elderly or debilitated person. Increased exposure to the mosquito vector, particularly in the home and its immediate environments, was associated with risk of acquiring WNV infection [11].

Table 2 Symptoms of West Nile Virus reported among Hospitalized Patients during Outbreaks in Romania (1996), New York State (1999) and Israel (2000) [16] Location Romania (n = 393)

New York State (n = 59)

Symptoma

% cases observed

Fever Weakness Nausea Vomiting Headache Changes in mental status Diarrhea Rash Cough Stiff neck Myalgia Arthralgia Lymphadenopathy

91

a b

53 77 34b

57

90 56 53 51 47 46 27 19 19 19 17 15 2

Israel (n = 233)

98

31 58 40b 19 21 29 15 10

Some listed symptoms were not reported in Romania and Israel. Reported as confusion.

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Fig. 3 Serologically confirmed cases of West Nile virus and other neurologic infections by district of residence and etiology, Romania, 1997 [3]

The continued occurrence of sporadic WN infections in southeastern Romania in consecutive years after the 1996 epidemic is consistent with local enzootic transmission of the virus. During 1997 and 1998 (Fig. 3), neurologic infections were diagnosed serologically as WN encephalitis in 12 of 322 patients in 19 southeastern districts and in 1 of 75 Bucharest patients [3]. During 1998–2000, 39 scattered human cases of clinical West Nile virus infection (mean, 10 per year; range, 5–14 per year)—including 5 (13%) fatal cases— were diagnosed serologically throughout the region, but epidemic disease did not recur [9].

7 Prevention and Control Effective surveillance, prevention, and control of WN virus diseases, require designated resources in local and country health departments. West Nile virus can cause sporadic human cases, clusters, or outbreaks of West Nile fever, around the world. Movement of the virus in the world seems to involve a set of conditions including infectious avian host, numerous mosquito vectors, and cross-species transmission to a numerous avian amplifying host (not necessarily the same species as the infectious host but the same location). Therefore, because outbreaks are dependent on a series of probabilities, the suitable wetland sites likely to receive the largest number of potentially infected hosts seem to be the most likely place for future outbreaks.

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The surveillance system for WNV should consist of these four main activities: 1. Human Surveillance: physicians will observe patients for clinical signs of WNV and conduct laboratory testing as appropriate. Enhanced passive human surveillance by general alerts to health-care providers to report viral encephalitis and, if resources permit, aseptic meningitis in humans. The main goals of surveillance for human cases are to: – assess the local and national public health impact of WNV disease and monitor national trends; – demonstrate the need for public health intervention programs; – allocate resources; – identify risk factors for infection and determine high-risk populations; – identify geographic areas in need of targeted interventions; – identify geographic areas in which it may be appropriate to conduct analytic studies of important public health issues. 2. Veterinary Surveillance: veterinarians will monitor horses, dogs, and cats for clinical signs of neurological disease and conduct laboratory testing when appropriate. 3. Wild Bird Surveillance: active bird surveillance to detect the presence of and to monitor WN virus activity in both wild and sentinel bird populations (sentinel chicken flocks). Surveillance for dead crows, in particular, is a sensitive means to detect the presence of WNV in an area. To provide an early warning of viral activity, dead bird surveillance requires capacity at the local level to let the public know where to report dead birds, as well as a system for answering phone calls, recording data, and collecting birds for testing. Resources for bird necropsies and laboratory testing are also required. 4. Mosquito Surveillance: surveillance of mosquito populations will be used to detect WNV, to help identify potential mosquito vectors in a particular area, and to monitor population densities of those vectors [1]. Active surveillance activities should be implemented through the winter in southern countries where mosquito activity continues throughout the year, or implemented early in the spring in northern countries where mosquito activity ceased with the onset of cold weather. Survey are essential for the planning, operation and evaluation of any effective mosquito-control program, weather for prevention of mosquito-borne diseases or lowering of populations of these biting insects to a level permitting normal activities without undue discomfort. Two types of surveys are recommended: – the original basic survey determines the species of mosquitoes, and their sources, locations, densities and flight ranges. It can also include information on life cycle, feeding preferences, larval habitats, adult resting places, transmission of human and animal diseases and susceptibility to insecticides.

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– the operational survey or surveillance is a continuing evaluation, which is extremely valuable in the daily operation of a mosquito-control program. It furnishes information on the effectiveness of control operations and data for comparison throughout a season or from year to year. Prevention and control of arboviral diseases is accomplished most effectively through a comprehensive, integrated mosquito management program based on an understanding of the underlying biology of the transmission system, and utilizes regular monitoring to determine if and when interventions are needed to keep pest numbers below levels at which intolerable levels of damage, annoyance, or disease occur. It is based on these broad general strategies: – Surveillance—effective mosquito control begins with a sustained, consistent surveillance program that targets pest and vector species, identifies and maps their immature habitats by season, and documents the need for control. – Source reduction is the alteration or elimination of mosquito larval habitat breeding. This remains the most effective and economical method of providing long-term mosquito control in many habitats. Source reduction can include activities as simple as the proper disposal of used tires and the cleaning of rain gutters, bird baths and unused swimming pools by individual property owners, to extensive regional water management projects conducted by mosquito control agencies on state and/or federal lands. Source reduction activities can be separated into the following two general categories: sanitation and water management. – Chemical control: insecticides can be directed against either the immature or adult stage of the mosquito life cycle when source reduction and water management are not feasible or have failed because of unavoidable or unanticipated problems, or when surveillance indicates the presence of infected adult mosquitoes that pose a health risk. Fradin and Day [8] indicate that DEET-based repellents may be superior to other repellents in repelling mosquitoes that carry WNV. – Biological control is the use of biological organisms, or their by-products, to control pests. Larvivorous fish are the most extensively used biocontrol agent for mosquitoes. – Continuing education of mosquito control workers is directed toward operational workers to instill or refresh knowledge related to practical mosquito control. – Health education, public information, and human behavior change includes use of print materials (posters, brochures, fact sheets), electronic information (Web sites), presentations (health experts or peers speaking to community groups), and the media. More than one approach is available to protect the public from transfusion associated infections, including the exclusion of potential donors at risk, screening of donated blood for the presence of infectious agents, and the treatment of donated blood products to destroy infectious agents.

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8 Conclusions The best approach to minimizing effects of the virus on humans should involve a West Nile Virus surveillance system to monitor the geographic and temporal spread of WNV over the world, to further develop national public health strategies for WNV surveillance, prevention, and control, to develop a more complete regional picture of the geographic distribution and incidence of similar viruses, and to provide national and regional information to public health officials, elected government officials, and the public. Future research should define criteria for predicting where the virus will go next. Reasonably accurate and comprehensive maps are essential in planning a mosquito control operation, in field survey and control operations, in program evaluation, and in reporting for informational and budgeting purposes. Acknowledgments This study was undertaken as a part of the CEEX project —“SIMONPAN” 128/2006.

References 1. CDC– (Centers for Disease Control and Prevention) (2003) Epidemic/Epizootic West Nile virus in the United States: guidelines for surveillance, prevention, and control, 3rd ed. Atlanta, GA: US Department of Health and Human Services, CDC; 2003. Available at http://www.cdc.gov/ncidod/dvbid/westnile/resources/wnv-guidelines-aug-2003.pdf 2. CDC – (Centers for Disease Control and Prevention) (2004) West Nile virus activity in the United States, 2004. MMWR July 23, 2004/53(28);638–639 3. Cernescu C, Nedelcu NI, Tardei G, Ruta S, Tsai TF (2000) Continued transmission of West Nile virus to humans in southeastern Romania, 1997 1998. J Infect Dis 181:,710–712 4. Chowers MY, Lang R, Nassar F, Ben-David D, Giladi M, Rubinshtein E et al (2001) Clinical characteristics of the West Nile fever outbreak, Israel, 2000. Emerg Infect Dis 7:675–678 [PMID: 11585531] 5. Crans WJ (2004). A classification system for mosquito life cycles: life cycle types for mosquitoes of the northeastern United States. Journal of Vector Ecology. 29:1–10 6. EMEA (2003) The European agency for the evaluation of medicinal products evaluation of medicines for human use. CPMP Position statement on West Nile Virus and plasma – derived medicinal products EMEA/CPMP/BWP/3752/03, London. Available at: http://www.ema.europa.eu/pdfs/human/bwp/375203en.pdf 7. EC (European Commission, Health & Consumer Protection Directorate-General) (2005) Updated Opinion on “the Safety of Human Substances with Regard to West Nile Virus”. Available at: http://ec.europa.eu/health/ph_risk/committees/04_scenihr/docs/scenihr_o_ 002.pdf 8. Fradin MS, Day JF (2002) Comparative efficacy of insect repellents against mosquito bites. N Engl J Med 347:13–18 9. Campbell GL, Ceianu CS, Savage HM (2001) Epidemic West Nile Encephalitis in Romania. Ann NY Acad Sci 951:94–101 10. Huhn GD, Sejvar JJ, Montgomery SP, Dworkin MS (2003) West Nile virus in the United States: an update on an emerging infectious disease. Am Fam Physician 68(4):653–660 11. Han Linda L et al (1999) Risk factors for West Nile virus infection and Meningo-encephalitis, Romania, 1996 J Infect Dis 179:230–233 12. Hubálek Z, Halouzka J (1999) West Nile fever – a reemerging mosquito-borne viral disease in Europe. Emerg Infect Dis 5(5):643–650 13. Hubalek Z (2000) European experience with the West Nile virus ecology and epidemiology: could it be relevant for the New World? Viral Immunol 13(4):415–426

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14. Rappole JH, Derrickson SR, Hubálek Z (2000) Migratory birds and spread of West Nile virus in the Western Hemisphere. Emerg Infect Dis 6(4):319–328 15. Lyle RP, John T (2001) Roehrig West Nile virus: a reemerging global pathogen. Biomed Rev 12(3):208–216 16. Lyle RP, Anthony AM (2002) West Nile virus: a primer for the clinician 6 August 2002. Ann Intern Med 137(3):173–179 17. Mullen G.R., Durden L.A. (2002) Medical and veterinary entomology. Academic Press/Elsevier Science, San Diego. xv + 597 pp. ISBN 0-12-510451-0 18. Platonov AE, Shipulin GA, Shipulina OY, Tyutyunnik EN, Frolochkinati TI, Lanciotti RS et al (2001) Outbreak of West Nile virus infection, Volgograd Region, Russia, 1999. Emerg Infect Dis 7:128–132 [PMID: 11266303] 19. Reiter P (2001) Climate change and mosquito-borne disease. Environ Health Perspect 109(1):141–161 20. Tsai TF, Popovici F, Cernescu C, Campbell GC, Nedelcu NI (1998) An epidemic of West Nile encephalitis in southeastern Romania. Lancet 352:767–771

The Determinants of Improved Water Supply for Rural Households in Kenya: A Differential Diagnosis Framework for Community Health David W. Nerubucha

Abstract Water is life, for people and for the planet. The supply and demand for improved water plays a paramount role in the analyses of community health. The general objective of this study is to investigate whether improved water supply reduces incidents of water-borne disease and that access to latrines and water for washing reduces incidents of sanitary/hygienic-related disease, enhancing peoples’ livelihood as a result. Arising from the dearth of knowledge on rural water supply services in Kenya, this study intends to show the extent to which rural households participate in decision-making about improved water supply, assess their choices of water supply, and identify the likelihood of exclusion from the use of improved water sources among the rural households. The study proposes to use the Ordinary Least Squares Method in the analysis to verify the hypothesis that greater access to water supply will provide more available time for individuals (mostly women), to utilize in other endeavors that can influence the economic welfare (or wellbeing), and improve overall health and basic sanitation of the community. Keywords Rural household · Water · Demand · Supply

1 Background and Research Problem The challenge of providing safe water where it is needed most is at the heart of the Millennium Development Goals. In 2002, 1.1 billion people lacked access to improved water sources such as a protected well or piped water, and an additional 2.6 billion people, approximately 40% of the global population, lack adequate sanitation [17]. This lack of basic services, combined with inadequate hygiene, exposes people to bacteria, viruses, and parasites in water and faeces. The Millennium D.W. Nerubucha (B) Lecturer of Economics, United States International University, Nairobi, Kenya e-mail: [email protected] This happens to be the first statement of Chapter 1 in the Introduction to the Overview. UN Millennium Project (2004), p 9.

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Development Goals (MDGs) seek to reduce by half the proportion of people who do not have access to improved water sources and adequate sanitation by the year 2015 [16] in order to contribute to the goal of reducing extreme poverty also known as Target #10.1 Improved access to water and sanitation is a target of Goal 7 to ensure environmental sustainability. Rheingans et al. [13] note that meeting this target is essential for other aspects of poverty reduction and health improvement MDGs, through increased productivity and income generation activities (Goal 1); improved access to education, especially for girls (Goal 2); decreased water collection times for women and greater gender equity (Goal 3); reduced childhood diarrhoeal disease morbidity and mortality (Goal 4); decreased prevalence of vector breeding areas, disease transmission, and injuries during water collection (Goals 5 and 6); and a promotion of participatory, community-focused approaches to development (Goal 8). To help the international community as a whole reach the Millennium Development Goals, the United Nations established the Millennium Project, which focuses on the question “what will it take to achieve the MDGs?”2 The report extensively highlights the paramount importance of improving water resources management as a critical factor for meeting most of the goals, which include eradicating extreme poverty and hunger; achieving universal primary education; promoting gender equality and women’s empowerment; reducing child mortality; improving maternal health; combating major diseases; and improving environmental sustainability. Engel, et al. [6] pointsout that in the past, water supply was typically planned and operated by the central government or a national authority. Budget constraints, low revenues, and shortfalls in operation and maintenance have resulted in insufficient expansion of the system and gradual degradation of service at the same time that water demands increased and scarcity worsened. The study argues that this development has led to the recognition that water should no longer be seen as a public good only, but also as an economic good. It is now widely accepted that households should pay for improved water, and revenues should cover at least the operation and maintenance cost. The study asserts that, a withdrawal of the central government from supplying water and operating the system, and the introduction of public-private partnerships [10], (PPP),3 in water supply have been shown to help relieve budget constraints and 1 See

UN Millennium Project (2004). This MDG goal is the stated target of reducing by half the proportion of people without sustainable access to safe drinking water (and basic sanitation), p. 29. 2 See Interim Report of Task Force 7 on Water and Sanitation, UN Millennium Project (2004), in particular, the Task Force’s outlined goals, p. 17 and “The Way Forward: Who needs to do what?”, p. 110. 3 A Public Private Partnership, (PPP), is typically a partnership between the public and private sector for the purpose of delivering a project or service traditionally provided by the public sector. It is a different method of procuring public services and infrastructure by combining the best of the public and private sectors with an emphasis on value for money and delivering quality public services. See also co-authored article “Entrepreneurial Strategies for Millennium Development Goals: A Differential Diagnosis Framework” at http://www.africanexecutive.com/ 28–05 July 2006

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improve supply efficiency, if implemented appropriately. For rural areas, community management of water resources under government guidance has been advocated [3, 1, 9]. Ensuring access to a minimal package of water and sanitation services (i.e. pointof-use treatment options, hygiene promotion, sanitation alternative education) to the populations that need them the most is a feasible goal for the international community, but it requires alternative and innovative approaches to both technology and its delivery [13]. One largely unexplored strategy for doing so is the use of existing social structures that currently reach large portions of the population, including schools, health care systems, and markets. For example, approximately half of the schools in low- and middle-income countries do not have safe water and appropriate sanitation facilities [18]. The lack of gender-appropriate sanitation in schools is often cited as a cause of declining enrolment of girls, especially after puberty [18]. School-based interventions could include: hygiene education, hand-washing facilities, sanitation, water treatment and safe storage, and improved water supply Rheingans et al. [13]. In addition to the direct benefits for students, school-based interventions can potentially leverage change beyond the immediate school environment. While few long-term studies of health impacts are available, evaluations of existing school projects suggest that behaviour and attitudinal changes in school result in changes in the home. The evaluation of a school hygiene and sanitation project in Bangladesh found an increase in the proportion of homes with latrines and the proportion of family members using latrines, as well as improved hand-washing behaviours among adult family members following the intervention [15]. School-based water supply improvements can also serve as a source of improved water for the surrounding community or as a distribution point (or vendor) of point-of-use water treatment supplies Rheingans et al. [13]. School-based interventions however, face several potential limitations that must be addressed before they can reach their full potential. Interventions must be sustainable. This can be challenging, not only in terms of financial sustainability, but also in terms of the human resource strains faced by many teachers in the developing world. The active involvement of educators, the ministry of education, and community members is essential for the development and long-term success of school-based programs [18]. If school-based interventions are to have a significant impact on the burden of water and sanitation related illness, schools must also serve as a catalyst for change at a household and community level. Operations research is needed to identify the best strategies for accomplishing this Rheingans et al. [13]. In Kenya the Nyanza Healthy Water Project promoted water treatment and safe storage through an approach that combined community mobilization and social marketing. Because the local population preferred using clay pots for water storage, rather than plastic jerry cans, the pots were modified for safe storage and field tested. During the first 4 months of the project, one third of the population purchased and used water disinfectant, and one fifth purchased modified clay pots Makutsa et al. [8].

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Although improving water and sanitation coverage impacts many of the MDG targets, the established definitions of access reveal a focus on development rather than on public health. Access to water is defined as having regular access to 20 l of water per person per day within 1 km of the house from an improved source including piped water, protected wells, protected springs, or rainwater [17]. While “improved” sources are considered safer than unprotected surface water, they are not necessarily free of pathogens; the two most notable examples are urban piped water supplies that are inadequately chlorinated and rural water that is collected from a safe source but not safely stored [4, 19]. Similarly, the sanitation indicator focuses on access to improved services such as flush toilets, VIP latrines, and simple pit latrines. It does not directly consider whether sewage is treated or properly disposed. Since the MDG targets for water and sanitation are constructed from the development point-of-view, rather than from a public health point-of-view, primary emphasis has been given to improvements in coverage. Less attention has been given to ensuring that these improvements in water and sanitation access actually align with and contribute to the stated reductions in childhood mortality, poverty, and gender equality. While the MDG indicators provide important benchmarks for monitoring, they may not be sufficient to ensure that improvements in water and sanitation have an impact on health, poverty alleviation, and gender equality, Rheingans et al. [13]. On the basis of this background, this study will be an attempt to scale up lessons learned from Sauri, the Millennium Village Project, of providing sustainable access to water sources which includes river water for communities in Transnzoia.

2 Objectives of Study The study seeks to achieve the following objectives: 1. Investigate the determinants of improved water supply for rural households. 2. Investigate whether improved access to water and latrines reduces incidents of water-borne disease (diarrhea, dysentery, giardia, cholera, typhoid trachoma, pink eye, scabies, hookworm, and roundworm). 3. Investigate whether improved water supply will enhance peoples’ economic welfare More specifically, the factors that determine households’ decisions in using a specific are examined with the following questions in mind: 1. To what extent do rural households participate in decision-making about improved water supply? 2. why do some households participate – thereby influencing the outcomes in their favor – while others do not? 3. are households likely to be excluded making it less likely for them to use improved water sources?

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3 Hypothesis Five groups of variables supposed to influence water supply are analyzed in the study: variables related to access to household water sources; variables related to type of water use (drinking, washing/bathing, animals): variables capturing characteristics of end-users (schools, hospitals, size of household, women): variables capturing participation in decisions on improved water supply (communal well or communal/coop water tank); and variables capturing per capita consumption of improved water. After identifying the variables of importance, the following hypothesis will be tested: Greater access to water supply will influence the economic welfare (or wellbeing) and improve overall health and basic sanitation of the community.

4 Justification of the Study Many studies have pointed out that water projects implemented over the last three decades in developing countries are considered failures [21]. In fact, according to a recent report,4 governments often know much less about those who lack water supply and sanitation services as compared to those who do have access. The report asserts that, a “one-size-fits-all” policy and planning for the water and sanitation sector may not reflect the supports and strategies needed to reach the unserved.5 In a study done on Ghana’s rural households, Engel et al. [6] observe that access to water supply does not imply that all households in communities actually use the improved source and that even households using improved sources typically supplement their water needs with other sources, even for drinking and cooking purposes. The study affirms that this has potentially adverse health implications and points to the need to better understand household decision-making for domestic water use. The dearth of studies of this nature can be traced to a shortage of comprehensive rural household level data only until recently. Despite the importance of access to improved water supply for rural households and employing a demand-responsive approach,6 where users make choices and commit resources in support of these choices, it is difficult to find in literature

4 See

“Who lacks service? A typology of communities lacking access to water supply and sanitation”, Chapter 6, for depiction of a typology of communities with low water supply and sanitation service coverage, p 58, UN Millennium Project (2004). 5 See Table 6.1, “Water supply: typology of un- and under-served communities”, p 66, and Table 6.2, “Sanitation: Typology of un- and under-served communities”, p 71, UN Millennium Project (2004). 6 See Making rural water supply sustainable: Recommendations from a global study. The study found that sustainability was markedly higher in communities where household members made informed choices about whether to build a system and what type and which level of service they preferred, p 4.

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studies that have an empirical account of the Differential Diagnosis7 approach to domestic water access and sanitation services of Kenya’s rural household population. Indeed, little or no literature is also available on constraints in the management of water resources8 among rural households. Arising from the relevance of safe water to community health and the stipulations of the other 9 Millennium Development Goals, the motivation of this study emanates from the fact that the disparity between improved water supply and the demand responsiveness to the quantity and quality of water is unequal. This inequality suggests that different types of policies may be needed for access to safe water supply in order to ensure community health among rural households in Kenya. Secondly, much of the recent interest in safe drinking water as the basis for community health stems from the recognition that water is critical to other facets of sustainable development.9 Thirdly, this study will instigate the Government of Kenya and policy makers elsewhere to proactively take measures to improve water and sanitation services in rural households as incidents of water-borne diseases is expected to show significant and sustained decrease from year 1 to year 5.

5 Methodology The methodology builds on that employed by Engel et al. [6] in Improved Water Supply in the Ghanaian Volta Basin: Who Uses it and Who Participates in Community Decision-Making? The Engel study combined the supply and demand characteristics of rural household water supply to show that a household is expected to choose the improved water source if the expected utility from doing so exceeds the expected utility from using the non-improved source. Mathematically, this condition can be written as: E(U iI) − E(U jN) ≥ 0 where U ij denotes household’s i’s indirect utility from using source j (j C {I,N}), I denotes the improved water source, and N denotes the unimproved water source. 7 In

the soft paperback publication, The end of poverty: How we can make it happen in our lifetime, 2005, pp 82–89, Professor Jeffrey Sachs describes in Table 1, p 84, “a seven-part diagnostic checklist that should be part of the ‘physical exam’ of any impoverished country”. 8 According to the Interim Report of Task Force 7, Water and Sanitation, (2004), the term “water resources” is used to refer to the management of water as a resource for meeting the MDGs as a whole, including the infrastructure needed to manage the resource. 9 See UN Millennium Project (2004). The report lists: From environmental protection and food security to increased tourism and investment, from the empowerment of women and education of girls to reductions in productivity losses due to morbidity and malnutrition – p 9.

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In econometric terms this relationship can be estimated as a Logit model with the dependent variable being a dummy reflecting whether the improved source was chosen by the household or not. The focus will be on households’ main domestic water source, even for specific uses, and where no other improved source is available. However, by using the Differential Diagnosis approach, the model and estimation technique is of interest in determining the hypothesized direction of the household’s choice of water source. The following list provides water sources to be used on probability of using improved source as main water source IMPRVD (Dependt.) HEADAGE DEDUC DISTDIF IMPBW FCAP RIVQD ROOF HEADSEX HHSIZE DISTIMP

Dummy variable, = 1 if main water source is unimproved source, = 0 otherwise Age of household head Dummy variable, = 1 if household head has no formal education, = 0 otherwise Difference in distance between river and the improved source Per bucket price of improved water Flat rate per capita Dummy for perceived quality of the river (0 = bad, 1 = good) Roof quality dummy (0 = if mud, thatch or wood, = 1 if iron sheet, cement, or asbestos) Gender of the household head (= 1 if female, = 0 if male) Size of household excluding members not living at home Distance to improved water source

In the model it is expected that the lower the cost of using improved water source the higher the likelihood that households will use it. The main alternative for all households is the river. (IMPRVD) this variable is proxied by households that use unprotected water sources such as communal well, coop water tank, spring and lake. The variable (RIVDQ) is used to capture households’ perceptions of the quality of river water. The water cost for a source consists of the financial cost and the opportunity cost of the time spent collecting the water. (DISTDIF) is used to capture the opportunity cost of time, the difference in distance from the house to the river and to the improved source is used. This difference is expected to have an important effect on the proposed hypothesized determinants. (ROOF) variable is an income proxy used to test for roof quality for households who may not be able to pay for improved water at rates set by communities. Higherincome households should be more likely to use the improved source. (HHSIZE) the decision whether to use improved source or not is depended on overall water demand. Given income, it is expected that larger households are less likely to use the improved water source. The effect would be different for a flat-rate, (FCAP), system where larger households would be expected to use the improved source.

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(HEADAGE), (DEDUC), and (HEADSEX) are used as proxies for preferences. The effect of age may be uncertain but it is assumed that older people are more knowledgeable about the potential health problems associated with the consumption of unimproved water. It is also expected that more educated people are more aware of the health issues and therefore more likely to use the improved source. Women are hypothesized to care more about the health of their family, making them more likely to use the improved source. The above analysis considers whether a household chooses the improved water source as the main source or not. The probability of a household using the improved source is estimated using specifications outlined above. In the following stage, the per capita quantity of improved water is analyzed. The variables to be used are listed below. Variables to be used for quantity of improved water demanded IMPPCI (Dependt.) NUMKID DEDUC DEDUCW

RIVDIST IMPBW RIVQD ROOF HEADSEX WATSEX EXCHSIZ

Per capita consumption of improved water Proportion of children below the age of 18 in NUMKID Dummy variable, = 1 if household head has no formal education, = 0 otherwise Dummy variable, = 1 if person indicated to take decisions on water in household has no formal education, 0 = otherwise. Distance to river Per bucket price of improved water Dummy for perceived quality of the river (0 = bad, 1 = good) Roof quality dummy (0 = if mud, thatch or wood, = 1 if iron sheet, cement, or asbestos) Gender of the household head (= 1 if female, = 0 if male) Gender of person indicated to take decisions on water in household (= 1 if female, = 0 if male) Size of household excluding members not living at home

6 Literature Review According to the Task Force on Water and Sanitation of the UN Millennium Project [22, 23], 34 countries have made little to moderate progress in reaching the MDG targets for water and sanitation access [13]. National-level estimates on the number of child deaths attributable to diarrhoea were calculated by dividing the total number of child deaths in 2002 [17] by nation-specific estimates on the proportion of child deaths attributable to diarrhoea prepared by Parashar et al. [12]. The 34 countries in danger of not reaching either the water or sanitation MDG targets account for approximately 60% of the global population under 5 years old population (calculated from [17]), but over 67% of child diarrhoea mortality. Those nations identified as having both low access and little progress in expanding either water or

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sanitation coverage account for over twice the proportion of child deaths attributable to diarrhoea than their proportion of the total population under the age of 5 years. National-level estimates on the number of child deaths attributable to diarrhoea were calculated by dividing the total number of child deaths in 2002 [17] by nationspecific estimates on the proportion of child deaths attributable to diarrhoea prepared by Parashar et al. [12]. The 34 countries in danger of not reaching either the water or sanitation MDG targets account for approximately 60% of the global population under 5 years old population (calculated from UN 2004), but over 67% of child diarrhoea mortality. Those nations identified as having both low access and little progress in expanding either water or sanitation coverage account for over twice the proportion of child deaths attributable to diarrhoea than their proportion of the total population under the age of 5 years. Rheingans et al. [13] point out that disparities in access also exist within individual, where coverage differs based on geography and household characteristics. In developing countries, urban households are 30% more likely to have improved water source and 135% more likely to have improved sanitation facilities, compared to rural households [17]. Potential explanations for this disparity include: differences in income, increased costs of providing services to lower density rural populations, greater demand for water and sanitation services in urban areas, and less political power or influence for rural communities. Within urban and rural areas there are additional inequalities due to differences in income and wealth. Households in the lowest wealth quintile are 5.5 times more likely to lack improved water access and 3.3 times more likely to lack adequate sanitation, compared with households in the highest wealth quintile in the same country (based on Demographic and Health Surveys in 20 developing countries) [17]. In middle- and low-income countries, households earning less than US$ 1 per day are almost nine times as likely to lack improved water or sanitation, in comparison to those earning more than US$2 per day [2]. Furthermore, [13] assert that these disparities may be further exacerbated when implementers seek to scale up programs or to ensure sustainability by requiring community “buy-in”. Development agencies and other providers have increasingly required households to commit financial resources for infrastructure construction and household hook-up, in-kind labour or materials, and for communities to retain responsibility for oversight, operation, and maintenance of the systems. This has proven to be essential in order to ensure that services are adequately valued, maintenance is provided, over-use of scarce resources is avoided, and that limited external resources can be stretched as much as is practical. However, the combined pressures of scaling up and ensuring sustainability may also have an unexpected impact on equity. Fees can provide obstacles to communities and households, resulting in inequitable benefits. This has historically led to subsidized water tariffs that are unsustainable and limit incentives for providers to extend services to lower income areas [11]. In addition, the MDGs call for improvements in access to improved water sources, while the larger issue of water quality remains unmentioned [13]. Sources categorized as “improved” are generally considered to be of better quality than

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untreated surface water, yet the actual safety of these improved sources is less understood. However, improvements in water quality show an equal (if not greater) reduction in diarrhoea incidence as improvements in water availability [7, 5]. Engel et al. [6], examine rural households in Ghana using the supply and demand characteristics for improved water supply and find quality perceptions play an important role in households’ choice of water source. The rural households were one of the first countries to introduce a community-based approach to rural water supply on a large scale. Specifically, households that consider the unimproved source to be of bad quality are significantly more likely to choose the improved source as their main water source. The study determined that differences in quality perceptions across households can be due to either actual quality differences or to differences in awareness. Interestingly, another study found that sustainability was markedly higher in communities where household members made informed choices about whether to build a system and what type and which level of service they preferred. Community and household surveys indicated that projects were sometimes supply-driven (not offering community members options or informing them of expected costs or responsibilities) and at other times were demand-responsive (spending time informing communities about their options and giving them a lead role in the decisionmaking process), UNDP-World Bank [20]. One of the most comprehensive dossiers written on the role of water as essential to the well being of humankind, a vital input to economic development, and a basic requirement for the healthy functioning of all the world’s ecosystems is perhaps, the UN Millennium Project [22] report on Water and Sanitation. With the exception of the disclaimer, the facts reported therein will be extensively referred to in an important twin-pillar approach that involves the Differential Diagnosis framework developed by Sachs [14]. The nexus between the findings of the UN report and the diagnostics to be used is a point of interest in the research study.

References 1. Altaf MA, Whittington D, Jamal H, Smith KV (1993) Rethinking rural water supply policy in Punjab, Pakistan. Water Resources Res 29(7):1943–1954 2. Blakely T, Hales S, Kieft C, Wilson N, Woodward A (2005) The global distribution of risk factors by poverty level. Bull World Health Organ 83:118–126 3. Brookshire D, Whittington D (1993) Water resources issues in the developing countries. Water Resources Res 29:1883–1888 4. Conroy RM, Meegan ME, Joyce T, McGuigan K, Barnes J (1999) Solar disinfection of water reduces diarrhoeal disease: an update, Arc Dis Child 81:337–338 5. Cutler D, Miller G (2005) The role of public health improvements in health advances: the twentieth-century United States, Demography 42:1–22 6. Engel S, Iskandarani M, Useche M (2005) Improved water supply in the Ghanaian Volta Basin: who uses it and who participates in community decision-making? http://www.ifpri.org/divs/eptd/dp/papers/eptdp129.pdf 7. Fewtrell L, Colford JM (2004) Water, sanitation and hygiene: interventions and diarrhoea, a systematic review and meta-analysis. Published report by the World Bank

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8. Makutsa P, Nzaku K, Ogutu P, Barasa P, Ombeki S, Mwaki A, Quick R (2001) Challenges in implementing point-of-use water quality intervention in rural Kenya. http://www.cdc.gov/safewater/publications_pages/2001/makutsa_2001.pdf 9. Munasinghe M (1992) Water supply and environmental management. Chapter 1. Westview, Boulder, CO 10. Nerubucha DW, Wambalaba F, Wambalaba A (2006) Entrepreneurial strategies for millennium development goals: a differential diagnosis framework. African Executive, http://www.africanexecutive.com/ 11. Olmstead S (2003) Water supply and poor communities: what s price got to do with it? Environment 45:22–35 12. Parashar UD, Hummelman EG, Bresee JS, Miller MA, Glass RI (2003) Global illness and deaths caused by rotavirus disease in children, Emerg Infect Dis 9:565–572 13. Rheingans R, Dreibelbis R, Freeman MC (2006) Beyond the millennium development goals: public health challenges in water and sanitation. Global Public Health 1:31–48 14. Sachs J (2005) The end of poverty: how we can make it happen in our lifetime. Penguin, New York 15. Snel M (2004) The worth of school sanitation and hygiene education. IRC Water and Sanitation Center, The Hague, The Netherlands 16. UN (2000) United Nations Millennium Declaration. United Nations. United Nations, New York City 17. UNICEF (2004) Millennium development goals – midterm assessment report. UNICEF, New York City 18. UNICEF (2005) State of the World’s children 2005: childhood under threat. UNICEF, New York City 19. WHO/UNICEF (2000) Global water supply and sanitation report 20. World Bank – UNDP, Sara J, Katz T (1998) Making rural water supply sustainable: recommendations from a global study. http://www.wsp.org/publications/global_ruralreport.pdf 21. World Bank (1992) Water supply and sanitation projects: the Bank’s experience 1967–1989, Rep. 10789:137, Operations Evaluation Department, The World Bank, Washington, DC 22. UN Millennium Project (2004) Achieving the millennium development goals for water and sanitation: what will it take? Task force on water and sanitation. UN, http://www.cepis.opsoms.org/bvsacd/milenio/tf7interim.pdf 23. Lento R, Wright AM, Lewis K (2005) Health, dignity, and development: what will it take?

Health Effects Due to Indoor Air Pollution John A. Hoskins

Abstract The indoor environment can be very polluted with pollution levels indoors higher than those outdoors, particularly so when there are combustion processes associated with cooking heating or smoking and poor ventilation. About half the world’s population have to rely for cooking; and associated space heating on simple household stoves using unprocessed solid fuels that have high emission factors, with the consequence that they are exposed to high levels of health-damaging air pollutants. Cooking may produce very high concentrations of particulate matter particularly when biomass is used as fuel. Tobacco smoke may add to the pollution and these together cause considerable human ill health world-wide. Many pollutants directly affect the respiratory and cardiovascular systems and the severity varies according to the intensity and the duration of exposure. The health status of the population exposed varies with some people at greater risk than others. Several chemicals found in the indoor environment are classed as carcinogens although at the levels found the probability that they will cause cancer is extremely low. This is not to lessen the problem. In a 1987 study, the US Environmental Protection Agency ranked indoor air pollution fourth in cancer risk among the 13 top environmental problems analysed. Keywords Pollution · Population · Cancer · Risk

1 Introduction We spend most of our time indoors in an environment filled with things that can produce air pollution including many consumer products, gas appliances, cigarettes, and furniture, and of course ourselves. The outdoor environment, particularly the outdoors urban environment with its vehicular traffic, adds a contribution as do building materials [1–7]. Over most of the world cooking and heating add J.A. Hoskins (B) Grey Cross, Haslemere, Surrey GU27 2 JH, UK e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_61,

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a considerable contribution to the overall air pollution load in a dwelling [8]. Because of this indoor spaces are important micro-environments when considering the impact of air pollution on health [9–11]. The problem is, in fact, compounded for the indoor environment because pollution levels indoors are generally higher than those outdoors. The World Health Organization (WHO) said that in the year 2000 3 million people were killed world-wide by outdoor air pollution annually from vehicles and industrial emissions and 1.6 million indoors through using solid fuel add to this the 2.7% of the global burden of disease (in Disability-Adjusted Life Years or DALYs) [12]. Most of the people affected were in poor countries. This makes air pollution as a risk factor the second biggest environmental contributor to ill health, behind unsafe water and sanitation. Its importance as a public health threat varies drastically according to the level of development of a country: in the poorest countries indoor air pollution is responsible for up to 3.7% of the burden of disease it no longer features in the top 10 risk factors in industrialised countries. Research has shown that the indoor levels of some pollutants, such as formaldehyde [13], chloroform [14], and styrene [15], range from 2 to 50 times higher than outdoor levels. Overall, though, in many countries, pollutant concentrations indoors are similar to those outdoors, with the ratio of indoor to outdoor concentration falling in the range 0.7–1.3. Higher levels of indoor pollution are usually the result of combustion processes associated with cooking or heating coupled with poor ventilation. Exposure to some pollutants such as environmental tobacco smoke and radon occurs almost entirely indoors. Indoor sources may lead to an accumulation of some compounds that are rarely present in the ambient air. Conversely the urban outdoor air is dominated by the signature group of petroleum VOCs known as BTEX (benzene, toluene, ethylbenzene, xylenes). Concentrations of combustion products in indoor air can be substantially higher than those outdoors when heating and cooking appliances are used. This is particularly true in countries where ovens and braziers are used with imperfect kitchen and stove designs [16–19]. In many countries exposure to emissions from cooking and heating may produce the highest indoor air pollution exposures to many pollutants. Today about half the population of the world has to rely for cooking and associated space heating on simple household stoves using unprocessed solid fuels that have high emission factors for a range of health-damaging air pollutants [18, 20]. Specific health effects are often claimed for individual pollutants, particularly causes of cancer from the presence of carcinogens in the air. Health effects from exposure to the whole mixture of pollutants are often held responsible for vaguely defined syndromes or conditions such as sick building syndrome (SBS) or building related illnesses (BRI) [21, 22]. SBS is the occurrence of specific symptoms with unspecified aetiology, that are experienced by people while working or living in a particular building, but which disappear after they leave it. Symptoms include mucous membrane, skin and eye irritation, chest tightness, fatigue, headache, malaise, lethargy, lack of concentration, odour annoyance and influenza symptoms. SBS usually cannot be

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attributed to excessive exposure to any one contaminant or to a defective ventilation system although this is often claimed. A number of factors may be involved and it is assumed that the interaction of these factors, involving different reaction mechanisms, cause the syndrome, but there is as yet no clear evidence of any exposure-effect relationship [23, 24]. Although the definition is vague BRI is often defined as an illness related to indoor exposures to biological and/or chemical substances (e.g. fungi, bacteria, endotoxins, mycotoxins, radon, CO, HCHO). It is experienced by some people working or living in a particular building and it does not disappear after leaving it [25]. Illnesses include respiratory tract infections and diseases, legionnaires’ disease, and more controversially, cardiovascular diseases and lung cancer.

2 Factors That Affect Indoor Air Quality The air quality inside buildings is affected by many factors. In an effort to conserve energy, modern building design has favoured tighter structures with lower rates of ventilation. By contrast, in some areas of the world only natural ventilation is used; in other areas mechanical ventilation is common [26]. In spite of the move to tighter structures there is still continuous air exchange between indoors and outdoors such that indoor concentrations of air pollutants are influenced by outdoor levels. The extent to which this occurs depends upon the rate of exchange between indoor and outdoor air; and these levels are subject to geographical, seasonal and diurnal variations [27]. Within buildings the factors that can have a negative effect on health and comfort range from chemical and biological pollutants, to occupant perceptions of specific stresses such as temperature, humidity, artificial light, noise and vibration [28]. Important sources of chemical pollutants indoors include not only outdoor air, but also human body and human activities, plus emissions from building materials, furnishings and appliances, and use of consumer products. Microbial contamination is mostly related to the presence of humidity. The heating, ventilating and air conditioning system can also act as a pollutant source, especially when it is not properly maintained. For example, improper care of filters can lead to re-emission of particulate contaminants. Biological contamination can proliferate in moist components of the system and be distributed throughout the building. One of the most important causes of indoor pollution is combustion [29]. The level of pollution produced depends on the fuel that is burnt and how it is burnt. The cleanest fuel is gas, although there are several types, but at the bottom of the energy ladder is biomass [9, 30]. Although part of human experience since the first controlled use of fire, air pollution from simple open combustion of biomass has been scientifically characterised only in the last two decades, largely due to rising concerns about wood-smoke pollution in developed countries [31]. Studies have shown high emission factors for many important pollutants, including respirable particulate matter, carbon monoxide, polycylic aromatic hydrocarbons, such as benzo[a]pyrene,

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and volatile organic compounds, such as formaldehyde and benzene. Biomass fuels emit hundreds of chemicals during small-scale combustion, such as in household cooking or heating stoves. It has been shown that such fuels produce 10–100 times more respirable particulate matter per meal as the result of low (combustion and heat-transfer) efficiencies. Although biomass makes up only 10–15% of total human fuel use, compared to modern fuels a much larger fraction is burned indoors, since nearly one-half of humanity cooks and/or heats with simple stoves burning traditional biomass fuels and in consequence suffers chronic bronchitis and obstructive airway disease. A recent study of women in Mexico showed that those cooking with biomass fuels had increased respiratory symptoms and a slight average reduction in lung function compared with those cooking with gas [32]. It is not known what fraction of biomass-burning households cook indoors on un-vented stoves, although it is clear that many hundreds of millions do so during some or all seasons of the year. There is also little information about the ventilation rates in the many thousands of housing types in developing countries or countries in transition although some studies have been made [19]. Monitoring such indoor environments is not often carried out but reports of studies are appearing in the literature [33]. The results of these are often quite striking. Very high concentrations of particles in indoor air can occur, sometimes for short duration, such as during cooking over solid fuel fires in rooms with poor ventilation [33]. The active and passive inhalation of tobacco smoke can lead to reduced pulmonary function which is decreased more in females than males [34, 35] and to an increased incidence of respiratory symptoms and infections, and to an increased incidence of lung cancer. Tobacco smoke is a fresh biomass smoke, which has been studied far more than any other pollutant mixture. Since there are similarities between ETS and biomass smoke from stoves, as hundreds of the organic compounds they both contain are similar it seems obvious that exposure to biomass smoke from open stoves must causes considerable human ill-health world wide. In the second-hand form as ETS, it is associated with adverse health impacts in adults and children at particle concentrations similar to those at which the epidemiological studies of health effects of outdoor particulate matter have been conducted. It should also be kept in mind that exposure to ETS and other air pollutants can act synergistically to produce adverse health effects [36].

3 Health Effects Since the early 1970s, interest in the health effects of indoor air pollution has increased annually. Consequently, a large body of literature is now available on diverse aspects of indoor air pollution: sources, concentrations, health effects and the engineering technology needed to ameliorate the problem [37–39]. More recently it has been realised that indoor air pollution from the use of open fires for cooking and heating is a serious problem in developing countries [12, 40].

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When it comes to health effects most indoor air pollutants directly affect the respiratory and cardiovascular systems and the severity of effect varies according to both the intensity and the duration of exposure, and also with the health status of the population exposed [41–45]. The importance of this is that some members of the population may be greater risk than others. Many of those who are especially susceptible to the health effects of indoor pollutants are those who will spend nearly all of their time indoors. These include infants and the elderly, those with heart and lung diseases and people with asthma, as well as hyper-responders and even the fitter members of society who are exercising [46]. A lot of the work on the health effects of indoor air pollution concentrates on a single pollutant, for example, sulphur dioxide, particulate matter, carbon monoxide, or nitrogen dioxide. This specificity is particularly so when the pollutant is a known human carcinogen such as benz[a]pyrene, benzene or radon. Although carcinogenicity may be a good reason for studying individual pollutants as stand alone causes, the fact that all pollutants differ in the health effects they cause would seem to be an equally good reason for discriminating between them. Thus, although we rarely breathe any one pollutant in isolation some pollutants, such as carbon monoxide, have such a dramatic effect on health that they should be considered separately [47]. Carbon monoxide causes disruption of the chemistry in several cell types, which, at low exposure levels, may be reversible. There are other pollutants that can cause cell damage and cell death, such as sulphur dioxide, nitrogen dioxide and particulate matter, and particularly mineral fibres. Cell death removes a cell but cell damage can have more serious consequences for the organism. On the other hand dead cells promote mitogenesis and this in its turn may lead to mutagenesis. A high level of mutagenesis may lead to inheritable changes in cell DNA and eventually to cancer.

3.1 Carbon Monoxide Acute exposure to high levels of carbon monoxide can be life-threatening but the consequence of chronic exposure to low levels is not really known [48, 49]. In kitchens with gas stoves, short-term values of up to 15 mg m−3 have been measured. High values have also been measured in bars and pubs, where smoking is common, with average concentrations of 10–20 mg m−3 and peak levels up to 30 mg m−3 [50].

3.2 Nitrogen Dioxide Nitrogen dioxide is an insidious pollutant that causes lung damage and for which there may be no threshold of action [38, 51, 52]. In countries that cook and heat by gas (used in 20–80% of houses in some countries) indoor levels of NO2 can be surprisingly high. In a UK study (noted with others in [53]), the average NO2

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concentrations (over a week) were in the range of 9.4–596 μg m−3 in kitchens, for houses with gas cookers and 11.3–353.4 μg m−3 in dwellings with electric cookers. Corresponding levels outdoors were 26.3−45.1 μg m−3 . These exposure levels may have an effect on respiratory function [54]. Peak values of up to 3800 μg m−3 for 1 min have been measured in the Netherlands in kitchens with unvented gas cooking ranges [50, 55].

3.3 Volatile Organic Compounds (VOCs) All indoor environments contain a number of volatile organic compounds (VOCs) [56]. Most of these are present at very low concentrations have no measurable or, at the worst, insignificant health effects. However, high levels may have health effects that range from sensory irritation to behavioural, neurotoxic, hepatoxic, and genotoxic effects [57] although these are more often associated with occupational exposure. Several of the VOCs that cause concern do so because they are real or suspected human carcinogens. Environmental tobacco smoke (ETS) is another mixture of organic compounds widely considered as an important factor in indoor air quality [58, 59]. ETS is a mixture of particle and vapour phases which together make a complex mixture of several thousand chemicals, including known carcinogens such as nitrosamines and benzene. One of the most commonly used indicators of environmental pollution by tobacco smoke is the concentration of PM10 . This measurement of the particulate phase is 2–3 times higher in houses with smokers than in other houses [60]. One commonly encountered volatile organic chemical that is not usually considered, as a VOC is formaldehyde. In five developed European countries HCHO concentrations in indoor air were reported to range from 9 to 70 μg m−3 . Higher values are occasionally encountered, especially in dwellings with urea-formaldehyde foam insulation [61] or with particle board use din their construction [62, 63]. Formaldehyde has been shown to be carcinogenic in rats and more recently it has been shown to be a human carcinogen [64]. A quartet of chemicals ubiquitous in the built environment is the petrol (gasoline) mixture of aromatics BTEX. For reasons known only to politicians and financiers this excites little comment, although it may be a major part of the total VOC level. However, the minor constituent, benzene, is a known human carcinogen and is therefore usually discussed as such. A recent study of environmental levels of benzene [65] noted that these were three orders of magnitude lower than the lowest exposures reported to be associated with observed adverse effects.

3.4 Radon Radon is the only radioactive pollutant found indoors. The evidence is good that it is a human carcinogen and this is its only property that causes concern. In general,

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average indoor levels of radon are 20–70 Bq m−3 [66], although they may be ten times higher in certain areas. So, there are reasons for studying individual pollutants in isolation and other reasons for looking at them altogether. Leaving aside industrial and occupational exposure, which may be to a single pollutant and may be to high doses, with the possible exception of nitrogen dioxide the pollutants found indoors that cause concern with regard to their possible health effects are those which have the potential for such an exposure to result in cancer.

4 Cancer Causing Chemicals in Indoor Air The causes of cancer were only discovered in comparatively recent times. One reason is that much cancer is a disease of the elderly and in the past conditions were so bad that few lived long enough for a tumour to develop. It was only in the twentieth century when life-expectancy increased considerably that it created the attention it has today. Ascribing the cause of cancer to exposure to pollution was something that probably only came about in the last 50 years or so. Studies continue classifying exposure according to levels of various pollutants such as benz[a]pyrene, particulates and sulphur dioxide/sulphate levels.

4.1 The Hazard – Carcinogens in the Indoor Environment A number of the chemicals found in the indoor environment are classed as carcinogens, although not all of them are well documented as human carcinogens. The list of organic compounds that may be found in the indoor environment is small and includes formaldehyde [67, 68], certain polycylic aromatic hydrocarbons (PAHs)E [69], benzene [65, 70] and 1,3-butadiene [71]. Tobacco smoke including ETS contains, among many other compounds, benzene, nitrosoamines and PAHs [72]. Several inorganic compounds are classified as carcinogens including, among others, arsenic, nickel and chromium in their elemental form or as compounds [73, 74]. Arsenic is a major problem in well water in many areas of the world including Bangladesh, West Bengal [75] and Taiwan [76] where it is an undoubted cause of cancer. In some areas of China and India, household coal use leads to high indoor concentrations of fluorine, which causes fluorosis but not cancer, [29] and arsenic [77] with consequent health effects. Other inorganic materials that can pollute the indoor environment include the various types of asbestos and other mineral fibres. Diseases from these include lung cancer and mesothelioma but almost always as a result of occupational exposure [78–80]. The only natural radioactive element to cause concern is radon. It is a proven lung carcinogen in both animals and man but the risks it poses, at least in the domestic rather than occupational setting, are still unclear.

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4.2 The Risks from Carcinogens in the Indoor Environment In a 1987 study, the US Environmental Protection Agency (EPA) ranked indoor air pollution fourth in cancer risk among the 13 top environmental problems analysed. Indoor radon ranked first in this list. The risk posed by the level of radon found in dwellings is still hotly debated with the ecologists finding an inverse relationship between lung cancer and radon levels [81] or that there is little correlation [82] and the epidemiologists promoting a linear no-threshold model which contradicts these findings [83, 84]. However, what may be so in America, is not necessarily so in the rest of the world. Relatively few studies, for example, have been conducted to determine the health effects of indoor exposures to air pollutants in developing countries, although data has become available in recent years to obtain some preliminary information on the type and very approximate magnitude of effects [29]. The one major difference between rich and poor nations that are responsible for differences in observed health effects is the way in which they generate energy. When energy generation is produced remote from the areas where people live, it has little impact on personal health. If energy generation for heating, lighting and cooking is confined to the dwelling-place and is almost entirely accomplished by direct combustion, then a greater or lesser effect on health is to be expected depending on the quality of the fuel that is burnt. The lower the fuel is down the energy ladder, the greater the pollution it causes and the greater the incidence of cancer caused by inhaling the polluted emissions. Lung cancer is a probable consequence of biomass burning [16] although not all studies find an association while coal for cooking and heating has been shown in many Chinese studies to yield a statistically positive relationship with coal smoke and disease [85–87].

5 Conclusion Air pollution is responsible for much morbidity and mortality in the world. Its heterogeneous nature, though, means that few generalisations about its cause and effects can be made. Higher levels of pollution are associated with poverty and most pollution comes from combustion of one sort or another. For the global population as a whole, indoor pollution is more important than outdoor pollution, although high ambient levels obviously adversely affect the indoor environment. Moving from poverty to wealth does not mean an escape from pollution, but rather exchanging some elements of it for others: radon has never been shown to be a problem in poor and draughty housing. Paradoxically, a wealthy lifestyle promotes greater concern about pollution, but in reality it means appreciably less ill health and death from environmental causes.

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Part VI

Environmental Awareness, Education and Ethics

Promotion of Nursery School Teacher and Junior Grade Teacher Education for Environment and Sustainable Development in the Republic of Croatia According to the Concept of Lifelong Learning Vinka Uzelac and Dunja Andic

Abstract The empiric data used in this work were gathered within a broader research called Further preschool teacher and junior grade teacher education for environment which was approved by the Ministry of Science, Education and Sports of the Republic of Croatia in 2001. The investigation was implemented on the sample of 283 preschool teachers and 202 junior grade teachers and was aimed at determination of their education practice and needs for future education for environment and its sustainable development. In addition, the purpose was to test whether there are differences between the mentioned professional profiles of educational employees. The results indicate that there are statistically significant differences concerning evaluation and that past practice of education for environment is, in several segments, dependent on a professional profile. What was also determined is a single-factor structure of the contents needed for future education and development of skills and abilities within the context of education for sustainable development. Looking at the whole, the research results indicate that, with certain cautiousness, it is possible to determine single approaches in evaluation of practice of nursery school teacher and junior grade teacher education for environment. It is also possible to determine the educational needs which are to a large extent mutually similar concerning the development of skills and abilities but to a lesser extent different concerning the evaluation of content selection in education for sustainable development. The authors draw attention to the educational employees, the significance of recognising their educational needs, taking the critical view of past practice and creating a new education for sustainable development of the environment for them. Keywords Environment · Sustainable development · Nursery school teachers · Junior grade teachers · Practice of education for environment · Educational needs for sustainable development

V. Uzelac (B) Faculty of Teacher Education, University of Rijeka, Trg Ivana Klobuˇcari´ca 1, 51000 Rijeka, Croatia e-mail: [email protected]

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1 Introduction First of all, what needs to be pointed out is the following: On one hand, numerous efforts for the public agreements encourage regarding the need for urgency initiation that refers to the sustainable life style of future generations and their enjoyment in the quality of living [14, 10, 12, 3]. On the other hand, however, this issue significantly affects the problem of understanding [11, 6]. In other words, the issue of sustainable development has a direct impact on all people but general understanding of allthese problems and their significance is rather low [8]. Furthermore, while educations long present as a key instrument for human consciousness raising [1, 10, 22] refered to environment and sustainable development, the rules that support practical educational changes are nearly not present at all [13, 5, 18, 19, 20, 21]. The implementation of such changes calls for educated professionals, especially teachers [2, 7]. If their number is not sufficient, what else can be said but: they are to be educated!

2 Methodology of Research 2.1 Research Problem and Aims In order to provide a better understanding of the problem of nursery school (preschool) teacher and junior grade (primary school) teacher education for environment and sustainable development, and, therefore, an adequate help, it is important to know to which extent is this problem also the problem of the past practice of our examinees and to get information about their educational needs for future education in the field of environment and sustainable development. The group of our examinees is particularly interesting due to the fact that, among other things, they can be divided in two smaller groups: the ones who can sense the problem of their education in the field of environment but are not educated enough and the ones who sense that problem to a lesser degree and are less inclined to such education. In accordance with all this, the following aims are set : 1. to determine certain dimensions of the past practice and future of nursery school teacher and junior grade teacher education for environment and sustainable development 2. to check if there is a difference between nursery school teachers and junior grade teachers concerning some characteristics of the past practice of education for environment 3. to check if there is a difference between nursery school teachers and junior grade teachers concerning their sense of having the educational needs for future education in the field of environment. A questionnaire that was previously made within a broader research Further preschool teacher and junior grade teacher education for environment, was also

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used in this research. In lesser part, it was formed on the basis of two questionnaires used in earlier researches: Environment – education – preschool teachers/junior grade teachers [17] and Education of teacher education college/faculty students for environment, while in larger part it was based on Huckle’s [18] works [4]. It encloses some characteristics of the past programmes of nursery school teacher and junior grade teacher education for environment – information accessibility in the context of the past practice of nursery school teacher and junior grade teacher education for environment. The scales of the past practice of education for environment are scored as follows: 1 = definitely not, 2 = mostly not, 3 = mostly yes and 4 = definitely yes. The questionnaire also encloses certain content related needs, as well as needs for the development of individual skills and abilities referring to future nursery school teacher and junior grade teacher education for environment. The scales of educational needs comprise of 21 particles referring to content related needs, and 9 particles referring to the development of skills and abilities in the context of education for environment and sustainable development. The reliability of the scale of content related needs is 0.92, and of the scale of skills and abilities 0.80 (Cronbach’s test). The scales of future education for environment are scored as follows: 1 = low need, 2 = medium need i 3 = high need. The examinnes were expected to mark the single statement frequency or choice with an X.

2.2 Procedure The research was implemented on a sample of nursery school teachers and junior grade teachers in Zagreb, Rijeka, Split and Osijek, in April and May 2005. Due to this work needs, the examinees’ data were included in the statistical analysis and divided in two categories: nursery school teachers and junior grade teachers. The category of nursery school teachers consists of 283 or 58.2% of the examinees, and the category of junior grade teachers consists of 202 or 41.6% of the examinees.

2.3 Methodological Remarks Since there was a small number of researches implemented in the Republic of Croatia, whose interests also are educational employees and their education for environment, the researchers encountered some problems of methodological nature. Before all, this refers to the questionnaire structure. However, we believe that further examining would contribute to its improvement. Taking into consideration that the results of this research are based on nursery school teacher and junior grade teacher self-assessment (what is also a methodological problem!), further researches should also include the assessments of other factors that would contribute to objectivity linked with the assessment of current state and vision of nursery school teacher and junior grade teacher education for sustainable development of environment.

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Regarding these further researches and in order to make the sample more representative, it might be useful to include some other nursery school teachers and junior grade teachers who work in different conditions.

3 Results and Discussion The data processing, whose results are outlined in this work, is implemented by the use of some standard statistical procedures (aritmetic mean and standard deviation). Since one of the aims of this work is comparison between examinees with different professional profiles, some adequate statistical tests were also used. A t-test was used in the analysis of importance of the differences of artimetic means and a factor analysis with common factor was derived.

3.1 Practice and Needs of Nursery School Teacher and Junior Grade Teacher Education for Environment and Sustainable Development 3.1.1 Information Accessibility in the Context of Current Practice of Nursery School Teacher and Junior Grade Teacher Education for Environment From the level of their comparison, it can be seen that the junior grade teachers used all three statement scores more frequently than the nursery school teachers, linked with the accessibility of information about environment. In other words, what is obtained is a statistically significant difference concerning their statements: A nursery school/primary school has at its own disposal enough literature on education of nursery school teachers and junior grade teachers in the field of environment (t = 2.86; p = 0.004), where a larger assessment is given by junior grade teachers (M = 2.84) than by nursery school teachers (M = 2.64); Nursery school teachers and junior grade teachers have access to data relevant for education in the field of environment (t = 4.30, p < 0.001), where a larger assessment is also given by junior grade teachers (M = 2.99) than by nursery school teachers (M = 2.68); and Nursery school teachers and junior grade teachers use contemporary educational technology in order to improve data flow and communication linked with education for environment (PC, electronic mail, etc.) (t = 6.57; p < 0.001), where a larger assessment is as well given by junior grade teachers(M = 3.00) than by nursery school teachers (M = 2.49). The research shows that the information accessibility in the context of the current practice of education for environment is tied to a profile of education in such a way where junior grade teachers outline a larger information accessibility. The obtained results could be explained by some characteristics of educational work in junior grade teaching, different styles of junior grade teacher education, as well as by bigger concern of the schools these teachers work in, regarding their education and improvement in the field of environment [2, 4]. On the other side and compared

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with the junior grade teachers, the nursery school teachers have probably less interest in a question of possible integration of literature and contemporary educational technology into the process of education for environment [3]. We are fully aware that this dimension is just a subsidiary indicator in the analysis of the current state in the practice of education for environment [6], which is, needless to say, imprecise as well in relation with educational programmes. However, due to the current inaccessibility of other data, we are obliged to use it as an indicator of the phenomenon of education for environment. 3.1.2 Content Related Needs in the Context of Future Nursery School Teacher and Junior Grade Teacher Education for Environment and Sustainable Development For some time past, nursery and primary schools in the Republic of Croatia have not been following desirable trends of education for environment, programme enrichment, massification, etc. It is indicative that the process of such education is even less observable, especially when talking about nursery school teachers and junior grade teachers. In order to get a more complete insight in the examined, content related, educational needs, we shortly introduce some of them and their medium values. The results obtained indicate that the nursery school teachers evaluated 12 statements (out of 21) and junior grade teachers evaluated 11 statements (out of 21) referring to the contents of education that have been provided to them, and they used marks 2 and 3, that is, medium need and high need. The highest average marks given by nursery school teachers refer to the following three statements: Preserving the future of environment (M = 2.88); Importance of cultural, social, economic and biological diversity of environment (M = 2.72) and Impact of personal action on environment and its sustainable devlopment (M = 2.70). The contents most necessary for the junior grade teachers are those referring to: Preserving the future of environment (M = 2.80); Preserving and rational use of environmental goods (M = 2.67) and Impact of technology on environment (M = 2.66). However, it needs to be said that the educational need which got lowest marks from the examinees was: Political dimension of the aspects of sustainability (M = 2.12; M = 2.20). Therefore and according to the degree of acceptance of these statements, we can say that the examinees are open for the entry of new contents in their own education. On the next level of the analysis and in order to examine the structure of the contents referring to education for environment and sustainable development, a factor analysis of needs for different contents was derived and a number of 21 needs was included in it. The factor analysis with common factors was derived and the Scree test was used as a criterion for an extraction of a sufficient number of factors. Its results indicate that in the basis of all the examined needs there is one general factor that explains 35.14% of common variant (varijanca) (the first five eigen values are 8.02, 1.73, 1.46, 1.10, 1.03). Table 1 shows a factor matrix of the needs analysed. The reliability of this factor internal consistency (Cronbach alpha) is very high with the figure of 0.92.

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Table 1 Facto matrix of the needs for different contents in future education for environment and its sutainable development Needs

FI

Ethical dimension of environment/sustainability Psychological dimension of environment/sustainability Impact of technology on environment/sustainable development Aesthetical dimension of environment/sustainability Changes and development within the current capacity of environment Impact of poverty on environment/sustainable development Importance of cultural, social, economic and biological diversity Impact of human communities on environment/sustainable development Civil rights and responsibility for environment/sustainable development Interdependence of society, economy and natural world What is education for environment/sustainable development? Political dimension of the aspects of environment/sustainability Impact of personal action/activity on environment/sustainable development Equality and justice Role of authorities and business world and their responsibility for environment/sustainable development Educational technology in the field of environment Problem of integration of education for environment/sustainable development Local activities and their possible global effects Strategy of teaching for environment/sustainable development Preserving and rational use of environmental goods Preserving the future of environment

0.70 0.66 0.64 0.64 0.63 0.60 0.60 0.60 0.60 0.59 0.59 0.59 0.58 0.58 0.58 0.57 0.57 0.57 0.53 0.52 0.47

Taking into consideration the meaning of these statements, it seems justified and suitable to say, first of all, that this factor is the indicator of free choice of contents in the field of education for environment and its sustainable development. At the same time, we can say that there are also highly interconnected educational needs among the examinees. Therefore, this factor can be considered as their optimistic orientation towards future education for environment and sustainable development. It is, after all, one of the top priority tasks of the institutions where they work, that is, of the whole society. Namely, considerations about the meaning of the stated factor indicate that education for environment is or should be understood as necessity and the object of possible and desirable professional and scientific discussions and actions. Regarding the fact that our examinees had belonged to different professional profiles of educational employees, on the next level we completed a t-test whose purpose was to identify potential differences among them (Table 2).

Table 2 Differences with regard to professional profile Independent variables

M

SD

t; p

Nursery school teachers Junior grade teachers

52.81 53.05

7.74 8.08

t = 0.31; p = 0.753

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Regarding the professional profile, the research shown that it has no significant influence on the examinees’ views of the choice of educational contents. Namely, the nursery school teachers and junior grade teachers do not differ significantly considering some average results linked with this factor. There is a minimal difference between these two groups of teachers and their answers are in a rather close coordination. Therefore, it is clear that professional profile has no significant influence on the views linked with this issue. It can be presumed that, while determining their educational needs, both groups of the examinees first assessed their own position in children’s/pupils’ education and the feeling of expectation coming from other factors in the environment. In short, the data synchronously show some aspects of pluralism and individualisation. In other words, the process of education of educational employees for environment is possible with the contents presented and where primary groups are formed of nursery school teachers and junior grade teachers. 3.1.3 Development of Skills and Abilities in the Context of Education for Environment and Sustainable Development Our intention was to test whether it is possible to set apart any dimension that, to a certain extent, explains the degree of answer variability in all the statements. That is, in order to test the structure of the offered statements, a factor analysis of the needs for the development of single skills and abilities was derived referring to future education for environment and sustainable development. A number of 8 skills and abilities was included in the analysis and a Scree test was used as a criterion for an extraction of a sufficient number of factors. The projections of single particles are shown in Table 3. The test results indicate that in the basis of all the examined needs Table 3 Factor matrix of skills and abilities referring to future education for environment/ sustainable development Skills and abilities

FI

Development of higher skills that include analysing, synthetising and formulating the conclusions linked with sustainable development Development of abilities of considering different points of view and reaching the compromise of thoughts linked with sustainable development Development of abilities of critical evaluation of personal and other people’s experience linked with sustainable development Development of communication skills such as introduction of ideas, asking and locating questions and presenting rational arguments linked with sustainable development Development of ability to work in a cooperative way on planning and implementing the tasks linked with sustainable development Development of skills of evidence analysing and identifying partiality within arguments and evidence linked with sustainable devlopment Development of skills of active learning where one has to reach the information linked with sustainable development independently

0.68 0.60 0.60 0.59

0.56 0.53 0.53

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M

SD

t; p

Nursery school teachers Primary school teachers

18.93 18.80

3.13 3.46

t = 0.43; p = 0.669

there is one general factor that explains 33.92% of common variant (varijanca) (the first five eigen values are 3.37, 1.21, 0.80, 0.67, 0.54). The reliability of internal consistency (Cronbach alpha) is satisfactory, with the figure of 0.80. According to the examinees’ perception linked with this factor, we can say that there are highly interconnected opinions of the development of certain skills and abilities in the context of education for environment and sustainable development. At the same time, we can also say that the examinees, more indirectly than directly, believe that the development of adequate skills and abilities will raise education for environment on a higher level. Finally, based on the dimensions obtained from the factor analysis, we notice that our examinees here as well express an optimistic orientation towards their own future education for environment and sustainable development. According to the t-test, the examinees did not show statistically significant differences regarding the scale of overall average results (Table 4). In other words, by the analysis of the aritmetic means, we notice that there is no deviations. This could be explained in various ways but what seems important in this case is the closeness of the two different categories of professions of educational employees. The examinees belong to such educational professions that are, regarding their practice, among first to be responsible for the development of children’s/pupils’ sensitivity for different issues of environment, that is, its preventive preservation. Therefore, the examinees hold similar opinions of the mentioned skills and abilities in the context of their own education for environment and sustainable development. All this could be extremely important for supporting and facilitating the proces of future nursery school teacher and junior grade teacher education for sustainable development.

4 Conclusion Based on a discussion about practice and future of nursery school teacher and junior grade teacher education for environment and sustainable development, the general conclusion is that the examinees indicate a rather similar situation. At this time, we can generally say that the junior grade teachers use some more successful strategies of education for environment. However, looking at the viewpoint of reforming global educational space whose important component is nursery school teacher and junior grade teacher education for environment, we believe that further improvement of this kind of education is not questionable at all, regarding other educational employees as well. In any case, the results indicate the need of correction of wider

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social-pedagogical views where educational employees are hold only responsible, instead of equally responsible together with all other active participants of society. Another important conclusion is that the improvement of certain measures of education for environment could reduce huge social-pedagogical damage where the postponement of youngest generation education, that is, preschool age children and primary school pupils’ education for environment is considered to have harmful consequences. In other words, educational influence on children/pupils will surely be put into question in a long term absence of qualitative communication between society and educational employees. In this respect and taking the determined and analysed results as a starting point, we offer certain generalisations of the solutions referring to the attempt to define lifelong learning for environment pedagogically (Appendix).

Appendix: A Strategy of Lifelong Learning in the Field of Environmental Education OVER LIFESPAN

INSTITUTIONAL AND NON-INSTITUTIONAL FORMS OF EDUCATION (THROUGH ALL EDUCATIONAL FIELDS)

VALUES OF EDUCATION AND NEW FUNDAMENTAL KNOWLEDGE AND SKILLS

INNOVATIONS IN LEARNING AND TEACHING

NETWORKS IN EDUCATION -INTERNET USE

REFLECTING ROLES OF LEADERSHIP AND COUNSELLING IN EDUCATION

Continuity of Learning Over the Lifespan

1. FORMAL EDUCATION IN VARIOUS EDUCATIONAL INSTITUTIONS 2. INFORMAL EDUCATION : A) organised at working place and B) in the form of various societies and associations

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Challenge 1. Cooperation between formal and informal education 2. Planned and organised instruction about the environment in educational institutions and in everyday life – with environmental self-learning processes

Environment Sustaining Education The Basic Function of the Concept Values • • • • • • • •

Respect of independence Respect of basic human needs Respect of equality among species Respect of democracy Respect of human rights Respect of intergenerational equality Respect of biodiversity Enlightened living

Knowledge • • • • •

Providing ecology-oriented knowledge Developing sensitivity and awareness of ecological and ethical values Fostering adequate ecology-oriented beliefs and attitudes Developing environment-appreciating behaviour patterns Developing instructional-methodological skills for future education within the environment

Skills COMMUNICATION SKILLS

LEARNING LEARNING SKILLS SKILLS NUMERICAL SKILLS

PROBLEM SOLVING SKILLS COMPUTOR SKILLS

PERSONAL AND SOCIAL SKILLS

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Innovations in Learning and Teaching Development of Efficacious Methods of Instruction and Learning 1. Based on the self-organised learning 2. A shift to the active acquisiton of knowledge 3. A measure of lifelong learning developmental level

Re-Consideration of Roles of Leadership and Counselling in Environmental / Environment Sustaining Education Assignment of an Expert in Leadership and Counseling is Manifested as (a) Identification and retrieval of valuable information useful for satisfying personal needs (b) Protection of education and permanent improvement from unprofessional and negative influences (c) Providing integral access to quality information on ecology and education (d) Helping people to finding one’s own way in the labyrinth of information

References 1 Cifri´c I (2002) Okoliš i održivi razvoj. Zagreb: Hrvatsko sociološko društvo 2 Gayford C (2001) Education for sustainability: an approach to the professional development of teachers. Eur J Teach Educ 24(3):313–327 3 Global vision. Communicating sustainability (2004). Philosophy. http://www.global-vision. org/philosophy/index.php 4 Huckle J (2006) Education for sustainable development. A briefing paper for the Training and Development Agency for Schools Final draft June 2005. Revised Edition, october 2006. http://john.huckle.org.uk/publications_downloads.jsp 5 International Association of Universities and Charles University (2003) Sustainable Future: Shaping the Practical Role of Higher Education for Sustainable Development. At Charles University, Karolinum, Prague, Czech Republic, 10–11 September, 2003. Reports from EE & ESD Meetings. International Conference on Education for Sustainable development. MEDIES: Prague. http://www.iau-aiu.net/sd/sd_confprague.html 6 Laj V (2005) Proizvodnja buducnosti Hrvatske: Integralna održivost i uˇcenje. Društvena istraživanja 14(3):311–335 7 Kaivola T (2004) Sustainable development in Academic Teaching and Learning, Baltic University Programme, Faculty of Behavioural Sciences. University of Helsinki, Helsinki 8 Kešina I (2002) Sociobiologija i «sebiˇcni gen». Moral i etika sa stajališta suvremene biologije. Društvena istraživanja 11(6):929–953 9 Pravdi´c V (2003) Održivi razvoj: znaˇcenje, poimanje i primjena. Društvena istraživanja 12(3–4):285–311 10 Rogi´c I (2003) Obzirni/održivi razvitak u iskustvu modernosti. Društvena istraživanja 12(3–4):361–379

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11 Sellin S (2003) The Haga Declaration. U: Education for sustainable development in the balticsea region, Chapter 2. Undervisnings Ministeriet. http://pub.uvm.dk/2003/learnersguide/ html/chapter02.htm 12 Starc (2003) Priroda, cˇ ovjek i figa u džepu. Društvena istraživanja 12(3–4):335–361 13 Stokes E, Edge A &West A. (2001) Environmental Education in the educational system of European Uninon. London Schools of Economics- European Comission. Retrieved May, 2006. from: http://ec.europa.eu/environment/youth/pdf/envedu_en.pdf 14 UNESCO (2001) Education for sustainability: An Agenda for Action. Chapter 1: Program for Change. http://www.gcrio.org/edu/pcsd/index.htm 15 UNESCO (2002) Teaching and learning for sustainable future – a multimedia teacher education programme. http://www.unesco.org/education/tlsf 16 UNESCO (2005) UN Decade of Education for Sustainable Development 2005–2014. International Implemention Scheme. Draft. January. Section for Education for Sustainable Development (ED/PEQ/ESD) Division for the Promotion of Quality Education, UNESCO. http://unesdoc.unesco.org/images/0014/001486/148654e.pdf 17 Uzelac V (1996) Okoliš – obrazovanje – odgajatelji/uˇcitelji. Zagreb: Hrvatski pedagoško književni zbor 18 Uzelac V (2002) Stanje i vizija obrazovanja studenata uˇciteljskih škola/nastavnickih fakulteta za okoliš. Zagreb: Hrvatski pedagoško-književni zbor 19 Uzelac V, Pejˇci´c A (2004) Od ekološke (ne)pismenosti prema cjeloživotnom uˇcenju za održivi razvoj. U: Ekologija u odgoju i obrazovanju. Gospi´c: Visoka uˇciteljska škola u Gospi´cu, str. 22–56 20 Uzelac V, Pejˇci´c A (2005) Polazišta i pristupi opismenjivanju odgajtelja i ucitelja za održivi razvoj. U: Zgodnje opismenjevanje – opismenjavanje od vrtca do univerze. Ljubljana: saveza društev pedagoških delavcev Slovenije, str. 215–222 21 Uzelac V, Pejˇci´c A (2006) Stilovi odgojno-obrazovnog rada odgajatelja i uˇcitelja u podruˇcju okoliša-procjene stanja implikacije. U: Zaviˇcajnost, globalizacija i škola / Vrci´c-Mataija, S, Grahovac-Praži´c, V. (ur.). 3. Dani Ante Starˇcevi´ca. Gospi´c : Visoka uˇciteljska škola u Gospi´cu, str. 359–388 22 Valchev R (2003) Environmental education in the formal schools of Southeastern Europe needs, achievements, partnerships, perspectives. General Report. http://www.openedbg.com/index_en.php?url=eeiseecar.php

Spatial Analyses for Environmental Impacts of Landfill Areas D.Z. Seker, S. Kaya, N. Musaoglu, H. Demirel, A. Tanik, and E. Sertel

Abstract This study presents significant spatial and temporal aspects of solid waste management on a case study conducted at the Istanbul Metropolitan area, where existing models of waste management have significant limitations due to limitations of handling spatiality and temporality. Since the decision making process should be performed over time and across space, remote sensing technology provides mature solutions. In order to analyze the changes IRS 1C PAN (5×5 m spatial resolution and dated 2000) and the IKONOS MS (4×4 m spatial resolution and dated 2004) images have been used. For the landfill areas, Istanbul Metropolitan area currently involves two sites, 1/5000 scaled map and both satellite images were overlaid in order to visualize the differences between reserved area and used area of the landfill. In order to analyze the flow direction of landfill areas towards watershed areas a Digital Elevation Model (DEM) was constituted and analyses were performed. The spatial and temporal changes of the two landfill areas were detected and results were discussed. Keywords Landfill · Waste management · Land use · Remote sensing · GIS

1 Introduction Urbanization has been the dominant demographic trend during the last century. With the high pace of social and economical development, cities became mega cities, having enormous population growths, lack of infrastructure, congested traffic, environmental degradation and housing shortage. Cities experienced biggest urban population boom, but also unprecedented global levels of economic activity. A new culture of production and consumption was followed by unexpected increase in the production of urban solid waste. The management of waste disposal is closely linked to the dynamics of the urban development, where it affects the demand for land for D.Z. Seker (B) Civil Engineering Faculty, Istanbul Technical University, 34469 Maslak Istanbul, Turkey e-mail: [email protected]

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landfill and the supply of suitable land to attend the demand. Land is an important limited and scarce resource. Additionally landfill areas become unusable for most beneficial uses such as for urban, commercial and industrial development. Landfills are facilities offer risks, therefore should be controlled, monitored and maintained, to the environment risk and public health. The planning and management of urban solid waste disposal is complex, involves uncertainty and requires judgment and diverse expertise [2]. Moreover, the decision making process should be performed over time and across space. Hence, Remote Sensing techniques and approaches serve adequate tools for aiding decision-makers during this process. The great strength of remote sensing is that it can provide spatially consistent data sets that cover large areas with both high detail and high temporal frequency, including historical time series and remote sensing data provide a means of monitoring change in urban land cover over time [1]. Due to spatial and temporal nature of environmental impact assessment, remote sensing technology enlighten the complex task of managers and decision makers by informing them of past and current land-use/cover changes and might aid to constitute transparent integrated policies. This study presents a usage example of Remote Sensing Technologies, although highly mature but under-covered, during environmental impact analyses of landfills. The application was conducted at the Istanbul Metropolitan area, where environmental risks and threats can not be underestimated. The main objectives of the study are to discuss and evaluate the land-use changes of the landfill areas and site selection for these.

2 Study Area Istanbul, being one of the oldest and crowded cities of the world, where the two continents, Europe and Asia, meet, is ranked as the 24th mega city among the 101 largest metropolitan areas of the world, by population. The city has about 20%

Fig. 1 Study area

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of the total population of the country while it makes up only 0.74% of the total surface area of Turkey. The city of Istanbul and its peripheries have been facing serious environmental problems within the past several decades due to migration from the rural areas, industrial and tourism oriented investments. Large quantities of commercial and municipal solid waste are produced in Istanbul every year, where this waste has disposed in landfills. There are two main landfill sites located each side of Istanbul are currently used. One of them is Gokturk, which is used in the European side of Istanbul, other one is Sile-Komurcuoda used for the disposal produced in the Asian side of the city. The most significant features of both sites are presence of many quarries and open mining areas. Location of these two landfills is given in Fig. 1. The reserved area, Gokturk, occupies 66 ha for the solid waste services.

3 Data and Methodology Using Remote Sensing, spatially accurate and timely information on landcover change patterns that supply required information on the previous and the current state of development and on the nature of changes that have occurred can be utilized by urban planners and decision-makers in the management and planning of urban space. Remote Sensing Technology provides a method for acquiring regular, current information about environment for monitoring these kinds of changes. Remote Sensing Technology, which has rapidly become popular, appears to be the most efficient method for thorough and rapid information gathering. Multi-temporal remotely sensed images are important and effective data sources for monitoring the rapid changes of land uses [7]. The use of remotely sensed data for water resources monitoring and management is basically for mapping, flood monitoring, wetland monitoring, lake and reservoir volumes, and irrigated land assessment [5, 4]. Timely and accurate change detection of surface features provides the basis for better understanding the relationships and interactions between human and natural phenomena to properly manage and use resources. Remote sensing data are primary sources extensively used for change detection in recent decades [3]. Assessment of the long-term impacts of land use and land cover change is important for optimizing environmental management [4]. Thus, through repetitive satellite coverage and the integration of satellite and spatial data, land-cover change analyses can be accelerated. The need for basic land-cover information is critical to both scientific analyses and decision-making activities [6]. In this study, IRS 1C PAN (5×5 m spatial resolution and dated 2000) and the IKONOS MS (4×4 m spatial resolution and dated 2004) images have been used for analyzing of the study area. Since the remote-sensing data are distorted by the Earth’s curvature, relief displacement and the acquisition geometry of the satellites, satellites images should be rectified. During this process 1:5000 scaled topographic maps were used. All satellite images were transformed into the same coordinate system, which was Universal Transverse Mercator (UTM). By means of transformed images the area of the landfill areas and peripheries were selected for both years 2000 and 2004. In order to analyze

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the changes within the years of 2000 and 2004, 1:5000 scaled maps were used. In order to analyze the flow direction of landfill areas towards watershed areas a Digital Elevation Model (DEM) is required, where DEM is frequently used to refer to any digital representation of a topographic surface. By means of elevation information, it is possible to carry out evaluations about the study area that would not otherwise be possible through two-dimensional analysis.

4 Results and Conclusions Landfill areas are examined using satellite images dated 2000 and 2004. Firstly Gokturk Landfill area, is digitized from 1/5000 scaled map and overlaid onto satellite image to visualize the differences between reserved area and used area of the landfill. After processing the image belonging to the year 2000, the landfill area was calculated as 29 ha. For the year 2004, the same area was calculated as 75 ha, where more than 13% of the reserved area is exceeded. In Fig. 2, the landfill map was given, where the study area image was overlaid afterwards. The red line represents the border of the reserved area. The Gokturk landfill area is colsely located to the Alibeykoy Reservoir. Over 90% of the water demands of Istanbul are currently supplied by seven drinking water reservoirs, four of which are located on the European side and three on the Asian side of Istanbul. Terkos, Buyukcekmece, Alibeykoy, and Sazlidere reservoirs are on the European side, and Omerli, Darlik, and Elmali are on the Asian side. Part of watershed zone borders and landfill area are given in Fig. 3, where watershed zones represented with red line. Slope direction of landfill area is analyzed using Digital

Fig. 2 Reserved area for the Gokturk landfill

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Fig. 3 Göktürk landfill and Alibey reservoir

Elevation Model, where regime of surface flow depends strongly on the physical properties of the area like slope, surface cover, vegetation etc. According to the results, the flow direction is not sloping towards the basin. The second landfill, Sile, which is located on the Asian side of Istanbul, was evaluated accordingly. It is located on the northern of Omerli dam reservoir and it doesn’t interfere with the reservoir border. Location of Sile Landfill and part of Omerli reservoir zones are given in Fig. 4. A significant increase in the open mining areas and quarries around the landfill area was observed between years 2000 and 2004, where the detected changes are presented in Fig. 5. According to the results of the analyses, the areas selected for the landfill ensures the conditions, evaluated regarding the topographic character and watersheds. Slopes are not towards the watersheds and landfill areas are not colliding with one another. Accurate, fast and low cost information can be obtained via remote sensing technology for determining the potentials of natural resources, monitoring their temporal changes and updating relevant information. Results present the spatial and temporal changes of the landfill areas. The spatial and temporal analyses have added an important capability to waste-disposal management, since environmental impact assessments involve time component. The analyses can be extended by means of a designed spatio-temporal model, where scenarios of waste

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Fig. 4 The Sile landfill and the Omerli reservoir

2000

2004

Fig. 5 Changes at the Sile landfill and peripheries

disposal, urban growth and land evaluation might be generated. The potential risks to environment and community over time can be visualized for taking rapid counter-measures.

References 1. Kaya S, ¸ Curran PJ (2006) Monitoring urban growth on the European side of the Istanbul metropolitan area: a case study. Int J Appl Earth Obs Geoinformation 8:18–25 2. Leao S, Bishop I, Evans D (2004) Spatial–temporal model for demand and allocation of waste landfills in growing urban regions. Comput Environ Urban Syst 28:353–385 3. Lu D, Mausel P, Brondizio E, Moran E (2003) Change detection techniques. Int J Remote Sens 25(12):2365–2407

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4. Musaoglu N, Tanik A, Kocabas V (2005) Identification of land-cover changes through image processing and associated impacts on water reservoir conditions. Environ Manag 35(2): 220–230 5. Seker DZ, Goksel C, Kabdasli S, Musaoglu N, Kaya S (2002) Environmental effects assessment of landfill sites by means of remote sensing imagery and GIS, ISWA World Environmental Congress and Exhibition, Appropriate Environmental and Solid Waste Management and Technologies for developing Countries, Istanbul, 8–12 July 8–12 6. Weber RW, Dunno GA (2001) Riparian vegetation mapping and image processing techniques, Hopi Indian Reservation, Arizona. Photogramm. Eng. Remote Sens. 67:179–89 7. Zhou S, Wang R, Huang MX, Landgraf D (2002) Detection of coastal saline land uses with multi-temporal landsat images in Shangyu City, China. Environ Manag 30(1):142–150

The Ethical Basis of Environmental Law Tapan Narayana

Abstract In the past decade and a half the question as to whether the environment itself deserves protection in addition to human health has come up quite often. Do the environmental laws reflect moral concerns? The answer must be ‘yes’, for without some basis in principle individual laws are no more than mere reactions to individual perceived problems lacking coherence, and likely to result in anomalies. The position of stewardship which is primarily human centered, accepts the need for a degree of resource conservation and environmental management based on notions of sustainable development and intergenerational equity. Moral issues do play an important role but by no means decisive, part in the creation and formulation of the law. The concept of sustainable development is an acceptable moral basis for environmental protection and regulation for many people. Our ethics can only be human centered. The concept of nature’s rights is no more than a fiction. Many human centered values are capable of being elaborated in ways which benefit environmental protection, although these may result only in the protection of aspects of the environment that are considered for human wellbeing.

1 Introduction Environmental ethics considers the ethical relationship between human beings and the natural environment. It exerts influence on a large number of disciplines including law, sociology, theology, economics and geography. Environmental ethics is a sub section of environmental philosophy, which includes environmental aesthetics, environmental theology and all the branches of philosophical investigation. The environmental regulation in different countries of the world focus on having law’s that provides the framework for the orderly management of the changing use of

T. Narayana (B) Hidayatullah National Law University, Raipur, Chhattisgarh, India e-mail: [email protected]

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land, and in public health law which is exclusively concerned with the protection of human beings. In the past decade and a half the question as to whether the environment itself deserves protection in addition to human health has come up quite often. But the question that often arises is whether the environmental laws reflect moral concerns. The answer must be ‘yes’, for without some basis in principle individual laws are no more than mere reactions to individual perceived problems lacking coherence, and likely to result in anomalies. Laws principles and moral precepts do not exist as hierarchies but, interact fluidly. Through my paper I would explore the subtle link between moral principles and law. Then my paper would go on to deal with the legal principles in environmental laws that have evolved in the course of time. I would deal with the idea of sustainable development, the precautionary principle, and the polluter pays principle. These were the most important principles that evolved with respect to environmental laws. They were also supplemented by other subsidiary principles that I would explain in the due course of my paper. I would also discuss relevant portions of some of the important reports like the Brundtland Report. My aim has been to sum up the evolution of the environmental laws with changing times.

2 Moral Basis for the Law It is often tempting to think of the law as being based on principles, which are themselves, derived from moral precepts: tempting but unsatisfactory, for what may be morally desirable is often not translated into law. Laws principles and moral precepts do not exist as a hierarchy, but interact fluidly. Even this model assumes that there is a moral basis for the law. Because of the diversity in the world with regard to religious, political and economic systems, there are different perceptions of the environment reflecting moral concerns. It ranges from intense utilitarianism through to the polar opposite of deep ecology. These moral positions are classified as anthropocentrism, enlightened anthropocentrism, extended anthropocentrism, non-anthropocentric individualism, concern for animal welfare, biocentrism, ecocentrism, land ethics, and deep ecology [1]. Human-centered utilitarianism is the least environmentally concerned moral viewpoint. It stresses on achieving the greatest happiness of the greatest number of humans. Those who believe in this viewpoint are economic liberals who are desirous of economic growth with an unregulated free market. Stewardship is a concept that is close to the above-mentioned position. It is primarily anthropocentric but accepting the fact that there is a need for a degree of resource conservation and environmental management based on sustainable development. But this viewpoint is resistant towards according a moral significance to non-human entities. Nature receives protection because resources need to be protected for the future generations. Biocentrism is also concerned with resource conservation but they have a restrictive attitude towards economic development. Animals and plants were to seen to

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have rights, often with the collective interests of all biota being give preference over the individual interests of species and individual specimens. Deep ecology is the most holistic and preservationist position, opposed to economic growth, favoring reduced use of natural resources and human populations. People never adhered to one point of view and had different moral perceptions. The four viewpoints that I mentioned represents the broadly recognizable, widely held points of view and moral perceptions with regard to the environment. Thus it appears fruitless to search for a single, unified, morally imperative basis for the law. Law and morality are different entities and simple because a matter is regarded as generally morally desirable does not mean that it will be translated into law. In the case of environment moral desirables can become legal actualities only when there is (a) a generally agreed social, political, and scientific, perception, of the existence of a problem, (b) a traceability of that problem to a particular cause, (c) an economic justification for taking action, (d) a sufficient body of social and political feeling that action should be taken. Moral issues do play an important role in the creation and formulation of law but not a decisive one. Many people find stewardship notions to be an acceptable moral basis for environmental protection and regulation. This recognizes that human beings as purposive, self-aware creatures have during our comparatively short time on this planet developed a collective power to alter drastically and dramatically in a way other living things cannot. To that extent we are separate from the rest of the natural order and our ethics can only be human centered [1]. The concept of nature’s right is no more than a fiction. Not every one accepts the inevitability of an anthropocentric environmental morality. Catherine Redgwell in her contribution to Human Rights Approaches to Environmental Protection (‘Life, The Universe and Everything: A critique of Anthropocentric Rights’) argued that the moral basis for environmental law need not be exclusively human centered, and that there can be additional moral underpinnings based on recognizing that other biotic and a biotic entities have a degree of moral status [2]. This may come about because, for example, we recognize that status as being as inherent as our own, arising from the simple fact that we all share a common existence, or may be because some religious impulse forces the conclusion that everything shares in the status of being created.

3 Sustainable Development Humanity’s numbers, styles of living and needs for adequate provision of food, shelter, employment, recreation, and that elusive concept ‘quality of life’, have to be considered globally and not in isolation, and in relation to the ability of the planet and its atmosphere to meet the demands made upon it. It is in this context that the concept of ‘sustainable development’ emerges. The World Conservation Strategy argued that [6]: ‘development and conservation are equally necessary for our survival’ and the report of the World Commission on Environment and Development

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(Brundtland Commission), Our Common Future (1987) [8] argued that sustainable development means global economic development sufficient to meet current needs while allowing future generations to achieve their needs.

4 The Relationship with Environmental Economics Sustainable development is a concept of rising real incomes coupled with increases in educational standards, the enhanced health of individuals and communities and improvements in the general quality of life. The point that is driven home is that the environment resources are not for free. Planning and forecasting is done over both the medium and long term timescales. The concept is based on three key ideas, namely, ‘environment, futurity, and equity’. The future generations should be compensated for reductions brought about by the actions of the present generations [6, 7]. The concept does not pit ‘growth’ against ‘environment’, but rather accepts that in some cases environmental protection and conservation can promote growth in the economy, and also stresses that the real issue is not ‘growth or no growth’ but how growth is to be attained. Sustainable development involves taking a broad view of development that values the wellbeing of individuals, their freedom and self-respect, and stresses cooperation. The focus of the concept of sustainable development has been to achieve an intergenerational equity.

5 Further Legal Development There is a human right to have an environment adequate to support life and well being. Principles of intergenerational equity in the use of the environment and national resources should be adopted. The essential ecosystems and ecological processes of the biosphere should be subject to conservation, and the need to preserve biological diversity. Adequate standards of environmental protection should be adopted and the changes in the quality and use of environmental resources need to be monitored. An activity that may result in significant impact on the environment or use of its resources should be subject to environmental assessment of its effects before a decision is taken as to whether it should be allowed to proceed, and environmental impact assessment of its subsequent effects.

6 For the Future ‘Sustainability’ is not just a principle environmental law, but also a basic principle of justice within society and between states. It calls for a greater flow of information so that all participants in the society can take a responsible part in decision taking.

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The state is seen as the strategic controller and supervisor of a system of public environmental order in which all individuals, groups and institutions in the society collaborate in achieving sustainable development. The natural systems have a degree of elasticity and resilience and thus humanity can continue to change and develop new ideas - but only up to the limit of the carrying capacity of the natural world. As a further thought on the future role of sustainable development, the arguments of those who see the principle not just as a goal to be achieved by law, but also as a process, needs to be noted. As a process sustainable development is a means of integrating environmental perspectives into economic, political and social policies so that all of these are directed towards, inter alia, the efficient use of resources, the management of demand and the minimization of environmental impact. These principles came out of the Earth Summit Conference at Rio (UNCED) that all those who are affected by environmental decision taking should be able to participate and that they should have effective remedies and redress for the wrongs they suffer as a result of environmental degradation [3].

7 The Precautionary Principle It is not always possible, and rarely easy to know what the environmental consequences may, at some unknown future date flow from particular uses of the environment and its resources, or from particular industrial, or agricultural processes nor the ways in which they may happen. This may be labelled the ‘principle of uncertainty’. The Rio Declaration states that where there are threats of serious or irreversible damage, lack of full scientific certainty shall not be used as a reason for postponing cost effective measures to prevent environmental degradation. The cost benefit equations should not be ignored while the government must remain committed to base its action on fact and not fantasy using the best scientific information available. A precipitate action on the basis of inadequate evidence is the wrong response.

8 The ‘Polluter Pays’ Principle Where a process is found to have unwanted consequences questions arise as to who should ‘pay’ for them. In some cases it may not be easy to identify a responsible individual and it may be considered to be economically and administratively more efficient in such circumstances to place the responsibility for, and costs of ‘clean up’ measures, on some other body. However there is a debate whether the ‘polluter pays’ principle is adequately satisfied if the polluter is simply allowed to treat pollution costs as mere overheads, which are then passed on to the customers as increased charges.

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This is a particular problem where a polluter is a large corporate organization and the ‘cost’ is in the form of a fine for an offence involving breach of environmental protection laws. There is an argument that fines convey no clear message that a corporate offence is socially intolerable, but may instead indicate that an offence is permissible provided a tariff is paid, thus reducing criminal law to an accounting exercise [4]. Alternative sanctions, which may be more appropriate, like enforcing corporate dissolution, disqualification from ability to undertake certain types of work for example, certain public contract activities; ‘stock dilution’ whereby a corporation is required to meet fines by issuing new shares equivalent in value to a deterrent level of fine, these shares being vested in some form of compensation fund. Corporate probation whereby corporations, which have offended, are required under supervision, to investigate and amend the ways which led to the offence. This might extend to requiring a polluter not just to introduce ‘state of the art’ anti pollution techniques but also to go further by developing new non-polluting technologies. Community service is another fallout by which a polluter might be required to set up a charitable or public service institution related to countering pollution. The application of ‘polluter pays’ principle is by no means a straightforward and non-contentious issue.

9 Conclusion The law must not only be well founded in terms of principles but there must also be a harmonization between legal and economic means of regulation. The government needs to ensure that its policies fit together in every sector and the policies should be based on harmonious set of principles rather than a clutter of expedients. The harmonization measures would work well only where the cost imposed on a polluting activity as clearly appreciated by all concerned, and where the incentive or penalty as the case may be is very accurately targeted. In 1992 the European commission proposed a punitive energy tax adding 14 pence to the price of a gallon of fuel by 2000 in order to drive down fuel consumption and cut CO2 emissions. Some such measures were also taken in the United Kingdom. The fuel duties were increased by 3% per annum in real terms so that consumption and emission levels were reduced. These measures have been seen more as a means to increase finances of the government and less a means of environmental protection. The introduction of the industrial energy tax aiming to encourage renewable energy production and efficient use of energy, tax relief on the use of ultra low sulphur petrol, lower vehicle excise duties for fuel efficient cars are some environmental protection measures. While it is not appropriate to examine the pros and cons of such policies, what is important is acceptance that legal regulation by itself is an insufficient means of environmental protection. Command and control strategies of regulation must be integrated with economic instruments.

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References 1. Alder J, Wilkinson D (1999) Environmental law and ethics. Macmillan, London 2. David H, Tim J, Jason L, Neil P, Paula de P (2002) Environmental law. Butterworths Lexis Nexis, London 3. Decleris M (2000) The law of sustainable development: General principles, Environment Directorate-General, Luxembourg, European Communities 4. Fisse B (1990) Sentencing options against corporations. 1 Criminal Law Forum 211 5. IUCN (1980) World Conservation Starategy, Living Resource Conservation for sustainable development. International union for conservation of nature and natural resoruces. 77p 6. Kerry Turner R, Pearce D, Bateman I (1994) Environmental economics: An elementary introduction. Harvester Wheatsheaf, New York 7. Pearce D, Markandya A, Barbier EB (1989) Blueprint for green economy, Earth Scan Publications Ltd., London 8. World Commission on Environment and Development (1987) Our common future, Oxford, Oxford University Press

The Creation of New Ways of Acting in the Water Administration Field – the Implementation of the EU-WFD in Sweden Petra Adolfsson

Abstract EU’s water framework directive (EU-WFD) demand geographical grouping of the administrative bodies in EU according to river basins [12]. In this paper we follow the implementation process in Sweden. The theoretical perspective is based on organizational theories, influenced by new institutionalism and sociology of translation. The study is based on observations of meeting between authorities and other actors in the west part of Sweden but also interviews with various actors taking part in the process. This paper shows that, this far, ways of working in order to establish cooperation differ among different local areas, e.g. the councils have adjusted their work depending on their interpretation of the existing situation in their own council. I claim that in one way we could say that old ways of acting, institutionalized action nets according to Czarniawska’s vocabulary, are questioned. New actions are taken in the field, replacing or complementing old actions. Actors try to see what actions that are needed, make sense of action taken and defend actions. Keywords Environment · Conservation · Water framework directive

1 Introduction The issue of water, or more specific clean drinking water is an issue debated globally, but has also implications in regional and local perspective; being important to flora and fauna but also human industrial production, energy production and the consumption of drinking water have environmental implications. The environmental impact related to water has been under discussion in EU (the European Union) for many years. According to the text of EU, the process of new EU water framework directive (EU-WFD) from the year 2000, has been going on for a decade. According P. Adolfsson (B) GRI, School of Business, Economics and Law, Göteborg University, Göteborg, Sweden e-mail: [email protected] Paper submitted for the ESS conference, Subtheme Integrated Water Resource Management, Cyprus, Feb. 2007

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_65,

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to the EU-WFD, river basins will be the basis of water management in all countries of the EU. In effect, the natural movement of water will determine how it will be administrated. This means that the Swedish authorities and other actors have to organize their work according to river basins instead of traditional organizational boundaries such as the administrative boundaries of local municipalities. The directive is based on periods of 6 years. The work includes: characterization of river basins (that is describing the watercourses), monitoring, objectives and norms, river basin management plans and operational programs of measures. The directive emphasizes cooperation and decision-making is to be executed after local actors have been consulted [12]. The water directive emphasizes an ecosystem perspective of water management in the sense that the natural flow of waters should be the basis of the administration [19, 16, 30]. The work related to all river basins in EU will undergo a cycle of 6 years including e.g. characterizing watercourses, goal setting, establishing action plans and monitoring programs. In the literature models are have been put forward about how cooperation and decisions should be manage in the river basin area e.g. the RESPECT model [14] och the CATCH-model [5]. The aim of both models is to handle conflicts and facilitate cooperation. Studies, from both EU and other countries in the world, have shown the importance of cooperation in the field of water administration (e.g. [34, 28]). Johnson et al. [17] claim that many cooperation projects in river basins fail because the local population needs, limits and restrictions are not taken into consideration. Huisman et al. [15] argue in their study that cooperation over national borders takes time and demands trust and voluntariness. In Sweden, a member of the European Union (EU), the environmental legislation is adjusted to the EU legislation. The legal system in Sweden has for many decades included environmental concern. It was initially a control based legal system but the last two decades there have been supplementary regulation forms based on cooperation [23, 11, 3]. Earlier studies of river basin management in Sweden suggest that the positive aspects of local participation are that it emphasizes democracy and legitimacy but also facilitates implementation and incorporates local knowledge into the process [18]. This paper is about organizational issues, that is actions and activities related to the EU-WFD in the west part of Sweden. It will highlight the new activities and actions that are performed in the process of the EU-WFD implementation in Sweden. It is a story of the striving for cooperation and the search for activities that the actors perceive as appropriate if we use March [26] vocabulary. The question this paper intends to analyze is: How are activities and actions connected when the EU-WFD is implemented in Sweden?

1.1 Disposition Next section will be a presentation of the theory used in the analysis of the field material and a description of how the field material was collected. After that the field material is presented, which is followed by a discussion based on the field material.

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2 Theoretical Influences In this paper a constructionist perspective is used to reveal the process of implementing EU-WFD in Sweden. According to the constructionist perspective there is no point in dividing our reality into nature and culture. The environment is therefore, in this paper, viewed simultaneously as a thing, the physical environment, and as ideas [7]. An idea travels through time and space and becomes part of a locality by the process of translation [4, 20, 7]. An idea is translated into a local context through action and materialisation and further on to new ideas [6]. This process includes both humans and non-humans, that is, entities able to act, and its understanding requires a performative perspective, where the meaning of words, things and actions is determined by their use in specific times and places. Therefore, a concept or a model does not have a single meaning that easily can be ‘diffused’. Instead, the meaning is created in a process of translation in the local context. In this paper the actors involved in the translation processes, e.g. where sustainable water management and river basin management are translated into e.g. new activities and classification systems. As Lindberg and Cazrniawska [22] claim, it is of vital importance to emphasize the actions, and not necessarily the actors, when conducting organizational studies (see also [10]). The focus will be on the new actions and activities that the translation of the EU-WFD generates. New activities and connections between actors arise and I will emphasize such activities and actions in order to be able to analyze the possibility that new nets of actions are created that may be the birth of new actors in the field of water management. Our surroundings and we are constantly changing, but the process of change can be fast or slow, which sometimes makes us see things as stable at a specific time. As Rottenburg shows, when describing the use of management systems such as TQM, new ideas or concepts can be seen as having life cycles. A concept like river basin management is observed by local actors who translate the concept into actions and documents. When these are apprehended as given and the ‘right’ way of thinking, the concept has been institutionalized. Later on it will probably be challenged and driven out of competition by other concepts and ideas presented as ‘new’, ‘modern’ and ‘logic’. Accordingly, actors do not necessary act according to logic of consequences as a rational perspective might expect. Instead, the actor act according to what he or she find appropriate (cf. [25, 26]). One way of acting is to imitate, that is to act like someone else but the reasons why you do it can differ, e.g. saving resources or achieving a desired identity. Nevertheless, imitation is about performance, it is not only to copy someone else [29]. The imitators act according to their conception of the situation, self-identity, and the identity of others. What method an organization will imitate and translate is then related to the identity of the organization. In the analysis I will also use the concept of boundary objects. It was used by Star and Griesemer [31] in their story about the creation of a museum. The boundary objects are objects that are solid, and can therefore maintain their identity when treated from different points of view, but also adaptable enough to be attractive to the representatives of those differing viewpoints. Star and Griesemer give examples of stuffed animals that were to populate Natural History Museums, which for scientists

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were objects of science, for businessmen objects of attraction, for local patriots the relics of the region and so on and so forth. In order to connect actors and activities the importance of non-human entities can not by forehand be neglected, instead it is vital to include them in studies of organizing issues (e.g. [20, 10, 22]) In many studies of environmental issues the concept of boundary object and boundary organization. Harvey and Chrisman [13] argue that the creation of boundary objects by negotiations between groups is important since the object it self has a vital validity and strength in a great deal of the society. The authors emphasize that the constructed object as its best is only stable enough for a moment and is object of renegotiations. Harvey och Chrisman’s study about the use of GIS (geographical information system) shows that there was always a boundary object involved when the negotiations, on a local solution on how GIS will be used, was wound up. The boundary object GIS contains several boundary objects. In their study of wetlands in US, an organization created a standard for classification of wetlands by scientific consensus and institutional agreements. The classification system became a boundary object by constituting the link between the different groups when they produce, use and distribute data from the database based on the classification system. Knowledge about the system means to be part of a network; to know certain persons, to know certain models and to know analyzing soft ware. In this way groups are connected to each other and opponents are excluded. The boundary objects work as both separators and integrators since they offer translations between groups.

3 Method Narratives are a form of knowledge and a way of communicate [24, 9]. Organization researchers handle a lot of various forms of narratives. The researchers collect narratives from the field and try to understand other authors’ narratives. These narratives are the basis for the researcher’s own story [32]. The paper is based on documents, interviews and observations of actors representing national, regional and local authorities but also local actors such as farmers. The focus has been on the work in one of the five created water districts in Sweden. The documents are regulatory documents from e.g. EU but also texts from different actors in Sweden, e.g. web sites and power point presentations. In these documents the actors present stories on actors, actions, ways of working etc. that they hold as vital for the process. The observations are done with openness for new connections, or new ‘data’, which Latour [21] calls a symmetric anthropology. As Baszanger and Dodier [2] say, this is the opposite of an in beforehand coded procedure. The aim of the interviews has been to obtain the interlocutors’ detailed accounts for what has happened [8]. As I see it, the interviews are situations where stories from the field are collected [27]. Accordingly, it is not an “objective truth”, instead, it is that person’s story of how e.g. he or she attends meetings or uses a database.

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4 The EU-WFD in Sweden 4.1 The EU-WFD Comes to Sweden In Sweden an investigator was commissioned by the Swedish Government to investigate how the water framework directive was to be implemented in Swedish legislation. In 2002 the investigator presented his report. The Swedish Government took the investigation into account and decided that five new water authorities were to be established. The water authorities are new governmental institutions that have an official mission to implement the EU-WFD in Sweden. As a result, the water authorities have the overall responsibility of water conservation in each created district and there are no legal hierarchic differences between the five water authorities. The water authorities are connected to one county administration each. The approx. 20 county administrations in Sweden are the national governments’ representatives in the Swedish regions (counties). The legislation in Sweden regarding water had to be changed in order to fulfill the content of the EU legislation. One immediate change was to rewrite the instructions that were the basis of the work of the county administrations. But also new guidelines are under development regarding e.g. how to describe and characterize the watercourses. Accordingly, the county councils have been given a vital part of the process since the Swedish Government have decided to place the new water authorities at five of these councils and the rest of the councils are still responsible for the work related to the watercourses in each geographical area. The water authorities have one delegation each who act like board. The five delegations consist of representatives from the university, the county administrations in each district and others. There is also a wish to have municipality representatives in the delegations but the Swedish Association of Local Authorities and Regions have refused to elect representatives. The association finds the role of the delegations vague and the financial effects for actors like municipalities because of the delegations’ future decisions are not analyzed. Municipalities in Sweden have a far-reaching right of self-determination in issues relating to the planning of land and water. How the municipality planning process and the water directive based water planning cycle will be connected is still under discussion. The final legal status between the two legal systems has not been decided yet. The national government has appointed a few investigators who has reported on these and related issues. As a result, in 2004 the water authorities were established but some of the guidelines that were to be the basis of some essential parts of the work were not established and legal aspects such as the legal role of various actors had not been made clear. For example it was not decided if the delegations of the water authorities, the national government or some other actor would be responsible for accepting or rejecting the locally developed documents related to the EU-WFD.

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4.2 A Search for Cooperation For many decades there has also been another vital actor in the field of water management. Water conservation associations are municipalities, companies, interest groups such as the Federation of Swedish Farmers and other local actors that often work together in order to fulfill programs for monitoring the water quality of the local watercourses. For example, companies responsible for waste water treatment and drinking-water must have a license in order to carry out their activities. In Sweden these companies are most often owned by local municipalities which therefore often are members of water conservation associations. The extent of the monitoring programs is decided by the authorities for all activities that have an impact on the environment. One aspect that has been discussed is to what extent the existing monitoring programs can live up to the requirements of the EU-WFD. For example, there is a long tradition in Sweden of monitoring chemicals like phosphorus but have not monitored biological factors to the same extent which are emphasized in the EU-WFD. The water conservation associations can also have joint programs of measures in order to restore the local watercourses. They are nonprofit organization and work voluntarily. So far it differs to what extent the water conservation associations are taking part in the water directive process. In the western parts of Sweden, where there are about 30 associations and the area consist of a lot of forestry, fishing and farming, several associations have contacted the water authorities and said that they want to be vital local actors in the water directive process. In meetings with the associations of water conservation, one by one, the water authority has encouraged local initiatives for implementing the EU-WFD. The water authority has also presented how such initiative can look like by suggesting the associations to transform themselves into a local water council. According to the water authority, local water council can be local cooperative partner when the characterizing will be carried out. One requirement is that the local water councils must have a wide representation of local actors such as companies, local authorities and interest groups. It is emphasized by the water authority that these local water councils can be local partners with great local knowledge. This knowledge is accentuated as vital when all watercourses will be characterized. For some existing associations this means that they have to include more interest groups in their organization in order to fulfill the requirements that the water authorities has put up. For example have two associations started such process which has resulted in two different suggestions of how the local water councils can be organized. The political acceptance of the suggested models has been highlighted. The water authorities cooperate in order to have the same work form when establishing cooperation with actors in each district. One course of action is to contact water conservation associations, and as mentioned above some of them have also contacted the water authorities, to see if there is an interest for being a vital partner in the working process, such as characterize the watercourses and develop programs of measures. This far, the way of working differs among the county administrations in Sweden. They have adjusted their work depending on their interpretation of the existing situation in their geographical area. For example county administrations

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have invited actors they find relevant to the work concerning water conservation and the EU-WDF. It has involved both large meetings to inform interested parties of the EU-WFD but also meetings with very few specific organizations represented. In turn these actors can invite relevant local actors in order to create a local water council in the area later on. Other country administrations, with many more existing water conservation associations in their geographical areas, have discussed the possibility to create water councils with the water conservation associations more directly e.g. in meetings. One aspect that has been recurrent in these meetings and discussions is how the future programs of measures will be financed. The programs of measures will focus on how to restore the watercourses to a status close to a situation where humans did not have any effects e.g. from waste water. The action which is needed can in other words be a heavy program for the local actors to accomplish. One solution that has been discussed, but not fully investigated by national authorities, is to raise the price of drinking-water etc. There have also been other suggestions of how the local work related to the EUWFD can be carried out. A lot of seminars have been conducted by various actors and reports have been written concerning such suggestions. In this way contacts have taken between different actors in the field. For example, the water authorities and the Association of Local Authorities and Regions have been given a joint seminar about the EU-WFD where different viewpoints have been discussed e.g. about roles and responsibilities, but also openings for how cooperation can be managed. The Swedish Water and Wastewater Association (SWWA) is one of the organizations that have suggested a similar local cooperation between local actors. SWWA claims that it is important that municipalities and companies that work with water and wastewater and other local actors must come together in an early stage of the process. If they do so, their local knowledge can be used. It is also a way to be able to take part of the important work of defining the goals of each local watercourse, which will be basis of the programs of measures later on. Also, the Federation of Swedish Farmers, has groups of farmers who cooperate in their local river basin area. The groups are based on voluntary work and each participant contribute as much as they can. The Federation also claims that modern science as well as the local knowledge of farmers and local citizens is needed for optimal solutions. In this process the work on databases are vital and representatives from the county councils, not only the water authorities, are involved in various working groups in order to create a system suitable not only for the reporting to the EU but also for the local work on water conservation. Thus, one aspect under consideration is to what extent the system could be developed in order to fulfill the needs for water conservation in general and not only connected to the EU reports. Then the aspects are how more detailed that the needs for the EU reports the system will be and how huge and complex the system can be in order to be managed by the existing data system and the potential users. The water authorities cooperate in order to characterize the watercourses and manage other classification aspects in the same way in order to have a national perspective on these issues and avoid local solutions that vary a lot, both in content and form. Pilot studies on various classification and measurement aspects are

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accomplished in the districts and joint groups are created in order to exchange experiences. But the aim is also to have a common way of acting towards other actors and avoiding mixed messages to local actors, since these actors can have relation to more that one district. This far the ways of working has in the west part of Sweden differ among the county councils in the area. The councils have adjusted their work depending on their interpretation of the existing situation in the area. For example has one county council invited actors it perceives as relevant for the conservation of water. Then these actors can involve relevant actors such as water conservation associations and discuss the possibility to create water councils. Another country council, with many more water conservation associations in its geographical area, has discussed the possibility to create water councils with the water conservation associations more directly.

5 Discussion In this paper I have elaborated on the ongoing process of translating a sustainable administration based on local participation in the field of water administration. The legal system is already based on environmental norms and classification systems and the new EU directive do not challenges that system as such even though they have to be modified. But still, the water directive changes the way various actors will be part of the process of defining objectives and take action in order to restore the water. The databases that the county councils are constructing are examples of how ideas on river basin management have been materialized. Nevertheless, cooperation is vital in the process and the water administration case shows that there is an ongoing translation process where new activities such as new form of meetings and cooperation when new databases are constructed. Interesting is also all the activities related to the definition of the river basins. Meeting between various actors with interest in local watercourses come together e.g. in order to discuss the possibility to construct local water councils. The concept of boundary object has received much attention in studies of technology, as it permits to understand how coherence can be developed and maintained across different but intersecting social worlds. Various objects may have different meanings in different social worlds, but they are recognizable in all these worlds, and are therefore a means of establishing commonalities. In the same way are the water authorities trying to build databases that will both fulfill the reporting to EU and be a useful tool for local actors in their daily work. The GIS technology, which they are obliged to use, have both trigger various actions and connect these actions to one another. As shown in an earlier study of water conservation in Sweden the way of working and measuring water quality were very much connected to various standardized systems and various boundary objects such as local water programs [1]. It was an institutionalized work process with fairly stable relationships between the parties. It was an established action net according to

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Czarniawska’s vocabulary [10]. In the case presented in this paper it is an ongoing process of creating a boundary object, that is the river basins and other boundary objects are also under construction, or at least are reconstructed from existing solutions, such as various databases become part of a new large database on water conservation. In the field of water administration, the standardized way of creating, storing, and presenting data also makes the aggregation of data possible. This is an aspect that is important to the actors involved. This has also organizational implications since it is easier to market the system as effective and useful to many various actors and thereby connect them to the system and the way of working. Regional, national, or even international organizations can collect data from local contexts, translate it into large databases, repackage and present it to various geographical areas: a city, a country, the EU. Nevertheless, the standardization process e.g. of how river basins should be characterized also gives the local actors room for local translations – why monitoring is conducted, for example, which can be for reasons other than legal ones. Various activities are connected e.g. large meetings in order to communicate with many actors about the need for a large database and local knowledge lead to contacts and meetings with few local participations e.g. where an associations of water conservation decides to transform into a local water council. Consequently, it is lot of activities and actions that are connected – it is an action net under construction. In this process traditional organizational boundaries sometimes blur and transform. An interesting issue is the new actor, the water authority, who can be described as an actor with legal status. At the same time it can be seen as an action-net-to-be since the activities and actions that others can relate to when talking about and define the water authority has just began. This situation has resulted in uncertainty regarding among the existing organizations (actors) since no one knows if their actions in the existing action nets in the field will be conducted by other (new or old) actors. Both authorities and local organizations put themselves out having contact and exchange experiences, and by doing so meaning and identity are also constructed. For example, some associations of water conservation prefer to act in order to be able to perform the actions presented as needed in the future by e.g. the water authority. In other words, as Lindberg and Czarniawska [22] claim, for researchers the importance of focusing on actions and not actors is vital. Actions construct the actor and not necessary the other way around. You do not necessarily become a local water council because you name yourself like that. Instead by contacting several local actors and invite them to meetings you start to perform the activities and actions that others will perceive as a local water council. The first associations that have started to perform these activities are seen as good examples and the model of local water council. The model can now start to travel through the field of water management. It is then translated in other local settings where the actors find slightly different actions appropriate. For example such local interpretations of the local water council model have resulted in different applications in areas close to each other geographically. In this sense the local water council has become one of the models of local participation and cooperation that have been translated into in Sweden during the implementation of the EU-WFD.

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As a conclusion, meetings between various actors are a vital action in the implementation of the EU-WFD in Sweden. In these meetings the identities of the existing actors are questioned but the meetings also serve as occasions where new activities can be discussed and actors can join the process where new boundary objects such as databases are created. The creation of such objects connects actions and actors and is part of the process where both new actors and actions arise and old actors and actions are reconstructed in the field of water administration. An interesting issue to follow in the future is to see if the local water councils can serve as a platform for both environmental and social assessment (see e.g. [33]).

References 1. Adolfsson P (2005) Environment’s many faces: On organizing and translating objects in stockholm. In: Czarniawska B, Sevón G (eds) Global ideas. Liber and Copenhagen Business School Press, Malmo 2. Baszanger I, Dodier N (1997) Ethnography: Relating the part to the whole. In: Silverman D (ed) Qualitative research. theory, method and practice. Sage, London 3. Borén T (1999) Källsortering för hållbar utveckling? Kretsloppssamhälle och förloppslandskap. Geographical Reports No 3, Stockholms Universitet, Stockholm 4. Callon M (1986) Some elements of a sociology of translation: Domestication of the scallops and the fishermen of St Brieu’s bay. In: Law J (ed) Power, action and beliefs. A new sociology of knowledge? Routledge and Kegan Paul, London 5. Collentine D et al (2002) CATCH: Decision support for stakeholders in catchment areas. Water Policy 4:447–463 6. Czarniawska B, Joerges B (1996) Travels of ideas. In: Czarniawska B, Sevón G (eds) Translating organizational change. Walter de Gruyter, Berlin 7. Czarniawska B, Sevón G (1996) Introduction. In: Czarniawska B, Sevón G (eds) Translating organizational change. Walter de Gruyter, Berlin 8. Czarniawska B (1992) Exploring complex organizations. A cultural perspective. Newbury Park, CA: SAGE 9. Czarniawska B (1998) A narrative approach to organization studies. Qualitative research methods series 43, SAGE university paper. SAGE Publications, London 10. Czarniawska B (2000) Att studera management som skapande och återskapande av handlingsnät. Nordiske Organisasjonsstudier 2(3):5–24 11. Dobers P (1997) Organising strategies of environmental control – towards a decentralisation of the Swedish environmental control repertoire. Nerenius & Santérus Förlag, Stockholm 12. EU (2000) 2000/06/EG Water framework directive 13. Harvey F, Chrisman N (1998) Boundary objects and social construction of GIS technology. Environ Plan A 30(9):1683–1694 14. Hofmann N, Mitchell B (1998) The RESPECT model: Evolving decision-making approaches in water management. Water Policy 1:341–355. Howe J, White I (2002) The potential implications of the European union water framework directive on domestic planning systems: A UK case study. Eur Plann Stud 10(8):1027–1038 15. Huisman P et al (2000) Transboundary cooperation in shared river basins: Experiences from the Rhine, Meuse and North Sea. Water Policy 2:83–97 16. Johansson B (2002) Friskt vatten och rena sjöar. Från VAV till Svenskt Vatten 1962–2002. Svenskt Vatten, Stockholm 17. Johnson N et al (2001) User participation in watershed management and research. Water Policy 3:507–520 18. Jonsson A, Lundqvist LJ (2006) På tal om vatten. Om vägen mot en hållbar vattenförvaltning. Vastra report 6, www.mistra.org, Sweden

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19. Kallis G, Butler D (2001) The EU water framework directive: Measures and implications. Water Policy 3:125–142 20. Latour B (1986) Powers of association. In: Law J (ed) Power, action and beliefs. A new sociology of knowledge? Routledge and Kegan Paul, London 21. Latour B (1987) Science in action. Harvard University Press, Cambridge, MA 22. Lindberg K, Czarniawska B (1996) Knotting the net of action, or organizing between organizations Scandinavian Journal of Management, 22(4):292–306 23. Lundqvist LJ (1996) Sweden. In: Christensen PM (eds) Governing the environment: Politics, policy and organization in the nordic countries. Nord 1996:5. Nordic Council of Ministers, Köpenhamn 24. Lyotard J-F (1979/97) The postmodern condition: A report on knowledge. Theory and history of literaturevol10. Manchester University Press, Manchester 25. March JG, Olsen JP (1989) Rediscovering institutions. The Free Press, New York 26. March JG (1991) How decisions happen in organizations. Hum-Comput Interact 6:95–117 27. Miller J, Glassner B (1997) The “Inside” and the “Outside”. Finding realities in interviews. In: Silverman D (ed) Qualitative research: Theory, method and practice. Sage, London 28. O’Hara SL (2000) Lessons from the past: water management in Central Asia. Water Policy 2:365–384 29. Sevon G (1996) Organizational imitation in identity transformation in: Czarniawska, Barbara & Guze Sevon (1996): Tranulating Organizational Change, Walter, de Gruyter, Berlin/New York 30. SOU (2002:105) Klart som vatten. Miljödepartementet, Stockholm 31. Star SL, Griesmer JR (1989) Institutional ecology, ‘translations’ and boundary objects: Amateurs and professionals in Berkley’s museum of vertebrate Zoology, 1907–39. Soc Stud Sci 19:387–420 32. Van Maanen J (1988) Tales from the field. Chicago University Press, Chicago 33. Vicente G, Partidário MR (2006) SEA- enhancing communication for better environmental decisions. Environ Impact Assess Rev 26:696–706 34. Vick RC (1999) Water focus: Region addresses legacy of toxic sediment. Pollut Eng 31(8): 23–24

Education for “Sense of Place” in a Wide, Complex Land. A Challenge for Environmental Education Andrew Brookes

Abstract Australia covers a large area, but its inhabitants live mostly in large European style cities on the coast. A large percentage of the population were born in other countries, and most Australians are descended from immigrants. While it is easy to argue that Australians must develop a sense of place if they are to understand and care about certain environmental issues, it is much more difficult to resolve what kinds of outdoor experiences Australians should have, what should be learned from such experiences, and how those experiences – and therefore that knowledge – should be distributed in the population. Where should Australians go, and what should they do when they get to there, to better understand environmental sustainability, in a country with so many environments? The paper argues that the situation in Australian can help illustrate some of the problems facing environmental sustainability when everyday life for much of a population is far removed from the sites of many environmental concerns and issues. As such, the case of Australia highlights both the potential importance of environmental education, and some limitations to universalist approaches to environmental sustainability. Keywords Education · Environment

1 Introduction I would like to begin this paper by thanking the conference organizers for providing a forum for interdisciplinary discussion about environmental challenges. My own work is broadly in the field of environmental education, and more specifically in environmental education in the out-of-doors. In this paper, I wish to describe some of the problems and challenges in this area. I welcome the opportunity to present these in such a diverse forum. My special interest is in the capacity of largely urban communities to respond knowledgably to non-urban environmental issues and concerns. I am interested in

A. Brookes (B) La Trobe University, Bendigo, VIC 3086, Australia e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_66,

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ways to improve the collective experience communities have of local and regional geography. This is a bold aim, and I should acknowledge straight away that this paper takes only a small step in that direction. Although environmental knowledge and understanding can be built in a community without requiring people to visit particular environments, it is far from decided that personal experience can be dispensed with entirely. Personal experiences can not only produce knowledge, but can also influence how individuals make connections with what they know; experiences might be thought of as linking people and knowledge through narratives. Patterns of geographical experiences within a community must be taken into account when appraising the capacity of any community to respond to environmental sustainability issues and challenges. I hypothesise that the more political power, economic activity, and cultural influences are concentrated in urban centres; the more attention must to be paid to a community’s capacity to respond intelligently and knowledgably to environmental issues located away from the centres or geographically dispersed. It might be helpful before discussing this topic to state some limitations and qualifications. I do not subscribe to the romantic notion that environmental sustainability simply requires enough individuals to have sufficient contact with “nature”. It is not difficult to find counter-examples to such a claim. For example, wars and other armed conflicts weave communities and places together in profound ways that might not be directed at environmental sustainability. I do not claim, either, that activities such as hunting, farming, fishing, or mountain climbing necessarily generate or distribute geographical knowledge that is certain to contribute to environmental sustainability. Moreover, in complex urban societies environmental sustainability will require more than distributed personal experience; it will require expert knowledge, and knowledge distributed through traditional education and media. Reports and experts are essential. What I do contend is that wherever power or influence over environments is distributed within a largely urban community – whether power is exercised through political activity, economic activity, or direct action – it would be reckless to disregard the question of how well the community knows and understands the environments it shapes, and in particular the contribution of personal experiences of those understandings. I will be discussing post-European settlement Australia, because settlement of Australia can be thought of as a large scale “experiment” on the effects of attempting to populate a continent about without knowing enough about it.

2 The Universal Educational Dilemma and Non-universal Environmental Education It is perhaps easy to find general agreement in favour of environmental education. Likewise, it is probably not difficult to find agreement in favour of providing city dwellers with more experiences of their country or region, or helping to ensure that what experiences they do have are directed towards understanding environmental sustainability. The difficult question, in environmental education as in all education, is which environmental education to choose from a multitude of possibilities,

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because time and money are limited. This is not a new problem. “What to leave out” has been the question of questions for much education since the nineteenth century: The question which we contend is of such transcendent moment, is not whether such knowledge is of worth, but what is it’s relative worth? When they have named certain advantages which a given course of study has secured them, persons are apt to assume they have justified themselves: quite forgetting that the adequateness of the advantages is the point to be judged. There is, perhaps, not a subject to which men [sic] devote attention that has not some value. ([22], p. 5)

Within debates about environmental sustainability, one central educational question is therefore: what environmental education is essential? In turn, what geographic experience is essential in a given community? Of course this question raises other questions. Who decides what is essential, and what qualifies them to decide? Perhaps the capacity of each generation to make sound decisions about environmental education depends, in part, on the quality of environmental education they themselves experienced. Environmental education it is also subject to tension, inherent in all educational debate, between maintaining cultural strengths and social strucutres on the one hand and providing for – perhaps driving – change on the other. I do not have much to say about these important questions in this paper, but will make one point. At the risk of stating the obvious, each of these considerations will take different forms in different countries and regions. Although I will concentrate on discussing the importance recognizing geographic diversity and complexity in environmental education curriculum, as an academic discussion, in the real world environmental education is always decided in particular political, cultural, social, and religious circumstances. I will not use “the environment” in this discussion. For my purposes there are many environments. I contend that the more one looks at the details of a particular environment – geographic, historical, social, and cultural – the clearer it becomes that many environmental education problems are not merely local or regional examples of global problems. Only some environmental issues and concerns are truly global. In environmental education, too often what is promoted as a universal solution turns out, on examination, to be the illegitimate imposition on one part of the world of ideas imported from somewhere else, often as a consequence of larger processes of colonisation, imperialism, or globalisation. Although I use Australian examples in what follows, some failures of universalist thinking applied to environmental education in Australia illustrate some more general flaws in universalising environmental education.

3 The Case of Australia The first British colony was established in Australia in 1788, as a penal colony.1 Those who know something about the history of European settlement of Australia 1 For more extended discussion see: Brookes, A. [5]. Gilbert White never came this far south. Naturalist knowledge and the limits of universalist environmental education. Can J Environ Educ 7(2):73–87. Brookes, A. (2006). Situationist outdoor education in the country of lost children.

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will know the story of how early settlers, mostly from Britain, struggled to make sense of a land very different from anything they had encountered previously. The naming and mapping of Australia by the British in the early 19th century reflected their struggles to make sense of land that did not fit their previous experience: [I]t was almost a commonplace among British residents that, in Australia, the laws of association seemed to be suspended. There seemed to be nothing that could accurately be named. There was, consequently, very little purchase for the imagination . . . ([7], pp. 42–43).

What was so distinctive about Australia? The environmental historian Bolton [2] has observed “[s]eldom were so few people in possession of such power to shape the environment of so much of the earth’s surface”; moreover, in comparison to other nations, “Australians have yet had less collective opportunity of getting to know their environment and learning how to come to terms with it” (p. 23). Paradoxically in a large land (8,000 km2 ) with a small population (20 million) almost since the time of first settlement, most Australians lived in cities. Nevertheless British occupancy – thinly spread – of the continent (apart from arid areas), was rapid. In 1815 most settlement was within 100 km of Sydney; within 50 years all of the land in eastern Australia that would be taken up for economic use had been [2]. However, over vast areas of the country attempts to establish close settlements, in the European manner, failed. European colonisation of Australia has from the outset been characterised by struggles to reconcile European categories and concepts with a landscape where experience confused even the most general metaphors, such as “tree” or “river”. Trees shed bark and limbs and refused to offer shade. Rivers failed to converge to the sea, and instead dispersed seasonal floodwaters across desert plains. Seasons failed to behave seasonally and pastures failed to sustain stock after one or two seasons – many native plants did not survive sheep grazing, and did not return even when a pasture was spelled [2]. Many Australian ecosystems reflect a very long evolutionary history and high levels of specialisation and diversity. But the colonisation of Australia has proceeded “influenced neither by the ideals of aristocratic taste nor by the sense of familiarity and appreciation which comes from generations of experience” [2].2 The biogeographical reasons why European colonists encountered such differences are well known. One hundred million years ago, Australia, together with Antarctica, Africa, South America and India was part of the southern supercontinent Gondwanaland. Around 45 million years ago, when mammals and flowering plants were beginning to evolve, Australia split away and began drifting to its present position [21]. Settlers in Australia thus encountered very different

Paper presented at the Widening horizons. Diversity in theoretical and critcial views of outdoor education. Retrieved. 2 This is not to suggest that there was universal indifference to the Australian landscape. On the contrary, some conservation impulses were evident from the beginning of colonisation [3], but these tended to derive from epistemologically narrow roots – aesthetic appreciation for the landscape or utilitarian concerns to preserve resources.

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evolutionary branches from those encountered in either Europe or the New World, and considerable diversity (Table 1). The history of early settlement is in part a story of struggles to come to terms with the incomprehensible nature of nature in Australia [15, 17], often (but not always) through attempts to apply imported ideas to the land, not to mention attempting to make it conform with European expectations and aesthetics [2]. The introduction of European farming practices, and non-indigenous species caused profound ecological disruption, the impacts of which continue to reverberate. Cattle and sheep, for example, compacted soil (Australia has no native hoofed animals), eliminated certain plants, and spread weeds [2, 14]. Rabbits when introduced multiplied in extraordinary numbers to devastating effect on native vegetation [10, 12].3 Table 1 Some comparisons between Canada (10 million km2 ) and Australia (7.7 million km2 ) Canada

Australia

Water

Most freshwater of any country

Driest continent – half the continent has water courses which are seasonal, mostly dry, and do not reach the sea 70% receives less than 500 mm per year 30% less than 200 mm year. Rainfall is highly variable from year to year Large areas have fewer than 25 days of rain annually

Number of flowering plants species (endemic %)

3,000 (3%)

20,000 (85%) 76 known extinctions 1,000 vulnerable or endangered

Number of mammals (endemic %)

194 (approx 1 or 2 species)

268 (84%) 19 known extinctions 43 endangered or vulnerable 25 introduced since white colonization

Birds (endemic %)

426 (?)

777 (45%) 20 known extinctions 50 endangered or vulnerable 32 introduced

Amphibians and reptiles (endemic %)

84 (?)

973 including 770 reptiles (approx 90%) 3 known extinctions 80 endangered or vulnerable

Forest cover

25%

5% (10% at time of white settlement)

Topography

varied

Mostly relatively flat

Sources: [13, 16] 3 Interpreting the impact of introduced species on Australian ecosystems is confounded by persistent beliefs that Australian species are inferior [10], and mistaken notions of evolution in terms of competition between species, rather than optimisation of ecosystems, and evolution as either a ladder of progress or cone of increasing diversity (rather than a branching tree). On the latter point see Gould [12].

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It might be worth emphasising here how different the Australian situation was from the earlier experiences of European colonisation of North America. Table one illustrates some important comparisons. I do not mean to give the impression that Australians have failed, in a simple way, to understand Australian environments. From the outset individuals and governments grappled with the problem of understanding, and, as is so often the case in environmental debate, an argument can be made that great strides have been taken in understanding Australian environments [19]. My argument is that it is far from certain that Australians understand enough. In circumstances in which so many Australians inhabit large cities on the east coast, and recreate only in selected environments, collective understanding of what is sometimes called “the bush” across the community, has, if anything, declined over the last century as cities have expanded, rural areas depopulated, and global economic and American cultural influences have increased. Even as a first approximation, it is evident that Australians’ collective experience of Australia, especially everyday experience, is predominantly urban [9, 11]; moreover, any rural areas frequented cannot be taken to “represent” the whole country. It is almost inevitable that individual Australians will have little or no experience of vast areas of the country. Relatively small numbers who do inhabit areas away from the large cities, including some aboriginal populations add complexity to the situation, but do not alter the overall picture I have described. Figures 1 and 2 illustrate how profoundly Australian populations are concentrated in certain areas, and how distant they are from many environments, even taking a very coarse measure of environmental diversity. Others details are revealed if one looks more closely. Australians shift locations, for economic or “lifestyle” reasons [6]. Many Australians were born in other countries (although nearly all immigrants live in the larger cities [8]. Some Australian

Fig 1 Estimated resident population, Australia [1] Source: Australian Bureau of Statistics

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Fig. 2 Broadscale ecological diversity (by vegetation class) [18]

occupy a more complex space centred on workplaces and residences, but including second homes, holidays, and recreation in rural areas. Thousands of Australians take to the roads after retirement from the workforce to travel slowly around the country (the so-called grey nomads). These details only add to the imperative to better understand what Australians know and understand of Australia, and how they know. We know far more about consumer habits and television watching preferences than we do about that question. It is one thing to observe that Australians are likely to be most familiar with urban environments together with certain limited rural areas, and might have experienced very little of vast areas of the country. It is quite another to consider what experiences might be most educationally defensible. At the level of individual initiatives – for example parents taking 6 months to “see Australia” with their children – where to go and what to do remains problematic. As a national initiative, supposing such a thing was possible, or as a thought experiment, which groups should experience what places? Several issues stand in front of any answer to that question.

4 Experiencing Places and Environmental Education – Some Issues 1. It is possible that what might be necessary is an education program that far exceeds in scale and scope what has been attempted previously, supported by research that has not been seriously contemplated. There is no rule that states

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that European occupation of Australia is bound to succeed, and so the possibility must be contemplated that environmental sustainability might be very difficult to achieve for a society where the reality of everyday life poorly represents geographical reality. At present, even obvious programs, such as systematic introductions to regions for new migrants, or education for new landholders are largely non-existent. Although there are many instances where sections of the Australian community have deliberately and more or less systematically developed particular knowledge and experience of some Australian environments (see, for example Brookes [5]), the overall patterns and distribution of experience has not been shaped by educational aims and purposes. Leaving aside rural economic activity, such as farming or mining, and continuing aboriginal occupation of some areas, tourism and recreation are stronger influences than education for sustainability on the construction of outdoor experiences for most Australians. Although tourism is superficially associated with education, it would require careful study to determine if tourism is a satisfactory vehicle for educational experiences that made a difference across communities, and not just to more or less random individuals. Although it is normal in English to speak of “seeing” as knowing, there are as many ways of “knowing” a geographical area as there are ways of experiencing it. Much work remains to be done to study relationships between forms of experience – and acquiring knowledge. Not every experience will produce knowledge that supports environmental sustainability. Experiential environmental education programs in Australia face major logistic problems, because of time and distance. While there may be no need for many Australians to traverse some desert areas, for example, the basin of the Murray-Darling river system, which supports a large proportion of Australia’s agriculture, extends for several thousand kilometres. Which Australians should have an understanding of that region, and how should knowledge of the region be divided up? It is possible that such concentrated populations (as Australia has) occupying such a large, diverse area (as Australia) is inherently unsustainable for epistemological and ontological reasons. As a generalization, more attention in Australian environmental education has been focussed on individual learning than on the questions of distribution: who should experience what area, and what areas “need” to be known by a section of the population. Arguably the problem of environmental education becomes more complex and difficult when it moves away from universalist forms. As a generalization, environmental education has tended to universalise experience of place. “A sense of place”, as a romantic ideal, might be achieved for many Australians by well-crafted holidays or recreational experienced. This may contribute to the psychological health of individuals, but not to the problem of distributing specific geographic knowledge in the community. Indeed, the preferred sites for neo-romantic experiences might be quite different from the places that need to be known for environmental sustainability. Bringing Australians “closer to nature” is not the same thing as embedding specific knowledge and understandings of Australian environments in Australian communities.

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7. Deeply embedded cultural tendencies may make it difficult to shape experiences premised on understanding the land. For example, I have found evidence of a militaristic epistemology in some forms of outdoor recreation. What I have called an “Anglo military epistemology” values personal attributes (character), training, and equipment above local knowledge. It is an epistemology based on fighting wars on foreign soil (the example of allied forces landing at Gallipoli is hard to go past), rather than geographical knowledge. If anything, it is epistemology designed to get around a lack of local knowledge. 8. Other universalisms, such as ecological principles, or concepts such as biodiversity, emphasise generalization rather than attention to the specifics of diversity and complexity.

5 Concluding Remarks The situation I have so briefly described in Australia is not the same as situations elsewhere. It is the differences between situations that environmental education must engage with, and perhaps marks a point of departure for environmental education from more universalist forms of education. Environmental problems and issues in Australia, can be seen as at least partly connected to failures to properly understand Australian environments. I suspect the same is true elsewhere; only the details will be different. The Australian experience illustrates some limitations of the universalist epistemologies which have travelled the globe firstly through British imperialism, and more lately through globalization. Acknowledgements This paper was prepared with the support of outside study leave from La Trobe University

References 1. Australian Bureau of Statistics (2003) Year book Australia. Population, population distribution. Retrieved January 20, 2006, from http://www.abs.gov.au/AUSSTATS/[email protected]/ Lookup/361F400BCE3AB8ACCA256CAE00053FA4 2. Bolton G (1992) Spoils and spoilers: a history of Australians shaping their environment, 2nd edn. Allen & Unwin, North Sydney 3. Bonyhady T (2000) The colonial earth. Melbourne University Press, Melbourne 4. Brookes A (2002) Gilbert White never cam this far south. Naturalist knowledge and limits of universalist environmental education. Can J Environ Educ 7(2):73–87 5. Brookes A (2002) Lost in the Australian bush: Outdoor education as curriculum. J Curriculum Stud 34(4):405–425 6. Burnley I, Murphy P (2004) Sea change: movement from metropolitan to arcadian Australia. UNSW Press, Sydney 7. Carter P (1988) The road to Botany Bay: an exploration of landscape and history. Alfred A. Knopf, New York 8. Castles S, Miller MJ (1998) The age of migration. International population movements in the modern world, 2nd edn. Macmillan, London 9. Day D (1997) Claiming a continent: a new history of Australia. Angus and Robertson, Sydney

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10. Flannery T (1994) The future eaters. Reed New Holland, Sydney 11. Forster C (1995) Australian cities: continuity and change. Oxford University Press, Melbourne 12. Gould SJ (1991) Wonderful life: The Burgess Shale and the nature of history. Penguin, Harmondsworth 13. Government of Canada (1996) The state of Canada’s environment 1996. Government of Canada, Ottawa 14. Low T (1999) Feral future. The untold story of Australia’s exotic invaders. Penguin Viking, Ringwood, VIC 15. Martin S (1993) A new land: European perceptions of Australia 1788–1850. Allen & Unwin, St Leonards 16. McLennan W (1998) 1998 Pocket year book Australia. Australian Bureau of Statistics, Canberra 17. Moyal AM (1976) Scientists in nineteenth century Australia: A documentary history. Cassell, Melbourne 18. National Land and Water Resources Audit (2001) Major vegetation groups. Retrieved 11 November 2005, from http://audit.ea.gov.au/ANRA/vegetation/docs/Native_vegetation/ nat_veg_fig8_popup.cfm 19. Office of the Commissioner for the environment (1992) 1991 state of the environment report: agriculture and Victoria’s environment resource report. Melbourne 20. Shore WH (ed) (1994) The nature of nature. Harcourt Brace and Co., San Diego, CA 21. Smith JMB (1986) Biogeography of Australian flora and fauna. In Recher HF, Lunney D, Dunn I (eds) A natural legacy: ecology in Australia. Pergamon Press, Sydney, pp 14–30 22. Spencer H (1911). Essays on education and kindred subjects. Dent, London

The Humanly Dimension of Media that Affects Masses and Various TV Programmes Arma˘gan Gökçearslan

Abstract Although Turkey is living with serious economical, social and political problems and trying to cope with big crisis incoming in every 3–4 years, TV programs such as ‘Somebody is watching us’ (Biri bizi gözetliyor), ‘I’m getting married’ (Ben evleniyorum), ‘Second spring’ (˙Ikinci bahar), ‘Be my bride’ (Gelinim olur musun?), ‘Pop Star’ (Pop star), ‘Academy Turkey’ (Akademi Türkiye), ‘Super Lady’ (Süper lady) are very popular and watching by large amount of people with great interest. This is a conflicting condition and should be evaluated and questioned elaborately. What are the main reasons of providing these kinds of programs to the public over and over? What are the main consequences of imposing degenareted culture to the public through these kind of programs, in the short and long term? How media is placed among popular culture, mass culture and cultural imperialism. In this study, the answers of these questions are trying to seek with a critical manner and several proposals are presented. Keywords Media · TV programmes

1 Introduction Great effect size of the media in effecting individual and the society direct several academicians, sociologists, communication specialists and related individuals to think and research about this topic. Oskay, is the one of the academician working on this field. According to Oskay, Media is both the creator and the product of the system. Today, there is no family, but media is present. No school, but media is present. No church, but media is present. Formerly, socialization period of human being is shaped by family and peer groups, from birth to adulthood. Now, till death, we are socialized by the media. Media is guiding us, allow us to accept what the system is approving and to reject what the system is refused’ (Oskay, 2004). A. Gökçearslan (B) Department of Graphics, Hacettepe University, Beytepe, Ankara, Turkey e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_67,

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Despite these negative aspects, the media has constructive functions such as giving news and providing information to the public that should not be ignored. By being a part of popular culture, the media could not be considered as negative from beginning to end. In a sense, popular culture has a chance of reaching much more people or, masses. In spite of reaching much more people with congruent and beneficial manner, via poor quality and degenerated programs masses are being benumbed in order to gain more rating, and positive side of media could not be used. The explanation of ‘Public want these programs’ is a very easy proposition. Then, why the programs like ‘Somebody is watching us’ are accepted by the masses? Why large amount of people are spending many hours to watch these programs? Eren, approched the phenomenon differently, and answers these questions as follows; These programs are watching since they resemble our lives. All of us living in similar situations in our whole lives or several sections of our lives. There are boundaries placed by our immediate environment, our society or even by ourselves.These programs are watching by people feeling disturbance from these boundries. in their lives. People thinking that they have too many boundries feel relaxed when they compare themselves with participants living with too many and too harsh boundries in the environments existing in these kind of programs, and they are turning into continuous viewers (Eren, 2005).

Media should be questioned in all it’s aspects, good and bad sides, producers/tv programmers and viewers, governors and governed people... In this study, negative affects of media on masses will be investigated in terms of concepts like social environment and popular culture, culture of masses, culture imperialism by considering the programs such as ; “I’m Getting Married” (Ben Evleniyorum), “Second spring” (˙Ikinci Bahar) and “Somebody is watching Us” (Biri Bizi Gözetliyor). As a beginning, it would be more fruitful to provide background information about programs that are being critically explicated in this article. Our first program is ‘Somebody is watching us’ (SWU). SWU, adopted from the original program called ‘Taxi Orange’, is the first example of these kinds of programs in Turkey. SWU, is telecasted in ‘Show TV’, in 2001 for two season and then transferred to ‘Star TV’ for following three season, in 2002–2003. SWU, starts in the specially designed home together with 15 people, selected among 15.000 people, declared by the producers. SWU home, furnished with elegant style, can be considered as comfortable and endowed by countless cameras and microphones. Whether, shower baths and restrooms have cameras or not is unclear, but there are no records related with these places. One can argue that ‘if there are recordsof these places, they may well be used for prevententing participants talk against to program/producers, even after completion. In order to live in SWU home, it is necessary to gain money by working as a taxi driver. There are also cameras in the taxi. Except for driving taxi, its forbidden to leave home. With the votes of viewers, in every week, one participant is elected as ‘the first’. The votes are also determine the participants that are not being sifted/disqualified (protected group). Premier of the week, has a right to sift one of the participants outside of the protected group. At the end of the 14 weeks, remaining participant is the winner of the program and get the bonus.

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‘We are getting married’, telecasted in 2003, at Show TV, is a program that occuring two different flats, together with 9 females and 3 males or 3 females and 9 males. The program lasting 8 weeks. Competitors are grouped in two different flats, and they are not allowed to get out during the program. Main theme of the program depends on the selection of males by females, or selection of females by males, resembling a type of ‘arranged marriage’. Every week, one of the competitors, with the votes of the viewers, elected as the premier. The premier of the week, has a right to eliminate one of the participants which are not protected by the votes of the viewers. The program will end with the marriage and the winning couple will get big awards like flat, car, honeymoon vacation, time share. ‘Second Spring’ is a program prepared in quite similar format of ‘We’are getting married’, just with one difference, the participants of ‘Second Spring’ program participants’ age are more mature, generally they are around their fourties. One of the main reason of liking of these kind of programs by the puplic could be shaping of the program by the votes of the public. This condition, allow viewers to interact with the TV program. After these programs, similar other programsa re produced. ‘Be my bride’, telecasted in 2004, at Show TV, is a kind of ‘arranged marriage’ program but selection committe is composed of mother-in-laws. ‘Could I say mom to you’ is a program telecasted at ‘Kanal D’, in 2005, again a type of ‘arranged marriage’ program and turning into mother-in-law, bride and groom triangle. ‘Pop Star’, adopted from one of the British programs, telecasted in 2003 first at Kanal D, later at Star TV, ‘Academy Turkey’ telecasted in 2004, at A TV, and ‘Super Lady’ telecasted in 2006, at A TV; are the programs could be considered as different versions of the SWU, and ‘We are gettin married’. ‘Pop Star’, ‘Academy Turkey’ and ‘Super Lady’ are the programs that their competitors performances are evaluated by the juries composing of famous people. At the end of the program, one competitor is elected as a premier by the votes of the viewers. The big award is being a famous singer, player or model. Firstly, it is necessary to look for the answer of the questions “What is media?” and “What is it for?” The term “Media” is the short way of an English idiom “Mass Media”. It means “Mass Materials” or “Mass Communication Materials” [22]. Newspapers, magazines, radio and televisions are qualified with the media terms [20]. When there is mass materials and mass communication, there is inevitably ‘masses’ influencing from this communication process [8]. It can’t deny the power of media on masses. Media can determine political formation in many countries, it can decide who will manage a country with which ideology, also can affect the life styles of people, eating habits, dreams and thoughts. In other words, media has power of directing societies. Why does media use this sanction power? The whole thing taking place under this sanction power is ‘economy’. It is known that the main reason of the war’s, which is made along the history, is economy. Because of that reason, especially “the western culture use media for creating a common consumption culture based on economy” [3]. When the subject is considered in terms marketing and business paradigms, according to the Rigel, “industry of media; bosses of media are practicing their daily and long-term decisions on the sleeping masses as an conscious leaders, without obeying any rule of democracy” [14].

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Media doesn’t form spontaneously. Human beings’ wishes about being informed are lay under the formation of media. Being well informed, is one of the main and important needs of human beings, but it is delivering negatively by media bosses (dominant power). As a result of that, masses who only want to be informed about the subject, encounter with a bombardment about violence, sex and magazines. All these bombardment reach to the masses with the way of television which is the most affective instrument of the media materials. “In Turkey, the average number of negative images that is broadcasted in a day is 3500” [2]. It should not be forgotten that most of the negative images is broadcasted by private television channels. The impressive expression of Nuri Colakoglu, the chairman of Radio Television Publishers Society and CNN Turk General Director, is Yet, our private channels are in the Wild West era (Zaman Newspaper 2001). TV, as an art and cultural expression material, “is also a ‘cultural dump’ according to Christopher Anderson” [4]. TV, as a culture conveyer on its own, do not want mental/cognitive participation through an original and critical interpretation in our developed cultural level perceptions. The only thing that is expected from TV viewer is superficial participation [13].

It is an important factor for forming a consumption society and to benumb the masses, that TV’s being a good amusement material besides being informed. The first step is “making the masses addict of TV and let them go under the effect area of this visual magician” [10]. Masses are becoming addict with the mediating of TV programs which don’t have any deepness. These programs are the reflection of the ordinary lives of ordinary people to the screen. According to Williams “most of the TV programs are the extension of daily ordinary speeches” [17]. “Shortly TV is the extension of ordinary, known senses and interests of people on the screen” [11, p. 12]. Television has also a negative effect on family structure. Although television draws a well – designed picture by gathering family members together in front of the screen, it increases the emotional distance. Family members who breath the same air in the same place are becoming stranger to each other. “ People sharing the same house may not know the problems of the family members as they know the problems of the soap operas that they watch or the private life of a football player and problems about him” [3]. Another problem arouses when the family members desire to watch different programs. At the end of this conflict, the family members have their own television and everyone watches their own television program in their own rooms. This situation leads to not only an unnecessary consumption but also build walls between the family members. Programs like SWU, ‘We are getting married’ and ‘Second Spring’ are a part of popular culture. But, what is the meaning of this concept that is encountered in every aspect of daily life? According to Dictonnarire Lorousse, popular means “ something appeals to the pleasure of society, huge number of people whose cultural level is mostly low and something which is liked and supported by society.” [6]. Popular culture is not absolutely “folk” culture. It is a different and new culture which is a combination of “elite” culture and “folk” culture. Popular culture is

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always criticized by intellectuals. However, nobody, even the intellectuals who criticize the popular culture, can not isolate himself completely from popular culture. Because popular culture surrounds every seconds and every place of life. Even a person who does not watch television at home may be influenced from popular culture. An intellectual person opposing and criticizing popular culture, could easily be faced with one of the popular culture products or stars while s/he is with his friends, in the bus, at lunch or waiting in a queue to pay her/his bills. When Ayse Arman [1] has asked “ The programs like ‘Pop star’, SWU, ‘ We are getting married’ are watched by the majority of society. What does it mean?” to Emre Kongar, a famous sociologist, in her interview; the answer of Emre Kongar is like that: The reality of era: Popular culture! And being opposed to it looks like being opposed to an earthquake. It is the same all over the world. Some of these programs are imported from abroad; to illustrate, Popstar. It comes from England; that is, from the cradle of democracy, where is seen as the most developed and the most modern country of the world. For this reason; when the effect of degeneration is taken into account, it is not only peculiar to Turkey. I say as sociologist; this development of popular culture can not be opposed to. Nobody can do this. Even a sociologist, a politician or a member of media! Programs such as ‘Popstar’, ‘SWU’, ‘We are getting married’ are guns. We need to use this gun to improve our cultural values, not to kill others (Hurriyet, 2004).

U. Oskay [13] saying these sentences about the ideological dimension of popular culture: “. . . it plugs the way of thinking that there is a different kind of living instead of real life; this diminishes offences, and the pain and shame of accepting the existent” Poor individual who can not find a way to exit and tries to afford with minimum price dreams in front of the screen, wastes time temporarily with the products of popular culture and forgets her/his pain. By behaving like that, the ideology of the dominant class is to prevent rebellion and struggle of poor individual; and then, the system works without a problem. Because of not taking ourselves from the popular or pop issues, we live so apart from the basic problems of human existence. Unfortunately, we are at the border of forgetting ourselves. In other words; because of this reason, we become stranger to ourselves [16].

Popular culture is a phenomenon that never ends and has continuity. How is the continuity of popular culture provided? May be the answer is hidden behind the fact that popular culture is “something like a candy”. You eat it, it tastes sweet, but it comes to an end. The business of popular culture is to plug new candy into your mouth before you finish previous one, in order to keep on its own continuity. If you start being addicted to the taste of candy; then, they will give a different candy which has a different taste. (http.gizliyuzler.roots.gen.tr/tasgeckismet/504.htm)

The chain of programs, started with SWU, has been followed by ‘ We are getting married’ ‘Be my bride’, ‘Second Spring’, ‘Pop Star’ ‘Academy Turkey’ ‘Super Lady‘ ‘Survivor’, Top Model with Deniz Akkaya (famous Turkish model) and ‘Turk Star’. The candy always exists but the dose and recipe of flavour are different (Fig. 1). These kind of programs have also affect negatively the moral values of society (Fig. 2).

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Fig. 1 The logos of programs mentioned above The impulse that directs to consider “good” superior than “bad” is morality. Morality is good behaviors of man towards his own individuality and also others’. In a common sense, it involves spiritual and mental duties and morality related to these duties that s/he feels as a must to follow [2].

When the relationship of competitors in mentioned programs is taken into account, a degenerated approach which is opposite of the morality being accepted as good by the society could be seen. How is it appropriate behaviour to the Turkish family norms that competitors, living in the same house and not acquinted with each other before, exploit each others’ sexuality behind the closed doors in order to stay one more week in the program? The viewpoint of society to the concepts of “good” and “bad” changes in the media, is expressed by Kerpeten like that (Fig. 3):

Fig. 2 Having been in prison because of murder could not have prevented Bayhan, participated in the competition Popstar, from supporting by public

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Fig. 3 Images from the funeral of Ata Turk, a competitor of ‘Be my bride’ and died from overdose. The image at the right shows Ata Turk and his mother “ Mother- in- law Semra” together For the sake of freedom of receiving information personal rights of individual are being raped, individual is reduced to material of news by being isolated from personal rights and qualities, dead person is starting to be much more valuable than living person and blood becomes much more important than rose and flower [10].

As Kerpeten states dead person has started to be much more valuable than living person. How has echoed the death of Ata Turk, competitors of ‘Be my bride’ on media. Related to this subject, Zeynep Gö˘gü¸s, column writer in Hurriyet Newspaper, expresses her opinion like that: The radio station which I was listening to on the way to work declared the tragic death of Ata as “a pleasant news for media in quotation mark”. Despite of being in quotation, according to me, using such a word, “pleasant”, for this kind of news is horrible. But, probably it was true. The death news of Ata was a gladiator, that has been put into the mouths of lions to be chopped and broken into pieces [9].

These kind of television programs change the concept of culture of nations, too. Now, culture is a property, is a product that is bought and sold. In addition to the disappeared variety, formulated, standardized and degenerated mass culture can be seen obviosuly in those days when the world is becoming a global village day by day. “Culture, that is formed by creativiy and spontaneity, then turning into an ordered product with its determined edge frames is the basic support of people who considers mass culture as a degenerated culture.” [18]. “Time Warner Turner, actives in more than 70 countries and includes in CNN, is one of the biggest media groups in the world.” [3]. This America-centered media group destroys authenticity by using culture imperialism and leads to spreading of hybrid culture to the under developed countries. A culturally hybrid individual can not decide how to act against to specific events. Becauses s/he owns a hybrid culture and s/he does not belong to either cultures. This formation, causing a contradiction for the individual, prevents individual from deciding correctly. So, individual takes shelter in the nearest culture to him in order not to be isolated [3].

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Furthermore, America based television channels yield a similar culture all over the world and creates a homogeneous mass culture that wears the same products, thinks the same ideas and consumes the same nourishment. Programs like “We are Getting Married”, “Second Spring” and “Someone is Watching Us” are narcotizing the masses along 24 hours and competitors are being subjects of the news. The most important element that makes these programs attractive is the wish of being famous. Like Andy Warhol said “everyone can be famous even for 3 minutes today” [5]. Ordinary human beings’ staying in a house along one month and being watched by millions of people like cavy mousses because of their wishes for being famous; must be evaluated within the ethical, legal and psychological dimensions. The events that lived in SWU house were turning around the love, violence, gossip and deciphered private life. Whole human beings couldn’t prevent themselves about making gossip without making any class difference. According to Gluckman “gossip makes the past alive, developed the feeling of being concern, if a group is closed the possibility of making gossip increases”. It is inevitable that people making gossip from back of each other if they are living in a closed house for a long time. The idea of attractiveness of gossip will attach the masses to the screen set the bosses into action and in the programs this dimension were strengthened. People always wonder about other persons’ lives. In these kinds of programs the individual rights of competitors are violated, and these programs must be evaluated regarding this subject. According to Zevkliler; Individuals are generally found in relation with others in permanent rates as being a part of society. Because of this relation, learning of some events and dimensions of other individuals’ lives is inevitable. Together with, no one wants to be learned fully by everyone [19].

The right of showing respect to private life, can define as a right, to continue their own existence freely without any external intervention [10]. When it is considered from the point of law; The private life of an individual forms from the secrets and the subjects that the person has a benefit by keeping them as secret. Individuals have a private life area helping to the development of the personality of an individual and no one can learn this area without the permission of that individual. Because of that violence of the communication confidentiality, learning of the secrets of individuals’ private and professional life, is contrary to the law [10].

Violence is one of the main phenomenon providing ratings to the programs. Pumping of the violence increases the ‘watching rates’ of these programs. The competitors who makes quarrel more than others, took more votes than the others. As a result, there is a kind of mass developed which saw that violence and quarrels are good materials of defense and makes premium. Also they reflect these kinds of negativity and didn’t avoid from practicing these negativities in their own lives. Another negative dimension of the programs containing violence, is making individuals insensitive to violence.

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Fig. 4 Tulin and Caner, a couple who can not marry in any way, from ‘We are getting married’

Along with the history, love is one of the holy feelings which were the subject of poets, art and literature. But these kinds of programs degenerated this holy feeling. In these programs couples becoming closed and live their feelings clearly, but this is contrary to the nature of love, so the feeling that couples live love or another feeling? Couples who come together in these programs, continue to their relations only not to be eliminated and to stay on the screens. So, it is necessary to insist on the reality that the thing that they live is not love (Fig. 4). The love story of Tülin and Caner (the couple of the ‘We are getting married’ program) is just a scenario lived with the insistence of media, in which big money involved in. Semercioglu, a column writer, expresses his opinions about these lovers, as below: Caner has been in hospital because of his love to Tulin, he is diabetic, Aydin has cried for his “dear friend”. People wants to scream by saying “Enough is enough!”. Aydin cries only for appearance; but, on the other hand, he tortures his “dear friend” by not saying whether Tulin has come or not. What makes me crazy is that housewives believe all this pack of nonsense. I regard the housewives, but the column writers believe it, too. All criticisms for the program are in the same direction; “what if Caner dies there, Aydin causes Caner being worse by increasing his excitement.” Don’t you understand that all those things are composed of just scenario? All of these programs are named as “unscripted show” all over the world; that is, they do not have written scenarios. But, in Turkey, a new scenario is written for each section. Program is directed by the demand of producer [15].

Competition is an indispensable aspect of life. But, persons’ eliminating each other in SWU house after being good friends and shared deeply senses, is a distorted situation. The masses watching this program could easily develop the opinion that being deprived of every valuable idea for competition is a true behavior and these programs constitute bad examples for the masses. In the places that individuals continuously let under watching, “it seems that personality develops slowly and individuals forcing to live together with other group of people, are tended to loose their creative cognitive abilities” [23]. In considering the intellectual profile of young people participating these programs, it seems that none of them reading books, magazines etc. Also, conversations among participants of SWU home are quite superficial. As a result, these kind of programs containing all these negativities, are viewed by masses along months. The true thing that must be done to intervene to this program by the Television Upper Committee (Televizyon Üst Kurulu), but it didn’t

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come true. These kind of programs have been moved to the National Assembly, but the result has not been taken. Yahya Akman, the chairman of petition commission of the Turkish Grand National Assembly, has declared that they receive a lot of personal complaints about these programs because of destroying the Turkish family structure and affecting the psychology of children and teenagers negatively [12]. Behaviors like turning face to your friends, always making quarrels, living and using sexuality till the end, living all the valuable ideas for your benefit and etc. transferred to the people who watch these programs, as the way of being strong and successful. This is the type of people that this epoch want and main thing is to suit this! According to Eren, in these kind of programs, people are transformed into first slaves, then drivers and then executioners. They are sifting their friends from the competition. They are living in a home together with many borders by loosing their freedom, and transformed to cage rats with their broken personalities. (Eren, 2005)

These kind of programs have a negative affects on attitudes and behaviours of the individuals and also play a significant role in diminishing quality of our lives. Hence, in order to prevent telecasting of these kind of programs necessary precautions should be taken. Television Upper Committee should get more responsibility in this subject matter. Non-governmental organizations and people sensitive to this topic should make their responses. To live in a better world, positive aspects of media should be revealed, and preparation of the quality programs leading the intellectual and cultural development of the public should be supported.

References 1. Arman A (2004) Popüler kültür kötü diyenin alnini kari¸slarim hürriyet gazetesi 2. Çali¸skaner Ö (2002) Medya’da Etik, Yayınlanmamı¸s Yüksek Lisans Tezi. Marmara Üniversitesi Sosyal Bilimler Enstitüsü, Istanbul 3. Cebeci K (2003) Kültürel Emperyalizm ve Medya, Yayınlanmamı¸s yüksek lisans tezi. Marmara Üniversitesi Sosyal Bilimler Enstitüsü, Istanbul 4. Cereci S (1992) Büyülü Kutu Büyülenmi¸s Toplum Sule ¸ Yay. ˙Istanbul 5. Demirer T, Akyol H (1996) Canavarla¸san Medya. Yorum Yay, ˙Istanbul 6. Dictonnarire Lorousse (1993–1994) Ansiklopedik Sözlük, Milliyet,s.1951 7. Düzel N (2004) Popstar’ı Kazanan Pavyona Dü¸ser. Ünsal Oskay’la Röportaj, Radikal Gazetesi 8. Erdo˘gan ˙I (2001) http://www.dorduncukuvvetmedya.com/arastirma/irfaner3.htm 9. Gö˘gü¸s Z (2005) Yeni Kahramanlar Hürriyet Gazetesi 10. Kerpeten R (2001) Özel Hayatın Tv Magazin Programlarına Yansıması ve Bu Yansımanın Hukuki, Etik Sınırları, yayınlanmamı¸s yüksek lisans tezi Marmara üniversitesi 11. Mutlu E (1999) Televizyon ve Toplum. T.R.T, Ankara 12. O˘ghan S¸ (2005) Gelin-Damat-Kaynana programları T.B.M.M’de Hürriyet Gazetesi 13. Oskay Ü (1981) Popüler Kültür Açısından Ça˘gda¸s Fantazya, Der yay. ˙Istanbul 14. Rigel N (1993) Medya Ninnileri, Der Yayınları, ˙Istanbul 15. Semercio˘glu C (2005) Hepsi Senaryo Hürriyet Gazetes 16. Sözen E (1997) Medyatik Hafıza, Tima¸s Yayınları, ˙Istanbul 17. Williams R (1992) Television: Technology and cultural form. London, University Press of New England

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18. Ülger G (2001) Medyanın Kültür Olu¸sturma ve Toplumu Yönlendirmede Kalite Olgusunu Kullanması, yayınlanmamı¸s doktora tezi Marmara üniversitesi 19. Zevkliler A (1995) Medeni Hukuk-Ki¸siler Hukuku, 4. Basım, Ankara 20. Öymen A (1993) Medya, Milliyet 21. Özcan Z (2001) TV’ler Vah¸si Batı Döneminde Zaman Gazetesi 22. Özer I (2001) http://www.byegm.gov.tr/SEM˙INERLER/denizli_iv/denizli-4.htm 23. Özsunay E (1979) Gerçek Ki¸silerin Hukuki Durumları, 4. Basım, ˙Istanbul

Engaging the Public in Environmental Decisions: Strategies for Environmental Education and Communication Martha C. Monroe

1 Introduction Environmental education and communication (EEC) includes a broad range of teaching methods, topics, audiences, and media channels all of which will be useful in moving our world toward sustainability. Experts in many nations have worked over the last 30 years to provide distinct definitions, guides, objectives, and standards that will help educators develop and evaluate effective programs. The North American Association for Environmental Education, for example, has developed four sets of guidelines for developing materials, for preparing environmental educators, for teaching youth, and for developing non-formal environmental education programs [12]. These guidelines are being converted into certification programs to help improve the profession. The majority of these resources, guidelines, and programs are designed for educators of youth. Indeed, the opportunities to influence the school curriculum and teacher preparation programs attract us to work with ministries of education to institutionalize environmental education. In these nations we have a chance to influence how youth perceive their environment and the skills they bring to decisions about sustainability. Where federal programs are not likely, out-of-school programs for youth through clubs and community centers offer substantial environmental education options. Youth-based environmental education programs provide information, build understanding, and improve skills needed for working together to achieve sustainability. The urgency of many environmental issues facing our planet, however, requires that we focus much of our environmental education efforts on adults. Community leaders, citizens, village chiefs, elected officials, religious leaders, homeowners, and nomadic herders all make decisions that affect the sustainability of their communities. For some issues and for some people, it may be enough to merely provide M.C. Monroe (B) School of Forest Resources and Conservation, University of Florida, PO Box 110410, Gainesville, FL 32611-0410, USA e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_68,

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information. When personal decisions must be made about which product to buy, for example, people seek find information, develop an opinion, and make a purchase. Or when a critical issue grips a community, such as the selection of a site for toxic waste storage, the development of a new road, or the designation of a wilderness area, the importance of the issue often compels people to voice opinions, find collaborators, develop solutions, and implement them. But more often than not, adults are too busy to seek information that does not directly pertain to their livelihood. They have many obligations and interests that fill their time. Attracting their attention is the first hurdle to sharing information about environmental issues. And unlike youth programs, where children are offered bias-free information, multiple points of view, and opportunities to make their own decisions, adults often claim that they just want to be told what to do. Environmental educators and communicators working with adults have a number of strategies they use to attract attention, provide information, build partnerships, make a new behavior popular, and convey answers (see Table 1). The first three types of education and communication activities (providing information, building understanding, and enhancing skills) presuppose that the educator knows what should be communicated and which skills are needed. In many cases this is true and there are many examples of these strategies operating around the world [6]. How should educators proceed when the answer is not certain?

Table 1 Formal and nonformal education strategies in environmental education and communication [9] Purpose To raise awareness, to inform To build understanding

Some formal youth education strategies

Some nonformal youth and adult education strategies

Textbook, lecture, video, film

Poster, brochure, sign, Public Service Announcement, news article, exhibit, website Workshop, presentation with discussion, charette, interactive website, simulation, case study, survey, focus group, interview Persuasion and social marketing strategies that use social norms, modeling, commitment, demonstrations, incentives, and prompts to encourage skills building and behavior change. Issue investigation Opportunities to conduct joint fact finding, mediation, alternative dispute resolution, negotiated rulemaking, adaptive collaborative management, action research

Discussion, role play, case study, experiment, game, field study

To build skills, to move toward a goal

Opportunities to build skills in group process, leadership, communication, critical thinking, cooperative learning, issue investigation

To transform, to build capacity, to resolve problems, to build civil society

Opportunities to define problems, design and select action projects, identify facts, and build skills in problem solving, communitybased problem solving and action taking.

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2 The Challenge of Creating Agreement on Environmental Issues Recent efforts to engage citizens in creating solutions to long-standing environmental challenges offer some suggestions for education and communication strategies that belong in this fourth category. The work of the Center for International Forestry Research in adaptive collaborative management, for example, suggests that a process of involving local communities in understanding the ecosystem management process, establishing indicators of expected change, and deciding how management should proceed is a successful strategy for involving citizens in community forest management [3]. The process requires building trust, involving experts and citizens in sharing perspectives and learning together, and time. Similarly, Collaborative Learning [4] is a strategy of engaging the public, through stakeholders, with experts in working through an issue, exploring options, collecting data, and learning about potential solutions. The greater the diversity of stakeholders represented at the table, conventional wisdom says, the more likely their decisions will stand the test of public scrutiny [15]. Good decisions are characterized by the amount and nature of learning that precedes and follows them, and that much of that learning is social learning—where groups of stakeholders and experts interact to explore the complexities of the system they are working in [7, 1]. Because decisions are generated from the group, however, one solution is not likely to work for another group. There is little generalizability because of the necessity of stakeholder participation in exploring, defining, and understanding their unique problem. There are many environmental issues, however, that are simply not urgent enough for people to voluntarily give the time required to participate in a collaborative working group. Perhaps people do not care enough; perhaps the costs or benefits are too distant to make the issue important enough. Perhaps there people recognize that the complexity of the issue is so great that they’ll never understand enough to make a significant contribution. Yet they do care that the decisions will respect the values they hold dear. There have been efforts to involve larger numbers of citizens in less intensive collaborative learning opportunities. These strategies are necessarily different in terms of the commitment of time and the anticipated outcome. In the United Kingdom, “deliberative and inclusionary processes or procedures,” DIPS, include citizen juries, roundtable discussions, and other forms of increasing engagement of the public in policy debates [14]. Community dinners, round tables, study circles, scenario workshops, charettes, and planning cells are other types of public engagement strategies [13]. A 25-year program of the Kettering Foundation, the National Issues Forum, allows citizens to learn, share opinions and then collects data for a report to Congress [8]. Each year, an issue book is designed to present three potential choices to a current social issue. A trained moderator introduces the choices in town meetings and engages the attendees in a discussion to consider the advantages and disadvantages of each. After this introduction, groups can decide to continue to explore solutions, or can complete a survey and conclude their participation. The

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Kettering Foundation compiles the results of all the surveys and presents the “public voice” to Congressional leaders. Many international documents talk about the importance of building civil society, public engagement, and social capital. The advantages of engaging the public in processes to make decisions are well documented in fields as diverse as conservation, international aid, political policy, community development, regional planning, and business. The question is how can we effectively involve the public, given their lack of information about complex environmental issues and the lack of time that plagues adult environmental education programs?

3 Guidelines for Education That Engages Adults in Environmental Issues For those environmental issues that do not yet have publicly accepted solutions, where citizens mildly care but their livelihoods are not threatened, and where it is not possible to attract a group of stakeholders to spend years working toward an agreement, educators and communicators need a new set of strategies. In keeping with the experiences of community-based adult education, or social learning, these new strategies should: 1. 2. 3. 4.

engage citizens and experts establish a neutral atmosphere allow for the transformation of the issue enable participants to share their concerns and feelings with decision makers

Allowing for citizens and experts to join forces recognizes that the issue is complex, that citizens must gain information in order to contribute to the decisionmaking process, and that the experts do not have all the answers. In many cases, scientific and economic expertise can only provide part of a solution. Cultural acceptability, community history, and social values play a role in determining an appropriate solution. Without educating the citizens, however, people will be contributing only impressions and biased opinions. The process must create informed judgment [16]. The recent unveiling of the Millennium Ecosystem Assessment project necessitated the interaction of ecologists and economists to develop future scenarios, but story-tellers were used to make that information understandable to non-experts [10]. Working across the barriers of expertise requires significant attention to the information and how it is communicated. A neutral atmosphere is necessary to both build trust and allow for learning to occur. In typical public gatherings to educate citizens in the United States, experts attempt to persuade and convince the audience of one solution. This practice can easily create defensive postures among those not predisposed to agree with this solution. Persuasive tactics makes it easy for opposing forces to draw battle lines and rally their supporters. This may not be the strategy that is most productive for public engagement.

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When experts and community leaders approach an issue without a solution in mind, it is easier to avoid using persuasive tactics. When experts and community leaders accept the possibility that their perception of the issue could change through interaction with the citizens, and that new ways of solving the problem may arise from this process, all participants are beginning on more equal footing. Allowing for the possibility of transformation is a useful criterion in the process of inviting citizens to learn and contribute to resolving a problem. While public engagement for the purpose of public education is laudable, people often want to know that their informed opinions and ideas will be shared with decision makers. Some strategy for doing so could be an important outcome of the process. In Nepal, community citizens created a video-letter to be shared with public officials [5]. In other examples the outcome of the deliberation is a public document that is circulated for comment.

4 A Case Study We have explored the use of community forums to engage the public in understanding an issue and provide their perspectives to community leaders. The issue is the use of woody biomass for local electricity production. The issue is complex, with aspects involving forest management and harvesting, transportation, estimates of supply and cost, engineering and power production, regional economic impact, land-use preferences, and deeply held values for local nature. The issue is further complicated by the fact that most Americans know very little about their energy sources [11]; a reliance on fossil fuels has successfully removed people from the sources and impacts of their energy. And finally, the issue is drawing attention as global attention on climate change suggests that all possible strategies for reducing our dependence on fossil fuels should be explored. The University of Florida is located in Gainesville Florida, a small but growing community of 120,000 [2] people in an agriculture and forested rural landscape. The forest industry operates a dozen of paper and plywood mills in the region and supplements their own harvest with privately owned pine plantations. The area surrounding Gainesville is rapidly developing, with a population increase of 9.5% in the last 5 years. Where communities are growing in forested areas, a number of sources of woody biomass are possible. The one-time use of cleared forests for home and road building generates waste wood. The on-going management of small, fragmented remaining forests near subdivisions requires thinning to reduce the risk of fire and to improve forest health. This also generates woody waste material. The South’s long growing season and homeowner’s preference for shady lots creates a steady supply of urban waste wood from trimming and storm damage. And finally, keeping the nearby private forests profitable could result in selling the woody residue from forest harvesting operations or provide competition for the pulp industry.

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The city commission believes an additional source of electrical power will be needed in 5–10 years and is entertaining the possibility of constructing a facility to use wood. A team of economists, engineers, foresters, and educators from the University of Florida offered to conduct a series of community forums to provide citizens with an opportunity to learn about the issues and ask questions. We created the following rules and guidelines for ourselves: 1. A group of experts would present information, reducing the perception that there is only one way to look at the issue. 2. Because the public does not know a lot about energy, an introduction to the issues will be needed. 3. Each expert would take about 5 min to explain some basic concepts associated with one aspect of the issue. 4. After a 20–30 min presentation, we will request questions from the audience. 5. An outside facilitator would introduce us and coordinate questions to reduce the appearance of bias. 6. Participants would be asked to complete pre- and post-forum surveys to help us understand how their perceptions changed, what questions they had that weren’t asked, and what features of a forum they believe are most useful. To encourage participants to return surveys, homemade cookies would be offered. We conducted six community forums in the evening and during lunch at different locations around Gainesville. From 4 to 60 people attended each, for a total of 172 participants. In all cases participants asked thoughtful and interesting questions. Surveys were completed by 108 participants. On reflection, we offer the following suggestions: 1. Despite knowing that the public knows little about energy, we were surprised how little the public knows about energy! We simplified our presentation several times and added explanations to provide background on forest management and the carbon cycle. 2. Academic experts do a fine job of answering questions but need some guidance on making presentations to the public. Slides were simplified and illustrated with photographs and graphics. Vocabulary was simplified. Analogies were provided. 3. It is possible to create an atmosphere conducive to social learning by doing a number of very specific things: a. Introducing the survey as a way the participants can teach the experts what is important and how they feel. b. Sincerely suggesting that the experts do not have the answer, only information to share. c. Avoid comments and phrases that suggest the experts know more than the citizens, such as “You’ve got to understand that. . .” and “My professional opinion is. . .”

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d. Inviting people to ask questions and responding warmly, “That’s a very important suggestion” or “Yes, some people believe that is a likely outcome. . .” e. If the presenters can’t answer some questions, offering to respond later by email, and doing so. f. Adopting a humble and self-effacing attitude while presenting. 4. Working with existing community clubs and adapting our presentation to their patterns and schedule was a better strategy to reach the public than holding our own forum at a library, although it can constrain the program to 30 min during lunch. 5. Publicity is important. If the issue is not currently being discussed by elected officials, it is not front page news, nor is it important enough for people to make a special trip for a meeting. The well attended meetings used current members, member newsletter, and radio and TV announcements to attract participants. 6. According to the self-reported survey results, participants gained information during the brief meeting (responses of “I have no idea” declined from 326 on a total of 10 questions to 91 on the same 10 questions, and self-reported assessment of knowledge improved. 7. The respondents believe that the following characteristics are very important for community meetings about local issues (reported in decreasing importance): a. b. c. d. e. f.

credible speakers an opportunity to ask questions of experts an opportunity to learn about issues an unbiased facilitator a comfortable atmosphere for contributing ideas an opportunity to share ideas with community leaders

Although we tried diligently to approach the topic of using wood for energy by exploring both advantages and disadvantages, the mere fact that we assembled this group of experts and could answer a limited set of questions was enough to suggest that we indeed promoted using wood for energy. We responded by claiming that we promote community discussions about using wood for energy, which aren’t helpful unless people have more information, which we are providing. But this response did not satisfy everyone. To advocate for using wood for energy, we reason, one must have a detailed plan. It is not enough to suggest that using wood is a good idea, the plan must describe the sources of wood, how they will be harvested and transported, the type of boiler and required fuel preparation, how the ask will be disposed, and how sustainable forest management will be assured. For a plan to be promoted, it must also have an estimate of the initial cost of the facility, the on-going cost of fuel and maintenance, and the price for which power could be sold. None of these details have been established or promoted, and many of them are contingent upon others. This is exactly where public input is needed. If, for example, it is clear that forest sustainability is a priority, a system could be developed where utility foresters would work with landowners and schedule timber stand improvement harvesting to keep

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the power plant in operation. Because our community forums are educational activities to assist in the development of such a plan, we are not advocating any particular outcome. Because the community will be able to participate in the development of this plan, the issue can be transformed as priorities are established and decisions made.

5 Summary Public participation comes in many sizes and shapes. It can be a formula-driven public hearing where public opinion is dismissed as being uninformed and the agency continues its business-as-usual. It can be a unique, lengthy, stakeholderdriven process to redefine a problem and create new solutions. Neither extreme is attractive to the majority of typical, busy, thoughtful-but-not-too-knowledgeable adults. Environmental educators and communicators need new strategies to conduct community-based environmental education for adults that engages them in decisions that affect sustainability. Our experience with community forums on wood to energy suggests that the following characteristics will help create an atmosphere conducive to learning and help people make a contribution to a decision: 1. Qualified experts make brief presentations and be available to answer questions 2. Speakers share multiple perspectives without aiming to persuade anyone 3. Speakers suggest the complexity of the issue requires thought and exploration, without suggesting they know the answer 4. The issue is portrayed not as a yes/no question but as a complex web of many decisions 5. The public is invited to share ideas and opinions 6. Participants have an opportunity to provide anonymous suggestions to the experts and opinions to the decision makers There are many venues that could meet these criteria. The Internet provides an attractive set of opportunities for public engagement that did not exist a decade ago. In our case, old-fashioned community meetings provided a ready audience and appropriate level of interaction. These strategies are critical to educate and engage adults in exploring environmental issues. The ability to achieve a more sustainable society may indeed rest on our ability to educate and motivate adults to participate in creating a new vision and new world.

References 1. Andrews E, Stevens M, Wise G (2002) A model of community-based environmental education. Chapter 10 In: Dietz T, Stern PC (eds), New tools for environmental protection: Education, information, and voluntary measures. National research council division of behavior and social sciences and education: Committee on the committee on the human dimensions of global change. National Academy Press, Washington, DC, pp 161–182

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2. City (2006) Official Website of the City of Gainesville, Florida, http://www. cityofgainesville.org/about/, accessed December 29, 2006 3. Colfer CJP (2005) The complex forest. communities, uncertainty,and adaptive collaborative management. Washington, DC, Resources for the future 4. Daniels SE, Walker GB (2001) Working through environmental conflict: The collaborative learning approach. Praeger, Westport, CT 5. Grieser M (2000) Participation. In: Day BA, Monroe MC (eds) Environmental education and communication for a sustainable world: Handbook for international practitioners. Academy for Educational Development, Washington, DC, pp 17–22 6. Jacobson SK, McDuff MD, Monroe MC (2006) Conservation education and outreach techniques. Oxford University Press, Oxford 7. Keen M, Brown VA, Dyball R (2005) Social learning: A new approach to environmental management. In: Keen M, Brown VA, Dyball R (eds) Social learning in environmental management: Towards a sustainable future. Earthscan, London 8. Matthews D (2006) Reviewing a review. Connections Summer:3–6 9. Monroe MC, Andrews E, Biedenweg K (unpublished manuscript). A framework for environmental education strategies, submitted to Applied Environmental Eduation and Communication 10. Ness, E. (2005) Four futures. Conserv Pract 6(4):20–27 11. Neetf – energy 12. North American Association for Environmental Education (NAAEE) (2000) Excellence in environmental education – Guidelines for learning (K–12). Washington, DC 13. Ogden L, Mahadev B, Dustin D, Gladwin H, Lipartito K, Rivera C, Taylor L (2003) A public engagement handbook for the Comprehensive everglades restoration planning process. A report to the National park service, everglades national park, by the Human Dimensions of the South Florida Environmental Group, Florida International University, Miami, FL 14. Owens S (2000) Commentary–Engaging the public: Information and deliberation in environmental policy. Environ Plann A 32:1141–1148 15. Wondolleck JM, Yaffee SL (2000) Making collaboration work: Lessons from innovations in natural resource management. Island Press, Washington, DC 16. Yankelovich D (1991) Coming to public judgment: Making democracy work in a complex world. Syracuse University Press, Syracuse, NY

Reconstruction of the Worldview as Strategy for Environmental Survival and Sustainability Ibrahim Shogar

What people do about their ecology depends on what they think about themselves in relation to things around them? Lynn White (1967)

Abstract The current ecological crisis is a matter of urgent global concern that seeks global solutions and sincere cooperation of nations and all parties of the human community: experts, policymakers, organizations and publics. The relevant solution, however, sought to be found associated with a precise identification and clear vision of root causes which, consequently, guide to the development of valid theories that capable to address the issue from its various dimensions. Although the distinguished scholars of various disciplines across the glob have been suggesting solutions of different kinds to the problem, they agree that the major part of environmental crisis comes from human actions. However, more significantly, scholars are in agreement that human actions are determined by his ideas and beliefs. This factor obviously identifies the strategic approach to deal with our ecological crisis; that is to rebuild our ideas and beliefs towards nature, i.e. reconstruction of the worldview. This work examines this hypothesis which asserts that the environmental crisis which experienced by mankind today are mainly due to his world view; i.e. misconception of the true relationship between man, nature and the ultimate truth. The study focuses on philosophical foundations of man- nature relationship, with objective of providing useful insights and perspectives that might contribute to uncover the root causes of our environmental crisis; and to establish a new united vision that capable to maintain the indispensable friendship of man and nature. To achieve these goals the study shall focus on the view that both man and nature are creatures of one Creator. However, nature has been made to serve man, not as a

I. Shogar (B) Kulliyyah of Science, International Islamic University Malaysia, Kuala Lumpur, Malaysia e-mail: [email protected], [email protected] Ibrahim Shogar is a researcher, author, and advisor, focused on Islamic philosophy of science. Currently he works as Assistant Professor of philosophy of science at “Kulliyyah of Science”, International Islamic University-Malaysia

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_69,

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machine dominated by human, but as “Amanah” or “Trust” which capable for utilization not destruction. Nature, according to this concept, has two main functions: to serve man in his physical needs, and to guide him morally to the right path, i.e. towards discovery of the Creator and His great wisdom in the natural phenomena. Keywords Nature · Environment · Sustainability · Reconstruction

1 Science, Technology and Ecological Crisis Over the course of time man has been developing many interconnected and validated ideas about the physical, biological and social worlds. Those ideas have enabled successive generations to achieve an increasingly comprehensive and reliable understanding of the world. The devices used to develop these ideas are particular ways of observing, thinking, and experimenting. Scientists, envisioned by originated systems in the natural world and inspired by biological engines of living creatures, have shown great efforts to create new scientific knowledge. When biochemists need complex molecular machines, they still have to borrow from cells of living creatures. Nonetheless, advanced molecular machines of living creatures have led biochemists to build nanomachines. Computer-aided design systems already have grown common, spurred by advances in computer technology. Biologists have achieved great advances because they have found chemical and physical explanations for every aspect of living cells yet studied, including their motion, growth, and reproduction[4].1 Scientists and engineers are of great concern to develop new theories and more advanced devices in various scientific disciplines. They started to deal with biological engineering in the same manner that they dealt with non-biological world. I.e. they are shifting from creation of devices and passive substances, to more complex patterns such as genetic engineering and biotechnology. Philosophers of science argue that the major purpose of science is to develop laws and theories to explain, predict, understand, and control the natural phenomena [3, 5].2 They suggest that the main objective of science is to control nature through its laws. Indeed, nature was the teacher of human and very foundation of his technology, which provided him with great insights to the natural phenomena, and imminent prospects of knowledge creation. However, the major difference between the natural process and human technology is “No waste or pollution in the natural process”. The natural property of self-regulation, self-maintenance and self-purification maintain almost an endless cycle of sustainable ecological balance. But, mankind unfortunately, has failed to learn this valuable lesson from nature. The immediate consequence of this failure was perfectly demonstrated by our current ecological crisis. New discoveries in biotechnology, for instance, have enabled man to master the living creatures, the entire genetic systems of organisms become known to the 1 Drexler, 2 See,

K. Eric, Engines of creation, http://www.foresight.org/EOC/EOC_Chapter_1.html for instance, Popper, Karl. R .[10],.

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scientists. But, this continuous scientific progress and creation of new technologies has produced its own challenges, it has brought up life in the planet earth into a critical turn. On 18 -NOV-1992, over 1,500 members of national, regional, and international science academies from various nations signed the “World Scientists’ Warning to Humanity”. The introduction to the warning declared that; “Human beings and the natural world are on a collision course. Human activities inflict harsh and often irreversible damage on the environment and on critical resources. If not checked, many of our current practices put at serious risk the future that we wish for human society, the plant and animal kingdoms, and may so alter the living world that it will be unable to sustain life in the manner that we know. Fundamental changes are urgent if we are to avoid the collision our present course will bring about”3 What type and nature of fundamental changes we need to avoid the collision with nature? That is the most important question of today. However, almost two decades has passed since this Warning was issued, and the situation at main time has worsened. The earth’s environment has further degenerated and life on it is threatened. Air quality is degrading and contributing to the destruction of ecosystems causing death to thousands of people every year. Global warming appears to be an established fact. It is having repercussions in the number of high intensity hurricanes, violent storms, tsunamis, etc. It is obvious man’s actions on nature have contributed to cause the environmental crisis. Man at main time no longer in a position to deny the escalating global crisis of environment and need for resolution. He also cannot deny his need to theories and suggestions concerning both the nature of crisis and the means for elimination, but what he can do? Various parties of this concern, scientists, philosophers and theologians, have suggested various approaches to answer this central question. Some scholars have held the view that; development of new sciences and technologies is the only strategy to meet the ecological challenges. But the opposite view feels that, although science and technology are necessary for the development, however, this suggestion seems to be unsuccessful due to two main factors: Firstly; this strategy characterized by mechanical view of the world, which considers nature as lifeless machine and encourages man to exploit nature. Therefore, the theory “more science and more technology” is not going to get us out of the present ecologic crisis.4 Secondly, this approach neglects the historical background of the current environmental problems. It does not consider the fundamental causes of the crises, instead it focuses on measures may produce new backlashes more serious than those they are designed to remedy [11].

3 http://www.religioustolerance.org/environment.htm 4 This is view held by many of contemporary scholars see, for instance, Professor Lyyn White who insisted: “I personally doubt that disastrous ecologic backlash can be avoided simply by applying to our problems more science and more technology. Our science and technology have grown out of Christian attitudes toward man’s relation to nature, which are almost universally held not only by Christians and neo-Christians but also by those who fondly regard themselves as post-Christians. White [11]

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With due consideration of these factors, other scholars have suggested that we should focus on the metaphysical foundations that underline modern technology and science [11]. That means we must rethink about our ideas instead of our actions.

2 The Worldview and Roots of Ecological Crisis Due to shortcomings associated with scientific view of the world; contemporary scholars are increasingly becoming supportive to the theologian perspective to deal with environmental problems.5 They held the view that our ecological crises are due to our beliefs towards nature. And because our actions are determined by our beliefs when we change our ideas towards nature the situation in environment will change as well. According to this approach our worldview is the root cause of our ecologic crises. Thus, the religion plays a crucial role to deal with environmental issues. The word “Worldview” in this context refers to the manner man answers the basic cosmic questions and interprets the world. It means the fundamental human assumptions towards man, nature and the ultimate being. Or it is set of presumptions which human holds, consciously or unconsciously, about the basic constructions of the world. To elaborate role of the worldview as strategy for environmental survival we review two of the earliest, yet original and reliable works in this concern. Namely, work of Professor Lynn White, entitled “The Historical Roots of Our Ecological Crisis”,6 written in 1967; and work of Professor Seyyed Hossein Nasr who contributed, since 1960s, with many topics in this field; latest of which was his remarkable work “Religion and the Order of Nature”7 published in 1996. Regarding the existing environmental crisis, both White and Nasr, stressed on two main points. First; both held the view that the contemporary scientific paradigm, dominated by a secularist worldview, have deeply contributed to cause ecologic crises in the modern world; therefore it bears, primarily, responsibility for the destruction of the environment. Second; they agree that the fundamental cause of the crises extends beyond this apparent cause to the worldview, which plays great role in shaping our attitude towards the natural world; therefore it can play a crucial role to ameliorate our ecological problems. The external crises of the natural environment,

5 According to Hossein Nasr even champions of secularism now speak of how significant the role of religion can be in averting a major global environmental catastrophes. “Religion and the Order of Nature” 6 This was an article written by Professor Lynn White, Jr. [11]. 7 Prof. Nasr, in his introductory remarks in this book, has pointed out that “This work follows our book Man and Nature, which comprised the text of our 1966 Rockefeller Lectures at the University of Chicago and which was one of the first works to predict the environmental crisis, and our 1981 Gifford Lectures, Knowledge and the Sacred, which itself was followed by The Need for a Sacred Science”. In this scholarly book Professor Nasr discusses the relationship of Western civilization to nature, and the alienation of humans from the natural world. He compares several religious traditions, as well as the viewpoint of secular science, and tries to identify ways in which we can revive our appreciation of the sacred in nature.

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according to White and Nasr, are only reminders of the internal crises within human self. These crises are not simply result of bad engineering but reflection of our worldview. Professor Nasr has expressed this meaning as following: Strangely enough, although the destruction of the sacred quality of nature by modern man dominated by a secularist perspective is directly responsible for this catastrophe, the vast majority of the human species, whether participating directly or indirectly in the havoc wreaked upon the natural environment, still lives within a worldview dominated by religion. The role of religion in the solution of the existing crisis between man and nature is therefore crucial”. He means misconception of man- nature relationship was root cause of our crisis, therefore he declares “Our aim in this study is to negate the totalitarian claims of modern science and to open up a space for the assertion of the religious view of the order of nature that various traditions developed over the centuries in their cosmologies and sacred sciences,. . .The religious view of the order of nature must be reasserted on the metaphysical, philosophical, cosmological, and scientific levels as legitimate knowledge without necessarily denying modern scientific knowledge [8].

The present increasing disruption of the global environment, according Professor White, is the product of a dynamic technology and science which originated in the Western medieval world. He argues, “Since both technological and scientific movements got their start, acquired their character, and achieved world dominance in the Middle Ages, it would seem that we cannot understand their nature or their present impact upon ecology without examining fundamental medieval assumptions and developments” [11]. His most significant conclusions of this examination of fundamental medieval assumptions were two things: First; man’s relation to the nature was profoundly changed. Man formerly had been part of nature, but now he became exploiter of nature. Distribution of land, for instance, now no longer based on needs of a family, rather on the capacity of a power machine to till the earth. Second: the spirits in natural objects, which formerly had protected nature from man, evaporated. These new developments in man-nature relationship, according to White, were introduced by religious tradition, namely Christianity, which shaped the Western attitudes towards nature. But what did Christianity tell people about their relations with the environment? Christianity, according to White, not only established a dualism of man and nature but also insisted that it is God’s will that man exploit nature for his proper ends. It held a view of nature that separated humans from the rest of the natural world, and encouraged man to exploit nature for his own purposes. According to this view, humans were seen as rulers of nature rather than part of nature [11]. However, the implications of Christianity for the conquest of nature emerged more obviously in the Western atmosphere through science and technology. According to Hossein Nasr, these developments constituted the historical process through which Western civilization moved away from the idea of nature as sacred and embraced a worldview which sees humans as alienated from nature and nature itself as a machine to be dominated and manipulated by humans [8]. Both scholars came into the same conclusion, i.e. reconstruction of the worldview as strategic approach to the resolution of environmental crises. Professor White concluded his discussion by asserting “What we do about ecology depends on our ideas of the man-nature relationship. More science and more technology are not going to get us out of the present ecologic crisis until we find a new religion, or rethink our

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old one” [11]. While Professor Nasr suggests, “The environmental crisis requires not simply rhetoric or cosmetic solutions but a death and rebirth of modern man and his worldview” [11] Reconstruction of the worldview, therefore, is only the strategic approach to deal with our ecologic problems, but how, and what we can do about ecology depends on what we think about ourselves in relation to things around us? No one yet knows, however, the religious concept of Tawhid, which considers man as Khalifah (vicegerent) and nature as Amanah (trust) may provide some alternatives to answer this central question.

3 New values for Man-Nature Relationship Since the root causes of environment troubles are so largely religious, the remedy must also be essentially religious. However, there are mainly two strategies: urgent and strategic. The first strategy deals with our actions, i.e. adding ethical values to the contemporary science and technology, while the second aims to change our current destructive beliefs towards nature to more constructive one in the future generations. This later strategy should base on religious framework which capable to sanctify our actions and relevant to build new values of man-nature relationship.

3.1 Man and Nature in Tawhidic Concept The three major monotheistic religions in world, i.e. Judaism, Christianity and Islam are based on concept of Tawhid, which means “God is the only Creator and ultimate cause of all things in the universes”. Tawhid, in its absolute sense, is a general view of reality, of truth, of space and time, of human history and his destiny. According to this concept, both man and nature are creatures of one God, who made man as his Khalifah8 on earth and nature as His Amanah (Trust) to man. This tawhidic concept sees man and nature at equal level in their relation to the Creator [1, 7]9 . However man, at his personal level, considered to be a multidimensional creature; stands between the spiritual and material worlds and partakes the nature of both. Spiritually, God breathed His own spirit in to him so that the spiritual world is reflected in him, the part that constitutes the relationship to his Lord. And from the other part God has originated him from clay, so the animal world is reflected10.

8 Khalifah or vicegerent means one who exercises delegated powers. There are three conditions to be a Khalifah with delegated authorities: first, utilization of the power that delegated to him for the benefit of the office and managing the affairs of the object over which he has been given authority (Amanah); second, to act according to the commands and guidelines of his Master or Principle, and lastly, to handle the burden and responsibility of any misuse of the power and authority that delegated to him. 9 Al-Farouqi IR (1992) Al-Tawhid: Its implication for thought and life. International Institute of Islamic Thought, (Herndon, Virginia) 10 See more details, Nasr, Seyyed Hossein, [7, p. 101].

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Due to this earthly part, man needs nature and resources of the material world for his personal and social needs. Knowledge and moral consciousness are, seems to be, the unique characters that have qualified man for the office of vicegerency. However, occupation of this office is not only element of honor, but also aspect of burden and responsibility. Duty of man, as Khalifah of God and bearer of Amanah, is to fulfill all requirements of the office either towards his Creator or towards nature. This means justice and knowledge are the most important requirements of man’s duty while he endeavoring to fulfill his responsibilities of vicegerency. Therefore, the Supreme Trust (Amanah) has given to a creature with intellect, capable of making choice to follow the right course, with capability for betraying the Trust. From pure Tawhidic perspective, khilafah system dose not provide any room of a secular realm in which man might act purely as a creature of this earth only and exploit nature. It dose not recognize the division between the worldly and the Sacred, which appears clearly in the current Western worldview.11

3.2 The Scientific and Religious Duty of Nature At ancient times man has maintained close relationship to nature due to two main reasons: First the undeveloped methods and technologies that were in use did not provide man the key to the secret of nature and made him feel as an integral part of it. Second: insufficient knowledge of man about nature created fear of it, forcing him to regard nature as superior, therefore man tried to maintain intimacy with nature and tread her friendly and kindly12. However, man main time maintains close relationship with nature not because of fear or ignorant, but because of his knowledge and confidence. Therefore, nature has two main duties towards man and the Creator: to serve man in his physical needs, and to guide him to the right path, equally with Scriptures, i.e. towards the discovery of the Creator and His great wisdom in the natural phenomena. Since nature has been made by God it definitely reveals the divine wisdom and plan behind creating of this world. Thus, nature has been a great teacher for mankind since the earlier stages of human history. Birds, bats, and bees have been good examples for designing of flying machines, aerodynamics, and flight projections. The entire universes, at both macrocosmic and microcosmic levels, are functioning in accordance to the great systems of nature. Galaxies and stars are working through motion laws such as gravity system. Biological laws govern all living creatures. Complex plant and animal life begins from a single cell of great complexity. Machines originated by God, such as protein, DNA, and cell, have guided humanity to the discovery of new technologies. The religious view that nature has no reason for existence save to serve man is true in this sense, which creates an inseparable friendship and peace between man and nature. To create a new set of constructive values towards nature, a progressive inculcation of this Tawhidic vision of man, nature and ultimate being, into human 11 Charles

LE Gai Eaton [6, pp. 370–371]

12 http://www.americanchronicle.com/articles/viewArticle.asp?articleID=7524

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generations is necessary. This inculcation should be the main goal of our entire education systems. Including this strategic goal, the urgent measures for environmental protection are necessary, the most important of which is to create awareness of environmental value.

4 Conclusion According to the Tawhidic vision, this physical world is Amanah (trust) of God to man to be utilized peacefully without any harm. To fulfill this requirement strategically, reconstruction of our worldview towards nature is necessary. However, at main time we can teach our children following steps: 1. Maintaining ecological system of the world, its wholesome cleanliness and promoting beautification of the environment. 2. Protection of the ecological balance between human, animals, and plant. 3. Environmental preservation for sustainable development, particularly preventing deforestation, depletion of natural resources, and pollution of land, sea, or air. 4. Bringing about a safer world by maintaining and promoting peace, avoiding war, and eliminating threat to human life and survival of the world, such as supporting the prohibition of nuclear, chemical, and biological weapons. As trustee of the earth, man should act as custodian of this planet by proper observation of everything in the planet according to commands of the Creator. He is not supposed to cause corruption in any form on earth whether to nature or his fellow human beings, or to other living creatures and the environment [2].

References 1. Al-Farouqi IR (1992) Al-Tawhid: Its implication for thought and life. International Institute of Islamic Thought, Herndon, Virginia 2. Al-Mahdi Muhammad, Understanding the Concept of Khalifah, http://www.islamic-world. net/?vo=11 3. Carnap R (1966) An introduction to the philosophy of science. Basic Books, New York 4. Drexler KE (1986) Engines of creation: See following website: http://www.foresight. org/EOC/EOC_Chapter_1.html 5. Hunt SD (1991) Modern marketing theory: Conceptual foundations of research in marketing. Southwestern Publishing, pp 17–18 6. Le Gai Eaton C (1991) Islamic spirituality. In: Nasr SH (ed) Crossroad, New York 7. Nasr SH (1990) Man and nature. Unwin Paperbacks, London 8. Nasr SH (1996) Religion and the order of nature. Oxford University Press, New York 9. Parsons HL (1975) Man east and west. In: Gruner BR (ed). Amsterdam, Hungary 10. Popper KR (1980) The logic of scientific discovery, Unwin Hyman, UK 11. White L (1967) The historical roots of our ecological crisis. Science 155(3767):1203-1207, 1967). See http://daphne.palomar.edu/calenvironment/religion.htm

Public Participation in Environmental Decision-Making on Major Energy Projects in Turkey: The Case of BTC Crude Oil Pipeline Project Nuriye Say and Deniz Babu¸s

Abstract Turkey, located between Europe and Asia, have been an important “Energy Corridor” for the transmission of the Middle East, Caspian area and Asia Country’s rich oil and natural gas resources to the Mediterranean thanks to projects like BTC (Bakü – Tbilisi – Ceyhan Pipeline Project). In this study, public consultation and involvement in during planning and construction of BTC Project was evaluated. The main objective of public participation is to provide support from all interested stakeholder and to be successful in the project in terms of both socio-economic and environmental issues. In order to attain this objective, the contributions of participation on the energy project have been mentioned in many studies. Public participation is a key step to improving and maintaining environment. But often it comes too late or not all. In this article it was studied whether changing point of view of local public on environmental effects of this project after this project was opened to run on 13 July 2006. Also it was analyzed the trend of public participation strategies and the encountered problems in Turkey. Keywords Crude-oil · EIA · Energy

1 Aims and Objectives of Public Involvement and Consult ation The main objective of public participation is to provide support from all interested stakeholder and to be successful in the project in terms of both socio-economic and environmental issues. In general, these benefits can be summarized as below [5, 9, 7, 8, 1, 10, 3, 4]. Public participation provides a democratic approach into the decision making process by means of informing and getting the public’s point of views on the proposal investments. Thus it provides a transparent decision making process. Public participation process include local information, expertise and discomfort into the decision making process. Thus it provides to take effective mitigation N. Say (B) Department of Landscape Architecture, Çukurova University, 01330 Balcali, Adana, Turkey e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_70,

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measures against the effects from the proposed activity and an increased trust and support of public about the decisions taken by the governments. According to BCC [2], in addition to the sustainable development, the other vital results of participation in the decision making process can be listed as; environmental protection, conflict management, project understanding, reduction of public opposition and economical benefits (Table 1).

Table 1 The Results of the contribution from participation [2] Sustainable Development

Environmental Protection

Conflict Management

Project Understanding and Reduction of Public Opposition

Economical Benefits

Public participation plays a crucial role in integrating economic, social and environmental objectives, i.e. in enhancing sustainable development by acting as a tool to raise public awareness of the delicate balance between economic and environmental trade-offs. Sustainable development can be achieved only through the involvement of all stakeholders in decision-making. This has been stated well by the United Nations: Principle 10 of the RIO DECLARATION recommended public participation to handle environmental issues: Environmental issues are best handled with the participation of all concerned citizens, on a relevant level. On a national level, each individual should have appropriate access to information concerning the environment that is held by public authorities, including information on hazardous materials and activities in their communities, and the opportunity to participate in decision making processes. Effective community consultation, early on in the project cycle, plays an important role in conflict prevention; conflicts during project preparation are costly both in terms of delays as well as in projects not approved as a result of conflict among stakeholders. Real participation will help to reach a broad public support for the final plan and reduce the public opposition in the execution phase of the project. In contrast, late or inefficient public participation leads to opposing the project. Public consultation, participation and involvement in the early stages of the project can prevent the dissemination of rumours and the rise of negative perceptions which are very difficult to change once they take root. Taxpayers must be considered as equal partners and have the right to be consulted when taking important decisions or making major plans. If the public is involved in the full decision making process, their concerns may be met early on in the planning process when changes may be easier to make, rather than late in the process when even small changes may cost both time and money.

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2 The Public Participation to Energy Activities The production and consumption of energy is one of the most significant activities which cause environmental problems and risks locally, regionally and globally. The energy investments are the projects which are frequently discussed nationally and internationally by both governments and public and in which there should be a common consensus. There have been some difficulties of determination of relevant parties, reaching these parties, information of them and evaluation of obtained views in the process of decision making relating either the national or the regional energy investments. Therefore, project and the public sometimes are in conflict as result of not changing the prejudice of public. The public participation in activities relating the factors affecting the environment in Turkey has realized in the process of EIA (Environmental Impact Assessment) according to the scope of EIA regulation. Even though the public participation has been performed for energy projects since 1997 when EIA has been enforced, an effective and active participation of all relevant parties could not be provided. Even after the project has been operated, the conflict between public and project continues time to time. Thus, there is a need to review of effectiveness of process of public participation. When investigated the problems and insufficiencies relating the public participation in Turkey, three issues which should be analyzed for an effective participation of public can be receive priority consideration. – The scope of the proposal, – the socio-economic status of public, – planning of participation process (Table 2). The determination of scope of the project at first stage will be useful for the analysis of stakeholders who contribute. Therefore, determination of prior parties who are to be given information and deliver opinion will be provided. The next stage is to determine the socio-economic status of these stakeholders. The socioeconomic status of public, education and environmental conscious level will give important hints for methods which will be determined in participation process. It will also shape the approach of voluntary organizations to public. Important charges devolve upon the voluntary organizations in order to inform the public about whether environment and the project. These foundations should also be powered and supported. The planning of participation process should be completed with referring to obtained data in order to ensure well-rounded, effective and complete participation. At this stage, determining effective methods and using the obtained information in suitable manner and in time could be provided for organizing wellround participation, announcing it to relevant parties, receiving information and informing.

Program

Plan

Scope Policy

Content-Subject – International relations – Sectoral policies – Legal regulations – Resources management – Protection strategies – Socio-Economic planning – Physical planning – Land use planning – Periodic investment – Economic – Environmental

1. The scope of the proposal

Scale – Global – International – National – Regional – Local – Urban – Rural

Objective – Stakeholder analysis – Determination of stakeholders – Target stakeholders – Prior stakeholders to be informed – Prior stakeholders to be consulted

Objective – Unemployment rate – Education level – Environmental awareness

2. The determination of socio-economic status

Table 2 The stages for an effective public participation

– What can the contribution of parties be? – Which methods will be used? – How will the opinions be collected? – How much time will the participation of public take? – The public participation will be where and when? – Who will fund the public participation?

3. The planning of public participation process

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3 BTC Pipeline Project Baku-Tbilisi-Ceyhan crude oil pipeline project comprises the construction of a pipeline which will transport crude oil taken out from oil petroleum reserves in Caspian Sea basins to Ceyhan located at the coast of Mediterranean of Turkey via

Fig. 1 Baku-Tbilisi-Ceyhan crude oil pipeline [6]

GEORGIA

BLACK SEA

ARMENIA

TÜRKİ YE IRAN

IRAQ

CEYHAN SYRIA

Fig. 2 The part of the BTC line in Turkey

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Azerbaijan and Georgia (Fig. 1). BTC pipeline has the capacity of carrying nearly 1 million barrels of crude oil per day. It has been planned that the Azerbaijani oil would be transported to Ceyhan and delivered with oil tankers to world markets within the context of BTC Project. This critical project aimed at facilitating a secure transportation system. Thus, a convenient and sustainable system of oil transportation will be facilitated in terms of economy and environment. BTC line has a length of 1768 km. Some part of the line in Turkey has a length of 1076 km. The line passes through a number of 248 residential areas (rural areas and city centers) such as Ardahan, Kars, Erzurum, Gümü¸shane, Erzincan, Sivas, Kayseri, Kahramanmara¸s, Osmaniye and Adana (Fig. 2). The route passes through different regions having different natural and socio-economic factors. While %17.9 of the route passes on a first class land, %20.3 of the route passes on second class land. Also, it passes on a protected area of 5 and first-level cultural heritage area of 26.

3.1 BTC Pipeline Project and the Public Participation A study of Environmental Impact Assessment (EIA) for BTC project was realized in accordance with national and international standards. The activities of informing the public and consulting the public were also performed intensively within the context of the project. Both the natural structure of areas and social structure where route pass on has been analyzed in EIA study. The residential areas affected by the project and the areas with a width of 2 km on both right and left of the pipeline were analyzed. The citizens living in these regions are included in the studies for public participation. The general aim of EIA process is to determine all potential effects on either environment or community eliminate these effects by taking preventions as much as possible or bring the effects down at a minimum level after the completion of pipeline construction and operation. The preventions for environment and social effect which will be performed by BOTAS¸ as an operator are designated in detail in EIA process. The EIA process, implemented for Turkey part of BTC Project, generally consists of several stages as given in Table 3. The connection of these stages with public participation is given below [6]. Informing the public and participation plan (IPPI) has been prepared in EIA study performed. This plan has been prepared in order to convey information on time and obtain the opinions and concerns about potential effects and preventions taken. The aims of IPPI are stated below. • To ensure for forming a sufficient mechanism for defining major effect groups, feedback for these and sharing the information

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Table 3 The EIA process, implemented for Turkey part of BTC Project and connection of these stages with public participation EIA Stages

Public Participation Process

Definition of the Project Determination of the Scope

Consultation

Collecting Data

Evaluation

Informing Public

Definition of relevant parties and pre-consultation, determination of environmental and socio-economic scope for project. This comprises both delivering information regarding the project to the main relevant parties (e.g authorities, NGOs) and defining the potential effects of the projects in detail with mutual meetings and workshop activities. Consultant activities and dialog are significant activities to be continued during construction and operation. This activity comprises the investigation of available data and definition of attitude about project and environmental and socio-economic status. This activity comprises the definition of all potential effects of construction and enterprise and determining the level of significance of these effects. Decreasing all potential negative effects and investigation of preventions aiming at increasing the advantages which anticipated development will provide has been added into this activity. The activities of informing the public has been started with brochures, web-site, and meetings were organized with various interest groups during the 60 days of informing public. The goal of informing the public is bidirectional. Procurement of necessary information which will be useful for understanding properly the anticipated project’s social and environmental effects and effect decreasing preventions to be performed Encouraging discussion and to deliver opinion about effect decreasing preventions. It has been added into EIA report after reviewing the opinions of public during informing the public.

• At local, national and international level to form information frame which will start at project planning stage and continue during construction of pipeline and marine terminal and operation stages. • To provide the prior issues put forward by project effect groups to be considered at the stages of determination the project and design as it is in EIA report. • To define resource level needed for applying the plan and auditing procedures for implementations and • To determine a complaint system for local project effect group. In addition to the process of informing public within the context of EIA study of BTC Project, an Environment Management and Auditing Plan (EMAP) has been prepared in order to determine the requirements which will decrease socio-cultural effects designated in EIA report. In addition to this plan, supportive plans are also

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developed. Social Management and Auditing Plan (SMAP) is one of plans supporting EMAP. Social Management and Auditing Plan (SMAP) has been developed in order to reach the goals given below. • To ensure positive and independent relationships between project and local people. • To optimize the potential advantages brought by the project • To decrease the negative effects caused by the project Other plans which are needed to apply the social effect decreasing preventions defined in the process of EIA and the plans involved in Social Management and Auditing Plan are given below [6] • Public Relations Management Plan determines the main features of necessary preventions for preventing negative effects which might be caused by construction workers or construction site and ensuring bilateral effective communication with local residential areas. • Construction Effects Management Plan gives the main features of necessary preventions for minimizing the effects occurred during the construction of the facilities. • Public Security Management Plan designates the main features of necessary preventions for ensuring the security of local communities. Most of these preventions are seen in other plans, however it is congregated here in order to manage and audit these. • Employment and Education Management Plan gives the main features of necessary preventions for increasing the facilities of employment in local areas where pipeline pass and marine terminal is. • Supply/Demand Management Plan gives the main features of necessary preventions for procurement of goods and services required by the project and increasing the opportunities of local regions where pipeline pass and communities affected by the project. Within the context of this study, a study of questionnaire was performed in order to determine the efficacy of public participation to BTC Project in the city center of Adana and Ceyhan district where are located on the route of project. The questionnaire form consisted of a number of 10 questions is given to nearly 100 people with a face-to-face talk method. According to the results of the questionnaire performed, all of the citizens not living on any residential area on the route of line did not obtain information about the project and deliver opinion either. However the citizens living on the route of line and settling especially in rural areas uttered their socio-economic expectations rather than the concerns over natural environment. We cannot also speak about the efficacy of non-governmental organizations showing activity in the region. The trade associations have not shown a proper participation related with the issue.

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4 Conclusion The route of BTC pipe line which is the 1768 km in length and pass through the tree different countries covers the quite large region which has different ecological and socio-economic structures. In this broad project area with considerably varying environmental factors, all interested groups also differ from each others in terms of the effects of any changes from the current situation. According to this fact, giving detailed information about the general properties and possible outcomes of the project to the all correspondents and having comments from them are so important and difficult to achieve. The main basic objectives of having participation in such a project are establishing the secure ambient, controlling the prejudice of the local public and sustaining the current social structure and preserving the natural resources. When the project stages are examined for today it can be seen that a systematic disclosure and social participation procedures are being performed. Also, immediately after the project is in operation, social monitoring and gathering the public comments program were activated. However, although the participation process is well-planned, the efficiency of the participation studies till operating the project is not in desired level. The socio-economic structure is one of the major issues which denote the local public participation level, especially in developing and underdeveloped countries for such a big scale projects. The BTC pipe line generally passes through from the rural areas of the people with relatively under average salary and education level. This situation is one of the most important matters which determine the expectations of the local public from project outcomes. The results of the questionnaire, made in the scope of this study, showed that the people living out of the settling area of project route could not sufficiently be informed about project related issues. As known from former studies, sectors, free from any socio-economic expectation, taken a part in the project especially relating to the environmental issues in an objective point of view. As a result, increasing the public participation efficiency and the public awareness should be preferential subjects for such kind of large-scale investments.

References 1. Abaza H, Bisset R, Sadler B (2004) Environmental impact assessment and strategic environmental assessment: Towards an integrated approach, UNEP, Geneva 2. BCC (2006) Public purticipation, Biodiversity Concervation Center, Russia. http://www. biodiversity.ru/coastlearn/pp-eng/index.html 3. Cadariu A, Ikonomov L, Vasiliu F, Angelov D, Anghel I (2005) Methods and tools for practical application of the espoo convention In Romania and Bulgaria. Environmental Experts Association, Romania, Institute For Ecological Modernisation, Bulgaria 4. Dalkmann H (2005) Public participation in strategic environmental assessment. Harbin, China November 8–10–2005. Presenting author: Wuppertal Institute for Climate, Environment and Energy Research Group 2: Energy, Transport and Climate Policy 5. Dusik J, Sadler B, Mikulic N (2001) Developments in SEA in central and eastern Europe. In: Dusik J (ed) Proceedings of International Workshop on Public Participation and Health

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N. Say and D. Babu¸s Aspects in Strategic Environmental Assessment, Regional Environmental Centre for Central and Eastern Europe, Szentendre, Hungary EIA Report (2002) Bakü-Tiflis-Ceyhan Ham Petrol Boru Hatti: Türkiye Çevre Bakanli˘gi Onayli Çevresel Etki De˘gerlendirmesi Çali¸smasi. Uzman Dani¸smanlar Envy, Kora, Erm IAIA (2002) Strategic environmental assessment performance criteria. January 2002 Special Publication Series No. 1. International Association For Impact Assessment, USA Kravchenko S (2003) Public participation in strategic environmental decisions. Guid for environmentsl Citizens Organizations. European ECO Forum, Belgim Sadler B (2001) A framework approach to strategic environmental assessment: aims, principles and elements of good practice. In: Dusik J (ed) Proceedings of international workshop on public participation and health aspects in strategic environmental assessment, Regional Environmental Centre for Central and Eastern Europe, Szentendre, Hungary Therivel R (2004) Strategic environmental assessment in action. Earthscan Publications Ltd. United Nations Economic Commission for Europe. Convention on Access to Information, Public Participation in Decision-Making And Access to Justice in Environmental Matters, 25 June 1998 (Aarhus Convention). Geneva, UNECE, 1998

From Human Social “Matrix” to Perception of Social Structures and Corporate Actors David Schnaiter

Abstract Corporate actors like institutions, corporations, governments, companies, organizations, political parties, universities, NGOs, states, interest groups, associations and all other supra-individual collectives play a key-role for the socialization of human beings and for the creation of the reality we believe in and live with. The creation of these realities within our socialization leads to different matrices forging our self-understanding and influencing our behavior, lifestyle, ideals, goals and conducts. “Wirklichkeit” – actualitas – as a term going beyond the significance of reality, is a creation/invention of the human brain and also the most important building blocks of our world-views base their existence only on agreements between individual human actors: Corporate actors are considered as legal persons within our juridical systems, seem to be acting as independent entities, outlast the single actors steering them from within and have a vast impact on our lives, but in the end they only persist due to the fact that there is a common consent about their necessary existence. Different theories, mostly within sociologic frames, approach the role supra-individual entities fill out in our societies but do hardly take into account the gap between individual und corporate actors. The “Extended View” as “real theory” in the sense of Einstein’s logics classifies corporate actors as paraautonomous actors with clearly defined abilities and structures. On behalf of this theory a step to understand in an emergent way the creation of social structures as human social matrices and the characterization of supra-individual collectives within and in constant relation with these matrices is tried to be made. Keywords Association · Company · Corporate actor · Corporate identity · Corporation · Evolution · Extended view · Habitualization · Institution · Institutionalization · Intention · Legal person · Matrix · NGO · Para-autonomous actors · Potential · Reality · Regulation · Social order · Social science · Social

D. Schnaiter (B) Division of Social Medicine, Department for Hygiene, Microbiology and Social Medicine, Medical University of Innsbruck, Sonnenburgstrasse 16, A-6020 Innsbruck, Tirol, Austria e-mail: [email protected]

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structure · Socialization · Society · Sociology · Task distribution · Task specialization · Wirklichkeit

1 Introduction Based on the assumptions proposed within the so-far published explanations about the supposed nature of basic entities/actors by W. Kofler’s “Extended View” [1–7] we learnt about the abilities and symbol-intentions attributed to restricted autonomous actors, about their emergent creation and about the theory of matrixworlds on the level of quanta until life. But also every human being fits into this description/attribution of a restricted autonomous actor as well as the mentioned somatic cells or slime molds (myxomyceta) do. Although on the level of mankind we face new possibilities and structures that have to be taken in consideration. – What about all the supra-individual entities we humans created? Why and how are they created? How do they fit into the “Extended View”? Which potential do they have and are they really real? Following the “Extended View” we call these supra-individual entities like corporations, governments, political parties, organizations, universities, NGOs etc.: PAAs – which means “para-autonomous actors” [7, 6, 2]. One of the basic principles of the “Extended View” is to attribute – beneath energetic and discrimination potential – (symbol-)intentions and a certain kind of individuality or autonomy to every actor within the realms of its possibilities and in dependency of the actors evolutionary level as well as its surrounding given environment. Para-autonomous actors – PAAs – are structures built up by humans that only exist because there is a common agreement about their meaning. In contradiction to autonomous or restricted autonomous actors, paraautonomous actors only seem to have intentions, potentials and abilities, but we will see that this is only an appearance – one part of our human social matrix.

2 Corporate Actors – Para-autonomous Actors At a first glance we would say PAAs are socio-structural media through which the goals or even the values of individuals are expressed. Individual personalities steer them, give them direction, shape them etc. – So far nobody would say PAAs are autonomous entities. But because all organizations, companies, authorities, NGOs, states, interest groups, associations, institutions and all other supra-individual collectives seem to be acting like an independent entity we automatically ascribe “intentions”, “goals” or “attitudes” to these PAAs and soon nobody doubts their ability to have them. The circumstance that the energetic potential, its intentions and the abilities to discriminate and systemize are brought in by its anonymous human restricted actors from

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within the PAA is not visible any more and so the PAA itself seems to become a fully autonomous actor. Today PAAs or “corporate actors”, as they are usually called in modern sociology, are considered as actors sui generis and they are even defined in this way by the legislator. They have to act within legal norms and are legally independent of their members and even owners. We also do perceive lots of PAAs in this way: E.g. “Corporate Identities” have to respond to lots of different even social expectations of individual humans like consumers, shareholders, creditors and also other PAAs. Organizations need to present themselves always as fully competent actors in order to acquire public trust and reputation. Individual humans may fail or claiming a status of tiredness, sickness, diminished responsibility etc. – PAAs cannot do so. Every single action of a PAA is considered as a conscious act of the whole corporate actor – even if the action has been undertaken by one single member of the PAA or the consequences of the action have not been foreseen – are unintended. Publicity, marketing, sponsoring and advertising play a key-role in the identification of companies as PAAs nowadays and Corporate Identity in the perception of the consumers, customers or members is created to a high amount through these public actions. Globalization and “Global playing” institutions also contribute to the idea of PAAs as independent entities – the matrix creates itself.

3 Corporate Actors as Finality-Related “Legal persons” The climax of the acknowledgement of corporate actors – PAAs (para-autonomous actors) – consists in their recognition as “legal persons” within our juridical systems. PAAs can conclude contracts, pay their taxes, have hardly any individual human right including the right to the protection of property, freedom of contract, speech etc. Due to their very often given financial background PAAs are frequently even privileged compared to individual humans – not to talk of animals. The influence of lots of these corporate actors – following terms of sociology – or para-autonomous actors – following the “Extended View” – is a lot more far-reaching than the influence any human being can have. Strange legal situations can arise if a stock corporation re-purchases a majority of its own shares and no precautious laws are in function that deal with that situation – so happened in Japan some decades ago: In this case an incorporated company as a legal person owns itself as a legal person – a circumstance that leads to inter-organizational re-structuring and actions that do not fit in the concept of stock corporations any more. One of the most important features PAAs show in comparison to human beings is, that they (normally) don’t have to “die”. Big companies, institutions, states, associations etc. have a longevity or persistence far beyond centuries. Comparing single-cellular in multi-cellular like myxomyceta (slime molds) who give up their

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immortality for another purpose, we can now define a big distinction to PAAs in human society. PAAs are assemblies/associations of human actors that because of their essential form of existence outlast the single actors more or less steering them from within. So there is a kind of throwback to be stated and that is why PAAs are considered in our agreements as entities with some kind of a higher level meaning – not to say, as entities connected with finality. Think of legal matters again and the frequency with which courts convict organizations with severe sentences because of their responsibility e.g. for our environment. PAAs like governments, the UN, the WHO, NGOs or the NATO have to assure and realize the highest human goals and values like global peace, welfare, health etc. and there is a large world-wide agreement that these institutions are entrusted with these duties. All of us are members – restricted autonomous actors – in lots of different corporate actors and in our matrix these PAAs take over two extremely important roles for us: – They take over quite a large part of our personal responsibility and define in a vast way the idealistic and ideational perception of our given world – They produce and assure the existence of (different) social orders we can live in as individuals and assure the absence of anarchy = the absence of a matrix = one of the most essential human fears

4 Social Orders – Social Structures: The Matrix and Its Paas Social order is not part of the “nature of things” and it cannot be derived from the “laws of nature”. Social order exists only as a product of human activity. [8]

Social order is the most basic prerequisite for human existence and in constant production. The biological equipment – in terminology of the “Extended View” we would speak of one of the arches of the bridge-layer-model – forced us to specialize from the early beginning to assure our survival. Therefore consents within the first groups of humans had to be found to allow a common win-win-situation or the most basic possibilities for survival. “Homo sapiens is always, and in the same measure, homo socius” [8]. To free and gain potential for additional actions – following the “Extended View” in its two basic forms of energy and discrimination potential – humans have two major possibilities: – Habitualization: conscious actions connected with constant attention and decision-making can be led into adaptive (automatic) control mechanisms. This could be called and is very closely associated with some kind of “learning”.

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E.g. When you first drove a car all your attention had to be paid to the different tasks you had to fulfill moving the vehicle (steering, using the panels, pay attention to traffic etc.). There was no possibility for you to do anything else; all your potential to fulfill actions was dedicated uniquely to the task of driving the car. But after some time driving a car gets an automatic action. You still will pay some attention to your driving (hopefully) but now you have potential left to talk, listen to music, make a phone-call, smoke, think about other things etc. contemporaneously – your potential is not fully absorbed by the driving process any more. It has become an automatic, controlled, “regulated” mechanism how the steering wheel, the pedals etc. are to be handled – it became a habitualized activity. – Task specialization and task distribution: Even in its most rudimentary form as a prerequisite for survival, task specialization and task distribution lead to different role allocations and directly to the establishment of social orders. In both cases additional energy/potential for deliberation, realization and innovation has been won. Humans can reach the absolute highest level in habitualization and specialization among all entities on this planet. This is one of the most important attribute and reason for development, innovation and the so called progress of mankind. Based on these two principles humans create a multi-dimensional (social, economic, political etc.) system to live in and are building up institutions as supra-individual actors that manifest agreements concerning the system. Predefined patterns of control and conduct for every member of the particular social group find their setup in institutionalization. Monogamous couple building and its institutionalization as “marriage” as one of the most common and fundamental basis of our social order demonstrates the significance and far-reaching impact of the most basic idealistic agreements, as to say para-autonomous actors, our human matrix consists of. Following Durkheim these principles seem to be indisputably coherent and empirically proven from the first final-oriented societies up to nowadays [9, 10]. Even if he and with him sociologists like Luhmann leave little or no space for individual actors within their conception of a social system and are therefore to criticize. Compare also [11]. Human beings are consent-oriented by their nature and our subjective world view gets created through socialization. Already in our earliest socialization our involvement in and knowledge about institutions and social textures is structuring our everyday life. Roles, traditions and norms get internalized and are representing the social order we live in. The social structures surrounding every one of us are constantly legitimized by institutions, by PAAs of symbolic and also of material nature and define our societies final- and sense-oriented purpose. See also [8]. Time hardens the objectivity of institutions as PAAs and lots of them get part of the apparently given world that is not taken in question any more. Especially children accept the built up social matrix of their parents, their relatives etc. as structures that form their reality/actuality, and the consensus initially voluntarily given to recognize an institution gets an indisputable part of their world view comparable to the realities of their natural world surrounding them.

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5 The Matrix as Individual “Wirklichkeit” This individual world view – this unintended created matrix – in contradiction to the (misleading) use of the term “reality” – can be designated as “Wirklichkeit”, a term Master Eckhart introduced already in the 13th century as a translation of the Latin word “actualitas” into German language. There is no real English terminology for “Wirklichkeit” existing – in philosophy “actuality” is used as English translation. Following Kant it can be defined as existing individual reality that goes beyond physical existence and includes everything that merely seems (compare also [10]). If we have a look at quantum mechanics it gets clear that “reality” can’t be defined properly within the physicists dogmatic systems of natural laws (think of the particle-wave nature of light and Schrödingers cat). Einstein, Podolsky and Rosen tried to solve this problem for natural sciences by defining the criterion of physical reality in 1935: In a complete theory there is an element corresponding to each element of reality. A sufficient condition for the reality of a physical quantity is the possibility of predicting it with certainty, without disturbing the system. This is not possible [13].

They decided that the description of the wave-nature and/or the description of the particle-nature of light were not complete and that simultaneously given realities of the same entity cannot be possible.1 Following the model of Kofler different consents are observable on different evolutionary levels but from the position of the observer the connectivity of the observer to his subject is not reached (yet) and in many cases not to be reached at all. The reference has always to be the observer himself. Not because of an idealistic or human-centered basic philosophy but because of the fact that the abilities of alignment are decisive for any judgment about the observed and the therefore following actions. So we lack objectively correct answers about the Wirklichkeit of any restricted autonomous actor if we do not share the same consent – and are therefore lacking connectivity. We can only try to describe images of facts we observe and suppose symbol-intentions and -potentials, like the “Extended View” supposes, to deal with the given2 – thing most of the non-natural sciences have already accepted and integrated in their scientific self-understanding (compare e.g. the use of Max Weber’s “ideal type” [17] within historical sciences). This is exactly the crucial point why on every evolutionary stage as well as on the level of human societies and therefore also

1 Attempts to prove the multi-universe or multi-dimensional superstring theories are not taken in consideration; for interesting new theoretical approached compare e.g. Deutsch: The fabric of reality [14]. 2 This view is also in accordance with lots of modern sociologists and philosophers. Compare e.g. Watzlawick [15, 16].

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in our sectoral sciences massive differences between given realities/Wirklichkeiten do exist. Philosophy is asking those questions, which not to have asked was the success condition of the scientific procedure. Thus it is stated that science owes its success among other things to the renouncement of placing certain questions. ([18]; author’s translation)

However, the understanding that Wirklichkeit differs from one person/one actor to the next is the point to comprehend the idea, the creation and the acceptance of human matrix-worlds and the role PAAs play for our socialization. “. . . [The] most valuable attribute [of a theory] is that it explains the fabric of reality itself ” [14] – PAAs are free inventions of the human brain, ideas with far-reaching consequences based on the agreement to accept them as quasi-physical entities. Ideas don’t die if they are thought again and again – their inventors do. Therefore PAAs can persist until the agreement of their existence gets lost. They represent images of the matrix we live in, are constructed objectivities and persist until we decide to change our Wirklichkeit, or circumstances outside our restricted control force our reality/actuality to be modified. Para-autonomous actors with vast influence in their time have “died” or were altered/overformed fundamentally and are nowadays perceived as history: e.g. the Roman Empire, the East India Company, the Holy Alliance and the USSR. – And so will most of our actual PAAs be gone when the consent about their necessary existence gets lost. The conscious perception that we live in constant relations to PAAs that are in reality only inventions within our matrix may be a big advantage in very many daily-life situations. – Who are the “real” conductors, the clockmakers, the helmsmen, the steering parts of these social matrix-worlds remains the question that continuously has to be asked – although, as within the evolutionary process, most of the matrices that form our Wirklichkeit are unintended consequences of intended actions and do not have a master-brain behind that consciously steers them. Also this in good accordance to state-of-the-art knowledge within science: Watzlawick states: “. . . any so-called reality is – in the most immediate and concrete sense – the construction of those who believe they have discovered and investigated it. In other words, what is found is an invention whose inventor is unaware of his act of invention, who considers it as something that exists independently of him . . .” [15]. The “Extended View” is not to be classified as part of idealistic, constructivist or cybernetic scientific frames but offers an integrative approach to different sectoral sciences and different schools within those sciences. The concept presented by the “Extended View” seems to be compelling and is certainly applicable and useful also to social sciences. The understanding how matrix-worlds are created on different evolutionary levels up to humans, how para-autonomous actors are to be considered, how relevant the individual intentions and valuations every one of us implements constantly are and how realization-luxury can be won by deceleration and regulation, are extremely important for every inter-sectoral scientific exchange and collaboration.

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– But also for the handling of questions/problems exaggerating the capacity of particular cultural views, scientific frames or local policies – problems like health and sustainability. Verum ipsum factum (Giambattista de Vico: De Antiquissima)

References 1. Kofler W, Schnaiter D (2007) Workbook for the international satellite symposium of ICSD/IAS H&E within the international conference: “Environment: Survival and Sustainability”, International Academy of Science Health & Ecology, Nicosia, Northern Cyprus 2. Kofler W (2007) I.M. Sechenov (1829–1905) and the relevance of paradigms for medical science. J History Neurosci 16(1–2):30–41 3. Kofler W, Schnaiter D (2006) What is pain? An attempt of an explanation by an “extended view”, in Science without borders. In: Kofler W, Khalilov E, Schnaiter D (eds) Transactions of the International Academy of Science H&E, vol. 2. International Academy of Science H&E, Innsbruck, pp 28–41 4. Kofler W (2006) The “extended view” of a human as a social being: Application to the placebo phenomenon. P.K. Anokhin Institute of Normal Physiology, Moscow 5. Kofler W (2006) An “extended view” of a human person as a social being: The health relevance of environmental factors. Herald Int Acad Sci (Russian Section) 2:11–17 6. Kofler W (2005) The relevance of Sechenov for the development of the theory of an “extended view” of a human person as a social being, In 14th Sechenov Lectures, Russian Academy of Science et al (ed) International Academy of Science H&E, Moscow, pp 3–68 7. Kofler W (2004) A comprehensive model of humans as social beings and the health relevance of their interactions with and expectations on their environment. Th. Kuhn Honour Lecture 2004, 13th World Clean Air and Environment Congress, London 8. Berger PL, Luckmann T (1993) Die gesellschaftliche Konstruktion der Wirklichkeit. Eine Theorie der Wissenssoziologie, Tausend edn. Fischer Taschenbuch Verlag, Frankfurt am Main, pp 32–33 9. Durkheim E (1984), Die elementaren Formen des religiösen Lebens, 2nd edn. Frankfurt am Main 10. Durkheim E, Luhmann N (1988) Ueber soziale Arbeitsteilung. Studie ueber die Organisation hoeherer Gesellschaften, 2. Aufl. edn. Suhrkamp, Frankfurt am Main 11. Porpora DV (1987) The concept of social structure. Greenwood Press, New York 12. Yolton JW (2000) Realism and appearances. An essay in ontology. Cambridge University Press, Cambridge 13. Einstein A, Podolsky B, Rosen N (1935) Can quantum-mechanical description of physical reality be considered complete? Physical Rev 47(10):777 14. Deutsch D (1997) The fabric of reality. The science of parallel universes– and its implications. Allen Lane, New York 15. Watzlawick P (1995) Die erfundene Wirklichkeit. Wie wissen wir, was wir zu wissen glauben? Beiträge zum Konstruktivismus (9. Aufl. [64–66. Tsd.] edn). Piper, München 16. Watzlawick P (2005) Wie wirklich ist die Wirklichkeit? Wahn, Täuschung, Verstehen, Taschenbuchsonderausg (3. Aufl edn). Piper, München 17. Weber M (1995) Die “Objektivität” sozialwissenschaftlicher und sozialpolitischer Erkenntnis. Wiss. Verl., Schutterwald/Baden 18. Weizsäcker CFv (1978) Deutlichkeit. Beiträge zu politischen und religiösen Gegenwartsfragen. Hanser, München

Negative Effects of Creating Environmental Awareness of Public Relations Applications by Alming of Political Propagandas Emel Tozlu Aslan

Abstract This is the deniable truth that public relations applications increased by aiming to political propagandas as the day passed in Turkish Republic of North Cyprus as in world. The difficult questions are formed which is need to be replied about how much reached to its aim of these applications, how much created an opposite reaction and how much it persuasive became. The aim of this study is explaining with examples by stressing the effect in the time of environmental awareness of public relations applications. Public relations is the process of applications in carefully of continual and planned efforts by developing relations by having a goal of providing power and support of related people and groups by defining its aims and facilities of an organization. The applications which was done far from in an unplanned and fixed program and out from logic of honest public relations as it will make a problem come alive in reaching to the target at the same time it caused to opposite reaction and became misleading element for the people. Keywords Public relations · Environmental awareness · Political propagandas

1 Introduction 1.1 Public Relations In our daily life, which was seen a dense competition, which was lived of changes of social, economic and technologic for continuing for their existence, they should be clear to reactions which came from environment and they should regulate themselves to environmental reactions and changes. In this mean, a public relations is seen as one of the methods which makes simples of introducing extensive mass themselves. A public relations as in all administrations is a managerial function which facilitates the changes of organizational in the political party administration. E.T. Aslan (B) Faculty of Communication, Near East University, T.R.N.C – Nicosia Cyprus e-mail: [email protected]; [email protected]

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Public relations unit provides establishing positive relations between the organization workers and outer environment by developing positive relations between society expectations and organization by providing harmony [1]. The other unit of public relations is getting rid of lack of knowing recognizing, sharing the responsibilities with the people, telling the works which were done. The application of public relations became the process of political propaganda after they learned the wishes of people and transformed to procedure and action after they evaluated these wishes [3].

1.2 Main Principles of Public Relations The basis of public relations had been found on respect. This view reflects humanistic approach. This respect form of core of ethics rules. But the benefit in the daily life, deviations and correspondences in the community got out of insight of necessity of ethic principles and rules in the public relations [2]. 1.2.1 Conform with the Ethic Rules of Professional In public relations ethic means the total of standards which determines what the truth and the wrong is in carrying out of public relations. Absolutely by all public relations experts should be carried out. Public relations professional ethic law was formed in a general session in Atina, Greece in 1965 by International Public Relations Association. According to this law, in summary, a public relations expert should be honest, avoid giving wrong and deceptive information, move with the feeling of responsibility, respect to the human rights and also protection of their customers secrecy rights [1–2]. 1.2.2 Public Relations Applications Should Reflect the Realities and Should Be Honest It should not be forgotten that if public relations is used for hiding the realities or showing different except for should be and camouflage the mistakes, it means that professional aims and ethic rules are ignored [1]. 1.2.3 Persuasiveness It is necessary that for being persuasive in the messages, it should be consistent in the results which are obtained and also one should choose the words carefully which is used in preparing of messages [1]. 1.2.4 Public Relations Applications Should Be Continuously Public relations should work in a planned and programmed way. It should be continuous because it is not possible to get a result in a short time as in advertisement. Public relations is a kind of studying which would achieve results in long time [1].

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1.2.5 Public Relations Applications Should Be Carried Out by Experts There is a mark of every profession’s responsibility and adequacy according to itself. Public relations applications should absolutely be realized by professionals who got education about public relations [1]. 1.2.6 Common Responsibility The importance of public relations should be appropriated by all the institution workers and should be moved with all together [1]. 1.2.7 Repetitions The message which is desired to give should be repeated up to reach to target mass [1]. 1.2.8 Public Relations Applications Should Be A Communication Process Which is Based on Two Aspects of Relationship It should be provided of interaction and acknowledgement of two sides by way of healthy communications which is formed between community and business enterprise [1].

2 Method and Research Area The application was determined by considering a public relations application which aimed political propaganda and was done in a wrong way and also brought a voice in Turkish Republic of North Cyprus. After “Kıbrıs” and “Yeni Düzen” newspaper’s scanning was done to the archives, the documents which were supplied, they had been compared to each other and they had been interpreted by choosing samples.

3 Results and Discussion In a public relations application which was done by aiming a political propaganda, if is not complied with the basic principle of public relations, with what kind of things can be met? The answer of this question can be given by investigating a public relations application which was done by aiming a political propaganda unless you comply with the basic rules of public relations. The sample news which were obtained after archive scanning has shown that a public relations application which was done by aiming a political propaganda unless you comply with the basic rules of public relations how caused the image to go wrong of a politician who is in a subject position but at the same time how effected of environmental awareness process of people [5–6].

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The news, which took place in different time pieces and took place in “Kıbrıs” News and “Yeni Düzen” News belongs to a public relations application which was done by aiming a political propaganda in a wrong way. A public relations application which was done by aiming a political propaganda and took place in [5, 6] and obtained from “Kıbrıs” News and “Yeni Düzen” News archives is an application which is contrary elements to basic principle of public relations in it, which was realized by the government of Nicosia Municipality chief, Cemal Buluto˘gulları in Turkish Republic of North Cyprus on the date of 28 November 2006.

3.1 The Points Which Do not Comply with the Basic Principles of Public Relations in the Given Sample It was not compatible with the principle of “Adapt to Professional Ethic Rules” and it had been moved to the principle of “Public Relations Should Reflect The Realities and Should be Honest”. “The Ethic Law of Profession of Public Relations” which was expressional under the heading of basic principles of public relations in up wards entirely violated in the application of public relations completely. According to this law, in a summary, a public relations employee should be honest, should abstain from giving wrong and deceptive information, should move with the feeling of social responsibility should respect human rights and carry the responsibility of saving secrecy rights of expert clients [2]. In public relations application which was moved out of feeling of social responsibility, public relations expert by admission of Nicosia Municipality Chief, Cemal Buluto˘gulları, emerged out of profession ethic rules, in the application which he did, by giving a place to decisive words for people, he acted against the principle of “Public Relations Applications Should Reflect the Realities and Should be Honest”. For example, in the news which was published on the 28th November 2006 in “Kıbrıs” News it took place under the heading of “Well make green the Dikmen Garbage with People” and his this words. “Cemal Buluto˘gulları said that he has been carrying out his works about Dikmen Garbage which is one of the problem of Nicosia, and in a short time, by making a call to people, they will plant trees” “Buluto˘gulları recorded that they started to sprout works until month, in a beautiful day, by calling people to garbage, he recorded that by having a picnic, they plan to plant trees [5]” This news which was published in the “Kıbrıs” newspaper, is completely in deceptive situation. From this situation, newspaper writers are uncomfortable who looks objective to events which is in pressed broadcast [6]. The photographs which were given at down, which were taken in Nicosia Dikmen Garbage after a month dating of 28th November 2006 when Nicosia Municipality Chief, Cemal Buluto˘gulları, called people to a picnic (taken by myself) on 23 May 2007 are the best evidence of this (photos 1, 2).

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Photo 1 23 May 2007/Nicosia, Dikmen Garbage

Photo 2 23 May 2007/Nicosia, Dikmen Garbage

3.2 It Was Not Complied with the Principle of “Public Relations Applications Should Be a Communication Process Which Based on Two-Sided Relationship” In community and public relations application, which took place between two people, it should be provided the interaction and acknowledgement of two people by healthy communication canals [1]. But in the public relations application in the example which was done in the wrong way, this situation cannot be valid. The reason of this is causing calamities between politicians and the community by ignoring to the principles. The people who are in politics should remain true to basic aims and principles of public relations while they are doing public relations applications which are done by managing numerical logic by politician in front plan, for it would not create a reflection in the means of responsibility it is a subject matter that effects the politicians in a negative way. In the sample, this situation had been realized.

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It had been planned to bring a voice by sending the quantity of public relations applications to back importance but this situation had effected in a bad way of politicians image whose name took place. The confidence of people to the politicians, whose name took place had been jolted. These kinds of public relations applications which carry out the quantity of political propaganda which was done in the way of deceiving people by using the environment, it means that this carry a meaning of deceiving people who are sensitive against the environment. This situation effects the process of environmental awareness and bring insensitive situation of the community.

4 Results and Discussion As it is shown in the sample, public relations applications which carry a quantity of political propaganda and by aiming to stay on the agenda, cause damages which mending is hard in the process of environmental awareness of community of a process whose formation is in the hand of the community in environmental awareness process and same problems come out like desensitizing against the environment of the community. One of the fields of public relations is crisis administration [4]. Against the wrong applications which can be administration should be ready on available. In the public relations application which was given in the sample, if Nicosia Municipality Chief, Cemal Buluto˘gulları apologized in the name of himself and the constitution by receiving the fault after the crisis, could be a positive behavior against the community. When the situations which can be turned to positive of public relations applications in the sample, actually, extremely good applications could be revealed by thinking the community unless damage of the constitution’s image. For example, the studies which will be done can be announced and unless the time concept Nicosia Dikmen Garbage which wants to be turned in to a picnic area, can be stressed, so the sensitivity of people’s environment could not be exploited.

References 1. Baskin O, Aronoff C, Lattimore D (1997) Public relations: The profession and the practice. Boston, MA, Mc Graw Hill 2. Bülbül RA (2001) ˙Ileti¸sim ve Etik. Ankara, Nobel Press (In Turkish) 3. Kazancı M (1995) Kamuda ve Özel Sektörde Halkla ˙Ili¸skiler. Ankara, Turhan Press (In Turkish) 4. Okay A, ve Okay A (2005) Halkla ˙Ili¸skiler, Kavram, Strateji ve Uygulamaları. ˙Istanbul, Der Press (In Turkish) 5. Kıbrıs Newspaper (2006) Lefko¸sa yı ye¸sile bo˘gaca˘gım, http://www.kibrisgazetesi.com/ index.php/cat/2/news/34460/PageName/Ic_Haberler. Accesed 28 Nov 2006 6. Yeni Düzen Gazetesi (2007) Pikni˘ge gideniniz var mı çöplü˘ge? http://www.yeniduzengazetesi. com/template.asp?articleid=1109&zoneid=16. 12 Jan 2007

Part VII

Environmental Science and Technology

Monitoring of Wetlands by Using Multitemporal Landsat Data; A Case Study from Fethiye – Turkey ˙ Ozdemir, K. Ozkan, A. Mert, and S. Gülsoy I.

Abstract In the last two decades, tourism has led to a drastic conversion of the wetlands into settlement areas in the surroundings of Fethiye town located in the Mediterranean region of Turkey. The coast of Fethiye Bay abounds in coastal wetlands, riparian corridors, marshes, forested wetlands, swamps and grasslands that need urgent conservation. In addition to tourism activities, pollution resulting from residential and agricultural areas, urbanization, and other activities are threatening the wetland ecosystems in the area. The transformation of wetlands has resulted in a loss of biodiversity. The wildlife, notably many water birds are under a threat of extinction. These biotopes need to be monitored at short time intervals, as changes in the wetlands are rapid and serious due to these factors. Accurate and timely information will play a vital role in supporting decision making and effective sustainable management of these wetlands. In this connection the ground based survey for monitoring purpose is not entirely well-suited because of transportation difficulties as well as the working conditions. On the other hand, satellite data can provide an effective tool for mapping and monitoring of these areas. While high resolution satellite imageries including Ikonos and Quickbird generally provide detailed vegetation mapping, medium resolution satellite imageries including Landsat and Spot have been widely used for detecting the changes during definite time intervals. The aim of this study is to detect the changes in the wetlands between 1990–2001 along the coast of Fethiye and its inland parts by means of multitemporal Landsat data. Keywords Landsat · Wetland · Biodiversity

˙I. Ozdemir (B) Department of Forest Management, Faculty of Forestry, Suleyman Demirel University, Isparta, Turkey e-mail: [email protected]

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1 Introduction Wetlands are of particular importance for biodiversity because they exhibit a unique composition and high species richness in both flora and fauna. These areas contain large numbers of endemic or threatened species; have social, economic, cultural or scientific importance; or are representative for biological research [1]. Wetlands can be classified into various groups. Cowardin [2] classify wetlands into five major categories, which are marine, estuarine, lacustrine, riverine, and palustrine. The wetlands in this study fall into almost all these categories. The coastal wetlands, riparian corridors, marshes, forested wetlands, swamps and grasslands exist within the selected study area along Fethiye Bay coast. This area was selected as focus of this research due its urgent conservation needs. Tourism activities, pollution resulting from residual and agricultural areas, urbanization, and conversion to agriculture are some of the main factors that threaten the wetland ecosystems in Fethiye. The transformation of wetlands by human actions, summerhouses aimed, has caused environmental problems and biodiversity loss. The wildlife, notably many water birds, is therefore threatened with extinction. These biotopes need to be monitored by at short time intervals, as changes in the wetlands are rapid and serious due to these factors. Accurate and timely information plays a vital role in supporting decision making and effective sustainable management of these wetlands. Ground based survey for monitoring purpose is not entirely well-suited because of difficult reaching and working conditions in these areas. On the other hand, satellite data have provided an effective tool for mapping and monitoring of wetland environment [3]. Passive and active sensors which have various spatial resolutions have been employed for assorted mapping and monitoring tasks [4–5]. While high resolution satellite imageries including Ikonos and Quickbird generally provide detailed vegetation mapping [6], medium resolution satellite imageries including Landsat and Spot have been widely used for detecting the changes in wetland ecosystems [7–8]. This case study assesses the suitability of multitemporal Landsat data for monitoring the wetland ecosystems along Fethiye Bay coast and inland located in South-western Mediterranean Region of Turkey.

2 Material and Method 2.1 Study Area The study area (15,085 ha) is located between longitudes 29:01:04 and 29:94:20 East and 36:36:30 and latitudes 36:43:12 North (Fig. 1). The study site consists of residential areas, wetlands, forests and agricultural areas. The dominant tree species is Calabrian Pine (Pinus brutia Ten) in forested areas. The most of forested wetlands are dominated by Sweetgum (Liquidambar orientalis L.) which is one of endemic

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Fig. 1 Study area

tree species of Turkey. Oriental Plane (Platanus orientalis L.), Taurus Alder (Alnus glutinosa L. supsp. antitaurica), and Fraxinus ssp. are other tree species of the forested wetlands. The dominant vegetation found in the other wetlands are Carex ssp., Typa ssp, Tamarix parviflora DC., and Juncus ssp.

2.2 Satellite Data A change detection study requires the main following steps; (1) collect appropriate remote sensing data, (2) precise geometric registration of multitemporal images, (3) Radiometric correction, (4) select appropriate change detection algorithm, (5) acquire ground truth reference data, (6) apply accuracy assessment [9]. The appropriate selection of imagery acquisition date is extremely important in change detection applications. Anniversary or near-anniversary image acquisition date minimize the differences in pixel values resulting from seasonal vegetation fluxes and sun elevation/azimuth angle differences [10]. In this study, very nearanniversary dates the two Landsat TM scenes acquired on the 1st of August 1990 and 30th of July 2001 were used for change detection analysis. The two images were of high to excellent quality with little atmospheric noise. Soil moisture condition was the same, as no precipitation was recorded during to last a few days (Table 1). Sun azimuth and elevation angles in data acquisition time are 123.8◦ and 61.1◦ for

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788 Table 1 Some meteorological data from Fethiye 1990

July 27

July 28

July 29

July 30

July 31

Aug 1

Aug 2

Precipitation Max temperature ◦ C Min temperature ◦ C Mean temperature ◦ C Relative humidity %

No 36.6 18.4 28.0 57.0

No 33.4 20.0 27.2 65.3

No 35.4 23.6 29.3 32.0

No 33.8 24.3 27.8 45.3

No 34.5 16.4 28.0 39.3

No 36.6 16.8 27.4 53.0

No 35.8 16.4 26.7 61.7

2001

July 27

July 28

July 29

July 30

July 31

Aug 1

Aug 2

Precipitation Max temperature ◦ C Min temperature ◦ C Mean temperature ◦ C Relative humidity %

No 37.3 23.8 30.6 49.3

No 37.0 23.8 30.2 55.0

No 34.0 23.4 29.4 61.7

No 35.4 25.0 29.9 60.7

No 34.0 23.0 29.2 60.0

No 33.4 33.2 28.8 64.7

No 34.6 25.0 29.0 62.3

1990 image and 116.3◦ and 58.7◦ for 2001 image respectively. Since wetland areas are located in flat areas, these differences between the sun angles were ignored. To perform a reliable comparison between the multi-date images, a precise registration of images is vital for digital change detection. [10] For this aim, the image pair was registered to the same Universal Transverse Mercator UTM projection using 27 ground control points (GCP), producing an average root mean square error (RMSE) of 14 m (less than 0.5 pixel). The GCPs were selected from 1/25000 scaled topographic maps. This RMSE calculated can be accepted for change detection applications. Following nearest neighbour resampling method was employed in order to preserve original pixel values.

2.3 Algorithm Used Many techniques are available for digital change detection. The most commonly used methods given by Lu et al. [10] for this job include image algebra, post-classification comparison, transformation, advanced models, Geographical Information System (GIS) approaches, and visual interpretation. Advantages and disadvantages of these methods are discussed thoroughly in that review article. Choosing a method appropriate for purpose of study is very important step of change detection using satellite remote sensing data. In this study, the post-classification comparison method which is widely used and easy to understand was preferred for detecting the changes in the wetlands. The most important advantage of this method is to reduce external impact from atmospheric differences between the multi-temporal images and provide a matrix of change information. On the other hand, the major disadvantage of this approach is generally the lack of land cover information related to the old date image. As the success of this technique depends on the accuracy levels of each image classification map, the absent of reference map for historical image classification result

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in decreasing accuracy of classified image. Thus, low accurate classification of one of multitemporal images often leads to unsatisfactory change detection results. Fortunately, there were city plan maps showing the wetlands of the study region, near to image accusation date of satellite data for selecting sampling areas to train the classifier. The Object-Oriented approach was used in the classification of Landsat data. In this approach, the pixels were initially grouped according to both spectral and spatial properties of image objects by means of Multi-resolution Image Segmentation algorithm. Because each segmentation process produces a result unique to the image data, several scale parameters and a range of homogeneity criteria combinations were trialled in order to achieve an appropriate segmentation of the study image [10]. After appropriate multi-resolution segmentation, the standard nearest neighbour algorithm offered by eCognition was used to assign these independent segments to land cover classes.

2.4 Ground Reference Data One of the prerequisite of this post-classification method is high-quality and sufficiently numerous training samples for image classification [9]. The training samples for 2001 image were collected from ground using Handheld Global Positioning System device (GPS). The other training areas concerning the historical imagery were obtained from the city and forest management maps. We also made interviews with the official foundations to obtain the ground truth data. The reference test data are also needed for post-classification comparison method in order to perform an accuracy assessment on the resulting classifications. Accuracy assessment was carried out by comparing the classification maps with reference data. A confusion or error matrix where columns represent the reference data while rows display the classified data was developed to calculate the users and producers accuracy for classified classes. The classified image belonging to 2001 year was controlled by field verification with 71 reference test pixels in order to estimate the accuracy assessment. The classified image of 1990 year was controlled by comparing classified pixels with 77 reference data which are collected from city and forest maps, and archive documents.

3 Results and Discussions The Landsat images were classified to 13 land use classes. This classification were then harmonised by merging classes, resulting in wetlands and non-wetlands areas (Fig. 2). The statistics of the accuracy assessment for the two classified images were summarised in the Table 2. The wetlands were able to be mostly separated from the other land covers.

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790 Fig. 2 The classified images (a) belonging to 1990 year, (b) belonging to 2001 year

Table 2 Accuracy assessment of the classified images Classified image

For all classes Wetlands The other land uses Water

Overall accuracy KIA Producer’s accuracy User’s accuracy Producer’s accuracy User’s accuracy Producer’s accuracy User’s accuracy

Belonging to 1990

Belonging to 2001

0.94 0.90 0.92 0.89 0.91 0.94 1.00 1.00

0.93 0.89 0.88 0.92 0.93 0.91 1.00 1.00

The accuracy assessment results showed that accuracies of the classified Landsat images are enough for post-classification comparison algorithm used in the study. The resulting classified two images were incorporated by means of MAP INFO GIS software package and changed areas were localised (Fig. 3). The results showed that the wetland areas partly expand and partly narrow between 1990 and 2001 years. An enlargement with 40 ha is due to the fact that some areas classified as bare land in 1990 image were separated as wetland in 2001 image. This may result from the increase of water level after 1990 and some wetland plants may colonize until 2001. On the other hand, approximately 167 ha wetland was disappeared between 1990 and 2001 years. Similarly, a small part of this decrease may be due to a decline of water level and therefore these areas were classified as bare land in 2001 image. However, there is no doubt that a significant part of 167 ha is disappeared in the cause of urbanization. The analysis indicated that the most devastation in the wetlands was occurred in the area close to city center. In this period, many wetlands were filled with soil in order to gain a space for buildings. Besides, the sedges and mosses in the small streams were removed for the purpose of struggling against mosquitoes. These destroying activities on wetlands cause some environmental problems immediately. For example, we become aware of a drastic reduction of the number of some saltwater fishes which drop eggs in freshwater as there is left a little suitable area in the

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Fig. 3 The impact of urbanization on wetland ecosystems (green areas show increase of wetland, red areas show conversion of the wetlands into settlement)

cleaned river and the filled puddles. Filling of wetlands with soil also brings about the deformation of drainage systems of the surrounding agricultural field. In addition to summerhouses, some approbation for location in forested wetlands had given to holiday villages. For example, the holiday village shown in figure occupies a considerable amount wetland in Yanıklar river delta (Fig. 4). This occupation was not detected in the research as the holiday village had already constructed before 1990.

Fig. 4 The occupation of wetlands by holiday villages

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There was only little decreasing of the forested wetlands mostly consist of sweetgum species. Urbanization is limited in the forested wetlands as these areas officially located in forest regimes. The other gladsome issue is to be not changed the Karagol wetland in Yaniklar village until now. Karagol wetland region is still suitable habitat for wildlife and so should be carefully protected and managed. On the other hand, small wetland devastations were not able to be located in the study as spatial resolution of Landsat image (30× 30 m) was not sufficient for detecting these changes. When more detailed spatial information is needed, Spot-5, Ikonos and Quickbird satellite data with higher spatial resolution may be preferred. As a result, Landsat data seems an appropriate information source for monitoring the wetlands in large areas in order to make strategic planning in Mediterranean region. It is very important to detect the changes in wetlands on time in order to take the urgent conservation precautions for sustainable management of wetlands.

4 Conclusions The wetlands around of Fethiye city are very important habitat in terms of biological conservation. Unfortunately, as a result of intensive urbanization in the last two decades, a considerable part of these ecosystems has been lost during this period. Now, the left wetlands should be carefully defended from human activities for sustainability of these sensitive ecosystems. Therefore, constructions must be forbidden in wetlands and their surroundings. Besides, the pressures regarding to use a boat slip area of the coastal of Karagol wetland has been increasing gradually. Authorized foundations should not allow being a boat slip area of Karagol coastal.

References 1. Sarkar SK (2004) Sustainable management of wetlands: Biodiversity and beyond. In: Sage Publications India Pvt. Ltd. (ed) Jyoti Parikh and Hemant Datye, New Delhi, India, pp 290–291 2. Cowardin LMV, Carter FC, Golet ET (1979) Classification of wetlands and deepwater habitats of the United States. U.S. Department of the Interior, Fish and Wildlife Service, Washington, DC, 131 pp 3. Fuller RM, Groom BB, Mugisha S, Ipulet P, Pomeroy D, Katende A, Bailey R, Ogutu-Ohwayo R (1998) The integration of field survey and remote sensing for biodiversity assessment: A case study in the tropical forests and wetlands of Sango Bay, Uganda. Biol Conserv 86:379–391 4. Chopra R, Verma VK, Sharma PK (2001) Mapping, monitoring and conservation of Harike wetland ecosystem, Punjab, India, through remote sensing. Int J Remote Sens 22:89–98 5. Harvey KR, Hill GJE (2001) Vegetation mapping of a tropical freshwater swamp in the Northern Territory, Australia: A comparison of aerial photography, Landsat TM and SPOT satellite imagery. Int J Remote Sens 22:2911–2925 6. Wang L, Sousa WP, Gong P (2004) Integration of object-based and pixel-based classification for mapping mangroves with IKONOS imagery. Int J Remote Sens 25:5655–5668 7. Nayak S, Pamdeya A, Gupta MC, Trivedi CR, Prasad KN, Kadri SA (1989) Application of satellite data for monitoring degradation of tidal wetlands of the Gulf of Kachchh, Western India, Acta Astronaut 20:171–178

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8. Bock M (2003) Remote sensing and GIS-based techniques for the classification and monitoring of biotopes, Case examples for a wet grass- and moor land area in Northern Germany. J Nat Conserv 11:145–155 9. Jensen RJ (1996) Introductory digital image processing: A remote sensing perspective. Prentice Hall, Upper Saddle River, NJ, 318 pp 10. Lu D, Mausel P, Brondizio E, Moran E (2004) Change detection techniques. Int J Remote Sens 25(12):2365–2407

Analyzing Changes in Coastal Biospheres using Remote Sensing and Geographic Information System Techniques, Northern Nile Delta, Egypt H. Effat, M.N. Hegazy, and H.El. Gameely

Abstract The Northern Nile Delta coastal zone in Egypt has unique environmentally sensitive conditions. The area contains a coastal lagoon protectorate El Burullus lagoon which is the landing for immigrant birds from Europe. The area contains several urban features such as an international highway, a port and some towns. Several stressors occur in the area. These are reflected by the sea level rise problem ranging between 1.2–1.3 mm/yr. The problem is magnified by land subsidence, sea water intrusion and shoreline erosion. Despite the stress, the Northern Nile Delta coastal zone is exerting severe changes. Those changes are both natural and anthropogenic causing environmental degradation of the area. This paper aims at conducting an analysis for the changes occurring and their causes. The area is studied during a period of 13 years during which major development decisions took place. Two multi-date satellite imageries, Landsat-5TM and Landsat-7 ETM+ acquired in 1987 and 2000 were used. The rectified images were classified to produce the Land use/Land cover maps and a Matrix function is applied to detect and quantify the changes that occurred in each class. A model was used to discriminate the accretion and erosion zones of the shoreline. The results of the study show that the study area is undergoing both anthropogenic and natural changes. The most significant changes are reflected in the transformation of the wetlands either to water bodies used as fish farms or dried up for urbanization amounting to 23.4 km2 or for land reclamation amounting to 25.5 km2. Eroded shoreline amounted to 6.87 km while accreted shoreline amounted to 7.97 km during the study period. The use of Remote Sensing and geographic information system techniques provided an integrated vision for understanding the various trends and patterns of changes in the study area. Keywords Satellite data · Geographic information system (GIS) · Shoreline erosion · Land use changes · Classification · Matrix · Nile Delta · Egypt

H. Effat (B) The National Authority of Remote Sensing and Space Science (NARSS), Cairo, Egypt e-mail: [email protected]

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1 Introduction The study area extends between the two branches of the Nile outlets for 160 km occupying the Northern delta coastal zone between 30◦ 20 and 31◦ 55 East and 31◦ 20 and 31◦ 40 North. The study area extends for 160 km between the two branches of the Nile outlets The Mediterranean Sea borders its northern boundaries as shown in Fig. 1. The area of the site is about 864 km2 . The soil of the Nile delta is mainly alluvial consisting of either clays or clay loams of about one meter depth, overlying marine shells, sand and silts. El Burullus lagoon protectorate comprises a body of water of area 410 km2 and is considered a worldwide habitat for international immigrant birds. The most significant activities in the region are the natural gas extraction that started in 1975 with a rate of 200 m3 /day and increased to 8.5 million m3 /day in 1989. Salt marshes are available near Abu Maddy with annual production of 9–12 tons. The northern Nile delta has a low population density compared to the mid and south parts of the delta. The population in Damietta sector reaches around 295,000 while in Gamassa /Baltim sector it is around 80,000 [4]. The northern Nile delta coast, which extends a 50 km wide

Fig. 1 Location and extent of the study area

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land strip, has an elevation less than two meters above sea level as a majority of its land and is protected by a one to 10 km wide coastal belt only (Fig. 2). The change detection in this study area was divided into two categories: 1. Change caused by human activities: this was obvious in the change of land cover due to a change in land use and building new features such as the international coastal hightway. 2. Change caused by the natural forces: such as the shoreline erosion and accretion.

2 Materials and Methods Two multi-dates Landsat TM scenes are used in this study. Each date was represented by two scenes. The first coverage is dated 1987 with path 177 and row 38 and path 176 and row 38 while the second dated 2000 with path 177 and row 38 and path 176 and row 38. Both images were acquired during July therefore share the same summer season which allows for a better correlation and comparison. Topographic map of the northern Nile delta scale 1:50,000 obtained from the Egyptian Survey Authority, [1] and the Geological Map of the Nile delta scale 1: 500,000 Hydro-geological Map of the Nile delta scale 1:500,000. Data were converted to UTM projection WGS 84. The Landsat scenes are geometrically corrected using the same map projection parameters as the base map. The two scenes of each date are mosaicked to produce the complete coverages for the study area. The different analyses are applied on the mosaicked scenes.

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2.1 Change Detection of Land Use and Land Cover The two satellite images were classified in order to identify and quantify the different categories of land use/land cover. The satellite image of 1987 was classified using a hybrid technique. The water bodies were separated in band 4 and masked out in the satellite image. The unsupervised classification was performed using thirty classes and eight iterations. A supervised classification was performed on the multispectral image using bands 7,4,2 and 3 layers stack and using 40 signatures. Using the geological map [2] of the same date of the satellite image as a visual reference, it was possible to discriminate and separate the sand dunes and the sand deposits and the sabkha. The vegetation and mixed bare land were separated from an unsupervised classification of band two. Classes are combined in a model using ERDAS imagine to produce the final LU/LC map for 1987 shown in Fig. 3. The satellite image 2000 was classified using a supervised classification technique and having the same LU/LC classes as the 1987 shown in Fig. 4. The two classified images Landsat TM 7 dated 1987 and Landsat ETM+ dated 2000 and used to detect changes in land cover were both acquired during the month of August. To detect and calibrate the changes in land use/land cover (LU/LC) a Matrix function applied on the result of the two multi-date classified thematic maps in ERDAS, the changes in each land use/land cover were produced as shown through Figs. 5, 6 and 7. The changes in shoreline were detected using a model to discriminate the changes into two classes erosion and accretion as shown in Figs. 7 and 8.

Fig. 3 Classification of the 1987 Landsat-5 TM imagery

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Fig. 4 Classification of the 2000 Landsat-7 ETM+ imagery

Fig. 5 Changes from wetlands to other land use

2.2 Change Detection of the Shoreline Changes The GIS model shown in Fig. 9 was used to compare the two images. The land was given a value of one while the sea was given the value of zero. The output of a pixel-to pixel comparison between the two images was one of three options. The

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Fig. 6 Changes from Sand dunes to other land use

Fig. 7 Result of the matrix showing the changes from and to various land use

same pixel value is considered not change in the shoreline. The change from land (carrying the value of 1) to water carrying the value of zero) means an erosion pixel. This model enabled the classification of the shoreline into three classes [5]. Those classes are the erosion, accretion and no-change areas. Thus was also possible to locate and quantify the eroded and the accreted zones that took place in the period between the two satellite images.

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Fig. 8 Results of the matrix showing the changes from water bodies to other land use

3 Results and Discussion 3.1 Results of the Matrix The result of the land cover change detection shows that severe changes have been occurring in the northern part of the Nile delta region. Sabkha and wetlands are mostly converted into water bodies amounting to 41.349 km2 that is used as fish farms or reclaimed for agriculture amounting to 25.58 km2. The conversions are mainly to water bodies to be used as fish farms or to vegetated lands following the land reclamation programs. Sabkhas bordering El Burullus lagoon are converted either to fish farms or to cultivated lands. Changes from sabkha or wetlands are shown in Fig. 5. The sand dunes changed from 153.8 to 165 km2 reflecting an immense decrease in it volume. Knowing the importance of the coastal sand dunes in stabilizing the shoreline, this change is considered an environmental degradation shown in Fig. 6.

3.2 Result of the Shoreline Changes Model The shoreline between the Rosetta and Damietta branches has been experiencing erosion and accretion detected and quantified from the multi-date satellite images. The eroded areas amounted to 6.874 km2 while the accreted areas amounted to 7.972 km2 as shown in Fig. 10. The result of running the shoreline changes model highlighted the severe erosion zone in Rosetta sector and the accretion zone around the Damietta Port that necessitates its routine clearance works.

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Fig. 9 Model for detection of shoreline changes from the two dates satellite images Land sat TM 1987 and Land sate ETM+ 2000

4 Conclusion 1. The classification of the two multi-date satellite images Landsat TM produced the land use/ land cover maps. It also produced a land inventory for the study area. This inventory result is used in detecting the changes in the land use/ land cover patterns during the period between the two multi-date satellite images. 2. Studying the pattern of changes in Land use/ land cover provides a baseline for studying the impact of development in the area on its environmental components. It also facilitates the environmental assessment of any proposed plan in addition to providing a baseline for setting an environmental management programs for the region. This is an important issue in urban and environmental planning.

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Fig. 10 Result of the shoreline changes model discriminating the shoreline changes as detected from the multi-date Landsat TM satellite imageries 1987 and 2000

3. The shoreline status map helps to locate the areas in need of future management and shoreline protection. It was also possible to locate stable zones where coastal resorts can be proposed in a development plan. As erosion is a problem that is costly to recover, it is advised to avoid locating new coastal resorts in such zones. Accression zones resemble problems to certain development projects such as the Damietta port. The use of remote sensing and geographic information system analysis techniques provided unveiled the problems in the study area. It also provided a tool for exploring the conditions suitable for sustainable land use decisions. Acknowledgement The Authors are greatly indebted to Prof Adel Yehia, Prof Ali Nasser and Prof Magda Ebeid, Ain Shams University, Egypt for their review and support to this study.

References 1. 2. 3. 4.

Egyptian General Authority of Survey (1993) Topographic map for the Nile delta scale 1:5000 Egyptian General Petroleum Corporation, Conoco Coral (1987) The Geological map of Egypt Erdas (1999) ERDAS Field Guide, ERDAS, Inc., 5th ed. Atlanta, GA, 665p Egyptian Ministry of Housing and New Communities; The General Organization for Physical Planning (2002) The integrated development plan for the Northern Nile Delta as a New Urban Community. (Arabic) 5. Effat H (2004) Environmental assessment of the plans of urban development on coastal zones using remote sensing and geographic information technologies. PhD thesis, Ain Shams University, Cairo, Egypt

Exploring the Egyptian Terrain Characteristics from Space for Strategic Planning M.N. Hegazy and H. Effat

Abstract Shuttle Radar Topographic Mission (SRTM) data have been used in this study for mapping the terrain characteristics of the Egyptian territory. The 30 arc second (=900 m) resolution data is found to be the most suitable for the national scale mapping. The Egyptian political boundary was used to clip USGS GTOPO_U30 topo data Digital Elevation Model (DEM) for the Egyptian terrain. Using the DEM produced by the SRTM, different GIS layers were created using the ARC/G1S 9.0 software. These layers include all the necessary base map layers for terrain analysis, namely Contour, Elevation zones, Slope angle, Aspect, Hillshade, Drainage network and basins. Each layer map gives a clear idea about one parameter of the terrain as elevation zone map explains the topography distribution, highest and lowest altitudes. Slope angle map shows the distribution of sleep and gentle slope areas in Egypt. Aspect map explains the direction of the land slope differentiating as example areas facing north from others facing south. Hillshade map classifying Egyptian terrain into areas with more or rare shade, Maps of the drainage network and basins outlines the Egyptian terrain into different drainage basins regarding the surface runoff and consequently point out areas vulnerable to flash flood hazard and others with more probability for ground water supply. A rather new idea of creating an active, desktop for the Egyptian terrain is established. This active desktop gives the values of five parameters for a chosen point by using the cursor These terrain five parameters include values of X. Y, Z, slope angle and Aspect. The study of terrain characteristics is essential for strategic Planning and pre-planning decisions. Unveiling the land potentials and constraints, the terrain characteristics related to surface analysis and GIS cartographic modeling is a decision support tool. Keywords Shuttle Radar Topography Mission (SKTM) · Slope · Aspect · Hillshade · Terrain Characteristics · GIS · Strategic planning · Egypt

M.N. Hegazy (B) The National Authority for Remote Sensing and Space Science (NARSS), Cairo, Egypt e-mail: [email protected]

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1 Introduction Egypt is a republic in Northern Africa situated in Africa except for Sinai Peninsula east of the Suez Canal which is situated in Asia, Egypt covers an area of almost one million square kilometers in North Africa and Western Asia. The country shares land borders with Libya to the West, Sudan to the South, and Israel and the Ghaza Strip to the northeast. It has coasts on the north and east by the Mediterranean Sea and the Red Sea respectively. According to the world Fact Book, 2006 Egypt is the fifteenth most populous country in the world. The vast majority of its 78 million populations (2006 estimation) are mainly concentrated in the Nile Valley and the Delta as well as in the coastal zone along the Mediterranean Sea. Inhabited area resembles only 4% of the total territory. The total area of Egypt amounts to 1,001,450 Km2 . Land occupies 995,450 Km2 and the water bodies occupying 6,000 Km2 . The ocastline is 2,450 km long while the land boundaries measures 2,689 km long. The border countries are Ghaza Strip 11 km, Israel 255 km, Libya 1,150 km, Sudan 1,27,1 km, 32,220 Km2 (2003) and occupies about 2% of the total area. The cultivated land is reflected by the Nile Delta and Valley.

2 Materials and Methods 2.1 The Remotely Sensed Data The main source of the data used in this study is The Shuttle Radar Topography Mission (SRTM). SRTM data obtained elevation data on a near-global scale to generate the most complete high-resolution digital topographic database of Earth. SRTM consisted of a specially modified radar system that flew onboard the Space Shuttle Endeavour during an 11-day mission m February of 2000. SHTM is an international project spearheaded by the National Geospatial-Intelligence Agency (NGA) and the National Aeronautics and Space Administration (NASA). The SRTM Digital Elevation Model was used to map the Egyptian’s Terrain from Space. The following arc descriptions of the Functions for Surface analysis used in this study: 2.1.1 Production of the Contours Map from the SRTM Digital Elevation Model Contours are polylines that connect points of equal values. Contours are produced by the interpretation of the raster surface model, Contours can be useful for finding areas of the same values, examining the elevation values for specific locations and examining the overall gradation of the land. The distribution of the polylines shows how values change across a surface. Where there is little change in a value, the polylines are spaced farther apart. Where the values rise or Tall rapidly, the polylines arc closer together. Contours are also a useful surface representation because they

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Fig. 1 The Contour map of Egypt derived from the SRTM data

allow to simultaneously visualizing flat and steep areas (distance between contours) and ridges and valleys (converging and diverging polylines). The contour function was run using the Digital Elevation Model for the Egyptian Territory. Result is shown in Fig. 1.

2.1.2 Production of the Elevation Zones Map A DHM is a raster representation of a continuous surface, usually referring to the surface of the Earth. The accuracy of this data is determined primarily by the resolution. The digital elevation model (DEM) produced by the SRTM was classified into zones. Those zones can be changed according to the threshold needed for each study. The Elevation zones for Egypt that were constructed in this study is shown in Fig. 2.

2.1.3 Production of the Slope Map The Slope function calculates the maximum rate of change between each cell and its neighbors, for example, the steepest downhill descent for the cell (the maximum

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Fig. 2 The elevation zones of Egypt as derived from SRTM data

change in elevation over the distance between the cell and its eight neighbors). Every cell in the output raster has a slope value. The lower the slope value, the flatter the terrain; the higher the slope value, the steeper the terrain. The output slope raster can be calculated as percent of slope or degree of slope. When the slope angle equals 45◦

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degrees, the rise is equal to the run. Expressed as a percentage, the slope of this angle is 100% as the slope approaches vertical (90◦), the percentage slope approaches infinity. Slope is the rate of maximum change in z value from each cell. The use of a Z-factor is essential for correct slope calculations when the surface z units arc expressed in units which are different from the ground x,y units. Degree of slope is a value between 0 and 90. The slope function is run using the SRTM Digital elevation model for Egypt. The product was the slope map of Egypt as shown in Fig. 3. 2.1.4 Production of the Aspect Map Aspect is the direction of maximum rate of change in Z value from each cell in a raster surface. It is expressed in positive degrees from 0 to 359.9, measured clockwise from the North. If a cell in the input raster is zero slope that is flat it is assigned a value of −1. Aspect identifies the down-slope direction of the maximum rate of change in value from each cell to its neighbors. (Aspect can be thought of as the slope direction). The values of the output raster will be the compass direction of the aspect (ARC/GIS9 Guide). Running the Aspect function on the slope image produced the Aspect map for Egypt shown in Fig. 4. 2.1.5 Producing the Hill Shade Map The Hillshade function obtains the hypothetical illumination of a surface by determining illumination values for each cell in a raster. It does this by setting a position for a hypothetical light source and calculating the illumination values of each cell in relation to neighboring cells. It can greatly enhance the visualization of a surface for analysis or graphical display, especially when using transparency. By default, shadow and light are shades of gray associated with integers from 0 to 255 (increasing from black to while). The azimuth is the angular direction of the sun, measured from north in clockwise degrees from 0 to 360. The Hillshade function computes values for a raster surface by considering the illumination angle and shadows. HillShade creates a shaded relief raster from a raster. The illumination source is considered to be at infinity. The analysis of shadows is done by considering the effects of the local horizon at each cell. Raster cells in shadow arc assigned a value 0. The Hillshade function is run for the SRTM elevation of Egypt. The product was the hillshade map for Egypt shown in Fig. 5. 2.1.6 Producing the Drainage Network and Basins An understanding of the shape of the Earth’s surface is useful for many fields such as regional planning, agriculture and forestry. These fields require an understanding of how water flows across an area, and how changes in that area may affect that flow. When modeling the flow of water, one may want to know where the water came from

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Fig. 3 The slope map of Egypt derived from SRTM data

and where it is going. The Hydrology model in Arc GIS 9 was run using the SRTM elevation data for the Egyptian Terrain in order to identify the stream networks and basins. Sinks were removed running the model to derive surface information Results are shown in Fig. 6.

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Fig. 4 The aspect of Egypt derived from SRTM data

2.1.7 Producing the Terrain Characteristics Active Desktop A rather new idea of creating an active desktop for the Egyptian terrain is established. This active desktop givcs the values of five parameters for a chosen point by using the cursor. These terrain five parameters include values of X, Y, Z, slope angle and Aspect. Using ERDAS imagine 8.7 software a layer stack function was

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Fig. 5 Drainage network and basins of Egypt derived from SRTM data

applied using the three layers; the elevation, the slope and the aspect. The result was a layer stack image (.img) that depicts those three parameters in addition to the two parameters (x and y) available in the image information in the viewer as seen in fig. 7.

3 Results and Discussions Elevation extremes: From studying the elevation zones of Egypt, the 30 elevation zones classified the Egyptian terrain into ranges as shown in fig. 2. The first range less than 1 m elevation occupies the narrow strip of the coastal zones for the Mediterranean Sea and its lagoons and the Red Sea. It also occupies vast areas in El Qattara Depression and its neighboring areas E1 Fayoum and its lake Qaroun. The Lowest point known as the Qattara Depression −133 m fell into the first zone Highest point: Mount Catherine 2,629 m. The result map shows the Egyptian Terrain elevation falling in the range of −150 to 2,700 m as shown in Fig. 3. The slope map : The Slope map shows the areas with the variations of slope zones within the Egyptian territory. Zones with gentle slopes are distributed between the

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Fig. 6 The active desktop in ERDAS imagine showing the five parameters: x–y (location), z (elevation), the slope angle, aspect (slope direction in Azimuth) for the cursor location

Nile Delta and the Nile Valley. Some scattered gentle slopes exist in the Qattara depression and some scattered zones in the Western desert. Zones of steepest slopes were found to exist in Zones in South Sinai and Red Sea mountainous areas as shown in Fig. 3. The Aspect Classes Map shows the zones of the various orientations within the Egyptian lands as shown in Fig. 4. This map is essential for the Land use planning and assignments of the various areas for different land use. The hydrologic analysis functions described here arc designed to model the water flow across a natural terrain surface. Results are the basins and the stream flow maps shown in Fig. 5. Those maps are essential for the studies of flash flood hazards and for potential areas for groundwater reservoirs.

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References 1. Arc GIS9 Desktop Software Help References 2. ERDAS imagine 8.5 Field Guide, 2004 3. Heffni K, Shatta A (2004) The underground water in Egypt. The ministry of water resources and irrigation. ARTS Press, 4. Shuttle Radar Topography mission (2000) United States geological survey (USGS). On-line satellite data. Accessed 2005 5. The Global Land Cover Facility (GLCF) University of Meryland. On-line satellite data. Accessed 2005

Composting and Solid Waste Management in Dhaka City Md. Niamul Bari, Md. Kumruzzaman, Mohammad Harun ur Rashid, and Md. Muzibur Rahman

Abstract Solid Waste Management (SWM) is one of the major environmental problems in many municipal towns and cities throughout the world. In most of the cases, municipal authorities are struggling to find the best method to manage their residents’ wastes. Approximately 3,500–4,000 metric tons of solid waste is generated in Dhaka City. Nearly 50% of generated solid waste is collected and dumped as crude landfill. The rest of the generated wastes remain uncollected and create serious environmental hazard in Dhaka City and uninhabitable situation/dismal for its dwellers. However, a little research works are conducted to find the appropriate solution of the problem. Recently, Waste Concern (Non Government Organization) takes initiative to tackle the problem employing composting technique in a small community such as Mirpur in Dhaka. Wastes are collected as house-to-house basis by rickshaw van. Subsequently, the inorganic parts are sorted out from the waste and organic parts are converted into compost (organic fertilizer) using windrow type aerator. In this study, the applicability of composting operation is studied in terms of technical, economical, social and environmental aspects as an alternative option of solid waste management. Also, a thorough investigation is carried out among the house owners/dwellers on environmental condition due to application of such method. Primary result indicates that this method is technically sound, environmentally safe, cost effective and socially viable. Keywords Composting · Community · Solid Waste Management

1 Introduction Solid Waste Management (SWM) is one of the major environmental problems in many municipal towns and cities. In most cases municipal authorities are struggling Md.N. Bari (B) Department of Civil Engineering, Rajshahi University of Engineering and Technology, Rajshahi, Bangladesh e-mail: [email protected]

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to find the best method to manage their residents’ wastes. The population of Dhaka, the capital of Bangladesh, is growing at a phenomenal rate overwhelming all the efforts to improve the living conditions and posing an enormous challenge to those responsible for management of its development and providing urban services to citizens. Approximately 3,500–4,000 metric tons of solid waste is generated per day, with an average generation rate of 0.5 kg/cap/day, from various residential, commercial and industrial activities [1]. Only 50% of this is collected and some of it is dumped as landfill [2]. The rest of the generated wastes remain uncollected, which makes environmental scenarios of Dhaka City gloomy and dismal for its dwellers. A Non Government Organization (NGO) named Waste Concern started community based waste management programs by employing composting at Mirpur, Dhalpur, Green Road and Bailey Road in Dhaka. Wastes are collected from house to house by rickshaw van from the mentioned area and organic wastes are converted into compost (organic fertilizer) after sorting into organic and inorganic part. This study tries to assess the feasibility of composting operation as an alternative option of solid waste management considering technical, economic, social, and environmental aspects.

2 Methodologies The compost plant at Mirpur section-2 operated by Waste Concern was considered for this study. To satisfy the objectives, a thorough investigation was conducted on number of family that are involved in this project, daily generation of waste, composition, physical characteristic, waste collection performance, plant operation performance, production of compost, respective expenditure and income of the project. To know the real picture of environmental condition and satisfaction level of the participant family, a questionnaire survey was conducted among the house owners at Mirpur section-2. Necessary data was collected from the authority of Waste Concern. Thus the collected data was analyzed and made a conclusion.

3 Study on Compost Plant at Mirpur Waste Concern started this program in the year 1995 at Mirpur. This is the first program. Lions Club of Mirpur supported the program by giving land beside their office. Wastes are collected from 850 house/family. Every day approximately 3,500– 4,000 kg wastes is produced in this area. Considering average waste production is 3,750 kg/day. Hence yearly production of wastes is 1,368.75 tons. Organic wastes are 75–80% of total generated wastes [3]. Rest inorganic wastes are disposed at nearest DCC waste collection container. Organic wastes are converted into compost. Compost production rate is 22.50% of organic waste [3].

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3.1 Waste Collection and Sorting Wastes are collected following house-to-house collection system. Only three rickshaw-van and 6 persons are engaged in waste collection. These three rickshaw vans are utilized for the collection of seven (7) trips of wastes. Each van is used atleast for two trips. Collection works are started at 10 a.m. and it takes almost six hours. Plate 1 shows the collection of waste. Collected wastes are unloaded from rickshaw van at waste sorting shade. Then these raw wastes are sorted out into organic and inorganic part. Organic wastes are piled for composting and inorganic wastes are stacked for disposal by DCC waste collection truck. Plate 2, Plate 3 and Plate 4 show the waste unloading and sorting activities and inorganic waste respectively.

Plate 1: Collection of Waste

Plate 3: Waste Sorting

Plate 2: Waste Unloading

Plate 4: Inorganic Waste

3.2 Composting of Waste At Mirpur site Waste Concern used windrow type aerator for waste composting (Fig. 1). The aerators are bamboo made in triangular shaped. Organic wastes are piled on this triangular shaped aerator. The length, base and height of aerator are 2.44 m, 0.66 m and 0.533 m respectively. Cross sectional area of triangle is 0.176 m2 and volume is 0.43 m3 . Air has flown through this cross sectional area and along the length of pile. The dimension of base of wastes on aerator is 1.68 m and height is 0.92 m. Its cross section is not accurately triangular shaped, but it may call semi parabolic. For

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0.66 m

Fig. 1 Windrow type bamboo made aerator

calculating cross sectional area it is measured an average width and it is (0.92 m + 1.68 m)/2 = 1.30 m. So cross sectional area is 1.20 m2 and volume is 2.93 m3 . The net volume of wastes on aerator is 2.93 m3 – 0.43 m3 = 2.50 m3 . Organic wastes are piled on aerator by a team of worker. Wastes then start to decompose aerobically with the help of bacteria. To accelerate the decomposition activity Waste Concern add effective microorganism (innoculums), it is called simply e.m. The decomposition period of organic wastes is in this case 25 days, but without e.m. it takes 40 days. Organic wastes on pile are stirred after few days interval. To control moisture and temperature water also added. After 25 days decomposed wastes is unloaded from aerator and stack for maturation on maturation place. Here decomposed waste is matured within 15 days. Then the matured compost is screened and graded as finish product. This finished product (compost/organic fertilizer) is stored for sale. Plate 5 and Plate 6 show the waste composting and compost screening respectively.

Plate 5: Waste composting

Plate 6: Compost screening

3.3 Performance Study of Worker Composting operation is being done manually. It is labor-intensive operation. In this project one project manager, one office assistant and one peon are the official

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Table 1 Performance of composting workers Type of work

Quantity (kg)

Worker

Time (h)

Capacity (kg/cap/h)

Raw wastes sorting Organic wastes piling Compost unloading Compost screening Compost storage

3,750 3,000 675 675 675

8 8 8 6 6

2.00 0.50 0.50 4.00 0.50

234.00 750.00 168.75 28.00 225

strength. There are eight (8) workers engaged for raw wastes sorting, organic wastes piling and decomposed wastes unloading from aerator. The time spent for these works are 2.5 h, 0.5 h and 1.0 h respectively. They sort out about 3,750 kg of raw wastes, piled approximately 3,000 kg organic wastes and unload from aerator 675 kg of decomposed wastes. Again six (6) workers are engaged for screening this 675 kg decomposed wastes after maturation. Requirement of time for this work is 6 h. After screening compost is categorized in different grades by this time. These 6 workers store this 675 kg of compost in only 0.5 h. The summery of performance of workers is shown in Table 1.

3.4 Study of Density Density of raw wastes was measured in two ways. A full bucket of raw waste was weighted and self-weight of bucket was deduced from the gross weight. The gross weight of raw waste was 15.50 kg and net weight was 14.50 kg. The dimension of this bucket was measured by measuring tape. Top diameter was 0.36 m, bottom diameter was 0.27 m and height was 0.34 m. Volume of bucket was calculated 0.0265 m3 . Then the density of raw waste was calculated 547.24 kg/m3. The weight of organic waste after sorting was taken as 15.15 kg in the same bucket. Density of organic waste was calculated 572.00 kg/m3 . After decomposition of waste, weight was taken as 16.20 kg and density was calculated 611.23 kg/m3. The weight of finished compost after screening was taken as 16.60 kg and density was calculated 623.00 kg/m3 . This is shown in Table 2.

Table 2 Density of waste in different stage Mixed waste (kg/m3 )

Organic waste (kg/m3 )

Decomposed waste (kg/m3 )

Matured compost (kg/m3 )

547.24

572.00

611.23

626.40

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3.5 Requirement of Area for Composting Collected wastes are unloaded in a place where raw wastes are also sorted out into the organic and inorganic wastes. It is steel angle framed tin shaded area, dimension of which is 4.6 m × 7.6 m and covered area is 350 m2 . Composting place is also steel angle framed tin shaded area. Composting shade is two numbers, whose one dimension is 12.20 m × 4.88 m and second dimension is 10.67 m × 7.62 m. Total covered area is (59.54 + 81.30) = 140.85 m2 . Decomposed wastes maturation place is open space. It is 9.15 m × 9.15 m = 83.70 m2 . Compost screening area is steel angle framed tin shaded place. It is 4 m × 5 m = 20 m 2 . Compost storage place is steel angle framed tin shaded and fenced by tin. It is 12.20 m × 4.88 m = 59.54 m2 . The project office is a brick made R.C.C. top slab single room. It is 10 m2 . The area for internal road and open space is approximately 35.9 m2 . Total land used for composting operation is 700 m2 . Table 3 shows the requirement of land for various activities of composting. Table 3 Requirement of area for compost plant Unload and Area (m2 ) sorting Composting Maturation Screening Storage Office Inter road Total 350.00 140.85

83.70

20.00

59.54

10.00

35.9

700

3.6 Economic Analysis The expenditure is mainly two types, capital cost and operation-maintenance cost. Heads of expenditure are wastes collection, compost production, electricity & water connection and marketing.

3.6.1 Wastes Collection Cost Waste Concern purchased three rickshaws vans each Tk.8,000 ∴ Total capital cost was 8,000 × 3 = Tk.24,000 Annual maintenance cost is 10% of capital cost = Tk.2,400 Monthly salary 5 collector is Tk.6,000@ Tk.1,200 Monthly salary of one rickshaw van driver is Tk.1,500 Total monthly salary for wastes collection is Tk.7,500 ∴ Yearly total salary for wastes collection is 7,500 × .12 = Tk.90,000 Yearly expenditure for collector uniform is Tk.3,000 @ Tk.500 ∴ Total annual operation and maintenance cost for waste collection is Tk.92,900

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3.6.2 Compost Production Cost Capital cost of compost production due to shade construction and land purchase. Total area of shade for wastes sorting, composting, screening compost storage and office is (350 + 140.854 + 20 + 59.54 + 10) = 580.39 m2. Capital cost of shade @ Tk.522.41 is Tk.303,201 Maintenance cost is 10% of capital cost = Tk.30,320 Wastes Concern did not purchase land. So, there is no expenditure for land. Monthly salary 13 workers @ Tk.1,200 is Tk.15,600 and one worker is Tk.1,500 Monthly salary for project manager, office assistant and peon is (5,000 + 3,000 + 1,500) = Tk.9,500 ∴ Yearly total salary for waste composting is (15,600 + 1,500 + 9,500) × 12 = Tk.319,200 Yearly expenditure for worker dress @ Tk.500 is Tk.7,000 Yearly expenditure for instrument and equipment is Tk.2,500 ∴ Total annual operation and maintenance cost for composting = (30,320 + 319,200 + 7,000 + 2,500) = Tk.359,020 and total capital cost is Tk.303,201 3.6.3 Water Supply and Electricity Connection Cost They have no water supply connection of WASA. They use tube well water. So, water supply cost is zero. Electricity supply charge is Tk.1,000 per month. So, yearly charge is Tk.12,000. 3.6.4 Compost Marketing Cost Waste Concern did not market compost directly. They sell compost to Map. Agro and they improve compost by adding nutrient and Alfa Agro market this. So, they have no marketing cost. But here marketing cost is considered as 10% of compost production cost. 3.6.5 Annual Expenditure of Project General Formula Annual Cost = Capital Cost × CRF + Annual O & M Cost − Salvage value × SF CRF = {i(1"+ i)n } / {(1 + i)n − 1} ! (Capital Recovery " ! Factor) 15 15 = 0.1(1 + 0.1) / (1 + 0.1) − 1 = 0.131 ! " SF = (Sinking Fund) = i/ {(1 + i)n − 1} = 0.1/ (1 + 0.1)15 − 1 = 0.031 i = Discount rate = 10% (assumed) n = Design period = 15 years Salvage value = 1% of capital cost Annual cost of wastes collection = Captial Cost × CRF + Annual O & M Cost − Salvage value × SF = 24,000 × 0.131 + 92,900 − 2,400 × 0.031 = Tk.95,969

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Annual cost of compost production = 303,201 × 0.131 + 359,020 − 30,320 × 0.031 = Tk.397,799 Annual cost of marketing = 0.1 × 397,799 = Tk.39,780 Annual cost of water and electricity = Tk.12,000 ∴ Total annual expenditure = Tk.95,969 + Tk. 397,799 + Tk.39,780 + Tk.12,000 = Tk.454,548

3.6.6 Income of the Project Waste Concern income from the households for waste collection and compost sale. Waste collection charge is Tk.15.00–Tk.20.00 per month. Wastes are collected from 850 households. Waste collection charge is @ Tk.20.00 from 650 households and @ Tk.15.00 from 200 households. Selling rate of compost is @ 2.50 Tk./kg. Annual production of compost is 246,375 kg. ∴ Income from waste collection is Tk.16,000.00 per month ∴ Annual income from waste collection is Tk.192,000.00 ∴ Annual income from compost sale is Tk.615,937.50 ∴ Total annual income is (Tk.192,000.00 + Tk.615,937.50) = Tk.807,937.50 ∴ Net income is (Tk.807,937.50 − Tk.545,548) = Tk.262,389.50 ∴ Net unit income is (262,389.5 ÷ 1,368.75) = Tk.192.00/ton of generated waste.

4 Community Response There are 850 household are involved with the composting activity of Waste Concern at Mirpur, Section-2. Field investigation from last week of October to second week of November of 2002 among 137 house owner out of 850 to assess the community response about the composting. About 80% of 137 households were involved from the beginning of waste collection and composting activities of Waste Concern. Cent percent household preserved their wastes to supply to waste collector. 96% households said their environment is non-odorous and 4% said moderately odorous. To assess the awareness about composting among that house owner, there were seven questions have asked. Awareness about composting, compost, organic fertilizer was found cent percent. Cent percent house owners were known that their produced wastes were converted into compost by Waste Concern and about 87% house owners were known the crop or vegetables that produced by using organic fertilizer (compost) are hygienic. Again 74% house owners were known about soil conditioner. The house owners pay Tk.20.00 per month to Waste Concern for waste collection purpose. That area was mostly educated and moderately sophisticated. Those house owners were in middle to upper middle-income level. So awareness level is satisfactory.

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5 Conclusion The following conclusions are drawn on the basis of results obtained from this study work and field investigation considering technical aspects, economic aspects, social aspects and environmental aspects.

5.1 Technical Aspects (i) Cent percent wastes may be collected by house-to-house wastes collection system. (ii) Only the inorganic non-reusable wastes are disposed of by the municipal authority. (iii) Total organic wastes (biodegradable) are converted into compost (an organic fertilizer).

5.2 Economical Aspects The net unit income from waste composting is Tk.192/ton of generated solid waste.

5.3 Social Aspects (i) About 80% of total generated solid wastes would be converted into compost. In this regard it reduce the maximum volume of generated waste. It saves the more requirements of land for sanitary landfill. (ii) The produced compost is a good soil conditioner. It would be used as an organic fertilizer. It would be used as a substitute of chemical fertilizer. (iii) The compost is screened for different grades; hence it will be able to fulfill the demand for different types of farmers. (iv) The market value of compost is very cheaper than chemical fertilizer. It would save the farmer’s money. (v) It can earn extra income from wastes, which was previously creating nuisance and polluting the environment. Now the wastes have turned into resource for community. (vi) It saves the scarcity of land.

5.4 Environmental Aspects (i) Waste composting is an aerobic system and less odorous, so, it is less harmful for environmental pollution.

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(ii) All these analyses performed in the present study lead to the conclusion that the composting of solid waste can be an appropriate and profitable alternative option of solid waste management.

References 1. Ahmed MF, Rahman MM (2000) Water supply and sanitation: Rural and low-income urban communities. ITN, Bangladesh 2. DCC (1999) Solid waste management of Dhaka city. Dhaka City Corporation, Dhaka 3. Enayetullah I, Sinha AHMM (1999) Potential Site for decentralized composting in Dhaka: A spatial analyses. Aborjana O Paribesh, 3:3–4

Assessment of Dissolved Pollutants in Krishna River Using Mass Balance Approach M. Chandra Sekhar and B. Shailamber

Abstract The River Krishna in Andhra Pradesh is typical receiving water body for urban and rural runoff. The river shows strong seasonal dependence for various constituents and the water quality deteriorates sharply as municipal and Industrial wastes are joining the River Krishna. The important characteristic associated with the pollution of the river is the slightly reduction of self-purification process over a stretch of about 85 km. A chemical mass balance approach has been used for measuring changes in the concentration and/or load to the river, which in turn calculates the transport of pollutants. The mass balance calculations conducted for certain water quality constituents indicated that additional inputs are needed to account for the observed differences in load along the river. The sources may include nonpoint sources of pollution due to agricultural activities, sediment remobilization or entrainment, ground water intrusion or a combination of these sources. Mass balance calculations over a 4 years period indicate that pollutants are retained in the sediments of the investigated 85-km long reach of the stream (2,500 kg of Potassium, 40,000 kg of Sodium, 25,000 kg of Chloride, 2,000 kg of Fluoride and 2,000 kg of Silicates). Other pollutants such as Calcium, Magnesium and Sulphate appear to retained and washed-out, depending on leading rates and local stream conditions. The retained pollutants represent a substantial part of the total mass transport through the stream (10–75%). Almost 80% of the transported Potassium is retained within the stream sediment. Subsequently, the deposited pollutants represent a potential pollutants source. Keywords Chemical mass balance · Dissolved pollutants · Krishna river

M.C. Sekhar (B) Water and Environment Division, Department of Civil Engineering, National Institute of Technology, Warangal 506 004, India e-mail: [email protected]

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1 Introduction Studies on in-stream reactions have received increased attention during recent years. There are several reasons for this. Because of substantial efforts to reduce point pollution sources, the relative effect of nonpoint pollution has increased. This has increased the need to identify major sources of nutrients and trace elements deposited with in the river system. The increasing environmental problems due to acidification and metal contamination of streams have also required a more fundamental understanding of pathways for dissolved and particulate metal transport. A commonly used approach to study in stream reactions, deposition, erosion, or resuspension is chemical mass balances. This approach may be useful when dynamic and highly variable relationships between physical and chemical mechanisms on a larger scale with in a given reach of a river must be understood. This work presents detailed water budgets and mass balances of water quality constituents such as Potassium, Sodium, Calcium, Magnesium, Nitrogen, Chloride, Fluoride, Sulphates, Silicates for a 85-km-long river reach in the A.P. Katz et al. [7], Paces [9] and Christophersen and Wright [4] used chemical mass balance approach to study in-stream reactions, deposition, erosion, or resuspension phenomena. Berndtsson [3] used chemical mass balance approach for river Hoje in Sweden. The results of the study indicated that an essential pollution build up seems to take place in stream sediments which receive rural and urban runoff. Water budgets and mass balances of some water quality constituents are also established. Albek [1] has investigated the chloride-discharge relationship at several stations on Turkish streams, to identify natural and anthropogenic sources of chloride. Comparison between upstream and downstream monitoring sites reveal changes in the concentration and load to the river and can be used to discriminate between point and non point sources of pollution for the parameters considered in the river [5, 6, 11].

2 Description of the Study Area Krishna River is one of the major perennial rivers, which drains three important States of South India. The river basin is the second largest river basin which is situated in the Deccan plateau. The river Krishna drains an area of 258,948 km2 , which is nearly 8% of the total geo-graphical area of the country. The total population in the basin as per 1991 causes has been estimated as 60.78 million. There are about 25 towns within the basin with the population more than hundred thousands. The river and its tributaries flow through different terrain having varied land use activities, soil conditions, vegetation and agricultural practices. The water potential of the River Krishna and its tributaries are mainly used for drinking, industries, irrigation and power generation. The study area in particular is part of the Krishna River reach between two monitoring stations: Pondugala (upstream) and Wadenapalle (downstream) separated by 80 km. In addition to other districts, major parts of

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Nalgonda and Guntur districts drain into this part of the Krishna river reach in Andhra Pradesh. Typical tropical climate with two seasons: dry (December–May) and wet (June–November) seasons prevails in the area.

3 Methodology The Central Water Commission (CWC) of Government of India is collecting hydrological data i.e., gauge and discharge observations and water quality data in River Krishna. Standard methods for examination of water and wastewater [2] are being adopted for collecting water quality data. Mass balances are used for the pollutant loads observed at upstream and downstream monitoring sites during different seasons [8, 11, 12]. Indirect estimation of loads from polluting sources using upstream and downstream river water quality is quite helpful for monitoring studies with limited data. If one is interested in information of constituents from individual sources, then indirect measurement of the sum the sources is possible in the receiving water using the following equation. QD CD − QU CU =

n

Li

i=1

where QD and QU are downstream and upstream flows, CD and CU are the downstream and upstream concentrations in the river water and Li , is the sum of all individual point loadings to the river. The equation represents the mass budget and can be used to determine a much more accurate estimate of than that likely to be obtained from summing the individual loadings. Here, the term Li is not only the sum of loadings entering the receiving water body, but rather the net effect of the loading plus any loss/generation within the water body. For pollutants that undergo significant volatilization/degradation, this approach will not give accurate segments, unless the time of travel between upstream and downstream stations is small compared to the pollutant decay constants.

4 Results and Discussions The present study has shown significant contributions from the basin drained by the river stretch under study. In certain cases this type of study also can be used to study the essential pollution build-up in stream sediments which receive urban and rural runoff. However, due to short travel time between the monitoring stations, which is 12–14 h in the lean period, the possibility of pollution retention/accumulation is insignificant in the present study. Pollutants such as Calcium and Magnesium appear to washed out, depending on loading rates and local stream conditions. The contributions represent a substantial part of the total mass transport through the stream (5–65%). Subsequently, the contributions represent a potential source of pollution

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Table 1 Contribution of pollutants from the river reaches through chemical mass balances

K+ Na+ Ca++ Mg++ Cl− F− SO4 2− SiO3 2−

Post monsoon t/day

% Contribution

Pre monsoon t/day

% Contribution

2 25 79 115 60 89 19 −270

27 30 19 24 27 24 17 12

1 8 –2 13 9 0.5 −1 3

2 10 –9 21 −3 −4 −0.5 18

which however, also depends on their form and speciation. At present, flushing of bottom sediments at the investigated reach is a natural phenomena, due to the variations in discharges between pre-monsoon and post monsoon season, due to heavy flows in the river, and hence accumulation in the sediments may not be considerable over the years which demands dredging of sediments. However, possibility of pollutants in the sediments may not be completely ruled out without sediment investigations, which are beyond the scope of the present study. The mass budgets display the typical annual cycle. It appears that the premonsoon period represents the period when flow contribution is mainly due to base flow and the discharge in more or less constant (continuous contribution). This period is followed by a period when water is drained from the surroundings to the stream (continuous negative balances) due to rainfall events. A continuous contribution occurs for most of the constituents. Table 1 shows the deviation in total contribution divided by the total influx to the reach. The relation between the total contribution and total mass flux into the reach is also given. It is seem that the contribution in most cases is a substantial part of the total flux. The negative loads for some of the pollutants indicate reduction in the flux over the 4 year period especially in the pre-monsoon period cannot be explained with the help of data available. More classified data pertaining to individual sources of pollution, base flow and land use characteristics are necessary to explain such variations.

5 Conclusions The Krishna river is polluted due to various activities such as Industrial, Agricultural, and also due to urbanization. Industries are discharging their partially treated waste into the river and the runoff from Agricultural lands and Urban areas are also entering into the river and responsible for river quality degradation. It is necessary to make a detailed study of the water quality of river, to estimate the level of pollution and also the main sources of pollution. This will help in developing strategies to control the pollution in the river. In present study statistical analysis of

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water quality is taken up at two sites on river Krishna to understand the water quality dynamics. Large variations in flow are significant at both the monitoring stations and the rainfall pattern & distribution in the study area support such conclusion. These variations affect water quality of the river. Cyclical nature is observed in some parameters both at upstream and downstream. It is observed from the time series plot that the seasonal variations are more. Sodium, Calcium, Fluoride, sulphates, silicates are showing more seasonal variations at both upstream and downstream site compared to Potassium and Magnesium. Potassium, Chloride and magnesium both at upstream and downstream are showing less significant seasonal variations.

References 1. Albek, E (1999) Identification of the different sources of chlorides in streams by regression analysis using chloride-discharge relationships, Water Environ. Res. 71:1310–1319 2. APHA (1992) Standard methods for the examination of water and wastewater, 18th edn. APHA, New York 3. Berndtsson R (1990) Transport and sedimentation of pollutants in a river reach: A chemical mass balance approach. J Water Resour Res 26(7):1549–1558 4. Christophersen, N Wright, RF (1981) Solphate budget and a model for sulfate concentration iin stream water at Birkenes, a small forested catchment in Southenmost Norway. Wat. Resour. Res., 17:377–389 5. Dolan DM, El-Shaarawi AH (1989) Inferences about point source loadings from upstream and downstream river monitoring data. Water Resour Res 26(7):343–357 6. Jain CK (1996) Application of chemical mass balance to upstream/downstream river monitoring data. J IAHS 182:105–115 7. Katz, BG Bricker, DP Kennedy, MM (1985) Geochemical mass-balance relationship for selected ions in precipitation and stream water: Catoctin Mountains, Maryland. American Journal of Science, 285:931–962 8. Latimer LS, Carey CG, Hoflman EJ, Quinn JG (1988) Water quality in the Pawtuxet River; metal monitoring and geochemistry. Water Resour Bull 24(4):791–800 9. Paces, T (1985) Sources of acidification in central Europe estimated from elemental budgets in small basins. Nature 385:31–36 10. Plummer LN, Back W (1980) The mass balance approach: Application to interpreting the chemical evaluation of hydrologic systems. Am J Sci 280:130–142 11. Sekhar MC (2001) Immission approach for modelling dissolved solids in a river and separation of point and nonpoint loads, Ph.D. Thesis, Regional Engineering College, Warangal, India 12. Yuretich RF, Batchelder GL (1988) Hydro chemical cycling and chemical denudation in the fort river watershed, Central Massachussetts: An approach of mass balance studies. Water Resour Res 24(1):105–114

Copper (II) Removal from Water by Natural Zeolites Sukru Dursun, M. Emin Argun, Nazan Celik, and Fatma Celebi

Abstract Clinoptilolite adsorption capacity as a natural matter of the copper (II) ions from artificial polluted water was investigated in this study. In the experimental studies, zeolite mineral which is 25–140 mesh size was used by activating with 0.1 M HCl, and copper ion removal efficiencies were determined. Experiences that were under batch condition were studied at different pH values, temperatures and shaking speeds. In the studies, at different pH’s; maximum efficiency was found as about 87% at pH 5. Similarly, experiments were carried out at different temperature values, and the maximum efficiency was obtained at 30◦ C. The efficiency obtained under these conditions is 89.95%. The highest copper removal efficiency was obtained at 200 rpm, and the removal efficiency was measured as 89.62%. Keywords Heavy metal · Copper · Adsorption · Zeolite · Clinoptilolite · Removal efficiency

1 Introduction One of the important environmental problems is heavy metal ions in the contaminated water originated from industry. Wastewaters containing heavy metals have low BOD (biological oxygen demand) and these waters have very high toxicity for microorganisms responsible for biological treatment. There are many heavy metals produced from the industry. One of the most popular metal, copper may be found a lot of industrial wastewater. Heavy metal pollution exists in many industry waste waters, such as metal plating facilities, mining operations, nuclear powerhouse, fertilizer industries, paints and pigments, municipal and storm water run-off, battery and tannery industries [17]. The soils surrounding many military bases are S. Dursun (B) Department of Environmental Engineering, Engineering Faculty, Selcuk University, Konya, Turkey e-mail: [email protected]

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also contaminated and have a risk of metal contaminations for ground and surface water. Some metals associated with these activities are as follows; copper, cadmium, chromium and lead. Heavy metals are not biodegradable and tend to accumulate into living organisms, causing various diseases and disorders. Copper and its compounds are found frequently in surface water, because it is a ubiquitous metal in the environment. The most widely used methods for removing copper (II) are as follows; precipitation with chemical and electrochemical methods or sometimes with sulphides [7, 13, 18]. A major problem with this type of treatment is the disposal of the precipitated wastes. Ion exchange treatment which is the second most widely used method for copper removal does not present a sludge disposal problem and has the advantage of reclamation of Cu (II) [19]. This method can reduce heavy metals to very low levels. However, ion exchange treatment does not appear to be economical. Activated carbon is also efficient for removal of trace elements from the waste water, but its high cost has prevented its wide usage. The adsorption phenomenon has still been found economically appealing for the removal of toxic metals from wastewater by choosing some adsorbents under optimum operation conditions. It has been reported that some aquatic plants [23, 6], agricultural by-products [4, 5, 11, 20], sawdust [16], clay [15], zeolite [1], turba [22, 10] and microorganisms [12] have the capacity to adsorb and accumulate heavy metals. Cost comparisons are difficult to make due to the scarcity of consistent cost information. Although many experiments have been accomplished in the area of low-cost sorbents, a great deal of work is necessary to understand better low-cost adsorption processes and to demonstrate the technology. Natural zeolites have ion exchange and removal capacity. Clinoptilolit has high removal capacity of metal ions Pb+2 , Cu+2 , Zn+2, Cd+2 , Ni+2 , Fe+2 and Mn+2 . Clinoptilolites exist at Balıkesir, Bigadiç and Gördes in Turkey. It is an economical ion exchange material comparing with the synthetic resin. Natural zeolites have been used as adsorbent and ion exchanger with discovering crystal feature and some chemical structure (Table 1). It is physical structure look like a selective sieve and named as moleculer sieve by Mc Bain [14].

Table 1 Ion exchange of capacity of some zeolites [9] Mineral

Chemical composition

Ion exchange of capacity (meq/g)

Analsim Lavmontit Natrolit Mordenit Flipsit Eriyonit Shabazit Klinoptilolit

Na16 (Al16 Si32 O96 ) 16H2 O Ca4 (Al8 Si46 O108 ) 16H2 O Na16 (Al16 Si24 O80 ) 12H2 O Na8 (Al8 Si40 O96 ) 24H2 O (Na, K)10 (Al10 Si22 O64 ) 24H2 O (Na, K, Ca)9 (Al9 Si27 O72 ) 27H2 O (Ca, Na)6 (Al12 Si24 O72 ) 40H2 O (K4 Na4 )(Al8 Si40 O96 ) 24H2 O

4.54 4.25 5.26 2.29 3.87 3.12 3.81 2.54

Copper (II) Removal from Water by Natural Zeolites

Zeolite A

833

Zeolite Z

Fig. 1 Crystal structure of A and Z Zeolite

General formula of the Zeolites is Mx/n .Al2 O3 .xSiO2 .yH2 O. M is a cation (Na+ , K+ , Ca++ etc.) which ratio (y/x) changes from 1 to 5. SiO4 and AlO4 octahedrals are the monomers of the zeolites that Si or Al was centre of the structure and oxygen was on the corners. Crystal structure of A and Z zeolites are given the Fig. 1 [24]. Zeolite potential of Manisa-Gördes, operating by M.T.A (Mine Technical Search Institute), is 20 million tonnes reserve capacity. Balıkesir-Bigadiç has 500 million tonnes zeolite reserve capacity and total zeolite capacity of Turkey is 50 billion tonnes [3]. Clinoptilolit, mordenit, shabazit and filipsit etc. natural zeolites were used for removal of NH4 + ion due to its low price and providing easily. Specially, clinoptilolit gave high performance, and have been used for treatment of liquid wastes. Natural zeolites were also uses at industrial fish ponds [2]. Chelischev [8] used clinoptilolit as ion exchanger for heavy metals. Similarly Sato and Fukagawa [21] used clinoptilolit for nitrogen removal at detergent industry waste water. The aim of this study was removal of the ionic copper pollution from the preliminary treated water using clinoptilolit as a natural and economical material.

2 Materials and Method In this study, Beyköy region clinoptilolite was used provided from Susurluk town of Balıkesir city in Turkey. Its chemical analysis showed that it is member of hydrated alumina-silicate mineral containing mostly alkali and soil alkali metals originated in hols of volcanic rocks. They contain hydrate in hols connected each other. Chemical composition of the clinoptilolite is given in Table 2. Particle size is 50–2000 μ of 82.56% materials and 2–50 μ others. Porosity ratio was about 50% and natural hydrate capacity and ion exchange capacity were 25.68% and 71.73 meq/100 g respectively. Materials used in this study were between 25–140 mesh size.

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Colour (dry)

5Y 8/1 (White)

Useful heavy metal and microelements (ppm)

Colour (wet) Sand (%) Clay (%) Silt (%) Structure

5Y 6/3 (Light olive) 82.56 3.44 14.00 Silty sand

Fe Cu Zn Mn Total elements

2.33 0.032 0.31 2.34

Density Volume weight Porosity (%) Natural hydrate capacity (%) Colourless point (%) Useful hydrate (%) Humidity (%) pH Total salt (%) CaCO3 (%) Org. matter (%) Total nitrogen (%) Useful phosphor (%) Cation exchange capacity (me/100g) Changeable cations (meq/100g)

2.14 g/cm3 1.10 g/cm3 48.47 25.68 23.24 2.44 5.84 7.62 0.03< 1.25 0.34 0.0084 (84 ppm) 0.0068 (68 ppm) 71.73

SiO2 (%) Al2 O3 (%) Fe2 O3 (%) CaO (%) MgO (%) Na2 O (%) K2 O (%) MnO (%) Pb3 O4 (%) ZnO4 (%) Cu (ppm) Zn (ppm) Cd (ppm) Ni (ppm) Co (ppm)

70.05 9.84 0.96 2.15 0.58 0.24 1.44 0.05 0.0014 0.0044 1.56 34.95 0.09 4.25 0.43

Ca++ Mg++ Na+ K+

21.00 12.00 11.52 27.18

Cr (ppm) Mo (ppm) Fire lost (%) –

2.36 trace 14.06 –

Gallenkap (U.K.) thermostatic shaker incubator was use for batch experiments. Copper concentrations were measured by Dr. Lange Cadas-200 Spectrophotometer (Germany). The pH was adjusted to required values using Jenway 3010 pH meter. 25–140 mesh size clinoptilolite was treated with acid or base solution in different concentration to improve its adsorption capacity. For this process, 2.0 g of clinoptilolite in 100 ml distilled water containing different amounts of acid or base was shaken at different shaking seeped and temperature, and finally 1 h 200 rpm and 23 h 100 rpm at 30◦ C stable temperature. Clinoptilolite samples were washed twice with distilled water after treating aside solution. With this procedure, the best activation media was determined 5.0 ml 0.1 N HCl additions. For this reason, activated Clinoptilolite samples with 5 ml 0.1 N HCl were used in following experiments. After designing the activation media, to optimum adsorbent amount, each 2 g of activated clinoptilolite was added in 100 ml tap water contains different concentration of Cu2+ . After 1 h contact time in batch rector, clinoptilolites were filtered form fine nylon filter and concentration for Cu2+ was measured using Curvette test via Cadas 200 UV-Vis spectrophotometer. Effect of pH on the adsorption capacity of 2 g of clinoptilolites was tested adjusting pH of the 100 ml adsorption

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solution (40 mg/l) via adding different amount of acid or base. Effect of ambience temperature was also investigated. Experiments were run at the temperatures of 5, 10, 20, 25, 30 and 35◦C the conditions designated earlier experiments. Four different shaken speeds 150, 200, 250 and 300 rpm were studied to test effect of shaken speed on adsorption.

3 Results 3.1 Activation Exponents Clinoptilolite samples were activated using 0.1 N HCl (Fig. 2) or NaOH (Fig. 3) to increase the adsorption capacity. Figure 2 shows that the best activation condition was addition of 5 ml 0.1 N HCl in 100 ml distilled water containing 2 g of clinoptilolite.

Cu+2 removal efficiency (%)

50 40 30 20 10 0

Fig. 2 Effects of 0.1 N HCl additions on Clinoptilolite activation

0

1

2

3

5

4

6

7

8

Addition of 0.1 M HCl amount (ml)

Cu+2 removal efficiency (%)

35 30 25 20 15 10

Fig. 3 Effect of 0.1 N NaOH onto Clinoptilolite activation

0

1

2

3

4

Addition of 0.1 M NaOH amount (ml)

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3.2 Effect of Initial Cu(Ii) Concentration by the Clinoptilolite Adsorption

Fig. 4 Removal efficiency of Cu+2 from different Cu+2 solutions

Cu2+ removal efficiency (%)

Determination of effective Cu2+ concentration on removal efficiency of clinoptilolite was studied with addition of 2.0 g of activated adsorbent in different concentration of 100 ml Cu2+ solution. Figure 4 shows that the maximum removal efficiency was obtained with 40 mg/L Cu2+ concentration, and than increasing the initial heavy metal concentrations in the solutions decreased the removal efficiency. It is likely that a given mass of adsorbent material has a finite number of adsorption sites, and that as metal concentrations increase, these sites become saturated. That is, there is some metal concentration that produces the maximum adsorption for a given adsorbent mass, and thereafter, adding more metal cannot increase adsorption because no more sites are available: all are occupied [4]. 80 70 60 50 40 30 0

30

60

90

120

150

Cu2+ concentration (mg l–1)

3.3 Solution pH Effect on Adsorption Capacity Effect of pH on the adsorption of Cu(II) by the clinoptilolite was investigated with the changed pH values from 2 to 9. Figure 5 depicting the dependence of the Cu (II) removal as a function of pH shows that maximum removal efficiencies have

Cu2+removal efficiency (%)

100

Fig. 5 Effect of solution pH on removal efficiency of Cu+2 from water

80 60 40 20 0 2

3

4

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6

7

pH of adsorption solution

8

9

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been achieved to be 88.89 % at pH 5. According to different pH values Cu ions may present in different forms. Cu+2 ions dominates at pH<6 and Cu(OH)2 dominates at pH>6 [5].

3.4 Effect of Sample Temperature on Cu2+ Removal Capacity of Clinoptilolite Activated 2 g of clinoptilolite in 100 ml water at pH 5 was tested for adsorption of Cu+2 at different temperature between 5 to 35◦C. Figure 6 shows that optimum working temperature was 30◦C. Removal of Cu+2 from the water was 83.95% at this temperature, it was lowered at higher and lower temperature.

3.5 Effect of Shaking Speed on Cu+2 Adsorption of Clinoptilolite from the Water

Fig. 7 Cu+2 removal efficiency from the water at different shaking speeds

100 80 60 40 20 0 0

10

20

30

40

o

Temperature ( C)

Cu2+ removal efficiency (%)

Fig. 6 Effect of medium temperature on the clinoptilolite removal efficiency of Cu+2 from the water

Cu2+ removal efficiency (%)

Experiments were run at different shaking speed from 150 to 300 rpm that 200 rpm was optimum shaking speed for this study. 89.62% Cu+2 removal efficiency of

100 80 60 40 20 0 150

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from the water was obtained at 200 rpm shaking speed. Figure 7 demonstrated that removal efficiency of Cu (II) increased with increasing shaking speed until 200 rpm, and than decreased. This may be explained with the existence of electrostatic bond between Cu(II) and clinoptilolite which may break off at high speed. This effect can also be attributed to the decrease in boundary layer thickness around the adsorbent particles as a result of increasing the degree of mixing.

4 Discussions This paper presents the results of Cu(II) ions removal from aqueous solution using a common, naturally occurring clinoptilolite. Operational parameters such as initial Cu(II) concentrations, pH of the solution, temperature, and shaking speed clearly affect the removal efficiency. The optimum Cu(II) removal by the clinoptilolite was obtained at pH 5. At pH higher than 6, copper removal probably resulted primarily from precipitation rather than adsorption. According to results reported in this study, copper adsorption mechanisms by clinoptilolite may be explained as follows: 1. Vander-walls and hydrogen binding of copper with hydroxyl group of clinoptilolite surfaces. 2. Ion exchange between Cu(II) ions and exchangeable cations (Na, K etc.) which balance negative charge of aluminium atoms. 3. Diffusion of Cu(II) through selective sieve of clinoptilolite named as molecular sieve [14]. According to these results, natural clinoptilolite appeared to be a promising adsorbent for the removal of the copper from the polluted water. A process using the clinoptilolite for the removal of heavy metal seemed to be potentially more economical than current process technology. However, further studies would be suggested, since different metals and different adsorbents are known to have different properties structures. Heavy metals affect to human health because of their harmful effect. Nevertheless, a lot of heavy metals were using in the industry and they join to food chain. In this respect, wastewaters coming from pollution sources must be treated to decrease their concentration down to limits given in water regulations before to give in the environment. Main principle removal processes base to chemical precipitation of metal ions as -hydroxide or -sulphide. Adsorption, ion exchange, membrane filtration and reverse osmosis etc. were used for advanced treatment. Removal of the metal pollution from the water with the classical methods was not enough sufficient, practical and economical. Ion exchange method may be used after pre-treatment operation [25]. Most of the heavy metals recovery was not easy from the precipitate and economic. For this reason, adsorption processes by the natural zeolites may be preferred in the application.

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In this investigation, a natural zeolite, clinoptilolite, as an adsorobent was used for removal of copper from the water and very high removal efficiencies were found with different working conditions. Clinoptilolite was activated treating with different concentrations of acid and alkali solution in the first step. Tests in this investigations show that optimum activation condition was addition of 5 ml 0.1 N HCl in100 ml distilled water containing 2 g of clinoptilolite. After activation process, other experimental conditions were investigated. Second test was determination of usage of concentration of Cu+2 which is optimum at 40 mg L–1 . Removal rate was reached about 75% with this copper concentration. Activated clinoptilolite with same condition given above and 40 mg L−1 Cu+2 concentrations adsorption solution were used in the following experiments to test other conditions. pH of the adsorption solution was other important condition which was tested. A maximum 84% removal efficiency was found at pH 5. This showed that clinoptilolite was activated in acidic condition changing cations with H+ ions and Cu was 2+ ions form in the working solution. After this experiment temperature and mixing rate were determined. Removal efficiency was increased until 30◦C, and then decreased. Acknowledgment The authors thank the Selcuk University Research Found (BAP) for providing financial support of the work described in this paper (Project no: 06201004).

References 1. Álvarez-Ayuso E, Garcia-Sánchez A, Querol X (2003) Purification of metal electroplating waste waters using zeolites. Water Res 37(20):4855–4862 2. Ames LL (1967) Zeolitic removal of ammonium ions from agricultural waste waters, In Proceedings of the 13th Pacific Northwest Industrial Waste Conference, Washington State University, Pullman, WA, pp 135–152 3. Anonym (1996) Di˘ger Endüstri Mineralleri Çalı¸sma Raporu. TC Ba¸sbakanlık Planlama Te¸skilatı, DPT No. 2421 Ö˙IK 48 Cilt-10, Ankara 4. Argun ME, Dursun S, Gür K, Özdemir C, Karatas M, Dogan S (2005) Adsorption of copper on the modified wood (pine) materials. Cell Chem Technol 39:581–593 5. Argun ME, Dursun S, ¸ Özdemir C, Karata¸s M (2006) Heavy metal adsorption by modified oak sawdust: thermodynamics and kinetics. J Hazardous Mat 141:77–85 6. Axtell NR, Sternberg SPK, Claussen K (2003) Lead and nickel removal using Microspora and Lemna minor. Bioresour Technol 89(1):41–48 7. Chen JP, Yoon JT, Yiacoumi S (2003) Effects of chemical and physical properties of influent on copper sortion onto activated carbon fixed-bed columns. Carbon, 41:1640–1649 8. Chelischev NF (1974) Ion exchange of heavy metals on Clinoptilolite. Doklady Akademii nauk SSSR 217:1140–1141 9. Hanson A (1995) Natural zeolites. Industrial Minerals, Dec, pp 40–55 10. Ho YS, Wase DAJ, Forster CF (1995) Batch nickel removal from aqueous solution by sphagnum moss peat. Water Res 29:1327–1332 11. Karata¸s M (2004) Konya Ana Tahliye Kanalında A˘gır Metallerin ˙Incelenmesi Bitki ve Topraktaki Birikiminin Tespiti, Selçuk Üniversitesi Fen Bilimleri Enstitüsü, Yüksek Lisans Tezi, Konya 12. Li Q, Wu S, Liu G, Liao X, Deng X, Sun D, Hu Y, Huang Y (2004) Simultaneous biosorption of cadmium (II) and lead (II) ions by pretreated biomass of Phanerochaete chrysosporium. Sep Purif Technol 34(1–3):135–142

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13. Marani D, Macci G, Pagano M (1995) Lead precipitation in the presence of sulphate and carbonate testing of thermodynamic predictions, Water Res 29(4):1085–1092 14. Mc Bain JN (1932) The Sorption of Gases and Vapors by Solids, G. Rutledge Sons, London 15. Márquez GE, Ribeiro MJP, Ventura JM, Labrincha JA (2004) Removal of nickel from aqueous solutions by clay-based beds. Ceram Int 30(1):111–119 16. Özdemir C (2005) Chromium removal from the wastewater on raw material of saw dust. Cell Chem Technol 39:325–329 17. Patterson JW (1977) Wastewater treatment. Ann Arbor Science Publisher Inc. New York 18. Patterson JW (1985) Industrial wastewater trearment technology. Butterworths, Boston 19. Petrus R, Warchol J (2003) Ion exchange equilibria between clinoptilolite and aqueous solutions of Na+ /Cu2+ , Na+ /Cd2+ and Na+ /Pb2+ . Micropor Mesopor Mat 61:137–146 20. Ricordel S, Taha S, Cisse I, Dorange G (2001) Heavy metals removal by adsorption onto peanut husks carbon: Characterization, kinetic study and modelling. Sep Purif Technol 24(3):389–401 21. Sato M, Fukagawa K (1976) Treatment for Ammoniacal Nitrogen Containing Water, Japan. Kokai, 76068967, 4 22. Twardowska I, Kyziol J (2003) Sorption of metals onto natural organic matter as a function of complexation and adsorbent–adsorbate contact mode. Environ Int 28(8):783–791 23. Volesky B, Weber J, Park JM (2003) Continuous-flow metal biosorption in a regenerable Sargassum column. Water Res 37(2):297–306 24. Yörüko˘gulları E (1997) Do˘gal Zeolitlerde Fiziksel Adsorpsiyon Uygulamaları. Anadolu Üniversitesi Yayınları No. 988, Eski¸sehir 25. Yurdakoç MK, Güzel F, Tez Z (1989) Katyon de˘gi¸sim kapasitesi (KDK) ve belirleme yöntemleri. IV. Ulusal Kil Sempozyumu, Cumhuriyet Üniversitesi, Sivas, s. 183–187

Biodegradation of 4-Chlorophenol in Biosurfactant Supplemented Activated Sludge Ayla Uysal and Aysen Turkman

Abstract Biosurfactants improve the removal of some recalcitrant pollutants in contaminated water and soil. The production and usage of man-made chemicals in industry has led to the entry of any xenobiotics into the environment. One such group of xenobiotics is chlorinated phenols. In this study, the treatment performance of 4-chlorophenol (4-CP), which is one of the most recalcitrant chlorophenols, was investigated using a biosurfactant added activated sludge bioreactor system with changing sludge retention time. Glucose was used as co-substrate and the COD concentration was kept constant during the experiments. JBR 425 rhamnolipid was used as biosurfactant. A control reactor (without biosurfactant; R1) and a test reactors (with biosurfactant addition; R2 and R3) were used in parallel tests. Three lab-scale continuous reactors were run in parallel with the same chemical oxygen demand (COD) and 4-CP loading rates. COD, 4-CP removal efficiencies and biomass concentrations with varying sludge age (3–25 days) were investigated. The effects of food to mass (F/M) ratio on the COD and 4-CP removal efficiencies were also investigated in the reactors. Operation at a sludge age of 3 days resulted in more than 77% COD and 46% 4-CP and 81% COD and 63% 4-CP removals in R2 and R3, while it resulted 61% COD and 19.15% 4-CP removals in R1. Keywords Sludge retention time · F/M ratio · 4-Chlorophenol · Biosurfactant · Activated sludge

1 Introduction Due to their high toxicity, strong odor emission and persistence in environment and suspected carcinogenic and mutagenic characteristics to the living organisms, chlorophenols pose a serious ecological problem as environmental pollutant [2]. A. Uysal (B) Department of Environmental Engineering, Dokuz Eylul University, Tınaztepe Campus, Buca, Izmir, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_79,

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Their fate in the environment is of great importance. Hence, the removal of phenol and chlorinated organic compounds from wastewater is a necessary task to conserve the water quality of natural water resources [8]. 4-chlorophenol (4-CP) is formed from chlorination of wastewater, from chlorine bleaching of pulp and from breakdown of phenoxy herbicides such as 2,4-dichlorophenoxyacetic acid [13]. 4-CP is used as a disinfectant in homes, farms, hospitals, and as an antiseptic for root canal treatment. Despite the recalcitrant nature of chlorophenols, there are still some efforts being made toward their biological treatment with specialized culture conditions, because of economical reasons and a low possibility of by-product formation. The microorganisms used are usually aerobes. Aerobes are more efficient at degrading toxic compounds because they grow faster than anaerobes and usually achieve complete mineralization of toxic organic compounds, rather than transformation as in the case of anaerobic treatment [10]. Surfactants can either be chemically synthesized (synthetic) or microbially produced (biosurfactants). Biosurfactants are usually classified based on their biochemical nature and the microbial species producing them [7]. For specific applications, biological surfactants have advantages over synthetic surfactants due to their structural diversity, biodegradability, and effectiveness at extreme temperatures, pH and salinity [15]. Sludge retention time (SRT) is one of the important factors in determining the state of the biomass in activated sludge system, and is also an important parameter affecting effluent wastewater quality, COD and chlorophenols removal efficiency. The concentration of mixed liquor suspended solid (MLSS) in the bioreactor increases with increasing SRT. A number of researchers indicated surfactant enhancement in microbial degradation of organic contaminants [3, 4, 16, 12, 14, 5]. However, no study was on enhanced biodegradation of 4-chlorophenol using a surfactant in an activated sludge. The main purpose of this study was to investigate the potential effects of sludge retention time on the treatability 4-CP and COD in the biosurfactant added activated sludge bioreactor systems.

2 Materials and Methods 2.1 Experimental System A continuously stirred tank reactor (CSTR) was used in the experimental study. Volume of the aerobic reactor was 8.75 l and the volume of the settling unit, 1.15 l. The influent wastewater was continuously fed through the top of the reactor by a feed pump and the reactor was aerated by an air pump. Passage of the effluent wastewater from the aeration tank to the sedimentation tank was through the

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holes in the inclined plate. The effluent from the sedimentation tank was collected in an effluent tank. The sludge age was adjusted by discarding a certain volume of activated sludge from the aeration step of the aerobic reactor every day.

2.2 Organisms and Wastewater Composition A mixed culture was used in the aerobic reactors. The activated sludge culture was obtained from the wastewater treatment plant of Pak Maya Bakers Yeast Company in Izmir, Turkey. The aerobic reactors were inoculated with this culture. The synthetic wastewater used throughout the studies was composed of glucose as carbon source, urea as nitrogen source (150 mg/l), KH2 PO4 as phosphorus source (30 mg/l), MgSO4 7H2 O (75 mg/l), CaCl2 (50 mg/l), FeCl3 (2 mg/l) and constant concentrations of 4-CP (250 mg/l). In experiments, influent contained 1,500 mg/l COD, and nitrogen and phosphorus concentrations were adjusted to maintain C/N/P= 100/10/2. Water solubility of 4-CP is about 27 g/l at 20◦C [6]. 4-CP was dissolved in water solution to prepare 5,000 mg/l stock solution and added directly from stock solution to obtain the desired concentration. COD concentration was kept constant at 1,500 mg/l in experimental study, by adjusting glucose concentration depending on the other additions. When biosurfactant was added to the tests reactors at critical micelle concentration (15 mg/l) or 2CMC (30 mg/l), it means that organic matter was also added since COD value of biosurfactant was determined as 50 mg/l COD (for CMC) and 100 mg/l COD (for 2CMC). Consequently, amount of glucose to be added synthetic wastewater was determined by both 4-CP and biosurfactant amounts.

2.3 Biosurfactant The rhamnolipid (designated JBR 425) was kindly donated by Jeneil Biosurfactant Company, Saukville, WI, USA as a mixture of R1 and R2. R1 had the chemical formula C26 H48 O9 , and R2, C32 H58 O13 . JBR 425 was chosen because the biosurfactant showed no toxicity to activated sludge biomass with an EC50 (effective concentration) = 1,000 mg/l. This is the best test result possible. This means that this surfactant could be added to wastewater treatment plants at concentrations <1,000 ppm with no adverse effects. The biosurfactant used in the study has been tested by the producer company for the biodegradability. Test was accomplished in accordance with OECD (Organization for Economic Cooperation and Development) 301D for ready biodegradability. According to OECD 301D “Ready Biodegradability” test, the biosurfactant showed a biodegradability rate of 68.4% on the 10th day of the 28-day test cycle. This is an excellent test result clearly demonstrating that JBR 425 is readily biodegradable [11].

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2.4 Experimental Procedure Three reactors with the same structure and volume as described above were used in parallel tests. Continuous activated sludge experiments were performed at different sludge ages between 3 and 25 days while hydraulic residence time (HRT) was kept constant throughout the experiments at θH = 17 h. The feed COD and influent 4-CP concentration were kept constant throughout the experiments as COD0 =1,500 mg/l and 4-CP0 =250 mg/l. Sludge was removed from the reactor periodically to adjust the sludge age to the desired level, and it was varied gradually from the highest to the lowest level. Sludge age, i.e. mean cell residence time, was changed by removing a certain fraction of the sludge from the aeration tank every day. For example, 10% (1/10) of the sludge was removed from the aeration tank every day to adjust the sludge age to 10 days. Every experiment was conducted until the systems reached the steady-state condition, yielding the same COD and 4-CP concentrations in the effluent for the last 3 days. The samples collected from the feed and effluent wastewater at steady-state were analyzed for COD and 4-CP contents after centrifugation. In all the experiments, temperature and pH were kept at T = 20 ± 2◦ C and pH = 7 ± 0.6. Dissolved oxygen (DO) concentration was kept around 3 mg/l in the reactors.

2.5 Analytical Methods Samples were centrifuged at 6,000 rpm for 25 min to remove biomass and other solids from the liquid medium. The clear supernatant was analyzed for COD and 4-CP. Standard methods based on digestion and reflux were used for COD analyses. The 4-CP analysis were carried out on the clear supernatant using the 4-aminoantipyrine colorimetric method based on the procedure detailed in Standard Methods for the Examination of Water and Wastewater [1]. Biomass concentrations in the liquid phase were determined by filtering samples from 0.45 μm pore size membrane filters and drying the filter paper in an oven at 103◦C until constant weight. DO and pH measurements were carried out by using the DO and pH meter probes and a WTW MultiLine P3 pH/OXI-SET Analyser. The dissolved oxygen probe contains also a temperature probe which was used for measuring the temperature in the aerobic tank. All the experiments and measurements were done in duplicate and arithmetic averages were taken throughout the analysis.

3 Results and Discussion A set of experiments were performed at six different sludge ages varying between 3 and 25 days while the feed COD, 4-CP contents and the HRT were constant at 1,500 mg/l, 250 mg/l and 17 h, respectively.

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Effluent 4-CP Concentration (mg/l)

225 200

R1

R2

R3

175 150 125 100 75 50 25 0 0

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10 15 Sludge Retention Time (days)

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Fig. 1 Comparison of effluent concentrations of 4-CP in the control and test reactors at different SRT values

Figure 1 shows the variety of effluent concentration of 4-CP at different SRT values. Although effluent concentration of 4-CP ranged from 2.125 to 61.875 mg/l and from 0.825 to 3.95 in R2 and R3 between the sludge ages 5 and 25, it ranged from 1.275 to 171.8 mg/l in R1. Effluent concentration of 4-CP increased to 202.125, 134.975 and 90.775 mg/l in R1, R2 and R3, respectively, when the sludge age was decreased from 5 to 3 days. Effluent 4-CP concentrations were much higher in R1 than that of R2 and R3. Biosurfactant helped to maintain activated sludge bioactivity and prevent the system from 4-CP toxicity. For sludge ages between 5 and 25 days, although effluent concentration of COD varied from 88.05 to 453.75 mg/l in R1, it was ranged in 58.35–231.75 mg/l and 55.20–103.50 mg/l in R2 and R3. Effluent concentration of COD increased to 577.05, 333.75 and 282.00 in R1, R2 and R3, respectively, when the sludge age was decreased from 5 to 3 days. The test reactor systems could give the lower effluent COD due to the positive effect of biosurfactant (as seen Fig. 2). Data about the operational conditions and removal efficiencies are summarized in Table 1. F/M ratio values decreased with the increase of sludge ages as shown in Table 1. When the sludge age was increased from 3 to 25 days, F/M ratio was decreased 3.850 to 0.487 day−1 in R1, it was decreased 2.020–0.455 day−1 in R2 and 1.410– 0.460 day−1 in R3. At the lower sludge ages, the better removal efficiencies were achieved at the lower F/M ratio in R3 relative to in R1 and R2. Their results were influenced by the fact that lower F/M ratios were achieved by an increase in biomass concentration in the R3 while the substrate feeding rate was kept constant. Biomass concentrations and 4-CP contents in the aeration tank affected the efficiency of COD and 4-CP removal. Therefore, increase in removal efficiency might partly be attributed to higher biomass concentrations in R2 and R3. At the 3 days sludge age, while COD and 4-CP removal efficiencies were 61.53 and 19.15% in R1, they were 77.75 and 46.01% in R2, 81.20 and 63.69% in R3.

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Effluent COD Concentration (mg/l)

650 R1

550

R2

R3

450 350 250 150 50 0

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10 15 Sludge Retention Time (days)

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Fig. 2 Comparison of effluent concentrations of COD in the control and test reactors at different SRT values Table 1 Comparison of operational parameters of the reactors with different sludge ages Reactor

Run

SRT (day)

F/M (day–1 )

COD removal efficiency (%)

4-CP removal efficiency (%)

R1

Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 1 Run 2 Run 3 Run 4 Run 5 Run 6

3 5 10 15 20 25 3 5 10 15 20 25 3 5 10 15 20 25

3.850 2.490 0.864 0.632 0.529 0.487 2.020 1.210 0.694 0.536 0.501 0.455 1.410 0.901 0.504 0.487 0.481 0.460

61.53 69.75 74.26 90.76 93.99 94.13 77.75 84.55 94.38 95.18 95.20 96.11 81.20 93.10 94.90 95.00 94.38 96.32

19.15 31.28 59.99 91.85 99.78 99.49 46.01 75.25 99.85 99.81 99.83 99.15 63.69 98.42 99.87 99.41 99.76 99.67

R2

R3

In the study of Kargi and Eker [9], at the 5 days sludge age, COD and 2,4-DCP removal efficiencies were determined as 58 and 15% respectively in the activated sludge reactor (COD=2,500 mg/l, 2,4-DCP=200 mg/l). Figure 3 depicts variation of 4-CP volumetric removal rates (R4−CP = (4-CPo − 4-CPe )/θH ) with the F/M ratio. Sharp decrease in 4-CP volumetric removal rate with the F/M ratio in R1 is because of high decreases in biomass concentrations

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4-CP Volumetric Removal Rate (mg/l.day)

400 350

R1

R2

R3

300 250 200 150 100 50 0

0.5

1

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2 2.5 F/M (day–1)

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Fig. 3 The effect of F/M ratios on 4-CP volumetric removal rates in the control and test reactors

with decreasing sludge age. Higher F/M ratio values were obtained in R1 relative to R2 and R3. Lowest 4-CP volumetric removal rate (67.54 mg/l.day) was obtained at highest F/M ratio (3.85 day−1 ) in R1 because of toxic effects of high 4-CP contents on the microorganisms. Based on the Fig. 3, it is apparent that the F/M ratio lower than 0.5 day−1 has no significant effect on the 4-CP volumetric removal rates in all reactors. At the lower sludge ages, volumetric removal rate of 4-CP was greatly enhanced in R2 and R3 as compared to R1 due to higher biomass concentrations. Low COD volumetric removal rates (RCOD = (CODo − CODe )/θH ) in R1 can be observed at high F/M ratio values and low sludge ages resulting in low microorganisms concentrations (Fig. 4). At the lower F/M ratio ( 2.5 day−1 ), while

COD Volumetric Removal Rate (mg/l.day)

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1900 1775 1650 1525 1400 1275 0

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Fig. 4 The effect of F/M ratios on COD volumetric removal rates in the control and test reactors

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COD volumetric removal rates was varied between 1,477.06 and 1,993.34 mg/l.day in R1, it was ranged between 1,646.47 and 2,035.27 mg/l.day, 1,719.53 and 2,039.72 mg/l.day in R2 and R3, respectively.

4 Conclusions Treatment performance of mixture of glucose and 4-CP has been studied in control and biosurfactant added test reactors by changing sludge retention time. Operation of the all reactors at high sludge ages resulted in high biomass and low 4-CP concentrations in the aeration tanks which are the main causes for high COD and 4-CP removals at high sludge ages. Lower sludge ages resulted in decreased removal capacity in the control reactor because the biomass was affected from the toxicity of chlorophenols due to decrease in adaptation periods. This study demonstrated that biosurfactant addition promoted 4-CP and COD removals. The results of this study show that 4-CP can be degraded in the presence of biosurfactant in the test reactors at lower sludge ages. At the low F/M ratio ( 2 day−1), biosurfactant added systems could better efficiencies of COD and 4-CP removal by the positive role of biosurfactant to reduce 4-CP toxicity relative to control reactor. Low F/M ratio which resulted from long sludge ages, resulted in high removal rate of substrate in R2 and R3. Since biosurfactant can be utilized as an available carbon source, biosurfactant addition could be the reason of promoted microbial growth in the test reactors. Biosurfactant was also used as a carbon source in addition to glucose in activated sludge unit. Consequently, biosurfactant enhancement could also be the result of cometabolism between biosurfactant, glucose and 4-CP. This effect of biosurfactant addition was particularly important in lower sludge ages because microorganisms were affected more from 4-CP toxicity in lower sludge age values. Activated sludge systems are sensitive to toxic compounds. Biosurfactant presence may have attenuated the toxicity of 4-CP due to the increased biomass density, and consequently enhance the biodegradation rate of 4-CP and COD.

References 1. APHA (American Public Health Association) (1992) Standard methods for the examination of water and wastewater, 18th edn. APHA, Washington, DC 2. Armenante PM, Kafkewitz D, Lewandowski GA, Jou CJ. (1999) Anaerobic-aerobic treatment of halogenated phenolic compounds. Water Res 33:681–692 3. Aronstein BN, Alexander M (1993) Effect of a non-ionic surfactant added to the soil surface on the biodegradation of aromatic hydrocarbons within the soil. Appl Microbiol Biotechnol 39:386–390 4. Bury SJ, Miller CA (1993) Effect of micellar solubilization on biodegradation rates of hydrocarbons. Environ Sci Technol 27:104–110 5. Cort TL, Song M-S, Bielefeldt AR (2002) Nonionic surfactant effects on pentachlorophenol biodegradation. Water Res 36:1253–1261

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6. Czaplicka M (2004) Sources and transformations of chlorophenols in the natural environment. Sci Total Environ 322:21–39 7. Edwards KR, Lepo JE, Lewis MA (2003) Toxicity comparison of biosurfactants and synthetic surfactants used in oil spill remediation to two estuarine species. Mar Pollut Bull 46:1309– 1316 8. Ha SR, Qishan L, Vinitnantharat S (2000) COD removal of phenolic wastewater by biological activated carbon-sequencing batch reactor in the presence of 2,4-DCP. Water Sci Technol 42:171–178 9. Kargi F, Eker S (2006) Effect of sludge age on performance of an activated sludge unit treating 2,4-dichlorophenol-containing synthetic wastewater. Enzyme Microb Technol 38:60–64 10. Kim JH, Oh KK, Lee ST, Kim SW, Hong SI (2002) Biodegradation of phenol and chlorophenols with defined mixed culture in shake-flasks and packed bed reactor. Process Biochem 37:1367–1373 11. Jeneil Biosurfactant Co., USA (2001) http://www.biosurfactant.com 12. Mulligan CN, Eftekhari F (2003) Remediation with surfactant foam of PCP-contaminated soil. Eng Geol 70:269–279 13. Pritchard PH, O’Neill EJ, Spain CM, Ahearn DJ (1987) Physical and biological parameters that determine the fate of p-chlorophenol in laboratory test systems. Appl Environ Microbiol 53:1833–1838 14. Royal CL, Preston DR, Sekelsky AM, Shreve GS (2003) Reductive dechlorination of polychlorinated biphenyls in landfill leachate. Int Biodeterioration Biodegrad 51:61–66 15. Thangamani S, Shreve GS (1994) Effect of anionic biosurfactant on hexadecane partitioning in multiphase systems. Environ Sci Technol 28:1993–2000 16. Zhang C, Valsaraj KT, Constant WD, Roy D (1998) Nutrient and surfactant enhancement for the biodegradation of chlorinated hydrocarbons in the wastewater from a Louisiana Superfund site. J Hazard Mater 62:41–58

Use of Silk Industry Waste – Silkworm Pupa: A Remediation of Environmental Pollution B. Noroozi, S.H. Bahrami, and M. Arami

Abstract The main concern of every industry is the clean and green production. In spite of all the efforts to achieve this goal the byproducts which are sometimes considered as waste are always a problem. In silk industry the pupa which is a protein rich material in many places is considered as waste. In this work silkworm pupa has been used as a natural adsorbent for the removal of cationic and acid dyes from textile industry waste water. The amino acid nature of the pupa provided a reasonable capability for dye removal. Equilibrium adsorption isotherms were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results showed that the adsorption behavior of the dye could be described reasonably well by either Langmuir or Freundlich models. The characteristic parameters for each isotherm have been determined. The adsorption was dependent on the pH of the solution because of the ionization of amino and acid groups existing on the surface of the adsorbent. Results showed that silkworm pupa not only can be used as an effective natural source for adsorbent but also has a desirable adsorption capability for the removal of dyes from colored wastewater. Chitin and chitosan has been extracted from silk pupa and their properties have been investigated. The silk worm pupa has been treated with HCl and NaOH to extract chitin and then treated with 50% NaOH under nitrogen atmosphere to convert it in to chitosan. Results show that it contains up to 6% chitin. The degree of deacetylation of chitosan obtained determined by FTIR was 82%. Keywords Chitin · Chitosan · Silkworm pupa · Adsorption · Wastewater

B. Noroozi (B) Textile Engineering Department, Amirkabir University of Technology, Tehran, Iran e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_80,

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1 Introduction Remediation of contaminated land and groundwater is an environmental issue of worldwide significance [1]. The environment is becoming more and more polluted by waste materials which cause damage to plants, animals and man. There are three main requirements for sustainable development: resource conservation (water, energy, nonrenewable raw materials), environmental protection (reduction of the adverse impact on the environment of all man activities), and social and economic development (restraint of population growth) [2]. Materials that can not be integrated must be completely recycled in the production processes or must be put back into the lithosphere. Industrial processes are one of the largest producers of waste materials which are mostly released into the environment after partial treatment. Prevention and reduction of waste by introducing appropriate process should be a major aim [2]. Among the industries, textile industry is one of the most productive and active sectors of industry. Moreover, the capability to select and apply environmentally optimized processes, which minimize the pollution of the environment according to the presence standards, is a key factor of efficiency. Because of the lack of appropriate systems for environmental pollution control, most of the textile industries make a rough estimation of the economic and environmental cost. Hence, they usually operate at levels which are far from the environmental pollution standards [3]. The textile industry uses large volumes of water in wet processing operations and, thereby, generates substantial quantities of wastewater containing large amounts of dissolved dyestuffs and other products [4, 5]. The major environmental problem that arises from the use of colorants is the removal of dyes from effluent [6]. The colored dye effluents are considered to be highly toxic to the aquatic life and affect the symbiotic process by disturbing natural equilibrium by reducing photosynthetic activity due to the colorization of the water [7]. Decoloration of textile dye effluent usually does not occur when treated aerobically by conventional municipal sewerage systems [8, 9]. Therefore, it is necessary to find an effective method of wastewater treatment capable of removing color and toxic organic compounds from textile effluents [10]. Adsorption is one of the most efficient methods of removing pollutants from wastewater, especially if the adsorbent is inexpensive and readily available [11]. Since the cost is an important parameter in most developing countries, efforts have been made to explore the possibility of using various low cost adsorbents. Most of the adsorbents explored for decolorization studies are cheap, require little or no processing, are easily available and are biodegradable or easily disposed by incineration thereby providing energy [12]. Silkworm pupa (SWP) which is a protein rich material in many places is considered as waste of silk spinning industry. In the present work use of silkworm pupa as a useful waste has been studied. For this purpose, two subjects have been investigated. First, SWP has been used without any pretreatment for the adsorption of two textile dyes namely Basic Blue 41 (BB41) and Acid Blue 239 (AB239) [17]. The obtained experimental data were correlated by Langmuir and Freundlich adsorption

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isotherm models. Second, natural polymers namely chitin and chitosan have been extracted from SWP by treating with HCl and NaOH.

2 Materials and Methods 2.1 Materials The Dyes BB41 and AB239 were obtained from Ciba, Tehran, Iran. BB41 is a mono-azo basic dye and AB239 is an anthraquinone acid dye. SWP wastes, obtained from silk spinning process of Pileh va Abrisham Shomal Co., Rasht, Iran, were washed with distilled water, dried, and ground. The powdered pupa was sieved (50– 100 mesh) and used as an adsorbent. The general analysis of SWP showed that it contains about 58% protein, 24% minerals, 8% fat, 5% water and 5% ash.

2.2 Methods 2.2.1 Dye Adsorption Experiments Batch adsorption isotherm experiments consisted of 0.2 g SWP; 50 ml of the dyes solution at a concentration range between 100 and 500 mg/l, temperature of 30◦C and contact time of 2 h. The mixture, in a 100-ml beaker, was stirred by a heater stirrer (Yellow line–MST) equipped with temperature controller. After equilibration the mixture was allowed to settle and was centrifuged by Rotana 460R at 3,500 rpm. The dyes solution concentration after adsorption process was determined by a spectrophotometer (Cintra 10 UV-Vis Spectrometer) in the maximum wavelength of the dyes, i.e. 609 nm.

2.2.2 Extraction of Chitin and Chitosan Firstly, the dried SWP were treated with HCl 1.2 M for 24 h at room temperature for the elimination of minerals i.e. Ca, Mg and K. After rinsing with water and filtration the residue washed repeatedly with distilled water in order to neutralize the excess of acid. After drying in the oven and weighing the sample, the treatment with NaOH 5 wt% at 80◦ C for 2 h was conducted in order to proteins elimination. The hot solution was filtrated in Büchner funnel, washing several times with water to remove the excess of NaOH. The crystals of chitin were washed with distilled water several times, dried in an oven at 80◦ C. The deacetylation reaction of chitin was made using NaOH 50 wt% solution under nitrogen using a reactor at 121◦C for 6 h. After neutralizing with dilute acid solution and rinsing with distilled water the obtained chitosan was dried in the oven at 80◦ C. The extracted chitin and chitosan characterized by FTIR spectrometer (Nicolet-Magna-IR 560).

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3 Results and Discussion The pH of the point of zero charge, pHpzc , i.e. the pH above which the total surface of the adsorbent particles is negatively charged, was measured for SWP by the socalled pH drift method [13]. Results showed that the pHpzc is equal to 5.8 for SWP (Fig. 1). Figure 2 represents the adsorption of BB41 and AB239 on the SWP at 30◦ C. The obtained experimental equilibrium adsorption data (Fig. 2) were then compared with the adsorption isotherm models. Two models were used: Langmuir [14] and Freundlich [15]. The linearized Langmuir model is given by: Ce Ce 1 + = qe Q0 b Q0

(1)

where, Ce is the concentration of adsorbate (mg/l) at equilibrium, qe is amount of solute adsorbed at equilibrium (mg/g), constant Q0 signifies the adsorption capacity (mg/g) and b (l/mg) is related to the energy of adsorption. The Freundlich model assumes a heterogeneous adsorption surface with sites that have different energies of adsorption and are not equally available. The Freundlich isotherm is more widely used but provides no information on the monolayer adsorption capacity in contrast to the Langmuir model and can be written as:

14 12

Final pH

10 8 6 pH = 5.8 pzc

4 2 0 0

2

4

6

8

Initial pH

Fig. 1 pHpzc for SWp

10

12

14

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160 140 120

qe (mg/g)

100 80 60 40 AB239 BB41

20 0 0

20

40

60 Ce (mg/l)

80

100

120

Fig. 2 Adsorption isotherm of BB41 and AB239 on SWP at 30◦ C

log qe = log kf +

log Ce n

(2)

where, qe is amount of adsorbate at equilibrium (mg/g), Ce is the adsorbate concentration in the solution (mg/l) at equilibrium and Kf and n are constants incorporating all factors affecting the adsorption process such as adsorption capacity and intensity [16]. Parameters related to each isotherm were determined by using linear regression analysis and the square of the correlation coefficients (R2 ) have been calculated. A list of the parameters obtained together with R2 values is provided in Table 1. A comparison of the experimental isotherms with the adsorption isotherm models showed that the best fitted isotherm equation was Langmuir for the both dyes with R2 = 0.99 and R2 = 0.97 for BB41 and AB239, respectively. Based on the obtained data fitted to the Langmuir equation, the monolayer capacity was calculated about 200 and 238 mg/g for BB41 and AB239, respectively. The effect of the initial pH of the dye solution on the amount of adsorption of the dyes by SWP showed that the significant dye adsorption occurred between pH 4–9 for BB41 and between pH 2–5 for AB239. These results could be due to the chemisorption occurring between the Table 1 Regression parameters for the different isotherm equations Dyes

Langmuir isotherm R2

Freundlich isotherm

Q0 (mg/g) b (l/mg) R2

BB41 0.99 200 AB239 0.97 238

0.034 0.010

Kf (mg/g)/(mg l)n n

0.96 11.78 0.92 7.69

0.614 0.596

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dye and SWP. As it is known, chemisorption is a type of adsorption occurring with − a single layer. The dyes are ionic with −NH+ 3 or −SO3 groups in their structures. The amino acid groups in the structure of SWP are both positively and negatively charged when they are in ionic solutions due to the acidity of aqueous solutions of the dyes. A chemical affinity then can forms between the opposite charges of SWP and the dyes. As a result of this chemical affinity, the resistance of the boundary layer surrounding the adsorbent weakens [11]. Recently, research on natural polymers such as chitin and chitosan is being vigorously carried out in a variety of industrial fields. Chitin has been used as medical materials, raw materials for cosmetic, food additives, and functional fibers. Chitin is the principal structural polysaccharide of the arthropods (for example, crabs and insects) consisting of β-linked N-acetyl-D -glucosamine and the second most abundant polysaccharide, next to cellulose [18, 19]. Chitosan is a derivative of chitin after deacetylation, as shown in Fig. 3 [20]. Chitosan has many useful biological properties such as high biocompatibility, bioabsorbability, wound-healing, an antibacterial effect, etc. In addition, chitosan is easy to handle for clinical use because of its resistive nature to heating due to intramolecular hydrogen bonds formed between hydroxyl and amino groups. Therefore, much attention has been paid to chitosan-based biomedical materials, e.g. drug delivery carriers, wound healing agents, etc [21]. There have been few reports on the preparation and characterization of chitin from insects. Pupa skin is one of the high potential commercial raw materials for various industries. It is available in the reeling and grainage industries as a waste. It has been found that the pupa skin is made up of chitin. Pupa skin is being thrown as a waste, causing pollution problem. In the present work insect chitin was isolated from silkworm pupa, and analyzed by FTIR spectroscopy. FTIR spectroscopy of

Fig. 3 Structures of chitin and chitosan

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Fig. 4 FTIR spectroscopy of chitin and chitosan

initial and unpurified chitin and chitosan (Fig. 4) contained a wide absorption band at 3,431 cm−1 and wide but weak bands characteristic of CH and CH2 groups in the 2,880−3,000 cm−1 region. Also presented C=O stretching of the amide-I group at 1,650 cm−1 and amide- II group at 1,570 cm−1 . The degree of deacetylation (DD), or the percentage of free amine groups in chitosan, was determined by infrared spectroscopy. The method is based on the relationship between the absorbance value at 1,650 cm−1 , which is attributed to amide I, and the corresponding value of the hydroxyl band at 3,430 cm−1 [22]. By applying the Eq. (3), DD of the extracted chitosan was calculated about 82%.

A1650 DD = 97.67 − 26.486 × A3430

(3)

4 Conclusion Prevention and reduction of silk spinning industry waste i.e. SWP has been done by using it as adsorbent for wastewater treatment and as a source of chitin and chitosan. Equilibrium and kinetic studies were studied for the adsorption of BB41 and AB239 from their aqueous solutions by SWP. The equilibrium data have been analyzed against Freundlich, and Langmuir models. The characteristic parameters for each isotherm have been determined. The results showed that the experimental data were best correlated by the Langmuir adsorption isotherms. This adsorbent has adsorption capacity with a monolayer adsorption capacity of 200 and 238 mg/g for BB41 and AB239, respectively. The adsorption was dependent on the pH of the

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solution because of the ionization of amino and acid groups existing on the surface of the adsorbent. Chitin and chitosan were extracted from silkworm pupa. The chitin and chitosan were characterized by FTIR spectroscopy. Degree of deacetylation was an average of 82% for the obtained chitosan.

References 1. Rivett MO, Petts J, Butler B, Martin I (2002) Remediation of contaminated land and groundwater: experience in England and wales. J Environ Manage 65:251–268 2. Petek J, Glavic P (1996) An integral approach to waste minimization in process industries. Resour Conserv Recycl 17:169–188 3. Metaxiotis K (2004) Recot: an expert system for the reduction of environmental cost in the textile industry. Environ Monit Assess 12:218–227 4. Figueiredoa SA, Loureirob JM, Boaventurab RA (2005) Natural waste materials containing chitin as adsorbents for textile dyestuffs: batch and continuous studies. Water Res 39:4142–4152 5. Sourja C, Sirshendu D, Sunando D, Jayanta KB (2005) Adsorption study for the removal of a basic dye:Experimental and modeling. Chemosphere 58:1079–1086 6. Papic S, Koprivanac N, Bozic AL (2000) Removal of reactive dyes from wastewater using fe (iii) coagulant. JSDC 116:352–358 7. Ravikumar K, Ramalingam S, Krishnan S, Balu K (2006) Application of response surface methodology to optimize the process variables for reactive red and acid brown dye removal using a novel adsorbent. Dyes Pigments 70:18–26 8. Gocalves IMC, Gomes A, Bras R, Ferra M, Amorim M, Porter RS (2000) Biological treatment of effluent containing textile dyes. JSDC 116:393–397 9. Robinson T, McMullan G, Marchant R, Nigam P (2001) Remediation of dyes in textile efluent: a critical review on current treatment technologies with a proposed alternative. Bioresource Technol 77:247–255 10. Ledakowicz S, Solecka M, Zylla R (2001) Biodegradation, decolourisation and detoxification of textile wastewater enhanced by advanced oxidation processes J Biotechnol 89:175–184 11. Ilhan U (2006) Kinetics of the adsorption of reactive dyes by chitosan. Dyes Pigments 70:76–83 12. Sanghi R, Bhattacharya B (2002) Review on decolorisation of aqueous dye solutions by low cost adsorbents. Color Technol 118:256–269 13. Lopez-Ramon MV, Stoeckli F, Moreno-Castilla C, Carrasco-Marin F (1999) On the characterization of acidic and basic surface sites on carbons by various techniques. Carbon 37:1215–1221 14. Langmuir I (1916) The constitution and fundamental properties of solids and liquids. J Am Chem Soc 38:2221–2295 15. Freundlich HMF (1906) Uber die adsorption in losungen. Zeitschrift fur Physikalische Chemie 57:385–471 16. Davila JMM, Elizalde GMP, Pelaez CAA (2005) Adsorption interaction between natural adsorbents and textile dyes in aqueous solution. Colloids Surf A Physicochem Eng Aspects 254:107–114 17. Liversidge RM, Lloyd GJ, Wase DAJ, Forster CF (1997) Removal of basic blue 41 from aqueous solution by linseed cake. Process Biochem 32:473–477 18. Min B-M, Lee SW, Lim JN, You Y, Lee TS, Kang PH, Park WH (2004) Chitin and chitosan nanofibers: electrospinning of chitin and deacetylation of chitin nanofibers. Polymer 45:7137–7142

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19. Percot A, Viton C, Domard A (2003) Optimization of chitin extraction from shrimp shells. Biomacromolecules 4:12–18 20. Ravi Kumar MNV (2000) A review of chitin and chitosan applications. React Funct Polym 46:1–27 21. Yamaguchi I, Itoh S, Suzuki M, Osaka A, Tanaka J (2003) The chitosan prepared from crab tendons: Ii. The chitosan/apatite composites and their application to nerve regeneration. Biomaterials 24:3285–3292 22. Oyrton AC, Monteiro J, Claudio A (1999) Some thermodynamic data on copper–chitin and copper–chitosan biopolymer interactions. J Colloid Interface Sci 212:212–219

Using Susceptibility Measurements on Polluted Areas by Exhaust Gases Ali Aydin

Abstract Exhaust gases pollution is one of the most important environmental threats; therefore its detailed study is of great importance. Rapid and cheap methods have been developed recently which is shown the dimensions of distribution of the heavy metal pollution, one of them being based on soil-magnetic parameters. These methods are cheaper and less time-consuming against chemical methods. In the present paper, it was examined the use of soil magnetic susceptibility methods designed to assess the degree of pollution in the samples taken from the soil surface of side of heavy traffic roads. Heavy metal pollution at near highways were tried to show by field and laboratory magnetic susceptibility measurements. These measurements were made to find out the distribution of heavy metallic elements deposited from exhaust gases in area near the high way. The first field was selected form west of Trabzon; the other one is west of Erzurum. When these areas were selecting, it was paid attention to little variation sediments homogeneity. Then taken samples from these areas were used to take laboratory susceptibility and geochemical measurements. The samples (taken Portland cement to be homogeny) exposed to exhaust gases, which were diesel, gasoline and gasoline containing lead for showing the changing with time. Geochemical results confirmed that near highway had relatively low magnetic susceptibility values, whereas sediments away from the highway exhibited relatively high magnetic susceptibility levels consistent with normal background geology. It is concluded that using low field magnetic susceptibility measurements could provide heavy metal pollution distribution at near highway. Keywords Heavy metals · Magnetic susceptibility · Pollution

A. Aydin (B) Geophysical Engineering Department, Engineering Faculty, Pamukkale University, 20017 Kınıklı, Denizli, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_81,

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1 Introduction The increasing number of motor vehicles and automobiles requires continuous air quality monitoring in large urban areas. This study is a sample a fast and simple method for analyzing polluted areas of near highways based on magnetic susceptibility measurements, which is suitable for systematic pollution monitoring of extensive areas at low costs and in less time. More recent sampling of heavy metal polluted areas has been supplemented with monitoring of chemical analyses and magnetic measurements system. Magnetic measurements methods are one of such approximate indicators, which are the concentration of magnetic particles of anthropogenic origin. In firstly investigations, it was placed on Pb, Cu and Zn [24]. But before this date, some researchers were interested pollutions sourced from automobile exhaust and other pollutions sources and they shown amount of trace metals in soils and vegetation near highways and settlements areas and their changing with distance [25, 1, 2, 11, 16, 22, 23]. Pb, Zn, Cu, Ni and Cr had been the metals of interest in these investigations. Also another study showed that high values of heavy metals ratios could be attributed to anthropogenic effects related to automobile, while Cr and Ni variations were best recognized to natural processes. There have been many studies of Pb contamination of soils along highways for the severe adverse health effects of Pb and roadside soils may constitute a health hazard if the metals are transferred to other reservoirs (e.g. [24, 4, 6, 7, 10, 13, 14, 15, 17, 18, 19, 20, 21]). These studies suggest that heavy metals coming from highways can be a considerable, unsuspected source of metal contamination in streams and was showed high correlation between magnetic susceptibility and heavy metal concentrations. Hewitt and Candy [8] reported that Pb and Zn but not Cr showed a strong relationship to vehicle traffic and they compared the distributions of metals along a roadway. In areas with knowing heavy metal contamination, took the magnetic susceptibility measurements on stream sediments. The same studies showed obviously that magnetic properties could be beneficially used as a proxy tool in estimating contamination in various pollution sources [12, 9]. It was found out; examined sites with the minimal values of a magnetic susceptibility were connected to heavy traffic activity. Practically all areas of high values of soil magnetic susceptibility at the far away from highway were not effected heavy elements. By another study, it was showed decreases with depth and distance from the roadway for Cu, Pb, and Zn, but that the strongest predictor of metal concentration was the amount of organic matter in the soil, suggesting that individual soil components need to be studied to predict metal behavior [21]. A study at the same site that was named Site #1 in this study made by Gelisli and Aydin [5] of Pb showed highcontaminated levels sides of the highway in Trabzon, Turkey. Highways soils had long been known to contain of heavy metals, such as Pb, Zn, Cu, Ni and Cr that were decrease in concentration with depth and with distance from the roadway. The aim of this study was to examine in side soils of the highways (Trabzon and Erzurum, Turkey) in terms of their magnetic mineralogy, and to establish links between enhanced concentrations of anthropogenic magnetic particles, concentrations of Pb, Zn, Cu, Ni and Cr. It was investigated the detailed distribution horizontally, of heavy metals, Pb, Zn, Cu, Ni and Cr at two sites in Trabzon, to

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compare to another two working sites in Erzurum. These cities are very different of geographic and climatic sides. Trabzon provides a contrasting climate, very rainy enough to rarely road salting in the winter, but Erzurum is very snowy with dense road salting.

2 Geological, Environmental Settings of Study Areas and Sampling Trabzon and Erzurum are the two of more crowded cities in Black Sea and East Anatolian Regions, Turkey, respectively. So these cities maybe the most polluted by anthropogenic activity coming from pollution contamination source and will be the most polluted cities at near time. Last 20 years, there are very economical developments of both cities, as a result of economical developments, their traffic increase six times from 1995 to now. Both of cities are poor industries but heavy traffic causes high concentration of heavy metals in atmosphere that may cause weakening of the inhabitants’ health. The aim of this study was to determine distribution of the heavy metal concentration sourced exhausts gasses of the sample areas selected from Erzurum and Trabzon and sediments were selected two sites using geochemical and magnetic analysis. Magnetic susceptibility measurements have been applied as a proxy method for detecting the applicability of this method to soil contamination analysis. Sediment samples were collected from the sea sand in Trabzon and agriculture soil in Erzurum near the heavy traffic road outside of the cities (Fig. 1). Taken 18 samples from the top approximately 5 cm of the soil had been collected from selected sites of these cities for using chemical analysis. The sediments in the both of areas represent natural sinks of minerals and heavy metals of lithogenic, pedogenic and anthropogenic origin. Anthropogenic sources of pollution basically comprise especially wastes of automobile exhausts. Magnetic susceptibility values of these samples were taken by using laboratory measurement system. Using the field measurements system, 280 and 180 field measurements were taken from Erzurum and Trabzon studies area where there was little variation in sediment and soil type. Then taken these values, the contour maps were drawn by using surfer software. In the all counter maps, litter

Fig. 1 Location map of the study areas

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areas showed relatively unpolluted parts of the areas, and the darker parts shows polluted parts by heavy metals sourced exhaust gases. Two sites were chosen within Trabzon to reflect differences in land use within an urban setting (Fig. 1). The first was designated Site #1, which was far from the city center in an area with mostly automobile traffic. The second site that Site #2 has a much traffic volume due to first site. Another two sites from Erzurum Site #3 and Site #4 were selected but these sites were different from before sites for low traffic volume. Trabzon City, which lies in the coast of Northern Turkey, is the biggest city center with not much industry and much agricultural concentrated in east–west band along highway E97. A study at Site #2 made by Gelisli and Aydin [5] of Pb showed high levels sides of this highway. They analyzed the Pb content of soil samples taken from sides of the highways. Their results and data were used again in this study, and replotted susceptibility anomaly map Site #2. In those studies, the mean Pb values were given 405 ppm for near the highway, 33 ppm for 70 m from the highway. In this study, capable of that study were getting large and detailed and consequently it was chosen two sample sites from side of E80 and one from side of E97 to test the range of soil contamination, and these measurements were compared magnetic susceptibility values. Both areas also compared together. The first study area is placed in near of E97 highway at Be¸sirli (Site #1) and Yıldızlı (Site #2) 1 and 8 km from city, west of Trabzon had a daily traffic volume of 60,448 in 2003, as reported by the General Directorate of Highways. The second location (Site #3) and (Site #4) near on E80 highway is at west of Erzurum, about 30 km from city center, had a low traffic volume of 3,074 due to fist study area. While Trabzon has an average temperature of 18◦ C and rainfall of 823 mm3 , Erzurum has 11.4◦C and 453 mm3 (Reported from Turkish State Meteorological Service, 2006). Annual snowfall is only about 0.25 cm in Trabzon, so road salting is not practiced, in contrast to Erzurum where salt is used extensively in the long winter sessions for deicing so annual snowfall of Erzurum is about 2 m. However, Trabzon does receive salt from marine aerosols and by wind from sea. The winds from sea do not allow for northward atmospheric transport of pollutants, so big amount of pollution are gotten down in near side of highways in the sites of Trabzon. However in the second test area, the winds are very hard ever direction from highway, so the particles of heavy metals are transported far from the sources in the sites of Erzurum. Therefore we assumed that magnetic susceptibility signature of heavy traffic contributions should be well pronounced in the solid and our collected data should well correlate with heavy metals distributions.

3 Magnetic Susceptibility and Geochemical Methods Eighteen soil samples were taken along a profile that was perpendicular to the highways in Site #2. Only four samples were taken from both studies area for comparing together. Surface samples were taken from each station along the profile that lied in Site #2. An instrumental method of analysis was applied for the research,

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wavelength dispersive X-ray fluorescence that was named XRF method to determine bulk metal content of the samples. XRF analysis, samples were first dried and then ground using steel ball mill and pressed pellets. The magnetic susceptibility measurements and the geochemical analyses were made in the laboratories of Geology and Geophysics Departments of Black Sea University and of Pamukkale University. The samples are used that measuring susceptibility were not dried for not effecting on the measurements. It was investigated behaviors of low-field magnetic susceptibility during drying of the samples. The study showed that there was a linear correlation of the mass-specific susceptibility changes with the weight changes indicated that susceptibility changes were controlled by sample density rather than changes in mineralogy due to diagenetic processes [3]. In our study magnetic susceptibility was measured on sediment and soil samples using a Bartington MS2 measurements system. MS2D and MS2B sensor types were used for taken fields and laboratory measurements. All the values for magnetic susceptibility are express in 10−6 SI. The magnetic minerals in soil and sediments are controlled by several factors, these are nature of the parent material, intensity of soil processes and anthropogenic input, measured values of susceptibility were variable place to place. However in this study was observed that in most of cases lower values of susceptibility were recorded in samples collected near roads than in those situated far from roads.

4 Results As a preliminary study, the exhaust gases of a car running on diesel, lead and unlead gasoline was shown the effect on the values of susceptibility that using Portland cement samples. The samples were exposed the exhaust gases every 5-min time intervals then susceptibility measurements were taken, changing of the susceptibility measurements against to the exhaust types were given in Table 1 and Fig. 2.

Table 1 Magnetic susceptibility values taken different exhaust sources (diesel, lead and unlead gasoline) versus time Susceptibility (×10−6 SI) Time (min)

Diesel

Lead gasoline

Unlead gasoline

0 5 10 15 20 25 30

62.7 58.1 57.3 55.8 57.1 58.2 55.1

63.8 62.4 59.4 55.8 53.4 49.2 46.3

62.2 61.9 60.8 59.5 58.7 58.5 57.4

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Fig. 2 Showing graphical of magnetic susceptibility values vs. time given in Table 1

Diesel Unlead Gaoline Lead Gasoline

Susceptibility (x10–6 SI)

65 60 55 50 45 40 0

5

10 15 20 25 Time (minutes)

30

Table 2 Susceptibility values of Portland cement samples that exposed to the exhaust gases of a car running on gasoline are changing heavy metals contents between 5-min intervals Time (min) Metals

0

5

10

15

20

25

30

Pb Zn Cu Ni Cr Susceptibility

1 39 33 21 507 70

12 48 33 21 511 71

35 55 35 29 512 69

37 69 30 28 518 58

51 67 38 38 529 56

75 107 42 36 533 55

81 112 45 38 538 52

Portland cement samples were exposed to the exhaust gases of a car running on lead its susceptibility was measured 5-min intervals, to see if the susceptibility changed given in Table 2. The measurements show that the susceptibility decreases as the heavy metals pollution increases (Fig. 2). It was found a good correlation between susceptibility and Pb (R2 = 0.78). As the magnetic susceptibility increases, the amounts of Pb decrease with time (Fig. 3). The same kind variations could be also seen for Zn, Cr and Cu. There is a strong correlation between exposed times and the magnetic susceptibility values such as heavy metals. In addition, seven samples from a profile starting from the highway to 80 m a way were collected and analyzed geochemically to determine the heavy metals contents. Values of heavy metal concentrations changing with distance at Site #2 are presented in Table 3. Taken results offer a good image for topsoil’s heavy metal contamination in other research sites. Geochemical analysis results of these areas guidelines show relatively high heavy metals concentration in the study areas. It was found a good correlation between Pb–Zn (R2 = 0.67) and susceptibilityPb (R2 = 0.77). As the magnetic susceptibility increases, the amounts of Pb

Using Susceptibility Measurements on Polluted Areas by Exhaust Gases 80

Susceptibility (x10–6SI)

90

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867

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y = –3,3x + 244

70

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R = 0,78

Pb (mg/kg)

60 50 40 30 20 10 0 50

60

70

80

–6

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Fig. 3 Pb ratio of Portland cement samples and susceptibility measurements values versus with time. Pb ratio vs. susceptibility values

Table 3 Heavy metals concentrations in the top 5 cm of the sediments and susceptibility values versus distance at Site #1 Distance (m) Heavy metals

1

5

10

20

30

50

80

Pb Zn Cu Ni Cr Susceptibility

586 309 90 45 192 405

612 294 71 49 155 420

556 233 66 42 83 445

344 312 61 33 51 550

91 182 63 39 45 530

62 50 42 48 41 710

40 21 20 40 57 790

decrease with distance from road (Fig. 4). The same kind of trend could be also seen for Zn, Cr and Cu, but not for Ni. Whereas there were a strong positive correlation between distance and the magnetic susceptibility values, it was seen negative correlation distance and heavy metal contaminations. Highly critical values were measured for lead in Site #2 that exceeds also the intervention limit (limit for lead is 100 ppm). Pb, Zn and Cu concentrations are high enough that it could be suggested reasons of existence caused by anthropogenic

868

A. Aydin 700

700 600

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R = 0,77

y = 1,8x –19 2 R = 0,67

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700

700 600

500 400 300 200

500 100 0

400 0

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40

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Distance (meters)

80

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Distance (meters)

Fig. 4 Pb vs. Zn and susceptibility vs. Pb with relationship coefficient, also susceptibility and Pb values change with distance

activity coming from the same pollution source. It was seen that the susceptibility values increasing with distance and Pb values decreasing. In the sites, we could observe decrease in magnetic susceptibility values as well as increase in concentration of Pb, Zn, Cu on sediments of sides of highway. At Site #3 and Site #4, the heavy metal values are homogenous and low; the heavy traffic road samples are heterogenous due to the soil type variations. The same trend can be observed on the lead values recorded in the both Site #1 and Site #2 (Figs. 5 and 6). Lowest values of susceptibility and highest contents of lead are recorded in the area of near highways. Samples collected from near of the heavy traffic road show similar mean values for susceptibility and lead content both near and far from road. Our data show that there is a significant trend to have higher reverse correlations values between magnetic susceptibility and lead content in samples collected from sediments of near the highway. These results obviously show that almost certainly the main source both for low magnetic minerals and heavy metals is the contamination produced by the high vehicle traffic.

Using Susceptibility Measurements on Polluted Areas by Exhaust Gases 40

DISTANCE (meter) 30 20

0

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DISTANCE (meter) 30 20

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580

10

0

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–6 SI)

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AKCAABAT

Road E97

Site #2

10

420

DISTANCE (meter)

460

50

–6

500

50

Susceptibility (x10

60

SI)

540

TRABZON

Fig. 5 Contour maps of surface magnetic susceptibility measured at Site #1 and Site #2 near of E97 highway. Data set of Site #2 was used from Gelisli and Aydin [5]

4.1 Site #1 and Site #2 This site is at the entrance of Trabzon at towards west about 8 km, an area with traffic volume of 55,012 vehicles per day in 2003. Samples were also taken from surface soils near the road and surface measurements are taken 5-m intervals. Susceptibility counter map was given in Fig. 5, the values started increasing at 20 m, so it could be said that concentration Pb, Zn, Cu and Cr were high in this part, but at the other part was lower than at Site #2. As at Site #1, heavy metal concentrations tend to decrease with distance (Fig. 4). The concentrations generally do not show the consistent decreasing trend with distance from the roadway that was seen at Site #1. The counters of susceptibility show values that are somewhat lower than for the near highway sediments, but values of parts of away from road as much as two times values. Susceptibility values of counter map given in the Fig. 5 were found to increase away from the road, from 140 × 10−6 SI to 560 × 10−6 SI. Site #2 only one entrance from west point to Trabzon because this city has one highway from west to east, this way lay parallel to coast. Therefore this highway has very heavy traffic so daily traffic volume was 60,448 in 2003. Heavy metals concentrations of the sediments and susceptibility values versus distance are given in Table 3. Although metals concentrations were very high, susceptibility values were low. The lowest value came from the sample at 1 m, the highest value at 80 m distance from the road. At 1 m, while Pb was 586 ppm, taking this sample as representative of the local background yields values of 309 ppm for Zn, 90 ppm for Cu, 45 ppm for Ni and 192 ppm for Cr. While the measurement susceptibility value at 1 m is 405 × 10−6SI, the value at 80 m is 790 × 10−6SI. The maximum Pb value,

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which was in a sample from 5 m away from the road, was 612 ppm. But the highest concentrations for Zn, Cu, and Cr came from 1 m away from the road and were 309 ppm, 90 ppm and 192 ppm, respectively. It is also important to note the negative relationship between distance from road and heavy metal concentrations. As can be seen in Table 3, for Site #1, there is a negative correlation between heavy metal concentrations (except for Ni) and the magnetic susceptibility measurements values. Susceptibility values of counter map given in the Fig. 5 were found to increase away from the road, from 360 × 10−6 SI to 780 × 10−6 SI.

4.2 Site #3 and Site #4

100

90

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60 50 40 DISTANCE (Meter)

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0

The Site #3 and Site #4 near on E80 highway is at west of Erzurum, about 30 km from city center, had a low traffic volume of 3,074 per day in 2003. This site is at the entrance of east region of Turkey. The samples areas were placed near E80 highway. Samples were also taken from surface soils near the road and surface measurements are taken 5-m intervals along 100-m profile. Susceptibility counter map was given in Fig. 6, the values of susceptibility started increasing at 30 m in the both sites, for that reason, it could be said that concentration Pb, Zn, Cu and Cr were high in this part, but at the other part was lower. The concentrations generally do show the consistent decreasing trend with distance from the roadway that was seen as at Site #1 and Site #2. The counters of susceptibility show values that are somewhat lower than for the near highway soils, but values of parts of away from road as much as three times values. Susceptibility values of counter maps given in the Fig. 6 were found to increase away from the road, from 220 × 10−6 SI to 780 × 10−6 SI.

Fig. 6 Contour maps of surface magnetic susceptibility measured at Site #3 and Site #4 near of E80 highway

5 Discussion The heavy metal concentrations in Site #2 are very high compared to Site #3. Pb concentrations in the surface samples collected in this study are also above the average of 424 ppm, however, the highest Pb concentration was measured (802 ppm)

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Table 4 The heavy metal concentrations in Site #2 are very high compared to Site #3 Site #2

Site #3

Mean

Heavy metal

Clean

Polluted

Clean

Polluted

Polluted

Pb Zn Cu Ni Cr Susceptibility

132 111 84 95 112 518

802 402 125 45 181 341

115 102 65 33 43 818

645 233 81 55 192 420

424 212 89 57 132 524

at site #2. The Pb, Zn and Cu concentrations in sediments along E97 in Trabzon were higher than the ones measured along E80 in Erzurum (Table 4). This might be expected because of the difference in daily traffic volumes between the two cities, about 60,448 per day on E97 near Trabzon and about 2,900 per day for the Erzurum sites. It was concluded that Ni and Cr in the soils and sediments of both cities are controlled by parent material, whereas largely anthropogenic processes control the concentrations of Pb, Zn and Cu. Lead gasoline contains Pb about 0.15 g/lt, super gasoline 0.40 gr/lt and unlead gasoline about 0.013 g/lt dir. Composition of exhaust gases are N2 = 45 − 56%, CO2 = 11 − 29%, H2 O = 10 − 39%O2 = 3 − 10%, Remainder <1%. Heavy metals and others composites are very few, but amount dimensions of these waste distribution on the world are not dreamed. An estimate of how much metal had been remobilized could be obtained knowing the amount of excess Pb in the roadside soils and the amount of Pb coming from vehicle exhausts. To calculate the amount of lead coming from vehicle exhaust, 40 μg Pb per meter of roadway per day per vehicle [24]. For the years after 1970 when Pb usage was gradually declining, but using this approach the amount of Pb coming from exhausts of the vehicles before 2003 was calculated as 0.8 kg/m per year at Site #1, 0.7 kg/m at Site #2 and 0.1 kg/m at Site #3 and Site #4.

6 Conclusions The opportunity of use of a developed method such as magnetic susceptibility for an estimation of heavy traffic soil pollution was appreciated. Study showed that magnetic susceptibility measurements could be used as an express showing method of the polluted areas of near highway sediments. Heavy metal contamination in soils and sediments from two different localities along E97 near Trabzon, and along E80 near Erzurum, Turkey, was very high in the top 5 cm of the soil compared to local background values for Pb, Zn and Cu and correlated magnetic susceptibility measurements. These heavy metals appear to be controlled by anthropogenic sources. In Site #2 that closed to the city center, the concentrations of heavy metals were highly bigger other sites which were far

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from cities centers. The concentration of heavy metals at four sites decreases with distance, while decreasing with increasing magnetic susceptibility. Areas included that the high concentrations of Pb, Cu and Zn are caused by anthropogenic emission, especially along roads which were potentially contaminated by traffic emissions could be easily identified using magnetic susceptibility. Anomalies in the behaviors of magnetic susceptibility values of roadside sediments from Trabzon and Erzurum can be interpreted in terms of anthropogenic input. This is mostly due to a presumably negligible lithogenic contribution (basalts and bazanite have that high concentration of magnetically significant minerals) as well as due to the ambiguous identification of iron-rich spherules of typically combustion origin in the soil and sediments of both study area. Heavy metals coming from roadside soils and entering either groundwater or surface water are very high health risk from particulates derived from these soils and sediments. It is described that a serious health risk from dust inhalation exists for workers and living people along urban highways. Acknowledgements Author wishes to thanks Dr. Zafer ASLAN Gümü¸shane Engineering Faculty, Department of Geology for the some sample preparation and taken geochemical measurements.

References 1. Dann BJL, Dearing JA (1994) Mapping and classification of Welsh using magnetic properties. Ann Geophysicae. Part 1. Solid Earth Geophys Nat Hazards Suppl 1 12:C163 2. Dekkers MJ (1997) Environmental magnetism: an introduction. Geologie en Mijnbouw 76:163–182 3. Desenfant F, Petrovski E, Rochette P (2004) Magnetic signature of industrial pollution of stream sediments and correlation with heavy metals: case study from South France. Water Air Soil Pollut 152:297–312 4. Francek MA (1992) Soil lead levels in a small town environment a case study from Mt. Pleasant, Michigan. Environ Pollut 76:251–257 5. Gelisli K, Aydin A (1998) Investigation of environmental pollution using magnetic susceptibility measurements. Eur J Environ Eng Geophys 3:53–61 6. Georgeaud V, Noack Y, Rochette P, Williamson D (1994) Magnetic parameters versus heavy metals in present day particles from the Etang de Berre. Ann Geophysicae. Part 1. Solid Earth Geophys Nat Hazards Suppl 1 12:C164 7. Hafen MR, Brinkman R (1996) Analysis of lead in soils adjacent to an interstate highway in Tampa, Florida. Environ Geochem Health 18:171–179 8. Hewitt CN, Candy GBB (1990) Soil and street dust heavy metal concentrations in and around Cuenca, Ecuador. Environ Pollut 63:29–136 9. Jordanova D, Veneva L, Hoffmann V (2003) Magnetic susceptibility screening of anthropogenic impact on the Danube River sediments in Northwestern Bulgaria, Preliminary results, Studia Geophys 47:403–418 10. Nulman AA, Mesheheryakov PV (1994) Magnetic susceptibility of soils in zone of EURT as characterisation of ecological conditions of pedosoils. Ann Geophysicae Part I. Solid Earth Geophy Nat Hazards Suppl 1 12:C165 11. Oldfield F (1991) Environmental magnetism – a personal perspective. Quat Sci Rev 10:73–85 12. Petrovski E, Kapicka A, Jordanova N, Knab M, Hoffmann V (2000) Low-field magnetic susceptibility: a proxy method of estimating increased pollution of different environmental systems. Environ Geol 39:312–318

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13. Sansalone JJ, Buchberger SG (1997) Partitioning and first flush of metals and solids in urban roadway stormwater. ASCE J Environ Eng 123:134–143 14. Scholger R (1997) Magnetic susceptibility as tools for mapping of heavy metals contamination of sediments and soils: cast studies from Styria. Austria. Ann Geophysicae. Part I, Solid Earth Geophys Nat Hazards Suppl I 15:C105 15. Scholger R (1998) Heavy metal pollution monitoring by magnetic susceptibility measurements applied to sediments of the RiverMur (Styria, Austria). Eur J Environ Eng Geophys 3:25–37 16. Sithole SD, Moyo N, Macheka M (1993) An assessment of lead pollution from vehicle emissions along selected roadways in Harare (Zimbabwe). Int J Environ Anal Chem 53:1–12 17. Sutherland RA (2000) Depth variation in copper, lead, and zinc concentrations and mass enrichment ratios in soils of an urban watershed. J Environ Qual 29:1414–1422 18. Sutherland RA, Tolosa CA (2001) Variation in total and extractable elements with distance from roads in an urban watershed, Honolulu, Hawaii. Water Air Soil Pollut 127:315–338 19. Spassov S, Egli R, Heller F, Nourgaliev DK, Hannam JA (2004) Magnetic quantification of urban pollution sources in atmospheric particulate matter. Geophys J Int 159:555–564 20. Spassov S, Egli R, Zananiri I, De Marco E, Lüscher P, Kretzschmar R (2004) A detailed chemical and rock magnetic investigation of a soil profile in Switzerland, EGU04-A-06299, EGU 1st General Assembly, Nice, France, 25–30 Apr (oral presentation) 21. Turer DG, Maynard JB (2003) Heavy metal contamination in highway soils. Comparison of Corpus Christi, Texas and Cincinnati, Ohio shows organic matter is key to mobility, Clean Techn Environ Policy 4:235–245 22. Versteeg KJ, Morris WA, Rukavina NA (1995) The utility of magnetic properties as a proxy for mapping contamination in Hamilton Harbour sediments, J Great Lakes Res 21:71–83 23. Verosub KL, Roberts AP (1995) Environmental magnetism: past, present, and future. J Geophys Res 100:2175–2192 24. Ward NI, Reeves RD, Brooks RR (1975) Lead in soil and vegetation along a New Zealand state highway with low traffic volume. Environ Pollut 9:43–251 25. Wheeler GL, Rolfe GL (1979) The relationship between daily traffic volume and the distribution of lead in roadside soil and vegetation. Environ Pollut 18:265–274

Biowaste as a Resource for Bioproduct Development J. Pieter H. van Wyk

Abstract Environmental pollution is a major concern for many countries due to increasing amounts of solid waste production, the release of dangerous gases into the atmosphere during fossil fuel combustion, and the lack of effective waste management policies. A major component of solid waste is waste paper with cellulose, a glucose polymer as the major building block. Waste paper can be recycled for a limited number of times before the quality of fibers deteriorate to such an extent that it can’t be used anymore in the paper making process. When reaching this stage used paper becomes part of solid waste and is described as waste paper that is mostly dumped or burnt, both contributing towards environmental pollution with the loss of a major resource of renewable energy as the cellulose component is also destroyed. Cellulase enzymes have the ability to hydrolyze cellulose into glucose and the cellulase from Penicillium funiculosun and Trichoderma viride were used to bioconvert the cellulose component of news paper, foolscap paper, filter paper and office paper into fermentable sugars. Cellulase enzymes are complex systems and their multicomponent nature has been verified by separating it into various components by means of DEAE-Sephadex A-50 column chromatography. Glucose released during treatment of the different paper materials with cellulase were identified and quantified by High Pressure Liquid Chromatography (HPLC). Keywords Waste paper · Glucose · Cellulase · HPLC · DEAE-Sephadex A-50 chromatography

J.P.H. van Wyk (B) Department of Pharmacology and Therapeutics, University of Limpopo, Box 225, Medunsa Campus, 0204, Medunsa South Africa e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_82,

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1 Introduction Live is associated with waste production and the elaboration of these materials as a renewable resource for bio-product development could be a major challenge for biotechnology. On average about 80% of the dry municipal solid waste weight is organic materials (Table 1) that is define as the biodegradable part of households refuse, market garbage, yard rubbish, animal and human waste. Organic waste is widely generated ranging from households, yards, offices, industries, construction sites and comprises mainly of wastepaper, food, yard as well as wood waste. Add the amount of organic agricultural waste such as corn stalks, leaves and wheat straw then this component of solid waste could be a principal resource for bio-development [1]. Materials of organic origin are known as biomass and are of major importance to sustainable development, because they can be grown and are renewable as opposed to non-organic materials (metals, minerals) and fossil carbohydrates. During the past few years, consumers and environmentalists have become increasingly concerned about the environment and resource depletion, consequently the demand for bio-based products has increased [2]. Bioproducts are defined as commercial or industrial products that use biological, renewable agricultural or forestry materials, agricultural food and feed crops residues, wood and wood residues as well as animal wastes as starting materials. Although biotechnology has been applied in waste management it has made relative little contribution to the biorecycling of organic waste despite its great potential. The treatment of aqueous and solid wastes of industrial, agricultural and domestic origin offers a number of opportunities to apply a wide range of biotechnology methods. The efficiency of these methods is based on the capacity of organisms

Table 1 Average composition of municipal solid waste reflecting the contribution of waste cellulose materials to it with used paper materials the major section of biowaste

Constituent Paper and paper products Food waste Yards waste Wood wastes Total: Cellulose waste Plastic Rubber and leather Textiles Glass and ceramics Metals Miscellaneous Total

Weight (%) 37.8 14.2 14.6 3.0 69.6 4.6 2.2 3.3 9.0 8.2 3.1 100.00

Biowaste as a Resource for Bioproduct Development

O

H

CH2OH CH2OH O O H H H O O OH H OH H H H H OH H OH Cellulose

877

CH2OH O H H O OH H H H OH

CH2OH O H H O OH H H H OH

Hydrolysis of cellulose

CH2OH OH H H OH H OH HO H OH Glucose

+

CH2OH O H O OH H H HO H

H OH Cellobiose

H

CH2OH O OH H OH H H H

OH

Fig. 1 Hydrolysis of cellulose into glucose and cellobiose

to degrade organic materials and bacteria [3], microalgae [4], fungi [5] and yeasts [6] have already been shown to degrade organic wastes to some extent. As the cost involved with pollution control, waste treatment and disposal are rising waste biotechnology needs to be applied to protect the environment by creating valuable bioproducts from organic wastes. The use of bio-waste as raw material can broaden the options of the chemical industry giving it more flexibility and a broader application range [7]. To develop the carbohydrate potential of organic waste materials, its cellulose content have to be converted into sugars like glucose that could be used as a starting compound for the biosynthesis of many bioproducts. Enzymatic hydrolysis of waste cellulose can be performed with cellulase, a multi-component system produced by bacteria and fungi [8], which are highly specific with no by-product formation. Enzymatic reactions take place at mild conditions and achieve high yields with relative low amounts of catalysts. Glucose and cellobiose are formed during the cellulose catalyzed hydrolysis of cellulose (Fig. 1). Enzymes are naturally occurring compounds that are biodegradable, environmentally benign and can be recycled for multiple catalyzes. A major obstacle in the bioconversion process is the crystalline nature of cellulose and to make it more susceptible for enzymatic catalyzed degradation it can be exposed to pretreatments such as milling and acid treatment. The role of chromatography in this research is inevitable as column chromatography is used to isolate and separate the different components of the cellulase enzyme while HPLC is used to identify and quantify the sugars produced during the hydrolysis of waste paper.

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2 Materials and Methods 2.1 Source of Enzymes and Paper Materials Cellulase (E.C. 3.2.1.4) from P. funiculosum and T. viride was obtained from Sigma and prepared separately at a concentration of 0.2 mg/mL in 0.05 mol/dm3 Naacetate buffer, pH 4.5. Used foolscap paper (unglazed ruled manuscript paper), office paper (used for photocopying and printing), filter paper (Whatman no. 1) and newspaper were prepared as pieces of 0.5 cm × 0.5 cm (non-pretreated) as well as milled into a fine structure (pretreated) prior to enzymatic treatment. Carboxymethyl cellulose (1%) was prepared in 0.05 mol/dm3 Na-acetate buffer, pH 4.5 to determine the endoglucanase activity of the cellulase while the filter paper activity is an indication of the exoglucanase activity. β-Glucosidase activity was determined by using p-nitrophenyl-β,D-glucoside as substrate and the p-nitrophenol released was detected at 510 nm.

2.2 Enzymatic Treatment All non-pretreated and pretreated paper materials (50.0 mg) were mixed separately with 2.0 ml of each cellulase solution and incubated for 4 h at 50◦ C indicating the relative activity of these enzymes on the various paper materials. The various paper materials were also treated with P. funiculosum cellulose to obtain the glucose formation over a period of 10 h incubation, glucose formation from different amounts of the paper materials as well as glucose formation when a fix amount of the paper materials were treated with a fix amount of the enzyme. All incubations were performed in triplicate.

2.3 Analytical Methods Total reducing sugars produced during the cellulase action were determined colorimetrically with the dinitrosalicylic reagent by using glucose as a standard [9] while enzyme concentrations were determined by the Lowry’s method with bovine serum albumin as standard [10]. The sugars produced are expressed as a percentage of the initial amount of used paper incubated with cellulases. Glucose resulted from cellulase acting on different cellulose materials was determined by hplc using a Supelcosil-NH2 column (Sigma). A 1.0% H2 SO4 solution prepared in hplc-grade water was used as mobile phase at a flow rate of 1.0 ml/min with a refractive index detector employed for glucose identification and quantification.

2.4 Column Chromatography An ion-exchange column was prepared by equilibrating Deae-Sephadex A-50 in a glass column (25 cm × 2.5 cm) with 0.05 mol/dm3 sodium acetate buffer, pH 5.

Biowaste as a Resource for Bioproduct Development

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The crude cellulase from T. viride (0.5 g) was dissolved in 10 ml of the buffer and centrifuged to remove impurities where after it was applied onto the column. The chromatography was developed with the equilibrating buffer at a rate of 0.1 ml/min and fractions of 2.0 ml collected. After 20 h the mobile phase was replaced by a gradient elution using sodium chloride which concentration gradually increased over a period of 25 h to reach a concentration of 0.2 mol/dm3. All fractions were analyzed for protein content (520 nm), and endoglucanase activity (750 nm), exoglucanase activity (750 nm) as well as β-glucosidase activity (520 nm) of the cellulase enzyme.

3 Results and Discussion There is widespread concern that increasing concentrations of carbon dioxide and other greenhouse gases in the earth’s atmosphere will ultimately lead to changes in the earth’s climate. Recognizing the important role that fossil fuels play in the economies and lifestyles of people throughout the world, it is reasonable to ask if the global economy can be powered in ways that might have less impact on the environment because they discharge less carbon dioxide. During the past few years, consumers and environmentalists have become increasingly concerned about the environment and about resource depletion, consequently the demand for bioproducts has increased [11]. A way of addressing this sensitive issue could be through the biodevelopment of biowaste as an alternative and renewable energy resource. Increasing knowledge on the mode of action of cellulase and their application has greatly increased the prospects of enzymatic hydrolysis over chemical processes, because of its potentially high saccharification efficiency [12] and low pollution impact [13]. Used paper has already been described as a resource of bioenergy with newspaper [14], filterpaper [15], office and foolscap paper [16] already been identified as potential alternative energy resources. Cellulase has also been used in the bioconversion of other cellulose waste such as rice straw [17] and sugar cane bagasse [18] to sugars. In addition the feasibility of bioconverting waste cellulose into lactic acid, a building block of biodegradeable materials has also been proved. [19]. During bioconversion of the non-pretreated paper material (Fig. 2) the cellulase from T. viride showed a higher activity on all the paper materials than observed with the P. funiculosum cellulase. The highest extent of bioconversion was obtained with filterpaper while office paper exhibited the lowest susceptibility for cellulase from T. viride. Office paper also resist the bioconversion with P. funiculosum cellulase the strongest. With filterpaper the cellulase from T. viride resulted in 300% higher degradation than obtained with P. funiculosum cellulase acting on the same paper material. After pretreatment of the paper materials the cellulase from T. viride (Fig. 4) was still the more effective enzyme system and an increased degradation was observed with all the paper materials when treated with T. viride cellulase. The bioconversion using P. funiculosum cellulase was also higher on all the paper materials. The relative susceptibility of the paper materials for T. viride cellulase

880

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T.Viride

Concentration of Sugars (mg / ml)

1.4 1.2 1 0.8 0.6 0.4 0.2 0 Filter paper

Foolscap paper Newspaper Paper Materials

Office paper

Fig. 2 Bioconversion of non-pretreated paper materials into sugars by cellulase from P. funiculosum and T. viride

Concentration of Sugars (mg / ml)

P. funiculosum

T.Viride

2.5 2 1.5 1 0.5 0 Filter paper

Foolscap paper

Newspaper

Office paper

Paper Materials

Fig. 3 Bioconversion of pretreated paper materials into sugars by cellulase from P. funiculosum and T. viride

systems changed after the pretreatment as the foolscap paper was more susceptible for hydrolysis by this enzyme while P. funiculosum cellulase showed maximum bioconversion of non-pretreated and pretreated foolscap paper. (Fig. 3). During an incubation period of 10 h with P. funiculosum cellulase all the paper materials showed an increased glucose production that reached a maximum degree of bioconversion after 5 h of incubation. The paper materials produced different glucose releasing patterns with foolscap paper exhibiting the highest extent of bioconversion and office paper the lowest (Fig. 4).

Biowaste as a Resource for Bioproduct Development

1.10-4 umol glucose / s

14

Foolscap paper

Filter paper

881 Newsprint

Office paper

12 10 8 6 4 2 0 0.5

1

3 5 Incubation Period

7

10

Fig. 4 Glucose formation during saccharification of different cellulose materials with cellulase from P. funiculosum Foolscap paper

1.10 umol glucose / s

24

Filter paper

Office paper

Newsprint

20 16 12 8 4 0 0

2.5

5 10 15 Paper Concentration (mg / ml)

20

25

Fig. 5 Glucose formation from different cellulose concentrations during saccharification with cellulase from P. funiculosum

When increasing amounts of the paper materials were incubated with a fix P. funiculosum cellulase concentration an increasing amount of glucose was released from all the paper materials and a maximum degree of bioconversion was reached with al paper materials at a concentration of 20 mg/ml (Fig. 5). Maximum bioconversion was obtained with foolscap paper followed by filterpaper, newspaper and office paper offering the strongest resistance against degradation. Figure 6 reflects the influence of changing P. funiculosum cellulase concentration on the biodegradation of a fix amount of the various paper materials. The amount of glucose produced increased with increasing amounts of cellulase applied and the relative susceptibility of the paper materials was similar to the tendency concluded when different amounts of paper was used. The multi-component character of T. viride cellulase has been confirmed by applying it to Deae-Sephadex chromatography (Fig. 7) that resulted in a number of peaks reflecting the presence of the three major enzyme components of cellulase enzyme namely exoglucanase, endoglucanase and β-glucosidase activity. Each

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1.10–4 u mol glucose / s

Foolscap paper

Filter paper

Newsprint

Office paper

15 12 9 6 3 0 0

0.25

0.5

1

2 4 8 P. funiculosum amount (mg)

10

12

14

Fig. 6 Saccharification of cellulose materials with different concentrations of cellulase from P. funiculosum Endoglucanase activity

Filter paper activity

B-Glucosidase activity 0.25

Increase in Sodium Chloride Concentration

3.5 0.2

Absorbance

3 2.5

0.15

2 0.1

1.5 1

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90 10 0 11 0 12 0 12 2 13 3 14 4 15 0 15 5 16 0 16 6 17 0 17 5 18 5 19 0 20 0 21 0

70 80

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35 45

24

0

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Fig. 7 DEAE-Sephadex A-50 chromatography of a cellulase system derived from T. viride

component is responsible for a specific role during the degradation of cellulose and although the complete mechanism for cellulase degradation is not yet resolved the relative content of these cellulase components differ for the various cellulolytic microorganisms.

4 Conclusions Waste management should be the responsibility of every individual, company and governmental authority. Organic waste, the major component of solid waste offers the potential to be utilized by bio-developing its carbohydrate section as a resource for chemical expansion into products such as bio-ethanol, lactic acid, biodegradable polylactic acids and bio-pharmaceuticals. The role of chromatography in the development of bioproducts is of great importance since it allows the detections, identification and quantification of various intermediates as well as products produced during the bioconversion procedure. The limiting of organic waste would not

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be the only advantage of such a bioconversion process but many industries like the food, pharmaceutical, cosmetic, and petroleum sectors could gain from this process, where biotechnology supported by chromatography plays a central role, thus ensuring a sustainable environment.

References 1. Louwrier A (1998) Industrial products: the return to carbohydrate-based industries. Biotechnol Appl Biochem 27:1–8 2. Kenneth B, Thomas, WJ (1994) Impacts of privatisation policy in Europe. Contemp Econ Polic 12:22–32 3. Boisset C, Fraschini K, Schulein M, Henrissat B, Chanzy H (2000) Imaging the enzymatic digestion of bacterial cellulose ribbons reveals the endo character of the cellobiohydrolase Ce16A from Humicola insolens and its mode of synergy with cellobiohydrolase Ce17A. Appl Environ Microbiol 66(4):1444–1452 4. Schiewer S, Wong MH (2000) Ionic strength effects in biosorption of metals by Marine Algae. Chemosphere 41(1–2):271–281 5. Pakula TM, Uusitalo J, Salonen M, Aarts RT, Peuttila M (2000) Monitoring the kinetics of glycoprotein synthesis and secretion in the filamentous fungus Tricholerma reesei: cellobiohydrolase I (CBHI) as a model protein. Microbiology 146:223–232 6. Wang H, Jones RW (1999) Properties of the macrophomina phaseolina Endoglucanase (EGL1) gene product in bacterial and yeast epression systems. Appl Biochem Biotechnol 81(3):153–160 7. Wyman CE, Goodman BJ (1993) Biotechnology for production of fuels, chemicals and materials from biomass. Appl Biochem Biotechnol 39:39–59 8. Goyal A, Ghosh B, Eveleigh D (1991) Charactristics of fungal cellulases. Bioresour Technol 36:37–50 9. Miller GL, Blum R, Glennon WE, Burton AL (1959) Measurement of carboxymethylcellulase activity. Anal Biochem 1:127–132 10. Lowry OH, Rosebrought NJ, Farr AL, Randall RJ (1951) Protein measurement with the Folin Phenol reagent. J Biol Chem 193:261–215 11. Block D (1999) Executive order and proposed bill will boost biiobased products and bioenergy. Biocycle Mag 40:55–57 12. Latif F, Rajoka MI, Malik KA (1994) Saccarification of Leptochloa fusca (kallar grass straw) by thermostable cellulases. Bioresour Technol 50:107–114 13. Kubicek CP, Messner R, Guber F, Mach RL, Kubicek-Pranz EM (1993) The Trichoderma cellulase regulatory puzzle: From the interior life of a secretory fungus. Enz Microb Technol 15:90–95 14. Kai Y, Maekawa E, Nishida T, Ogawa Y, Tanzawa S, Teratani F (1997) Hydrolysis of watersoluble cellulose acetate prepared from waste newspaper by immobilized cellulase. J Jpn Wood Res Soc 43(11):956–964 15. Nidetzky B, Steiner W, Hayn M, Claessens M (1994) Cellulose hydrolysis by the cellulases from Trichoderma reesi: a new model for synergistic interaction. Biochem J 298(3):705–710 16. Van Wyk JPH, Mogale AM (1998) Saccrharification of paper materials by mixtures of cellulase from penicilium funiculosum and Aspergillus Niger. Australasian Biotechnol 8(6):357–359 17. Kaur PP, Arnmeja IS, Singh J (1998) Enzymic hydrolysis of rice straw by crude cellulase from Trichoderma reesi. Biores Technol 66(3):267–269 18. Deschamps FC, Ramos LP, Fontana JD (1996) Pretreatment of sugarcane bagasse for enhanced ruminal digestion. Appl Biochem Biotechnol 57–58:171–182 19. Luo L, Xia L, Lin J, Cen P (1997) Kinetics of simultaneous saccharification and lactic acid fermentation processes. Biotechnol Prog 13(6):762–767

Textile Azo Dyes Decolourization by Combined Ultrasonication and Microbial Removal H. Tu˘gba Gümü¸sdere, Tuba Artan, Afife Güvenç, Gönül Dönmez, and Ülkü Mehmeto˘glu

Abstract Textile industry involves several processes generated large quantities of wastewaters. These effluents have some properties such as strong color due to residual dyes, recalcitrance due to the presence of compounds such as dyes, surfactants and sizing agents or high salinity, high temperature and variable pH. Remediation by a combination of various physical, chemical and biological techniques of these effluents requires due to their complex and bioresistant characters. Ultrasonication is one of the advanced oxidation processes which are degradation method of organic compounds. It has the potential for use in environmental remediation due to the formation of highly concentrated oxidizing species. In this study, the decolourization of Reactive Red 2 (RR2), Reactive Blue 4 (RR4) and Basic Yellow 2 (BY2) were studied in the first step by continuous ultrasonic irradiation at 20 kHz and in the second step by microbial. The maximum decolourizations were found as 97, 89 and 46% for RR2, RB4 and BY2, respectively by an ultrasonic/ microbial combined method. Keywords Decolourization · Ultrasound · Microbial · Reactive blue 4 · Reactive red 2 · Basic yellow 2

1 Introduction The textile industry consumes large volumes of water in different wet process. Therefore, it produces enormous amounts of textile wastewater which heavily charged with unconsumed dyes and other chemicals [1, 2]. These dyes include several structural varieties of dyes, such as acidic, reactive, basic, disperse, azo, diazo, antraquionone-based and metal complex dyes [3]. Dyes represent a class of Ü. Mehmetoˇglu (B) Chemical Engineering Department, Faculty of Engineering, Ankara University, Tando˘gan, 06100 Ankara, Turkey e-mail: [email protected]

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organic pollutants such that they or their derivatives may be of a toxic nature and consequently their treatment cannot depend on biodegradation alone. Nevertheless, azo dyes aren’t toxic. However, under anaerobic conditions azo dyes are cleaved by microorganisms to form potentially carcinogenic aromatic amines [4]. Advanced oxidations process which are method of degradation organic compounds, may be listed in order as UV, ozonization, H2 O2 , radiolysis, photocatalysis and sonolysis. Sonolysis is called to use of ultrasound in chemistry [5, 6]. Ultrasound occurs at a frequency above 16 kHz, higher than the audible frequency of the human ear, and is typically associated with the frequency range of 20–500 MHz. Ultrasonic waves cause the cavitation of gas bubbles in liquids, e.g. water, leading to local temperatures of 2000–5000 K, the pressure may reach up to nearly 100 atm, sufficiently high to break any chemical bond. It is called hot spot theory. These rather extreme conditions are very short-lived but have shown to result in the generation of highly reactive species including hydroxyl (OH·), hydrogen (H·) and hydroperoxyl (H2 O2 ·) radicals, and hyrogen peroxide [7, 8]. These radicals are capable of initiating or promoting many fast reduction-oxidation reactions. These phenomena cause degradation of organic compounds such as textile dyes in aqueous solutions [9]. Thus ultrasonic irradiation has the potential for use in environmental remediation. It has been followed by literature survey that several studies in which ultrasound is used individually [1, 4, 10, 11] or combined [9, 11–14] with the other methods such as UV irradiation, ozonization, H2 O2 degradation, photocatalytic oxidation for decolourization of different textile dyes has been carried out. Many bacteria and fungi are used for the development of biologic processes for the treatment of textile effluents [15–19]. Recently, different kinds of dyes decolorizing yeast strains were isolated from textile effluent in the media containing dyes [20]. Molasses is the residual syrup derived from the sugar beet pulp that strongly stimulates microbial growth. Therefore, molasses was used as the carbon source in the media for the biomass production experiments described in this study. The studies on microbial decolourization by yeast strains are limited in the literature. Also, the studies used a combined method such as ultrasonic/microbial decolourization are absent in the literature. The aim of this study is the decolourization of textile dyes by ultrasonic/ microbial combined method. The decolourization of three dyes which are RR2, RB4, BY2 were studied by ultrasonication in the first step and by microbial removal in the second step. The results obtained for three dyes were compared with each other.

2 Materials and Methods 2.1 Chemicals The dyes and their chemical structure used in this study are shown in Table 1. The test dyes of RR2, RB4, BY2 were obtained from Sigma-Aldrich.

Basic yellow 2

Reactive blue 4

Reactive red 2

Dyes

(CH3)2 N

Structure

NH 2

N H

O

N

O

N

NH . HCl

SO3 Na N

N

N

Cl

N

Cl

Cl

N

Cl

N (CH3)2

N SO3 Na

N H

HN

NaSO3

OH

C17 H22 N3 Cl

C25 H18 Cl2 N6 O2

C20 H14 Cl2 N6 O

Table 1 The dyes and their chemical structure

303.5

505.37

425.28

Molecular weight (g/mol)

430

596

538.5

λ max (nm)

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2.2 Ultrasonic Treatment In the first step of decolourization of dyes, the ultrasonic treatment was carried out at 20 kHz. The initial concentration of dye solutions was 100 mg/l. The ultrasonic decolourization system was given schematically in Fig. 1. It consists of a 100 ml cylinder-glass reactor surrounded by cooling jacket in which mixture of water/ethylene glycol passed through, magnetic stirrer, ultrasonic homogenizer and titanium probe with diameter of 13 mm, cooling bath and circulator. Ultrasound was applied continuously by mixing during 5 h. 1 ml sonicating aqueous dyes solution was taken for analysis at every hour. It was added in 2 ml distilled water and then it was analyzed spectrophotometrically.

2.3 Microbial Treatment Microorganism and Growth Conditions: A yeast, Rhodotorula sp. SE1 isolated from textile wastewater was used in this study. The strain was maintained on potatodextrose agar (Difco) slants by subculturing every second month. Cells grown for 24 h in 250 ml shaken flasks containing 100 ml of molasses medium. The composition of the growth medium is molasses solution (nearly equivalent to 10 g l–1 sucrose), 1.0 g l−1 NH4 SO4 and 0.5 g l−1 KH2 PO4 . The pH of the growth medium was adjusted to 5 by dilute (0.01 M) and concentrated (1 M) sulphuric acid or sodium hydroxide solutions. Biomass (4 g dry cells l−1 ) from shake flask cultures was harvested by centrifugation (2300 × g for 10 min) in a centrifuger (Hettich EBA12 model), washed twice with sterile saline water and used for microbial decolourization studies. Biomass concentration was determined by measuring the fresh weight using a standard curve against dry cell mass. Dry cell mass was determined at 80◦ C until constant weight.

Titanium Probe

Ultrasonic homogenizer

Cooling bath and circulator

cylinder-glass reactor

Magnetic stirrer

Fig. 1 Ultrasonic decolourization system

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Microbial Decolourization: Rhodotorula sp. SE1 cells were transferred in 150 ml Erlenmeyer flasks containing 50 ml of ultrasonicated dye suspensions at 25±1◦C on a rotary shaker (New Brunswick Scientific innova 4230) at 100 rpm for 8–48 h.

2.4 Analysis The dye solutions, before and after ultrasonic irradiation, were analyzed by Schimadzu UV-Vis spectrophotometer. The absorbance’ of the dye solutions were recorded for RR2, RB4 and BY2 at 538 nm, 596 nm and 430 nm, respectively. The percentage removal of azo dyes was calculated from Decolourization % = ((Co − Cf ) ÷ Co) × 100 In this equation, Co and Cf the initial and final dye concentrations (mg l−1 ), respectively. Cuo and Cuf represent as initial and final dye concentration after ultrasonic treatment. Cmo and Cmf represent as initial and final dye concentration after microbial treatment.

3 Result and Discussion Decolourization of textile dyes was studied by a combined decolorization method (ultrasonic/microbial) for RR2, BY2 and RB4. The effects of treatment time and type of examined method on the decolourization of three dyes were investigated. Firstly, the ultrasonic decolourization was carried out continuously during 5 h at 20 kHz. Change of decolourization percent with ultrasonic treatment time was given for each three dyes at Fig. 2. As shown in Fig. 2, the ultrasonic decolourization moderately increased with increasing treatment time for each three dyes. The maximum decolourization yields at the end of 5 h were found 23, 28 and 16% for RB4, RR2 and BY2, respectively. The highest decolourization yield was obtained for RR2. When the treatment time was longer than 5 h, ultrasonic decolourization was not economic. After the ultrasonic treatment, the effect of the yeast on dye decolourization during the incubation period are shown in Figs. 3 and 4. The decolourization yield of the yeast for RR2 and RB4 were similarly high between 65−70% at the end of the incubation period (Fig. 3). In the experiments, the decolourization yield of these dyes was significantly higher than that of BY2 (Fig. 4). As shown in Fig. 4, the decolourization yield of BY2 started after a long lag phase of approximately 24 h, reaching a maximum after about 48 h. At the end of this period, the highest dye removal yields measured was 30% for 107 mg l−1 initial dye concentration. Concordant results were obtained at both ultrasonic and microbial treatment studies (Fig. 5). The lowest dye decolourization yield was observed as 16% after the ultrasonic treatment and 30% after the microbial treatment in the samples with BY2.

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Ultrasonic Decolourization (%)

35 Reactive Blue 4 Reactive Red 2 Basic Yellow 2

30 25 20 15 10 5 0 0

1

2

3

4

5

6

Time (hour)

Fig. 2 The effect of ultrasonic treatment time on the decolourization of three dyes, (20 kHz, Cuo : RB4=94 mgl−1 , RR2=104 mgl−1 , BY2=107 mgl−1 )

80 70 Decolourization (%)

Fig. 3 The effect of microbial treatment time on the decolourization of RB4 and RR2. (Cmo : RB4=72 mg l−1 , RR2=75 mg l−1 T: 25±1◦ C; Stirring rate: 100 rpm)

60 50 40 30 20 Reactive blue 4

10

Reactive Red 2

0 0

2

4

6

8

10

Time (h)

As shown in Fig. 5, the yeast is highly affected by the high initial BY2 concentration for microbial treatment and decolourization yield decreased. The highest dye decolourization yield was obtained in the RB4 and RR2 samples having low initial dye concentration after the ultrasound applications. The RB4 and RR2 removal values were relatively similar after the combine applications (Fig. 6). The highest decolourization yield was determined to 97% in the sample with RR2 at about 100 mg l−1 initial dye concentration. At the end of the experiment, the lowest dye removal yields measured was 46% for about 107 mg l−1 initial BY2 concentration.

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Decolourization (%)

35 30 25 20 15 10 5 0 0

10

20

30

40

50

60

Time (h)

Fig. 4 The effect of microbial treatment time on the decolourization of BY2. (Cmo : 83 mg l−1 ; T: 25±1◦ C; Stirring rate: 100 rpm)

concentration

100 80 Co Cuf Cmf

60 40 20 0

Reactive Blue 4

Reactive Red 2

Basic Yellow 2

Fig. 5 The effect of ultrasonic and microbial treatment on the concentrations of three dyes. (Co: initial, Cuf: ultrasonic, Cmf: microbial final dye concentrations (mg l−1 ))

100 Ultrasonic

Decolourization (%)

90

Ultrasonic/Microbial

80 70 60 50 40 30 20 10 0 Reactive Blue 4

Reactive Red 2

Basic Yellow 2

Fig. 6 The effect of ultrasonic and microbial treatment on the decolourization of three dyes. (Cuf : ultrasonic, C(u + m)f : ultrasonic + microbial final decolourization yield)

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Acknowledgments The authors gratefully acknowledge the founding of this work by Ankara University, Scientific Research Council (Turkey) (Project No: 2005–0745006HPD; 2006–0705008HPD).

References 1. Vajnhandl S, Marechal AM (2005) Ultrasound in textile dyeing and the colouration/mineralization of textile dyes. Dyes Pigments 65:89–101 2. Banat IM, Nigam P, Singh D, Marchant R (1996) Microbial decolorization of textile-dyecontaining effluents: A review. Bioresour Technol 58:217–227 3. Forgacs E, Chershati T, Oros G (2004) Removal of synthetic dyes from wastewater: a review. Environ Int 30:953–971 4. Rehorek A, Tauber M, Gübitz G (2004) Application of power ultrasound for Azo Dye degradation. Ultrason Sonochem 11:177–182 5. Gogate PR, Pandit AB (2004a) A review of imperative technologies for wastewater treatment I: Oxidation technologies at ambient conditions. Adv Environ Res 8:501–551 6. Gogate PR, Pandit AB (2004b) A review of imperative technologies for wastewater treatment II: Hybrid methods. Adv Environ Res 8:553–597 7. Thompson LH, Doraiswamy LK (1999) Sonochemistry: Science and engineering. Ind Eng Chem Res 38:1215–1249 8. Suslick K.S. (1988) Ultrasound, vol 1. VCH Publishers, New York, pp. 129–130, 144 9. Drijverset D, Langenhove HV, Beckers M (1999) Decomposition of phenol and tricloroethylene by the ultrasound/H2 O2 /CuO Process. Water Res 33(5):1187–1194 10. Ince HI, Tezcanlı-Güyer G (2004) Impacts of pH and Moleculer structure on ultrasonic degradation of azo dyes. Ultrasonics 42:591–596 11. Tezcanlı-Güyer G, Ince HI (2004) Individual and combined effects of ultrasound, ozone and Uv irradiation. A case study with textile dyes. Ultrasonics 42:603–609 12. Velegraki T, Poulios I, Charalabaki M, Kalogerakis N, Samaras P, Mantzavinos D (2006) Photocatalytic and sonolytic oxidation of acid orange 7 in aqueous solution. Appl Catal B: Environ 62:159–168 13. Ince NH, Tezcanli G (2001) Reactive dyestuff degradation by combined sonolysis and ozonation. Dyes Pigments 49:145–153 14. Vonˇcina DB, Majcen-Le-Marechal A (2003) Reactive dye decolorazaiton using combined ultrasound/H2 O2 . Dyes Pigments 59:173–179 15. Knapp JS, Newby PS (1999) The decolourization of a chemical industry effluent by white rot fungi. Water Res 33:575–577 16. Fu Y, Viraraghavan T (2001) Fungal decolorization of dye wastewaters: A review. Bioresour Technol 9:251–262 17. Kapdan IK, Kargi F, McMullan G, Marchant R (2000) Decolorization of textile dyestuffs by a mixed bacterial consortium. Biotechnol Lett 22:1179–1181 18. Nigam P, Banat IM, Singh D, Marchant R (1996) Microbial process for the decolorization of textile effluent containing azo, diazo and reactive dyes. Process Biochem 31(5):435–442 19. Robinson T, McMullan G, Marchant R, Nigam P (2001) Remediation of dyes in textile effluent: A critical review on current treatment technologies with a proposed alternative. Bioresour Technol 77:247–255 20. Aksu Z, Dönmez G (2005) Combined effects of molasses sucrose and reactive dye on the growth and dye bioaccumulation properties of Candida tropicalis. Process Biochem 40: 1437–1444

Identification of Wastewater Leaching into the Wells by HPLC-SEC Using UV and Fluorescence Detection Hilda Marta Szabo and Tuula Tuhkanen

Abstract In this study, 36 small-scale wastewater purification systems effluents and 36 wells from sparsely populated and agricultural areas located in Pirkkanmma, Western Finland were analyzed during summer and fall 2006 by HPLC-SEC- (High Performance Liquid Size Exclusion Chromatography) coupled with on-line UV and fluorescence detector. In addition DOC (Dissolved Organic Carbon) of wastewater samples and wells nitrate concentration of the wells were determined. Two UV detection wavelengths, 224 and 254 nm respectively two excitation/emission wavelengths: 270 nm/355 nm (tryptophan-like fluorescence) and 270 nm/310 nm (tyrosine-like fluorescence) were used for detection. Wastewater leaching into the wells was not identified by tyrosine- and tryptophan-like fluorescence detection in whole-water samples. HPLC-SEC-UV at 224 and 254 nm was useful in indicating increased humic content and increased NO3 , which could be caused by wastewater leaching. Keywords Well water · DOM · Wastewater · Leaching · HPLC-SEC

1 Introduction In the developed countries the highest number of waterborne outbreaks is caused by contaminated private- and small, non-disinfected public wells. This indicates that in addition to preventive actions there is a need of new water quality indicators and more fast and efficient methods to identify the wells under the influence of wastewater leaching. DOM (Dissolved Organic Matter) containing beside humic

H.M. Szabo (B) Environmental Engineering and Biotechnology Laboratory, Department of Chemistry and Bioengineering, Tampere University of Technology, P.O. Box 541, Fin-33101, Tampere, Finland e-mail: [email protected]

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and fulvic acids also low molecular weight proteins, organic acids, carbohydrates and other, possible anthropogenic compounds, could be one of these indicators. HPLC-SEC- (High Performance Liquid Size Exclusion Chromatography) coupled with on-line UV and fluorescence detector has shown to be a powerful tool in analysis of the DOM of water samples. This system provides quantitative and qualitative information on MW (Molecular Weight) components of DOM of different type of water samples. The scope of this study was to identify wells under the influence of wastewater, using HPLC-SEC-UV- FLU analysis of whole-water samples.

2 Materials and Methods In this study, we sampled the effluent from 36 small-scale wastewater purification systems (mainly 2 or 3 compartment septic systems), and 36 wells from sparsely populated, agricultural areas located in Pirkkanmma, Finland. Samples were analysed during summer 2006. Eleven of the wastewater samples were greywater, and 25 were mixed wastewater.

2.1 HPLC-SEC Analysis Wastewater and well water samples were fractionated by a Hewlett-Packard HPLC 1100 system with a TSK gel G3000SW column and two detectors: a diode array UV detector and a fluorescence detector. An eluent solution of 10 mM sodium acetate was used. Two UV detection wavelengths, 224 and 254 nm, were selected based on previous studies [1]. In order to establish the optimal excitation/emission wavelengths for fluorescence detection of organic matter characteristically found in wastewater, samples were scanned at excitations between 200 and 300 nm, and emissions between 300 and 500 nm. All of the wastewater samples analysed had excitation/emission maximas of 270 nm/355 nm (tryptophan-like fluorescence) and 270 nm/310 nm (tyrosine-like fluorescence), as indicated in previous studies [2, 3]. These excitation/emission wavelengths were used for fluorescence measurements in this study.

2.2 Other Analyses All wastewater and well water samples were analysed for DOC-(DissolvedOrganic Carbon), well water samples were also analyzed for Nitrate.

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3 Results and Discussions 3.1 Wastewater Analyses As expected, greywater samples had lower DOC content (average 71 mg/l) than mixed water samples (average 107 mg/l). At UV 254 nm detection, 10 clearly distinguishable fractions were eluted: HMW (high molecular weight) humic: fractions I, II and III (elution times: 4, 8 min, 6, 8 min and 7, 3 min); IMW (intermediate molecular weight) humic: fractions IV and V (elution times 7, 5 and 8, 3 min); and LMW (low molecular weight) non-humic fractions: VI, VII, VIII; IX and X ( elution times 9, 2 min, 11, 3 min, 12, 7 min, 13, 7 min and 15 min). Fractions VI and VII were intensive in mixed wastewatwer samples but almost not present in the greywater samples. (Fig. 1) Fluorescence detection revealed other additional LMW fractions: XI and XII at elution times 18, 5 and 20 min. There was also an intensive fraction VIb at the 10 min elution time with clear tryptophan character and an intensive fraction VI at elution time 9, 7 min with clear tyrosine character. Fraction I was clearly detectable by FLU, which indicates its non-humic nature (Fig. 1). m A U , LU

VI

10

m AU, LU

WW A

I

VI

7

XI

WW C

6

8

T y ro sin e- like fluo r es ce n ce

Tyrosine-like fluorescence

III II

5

V

XI

IV

6

VII 4

IV

V

III

4

3

Tryptophan-like fluorescence

VIa II

VI

T ry pto p h a n- like flu o re sc e n ce

V Ib

2

V II

2

X II

X

1

X

U V a b so r ba n ce a t 2 5 4n m

I 0

UV absorbance at 254nm

0

0

5

10

15

20

25

m in

0

5

10

15

20

25

m in

Fig. 1 Typical chromatograms of greywater (A) and mixed wastewater (C) and wells at UV 224 nm

3.2 Well Analyses The DOC of the wells varied from 0, 78 mgC/l to 6, 45 mgC/l. None of the wells presented tyrosine-like fluorescence. However, some of the wells showed detectable tryptophan-like fluorescence (Fig. 2).

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mAU, LU

mAU, LU

IV

III

4

IV

WELL C

WELL A III

2

3.5

II

V

Tryptophan-like fluorescence

V

3 1.5

9,2 2.5

Tryptophan-like fluorescence

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VI 1

VI 1.5

UV absorbance at 254 nm

1

1.5

UV absorbance at 254nm

0.5 0

0 0

2.

5

7.

10

12.

15

17.

min

0

2.5

5

7.5

10

12.5

15

17.5

min

Fig. 2 Typical chromatograms of the wells (DOC-A=5, 76 mgC/l; DOC-B=3, 11 mgC/l; NO3 A=10, 7 mg/l; NO3 -B=22, 4 mg/l)

mAU

VI

mAU

VI

50

80

Well A at UV 224nm

40

70

Well C at UV 224nm

60 30 50

V

40

20

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Wastewater A at UV 224nm

IV

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VII

Wastewater C at UV 224nm

IV V

10 0

VII

0 0

5

10

15

20

25

min

0

5

10

15

20

25 min

Fig. 3 Typical chromatograms of greywater (A) and mixed wastewater (C) and wells (A & C) at UV 224 nm

Humic-like HMW, IMW and one non-humic LMW (VI) fractions were present in the samples, all of the smaller molecular weight fractions present in the wastewaters were absent in the wells. These fractions were likely to be easily decomposable protein-like compounds. UV 224 nm measurements revealed an intensive peak at 9, 4–9, 8 min, corresponding to the LMW fraction VI. This intensive signal is due to nitrate NO3 , that absorbs strongly at 224 nm (Fig. 3).

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4 Conclusions In this study no direct relationship between small-scale wastewater effluents and well water samples was revealed by FLU detection. Wastewater leaching into the wells was not identified by tyrosine- and tryptophan-like fluorescence detection in whole-water samples. However HPLC-SEC-UV at 224 and 254 nm was useful in indicating increased humic content and increased NO3, which could be caused by wastewater leaching. Acknowledgements This study was financed by Maj and Tor Nessling Foundation, Finland.

References 1. Nissinen TK, Miettinen IT, Martikainen PJ, Vartiainen T (2001) Molecular size distribution of natural organic matter in row and drinking waters. Chemosphere 45:865–873 2. Baker A (2002) Fluorescence properties of some farm wastes: Implications for water quality monitoring. Water Res 36:189–195 3. Ahmad SR, Reynolds DM (1995) Synchronous fluorescence spectroscopy of wastewater and some potential constituents. Water Res 29(6):1599–1602

Removal of Methylene Blue from Aqueous Solution Using Cotton Stalk: As a Bioadsorbent Murat Erta¸s, Bilal Acemio˘glu, M. Hakkı Alma, and Mustafa Usta

Abstract A batch adsorption system using cotton stalk as a bioadsorbent was investigated to remove methylene blue from aqueous solution. The system variables studied include adsorbent particle size, initial dye concentration and adsorbent dose. Based on the isotherm data obtained from the fittings of the adsorption kinetics, the Freundlich model (Regression coefficient R ≈ 0.99) appears to fit the adsorption better than the Langmuir model (Regression coefficient R ≈ 0.89). The Freundlich and Langmuir monolayer capacity had a mean values of 1.29 l/g and 1.054 mg/g, respectively. Keywords Methylene blue · Adsorption · Langmuir · Freundlich · Kinetic

1 Introduction Adsorption is relevant to environmental pollution and protection with reference to water and wastewater treatment [1]. The removing of toxic materials, hazardous ions and dyes from industrial effluents by way of adsorption are of great significant in connection with environmental and human health safety. Adsorption by solids decreases the toxicity of the wastewater or removes non-safe organic materials from industrial effluents, etc. [2, 3, 4]. Effluent from the dyeing industry contains highly coloured species; such highly coloured wastes are not only aesthetically displeasing but also hinder light penetration and may in consequence disturb biological processes in water-bodies. In addition, dyes are toxic to some organisms and hence harmful to aquatic animals. Furthermore, the expanded uses of azo dyes have shown that some of

M. Erta¸s (B) Department of Industrial Engineering of Forestry, Faculty of Forestry, University of Kahramanmaras Sutcu Imam, Kahramanmaras, 46100, Turkey e-mail: [email protected]

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them and their reaction products such as aromatic amines are highly carcinogenic [5, 6]. Therefore, the removal of dyes before disposal of the wastewater is necessary. Methods of effluent treatment for dyes and/or their effluents may be divided into three main categories: physical, chemical, and biological treatments [7, 8]. Among them, adsorption technology is generally considered to be an effective method for quickly lowering the concentration of dissolved dyes in an effluent [9]. Among various treatment technologies, adsorption onto activated carbon has proven to be one of the most effective and reliable physicochemical treatment methodologies [10– 15]. In this regard, activated carbon has been evaluated extensively for the removal of color resulting from the different classes of dyes, that is, acid, direct, basic (cationic), reactive, and disperse [16]. However, commercially available activated carbons are very expensive. Therefore, there is a need to produce low cost and effective carbons that can be applied to water pollution control. There is a growing interest in using low cost, commercially available materials for the treatment of wastewater. A wide variety of low cost materials, such as clay minerals [17], bagasse pith [18], wood [19], maize cob [20] and peat [21] are being evaluated as viable substitutes for activated carbon to remove dyes from coloured effluents. Most dyestuffs are designed to be resistant to environmental conditions like light, effects of pH and microbial attack. Hence, their presence in wastewater is unwarranted, and it is desirable to remove coloring material from effluents, before their discharge into the environment. This is important for regions where water resources might be scarce or sensitive. We made an attempt to utilize cotton stalk as an adsorbent for the removal of a basic dye, methylene blue (MB). MB is a thiazine (cationic) dye, which is most commonly used for coloring among all other dyes of its category. It is generally used for dyeing cotton, wool, and silk. The dye causes eye burns, which may be responsible for permanent injury to the eyes of human and animals. If swallowed, the dye causes irritation to the gastrointestinal tract with symptoms of nausea, vomiting, and diarrhea. It may also cause methemoglobinemia, cyanosis, convulsions, tachycardia, and dyspnea, if inhaled. It is likely to cause irritation to the skin [22, 23]. Hence, it is necessary to remove MB before its transformation. In order to design adsorption treatment systems, the knowledge of kinetic and mass transfer processes is essential. The purpose of this work is the study of the removal of MB from water, by adsorption on cotton stalk, in batch system.

2 Materials and Methods 2.1 Materials Sun-dried cotton stalk, Gossypium hirsitum, collected from the region of Kahramanmaras province, located in the southern part of Turkey. No form of pretreatment was applied except for sieving into various particle size ranges. The

Removal of Methylene Blue from Aqueous Solution Using Cotton Stalk Table 1 Chemical analysis values of cotton stalk used for adsorption experiments

Parameter Cellulose (%) Alcohol-benzene extraction (%) Hollocellulose (%) Lignin (%) Ash (%)

901 Value 47.8 4.7 77.5 21.2 1.3

material was ground with Willey mill and dried in an oven at 105◦C for 24 h. Cotton stalks of 20, 100, 200 mesh sizes were used for the adsorption experiments. Chemical analysis values of cotton stalk are shown in Table 1. A cationic dye of amorphous nature, methylene blue (MB), having molecular formula C16 H18 N3 SCl (mol. wt. 320) with CI No. 52015, was chosen as adsorbate. The structure is

All the chemicals used were obtained from Merck. A stock solution (1,000 mg/l; pH 6.33; λmax = 663 nm) of dye was prepared using distilled water. Dye concentration was determined using absorbance values measured after treatment, at 663 nm with an UV/vis spectrophotometer (Model, Janway 6100). Initial pH was controlled by addition of dilute HCl and NaOH solutions.

2.2 Adsorption Experiments In each adsorption experiment, 50 ml of dye solution of known concentration and pH was added to 250 mg of cotton stalk in a 250 ml conical flask at room temperature (20 ± 1◦ C) and mixture was stirred on a rotary orbital shaker at 125 rpm. The samples were withdrawn from shaker at the predetermined time intervals by using a micropipette. The experiments were done by varying the amount of adsorbent (0.5, 1.0, 1.5, 2.0 and 3.0 g/100 ml); concentration of dye solution (25–100 mg/l) and the particle size of adsorbent (20, 100, 200 mesh) at different intervals. The amount of dye adsorbed onto cotton stalk, qe (mg/g), was calculated by the following mass balance relationship:

C0 − Ce · V qe = W

(1)

where, C0 and Ce are the initial and equilibrium liquid-phase concentrations of dye, respectively (mg/l), V the volume of the solution (l), and W is the weight of the adsorbent used (g).

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3 Results and Discussion 3.1 Effect of Initial Dye Concentration and Contact Time Increase in initial dye concentration decreased the percent adsorption by cotton stalk that remained constant after equilibrium time (Table 2). The actual amount of dye adsorbed increased with increase in the concentration of the dye solution. The process was found to be very rapid initially, and a large fraction of the total amount of dye was removed within a few minutes. The experimental results of adsorption of MB on cotton stalk at various concentrations (25, 50, 75, and 100 mg/l) with contact time are shown in Fig. 1. The unit adsorption for MB was increased from 2.1 to 5.9 mg/g as the MB concentration increased from 25 to 100 mg/l.

Table 2 Effect of concentration on dye removal (adsorbent dosage = 0.5 g/100 ml; particle size = 200 mesh; initial pH = 7; temperature = 20◦ C) Percent dye removal with time (min) Initial dye concentration (mg/l)

15

30

45

60

90

120

25 50 75 100

31.8 28.1 28.4 26.6

35.6 30.4 29.7 27.7

39.4 31.2 31.3 28.4

41.5 31.9 32.3 29.2

42.2 32.2 32.4 29.3

42.3 32.2 32.3 29.4

7 6

qe (mg/g)

5 4 3 2

25 mg/l 50 mg/l 75 mg/l 100 mg/l

1 0 0

30

60

90

120

150

Time (min)

Fig. 1 Effect of contact time and initial dye concentration (adsorbent dosage = 0.5 g/100 ml; particle size = 200 mesh; initial pH of MB solution = 7; temperature = 20◦ C)

Removal of Methylene Blue from Aqueous Solution Using Cotton Stalk

903

35

Percent dye removal

30 25 20 15

20 mesh 10

100 mesh 200 mesh

5 0 0

30

60

90

120

150

Time (min)

Fig. 2 Effect of adsorbent particle size (initial dye concentration = 50 mg/l; adsorbent dosage = 0.5 g/100 ml; initial pH of MB solution = 7; temperature = 20◦ C)

3.2 Effect of Adsorbent Particle Size The higher dye uptake by smaller particles is attributed to greater accessibility to pores and greater surface area for bulk adsorption per unit weight of the adsorbent. The shorter equilibrium time for smaller particles may be due to the dominance of intraparticle diffusion in smaller particles. It is also believed that the breaking up of large particles to form smaller ones opens some tiny sealed channels, which might then become available for adsorption, and so the adsorption by smaller particles is higher than that by larger particles. The experimental results of adsorption of MB onto cotton stalk at various particle size (20, 100 and 200 mesh) with contact time are shown in Fig. 2.

3.3 Effect of Adsorbent Dosage The adsorption of MB on cotton stalk was studied by changing the quantity of adsorbent (0.5, 1.0, 1.5, 2.0 and 3.0 g/100 ml) in the test solution while keeping the initial dye concentration (50 mg/l), temperature (20 ± 1◦ C) and pH (7.0) constant at equilibrium time (90 min). The percent adsorption was increased with adsorbent dose (Table 3). The adsorption increased from 35.1 to 48.4%, as the cotton stalk dose was increased from 0.5 to 3.0 g/100 ml at equilibrium time (90 min). Increase in the adsorption with adsorbent dose can be attributed to increased adsorbent surface area and availability of more adsorption sites [24]. But unit adsorption decreased with increase in adsorbent dose. Unit adsorption was decreased from 3.5 to 0.8 mg/g as the adsorbent dose was increased from 0.5 to 4.0 g/100 ml in the test solution. This may be attributed to overlapping or aggregation of adsorption sites resulting in

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Table 3 Effect of adsorbent dosage on dye removal (dye concentration = 50 mg/l; particle size = 200 mesh; initial pH = 7; temperature = 20◦ C, agitation time = 90 min) Adsorbent dosage (g/100 ml)

Percent dye removal

Adsorbed dye on adsorbent (qe) (mg/g)

0.5 1.0 1.5 2.0 3.0

35.1 40.0 44.7 46.9 48.4

3.5 2.0 1.5 1.2 0.8

decrease in total adsorbent surface area available to MB and an increase in diffusion path length [24, 25].

3.4 Adsorption Isotherms The well-known Freundlich isotherm, Eq. 2, is widely used to describe adsorption on a surface having heterogeneous energy distribution. The Langmuir isotherm, Eq. 3 on the other hand is strictly applicable to monolayer chemisorption. The experimental data are tested with respect to both these isotherms: 1/n

Freundlich isotherm: qe = Kf · Ce Langmuir isotherm: qe =

(2)

Q0 · b · Ce 1 + b · Ce

(3)

where, qe is the amount of dye adsorbed at equilibrium in unit mass of cotton stalk, Ce is the concentration of the dye in aqueous phase at equilibrium, n and Kf are Freundlich coefficients, Q0 and b are Langmuir coefficients.

7 6

Ce/qe

5 4 3 2 1

Fig. 3 Freundlich isotherms for the adsorption of MB adsorption of MB at 20◦ C

0 4

6

8

10 Ce (mg/l)

12

14

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2

Fig. 4 Langmiur isotherms for the at 20◦ C

ln qe

1,5

1

0,5

0 2

2,5

3

3,5

4

4,5

ln Ce (mg/l)

Freundlich and Langmiur isotherms for the adsorption of MB on cotton stalk are shown in Fig. 3 (Regression coefficient R≈0.99) and Fig. 4 (Regression coefficient R≈0.89), respectively. The Freundlich coefficient, n, which should have values in the range of 0 < n < 1 for favourable adsorption, was found 1.35. The Freundlich adsorption capacity, Kf , had value of 1.29 l/g. The Langmiur monolayer adsorption capacity, Q0 , and Langmiur adsorption intensity, b, had values of 1.054 and 0.195 l/mg, respectively. Based on the isotherm data and regression coefficient, the Freundlich isotherm model appears to fit the adsorption better than the Langmuir isotherm model.

4 Conclusions The removal of MB from simulated wastewater using cotton stalk has been investigated under different experimental conditions in batch mode. The adsorption of MB was dependent on adsorbent particle size, adsorbent dose and MB concentration in the wastewater. Maximum dye was removed within 5 min of the start of every experiment. The experimental data produced perfect fit with the Freundlich isotherm showing that the surface of the cotton stalk particles was heterogeneous, non-specific and nonuniform in nature. The adsorption capacity was found to be 1.29 l/g.

References 1. Derylo-Marczewska A (1993) Analysis of adsorption equilibrium for the system dilute aqueous solution of dissociating organic substance activated carbon. Langmuir 9(9): 2344–2350 2. Onganer Y, Temur C (1998) Adsorption dynamics of Fe (111) from aqueous solutions onto activated carbon. J Colloid Interface Sci 205(2):241

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3. Wang J, Huang CP, Allen HE, Cha DK, Kim DW (1998) Adsorption characteristics of dye onto sludge particulates. J Colloid Interface Sci 208(2):518 4. Malik PK (2004) Dye removal from wastewater using activated carbon developed from sawdust: Adsorption equilibrium and kinetics. J Hazardous Mater B113:81–88 5. Boeniger MF (1980) In Carcinogenity of azo dyes derived from benzidine. Department of Health and Human Services (NIOSH), Pub. No. 8-119, Cincinnati, OH 6. Kirk-Othomer (1994) Encyclopedia of chemical technology, John Wiley & Sons Inc. 8th edn. pp 547–672 7. Slokar YM, Majcen Le Marechal A (1998) Methods of decoloration of textile wastewaters. Dyes Pigments 37:335–356 8. Hao OJ, Kim H, Chiang PC (2000) Decoloration of wastewater. Crit Rev Environ Sci Technol 30:449 9. Reife A, Freeman HS (1996) In: Reife A, Freeman HS (eds) Environmental chemistry of dyes and pigments. Wiley, New York 10. McKay G (1996) Use of adsorbents for the removal of pollutants from wastewaters. CRC Press, Boca Raton, FL 11. Gharaibeh SH, Moore SV, Buck A (1998) Effluent treatment of industrial wastewater using processed solid residue of olive mill products and commercial activated carbon. J Chem Technol Biotechnol 71(4):291–298 12. Pala A, Tokat E (2002) Color removal from cotton textile industry wastewater in an activated sludge system with various additives. Water Res. 36(11):2920–2925 13. Karthikeyan J (1988) In: Trivedy RK (ed) Pollution management in industries. Environmental Publication, Karad, India, p 189 14. Mohan SV, Karthikeyan J (1997) Removal of lignin and tannin colour from aqueous solutions through an adsorption onto activated charcoal. Env. Pollut 97:183–187 15. Sankar M, Sekaran G, Sadulla S, Ramasami T (1999) Removal of dizdo and triphenylmethane dyes from aqueous solutions through an adsorption process. J Chem Technol Biotechnol 74(4):337 16. Allen SJ (1996) In: McKay G (ed) Use of adsorbents for the removal of pollutants from wastewaters. CRC Press, Boca Raton, FL 17. Nassar MM (1994) Energy consumption and mass transfer during adsorption using gas and mechanical stirring. In Proceedings of the International Meetings on Chemical Engineering and Biotechnology, ACHEMA-94, Frankfurt, 5–11 June 18. Nassar MM, El-Geundi MS (1991) Comparative cost of colour removal from textile effluents using natural adsorbents. J Chem Tech Biotechnol 50:257–264 19. Asfour HM, Fadali OA, Nassar MM, El-Geundi MS (1985) Colour removal from textile effluents using hardwood sawdust as an adsorbent. J Chem Technol Biotechnol 35A:28–35 20. El-Geundi MS (1991) Colour removal from textile effluents by adsorption techniques. Water Res 25(3):271–273 21. McKay G, Allen SJ (1983) Single resistanca mass transfer models for the adsorption of dyes on peat. J Separ Proc Technol 4(3):1–7 22. Senthilkumaar S, Porkodi K, Vidyalakshmi R (2004) Photodegradation of a textile dye catalyzed by sol-gel derived nanocrystal line TiO2 via ultrasonic irradiation. J Photochem Photobiol A170:225–232 23. Senthilkumaar S, Varadarajan PR, Porkodi K, Subbhuraam CV (2005) Adsorption of methylene blue onto jute fiber carbon: Kinetics and equilibrium studies. J Colloid Interface Sci 284(1):78–82 24. Garg VK, Amita M, Kumar R, Gupta R (2004) Basic dye (methylene blue) removal from simulated wastewater by adsorption using Indian rosewood sawdust: A timber industry waste. Dyes Pigments 63:243–250 25. Acemio˘glu B, Alma MH (2001) Equilibrium studies on adsorption of Cu (II) from aqueous solution onto cellulose. J Colloid Interface Sci 243:81–84

Removal of Cyanide from Solutions by Air Oxidation and Adsorption ˙ Ersin Yener Yazici, Hacı Deveci, Ibrahim Alp, Tu˘gba Yılmaz, and Oktay Celep

Abstract In this study the removal of free cyanide from aqueous solutions by air oxidation and adsorption was investigated. Effects of air and pure oxygen, and catalyst on the rate and extent of the removal of cyanide were studied. It was found that the oxidative removal of cyanide by air/oxygen was very limited although it tended to improve in the presence of pure oxygen and catalyst such as activated carbon and copper sulphate. In the presence of continuous aeration, the non-oxidative removal of cyanide was correlated with a decrease in pH effected apparently by the transfer of carbon dioxide from air phase into the medium. The removal of cyanide by adsorption on activated carbon (AC), nut shell (NS) and rice husk (RH) was also examined. Adsorption capacity of activated carbon was shown to be significantly enhanced via impregnation of activated carbons with metals such as copper (AC-Cu) and silver (AC-Ag). In the column tests, the breakthrough capacity of adsorbents was found to be in an increasing order of RH
1 Introduction Cyanide has been the most preferred solvent in the extraction of gold and silver ores over a century due to its strong complexing capability, readily availability, relatively low cost and its well-known chemistry [22, 21, 23]. Cyanide is also most extensively used in metal finishing and production of plastics [13, 15, 33]. Wastewaters generated in these operations often contain cyanide species i.e. free and metal-cyanides and cyanide related compounds at various levels [12, 33, 27]. Regarding the toxicity of cyanide species with the free cyanide being the most toxic, treatment of cyanide containing effluents is prerequisite to lower cyanide content to admissible levels to fulfil environmental regulations. E.Y. Yazici (B) Mineral Processing Division, Department of Mining Engineering, Karadeniz Technical University, 61080 Trabzon, Turkey e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_86,

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Natural attenuation, chemical and biological oxidation, complexing/precipitation and recovery/recycling processes are currently exploited to remediate the effluents containing cyanide [31, 16, 10, 4, 5]. Natural attenuation a slow process and closely controlled by climate conditions [14, 25, 26, 22, 4]. Oxidative treatment methods e.g. ozonation, hydrogen peroxide and SO2 /air are effectively used for removal of weak acid dissociable (WAD) cyanide compounds (pK<30) [9, 4, 30]. However, these are expensive and not effective for the treatment of strong acid dissociable (SAD) cyanides (pK>30). Activated carbon and various agricultural products can be used as adsorbent for the removal of cyanide from effluents [1, 28, 22, 2, 11]. Activated carbon can also play a catalytic role for the oxidation of many compounds including cyanides in the presence of air [7, 3]. In this study the removal of cyanide from aqueous solutions by catalytic air oxidation and adsorption was investigated. Effect of solution pH and catalyst such as copper and activated carbon in the presence of air/oxygen on the rate and extent of cyanide removal were examined. Removal of cyanide using plain and metalimpregnated activated carbons and agricultural by products i.e. rice husk and nut shell were also studied thorough batch and column tests.

2 Experimental 2.1 Reagents and Adsorbents Reagent grade sodium cyanide (NaCN), copper chloride (CuCl2 .2H2O), copper sulphate (CuSO4 .5H2 O), silver nitrate (AgNO3 ), sodium hydroxide (NaOH) and hydrogen peroxide (H2 O2 , 35% w/w) were used to prepare stock solutions in distilled water.

2.2 Air Oxidation Studies Air oxidation tests were performed in a closed system consisting of two glass reactors i.e. oxidation and absorption reactors (Fig. 1). Oxidation reactor (OR, 1 l) contained cyanide waste solution (100 mg/l CN− , 800 ml) and NaOH solution (400 ml) was used in the Absorption Reactor (AR) to entrap HCN gas formed in the oxidation reactor. Air was supplied using a sparger to oxidation reactor at a flow rate of 0.27 l/min. Effect of pH control, the use of pure oxygen and the catalytic effect of activated carbon (10–20 g/l) and copper sulphate (20 mg/l) on the oxidative removal of cyanide was also determined.

2.3 Adsorption Studies Coconut shell activated carbon (−4 + 1mm, BET: 546m2/g) as plain (AC) and impregnated with copper (AC-Cu) and silver (AC-Ag), hazel nut shell (−4 + 1mm)

Removal of Cyanide from Solutions by Air Oxidation and Adsorption Fig. 1 Experimental setup for air oxidation ([CN− ]0 : 100 mg/l, [CuSO4 ]0 : 0–20 mg/l in OR)

909

Air Inlet HCN(g)

Air Outlet CN

-

-

Air Sparger

NaOH

(OR)

(AR)

with/out heat treatment (for 15 min at 300◦C) and rice husk (−2 + 1mm) were used in adsorption tests. Details of the preparation of these adsorbents for experiments can be found elsewhere [29]. The adsorption tests were carried out in Pyrex beakers (600 ml) with an initial cyanide concentration of 100 mg/l (300 ml) at an adsorbent dosage of 1 g/l. Magnetic stirrers were used to agitate the reactor contents. In equilibrium studies, practical and theoretical adsorption capacities of adsorbents were determined. Adsorbents (1 g/l) were added to aerated cyanide solutions of different strengths (10–200 mg/l in 15 ml, pH 11) in 34-ml PTFE bottles. Then, they were allowed to equilibrate over a period of 72 h. on a reciprocal shaker operating at 180 rpm. Column tests were performed in PTFE columns with an inside diameter (ID) of 26 mm (145 mm in length) at an adsorbent charge of 5 g. Fresh cyanide solution (100 mg/l CN− ; pH 11) was fed from the top of the column at a flow rate of ≈1.5 ml/min. Samples were taken from the effluent solution at certain intervals to construct the breakthrough curve. Concentration of cyanide in solution was determined by silver nitrate titration in the presence of p-dimethylaminobenzylrhodanine (0.02% w/w in acetone) as indicator [24]. pH was controlled by the addition of 1 M NaOH, if required.

3 Results and Discussion 3.1 Removal of Cyanide by Air Oxidation No significant change in cyanide concentration in oxidation reactor (OR) was observed over an initial period of 22 h as shown in Fig. 2. However, cyanide level in solution decreased to 76 mg/l between 22 and 46 h apparently in coincidence

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100

160

80

120

60 Oxidation Reactor (OR) Absorption Reactor (AR)

40

80

CN– (mg/l) in AR

CN– Removal (%) in OR

Fig. 2 Effect of aeration (0.27 l/min) on the removal of cyanide ([CN− ]0 : 100 mg/l in oxidation reactor (OR))

40

20 0

0 0

20

40

60

80

Time in hours

14

Fig. 3 Evolution of pH in oxidation (OR) and absorption reactors (AR)

13

pH

12 11 10 9

Oxidation Reactor (OR) Absorption Reactor (AR, pH >11)

8 0

20

40 Time in hours

60

80

with the corresponding decrease in pH (Fig. 3). Following this period, a further substantial reduction in cyanide level (from 76 to 3 mg/l) was also consistent with the further decrease in pH (Fig. 3) and with the accumulation of cyanide in absorption reactor (AR) over the same period. This change in cyanide level depending on pH was strongly related with volatilisation of cyanide as HCN (g) due to the acidifying effect of atmospheric carbon dioxide in air: + H2 O + CO2 (g) ↔ H2 CO3 ↔ HCO− 3 +H

(1)

H + + CN − ↔ HCN(g)

(2)

In natural attenuation process, loss of cyanide by volatilisation was proposed to be the most important contributing to ≈ 90% of cyanide removal [8, 15]. This can be

Removal of Cyanide from Solutions by Air Oxidation and Adsorption

911

100

100

80

80 60

Oxidation Reactor (OR, pH>11) Absorption Reactor (AR, pH>11)

40

40

20

20

0

-

60

CN (mg/l) in AR

CN– Removal (%) in OR

related with the ready volatilization of HCN (g) due to its high vapor pressure and low boiling point compared with water [20, 32, 21]. Consistent with the literature, current findings (Figs. 2 and 3) apparently showed that volatilization of cyanide as HCN is the most significant mechanism on the rate and extent of cyanide removal. Figure 4 illustrates the cyanide removal (19%) in the presence of aeration and copper at ≥pH 11 over 72 h. More extensive (by 3.4- to 4.3-fold over 45 h) removal of cyanide was observed in the presence of pure oxygen with/without copper (Fig. 5). The concentration of dissolved oxygen were also monitored and found to be around 6 mg/l and 11 mg/l for the tests performed with air (Fig. 4) and pure oxygen (Fig. 5), respectively. These also reveal the relationship between higher cyanide removal and oxygen content in the medium.

0 0

20

40

60

80

Time in hours Fig. 4 Effect of copper as catalyst on the oxidative removal of cyanide in the presence of aeration (0.27 l/min) ([CN− ]0 : 100 mg/l and [CuSO4 ]0 : 20 mg/l in oxidation reactor (OR))

100 [CuSO4]0: 0 mg/l [O2] [CuSO4]0: 20 mg/l [O2]+CuSO4

–

CN (%)

80

60

40

Fig. 5 Removal of cyanide in the presence of pure oxygen (0.27 l/min) ([CN− ]0 : 100 mg/l, [CuSO4 ]0 : 20 mg/l, pH 11)

20 0

10

20

30

Time in hours

40

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3.2 Catalytic Effect of Activated Carbon on Cyanide Removal Figure 6 illustrates that aeration was found to exert a significant effect on the catalytic removal of free cyanide in the presence of AC (10 g/l) i.e. 44% CN− removal (with aeration) compared with 12% (no aeration). The increase in AC dosage from 10 to 20 g/l led to an improvement in cyanide removal (Fig. 6). Addition of copper sulphate (10 mg/l) and hydrogen peroxide (10 mg/l) was found to produce a negligible effect on the cyanide removal (Fig. 6). Activated carbon is known to act as a catalyst in the presence of air since it promotes chemical reactions such as oxidation of cyanide (Eqs. 3–5) [6, 18, 3, 17]. The generation of H2 O2 (0.17 mg/l over 0.5 h. at pH 10.5–11) in the presence of air was confirmed in a separate experiment. This suggests that a portion of CN− could have been catalytically oxidized by activated carbon (Eqs. 4 and 5) in the current tests. It is mooted that cyanide is first adsorbed on the surface of activated carbon, and then catalytically oxidized [7, 22]. CN − + 0.5 O2 (aq) 2H2 O + O2 + 2e−

Act.Carbon −−−−−−−→

2CN − + H2 O2 + 2OH −

CNO−

(3)

H2 O2 + 2OH −

(4)

Act.Carbon −−−−−−−→

Act.Carbon −−−−−−−→

2H2 O + CNO−

(5)

100 90

CN– (%)

80 70 60 10 g/l (no aeration, Control) 10 g/l (aeration) 10 g/l (aeration+copper) H2O2) 10 g/l (aeration+copper+H2O2) 20 g/l (aeration)

50 40 30 0

2

4 6 Time in hours

8

10

Fig. 6 Removal of cyanide from solutions via catalyst assisted air oxidation (0.27 l/min.) over a period of 10 h (Activated carbon dosage: 10–20 g/l, [CN− ]0 : 100 mg/l, [CuSO4 ]0 : 10 mg/l, [H2 O2 ]0 : 10 mg/l, pH 10.5–11)

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3.3 Adsorption of Cyanide by Activated Carbon and Agricultural By-products Figure 7 illustrates that activated carbon was more effective than agricultural byproducts for the removal of cyanide and impregnation of activated carbon with metals remarkably enhances the extent of cyanide removal in the absence/presence of aeration. Aeration appeared to induce a profound effect on the extent of cyanide removal for all type of adsorbents used in this study i.e. 3.2–25.6 fold higher than that in the absence of air, in consistent with current findings (Fig. 7). This enhancement in the extent of cyanide removal could be attributed to the catalytic oxidation of cyanide in the presence of air as discussed above.

70 No aeration

With aeration

50 40 30

–

CN Removal (%)

60

20 10 0 RH

NS

ANS AC Adsorbent Type

AC-Cu AC-Ag

Fig. 8 Adsorption capacities for plain (AC), copper(AC-Cu) and silver-impregnated (AC-Ag) activated carbons, rice husk (RH) and activated nut shell (ANS) (Adsorbent dosage: 1 g/l)

Q (mg CN– / g Adsorbent) aaaaa

Fig. 7 Removal of cyanide by plain (AC), copper- (AC-Cu) and silver-impregnated (AC-Ag) activated carbons, rice husk (RH), nut shell (NS) and activated nut shell (ANS) over 10 h in the absence/presence of air (Adsorbent dosage: 1 g/l, [CN− ]0 : 100 mg/l, pH 10.5–11)

40 Theoretical

Experimental

30

20

10

0 RH

ANS

AC

AC-Cu

Adsorbent Type

AC-Ag

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CN– (mg/l)

80 60 AC-Ag

40

AC-Cu AC RH

20 0 0

500

1000 1500 2000 Effluent Volume (ml)

2500

3000

Fig. 9 Breakthrough curves for cyanide adsorption by plain (AC), copper- (AC-Cu) and silverimpregnated (AC-Ag) activated carbons and rice husk (RH) ([CN− ]0 : 100 mg/l, pH 11)

Figure 8 illustrates the maximum adsorption capacities for cyanide on various adsorbents where the theoretical capacities were determined by Langmuir isotherm. Adsorption capacities were found to be in the order of RH
4 Conclusions Following conclusions can be drawn from the current study: • In the presence of aeration non-oxidative removal of cyanide induced by the decrease in pH was found to be the leading mechanism while the oxidation of cyanide by air was rather limited. • Oxidative removal of cyanide can be improved by supplying pure oxygen into the solution in the absence/presence of copper. • Activated carbon can be used as catalyst for the oxidative removal of cyanide in the presence of air. • Activated carbon and agricultural by-products have relatively low capacity for cyanide removal. However, adsorption capacity of activated carbon was shown to be significantly enhanced via impregnation with metals, silver (AC-Ag), in particular. AC-Ag was shown to have the highest breakthrough capacity (≈500 ml, 50 bed volume) compared with plain activated carbon and agricultural by-products.

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Acknowledgments The authors would like to express their sincere thanks and appreciation to the Research Foundation of Karadeniz Technical University for the financial support (Project No: 2002.112.8.3), to Erol Yılmaz (University of Quebec in Abitibi-Temiscamingue), Dr. Celal Duran (KTU) and E. Sıla Balo˘glu (KTU) for their technical support and to the Newmont Mining Co. for kindly providing the activated carbon samples.

References 1. Adams MD (1994) Removal of cyanide from solution using activated carbon. Miner Eng 7(9):1165–1177 2. Adhoum N, Monser L (2002) Removal of cyanide from aqueous solution using impregnated activated carbon. Chem Eng Process 41:17–21 3. Ahumada E, Lizama H, Orellana F, Suárez C, Huidobro A, (2002) Catalytic oxidation of Fe(II) by activated carbon in the presence of oxygen. Carbon 40(15):2827–2834 4. Akcil A (2003) Destruction of cyanide in gold mill effluents: Biological versus chemical treatments. Biotechnol Adv 21:501–511 5. Akcil A, Mudder T (2003) Microbial destruction of cyanide wastes in gold mining: Process review. Biotechnol Lett 25:445–450 6. Bailey PR (1987) Application of activated carbon to gold recovery. In: Stanley GG (ed) The extractive metallurgy of gold in South Africa, vol 1. SAIMM, Johannesburg, pp 379–611 7. Bernardin FE (1973) Cyanide detoxification using adsorption and catalytic oxidation on granular activated carbon. J Water Poll Control Fed 45:221–231 8. Botz M, Mudder T (2000) Modelling of natural cyanide attenuation in tailings impoundsments. Mineral Metall Process 17(4):228–233 9. Botz M, Mudder T (2001) An overview of cyanide treatment and recovery methods. The cyanide monograph, 2nd edn. Mining Journal Books, London, England, p 605 10. Çelik H, Mordo˘gan H, ˙Ipekdo˘gan Ü (1997) A review of treatment methods for gold processing effluents containing cyanide, Madencilik. J Chamber Mining Eng Turkey 36(1):33–45 (in Turkish) 11. Deveci H, Yazıcı EY, Alp ˙I, Uslu T (2006) Removal of cyanide from aqueous solutions by plain and metal-impregnated granular activated carbons. Int J Miner Process (IJMP) 79(3):198–208 12. EPA (1994) Technical report – Treatment of cyanide heap leaches and tailings. U.S. Enviromental Protection Agency, Rap. No: EPA 530-R-94-037 NTIS PB94-201837, p 48 13. EPA (2000) Capsule report-managing cyanide in metal finishing. U.S. Environmental Protection Agency, Rap. No:625/R-99/009, p 23 14. Gagnon I, Zagury GJ, Deschênes L (2004) Natural attenuation potential of cyanide in groundwater near a SPL landfill. Proceedings of the 8th International Symposium on Environmental Issues and Management of Waste in Energy and Mineral Production SWEMP 2004. In: Pasamehmetoglu AG, Ozgenoglu A, Yesilay AY (eds) Atılım University, Ankara, Turkey, pp 451–456 15. García IR (2003) Constructed wetlands use for cyanide and metal removal from gold mill effluents, MSc Thesis, Royal Institute of Technology, Department of Land and Water Resources Engineering, Stockholm 16. Gönen N, Demir E, Köse HM, Özdil G (1996) Natural degradation, chemical destruction and regeneration process of cyanide. Changing scopes in mineral processing, Proceedings Book, pp 603–606 17. Gupta CK (2003) Chemical metallurgy: Principles and practice. Wiley-VCH, Weinheim, Germany, p 811 18. Hayden RA, Spotts SD (1994) Fundamentals of catalytic activated carbons. www.environmental-expert.com

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19. McDougall GJ, Fleming CA (1987) Extraction of precious metals on activated carbon. In: Streat M, Naden D (eds) Ion exchange and sorption processes in hydrometallurgy. Critical reports on applied chemistry, vol. 19, The Society of Chemical Industry, John Wiley&Sons, pp 56–126 20. Meehan S (2000) The fate of cyanide in grounwater at gasworks sites in south-eastern Australia. PhD Thesis, School of Earth Sciences, The University of Melbourne, Australia 21. MERG (2001) Cyanide-The facts, by Laberge Environmental Services, MERG (Mining Environmental Research Group) Report 2001–2002, Yukon, Canada (Available from: www.emr.gov.yk.ca) 22. Mudder TI, Botz MM, Smith A (2001) Chemistry and treatment of cyanidation wastes, 2nd edn. Mining Journal Books Ltd., London, p 373 23. Mudder TI, Botz MM (2004) Cyanide and society: A critical review. Eur J Miner Process Environ Protect 4(1):62–74 24. Patnaik P (1997) Handbook of environmental analysis: Chemical pollutants in air, water, soil and solid wastes. Lewis Publishers, New York, USA, p 604 25. Shehong L, Baoshan Z, Jianming Z, Xiaoying Y, Binbin W (2005) Natural cyanide degradation and impact on Ili River drainage areas from a goldmine in Xinjiang autonomous region, China. Environ Geochem Health 27:11–18 26. Stevenson J, Botz M, Mudder T, Wilder A, Richins R, Burdett B (2001) Recovery of cyanide from mill tailings. In: Mudder TI, Botz MM (eds) The cyanide monograph. Mining Journal Books Ltd., London, pp 265–298 27. Vapur H, Bayat O, Mordogan H, Poole C (2005) Effects of stripping parameters on cyanide recovery in silver leaching operations. Hydrometallurgy 77(3–4):279–286 28. Williams NC, Petersen FW (1997) The optimisation of an impregnated carbon system to selectively recover cyanide from dilute solutions. Miner Eng 10(5):483–490 29. Yazıcı EY (2005) Removal of cyanide from wastewaters using hydrogen peroxide, activated carbon adsorption and ultrasonic waves. MSc Thesis, Karadeniz Technical University, Trabzon (in Turkish) 30. Yazıcı EY, Deveci H, Alp ˙I, Uslu T, Celep O (2006) Factors affecting decomposition of cyanide by hydrogen peroxide. XXIII. International Mineral Processing Congress (IMPC), 3–8 Sep, ˙Istanbul, vol 3, pp 2439–2444 31. Young CA, Jordan TS (1995) Cyanide remediation: Current and past technologies. Proceedings of the 10th Annual Conference on Hazardous Waste Research, Great Plains/Rocky Mountain Hazardous Substance Research Center, Kansas State University, Kansas 32. Young CA (2001) Remediation technologies for the management of aqueous cyanide species. In: Young CA (ed) Cyanide: Social, industrial and economic aspects. TMS, Warrendale, PA, pp 175–194 33. Zagury GJ, Oudjehani K, Deschênes L (2004) Characterization and availability of cyanide in solid mine tailings from gold extraction plants. Sci Total Environ 320(2–3):211–224

Effects of Various Backwash Scenarios on Membrane Fouling in a Membrane Bioreactor N. Yigit, G. Civelekoglu, I. Harman, H. Köseo˘glu, and M. Kitis

Abstract The main objective of this work was to determine the impacts of various backwash scenarios on fouling in a pilot-scale submerged membrane bioreactor (MBR) aerobically treating domestic wastewater. A total of seven different backwash scenarios were tested. The degree of membrane fouling was determined employing the flux-step method and using the resistance-in-series model for each backwash scenario. Fouling rates and total membrane resistances generally decreased with more frequent backwashing; decreasing of filtration duration improved fouling control. A higher rate of fouling was observed above critical flux for all scenarios. As the backwashing scenarios approached to “no-backwashcontinuous filtration”, permeabilities deviated more from linearity indicating a higher degree of fouling. At a flux of 20 L/m2 -h, fouled membrane resistance was reduced by 1.63-fold with 9 min 45 s of filtration followed by 15 s of backwash compared to continuous filtration. The negative impacts of filtration duration on total membrane resistances were more pronounced than the positive impacts of backwash duration, i.e., as the ratio of filtration/backwash duration increased resistances also increased linearly (R2 : 0.96). The strong correlation found among this ratio and the total membrane resistance suggests that the use of this ratio may be an effective tool in the optimization of fouling control in submerged MBRs employing routine backwashing. Scenarios 4 (9 min 55 s of filtration followed by 5 s of backwash) and 5 (9 min 45 s of filtration followed by 15 s of backwash) were found to be optimum based on fouling control and net daily volume of permeate production. The reversible fouling caused mainly by pore blocking and cake layer was effectively removed by these filtration/backwash scenarios as long as the operating flux was less than the critical flux. Keywords Backwash · Fouling · Membrane bioreactor · Wastewater

M. Kitis (B) Department of Environmental Engineering, Suleyman Demirel University, Isparta, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_87,

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1 Introduction Membrane bioreactor (MBR) is a suspended growth activated sludge (AS) treatment system that relies upon membrane equipment for liquids/solids separation prior to discharge of the treated effluent, thereby replacing the solids separation function of the secondary clarifiers in AS processes [10, 28, 15]. MBRs have been increasingly researched and used in full-scale applications in the last decade for wastewater treatment and reuse. Membrane costs have declined by an order of magnitude over the past decade, dramatically reducing MBR costs [5]. The benefits of MBRs generally include: biomass can be completely retained in the bio-reactor; long solid retention time (SRT) can be achieved thus reducing sludge production and improving nitrification; SRT can be reliably separated from hydraulic retention time (HRT) allowing independent control of both; secondary clarifiers and/or conventional filters can be eliminated reducing plant footprint area; unlike clarifiers, the quality of solids separation is not dependent on the mixed liquor suspended solids (MLSS) concentration or characteristics; since elevated MLSS concentrations are possible, the bioreactor volume can be reduced, higher organic loadings can be applied and the biomass can be more tolerable to shock toxic loadings; excellent effluent quality can be obtained generally suitable for reuse; processes are easily automated; membranes provide high removals of pathogens including bacteria, protozoa and viruses [2, 4, 8, 27, 29, 7, 22, 5, 17, 30]. The effluent quality typically obtained by MBRs treating municipal wastewaters is as following: chemical oxygen demand (COD): <10 mg/L, biological oxygen demand (BOD5 ): <2 mg/L, total suspended solids (TSS): <1 mg/L, NH3 -N: <1 mg/L (in nitrifying plants), turbidity: <0.5 NTU, and >5–6 logs of coliform reduction [16]. One major concern in MBR applications is the membrane fouling which may reduce productivity and thus increase maintenance and operating costs due to the requirement of extra cleaning and backwashing and increased transmembrane pressures (TMP) to obtain constant permeate production. Fouling may occur on the membrane surfaces and/or inside the pores. The reversible fouling, which is the deposition of particles on surfaces as a gel or cake layer, can be eliminated at least partially by aeration and backwashing. However, internal clogging of pores by the adsorption of colloidal and dissolved materials (irreversible fouling) is more problematic, and can hardly be eliminated by vigorous chemical cleaning [3, 18, 19, 9]. Three main factors affecting membrane fouling are the biomass characteristics (MLSS concentration, particle size distribution, concentrations of soluble microbial products and extracellular polymeric substances), operational conditions (cross-flow velocity, aeration intensity, HRT, SRT, operating flux, the degree of pre-treatment, the type and frequency of backwashing and chemical cleaning), and membrane physicochemical characteristics (pore size, surface energy and charge, hydrophilicity/hydrophobicity). Once all these parameters and their potential interactions are considered, it is apparent that understanding and control of membrane fouling is a complex phenomenon [11, 6, 23, 1, 3, 14, 9]. In addition to design parameters such as operating flux, membrane configuration and surface area, operational conditions including the intensity, duration and frequency of backwashing and chemical cleaning of the membranes are also critical in

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minimizing membrane fouling in MBRs [24, 20]. Backwashing has been found to successfully remove most of the reversible fouling due to pore blocking and partially dislodge loosely attached sludge cake from the membrane surface. Backwashing may also partially remove or loosen clogging near the membrane surface [20]. For given conditions of aeration, periodic backwashing provided an additional efficiency by decreasing internal fouling [1]. Jiang et al. [13] tested three scenarios of filtration/backwashing conditions for approximately 24 h each at a fixed gross flux of 30 L/m2 -h: scenario 1 (200 s filtration/15 s BW), scenario 2 (400 s filtration/30 s BW) and scenario 3 (600 s filtration/45 s BW). They found that less frequent, but longer backwashing (600 s filtration/45 s BW) was more efficient than more frequent backwashing (200 s filtration/15 s BW). This observation was interpreted as the role of filter cake, which reduced the direct contact of small colloidal particles with the membrane and consequently reduced the membrane pore blocking (e.g. the adsorption of small colloidal organic particles) [13]. Membrane pore blocking is often reported to be more difficult to clean than filter cake using backwashing [21]. Similarly, pore blocking was not completely reversible by backwashing and suggested to partially remain contributing to irreversible fouling, and increase the initial resistance immediately after backwashing [12]. Suction time (between 8 and 16 min) exhibited more effect on fouling removal than both the aeration intensity (0.3–0.9 m3 /m2 -h) and the backwash time (25–45 s) [25]. Although more fouling is expected to be removed when backwashing duration and frequency are increased, optimization of backwashing is necessary for energy and permeate consumptions [20]. Smith et al. [26] designed a generic control system which automatically optimized the duration of the backwash according to the monitored value of TMP. In optimal conditions of backwashing (15 s every 5 min) the resistance was decreased by 3.5-fold [1]. For each specific application, mainly due to the complex interactions among biomass characteristics, operational conditions, membrane physicochemical characteristics, and fouling types as discussed above, there is a need to optimize backwashing conditions to control fouling. Optimization of the backwashing and chemical cleanings in MBR plants is important not only from the perspective of sustainable filtration but also from the use of permeate for backwashing and stopping of filtration during backwashing, i.e., net volume of permeate production. In addition, very frequent change of filtration and backwashing modes may result in the premature damage on mechanical equipment (i.e., pumps) and membranes. The main objective of this work was to determine the impacts of various backwash scenarios on fouling (as measured by the rate of TMP increase) in a pilot-scale submerged MBR aerobically treating domestic wastewater. A total of seven different backwash scenarios were tested using the flux-step method.

2 Methodology The MBR unit (ZW-10, Zenon Environmental Inc.) consisted of a single tank in which both bio-oxidation and biomass separation via an immersed hollow fiber membrane module (0.9 m2 active membrane area) took place (Fig. 1). The

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Fig. 1 Process diagram of the MBR unit (ZW-10, Zenon Environmental Inc.)

membrane module had a nominal pore size of 0.04 μm. The treatment capacity of the unit was 380–1500 L/day. The pilot-scale MBR system consisted of a 1000-L polyethylene feed tank, 25-L HDPE (high-density polyethylene) back pulse tank, 1000-L polyethylene permeate collection tank, and the bioreactor, which was located in a closed building. The bioreactor (HDPE tank) with 230-L solution volume was continuously fed by screened raw domestic wastewater withdrawn from the sewage system of the university campus. Permeate was collected from the MBR through the membrane module using a bi-directional vacuum pump, which was also used for backwashing the membranes with collected permeate to remove foul ants deposited on the outside of the fibers. An air supply blower with a control valve and flow-meter was used to provide air for bio-oxidation and membrane scour and to adjust aeration velocity. The system was partially automated with a central control panel. The durations of permeation and backwashing were controlled automatically using a timer in this panel. The wastewater was pumped from the feed tank to MBR using a peristaltic pump after pre-screening (1-mm) to remove materials which may damage membranes. Permeate was pumped from the back pulse tank to the permeate collection tank using a peristaltic pump. A total of seven different backwash scenarios were tested to investigate the impacts of these scenarios on fouling control. All the experiments were conducted at MLSS concentration and membrane module aeration velocity of about 6600–6800 mg/L and 0.141 m/s, respectively. During the tests, the employed HRT was 13–15 h and no sludge was wasted. The water temperature in the bioreactor was controlled at 12–13◦C, thus eliminating the impact of viscosity on permeate flux and

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fouling measurements. Before starting fouling experiments for each backwash scenario, the unit was operated at a target flux of 20 L/m2 -h for 12 h to achieve stable conditions. A routine backwash regime (15 s of backwash after each 9 min and 45 s of permeation) was employed during this 12-h period. After this phase, the unit was further operated for 6 h at the conditions of the scenario to be employed. These two operational phases were employed before each scenario to prevent the synergistic impact of a former scenario on the latter. The backwash flowrate was set constant at 600 ml/min during all tests. The degree of fouling during each tested scenario was determined using the fluxstep method [3, 18, 19]. This method included 60 min of operation at each tested flux-step, from 5 to 40 L/m2 -h, by 5 L/m2 -h increments. TMP (mbar) values were measured at t:0 and t:60 min of each flux-step. A backwash with 60-s duration was employed to prevent the transfer of reversible fouling to the next step after each fluxstep. Initial TMP increase, rate of TMP increase (dP/dt, 0−60 min), average TMP, permeability (K), total (Rt ), clean (Rm ) and fouled membrane (Rf ) resistances were measured and/or calculated in each flux-step using the resistance-in-series model as shown by the below equations [18, 19]. Separate flux-step experiments were conducted using tap water to determine the clean membrane resistance and clean water permeability. Initial TMP increase: Po = TMPni − TMPn−1 f TMPnf − TMPni dP = Rate of TMP increase: dt tfn − tin TMPnf + TMPni Average TMP: Pave = 2 Jn Permeability :Kn = Paven TMP TMP Resistance - in - series model: J = = μRt μ(Rm + Rf ) Qpermeate Flux in each step: J = Amembrane Fouled membrane resistance: Rf = Rt − Rm

(1) (2) (3) (4) (5) (6) (7)

where, n: number of flux-step; t: time (min); TMPni : n. step initial TMP; TMPn−1 : f (n − 1). step final (t:60 min) TMP; J: flux (L/m2-h); Kn : n. step permeability (L/m2 -h-bar); μ: viscosity (mPa-s); Rt : total membrane resistance (m−1 ); Rm : clean membrane resistance (m−1 ); Rf : fouled membrane resistance (m−1 ); Qpermeate: permeate flowrate (L/h); Amembrane : nominal membrane surface area (m2 ). Module aeration velocity was calculated by Eq. 8: UG =

Qair Alumen

(8)

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where, UG : air velocity on the membrane lumen cross-sectional area (m/s); Qair : air flowrate (m3 /s); Alumen: lumen cross-sectional area (m2 ).

3 Results and Discussion The tested backwash scenarios and net volume of daily permeate productions relative to continuous filtration (i.e., no backwashing) are shown in Table 1. A wide range for filtration and backwash durations and frequencies was selected ranging from about 5 min of filtration to about 60 min. The tested backwash durations were 5, 15 and 20 s. The ratios of filtration to backwash durations ranged between 19 and 239 (s/s). In the first scenario, continuous filtration without backwashing was employed starting from 5 to 30 L/m2 -h flux steps for 60 min in each step. Since the TMP values exceeded 600 mbar (the highest permissible level for the membrane module) the flux steps of 35 and 40 L/m2 -h could not be tested for the scenario without backwashing. Similarly, the flux of 40 L/m2 -h could not be tested for scenario 2 with the least frequent backwashing. As shown in Table 1, net volume of daily permeate productions relative to continuous filtration ranged between 85.3 and 98.8%. The use of collected permeate for backwashing was also considered in the calculations/ measurements. As expected, the lowest net permeate production was found for scenario 7 with 4 min 45 s of filtration followed by 15 s of backwash, which is a quite frequent of backwashing compared to those typically employed in full-scale MBR plants. Figure 2 shows the impacts of filtration and backwash scenarios on the fouling rates for each flux-step. Fouling rates increased with increasing applied flux, as expected. The highest fouling rates were observed for continuous filtration at each flux. On the other hand, the lowest fouling rates were found for scenario 7

Table 1 Backwash scenarios

Scenario no. S1 S2 S3 S4 S5 S6 S7 a Duration

Duration of filtration (min:s) Continuous (60:00)a 59:45 24:45 09:55 09:45 09:40 04:45

Duration of backwash (min:s)

Net volume of daily permeate production with respect to continuous filtrationb (%)

-

100

00:15 00:15 00:05 00:15 00:20 00:15

98.8 97.2 97.6 92.7 90.1 85.3

of each step in the employed flux-step method was 60 min for target permeate flux of 20 L/m2 -h. Reported values are averages of duplicate flowrate measurements

b Measured

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5.0 S1 No Backwashing S2 59.45 – 00.15 S3 24.45 – 00.15 S4 09.55 – 00.05 S5 09.45 – 00.15 S6 09.40 – 00.20 S7 04.45 – 00.15

dP/dt (mbar/min)

4.0

3.0

2.0

1.0

0.0 5

10

15

20 Flux

25 (L/m2

30

35

40

-h)

Fig. 2 The impacts of filtration and backwash scenarios on the fouling rates in the flux-step method

with the most frequent backwashing, i.e., 15 s in each 5 min of filtration. Fouling rates were 3.1 and 1.1 mbar/min at the flux-step of 30 L/m2 -h for continuous filtration and most frequent backwashing, respectively. As a general trend, fouling rates decreased with more frequent backwashing, from scenario 1 to 7. In other words, decreasing of filtration duration improved fouling control, consistent with the literature in which filtration time exhibited more effect on fouling removal than both the aeration intensity and the backwash time [25]. On the other hand, less frequent, but longer backwashing (600 s filtration/45 s BW) was more efficient than more frequent backwashing (200 s filtration/15 s BW) [13]. Very similar fouling rates were found for scenarios 4 and 5 among which the difference in filtration duration was only 10 sec. For flux values larger than 25–30 L/m2 -h, a higher rate of fouling was generally observed compared to lower flux values. For example, even at the most frequent backwashing (scenario 7) a high fouling rate (3.2 mbar/min) was found at a flux of 40 L/m2 -h. This is consistent with our previous work in which the critical flux value for the same domestic wastewater source was found to be 20 L/m2 -h at the same MLSS concentration (6600 mg/L) and aeration velocity (0.141 m/s) [31]. Thus, a higher rate of fouling was observed above critical flux for all scenarios. On the other hand, below critical flux, fouling rates were consistently low (i.e., <1 mbar/min) for scenarios 4, 5, 6, and 7 with similar filtration and backwashing frequencies. Apparently, the reversible fouling caused mainly by pore blocking and cake layer was effectively removed by these filtration/backwash scenarios as long as the operating flux was less than the critical flux. The impacts of filtration and backwash scenarios on the permeability are shown in Fig. 3. Clean membrane permeability for the tap water was found to be 363 L/m2 -h-bar. As expected, due to fouling effects, lower permeabilities were found

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50 S1 No backwashing S2 59.45 – 00.15

40 Flux (L/m2 -h)

S3 24.45 – 00.15 S4 09.55 – 00.05

30

S5 09.45 – 00.15

20

S6 09.40 – 00.20 S7 04.45 – 00.15

10

clean membrane-tap water

0 0

200

400

600

800

1000

Pave (mbar)

Fig. 3 The impacts of filtration and backwash scenarios on the permeability (flux vs. average TMP relations)

for the wastewater tests in all scenarios compared to that of tap water. Consistent with the results for the fouling rates, as a general trend, permeability (i.e., the slope of flux/average TMP) increased with more frequent backwashing, from scenario 1 to 7. As the backwashing scenarios approached to “no-backwash-continuous filtration”, permeabilities deviated more from linearity indicating a higher degree of fouling. At a typical flux of 20 L/m2 -h, the permeability values calculated for the most frequent backwashing and continuous filtration scenarios were 71.2 and 45.9 L/m2 -h-bar, respectively, providing a 36% increase in permeability by backwashing. Again, the flux steps of 35 and 40 L/m2 -h could not be tested for the scenario without backwashing due to excessive increase in TMP. Figure 4 shows the impacts of filtration and backwash scenarios on the total membrane resistances. Clean membrane resistance (Rm ) was found to be 9.5 × 1011m−1 . Total membrane resistances increased with increasing flux-step for each scenario. Again, consistent with the results found for fouling rates and permeabilities, higher total membrane resistances were found at each flux-step as the filtration duration was increased. In other words, more frequent backwashing reduced total membrane resistances. For example, at a flux of 20 L/m2 -h, fouled membrane resistance was 6.53 × 1012m−1 (Rt : 7.48 × 1012m−1 ) for continuous filtration scenario, indicating a significant degree of fouling. Fouled membrane resistance at the same flux was 4 × 1012m−1 for scenario 5 with 9 min 45 s of filtration followed by 15 s of backwash, exhibiting a 1.63-fold reduction. If considered in terms of total membrane resistance, such reduction is 1.51-fold. For scenario 7 with the most frequent backwashing, reductions in total membrane resistance as high as 1.77-fold were found with respect to no backwashing scenario. In a similar study at

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1.0E+13

S1 No Backwashing S2 59.45 – 00.15

8.0E+12

S3 24.45 – 00.15 S4 09.55 – 00.05

–1

R t (m )

Effects of Various Backwash Scenarios on Membrane Fouling

6.0E+12 S5 09.45 – 00.15 S6 09.40 – 00.20

4.0E+12

S7 04.45 – 00.15

2.0E+12

Rm (clean membrane)

9.0E+09 0

5

10

15

20

25

30

35

40

Flux (L/m2-h)

Fig. 4 The impacts of filtration and backwash scenarios on the total membrane resistance

no-backwash conditions and 20 L/m2 -h flux, Bouhabila et al. [1] found a total membrane resistance of 9.5 × 1012 m−1 for 27 g/L MLSS and 1.8 m3 /h air flowrate. This value is somewhat higher than the one obtained in this study as would be expected due to higher MLSS level and different test conditions (air flowrate of 2.7 m3 /h was employed in our study). However, comparable to this study, they found a 3.5-fold reduction in resistance in optimal conditions of backwashing (15 s every 5 min). Backwash duration exhibited a positive impact on the average total membrane resistance of all the flux-steps (Fig. 5). Backwash duration and average Rt correlated linearly. As the backwash duration was increased from 5 to 20 s at almost constant filtration duration, total resistance was decreased from 5.42 × 1012, to 5.6E+12

Fig. 5 The impacts of backwash duration on the average total membrane resistance during the flux-step test (for 09:40, 09:45 and 09:55 (min:s) filtration durations)

Average Rt (m–1)

5.5E+12 5.4E+12 5.3E+12 5.2E+12 5.1E+12 5.0E+12 0

5

10 15 Backwash duration (s)

20

25

926 6.6E+12

5

59.4

6.4E+12 6.2E+12 –1

Average Rt (m )

Fig. 6 The impacts of filtration duration on the average total membrane resistance during the flux-step test (at constant backwash duration of 15 s)

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6.0E+12 5.8E+12 5.6E+12 5

24.4

5.4E+12 5.2E+12

9.45

5.0E+12

4.45

4.8E+12 0

10

20

30

40

50

60

70

Filtration duration (min.s)

5.11 × 1012m−1 corresponding to about 1.1-fold reduction. On the other hand, filtration duration at constant backwash duration had more impact on total resistances compared to backwash duration (Fig. 6). For example, a 1.3-fold reduction in total resistance was obtained as the duration of filtration was reduced from about 60 to 5 min. Duration of filtration also correlated linearly with Rt . These results suggest that the duration of filtration is more important on fouling control based on total membrane resistance measurements. This finding is further supported by the relation between the ratio of filtration/backwash duration and the average total membrane resistance (Fig. 7). As this ratio was increased the resistance also increased almost linearly. Apparently, the negative impacts of filtration duration on resistances were more pronounced than the positive impacts of backwash duration. This is in agreement with the finding that filtration time exhibited more effect on fouling removal than both the aeration intensity and the backwash time [25]. It should be however noted that the range of filtration and backwash durations tested in this work was 5–60 min and 5–20 s, respectively. Although these are wide ranges capturing

6.6E+12 6.4E+12

–1

Average Rt (m )

6.2E+12

Fig. 7 The impacts of the ratio of filtration/backwash duration (seconds/seconds) on the average total membrane resistance during the flux-step test

6.0E+12 5.8E+12 5.6E+12 5.4E+12 5.2E+12 5.0E+12 4.8E+12 0

50

100

150

200

Filtration/Backwash Ratio (s/s)

250

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values typically employed in full-scale plants, the trends found in this work may not be valid for filtration and backwash durations outside this range. The strong correlation (R2 : 0.96) found among the ratio of filtration/backwash duration and the total membrane resistance suggests that the use of this ratio may be an effective tool in the optimization of fouling control in submerged MBRs employing routine backwashing. Once considered in terms of both fouling control and net daily volume of permeate production, scenarios 4 (9 min 55 s of filtration followed by 5 s of backwash) and 5 (9 min 45 s of filtration followed by 15 s of backwash) appear to be the optimum ones. The net volume of daily permeate productions with respect to continuous filtration for scenarios 4 and 5 were 97.6 and 92.7%, respectively, resulting in about 5% difference (Table 1). While scenario 4 is more advantageous in terms of volume of permeate production scenario 5 exhibited 1.05-fold less total membrane resistance. Thus, these scenarios exhibited very similar performance from the fouling control and permeate production point of views with differences within 5%. The percent coefficient of variations for flowrate and TMP measurements ranged between 3 and 6% for all tests. Therefore, the 5% difference found among scenarios 4 and 5 is within the experimental error. Although scenarios 6 and 7 were also very effective in fouling control they provided about 10 and 15% less permeate production compared to continuous filtration. This may be a significant drawback in terms of plant capacity thus capital cost.

4 Conclusions A total of seven different backwash scenarios were tested using the flux-step method to determine their impacts on membrane fouling in a pilot-scale submerged MBR aerobically treating domestic wastewater. The highest fouling rates were observed for continuous filtration at each flux. The lowest fouling rates were found for scenario 7 with the most frequent backwashing, i.e., 15 s in each 5 min of filtration. Fouling rates generally decreased with more frequent backwashing; decreasing of filtration duration improved fouling control. A higher rate of fouling was observed above critical flux for all scenarios. Fouling rates were consistently low (i.e., <1 mbar/min) for scenarios 4, 5, 6, and 7 with similar filtration and backwashing frequencies at below critical flux. Similarly, permeability increased with more frequent backwashing. As the backwashing scenarios approached to “no-backwashcontinuous filtration”, permeabilities deviated more from linearity indicating a higher degree of fouling. Consistent with the results found for fouling rates and permeabilities, higher total membrane resistances were found at each flux-step as the filtration duration was increased. At a flux of 20 L/m2 -h, fouled membrane resistance was reduced by 1.63-fold with 9 min 45 s of filtration followed by 15 s of backwash compared to continuous filtration. Both the duration of filtration and backwashing correlated linearly with total membrane resistance. While increasing backwash duration decreased total

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membrane resistances for all the flux-steps, increasing filtration duration at constant backwash duration significantly increased resistances. However, the negative impacts of filtration duration on resistances were more pronounced than the positive impacts of backwash duration, i.e., as the ratio of filtration/backwash duration increased resistances also increased linearly. The strong correlation found among this ratio and the total membrane resistance suggests that the use of this ratio may be an effective tool in the optimization of fouling control in submerged MBRs employing routine backwashing. Scenarios 4 (9 min 55 s of filtration followed by 5 s of backwash) and 5 (9 min 45 s of filtration followed by 15 s of backwash) were found to be optimum based on fouling control and net daily volume of permeate production. The reversible fouling caused mainly by pore blocking and cake layer was effectively removed by these filtration/backwash scenarios as long as the operating flux was less than the critical flux. ˙ Acknowledgements This work was partially supported by a Research Grant (IÇTAG-Ç086 103I033) from the Scientific and Technical Research Council of Turkey (TUBITAK); however, it has not been subjected to TUBITAK’s peer and policy review and therefore does not necessarily reflect the views of TUBITAK and no official endorsement should be inferred. The authors thank Zenon Environmental Inc. (now GE Water & Process Technologies) for providing the ZW-10 unit.

References 1. Bouhabila EH, Aim RB, Buisson H (2001) Fouling characterization in membrane bioreactors. Sep Purif Technol 22–23:123–132 2. Buisson H, Cote P, Praderie M, Paillard H (1998) The use of immersed membranes for upgrading wastewater treatment plants. Water Sci Tech 37(9):89–95 3. Chang IS, Le Clech P, Jefferson B, Judd SJ (2002) Membrane fouling in membrane bioreactors for wastewater treatment. J Environ Eng-ASCE 128(11):1018–1029 4. Cicek N, Franco JP, Suidan MT, Urbain V (1998) Using a membrane bioreactor to reclaim wastewater. J Am Water Works Assoc 90:105–113 5. Daigger GT, Rittmann BE, Adham S, Andreottola G (2005) Are membrane bioreactors ready for widespread application? Environ Sci Technol 39(19):399A–406A 6. Defrance L, Jaffrin MY (1999) Reversibility of fouling formed in activated sludge filtration. J Membr Sci 157:73–84 7. Fane A, Chang S (2002) Membrane bioreactors: Design and operational options. Filtr Sep 39:26–29 8. Gander M, Jefferson B, Judd S (2000) Aerobic MBRs for domestic wastewater treatment: A review with cost considerations. Sep Purif Technol 18:119–130 9. Germain E, Stephenson T, Pearce P (2005) Biomass characteristics and membrane aeration: Toward a better understanding of membrane fouling in submerged membrane bioreactors (MBRs). Biotechnol Bioeng 90(3):316–311 10. Gunder B (2001) The membrane-coupled activated sludge process in municipal wastewater treatment. Technomic Publishing, Lancaster, PA 11. Hodgson PH, Fane AG (1992) Crossflow microfiltration of biomass with inorganic membranes: The influence of membrane surface and fluid dynamics. Key Eng Mater 61–62: 167–174 12. Jiang T, Kennedy MD, Van der Meer WGJ, Vanrolleghem PA, Schippers JC (2003) The role of blocking and cake filtration in MBR fouling. Desalination 157:335–343 13. Jiang T, Kennedy MD, Guinzbourg BF, Vanrolleghem PA, Schippers JC (2005) Optimising the operation of a MBR pilot plant by quantitative analysis of the membrane fouling mechanism. Water Sci Technol 51(6–7):19–25

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14. Judd SJ (2004) A review of fouling of membrane bioreactors in sewage treatment. Water Sci Technol 49:229–235 15. Judd SJ (2006) The MBR book: Principles and applications of membrane bioreactors in water and wastewater treatment. Elsevier, Oxford 16. Kitis M, Koseoglu H, Gul N, Ekinci FY (2003) The membrane bioreactors in wastewater treatment and reclamation (in Turkish). 5th National Environmental Engineering Conference, Oct. 1–4, Ankara, pp 463–480 17. Kraume M, Bracklow U, Vocks M, Drews A (2005) Nutrients removal in MBRs for municipal wastewater treatment. Water Sci Tech 51(6–7):391–402 18. Le-Clech P, Jefferson B, Judd SJ (2003a) Impact of aeration, solids concentration and membrane characteristics on the hydraulic performance of a membrane bioreactor. J Membr Sci 218:117–129 19. Le-Clech P, Jefferson B, Chang IS, Judd SJ (2003b) Critical flux determination by the flux-step method in a submerged membrane bioreactor. J Membr Sci 227:81–93 20. Le-Clech P, Chen V, Fane TAG (2006) Fouling in membrane bioreactors used in wastewater treatment. J Membr Sci 284:17–53 21. Lee J, Ahn WY, Lee CH (2001) Comparison of the filtration characteristics between attached and suspended growth microorganisms in submerged membrane bioreactor. Water Res 35(10):2435–2445 22. Lesjean B, Rosenberger S, Schrotter JC, Recherche A (2004) Membrane-aided biological wastewater treatment – An overview of applied systems. Membr Technol 8:5–10 23. Madaeni SS, Fane AG, Wiley DE (1999) Factors influencing critical flux in membrane filtration of activated sludge. J Chem Technol Biotechnol 74:539–543 24. Psoch C, Schiewer S (2005) Critical flux aspect of air sparging and backflushing on membrane bioreactors. Desalination 175:61–71 25. Schoeberl P, Brik M, Bertoni M, Braun R, Fuchs W (2005) Optimization of operational parameters for a submerged membrane bioreactor treating dyehouse wastewater. Sep Purif Technol 44:61–68 26. Smith PJ, Vigneswaran S, Ngo HH, Ben-Aim R, Nguyen H (2005) Design of a generic control system for optimising back flush durations in a submerged membrane hybrid reactor. J Membr Sci 255:99–106 27. Stephenson T, Judd S, Brindle K (2000) Membrane bioreactors for wastewater treatment. IWA Publishing, London 28. Van der Roest HF, Lawrence DP, van Bentem AGN (2002) Membrane bioreactors for municipal wastewater treatment. IWA Publishing, London 29. Visvanathan C, Ben Aim R, Parameswaran K (2000) Membrane separation bioreactors for wastewater treatment. Crit Rev Environ Sci Technol 30:1–48 30. Yang W, Cicek N, Ilg J (2006) State-of-the-art of membrane bioreactors: Worldwide research and commercial applications in North America. J Membr Sci 270:201–211 31. Yigit NO, Civelekoglu G, Kitis M (2006) Impacts of biomass characteristics and operational conditions on membrane fouling in a submerged membrane bioreactor. 232nd American Chemical Society National Meeting, Sept. 10–14, San Francisco, USA

NOx Formation of Co-combustion of Sweet Sorghum – Lignite (Orhaneli) Mixtures in Fluidised Beds M. Handan Çubuk, Derya B. Özkan, and Özlem Emanet

Abstract Nitric oxide is an acid rain precursor and participates in the generation of photochemical smog through ozone production. In addition, nitrous oxide is a greenhouse gas. Thus, the reduction of emissions of nitrogen oxides is currently a major environmental issue. In this study, Sweet sorghum was chosen as the energy plant. Combustion experiments of lignite and lignite-sweet sorghum mixtures were carried out in a fluidized bed system. The fuel-feeding ratio was set such that the thermal output of the system remained constant. Addition of Sweet sorghum to the lignite reduces the pollutant concentration. The results were supported by experimental results. Keywords Sweet sorghum · Co-combustion · Fluidized bed · Nitrous oxide

1 Introduction It is impossible to evaluate energy sources independent from their influence on the environment. CO2 , SO2 and NOx emissions from fossil fuel combustion play an important role on atmospheric pollution. The emissions of hazardous air pollutant from coal combustion have become an important issue in light of the new environmental regulations in several developed countries and these pollutants have been the subject of important research activities in recent decades [1]. Global warming is considered a potentially serious environmental problem and the use of fossil fuels for electricity production is one of its main causes [2]. Certain gases in the tropospheric atmosphere that have the ability to absorb infrared radiation and bring out greenhouse effect or global warming are called greenhouse gases such as carbon dioxide (CO2 ), methane (CH4 ) and nitrous oxide M.H. Çubuk (B) Mechanical Engineering Faculty, Heat and Thermodynamics Division, Yıldız Technical University, 80750 Yıldız, Istanbul, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_88,

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M.H. Çubuk et al. Table 1 Mixture ratio

Lignite (kg h−1 ) Sweet sorghum (kg h−1 ) Total feeding rate (kg h−1 ) Calorific heating value (kJ kg−1 )

R =0 (100% lignite)

R =1 (5% SS)

R =2 (10% SS)

R =3 (15% SS)

2.702 0 2.702 15,494.06

2.567 0.129 2.696 15,527.99

2.432 0.258 2.690 15,562.07

2.296 0.388 2.684 15,596.44

(N2 O). Although N2 O is not the major contributor to the global warming (ca. 6%), it is much more potent than CO2 and CH4 due to its long atmospheric lifetime of ca. 120 year and large global warming potential of 310 times compared to that of CO2 on 100-year integrated time horizon. Therefore, agricultural sector is by far the largest anthropogenic source of N2 O emissions, representing over two thirds of N2 O emissions overall from developing countries. Further, the fossil energy consumption and industrial processes are generally ranked as the second and third important sources of N2 O emissions, respectively [3]. Turkey currently imports over 70% of its energy needs from other countries [4]. Turkey has to turn towards its own natural sources. The most important reserve is the lignites, unfortunately low quality exerting high environmental pollution with high sulfur and ash contents. Scarcity of the primary energy sources should draw our attention more on renewable energy sources. Renewable forms of energy, such as biomass, are considered promising and environmentally friendly alternatives to fossil fuels [5]. To investigate the NOx formation, Orhaneli lignite was burned alone, initially in the fluidized bed combustion reactor (defined as R = 0). In order to replace the fuel partially with a renewable source Sweet sorghum, a biomass plant, was fed into the reactor at different ratios, 5, 10 and 15% and the emissions were monitored and compared. The ratios have been defined as R = 1, 2 and 3 respectively and their properties are given in Table 1.

2 Lignite and Biomass 2.1 Turkish Lignites and Their Characteristics Turkish coal reserves constitute 0.88% of the European reserves and 0.11% of the total world reserves. Analyses show that the ash, moisture and sulfur content of domestic lignites vary a lot [6, 7]. The share of the lignites containing less than 20% ash among the reserves is only 3.73%. Therefore nearly 96% of the lignites have high ash content. Lignites with less than 20% moisture content constitute 15.14% of the total reserves. Moreover approximately 69% of the lignites have calorific values under 8400 kJ/kg.

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Fluidized bed combustion is generally considered to be an environmentally favorable combustion technology where control of emissions can be integrated into the combustion system. FBC system operating at low temperatures around 800–900◦C not only prevent thermal NO formation but promote NO-reducing reactions during the combustion process [8].

2.2 Biomass Energy and Sweet Sorghum Biomass has an important potential among new and renewable energy sources. Generally biomass, consuming CO2 in the air during its growth shows an interesting character among other fuels and is easy to produce. Biomass is an organic fuel, which does not originate from fossils. The total energy equivalent of biomass as a renewable energy source is around 65376 Mtoe, which is approximately 8 times the total global energy consumption for the year 1997 [9, 10, 11]. Only 8% of this potential is being currently used. During combustion of a biomass, CO2 is released, making a closed cycle with CO2 fixation by the plant. Globally, it results in no net increase of CO2 in the atmosphere [12]. In developing countries, over 2 billion people depend on biomass as their primary source of energy; 70% of the population live in rural areas, and biomass accounts for about 43% of total energy used [13]. Energy production utilizing biomass is an important source for Turkey due to her vast farming areas and her suitable climate. Sweet sorghum used in this study is known to be an annual C4 plant of tropical origin with a calorific value between 16,744 and 17,580 kJ/kg on a dry basis. It is well adapted to sub-tropical and temperate regions, being highly biomass-productive and water efficient. It grows rapidly, widely, is easily cultivated over a wide range of climates and its cost per ton is less than the other biomass. [14, 15]. It does not need much fertilizer, pesticides or irrigation, has high photosynthetic efficiency (about 2–3%) and high productivity [16].

3 Method and Material 3.1 Experimental Setup Experimental measurements were carried out in the fluidized bed laboratory at TUBITAK Marmara Research Centre (MRC). The reactor was designed to sustain stable combustion with continuous coal feed. The combustor consists of a 150 mm internal diameter with 300 mm high active bed and 210 mm internal diameter with 900 mm high free board sections. Both sections were equipped with ports to serve as probe inlets for temperature and concentration measurements, ash removal and coal feed. The free board was designed to minimize particle transportation. Fluidization air was provided from a compressor and the flow rates were measured using three rotameters at different ranges. Flue gases were collected and removed through a fan

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system and were analyzed using a Flue Gas Analyzer, taking measurements every 40 s. O2 , CO, SO2 and NOx gas concentrations were monitored. The initial bed material was foundry sand having a particle size distribution between 0.5 and 1 mm with a density of, ρ = 2.64g/cm3 . The static bed height was 70–80 mm and the dynamic bed height approximately 200 mm. The feeding of mixture was carried out 20 mm above the distributor plate directly into the foundry sand. The coal particles entering the feed-pipe entrance were conveyed with the secondary air stream, which was metered by a separate rotameter. Biomass was also fed utilizing the same system, mixed into the coal before loading into the fuel entrance bin. Because of the agglomeration occurred with insulated bed, the bed region has not been insulated during the experiments.

3.2 Experiments The bed was kept at around 850◦C during the experiments using only coal or coal/biomass mixture. The mixture-feeding rate can be controlled through the helical feeding mechanism. To maintain the dynamic bed height at a constant level, ashes were removed from the bed through an overflow pipe connected to the reactor. Ashes were collected in a separate container to determine their composition. Sweet sorghum and coal were pre-mixed in a RETCH brand blender for 30 min, stored in a bin under controlled atmosphere to be used in the experiments. The lignite used in the study was supplied from Orhaneli Thermal Power Plant and sized between 1 and 2 mm. Sweet sorghum was grown at TUBITAK – MRC,

Table 2 Analysis of the experimental materials R =0

R =1

R =2

R =3

Proximate analysis (wt%; as received) Moisture Volatile matter Fixed carbon Ash Calorific heating value (kJ kg−1 )

22.32 54.19 30.70 15.11 15,494.06

21.61 55.34 29.95 14.71 15,527.99

20.90 56.50 29.19 14.31 15,562.07

20.17 57.67 28.42 13.90 15,596.44

Ultimate analysis (wt%; daf) Carbon Hydrogen Oxygen Nitrogen Sulfur Combustible sulfur

59.70 4.91 32.85 0.59 1.94 1.10

59.03 4.95 33.56 0.60 1.85 1.05

58.37 4.99 34.26 0.62 1.76 1.00

57.70 5.03 34.97 0.63 1.67 0.95

NOx Formation of Co-combustion of Sweet Sorghum

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harvested, chopped into pieces between 0.5 and 1 mm in special grinders, pressed under a pressure of 150 kgf / cm2 to remove its structural water and left to be dried at ambient conditions. Proximate and elemental analyses of both materials have been carried out to determine their characteristics [17]. The results are presented in Table 2 for Orhaneli lignite and Sweet sorghum respectively. All loose Sweet sorghum and lignite analyses were made according to ASTM Standards [17]. A Fisher 490 model proximate analysis system, LECO-SC-32 model sulfur analyzer and LECO AC-200 model calorimeter were utilized within this frame.

4 Results and Discussion To establish the combustion characteristics of lignite-sweet sorghum mixtures, they were burned in a fluidized bed combustor and the flue gas concentrations were measured together with temperatures at different locations in the system. The Flue Gas Analyzer measures O2 , CO, SO2 and NOx concentrations and calculates CO2 and H2 O concentrations. Since the analyzer calculates these values from a pre-assumed fuel type, CO2 and H2 O were calculated based on the original fuel composition and these results were used in the analysis. The flue gas emissions were measured every 40 s for 2 h during the experiments; the average value for NOx emissions is presented in Fig. 1. During combustion, nitrogen from the air or fuel is converted to nitrogencontaining pollutants such as NO, NO2 , N2 O, NH3 and HCN. The pollutant species formed depends principally on the temperature and fuel/oxygen ratio in the combustion zone. Nitric oxide is an acid rain precursor and participates in the generation of photochemical smog through ozone production. In addition, nitrous oxide is a greenhouse

225

NOx (ppm)

220 215 210 205 200

Fig. 1 Experimental NOx emissions

0

1 2 R (mixing ratio)

3

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gas. Thus, the reduction of emissions of nitrogen oxides is currently a major environmental issue. During coal combustion, NO may be produced from the oxidation of: (a) the molecular nitrogen present in the combustion air (Thermal NO); (b) compounds produced by the attack of hydrocarbon free radicals on N2 (Prompt NO); and (c) the organic nitrogen present in the coal (Fuel NO). The last pathway may also be a source for N2 O, particularly at low temperatures, as in fluidized bed reactors [18]. Fuel NO and N2 O are produced by the oxidation of the volatiles present in the coal and by the oxidation of the nitrogen present in the residual char. The nitrogen oxides produced from coal volatiles have traditionally being reduced by modifying the air–fuel mixing in the combustion chamber with acceptable success. Nitrous oxide (N2 O) contributes to the greenhouse effect in the troposphere and participates in ozone depletion in the stratosphere. Several investigators have shown that N2 O emissions are not typically significant within coal combustion systems. N2 O can be formed by a number of reactions in gas and coal reactors, but it rapidly reacts with H and OH radicals to form N2 . Some N2 O does result from fluidized bed combustion due to their lower operating temperatures [19]. N2 O emission cannot be measured by this device. To estimate the N2 O concentrations, results from the literature have been used. In the study by Liu and Gibbs a model for NO and N2 O emissions from biomass (firewood chips) has been developed and evaluated [20]. This model gives the desired variation for NO and N2 O formation as a function of the fuel N-content (%) and the bed temperature on diagrams (Figs. 2 and 3 respectively). The measurements obtained during our experiments were compared and evaluated using these results to estimate the N2 O formation. NO formation as a function of the bed temperature is also available in this study. The outcome is summarized in Tables 3 and 4. As can be followed from Table 3, the NO conversion percentages as a function of the fuel-N content for different mixture ratios agree well with the NO

Fig. 2 The conversion of fuel-N to NO and N2 O emission [20]

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Fig. 3 Predicted effect of bed temperature on NO and N2 O emissions and the measured effect of bed temperature on NO emissions [20] Table 3 Effect of the fuel-N content on NO formation [20] R

0 1 2 3

NO

N2 O

Experimental NO

Estimated N2 O

(%)

(%)

(%)

(gr/h)

(gr/h)

22–40 22–40 24–39 24–39

5 5 5.4 5.5

44 43 42.8 44

4.83 4.87 4.93 5.20

~0.55 ~0.56 ~0.62 ~0.65

Table 4 Effect of the bed temperature on NO formation [20] R

0 1 2 3

NO

N2 O

Experimental NO

Estimated N2 O

(ppm)

(ppm)

(ppm)

(ppm)

125–195 125–195 125–200 123–197

4.7–6.2 4.7–6.2 4.1–5.9 4.4–5.9

184 186 191 199

~5 ~5 ~5 ~5

percentages obtained from the experiments. Based on this agreement the same diagrams have been used to estimate the N2 O formation during combustion of the sweet-sorghum/lignite mixture. Another study [21] on the modelling of N2 O and NO formation gives results in the form of non-dimensional functions (Eqs. 1 and 2). The calculated NO and N2 O

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Fig. 4 Result of parametric study of the net char-nitrogen conversion to NO and N2 O [21]

conversion rates according to the bed temperature were given on graphs for different particles sizes (Fig. 4). The functions indicated on the graphs are defined as using the following relations: fNO = [NO] / {(N/C) ( [CO] + [CO2 ] )}

(1)

fN2 O = (2 [N2 O] ) / {(N/C) ( [CO] + [CO2 ] )}

(2)

The values taken from the graphs for a particle size of 1–2 mm have been compared with the experimental results in Table 5. Table 5 indicate that the NO conversion ratios calculated from Eq. 1 for the bed temperature and the experimental results are in good agreement. This allows us to calculate the N2 O conversion ratio from Eq. 2, to determine the N2 O concentration during combustion. The results also agree well with the study by Liu and Gibbs. From the above observations it was concluded that the N2 O emission for our case was in the order of 0.5–0.6 g/h. This value was used later in the analysis. The components in the fuel and air have also been compared with the measured flue gas emissions in Table 6.

Table 5 Comparison of the experimental data with the values taken from literature for a particle size 1-2 mm [21] R

T [K]

Experimental fNO [%]

fNO from Eq. 1 [%]

fN2 O from grafic

N2 O (gr/h)

0 1 2 3

1107 1106 1111 1119

22 21 22 22

22 21 22 22

3.5 3.5 3.5 3.5

0.567 0.583 0.575 0.609

154.65 1063.78 10.54

585.52 535.98 3227.1 4348.6 34.58 22.98 11.6

H C Nfuel

Oxygen : Ofuel OW Oair Total O : Sfuel Scomb Unburned S

18.15

4346.12

152.66 1040.67 2.39 as NO 0.55 as N2 O 607.95 517.88 3227.1 4352.93 33.16 21.95 11.21

154.24 1062.76 11.05

Fed (in)

Fed (in)

Measured

R =1

R =0

20.53

4347.35

152.4 1019.65 2.42 as NO 0.56 as N2 O

Measured

630.27 499.74 3227.1 4357.11 31.47 20.90 10.57

153.93 1062.01 11.29

Fed (in)

R =2

20.22

4365.97

152.10 987.85 2.47 as NO 0.62 as N2 O

Measured

Table 6 Comparison of the components in the fuel and air with the flue gas emissions

652.75 481.21 3227.1 4361.06 30.06 19.86 10.20

153.55 1060.98 11.81

Fed (in)

R =3

17.72

4372.93

151.73 994.53 2.62 as NO 0.65 as N2 O

Measured

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5 Conclusions Results show a slight increase in the NOx . The NOx increase is due to the local increase in temperature around the Sweet sorghum particles. A better mixing of the fuel will reduce this increase. However, the variation is within acceptable limits and could be regarded as unaffected (Fig. 1). Sweet sorghum has a lower density compared to coal. Since the bed air velocity is adjusted according to the coal and ash particles present in the bed, Sweet sorghum is conveyed to the free board region. Biomass completes its combustion in the free board. The flue gas concentrations were taken at a point within the region and therefore the combustion of the biomass particles are not completed. The feeding point of the mixture is also near the top of the bed, which enhances the carry-over. Pelletizing Sweet sorghum before feeding into the bed will solve this problem. Addition of Sweet sorghum into the lignite results in a non-homogenous mixture, which effects the temperature distribution in the bed. Combining the O2 present in the plant composition creates high temperature spots locally. This process is thought to be the slight increase in the NOx concentrations.

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15. Chiaramonti D, Grimm HP, Bassam N, Cendagorta M (2000) Energy crops and bioenergy for rescuing deserting coastal area by desalination: Feasibility study. Bioresour Technol 72: 131–146 16. Grassi G, Moncado P, Zibetta H (1992) Promising industrial energy crop: Sweet-sorghum. Commission of the European Communities publication, Elsevier, Oxford 17. Çubuk MH (1998) Investigation of the environmental pollution characteristics of Orhaneli lignite-biomass mixtures in fluidised beds. YTÜ Graduate Institute, Ph.D. Thesis, ˙Istanbul 18. Molina A, Eddings EG, Pershing DW, Sarofim AF (2000) Char nitrogen conversion: Implications to emissions from coal-fired utility boilers. Prog Energ Combust Sci 26:507–531 19. Hill SC, Smoot LD (2000) Modeling of nitrogen oxides formation and destruction in combustion systems. Prog Energ Combust Sci 26:417–458 20. Liu H, Gibbs BM (2002) Modelling of NO and N2 O emissions from biomass-fired circulating fluidized bed combustors. Fuel 81:271–280 21. Kilpinen P, Kallio S, Konttinen J, Barisic V (2002) Char-Nitrogen oxidation under fluidized bed combustion conditions: Single particle studies. Fuel 81:2349–2362

Pretreatment of Ceftriaxone Formulation Effluents: Drawbacks and Benefits T. Tezgel, F. Germirli Babuna, I. Arslan-Alaton, G. Iskender, and O. Okay

Abstract As a result of its high inert COD content (approximately 250 mg/l accounting for 63% of the total COD) and the possibility to evoke antibiotic resistance, Ceftriaxone sodium antibiotic formulation effluent (molecular formula = C18 H16 N8 Na2 O7 S3 ) requires an additional treatment process preferably as chemical pretreatment along with the biological one to meet the discharge standards. The present study dealt with the effect of applying ozonation and the H2 O2 /O3 process (perozonation) as a partial pretreatment stage to the mentioned antibiotic formulation effluent. 20 min of ozonation at a rate of 1500 mg/(l·h) removed 48% COD, whereas a COD removal efficiency of 53% could be achieved via perozonation in the presence of 31 mM H2 O2 . Ozonation completely eliminated the inhibitory effect of the effluent towards activated sludge, however at the same time it also resulted in an increase in acute toxicity towards the marine microalgae Phaeodactylum tricornutum. On the other hand, by perozonation a considerable reduction in the inhibitory effect of the studied effluent towards heterotrophic biomass was achieved, unfortunately perozonation also increased the toxicity of the effluent towards the marine microalgae. Keywords Acute toxicity · Pharmaceutical industry · Antibiotic formulation effluents · Inert COD · Activated sludge inhibition · Ozonation · Advanced oxidation processes

1 Introduction From the environmental point of view, antibiotics are known for their toxic and xenobiotic character [1, 18]. Thus, the uncontrolled release of antibiotics to the environment causes a variety of environmental problems including the stimulation F.G. Babuna (B) Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey e-mail: [email protected]

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of antibiotic resistant microorganisms in the receiving media [15]. The microbial community of conventional sewage treatment plants has also been affected from the mentioned phenomenon of resistance. Although the level of antibiotic resistant bacteria in the effluent of such a treatment plant is observed to be much lower than the domestic wastewater itself, the incidence of antibiotic resistance in the receiving water increases upon discharging this treated wastewater into it [13]. Therefore effluents from pharmaceutical industry containing antibiotic residues must be managed in a way not only to eliminate the conventional pollutant parameters and toxicity but also the possibility to cause antibiotic resistance has to be considered. Development of such a delicate management strategy on the other hand requires a detailed evaluation of treatability. Besides due to the biorecalcitrant nature of antibiotic wastewaters [14] and obscure impacts of releasing antibiotic containing wastes to an environment rich with bacteria, a partial chemical pre-treatment prior to biological one must be prescribed for these effluents. Among one of the most commonly used antibiotics of the beta lactam group, i.e. the cefalosporins, Cefriaxone sodium is selected as the target compound in the present study. The objective was to investigate the treatability of Ceftriaxone sodium formulation effluents by means of advanced oxidation processes (AOPs), namely ozonation at elevated pH and the O3 /H2 O2 process (i.e. perozonation). The effects of ozonation and perozonation on the inert COD fractions of the effluent were assessed to evaluate the biodegradability improvement of the effluent. A standard activated sludge inhibition test was also performed on raw and treated effluents. The acute toxicity towards the marine algae Phaeodactylum tricornutum from the family Bacillariophyceace was experimentally determined to evaluate the possible toxic effect of raw and treated ceftriaxone sodium effluent on the marine environment that can be thought as the most common effluent discharge medium of the country.

2 Materials and Methods 2.1 Synthetic Antibiotic Formulation Effluent Due to the fact that effluents from pharmaceutical formulation industry contain almost solely the active substance, all the experiments were conducted on synthetic samples prepared by dissolving appropriate amounts of Ceftriaxone sodium (C18 H16 N8 Na2 O7 S3 ; 598.54 g/mol) powder in deionized water to get an initial COD of 400 mg/l. Such a COD concentration was selected to simulate the actual effluents originating from a formulation plant manufacturing Ceftriaxone sodium (Ceftriaxone-Na) salt as given in literature [5, 6].

2.2 O3 and O3 /H2 O2 Experiments Ozonation and perozonation processes were applied to 1,000 ml synthetic Ceftriaxone sodium formulation samples in a 1,500 ml capacity semi-batch bubbled

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gas washing bottle with an effective depth of 23 cm, under the same conditions; 15 psi (103.45 kPa) pressure by a feed gas (ozone + pure oxygen mixture) flowrate of 1.42 l/min. Ozone was produced by a PCI GL1 model pilot scale ozone generator at a rate of 1,500 mg/(l·h). Ozone gas was supplied at the bottom of the reactor through a sintered glass plate diffuser. All pieces in contact with ozone were stainR In order to determine the input and output ozone gas less steel, glass or Teflon. levels, gas washing bottles containing 2% w/w potassium iodide solution were connected to both inlet (two gas washing bottles in series) and outlet (two gas washing bottles in series) of the reactor. The ozonation and perozonation experiments were carried out for 5, 10, 20, 40 and 60 min at an initial pH of 11.0. In the case of perozonation 31.25 mM H2 O2 was applied to the Ceftriaxone-Na formulation effluent at the beginning of the experiment. This H2 O2 dose was selected considering the optimum COD: H2 O2 molar ratio needed for the achievement of the highest COD removal efficiency obtained in previous perozonation studies conducted with real and simulated penicillin formulation effluent [3, 4].

2.3 Acute Toxicity Experiments The acute toxicity tests run with marine microalgea Phaeodactylum tricornutum were performed as previously described by Okay et al. [17]. The principle of the adopted procedure is based on the US EPA bottle test [16]. The experiments were conducted at constant temperature (20 ± 2◦ C) and light (3,500–4,000 lux) conditions. Seawater filtered from Millipore filters with 0.45 μm pore sizes together with NaCl solution (13.5 g NaCl/L to simulate seawater) were used to prepare raw and treated (ozonated and perozonated) antibiotic sample dilutions respectively. Several dilutions of stock solutions of raw (in filtered sea water) and ozonated and perozononated samples (with 13.5 g/L NaCl) were incubated together with algal species in 250 mL Erlenmeyer flasks. Batch cultures were maintained in standard f/2 algal growth media [10]. A starting concentration of 10,000 cells/ml was added and the production rate was followed by counting the cells with a Coulter Counter (Beckman Z2) for 1 week. The flasks were repositioned daily within the experimental space to minimize possible spatial differences in illumination and temperature on growth.

2.4 Activated Sludge Inhibition Test Activated sludge inhibition tests were conducted in accordance with a test procedure described in ISO 8192 [12]. All experiments were run at a constant temperature (20 ± 2◦ C). The heterotrophic mass used in the activated sludge inhibition test was previously acclimated with a synthetic medium resembling municipal wastewater of “readily biodegradable” nature (SWW) for 2 months. As the activated sludge inhibition experiments were performed on the raw, ozonated and perozonated Ceftriaxone-Na formulation samples, each of these samples were

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diluted with appropriate amounts of SWW (for raw Ceftriaxone-Na formulation CODSWW = 400 mg/L; for ozonated Ceftriaxone-Na formulation CODSWW = 210 mg/L; for perozonated Cefazolin–Na formulation CODSWW = 190 mg/L) to obtain a series of different COD fractions thereby keeping a constant total COD in the raw/ozonated/perozonated antibiotic + SWW effluent mixture at 400; 210 and 190 mg/L, respectively. During a typical run, SWW as well as raw or ozonated or perozonated antibiotic samples were aerated for up to 60 min in test beakers containing proper amounts of the SWW-acclimated, activated sludge. A food-to-microorganisms (F/M) ratio of 0.13 mg COD mg MLVSS−1 day−1 (for experiments with raw Ceftriaxone-Na formulation MLVSS = 3,000 mg/L; for tests with ozonated Ceftriaxone-Na formulation MLVSS = 1,600 mg/L and for experiments with perozonated Ceftriaxone-Na formulation MLVSS = 1,500 mg/L) was applied for all experiments. The decrease in dissolved oxygen (DO, in mg/L) in the synthetic wastewater control (SWW) as well as in different dilutions of raw and chemically treated antibiotic samples was monitored for up to 5 min using a WTW Oxi Digi 2,000 model oxygen meter. Microbial oxygen uptake rates (OUR’s), expressed in mg L−1 h−1 , measured in SWW and SWW-diluted antibiotic samples were calculated based on the linear part of decreasing DO curves as a function of aeration time. Percent inhibition of OUR, i.e. IOUR, for every tested sample dilution, was calculated using the following equation: IOUR (%) = [(RB − RT ) 100] /RB

(1)

where RT refers to the OUR of the sample (carrier + SWW) mixture; RB is the OUR of the control (sample blank, i.e. SWW). The obtained IOUR values were thereafter plotted against the natural logarithm of the carrier COD’s (ln COD’s). The COD content of raw and chemically treated antibiotic formulation effluent samples resulting in 50% decrease in OUR (i.e. EC50 values; in mg/L COD) after 30 min of aeration was calculated by interpolation of the “lnCOD” (x axis) versus percent “IOUR” (y axis) plots obtained for different dilutions of raw and chemically treated antibiotic formulation effluent samples. The heterotrophic sludge sensitivity was checked by the reference test chemical 3,5-dichlorophenol [12].

2.5 Inert COD Experiments The inert COD content of both raw, ozonated and perozonated Ceftriaxone-Na formulation samples, were assessed according to an experimental procedure given in literature [7]. The method involves running two aerated cylindrical batch reactors, one fed with the sample itself, and the other with glucose solution having the same dilution, of 3,000 ml volumetric capacity. The seed was obtained from a lab-scale fill and draw aerobic reactor operated under steady state with a food to microorganism ratio of 0.6 mg COD (mg VSS. day)−1 for about 40 days. A mixture of 50% glucose and 50% raw (or ozonated or perozonated) sample was applied as the feed for this fill and draw aerobic reactor. An initial biomass concentration of 50 mg/l VSS was

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sustained in both of the batch reactors (run with raw/ozonated/perozonated sample and with glucose) where inert COD tests were performed to hinder the interference of the residual COD that can form from the endogenous respiration of initial inoculums. Aliquots removed periodically from the mixed liquor of each reactor were analyzed for soluble COD. To avoid erroneous results, a strict accounting was kept of all samples removed from the reactors, so that any water loss by evaporation was replaced with distilled water prior to sampling. Experiments were continued and data were collected until the observation of a stable soluble COD plateau where the threshold level was established as less than 3–5% variation between consecutive samples. In the batch tests the samples were adjusted to a pH of 7–8, a range suitable for biological activity. Nitrification inhibitor (Formula 2533TM, Hach Company) was added to all bioreactors in order to avoid possible interferences.

2.6 Analytical Procedure Apart from COD, all analyses for conventional characterization were performed as defined in Standard Methods [2]. COD measurements were accomplished by ISO 6060 method [11]. All experiments were conducted at room temperature. pH adjustments were made by NaOH or H2 SO4 solutions. Filtrates of samples subjected to vacuum filtration by means of Millipore membrane filters with a pore size of 0.45 μm are defined as soluble fractions. Each data point was calculated as the mean of three replicate measurements.

3 Results and Discussion The BOD5 /COD ratio which is thought to be a rough indicator of biodegradability [8] was found as approximately 0.01 for the synthetic Ceftriaxone-Na formulation effluent. Even though the current understanding of environmental biotechnology mainly focuses on the inert COD concept rather than employing the rather unreliable BOD5 /COD ratio to investigate the biodegradability of effluents, at this stage of the study the BOD5 /COD ratio was used as a rough tool to screen the pretreatment data. It should be mentioned herein that according to the legislative limitations the COD of the formulation effluent has to be reduced to a level under 150 mg/L prior to discharge into the adjacent marine environment.

3.1 Treatment with O3 and O3 /H2 O2 Figure 1 presents ozone utilization and COD abatement rates as well as BOD5 /COD ratios and ozonation yields (YO3 values, i.e. mg COD removed per mg O3 utilized; mg COD/mg O3 ) obtained during 1 h-ozonation (a) and perozonation (b) of Ceftriaxone-Na formulation effluent. From the figure it is evident that considering

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1000

(a)

0.7

800 0.6 0.5

600

0.4 400

0.3 0.2

200

0.1 0

0 0

10

20

Utilized Ozone (mg)

30

Time (min) COD (mg/l)

40

50

BOD/COD

60

YO3

1000

0.9 0.8

(b)

800

0.7 0.6

600

0.5 0.4

400

0.3 0.2

200

0.1 0

0 0

10

20

Utilized Ozone (mg)

30

Time (min) COD (mg/l)

40

50

BOD/COD

60

YO3

Fig. 1 Ozone utilization rates, COD abatement rates, BOD5 /COD ratios and YO3 values obtained during 1 h-ozonation (a) and perozonation (b) of Ceftriaxone sodium formulation effluent. Experimental conditions: CODo = 400 mg/L; pHo = 11.0; BOD5 /COD,o = 0.01; Applied ozone dose = 1,500 mg/(l·h)

ozone utilization and COD abatement, there was practically no difference between applying ozone or perozone to the antibiotic formulation effluent. Around 70% of the original COD could be removed by applying an ozone dose of 1,500 mg/l after one hour ozonation. As expected the ozone utilization efficiency decreased with increasing ozone dose (i.e. reaction time) due to the fact that oxidation products being less amenable to ozone and free radicals H2 O2 + O3 → ·OH + HO·2 + O2 produced via perozone where formed throughout the reaction as it proceeded.

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For both treatment processes ozone utilization was around 97–98% after 5 minozonation, but only 58–59% when 1,500 mg ozone was applied per litre of antibiotic formulation effluent after 1 h-ozonation. At the end of the reaction approximately 0.31–0.32 mg COD was removed per mg of ozone utilized and the BOD5 /COD ratio increased by a factor of 6 at the end of the reaction period. Considering the experimental results and the practical feasibility of the process it is advisable to apply 20–40 min ozonation when the ozone utilization rate is still high (>60%) and the BOD5 /COD ratio reaches its maximum value (=0.13−0.14). Moreover, taking into account the feasibility limit of applying ozone for wastewater treatment which is 2.0 mg O3 per mg initial COD [9] it can be concluded that even 40 min ozonation (corresponding to 2.5 mg O3 /mg CODo and exceeding the feasibility limit for ozonation) would economically be inappropriate. The pH gradually decreased from 11.0 to 6.6 during 1 h-ozonation. The pH drop indicates the formation of acidic intermediates throughout the reaction. In case of perozonation the decrease of pH was even more pronounced; at the end of the 1 hperozonation period the pH fell down to acidic levels (final pH = 3.77), speaking for differences in reaction mechanism and process pathway between ozonation and the perozonation process. Probably more carboxylic acids were produced in the presence of H2 O2 . However, the fall in pH might also be at least partially attributable to purging of formed CO2 from the reactor top, but doesn’t explain the significant differences in the pH changes during ozonation and perozonation.

3.2 Effects on Inert COD The effluent of a well operated biological treatment plant is composed of two COD fractions, namely, initially inert soluble COD, SI , and soluble residual microbial products generated through the course of biochemical reactions, SP (both expressed as mg/l COD). The former one originating from the raw wastewater discharges is of importance in evaluating the level biodegradability for industrial effluents. Thus an appraisal on inert COD fractions must be considered as an unavoidable part of defining a sound treatment scheme. In this context the effect of pretreatment with ozonation and perozonation on subsequent biological treatment in terms of inert COD fractions for the investigated Ceftriaxone-Na antibiotic formulation effluent are presented in Table 1. Raw formulation effluent was assessed to contain an initially inert soluble COD content of 250 mg/l, corresponding to 63% of the total COD. This highly recalcitrant character indicated the fact that biological treatment alone was not sufficient to reduce the effluent COD to a level defined by the discharge standards (According to the National Water Pollution Control Legislation an effluent COD of 150 mg/l must be secured). Application of 1,500 mg/h ozone for 20 min under an initial pH of 11, was observed to lower the initially inert COD to 180 mg/l. Although such a pretreatment provided 28% initially inert soluble COD removal, the related treatment scheme (ozonation followed by biotreatment) as a whole was evaluated to be inadequate in meeting the discharge limitations. On the other hand significantly better

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Effluent sample

Total COD CT (mg/l)

Initially inert soluble COD SI (mg/l)

Residual CODa SR = SI +SP (mg/l)

SI /CT (%)

Ceftriaxone-Na Pretreatedb Ceftriaxone-Na Pretreatedc Ceftriaxone-Na

400 210 190

250 180 110

260 185 115

63 85 58

a At

the outlet of a well operated biological treatment facility min ozonation at a rate of 1,500 mg/(l·h) under an initial pH of 11 c 20 min ozonation at a rate of 1,500 mg/(l·h) under an initial pH of 11 and an initial H O dose of 2 2 31.25 mM b 20

outcomes, i.e. 56% removal of initially inert soluble COD corresponding to 110 mg/l were obtained via perozonation. A treatment scheme composed of perozonation and a subsequent biological treatment was determined to yield approximately 115 mg/l residual COD at the outlet that was well below the discharge limits. Therefore both in terms of initially inert COD removal efficiencies and the lowest achievable effluent COD levels after bio-treatment, perozonation appeared to be the better (more convenient) alternative. That ozonation and in particular perozonation can at least partly remove the originally non-biodegradable COD fraction of real antibiotic formulation effluent was also demonstrated in another former study [3].

3.3 Effects on Acute Toxicity The results of the acute toxicity experiments performed on the marine microalgae Phaedactylum tricornutum for raw, ozonated and perozonated formulation effluent were summarized in Table 2. The percent volumetric ED20 and ED50 values given were estimated from the dose (concentration of antibiotic) – response (% inhibition

Table 2 Acute toxicity (in % v/v) of Ceftriaxone-Na samples on Phaedactylum tricornutum 4th day

7th day

Test sample

ED20 (%)

ED50 (%)

ED20 (%)

ED50 (%)

Untreated Ceftriaxone-Na Ozonateda Ceftriaxone-Na Perozonatedb Ceftriaxone-Na

–

–

9–10

–

1–2

2–3

2–3

4–5

2–3

4–5

3–4

19–20

a 20

min ozonation at a rate of 1,500 mg/(l·h) and an initial pH of 11 min ozonation at a rate of 1,500 mg/(l·h) under an initial pH of 11 and an initial H2 O2 dose of 31.25 mM b 20

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of test organism) curves for effective dilutions causing 20 and 50% inhibition of algal growth. According to the ED50 figures raw Ceftriaxone-Na wastewater did not exert any toxicity. However the ED20 values indicated that the same untreated sample having no toxicity after 4 days was observed to exhibit considerable toxicity towards Phaeodactylum tricornutum at the end of 7 days. The results showed that the toxicity of the effluent under investigation increased considerably after being subjected to ozonation and perozonation, although slightly better outcomes on ozonated samples were obtained. 20% dilution of both ozonated and perozonated effluents caused 90% growth inhibition on the Phaeodactylum tricornutum. An increase in acute toxicity of simulated penicillin formulation effluent after ozonation and in especially perozonation towards the freshwater cladoceran Daphnia magna was also observed in a recent study [4].

3.4 Effects on Activated Sludge Inhibition The EC50 values (in mg/l COD) obtained for untreated, ozonated and perozonated Ceftriaxone-Na formulation effluent and derived from the ln(COD) versus percent IOUR plots are given in Table 3. Raw Ceftriaxone-Na formulation effluent was observed to have an EC50 value of 240 mg/l COD. Such a finding indicated the fact that introducing 60% of raw wastewater causes 50% inhibition on heterotrophic biomass. On the other hand ozonation was determined to completely eliminate the activated sludge inhibition measured in terms of EC50 . 50% biomass inhibition was monitored upon addition of 84% perozonated effluent. Therefore although improvements in activated sludge inhibition were monitored by both of the pretreatment alternatives, a better outcome was obtained by ozonation, that is in agreement with previous related work dealing with the biodegradability and toxicity of simulated penicillin formulation effluent [4].

Table 3 Results of the activated sludge inhibition tests for raw and pretreated Ceftriaxone-Na formulation effluents Test sample

EC50 (mg/l COD)

Ceftriaxone-Na Ozonateda Ceftriaxone-Na Perozonatedb Ceftriaxone-Na

240 – 160

a 20

min ozonation at a rate of 1,500 mg/(l·h) and an initial pH of 11 min ozonation at a rate of 1,500 mg/(l·h) under an initial pH of 11 and an initial H2 O2 dose of 31.25 mM

b 20

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4 Conclusions Due to its high inert COD content and capacity to evoke antibiotic resistance Ceftriaxone sodium formulation effluent requires an additional treatment process preferably as pretreatment along with the biological one to meet the current discharge consents. Even though the application of pre-ozonation completely eliminates the inhibition on activated sludge, this alternative is determined to have two disadvantageous: first of all adequate COD removal efficiencies to fulfil the legal requirements are not achieved and furthermore a significantly elevated toxicity towards marine microalgae Phaeodactylum tricornutum is observed. In case of preperozonation on the other hand although a satisfactory outcome in order to meet the discharge standards together with a considerable improvement in inhibition of heterotrophic biomass can be obtained, a raise in the toxicity towards Phaeodactylum tricornutum is monitored. As a consequence it is recommended to expand the study by investigating the fate of Ceftriaxone-Na antibiotic formulation effluent under alternative pre-treatment processes and/or conditions. Acknowledgments This study was conducted as part of research activities of The Environmental Biotechnology Centre of The Scientific and Technical Research Council of Turkey.

References 1. Alexy R, Kümpel T, Kümmerer K (2004) Assessment of degradation of 18 antibiotics in the closed bottle test. Chemosphere 57:505–512 2. APHA-AWWWA-WPCF (1989) Standard methods for the examination of water and wastewater, 17th edn. American Public Health Association, Washington, DC 3. Arslan-Alaton I, Do˘gruel S, Baykal E, Gerone G (2004) Combined chemical and biological oxidation of penicillin formualtion effluent. J Environ Manage 73:155–163 4. Arslan-Alaton I, Ça˘glayan AE (2006) Toxicity and biodegradability of raw and ozonated procaine penicillin G formulation effluent. Ecotoxicol Environ Safety 63:131–140 5. Balcıo˘glu AI, Ötker M (2003) Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3 /H2 O2 processes. Chemosphere 50(1):85–95 6. Çokgör EU, Karahan Ö, Arslan-Alaton I, Saruhan H, Orhon D (2005) Biological treatability of raw and ozonated synthetic penicillin formulation effluent. Water Sci Technol 52(10–11):89–96 7. Germirli F, Orhon D, Artan N, Ubay E, Görgün E (1993) Effect of two-stage treatment on the biological treatability of strong industrial wastewaters. Water Sci Technol 28(2):145–152 8. Gilbert E (1987) Biodegradability of ozonated products as a function of COD and TOC elimination by example substituted aromatic substances. Water Res 21:1273–1278 9. Gottschalk C, Libra JA, Saupe A (2000) Application of ozone in combined processes, Chapter 6. In: Ozonation of water and wastewater. Wiley-VCH Verlag GmbH, Weinheim, Germany, pp 162–166 10. Guillard RRL (1972) Culture of phytoplankton for feeding marine invertebrates. In: Smith WL, Chanley MH (eds) Culture of marine invertebrate animals. Plenum Press, New York, pp 29–60 11. ISO (1986a) Water quality – Determination of the chemical oxygen demand. Ref. No. ISO 6060-1986 12. ISO (1986b) Water quality – Oxygen demand inhibition assay in activated sludge. Ref. No. ISO 8192-1986

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13. Iwane T, Urase T, Yamamoto K (2001) Possible impact of treated wastewater discharge on incidence of antibiotic resistant bacteria in river water. Water Sci Technol 43(2):91–99 14. Kümmerer K, Al-Ahmad A, Mersch-Sundermann V (2000) Biodegradability of some antibiotics, elimination of the genotoxicity and affection of wastewater bacteria in a simple test. Chemosphere 40:701–710 15. Lateef A (2004) The microbiology of a pharmaceutical effluent and its public health implications. World J Microbiol Biotechnol 20:167–171 16. Miller WE, Gree JC, Shiroyama T (1978) Experimental design, application and data interpretation protocol. Corvallis Environmental Research Laboratory, Office of Research and Development, US EPA-600/9-78-018, 97330, Oregon 17. Okay OS, Tüfekçi V, Donkin P (2002) Acute and chronic toxicity of pyrene to the unicellular marine alga Phaeodactylum tricornutum. Bull Environ Contam Toxicol 68:600–605 18. Sanderson H, Johnson DJ, Wilson CJ, Brain RA, Solomon KR (2003) Probabilistic hazard assessment of environmentally occurring pharmaceuticals toxicity to fish, daphnids and algae by ECOSAR screening. Toxicol Lett 144:383–395

Reducing the Toxicity and Recalcitrance of a Textile Xenobiotic Through Ozonation F. Germirli Babuna, N. Oructut, I. Arslan-Alaton, G. Iskender, and O. Okay

Abstract Lignosulphonates are known as biologically-difficult-to-degrade, multipurpose macromolecules that potentially may create toxicity problems in biological activated sludge treatment systems and/or in receiving water bodies. In the present experimental work a commercial lignosulfonate formulation (COD = 320 mg/g; BOD5 = 8 mg/g) frequently being used as an auxiliarly chemical in the cotton and polyester dyeing process was subjected to ozonation (≈ 3 g O3 /CODo ) at different pH (6 and 12) and ozone doses (1,400 and 5,300 mg/h) to improve its biodegradability and reduce its toxicity. Experimental findings have indicated that ozonation of lignosulphonates is a rather kinetically limited process. 20 min ozonation of lignosulfonate at a dose of 1,400 mg/h and an initial pH of 12 resulted in an 8-fold decrease in acute toxicity (EC50 = 3−4% v/v) towards the micralgae Phaedactylum tricornutum) and 50% reduction in its inert COD content (CODo = 600 mg/L). COD-based molecular size distribution indicated that the lignosulphonate formulation was cleaved to low-molecular-weight COD fractions after ozonation under the above mentioned conditions. Keywords Textile dyeing industry · Chemical pretreatment · Lignosulphonates · Ozonation · Biodegradability · COD fractionation · Acute toxicity

1 Introduction Lignosulphonates are the soluble derivatives of lignin, a major constituent of wood. While their exact nature is unknown, research has revealed that the molecule’s basic building unit is a phenyl propane derivative arranged in branched, polyaromatic

F.G. Babuna (B) Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey e-mail: [email protected]

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chains. Negatively charged sulphonate groups near the surface of the molecule maintain its solubility in water, while carboxylic and phenolic groups are also involved. The basic lignosulphonate molecule is isolated in the sulphite pulping process and used to manufacture high performance, speciality lignosulphonates with adhesive, agglomerating, sequestering, stabilizing, dispersing and wetting properties [8]. One of the main properties of lignosulphonates is their capacity to disperse solid particles and solutes in an aqueous environment. By electrokinetic action their negative charge is transferred to the solid particles or solutes, which mutually repel each other. In this way, stable suspensions, reduced viscosity and other surfaceactive properties can be obtained. This property permits the use of lignosulphonates in the textile dyeing industry as dispersing agents in conjunction with reactive, disperse and metal complex dyestuffs used to dye cotton, cellulose acetate and polyester fabrics, respectively [8]. As many other biologically-difficult-to-degrade textile auxiliaries lignosulphonates are generally categorized as xenobiotic chemicals [19]. Interestingly, although hundreds of research papers have already been published covering the fate and treatability of textile dyestuffs in dyehouse effluent, only few pertain the treatability and toxicity of textile auxiliaries other than dyestuffs [3, 4, 5]. The use of ozone as an oxidant has a whole number of advantages. Among these are its high reactivity and selectivity which allow conducting oxidation under relatively mild conditions facilitating a control over the oxidation degree of reactive products. The latter is of particular importance to alter/improve the biodegradability and toxicity of xenobiotic pollutants via partial oxidation [13]. The literature data concerning the kinetics and mechanism of ozonation of such complicated macromolecules is very scarce [1]. The main problem is that ozonation is a multistage process and a wide variety of oxidation intermediates are formed of which only collective environmental properties (such as organic carbon content measured in terms of BOD, COD or TOC etc.) can be identified. It is known that molecular ozone preferably oxidizes electron rich sites (aromatic, carbon-carbon double bonds and other non-saturated molecular structures). It is also known that during ozonation in water particularly at elevated pH, hydroxyl radical (· OH)-initiated reactions proceed along with direct ozonation. · OH reacts rather unselectively bringing about substantial structural changes in macromolecules including hydroxylation, decarboxylation and depolymerization producing low molecular weight products (carboxylic acids such as acetic, formic and oxalic acid) at high doses and polymerization products at small ozone doses. In both cases oxidation products being less amenable to further ozontion are formed and have to be treated biochemically for complete mineralization [20]. In this respect before prescribing partial ozonation to improve the negative environmental impacts of a xenobiotic compound, it is necessary to evaluate the changes induced by such partial chemical oxidation especially on the levels of recalcitrance and toxicity. From another point of view measuring the organic carbon content by BOD, COD or TOC and evaluating the level of recalcitrance on these collective parameters are stated to be inadequate or even misleading [12]. Instead a lot more attention is devoted to the inert COD contents according to the current understanding of environmental biotechnology.

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With the above mentioned facts in mind the purpose of the present study was to elucidate the effect of ozonation of a commercial textile lignosulphonic acid formulation on its biodegradability, toxicity and molecular size distribution. In the first stage of the study ozonation of the xenobiotic chemical was investigated under varying pH and applied ozone doses to optimize ozonation conditions for partial oxidation purposes. In the second stage of the experimental work the effect of pretreatment with ozone on the recalcitrance (i.e. changes in inert COD fractions), acute toxicity (towards the marine microalgae Phaedactylum tricornutum) and molecular size distribution was assessed in more detail.

2 Materials and Methods 2.1 Synthetic Wastewater Bearing Lignosulphonate Formulation The commercial lignosulphonate formulation was obtained from a local textile dyeing and finishing mill in Istanbul, Turkey, and used as received. During production the lignosulphonate was applied in batch-wise textile operations yielding a segregated wastewater discharge that contains the aqueous lignosulphonate formulation. To mimic the actual dye-bath discharge where this textile auxiliary was added, a sample was prepared by dissolving the lignosulphonate in deionized water at a concentration of 1.5 g/l (the original pH was 6.83). The original pH of the final solution was adjusted to (1) pH = 4−5 to simulate polyester dyeing conditions (with disperse dyestuffs) and (2) pH = 10−11 to simulate cotton dyeing conditions (with reactive dyestuffs). The BOD5 and COD content of 1,500 mg/L lignosulphonate were measured as 120 mg/L and 480 mg/L, respectively. Some physicochemical and ecotoxicological information derived from the product’s Safety Data Sheet is presented in Table 1. Table 1 Physicochemical and ecotoxicological properties of the lignosulphonate formulation Physical state and appearance ◦

Density at 20 C Chemical composition Ultimate biodegradabilitya a According

Dark brown liquid 1.13 g/cm3 Condensation product of a high molecular weight sulphonic acid and a methyl-chloro-sulphonate. Contains less than 1% butyl diglycol 70%

to the 28 d-Zahn-Wellens test

2.2 The Ozone Contactor Ozonation experiments were carried out for up to 60 min in an 800 mL-capacity borosilicate glass bubble column reactor which was initially filled with aqueous

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lignosulphonate solution of known initial pH and concentration. The reaction solution was continuously ozonated in semi-batch mode with respect to ozone gas. The ozone was produced from dry air by a pilot scale, 20 g/h maximum capacity ozone generator (PCI GL-1 model, USA) and supplied from the reactor bottom through a sintered glass diffuser at different doses varying between 600 and 5,300 mg/h. The effective mass transfer coefficient of the ozone contactor was determined as 1.60 min−1 by measuring bulk phase ozone concentrations at pH = 2 and an ozone dose 1,000 mg/h with the indigo colourimetric method [2]. For all the connections R in the experimental set-up Neoprene and Teflon tubing were used.

2.3 Determination of Inert COD Prior to the determination of inert COD, bioacclimation studies were conducted in 3 liter-capacity fed-batch reactors at ambient temperature and under sufficient oxygen/nutrient supply. In the bioreactors pH was regularly monitored and maintained between 6.5 and 7.5 using appropriate pH buffers. For the determination of the inert COD content in raw and ozonated (1,400 mgO3 /h for 20 min at an initial pH of 12) lignosulphonate samples, first two fill-and-draw bioreactors containing 50%v/v raw or ozonated lignosulphonate solution + 50% v/v glucose solution were operated at F/M (food-to-microorganism) ratios of 0.8 mg CODo /mg MLVSS and 0.6 mg CODo /mg MLVSS, respectively (MLVSS in both reactors was fixed at 700 mg/L). Then, using 30–50 mg/L MLVSS from the acclimated biomass of the above mentioned reactors as the seed source, inert COD experiments were initiated for untreated and ozonated lignosulphonate samples according to a procedure described in Germirli et al. [11]. The method involves running two aerated cylindrical batch reactors, one fed with the sample itself, and the other with glucose solution having the same dilution. Aliquots removed periodically from the mixed liquor of each reactor were analyzed for soluble COD. To avoid erroneous results, a strict accounting was kept of all samples removed from the reactors, so that any water loss by evaporation was replaced with distilled water prior to sampling. Experiments were continued and data were collected until the observation of a stable soluble COD plateau where the threshold level was established as less than 3–5% variation between consecutive samples. In the batch tests the samples were adjusted to a pH of 7–8, a range suitable for biological activity. Nitrification inhibitor (Formula 2533TM, Hach Company) was added to all bioreactors in order to avoid possible interferences.

2.4 Molecular Size Distribution Experiments The effect of ozonation on the molecular size distribution of lignosulphonate was examined by employing a series of filtration/ultrafiltration experiments in 400 mLcapacity cells (Amicon, Model 8400) under positive nitrogen gas pressure (0.4– 2.5 bar) and continuous mixing. For that purpose, untreated and ozonated (ozonation

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conditions: pHo = 12; CO3 = 1,400 mg/h; t = 20 min) lignosulphonate samples R HV, were filtered through 1,200–1,600 nm (Millipore AP40), 450 nm (Durapore R GV, PVDF) cutoff filters under 0.7 atm pressure. PVDF) and 220 nm (Durapore During the ultrafiltration experiments, samples previously filtered through 220 nm membrane filters were subjected to ultrafiltration using 100, 30, 10, 3 and 1 kDa molecular size cutoff membranes under 3.7 atm pressure. Obtained permeates and retentates were analyzed and fractionated for COD.

2.5 Acute Toxicity Experiments The toxicity testing is conducted at constant temperature of 20 ± 2◦ C and light of 3,500–4,000 lux by using indicator test organism of marine algea P. tricornutum from the family Bacillariophyceae. Apart from being the primary food source for many aquatic organisms and its common use in toxicity testing [9, 18], this specie is especially selected as the industrial wastewaters are mainly discharged into marine environment in Istanbul. The principle of batch toxicity tests is mainly based on the method of US EPA bottle test [16] and were performed as previously described by Okay et al. [17]. Diluted solutions of raw (500 mg/L in filtered sea water) and ozonated lignin sulphonic acid derivative (ozonation conditions: pHo = 12; CO3 = 1,400 mg/h; t = 20 min) are incubated together with the algal species in 250 mL glass Erlenmeyer flasks that contained 200 mL of test solutions. NaCl (13 g/L) was added to the ozonated lignin sulphonic acid solutions to obtain the desired salinity concentration for survival of the marine algae. Culture media was made of filtered clean seawater (0,45 μm-membrane Milipore) collected from the surface waters (20–22 ppt) of Marmara Sea (Istanbul Strait) known as relatively cleaner site and of modified f/2 nutrient medium [14]. A starting concentration of 10,000 cells/mL is added and the changes in algal concentration were determined by direct cell count using Coulter Counter (BECKMAN Z2) in every 2 days for a period of 1 week. The results were evaluated by comparing the Control cultures of corresponding series for raw and ozonated samples. The flasks were repositioned daily within the experimental space to minimize possible spatial differences in illumination and temperature on growth.

2.6 Analytical Procedure Samples collected at regular time intervals during ozonation, from the permeates and retentates of different molecular size filter cutoffs and during the inert COD experiments were all filtered through 0.45 μm-syringe filters (Millipore Corp.) and thereafter analyzed for soluble COD that was equal to their total COD content using the open reflux titrimetric method according to ISO 6060 [15]. The MLVSS concentration was determined in accordance with Standard Methods [2].

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3 Results and Discussion 3.1 Effect of pH on Ozonation Kinetics

Fig. 1 COD abatement kinetics of the lignosulphonate formulation effluent as a function of ozonation time at two different initial pH’s. Experimental conditions: CODo =615 ± 10 mg/L; Applied ozone dose=5,300 mg/h

–ln(COD/CODo)

Figure 1 displays COD abatement rates during ozonation (applied ozone dose = 5,300 mg/h) of aqueous lignosulphonate at two different (neutral and alkaline) pH values. 0,40 0,35 0,30 0,25 0,20 0,15 0,10 0,05 0,00

pH7

0

10

pH12

30 40 20 Ozonation Time (min)

50

60

From the figure it is evident that COD abatement rates followed first order kinetics with respect to COD; − ln COD/CODo = kCOD t

(1)

where kCOD is the first order COD abatement rate constant (in min−1 ). The kCOD’s were calculated as 0.0036 min−1 at pH 7 (final pH = 2) and 0.0068 min−1 at pH 12 (final pH = 7). The experimental findings indicated that pH had a significant effect on COD removal kinetics of lignosulphonate ozontion significantly revealing that the reactivity of ozone, i.e. the major oxidizing agent at acidic to neutral pH’s, is appreciably less than to that of ·OH, becoming the dominant oxidant at elevated pH, particularly at pH > 11.5 and independent of the substrate molecule. 25% (pH 7) and 32% (pH 12) COD removal was obtained after 60 min ozonation at the same applied ozone dose (=5,300 mg/h).

3.2 Effect of Applied Ozone Dose on Ozonation Kinetics The effect of increasing ozone dose on COD abatement rates during lignosulphonate ozontion is depicted in Fig. 2. In these experiments ozonation experiments were conducted at pHo = 12 (final pH 7–8) and varying ozone doses (i.e. 600, 1,400 and 5,300 mg/h). From the figure it is obvious that increasing the ozone dose from 1,400 to 5,300 mg/h did not significantly enhance COD removal rates. 28% (COD removal was obtained after 60 min ozonation at a rate of 1,400 mg/h instead of 32% COD removal at a rate of 5,300 mg/h at the same initial pH (=12). First order COD abatement rate constants

Fig. 2 COD abatement kinetics of the lignosulphonate formulation effluent as a function of ozonation time at varying ozone doses. Experimental conditions: CODo = 615 ± 10 mg/L; pHo = 12

-ln(COD/CODo)

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0

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were found as 0.0048 min−1 at 1,400 mg/h O3 and 0.0068 min−1 at an ozone dose of 5,300 mg/h. However, no COD removal occurred at an ozone dose of 600 mg/h at the same initial pH (not shown data). This observation supports an evidence of a rather kinetically limited reaction regime [6] for the ozonation of the macromolecule like lignosulphonate at a dose range of 1,400–5,300 mg/h. Considering the above experimental findings, optimum pre-ozonation conditions for lignosulphonate oxidation were determined as ozonation for 20 min at an inital pH of 12 and an ozone dose of 1,400 mg/h. Therefore all the data related to the ozonated sample presented below was obtained under these conditions.

3.3 Effect of Ozonation on Inert COD The experimental data obtained on the raw and ozonated lignosulphonate formulation effluents is outlined in Table 2. To assess the inert COD content of the untreated lignosulphonate solution two bioreactors, namely one containing lignosulphonate solution and another one with glucose control solution having the same initial COD content (i.e. 615 and 600 mg/L, respectively) were run for 56 days until their daily measured COD values levelled off. The ultimate COD reached in the lignosulphonate reactor was 340 mg/L, whereas that of the glucose control was only 40 mg/L. By using this data, the initially inert soluble COD of the lignosulphonate solution was determined as 320 mg/L, corresponding to 52% of the total COD. It’s evident that the problems arising from such a high recalcitrance can only be solved by applying at least a partial chemical treatment, i.e. ozonation to the segregated Table 2 Effect of ozonation on organic fractions

Sample

BOD5 /COD

Total COD CT (mg/l)

Raw Ozonateda

0.15 0.19

615 495

a 20 b At

Initially inert soluble COD, SI (mg/l)

Residual CODb SR = SI +SP (mg/l)

SI /CT (%)

320 163

340 187

52 33

min, 1,400 mgO3 /h at an initial pH of 12 the outlet of a well operated biological treatment facility

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effluent stream. The initially inert soluble COD was also determined for the samples being subjected to 20 min ozonation at an initial pH of 12 at a rate of 1,400 mg/h corresponding to a specific applied ozone dose of around 0.95 mg O3 /mg CODo that is a quite feasible dose for ozone application to industrial wastewater. The COD’s of the parallel bioreactors containing ozonated lignosulphonate and glucose solution (initial COD in both bioreactors=495 mg/L) were determined as 187 and 35 mg/L, respectively, after 56 days biotreatment. Accordingly, the initially inert soluble COD of the ozonated lignosulphonate solution was found as 163 mg/L. Upon comparison of the inert COD’s determined for the untreated and ozonated lignosulphonate samples one can conclude that the inert COD content could be reduced by 50% by applying pre-ozonation at an economically acceptable dose to improve its biocompatibility. Due to the formation of soluble metabolic products, when a biological treatment was prescribed to the raw lignosulphonate formulation effluent, it’s not possible to have an effluent quality better than 340 mg/l of COD. On the other hand a significantly better outcome (effluent COD of 190 mg/L) can be obtained with a treatment scheme composed of ozonation and a subsequent biological treatment. Although the tabulated data on BOD5 /COD ratios indicated that partial ozonation can not be used as a tool to significantly improve the biodegradability of the lignosulphonate formulation under investigation; quite a different picture can be obtained when inert COD levels were encountered. This finding strongly supports the fact that evaluating the biodegradability by using solely BOD5 /COD ratio can be misleading.

3.4 Effect of Ozonation on COD-Based Molecular Size Distribution Table 3 shows the COD-based molecular size distribution obtained for unreated and ozonated lignosulphonate samples. Upon closer inspection of Table 2 one can conclude that after ozonation the molecular size distribution of lignosulphonate significantly shifted from higher to lower filter cutoffs. For instance, while a considerable fraction (= 38%) of the total lignosulphonate COD was concentrated in the 0.22 μm−100 kDa range prior to ozonation, the major COD portions of the ozonated sample could be found between 30 and 10 kDa (31% of total COD) and particularly were less than 1 kDa (42%). This can be explained as follows; as expected, ozonation of the lignosulphonate formulation that is a mixture of high molecular weight aryl sulphonates and butyl gycol resulted in fragmentation of the lignosulphonate macromolecules into relatively smaller aromatic and aliphatic intermediates, such as phenols and carboxylic acids. That ozonation of polyaromatic compounds results in the formation of more polar and smaller molecular weight oxidation products has also been formerly evidenced in the scientific literature.

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Table 3 The effect of ozonation on the COD-based molecular size distribution of lignosulphonate solution Molecular size distribution 1.6−1.2 μm 1.2−0.45 μm 0.45−0.22 μm 0.22−100 kDa 100−30 kDa 30−10 kDa 10−3 kDa 3−1 kDa <1 kDa Total COD (mg/L) a 20

Ozonateda lignosulphonate

Raw lignosulphonate (mg/L COD)

(%)

(mg/L COD)

(%)

0 0 0 231 23 120 97 23 121 615

0 0 0 38 3 19 16 4 20 100

0 0 0 114 0 154 19 0 208 495

0 0 0 23 0 31 4 0 42 100

min, 1,400 mgO3 /h at an initial pH of 12

3.5 Effect of Ozontion on Acute Toxicity The ED50 values (causing 50% inhibition of algal growth) related to the acute toxicity of untreated and ozonated lignin sulphonic acid derivative for both 4 and 7 days of exposure were evaluated from dose-response curves and are presented in Table 4. According to the Table, after 7 days of exposure, the ED50 values was found as 6.0–8.0% which is indicating the lower toxicity compared to the results obtained after 4 days of exposure (ED50 = 3.0−4.0% ). There may be several reasons for that; one of those may be related with the batch wise design of the algal toxicity testing systems. The disadvantage of those systems is impossibility of reaching a stable steady state in the test chamber i.e. the parameters in the test vessels such as the concentration / the structure of the original chemical, the number of cells and the amount of nutrients change permanently. As a result of that, for example, the amount of chemical per cell has been decreasing during the exposure period and inhibition may decrease towards the end of the test. Another reason may be related with the adaptation of the algal culture to the test chemical. In those cases the effect may arise only with prolonged lag phases on the growth curve and results in the decrease of toxicity in long term tests with the adapted cultures. On the Table 4 Results of acute toxicity (in % v/v ED values) on Phaeodactylum tricornutum marine microalgea EC50 (%) Sample

Day 4

Day 7

Raw lignin sulphonic acid derivative Ozonateda lignin sulphonic acid derivative

3.0–4.0 25.0–30.0

6.0–8.0 30.0–35.0

a 20

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other hand, according to the outcomes of 4 and 7 days acute toxicity of lignin sulphonic acid derivative towards P. tricornutum marine microalgea is reduced significantly after being subjected to ozonation. In another words, ozonation of the solutions changes the degree of toxicity which may results from the generation of toxic compounds during the treatment process [7, 10]. This outcome emphasises the application of ozone as an appropriate pre-treatment method for the dyebath discharges containing lignin sulphonic acid derivative under investigation. The obtained acute toxicity results support the previous findings on inert COD removal efficiencies.

4 Conclusion and Recommendations In the present study, the effect of ozonation of a commercial lignosulphonate formulation on the toxicity, inert COD and COD-based molecular size distribution was investigated. The following conclusion could be drawn from the experimental findings; • The studied lignosulphonate formulation has a relatively high inert COD (accounting for 50% of the total COD) and acute toxicity. Due to the fact that the studied dye auxiliary chemical is a frequently used commercial product its ecotoxicological properties deserve special attention. • No COD removal could be obtained at an ozone dose of 600 mg/h. However, in the ozone dose range of 1,400–5,300 mg/h, the COD abatement rate was rather pH-dependent indicating a kinetically-limited oxidation mechanism. • A 50% decrease in the initially inert soluble COD can be obtained after ozonation for 20 min at an inital pH of 12 and an ozone dose of 1,400 mg/h. A treatment scheme composed of ozonation followed by a subsequent biological treatment was determined to yield approximately 190 mg/l residual COD at the outlet of the treatment plant. • COD fractionation demonstrated the effect of ozonation on the lignosulhpnate macromolecules; a dramatic decrease in the moleculer size was observed after ozonation under optimized conditions (pHo = 12; applied specific ozone dose ≈1 g O3 /g CODo ). • The acute toxicity of the lignosulphonate formulation towards the marine microalgae P. tricornutum was considerably high but decreased significantly after ozonation under the previously mentioned conditions. This may be at least partially attributable to the fragmention of the lignosulfonate formualation into several low-molecular-weight fractions. Acknowledgments This study was financially supported by TUBITAK (The Turkish Scientific and Technical Research Council) under project Nr. ICTAG−C−075 for our participation in EU COST Action 628 (Eco-efficiency and BAT for Textile Dyeing and Finishing Processes) and TUBA (Turkish Scientific Academy).

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References 1. Amy GL, Kuo CJ, Sjerca RA (1987) Ozonation of humic substances: Effects on molecular weight distributions of organic carbon trihalomethane formation potential. Oz: Sci Eng 10: 39–54 2. APHA-AWWA-WPCF (1998) Standard methods for the examination of water and wastewater, 20th edn. American Public Health Association, Washington, DC 3. Arslan Alaton I, Eremektar G, Germirli Babuna F, Selçuk H, Orhon D (2004) Chemical pretreatment of textile dye carriers with ozone: Effects on acute toxicity and activated sludge ınhibition. Fresenius Environ Bull 13(10):1040–1044 4. Arslan Alaton I, Eremektar G, Germirli Babuna F, Insel G, Selcuk H, Özerkan B, Teksoy S (2005) Advanced oxidation of commercial textile biocides in aqueous solution: Effects on acute toxicity and biomass inhibition. Water Sci Technol 52(10–11):309–316 5. Arslan-Alaton I, Insel G, Eremektar G, Germirli Babuna F, Orhon D (2006) Effect of textile auxiliaries on the biodegradation of dyehouse effluent in activated sludge. Chemosphere 62(9):1549–1557 6. Beltran F (2004) Ozone reaction kinetics for water and wastewater systems. Boca Raton, Florida: CRC press 7. Chu W, Ma C (2000) Quantitative prediction of direct and indirect dye ozonation kinetics. Water Res 34:3153–3160 8. Clapp CE, Hayes MHB, Swift RS (1993) Isolation, fractionation, functionalities, and concepts of structure of soil organic macromolecules. In: Beck AJ, Jones KC, Hayes MBH, Mingelgrin U (eds) Organic substances in soil and water. Royal Society of Chemistry, Cambridge, UK 9. Clarkson N, Redshaw CJ, Leftley JW, Meldrum DT, Watson J (1999) Evaluation of an algal bioassay cage-culture turbidostat method for the toxicity assessment of effluents. Mar Environ Res 47:157–173 10. Freire RS, Kunz A, Duran N (2000) Some chemical and toxicological aspects about paper mill effluent treatment with ozone. Environ Technol 21:717–721 11. Germirli F, Orhon D, Artan N, Ubay E, Görgün E (1993) Effect of two-stage treatment on the biological treatability of strong industrial wastewaters. Water Sci Technol 28(2):145–154 12. Germirli Babuna F, Ince O, Orhon D, Simsek A (1998) Assessment of inert COD in pulp and paper mill wastewater under anaerobic conditions. Water Res Tech Note 32(11):3490–3494 13. Gottschalk C, Libra JA, Saupe A (2000) Ozonation of water and waste water: A practical guide to understanding ozone and its application. Wiley-VCH, Weinheim, pp 2–23 14. Guillard RRL (1972) Culture of phytoplankton for feeding marine invertebrates. In: Smith WL, Chanley MH (eds) Culture of marine ınvertebrate animals. Plenum Press, New York, pp 29–60 15. ISO (1986) Water quality-determination of the chemical oxygen demand, Ref. No. ISO 6060 16. Miller WE, Gree JC, Shiroyama T (1978) The Selenastrum capricornutum printz. Algal assay bottle test. Experimental design, application and data interpretation protocol. Corvallis Environmental Research Laboratory Office of Research and Development, US EPA-600/978-018: Oregon 97330 17. Okay OS, Tüfekçi V, Donkin P (2002) Acute and chronic toxicity of pyrene to the unicellular marine alga Phaeodactylum tricornutum. Bull Environ Contam Toxicol 68:600–605 18. Pavlic Z, Vidakovic-Cifrek Z, Puntaric D (2005) Toxicity of surfactants to green microalgae Pseudokirchneriella subcapitata and Scenedesmus subspicatus and to marine diatoms Phaeodactylum tricornutum and Skeletonema costatum. Chemosphere 61:1061–1068 19. Rieger PH, Meier HM, Gerle M, Vogt U, Groth T, Knackmuss HJ (2002) Xenobiotics in the environment: Present and future strategies to obviate the problem of biological persistence. J Biotechnol 94:101–123 20. Takahashi N, Nakai T, Satoh Y, Katoh Y (1995) Ozonolysis of humic acid and its effect on decoloration and biodegradability. Oz: Sci Eng 17:511–525

Bioidentification of Xenobiotics in Water as a Part of Pollution Control Valerii Tonkopii

Abstract We have been developing non-traditional methods of the identification of pollutants, using various hydrobionts as biological objects and the study of the mechanism of toxic action of xenobiotics. The experiments were carried out with using of Daphnia magna. D. magna is a Crustacean in the order of Cladocera. This aquatic animal extensively used as a test organism in aquatic toxicology due to their small size, short life cycle and amenability to lab culture. D. magna is the most sensitive test-object in relation of different pollutants among all known biological objects including experimental animals. Experiments were performed with a 2-days old culture of D. magna. The toxicity of xenobiotics was determined by the value of LC50 , a concentration of the compounds causing death to 50% of hydrobionts during incubation with toxicants for 24 hours. In the first stage of the work, toxicity of organophosphates (Dipterex, DFP, DDVP, Paraoxon, Malathion, Malaoxon), carbamates (Aminostigmine, Physostigmine, Sevine), heavy metals (Hg, Pb, Cu, Co, Cd, Cr, As, Al), organochlorines (Aldrin, Dieldrin, Endrin, Aroclor, DDT, Lindane, PCBs etc.) and pyrethroids (Cypermethrin, Fenvalerate, Deltamethrin, Permethrin, Allethrin, Resmethrin, Phenothrin, Kadethrin, Cyphenothrin) was determined. The effects of a number of antagonists on the toxicity of xenobiotics were studied. At the first time we discovered that in experiments to D. magna some muscarinic cholinoreceptor blockers (atropine, glipine, pediphen etc.) reduced the toxic effect of organophosphates and carbamates. In the case of heavy metals the chelating agents (EDTA, Dithioethylcarbamate, Unithiolum, Sodium thiosulphuricum, l-Aspartic acid) were effective, for certain organochlorine poisonings – anticonvulsive drugs (diazepam, phenobarbital). In the case of pyrethroid’s poisonings the antagonist of glutamate receptor (ketamine), DOPA receptors (haloperidole) and blocker of calcium channel (nimodipine) reduced the toxicity of xenobiotics. As far as these antidotes have a specific treatment action only against definite classes of pollutants, we have elaborated the sensitive express-methods of bioidentification of pollutants.

V. Tonkopii (B) Institute of Limnology, Russian Academy of Sciences, 196105 St. Petersburg, Russia e-mail: [email protected]

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Keywords Xenobiotics · Pollution · Bioidentification · Dapnhia magna · Pesticides · Control

1 Introduction With a constant growth of the anthropogenic pressure on water bodies the development and usage of bioindication methods supplementing physical and chemical methods of xenobiotic identification acquires especial significance. In view of the fact that chemical analysis require special equipments, they are expensive to perform and do not allow to evaluate the environmental toxicity, during the recent decade large scale investigations have been performed to study various test-objects that are suitable for bioassay. At present biotesting plays an important role in the system of water quality control. On the currently used methods of bioassay provide only the integral evaluation of the pollutants effect but not the determination of the xenobiotics a origin [1]. We have been developing non traditional method for determination of different classes of pollutants using various hydrobionts as biological test-objects and our knowledges of the mechanism of toxic action of xenobiotics. Knowing the mechanisms of the specific toxic action of poisons, it is possible to use various pharmacological compounds to decrease or increase the effects of toxicants. This approach allows us to use biological objects to identify certain xenobiotics, poisoning from which can be prevented by means of poisoning’s antagonists. All above mentioned methods are widely used when employing experimental animals (mice, rats) as test-objects, but it has not been developed at all for alternative biological objects, particularly for hydrobionts. The elaboration of a new methods of bioidentification was founded on the study of Cholin-, GABA-, Dopamin- and Glutamateergic system of D. magna and usage of pharmacological antagonists of xenobiotics. Such new pharmacological approach with usage of D. magna as bioobject have made possible to perform the general identification of different classes of the most toxic for aquatic ecosystem health xenobiotics (organophosphates, carbamates, heavy metals, organochlorines, pyrethroids) without usage of chemical analysis.

2 Materials and Methods As a background of discussed method, we have chosen a big amount of anticholinesterase (antiChe) compounds, different heavy metals, organochlorine pesticides and pyrethroids. Many compounds of these classes are used as pesticides, drugs and chemical warfare agents. Currently, dozens of pesticides capable of polluting the aqueous media through the runoff from agricultural lands or as a result

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of chemical industry accidents are produced. The experiments were carried out with using of D. magna. D. magna is a Crustacean in the order of Cladocera. This aquatic animal extensively used as a test organism in aquatic toxicology due to their small size, short life cycle and amenability to lab culture. D. magna is the most sensitive test-object in relation of different pollutants (organophosphates, heavy metals, organochlorines, pyrethroids etc.) among all known biological objects including experimental animals [2]. Experiments were performed with a 2-days old culture of D. magna. During the experiments, hydrobionts were placed in beakers with 25 ml of dechlorinated settled tap water at 18–20◦C. The toxicity of xenobiotics was determined by the value of LC50 , a concentration of the compounds causing death to 50% of hydrobionts during incubation with toxicants for 24 hours. In the first stage of the work, toxicity of organophosphates and carbamates (Dipterex, DFP, DDVP, Paraoxon, Malathion, Malaoxon, Aminostigmine, Physostigmine, Sevine), heavy metals (Hg, Pb, Cu, Co, Cd, Cr, As, Al), organochlorines (Aldrin, Dieldrin, Endrin, Aroclor, DDT, Lindane, PCBs etc.) and pyrethroids (Cypermethrin, Fenvalerate, Deltamethrin, Permethrin, Allethrin, Resmethrin, Phenothrin, Kadethrin, Cyphenothrin) was determined. The effects of a number of poisons antagonists on the toxicity of xenobiotics were studied. Xenobiotics and their antagonists were added to the incubation mixture simultaneously.The results of the protection experiments are expressed as the protective coefficient (PC) – the ratio of LC50 value in treated and in untreated daphnids.

3 Results On the base of study of mechanism of xenobiotics action to D. magna and the usage of pharmacological antagonists of poisonings the new methods of bioidentification of different pollutants were elaborated. At the first time we discovered that in experiments to D. magna some muscarinic cholinoreceptor blockers (atropine, glipine, pediphen etc.) reduced a toxic the effect of organophosphates and carbamates (Table 1). In the case of heavy metals the chelating agents (EDTA, Dithioethylcarbamate, Unithiolum, Sodium thiosulphuricum, l-Aspartic acid) were effective (Table 2), for certain organochlorine poisonings – anticonvulsive drugs phenazepam, phenobarbital (Table 3). In the case of pyrethroid’s poisonings the antagonists of glutamate (ketamine), DOPA (haloperidole) receptors and blockers of calcium channel (nimodipine) reduced the toxicity of xenobiotics (Tables 4 and 5). As far as these antidotes have a specific treatment action only against definite classes of pollutants, we have elaborated the sensitive express-methods of bioidentification of pollutants. Such new pharmacological approach with use of hydrobionts as testobjects have made possible to perform the general identification of different classes of xenobiotics in fresh water.

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Table 1 The influence of cholinolytics on toxicity of DDVP and aminostimine in experiments to D. magna

PC

LC50 aminostigmine (mg/l)

PC

0.00021±0.00005

–

0.012±0.002

–

Atropine 1.0 2.0 6.0

0.00052±0.00004 0.00063±0.00007 0.00073±0.00006

2.5 3.0 3.5

0.018±0.002 0.042±0.009 0.042±0.009

1.5 3.5 3.5

Glipine 1.0 2.0

0.00042±0.00008 0.00074±0.0001

2.0 3.5

0.021±0.005 0.069±0.019

1.75 5.75

Pediphen 1.0 2.0

0.00032±0.00008 0.00063±0.00008

1.5 3.0

0.024±0.002 0.036±0.004

2.0 3.0

Drugs (mg/l)

LC50 DDVP (mg/l)

Control

Table 2 The influence of GABA-mymetics on toxicity of DDT and lindane in experiments to D. magna Compounds (mg/l)

LC50 mg/l DDT

PC

LC50 mg/l Lindane

PC

Control

0.08+0.02

–

0.12+0.02

–

Ethyl alcohol (g/l) 0.1 0.025

0.15+0.03 0.24+0.03

1.9 3.0

0.23+0.07 0.26+0.07

1.9 2.2

Phenobarbital 2.0 1.0

0.21+0.03 0.23+0.07

2.6 2.9

0.24+0.06 0.32+0.09

2.0 2.7

Phenazepam 0.1 0.05

0.32+0.09 0.25+0.07

4.0 3.1

0.28+0.09 0.23+0.08

2.3 1.9

4 Conclusion We have been developing non-traditional express- method of the identification of pollutants/organophosphates,carbamates,organochlorines, heavy metals and pyrethroids/using Daphnia magna as biological object and the study of the mechanism of toxic action of xenobiotics.The new method was proposed for water pollution control.

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Table 3 The influence of EDTA and Unithiolum on toxicity of Pb(NO3 )2 and HgCl2 in experiments to D. magna Chelates (mg/l)

HgCl2 LC50 (mg/l)

PC

Pb(NO3 )2 LC50 (mg/l)

PC

Control

0.16±0.06

–

1.70±0.52

–

EDTA 2.5 5.0 10.0 25.0

1.59±0.47 2.1±0.05 3.2±0.06 –

9.97 13.1 20.0 –

3.38±0.56 5.1±0.56 6.6±1.48 13.3±2.9

1.98 3.0 3.88 7.8

Unithiolum 25.0 50.0 100.0

0.46±0.11 1.38±0.38 1.69±0.28

2.87 8.60 10.6

3.38±0.56 7.67±1.79 13.45±2.24

1.98 4.5 7.9

Table 4 The influence of ketamine and nimodipine on the toxicity of pyrethroids in experiments to D. magna Pyrethroids (mg/l)

Cypermethrin LC50 (mg/l)

Control

PC

Phenothrin LC50 (mg/l)

PC

0.057±0.003

–

0.05±0.12

–

Ketamine 7.5 4.0

0.62±0.17 0.51±0.13

10.9 8.9

0.52±0.12 0.46±0.10

10.4 9.2

Nimodipine 25.0 12.5

0.29±0.03 0.16±0/02

5.1 2.8

0.42±0.03 0.21±0.09

8.4 4.2

Table 5 The influence of haloperidole on the toxicity of pyrethroids to D. magna Pyrethroids LC50 (mg/l)

Cypermethrin LC50 (mg/l) PC

Phenothrin LC50 (mg/l)

Control

0.057

– 8.1 8.4

Haloperidole 3.0 0.46 1.5 0.48

PC

Permethrin LC50 (mg/l)

PC

0.05

–

0.05

–

0.6 0.55

12.0 11.6

0.36 0.50

7.2 10.0

References 1. Flerov B (1989) Ecological and physiological aspects of toxicology of aquatic animals. Nauka, Leningrad, Russia, 205p 2. Peters R, De Bernardi R (1987) Daphnia. Verbania, Pallanza, Italy, 399p

Biosorption of CR+6 from Aqueous Solution with Activated Sludge Biosolids (Ref. NO: MT11-OP-475) Aziz Sencan, ¸ H. Cahit Sevindir, Mehmet Kiliç, and Mustafa Karaboyaci

Abstract Conventional methods using for removing heavy metals from waste water such as ion change, sedimentation, electrochemical and membrane processes, active carbon adsorption, evaporization and solvent extraction methods have high preliminary investments and operation costs. Furthermore, after the physicochemical refinement processes, subsidiary pollutants which are harmful to the environment occurs. Because of these reasons, biosorption processes improvement studies have been speeded up. Biosorption processes are the methods that are used for absorbing heavy metals from waste water by using biological substances. Using proper biomass is a cheaper process than those mentioned above. Moreover, the operation is easier than these processes. Many studies in the literature, it was determined that heavy metals were held on the surface of the dead bacteria, fungi and alga. In this study, it was also aimed to find out the capacity of heavy metal biosorption found in waste water by active sludge biomass which contains a number of bacteria, protozoa, fungi and rotifer kinds. Biosorption studies are carried out with batch technique. In this extent, the solutions which include chrome (VI) are used and optimum conditions on which biomass is successful in biosorpting these metals. The IR spectra’s of raw sludge and Cr+6 charged biomass were taken for determine the effective functional groups on the adsorption. And for the biosorption process, kinetics and isotherm studies were also conducted. Finally, it was determined that biosorption can be explained with second degree kinetic and isotherm datum is compatible with Freundlich and Langmuir’s isotherm modal. Keywords Biosorption · Activated sludge · FT-IR · Cr(VI) · Kinetic · Isotherm

A. Sencan ¸ (B) Engineering and Architecture Faculty, Environmental Engineering Department, Arts and Sciences Faculty, Chemistry Department, Süleyman Demirel University, Almaty, Kazakhstan e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_92,

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1 Introduction Environmental pollution due to developments in technology is one of the most significant problems of this century. Among all heavy metals, copper, chromium and zinc ingestion beyond permissible quantities causes various chronic disorders in human beings [21]. Chromium (Cr), which is present in the effluent of industries like leather tanning, electroplating, textile dyeing and metal finishing exists in hexavalent and trivalent forms and it is the hexavalent form that is more toxic and is reported to cause cancer in the digestive tract and lungs of human beings [4]. Wastewaters from tanning and textile industries not only have high chromium concentrations but also contain significant quantities of soluble salts [20]. Conventional methods for removing Cr(VI) ions from wastewater are includes chemical reduction, electrochemical treatment, ion exchange and evaporative recovery [20]. Such processes may be ineffective or extremely expensive when initial heavy metal concentrations are in the range of 1–100 gm−3 [25]. To compete with conventional procedures, new methods must be economically viable as well as successful in contaminant removal [9, 25]. Biosorption, an alternative process, is the uptake of heavy metals from aqueous solutions by biological materials. This novel approach is competitive, effective and cheap [24]. Biosorption of metals by biomass has been much explored in recent years. Different form of inexpensive, non-living plant material such as rice husk, alg [15], sawdust [13], pine bark and canola meal [2, 3] have been widely investigated as potential biosorbents for heavy metals. In biosorption research, there is a lack of information about the sorption sites and mechanisms responsible for the binding of metallic ions by the biomasses. Analytical techniques traditionally used in other research fields are being progressively introduced to give information about samples composed of biological materials charged with metallic ions. One of the aim of this work is to report on our investigations about chrome sorption by dried activated sludge using Fourier transform infrared spectroscopy (FT-IR). The FT-IR technique is proving its usefulness in biosorption studies, since it allows the determination of changes in molecular bonds inside the biomass, due to the presence of sorbed metallic ions [18]. In most cases, the structure of the biomass being then, the changes in some of these absorption peaks, already known, the absorption peaks of the molecular bonds can be found in the literature. due to the presence of the metal, can be easily detected and related with changes in the molecular bonds themselves. To perform the FT-IR analysis, a very small quantity of material is needed, largely compatible with the samples obtained in biosorption experiments. Worth noting is the complementarity of FT-IR spectroscopic techniques: in FTIR, we detect the biomass structure and the changes in chemical bonds caused by the presence of the metal [1]. This study was realized to make some contribution to the researches focused on removal of Cr(VI) ions from wastewater by low-cost biosorbents. In this study, inactive activated sludge was used to remove Cr(VI) ions from solutions. The effects

Biosorption of CR+6 from Aqueous Solution with Activated Sludge Biosolids

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of pH, contact time and quantity of biomass on biosorption process realized by the used biosorbent were investigated.

2 Experimental 2.1 Biosorbent An activated sludge supplied by a sewage treatment plant in Isparta (Türkiye) was centrifuged. The pellets obtained were dried at 60◦ C at constant weight and then ground under 0.149 mm particle size.

2.2 Chemicals and Measurements All the solutions used in this study were prepared from doubled-distilled deionized water. Cr(VI) stock solution was prepared by solid K2 Cr2 O7 . NaOH and HCl solutions were used to adjust the solution pH. Concentration measurements of Cr(VI) ions were done by a spectrophotometer (Hach DR 2000) with 1,5 diphenyl carbazide method at 540 nm wavelenght. In order to determine the amount of Cr(VI) ions reduct to Cr(III) or whether there is a reduction of Cr(VI) to Cr(III) or not, total Cr experiments were also done in this study. Total Cr measurements were conducted in a spectrophotometer (Hach DR 2000) with alkaline hypobromide oxidation method at 540 nm wavelength.

2.3 Biosorption Experiments All biosorption experiments were performed in a rotary shaker operating at 150 rpm and room temperature. Samples were prepared by adding a known quantity of the dried biosorbent into the metal bearing solution of a given concentration in vials of 40 ml. The prepared samples were shaked until equilibrium time. After these steps, the metal content in the supernatant was determined by spectrophotometer after filtering the sample with 0.45 μm pore size milipore filter paper. To determine the effect of pH on the biosorption capacity, batch biosorption experiments were also carried out at different initial pH values ranging from 1 to 3.5. The amount of metal biosorbed by activated sludge leaves was calculated from the differences between initial metal concentration and metal concentration of the supernatant using the following equation: Q = C0 − Cf

V M

(1)

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where Q is the metal uptake (mg.g−1); C0 and Cf are the initial and equilibrium metal concentrations in the solution (mg.l−1 ), respectively; V is the solution volume (l); and M is the mass of biosorbent (g).

2.4 Kinetic Studies Three-hundred milligrams of dried biosorbent was added into the 25 ml metal bearing solution of a given concentration in vials. The biosorption medium was mixed at 150 rpm constant speed for equilibrium time at room temperatures. The samples were taken at definite time intervals and were filtered immediately to remove biomass and the remaining Cr(VI) in the solution was analysed. The unadsorbed Cr(VI) in the adsorbtion medium was determined with the spectrophotometer.

2.5 Isotherm Studies Isotherm experiments were conducted for biosorption of 100 mg.l−1 initial Cr(VI) concentration at optimum pH value and room temperature. Samples containing varying amounts of biomass were added into a certain volume of metal solutions. Then, mixtures were shaken until equilibrium time at 150 rpm. Afterwards, samples were filtered and metal ion concentration was measured in the filtrate.

2.6 FT-IR Spektroskopi Analyses FT-IR spectrums of dried and metal loaded biomass were run up to specify the functional groups, which responsible from removal of Cr(VI) ions by activated sludge and the structures which will be effective for the biosorption mechanism were appointed by comparing these spectrums. FT-IR analyses were achieved in a infrared spectrophotometer (Perkin Elmer FT-IR BX-II) with KBr method. Before the FT-IR spectrums were taken, an amount of biomass (5 mg) had been became a semi-transparent disc by covering its surface with KBr and applying a pressure of 8 tons. And then the spectrums were taken.

3 Results 3.1 Effect of Contact Time on Biosorption Process Studies on the effect of contact time were conducted for two different pH values (pH:1 and pH:2). Changes in biosorption capacity versus t were shown in Fig. 1. It is clearly seen on the figure, there are two important phases. First phase, which results in completing 75% of biosorption phenomena, is the rapid surface binding

qe, mg/g

Biosorption of CR+6 from Aqueous Solution with Activated Sludge Biosolids 8 7 6 5 4 3 2 1 0

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pH: 1 pH: 2

0

5

10

15 30 60 Time, min.

90

120

150

Fig. 1 Effect of contact time on biosorption capacity of Cr(VI) (agitation rate: 150 rpm, T: room temperature, dosage of biomass: 4 g.l− , C0 : 50 mg/l)

and the second is the slow diffusion into the pores of biomass. In case of surface binding, electrostatic interactions may be effective due to the van der Waals forces. However, chemical interactions between the biomass and the metal ions may be effective in the second phase. Equilibrium time was found 75 min after the experimental studies. The biosorption capacity didn’t show remarkably change after this time. Kiff and Little [16] reported that 90% of the biosorption of Cd(II) by A. oryzae occurred within 10 min and equilibrium time was found 60 min. Equilibrium time of the biosorption of Zn(II) by activated sludge was also reported as 90 min by Atkinson et al. [7]. In this study, rapid phase of the process completed within first 15 min and approximately 90% of the total biosorption capacity resulted in after that time. Jianlong et al. [14] observed that equilibrium time of the biosorption of Pb(II) by Aspergilus niger, which forms as a waste material after using at the citric acid fermentation industry, was 4 h.

3.2 Effect of pH

Fig. 2 Effect of pH on the biosorption capacity (agitation rate: 150 rpm, C0 : 50 mg.l−1 , T: room temperature, dosage of biomass: 4 g.l−1 )

qe, mg/g

pH is an important parameter for biosorption processes since it affects sorbent surface and solution chemistry [23]. The effect of pH on biosorpton capacity is shown at Fig. 2.

8 7 6 5 4 3 2 1 0 1

1,5

2 pH

2,5

3

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It is understand from the figure, biosorption capacity significantly decreases with increasing pH. There was no binding after pH 3. Some functional groups, such as amines, are positively charged when protonated and may electrostatically bind with negatively charged metal complexes. The decrease in the adsorption with increase of pH may be due to the decrease in electrostatic force of attraction between the sorbent and sorbate ions. At lower pH ranges, due to the high electrostatic force of attraction, the percentage of Cr(VI) removal is high. At very low pH value, the surface of sorbent would also be surrounded by the hydronium ions which enhance the Cr(VI) interaction with binding sites of the biosorbents by greater attractive forces. A sharp decrease in adsorption above pH 1 may be due to occupation of the adsorption sites by anionic species like HCrO4 − ; Cr2 O2 −7 ; CrO2 −4 , etc., which retards the approach of such ions further toward the sorbent surface [11]. The decrease in adsorption at high pH values may be due to the competitiveness of the oxyanion of chromium, the overall surface charge on activated sludge became negative and biosorption decreased.

3.3 Equilibrium Modeling Analysis of equilibrium data is important for developing a model that can be used for the design of adsorption systems. Several isotherm equations have been used for equilibrium modeling of biosorption systems [5]. Two classical adsorption models, i.e., Langmuir and Freundlich isotherms, are most frequently employed. In this work, the two models were used to describe the relationship between the amount of Cr+6 adsorbed and its equilibrium concentration in solutions.

3.3.1 Langmuir Isotherm The Langmuir isotherm is valid for monolayer adsorption onto a surface with a finite number of identical sites. It is given as (2): qeq =

abCeq 1 + aCeq

(2)

where Ceq and qeq are equilibrium concentration (mg/l) and the amount of adsorbed at equilibrium time (mg/g), respectively. b and a are Langmuir constants related to the capacity and energy of adsorption, respectively. The linearized form of the Langmuir equation is as follows: Ceq Ceq 1 + = qeq ab b b and a can be determined from the linear plot of Ceq /qeq versus Ceq [8].

(3)

Fig. 3 Linearized Langmuir isotherm [agitation rate: 150 rpm, T: room temperature, mixing time: 75 min, pH: 1, C0 : 50 mg.l−1 ]

Ce/qe

Biosorption of CR+6 from Aqueous Solution with Activated Sludge Biosolids 4 3,5 3 2,5 2 1,5

6

16

26

36

979

46

56

Ce

The adsorption isotherms and linearized Langmuir adsorption isotherms of activated sludge biomass is illustrated in Fig. 3. The values of b and a calculated from the slope and intercept of the plots. 3.3.2 Freundlich Isotherm The Freundlich equation based on sorption on a heterogeneous surface is given below as (4): 1

qeq = KF C n

(4)

where KF and n are the Freundlich constants, whereas KF and n are indicators of adsorption capacity and adsorption intensity of the sorbents, respectively [19]. Equation (4) can be linearized in logarithmic form as (5): log qeq = log KF +

1 log Ceq n

(5)

The values of KF and n can be estimated respectively from the intercept and slope of a linear plot of experimental data of log qeq versus logCeq . The Freundlich isotherm provides no information on the monolayer adsorption capacity in comparison with the Langmuir model [19]. The linearized Freundlich adsorption isotherms of activated sludge biomass is shown in Fig. 4. The values of KF and n calculated from the plot. Constant values of Langmuir and Freundlich isotherms using for explanation of the biosorption process were shown at Table 1. The both models corroborated with the Cr(VI) sorption data while Freundlich isotherm model has been a better explanation for Cr(VI) on the basis of R2 . Calculated Langmuir adsorption isotherm constants may imply that there is close affinity between biosorbent and metal ions and activated sludge is a favorable biosorbent for Cr(VI) (Table 1). Kratochvil and Volesky [17] suggested that a favorable biosorbent has a lower a constant and a higher b constant. 1/n value for Freundlich isotherms relates to heterogeneity of the sorbent surface and this value ranges from 0 to 1. The more 1/n value closes to 0, the more binding surface is heterogen [6]. In this study, 1/n value was found 0.63. According to this result, the biosorbent used at this research is semi-heterogen.

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0,8 0,6 0,4 0,2 0 0,8

1

1,2

1,4

1,6

1,8

logCe

Fig. 4 Linearized Freundlich isotherm [agitation rate: 150 rpm, T: room temperature, mixing time: 75 min, pH: 1, C0 : 50 mg.l−1 ] Table 1 Constant values for Langmuir and Freundlich isotherms Freundlich

Langmuir

1/n

KF

R2

0.63

1.11

0.99

A

b

R2

0.03

20.8

0.97

Corresponding of the biosorption of Cr(VI) by activated sludge to Langmuir isotherm indicates that whole surface of the biomass is uniform in terms of energy. Explanation of the biosorption process with Freundlich isotherm signs that metal ions were bound to binding sites multilayer and physical sorption was dominant at the process.

3.4 Batch Kinetic Studies Biosorption kinetic defines the sorption rate of the metal ions present in the solution by biomass Assessing of the sorption rate is important for optimization of the processes based on biosorption The hydraulic retention time is based on the datas obtaining from the kinetic studies in the process. It is essential to carry out experimental studies for accurately determining the kinetic test datas [12]. First-order and second-order reaction kinetic graphics were shown at Figs. 5 and 6 to indicate the sorption rate of the process. Regression coefficients (R2 ) were calculated as 0.97 for first-order reaction kinetic and 0.98 for second-order reaction kinetic. First-order reaction kinetic graphic was created for time-course 0– 60 min. Regression coefficient is lower for time-course 0–75. On the other hand, second-order reaction kinetic studies correspond to time-course 0–75. First-order and second-order reaction kinetic constants were shown at Table 2. Biosorption kinetic is well explained by second-order reaction kinetic according to the R2 values. However, first-order reaction kinetic better implies biosorption process when experimental and calculated qe values comparison.

Biosorption of CR+6 from Aqueous Solution with Activated Sludge Biosolids 0,5

log(qe-q)

Fig. 5 First-order reaction kinetic graphic (initial metal concentration: 50 mg.l−1 , agitation rate: 150 rpm, T: room temperature, dosage of biomass: 12 mg.l−1 , pH: 1)

0

0

20

40

60

80

–0,5

–1

t, min.

25 20 t/q

Fig. 6 Second-order reaction kinetic graphic (initial metal concentration 50 mg.l−1 , agitation rate: 150 rpm, T: room temperature, dosage of biomass: 12 mg.l−1 , pH: 1)

981

15 10 5 0

0

10

20

30

40 t, min.

50

60

70

80

Table 2 First and second order kinetic models constants

Krom(VI)

qe

K1.ad

R2

K2.ad

qe

R2

qe, exp mg/g

2.85

0.04

0.97

0.012

4.21

0.98

3.41

3.5 FT-IR Studies In order to determine the mechanism of biosorption of Cr(VI) by activated sludge, FT-IR spectra of raw biomass and Cr(VI) loaded biomass were compared (Figs. 7 and 8). It is clearly seen on Fig. 8 that only the peaks between 400 and 425 cm−1 became sharp, while there was no change in terms of functional groups of the biomass (Fig. 7). The peaks take place between 400 and 425 cm−1 equal to C-Cr2 O7 = vibration [10]. From this point, it may be assumed that there is an interaction between carbon and chromate ions.

4 Conclusion Results of this research are listed below: Biosorption capacity decreased with increasing pH, Equilibrium of the process can be explained with Langmuir and Freundlich isotherms,

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Fig. 7 IR spectra of raw biomass

Fig. 8 IR spectra of Cr(VI) loaded biomass

Equilibrium time of the process was found as 75 min, Pseudo first and second-order reaction kinetics indicate the sorption rate,

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Physical forces are dominant on the biosorption process. Surface of the biomass has positive charges at pH 1. Cr2 O7 = ions are negative at pH 1 and it is thought that some parts of the ions may be bound to the biomass via electrostatic forces. When FT-IR spectra of raw and Cr(VI) loaded biomass are observed, it is clear that the peaks at 400–425 cm−1 equivalent to C-Cr2 O7 = vibration became sharp. Some parts of Cr(VI) ions may be biosorbed to the surface of biomass via chemisorption. Reasons of small changes in FT-IR spectra may be resulted from pH decreasing. Acknowledgements This project was funded by Süleyman Demirel University Scientific Research Project Foundation Fund (Project no: 1112-YL-05). The financial assistance from Research Project Foundation Fund on Biosorption of Cr(VI) from aqueous solution and tannery effluents with activated sludge biomass is thankfully acknowledged by the authors.

References 1. Ajıboye SI, Brown DR (1990) Electron-spin-resonance study of soluble copper(II) cellulose complexes. J Chem Soc Faraday Trans Artic 86(1):65–68 2. Al-Asheh S, Duvnjuk Z (1998) Binary metal sorption by pine bark: study of equilibria and mechanisms. Separation Sci Technol 33(9):1303–1329 3. Al-asheh S, Lamarche G, Duvnjuk Z (1998) Investigation of copper sorption using plant materials. Water Qual Res J Can 33(1):167–183 4. Alves MM, Ceca CGG, Carvalho RG, De Castanheira JM, Periera MCS, Vasconcelos LAT (1993) Chromium removal in tannery wastewaters polishing by Pinus sylvestris bark. Water Res 27:1333–1338 5. Aksu Z, Tezer S (2000) Equilibrium and kinetic modeling of biosorption of Remazol Black B by Rhizopus arrhizus in a batch system: Effect of temperature. Process Biochem 36(5): 431–439 6. Aksu Z, Çalık A, Dursun AY, Demircan Z (1999) Biosorption of iron(III)-cyanide complex anions to Rhizopus arrhizus: application of adsorption isotherms. Process Biochem 34: 483–491 7. Atkinson BW, Bux F, Kasan HC (1998) Waste activated sludge remediation of metal-plating effluents. Water SA 24:355–359 8. Batabyal D. Sahu A, Chaudhuri SK (1995) Kinetics and mechanism of removal of 2,4 diimethylphenol from aqueous solutions with coal fly ash. Separ Technol 5:179–186 9. Denizli A, Say R, Testereci HN, Arica MY (1999) Procein blue MX-36-attached-poly (HEMA) membranes for copper, arsenic, cadmium and mercury adsorption. Separation Sci Technol 34:2369–2381 10. Dikman E (1985) Enstrümental Analiz. Ça˘glayan Kitapevi. 271s. ˙Istanbul, Turkey 11. Donmez D, Aksu Z (2002) Removal of chromium(VI) from saline wastewaters by Dunaliella species. Process Biochem 38(5):751–762 12. Ho YS, McKay G (1999) Pseudo-second order model for sorption process. Process Biochem 34:451–465 13. Holan ZR, Volesky B (1995) Accumulation of cadmium, lead and nickel by fungal and wood biosorbents. Appl Biochem Biotechnol 53:133–146 14. Jianlong W, Xinmin Z, Decai D, Ding Z (2001) Bioadsorption of lead(II) from aqueous solution by fungal biomass of Aspergillus niger. J Biotechnol 87:273–277 15. Khalid N, Rahman A, Ahmad S, Kiani SN, Ahmed J (1997) Adsorption of cadmium from aqueous solutions on rice husk. Plant Soil 197:71–78 16. Kiff RJ, Little DR (1986) Biosorption of heavy metals by immobilized fungal biomass. In Immobilization of ions by biosorption. Ellis Hunt Publishers, 649s. Chichester, UK 17. Kratochvil D, Volesky B (1998) Biosorption of copper from ferruginous wastewater by algal biomass. Water Res 32:2760–2768

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18. Naja G, Denew-Mustın S, Mustın C, Rouıller J, Munıer-Lamy C, Berthelın J (1999) Potentiometric titration: a dynamic method to study the metal binding-mechanism of microbial biomass. In Amils R, Ballester A (eds) Biohydrometallurgy and the environment toward the mining of the 21st century. Elsevier, Amsterdam, p 201 19. Ning Z, Kennedy KJ, Fernandes L (1996) Biosorption of 2,4-dichlorophenol by live and chemically inactivated anaerobic granules, Water Res 30(9):2039–2044 20. Patterson JW (1985) Industrial wastewater treatment technology. 2nd Ed. Stoneham, MA Butterworth Publishers, USA. ISBN 0-409-90002-8 21. Prakasham RS, Merrie JS, Sheela R, Saswathi N, Ramakrisha SV (1999) Biosorption of chromium(VI) by free and immobilized Rhizopus arrhizus. Environ Pollut 104:421–427 22. Thyagarajan G (1992) Leather industry-in pursuit of better image. The Hindu Survey Environ 143–145 23. Veglio F, Beolchini F (1997) Removal of metals by biosorption: A review. Hydrometallurgy 44:301–316 24. Volesky B (2001) Detoxification of metal-bearing effluents: Biosorption for the next century. Hydrometallurgy 59:203–216 25. Volesky B (2003) Potential of biosorption. In: Volesky B (ed) Sorption and biosorption. BV sorbex Inc., Montreal – St. Lambert, Que., Canada

Effect of Chromium on Growth Attributes in Sunflower (Helianthus annuus L.) M. Fozia Anjum, M. Anjum Zia, M. Ashraf, and Z.M. Khalid

Abstract Phytoremediation, the use of plants for environmental restoration, is an emerging cleanup technology. To exploit plant potential to remediate soil and water, contaminated with a variety of compounds, several techniques have been established. In the present study, a pot experiment was conducted to evaluate the effect of chromium-contaminated soil on growth attributes in sunflower. Three different levels of chromium i.e. 20, 40 and 60 mg kg−1 were applied to three varieties of sunflower (G-3, G-9 and G-59). The results of morphological and yield parameters were recorded at crop maturity. The data showed that germination was affected by increasing chromium level as well as root and shoot length were decreased with increase in chromium concentration. A gradual decrease was observed for various morphological parameters like root fresh and dry weights, shoot fresh and dry weights and plant height with increase in chromium level. A comparison among chromium treatments obtained a significant decrease in yield parameters as achenes/capitulum, achenes/plant and 100 achenes weight in three varieties. Chromium significantly absorbed by roots but its transport to other parts of plants was slow and chromium uptake in seeds was very much lower than roots and shoots. Keywords Sun flower · Chromium · Growth attributes · Phytoremediation

1 Introduction Sunflower (Helianthus annuus L.) belonging to the family Asteraceae is the world’s fourth largest oil-seed crop. The genus Helianthus comprises 9 species and 19 subspecies with 12 annual and 37 perennial species [15]. Seeds of sunflower are used as food and dried stalk as fuel. Sunflower has also been used as an ornamental plant and for ceremonies. In addition, parts of this plant are used in making dyes for M. Anjum Zia (B) Department of Chemistry (Biochemistry), University of Agriculture, Faisalabad, Pakistan e-mail: [email protected]

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textile industry, body painting and other decorations. Sunflower meal is a potential source of protein for human consumption due to its high nutritional value and lack of anti-nutritional factors [6]. Chromium is considered a serious environmental pollutant, due to its wide industrial applications. Contamination of soil and water by chromium (Cr2+ ) is of recent concern. Toxic effects of Cr2+ on plant growth and development include alterations in the germination process as well as in the growth of roots, stems and leaves, which may affect dry matter production and yield [16]. Chromium is found in all phases of the environment, including air, water, and soil. Naturally occurring in soil, Cr2+ ranges from 10 to 50 mg kg–1 depending on the parental material. In ultramafic soils (serpentine), it can reach up to 125 g kg−1 [1]. In fresh water, Cr2+ concentrations generally range from 0.1 to 117 μg L−1 , whereas values for sea water range from 0.2 to 50 μg L−1 [10]. Leather industry is one of the major sources of pollution in Pakistan, which releases chromium during tanning process with various levels of impacts on plants, animals and human life. The chemicals used in the leather industry during the tanning operation include chromium sulfate, formic acid, sulfuric acid, sodium chloride, sodium bicarbonate, calcium hydroxide, magnesium sulfate, dyes, fat liquors etc. Similarly, textile industry is also a major consumer of chemicals i.e. soda ash, sulfuric acid, caustic soda and metals containing alloys etc. [19]. Chromium and its compounds have multifarious industrial uses. They are extensively employed in leather processing and finishing [10], production of refractory steel, drilling mud, electroplating cleaning agents and chromic acid. Hexavalent chromium compounds are used in industry for metal plating, cooling water treatment, hide tanning and until recently, wood preservation. These anthropogenic activities have led to the wide spread contamination that chromium shows in the environment and have increased its bioavailability and biomobility [9]. The present study was conducted to determine the response of sunflower to different concentrations of chromium in the soil and to phytoremediate the chromium from industrial regions specially tanneries by using sunflower.

2 Materials and Methods The present study was conducted at University of Agriculture, Faisalabad and National Institute for Biotechnology and Genetic Engineering, Faisalabad, to assess the influence of chromium on growth of three sunflower (Helianthus annuus L.) hybrid varieties V1 , V2 and V3 (G-3, G-9 and G-59) procured from Department of Plant Breeding and Genetics, University of Agriculture Faisalabad grown in chromium contaminated soil. Sowing of seeds: A total of 36 Petri dishes were used during this study, containing a single layer of filter paper was placed in each. Various concentrations of chromium i.e. 20 (T2 ), 40 (T3 ) and 60 (T4 ) mg kg−1 were applied with three replicates of each, while T1 was kept control. After germination, the data were collected daily for until

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7 days. Data from each treatment was observed for recording germination rate, shoot length (cm) and root length (cm) [16]. Soil analysis: The soil used was analyzed in Water Monitoring Laboratory, NIBGE. For the analysis of soil, the methods described in USDA Salinity Laboratory. Staff in Agriculture Handbook No. 60 was followed. Seed sowing: Sowing of seeds was done on 10 February 2005 at NIBGE, Faisalabad. Ten holes at equal distance and about 2 cm deep were made in each pot. One seed was put in each hole and it was observed that germination started 6 days after sowing. After 20 days of germination, the plants were thinned to maintain 5 seedlings in each pot. The plants were irrigated according to the requirement of the crop on alternate days. Two plants from each pot at mid of crop growth and three plants at maturity were observed for morphological and yield parameters. Morphological parameters: Plant height (cm) was measured from the stem base up to the tip of main stem using a meter rod and mean values were calculated. Roots of the two plants were removed to estimate the root fresh and dry weights. Shoot fresh and dry weights were recorded as shoots of the two plants were carefully removed and their fresh weights were taken and dried by placing them in an oven at 70◦ C for 72 h and then their dry weights recorded. Yield parameters: Total number of achenes per capitulum was counted from each replicate of the treatments. Achene yield/plant was noted as achenes from each plant of a treatment were collected and then weighed by an electronic balance. For the estimation of 100 achene weight, the achenes from each plant of a treatment were taken and counted. The weight of 10 seeds was taken by an electronic balance and the average was calculated [16]. Statistical analysis: Data for various morphological, yield and chemical parameters were statistically analyzed. Means were compared by applying Duncan’s New Multiple Range Test (DMRT) [18].

3 Results and Discussion Phytoremediation utilizes biological organisms for phytoextraction or removal of plant biomass containing concentrated levels of heavy metals taken up from polluted soils. Heavy metals influence the growth and tissue ionic concentration. According to Paiva et al., [11] dry weight of shoot and root showed a significant reduction with increase in the level of heavy metals. Such reduction becomes more damaging at higher levels of heavy metals so plants show greater variation ranging from morphological characters to physiochemical characters. In the present study, relative growth rate, relative increase in plant height and fresh weight were significantly reduced. Although there were remarkable reductions in various growth parameters, the effect was more pronounced with high chromium levels, which reduced more growth compared to control. It is noticeable that the fresh and dry weight parameters were better under control than that under chromium stress. This is probably due to the reason that toxicity of heavy metals significantly

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inhibited root vitality, preventing plant from absorbing inorganic nutrients and leading to decrease plant growth [20]. Germination percentage: Since seed germination is the first physiological process affected by chromium, the ability of a seed to germinate in a medium containing it would be indicative of its level of tolerance to this metal [12]. It was showed that germination percentage divulged maximum (100%) in control that was reduced with increasing level of chromium as in T4 (60 mg kg−1 of chromium) was 40%. Our results are in agreement to Rout et al. [14] who reported that seed germination of the weed Echinochloa colona was reduced to 25% with 200 μM chromium. Peralta et al. [12] found that 40 ppm of chromium reduced by 23% the ability of seeds of lucerne (Medicago sativa cv. Malone) to germinate and grow in the contaminated medium. Relative increase in root length: Data pertaining to relative increase in root length has showed higher values of during the 1st interval in three cultivars. In V1 maximum value (1.46 cm) was found in control and minimum value (1.23 cm) was observed in 60 mg kg−1 of chromium, indicated that with the increase in chromium concentration, root length was decreased. In the remaining intervals same trend was found in three cultivars of sunflower. However, in 6th interval relative increase in root length was much lesser as compared to preceding intervals. Decrease in root length/growth is a well documented effect due to heavy metals in trees and crops [16]. General response of decreased root growth was due to chromium toxicity. This may be due to inhibition of root cell division/root elongation or to the extension of cell cycle in the roots. Under high concentrations of chromium, the reduction in root growth could be due to the direct contact of roots with chromium in the medium causing a collapse and subsequent inability of the roots to absorb water from the medium [2]. Root length of wheat was affected by 20 mg Cr kg−1 soil as K2 Cr2 O7 [5]. Relative increase in shoot length: The comparison of relative increase in shoot length after every 24 h indicated much increase during 3rd and 4th interval in all the three varieties. In 3rd harvest, maximum relative increase in shoot length was observed was in control of three varieties 0.69, 0.68 and 0.65 cm, while minimum was found at highest concentration in three varieties. In 4th interval same trend was found however, in 5th and 6th interval toxic effect of chromium was pronounced, than the preceding intervals. According to Rout et al. [13], there were adverse effects of chromium on shoot length and plant height. Same results were obtained in our experiments as shoot length and plant height was reduced with the effect of 20, 40 and 60 mg kg−1 of chromium. It was obtained by statistical analysis that data regarding to harvest and treatments is highly significant while between varieties is non-significant in case of shoot length. Reduction in plant height due to chromium on Curcumas sativus, Lactuca sativa and Panicum miliaceum was reported by Joseph et al. [7]. The reduction in plant height might be mainly due to the reduced root growth and consequent lesser nutrients and water transport to the above parts of the plant. In addition to this, chromium transport to the aerial part of the plant can have a direct impact on cellular metabolism of shoots contributing to the reduction in plant height.

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3.1 Morphological Parameters Relative increase in plant height (cm/day): Relative increase in plant height decreased in response to increase in chromium levels (Table 1). During the 1st−2nd harvest V1 (G-3 variety) had the highest relative increase (0.040 cm) in T1 (control) while lowest (0.020 cm) in T4 (60 mg kg−1 ). Same were the results in case of V2 (G-9) and V3 (G-59) in which maximum value was observed in T1 (control) and minimum value was in T4 (60 mg kg−1 ). This decrease in plant height was gradual from T1 to T4 . During 2nd–3rd harvest interval the relative increase in plant height was the highest with respect to 1st–2nd and 3rd–4th harvest intervals. The highest value (0.096 cm) in V1 was shown by T1 (control) while the lowest (0.071 cm) by T4, while T2 and T3 showed a decrease in height of 0.085 cm and 0.076 cm. The same trend was observed in other two varieties. During 3rd–4th harvest interval the relative increase of height was less than 2nd–3rd and 1st–2nd harvest intervals and the results exactly tally with the other two harvests in all the three varieties. Relative increase in root fresh and dry weight (g day−1): Data in Table 2 represented the relative increase in fresh weight of roots in response to different chromium levels. Maximum growth was recorded in 1st–2nd harvest in all the three varieties and was followed by 2nd–3rd harvest and then in 3rd–4th harvest. All the three varieties showed the highest growth rate in T1 (control) and decreased by increasing chromium levels and it remained lower in T4 (60 mg Cr kg−1 soil) in all three harvest. At T1 level the highest growth rates were 0.89, 0.87 and 0.86 g in all the three varieties i.e, G-3, G-9 and G-59 while, minimum rates were recorded at T4 (60 mg kg−1 ) during the 1st harvest. In 2nd and 3rd harvest same trend was found, but levels of growth rates were reduced than the 1st interval. Data related the root dry weight of sunflower plants as affected by different levels of chromium given in Table 2. In all the three harvests the root dry weight was

Table 1 Effect of chromium on relative increase in plant height (cm day–1 ) of various sunflower varieties V1 Harvest

T1

V2 T2

T3

T4

T1

V3 T2

T3

T4

T1

T2

T3

T4

1–2 harvest 0.040 0.038 0.026 0.020 0.038 0.035 0.029 0.024 0.035 0.030 0.026 0.023 2–3 harvest 0.096 0.085 0.076 0.071 0.089 0.084 0.079 0.065 0.087 0.076 0.067 0.064 3–4 harvest 0.054 0.049 0.033 0.028 0.048 0.043 0.041 0.038 0.044 0.038 0.028 0.024 V1 : G-3 V2 : G-9 V3 : G-59 T1 : Control T2 : 20 mg kg−1 T3 : 40 mg kg−1 T4 : 60 mg kg−1

3rd harvest

0.23

0.009

0.023

0.018

0.032

0.47

0.45

0.65

0.031

0.058

2nd harvest

0.63

0.89

Fresh weight Dry weight Fresh weight Dry weight Fresh weight Dry weight

1st harvest

T2

T1

Harvest

V1

0.006

0.19

0.015

0.23

0.028

0.49

T3

0.004

0.12

0.014

0.19

0.022

0.38

T4

0.020

0.44

0.032

0.60

0.057

0.87

T1

V2

0.010

0.20

0.018

0.34

0.033

0.56

T2

0.004

0.18

0.013

0.29

0.026

0.47

T3

0.001

0.14

0.007

0.22

0.019

0.43

T4

0.022

0.46

0.033

0.62

0.057

0.86

T1

V3

Table 2 Effect of chromium on root fresh and dry weight (g day−1 ) of various sunflower varieties

0.007

0.22

0.015

0.34

0.032

0.52

T2

0.005

0.16

0.012

0.24

0.022

0.42

T3

0.002

0.09

0.006

0.17

0.020

0.34

T4

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3−4 harvest

0.65

0.013

0.018

0.029

0.038

0.71

0.85

0.93

0.046

0.064

2−3 harvest

1.05

1.18

Fresh weight Dry weight Fresh weight Dry weight Fresh weight Dry weight

1−2 harvest

T2

T1

Harvest

V1

0.009

0.52

0.013

0.78

0.021

1.02

T3

0.007

0.45

0.11

0.63

0.016

0.98

T4

0.014

0.75

0.031

0.91

0.062

1.13

T1

V2

0.009

0.50

0.024

0.75

0.049

1.05

T2

0.007

0.49

0.014

0.73

0.024

1.03

T3

0.006

0.43

0.012

0.69

0.016

0.99

T4

0.013

0.71

0.030

0.91

0.058

1.12

T1

V3

Table 3 Effect of chromium on shoot fresh and dry weight (g day−1 ) of various sunflower varieties

0.011

0.58

0.027

0.73

0.045

1.05

T2

0.007

0.44

0.012

0.68

0.022

1.02

T3

0.004

0.31

0.008

0.56

0.014

0.98

T4

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maximum at T1 (control) and minimum was recorded at highest concentration i.e, T4 treatment. But this decrease in trend with increasing levels of chromium (Cr2+ ) was slight. During the 1st interval the maximum values were 0.058, 0.057 and 0.057 g in G-3, G-9 and G-59 respectively, however, minimum values were seen at 60 mg kg−1 . Similar, results were found in the other two intervals. Relative increase in shoot fresh and dry weight (g day−1 ): Data in Table 3 presented the shoot fresh weight in response to different chromium levels. During the 1st–2nd harvest the shoot fresh weight was maximum in T1 (control) in all the three varieties, while this rate gradually decreased with increasing levels of chromium. Same trend was followed during the 2nd–3rd and 3rd–4th harvests. The increase in fresh weight was not as maximum as in 1st–2nd harvest. Data regarding to dry weight of shoot have been shown in Table 3. Again the maximum dry weight has been observed during the 1st harvest. This trend decreased from T1 (control) to T4 (60 mg Cr kg−1 soil) in all the three varieties. The dry weight decreased also in the 2nd and 3rd harvest. The prerequisite for higher yields in plants is an increase in biomass production in terms of fresh and dry matter/weights. Higher source size and increased photosynthetic process was found to be the basis for the building up of organic substances and dry matter production under heavy-metal stress in general and chromium in particular [4]. There was a significant decrease in fresh and dry weights of roots while reduction in fresh and dry weights of shoots was also observed. So, proving our results in a correct manner, Zurayk et al. [21] reported that salinity and chromium interaction caused a significant decrease in the dry weight of Portulaca oleracea. Kocik and Ilavsky [8] studied the effect of chromium on quality and quantity of biomass in sunflower and observed that dry matter production and uptake of chromium into plant organs was positively correlated with the contents in the soil.

3.2 Yield Parameters Number of achenes/capitulum: Data pertaining to number of achenes/capitulum as influenced by different levels of T1 (control) showed the maximum number of achenes in all the three varieties (G-3, G-9 and G-59) i.e., 104, 100 and 98. But these numbers were decreased with every increase in treatment from T1 level. Achene yield/plant (g): Here a marked difference between different treatments was observed. At T1 level the achene yield observed was 18.9 g/plant, but this amount reduced to 8.93 g/plant at T4 level in V1 , same trend was followed in other two varieties. 100 achene weight (g): Results of 100 achene weight showed a decrease in weight from T1 to T4 level in all the three varieties. The number of achenes/capitulum, number of achenes/plant and 100 achenes weight of T2 , T3 and T4 were differing in comparison to T1 (control). Barcelo et al. [3] concluded that yield and productivity was affected by chromium. Sharma and Mehrotra [17] found that achene’s dry weight yield was 2.11 g per plant without chromium and 0.39 and

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0.16 g with 20 and 200 ppm of chromium, respectively. The difference of our studies might be due to the reason that chromium uptake by seeds is very low as compared to other parts of the plant. More important is that sunflower can tolerate chromium and other heavy metals but up to a certain limit.

References 1. Adriano DC (1986) Trace elements in the terrestrial environment. Springer, New York, pp 105–123 2. Barcelo J, Poschenrieder C, Gunse B (1986) Water relations of chromium VI treated bush bean plants (Phaseolus vulgaris L cv contender) under both normal and water stress conditions. J Exp Bot 37:178–187 3. Barcelo J, Poschenrieder C, Vazquez MD, Gunse B, Vernet JP (1993) Beneficial and toxic effects of chromium in plants: Solution culture, pot and field studies. Paper Presented at the 5th International Conference on Environmental Contamination, Switzerland 4. Bishnoi NR, Chugh LK, Sawhney SK (1993) Effect of chromium on photosynthesis, respiration and nitrogen fixation in pea (Pisum sativum L) seedlings. J Plant Physiol 142:25–30 5. Chen NC, Kanazawa S, Horiguchim T, Chen NC (2001) Effect of chromium on some enzyme activities in the wheat rhizosphere. Soil Microorg 55:3–10 6. Chimenti CA, Person J, Hall AJ (2002) Osmotic adjustment and yield maintenance under drought in sunflower. Field crops Res 75:235–246 7. Joseph GW, Merrilee RA, Raymond E (1995) Comparative toxicities of six heavy metals using root elongation and shoot growth in three plant species. The Symposium on Environmental Toxicology and Risk Assessment, Atlanta, USA, pp 26–29 8. Kocik K, Ilavsky J (1994) Effect of Sr and Cr on the quantity and quality of the biomass of field crops. Production and utilization of agricultural and forest biomass for energy: Proceedings of a seminar held at Zvolen, Slovakia, pp 168–178 9. Kotas J, Stasicka Z (2000) Commentary: Chromium occurrence in the environment, and methods of its speciation. Environ Pollut 107:263–283 10. Nriago JO (1990) Global metal pollution: Poisoning the biosphere. Environment 32:7–33 11. Paiva HN, de Carvalho G, Siqueria JO (2000) Effect of Cd, Ni, Pb and Zn seedlings on Cedrela fissilis and Tabebuia impetiginosa (Mart.) standley in nutrient solution. Revista Arvore 24(4):369–378 12. Peralta JR, Torresdey JLG, Tiemann KJ, Gomez E, Arteaga S, Rascon E (2001) Uptake and effects of five heavy metals on seed germination and plant growth in alfalfa (Medicago sativa) L. Environ Contam Toxicol 66(6):727–734 13. Rout GR, Samantaray S, Das P (1997) Differential chromium tolerance among eight mungbean cultivars grown in nutrient culture. J Plant Nutr 20:473–483 14. Rout GR, Sanghamitra S, Das P (2000) Effects of chromium and nickel on germination and growth in tolerant and non-tolerant populations of Echinochloa colona (L). Chemosphere 40:855–859 15. Schilling EE, Heiser HCB (1981) Infragenic classification of Helianthus (Compositae). Taxonomy 30:393–403 16. Shanker AK, Cervantes C, Loza-Tavera H, Avudainayagam S (2005) Chromium toxicity in plants – A review. Environ Int 31(5):739–753 17. Sharma DC, Mehrotra SC (1993) Chromium toxicity effects on wheat (Triticum aestivum L cv HD 2204). Indian J Environ Health 35:330–332 18. Steel RGD, Torrie JH (1984) Principles and procedures of statistics. McGraw Hill Book Co., USA, p 332 19. Tahira SA (1999) Effect of tannery effluents on some morpho-chemical aspects of mustard (Brassica compestris) L. implication for phytoremediation. M.Phil. Thesis, University of Agriculture, Faisalabad, Pakistan

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20. Wensheng S, Chonytu L, Zhiquan Z (1997) Analysis of major constraints on plant colonization at Fankou Pb/Zn mine tailing. Chinese J Appl Ecol 8:314–318 21. Zurayk R, Sukkariyah B, Baalbaki R (2001) Common hydrophytes as bioindicators of nickel, chromium and cadmium pollution. Water Air Soil Pollut 127:373–388

Use of Surfactants in Soil and Groundwater Remediation Aras Gezer and Ahmet Karagunduz

Abstract Due to potential risks of hazardous materials to human beings and to environment, numerous research has been initiated to investigate their removal, control, transportation and monitoring. The major organic pollutants in the subsurface environment are pesticides, PCBs, PAHs, organic liquids (LNAPLs, DNAPLs), and organic sludges/solids. The removals of these compounds are difficult due to poor solubilities of these compounds in aqueous phase. In addition, the rate limited solubilization makes the problem even more complicated. Since the traditional remediation methods were unsuccessful in cleaning up most contaminated fields, new novel methods have been investigated. Surfactants have been used in soil remediation processes to improve removal of pollutants from soil and groundwater due to their unique properties like micelle formation. Surfactants are a class of natural and synthetic chemicals that promote the wetting, solubilization, and emulsification of various types of organic and inorganic contaminants. They are utilised within chemical–physical technologies like in situ soil flushing and ex situ soil washing for remediation of unsaturated zone and pump and treat for aquifer remediation. There are many other investigations on surfactant enhanced remediation technologies including bioremediation and electro kinetic remediation. In this study, the use of surfactants in remediation technologies is discussed. Their advantages and disadvantages for wider applications are outlined. Keywords Surfactant enhanced remediation (SEAR) · Surfactant · Hydrophobic organic contaminants (HOCs) · Micellar solubilization · Electrokinetics · Bioremediation · Pump and treat

A. Karagunduz (B) Department of Environmental Engineering, Gebze Institute of Technology, Gebze, Kocaeli 41400, Turkey e-mail: [email protected]

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1 Introduction On the Earth, 95% of the freshwater is groundwater. Because of its filtration through the porous media, groundwater is usually cleaner than surface water. Unfortunately, groundwater contamination due to industrial and agricultural activities has become one of the serious environmental problems. Discharges of toxic wastes into lakes, ponds and other receiving media may eventually reach to the groundwater. Improper discharges or accidental spills to the soil also contributed to the pollution of subsurface in greater extent. In addition, agricultural activities are a major source of groundwater pollution. High concentrations of pesticides, herbicides and other chemicals like nitrogen and phosphorous are introduced to subsurface. Organic compounds such as PCBs, PAHs, organic liquids (LNAPLs, DNAPLs) and organic sludges/solids are widespread contaminants in soil and groundwater in industrialized regions. Since the classical remediation technologies (i.e., pumpand-treat, natural attenuation) failed to clean up most contaminated sites down to desired levels, innovative technologies have been developed. Surfactants enhanced remediation has emerged as one of the potential remediation technologies. The objective of this paper is to outline fundamentals of surfactant enhanced remediation technologies. First, micellar solubilization, surfactant flushing and soil washing technologies will be discussed, then, surfactant enhanced electrokinetics will be presented. Finally, surfactant enhanced pump and treat will be briefly discussed.

2 Properties of Surfactants The term “surfactants” is a contraction of the term surface active agents. Surfactants are amphiphilic compounds that have two moieties: Hydrophilic head portion (polar) and hydrophobic (non-polar) tail portion. Hydrophobic portion of the surfactants is usually a long chain of hydrocarbons and hydrophilic portion of surfactants is usually ionic or highly polar groups [15]. Depending on the type of ionic groups, surfactants can be classified as cationic, ionic, non-ionic and zwitterionic. Surfactants may attract or repel each other in water since they posses both hydrophobic and hydrophilic forces [14]. If the surfactants are charged, their hydrophilic groups repel each other. When the charge density of the polar group is higher, the repulsion force becomes greater. However, as opposed to hydrophilic groups, hydrophobic groups of surfactants attract each other. At low surfactant concentration, interaction among monomers is minimal in aqueous solutions. As surfactant concentration increases, surfactant molecules form aggregates. Surfactant molecules orient their hydrophobic groups away from water and form micelles. The surfactant concentration at which micelle formation begins is called the critical micelle concentration (CMC). A linear enhancement in the solubility of organic compounds is typically observed above the CMC, which is attributed to the incorporation of the organic species within the hydrophobic core of the surfactant micelle. This type of

Use of Surfactants in Soil and Groundwater Remediation

Surfactant Monomers HOC Concentration

Fig. 1 Influence of surfactants on the solubilization of HOCs (Adapted from [13])

997

HOC

Micellar solubilized HOC

CMC

Surfactant Concentration

system is commonly referred as a Winsor Type I system [15]. The effect of surfactants on the solubilization of hydrophobic organic compounds (HOCs) is presented in Fig. 1.

3 Micellar Solubilization The solubility potential of a surfactant can be represented using either Molar Solubilization Ratio (MSR) or micelle partition coefficient. MSR is the ratio of aqueous HOC concentration to micelle concentration and can be calculated as follows: MSR =

CM,HOC − CM,HOC(CMC) CM,s − CM,s(CMC)

(1)

where, CM,HOC is the molar concentration of surfactant solubilized HOC, CM,HOC(CMC) is the molar concentration of HOC at CMC, CM,s is the molar surfactant concentration and CM,s(CMC) is the molar CMC [2]. CM,HOC(CMC) is equal to aqueous solubility of HOC if there is no solubility enhancement below the CMC. The MSR can be determined from the slope of the solubility curve above the CMC (Fig. 1) if the axes are plotted in units of mole/L. If the curve is plotted in the units of mg/L, then the slope is called Weight Solubilization Ratio (WSR). The other approach to determine solubilization capacity of a surfactant is based on the distribution coefficient of HOCs between aqueous and micellar phase [5] which is given as Kmc =

CM,HOC MCaq

(2)

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where, M is the molar micelle concentration CM,s − CM,s(CMC) and Caq is the molar water solubility of organic compound. If concentrations are used as mg/L instead of mole/L, the unit of Kmc becomes L/mg. If solubility enhancement is observed below the CMC, monomer–water partition coefficient (Kmn ) can be determined similar to micelle–water coefficient assuming that solubility increases linearly between surfactant concentrations of zero and CMC. Total HOC concentration in solution in the presence of surfactants can be estimated using the following relationship [8]: ∗ Sw = (1 + Cmn Kmn + Cmc Kmc ) Sw

(3)

where, Sw∗ is the apparent organic compound concentration in the presence of surfactant (M/L3 ), Sw is the aqueous (water) solubility (M/L3 ), Cmn and Cmc are the concentrations (M/L3 ) of monomer and micelle, respectively; and Kmn and Kmc are the partitioning coefficients (L3 /M) of monomers and micelles, respectively. In the presence of soil The HOC solid–liquid distribution coefficient in the presence of surfactants can be represented as follows: K∗ =

S∗ Mass of sorbed DDT per mass solid−phase = HOC ∗ Mass of DDT in solution−phase per bulk liquid volume Sw

(4)

∗ Substituting SHOC = (KD + Sss Kss ) Caq,HOC = KD 1 + fss/oc Kss/oc , K∗ can be represented as: K∗ =

KD + SssKss 1 + Cmn Kmn + Cmc Kmc

(5)

where, K∗ is the apparent solute soil-water distribution coefficient (L3 /M), fss/oc is equal to Sss /foc , and Kss/oc is equal to Kss /Koc , Sss is the mass of sorbed surfactant and Kss is the DDT distribution coefficient between sorbed surfactant and water. Change of apparent soil–water distribution coefficient as a function of Kss is presented for DDT and sodium dodecyl benzene sulfonate (SDBS). As the surfactant concentration increased K∗ decreased substantially (Fig. 2). Based on these results one can expect significant decrease in sorbed mass of HOCs in the presence of surfactants. The mass fraction distribution of DDT in surfactant monomer, micelle, aqueous phase and sorbed phase with increasing SDBS concentration is presented in Fig. 3. As the surfactant concentration increased, DDT fraction in micellar pahse increased and the soil phase decreased. Since the solubility of DDT increases substantially as a result of the presence of surfactants, flushing surfactants to soil and groundwater may be a viable alternative to remove HOCs in situ. For example as seen in Fig. 3, in the absence of surfactant almost 97% of the DDT mass was associated with soil, and only 3% was in aqueous phase. In the presence of 10,000 mg/L SDBS 97% of the DDT mass is in micellar phase which is desorbed from the soil.

Use of Surfactants in Soil and Groundwater Remediation

Fig. 2 Change of apparent solute soil–water distribution coefficient with SDBS

Fig. 3 Distribution of DDT among phases with SDBS concentration

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4 Surfactant Enhanced Electrokinetics Most of organic and inorganic contaminants resistant to remediation with traditional technologies because of the soils’ low hydraulic conductivities. Recently, attention has focused on developing in situ electrokinetic techniques for the treatment of low permeable soils contaminated with organic pollutants. Although electrokinetics has been used for decades to remove water from soils, in situ applications of electrokinetics to remediate contaminated soil is new. Electrokinetic remediation was mostly studied for the removal of charged metals from the soil. However, organic contaminant removal by electrokinetics has not widely investigated, since the majority of the organic contaminants do not carry a net charge. Therefore electrokinetics may be very limited for the organics contaminants. However, if the organics are entrapped within the charged surfactant micelles, they may be transported to the respective electrode in an electrokinetic setup. Surfactants enhanced electrokinetic remediation may provide potential solutions for in situ cleaning up of sites with low hydraulic conductivity. The process of surfactant enhanced electrokinetic method is complicated. A simplified conceptual model is presented in Fig. 2. Water moves toward anode or cathode either by electroosmosis (1) or hydraulic gradient (2). When direct current was applied to the soil anions and cations move to anode and cathode, respectively (6). While ions move to the respective electrode, the water of hydration moves with ions to the electrode. Due to the negative nature of soils, in the soil environment more cations present then anions. In addition, more hydrogen ion forms in the anode compartment than the hydroxide ion in the cathode compartment. Therefore, there is a net flow from anode toward cathode, which is called the electroosmotic flow [11]. Electroosmotic flow can be described by a relationship developed by Helmhotz-Smoluchowski [1]. qe = ke iA =

ke I = ki I σ

(6)

where, qe electroosmotic flow rate (cm3 /s), ke electroosmotic flow constant (cm2 /s V), electroosmotic gradient (V/cm), A cross sectional area (cm2 ), σ electrokinetic conductivity (amp/V cm), I current (Amp) and ki elektrokinetic transport constant (cm3/Amp s). Flow due to hydraulic gradient follows Darcys Law [4]. qh = Kih A = k

ρg ih A n

(7)

where, qh hydraulic flow (cm3 /s), K hydraulic conductivity (cm/s), ih hydraulic gradient (cm/cm), k permeability (cm2 ), ρ density of the fluid (kg/cm3), n kinematic viscosity (N s/cm2 ). When direct current was applied to the soil, free anions and cations moves to the respective electrode as mentioned above (6). This is the main principle of metal removal in electrokinetic remediation. However, most organic contaminants do not carry a net charge, therefore, can only transport to anode or cathode due to

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electroosmotic and/or hydraulic flow. In the presence of surfactants various other processes occur. First, surfactant monomers may strongly adsorb to the soil (3). Then, organic contaminants partition to the soil and adsorbed surfactants (4). The sorption of organic contaminant to the soil in the presence of surfactant has been significantly investigated. The linear sorption coefficient of hydrophobic organic to soil was decreased with increasing surfactant concentration. [16, 9, 7, 17, 3, 5]. Another process occurring in the presence of surfactants is the micellar solubilization (5). At low concentrations, surfactants exist as monomers in solution and have a minimal effect on the solubility of most organic compounds [12]. However, solubility enhancement may be more noticeable for relatively hydrophobic compounds (i.e., DDT, HCB) below the CMC for nonionic surfactants. This is primarily the result of the interaction between surfactant hydrophobic groups and HOCs [8]. In some cases, dimer and trimer formations also enhance the solubility of HOCs below the CMC [6] (Fig. 4). The major problem in use of surfactant in electrokinetic method is the type of surfactants. Cationic surfactant move toward cathode, which is the same direction of electroosmotic flow. However, cationic surfactants adsorbe to the soil and decrease the mobility of the contaminants. Therefore use of cationic surfactant is more limited. Anionic surfactants, however, are transported in the opposite direction of electroosmotic flow, which reduces the transport. Nonionic surfactants do not carry a net charge therefore only transported through electrosomotic flow. In Fig. 5, a column experiment is presented. A 15 cm long column was divided into three sections. The middle 5 cm was packed with DDT contaminated soil and the

2. Hydraulic Flow

Soil

1: Electroosmotic Flow

Soil

+

H

2: Movemement to electrodes

2

– 4: Partition of HOCs (to soil and adsorbed surfactant)

H+

–

Anionic micelle

3: Sorption of Surfactant

–

–

–

– –

–

–

5: Solubilization HOCs

cation +

OH– 2: Movemement to electrodes

6: Ion exchange

ANODE

Fig. 4 Conceptual model of electrokinetic remediation

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Fig. 5 Effect of direct current on the distribution of DDT in a soil column

other two pieces was packed with clean soil. 30-V direct current was applied. An anionic surfactant, sodium dodecyl benzene sulfonate (SDBS), was applied from cathode compartment. At the end of 30 day period DDT was observed to move anode compartment.

5 Surfactant Enhanced Pump and Treat Remediation Groundwater contaminated with dissolved organic and inorganic contaminants can be pumped out of the aquifer and be treated on the surface of the ground. The treated groundwater can either be returned to the pumped aquifer, or used, or discharged. The treatment method depends on the physical-chemical properties of the contaminants to be removed. This remediation scheme is known as pump-and-treat. Pump-and-treat systems are designed to: (1) Hydraulically contain and control the movement of contaminated groundwater and prevent continued expansion of the contamination zone. (2) Reduce dissolved contaminant concentrations to comply with cleanup standards and thereby restore the aquifer. (3) Combine the previous two objectives [10]. Use of surfactant with combination of pump and treat remediation technology for the removal of NAPLs from aquifer has been widely investigated. Pump and treat technology fails to remove NAPLs from the aquifers, since the NAPLs are trapped and strongly held within the pores due to capillary forces. Surfactants enhance the efficiency of pump and treat technology, by decreasing the interfacial tension and by increasing the solubilization of NAPLs in the aquifer. When interfacial tension

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decreased, capillary forces reduces. Therefore trapped NAPL is mobilized in the aquifer as a separate phase, which then can be pumped out. Mobilization has a greater potential than solubilization to increase the rate of remediation, but carries more risk because of the movement of free phase liquid.

6 Conclusions Removal of contaminants from soil and groundwater has been a major problem in decades. Conventional remediation technologies have deficiencies. Therefore new novel technologies have been widely investigated. Use of surfactants with existing technologies has been shown promising results in cleaning up soils and aquifers contaminated with organics. Surfactants increase the solubility of organic compounds above the CMC. This is the major mechanism for enhancement in soil washing, electrokinetics and bioremediation. Surfactants also reduce the interfacial tension. As a result capillary forces decreases within the pores and NAPLs are mobilized in aquifer that can be easily pumped out.

References 1. Acar YB, Gale JL, Hamed J, Putman G (1990) Acid base distribution in electrokinetic soil processing. Transp Res Rec 1288:23–24 2. Diallo MS, Abriola LM, Weber WJ (1994) Solubilization of nonaqueous phase liquid hydrocarbons in micellar solutions of dodecyl alcohol exhoxylates. Environ Sci Technol 28:1829–1837 3. Edwards DA, Liu Z, Luthy RG (1994) Experimental data and modeling for surfactant micelles, HOCs, and soil. J Environ Eng 120:23–41 4. Hillel D (1998) Environmental soil physics. Academic Press, San Diego, CA 5. Jafverd CT (1991) Sediment and saturated soil associated reactions involving an anionic surfactant (Dodecylsulfate): II. The partition of PAH compounds among phases. Environ Sci Technol 25:1039–1045 6. Jafvert CT, Van Hoof PL, Heath JK (1994) Solubilization of non-polar compounds by nonionic surfactant micelles. Water Res 28:1009–1017 7. Jafvert CT, Van Hoof PL, Chu W (1995) The phase distribution of polychlorobiphenyl congeners in surfactant-amended sediment slurries. Water Res 29:2378–2397 8. Kile DE, Chiou CT (1989) Water solubility enhancements of DDT and trichlorobenzene by some surfactants below and above the critical micelle concentration. Environ Sci Technol 23:832–838 9. Lee JF, Liao PM, Kuo CC, Yang KHT, Chiou CT (2000) Influence of a nonionic surfactant (Triton-X100) on contaminant distribution between water and several soil solids. J Colloid Interface Sci 229:445–452 10. Environmental Protection Agency (1994) Methods for monitoring pump-and-treat performance, EPA/600/R-94/123. Environmental Protection Agency, Washington, DC 11. Mitchell JK (1993) Fundamentals of soil behavior. Wiley, New York 12. Pennel KD, Abriola AM, Weber JR (1993) Surfactant enhanced solubilization of residual dodecane in soil columns 1. Experimental investigations. Environ Sci Technol 27:2332–2340 13. Pennell KD, Abriola LM, Pope GA (1996) Influence of viscous and buoyancy forces on the mobilization of residual tetrachloroethylene during surfactant flushing. Environ Sci Tech 30(4):1328–1335

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14. Porter MR (1994) Handbook of surfactants. Chapman Hall, New York 15. Rosen MJ (1989) Surfactant and interfacial phenomena, 2nd edn. Wiley, New York 16. Sun S, Inskeep WP, Boyd SA (1995) Sorption of nonionic organic compounds in soil-water systems containing a micelle-forming surfactant. Environ Sci Technol 29:903–913 17. Sun S, Boyd SA (1993) Sorption of organic compounds in soil-water systems containing petroleum sulfonate-oil surfactants. Environ Sci Technol 27:1340–1346

Co-digestion Approaches to Organic Fraction of Municipal Solid Waste with Primary Sludge for a Municipal Treatment Plant in Turkey R.K. Dereli, M.E. Ersahin, C.Y. Gomec, O. Ozdemir, and Izzet Ozturk

Abstract The comparison of wet anaerobic digesters fed with differently sorted organic fraction of municipal solid waste (OFMSW) was carried out by co-digestion approaches to the primary sludge taken from Kayseri municipal wastewater treatment plant (WWTP) located in the Central Anatolian Region of Turkey. The WWTP was designed in two stages. The second mesophilic anaerobic digester is planned to be constructed after 20 years in the second stage. In this study, the construction of the second digester and a pre-treatment unit for municipal solid waste were proposed in the current stage for co-digestion purposes. Two alternatives were proposed using different solid waste contents in the co-digesters. In order to provide the required solid content, some amount of the treated wastewater was recycled to each digester together with the primary sludge. Although the existing collection method was assumed to be characterized as mechanical sorted (MS-OFMSW) (Option 1), source sorted (SS-OFMSW) alternative was also evaluated in the study (Option 2). The total energy demand of Kayseri WWTP was reported as around 42,300 kWh per day. Utilizing the energy produced by the digester, only 30% of the total energy demand and all of the heat energy demand including administration building can be covered. Thus, the aim was to evaluate how energy production would be increased by the application of co-digestion of OFMSW together with the primary sludge in Kayseri WWTP. Results indicated that the best operational condition in the cases of organic loading rate (OLR), hydraulic retention time (HRT) and energy recovery could be provided using 10% solid content in each co-digester for both options. According to the approach in Option 1, almost 77% of the total energy demand could be covered by applying co-digestion of MS-OFMSW together with the primary sludge and 200 m3 treated wastewater recycle. On the other hand, almost 100%

R.K. Dereli (B) Department of Environmental Engineering, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_95,

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energy recovery could be obtained when co-digestion approach (Option 2) was performed according to SS-OFMSW together with the primary sludge at 150 m3 treated wastewater recycle. Significant amounts of sludge cakes (anaerobic compost) were produced after co-digestion and aerobic composting could be considered as an appropriate post treatment alternative. Co-digestion of OFMSW and sewage sludge may be an attractive alternative for sustainable management of two separate waste streams produced at large amounts in the developing countries. Keywords Co-digestion · Energy recovery OFMSW · Primary sludge · Source sorted OFMSW

·

Mechanically

sorted

1 Introduction The interest in alternative municipal solid waste (MSW) management strategies will likely intensify because the production of MSW continues to grow, while the disposal capacity via traditional landfilling and incineration is diminishing [10, 12]. Landfilling, which was formerly the main solid waste management method, is no longer a principle option in many European countries due to the scarcity of land, restrictions for biodegradable waste disposal in EU Landfill Directive [7], and uncontrolled long-term contamination with gas emissions and leachate. Recovery through recycling and composting already has increased substantially since the late 1980s and is expected to divert 30–40% of MSW streams in 2010 [6]. An alternative treatment strategy for organic fraction of municipal solid waste (OFMSW) is anaerobic biological treatment, either in anaerobic digesters or in landfill bioreactors [9]. Anaerobic biological treatment can be a sustainable alternative to current disposal strategies because it reduces the volume of OFMSW, stabilizes it, produces a residue that can be used for soil conditioning, and recovers energy from OFMSW in the form of methane. The co-digestion concept involves the treatment of several types of waste in a single treatment facility. The mixing of several waste types has positive effects both on the anaerobic digestion process itself and on the treatment economy. The profit of co-digestion in the anaerobic degradation process is mainly due to the increased methane yield and improved process stability. Co-digestion of the OFMSW and sludge from a municipal WWTP suggests an integrated wastewater treatment. Sewage sludge is one of the most appropriate co-substrate alternatives for co-digestion with OFMSW. By this way, co-digestion can be applied at existing treatment facilities without great investments and it combines the treatment of the two largest municipal waste streams [8]. In the framework of the Kyoto agreements, many countries in Europe have agreed to stimulate the production of methane from wastes, e.g. by subsidizing the electricity from biogas by as much as 0.1 C/kWh. The latter certainly will be a major support for anaerobic digestion of complex wastes. The European Union has set the target to increase the fraction of electricity produced with renewable resources (excluding large hydroplant) from 3.2% in 1997 to 12.5% in 2010. Electricity

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generated from municipal solid waste by means of anaerobic digestion can make a significant contribution towards this target The strategy of waste collection affects the characteristics of the organic wastes and determines the yields of anaerobic reactors not only in terms of biogas production but also in terms of final disposal of the effluent streams from the process [1]. According to EU Landfill Directive (99/31/EC), landfilling of the total biodegradable fraction of MSW including other biodegradable sludges and crop residuals must be reduced to the level of 35% based on 1,995 figures of biodegradable fraction of MSW in the near future (by 2020). EU adapted national waste management plan of Turkey has considered the dual collection system for MSW and biological treatment (i.e. composting and biomethanization) of the OFMSW [5]. The biomethanization of OFMSW will become a very feasible option by applying subsidies to electricity production from wastes. Current biomethane potential of the OFMSW in Turkey is about 109 m3 CH4 /year considering 50% biomethanization of 5 × 106 ton biodegradable waste (VS) per year. Thus, co-digestion of OFMSW with other types of wastes will further decrease the energy demand in Turkey. The aim of this study was to evaluate the applicability of co-digestion of OFMSW with primary sludge on a full-scale wastewater treatment plant located in Kayseri Province. Kayseri WWTP which is one of the biggest provinces in Turkey was selected due to its relatively high population. Waste minimization, biogas production and feasibility of the proposed co-digestion method were investigated which would also help to dispose the solid wastes together with the sludge in the existing WWTP. Different alternatives were evaluated in the cases of mass balances and energy productions using solid waste and wastewater treatment sludge characteristics of the investigated WWTP.

2 Present Situation in the Investigated Plant 2.1 Kayseri Wastewater Treatment Plant (WWTP) Kayseri Province is located in the central region of Turkey with a population of around one million. Kayseri WWTP has been operated since 2004 by Kayseri Metropolitan Municipality Water and Sewerage Directorate (KASKI) and was designed in two stages. First stage is serving for 800,000 PE and 110,000 m3 /day average dry weather flow. The WWTP contains activated sludge system with a biological nutrient removal process. The average operation data of the plant are presented in Table 1. Flow diagram of the plant is given in Fig. 1. In the first stage, a mesophilic anaerobic digester having an effective volume of 6,750 m3 was constructed. The thickened primary sludge is fed to the anaerobic digester. The capacity of the plant will be increased 20 years later in the second stage and a second digester is planned to be constructed. The produced biogas is used in two combined heat and power

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R.K. Dereli et al. Table 1 The average operation data of Kayseri WWTP

Parameter

Unit

Influent

Effluent

Efficiency (%)

Flow rate BOD5 COD SS NH4 -N NO3 -N Total N TP

m3 /day mg/L mg/L mg/L mg/L mg/L mg/L mg/L

140, 500 330 640 340 36 2 52 10

–

– 98 94 94 – – 85 70

8 40 20 3 3 8 3

Biological Nutrient Removal Nitrification&Denitrification

Secondary Sedimentation

Primary Sedimentation Screening Grit&Grease Chambers Pumping Station

Discharge

Bio-P

Thickening

CHP Unit

Returned Activated Sludge

Thickening

Belt Filter Sludge Mixing Tank

Fig. 1 The layout of the Kayseri wastewater treatment plant

(CHP) units of 400 kWh power of each one. With the produced energy, 30% of the daily total energy demand (∼42,300 kWh) of the treatment plant and all of the heat energy demand including administration building is covered. The digested primary sludge is then fed to the secondary sludge thickener. The thickened sludge from the secondary sludge thickener and the excess activated sludge are mixed in a sludge mixing tank, chemically conditioned by polyelectrolyte addition and sent to the belt-filter for dewatering. The sludge cake out of the belt-filter is disposed in a landfill. The average operation data of the primary sludge digester is presented in Table 2.

3 Evaluation of Co-digestion Approach for Kayseri Province Landfilling is the most widely used disposal method for solid wastes in Turkey. However, anaerobic treatment of OFMSW with different wastes has been gaining importance which has proved its applicability especially in Europe due to net energy

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Table 2 The average operation data of the primary sludge digester at Kayseri WWTP Parameter Effective reactor volume Qinfluent Organic loading rate Operating temperature TS content TSinfluent TVSinfluent TVSinfluent /TSinfluent CODinfluent TSeffluent TVSeffluent CODeffluent TS removal, ETS TVS removal, ETVS COD removal, ECOD Qmethane Alkalinity pH Energy production

Unit m3 m3 /day kg VSS/m3 day ˚C % mg/L mg/L – mg/L mg/L mg/L mg/L % % % m3 /day mg CaCO3 /L – kWh/day

Value 6,750 300 2.0 35 7.0 76,500 43,700 0.57 69,200 37,800 17,700 32,500 0.51 0.59 0.53 4,370 4,000 7.2 12,700

Table 3 Ultimate methane and biogas production for different types of OFMSW Substrate

B0 (m3 CH4 /kg TVS)

G0 (m3 /kg TVS)

MS-OFMSW SC-OFMSW SS-OFMSW

0.16–0.37 0.45–0.49 0.37–0.40

0.29–0.66 0.81–0.89 0.67–0.72

B0 : maximum methane potential, G0 : maximum biogas potential (55% CH4 )

yields and stability. High amounts of produced solid wastes and treatment sludges make this disposal method attractive for developing countries especially in Turkey. In this study, the existing solid waste collection as well as future source separation methods were evaluated while proposing different alternatives. The strategy used for waste collection can be considered as the first treatment step for solid wastes as it determines different yields of the anaerobic digestion processes and a different final disposal for the treated material such as composting and land application instead of incineration or landfilling. High yields in terms of biogas production and good compost quality are generally associated with the treatment of separately collected (SC-) or source sorted (SS-) municipal organic waste, while the mechanically sorted (MS-) OFMSW gives poorer biogas production and a residual material which should be disposed of in landfills or incinerated [2]. Maximum methane and biogas production potentials for different OFMSW types are given in Table 3 [3].

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3.1 Co-digestion of MS-OFMSW with Primary Sludge (Option 1) In Option 1, co-digestion of the primary sludge with MS-OFMSW (mechanically sorted-OFMSW) was evaluated in the anaerobic digester (wet process) of Kayseri WWTP. The existing collection method was assumed to be characterized as mechanical sorting. The construction of the second digester and a pre-treatment unit were proposed in the current stage for co-digestion purposes at Kayseri WWTP. Total solid (TS) content of the solid waste was 35% and total volatile content (TVS) of the TS was 60%. This alternative considers the treatment of some 100,000 tons per year of municipal solid waste (MSW) which undergo to a pre-treatment process in which around 70,000 tons of organic waste stream per year is produced. The pretreatment process typically includes at least one size reduction step, metal removal and more than one screen operation [3]. Energy input for the pre-treatment stage is considered as 70 kWh per ton of treated material [4]. After the addition of water in a pulper to match up a final total solid content of 10%, the OFMSW is fed to the digesters together with the primary sludge. In this alternative, solid waste content of the digester was taken as 10% and the necessary calculations were done. In order to provide 10% solid content (reported between 10 and 15% in the co-digesters for wet processes), 200 m3 treated wastewater was recycled to each digester together with the primary sludge [11]. OLR and HRT for each co-digester were calculated as 3.9 kg TVS/m3 .day and 15.4 day, respectively. The operating parameters are given in Table 4. According to the calculations in Option 1 (Fig. 2), total methane production was found as 16,300 m3 per day which corresponded to total electrical and thermal energy productions of some 47,500 and 79,000 kWh, respectively. The energy requirement for heating the second digester would be supplied by the steam which is usually recovered from the cooling water of the gas engines and the exhaust fumes. The energy consumption of the pre-treatment stage was calculated as some 19,000 kWh for about 272 tons of the processed waste per day. Since 61,300 kWh/day total energy requirement was calculated including the demand in the pre-treatment stage, almost 77% of the total energy demand could be covered by the application of the proposed system in Option 1. The calculations were repeated according to the solid waste contents of 8 and 12 in the digesters. 8% solid content for wet type of treatment was not appropriate due to the fact that the digesters could not be operated at full capacity. OLR and HRT Table 4 The operating parameters calculated for Option 1 Parameter

Unit

Primary sludge

MS-OFMSW

Combined waste

Flow TS TVS Waste load

m3 /day kg/day kg/day kg/day

150 11, 500 6, 500 153

87 33, 300 20, 000 95

437a 44, 800 26, 500 248

a 200

m3 water recycle for dilution

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23750 kWh 19000 kWh MSW 272 t/d

Co-digester

Water: 400 t/d Sorting line

Sludge: 306 t/d

Pulper

82 t/d inert and metals

Blending tank

23750 kWh

Co-digester

Thickening and dewatering

560 t wastewater

310 t cake to compost

Fig. 2 Flow scheme and total mass balance of the Option 1

values for each co-digester were calculated as 2.9 kg TVS/m3 .day and 16.6 day by recycling 200 m3 treated wastewater with the primary sludge, respectively. Results indicated that almost 64% of the total energy demand could be covered by providing 8% solid content in the digesters. When the calculations were done according to 12% solid content in the co-digesters (200 m3 treated wastewater recycle), OLR and HRT values were calculated as 5.1 kg TVS/m3 .day and 14.3 day, respectively. Results indicated that the most appropriate OLR and HRT values as well as energy recovery could only be provided when 10% solid content was provided in the codigesters.

3.2 Co-digestion of SS-OFMSW with Primary Sludge (Option 2) In Option 2, co-digestion of the primary sludge with SS-OFMSW (source sortedOFMSW) was evaluated in the anaerobic digester of Kayseri WWTP. The aim was to evaluate how collection method would affect the calculations compared to Option 1. Total solid (TS) content of the solid waste was 30% and total volatile content (TVS) of the TS was 70%. Solid waste contents of the digesters were taken as 8 and 10% and the necessary calculations were done. In order to provide these solid contents, 200 m3 treated wastewater was recycled to each digester together with the primary sludge. When 8% solid content was provided in the digesters, OLR and HRT were calculated as 3.3 kg TVS/m3 .day and 16 day, respectively. Total methane production was calculated as 16,500 m3 per day which corresponded to total electrical and thermal energy productions of some 47,700 and 80,000 kWh, respectively. The energy consumption of the pre-treatment stage was calculated as some 9,500 kWh for about 200 tons of the processed waste per day. Results indicated that almost 92% of the total energy demand could be covered by the application of the proposed system. When the calculations were repeated for 10% solid content, OLR and HRT for each co-digester were calculated as 4.7 kg TVS/m3 .day and 14.6 day, respectively. Although 100% of the total energy demand could be covered, the system would be

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MSW 235 t/d

Water: 300 t/d Sorting line

Co-digester

Sludge: 306 t/d

Pulper

Blending tank

47 t/d inert and metals

28000 kWh

Co-digester

Thickening and dewatering

510 t wastewater

260 t cake to compost

Fig. 3 Flow scheme and total mass balance of the Option 2 Table 5 The comparison of Option 1 and Option 2 Parameter

Unit

Option 1

Option 2

Treated organic solid waste TS content in the digesters HRT OLR Methane production Electrical energy production Energy recovery

ton/year % day kg TVS/m3 .day m3 /day kWh/day %

70,000 10 15.4 3.9 16,300 47,500 77

68,600 10 17.3 3.9 19,500 56,000 100

operated as overloaded due to high solid loading when 200 m3 treated wastewater was recycled. Therefore, 150 m3 treated wastewater was recycled to each digester at 10% solid content. Results indicated that OLR reduced to 3.9 kg TVS/m3 .day at a HRT of 17.3 day. Since this OLR value was acceptable in anaerobic digesters, 150 m3 wastewater recycle instead of 200 m3 was found to be suitable in Option 2. Total methane production was calculated as around 19,500 m3 per day corresponding to total electrical and thermal energy productions of some 56,000 and 95,000 kWh, respectively (Fig. 3). The energy consumption of the pre-treatment stage was calculated as some 11,750 kWh for about 235 tons of the processed waste per day. Results indicated that almost 100% of the total energy demand could be covered. The comparison of both options is presented in Table 5.

3.3 Aerobic Composting After Co-digestion of OFMSW with the Primary Sludge In the existing situation, the sludge cake out of the belt-filter is disposed in a landfill. Therefore, aerobic composting alternative was evaluated following co-digestion of MS-OFMSW and SS-OFMSW with the primary sludge having 10% solid content at each digester. The digestate from co-digestion is fed to a secondary sludge thickener and then dewatered by a belt-filter following conditioning with polyelectrolyte.

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Results indicated that the sludge amounts that would be given to the mechanical dewatering unit were around 65 and 55 tons for MS-OFMSW and SS-OFMSW, respectively. Since the solid capture efficiency of the belt filter was assumed as 95%, around 62 and 52 tons of total solids would be produced for MS-OFMSW and SS-OFMSW, respectively. If the solid content of the cake was assumed as 20% by the addition of a suitable polyelectrolyte after thickening and dewatering, then around 310 tons and 260 tons of cake for MS-OFMSW and SS-OFMSW could be disposed of by aerobic composting, respectively. Besides, almost 530 tons of water was produced which could be used for irrigation. Magnesium Ammonium Phosphate (MAP) precipitation could also be applied to this generated water which would be a valuable fertilizer for agricultural uses.

4 Conclusions and Recommendations In the study, co-digestion approaches were evaluated for OFMSW collected by different methods with the primary sludge taken from Kayseri WWTP. The second digester, which was planned to be built in the second stage, was proposed to be constructed with a pre-treatment unit in the current stage for co-digestion purposes. Two alternatives were proposed according to the collection methods (mechanical and source sorted) using different solid waste contents in the co-digesters. By the proposed co-digestion options, significant energy recovery could be achieved. Results indicated that the best operational condition in the cases of OLR, HRT and energy recovery could be provided with 10% solid content in each co-digester. When co-digestion was applied with SS-OFMSW, 30% more energy could be recovered compared to the energy recovery by MS-OFMSW. This could be attributed to higher volatile content of SS-OFMSW. When the energy balance was considered only for the pre-treatment stage, the produced energy was around 4.5 and 2.5 times higher than the consumed energy for SS- and MS-OFMSW, respectively. About 56,000 kWh/day energy recovery could be possible by co-digestion application in Option 2 at Kayseri WWTP. This corresponded to an annual income of about $2 × 106 from biomethane by simply using internal combustion engine and generator system without heat recovery according to the current law on “The Usage of Renewable Energy Sources for the Purpose of Electricity Production” in Turkey, [13]. This income will be doubled ($4 × 106 /year) if the subsidy is increased to additional C 0.1/kWh as currently in practice in the most EU member countries. The required investment for Option 2 would be about C 3 × 106 including the additional digester and the pre-treatment facilities for the SS-OFMSW. The payback period of the whole investment would be less than 3 years by considering the bioenergy recovery from the system. Since significant amounts of sludge cakes were produced after co-digestion of OFMSW together with the primary sludge, aerobic composting could be considered as an appropriate post treatment alternative. Besides, the supernatant from the digesters could also be used for irrigation purposes.

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References 1. Bolzonella D, Pavan P, Fatone F, Cecchi F (2005) Anaerobic fermentation of organic municipal solid wastes for the production of soluble organic compounds. Ind Eng Chem Res 44(10):3412–3418 2. Bolzonella D, Pavan P, Mace S, Cecchi F (2006) Dry anaerobic digestion of differently sorted organic municipal solid waste: a full-scale experience. Water Sci Tech 53(8):23–33 3. Cecchi F, Traverso P, Pavan P, Bolzonella D, Innocenti L (2002) Characteristics of the OFMSW and behaviour of the anaerobic digestion process. In: Mata-Alvarez J (ed) Biomethanization of the organic fraction municipal waste. IWA Publishing, London, UK 4. Cecchi F, Bolzonella D (2004) Full scale experiences of the anaerobic digestion of the organic fraction of municipal solid waste in Italy-from collection to energy and valuable end products. IWA 4th international symposium on anaerobic digestion of solid waste, Copenhagen, Denmark, 31 Aug–2 Sep, pp 60–71 5. ENVEST (2005) Technical assistance for environmental heavy-cost investment planning, Turkey: directive specific implementation plan for Turkey. Prepared by ENVEST Planners consortium for republic of Turkey Ministry of Environment and Forest 6. EPA (1996) Characterization of municipal solid waste in the United States: 1995 Update, Executive Summary. EPA 530-S-96-001, USA 7. EU (1999) Council Directive of 21 April 1999 on the landfill of waste, 99/31/EC 8. Hartmann H, Angelidaki I, Ahring BK (2002) Co-digestion of the organic fraction municipal waste with other waste types. In: Mata-Alvarez J (ed) Biomethanization of the organic fraction municipal waste. IWA Publishing, London, UK 9. Pohland FG (1996) Landfill bioreactors: fundamentals and practice. Water Qual Int Sept/Oct 9/10:18–22 10. Steuteville R (1995) The state of garbage in America. Biocycle 4:54–63 11. Vandevivere P, De Baere L, Verstraete W (2002) Types of anaerobic digester for solid wastes. In: Mata-Alvarez J (ed) Biomethanization of the organic fraction municipal waste. IWA Publishing, London, UK 12. Williams ME (1994) Integrated solid waste management. In: Handbook of solid waste management. McGraw-Hill Inc., New York 13. YKEUK (2005) The law on the usage of renewable energy sources for the purpose of electricity production, Oficial Gazet No: 5346, 10 May 2005

Radiochronological Methods as Tools to Study Environmental Pollution H.N. Erten

Abstract The study of the environmental impact of natural and anthropogenic events forms the essence of environmental pollution considerations. The nature of the polluting species as well as their time distributions are of primary importance with respect to identifying the polluting sources. Sediments are the most frequently used materials in such studies. Sediments act as the ecological memories of the environments of their formation. Besides classical chronological methods, radiochronological methods developed recently gave a big impetus to environmental pollution studies. One of the key radioisotopic technique is to utilize 210 Pb, a product of the 235 U radioactive series to date the last 200 years of the sediments. A number of supporting indicators are also utilized. One of them being anthropogenic 137 Cs which is used as a time-marker. Large amounts of 137 Cs radioactivity was released to the environment during 1954–1963, in time of the most intense atmospheric nuclear arms testing and again in 1986 during the Chernobyl nuclear accident. These intense 137 Cs activities form time-markers throughout sediment cores corresponding to their release years. During our studies extending over several years we have used radiochronological methods in dating several sediment cores from Zurich and Constance Lakes in Switzerland from east coast of Spain, Sea of Marmara, from the Black Sea region, Southern coast of Turkey and from North Cyprus. The distribution of several elemental concentrations of importance in pollution considerations along sediment cores were also determined. These studies allowes proposing time frames to pollution events and help inqueries in tracing possible sources of pollution. Keywords Environment · Pollution · Radiochronology

H.N. Erten (B) Department of Chemistry, Bilkent University, 06800 Ankara, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_96,

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1 Introduction The formation of our world and its age has been a curiosity of mankind since ancient times. With the discovery of radioactivity in 1896 the age of the world has been accurately determined using radioisotopic techniques as 4.5 × 109 years. The natural radioactive series of 238 U, 235 U and 232 Th and their decay products as well as cosmic ray produced radionuclides have been used for accurate dating of archeological artifacts. These techniques were also useful in establishing a time frame for the impact of natural and anthropogenic activities on the environment. During overground nuclear weapons testing significant amounts of radioisotopes were emitted to the atmoshere. These kinds of activities were most intense in the years 1953–1954 and 1963–1964. Also big nuclear accidents such as Chernobyl in 1986 led to the sharp increases in radioactivities of the various environmental samples. Because of its high fission yield and long half-life the radioisotope 137 Cs has been used as a convinient time marker. Radiochronological dating of sediments from various acquatic environments combined with the measurement of of their chemical profiles allow the study of the impact of natural and cultural events on the surrounding environment. The radionuclide 210Pb (t1/2 = 22.3 y), a member of the natural radioactive decay series of 238 U, provide a reliable possibility of dating sediments over the last 200 years [1]. This technique has since seen further refined and very widely used by many researchers [2–11]. This method of dating, requires the complete recovery of the topmost sediment layers. 7 Be (t1/2 = 53.3 d) a cosmic ray produced nuclide is expected to be present only in the uppermost sediment layers due to its short half-life. The presence of 7 Be in the sediments thus ensures complete core recovery. We have used the above mentioned radioisotopic methods over the years for the dating of sediments from Lakes Zurich and Constance, the sea of Marmara, southern Turkey, eastern Spain, the Black Sea region and northern Cyprus [5–11]. Elemental distributions along the sediment samples were determined using spectrocopic techniques such as XRF, AA. Utilizing the measurements together with the dating results allowed the determination of the time of pollution and their possible sources.

2 Dating Methods 2.1

210 Pb

Method

The commonly used radioisotope for dating sediments, 210 Pb, is a member of the natural radioactive series 238 U (t1/2 = 4.4 × 109 y). 210Pb is incorporated into the sediments through the following processes. The noble gas nuclide 222 Rn (t1/2 = 3.82 d), a member of the 238 U decay chain, diffuses out of the earth’s crust and is emmitted to the atmosphere. Radon gas decays completely while in the atmoshere leading to decay products such as 210Pb. 210 Pb radioisotopes returns

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to land and water surfaces with a constant flux as a result of wet and dry precipitation. In water marine environment 210 Pb is scavenged by suspended particulate matter and accumulates in the sediments. Following the activity of 210 Pb across sediment cores leads to the determination of sedimentation rates and hance dating of the sediment cores over a time scale of 200 years.

2.2

137 Cs

Method

As a result of extensive nuclear weapons test (1953–1964) and nuclear accidents (Chernobyl 1986) the distribution pattern of fission product 137 Cs exhits peaks corresponding to these dates across sediment cores. The positions of these time marker peaks in the sediments all calculations of sedimentation rates. This complementary dating method may be used together with 210 Pb dating.

2.3 7 Be Method Cosmic ray produced radionuclibe 7 Be (t1/2 = 53.3 d) is incorporated into the sediments via the same mechanisms as 210 Pb and 137Cs. Because of its short half-life however; the radioactivity of 7 Be can only be detected in the uppermost layers of sediments. Measurement of 7 Be in sediments thus ensures that no loss occurs in the upper parts of sediment cores during the sampling process. Any such loss leads to serious errors in sedimentation rates and thus corresponding dates.

3 Experimental Sediment cores were recovered using either a gravity corer or a box corer. The cores were immediately sampled in 0.5, 1 and 2 cm intervals after recovery. Part of the core sections were used for textural, mineralogical and chemical studies. 210 Pb was determined through its daughter 210 Po (t1/2 = 138.4 d) in radioactive equilibrium with its parent. Polonium was distilled from the sediment at 600◦C and was converted to the chloride form by several evaporations with HCl. It was taken in a 0.5 M HCl solution. SO2 gas was bubbled through the solution for 3 minutes at 93◦ C. Polonium was self-deposited on a silver disc which was suspended in the hot solution. One side of the disc was coated with RUTEX, liquid rubber, ensuring deposition on one side only. The overall chemical yield was 90% as determined by the 208 Pb tracer. Alpha activities were determined using surface-barrier α-detectors. The 210 Po activities were converted into 210 Pb activities using standard growth and decay equations. In some cases 210 Pb was determined directly by γ-rayspectrometry via the 46.5 keV line using a hyperpure Ge detector with 92 cm2 active area. The 137 Cs and 7 Be activities were determined by γ-ray spectroscopy using a well-type Ge (Li) detector.

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4 Results and Discussion Sedimantation rates obtained by the above mentioned methods from various regions are summarised in Table 1. The sedimentation rates obtained by three different methods in the dating of Lake Zurich sediments agree quite well with each other. Annual varves were not observed in the sediment samples from other regions. Sediment traps were used in Lake Constance and the rates obtained agree with those from 210 Pb and 137 Cs methods. The sedimentation rates at different regions of the Mediterranean and Black Sea given in Table 1 are considerably higher than those from the lakes. This probably arises due to the fact that the sediment cores were recovered very near the shores. Table 2 gives the distribution of trace elements across sediment cores of Lake Zurich sediments [12]. The trace element levels is seen to be low and somewhat constant before industrialization and gradually reaching maximum values with the beginning of industrialization. It is further observed that due to strict controls the trace element levels start to decrease after 1980. We analyzed the distribution of various trace elements throughout the sediment cores of the sea of Marmara using ICP-AES. Figure 1 shows the distribution of some of these trace element along the sediment depth. The elements Zn, Cu, P and possibly Pb show near surface enrichment corresponding to the last 200 years as found by 210Pb dating. Since no significant changes were observed in organic and inorganic contents in the sediment cores;enrichment by natural causes can be ruled out. This suggests anthropogenic causes for the observed increases. Towards the end of the eighteenth century, great changes were introduced in the Ottoman Army and Navy. New foundries, armament works, and shipyards were being constructed in and around ˙Istanbul. These activities may be responsible for the enrichment of the above mentioned metallic elements in the sediment cores.

Table 1 Summary of sedimentation rates obtained in our studies at various regions, using different dating methods Mass sedimentation rate(g.cm2 .y−1 ) Sediment core

210 Pb

Lake Zurich Lake constance Sea of Marmara Southern Turkey East Spain North Cyprus Black sea

0.073 ± 0.015 0.11 ± 0.02 0.087 ± 0.012 0.083 ± 0.013 0.21 ± 0.02 0.17 ± 0.03 0.22 ± 0.02

method

137 Cs

time marker

0.07 ± 0.01 0.09 ± 0.01 – – 0.13 ± 0.02 0.19 ± 0.02 0.17 ± 0.3

Varve counting

Sediment traps

0.07 ± 0.02 – – –

– 0.14 ± 0.09 – –

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Table 2 Distributions of trace elements across sediment cores from Lake Zurich [12] Sediment depth (cm) Calender year Cu (ug/g) Zn (ug/g) Pb (ug/g) Cd (ug/g) Hg(ug/g) 0.3 0.6 0.9 1.5 1.8 2.4 3.6 3.9 4.5 5.1 5.4 5.7 6.2 6.5 6.8 7.4 8.2 8.6 9.5 10.1 10.7 11.5 11.8 13.1 15.0 15.3 17.5 19.5 20.3 20.6 22.3 24.5 27.5 28.0 29.7 32.5 40.5 47.0 52.5

1989 1988 1987 1985 1984 1982 1978 1977 1975 1973 1972 1971 1969 1968 1967 1965 1962 1960 1957 1955 1953 1950 1949 1945 1936 1935 1930 1925 1921 1920 1918 1910 1902 1900 1896 1886 1839 1819 1801

48 45 42 47 38 44 49 37 46 37 46 55 55 51 52 61 78 67 67 65 56 65 56 55 53 55 47 47 57 62 67 65 77 57 32 27 20 22

224 235 182 218 197 258 259 232 273 300 308 375 475 398 300 675 587 375 476 350 429 170 347 250 270 375 202 167 205 202 165 150 150 117 82 60 55 55 50

69 68 57 72 62 86 108 97 102 105 109 130 137 116 107 144 104 125 116 150 106 77 134 120 111 142 130 105 138 115 122 112 112 112 115 17 40 12 10

1.1 1.0 0.75 1.0 0.8 1.0 1.5 1.7 2.5 2.5 2.4 3.2 4.0 2.6 6.5 6.25 13.4 nd 19.1 6.2 10.9 2.4 5.4 4.5 4.7 4.5 2.0 1.2 1.3 1.7 1.0 1.0 1.0 1.0 0.5 0.2 0.2 0.2 0.2

0.3 0.4

0.7

0.7

1 0.6 0.7

0.5

0.6 0.5 0.7 0.4

Another interesting example of the environmental impact on sediments was found in the Black Seas Samples. The distribution of some trace elements determined by XRF along the Black Sea sediments is shown in Fig. 2. It is observed that at about 20 cm depth there is a noticable increase in these elemental concentrations. This depth corresponds to about 120 years as determined by radiochronology. Examining different anthropogenic factors causing the increase it was noticed that the Creamian war (1854–1856) with intense sea and land fights

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Fig. 1 Distrubition of some trace elements along sediment depth of sea of marmara sediments

Depth (cm)

took place during this time. Thus suggesting a possible cause of the observed increases. The trace element distribution in the sediment cores from southern Turkey determined by XRF spectroscopy is shown in Fig. 3. The increase in the elemental concentrations at 11 cm depth may be attributed to the industrialization activities in this region. The trace element distrubitions across the sediment depth in the sediment samples from North Cyprus are shown in Fig. 4.

1021

Concentration

Radiochronological Methods as Tools to Study Environmental Pollution

Depth (cm)

Concentration

Fig. 2 The distribution of Ni, Co, Cr, Ca, Mg and S determined by XRF, along the Black sea sediments

Depth (cm) Fig. 3 Trace element distributions in the sediment cores from southern Turkey

H.N. Erten

Concentration

Concentration

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Depth (cm)

Depth (cm)

Fig. 4 Trace element distributions in the sediment cores from North Cyprus

A steady increase in elemental concentrations is observed at 24 cm depth corresponding to about 80 years and continue until the surface. Cyprus in known to be have rich reserves of copper mines. After 1974 the mining companies stoped their activities. As a result the region become a serious environmental disaster area. The mining activities as well as the remains of the copper mine works may be the primary sources of elemental pollution observed.

References 1. Goldberg ED (1963) Radioactive Dating. IAEA STI/PUB/68, Vienna, Austria, p 121 2. Krishnaswami S, Lal D, Martin JM, Meybeck M (1971) Geochronology of lake sediments. Earth Planet Sci Let 11:407–414 3. Robbins JA, Edgington D (1975) Determination of recent sedimetation rates in lake Michigan using Pb-10 and Cs-137. Geochim Cosmochim Acta 39:285–304 4. Smith PP, Valton A (1980) Sediment accumulation rates and geochronologies measured in the Saguenay Fjord using the Pb-210 method. Geochim Acta 44:225–240 5. Erten HN, von Gunten HR, Rössler E, Sturm M, Schweiz Z (1985) Dating sediments from lake Zurich (Switzerland) with 210 Pb and 137 Cs. Schweiz Z. Hydrol 47:5–11 6. von Gunten HR, Sturm M, Erten HN, Rössler E, Wegmüller F (1987) Sedimentation rates in the central lake Constance determined with 210 Pb and 137 Cs. Schweiz Z Hydrol 49:275–283 7. Evans G, Erten HN, Alavi SA, von Gunten HR, Ergin M (1989) Superficial deep-water sediments of the Eastern Marmara basin. Geo-Marine Lett 9:27–36 8. Tadjiki S, Erten HN (1994) Radiochronology of sediments from Mediterranean sea using natural 210 Pb and 137 Cs. J Radionanal Nucl Chem 181:447–459 9. Gökmen A, Yıldız M, Erten HH, Saliho˘glu I (1996) Dating of sea of Marmara sediments by a uniform mixing model. J Environ Radioactivity 33:91–104 10. Erten HN (1997) Radiochronologies of lake sediments. Pure Appl Chem 69(1):71–76 11. Ayçık GA, Çetaku D, Erten HN, Salihlio˘glu I (2004) Dating of Black sea sediments from Romanian coast using natural Pb-210 and fallout Cs-137. J Radioanal Nucl Chem 259:177– 180 12. von Gunten HR, Sturm M, Moser RN (1997) 200-year record of metals in lake sediments, their history, influence factors, regional differences. Environ Int. 31:63–75

Are Certain Invertebrate Species Sensitive Bioindicators of the Air Pollution? Liliana Vasiliu-Oromulu, Viorica Honciuc, Sanda Maican, Cristina Munteanu, Minodora St˘anescu, Cristina Fiera, Mihaela Ion, and Dorina Purice

Abstract The LIFE 02ENV/RO/000461 project is dedicated to the research of the flora and invertebrate fauna in downtown Bucharest, the city area most affected by intense car traffic and the consequent air pollution. The pilot zone is represented by three public parks (Izvor, Cismigiu and Unirea Parks). The zoological samples were collected from the herbaceous layer, from native and ornamental plants and from the soil, according to a transect method, from those park areas closest to the polluted downtown. The preliminary results revealed a change in invertebrate biodiversity. Some of the dominant species in the herbaceous layer are represented by Frankliniella intonsa, Haplothrips niger, Bagnalliella yuccae (Ord. Thysanoptera) Oulema melanopus and Labidostomis longimana (Ord. Coleoptera: Chrysomelidae). The Curculionidae species are present in the centre of the parks, the edges being populated with Apionidae species (Ord. Coleoptera). In the soil, Lithobiomorpha were more frequent than the other orders of centipedes. The Acari: Parasitus beta, Rhodacarellus pespicuus (Mesostigmata), Glycypagus sp. (Prostigmata) and Tectocepheus sarekensis, Ceratozetes minutissimus (Oribatida) and Cyphoderus bidenticulatus, Protaphorura quadrioculata (Collembola) are characteristic species. Could the dominant species be bioindicators of air pollution? A significant part of the project is dedicated to the study of heavy metal concentrations in those invertebrate species that act as bioindicators responding to the condition of the urban environment. Keywords Air pollution · Bioindicator · Invertebrata species

1 Introduction Few researches have been carried). out on the effects of air pollution on invertebrates’ fauna.

L. Vasiliu-Oromulu (B) Romanian Academy Institute of Biology, Spl. Independentei 296, Bucharest-6, Romania e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_97,

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Thysanoptera species Frankliniella intonsa and Thrips tabaci were considered resistant thrips in the most polluted industrial zone of Romania [4]. In a study of variation in antioxidant enzyme activity as a response to heavy metal pollution in four species of beetles representing carnivores, carrion eaters, omnivores and phytophagous, a Curculionidae specie Phyllobius betulae revealed a positive correlation with Pb concentration in birch leaves [5]. The Coleoptera families most frequent by roadsides are Carabidae, Curculionidae, Sirphidae and Tenebrionidae [9]. Pollutants in the form of acid depositions which contain SO2− 4 , NOx , H+ , heavy metals and some organic compound are not homogeneous distributed on the urban habitat. Airborne pollutants affect soil collembola both directly and as well as indirectly [8]. Hopkin [2] shows that with the exception of copper, differences in the concentrations of metals (Pb and Cd) in the tissues of Lithobius variegatus (Chilopoda) display a weak correlation with the degree of contamination of the site from which they were collected. Mesostigmats predatory mites are well suited as bioindicators. They are abundant species rich in variety of biotopes and play a key role in energy flow and the nutrition web of soil ecosystems. Additionally they are sensitive to human impact on soil and especially to the air pollution [7].

2 Material and Methods The pilot area is represented by three parks Cismigiu, Izvor and Unirea located in downtown Bucharest, polluted by the intense car traffic which is the source of 70% of air pollution. On top of that local industrial pollution (heavy metals, SO2 , powders in suspension) exceeds standard levels (Figs. 1, 2, and 3). The zoological researches carried out on transect from the edge – more exposed to air pollution – to the centre. The number of samples is statistically determined for each group.

Fig. 1 Cismigiu Park

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Fig. 2 Izvor Park

Fig. 3 Unirea Park

The invertebrate fauna was investigated in the herbaceous layer, by entomological sweep-net (30 cm), with five samples from each site (one sample = 50 sweeps) for Thysanoptera, Curculionidae, Chrysomelidae and from the canopy branch beating for Curculionidae. For the study of centipedes soil samples were employed (area 25 × 25 cm, depth 10 cm). Leaf litter, when present, was sampled together with the upper layer. The number of samples per each park was approximately proportional to its area (Izvor Park 25 samples – five on each side and five in the median zone; Unirea Park 12 samples – four on each of the two longer sides and four in the median zone; Cismigiu Park – 10 samples – five along the main alley and five on the patches across the manmade lake). Acari (Oribatida, Mesostigmata+Prostigmata) and Collembola from the soil were collected with MacFadyen borer, 10 samples from each site, the extraction methods being characteristic for each group.

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3 Results and Discussions The project was guided by priority tasks: defining bioindicators of air pollution, the biodiversity, the environmental management plants, a long-term monitoring and reporting system. Green spaces need to be managed in the context of an overall urban strategy. Urban faunistical communities are very efficient users of natural resources. The preliminary on a transect results revealed a changing in invertebrate biodiversity, the reduction of the species spectrum, the low number of populations and morphological changes especially on insects. Thysanoptera, the numerically dominant insects in the invertebrate communities from grassland ecosystems, are sensitive bioindicators of the climatic changes and of the air pollution [3, 10, 11]. The specific structure in the Izvor and Cismigiu parks is low, 15 species (19.23% from the total of characteristic praticolous species), which belong to the two trophodynamic modules, primary consumers (93.33%) and secondary ones (6.67%) (Tables 1 and 2, Figs. 4, 5, and 6). The numerical density by sweep method presents a monthly dynamics, varying between 50 and 860 ind/m2 in the Izvor and between 354 and 1,222 ind/m2 in Cismigiu with a pick in July (Figs. 4, 5, 6). The species Frankliniella intonsa (Trybom, 1895) (Fig. 7), was dominant in all parks with a relative abundance 54–81%. The thrips community in Cismigiu Park is more balanced due to the presence of both phytophagous and zoophagous species (Aeolothrips intermedius, A. fasciatus). Among the species of the thrips community Frankliniella intonsa and Thrips tabaci were identified in other grasslands near industrial areas in Romania as species resistant to different air pollutants [4]. This two species are vector for some viruses belonging to the Bunyaviridae Family. The biological effects of the pollutants on Frankliniella intonsa consisted of various decolourisation of different body parts, high variations in body dimensions, numerous individuals with monstrosity of the antennae, facts not observed in our previous studies from mountainous, non-polluted grasslands [10, 11]. By the roadside of the transect on the ornamental plants Yucca filamentosa, the thrips Bagnalliella yuccae Hinds, 1902 was not found, but the species were abundant on the same plant, in the middle of the park. Haplothrips niger was taken in high numbers from Trifolium pratense in order to be analyzed regarding the concentration of pollutants. The ecological indices of thrips populations (Tables 1 and 2) revealed low Shannon-Weaver values corresponding to the low equitability, on the Izvor and Cismigiu Parks, probably due to the air pollution? In the future, the heavy metals analysis on Frankliniella intonsa, Haplothrips niger and Bagnalliella yuccae could provide the accumulation of the pollutants and show which species is sensitive bioindicators of the air pollution. The Coleoptera Order is represented in the studied sites (Izvor, Cismigiu and Unirea Parks) by species belonging to the following families: Carabidae

14 94 22 8 2 140

32 694 8 4 18 104 860

2 10 12 2

June Aeolothrips intermedius Frankliniella intonsa Thrips atratus Thrips tabaci Haplothrips aculeatus

July Aeolothrips intermedius Frankliniella intonsa Thrips tabaci Haplothrips aculeatus Haplothrips leucanthemi Haplothrips niger

August Aeolothrips intermedius Chirothrips manicatus Frankliniella intonsa Thrips sp.

x/m2

H(S) 0.2 2.0 3.2 0.2

25.7 726.8 1.2 0.3 3.2 244.3 1,123.0

9.8 166.8 19.2 1.7 0.2 399.5 H(S)

s2

1.01 0.4 1.4 1.8 0.4

5.1 27.0 1.1 0.5 1.8 15.6 33.5

3.1 12.9 4.4 1.3 0.4 20.0 1.46

STDEV

0.09 0.28 0.36 0.09

1.01 5.39 0.22 0.11 0.36 3.13 6.70

0.63 2.58 0.88 0.26 0.09 4.00

s

Hmax 224 141 149 224

158 39 137 137 99 150 39

224 137 199 163 224 143 Hmax

CV

2.58 1.60 8.00 9.60 1.60

25.60 555.20 6.40 3.20 14.40 83.20 688.00

11.20 75.20 17.60 6.40 1.60 112.00 2.32

f.w/m2

0.20 1.00 1.20 0.20

3.20 69.40 0.80 0.40 1.80 10.40 86.00

1.40 9.40 2.20 0.80 0.20 14.00

d.w./m2

E% 0.04 0.20 0.24 0.04

0.64 13.88 0.16 0.08 0.36 2.08 17.20

0.28 1.88 0.44 0.16 0.04 2.80 E%

Energ. metab. ml O2 /m2

Table 1 The structural and functional indices of the thrips populations – Izvor Park

39.09 4 20 24 4

4 81 1 0 2 12 100

10 67 16 6 1 100 62.93

A%

20 40 40 40

40 100 40 40 60 80

20 40 40 40 20

C%

−0.056 −0.140 −0.149 −0.056

−0.053 −0.075 −0.019 −0.011 −0.035 −0.111 −0.304

−0.100 −0.116 −0.126 −0.071 −0.026 −0.440

pi log pi

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2 22 2 50

2 8 2 12

Haplothrips aculeatus Haplothrips niger Tubulifera larva

September Frankliniella intonsa Haplothrips aculeatus Haplothrips niger

x/m2

H(S) 0.2 0.7 0.2 0.7 H(S)

0.2 4.7 0.2 6.5

s2

2.04 0.4 0.8 0.4 0.8 1.25

0.4 2.2 0.45 2.5

STDEV

0.09 0.17 0.09 0.17

0.09 0.43 0.09 0.51

s

Hmax 224 105 224 70 Hmax

224 99 224 51

CV

2.81 1.60 6.40 1.60 9.60 1.58

1.60 17.60 1.6 40.00

f.w/m2

Table 1 (continued)

0.20 0.80 0.20 1.20

0.20 2.20 0.2 5.00

d.w./m2

E% 0.04 0.16 0.04 0.24 E%

0.04 0.44 0.04 1.00

Energ. metab. ml O2 /m2

72.56 17 67 17 100 78.97

4 44 4 100

A%

20 60 20

20 60 20

C%

−0.130 −0.117 −0.130 −0.377

−0.056 −0.157 −0.056 −0.613

pi log pi

1028 L. Vasiliu-Oromulu et al.

0.3 0.8 0.8 0.2 1,069.3

4 4 4 2 354

2 4 2 970 10 14 36 184 1,222

10 14 258

July Aeolothrips fasciatus Aeolothrips intermedius Chirothrips molestus Frankliniella intonsa Thrips tabaci Haplothrips aculeatus Haplothrips leucanthemi Haplothrips niger

August Aeolothrips intermedius Anaphothrips atroapterus Frankliniella intonsa

H(S) 3.0 9.8 339.7

H(S) 0.2 0.3 0.2 7,217.5 2.0 2.3 34.8 254.8 1,1206.7

0.2 668.0 43.5

2 240 100

s2

June Aeolothrips intermedius Frankliniella intonsa Hemianaphothrips articulosus Limothrips denticornis Thrips physapus Haplothrips angusticornis Haplothrips niger

x/m2

1.01 1.7 3.1 18.4

1.16 0.4 0.5 0.4 85.0 1.4 1.5 5.9 16.0 105.9

0.5 0.9 0.9 0.45 32.7

0.4 25.8 6.6

STDEV

0.35 0.63 3.69

0.09 0.11 0.09 16.99 0.28 0.30 1.18 3.19 21.17

0.11 0.18 0.18 0.09 6.54

0.09 5.17 1.32

s

Hmax 173 224 71

Hmax 224 137 224 88 141 108 164 87 87

137 224 224 224 92

224 108 66

CV

3.00 8.00 11.20 206.40

2.81 1.60 3.20 1.60 776.00 8.00 11.20 28.80 147.20 977.6

3.20 3.20 3.20 1.6 283.20

1.60 192.00 80.00

f.w/m2

1.00 1.40 25.80

0.20 0.40 0.20 97.00 1.00 1.40 3.60 18.40 122.2

0.40 0.40 0.40 0.2 35.40

0.20 24.00 10.00

d.w./m2

E% 0.20 0.28 5.16

E% 0.04 0.08 0.04 19.40 0.20 0.28 0.72 3.68 24.44

0.08 0.08 0.08 0.04 7.08

0.04 4.80 2.00

Energ. metab. ml O2 /m2

Table 2 The structural and functional indices of the thrips populations- Cismigiu park

33.78 2 3 54

41.20 0 0 0 79 1 1 3 15 100

1 1 1 1 100

1 68 28

A%

40 20 100

20 60 40 100 40 60 60 100

40 20 20 20

20 100 100

C%

−0.035 −0.045 −0.145

−0.005 −0.008 −0.005 −0.080 −0.017 −0.022 −0.045 −0.124 −0.305

−0.022 −0.022 −0.022 −0.013 −0.348

−0.013 −0.114 −0.155

pi log pi

Are Certain Invertebrate Species Sensitive Bioindicators of the Air Pollution? 1029

September Frankliniella intonsa Thrips tabaci Haplothrips niger

Hemianaphothrips articulosus Haplothrips aculeatus Haplothrips leucanthemi Haplothrips niger

18 4 2 24

4 14 184 478

4

x/m2

H(S) 9.2 0.3 0.2 11.3 H(S)

0.8 4.8 185.8 836.2

0.8

s2

1.42 3.0 0.5 0.4 3.4 1.04

0.9 2.2 13.6 28.9

0.9

STDEV

0.61 0.11 0.09 0.67

0.18 0.44 2.73 5.78

0.18

s

Hmax 169 137 224 140 Hmax

224 156 74.1 60

224

CV

2.81 14.40 3.20 1.60 19.20 1.58

3.20 11.20 147.2 382.40

3.20

f.w/m2

Table 2 (continued)

1.80 0.40 0.20 2.40

0.40 1.40 18.4 47.80

0.40

d.w./m2

E% 0.36 0.08 0.04 0.48 E%

0.08 0.28 3.68 9.56

0.08

Energ. metab. ml O2 /m2

50.73 75 17 8 100 65.67

1 3 38 100

1

A%

40 40 20

20 20 100

20

C%

−0.094 −0.130 −0.090 −0.313

−0.017 −0.045 −0.160 −0.429

−0.017

pi log pi

1030 L. Vasiliu-Oromulu et al.

Are Certain Invertebrate Species Sensitive Bioindicators of the Air Pollution?

1031

82 34

june july august september

20 41

3 1 0 Izvor Park

Fig. 4 The standard deviation of Thysanoptera fauna, Izvor 300

Fig. 5 The standard deviation of Thysanoptera fauna, Cismigiu

106 200

june july august september

100

33

29 3

0 Cismigiu Park

860 1000 140 50

12

500

Izvor Park Cismigiu Park

354 june

1222 july

478 august

24

0

september

Fig. 6 Numerical density of Thysanoptera populations

(Calosoma sicophanta), Malachiidae (Malachius bipustulatus), Coccinellidae (Coccinella septempunctata, Thea vigintiduopunctata, Propylaea quatuordecimpunctata, Adalia bipunctata), Cerambycidae (Plagionotus floralis), Elateridae, Nitidulidae, Curculionidae, Apionidae, Chrysomelidae (Oulema melanopus, Labidostomis longimana, Cryptocephalus octacosmus, Cryptocephalus sericeus,

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Fig. 7 Frankliniella intonsa

The list of Thysanoptera fauna

Species Aeolothrips intermedius Aeolothrips fasciatus Anaphothrips atroapterus Chirothrips manicatus Chirothrips molestus Hemianaphothrips articulosus Frankliniella intonsa Limothrips denticornis Thrips atratus Thrips physapus Thrips tabaci Haplothrips aculeatus Haplothrips angusticornis Haplothrips leucanthemi Haplothrips niger

Cismigiu Park + + +

Izvor Park +

+ + + + +

+ + +

+ + + + + +

+ + + +

Gastrophysa polygoni, Gonioctena fornicata, Phyllotreta nemorum etc.). Most of the above mentioned species have a large distribution in Romanian fauna, such as: Malachius bipustulatus, Coccinella septempunctata, Oulema melanopus, Labidostomis longmana, Cryptocephalus sericeus, Gastrophysa polygoni. In the invertebrate soil fauna, Centipedes, Collembola and Acari were most representative. The small number of collected centipedes, despite the relatively large number of samples, does not allow us to state anything about the effect of pollution. It is possible that the land type, size, management and fragmentation, has much more to do with the very low densities of centipede (low as 1.3 ind/m2 in Unirea, higher in Izvor up to 5.76 ind/m2 ), than air pollution. Collembola are suitable indicators of the effects of airborne pollutants at the ecosystem level.

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The density and species richness decreased in areas affected by airborne pollutants. Aggregation of some species Cyphoderus bidenticulatus, Protaphorura quadrioculata increased, whereas the frequencies of others Isotoma anglicana, Lepidocyrtus cyanaeus decreased. L. cyanaeus and I. anglicana may be affected by the airborne pollutants directly through a decreased growth rate, reproduction or survival [9] or indirectly through a change in food abundance or a decrease in predators. It is possible that these two species to be sensitive to pollution, because they are unable to avoid polluted food or also their preferred fungal species are sensitive to metals. As many as 50% of individuals from more polluted sites exhibited abnormally higher occurrences of non genetic purple, reddish- purple and dark- reddish body colours and decreased occurrences of the whitish and yellowish pigmentation that is normal in animals from unpolluted areas [6]. The effects of air pollution on soil inhabiting acari-oribatids mites in the three parks revealed only 38 species in the species community The urban environment generally minimizes the number of species in central urban regions. There are characteristic species represented by very small species as Tectocepheus sarekensis, Ceratozetes minutissimus and Punctoribates punctum. Taxonomical structure of the gamasids mites in the Izvor Park was formed by six families and seven species. Total numerical density was 1,040 ind/m2 (Table 3). The dominant species are: Asca bicornis, (453 ind/m2 ), Ameroseius fimetorum (320 ind/m2 ) and Amblyseius obtusus (173 ind/m2). The effect of the heavy metals of the gamasid mites from the soil is visible in the decrease in species number, the decrease number of individuals, the changes of the mature-immature ratio, the changes of the taxonomical structure and the changes of their spatial and temporal distribution in the soil [1]. 1,333 ind/m2 was recorded by five species belonging to four families in the Cismigiu Park (Table 3). Species with the highest density were the following: Rhodacarellus perspicuus (500 ind/m2 ), Rhodacarellus silesiacus (200 ind/m2) and Hypoaspis aculeifer (200 ind/m2).

The list of Gamasids fauna Izvor Park

Cismigiu Park

Unirea Park

Parasitidae Parasitus beta Ameroseiidae Ameroseius fimentorum Phytoseiidae Amblyseius obtusus Rhodacaridae Rhodacarellus perspicuus Asca bicornis Pseudolaelapidae Pseudolaelaps doderoi Laelaptidae Hypoaspis aculeifer

Parasitidae Parasitus beta Ameroseiidae Ameroseius fimentorum Rhodacaridae Rhodacarellus perspicuus Rhodacarellus silesiacus Laelaptidae Hypoaspis aculeifer

Ameroseiidae Ameroseius fimentorum Phytoseiidae Amblyseius obtusus Amblyseius meridionalis Rhodacaridae Rhodacarellus denticulatus Asca bicornis Pseudolaelapidae Pseudolaelaps doderoi Laelaptidae Hypoaspis aculeifer

1034 Table 3 Numerical densities/m2 of the gamasids mites

L. Vasiliu-Oromulu et al. Sites

May

August

Total

Izvor Cismigiu Unirea

440 600 450

600 733 1, 067

1,040 1,333 1,517

In the Unirea Park seven species of gamasids mites were identified belonging to five families. Their numerical density was 1,517 ind/m2 (Table 3). The dominant species are: Asca bicornis (100 ind/m2) and Ameroseius fimetorum (100 ind/m2).

4 Conclusions • The pilot area is represented by three parks located in downtown Bucharest, highly polluted by traffic cars (the parks of Cismigiu, Izvor and Unirea). • In each park the investigations were realised on a transect from the edge -more exposed to air pollution- to the centre. • In the herbaceous layer Thysanoptera, Chrysomelidae, Curculionidae present a change in their biodiversity on the transect. • Thysanoptera shows to be very sensitive to the pollutants. Frankliniella intonsa is the most resistant species; it could be the best bioindicators of the air pollution. • The monthly dynamics of thrips communities presents the pick of ecological indices value in July in Cismigiu Park; the spatial dynamics shows Cismigiu with the height biodiversity. • The Chrysomelidae species in the three parks are the followings: Oulema melanopus, Labidostomis longimana, Cryptocephalus octacosmus, Cryptocephalus sericeus, Gastrophysa polygoni, Gonioctena fornicate and Phyllotreta nemorum. • The diversity of curculionids fauna was low, only four species in a very few specimens. Therefore, we not recommend Curculionidae as bioindicators. At Curculionoidea Superfamily level specimens of the Apionidae family are more suitable, as they are more numerous. • Collembola are also suitable bioindicators for assessing ecological changes caused by pollutants. Collembola communities react sensitively to airborne pollutants and often do it in advance of other components of soil terrestrial ecosystems. • The small number of centipedes found till now does not allow us to state anything about the effect of pollution on them. • Small species of acari-oribatids are characteristics: Tectocepheus sarekensis, Ceratozetes minutissimus and Punctoribates punctum. • The common species of gamasids mites for the all three parks are: Ameroseius fimetorum and Hypoaspis aculeifer. The numerical density of the identified gmasids is much decreased in comparison with natural ecosystems where the values are higher (50,000 ind/m2).

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• A significant part of the project is dedicated to the study of heavy metal concentrations in those invertebrate species that act as bioindicators responding to the condition of the urban environment. • The methods that will be used in the next years of project include monitoring, assessment of exposure and the evaluation of effects in biota. Acknowledgments The authors are grateful to the National Administration of Meteorology, Environmental Protection Agency of Bucharest, Urban and Metropolitan Centre of Bucharest, Public Health Institute and Meteo France for collaboration.

References 1. Georgescu A. (1982) – Populatia de acarieni (Gamasida- Mesostigmata) liberi din unele tipuri de soluri forestiere. Teza de doctorat, Cluj 2. Hopkin SP, Martin MH (1983) Heavy metals in the centipedes Lithobius variegatus (Chilopoda). Environ Pollut 6B:309–318 3. Ionescu AL, Barnea M, Chiosil˘a I, Gavril˘a L, Ghinea L, Grou E, Gusic V, Mih˘ailescu A, Mohan, GH, Moscalu T, Popescu A, Pora EA, Rabega C, Râpeanu MD, Sanda V, Stoian V, Serb˘ ¸ anescu GH, Vasiliu L, Vl˘adescu C (1973) Efectele biologice ale polu˘arii mediului, cap. Mediul s¸i fauna, Acad RSR, pp 177–193 4. Kirk DJW (1997) In Lewis Trevor 1997, Thrips as crops pests, Cab International; 244 (ref. VASILIU- OROMULU, 1994, Effect of pollution on thrips populations) 5. Migula P, Laszczyca P, Augustyniak M, Wilczek G, Rozpedek K, Kafel A, Wołoszyn M (2004) Antioxidative defence enzymes in beetles from a metal pollution gradient. Biologia 59/5:645–654 6. Peter HU (1984) Über den Einfluss von Luftverunreinigungen auf Okosysteme. IV. Isopoda, Diplopoda, Collembola und Auchenorrhyncha aus Bodenfallen in der Umgebung eines Dungemittelwerkes. Wiss Z Univ Jena Nat Wiss Rep 33:291–307 7. Ruf A, (1997) Life-history strategies of predatory mites and characterisation of soil. A tool for bioindication of soil quality. Abh. Ber.naturkundemus.Gorlitz 69, 2: 209–216 8. Rusek J, Marshall Valin G (2000) Impacts of airborne pollutants on soil fauna. Ann Rev Ecol Syst 31:395–423a 9. Tischler W (1980) Biologie der Kulturlandschaft. Eine Einführung. Gustav Fischer Verlag, Stuttgart 10. Vasiliu-Oromulu L (1994) Ecological monitoring in thysanopterology. Courier Forschungsinstitut Senckenberg, Frankfurt am Main 178:101–106 11. Vasiliu-Oromulu L, B˘arbuceanu D, and Bianu E (2009) Thysanoptera capability for biomonitoring of urban polluted green spaces (Insecta: Thysanoptera). Acta Entomologica Serbica, 14(2):185–194

Determination of Heavy Metal Pollution in Some Honey Samples from Yozgat Province, Turkey Ahmet Aksoy, Zeliha Leblebici, and Yavuz Ba˘gci

Abstract The concentrations of heavy metals (Pb, Cd, Fe, Ni and Zn) in 21 different honey samples collected from 21 different farms in Yozgat, Turkey, were determined by ICP-OES after microwave digestion. It is observed that metal concentrations in honey samples ranged between 0.06 and 0.139 μg g−1 for Cd 0.03 and 1.20 μg g−1 , for Zn 0.035 and 1.690 μg g−1 , for Pb 0.006 and 2.332 μg g−1 for Ni and 0.703 and 8.150 μg g−1 for Fe. Although, the honey samples were in good quality, they were not free of heavy metals. It is interesting that the stations in which the metal concentration is maximum within the examined honey samples are near the settlement regions where the traffic and industry is especially intensive. According to these results; it is concluded that the heavy metal concentrations in honey samples excluding some stations which are close to the settlement regions are in acceptable borders. Keywords ICP-OES · Microwave · Honey · Heavy metal · Yozgat

1 Introduction Honey is a sweet, viscous liquid that bees produce from nectar collected from plant nectaries and store as food. As a food stuff used for healing purposes, honey must be free of objectionable contents. It should contain only small amounts of pollutants, such as heavy metals. Heavy metals are important in the daily diet, because of their essential nutritious value and possible harmful effects. Metals like iron, copper, zinc, and manganese are essential metals since they play an important role in biological systems; whereas lead, cadmium, etc. are non-essential metals which can be toxic even in trace amounts. A. Aksoy (B) Faculty of Art and Science, Department of Biology, Erciyes University, 38039 Kayseri, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_98,

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Turkey is an important country among the honey producing countries, since it is suitable for apiculture in terms of the flowers. In 1995, there were 3,686,000 hives, representing a yearly increase of 4.1%. Honey production in that year was 59.207 metric tons and increased to 80.000 tons in 1997. Honey is mainly produced in the middle and western regions of Turkey [4]. In addition, honey is a good indicator for the chemical constituents of the plants and their monitoring. Many researchers [20, 22, 19, 21, 16, 15, 12, 1, 6, 9] have published studies about trace elements in honey. Plasma Optical Emission Spectrometer (Inductively Coupled Plasma Optical Emission Spectrometry = ICP-OES) is suitable for heavy metal determination and it is preferred by many research centres [17, 11]. According to different researchers, using heavy metal contents of honey samples in determining the quality of environment is accepted as a valid method. In this study it is aimed to determine cadmium, nickel, zinc, lead, and iron contents of honey samples which are produced in the different regions of Yozgat province (Table 1) and to examine the determined results to determine whether they are within acceptable borders or not from the point of view of human health.

Table 1 The localities where the honey samples are taken Region no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

Region that the honey is taken Çandir county, near vineyard and garden Çandir county Çayiralan county, near arable land Çandir county near garden Çayiralan county, near wheat land Çayiralan county, near wheat land Bo˘gazliyan center Ba¸shoroz village (Bo˘gazliyan) Abdilli village (Bo˘gazliyan) Uzunlu village, near vineyard and garden(Bo˘gazliyan) Uzunlu village, near wheat land (Bo˘gazliyan) Uzunlu village, (Bo˘gazliyan) Çayiralan county center, steppe land Yozgat- Sivas highway,1.280 m Yozgat- Sivas highway,1.388 m Behind the watering pond, 1.381 m Near the Cehirlik region, 1.324 m Underside the New industry, 1.279 m Yozgat center, 1.251 m Gülpinar village, (Sefaatli), ¸ 1.037 m Yozgat center, 1.270 m

Distance to highway 2 km 1 km 4 km 1 km 3 km 2 km 1 km 500 m 300 m 200 m 3 km 4 km 3 km 200 m 50 m 2 km 9 km Near way 40 m Near way 10 m Near way 20 m 150 m

Determination of Heavy Metal Pollution in Some Honey Samples

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2 Materials and Methods 2.1 Apparatus A Varian Liberty Series II ICP-OES Spectrometer was used for metal determination. The instrument was operated in the following conditions: RF frequency, 27 MHz; operating power, 1.2 kW; pump rate, 15 rpm; plasma argon flow rate,12 l min−1 ; carrier argon flow rate, 0.75 L min−1 ; The Standard one-piece torch; ultrasonic nebuliser type Glass concentric; and nebulisation pressure, 160 kPa. A CEM Marsh X microwave digestion system (maximum pressure 600 psi, maximum temperature 280◦ C) was used. Teflon reaction vessels were used in all the digestion procedures. The reaction vessels were cleaned using 10 mL of concentrated nitric acid before each digestion.

2.2 Reagents and Solutions Standard stock solutions of different metal ions at a 1,000 μg ml−1 concentration were prepared from atomic absorption spectroscopic grade chemicals and used to make working solutions by appropriate dilution. Reagent-grade nitric acid, double distilled water, and the surfactant Merck were used.

2.3 Glassware Cleaning All glassware was washed with Merck, waited in 0.1 N nitric acid for 48 h and rinsed with double distilled water prior to use in order to avoid potential contamination.

2.4 Sample Preparation Natural honey samples were collected from 21 different localities in Yozgat in 2006 (Table 1). 1 kg honey samples were transferred to pots which had been sterilized before. Microwave digestion procedure was applied to the honey samples. 0.5 g of each sample was digested with 10 mL of HNO3 (65%) in a microwave digestion system. All sample solutions were clear. Digestion conditions for the microwave system were applied at 350 psi, 180◦C for 20 min. Afterwards, the digestion sample was diluted to 25 mL with deionized water. The samples were analyzed in triplicate. SPSS statistical program was used to calculate standard deviations and means.

3 Results and Discussion It is determined that the heavy metal contents of the samples decrease as the distance from settled regions increases, as seen in Table 2. ANOVA test and Duncan Test as Post Hoc were applied to the statistical analyses of the averages and it was found

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Table 2 Average Cd, Pb, Fe, Zn and Ni concentrations in the honey samples (μg g−1 ) and their standard deviations Sample

Zn

Pb

Fe

Cd

Ni

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

0.655±0.01b 0.882 ±0.03bc 0.963±0.01bc 0.257±0.02ab 1.207±0.05c 0.225 ±0.01ab 0.030±0.01a 0.143 ±0.02ab 0.242±0.04ab 0.536±0.01b 0.236±0.04ab 0.695±0.02b 0.738±0.01b 1.049±0.03bc 1.089±0.06bc 0.904±0.03bc 0.736±0.02b 1.096±0.01bc 0.791±0.02b 0.440±0.01b 0.149±0.03ab

0.634 ±0.02b 1.690 ±0.02c 1.110±0.05bc 0.362±0.01ab 1.090±0.02bc 0.106 ±0.01ab 0.035 ±0.04a 0.600±0.03b 0.402 ±0.07ab 0.144±0.04ab 0.284 ±0.02ab 0.160 ±0.01ab 0.553 ±0.05b 0.236 ±0.03ab 0.329±0.03ab 0.247 ±0.01ab 0.228 ±0.04ab 0.332±0.01ab 0.219 ±0.02ab 0.200±0.03ab 0.335±0.01ab

1.640±0.03b 2.281±0.02b 7.881±0.03bc 0.885±0.01ab 8.150±0.05c 0.851±0.01ab 0.703 ±0.01a 1.462 ±0.03b 1.086 ±0.02b 1.792±0.04b 0.834±0.01ab 1.349±0.01b 1.545 ±0.03b 6.901±0.02bc 7.429±0.01bc 4.655±0.05bc 4.344±0.03bc 5.995±0.02bc 4.681±0.05bc 3.915±0.01bc 5.331±0.04bc

0.099 ±0.01ab 0.136 ±0.03ab 0.103±0.01ab 0.100±0.04ab 0.101 ±0.01ab 0.104 ±0.02ab 0.060 ±0.01a 0.121±0.04ab 0.105 ±0.04ab 0.099±0.01ab 0.099±0.02ab 0.105±0.03ab 0.121±0.04ab 0.115 ±0.02ab 0.139 ±0.07b 0.095±0.01ab 0.113±0.01ab 0.110±0.02ab 0.101±0.01ab 0.099±0.03ab 0.129 ±0.03ab

0.134±0.05ab 0.426±0.03ab 2.332±0.09b 0.566±0.01ab 0.612 ±0.04ab 0.444±0.01ab 0.540 ±0.04ab 0.761 ±0.02ab 0.006±0.01a 0.319±0.02ab 0.518 ±0.01ab 0.393±0.02ab 0.268±0.03ab 0.722 ±0.02ab 0.799±0.04ab 0.721±0.02ab 0.718 ±0.01ab 1.027 ±0.03ab 0.738 ±0.02ab 0.707 ±0.01ab 0.769 ±0.01ab

For a given metal, mean concentrations followed by the same letter are not significantly different (p<0.05)

that our results are meaningful in the test according to p<0.05. The results of the test are given in Table 2. Codex Alimentarius Commission and The Turkish Food Codex (Official comminique number; 2002/63) has determined the maximum Cd, Zn, Pb, and Fe values that can be found in nutrients such as fruit juices and nectars [3, 5].

Codex Cd Zn Pb Fe

Our results 0.03 μg g−1 5 μg g−1 0.05 μg g−1 15 μg g−1

0.060–0.139 0.030–1.200 0.035–1.690 0.703–8.150

The higher Cd concentrations were found to be 0.139 μg g−1 in station 15. Cadmium is a non-essential toxic heavy metal that threatens human health seriously. It is seen that the values that are obtained from the stations for this element exceeds the given limits and the samples suffer Cd pollution. The most important reason that the pollution is high in the stations can be that they are close to the roadside. The

Determination of Heavy Metal Pollution in Some Honey Samples

1041

most important sources that cause cadmium pollution are fossil fuels of vehicles, metal business, plastics, house tools construction, and sewers [18]. Cadmium contents of honey samples in the literature have been reported as 0.008–0.027 μg g−1 [19], 0.11–0.18 μg g−1 [12], 0.078–0.222 μg g−1 [16] 0.005– 0.009 μg g−1 [21], 0.008 μg g−1 [2], <0.002–0.06 μg g−1 [10], respectively. The range of cadmium for the Yozgat province is similar to that reported by M.D. Ioannidou et al. and Demirezen and Aksoy. The level of cadmium of our samples was higher than some of the previous data [19, 21, 2, 10]. In Table 2, when we examine the statistical results obtained for Zn, we see that there are differences between the stations. The highest concentration of Zn is measured at a value of 1.20 μg g−1 at station 5. The most important reason for high pollution here is that it is an agricultural area. It is reported that the most important sources that cause Zn pollution are pesticides, fossil fuels, fertilizers, and metal alloys [18]. The values that are obtained from this study do not exceed these limits. In cases where limits of tolerance are exceeded, stain occurrence in the liver and cirrhosis, nervous system disorders, weakening of the kidney functions are seen and if the necessary medical treatments are not followed, death may occur [13]. Zinc values in honey samples have been reported in the range of 0.18–19.1 μg g−1 [15], 1.293–5.390 μg g−1 [1], 1.15–4.95 μg g−1 [21], 1.6–22.5 μg g−1 [14], 4.17–22.3 μg g−1 [19], respectively. The range of zinc in Yozgat is similar to that reported by Tuzen [21]. When Table 2 is examined for Fe, the highest value is seen station 5 at 8.150 μg g−1 . The reason for high Fe values here can result from soil and plants. The most important sources of Fe pollution are indicated as metal corrosion, digging and drilling [18]. The values that were obtained from this study do not exceed iron limits. Iron values in honey samples have been reported in the range of 0.40–52.51 μg g−1 [15], 3.45–8.94 μg g−1 [21], 0.97–1.91 μg g−1 [2], respectively. The values for the iron contents in our samples are generally at the same level as in the values cited in the literature [21, 2]. When Table 2 is examined for Pb, the highest value is seen in station 2 at 1.690 μg g−1 . The most important reason for the high Pb concentration here can be thought to be vehicles because they are close to the roadside. It is reported that the most important sources of Pb pollution are vehicles, fossil fuels, metal businesses, and refineries [18]. It is seen that the values that are obtained from the stations for this element exceeds the given limits and samples suffer Pb pollution. Lead data of honey samples around the world have been reported at 0.71–1.52 μg g−1 [8], 0.025–0.071 μg g−1 [19], 0.03–0.05 μg g−1 [21], 0.03–0.24 μg g−1 [2] and 0.003–0.04 μg g−1 [10], respectively. The range of lead in Yozgat is similar to that reported by Cerutti et al. [8] and Al-Khalifa and Al-Arify [2]. The low and high nickel concentrations were found to be 0.006 μg g−1 in the honey sample from Abdilli village, Bo˘gazliyan and 2.332 μg g−1 in the honey sample from Yozgat Çayiralan county respectively. Nickel values in the literature have

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been reported at 0.23–0.27 μg g−1 [7], for the honey samples from Italy. The nickel levels in our samples are higher than that reported by Caroli [7].

4 Conclusion The proposed method allows fast determination of the total content of heavy metals (Pb, Cd, Zn, Fe, and Ni) in mineralised honey, by b plasma optical emission spectrophotometry (ICP-OES) after microwave digestion satisfies the requirements of the efficient method that was listed before. The honey in the beehives located close to settled regions can be exposed to home, industrial, and traffic originated pollutants. Therefore, keeping the apiculture activities away from pollution threats is necessary. In conclusion, it is determined that the honey samples produced in Yozgat do not completely lack heavy metals, but they are within acceptable limits for some elements. Honey is an excellent indicator of environmental pollution.

References 1. Aksoy A, Leblebici Z (2006) Concentration of heavy metals in honey samples from Kayseri Province, 18. National Congress of Biology, Aydin, Turkey 2. Al-Khalifa AS Al-Arify IA (1999) Physicochemical characteristics and pollen spectrum of some Saudi honeys. Food Chem 67:21–25 3. Anonymous (1981) Codex alimentarius commission joint FAO/WHO food standards programme recommended European-regional standard 44 4. Anonymous (1997) Annual statistics of Republic of Turkey for 1997. DIE, Ankara, Turkey 5. Anonymous (2002) Turkish food codex, the official communiqué about the determination of food contaminants max level, 63 6. Bogdanov S, Imdorf V, Kilchenmann V, Charriere JD, Fluri P (2003) The contaminants of the bee colony. Bulg J Vet Med 2:59–70 7. Caroli S, Forte G, Lamicelli AL, Galoppi F (2000) Determination of essential and potentially toxic trace elements in honey by inductively coupled plasma-based techniques. Talanta 50:327–336 8. Cerutti S, Orsi RF, Gasquez JA, Olsina R, Martinez L (2003) On-line preconcentration/determination of lead traces in bee honey by inductively coupled plasma optical emission spectrometry (ICP-OES) using a conical minicolumn packed with activated carbon. J Trace Microprobe Tech 21(3):421–432 9. Conti ME (2000) Lazio region (central Italy) honeys: A survey of mineral content and typical quality parameters. Food Control 11:459–463 10. Conti ME, Botre F (2001) Honeybees and their products as potential bioindicators of heavy metals contamination. Environ Monit Assess 69:267–282 11. D’angelo JA, Martinez LD, Resnizky S, Perino E, Marchewsky EJ (2001) Determination of eight lanthanides in apatites by ICP-AES, XRF and NAA. J Trace Microprobe Tech 19:79–90 12. Demirezen D, Aksoy A (2005) Determination of heavy metals in bee honey using by inductively coupled plasma optical emission spectrometry (ICP-OES). Gazi Üniversity J Sci 18(4):569–575 13. Derrell RV (1991) Trace elements in human nutrition, micronutrients in agriculture, SSSA Book Series: 4 USA

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14. Downey G, Hussey K, Kelly JD, Walshe TF, Martin PG (2005) Preliminary contribution to the characterization of artisanal honey produced on the ˙Island of Ireland by palynological and physico-chemical data. Food Chem 91:347–354 15. Hernandez OH, Fraga JMG, Jimenez AI, Jimenez F, Arias JJ (2005) Characterization of honey from the Canary Islands: Determination of the mineral content by atomic absorption spectrometry. Food Chem 93:449–458 16. Ioannidou MD, Zachariadis GA, Anthemidis AN, Stratis JA (2004) Direct determination of toxic trace metals in honey and sugars using inductively coupled plasma atomic emission spectrometry. Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24, Thessaloniki, Greece 17. Lara RF, Wuilloud RG, Salonia JA, Olsina RA, Martinez LD (2001) Determination of low cadmium concentrations in wine by on line preconcentration in a knotted reactor coupled to an inductively coupled plasma optical emission spectrometer with ultrasonic nebulization. Fresenius’ J Anal Chem 371:989–993 18. Markert B (1993) Plant as biomonitors. VCH Press, Weinheim, Germany 19. Przybylowski P, Wilenzy´nka A (2001) Honey as an environmental marker. Food Chem 74:289–291 20. Sevimli H, Bayulgen N, Varinlio˘glu A (1992) Determination of trace elements in honey by INAA in Turkey. J Radioanal Nucl Chem 165:319–325 21. Tuzen M (2002) Determination of some metals in honey samples for monitoring environmental pollution. Fresenius Environ Bull 11:366–370 22. Yilmaz H, Yavuz O (1999) Content of some trace metals in honey from south-eastern Anatolia. Food Chem 65:475–476

Removal of Direct Orange-46 from Aqueous Solutions Using MN-Diatomite Selay Aksoy, Mesut Tekba¸s, Güleda Engin, and Nihal Bekta¸s

Abstract Textile industry wastewater is an important pollution source that contains high concentration of inorganic and organic chemical species. Clay minerals are useful due to their chemical and mechanical stability, high surface area and structural properties. Diatomite is a pa1e-coloured, soft, lightweight sedimentary rock composed principally of silica microfossils of aquatic unicellular algae. Diatomite can be used as an adsorbent in wastewater treatment due to its unique combination of physical and chemical properties such as highly porous structure, low density and high surface area. Naturally occurring low cost diatomite as an adsorbent offers great potential for removing dyes from industrial wastewater. The aim of this work is to evaluate the removal of direct orange-46 from aqueous solution using manganese conditioned diatomite. The results from isotherm studies were evaluated with different isotherm models. The constants and correlation coefficients of these isotherm models for the present system were calculated and compared. Keywords Aqueous · Direct orange-46 · MN-Diatomite · Solution

1 Introduction Coloured dye wastewater occur as a direct result of the production of the dye and also as a consequence of its use in the textile and other industries. Coloured effluents can cause problems in several ways: dyes can have acute and/or chronic effects on exposed organisms in many rivers and waterways. This kind of effluent is also resistant to biological degradation. Therefore removal of such coloured agents from aqueous effluents is a significant environmental issue. Precipitation, ion exchange, solvent extraction, filtration and electrochemical treatment are the conventional methods for the removal of dye from aqueous solutions [1]. All these methods have significant disadvantages such as incomplete ion removal, N. Bekta¸s (B) Environmental Engineering Department, Gebze Institute of Technology, 41400, Gebze, Turkey e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_99,

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high-energy requirements and production of toxic sludge or other waste products that require further disposal. Adsorption processes have gained considerable attention in the recent years to remove hazardous materials from wastewaters. Adsorption is a useful and simple technique, which allows gathering of both kinetic and equilibrium data without needing any sophisticated instrument. Moreover eco-friendly natural materials, which are less expensive and addressed local sources with high affinity toward toxic species, can be used in these processes. Diatomite is a siliceous, sedimentary rock consisting principally of the fossilised skeletal remains of the diatom, where the silica of the fossilised diatom skeleton resembles opal or hydrous, silica in composition (SiO2 ·nH2 O). Diatomite known as pa1e-coloured, soft, lightweight sedimentary rock consists of a wide variety of shape and sized diatoms [2]. The diatomite has unique physical and chemical properties, which make it suitable for a wide range of applications. Its low bulk density, high surface area and low thermal conductivity are attributes responsible for its use in a number of industrial applications such as functional filler, thermal insulator and catalyst carrier, as well as a substrate for adsorption of pollutants. Diatomite surface is terminated by OH groups and oxygen bridges, which act as adsorption sites. Numerous work related to wastewater treatment using diatomite has been used studied [3–6]. The aim of this paper is to investigate the ability of diatomite to remove direct orange-46 from aqueous solutions. The equilibrium data for the uptake process were also determined and investigated using different models. These parameters would be useful in understanding of sorption mechanism of dyes by diatomite from an aqueous environment.

2 Material and Methods 2.1 Chemicals and Characterization of Diatomite All chemicals used were analytical grade and used without further treatment. Distilled water was used in all experiments. A standard stock solution of the dyes was prepared and used by appropriate dilution at necessary concentration. The maximum wavelength of the dye solution was 415 nm. Merck photometer SQ 118 was used to determinate the concentrations of direct orange in solutions. Diatomite samples used in this work were obtained from Bey¸sehir, Konya, Turkey. All diatomite samples (Fig. 1a) were ground in a laboratory type ball-mill and washed with distilled water in order to remove the surface dust and impurities. Manganese oxide modification was then accomplished by the treatment with manganese chloride and sodium hydroxide. The diatomite samples were immersed in 6 M sodium hydroxide. The diatomite was then placed in 100 ml of 2.5 M manganese chloride (pH adjusted to 1–2 with hydrochloric acid) at room temperature for 10 h. The supernatant of this mixture was then discarded and the manganese-soaked diatomite was immersed in 6 M sodium hydroxide at room temperature for 10 h in order to precipitate the manganese hydroxide. The excess was decanted and the

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Washed and grounded diatomite

Mn-diatomite

(b)

(a)

Fig. 1 (a) Natural diatomite samples (b) Conditioned diatomite samples

diatomite was left exposed to air to facilitate oxidation of the manganese hydroxide to a mixture of hydrated manganese oxides. The sample was then washed, dried in an oven at 100◦C, desiccated and stored for future use. The modified diatomite will be referred to by Mn-diatomite (Fig. 1b).

2.2 Batch Experiments Adsorption studies were investigated by batch experiments. All batch-technique experiments were carried out in 100 ml glass flasks. Kinetic and equilibrium experiments were obtained by mixing 0.25 g of diatomite with 25 ml of dye solution in the conical flasks. In order to evaluate kinetic data, separate flasks were prepared for each time interval and only one flask was taken for desired time. The concentration of dye was 50 mg/L. Each isotherm consisted of eight dye concentrations varied from 5 mg/L to 50 mg/L. Then the suspensions were placed in a shaker. After desired shaking time, diatomite was separated from solutions through centrifugation (EAL1C02 Nuvefuge Centrifuge). Final dye concentrations in the equilibrium solution were then immediately analysed.

2.3 Adsorption Isotherms The concentration of adsorbed species on the adsorbent the batch contact test can be calculated using the following mass-balance equation; qe .m = V(C0 − C)

(1)

qe is the final concentration of species on adsorbent (mg/g or meq/g of adsorbent), C0 is the initial concentration of species (mg/L),

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C is the final concentration of species in solution (mg/L), m is the mass of adsorbent used (g) and V is the volume of solution (L) All these parameters, expect, qe which calculated from mass-balance equation, were measured experimentally. The data then can be correlated with a suitable isotherm. The equilibrium isotherm plays an important role in predictive modelling for analysis and design of adsorption systems. No single model has been found to be generally applicable, a fact which is readily understandable in the light of the assumptions associated with their respective derivations. The current research presents a method of direct comparison of the isotherm fit of several models to enable the best fit and best isotherm parameters to be obtained. 2.3.1 Langmuir Isotherm The Langmuir isotherm has been widely applied to pollutants adsorption processes. A basic assumption of the Langmuir theory is that the sorption takes place at specific homogenous sites in the sorbent. Moreover when a site is occupied by a solute, no further sorption can take place at site. The Langmuir adsorption isotherm can be written as follows [7]: Ce /qe = (1/Q0 b) + (1/Q0 )Ce

(2)

Q0 (mg/g). and b (L/mg) are Langmuir isotherm constants. A plot of Ce /qe versus Ce gives a straight line with slope 1/Q0 and intercepts 1/Q0 b. The value of Q0 gives the maximum sorption capacity of sorbent. 2.3.2 Freundlich Isotherm The Freundlich isotherm has been derived by assuming an exponentially decaying sorption site energy distribution. This experimental model can be applied to non-ideal sorption on heterogeneous surfaces as well as multi-layer sorption and is expressed by the linearised following Eq. (7); log qe = log Kf + n Log Ce

(3)

Kf and n are the Freundlich isotherm constants that can be related to the adsorption capacity and the adsorption intensity, respectively. The values of Kf and n may be calculated by plotting log(qe ) versus log(Ce ). The slope is equal to n and the intercept is equal to log Kf . The Freundlich constant 1/n is also an indicator for the adsorption strength and a measure of the deviation from linearity of the adsorption. If 1/n is equal to unity, the adsorption is linear. When n>1 or becomes larger (n>>1), the adsorption bond becomes weak.

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2.3.3 Dubinin-Radushkevich Isotherm The empirical equation proposed by Dubinin and Radushkevich, has been widely used to describe the adsorption of gases and vapors on microporous solids. In the case of liquid phase adsorption, several studies have shown that the adsorption energy can be estimated according to the Dubinin-Radushkevich equation. Assuming that the adsorption in micropores is limited to a monolayer and the Dubinin-Radushkevich equation is applicable, the adsorption capacity, q, can be written as [8], q = q0 exp(−Bε2 )

(4)

ε = (RT)ln(1 + 1/Ce )

(5)

q is the ultimate capacity per unit area in adsorbent micropores, B is the constant related to the adsorption energy, ε is the Polenyi potential, The most probable energy of adsorption, E, is given as follows; E = (2B)−1/2

(6)

2.3.4 Tempkin Isotherm Tempkin and Pyzhev considered the effects of some indirect adsorbate/adsorbate interactions on adsorption isotherms and suggested that because of these interactions the heat of adsorption of all the molecules in the layer would decrease linearly with coverage. The Tempkin isotherm has been used in the following form [9]: qe = RT/b(lnACe )

(7)

qe = RT/blnA + RT/blnCe

(8)

B = RT/b

(9)

A plot of qe versus ln Ce enables the determination of the constants A and B. The constant B is related to the heat of adsorption. 2.3.5 BET Isotherm The BET isotherm was developed by Brauner, Emmett and Teller. Unlike the Langmuir isotherm, BET type adsorption corresponds to multilayer adsorption. This

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isotherm indicates that more than one layer of adsorbate can accumulate at the surface, i.e. the first adsorbed layer serves as a site for adsorption of a molecule onto the second and so on. The BET isotherm is therefore more complex than the Langmuir isotherm Eq. (7). The BET isotherm can be expressed as Q0 bCe (Cs − Ce ) 1 + (b − 1) Ce /Cs

qe =

(10)

or in a simpler form it can be expressed as qe =

aCe (Cs − Ce ) [1 + bCe ]

(11)

This equation can be correlated to a quadratic function by doing necessary rearrangements Ce Cs = qe a

b bCs − 1 Ce − Ce2 a a

(12)

Cs : saturation concentration a and b: BET constants

3 Results and Discussions The effect of contact time was studied to monitor the uptake process. Figure 2 clearly indicates that the adsorption of dye is increased instantly at initial stages and then keeps increasing gradually until the equilibrium is reached. The equilibrium time was selected to be 180 minutes. 1,2

qt (mg/g)

1 0,8 0,6 0,4 0,2 0 0

30

60

90 120 t (minutes)

150 ◦

Fig. 2 Effect of the shaking time (C0 = 50 mg/L, 250 rpm, 25 C)

180

210

Removal of Direct Orange-46 from Aqueous Solutions Using MN-Diatomite 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0

qe (mg/g)

Fig. 3 Equilibrium isotherm graph (3 hours, 250 rpm, 25◦ C)

0

10

20 30 Ce (mg/L)

Langmuir Isotherm

40

50

Freundlich Isotherm log Ce

75 0

0

60

0,3

0,6

0,9

1,2

1,5

1,8

–0,2 45

log qe

Ce/qe (g/L)

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30

–0,4 –0,6

15

–0,8 0 0

10

20

30

40

50

–1

Ce (mg/L)

(b)

(a)

D-R Isotherm

Tempkin Isotherm 0

0,8

0

lnqe

0,6

qe

0,1

0,2

0,3

0,4

0,5

–0,5

0,4

–1 –1,5

0,2 –2

0

0

0,5

1

1,5

2

2,5

3

3,5

4

–2,5

ln Ce

E2

(c)

(d)

Ce/qe (g/L)

BET 70 60 50 40 30 20 10 0

0

10

20

30

40

50

Ce (mg/L)

(e) Fig. 4 Adsorption isotherms graphs. (a) Langmuir, (b) Freundlich, (c) Temkin, (d) D-R, (e) BET

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Isotherm name

Constants

Langmuir isotherm

Q0 b N Kf A B B qs E (J/mg) A B C Capacity (mg/g)

Freundlich isotherm Tempkin isotherm

Dubinin-Radushkevich isotherm BET isotherm

R2 1.008 0.041 0.572 0.078 0.477 0.204 3.067 0.467 0.736 −4.41 0.110 −66.44 0.699

0.914 0.992 0.922

0.712 0.994

Figure 3 shows the relationship between the amount of dye adsorbed per unit mass of diatomite (qe , mg/g) and its final concentration in the solution (Ce ). Linearised adsorption equations were calculated by experimental data using Eqs. (2), (3), (5), (8), and (12). The experimental and calculated models’ results can be seen in Fig. 4a–e. The corresponding correlation coefficients and the isotherm constants were calculated and presented in Table 1. As can be seen from table all models except D-R isotherm can fit to the experimental data. The Langmuir equation which is valid for monolayer sorption onto a homogeneous surface with a finite number of identical sites and the value of Q0 is the maximum amount of direct orange per unit weight of Mn-diatomite. The maximum adsorption capacity was found to be 1.008 and 0.699 mg/g from Langmuir and BET equation, respectively. In Freundlich equation, the value of n is indicative of adsorption intensity and the relative energy distribution on the adsorbent surface. Therefore it can be concluded that as the n value (0.57) for the adsorption by Mn-diatomite is lower than unity, a chemical adsorption rather than physical is probably dominant in dye adsorption by Mn-diatomite. Therefore, the affinity is high. In addition, low “n” values close to zero indicate the more heterogeneous systems. The Freundlich isotherm is also more widely used but provides no information on the monolayer adsorption capacity, in contrast to the Langmuir model.

4 Conclusion Diatomite was used as an adsorbent for removal of direct orange-48 from aqueous solutions. Diatomite is approximately 500 times cheaper than commercial activated carbon and also a locally available, low-cost adsorbent in Turkey. The preliminary results on direct oronge-46 uptake by Mn-Diatomite under the relevant conditions

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were presented. Batch model removal process demonstrated the partly ability of Mn-diatomite to remove dye from aqueous solutions. Further improvements should be examined for dye removal using diatomite.

References 1. Patterson CF (1991) Industrial Waste Water Control 1st edn. Academic Press, New York 2. Macdonald & Co Publishers Ltd (1983) The Macdonald encyclopaedia of rocks and minerals. Macdonald, London 3. Al-degs Y, Khraishehand AM, Tutunji F (2001) Sorption of lead ions on diatomite and manganese oxides modified diatomite. Water Res 35(15):3724–3728 4. Al-Ghouti MA, Khraisheh MAM, Allen SJ, Mahmad N (2003) The removal of dyes from textile wastewater: A study of the physical characteristics and adsorption mechanisms of diatomaceous earth. J Environ Manag 69:229–238 5. Erdem E, Çölgeçen G, Donat R (2004) The removal of textile dyes by diatomite earth. J Colloid Interface Sci 282:314–319 6. Aksöz Ö (2005) Removal of lead and cupper ions from aqueous solutions using diatomite. MSc Thesis, Gebze Institute of Technology, Gebze/Kocaeli, Turkey 7. Seader JD, Herley EJ (1998) Separation process principles. Wiley, New York 8. Hsieh C-T, Teng H (2000) Liquid phase adsorption of phenol onto activated carbons prepared with diffrent activation levels. J Colloid Interface Sci 230:171–175 9. Allen SJ, Mckay G, Porter JF (2004) Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems. J Colloid Interface Sci 280:322–333

Environmental Problems from the Open Dump in Gümü¸shane Province and Investigation of Biological Recycling for the Organic Solid Wastes S. Serkan Nas and Adem Bayram

Abstract This paper presents a general overview of current municipal waste management in Gümü¸shane Province. Both the drawbacks of present disposal method are discussed and solution proposals are submitted. The solid waste samples, one sample in every week and total fifty two samples in a year, were taken from the municipal solid waste open dumping area during a year, 2004 March-2005 February. Compostable organic parts of the samples, separated from the mixed municipal solid waste, were analyzed in order to determine the suitability of composting for the disposal of municipal solid wastes in Gümü¸shane. The moisture content, C/N ratio and pH for all samples were determined and evaluated. The values with high moisture content being 78% (74% in spring, 83% in summer, and 78% in autumn and 77% in winter), relatively low C/N ratio being 21.6/1 (22.2/1 in spring, 16.2/1 in summer, 23.7/1 in autumn and 27.5/1 in winter), and low pH being 4.73 (5.50 in spring, 4.25 in summer, 4.45 in autumn and 4.72 in winter) disclose that composting of the organic wastes aren’t suitable. Keywords Open dump · Municipal solid waste · Organic waste · Composting

1 Introduction In most parts of the world today, solid wastes are disposed of either in open dumps or sanitary landfills, or by incineration. As incineration and sanitary landfilling are expensive-both in initial investment and throughout their operation-their use is mostly confined to developed countries, while open dumping, at no cost, is the

S.S. Nas (B) Gümü¸shane Engineering Faculty, Department of Civil Engineering, Karadeniz Technical University, 29000 Gümü¸shane, Turkey e-mail: [email protected]

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method used in economically developing countries. Turkey’s traditional means of disposing of solid waste has been to dump it at these open sites (it has 2,020) or at sea [9]. In Turkey, there are 3,215 municipalities, and 16 of them are metropolitan municipalities. A total of 2,984 municipalities have solid waste management services. There are 12 sanitary landfills, 4 composting plants and 3 incineration plants. In most municipalities, medical wastes are not collected separately from other wastes. Separate collection of medical wastes is only practiced in 471 municipalities [10, 13]. The composting and sorting plants, which were the first plants in Turkey and have 150 ton/day capacities, were set up in Çi˘gli and Halkapınar in 1968, ˙Izmir. These plants were built with Denmark technology, and operated by 1985. Later, a new composting plant, which has 500 ton/day capacity, was set up in Uzundere in 1985, ˙Izmir. This plant began to operate in 1988, and the other old plants weren’t operated. The composting and sorting plant, which is the biggest plant in Turkey at the moment and has a closed area with 32,000 m2 size, in Kemerburgaz/I¸sıklı village, processes 1,000 ton/day of municipal solid waste of Istanbul, and produces 250 ton/day compost. Organic wastes constitute a major part of municipal solid waste. They cause some unwanted problems both in sanitary or unsanitary landfilling and incineration of municipal solid waste. Some of the problems in sanitary or unsanitary landfilling are leachate, which have polluting potential for groundwater and superficial water sources, generated as a result of degradation and decomposition of organic materials, uncontrolled release of landfill gases, which may cause serious health problems when inhaled, such as hydrogen sulphur (H2 S), carbon dioxide (CO2 ) and methane (CH4 ). Some of the problems in incineration are that additional fuel is needed due to the fact that organic materials have high moisture content and low calorific value, and air pollution, which is caused by some unwanted gases generated as a result of incineration. There are solutions for these problems but increase the cost to a great degree. The studies was started in order to produce economical and environment-friendly solutions for these problems together with municipal solid waste management having importance. In the end, the opinion appeared that organic waste can be utilized as a soil conditioner or fertilizer by composting. Composting was accepted and put into practice as a solid waste disposal alternative to sanitary or unsanitary landfilling. Composting is one element of an integrated solid waste management strategy that can be applied to mixed municipal solid waste (MSW) or to separately collected leaves, yard wastes, and food wastes [12]. Composting is the biological decomposition of the biodegradable organic fraction of MSW under controlled conditions to a state sufficiently stable for nuisance-free storage and handling and for safe use in land applications [4, 5, 2]. The application of compost to soil systems is of great concern because the frequent supply of compost may lead to the accumulation of heavy metals in the soil. Increased levels of heavy metals in topsoil due to atmospheric deposition from industrial activities and input via fertilizers, pesticides and animal manure have

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already been observed. The heavy metal content of composts should be limited in order to guarantee the safe use of compost [8, 15].

2 Material and Method Gümü¸shane, located in the Eastern Black Sea region of Turkey, lies between the 38◦ 45 and 40◦ 12 eastern longitudes and 39◦ 45 and 40◦ 50 northern latitudes. Gümü¸shane is characterized by a rugged topography. The area of Gümü¸shane is some 6,437 km2 at an elevation of 1,210 m. The lowest and highest elevations in the zoning plan are 1,105 m and 1,455 m, respectively. The temperature and other climatic conditions of Gümü¸shane vary drastically: the average minimum temperature is found to vary from −15◦C in February months to 9◦ C in August months, and the average maximum temperature is found to vary from 10◦ C in January months to 37◦ C in July months. Gümü¸shane receives a yearly average rainfall of 461 mm [14]. Har¸sit stream passing from the city centre and Kelkit stream and their branches constitute the most important water sources of the province. Gümü¸shane has spider forest with fir trees, which are the highest of Europe, and spruce trees, which are the highest of Turkey. In Gümü¸shane Province and its towns, unsanitary landfill is the only option that is undertaken for the management of the municipal solid wastes. The solid waste collection method used in Gümü¸shane is the curb-side collection method. Gümü¸shane’s municipal solid waste generally consists of wastes generated from residential and commercial areas, parks and streets, and is not sorted at the source, but stored in the same waste containers, in sizes of 0.4 and 0.8 m3 . The dimensions and numbers of containers vary according to the width of the street and the quantity. The number of containers is 660. Solid wastes stored in containers are collected and transported to the unsanitary landfill area by vehicles belonging to the Municipality of Gümü¸shane [1]. There are six unsanitary landfills in Gümü¸shane Province and its towns, Torul, Kürtün, Kelkit, Siran ¸ and Köse. Total 70 ton/day municipal solid waste is generated in central locations, 30 ton/day of which is generated in the centre of the city. These wastes are collected from the galvanized containers. Disposal type of these wastes is open dumping. These wastes are disposed by dumping in Kurudere valley in southwest side of Parmaklık hill (1,633 m). The distance from the centre of the city is about 4.5 km and also fairly close to the water source, Har¸sit stream. Until 1984, Gümü¸shane’s municipal solid wastes were being dumped into Har¸sit stream banks. After that, the disposal of solid wastes in open dumps became a common practice. In spite of the publication of the Solid Waste Control Regulation, continuously updated, in 1991, the practice has been kept on so far. Although the term “waste management” refers to source minimization, collection, transformation, reuse or/and recycling and disposal in accordance with the regulations, it only refers to collection, transportation and unsanitary landfilling of wastes in Gümü¸shane like in many municipalities of Turkey.

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The total population of Gümü¸shane Province is 186,953, 41.5% of which live in city centres and 58.5% of which live in villages, according to the last census in 2000 [10]. The population of the city centre is 30,270 and the present solid waste production per capita is some 1 kg/day. The physical and chemical properties of the solid wastes of Gümü¸shane are different for every season. Because any cover material, for example soil, is never placed on these wastes both light materials such as paper, plastic bag are carried to faraway by winds, thus unpleasant views in respect of aesthetic are revealed as the open dumping area is very near the forest. The green wastes in the municipal solid wastes give the possibility for unfettered animals such as cats, dogs and also rodents and birds in order to feed and reproduce as the open dumping area is uncontrolled and unclosed. Neighbourhood people’s animals are also fed from time to time. There are both serious odour and fly problems due to the slaughterhouse wastes disposed at the area. Especially both the municipality workers deal with solid waste affairs and the person dealing with the recovery in the area are under the threat in respect of health. Medical wastes are also dumped into this area as mixed with other solid wastes in spite of the publication of the Medical Waste Control Regulation in 1993 [1]. In Gümü¸shane, uncontrolled disposal activity has threatened the quality of air and water resources and the health of people. Air pollutants as a result of fires at the unsanitary landfill site have adverse effects on human health. Due to decomposition of organic wastes, CO2 , H2 S and CH4 are generated and released to the atmosphere.

2.1 Sample Collection The solid waste samples were taken from the municipal solid waste open dumping area during a year, 2004 March-2005 February. One sample was taken in every week, and total fifty two samples were taken in a year. The samples were taken without sorting immediately after the solid waste was thrown out, but big materials such as car tires, old house belongings and also medical wastes. Container with 0.72 m3 volume was used in sampling process. To obtain a representative sample, 0.288 m3 of municipal solid waste was collected. Then, the samples were sorted in the laboratory. The green wastes were manually separated from other municipal solid wastes.

2.2 Sample Processing (Drying and Grinding) The green wastes were made smaller in size with pre-breaking and manually homogenized in a plastic container. 4–5 kg sample was used for roughly grinding. Four samples with 125 g were taken from roughly grinded homogenized green wastes and dried in an oven for 24–48 h at 75◦ C until a constant weight was obtained. The dried samples being called dry matter (DM) were then placed into desiccators for cooling and ground to obtain a particle size of less than 0.2 mm and stored in desiccators for analysis.

Environmental Problems from the Open Dump in Gümü¸shane Province

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2.3 Analysis The moisture content of samples was determined by weighting before dried-cooled samples were grinded to a powder. The pH of the samples was determined with handheld pH meter (pH 330i) according to EPA Method 9045C. TOC and TN of the samples were determined with UV-VIS spectrophotometer (Cadas 200) and TOC determinations (2–65 mg/l TOC) and TN cuvettes (20–100 mg/l TN). Grinded samples were extracted according to EPA Method 1310B before the determination of TOC and TN.

3 Results and Discussion

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Figure 1 shows monthly distribution (as wet weight percent) of compostable organic wastes. The organic fraction of biological origin makes up about 30% of the total amount of the municipal solid waste by weight (19% in winter, 24% in spring, 41% in summer and 35% in autumn). In fact, this value is lower than the expected. Because the people utilize the organic fraction, especially food remains and grass clippings, as feed for their animals. The green wastes are composed of organic waste products from indoors and outdoors. The indoor fraction is composed of organic matter collected in the kitchen (e.g. food scraps and tea residues) and indoor plant material, such as flowers and houseplants. The outdoor fraction is mostly collected in parks and yards and mainly consists of leaves, grass and branches (especially in October with 48% the green waste of total amount of municipal solid waste), but also of garden topsoil. In this way, soil components can contribute to green wastes. Figure 2 shows monthly distribution of moisture content of compostable organic wastes. The average moisture content of the green wastes is 78% (77% in winter, 74% in spring, 83% in summer, and 78% in autumn). The present moisture content

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of the wastes is increased by the way of rainfall. In general climate is fairly dry in summers with the average 62 mm rainfall but rainy in winter, spring and autumn with the average 97 mm, 181 mm and 121 mm rainfall respectively, and total average rainfall for last 10 years is 461 mm in Gümü¸shane Province [14]. Therefore, the climate affects the moisture content of the green wastes increasing it especially in spring, autumn and winter respectively as the lids of containers are open. The moisture content value being 78% for the green wastes is fairly high for composting and excess moisture must be removed. Water is the key ingredient that transports substances within the composting mass and makes the nutrients physically and chemically accessible to the microbes [7]. Microorganisms require moisture to assimilate nutrients, metabolize new cells, and reproduce. They also produce water as part of the decomposition process. If water is accumulated faster than it is eliminated via either aeration or evaporation (driven by high temperatures), then oxygen flow is impeded and anaerobic conditions result [6]. This usually occurs at a moisture level of about 65% [11]. If the moisture level drops below about 40–45%, the nutrients are no longer in an aqueous medium and easily available to the micro organisms. Their microbial activity decreases and composting process slows. Below 20% moisture, very little microbial activity occurs [7]. It can be said that the optimum moisture content is 55%. Figure 3 shows monthly distribution of pH of the compostable organic wastes. The yearly average value of pH of the organic wastes is 4.73. This value is fairly lower than the required as a pH between 6 and 8 is considered optimum. pH affects the amount of nutrients available to the micro organisms, the solubility of heavy metals, and the overall metabolic activity of the micro organisms [3]. pH may be increased with the addition of buffering agents, such as lime [Ca (OH)2 ]. The optimum pH range for most bacteria is between 6.0 and 7.5, whereas the optimum for fungi is 5.5–8.0 [12]. If the pH drops below 6, micro organisms, especially bacteria, die off and decomposition slows [16]. If the pH reaches 9, nitrogen is converted to ammonia and becomes unavailable to organisms [11]. This too slows the decomposition process.

Environmental Problems from the Open Dump in Gümü¸shane Province

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Total Carbon (TC), ppm

Fig. 3 Monthly distribution of pH of compostable organic wastes

Fig. 4 Monthly distribution of TC and TIC of compostable organic wastes

Figure 4 shows monthly distribution of Total Carbon and Total Inorganic Carbon of compostable organic wastes. Figure 5 shows monthly distribution of Total Organic Carbon and Total Nitrogen of compostable organic wastes. Figure 6 shows monthly distribution of C/N ratio of compostable organic wastes. The carbon-to-nitrogen ratio (C/N) of the green wastes changes between 27.5/1 in winter (the highest value) and 16.2/1 in summer (the lowest value), and the average C/N ratio is 21.6/1. The C/N ratio is lower than the required and must be increased a little with the addition of a carbonaceous waste (e.g. hay, dry leaves, paper). In general, an initial C/N ratio of 30/1 is considered ideal. When the C/N ratio is greater than 35/1, the composting process slows down. When the ratio is less than 25/1, there can be odour problems due to anaerobic conditions, release of ammonia, and accelerated decomposition. As the composting process proceeds and carbon is lost to the atmosphere, this ratio narrows. Finished compost should have ratios of 15 to 20/1 [3].

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Fig. 5 Monthly distribution of TOC and TN of compostable organic wastes 29,7

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Fig. 6 Monthly distribution of C/N ratio of compostable organic wastes

Carbon is oxidized to produce energy and metabolized to synthesize cellular constituents. Nitrogen is an important constituent of protoplasm, proteins, and amino acids. An organism can neither grow nor multiply in the absence of nitrogen in a form that is accessible to it. Although microbes continue to be active without having a nitrogen source, the activity rapidly dwindles as cells age and die [12].

4 Conclusions Municipal solid wastes should be stored in different containers according to waste types. One or two containers can be used for recyclable wastes (paper and cardboard-other recyclable materials), one container can be used for compostable wastes, and one container can be used the other wastes destined for disposal. Thanks to separately storing of green wastes at source and its composting, both the problems originated from decomposition of green waste in sanitary landfill can be overcame, and contamination of the green wastes with heavy metals can be prevented. And

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also, the ash and scoria generated in autumn and winter months should be stored in different containers separately from other solid wastes, and it is thought to use as a road filling material. The present disposal method, open dumping, must be immediately abandoned, and a sanitary landfill should be prepared for the municipal solid waste disposal. Initially, composting of the green wastes generated in Gümü¸shane Province isn’t proper in respect of high moisture content being 78%, relatively low C/N ratio being 21.6/1, and low pH being 4.73. Even if the composting is possible decreasing the moisture content, increasing C/N ratio a little and pH, the quantity of the generated green wastes isn’t enough for the municipal solid wastes of the city if a composting plant is thought to be set up. Because the average amount of the green waste is about nine tones for a day. But total amount reached to fifty tones for a day in Gümü¸shane Province. The green wastes should be transported from towns to a central place and composted instead of open dumping.

References 1. Bayram A (2004) Determining and feasibility study for disposal methods of Gümü¸shane central municipal solid waste characteristics, M.Sc. Thesis, Karadeniz Technical University, Trabzon, Turkey. (in Turkish) 2. Diaz LF, Savage GM, Eggerth LL, Golueke CG (1993) Composting and recycling municipal solid waste. Lewis Publishers Inc., Ann Arbor, MI 3. Environmental Protection Agency (EPA) (1995) Decision-maker’s guide to solid waste management, 2nd edn. Washington, DC, pp 7–13 4. Golueke CG, McGauhey PH (1955) Reclamation of municipal refuse by composting. technical bulletin 9. Sanitary engineering research laboratory. University of California, Berkeley, CA 5. Golueke CG (1972) Composting: A study of the process and its principles. Rodale Press Inc., Emmaus, PA 6. Gray KR, Sherman K, Biddlestone AJ (1971) A review of composting Part 2- The practical process. Process Biochem 6(10):22–28 7. Haug RT (1980) Compost engineering principles and practice. Ann Arbor Sci Publishers Inc., Ann Arbor, MI 8. Kabata-Pendias A, Pendias H (1985) Trace elements in soils and plants. CRC Press Inc., Boca Raton, FL 9. Kocasoy G (2002) Solid waste management in Turkey. Waste Manag World Jan–Feb 10. Republic of Turkey. Prime Ministry State Institute of Statistics (SIS). 28.12.2004. Solid Waste Statistics 11. Rynk R (1992) On-farm composting handbook. Cooperative Extension. Northeast Regional Agricultural Engineering Service, Ithaca NY 12. Tchobanoglous G, Kreith F (2002) Handbook of solid waste management, 2nd edn. McGraw-Hill, New York 13. Tınmaz E, Demir ˙I (2006) Research on solid waste management system: To improve existing situation in Çorlu town of Turkey. Waste Manag 26:307–314 14. Turkish State Meteorological Service (TSMS) (2006) Annual climate report of Turkey. TSMS publications. Turkey 15. Veeken A, Hamelers B (2002) Sources of Cd, Cu, Pb and Zn in biowaste. Sci Total Environ 300:87–98 16. Wiley JS (1956) Proceedings of the 11th industrial waste conference. Series 91. Purdue University, West Lafayette, IN

Adsorption Behavior of Radionuclides, 137 Cs and 140 Ba, onto Solid Humic Acid O. Çelebi and H.N. Erten

Abstract In this research, the adsorption behaviors of two important fission product radionuclides (137Cs and 133 Ba) onto sodium form of insolubilized humic acid (INaA) were investigated as a function of time, cation concentration and temperature, utilizing radiotracer method. The resulting data was fitted well to the Freundlich and Dubinin-Radushkevich (D-R) isotherms. Thermodynamic constants such as; free energy (Gads), enthalpy (Hads), entropy (Sads ) of adsorption were determined. Temperature change didn’t effect sorption processes significantly. Best fitting kinetic models were found for a better understanding of adsorption mechanisms. It was found that Ba2+ was adsorbed five times more than Cs+ onto structurally modified humic acid and kinetic studies indicated that adsorption behaviors of both ions obey the pseudo second order rate law. The effect of pH changes on adsorption was also examined and optimum pH range was found in the range of pH 6–8. FTIR and solid state carbon nmr (13 CNMR) spectroscopic techniques were used to understand the structural changes during insolubilization process. Quantitative determination of adsorption sites was carried out using potentiometric titration method and the resulting data was treated by using appropriate Gran functions. Keywords Adsorption · Isotherm models · IHA · Thermodynamic constants · Kinetic studies · Distribution ratio · HA · INaA · Radiotracer method · Radionuclide · Batch method · Spectroscopy · pH

1 Introduction There is an increasing effort for removing highly soluble radiocontaminants from aqueous waste streams by fixing them onto solid waste forms that can be disposed of in a repository. In this way, the high-volume aqueous streams are transformed O. Çelebi (B) Department of Chemistry, Bilkent University, 06800 Bilkent Ankara, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_101,

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from a high-level radioactive waste into a low-level radioactive waste that is much cheaper to treat. However, the removal of this species may not only serve environmental initiatives, but it may also serve as a means of producing useful materials for use in science and industry. It is known, for example, that 137 Cs is an excellent γ source for medical applications such as instrument disinfection and radiotherapy. Similarly, 137 Cs has also proven to be useful as source for sterilization in the food industry. The radionuclide 137 Cs is produced in high yield during the fission process and due to its long half-life (T1/2 = 30.17 years) and its high solubility in aqueous media, it is a principal radiocontaminant in radioactive wastes [1, 2]. Barium is an alkaline earth element (Z = 56), its radioactive isotope 140 Ba (T1/2 = 12.79 day) is a fission product with a high yield (6.21%). This radionuclide is a serious radiocontaminant, furthermore being a homologue of Ra, Ba2+ is a suitable cation for the radiochemical study of Ra2+ , which have several radioisotopes that are important in radioactive waste considerations. 133 Ba2+ was chosen as a radiotracer in our studies because of its long half-life (T1/2 = 10.7 years) and a γ-ray at 356 keV energy [3]. Humic substances (HS) are the most abundant reservoir of carbon on earth. Humic acids (HAs) are operationally defined as the fraction of HS that is insoluble in water at low pH(<2) and soluble at higher pH (>2). HAs perform various roles in soil chemistry. They act as soil stabilizers, nutrient and water reservoirs for plants, sorbents for toxic metal ions, radionuclides and organic pollutants, stimulate plant growth, and biotransform toxic pollutants. When leached into surface waters, they also play a pivotal role in the aquatic environment. For example, they bind and transport metal ions. In earlier studies it was classified as a natural or biopolymer which is not a well-defined molecular species, polydisperse (composed of many molecular weights [MWs]), irregular in structure, and varies in elemental composition with its natural origin [4, 5]. However, recent information gathered using spectroscopic, microscopic, pyrolysis, and soft ionization techniques is not consistent with the “polymer model” of humic substances. A new concept of humic substances has thus emerged, that of the supramolecular association, in which many relatively small and chemically diverse organic molecules form clusters linked by hydrogen bonds and hydrophobic interactions. A corollary to this model is the concept of micellar structure, i.e., an arrangement of organic molecules in aqueous solution to form hydrophilic exterior regions shielding hydrophobic interiors from contact with vicinal water molecules [6]. Generally, humic acid is soluble above pH 3 in aqueous media and this makes humic acid an inappropriate sorbent for traditional operations such as adsorption and recovery of metal ions in aqueous media. The solubility of humic acid in aqueous media depends on the number of −COOH and −OH groups present on humic acid on a large scale and with increasing content of these groups solubility increases. These groups also give humic acid the ability to interact with metal ions through adsorption, ion-exchange, and complexation mechanisms. However, the high solubility of humic acid in aqueous media is a limiting problem for taking advantage of the interaction ability of humic acid (as a solid phase) with metal ions. Accordingly,

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it is not advisable to use untreated humic acid as a sorbent in aqueous media, so an appropriate treatment of humic acid is needed [7]. The process developed by Seki and Suzuki [8] is called “insolubilization of humic acid” and with this method humic acid can be converted to a form which is insoluble up to pH 10 in aqueous media. To properly understand an adsorption process, we must understand two basic phenomena: equilibrium and kinetics. With regards to adsorption processes, thermodynamic data only provide information about final state of a system, but kinetics deals with changes in chemical properties in time and is concerned especially with rates of changes. Adsorption kinetics is of interest for many aspects of surface chemistry, from understanding of adsorption mechanisms to more practical problems such as removal of pollutant components from solutions [9]. In this research, the adsorption behaviors of the fission product radionuclides 137 Cs and 133 Ba onto insolubilized humic acid were investigated both thermodynamically and kinetically and resulting data was analyzed by using Freundlich and Dubinin-Radushkevich (D-R) isotherms. The structural changes during insolubilization process were determined by spectroscopic techniques and also quantitative determination of adsorption sites was carried out. A number of articles have been published in the field of adsorption of cations onto insolubilized humic acid. Gezici et al. [7] reported the sorption behavior of a nickelinsolubilized humic acid system in a column arrangement. In another study Baker and Khalili [10] published the analysis of the removal of lead(II) from aqueous solutions by adsorption onto insolubilized humic acid. El-Eswed and Khalili [11] reported the adsorption of Cu(II) and Ni(II) on solid humic acid. However, no published report on the study of the adsorption behavior of cations onto insolubilized humic acid using radiotracers was found in our literature. This study is a chemical approach in the study of the adsorption behavior of radiocontaminants onto natural materials and also shows the use of solid humic acid as a good adsorbent for the sorption of radionuclides.

2 Mathematical Relations 2.1 The Distribution Ratio The experimental data in adsorption are expressed in terms of the ditribution ratio, Rd , defined as the ratio of adsorbate concentration on solid phase to its concentration in liquid phase. The distribution ratio of adsorption is defined as: Rd =

[C]s [C]l

(1)

where [C]s (mmol/g) and [C]l (mmol/ml) are the concentrations of species C in the solid and liquid phases, respectively. At the beginning of the sorption step, V (ml) of solution with initial concentration [C]◦ (mmol/ml) is used and at the end

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of the sorption step V (ml) of solution with concentration [C]l are present, hence the concentration of C in the solid phase after sorption can be expressed as: [C]s =

V([C]◦ − [C]l ) Ws

(2)

In terms of radiactivity, [C]l can be written as: [C]l =

Al [C]◦ A◦

(3)

From Eqs. (1), (2), and (3), the following equation is obtained: Rd =

VA◦ − VAl Al Ws

(4)

where A◦ is the initial count rate of solution added for sorption (cps)/ml, Al is the count rate of solution after sorption (cps)/ml, Ws is the weight of solid material (g) [12].

2.2 Adsorption Isotherms An isotherm describes the relationship of the concentrations of a solute between two separate phases at equilibrium at a constant temperature. An adsorption isotherm, then would express the relation between the amount of solute or vapor adsorbed as a function of the equilibrium concentration of the solute or vapor in solution. A sorption isotherm describes the process without reference to the mechanism [13]. 2.2.1 Freundlich Isotherm3 Freundlich isoterm model is one of the most used non-linear model for describing the dependence of sorption on sorbate concentration. This model allows for several kinds of sorption sites on solid and represents properly the sorption data at low and intermediate concentrations on heterogeneous surfaces. The general expression of Freundlich isotherm is given as: [C]s = k[C]nl

(5)

Where [C]s is the amount of ionic species adsorbed on the solid matrix at equilibrium (mmol/g), [C]l is the concentration of the cation in solution at equilibrium (mmol/ml), k and n are Freundlich constants. This expression can be linearized as: log [C]s = log k + n log [C]l

(6)

Plotting log [C]s versus log [C]l yields n as the slope and log k as the intercept.

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2.2.2 Dubinin Raduskevich (D-R) Isotherm3 The D-R isotherm model is valid at low concetration ranges and can be used to describe sorption on both homogeneous and heterogeneous surfaces. It can be represented by the general expression: [C]s = [C]m exp −(Kε2 )

(7)

where [C]s and [C]l are as defined above, ε is the polanyi potential, given as RT ln(1+1/[C]l), R is the ideal gas constant (8.3145 J/mol.K), T is the absolute temperature(K), K is a constant related to the energy of sorption and Cm is the sorption capacity of adsorbent per unit weight (mmol/g). The linear form of the equation above can be obtained by rearranging it to give: ln [C]s = ln [C]m − Kε2

(8)

If ln [C]s is plotted against ε2 , K and lnCm will be obtained from the slope and the intercept, respectively. The value of K (mol/kJ)2 is related to the adsorption mean free energy, E (kJ/mol), defined as the free energy change required to transfer one mole of ions from infinity in solution to the solid surface. The relation is given as: E = (2 K)−1/2

(9)

3 Experimental 3.1 Chemicals All used chemicals were of analar grade. Humic acid sample was taken from Ankara university, Agricultural Faculty, Soil Science department.

3.2 Isolation and Insolubilization of Humic Acid Humic acid was isolated from a partially purified soil (contains 55% humic acid, 30% fulvic acid, %12 K2 O) by the following procedure; Stirring crude humic acid in 1% NaOH solution for 1 h and subsequent centrifugation at 5,000 rpm, dissolved fraction was taken and adjusted pH 2 with HCl, stirred for 4 h and subsequent centrifugation at 5,000 rpm. Resulting precipitate was taken and repeated this procedure two more times. The precipitate was rinsed with deionized water many times to remove chloride ions. After dechlorination step, HA was dried at 95◦ C for 4 h. Humic acid was insolubilized by heating in a temperature controlled oven at 330◦C for 1.5 h and solid phase (IHA) was converted to its sodium form (INaA) by stirring IHA in a 1 M NaNO3 solution for 2 days, resulting solid phase was dried at 80◦C.

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3.3 Quantitative Determination of Adsorption Sites on HA Adsorption sites (carboxylic and phenolic groups) were determined quantitatively by using potentiometric titration method. Model 5669-20 pH meter, Cole Parmer Instrument Company, was used for pH measurements. Titration was carried out from pH 3.5 to 10.58 using 0.1 M NaOH as titrant. Analyte was containing 50 ml suspension of humic acid (576 mg l−1 ). This value was also used by other studies[14]. Nitrogen gas was passed through the solution until titration finished to prevent CO2 interference. Resulting data was linearized by using the appropriate Gran functions [15]. Total acidity value was supposed to the total of carboxlic and phenolic acidities.

3.4 Adsorption Experiments 3.4.1 Radiotracer Method Batch method was applied throughout the study. The tracers used in sorption experiments were 137 Cs (T1/2 = 30.17 years) and 133 Ba (T1/2 = 10.7 years). 1 L of stable isotope solutions were spiked with few microliters (∼400 μL) of the corresponding radionuclide solutions used in different experiments. The initial count rates were measured for 2.5 ml aliquots of cesium and barium solutions using the prominent γ rays of 662 and 361 keV, respectively. Initial acitivity was adjusted not to be lower value than 10,000 (cps)/ml. A NaI(Tl) detector detector was used during radioactivity measurements of samples. All the experiments were performed in duplicates. In order to check any loss in activity originating from adsorption on the inside wall of tubes, blank experiments were performed using solutions without adsorbent. The results showed that adsorption onto the tube walls was negligible. 3.4.2 Kinetic Studies To each of a set of INaA samples placed in tubes, 7.5 ml of Cs+ solution (prepared from CsCl salt) containing an appropriate amount of 137Cs radiotracer was added. The initial concentration of solution was 1×10−4 M. Samples were shaken at room temperature for periods ranging from 5 min to 48 h. They were centrifuged and 2.5 ml portions of the liquid phases were counted to determine their activities. The same procedure was applied for barium sorption studies using 9 ml of Ba2+ solution (prepared from BaCl2 salt) having an appropriate amount of 133Ba radiotracer. 3.4.3 Effect of Loading, Temperature and pH Loading experiments were carried out to investigate the effect of initial cation concentrations on sorption at four different temperatures; 15, 25, 35, 45◦ C and at the initial concetrations of 5×10−4 , 1×10−4 , 1×10−5, 5×10−6 (mmol/ml) for Cs+

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sorption. In the case of Ba2+ sorption the maximum temperature was 55◦ C and concentrations used were 1×10−4, 1×10−5, 5×10−6 , 1×10−6 (mmol/ml). Samples were prepared as in the case of kinetic experiment, but all concentrations were used instead of only 1×10−4 M. The effect of pH upon sorption behavior of Ba2+ onto INaA was investigated at a fixed concentration (1×10−5) and room temperature with varying pH values ranging from 1.5 to 10. The samples were shaken for 1 day, centrifuged and 2.5 ml of portions of the liquid phase were counted. Shaking was done in a temperature controlled environment using a Nuve ST 402 water bath shaker equipped with microprocessor thermostat. The fluctuation in controlled temperature was ± 1◦ C.

3.5 Spectroscopic Characterization of Humic Acid and Insolubilized Humic Acid 3.5.1 FTIR FT-IR spectra were recorded using a Bruker Tensor 27 FTIR spectrometer with a standard high sensitivity DLATGS detector, with a resolution of 4 cm−1 and 64 scans, The KBr pellets were obtained by pressing a mixture of 1:100 ratio of humic acid samples and KBr, respectively. 3.5.2

13 C

CP/MAS NMR

Solid-state 13 C NMR spectra were obtained at the 13 C resonance frequency of 125.721 MHz on a Bruker Avance ASX 500 spectrometer, equipped with a double resonance HX probe. The samples were confined in a zirconium oxide rotor with an external diameter of 2.5 mm. The Cross-Polarization Magic Angle Spinning CPMAS technique was applied with a contact time of 1 ms, a spinning speed of 15 kHz MAS and a pulse delay of 2s.

4 Results and Discussion 4.1 Potentiometric Titration To quantify the acidic functional (carboxylic and phenolic) groups, potentiometric titration method was used. It is usual to plot the differential curves, pH/V or E/V against volume of titrant added, but when the titration curve is not symmetrical about the equivalence point, as in Fig. 1, then it is possible to obtain erroneous results. Therefore, G. Gran [15] developed mathematical expressions to linearize various titration curves. In our data treatment, we chose the following equation, assuming humic acid as a polymeric acid and titration type as weak acid-strong base titration Fig. 2.

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Fig. 1 Potentiometric titration curve of HA

11 10 9

PH

8 7 6 5 4 3 0,0

0,5

1,0

1,5

2,0

2,5

2,0

2,5

Volume of NaOH (ml)

Fig. 2 Linearized plot potentiometric titration curve of HA

1,6

Gran Function, G

1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0 0,0

0,5

1,0

1,5

Volume of NaOH (ml)

G = V × 10pH− k

(10)

where V represents the amount of titrant used (ml) and k is an arbitrary constant with a value such that the antilogarithms will fall in a suitable range such as 0 to 100–1,000. After conversion of the potentiometric titration data to linearized form Fig. 2 using Gran functions, two associated linear curves were obtained. The following quantitative acidic functional group and total acidity values are given in Table 1.

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Table 1 Acidic functional group contents obtained experimentally using potentiometric titration (meq/100 g) of humic acid HA

-COOH

-C6 H5 OH

Total acidity

249.0

190.0

439.0

4.2 FTIR and 13 C NMR Spectra of HA and INaA FTIR spectroscopic technique was used to examine the structural changes after insolubilization process. The peaks and corresponding functional groups in FTIR spectrum shown in Fig. 3 are as follows; a broad band at 3,387 cm−1 primarily corresponds to O-H stretching and secondarily to N-H stretching, the peak at 3,071 cm−1 represents stretching of aromatic C-H, absorption bands at 2,928 and 2,857 cm−1 are attributed to aliphatic C-H stretching in CH2 and CH3 , respectively, Broad bands at 2,500 cm−1 is overtone from carboxylic groups stretching (2 × 1,246 cm−1 ) and at 2,000 cm−1 is overtone from C-O polysaccharides stretching mode (2 × 1,060 cm−1 ), Strong absorption band at 1,704 cm−1 is due to C=O stretching of carboxylic acid and ketone and absorption bands at 1,602 cm−1 and 1,372 cm−1 are ascribed to stretching of carboxylate ion and the peak at 1,602 cm−1 can also be attributed to structural vibrations of aromatic C=C bonds, the peak at 1,222 cm−1 represents C-O stretching in phenols and O-H deformation of COOH. The absorptions from deformation of aliphatic C-H and, H-bonded C=O of conjugated ketones and water deformation occurs at 1,448 cm−1 , the band at 1,033 cm−1 represents C-O stretching of polysaccharides. [16, 17, 18].

COOH Phenol

COOKetones

COOH Ketones Aliphatic Aromatic CH CH

COOH overtone

A

HA Aliphatic CH ; COO-

polysaccharides overtone 500

1000

1500

2000

2500

wavenumber (cm–1)

Fig. 3 FTIR spectra of HA and INaA

OH;NH

3000

INaA 3500

4000

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Fig. 4 13 C NMR spectra of HA and INaA

The 13 C spectra in Fig. 4 of HA and INaA include following peaks: (a) alkyl carbons and O-alkyl carbons (aminoacids/carbons adjacent to ester/ether/hydroxyl) (0–60 ppm), because that peak was not well resolved we observe those two groups in a broad band; (110–145) ppm is assigned to aromatic carbon, the at (150–190) ppm include phenolic and carboxylic carbons [19, 20, 21]. When we examine FTIR and 13 C NMR spectra of HA and INaA, we observe that there is a decrease at the intensities of aliphatic alkyl groups, -COOH group and phenolic groups, the effect causing insolubilization is mainly due to loss in carboxyl groups, but as we see on spectrum, all of the adsorption sites are not lost during insolubilization. In literature [8] it was found by titration methods that the lost in percentage of acidic functional groups is nearly 25%. By this way, the ability of HA to make hydrogen bonding decreased and that caused the insolubilization of HA in water at high pH values. It is also clear from the 13 C NMR that aromatic part of HA is not affected after insolubilization, because there is no intensity change.

4.3 Kinetic Studies The sorption studies of Cs+ and Ba2+ ions on INaA as a function of time were performed for time intervals ranging from 5 min up to 48 h. Plots of the variation of Rd as a function of time for Cs+ and Ba2+ ions are given in Figs. 5 and 6, respectively. It is apparent that, equlibrium is reached after several hours of contact. Such a rapid process indicates that sorption is primarily a surface phenomena where the humic acid surface is readily accessible to ions in solution. On the basis of the obtained results an equilibrium period of 1 day was selected as a fixed parameter for further experiments, where the effects of loading and temperature, were examined.

Adsorption Behavior of Radionuclides, 137 Cs and 140 Ba, onto Solid Humic Acid Fig. 5 Variation of Rd values with shaking time for Cs+ sorption on INaA at 25◦ C

1075

Rd (ml/g)

500

400

0

500

1000

1500

2000

2500

3000

Time (min)

3,9

Fig. 6 Variation of log Rd values with shaking time for Ba2+ sorption on INaA at 25◦ C log Rd (ml/g)

3,8 3,7 3,6 3,5 3,4 3,3 0

500

1000

1500

2000

2500

Time (min)

Kinetic studies were also used to determine best fitting rate equations and rate constants of cation sorption. S. Azizian [9] has published kinetic models for the sorption behavior of solutes onto adsorbent and in his research it has been shown that at lower initial concentration of solute, the mechanism obeys pseudo second order model. The rate law for this system is expressed as: dq = k2 (qe − q)2 dt

(11)

where q and qe are the amount of solute sorbed per gram of sorbent at any time and at equilibrium, respectively, and k2 is the pseudo second order rate constant of sorption. After integration and rearrangement of the above equation, the following equation is obtained with a linear form,

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Table 2 Amount of sorbed cation per gram of sorbent, pseudo second order rate constants and correlation coefficient values for cesium and barium sorption Sorbed cations

qe (mol/g)

k2 (g.mol−1 . min−1 )

R2

Cs+ Ba2+

29.44 × 10−3 141.30 × 10−3

9.998 0.432

0.9998 0.9997

1 1 t = + t 2 q q k2qe e

(12)

# # 2 The # plot of t q versus t gives a straigt line with slope of 1 k2 qe and intercept of 1 qe . So the amount of cation sorbed per gram of sorbent (INaA) at equilibrium qe and sorption rate constant k2 could be evaluated from the slope and intercept, respectively. The results obtained are shown in Table 2. It is apparent from qe values that barium ions are sorbed five times more than cesium ions and rate constant values show that cesium much more rapidly adsorbed by INaA, rate constant value of cesium sorption is obviously greater than barium sorption. Correlation coefficient values indicate that pseudo second order rate equation almost completely fit for sorption behavior of low concentration of cesium and barium ions onto INaA. The reason for the less sorption tendency of cesium ions onto INaA can be explained by their charge. An increase in the oxidation state favors the accumulation of the ions on the sorption surface leading to electrostatic stability.

4.4 Loading Experiments and Effect of pH Loading experiments were carried out to investigate the effect of initial concentration on sorption. Rd values of Cs+ and Ba2+ sorption on INaA at different initial cation concentrations and temperatures are given in Table 3 and Table 4, respectively. The tables show that as the initial concentration increases, the Rd values decrease. This stems from the fact that as the initial concentration of the sorbate cation is Table 3 The distribution ratio, ln Rd (ml/g), values of Cs+ sorption onto INaA at different temperatures and initial concentrations, [C]◦ (mmol/ml) ln Rd values at different temperatures (K) Sorbent

[C]◦ (mmol/ml)

288

298

308

318

INaA

5 × 10−4 1 × 10−4 1 × 10−5 9,30424

6,11914 8,42243 9,19511 9,33636

6,22862 8,26722 9,26427 9,44074

6,00389 7,94094 9,27734 9,42674

5,80513 7,8917 9,33891

5 × 10−6

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Table 4 The distribution ratio, ln Rd (ml/g), values of Ba2+ sorption onto INaA at different temperatures and initial concentrations, [C]◦ (mmol/ml) ln Rd values at different temperatures (K) Sorbent

[C]◦ (mmol/ml)

298

308

318

328

INaA

1 × 10−4 1 × 10−5 5 × 10−6 10,98316

8,91547 9,80171 10,17173 10,20455

9,02099 10,04055 10,38492 10,53175

8,77017 10,05589 10,18572 10,67555

8,83871 – 10,54944

1 × 10−6

increased, the ratio of the ions that are accommodated by the solid surface to those remaining in solution decreases, since a limited number of sites on the INaA are available for sorption. The loading curves were constructed by plotting log Rd values against log [C]s, at four different temperatures, in Figs. 7 and 8 for cesium and barium ion sorptions, respectively. According to those curves, Cs+ and Ba2+ sorption show similar shapes indicating that the sorption occurs on single sorption site between 5×10−4 and 1×10−6 concentration ranges. This sorption site is negatively charged oxygen atoms belonging to carboxylate and phenolate groups on INaA. The increase of pH value has a substantial effect upon sorption of Ba2+ onto INaA, as shown in Fig. 9. It is seen that there is almost no adsorption between pH (1–2) range. In literature [7, 10] it is also emphasized that in aqueous media there is a competition between H3 O+ and metal ions toward the solid phase, at low pH value, the surface of the adsorbent is closely associated with the hydronium ions and repulsive forces limit the approach of the metal ions. As we increase the pH value, we observe a dramatical increase at the uptake of Ba2+ by sorbent, due to the fact that principal adsorption sites -COOH and -COH dissociated to their anionic form COO− and -CO− . This dissociation caused a negatively charged surface and cations

4,2

15C 25C 35C 45C

4,0

log Rd (ml/g)

3,8 3,6 3,4 3,2 3,0 2,8 2,6 2,4

Fig. 7 The loading curves for sorption of Cs+ onto INaA at different temperatures

–2,6 –2,4 –2,2 –2,0 –1,8 –1,6 –1,4 –1,2 –1,0 –0,8 –0,6

log[Cs]s (mmol/g)

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Fig. 8 The loading curves for sorption of Ba2+ onto NaIA at different temperatures

4,8

25C 35C 45C 55C

4,6 4,4

log Rd (ml/g)

4,2 4,0 3,8 3,6 3,4 3,2 3,0 2,8 2,6 –2,2

–2,0

–1,8

–1,6

–1,4

–1,2

–1,0 –0,8

–0,6

log[Ba]s (mmol/g)

25000

Fig. 9 Effect of pH upon sorption of Ba2+ onto INaA

Rd (ml/g)

20000 15000 10000 5000 0 0

2

4

6

8

10

pH

could more easily adsorbed to solid surface. When pH value passes 8, we observe a sharp decrease at sorption capacity of sorbent, because INaA starts to dissolve and binded Ba2+ passes from solid phase to solution phase. As a result adsorption capacity of sorbent (INaA) increases with increasing pH as long as INaA doesn’t dissolve in liquid phase.

4.5 Freundlich Isotherm The isotherm plots for two cations at different loadings and temperatures on INaA are given in Figs. 10 and 11. The freundlich constants n and k obtained for different sorption cases are given in Tables 5 and 6.

Adsorption Behavior of Radionuclides, 137 Cs and 140 Ba, onto Solid Humic Acid Fig. 10 Freundlich isotherm plots for sorption of Cs+ onto INaA at various temperatures

15C 25C 35C 45C

0,0

log[Cs]s (mmol/g)

1079

–0,5 –1,0 –1,5 –2,0 –2,5 –7

–6

–5 –4 –3 log[Cs]liq (mmol/ml)

–2

–0,5

Fig. 11 Freundlich isotherm plots for sorption of Ba2+ onto INaA at various temperatures

25C 35C 45C 55C

log[Ba]s (mmol/g)

–1,0 –1,5 –2,0 –2,5 –3,0 –8,0

–7,5

–7,0

–6,5

–6,0

–5,5

–5,0

–4,5

log[Ba]liq (mmol/ml)

Table 5 Freundlich constants, n and k, obtained from the least square fits of the sorption data of Cs+ onto INaA (The linear correlation coefficients were all greater than 0.9905) Temperature (K) Sorbed cation

Freu. constant

288

298

308

318

Cs+

n k

0,4706 4,864

0,5305 11,405

0,4687 4,898

0,4455 3,511

The values of n being less than 1.0 in all cases indicate a non-linear sorption that takes place on a heterogeneous surface. The non-linearity represents that the sorption energy barrier increases exponentially as the fraction of filled sites on sorbent increases. When we compare n values of Cs+ and Ba2+ ions sorption on sorbent, it’s

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Table 6 Freundlich constants, n and k, obtained from the least square fits of the sorption data of Ba2+ onto INaA (The linear correlation coefficients were all greater than 0.9908) Temperature (K) Sorbed cation

Freu. constant

298

308

318

328

Ba2+

n k

0,6814 226,93

0,6777 243,61

0,7069 307,26

0,6891 257,57

obvious that non-linear sorption behavior of Cs+ is more than Ba2+ , this is one of the reason which explains lower Rd values of Cs+ sorption. The magnitude of k is proportional to sorption affinity. The significant difference between k values for the sorption behavior of two ions show that sorbent has a much higher tendency to adsorb barium ions when compared with cesium ions. It can be explained by charge. An increase in the oxidation state favors the accumulation of the ion on the sorption surface leading to electrostatic stability. Increase of temperature has no pronounced effect on n values, but the k values in case of Ba2+ sorption has an increasing trend and for Cs+ sorption, it has a decreasing trend, but the changes are not significant.

4.6 Dubinin-Radushkevich (D-R) Isotherms The sorption datas of Cs+ and Ba2+ fitted the D-R model well as shown in Figs. 12 and 13. The corresponding values of Cm , K and E are given in Tables 7 and 8. Cm values indicate that barium ions are sorbed 5 times more than Cs+ ions and decrease with increasing temperature, but changes are not significant. In all cases,

0 15C 25C 35C 45C

ln[Cs]s (mmol/g)

–1 –2 –3 –4 –5

Fig. 12 Dubinin-raduskevich isotherm plots for sorption of Cs+ onto INaA at various temperatures

–6 0

2

4

6

8

10

ε2x108 (J/mol)2

12

14

16

18

Adsorption Behavior of Radionuclides, 137 Cs and 140 Ba, onto Solid Humic Acid Fig. 13 Dubinin-raduskevich isotherm plots for sorption of Ba2+ onto INaA at various temperatures

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–2

25C 35C 45C 55C

ln[Ba]s (mmol/g)

–3 –4 –5 –6 –7 6

8

10

12

14

16

18

20

22

ε x10 (J/mol) 2

8

2

Table 7 The D-R ısotherm constants, K (mol/kJ)2 , Cm (mmol/100 g), and E (kJ/mol) obtained from the least square fits for the sorption data of Cs+ onto INaA. (The linear correlation coefficients were all greater than 0.9915) Temperature (K) Sorbed ion

D-R constant

288

298

308

318

Cs+

Cm K 11,048

71.1 4.096×10−3 11,481

71.1 3.793×10−3 11,881

74.4 3.542×10−3 12,575

60.0 3.162×10−3

E

Table 8 The D-R isotherm constants, K (mol/kJ)2 , Cm (mmol/100 g), and E (kJ/mol) obtained from the least square fits for the sorption data of Ba2+ onto INaA. (The linear correlation coefficients were all greater than 0.9973) Temperature (K) Sorbed ion

D-R constant

298

308

318

328

Ba2+

Cm K 10,613

349.2 4.439×10−3 11,258

310.0 3.945×10−3 11,641

276.4 3.690×10−3 12,163

276.1 3.380×10−3

E

the mean free energy of sorption, E, is in 8–16 kJ/mol energy range corresponding to ion-exchange type of sorption [22]

4.7 Thermodynamic Results The values of H◦ and S◦ of Cs+ and Ba2+ sorption were obtained by fitting the experimental data to Arrhenius equations (11) and (12) given below. The results are shown in Figs. 14 and 15.

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lnRd (ml/g)

Fig. 14 Arrhenius plots for sorption of Cs+ onto INaA

15 1E-2M 14 5E-4M 13 1E-4M 12 1E-5M 11 5E-6M 10 9 8 7 6 5 4 3 2 1 3,10 3,15 3,20 3,25 3,30 3,35 3,40 3,45 3,50 1/T * 10–3 (1/K)

14

Fig. 15 Arrhenius plots for sorption of Ba2+ onto INaA

lnRd (ml/g)

12

1E-4M 1E-5M 5E-6M 1E-6M

10

8

6 3,00 3,05 3,10 3,15 3,20 3,25 3,30 3,35 3,40 1/T * 10–3 (1/K)

ln Rd =

S◦ H ◦ − R RT

G◦ = H ◦ − TS◦

(11a) (12a)

The results are given in Tables 9 and 10 and Figs. 14 and 15. Enthalpy changes show the dependence of sorption processes to the temperature. When we examine the H◦ values for Cs+ and Ba2+ sorption onto INaA, it is clear that those processes are not significantly affected by the temperature change, because H◦ values are quite close to zero. However, sorption behavior of Cs+ onto INaA is an exothermic, and for Ba2+ , it is an endothermic process. In liquid-solid

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Table 9 The average values of the enthalpy change, H◦ av (kJ/mol), entropy change, S◦ av (J/mol.K) and the calculated values of the Gibbs free energy change, G◦ (kJ/mol), obtained at different temperatures for the sorption case of Cs+ onto INaA G◦ (kJ/mol) at different temperatures (K) Sorbed ion

H◦ av (kJ/mol)

S◦ av (J/mol.K)

288

298

308

318

Cs+

−3.673

48.85

−17.74

−18.23

−18.72

−19.21

Table 10 The average values of the enthalpy change, H◦ av (kJ/mol), entropy change, S◦ av (J/mol.K) and the calculated values of the Gibbs free energy change, G◦ (kJ/mol), obtained at different temperatures for the sorption case of Ba2+ onto INaA G◦ (kJ/mol) at different temperatures (K) Sorbed ion

H◦ av (kJ/mol)

S◦ av (J/mol.K)

298

308

318

328

Ba2+

2.102

89.522

−24.575

−25.470

−26.366

−27.261

systems, when temperature is increased, the behavior of ions in solution or on the solid will subject to factors such as the interionic forces, the hydration energy, the availability of sorption sites and the relative stability of sorbed ions at these sites [23]. Exothermic behavior of Cs+ ion sorption onto INaA can be explained by the thermal destabilization leading to an increase of the mobility of cesium ions on the surface of the solid as the operating temperature is increased, thus enhancing the desorption steps, that is, increasing thermal energy of ions do not favor to be bound of ions to the surface. Positive Hº value for Ba2+ sorption and therefore, we should think of the differences which makes more the difficult the uptake of Ba2+ ions onto INaA. There is a large difference in hydration enthalpies [24], being −276 kj/mol for Cs+ and −1,305 kj/mol for Ba2+ ions. In literature [25] it is reported that metal ions with high hydration energies are well solvated in water and for cations that are solvated well in water, sorption requires that such ions should be stripped out to a certain extent of their hydration shell which is a process that requires energy input. If this dehydration energy exceeds the exothermicity associated with the sorption of a metal ion on a solid, then the overall energy balance will lead to an endothermic behavior. H◦ values for Cs+ and Ba2+ sorption onto INaA indicate the physical nature of the sorption process which correspond to weak electrostatic attractions. Sorption behavior of Cs+ onto INaA is an exothermic, and for Ba2+ , it is an endothermic process. In all cases, positive S◦ values were obtained upon Cs+ and Ba2+ sorption. Positive S◦ values are usually associated with a spontaneuos process where the system shows an endothermic behavior or even a weak exothermic behavior and also it can be said that more disorder is generated in the system upon sorption.

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As the exothermic behavior becomes more pronounced negative S◦ values are obtained [26]. It was also found in Tables 9 and 10 that, S◦ value of Ba2+ sorption onto INaA is approximately two times more than Cs+ . In literature, it’s reported that the positive values of Sº resulting from sorption of divalent cations (Ba2+ in this case) on solid surfaces might suggest that ions displaced from the solid surface are greater in number than the sorbed Ba2+ ions, which means that two monovalent ions (Na+ in this case) may be exchanged for a single Ba2+ ion [27, 26]. The calculated negative values of G◦ for all cases indicate that the sorption process of each is spontaneous and preferentially driven toward the products. Temperature change has no significant effect on G◦ values for both sorptions.

References 1. Shahwan T, Erten HN (2002) Thermodynamic parameters of CS+ sorption on natural clays. J Radioanal Nucl Chem 253(1):115–120 2. Ebner AD, Ritter JA, Navratil JD (2001) Adsorption of Cesium, strontium and cobalt cons of Magnetite and magnetile-silica composite. Ind Eng Chem Res 40:1615–1623 3. Shahwan T, Erten HN (2004) Temperature effects in Barium Sorption on Natural Kaolinite and Chlorite-Illite Clays. J Radioanal Nucl Chem 260:1, 43–48 4. Diallo MS, Simpson A, Gassman P, Faulon JL, Johnson Jr JH, Goddard WA III, Hatcher PG (2003) 3-D structural modeling of humic acids through experimental characterization, computer assisted structure elucidation and atomistic simulations. Environ Sci Technol 37:1783–1793 5. Steelink C (2002) Investigating Humic Acids in soils. Anal Chem A-Pages 74:326A–333A 6. Sutton R, Sposito G (2005) Environ Sci Technol 39:9009–9015 7. Gezici O, Kara H, Ersöz M, Abali Y (2005) The sorption behavior of Nickel immobilized Humic Acid System in a Column arrangement. J Colloid Interface Sci 292:381–391 8. Seki H, Suzuki A (1995) Adsorption of Heavy metals ontu insolubilized Humic Acid. J Colloid Interface Sci 171:490–494 9. Azizian S (2004) Kinetic models of sorption: a theoretical analysis. J Colloid Interface Sci 276:47–52 10. Baker H, Khalili F (2004) Analysis of the removal of lead (II) from aqueous solution by adsorption onto insolubilized humic acid: Temperature and pH dependence. Anal Chim Acta 516:179–186 11. El-eswed B, Khalili F (2006) Adsorption of Cu (II) and Ni (II) on solid humic acid from the Azrageria Jordan. J Colloid Interface Sci 299:497–503 12. Shahwan T, Suzer S, Erten HN (1998) Sorption studies of CS+ and Ba 2+ cations on magnasite. Appl Radiat Isot 49:8, 915–921 13. Tinsley IJ (2004), Chemical concepts in pollutant behavior, Wiley-Interscience, New York 14. Masini JC, Abate G, Lima EC, Hahn LC, Nakamura MS, Lichtig J, Nagatomy HR (1998) Comparison of methodologies for determination of carboxylic and phenolic groups in humic acids. Anal Chim Acta 364:223–233 15. Gran G (1952) Determination of Equivalence Point in Polentiomertic titrations. Analyst 77:661 16. Benites VM, Mendonca E, Schaefer CEGR, Novotny EH, Reis EL, Ker JC (2005) Properties of black soil humic acids from high altitude rocky compleves in Brazil. Geoderma 127:104– 113 17. Shirshova LT, Ghabbour EA, Davies G (2006) Spectrosegnic characterization of humic acid fractions isolated from soil using different extraction procedures. Geoderma 133:204–216

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18. Xu D, Zhu S, Chen H, Li F (2006) Non-covalent association between hydrophobic organic contaminants and dissolved organic material observed by NMR. Colloids Surf A Physicochem Eng Aps 276:1–7 19. Simpson MJ, Simpson AJ, Hatcher PG (2004) Structural characterization of a Fulvic acid and a Humic acid using Solid-state Ramp-CP-MAS 13 CNMR. Environ Toxicol Chem 23(2):355– 362 20. Cook RL, Langford C (1998) Structural differences between humic fraction from different soil types as determined by FT-IR and 13 C-NMR. Environ Sci Technol 32:719–725 21. Frund R, Ludemann HD, Gonzalez-Vila FJ, Almendros G, del Rio JC, Martin F (1989) Structural differences between humic fraction from different soil types as determined by FT-IR and 13 C-NMR. Sci Total Environ 81/82:187–194 22. Helferrich F (1964) Ion exchange. Mc Graw Hill, New York 23. Shahwan T, Erten HN, Unugur S (2006) A characterization study of some aspect of the adsorption of aqueous Co (2+) ions on a natural bentonite. J Colloid Interface Sci 300:447–452 24. http://www.science.uwaterloo.ca/?cchieh/cact/applychem/hydration.html 25. Akar D, Shahwan T, Eroglu AE (2005) Kinetic and thermodynamic investigation of Strontium ions Retention by natural kaolnite and chlinoptilite Minerals. Radiochimica Acta 93:477–485 26. Khan SA, Reman RU, Khan MA (1995) Adsorption of CS (I), Sr (II) and Co (II) on Al2 O3. J Radioanal Nucl Chem 190:81 27. Shahwan T (2000) Ph.D Thesis, Department of Chemistry, Bilkent University, Ankara, Turkey

The Fate of Chlortetracycline During the Anaerobic Digestion of Manure from Medicated Calves Osman A. Arikan

Abstract The fate of antibiotic residues in the manure of treated animals is of considerable concern because of the potential development of antibiotic-resistant bacteria in the environment. The objective of this study was to determine the fate of chlortetracycline (CTC) during the anaerobic digestion of manure from medicated calves. Five beef calves were medicated for 5 days with 22 mg/kg/day of CTC. Manure samples collected from calves prior to and after medication were diluted 5-fold with water, loaded into triplicate 1 l anaerobic digesters and incubated at 35◦ C. Approximately 75% removal of buffer extracted CTC was achieved in 33 days by anaerobic digestion, yielding a half-life of about 18 days. Although the levels of buffer extracted CTC epimer, 4-epi-chlortetracycline (ECTC), declined during anaerobic digestion, buffer extracted and water soluble CTC metabolite, iso-chlortetracycline (ICTC), concentrations increased. In addition, water soluble ECTC levels also increased during anaerobic digestion. Because degradation products distributed more towards the water phase compared with the parent CTC, the degradation products present in digested manure slurry will be the ones potentially encountered in water. Keywords Chlortetracycline · Anaerobic digestion · Manure · Antibiotic · Fate

1 Introduction Chlortetracycline (CTC) is a broad-spectrum antibiotic used for propylactic and therapeutic use in poultry, pigs and calves. CTC and oxytetracycline are two of only 10 antibiotic compounds licensed in the U.S.A. for use as growth promoters for livestock [16]. 4-epi-chlortetracycline (ECTC) and iso-chlortetracycline (ICTC) are the main degradation products of CTC. The chemical structures of CTC, ECTC O.A. Arikan (B) Department of Environmental Engineering, Istanbul Technical University, Istanbul 34469, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_102,

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Chlortetracycline (ECTC)

4-epi-chlortetracycline (ECTC)

Iso-chlortetracycline (ICTC)

Fig. 1 Chemical structures of CTC and its main metabolites (ECTC and ICTC)

and ICTC are shown in Fig. 1. Elmund et al. [6] showed that approximately 75% of the CTC was excreted in manure. The release of antibiotics into the environment is of considerable concern because persistent antibiotic residues may lead to development of antibioticresistant bacteria [5]. The widespread use and relative persistence of CTC have lead to its detection in soil [9] and surface waters [10]. Hamscher et al. [9] detected average concentrations of 9.5 μg/kg CTC in the upper 10 cm of the soil from eight fields that had been manured with animal slurry 2 days before sampling. Concentrations decreased with depth to about 0.7 μg/kg below 80 cm. In a subsequent study, CTC levels between 0.17 and 0.22 μg/l were found in water samples collected at 80 and 120 cm depth by the same researchers. CTC was found in 2.4% of the 84 surface water samples with the maximum concentration of 0.69 μg/l by Kolpin et al. [10]. They speculated that the low frequency of CTC detections in water samples was likely due to the hydrophobic nature of tetracyclines and that such compounds would be more likely to be present in stream sediments than in stream water. Anaerobic digestion is an established technology for the treatment of animal manure. Although a number of investigators have studied the fate of antibiotics in soil interstitial water [15], and in anaerobic lagoons [13, 11], there is very limited information on the fate of CTC during anaerobic digestion of manure. Moreover, most studies have been conducted by adding antibiotics into the reactor as opposed to using manure from medicated animals. Fedler and Day [7] observed that the antibiotics themselves may not inhibit bacterial activity but that antibiotic metabolites produced in the gastrointestinal tract of the animal may. Therefore, to best evaluate the fate of antibiotics during anaerobic digestion, manure should be used from animals treated with antibiotics at therapeutic rates. The fate of oxytetracycline in manure from medicated calves during manure digestion was recently studied [2].

The Fate of Chlortetracycline During the Anaerobic Digestion of Manure

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The objective of this study was to determine the fate of CTC during the anaerobic digestion of manure from medicated calves.

2 Materials and Methods 2.1 Chemicals Chlortetracycline hydrochloride (Mw = 515, CAS no. 64-72-2), 4-epi-chlortetracycline hydrochloride (Mw = 515, CAS no. 101342-45-4), iso-chlortetracycline hydrochloride (Mw = 515, CAS no. 89835-80-3), and demeclocycline hydrochloride (Mw = 502, CAS no. 64-73-3) were purchased from Acros Organics N.V. (Fair Lawn, NJ). HPLC-grade methanol was obtained from Fisher Scientific (Fair Lawn, NJ). All others reagents used in this study were analytical grade. The water used in the experiments was purified by using reverse osmosis and activated carbon. McIlvaine buffer was prepared by mixing aqueous solutions of 0.1 M citric acid and 0.2 M disodium hydrogen phosphate (62:38, v/v). Methanolic oxalic acid (0.01 M) was prepared by dissolving oxalic acid in methanol.

2.2 Animal Medication and Sample Collection Five male and female beef calves, 5–7 months old and ranging from 190 to 350 kg in body mass, were kept in individual pens in a beef barn. Pens were scraped clean daily, after which approximately 2 kg of sawdust was scattered on the floor of each pen as bedding material. After a 2-week acclimatization period for the animals, the manure-sawdust mixture from each pen was collected (averaging 15 kg/animal/day), pooled, mixed, and 75 kg of this mixture was stored at 4◦ C until later use as the “unmedicated” manure. The calves were then medicated for 5 days at 22 mg/kg body mass per day of CTC (a standard dosage in agricultural practice) [3] by ingestion of the daily ration containing CTC as a feed additive. Feed consisted of a mixture of Ncf2 beef creep pellet (31%), corn silage (43%), and grass silage (26%). Medicated grain was given to the animals prior to other constituents in order to insure complete consumption of the CTC dose. Medicated manure-bedding mixtures collected on the fifth day of medication were combined and used in laboratory composting experiments as the “medicated manure”.

2.3 Anaerobic Digestion Anaerobic digestion experiments were carried out batch-wise in nine laboratory digesters (Bellco Biotechnology, NJ, US) each with a working volume of 1 l. Medicated manure from the fifth day of antibiotic treatment was diluted 5-fold

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Table 1 Characteristics of diluted unmedicated and medicated (high and low) manure slurries used in anaerobic digesters (mean ± std. error) Constituent pH Total alkalinity, mg CaCO3 /l Total solids, mg/l Volatile solids, mg/l Ammonium-N, mg/l Chemical oxygen demand, mg/l

Unmedicated manure slurry

Medicated manure slurry, High

Medicated manure slurry, Low

7.7 ± 0.1 3,160 ± 87

7.6 ± 0.1 2,950 ± 29

7.6 ± 0.1 3,137 ± 96

40,000 ± 1,000 36,000 ± 1,000 560 ± 2 47,520 ± 3,150

47,000 ± 2,000 42,150 ± 1,600 640 ± 20 52,240 ± 3,900

40,000 ± 3,000 35,500 ± 2,700 570 ± 2 49,100 ± 4,560

with tap water to approximately 5% total solids (a level that is representative of digester influent in commercial farm operations) [18], and 800 ml of manure slurry was loaded into each three digesters (referred to in this study as medicated-high digesters). Comparably diluted manure slurry from animals prior to medication was loaded into each another three digesters (referred as unmedicated digesters). In order to determine the fate of lower CTC concentrations, the manure from medicated calves was first diluted 5-fold with unmedicated manure, then the mixture was diluted 5-fold with tap water to approximately 5% total solids, and 800 ml of manure slurry was loaded into the remaining three digesters (referred to in this study as medicated-low digesters). 200 ml of effluent from a dairy manure digester was added to each digester as inoculum. Table 1 shows characteristics of the diluted unmedicated and medicated (high and low) manure slurries that were loaded into the digesters. After the digesters were filled, the headspaces were flushed with nitrogen gas to remove traces of oxygen. The digesters were stirred continuously to avoid compaction and incubated at a mesophilic temperature (35 ± 1◦ C). Manure slurry samples (30 ml) were collected from each digester on days 0, 12, 23 and 33 and analysed for CTC, and its metabolites. Manure slurry samples were collected using 50 ml syringe under nitrogen gas. Digesters were stirred continuously in order to collect homogeneous samples during the sample collection. Levels of pH, total solids (TS), volatile solids (VS), total alkalinity, ammonium-N and chemical oxygen demand (COD) were determined only for day 0 samples. TS, VS and total alkalinity were determined according to APHA [1]. Ammonium-N was determined colorimetrically by flow injection analysis (Lachat Instruments, Milwaukee, WI). Hach COD Reactor (digestion at 150◦C for 2 h) and a Hach spectrophotometer were used for chemical oxygen demand (COD) analyses. Removal of compounds was assumed to follow first-order kinetics. A rate constant, k, was determined as the slope of the curve calculated by linear regression. The half-life, T1/2 , was then calculated as T1/2 =ln(2)/k.

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2.4 Extraction of CTC and Its Metabolites Water soluble and buffer extracted CTC and its metabolites in manure slurry samples were determined in duplicate. To determine water soluble part of CTC and its metabolites, 5 ml manure slurry samples were centrifuged (7,000 × g, 20 min, 5◦ C), then 0.5 ml supernatant and 0,5 ml water were added to the tube, and the tube was vortexed for 30 sec. The mixture was transferred to a 2 ml amber autosampler vial. Finally, 20 μl of demeclocycline as an internal standard was added to each vial. For buffer extraction, the method described by Capone et al. [4] was used. Briefly, 2 ml samples were extracted three times with 3 ml of 0.1 M Na2 EDTA-McIlvaine buffer by vortexing for 30 sec followed by sonication for 3 min in a 100 W sonication bath (Bronson Ultrasonics, Danbury, CT). After each extraction, the extracts were subjected to centrifugation (500 × g, 5 min, 5◦ C), the supernatants were pooled, again subjected to centrifugation (7,000 × g, 20 min, 5◦ C), filtered through Whatman glass microfiber (grade GFB) filter paper, and passed through pre-washed Waters 60-mg HLB Oasis cartridges. The cartridges were prewashed with 5 ml of methanol followed by 10 ml of 0.1 M Na2 EDTA-McIlvaine buffer. After the extracts were loaded, the cartridges were flushed with 20 ml distilled water, followed by sample elution using 8 ml of 0.01 M methanolic oxalic acid. The eluents were concentrated under a flow of N2 to a volume of 0.5 ml by evaporation. Then, 0.5 ml water was added to the tube, and the tube was vortexed for 30 sec. The resulting mixture was transferred to 2 ml amber autosampler vials. Finally, 20 μl of demeclocycline as an internal standard was added to each vial prior to analysis by LC/MS/MS.

2.5 LC-MS/MS Analysis The analyses of CTC and its metabolites were performed using LC-MS/MS. The LC instrument was a Waters 2690 XE (Waters Corp., Milford, MA) separations module with an Xterra MS C18 column (150 mm × 2.1 mm i.d., 5 μm) (Waters Corp., Milford, MA) at 50◦ C; the injection volume was 10 μl. A mobile-phase gradient was necessary to separate the compounds. Atmospheric pressure ionization-tandem mass spectrometry was performed on a benchtop triple quadrupole mass spectrometer (Quattro LC from Micromass Ltd., Manchester, U.K.) operated in electrospray ionization mode. The source parameters were as follows: capillary voltage was set at 3.5 kV and extractor voltage was set at 3 V, respectively; rf lens at 0.1 V; source and desolvation temperatures were 150 and 450◦C. Liquid nitrogen was used to supply the nebulizer and desolvations gas (flow rates were approximately 80 and 600 l/h, respectively). Argon was used as collision-induced decomposition gas to fragment the parent ions; the typical pressure was 2.6 × 10−3 mbar. Both high and low mass resolutions were set at 12.0 for both quadrupoles. Optimization was performed by infusion of the standards from a syringe pump (10 μl/min) mixed with the LC effluent (100% A; 200 μl/min), with high- and low-mass resolution set at 15.0. Detector was a photomultiplier set at 650 V. Analyte concentrations were calculated by the

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internal standard method using demeclocycline as an internal standard [20]. Peak integration and quantitation were performed automatically using the MassLynx 3.5 software (Waters Corp., Milford, MA).

2.6 Determination of Extraction Efficiencies for CTC and CTC Metabolites To determine extraction efficiencies, duplicate samples of unmedicated manure slurry were spiked at 0.5 and 5 mg/l for CTC, ECTC and ICTC incubated 30 min, and extracted as described above. Recovery results shown in Table 2 were calculated as a means of duplicate samples at each concentration. There was no conversion of CTC to its metabolites during the experimental procedure. Recoveries of 0.5 mg/l spikes for CTC and metabolites were higher than recoveries of 5 mg/l spikes. Average recoveries of CTC, ECTC and ICTC were about 90, 85 and 78%, respectively. Table 2 Recovery of CTC and its metabolites in manure slurry

% mean recovery (95% confidence limits) Spike level, mg/l Compound

0.5

5.0

CTC ECTC ICTC

92 (88–96) 89 (87–91) 79 (75–84)

88 (82–94) 81 (75–87) 77 (75–79)

Recovery values are the means from duplicate samples

3 Results and Discussion Anaerobic digesters were incubated for 33 days at 35◦ C using 5-fold diluted manure collected from calves prior to and after CTC medication. The levels of water soluble and buffer extracted CTC and its metabolites during anaerobic digestion are shown in Fig. 2. The buffer extracted CTC levels decreased from initial 5.9 ± 0.3 and 1.0 ± 0.1 mg/l to 1.4 ± 0.1 mg/l and 0.3 ± 0.1 mg/l at the end of the study, for medicated high and low digesters, respectively (Fig. 2a). Overall, 74 and 75% removals of buffer extracted CTC were achieved for medicated high and low digesters, respectively, during 33 days of anaerobic digestion, yielding calculated CTC half-life values of 19 and 17 days for medicated high and low digesters, respectively. The water soluble CTC levels decreased from 0.32 ± 0.03 mg/l to 0.04 ± 0.02 mg/l (a 84% reduction, half-life value of 12 days) within 33 days for medicatedhigh digesters (Fig. 2b). The initial water soluble CTC concentrations were 0.02 ± 0.01 mg/l for medicated-low digesters and decreased to under the detection limit (0.01 mg/l) by day 33. When water soluble and buffer extracted CTC levels were

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water soluble

buffer extracted

0,4

8

Medicated, High Medicated, High

Medicated, Low

Medicated, Low

0,3

CTC, ppm

CTC, ppm

6 4

0,2

0,1

2 0

0,0 0

10

20

30

0

10

Time, days

(a)

20 Time, days

30

(b) water soluble

buffer extracted

1,2

6

Medicated, High Medicated, High

1,0

Medicated, Low

ECTC, ppm

ECTC, ppm

Medicated, Low

4

2

0,8 0,6 0,4 0,2

0

0,0 0

10

20

30

0

10

Time, days

(c)

30

(d) water soluble

buffer extracted

3,0

6

Medicated, High

Medicated, High

2,5

ICTC, ppm

Medicated, Low

ICTC, ppm

20 Time, days

4

2

Medicated, Low

2,0 1,5 1,0 0,5

0

0,0 0

10

20

30

0

10

20

Time, days

Time, days

(e)

(f)

30

Fig. 2 Water soluble and buffer extracted concentrations of CTC, ECTC and ICTC during anaerobic digestion of medicated calf manure slurry. Values are the means from triplicate digesters. Standard errors are shown as error bars

compared it was found that only about 5% of CTC was water extractable. Winckler and Grafe [19] reported a 55–57 day tetracycline half-life value using 20 and 100 μg/ml spiked concentrations in pig slurry incubated at 8◦ C. They also reported a 105 day half-life value using 20 μg/ml spiked concentration in outdoor experiments. In contrast, Kuhne et al. [12] reported half-life values of only 4.5 and 9 days at ambient temperature for tetracycline in aerated and non-aerated pig manure (containing

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200 μg/ml tetracycline), respectively. In our recent study, we determined oxytetracycline half-life value of 56 days for 10 mg/l initial concentration using calf manure at 35◦C [2]. For medicated-high digesters, buffer extracted ECTC levels decreased gradually from 4.1 ± 0.4 mg/l at the start of experiment to 2.5 ± 0.1 mg/l on day 33, yielding a calculated half-life value of 39 days, while water soluble ECTC concentrations increased from 0.5 ± 0.03 mg/l on day 0–0.93 ± 0.1 mg/l on day 33 (Fig. 2c, d). For medicated-low digesters, buffer extracted ECTC levels decreased from 0.56 ± 0.09 mg/l at the start of experiment to 0.39 ± 0.04 mg/l on day 33, yielding a calculated half-life value of 50 days, while water soluble ECTC concentrations increased from under the detection limit (0.01 mg/l) on day 0–0.08 ± 0.03 mg/l on day 33. The buffer extracted ICTC levels increased gradually from initial 2.3 ± 0.2 and 0.28 ± 0.02 mg/l to 4.6 ± 0.1 mg/l and 0.72 ± 0.03 mg/l at the end of the study, for medicated high and low digesters, respectively (Fig. 2e). Similarly, water soluble ICTC concentrations also increased from initial 1.03 ± 0.1 and 0.05 ± 0.02 mg/l to 2.66 ± 0.2 mg/l and 0.37 ± 0.03 mg/l at the end of the study, for medicated high and low digesters, respectively (Fig. 2f). The CTC metabolites of ECTC and ICTC were present in the manure from medicated calves. Therefore, both medicated high and low digesters had some initial concentrations of these metabolites. Although buffer extracted ECTC levels declined during anaerobic digestion, buffer extracted and water soluble ICTC concentrations increased for both medicated high and low digesters. In addition, water soluble ECTC levels increased during anaerobic digestion for both medicated high and low digesters. These results agree with a previous study in which decreases in CTC and ECTC levels and an increase in the level of ICTC were observed over time in outdoor anaerobic pig lagoons [14]. A study regarding the sorption of CTC and selected degradation products showed that the distribution coefficient to soil of the degradation products distributed more towards the water phase (Kd, ICTC < Kd, ECTC < Kd, CTC ) compared with the parent CTC, suggesting that the mobility of the degradation products was higher than of the parent compound [17]. This suggests that the degradation products present in digested manure slurry, even though these compounds are expected to be less potent than the parent compound [8] will be the ones potentially encountered in water and not the parent compounds.

4 Conclusions Approximately 75% removal of buffer extracted CTC was achieved in 33 days by anaerobic digestion at 35◦C yielding a calculated value half-life of about 18 days. However, our experiments do not resolve whether the reduction of CTC is caused by degradation, mineralization or binding of CTC to the organic matrix. Although buffer extracted ECTC levels declined during anaerobic digestion, buffer extracted

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and water soluble ICTC concentrations increased for both medicated high and low digesters. In addition, water soluble ECTC levels also increased during anaerobic digestion for both medicated high and low digesters. Because degradation products distributed more towards the water phase compared with the parent CTC, the degradation products present in digested manure slurry will be the ones potentially encountered in water. Acknowledgments The author is grateful to Dr. Walter Mulbry and Dr. Clifford Rice from U.S. Department of Agriculture for their contributions to this study.

References 1. American Public Health Association (APHA) (1992) Standard methods for the examination of water and wastewater, 18th edn. Washington, DC 2. Arikan O, Sikora LJ, Mulbry W, Khan SU, Rice C, Foster GD (2006) The fate and effect of oxytetracycline during the anaerobic digestion of manure from medicated calves. Process Biochem 41:1637–1643 3. Bennett K (1993) Compendium of veterinary products, 2nd edn. North American Compendiums Inc., Port Huron, MI 4. Capone DG, Weston DP, Miller V, Shoemaker C (1996) Antibacterial residues in marine sediments and invertebrates following chemotherapy in aquaculture. Aquaculture 145:55–75 5. Chee-Sanford JC, Aminov RI, Krapac IJ, Garrigues-Jeanjean NG, Mackie RI (2001) Occurence and diversity of tetracycline resistance genes in lagoons and groundwater underlying two swine production facilities. Appl Environ Microbiol 67:1494–1502 6. Elmund GK, Morrison SM, Grant DW, Nevins MP (1971) Role of excreted Chlortetracycline in modifying the decomposition process in feedlot waste. Bull Environ Contam Toxicol 6(2):129–132 7. Fedler CB, Day DL (1985) Anaerobic digestion of swine manure containing an antibiotic inhibitor. Trans ASAE 28:523–530 8. Halling-Sørensen B, Sengeløv G, Tjørnelund J (2002) Toxicity of tetracyclines and tetracycline degradation products to environmentally relevant bacteria including selected tetracycline resistant bacteria. Arch Environ Contam Toxicol 42:263–271 9. Hamscher G, Abu-Quare A, Sczesny S, Höper H, Nau H (2000) Determination of tetracyclines and tylosin in soil and water samples from agricultural areas in Lower Saxony. In: van Ginkel LA, Ruiter A (eds) Proceedings of the Euroside IV Conference, National Institute of Public Health and the Environment (RIVM), Bilthoven, Netherlands, pp 522–526 10. Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT (2002) Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999–2000: A national reconnaissance. Environ Sci Technol 36:1202–1211 11. Kolz AC, Moorman TB, Ong SK, Scoggin KD, Douglass EA (2005) Degradation and metabolite production of Tylosin in anaerobic and aerobic swine-manure lagoons. Water Environ Res 77:49–56 12. Kühne M, Ihnen D, Mölller G, Agthe O (2000) Stability of tetracycline in water and liquid manure. J Vet Med A 47:379–384 13. Loftin KA, Henny C, Adams CD, Surampali R, Mormile MR (2005) Inhibition of microbial metabolism in anaerobic lagoons by selected sulfonamides, tetracyclines, lincomycin, and tylosin tartrate. Environ Toxicol Chem 24:782–788 14. Meyer M (2005) Pharmaceuticals and other emerging contaminants in US water resources: methods, results, and a developing national perspective. Workshop to identify emerging contaminants of concern and their implications for the estuarine and human health, May 11–12, Washington, DC, USA

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15. Søeberg T, Ingerslev F, Halling-Sørensen B (2004) Chemical stability of chlortetracycline and chlortetracycline degradation products and epimers in soil interstitial water. Chemosphere 57:1515–1524 16. Swick RA (1996) Role of growth promotants in poultry and swine feed. American Soybean Association. Tech Bull AN04:10 17. Tjørnelund J, Jensen RB, Ma HP, Halling-Sørensen B (2000) Sorption of chlortetracycline and its decomposition products in soil. Dans Kemi 81:12–14 18. Wilkie A (2005) Anaerobic digestion of dairy manure: design and process considerations. In: Proceedings of the Dairy Manure Management Conference, Natural Resource, Agriculture and Engineering Service, Cornell University, Ithaca, NY, pp 301–312 19. Winckler C, Grafe A (2001) Use of veterinary drugs in intensive animal production: Evidence for persistence of tetracycline in pig slurry. J Soils Sediments 1:66–70 20. Zhu J, Snow DD, Cassada DA, Monson SJ, Spalding RF (2001) Analysis of oxytetracycline, tetracycline, and chlortetracycline in water using solid-phase extraction and liquid chromatography tandem mass spectrometry. J Chromatogr A 928:177–186

Adsorption of Methylene Blue from Aqueous Solution onto Bentonite J. Krsti´c, Z. Mojovi´c, A. Abu Rabi, D. Lonˇcarevi´c, N. Vukeli´c, and D. Jovanovi´c

Abstract Technological development brought a number of advantages and conveniences to the modern life, but also brought many problems, environment pollution above all. Although a number of methods for water refining are already developed, there is still a demand to find a more efficient, cheaper and ecologically more acceptable sorbents. Possibility of using bentonite as naturally occurring material for methylene blue (MB) removal from its aqueous solutions was investigated in this paper. Characterization of starting material has been conducted by chemical analysis, XRD, particle size analysis, and N2 physisorption at –196◦C. The influence of the acidity of the initial MB solution on bentonite sorption characteristic was examined. Equilibrium sorption isotherms were determined. It was shown that with increase of pH and temperature the amount of sorbed MB increases. Keywords Bentonite · Methylene blue · Sorbent · Adsorption isotherm · Acidity

1 Introduction Synthetic dyes were used extensively by numerous industrial branches. Products of modern textile, food and cosmetic industry would be unrecognizable without synthetic dyes. It was estimated that 10–15% of all manufactured dyes were lost in the dye effluent during dyeing processes. There are numerous conventional methods for treating dye-containing wastewaters, such as coagulation and flocculation, reverse osmosis and ionic exchange. Activated carbon adsorption is particularly interesting due to its exceptional capacity and excellent efficiency. Still, large amounts of wastewaters cause strong economic pressure for finding cheap adsorbent, and with simple and quick technological use. J. Krsti´c (B) Department for Catalysis and Chemical Engineering, ICTM, Njegoševa12, 11000 Belgrade, Republic of Serbia e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_103,

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It seems that sorption of dyes from wastewaters on clays fulfill these demands. Use of this kind of sorbent is particularly convenient since it would not cause secondary environmental pollution. Several factors influence the adsorbability of ions on clays, including degree of loading on the adsorbent, presence of ligands, complex formation, pH and concentration of the dye solution. However, there are diverse results about the effect of pH on the organic cation adsorption in the literature. For example, Kar et al. [1] found that dye adsorption capacity of silicates increases with the increase of pH. On the other hand, Narine and Guy [2] have reported that the adsorption capacity of bentonite was essentially independent of pH in the range 4.5–8.5. There are numerous literature data on application of various natural and activated clays in decolorization process [3–6]. In this paper bentonite was used as decolorization agent. Bentonite is hydrated aluminosilicate clay mainly composed of the smectiteclass mineral montmorillonite [7]. It is a 2:1 type aluminosilicate having crystalline structure consisting of alumina octahedral layer between two tetrahedral layers of silica. Isomorphic substitution within the layers generates negative charges that are counterbalanced by alkaline or alkaline earth cations. Bentonite has the capacity to exchange these cations with the ones present in aqueous solutions [8]. The ideal formula of mineral montmorillonite is (Na, Ca)0.33 (Al1.67, Mg0.33)Si4 O10 (OH)2 ·nH2 O [9]. The aim of this paper was to estimate the influence of the acidity of the initial aqueous MB solution on adsorbent behavior of bentonite. Influence of the contact time between bentonite and MB solution as well as the influence of the temperature of the initial solution was also investigated. Equilibrium sorption isotherms were determined. It was estimated that simple preparation of bentonite enables use of bentonite as promising sorbent.

2 Experimental Bentonite from coal mine, Bogovina -East Serbia was used as sorbent in all experiments. Raw bentonite was milled in the ball mill (120 min) and the fraction <74 μm was separated by sieving. The classical chemical silicate analysis of this fraction was performed. Dimensions and particle size distributions were determined by particle dimension laser analyzer Mastersizer 2000, (Malvern Instruments). The measurements were performed with 0.0054% water suspension obtained after 10 min of ultrasonic disaggregating. Disaggregation time was determined in preliminary experiment consisting of 10 successive measurements. Particle dimension measurement was performed in the range 20 nm−74 μm. The refraction index for dispersant and dispersion agent were 1.650 and 1.330, respectively. The phase identification was obtained by XRD analysis using Philips PW 1710 X-ray powder diffraction spectrometer with copper anticathode (λ=0.154178 nm) operating at 40 kV and 30 mA. Nitrogen adsorption-desorption isotherm was measured using Sorptomatic 1990

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N

Fig. 1 Structural formula of methylene blue

(H3C)2N

S Cl

N(CH3)2 –

(Thermo Finnigan). Before measurement the sample was outgassed at 180◦C for 10 h. Software-WinADP(CE Instruments) was used to analyze the obtained isotherm and calculate the total pore volume at p/p0 >0.99 (Vtot), volume of micropores (Vmic )- according to Dubinin-Raduschkevich equation [10], specific surface area (SBET ) -according to Brunauer, Emmett, Teller [11] and mesopore volume (Vmes ) from desorption branch of isotherm according to Barret, Joyner, Halenda model [12]. Methylene blue is well studied cationic thiazine color. Figure 1 presents the structure of methylene blue. The ionic nature of MB is a result of delocalized positive charge. Ionic nature can play important role in holding species on the sorbent surface, leading to chemical reaction beside the adsorption phenomena. In order to determine equilibrium contact time between dye and clay three test dye/clay systems were examined in Erlenmeyer flasks with ground rim cap. In each flask the 50 ml MB solution concentration of 2.0 mg/dm3 was added and pH of solution was adjusted to 3.0, 5.8 and 11.0 pH unit. The shaking at orbital shaker started after adding 1.0 ml of bentonite suspension having concentration of 250 mg/dm3. Test samples for spectrofotometric measurement were taken after 15, 30, 45, 60, 90 and 120 min starting from the moment of dye/clay contact. Afterwards sampling was performed each 2 h, having the last sample taken after 24 h. Determination of MB adsorption isotherms was performed with aqueous solutions of MB having concentrations in range 0.5–10.0 mg/dm3. Acidity of all solutions was adjusted on two working values: 3.0 and 11.0 by adding micro liter volumes of 4 mol/dm3 either HCl or NaOH solution. All pH values were measured by pH–meter 3320 JENWAY equipped with ATC probe. Anthelie Advanced 5, (Secomam, France) spectrophotometer in the interval of wavelengths 640–690 nm and calibration curve method was used for all spectrophotometric measurements.

3 Results and Discussion The results of chemical analysis are given in Table 1. Although, the chemical composition has provided insufficient information to estimate the type of investigated clay, the obtained results were in accordance with previously published data for naturally occurring bentonite [13, 14]. Diffractogram of investigated sample is presented in Fig. 2. The phases were identified according to JCPDS [15]. The X-ray patterns of bentonite showed the

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J. Krsti´c et al. Table 1 Results of chemical analysis Oxide

SiO2

Al2 O3

Fe2 O3

MgO

CaO

Na2 O

K2 O

Mass, %

57,51

17,13

7,67

2,35

1,81

0,75

1,18

Q

180

Intensity, a.u.

160 140 80

S Q

60 40

S Q

C

S

F

I

C/Q Q Q

20 0 10

20

30

40

50

2Θ,o

Fig. 2 X-ray diffraction patterns of samples (S=smectite, Q=quartz, C=calcite, F=feldspar, I=illite)

presence of montmorillonite, quartz, illite, calcite and feldspar. The diffusion peak between 15 and 35◦ 2θ indicated the presence of small amounts of amorphous phase. According to XRD results the main constituent of bentonite admixture was montmorillonite [16]. Figure 3(a) shows the results of particle size measurement in the range 0.4–4.0 μm. This interval was chosen since 99.1% of all particles have diameter smaller than 4.0 μm, and almost no particles smaller than 0.5 μm were present. This was of (a)

(b) 5 4 Volume, %

Frequency, %

20 15 10

3 2

5

1

0

0 0.4

0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6 4.0 Particle size, μm

1

10 Particle size, μm

Fig. 3 Particle size distribution (a) and volume size distribution (b) of bentonite powder

Adsorption of Methylene Blue from Aqueous Solution onto Bentonite

1101

special interest considering that such uniformity was accomplished by simple, not economically demanding, technological procedure like milling and sieving. Exactly 50.0% of all particles (D0.5 ) had diameter smaller than 1.01 μm. Figure 3(b) shows the pore volume distribution of entire bentonite particles. Particles with diameter smaller than 11.1 μm occupy 90.0% of total volume of raw material (D0.9). Occurrence of particles smaller than 4.0 μm expressed as total volume ratio was 59.05%. Considering the contribution of larger fraction, disagreement of results presented as volume fractions and particle diameter frequency was not surprising. For example the sphere particle having diameter of 2.3 μm occupies the same volume as 100 spheres with 0.5 μm in diameter. Based on the adsorption-desorption isotherm N2 at −196◦C, calculated textural parameters of tested fraction of bentonite are: SBET =96 m2 /g, total pore volume Vtot = 0.111 cm3 /g, mesopore volume Vmes =0.064 cm3 /g and micropores volume Vmic =0.045 cm3 /g. Textural properties of investigated bentonite are comparable with bentonite from other localities in the world. For example: the value for SBET was higher than specific surface area of commercial Wyoming bentonite (44 m2 /g), and slightly lower than Moosburg montmorillonite (124 m2 /g) and Otay montmorillonite (144 m2 /g) [17]. Although the mechanisms of MB sorption on bentonite are significantly different from nitrogen physisorption, the results obtained for SBET suggested the assumption of significant sorptive power of investigated bentonite fraction. The bentonite was added in the form of suspension since the small amounts of bentonite were sufficient. The obtained calibration diagram of water–bentonite suspension had confirmed that absorbance was directly proportional to the concentration of bentonite in the wide UV range. Dependence of absorbance on concentration of bentonite suspension in interval 100–350 mg/dm3 for λ=240 nm is presented in Fig. 4. One of the parameters that also have the influence on adsorption is contact time between dye and clay. There is no all-explaining mechanism of adsorption of cation dyes (like methylene blue) on layered silicate surface. Dominant hypothesis explains dye elimination process by unspecific adsorption mechanism e.g. ionic exchange. The formations of relatively weak nonselective dye-particle complexes,

A

1,2

0,8

0,4

Fig. 4 Absorbance vs. bentonite suspension concentration

100

200

300

C, mg/dm3

400

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together with reversibility of process are typical for reactions controlled by diffusion. Still, some parameters (efficiency of dye elimination from suspension depend on pH value) indicate the contribution of surface precipitation. Above all contributions mentioned mechanism of dye adsorption is also modified by aggregation of organic cations. The authors of this paper have also noticed this phenomenon. The aggregation changed the light absorbing properties of chromophore significantly. The mixing of clay suspension with MB solution caused the immediate significant change in color of the investigated system as a direct consequence of aggregation of dye molecules. In order to determine contact time between dye and clay sufficient for reaching equilibrium condition, three test dye/clay systems were examined in the procedure referring to Experimental section. Results for all three pH values are presented in Fig. 5. The obtained results indicated several conclusions. First, dye aggregation and bonding with bentonite particles is fast process (takes only few minutes). Dye disaggregation and reaching equilibrium are slow processes, probably controlled by ratio between number of accessible bonding centers and dye concentration in suspension. In the previously published data there was a wide range of estimated equilibrium times [18, 19]. Figure 5 shows that measurements of equilibrium concentration for contact times less than 20 h wouldn’t be taken at equilibrium conditions. Therefore all measurements were performed with dye-bentonite contact time of 24 h. Experimental conditions for isotherm measurement were determined after preliminary tests. Figure 6 presents adsorption spectra of MB solution having concentration of 4.0 mg/dm3 for unadjusted pH=5.8 and adjusted at pH =11.0 and pH=3.0. The obtained results indicated that difference in intensity of adsorption spectra arose from dye auto-aggregation which was undoubtedly present in alkali solution similar to Al-Ghouti results [20]. It was obvious that all the spectra had the same shape for observed pH values, indicating the absence of any chemical reactions with ions added during pH adjustment. These results suggested that caution should be taken in interpretation of color elimination results in order to distinguish the contribution of sorption agent from the characteristics of dye itself. Literature data for adsorption curve maximum for diluted aqueous solution were in the interval

pH=3.0 pH=5.8 pH=11.0

A

0,3

0,2

Fig. 5 Equilibrium time estimation in system bentonite/MB

0,1 0

400

800 Time, min

1200

Adsorption of Methylene Blue from Aqueous Solution onto Bentonite

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Fig. 6 Effect of pH of methylene blue solution on absorbance

of 664–668 nm due to either auto aggregation or/and presence of impurities [21]. However, in this experiment and with given instrument maximum was over the range 663–665 nm, at all investigated pH values. Spectrophotometric calibration diagrams were recorded for each measurement using solutions in 0.5–10.0 mg/l concentration range, prepared on daily bases (with proper pH adjustment). The correlation factor for all calibration curves was ≥ 0.99. Besides the usual limitation of the LambertBeer law, the solutions of MB with concentrations higher than 10 mg/dm3 aggregate shift the wavelength of absorption maximum. The adsorption data were analyzed according to the Langmuir equation [22] where Ceq was the equilibrium concentration of solute remaining in the solution (mmol/dm3), x/m was the quantity of solute adsorbed per unit mass of adsorbent (mmol/g), qL and KL were Langmuir constants. These constants are called adsorption capacity (solute monolayer capacity) and bonding energy constant, respectively. The experimental data were fitted with straight lines by the least squares method, where the slope of the regression line was 1/qL and the intercept was 1/(KL ·qL .). The linear regression lines obtained had highly significant correlation coefficients (r), indicating a good agreement with the Langmuir equation. Ceq 1 1 = + · Ceq x/m KL · qL qL

(1)

Linear form of Langmuir isotherms are shown in Figs. 7 and 8, while Langmuir constants are given in Table 2. The correlation coefficients (r) almost have reached the ideal value of 1 indicating the excellent agreement between chosen model and experimental data. In this way the concept of monolayer adsorption for investigated interval of MB solution concentrations was confirmed. The values of Langmuir constants unambiguously showed the existence of dependence between sorptive properties of bentonite and acidity of initial MB solution for both investigated temperatures. With higher pH value the higher adsorption capacity was obtained. The

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Fig. 7 Equilibrium adsorption isotherms at 18◦ C Ceq/(x/m), g /dm3

0.020 0.015

T=18°C pH=3 pH=11

0.010 0.005 0.000 0.000

0.010

0.005

0.015 0.020

0.025

Ceq, mmol/dm3

0.020

Fig. 8 Equilibrium adsorption isotherms at 28◦ C Ceq/(x/m), g/dm3

T=28°C 0.015

pH=3 pH=11

0.010

0.005

0.000 0.000

0.005

0.010

Ceq, mmol/dm3

Table 2 Parameters of Langmuir isotherm Langmuir parameter qL (mmol/g) KL (dm3 /mmol) r

T=18◦ C

T=28◦ C

pH = 3

pH = 11

pH = 3

pH = 11

0.67 2.42×103 0.997

1.40 1.65×103 0.996

0.77 0.88×103 0.991

2.35 0.50×103 0.955

influence of pH is more significant for higher temperature, which can be assigned to the effect of solvent on solid phase of sorbent as G. Atun et al. well noticed [23]. The adsorption capacity, at constant pH, increase with increase of temperature that is in accordance with the behavior of previously published natural silicate materials [23, 24]. It should be pointed out that the increase of the adsorption at higher temperature might be caused by easier penetration of MB in the interlamelar layer of bentonite.

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4 Conclusion The possibility of using natural bentonite from locality “Bogovina”- East Serbia for methylene blue removal from its aqueous solutions was investigated. Chemical and XRD analysis confirmed dominant presence of montmorillonite in sample. It was shown that simple preparation of bentonite, milling and sieving enables the use of bentonite as promising sorbent. Equilibrium sorption isotherms for all investigated pH values confirmed that equilibrium can be reached after 20 h. The good agreement with Langmuir type of isotherm confirmed the concept of monolayer adsorption on bentonite for investigated MB solutions. The adsorption capacity increases both with the increase of pH of initial MB solution and with the increase of temperature. Acknowledgments This work was partially supported by the Ministry of Science & Environmental Protection of Republic of Serbia (Projects: TR 6712B and TD -7057B).

References 1 Kar HS, Mundhara GL, Sharma GL, Tiwari JS (1991) Sorption—desorption studies of cationic dyes on silica gel pretreated with alkalis in relation to chromatography. Colloids Surf 55:23–40 2 Narine DR, Guy RD (1981) Interactions of some large organic cations with bentonite in dilute aqueous systems. Clays Clay Miner 29:205–212 3 Konta J (1995) Clay and man: clay raw materials in the service of man. Appl Clay Sci 10:275– 335 4 Tsai WT, Chang YM, Lai CW, Lo CC (2005) Adsorption of basic dyes in aqueous solution by clay adsorbent from regenerated bleaching earth. Appl Clay Sci 29(2):149–154 5 Miyamoto N, Kawai R, Kuroda K, Ogawa M (2000) Adsorption and aggregation of a cationic cyanine dye on layered clay minerals. Appl Clay Sci 16(3–4):161–170 6 Orthman J, Zhu HY, Lu GQ (2003) Use of anion clay hydrotalcite to remove coloured organics from aqueous solutions. Separation Purif Technol 31(1):53–59 7 Kawatra SK, Ripke SJ (2001) Developing and understanding the bentonite fiver forming mechanism. Min Eng 14:647–659 8 Rodriguez-Sarmiento DC, Pinzon-Bello JA (2001) Adsorption of sodium dodecylbenzene sulfonate on organophilic bentonites. Appl Clay Sci 18:173–181 9 Grim RE (1968) Clay mineralogy, 2nd edn. McGraw–Hill, New York, NY 10 Dubinin MM (1975) Progress in surface and membrane science, vol 9. Academic, New York, NY 11 Rouquerol F, Rouquerol J, Sing K (1999), Adsorption by powders and porous solids. Academic, London 12 Barret EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J Am Chem Soc 73:373–380 ˇ 13 Vejsada J, Hradil D, Randa Z, Jelínek E, Štulík K (2005) Adsorption of cesium on Czech smectite-rich clays—A comparative study. Appl Clay Sci 30(1):53–66 ˇ ce B (1978) Dissolution of smectites in hydrochloric acid; II, Dissolution rate as a 14 Novak I, Ciˇ function of crystallochemical composition. Clay Clay Miner 26(5):341–344 15 Jenkins, R., and Holomany M (1987) PC-PDF: A search/display system utilizing the CDROM and the complete powder diffraction file. Powder Diffraction 2(4):215–219 16 Milutinovi´c-Nikoli´c A, Vukovic Z, Krstic J, Roži´c LJ, Jovanovi´c D (2005) Acid-activated bentonite as potential mesoporous catalyst. Proceedings of the EUROPACAT-VII, Sofia, p 81

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17 Van Bekkum H, Flanigen EM, Jansen JC (1991) Studies in surface science and catalysis. Introduction to zeolite science and practice, vol 58. Elsevier, Amsterdam 18 Panaiotova T, Obretenov TS, Panaiotov P (1977) Adsorption of some natural clay materials, Bulg, vol 11. Godishnik na Visshiya Khimiko-Tekhnologichen Institut, Burgas, pp 47–52 19 BilgiçC (2005) Investigation of the factors affecting organic cation adsorption on some silicate minerals. J Colloid Interface Sci 281:33–38 20 Al-Ghouti MA, Khraisheh MAM, Allen SJ, Ahmad MN (2005) Thermodynamic behaviour and the effect of temperature on the removal of dyes from aqueous solution using modified diatomite, pp. A kinetic study. J Colloid Interface Sci 287:6–13 21 Bergmann K, O‘Konski CT (1963) A spectroscopic study of methylene blue monomer, dimmer, and complexes with montmorillonite. J Phys Chem 67:2169–2177 22 Langmuire I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 40(9):1361–1368 23 Atun G, Hisarli G, Sheldrick WS, Muhler M (2003) Adsorptive removal of methylene blue from colored effluents on fuller s earth. J Colloid Interface Sci 261(1):32–39 24 Dogan M, Alkan M, Onganer Y (2000) Adsorption of methylene blue from aqueous solution onto perlite. Water, Air Soil Pollut 120:229–248

The Evaluation of the Pb(II) Removal Efficiency of Duckweed Lemna Minor (L.) from Aquatic Mediums at Different Conditions Ya˘gmur Uysal and Fadime Taner

Abstract Recently, the investigations have focused on the study of aquatic macrophytes as promising candidates for pollutant uptake and biological indicators of heavy metals in aquatic systems. Macrophyte-based treatments such as constructed wetlands appear to be highly competitive among the existing secondary treatment methods. Vegetation is important components of constructed wetlands designed to treat metal contaminated water. Waste effluents are characterized by substantial variations in pH values, and may have different heavy metal ions at variety concentration range. In this study, the effects of pH (4.5–8.0), temperature (15–35◦C) and concentration (0.1–10.0 mgPb/L) on the bioremoval capacity of duckweed Lemna minor were investigated. The amount of biomass obtained in study period on dry basis, the concentrations of Pb(II) in tissue and in medium, and net uptake of Pb(II) by Lemna have been determined in different conditions. The percentages of Pb(II) uptake ratios were calculated for each condition. It was found that bioaccumulated Pb(II) concentrations and the maximum percentage removal were obtained at pH 4.5 and at 30◦ C. It was found that the concentration of Pb(II) in the plant biomass gradually increased with increase in concentration of Pb(II) in culture medium, but opposite trend was observed for the percentage of Pb(II) uptake. Keywords Duckweed · Lead · Lemna minor · Metal uptake · Phytoremediation

1 Introduction In recent years, phytoremediation technologies i.e. the use of plants to cleanup water and soils contaminated with different organic and inorganic pollutants such as heavy metal ions are showing a promising method. Plants can be used to remove, transfer,

Y. Uysal (B) Kahramanmara¸s Sütçü ˙Iman University, Av¸sar Campus, 46100 Kahramanmara¸s, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_104,

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stabilize and/or degrade heavy metal contaminants [1]. This technique has many advantages compared with the other remediation procedures: low economic costs, the generation of recyclable materials and the possibility of being applied to soil and water causing a minimum environmental impact [2]. Phytoremediation was first adapted to constructed wetlands, reed beds and floating plant systems for the treatment of contaminated ground and wastewaters for years [3, 1]. Constructed wetlands are among the recently proven efficient technologies for wastewater treatment. Compared to conventional treatment systems, constructed wetlands are low cost and easily operated systems for wastewater treatment. Plants play important roles in constructed wetlands for the removal of pollutants [4]. They not only take up nutrients, but are also able to absorb and accumulate metals in their tissues [5]. The advantage of using living biomass in these systems is the rapidly regenerating supply of biomass [6]. Duckweeds, Lemnaceae family are simple small flowering aquatic plants. This family consists of five genera Lemna, Spirodela, Wolffia, Wolffiella, and Landoltia. The individual green structures (usually named “fronds”) float on the surface of water or just below it. These plants are quite suitable for aquatic treatment systems in temperate and temperate-continental regions [7]. For instance, duckweeds have a wider geographic range, so that they can vegetate at temperatures between 7 and 30◦ C. Duckweed can be used in water treatment systems to remove various pollutants such as heavy metal ions. Lemna species are commonly used in constructed wetlands. Lemna species have been also widely used in toxicity testing of chemicals and effluents [8]. Waste effluents are characterized by substantial variations in pH, and may have different heavy metal ions at variety concentration range. In addition, bioaccumulation of metal ions depends upon numerous biotic and abiotic factors, such as temperature, pH and dissolved ions in water [9]. The choosing of the most suitable plant species for phytoremediation is an important factor to obtain successful treatment for metal ions. However, selection of an optimal aquatic plant species will also depend on the ease of growth of the plant. Thus, this paper reports the results of the study on the uptake of Pb(II) by freshwater macrophyte duckweed Lemna minor grown in different aquatic medium conditions such as initial pH (4.5–8.0), temperature (15–35◦C) and concentrations (0.1–10.0 mgPb/L). It was also determined the amount of biomass produced during the study period on dry basis. The Pb(II) concentrations in the tissue and medium, and net uptake of Pb(II) by duckweed for different conditions were determined. The percentages of Pb(II) uptake were calculated for each condition.

2 Material and Methods 2.1 Plant Material and Growth Conditions The test species Lemna minor was collected from quiescent fresh water canals used for irrigation of agricultural areas in Mersin (Turkey). Plants taken to laboratory

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were first washed carefully with tap water several times to remove dirt, sludge and other debris. Then, the plants were set into culture pots with a capacity of 1 L and filled with Synthetic Duckweed Nutrient Solution (DNS) [10]. They were grown in this culture solution and allowed to acclimate to the laboratory conditions for a month before addition of metal solutions. All stock cultures were maintained in a growth chamber at 27±2◦C with 16 h photoperiod at a photosynthetic photon density of 2,100 lux.

2.2 Test Procedures Experiments were carried out in flasks at different conditions. At each condition, the experiments were run in triplicate and the average results were reported. Each experiment was run for 168 h. At the beginning of each run, 40 fronds were set in each flask of 250 mL capacity containing 200 mL DNS. Plants which are healthy, in light green and in same sizes were chosen. Metal solutions were added directly to the nutrient medium. The initial pH of solutions was adjusted with HCI and NaOH solutions, and the pH change of each experimental set was monitored daily. In these sets established to determine the effect of initial pH on the Pb(II) uptake of Lemna, the medium temperature was used as laboratory temperature at 25–27◦C. In order to search lead removal activity of plants at different temperatures, the medium temperature was set at 15–35◦C range. For all studied conditions, the residual concentrations of Pb(II) in each solution were analyzed with time (at 24, 72, 120, and 168 h) and the equilibrium concentrations (Ce ) of Pb(II) were determined. At the end of the study period, plant samples were collected from the medium. All plants of each replicate were then washed with deionized water, and dried at 70◦ C to a constant weight. Dried plant samples were weighed (Xm ) and digested on a hot-plate with following the digestion process [11] to measure of accumulated metal ion amount per unit mass (mgPb/g). The lead content of all digested water and plant samples was determined by Graphite Furnace Atomic Absorption Spectrophotometer (GFAAS). A reagent blank was also digested in the same manner. The culture solutions having any plant samples were used as controls for each set were used to determine if there is any adsorption mechanism on flask wall. These samples were also subjected the same operations.

2.3 Reagents All solutions were prepared with high purity deionized water. All reagents used were of analytical grade. Lead stock solutions were prepared with lead (II) nitrate Pb(NO3 )2 (Merck).

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2.4 Calculations Concentrations of Pb(II) were measured directly by GFAAS using sample standards and calibration curves done internally on the GFAAS unit. The bioremoval potential of Lemna was expressed as percentage of metal ion uptake (PMU) and calculated according to following Eq. 1. The mass balance was also determined as the sum of lead mass in solution and plants. Mass of Pb(II) in Lemna × 100 (1) Mass of Pb(II) in medium

PMU (The percentage of Pb(II) uptake) =

3 Results and Discussion 3.1 The Effect of Initial pH of Culture Medium on the Uptake of Pb(II) Ions by L. Minor In order to investigate the effect of initial pH of culture solution on the lead accumulation, water samples were collected from the flasks having different initial pH at 4.5–8.0 range and containing lead ions in 0.1–10.0 ppm. In order to determine the equilibrium Pb(II) concentrations, water samples were withdrawn at certain periods. It was found that the lead ion concentration in the culture solution did not change significantly with initial pH of culture medium. Pb(II) concentrations of these culture media declined rapidly at first 24 h, then slowly to 72nd h, and then remained stable after 72 h [12]. In addition, the highest Pb(II) concentration in the dry mass of plant biomass was found at pH 4.5, temperature at 25◦C, and initial Pb(II) concentration of 10.0 mg/L (Fig. 1). It decreased at pH 4.5–6.0 range, but it did not change

14.00

mgPb(II)/g

12.00 10.00 8.00 6.00 4.00 2.00 0.00 4.5

5

5.5

6

6.5

7

Pb 2.5

Pb 5.0

7.5

8

pH Pb 0.1

Pb 0.5

Pb 1.0

Pb 10.0

Fig. 1 The effect of initial pH on accumulated Pb(II) concentrations (0.1–10.0 mgPb/L, 25◦ C)

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Table 1 The effects of initial pH on Pb(II) accumulation capacity of Lemna (0.1–10.0 mgPb/L, 25◦ C, pH 4.5–8.0) pH 4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

C0 = 0,1 mgPb/L Ce (mg/L) 0.042 ±SD ±0.008 Xm (g/L) 0.103 mgPb/g 0.555 ±SD ±0.004 %PMU 56.90

0.040 ±0.005 0.115 0.519 ±0.010 59.70

0.030 ±0.005 0.110 0.544 ±0.042 59.90

0.025 ±0.005 0.150 0.464 ±0.017 69.60

0.024 ±0.002 0.145 0.491 ±0.052 71.20

0.025 ±0.002 0.162 0.413 ±0.027 66.90

0.023 ±0.006 0.162 0.300 ±0.015 48.80

0.021 ±0.006 0.149 0.342 ±0.033 50.80

C0 =0.5 mgPb/L Ce (mg/L) 0.320 ±SD ±0.010 Xm (g/L) 0.108 mgPb/g 1.179 ±SD ±0.027 %PMU 25.50

0.290 ±0.019 0.122 1.024 ±0.017 24.90

0.311 ±0.021 0.115 0.972 ±0.021 22.30

0.216 ±0.060 0.108 0.723 ±0.024 15.60

0.240 ±0.032 0.122 0.778 ±0.023 18.90

0.214 ±0.022 0.108 0.753 ±0.028 16.30

0.200 ±0.028 0.128 0.554 ±0.010 14.20

0.182 ±0.064 0.122 0.641 ±0.010 15.60

C0 =1.0 mgPb/L Ce (mg/L) 0.450 ±SD ±0.013 Xm (g/L) 0.103 mgPb/g 1.875 ±SD ±0.079 %PMU 19.20

0.400 ±0.006 0.119 1.242 ±0.116 14.80

0.335 ±0.015 0.113 0.997 ±0.079 11.30

0.320 ±0.012 0.124 0.836 ±0.120 10.40

0.345 ±0.015 0.135 0.764 ±0.072 10.30

0.310 ±0.015 0.146 0.752 ±0.054 11.00

0.397 ±0.012 0.146 0.820 ±0.036 12.00

0.300 ±0.007 0.140 0.685 ±0.104 9.60

C0 =2.5 mgPb/L Ce (mg/L) 1.100 ±SD ±0.174 Xm (g/L) 0.124 mgPb/g 1.917 ±SD ±0.134 %PMU 9.50

0.910 ±0.171 0.113 1.525 ±0.111 7.00

0.870 ±0.125 0.119 1.362 ±0.118 6.50

1.100 ±0.100 0.113 1.385 ±0.299 6.30

0.880 ±0.200 0.119 1.362 ±0.043 6.50

0.976 ±0.200 0.124 1.226 ±0.092 6.10

0.820 ±0.126 0.130 1.322 ±0.177 6.90

0.595 ±0.093 0.135 1.481 ±0.061 8.00

C0 =5.0 mgPb/L Ce (mg/L) 2.875 ±SD ±0.324 Xm (g/L) 0.142 mgPb/g 2.401 ±SD ±0.222 %PMU 6.80

2.750 ±0.160 0.142 2.205 ±0.112 6.30

2.425 ±0.205 0.142 1.820 ±0.109 5.20

2.335 ±0.167 0.128 1.580 ±0.067 4.00

2.300 ±0.356 0.151 1.347 ±0.078 4.10

2.600 ±0.194 0.128 1.380 ±0.094 3.50

2.660 ±0.435 0.123 1.418 ±0.138 3.50

2.550 ±0.500 0.142 1.420 ±0.058 3.50

C0 =10.0 mgPb/L Ce (mg/L) 4.600 ±SD ±0.668 Xm (g/L) 0.118 mgPb/g 3.599 ±SD ±0.116 %PMU 4.30

4.160 ±0.442 0.113 2.866 ±0.164 3.30

3.744 ±0.836 0.123 2.196 ±0.180 2.70

3.760 ±0.130 0.123 1.628 ±0.124 2.00

3.780 ±0.323 0.128 1.570 ±0.163 2.00

3.680 ±0.492 0.113 1.580 ±0.185 1.80

3.920 ±0.581 0.132 1.441 ±0.171 1.90

3.140 ±0.671 0.118 1.416 ±0.113 1.70

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above pH 6.0, significantly. It was also found that the amount of lead ion concentrations of plant biomass increased with the increase of lead ion concentration of medium. In order to determine the bioremoval capacity of Lemna, denoted as PMU was calculated for each initial pH and the concentration. The PMU values, the initial, the equilibrium and the accumulated concentrations of Pb(II), and the amount of biomass grown in these media were determined and are shown in Table 1. It can be seen from the Table 1 that PMU changed depending on the initial pH in every concentration of Pb(II). The maximum PMU was obtained at pH 4.5, but it decreased at pH 4.5–6.0 range, and it did not change above pH 6.0, generally. The findings showed that accumulated Pb(II) concentration in the plant biomass and PMU decreased with the increase of pH. The maximum PMU was obtained as 71.20−48.80% in 0.1 ppm, and the minimum PMU was obtained 4.30−1.70% in 10.0 ppm. These values also showed that the percent removal of Pb(II) decreased with increase of Pb(II) concentration in the culture medium while an opposite trend was observed with the uptake of Pb(II) by the plants. Although the initial pH’s of culture media for each experimental set were adjusted to pH 4.5–8.0 range, pH values of samples raised up to 7.0–8.0 range. In addition to this, some lead ion losses were determined in mass balance calculations. In order to determine the reason of the increase of pH, the control samples were prepared by adjusting the initial pH to 5.0, and pH’s were determined with time. These control samples had only lead ions at different concentrations. The control samples were also used to determine both the metal uptake efficiencies of plants and the probable metal losses in the culture medium. In the same way, water samples were withdrawn from these controls and lead ion concentrations were analyzed (Fig. 2). It was found that there is no change in pH of control samples. It was also determined that while lead ion concentrations of controls did not decrease significantly with time, lead concentration of sample decreased to half at first 24 h.

Concentration (mgPb(II)/L)

12 10 8 6 4 2 0 0

24

48

72

96

120

144

168

t (h) Pb

control Pb

Fig. 2 The change of Pb(II) concentrations with time (10.0 mgPb/L; pH 5.0; 25◦ C)

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The pH change of culture media may be the result of the photosynthetic activity of plants. During photosynthesis, aquatic plants remove free CO2 from water. This result in less combined hydrogen and carbon dioxide (carbonic acid) in the water and a corresponding rise in the pH reading. The other reason may be weak acid anion of metabolic substances released by plants that may cause to rise of pH. Wang et al. [13] showed that Myrophyllum sp. caused an increase in pH of culture medium from pH 3.0 to pH 8.0. The bioavailability of metal ions to plants is an important factor to obtain successful phytoremediation. However, Sheng et al. [14] reported that bioavailability of lead compounds is limited due to low solubility of these compounds. These compounds tend to form complexes with organic and inorganic colloids, and precipitate in the hydroxyl, carbonate and phosphates forms. They investigated the Pb(II) and Cd(II) biosorption of marine algae Sargassum sp., Pasina sp., Ulva, sp. and Gracillaria sp., and they found that Pb(II) exists as free ion form at pH 5.5, but it changes to solid Pb(OH)2 form above this pH. Similarly, Low et al. [15] investigated the Pb(II) sorption capacities of spent grain and reported that for pH greater than 6.0 precipitation of Pb(OH)2 occurred. Therefore, they carried out experiments below pH 6.0. Thus, we believe that Pb(II) ions could be precipitated by forming the less soluble compounds such as Pb(OH)2 , PbCO3 , Pb3 (PO4 )2 or PbSO4 as indicated by the rise of pH. At the bottom of the some experimental flasks, it was also seen that there were some solid residues settled especially in the high lead concentrations. When the solid residues were separated and analyzed, the existence of such undissolved lead compounds were determined qualitatively.

3.2 The Effect of Temperature on the Uptake of Pb(II) Ions by L. Minor In order to determine the effect of temperature on the lead ion uptake of Lemna, plants were grown in different culture media of initial pH 5.0 and Pb(II) concentrations in 0.1–10.0 ppm, but different temperatures of 15–35◦C range. For each temperature, the equilibrium Pb(II) concentration in culture media was determined and found that Pb(II) concentrations decreased rapidly in 24 h, then slowly up to 72nd h, and then remained stable after 72 h [12]. The PMU; the initial, the equilibrium and the accumulated concentrations of Pb(II), and the amount of biomass produced at different temperature are shown in Table 2. These results showed that the lead ion uptake of plants increased with increase of the temperature up to 30◦ C, but it decreased again at 35◦C (Fig. 3). The maximum Pb(II) uptake was obtained at 30◦ C, the minimum Pb(II) uptake was obtained at 15◦ C. Similarly, PMU was found maximum at 30◦C, and minimum at 15◦ C, but it decreased with increase of lead concentration. The maximum PMU at 30◦ C was obtained as 72.90% in 0.1 ppm and 16.0% in 10.0 ppm, and the minimum PMU was obtained at 15◦C as 36.70% in 0.1 ppm and 4.40% in 10.0 ppm. In addition, to increase of lead concentration in the culture media caused to increase of lead amount in the biomass.

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Table 2 The effects of temperature on Pb(II) accumulation capacity of Lemna (0.1–10.0 mgPb/L, 15–35◦ C, pH 5.0) T(◦ C) 15 C0 =0.1 mgPb/L Ce (mg/L) ±SD 0.026 ±0.007 Xm (g/L) 0.126 mgPb/g ±SD 0.291 ±0.023 %PMU 36.70 C0 =0.5 mgPb/L Ce (mg/L) ±SD 0.350 ±0.040 Xm (g/L) 0.138 mgPb/g ±SD 0.355 ±0.029 %PMU 9.80 C0 =1.0 mgPb/L Ce (mg/L) ±SD 0.476 ±0.037 Xm (g/L) 0.144 mgPb/g ±SD 0.625 ±0.063 %PMU 9.00 C0 =2.5 mgPb/L Ce (mg/L) ±SD 1.180 ±0.046 Xm (g/L) 0.141 mgPb/g ±SD 1.135 ±0.122 %PMU 6.40 C0 =5.0 mgPb/L Ce (mg/L) ±SD 2.100 ±0.411 Xm (g/L) 0.144 mgPb/g ±SD 2.245 ±0.118 %PMU 6.50 C0 =10.0 mgPb/L Ce (mg/L) ±SD 3.220 ±0.455 Xm (g/L) 0.153 mgPb/g ±SD 2.873 ±0.164 %PMU 4.40

20

25

30

35

0.023 ±0.007 0.140 0.480 ±0.026 67.20

0.036 ±0.009 0.120 0.524 ±0.021 62.90

0.026 ±0.006 0.135 0.540 ±0.025 72.90

0.031 ±0.019 0.145 0.458 ±0.048 66.40

0.260 ±0.014 0.177 0.620 ±0.034 21.90

0.310 ±0.060 0.171 0.959 ±0.087 32.80

0.251 ±0.028 0.130 1.750 ±0.034 45.50

0.285 ±0.032 0.185 0.691 ±0.036 25.60

0.509 ±0.172 0.189 0.810 ±0.075 15.30

0.385 ±0.035 0.180 1.985 ±0.175 35.70

0.353 ±0.049 0.156 3.893 ±0.120 60.00

0.461 ±0.055 0.222 0.930 ±0.032 21.00

1.000 ±0.118 0.189 1.920 ±0.130 14.50

0.930 ±0.116 0.198 2.358 ±0.222 18.70

0.750 ±0.134 0.192 6.411 ±0.375 49.20

0.785 ±0.061 0.240 1.810 ±0.150 17.40

1.570 ±0.176 0.183 2.576 ±0.160 9.40

1.800 ±0.131 0.174 2.985 ±0.311 10.40

1.400 ±0.160 0.192 7.531 ±0.138 28.90

2.000 ±0.111 0.246 2.356 ±0.182 11.60

4.000 ±0.847 0.144 3.285 ±0.220 4.70

3.580 ±0.272 0.180 3.852 ±0.138 6.90

4.810 ±0.210 0.190 8.622 ±0.222 16.00

3.150 ±0.700 0.205 3.021 ±0.253 6.20

The amount of dry biomass changed with temperature, and it was found maximum at 35◦ C and minimum at 15◦ C. Hillman [16] detected that duckweed fronds can store starch under the stress conditions. Similarly, Dirilgen and Inel [17] reported that dry biomass amount of L. minor increased due to storing of starch when exposed to toxic metal ions and stress conditions. In our study, high temperature and lead ion content of growth medium may have caused the stress effects on plants. Consequently, it was suggested that the reason of high amount of dry biomass at 35◦ C may be resulted from the starch storing in frond of plants in the existence of Pb(II) and high temperature. It was suggested that the influencing of metabolic activities of plants due to probable toxic effect of lead ions might have affected the metal uptake. But it wasn’t

The Evaluation of the Pb(II) Removal Efficiency of Duckweed Lemna Minor (L.)

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10.00

mgPb(II)/g

8.00 6.00 4.00 2.00 0.00 10

15

20

25

30

35

40

T(0C) Pb 0.1

Pb 0.5

Pb 1.0

Pb 2.5

Pb 5.0

Pb 10.0

Fig 3 The effect of temperature on accumulated Pb(II) concentrations (0.1–100.0 mgPb/L, 15– 35◦ C, pH 5.0)

observed any appeared toxic effect on plants during the experiment period. Mohan and Hosetti [18] reported that L. minor developed metal resistance when the concentration of the metal in growing media is tolerable to plants. They were also reported that plants grown at 0.25 mM Pb(II) concentration did not show any visible signs of phytotoxicity. Therefore, if the metal was not extremely toxic to plant, the regularly harvesting of plants would be allowed to renew of the system automatically. Harvesting of these plants can be easily made by collecting them from water surface. In this way, absorbed heavy metals can be removed from the treatment system and regained from the dried biomass with different recovery methods.

4 Conclusion According to findings in this study, it was found that the accumulated lead ion concentration in plant biomass was maximal at pH 4.5, and then it decreased towards pH 6.0, but it did not change at 6.0–8.0 range. In addition to this, it was also found maximum at 30◦ C and minimum at 15◦C. The PMU was also found maximum at 30◦ C and pH 4.5. From the results, we determined two main subjects. The accumulated lead concentration increased but percentage of lead uptake decreased with the increase of lead concentration in the aqueous media. If the main goal of the treatment of wastewater or soil is to reach the maximum metal removal, the choosing of the most suitable plant species for phytoremediation will be an important factor to obtain successful treatment. Plants must have high accumulation capacity and must grow rapidly to produce high amount of biomass. In the results of this study, the lead uptake efficiency of L. minor was found low, and it was decided that Lemna is a poor accumulator for Pb(II). Because of the short structure of roots of Lemna, we think that the plants could not reach to lead ions, precipitated at the bottom. Thus, we suggested that with the use of many aquatic

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plant species having different physiologic properties such as submerged or emerged plants with a developed root system attaching to sediment will provide a successful water treatment to remove metal ions. Furthermore, the plant density and the accumulated metal concentration in harvested biomass should also be taken into consideration.

References 1. Khan AG, Kuek C, Chaudhry TM, Khoo CS, Hayes WJ (2000) Role of Mycorrhizae and phytochelators in heavy metal contaminated land remediation. Chemosphere 41:197–207 2. Clemente R, Walker DJ, Bernal MP (2005) Uptake of heavy metals and As by Brassica juncea grown in a contaminated soil in Aznalcollar (Spain): The effect of soil amendments. Environ Pollut 138:46–58 3. Cunningham SD, Berti WR, Huang JW (1995) Phytoremediation of contaminated soils. Trend Biotech 13:393–397 4. Brix H (1994) Functions of macrophtes in constructed wetlands. Water Sci Technol 29(4):171–178 5. Cheng S, Grosse W, Karrenbrock F, Thoennessen M (2002) Efficiency of constructed wetlands in decontamination of water polluted by heavy metals. Ecol Eng 18:317–325 6. Sternberg SPK, Dorn R (2002) Cadmium removal using Cladophora in batch, semi-batch and flow reactors. Bioresour Technol 81:249–255 7. Boniardi N, Vatta G, Rota R, Nano G, Carra S (1994) Removal of water pollutants by Lemna gibba. Chem Eng J 54:B41–B48 8. Wang W (1990) Review: Literature review on duckweed toxicity testing. Environ Res 52:7–22 9. Demirezen D, Aksoy A (2004) Accumulation of heavy metals in Typha angustifolia (L.) and Potamogeton pectinatus (L.) living in Sultan Marsh (Kayseri, Turkey). Chemosphere 56:685– 696 10. Eaton AD, Clesceri LS, Greenberg AE (1995) Standard methods for the examination of water and wastewater, 19th edn. APHA, 1015 Fifteenth Street, NW Washington, DC 20005 11. Sen KA, Mondal NG (1990) Removal and uptake of copper (II) by Salvinia natans from waste water. Water Air Soil Pollut 49:1–6 12. Uysal Y (2004) Sulu ortamda Pb(II) ve Cd(II) iyonlarının Lemna minor L. ile alımının ara¸stırılması. Ph.D. Thesis, University of Mersin, Mersin, Turkey 13. Wang TC, Weissman JC, Ramesh G, Varadarajan R, Benemann JR (1996) Parameters for removal of toxic heavy metals by water milfoil (Myrophyllum spicatum). Bull Environ Contam Toxicol 57:779–786 14. Sheng PX, Ting Y, Chen JP, Hong L (2004) Sorption of lead, copper, cadmium, zinc and nickel by marine algal biomass: Characterization of biosorptive capacity and investigation of mechanisms. J Colloid Interface Sci 275:131–141 15. Low KS, Lee CK, Liew SC (2000) Sorption of cadmium and lead from aqueous solutions by spent grain. Process Biochem 36:59–64 16. Hillman WS (1961) The Lemnaceae or Duckweeds. Bot Rev 27:221–283 17. Dirilgen N, Inel Y (1994) Effects of zinc and copper on growth and metal accumulation in duckweed, Lemna minor. Bull Environ Contam Toxicol 53(3):442–448 18. Mohan BS, Hosetti BB (1997) Potential phytotoxicity of lead and cadmium to Lemna minor grown in sewage stabilization ponds. Environ Pollut 98(2):233–238

Biodegradation of a Tannery and Chemical Plant Producing Asetilsalisilikat Wastewater Mixture E.U. Cokgor, O. Karahan, and D. Orhon

Abstract The oxygen uptake rate, (OUR), may be regarded as one of the most significant modeling tools for the understanding and interpretation of behavior of complex microbial cultures sustained under aerobic conditions. The wastewaters investigated in this study were obtained from a tannery and a chemical plant producing asetilsalisilikat, (ASS). The scope of the study, involved aside from conventional characterization, an assessment of significant kinetic and stoichiometric coefficients for chemical plant and tannery wastewaters and their mixtures, by using respirometric measurements. Results have shown that the addition of pharmaceutical effluents having a biodegradable character on tannery wastewaters would not therefore cause any negative effect on the biodegradability of tannery wastewaters. Keywords Biodegradation · COD · Wastewater

1 Introduction Pharmaceutical industry often generates high strength wastewater changing in character and quantity depending upon the used manufacturing processes and seasons [8]. Generally conventional biological processes are used for the treatment of wastewater at the pharmaceutical industries [1, 5, 11, 6, 2]. Rosen et al. [11] reported that the biological treatment of chemical synthesis based pharmaceutical wastewater provided high removal of COD and toxicity. Tannery industry effluents are also highly loaded wastewaters in terms of organic carbon and nitrogen. Although stream segregation and chemical treatment is mostly applied to wastewater streams containing chromium and sulfur, pretreatment of tannery wastewaters is finalized with biological treatment [9]. The conducted case study is the investigation of the biodegradation characteristics of tannery and pharmaceutical industry effluents together with the effect of the E.U. Cokgor (B) Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_105,

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addition pharmaceutical effluents on the biodegradability of tannery wastewaters. The investigated tannery industry wastewaters are generated from Tuzla Organized Industrial District specialized on tannery production and the pharmaceutical plant under concern is specialized on acetylsalicylic acid production. The biodegradability studies were conducted in order to investigate the COD removal efficiency of tannery and pharmaceutical effluents and different mixtures of these wastewaters. Respirometric tests were also conducted to further study the biodegradation kinetics of both wastewaters and their mixtures.

2 Materials and Methods The biomass sampled from the Tuzla Tannery Organized Industrial District wastewater treatment plant was used in biological treatability experiments. The reactor in 4-L fill-and-draw reactors, equipped with diffused aeration devices was operated at steady state with a sludge age of 10 days and a hydraulic retention time (HRT) of 1 day for a period of 2 months. All analyses in terms of conventional parameters were performed as defined in Standard Methods [12]. The soluble (filtrated) COD was defined as the filtrate through Whatman GF/C glass fiber filter that were also used to assess VSS and SS parameters. The respirometric procedure for the assessment of major kinetic and stoichiometric constants such as the readily biodegradable COD, SS , the maximum heterotrophic growth rate, μH , and the heterotrophic yield coefficient, YH , involved using 1 L batch reactors. In the OUR test was conducted with an inhibitor (Formula 2533TM, Hach Company, Loveland, Colorado) for the prevention of any possible interference induced by simultaneous nitrification. The reactor was initially fed with the wastewater sample, seeded with appropriate biomass to start with a suitable initial substrate/biomass (CT1 /XT1 ) ratio and constantly aerated to maintain a dissolved oxygen concentration of 6–8 mgL−1. The biomass was previously acclimated to the same sample in a fill and draw reactor operated in aerobic conditions at a sludge age of around 10 days. The readily biodegradable COD was determined in accordance with the method suggested by Ekama et al., [4]. For the assessment of the maximum heterotrophic growth rate, the OUR reactors were run at a CT1 /XT1 ratio of 4–5 g COD/g VSS as recommended by Kappeler and Gujer [7]. The value of heterotrophic yield was assessed by using the experimental method given by Cokgor [3]. OUR measurements were conducted with a WTW OXI DIGI oxygen meter. Hydrolysis rate constants, kh and KX , and half saturation constant, KS were determined by applying curve fitting techniques to the OUR profile obtained for SS1 determination. The modeling studies were performed using the simulation program Aquasim [10].

3 The Case Study The investigated pharmaceutical industry is an acetylsalicylic acid production (AAP) facility. The plant is located near the Tuzla Organized Leather Tanning Industrial District, established on 80 hectare land. The operation is carried out

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Table 1 Average water consumption and wastewater generation in the plant Water consumption (m3 /day)

Wastewater generation (m3 /day)

Processes Boilers Thickeners (no-contact) Domestic use Demineralized water

2.5 (max. 5) 8 8 20 5

5 6 3 20 5

Total

46

39

in 3 shifts of 8 hours each, with a total of 23 personnel. The production capacity is 4,500 kg/day in a batch wise operation during 6 days of the week and 300 days of the year. The production is stopped during July every year. Water used in the plant is taken from the water wells and the daily amount of water consumption varies between 40 and 50 m3 /day. The water consumption and wastewater production in specific operations within the plant is given in Table 1. As shown in Table 1, the averaged wastewater generation for one period of operation is 39 m3 . The biological treatment plant of Tuzla Organized Leather Tanning Industrial District is one of the biggest tannery effluent treatment plants in the world. The treatment plant has physical, chemical and biological treatment stages. The treatment plant personnel consist of 20 technicians working in 3 shifts. The conventional wastewater characterization study of tannery effluents entering the biological treatment unit has been conducted during a period of 5 months and that of pharmaceutical industry has been carried out for a period of 3 months. The results of the conventional wastewater characterization studies for tannery and pharmaceutical industry effluents are given in Tables 2 and 3, respectively. Table 2 Conventional wastewater characterization of Tuzla organized leather tanning industrial district prior to biological treatment Parameter

Unit

Value

Average

pH TSS Total COD Filtered COD BOD5 TKN Filtered TKN NH4 -N S−2 Total Cr SO4 −2 Cl− Alkalinity Oil and grease Flowrate

– mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L m3 /day

6.9–8.7 430–1,080 1,165–3,000 560–1,915 500–1,600 170–330 112–282 73–210 10–145 15–65 1,145–2,345 4,100–7,130 510–2,200 110–1,475 2,948–17,838

7.4 735 2,170 1,070 1,110 245 195 130 70 35 1,700 5,910 1,220 355 12,175

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Amount (kg) pH Total COD (mg/L) Total COD (kg)

Value

Average

Standard Deviation

– 6–9 8,085–75,700 82–808

– 7 40,435 409

– 0.54 14,825 152

4 Experimental Results 4.1 Biodegradability Studies Fill and draw reactors with 4 L volume and an organic loading rate of 0.2 g COD/g MLSS.day obtained feeding tannery effluents were operated. The steady state results have shown that tannery wastewaters were 72% biodegradable in terms of COD removal. The current tannery wastewater flowrate in the treatment system is 80.000 m3 /week and the weekly pharmaceutical wastewater flowrate is 20 m3 /week (assuming that pharmaceutical wastewaters are continuously discharged and mixed with tannery effluents). In terms of flow proportional composites 1 L of tannery effluent is combined with 0.25 mL of pharmaceutical wastewater. The experimental study was conducted with the addition of 0.3, 0.5, 1, 2, 3, 6, and 10 mL of pharmaceutical wastewater for 1 L tannery effluent, corresponding to 0.6, 1, 1.9, 3.8, 5.7, 11, and 19% of the total COD in the mixture, respectively. The addition of different amounts of pharmaceutical wastewaters on tannery effluent resulted in 70–77% degradation in terms of COD. The effluent COD results obtained for different tannery-pharmaceutical wastewater mixtures are given in Fig. 1.

4.2 Respirometric Studies The OUR tests were conducted for the assessment of major kinetic and stoichiometric constants such as the readily biodegradable COD, SS , the maximum heterotrophic growth rate, μH , and the heterotrophic yield coefficient, YH . The respirometric studies were first carried out for tannery and pharmaceutical wastewaters alone and then for different mixtures of these two effluents. The results obtained in the OUR tests were evaluated according to the endogenous decay model. The matrix representation of the model is given in Table 4. The OUR tests for the determination of maximum heterotrophic growth rate, μH , was found as 2.5 1/day as given in Fig. 2. The addition of different amounts of pharmaceutical effluents did not exert a significant effect on the maximum heterotrophic growth rate of the system.

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450 Only Tannery Tannery + 0.6% of Total COD Tannery +1% of Total COD Tannery + 1.9% of Total COD Tannery + 3.8% of Total COD Tannery + 5.7% of Total COD Tannery + 11% of Total COD Tannery +19% of Total COD

400

Effluent COD, (mg/L)

350 300 250 200 150 100 50 0 0

10

20

30

40

50

Time, (day)

Fig. 1 The results of effluent COD for different tannery-pharmaceutical wastewater mixtures

Table 4 Process kinetic and stoichiometry for carbon removal involving endogenous decay Component→

1

2

3

4

5

6

Process Rate

Process↓

SS

XS

XH

XP

SP

S0

ML−3 T−1

Growth

− Y1H

Hydrolysis

1

Decay Parameter, ML−3 COD

1

H) − (1−Y YH

μ

SS (KS +SS ) XH

S /XH kh (KXX+X XH S /XH )

−1

−1 fEX fES −(1-fEX -fES ) bH XH COD Cell COD COD COD O2

The experimental value of μH 2.5 1/d value has been used to determine the activity coefficient of biomass and the estimated activity coefficient was approximately 0.67. The readily biodegradable COD fraction, COD, SS1 , has been estimated according to the method described by Cokgor, [3] with the heterotrophic yield coefficients, YH for tannery wastewaters as 0.67 mg cellCOD/mg COD [9], and as 0.55 mg cellCOD/mg COD for pharmaceutical wastewaters. The modeling studies revealed that tannery wastewater had a dominant character. Thus, the heterotrophic yield coefficient has been used as 0.67 mg cellCOD/mg COD for the experimental evaluation of the mixtures. The endogenous decay rate, bH , was accepted as 0.15

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ln (OUR/OURo)

0,3 0,25 0,2 0,15 0,1 0,05 0

0

50

100 150 Time, (min)

200

250

Fig. 2 Maximum heterotrophic growth rate of the biomass

1/d [9]. Other kinetic constants were determined by modeling using curve fitting techniques. The COD fractions and modeling data generated for tannery, pharmaceutical effluents and their varying mixture ratios are summarized in Tables 5 and 6. The OUR data and the modeling results are presented in Fig. 3a, b. The experiments have shown that the fraction of readily biodegradable COD, SS1 /CT1 , was 15% for tannery wastewaters, whereas this ratio was found to be 56% for pharmaceutical effluents. Therefore the addition of pharmaceutical effluents on tannery wastewaters increases the fraction of readily biodegradable COD in the mixtures. The half saturation coefficient, KS , was estimated as 5 mg COD/l for tannery wastewaters and as 9 mgCOD/l for pharmaceutical effluents. The hydrolysis rate constant, kh , was between 1.2 and 2.0 1/d in all mixture sets and the half saturation coefficient for hydrolysis, KX , is estimated as 0.10 mgCOD/mgcellCOD for tannery wastewaters, as 0.05 mgCOD/mg cellCOD for pharmaceutical effluents and as 0.15 mgCOD/mg cellCOD for mixtures.

Table 5 COD fractions for waste water mixtures and kinetic constants for models Fraction of pharmaceutical effluent added

CT1

Wastewater

(% Total COD)

mg/L

Run 1 (Tannery) Run 2 (Pharmaceutical effluent) Run 3.1 (Mixture) Run 3.2 (Mixture) Run 3.3 (Mixture) Run 3.4 (Mixture)

– 100 1 2 16 38

SS1

XS1

CI1

2,184 688

324 390

1,367 230

493 68

2,215 2,245 2,820 3,520

335 350 530 900

1,385 1,400 1,580 1,850

495 495 710 770

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Table 6 Kinetic constants obtained for wastewater mixtures

Wastewater Run 1 (Tannery) Run 2 (Pharmaceutical effluent) Run 3.1 (Mixture) Run 3.2 (Mixture) Run 3.3 (Mixture) Run 3.4 (Mixture)

Fraction of pharmaceutical effluent added

YH

kh

(% Total COD) – 100

gCOD/gCOD 0.67 0.55

1/d mg/L gCOD/gCOD 1/d 2.0 5 0.1 2.54 2.2 9 0.05 2.50

1 2 16 38

0.67 0.67 0.67 0.67

1.9 1.8 1.8 1.2

KS

10 12 12 50

μH

KX

0.15 0.15 0.15 0.15

2.45 2.40 2.35 2.2

RUN 1 250 data model

OUR (mg/l.h)

200 150 100 50 0 0

0.01

0.02

0.03

0.04

0.05

0.06

Time (day)

(a) RUN 2 120 data model

OUR (mg/l.h)

100 80 60 40 20 0 0

0.05

0.1

0.15

0.2

Time (day)

(b) Fig. 3 OUR Profiles obtained for (a) tannery wastewaters (b) pharmaceutical effluents

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All the experimental and modeling results have shown that the pharmaceutical effluents have a biodegradable character. The addition of pharmaceutical effluents on tannery wastewaters would not therefore cause any negative effect on the biodegradability of tannery wastewaters. In fact, the addition of these effluents improves the biological activity of the system.

5 Conclusions On the basis of the experimental results summarized and evaluated, the concluding remarks of this study may be expressed as follows. (a) Wastewater characterization is a prerequisite for the evaluation of biological treatability of tannery and pharmaceutical plant effluents and their mixture, as it is for other domestic and industrial wastewaters. Characterization studies should involve aside from conventional parameters, a detailed COD fractionation and the assessment of stoichiometric and kinetic coefficients. (b) Mathematical models primarily defined for domestic sewage, may also be applicable to tannery and pharmaceutical plant effluents and their mixtures. (c) There is a great need for similar experimental studies on tannery and pharmaceutical plant effluents, as well as on other industrial effluents, for the compilation of a reliable data base that would be used in the modeling and design of activated sludge systems.

Nomenclature bH CT1 fa fEX fES kh KS KX OUR SH SI S0 SP SS ST1 XH XI XP

endogenous decay rate total influent COD activity coefficient particulate inert fraction Soluble residual fraction maximum specific hydrolysis rates half-saturation constant half-saturation constants for hydrolysis oxygen uptake rate rapidly hydrolysable COD soluble inert COD oxygen concentration soluble residual COD generated as metabolic products readily biodegradable COD influent soluble COD active heterotrophic biomass particulate inert COD particulate inert metabolic products

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slowly hydrolysable COD yield coefficient maximum specific growth rate

Acknowledgements This study was conducted as part of the sponsored research activities of the Environmental Biotechnology Center of the Scientific and Technical Research Council of Turkey (TUBITAK).

References 1. Andersen RD (1980) Pharmaceutical wastewater treatment. Case Study, Proceedings of the 35th Industrial Waste Conference, 35, Lafayette, Indiana, pp. 456–462 2. Bernard S, Gray NF (2000) Aerobic digestion of pharmaceutical and domestic wastewater sludges at ambient temperature. Water Res 34:725–734 3. Cokgor EU (1997) Aerobik Sistemlerde Proses Kineti˘gi ve Stokiyometrisinin Respirometrik Olarak De˘gerlendirilmesi, PhD Thesis, Institute of Science and Technology, Istanbul Technical University, Istanbul, Turkey 4. Ekama GA, Dold PL, Marais GVR (1986) Procedures for determining influent COD fractions and the maximum specific growth rate of heterotrophs in activated sludge Systems. Water Sci Technol 18:91–114 5. Gohary FA, Abou-Elale SI, Aly HI (1995) Evaluation of biological technologies for watewater treatment in the pharmaceutical industry. Water Sci Technol 32:13–20 6. Halling-Sorensen B, Nielsen N, Nors S, Lankzky PF, Ingerslev F, Lützhoft Holten HC, Lorgensen SE (1998) Occurrence, fate and effects of pharmaceutical substances in the environment- A review. Chemosphere 36(2):357–393 7. Kappeler J, Gujer W (1992) Estimation of kinetic parameters of heterotrophic biomass under aerobic conditions and characterization of wastewater for activated sludge modeling. Water Sci Technol 25(6):125–139 8. Nemerow NL (1978) Industrial water pollution: Origins, characters and treatment. AddisonWesley, New York 9. Orhon D, Genceli Ate¸s E, Cokgor EU (1999) Characterization and modelling of activated sludge for tannery wastewaters. Water Environ Res 71:1, 50–63 10. Reichert P, Ruchti J, Simon W (1998) Aquasim 2.0. Swiss federal institute for environmental science and technology (EAWAG), CH-8600, Duebendorf, Switzerland 11. Rosen M, Welander T, Lofqvist A, Holmgren J (1998) Development of a new process for treatment of a pharmaceutical wastewater. Water Sci Technol 37:251–258 12. Standard Methods for the Examination of the Water and Wastewater, 20th edn (1998) Water Environment Federation, Alexandria, VA

Boron Removal in Seawater Desalination by Reverse Osmosis Membranes – the Impacts of Operating Conditions H. Köseo˘glu, N. Kabay, M. Yüksel, S. Sarp, Ö. Arar, and M. Kitis

Abstract Production of drinking water through seawater desalination using reverse osmosis (RO) membranes is becoming increasingly attractive especially in coastal areas with limited freshwater sources. However, one challenge in such conventional desalination RO plants is the difficulty of meeting boron standards in product waters. Therefore, most of the current desalination plants employ additional treatment steps including pH adjustment of feedwater, dilution of RO permeate with other sources, ion exchange post-treatment of RO permeate, and/or double-pass staging for permeate. All these further treatment options increase the cost of desalination. Although membrane manufacturers have been developing modified RO membranes with enhanced boron removal capacities such membranes still should be improved from operational flux and pressure perspectives. The main objective of this work was to determine the impacts of operational conditions (membrane pressure, cross-flow velocity and flux) and water chemistry on boron rejections using two commercial RO membranes specified for enhanced boron removal (TorayTM UTC-80-AB and FilmtecTM SW30HR). A lab-scale cross-flow flat-sheet configuration test unit (SEPA CF II, Osmonics) was used for all RO experiments. Seawater samples were collected from the Mediterranean Sea, Alanya-Kızılot shores, south Turkey. For all experiments, mass balance closures were between 91 and 107%, suggesting relatively low loss of boron on membrane surfaces during 14 h of operation. Boron rejections were relatively constant (a maximum change of ±3%) during the 14 h of operation period for all experiments, suggesting that steady state dynamic membrane conditions were immediately achieved within couple hours. Boron rejections obtained with Toray and FilmTec membranes at pH of original seawater (8.2) and at other various operating conditions ranged between 85 and 92%, resulting in permeate boron concentrations of about 0.2–0.9 mg/L. On the other hand, for both membranes, much higher boron removals were achieved at a pH of 10.5 (>98%), resulting in permeate boron concentrations less than 0.1 mg/L. The charged boron

M. Kitis (B) Department of Environmental Engineering, Suleyman Demirel University, 32260 Isparta, Turkey e-mail: [email protected]

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species are expected to be dominant at pH values >9.24 (pKa of boric acid) compared to the neutral boric acid. Therefore, as expected, both membranes exhibited higher boron rejections at a pH of 10.5. Salt rejections (as measured by conductivity) were generally 97–99% at both pH values. Boron rejections were independent of feed water boron concentrations up to 6.6 mg/L. For each membrane type, permeate fluxes at constant pressure were generally lower at pH of 10.5. The ranges of permeate fluxes measured in all experimental conditions were 11–15, 13–17 and 19–21 L/m2 -h for 600, 700 and 800 psi (41, 48 and 55 bar) pressures, respectively, after an operation period of 14 h. For all experimental conditions, permeate fluxes gradually decreased during the 14 h operation although a leveling off was observed after 12 h. At constant membrane pressure of 800 psi and pH of 8.2, feed flowrate thus the cross-flow velocity (0.9 and 0.5 m/s) did not exert any significant impact on boron rejection. Keywords Boron · Desalination · Membrane · Reverse osmosis · Seawater · SWRO

1 Introduction Due to increasing demand for water, both potable and for irrigation, coupled with a decrease in suitable water sources suppliers have to turn to alternatives. Seawater desalination or treatment of high saline, eventually contaminated surface waters have become standard [1, 2]. The cost of seawater desalination by reverse osmosis (RO) membranes has significantly decreased. Both greater competition and improved technology have contributed to this reduction in desalted water prices [3]. Producing potable water by RO desalination has been performing successfully for nearly 25 years [4]. Seawater (4–5 mg/L), municipal wastewaters (0.5–2 mg/L) and groundwaters (up to 8 mg/L in Cyprus, Italy and Greece) in some areas contain high concentrations of boron. European Union (EU) is classifying boron as a pollutant in potable water regulations [5]. Laboratory studies showed impediments on male reproductive system caused by boron [6]. Also, sensitive crops, including most citrus species, have a boron tolerance of only 0.40–0.75 mg/L, while vegetables are more boron tolerant with maximum thresholds of 1–4 mg/L [7]. As a result, World Health Organization (WHO) set 0.5 mg/L for maximum boron concentration in potable waters [8]. Boron exists as non-ionic boric acid form at the natural pH level of seawater which is about 8.2. From the level of pH 9.5, concentrations of borate and other ionic forms of boron become dominant compared to non-ionic forms, which is very critical by the point of boron rejection in RO membranes. While the rejection of boric acid in conventional RO membranes is only about 60–70%, it is 90–98% for borate ion [9]. Thus, boron rejection at RO desalination plants operating at natural pH level of seawater is relatively low. Non-ionic boron species, such as boric acid, permeate through the RO membranes more than the charged, ionic species. In recent years, membranes with boron rejections of 91–93% even at natural seawater

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pH are taking place on the market [10]. Although membrane manufacturers have been developing modified RO membranes with enhanced boron removal capacities most of the current desalination plants employ additional treatment steps including pH adjustment of feedwater, dilution of RO permeate with other sources, ion exchange post-treatment of RO permeate, and/or double-pass staging for permeate. In addition, a number of process configurations have been proposed to achieve low boron concentrations in seawater RO desalination plants [3, 10]. All these further treatment options increase the cost of desalination. Although membrane manufacturers have been developing modified RO membranes with enhanced boron removal capacities such membranes still should be improved from operational flux and pressure perspectives. The main objective of this work was to determine the impacts of operational conditions (membrane pressure, cross-flow velocity and flux) and water chemistry on boron rejections using two commercial RO membranes specified for enhanced boron removal (TorayTM UTC-80-AB and FilmtecTM SW30HR).

2 Methodology 2.1 Test Unit A lab-scale cross-flow flat-sheet configuration test unit (SEPA CF II, Osmonics) was used for all membrane separation experiments (Fig. 1), which simulates the flow dynamics of larger, commercially available spiral-wound membrane elements.

Fig. 1 The schematic of the membrane test system

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The membrane test unit accommodates any 19 cm × 14 cm (7.5 inch × 5.5 inch) flat-sheet membrane for a full 140 cm2 (22 inch2) of effective membrane area. Maximum operating pressure of the unit is 69 bar (1,000 psi). Permeate flowrate is approximately proportional to driving pressure.

2.2 Membranes Two commercial desalination RO membranes, TorayTM (UTC-80-AB) and FilmtecTM (SW30HR), were tested for boron rejections. Membrane sheets were obtained from the manufacturers and used as-received.

2.3 Experiments Seawater samples were collected from the Mediterranean Sea, Alanya-Kızılot shores (south Turkey). All seawater samples were filtered (1 μm cartridge filters) and kept at dark in the laboratory prior to use for membrane tests. Membrane operating pressures tested were 600, 700 and 800 psi. The tested feed water pH values were 8.2 (seawater pH) and 10.5, which simulated the high pH level necessary for the formation of charged, ionic boron species. The tested membrane feed flowrates were 3.8 and 2 L/min with corresponding cross-flow velocities of about 0.9 and 0.5 m/s, respectively. A new membrane was used for each test after conditioning the membrane for about 5–6 h of feeding with distilled and deionized water (DDW) at the conditions of the experiment to be conducted. Two operation modes were employed in the experimental matrix: batch concentration and constant feed tank volume. The duration of each membrane test was about 14 h. Samples from feed tank and permeate were taken each hour for boron, total dissolved solids (TDS), conductivity, pH, and temperature measurements. To maintain constant pH in the feed tank depending on the experimental matrix, pH was monitored and adjusted with various concentrations of HCl and/or NaOH solutions, if necessary. Flowrates of concentrate and permeate streams, membrane unit and pump outlet pressures were also recorded each hour. In an effort to calculate overall mass balances on boron, the volumes remaining in feed and permeate tanks and tubings after the experiments, sample volumes and the associated boron concentrations in these volumes were measured.

2.4 Analytical Measurements Spectrophotometric curcumine method was employed for boron analysis. In this method, curcumine solution forms an orange-red complex compound with borate ions and the absorbance of this compound is measured at λmax of 543 nm.

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Conductivity and TDS were measured using WTW Inolab Cond. Level 1 conductivity meter. pH was measured using a bench-scale Schott Handylab 1 pH meter. All chemicals used were reagent grade. Distilled and deionized water was used for stock solution preparations and dilutions.

3 Results and Discussions Table 1 presents the mass balance calculations performed on boron for each experiment. Percent mass balance closure represents the ratio of the boron mass obtained from all points (i.e., feed tank, permeate collection tank, tubings and samples) at the end of the experiment to the boron mass initially applied to the system. For all experiments, mass balance closures were between 91 and 107%, suggesting relatively low loss of boron on membrane surfaces during 14 h of operation. It should be noted that many independent parameters including volumes of various tanks/samples and boron concentrations are measured and take place in mass balance calculations. Therefore, experimental errors in volume and concentration measurements are expected, which may result in mass balance closures lower or higher than 100%. Boron measurements were conducted in duplicates. Percent coefficients of variations between duplicate measurements were generally less than 12%, averaging about 5%. Thus, an error degree of approximately ±5% is inherent in mass balance calculations. Figure 2 shows the impact of solution pH on boron rejection in seawater experiments. For both Toray and FilmTec membranes, much higher boron rejections were obtained at pH of 10.5 (>98%) than those at original seawater pH (about 86–90%). Permeate boron concentrations less than 0.1 mg/L were easily achieved at pH 10.5 by both membranes. The acid dissociation constant (pKa) of boric acid is 9.24. Therefore, the charged boron species are expected to be dominant at pH values >9.24 compared to the neutral boric acid. At a pH of 8.2, about 80% of boron is in neutral form. For many compounds, it is known that charged species are rejected to a greater extent by many RO membranes through electrostatic repulsion. Therefore, as expected, both membranes exhibited higher rejections at a pH of 10.5. Figure 3 shows the impact of operation mode on boron rejections. In the batch concentration mode, feed tank boron concentration increases with operation period. After 3 h of operation to reach steady state rejections, operation mode did not have any impact on boron rejections, which were consistently larger than 98%. This result indicates that boron rejections are independent of feed water boron concentrations

Table 1 Mass balance calculations on boron in seawater experiments Exp. No.

1

2

3

4

5

6

7

8

9

% Mass balance closure

91.0

94.6

99.2

93.8

107.7

100.7

97.6

98.6

100.2

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H. Köseo˘glu et al. 100

Boron Rejection (%)

95

90

85 Filmtec SW pH=8.2 Filmtec pH=10.5

80

Toray SW pH=8.2 Toray pH=10.5 75 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Operation Time (h) Fig. 2. Impact of solution pH on boron rejection by Toray and FilmTec membranes (batch concentration mode, initial feed boron concentration: 5.1 mg/L, pressure: 700 psi, feed flowrate: 3.8 L/min, feed temp: 22–24◦ C)

100

B-Rejection (%)

98

96

94

Batch-Concentration

92

Constant Feed Tank Volume 90 0

1

2

3

4

5

6 7 8 9 Operation Time (h)

10

11

12

13

14

15

Fig. 3 Impact of operation mode on boron rejection (Toray membrane, initial feed boron concentration: 5.1 mg/L, pressure: 700 psi, pH: 10.5, feed flowrate: 3.8 L/min, feed temp: 23–24◦ C)

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resulting in similar permeate boron concentrations. However, it should also be noted that the operation period was only 14 h and that concentration factors in batch mode operations were only about 1.1–1.3 making feed water boron concentrations in the range of 5.6–6.6 mg/L. Higher operation periods and higher feed boron concentrations may lead to higher boron passage through membranes due to concentration polarization thus enhanced diffusion effects. Boron rejections were relatively constant (a maximum change of ±3%) during the 14 h operation period for all experiments, suggesting that steady state dynamic membrane conditions were immediately achieved in seawater. However, it should be noted that before each test a new membrane was conditioned for about 5–6 h of feeding with DDW only at the conditions of the experiment to be conducted. It was found in the preliminary single solute (boron) experiments in DDW that about 4–5 h of operation was necessary to reach steady state boron rejections. This time period had also varied depending on membrane type or experimental condition. Although boron rejections were relatively constant in seawater experiments during the 14 h operation period, permeate fluxes gradually decreased in all experiments. This observation suggests that membranes immediately reach steady state conditions for boron rejection but not for permeate production rate in the first 14 h of use. Figure 4 shows the impact of pH and membrane type on permeate fluxes. For each membrane type, permeate fluxes at constant pressure were generally lower at 40 Filmtec SW pH = 8.2

35

Permeate Flux (L/m2 -h)

Filmtec pH = 10.5

30

Toray SW pH = 8.2 Toray pH = 10.5

25 20 15 10 5 0 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Operation Time (h)

Fig. 4 Impact of pH and membrane type on permeate flux (batch concentration mode, initial feed boron conc: 5.1 mg/L, pressure: 700 psi, feed flowrate: 3.8 L/min, feed temp: 22–24◦ C)

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pH of 10.5. This impact was more pronounced for FilmTec membrane, i.e., about 15–40% reduction in fluxes was observed at pH of 10.5 compared to pH of 8.2. This phenomenon can be partially explained by membrane fouling and enhanced scale formation by Mg and Ca compounds at higher pH values. Scale formation on the membrane surfaces caused by super saturation is the disastrous effect of the concentration polarization which results in considerable flux decreases. In addition, the use of NaOH for elevating the pH to 10.5 further increased the solute concentration in the feed water, resulting in an increase in osmotic pressure and concentration polarization effect, which both gradually decrease permeate flux. Figure 5 shows the impact of pressure on permeate flux. As expected, as the membrane pressures were increased from 600 to 800 psi permeate fluxes also increased for both membrane types. Similar fluxes were obtained for Toray and FilmTec membranes at constant pressure. However, for all experimental conditions, permeate fluxes gradually decreased during the 14 h operation period although a leveling off was observed after 12 h at all tests. This result suggests that longer operation period than 14 h may be required to reach steady state permeate production rate. As discussed previously, fouling and concentration polarization appear to be important factors in flux reductions even at the very beginning of experiments with new membranes. Typical average permeate flux in commercial seawater RO desalination plants with spiral wound membranes ranges between 14 and 16 L/m2 -h. The ranges of permeate fluxes measured in all different experimental conditions in this work were 11–15, 13–17 and 19–21 L/m2 -h for 600, 700 and 800 psi (41, 48 and 55 bar) pressures, respectively, after an operation period of 14 h (new membranes were used for each experiment). The range of flux values obtained in this work is somewhat higher those in commercial RO systems. This can be explained by two facts: 1) flat-sheet test units as used in this study exert lower degree of pressure loss compared to spiral wound commercial systems, and 2) prolonged operation periods after 14 h may further reduce the fluxes, based on the gradual-decrease trend observed in this study. The impact of pressure on boron rejections is shown in Fig. 6. Boron rejections varied between 85 and 92% for all pressures at a pH of 8.2. As a general trend, Toray membranes exhibited somewhat higher rejections as the pressure was increased from 600 to 800 psi although there was some scatter in the data. Similar boron rejections were found for Filmtec membrane at pressures 700 and 800 psi; again the data was somewhat scattered. Since the differences in boron reductions are relatively small the inherent experimental errors in permeate boron measurements should also be considered. Figure 7 shows the impact of pressure on salt rejections. After steady state conditions were achieved, similar salt rejections were found (97–99%) for both membranes independent of pressure. This result indicates that the rejection of salts in seawater may not correlate well with boron rejection at constant conditions. Figure 8 shows the impact of feed flowrate on boron rejection. At constant membrane pressure of 800 psi and pH of 8.2, feed flowrate thus the cross-flow velocity did not exert any significant impact on boron rejection.

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40 Toray 600 psi Toray 700 psi Toray 800 psi FilmTec 700 psi FilmTec 800 psi

35

Permeate Flux (L/m2-h)

30 25 20 15 10 5 0 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Operation Time (h)

Fig. 5 Impact of pressure on permeate flux (batch concentration mode, initial feed boron conc: 5.1 mg/L, pH: 8.2, feed flowrate: 3.8 L/min, feed temp: 22–24◦ C)

100 Toray 600 psi Toray 700 psi Toray 800 psi FilmTec 700 psi FilmTec 800 psi

98

Boron Rejection (%)

96 94 92 90 88 86 84 82 80 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Operation Time (h)

Fig. 6 Impact of pressure on boron rejection (batch concentration mode, initial feed boron conc: 5.1 mg/L, pH: 8.2, feed flowrate: 3.8 L/min, feed temp: 22–24◦ C)

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100 98 Conductivity Rejection (%)

96 94 92 90 88 86

Toray 600 psi Toray 700 psi Toray 800 psi FilmTec 700 psi FilmTec 800 psi

84 82 80 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Operation Time (h)

Fig. 7 Impact of pressure on salt (as conductivity) rejection (batch concentration mode, initial feed boron conc: 5.1 mg/L, pH: 8.2, feed flow rate: 3.8 L/min, feed temp: 22–24◦ C)

100 98

Boron rejection (%)

96 94 92 90 88 86 2 L/min

84

3.8 L/min

82 80 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Operation Time (h)

Fig. 8 Impact of feed flowrate (cross-flow velocity) on boron rejection (Toray membrane, batch concentration mode, initial feed boron conc: 5.1 mg/L, pressure: 800 psi, pH: 8.2, feed temp: 22–24◦ C)

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4 Conclusions Mass balance closures were between 91 and 107%, suggesting relatively low loss of boron on membrane surfaces during 14 h of operation. Although membranes reached steady state conditions for boron rejection within about 4–5 h of operation permeate fluxes gradually decreased in the 14 h of operation. However, a general leveling off was observed for fluxes after 12 h. For both Toray and FilmTec membranes, much higher boron rejections were obtained at pH of 10.5 (>98%) than those at original seawater pH of 8.2 (about 85–92%). Permeate boron concentrations less than 0.1 mg/L were easily achieved at pH 10.5 by both membranes. Similar salt rejections were found (97–99%) for both membranes independent of pressure and pH. Operation modes did not have any impact on boron rejections, indicating that boron rejections were independent of feed water boron concentrations up to 6.6 mg/L. For each membrane type, permeate fluxes at constant pressure were generally lower at pH of 10.5, which may be partially explained by membrane fouling and enhanced scale formation by Mg and Ca compounds from concentration polarization effect at higher pH values. As the membrane pressures were increased from 600 to 800 psi permeate fluxes also increased for both membrane types as expected. At constant membrane pressure of 800 psi and pH of 8.2, feed flowrate thus the cross-flow velocity did not exert any significant impact on boron rejection. Acknowledgement The financial support of the Middle East Desalination Research Center (MEDRC) (Project Number: 04-AS-004) for this work is well acknowledged. The authors thank Toray Industries, Inc. and FilmTec Corp. for providing the membranes.

References 1. Redondo J (2001) Brackish, sea and waste water desalination as sustainable water sources. Technical-economical and ecological answers based on membrane technology. Desalination 138:29–40 2. Redondo J, Busch M, De Witte JP (2003) Boron removal from seawater using FILMTECTM high rejection SWRO membranes. Desalination 156:229–238 3. Wilf M, Bartels C (2005) Optimization of seawater RO systems design. Desalination 173:1–12 4. Busch M, Mickols WE (2004) Reducing energy consumption in seawater desalination. Desalination 165:299–312 5. Polat H, Vengosh A, Pankratov I, Polat M (2004) A new methodology for removal of boron from water by coal and fly ash. Desalination 164:173–188 6. Mastromatteo E, Sullivan F (1994) Summary: International symposium on the health effects of boron and its compounds. Environ Health Perspect 102:139–141 7. Bick A, Oron G (2005) Post treatment design of seawater reverse osmosis plants: Boron removal technology selection for potable water production and environmental control. Desalination 178:233–246 8. Taniguchi M, Fusaoka Y, Nishikawa T, Kurihara M (2004) Boron removal in RO seawater desalination. Desalination 167:419–426 9. Nadav N (1999) Boron removal from seawater reverse osmosis permeate utilizing selective ion-exchange resin. Desalination 124:131–135 10. Glueckstern P, Priel M (2003) Optimization of boron removal in old and new SWRO systems. Desalination 156:219–228

Respirometric Evaluation of Strong Wastewater Activated Sludge Treatment for a Complex Chemical Industry E. Ubay Cokgor, G. Insel, E. Aydın, S. Ozdemir, and D. Orhon

Abstract This study deals with respirometric modeling of biodegradation of complex organic matter generated from a chemical industry. Evaluation with a multi-degradation model indicated that organic matter in raw wastewater has four types of biodegradable components having different biodegradation characteristics. The model evaluation of batch respirogram indicated that the acclimated biomass exhibited a delayed response after the addition of raw wastewater to endogenous biomass. The delayed phase was characterized by Haldane type inhibition kinetics. The inhibitory effect of raw wastewater was also supported by standard toxicity test result yielding EC50 at 1.5% dilution. Keywords Chemical industry · Strong wastewater · Substrate inhibition · Modeling · Haldane kinetics

1 Introduction Industrial sectors generate high amount of pollutants in terms of organic and specific substances. The wastewater contains vast array of chemicals that have different chemical structures. The chemicals used in the process finally end up with discharge which results in concentrated streams including specific pollutants. As a result, the existence of inhibitory and toxic compounds in process production cause severe problems during wastewater discharge to the environment [5, 6]. The activated sludge treatment has been used efficiently and it serves as the most economic solution for domestic wastewater treatment for organic carbon removal [13]. The trends in the application of activated sludge technology to industrial wastewater treatment have now been increasing in parallel to the valuable E.U. Cokgor (B) Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_107,

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experiences gained from pilot and full-scale applications. On the other hand, difficulties still arise in the treatment of an industrial wastewater since it contains highly concentrated organic pollutants that have poor biodegradation characteristics. Nevertheless, the concentration level and biodegradation characteristics considerably deviate from domestic wastewaters which make the system more susceptible to environmental conditions. Hence, more information on the biodegradability under different conditions should be gathering for each industrial activity. Respirometry is one the most commonly used method for the determination of biodegradable substrate together with degradation kinetics of organic matter [16, 1, 8]. This method serves as a rapid tool for fingerprinting the biodegradable substrate and biodegradation characteristics of organic matter in wastewaters. In this respect, the oxygen uptake rate (OUR) profile contains ample information on the utilization of organic matters by heterotrophic biomass. The interpretation of OUR profile with the aid of selected biodegradation model allows to estimate relevant kinetic and stoichiometric parameters which can be used in activated sludge process design and system operation. Moreover, respirometric modeling can also be used for the evaluation of inhibitory effects (ie: substrate level, specific toxic compounds, xenobiotics) on model parameters which give clues about the shifts in bacterial metabolism. Microbial tests have been widely used in environmental toxicity screening due to similarity of complex biochemical functions in bacteria and higher organisms, ease of handling, short testing time. The use of bioassays in evaluating the eco-toxicology is widely used in integrated assessment of the overall impact on the environment [11, 12]. The work presented in this paper focuses on the biodegradation structure of organics in wastewater generated from a complex chemical industry producing more than hundred types of organic chemicals. The degradation characteristic of organic matter was investigated under aerobic conditions by short-term respirometry and modeling work. In addition, standard toxicity test was conducted to envisage the impact of wastewater to the aquatic environment.

2 Materials and Methods 2.1 Wastewater Characteristics and Treatment Plant Performance The chemical industry production is composed of hundred types of chemicals. The wastewater generated from the industry has been treated by wastewater treatment plant including the units of (1) equalization tank, (2) coagulation using FeCl3 and lime (3) flocculation with polyelectrolyte (3) settling, (4) neutralization and (5) activated sludge treatment. The historical data shows that the average COD concentration in the equalization basin is recorded as 8,340 mgCOD/L which falls in the range of 3,770–15,490 mgCOD/L. The ammonia nitrogen was measured around 80 mgN/L (20–235 mg/L). The phosphorus was externally supplied before the

Respirometric Evaluation of Strong Wastewater Activated Sludge Treatment

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activated sludge treatment. The COD concentration in WWTP effluent was measured to be 315 mgCOD/L (95–473 mg/L). The hydraulic retention time of the activated sludge system is 20 hours.

2.2 Influent COD Fractions and Biodegradability The inert COD fractions XI1 and SI1 were determined using the method developed by Orhon et al. [14]. The method involves three aerated batch reactors fed with the unfiltered, filtered wastewaters and the glucose seeded with a very small amount of biomass previously acclimated to the glucose and wastewater mixture. Inert fractions are calculated using final threshold values of the glucose, total and soluble COD in three reactors after a period where all biological activity is practically completed. The respirometric tests were conducted with acclimated biomass sampled from activated sludge unit of wastewater treatment plant. Batch respirometric (OUR) experiment was conducted at desired initial Food/Microorganism (S/X) ratio. The OUR measurements were performed with Applitek Ra-Combo continuous respirometer with PC connection. A nitrification inhibitor (Formula 2533TM, Hach Company) was added to the reactors to prevent possible interference induced by nitrification. The biomass and wastewater mixture was continuously aerated with compressed air in order to keep the dissolved oxygen level above 5 mgO2 /L in the aeration vessel. The respirometric test was performed with approx. 5 times diluted wastewater sample. After observing the endogenous OUR level, a wastewater sample is added to mixed liquor having 2,000 mgVSS/L was added in order to maintain the S/X ratio at 1.3 gCOD/gVSS.day. The model parameters were estimated in accordance with the method proposed by [8, 3]. Model simulations and parameter estimation works were performed using AQUASIM program [15]. The COD was measured according to ISO 6060 method [9]. For soluble COD determination, samples were subjected to vacuum filtration by means of Millipore membrane filters with a pore size of 0.45 μm. The Millipore AP40 glass fiber filters were used for total suspended solids (TSS) and volatile suspended solids (VSS) measurements. TSS, VSS experiments were performed according to the Standard Methods (1998).

2.3 Toxicity Experiments Toxicity test was carried out according to ISO 11348-3 procedure. Pure cultures of bacteria in freeze dried form should be reconstituted with reconstitution solution in 15◦C in a chiller. pH of the sample was adjusted to 7±0.2 if it is beyond the interval of 6–8.5. The salinity of the sample was adjusted to be equivalent of 2% NaCl solution with Sample Diluent (20% NaCl). Several dilutions of the sample which would have been tested are prepared with dilution solution (2% NaCl) in

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order to make it react with Vibrio fischeri and assess EC50 value. Light intensity of the cuvette containing only bacterial suspension is measured and then, immediately, sample is added to the cuvette [2]. After exposure period light intensity is measured again [10]. V. fischeri is marine luminescent bacteria. The bioassay with V. fischeri requires only a short period of time to obtain reliable toxicity results which is one of its major advantages compared with other tests such as fish bioassays, which normally require several days. Light production is the result of a chemical reaction involving the oxidation of a substrate, generally called luciferin, mediated by an enzyme called luciferase in the presence of an ionic co-factor; the intensity of produced light is proportional to the amount of reagents involved in the chemical reaction. A decrease in the intensity of the light produced therefore indicates alteration of one of the events leading to light production: either the chemical reaction (e.g., configurational inactivity of reagents), the expression of genes coding for the reagents, and/or any physiological control associated with the process. A blank sample with no toxicant (control) was used for all sets of experiments to correct for the time-dependent change in the light production of the bacteria themselves in order to isolate the toxic effects of the sample alone, as well as to account for small effects due to dilution arising from sample transfer, pipette error, and introduction of reagents [12].

3 Results and Discussion 3.1 Wastewater Characterization and Treatability Study The wastewater sample obtained from the chemical industry contains 12,800 mg/L of total COD with a soluble fraction of 87%, Total Nitrogen of 1,160 mgN/L and total phosphorus of 162 mg/L (Table 1). It was observed that there was around 90% reduction in the biological COD removal efficiency (Fig. 1). After toxicity test, it was found that 1.5% of the wastewater as volume cause 50% inhibition in the light intensity of marine luminescent bacteria (EC50=1.5%).

Table 1 Influent wastewater characterization Parameters

Unit

Concentration

Total COD Filtered COD (0.45 μm) Total suspended Solids, TSS Volatile suspended Solids, VSS Total kjeldahl nitrogen, TKN Ammonia nitrogen, NH4 -N Total phosphorus, TP Ortho phosphate, PO4 -P pH

mgCOD/L mgCOD/L mg/L mg/L mgN/L mgN/L mgP/L mgP/L -

12, 800 11, 100 1, 045 895 1, 160 1, 120 162 66 6.3

Respirometric Evaluation of Strong Wastewater Activated Sludge Treatment

1143

12000 10000 8325

COD, (mg/L)

8000 6000

4260

4000

2810 2000 1160 0 0

1

2

3

4

5

Time, (day)

Fig. 1 Soluble (filtered) COD concentrations versus time in fill and draw reactor

3.2 Inert COD Fraction Determination

3000

COD Concentrations, (mgCOD/L)

COD Concentrations, (mgCOD/L)

The results of COD profiles obtained from inert COD experiments are illustrated in Fig. 2a, b. Total inert COD concentration was found to be 845 mg/L which covers 7% of total COD. The soluble and particulate inert COD fractions can be calculated as 5 and 2%, respectively. The assessment of inert components showed that organic content of the chemical industry wastewaters was mostly soluble and biodegradable. Thus, the total COD in raw wastewater was found to be 93% biodegradable (Figs. 2 and 3).

2500 Total Soluble

2000 1500 1000 500 0

0

10

20

30 40 50 Time, (day)

(a) Total Reactor

60

70

80

3000 2500 Total Soluble Glucose

2000 1500 1000 500 0 0

10

20

30 40 50 Time, (day)

60

70

80

(b) Soluble (Filtered) and Glucose Reactor

Fig. 2 COD profiles for the determination of inert COD fractions

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Concentrations, (mg/L)

14000

12800

11000

11955

12000 10000 8000 6000 4000 610

2000

235

0 CT1

ST1

CS1

SI1

XI1

Fig. 3 Influent COD fractions

3.3 Respirometric Modeling Respirometric method was extensively used for the interpretation of biodegradation characteristics of organic matter in raw wastewater. First, batch oxygen uptake rate (OUR) data was collected every minute interval during 800 minutes (34 hours). The dotted graph shown in Fig. 3 illustrates the experimental OUR data obtained from batch experiment summarizing the overall degradation picture starting from endogenous decay level. After wastewater spike into the aerated endogenous biomass at time (t=0), the initial logarithmic increase of OUR level of 140 mg/L.h was observed within 300 minutes. This delayed increase can be attributed to the presence of inhibitory substances in raw wastewater. Because, the experiment was initiated with high acclimated biomass concentration around 2,000 mgVSS/L sampled from activated sludge unit of WWTP. It can be expected to have instant increase due to the activity of biomass at this concentration. It should be noted that the raw wastewater was used in the experiment without applying any chemical pretreatment as applied in wastewater treatment plant. After 300 minutes, the OUR dropped to a 2nd, 3rd and 4th plateau levels at 100, 80 and 40 mg/L.h, respectively. The results obtained from Fig. 3 indicate the availability of 4 types of biodegradable organic matters that have different biodegradation characteristics. The use of multi-component model mimic the overall degradation of organic compounds fingerprinted by the OUR experiment. Thus, a degradation multi-degradation model was built considering the long term inert COD experiments (Fig. 3) and OUR data (Fig. 4). According to inert COD experiment, the fraction of biodegradable organic matter fraction was found to be 93% of total COD, from mass balance. So, the biodegradable COD fraction of 93% covers four types of organic matter in raw wastewater. The structure of multi-degradation model is summarized in Peterson Matrix format as illustrated in Table 2. Shortly, the biodegradable substrates were characterized with the state variables of SS1 and SS2 , SS3 and SH1 . The degradation rate

Respirometric Evaluation of Strong Wastewater Activated Sludge Treatment

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200 Data Model

OUR (mg/L.h)

160 SS1

SS2

120

SS3 80 SH1 40

0 0

100

200

300

400 500 time (min)

600

700

XH

Rate

800

Fig. 4 Respirometric modeling results Table 2 Multi degradation model Processes

SO2

Growth on SS1

H − 1−Y YH

Growth on SS2

H − 1−Y YH

Growth on SS3

H − 1−Y YH

Hydrolysis of SH Biomass Decay

SS1

SS3

SH

− Y1H −1

1 − Y1H

μH1

(KS +

SS1 S2 S1 KI )+SS1

XH

1

KS S2 μH2 K S+S XH S2 S2 KS +SS S K S3 S μH3 K +S K +S XH S3 S3 S S H /XH kh KXS+S X H H /XH

−1

bH XH

1 − Y1H

1 1−fp

SS2

−1

of the first three components was assigned to Monod type degradation kinetics as shown in rate equation in Table 2. Basically, the rate equation is controlled by the maximum growth rate μH1 and half saturation constant (KS ) parameters. The only difference in the process rate of SS1 degradation is that an inhibition parameter (KI ) was added in order to model the logarithmic OUR increase within 300 minutes at initial high biomass concentration. Thus, a model can simulate the logarithmic OUR phase with substrate inhibition. The degradation rates for SS2 , SS3 take place after the utilization of primary substrate of SS1 . The degradation of final substrate (SH ) was characterized with hydrolysis process since its degradation rate is much lower than that of others [1]. It can be seen from Fig. 4, the OUR level pertaining to SH degradation is much lower than the first, second and third plateau. At this level, the OUR gradually declined which indicated much lower degradation rate [4]. Finally the loss of heterotrophic biomass activity is subjected to biomass decay process [13] as shown in Table 2. Below, the estimated model parameters and state variables using OUR profile were listed in Table 3. A good match between simulated and experimental data can be observed from Fig. 4.

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E.U. Cokgor et al. Table 3 Estimated model parameters

Model Component Stoichiometry Heterotrophic yield coefficient, YH Kinetics Maximum growth rate, SS (μH1 ) Inhibition concentration for SS1 , KI Maximum growth rate, SS2 (μH2 )

Maximum growth rate, SS3 (μH3 ) Half saturation constant for SS1 , KS1 Half saturation constant for SS2 , KS2 Half saturation constant for SS3 , KS3 Maximum hydrolysis rate, kh Hydrolysis half saturation constant, KX Initial States Active biomass concentration, XH0 Initial total biodegradable COD, CS1 Readily biodegradable COD, SS1 Second biodegradable COD, SS2 Third biodegradable COD, SS3 Hydrolysable COD, SH

Unit

Value

gcellCOD/gCOD

0.64

day−1 mgCOD/L

5.10 150

day−1

0.70

day−1 mgCOD/L mgCOD/L mgCOD/L day−1 gCOD/gcellCOD

0.69 60 10 25 1.3 0.3

mgcellCOD/L mgCOD/L mgCOD/L mgCOD/L mgCOD/L mgCOD/L

1,300 2,824 510 200 495 1,619

Default parameters: bH =0.15 day−1 , fP = 0.2

In state estimation, the initial biodegradable COD (CS1 ) can be subdivided into SS1 , SS2 , SS3 and SH1 with the fractions of 510, 200, 495 and 1,619 mgCOD/L, respectively. The maximum growth rate μH1 for SS1 degradation was found to be 5.1 day−1 which is comparable with domestic wastewater treatment, suggested as 6.0 day−1 [7]. On the other hand, the logarithmic increase in OUR was modeled with substrate inhibition which was delineated with inhibition parameter KI of 150 mgCOD/L at high active biomass concentration at 1,300 mgcellCOD/L. The values for half saturation affinity constant, KS exhibit high variations for different substrate degradation. The KS values of having a wide range in 5–20 mgCOD/L were suggested for readily biodegradable COD for the activated sludge systems treating domestic wastewater. However, in this model evaluation, only KS1 of 60 mg/L is comparably higher which indicates that the affinity of biomass to this substrate is lower than others. In addition, the maximum hydrolysis rate (kh ) and half saturation for hydrolysis parameter (KX ) estimated for SH hydrolysis were estimated to be 1.3 day−1 and 0.3 gCOD/gcellCOD, respectively. In comparison with domestic wastewater counterparts (kh =3.0 day−1 and KX =0.3 gCOD/gcellCOD), the SH degradation rate is much lower than that of domestic wastewater. As listed in Table 3, the amount of SH has the highest COD fraction and the lowest degradation rate. As a result, the treatment performance is adversely affected if any pretreatment is not applied. In addition, the SS1 causes substrate inhibition

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which may also affect the effluent COD level of activated sludge plant. It is interesting that current WWTP can handle the COD load and it yields a COD removal efficiency of 90% at 20 hours of hydraulic retention time in biological reactor after chemical pretreatment of raw wastewater.

4 Conclusions The treatment of strong wastewaters generated from chemical industry without pretreatment caused inhibitory effect on activated sludge treatment. The treatment of raw wastewater of chemical industry in this study caused an inhibitory effect on biomass activity under aerobic conditions. The evaluation of respirometric profile with multi-degradation model revealed that substrate inhibition can be modeled with the aid of Haldane kinetics in spite of the fact that the acclimated biomass to chemically treated wastewater was used in the experiment. Moreover, the modeling study indicated the presence of organic matter which can be subdivided into 4 different substrates. These individual substrates were found to have different level of impacts on the biodegradation kinetics. According to eco-toxicological experiments conducted in parallel to respirometric experiments, the raw wastewater generated could cause severe toxicity to the environment even at very low dilution level. More elaborative work should be dedicated on biodegradation process considering the effects of enzymatic response of biomass under different environmental conditions such as acclimation period, biomass history etc. The advanced collaborative work between modelers and microbiologists will certainly provide broad perspective on microbial population dynamics under variable conditions.

References 1. Cokgor EU, Sözen S, Orhon D, Henze M (1998) Respirometric analysis of activated sludge behaviour I. Assessment of the readily biodegradable substrate. Wat Res 32(2):461–475 2. Deheyn DD, Bencheikh-Latmani R, Latz MI (2004) Chemical speciation and toxicity of metals assessed by three bioluminescence-based assays using marine organisms. Environ Toxicol 19(3):161–178 3. Dochain D, Vanrolleghem PA, Van Daele M (1995) Structural identifiability of biokinetic models of activated sludge respiration, Wat Res 29(11):2571–2579 4. Ekama GA, Dold PL, Marais GvR. (1986) Procedures for determining influent COD fractions and the maximum specific growth rate of heterotrophs in activated sludge systems. Water Sci Technol 18:91–114 5. Germirli F, Tünay O, Orhon D, MeriçS (1997) A systematic approach to asses the pollution characteristics in the textile industry. Fresenius Environ Bull 6:254–259 6. Germirli Babuna F, Orhon D, Ubay Çokgör E, Insel G, Yapraklı B (1998) Modelling of activated sludge for textile Wastewaters. Water Sci Technol 38(4–5):9–17 7. Henze M, Gujer W, Mino T, van Loosdrecht MCM (2000) Activated sludge models: ASM1, ASM2, ASM2d and ASM3. Scientific and Technical Report No:9, IWA Publishing, London 8. Insel G, Orhon D, Vanrolleghem PA (2003) Identification and modelling of aerobic hydrolysis mechanism-application of optimal experimental design. J Chem Technol Biotechnol 78(4):437–445

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9. ISO (1986) Water quality – Determination of the chemical oxygen demand. International Standards for Business, Government and Society Ref.No. ISO 6060-1986 10. ISO (1999) Determination of the inhibitory effect of water samples on light emission of Vibrio fischeri (Luminescent Bacteria Test), ISO 11348-3 11. Mowat FS, Bundy KJ (2001) Correlation of field-measured toxicity with chemical concentration and pollutant availability. Environ Int 27(6):479–489 12. Mowat FS, Bundy KJ (2002) Experimental and mathematical/computational assessment of the acute toxicity of chemical mixtures from the Microtox(R) assay. Adv Environ Res 6(4):547– 558 13. Orhon D, Karahan Ö, Sözen S (1999) The effect of microbial products on the experimental assessment of the particulate inert COD in wastewaters. Water Res 33(14):3191–3203 14. Orhon D, Artan N (1994) Modelling of activated sludge systems. Technomic, Lancaster, PA 15. Reichert P, Ruchti J, Simon W (1998) Aquasim 2.0. Swiss Federal Institute for Environmental Science and Technology (EAWAG), CH-8600, Duebendorf, Switzerland 16. Spanjers H, Vanrolleghem PA (1995) Respirometry as a tool for rapid characterization of wastewater and activated sludge. Water Sci Tech 31(2):105–114

Cellulose Acetate-Polyethersulfone (CA-PS) Blend Ultrafiltration Membranes for Palm Oil Mill Effluent Treatment Ani Idris and Iqbal Ahmad

Abstract The objective of this research is to investigate the possibility of using ultrafiltration blended cellulose acetate (CA) and polyethersulfone (PES) membranes in the treatment of palm oil mill effluent (POME). Thus, series of distinctive formulations such as pure CA and blended CA/PES using N, N-dimethylformamide (DMF) as solvent were formulated and prepared by phase inversion method. The blended membranes were initially subjected to the separation of BSA and then POME. The performances of these membranes were evaluated in terms of pure water and permeate flux, percentage removal of total suspended solids (TSS), chemical oxygen demand (COD) and biochemical oxygen demand (BOD). Blending of 19% CA, 1% PES and 80% of DMF solvent were discovered as the best membrane formulation. The morphology of the blended membranes produced were analyzed using scanning electron microscope (SEM). Keywords Blend membrane · Cellulose acetate · Polyethersulfone · Palm oil mill effluent

1 Introduction Ultrafiltration (UF) is a membrane process capable of separating or collecting submicrometer-size particles and macromolecules from a suspension or solution [18]. It has been widely used to concentrate or fractionate a solution containing macromolecules, colloids, salts, or sugars. Synthetic polymers such as polysulfone, polyethersulfone, cellulose acetate, etc. are widely used for the ultrafiltration membranes. Polyethersulfone is a hydrophobic polymer. It has wide pH tolerances, good

A. Idris (B) Faculty of Chemical and Natural Resources Engineering, Department of Bioprocess Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia e-mail: [email protected]

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chlorine resistance and easy to fabricate membrane in a wide variety of configurations. Polyethersulfone ultrafiltration membranes have advantages of good thermal stability because it has wide temperature limit and higher dry heat capability. Apart from that, it has good chemical resistance to aliphatic hydrocarbons, alcohols and acids [4]. Meanwhile CA being hydrophilic offers a good fouling resistance but is not suitable for more aggressive cleaning, has low oxidation and chemical resistances and poor mechanical strength and hence the modification of cellulose acetate gains importance [11, 12, 13]. New, less expensive types of materials with an extensive variety of properties intermediate between those of pure components could be obtained using polymer blending. Tomohiro et al. [6] and Sivakumar et al. [4] have reported that the blend membranes produced have better perm selectivity and permeability than that of membrane composed by the individual polymers and the synthesis of a polymer blend membrane is motivated by the necessity to superimpose requisite properties upon the basic transport properties of base polymer. Polymer blend membranes composing of hydrophobic and hydrophilic polymers such as polyacrylonitrile (PAN) with polyvinylchloride (PVC), cellulose acetate (CA) and polysulfone, (PSf), cellulose acetate (CA) and polyethersulfone, (PES),has been investigated [16, 8, 7, 14]. In both of the later blends the additives polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) has been added as additives. Thus in this study the possibility of blending only cellulose acetate (CA) and polyethersulfone, (PES) without any additives for the treatment of POME is explored. Membrane separation in wastewater treatment has been widely used and has successfully proven its efficiency in various types of industries. Several researches have been carried out on waste water treatment through membrane technology [1]. Turano et al. [17] successfully reduced the COD value to 90% using an organic UF membrane for olive mill washing water. Sridhar et al. [15] used RO to treat vegetable oil industry effluent with a resulting high rejection of TDS (99.4%), COD (98.2%) and also complete rejection of color and BOD. A combination of microfiltration (MF) and UF membranes has also been used for the treatment of kraft spent liquor with more than 80% efficiency in silica rejection [6]. Afonso and Borquez [2] studied microfiltration (MF) and ultrafiltration (UF) membranes to treat wastewater from fishmeal production. They succeeded in recycling the water for plant use as well as recycle protein into fishmeal process. Mavrov and Belieres [9] carried out their research on recovery and recycling of water from food industry wastewater using nanofiltration (NF) and reverse osmosis (RO) combined with cartridge filtration and disinfection as a pretreatment. The combination of biological treatment with UF, NF and RO membranes in treating municipal wastewater was also studied by Rautenbach et al. [10] where 97% water recovery was achieved. The palm oil industry is one of the major agro-industries in Malaysia. It requires a large amount of water for its operation and discharges considerable quantities of wastewater. This creates a serious threat to the environment and sources of potable water. Membrane technology is a highly potential solution for the treatment of POME since current conventional treatment system shows its lack of efficiency and leads to the environmental pollution issues [3]. It is important to develop locallymade membranes in Malaysia not only to gain better approach in terms of the

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technology but also to reduce the production cost. In order to achieve the mission, self made ultrafiltration blended membrane from cellulose acetate (CA) and polyethersulfone, (PES) without any additives were fabricated and the performances of the membranes produced were evaluated using palm oil mill effluent waste water in terms of flux and percentage rejection of total suspended solids, COD, BOD and turbidity. The morphology of the cross section of PES membranes were obtained by high voltage scanning electron microscope.

2 Material and Method Polyethersulfone (PES) was the polymer used which was supplied by BASF. N, N-dimethylformamide (DMF) was purchased from Labscan Asia Co. Ltd, as solvent without further purification. Bovin serum abumine (BSA) with molecular weight of 69,000 Daltons was supplied by Merck and was used as the feed solution. Cellulose acetate (CA) with 39.8 acetyl content from Acros organic was used. For UF experiments, samples of palm oil mill effluent (POME) at 80◦ C were collected from the Felda Bukit Besar Kulai, Johor. These samples were allowed to cool to room temperature and left to sediment by filtration process. Portions of the suspension were withdrawn and analyzed.

2.1 Dope Preparation Polyethersulfone and cellulose acetate were dried before dope solutions were prepared. The blend polymer concentration was fixed at 20% and their proportions are shown in Table 1. A 500 mL Schott Duran is used as the sample reaction vessel at atmospheric pressure. Table 1 Dope solution compositions

Composition in Wt. % Dope solution

CA

PES

DMF

1 2 3 4 5 6

20 19 18 17 16 15

0 1 2 3 4 5

80 80 80 80 80 80

2.2 Membrane Casting In this study, the membranes are prepared by phase inversion method. The dope solution thus obtained was spread over a smooth glass plate with the help of a knife edge. The thickness of the membranes was controlled by varying the thickness of adhesive tapes at the sides of the glass plate. The glass plate was kept in an

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environment of controlled temperature and humidity during membrane casting. No deliberate solvent evaporation period was allowed. The glass plate was subsequently immersed in a gelling bath, which is generally distilled water maintained at a known temperature.

2.3 Pretreatment for POME Wastewater The raw POME was collected from oil palm refinery of Felda Bukit Besar, Kulai. The sample was treated via filtration process to remove the suspended matter. The pH of POME before the treatment was 8 and after the pretreatment process was 6.5 and density was 1.25 gm/cm3 at 30◦ C. The POME were also analyzed in terms of turbidity, TSS, BOD and COD.

2.4 Experimental Methods Membrane performances were investigated by ultrafiltration experiments with POME samples after pretreatment. Pure water or the feed solution was pumped to the flat sheet module by a pump at 3.5 bar, and was circulated through the module for 1 h (pressure drop = 0.5 psig). Then, permeate was collected for a predetermined period and the permeate volume was measured. The permeate sample was further subjected to a series of analysis. After the completion of each ultrafiltration experiment, feed POME solution was switched to pure water and the system was washed for 3 h by circulating the pure water. The pure water flux (PWP) was calculated from the Eq. (1) Pure water flux (lit / hr. A) = Q/At

(1)

where Q is the volume of permeate (m3), A is the area of the membrane (m2 ) and t is the permeation time. In POME ultrafiltration process, the permeate comes out from each membrane was collected after 1 h.

3 Analytical Methods 3.1 Chemical Oxygen Demand Test Two ml sample was put into contact with the oxidizing acid solution that was then held at 148◦C for 2 h. After cooling, the sample was then analyzed in the HACH DR/2000 and DO readings were taken at 435 nm wavelengths. The color of the sample varied from orange to dark green indicating COD strength in the range of 0–15,000 mg/L.

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3.2 Biochemical Oxygen Demand Test Samples may have to be diluted in order for the DO range to be detected by the meter. Once all the bottles have been filled, in a 500 mL BOD flask the initial DO’s of each solution is determined using dissolved oxygen meter (model YSI 5402). Once recorded, the bottles are capped with ground glass stoppers to avoid excess bubbles. After 5 days of incubation at 4◦ C, the samples are ready to be analyzed. The samples are removed from the incubator and allowed to equilibrate to room temperature. Once the DO meter is calibrated, the samples are read starting with the blanks and ending with the actual samples. The final DO of each solution is recorded and the initial and final readings will be used to calculate the BOD.

3.3 Turbidity and Total Suspended Solid Test The turbidity of the samples was measured using HACH Ratio/Xr Turbidimeter which was calibrated. Total suspended solids were measured by inserting a glass microfiber filter disc with wrinkled side up in the filtration apparatus. Vacuum and wash disc with 50 mL of reagent-grade water is then applied. Suction is sustained to remove all traces of water. Next, the vacuum is then turned off. Sample is to be dried in an oven at 103–105◦C for an hour. Next, the sample was then cooled down to room temperature before weighing. The cycle of vacuum, drying, cooling and weighing with 20 mL of sample is repeated. The total suspended solid is calculated according to Eq. 2.

Total suspended solids mg/L =

(A − B) × 1000 v

(2)

where A is weight of filter + dried residue, mg, B is weight of filter, mg and v is volume of sample used.

3.4 Total Removal of the Component The efficiency of the membrane fabricated is highly dependent upon the total removal of the component using the following equation:

Total removal (%) =

Initial Concentration-Final Concentration × 100 Initial Concentration

(3)

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3.5 Scanning Electron Microscope (SEM) CA/PES blend membrane’s cross section was obtained by a high voltage scanning electron microscope. Samples of membranes were frozen in liquid nitrogen which gives generally clean break [5]. The samples were placed on a sample stand and sputtered coated with gold before being viewed with the SEM Model SUPRA 35VP.

4 Results and Discussion 4.1 BSA Separation and Pure Water Permeation

–2

Pure water flux, l.m .hr

–1

The efficiency of the blend membranes produced were tested using solutions of both BSA solutions and POME. The pure water permeation and BSA rejection rate results were depicted in Figs. 1 and 2 respectively. The performances of the membranes in terms of pure water permeate produced from the various solutions were depicted in Fig. 1. It is observed that the membranes produced from dope solution 5 containing 5% PES exhibits highest pure water permeation rates compared to those produced by from dope solutions 1–4. However the rejection rates of this membrane is the lowest compared to the other membranes containing less amounts of PES in CA. Apparently membranes produced from the dope solution 1–2 exhibits highest rejection rate with molecular cut off (MWCO) at 90% of approximately 69 kDa (BSA) as shown in Fig. 2. 45 40 35 30 25 20 15 10 5 0 0

1

2 3 Polyethersulfone, wt%

4

5

Fig. 1 Pure water permeation flux of blend membranes

4.2 POME Separation In the case of the POME separation, filtration is used as pretreatment for the samples before undergoing ultrafiltration process. Pretreatment steps indicate that it would eliminate a large portion of solid fraction in the samples. As shown in Table 2 and Fig. 3(E) and (F), it is observed that the raw POME sample has high concentration

CA-PS Blend Ultrafiltration Membranes for Palm Oil Mill Effluent Treatment 100 BSA rejection, %

Fig. 2 BSA rejection rate versus amount of PES in the blend membranes

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90 80 70 60 50 0

1

2

3

4

5

Polyethersulfone, wt %

Table 2 The efficiency of pretreatment

TSS (mg/L) Turbidity (NTU) COD (mg/L) BOD (mg/L)

Raw POME

POME After filtration

Reduction

Percentage of removal, %

11, 985 7, 140 3, 156 451.00

585 314 1, 862 265.00

11, 400 6, 826 1, 294 186.00

95.12% 95.602% 41.0% 41.24%

Fig. 3 The visual display of samples, E is sample after pretreatment and F is raw POME

of waste. This study abides by the same trend of pretreatment via centrifugation, a process which is used to remove organic pollutant loads before ultrafiltration experiments. The results indicates that there is a reduction of 186 mg/L or 41.24% in BOD, 1,294 mg/L or 41.0% in COD, 11,400 mg/L or 95.12% of suspended solids and 6,826 NTU or 95.12% turbidity. This implies that some of the organic and suspended solids content has been removed by filtration before ultrafiltration process. Results obtained from 1% PES flat sheet membranes indicate significant changes in visual display on samples as shown in Fig. 3. It appears that the presence of low amounts of PES has improved the membrane permeation flux and rejection rate of the membranes. Apparently the presence of PES acts as a pore former in the dope

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POME flux lm–2 hr–1

Fig. 4 Flux during POME separation

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2 1.5 1 0.5 0 0

1

2 3 Polyethersulfone, (wt%)

4

5

Fig. 5 Percentage of removal in terms of total suspended solid (TSS), turbidity (NTU), COD and BOD for the membranes tested

100 90 80 70 60 50 40 30 20 10 0 0

1

TSS

NTU

COD

BOD

2

3

Amount of PES, wt%

4

100 90 80 70 60 50 40 30 20 10 0 5

COD, BOD (%)

TSS, NTU, (%)

solution where permeation rates are observed to increase but the rejection decreases. In order to produce membranes which exhibited both high rejection and permeation rates the percentage of PES added should not exceed more that 1.5% as observed in Fig. 4. The presence of higher % of CA not only improved the membranes performance in terms of rejection rates but also reduce the production cost of the membranes because it is a cheaper polymer compared to PES. The results in Fig. 4 revealed that membrane 6 which consists of 5% PES exhibits the highest permeate flux during the POME ultrafiltration process, followed by membrane 5, 4, 3, and 2. However the permeate flux decreased with time regardless of % of PES in blend membranes due to concentration polarization. Results in Fig. 5 shows that the separation performance of POME in terms of total suspended solids (TSS), turbidity (NTU), COD and BOD for the membranes tested. The blended membranes fabricated are capable of reducing POME turbidity to 95.602% and its total suspended solid by 95.12%. This directly implies that some content of suspended solids has been removed prior to membrane treatment stage. The results also proved that blended CA-PES membranes exhibit excellent performance in POME waste water treatment. Membrane 2 shows the best result with 99.972% of turbidity removal and 98.71% in removal of TSS. This is followed by membrane 3, membrane 4, membrane 5 and membrane 6.

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COD is an indication of the overall oxygen load that a wastewater will impose on an effluent stream. COD is equal to the amount of dissolved oxygen that a sample will absorb from a hot acidic solution containing potassium dichromate and mercuric ions. The performance of COD shows the reduction by 54.75% for the membrane 2, 49.37% for membrane 3, 48.73% for membrane 5 and 47.72% for membrane 6. The BOD of wastewater expresses the amount of oxygen used by biodegradable organic substances. The BOD reduction shows a similar trend to the COD reduction as illustrated in Fig. 5. The amount and presence of PES membranes plays an important role in reducing the BOD percentage to 54.55, 54.77, 49.38, 48.75 and 47.74% for membrane 2, 3, 4, 5 and 6 respectively. The evidence seems to suggest that the hydrophilic property of aromatic series PES is raised when it is mixed with cellulose acetate [16] as shown by the increase in the pure water permeate flux and POME flux. However PES and CA are not compatible chemically since the hydrophobic and hydrophilic bonds are not balanced and these results in the rejection rate to decrease as the PES content is increased. The scanning electron microscope (SEM) images indicated that the CA-PES blended membranes have semi-permeable membrane structure. It can be observed from Fig. 6 that PES/CA blended membranes have big macrovoids and nodules.

(a)

(b)

(c)

(d)

Fig. 6 SEM images of CA-PES blends (a) 1% (b) 2% (c) 3% (b) 5% PES

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As shown in Fig. 6 macrovoids increased in size as higher percentage of PES was added. The higher amounts of PES in PES/CA blended membranes have higher fluxes but lower rejection rates. SEM images of PES/CA blended membranes exhibit finger-like macrovoids in the support layer with the presence of nodules.

5 Conclusion The performance of blended CA-PES ultrafiltration membranes fabricated has been tested using BSA solution and POME and found to be capable of giving good separation in terms of percentages of removal for turbidity, TSS, COD and BOD and exhibit good permeate flux,. The performances of the PES ultrafiltration membranes revealed that membranes with the formulation, 1% PES, 19% CA and 80% DMF exhibited the best rejection rates and reasonably high fluxes. The pure water permeate flux of the best formulation membranes was 15 L/m2 .hr, the percentages of removal for turbidity, TSS, COD and BOD were 99.975, 99.12, 54.75 and 54.77% respectively. Acknowledgements Financial support from the Ministry of Science, Technology and Environment through the IRPA funding vote no 74246 is gratefully acknowledged.

References 1. Abdessemeda D, Nezzala G, Aimb RB (2000) Coagulation–adsorption–ultrafiltration for wastewater treatment and reuse. Desalination 1(1):525–532 2. Afonso MD, Borquez R (2002) Review of the treatment of seafood processing wastewaters and recovery of proteins therein by membrane separation processes – prospects of the ultrafiltration of wastewaters from the fish meal industry. Desalination 142(1):29–45 3. Ahmad AL, Ismail S, Bhatia S (2005) Membrane treatment for palm oil mill effluent: Effect of transmembrane pressure and crossflow velocity. Desalination 179:245–255 4. Cheryan M (1998) Ultrafiltration and microfiltration handbook. Technomic Publishing Corporation, Lancaster, UK 5. Idris A (2001) Fabrication and optimization of asymmetric hollow fiber membranes for reverse osmosis, Ph.D Thesis, Universiti Teknologi, Malaysia 6. Liu GL, Liu YS, Ni JR, Shi HC, Yi Q (2004) Treatability of kraft spent liquor by microfiltration and ultrafiltration. Desalination 160(2):131–141 7. Mahendran R, Malaisamy R, Arthanareeswaran G, Mohan D (2002) Cellulose acetate and sulfonated poly(ethersulfone) blend ultrafiltration membranes. II Appilication studies. J Appl Polymer Sci 92:3659 8. Malaisamy R, Mahendran R, Mohan D (2002) Cellulose acetate and sulfonated polysulfone blend ultrafiltration membranes.II Pores statistics, molecular weight cutoff and morphological studies. J Appl Polymer Sci 92:3659 9. Mavrov V, Belieres E (2000) Reduction of water consumption and wastewater quantities in food industry by water recycling using membrane processes. Desalination 131(l–3):75–86 10. Rautenbach R, Vossenkaul K, Linn T, Katz T (1996) Wastewater treatment by membrane processes – new development in ultrafiltration, nanofiltration and reverse osmosis. Desalination 108(1–3):247–253 11. Sivakumar M, Mohan D, Rangarajan R (1998) Preparation and performance of cellulose acetate- polyurethane blend membranes and their applications. Part I, Polymer Int 47:311

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12. Sivakumar M, Malaisamy R, Sajitha CJ, Mohan D, Mohan V, Rangarajan R (1999) Ultrafiltration application of CA-PU blend membranes. Eur Polymer J 35(9):1647–1651 13. Sivakumar M, Malaisamy R, Sajitha CJ, Mohan D, Mohan V, Rangarajan R (2000) Preparation and performance of cellulose acetate- polyurethane blend membranes and their applications – II. J Membr Science 169(2):215–228 14. Sivakumar M, Mohan DR, Rangarajan R (2006) Studies on cellulose acetate-polysulfone ultrafiltration membranes: II. Effect of additive concentration. J Membr Sci 268(2):208–219 15. Sridhar S, Kale A, Khan AA (2002) Reverse osmosis of edible vegetable oil industry effluent. J Membr Sci 205:83–90 16. Tomohiro F, Yasuhiko N, Yasushi N (1994) Polysulfone solution composition. Japanese Patent, Publication number: 06-256656, Japan patent office 17. Turano E, Curcio S, De Paola MG, Calabro V, Dorio G (2002) An integrated centrifugationultrafiltration system in the treatment of olive mill wastewater. J Membr Sci 20(2):519–531 18. Verrall MS, Hudson MJ (1987) Separations for biotechnology. Ellis Horwood Limited, UK

Rehabilitation of Wastewater Treatment Plant of Sakhnin City in Israel by Using Advanced Technologies Yasar Avsar, Hussein Tarabeah, Shlomo Kimchie, Izzet Ozturk, and Hadi Naamneh

Abstract This study deals with the rehabilitation of waste water treatment plant (WWTP) of Sakhnin city in Israel. To increase low removal efficiency of the facultative pond (FP) and seasonal reservoir (SR) of the WWTP, different kinds of reactors having different operating conditions were established by the name of two tasks such as intermittent trickling bio filters (ITBFs) and concrete tunnels, respectively. According to the evaluation of the results, it was observed that ITBFs and tunnel units contribute to reasonable removal capacity on sCOD, TSS, NH3 -N and PO4 -P parameters. When it is considered establishing a full scale treatment plant to rehabilitate FP and SR units of available WWTP, this study will be able to a guide for decision makers. Keywords Facultative · ITBF · Rehabilitation · WWTP

1 Introduction There is no doubt that the lack of water in the Middle East and other developing countries is one of the most serious problems we have to face. The problem has been exacerbated in recent years due to the sharp increase in the domestic water demand, caused by an increasing demand from larger populations as well as moves to raise the standard of living. The Towns Association for Environmental Quality (TAEQ) is an organization based on an initiative of local professionals and key persons in the local municipality. Established in 1993 as a regional environmental quality unit, it is funded by the local municipalities and the Ministries of Environment and Interior in Sakhnin city of Israel. Y. Avsar (B) Faculty of Civil Engineering, Department of Environmental Engineering, Yildiz Technical University, Istanbul, Turkey e-mail: [email protected]

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The Sakhnin wastewater treatment plant (WWTP) includes sewage treatment facilities consisting of two settling anaerobic ponds, a facultative oxidation pond, and a storage pond with a volume of 180,000 m3 . After the treatment process, the water in this storage pond is acceptable for the irrigation of certain crops, most notably olive groves, which surround the facility and are prevalent throughout the region. As part of the LIFE Third Countries initiative of the European Commission, TAEQ will began to technologically upgrade the existing wastewater treatment facilities to produce improved quality effluent for local agricultural irrigation. This study was performed mainly in the facilities of the Sakhnin Rural Development Center (SRDC) in Israel [1]. The WWTP plant of Sakhnin given in Fig. 1 treats about 2,000 m3 each day of the town’s wastewater with conventional technology that includes a series of ponds as follows: • Two anaerobic ponds (sedimentation ponds which are based on biological activity without oxygen, each with a volume of 5,000 m3 ). • One facultative pond (FP) (a pond where biological activity is combined with anaerobic bacteria). • One 150,000 m3 wastewater seasonal reservoir (SR). • An effluent chlorination unit. The “series of ponds” technology is a very common WWTP technology in rural areas and is operating widespread in Israel [2]. Upgrading the technologies used in connection with this type of technology will help save water (by using the effluent for irrigation), protect other water resources, and prevent odor nuisances. The problem of water scarcity in Israel led to the development of WWT and effluent reuse technologies.

Fig. 1 Available wastewater treatment plant of Sakhnin

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The goals are to achieve a purification stage which is acceptable in agriculture rising in the area, developing irrigation systems land on recycling water to enable saving good water for purposes other than irrigation. TAEQ recently received funding from the European Commission to implement a LIFE Third Countries project. This project will technologically upgrade existing wastewater treatment facilities to produce improved quality effluent for local agricultural irrigation. One of the primary educational programs developed will encourage international cooperation between Israeli and Turkish professionals on environmental problems dealing with wastewater treatment and reuse. This research conducted at the Sakhnin center on wastewater treatment will serve as a model to all rural communities throughout the world.

2 Materials and Methods For the rehabilitation of the WWTP, different advanced treatment tasks such as ITBFs and stripped concrete tunnels were constructed to rehabilitate the facultative pond FP and seasonal reservoir SR, respectively. During the establishing of the ITBFs, 16 experimental units were manufactured, according to specially designed feeding system, sampling means, inlet and outlet lines. Two basic models were produced: 8 units of regular size model (1.5 m high) and 8 units of the longer size units (2.5 m high). The working volumes of the two models are 120 and 200 L, respectively. Air distribution pipes were installed into some of the ITBF reactors and the proportions of air to liquid was 10/1. The dosing pumps are timer controlled and the system includes a complete pumping station and intermediate tank in order to provide the system with effluent from the available FP of the full scale Sakhnin WWTP. Several types of fixed medium materials were purchased (chopped olive wood and chopped pine wood of two sizes each). When the installation of tunnels as a simulation of present SR, the experimental units for testing the project’s hypothesis were designed in the shape of tunnels for simulating the flow regime in the SR. Tunnel dimensions are 8 m long, 2 m deep, and 1 m wide. Three tunnels were constructed from concrete cast and are located about 30 m from the bank of the Sakhnin WWTP. Arrangements were done to feed the experimental SR ponds with the same quality of wastewater that is feeding the full scale operating SR. There is an array consisting of a pump, intermediary tank, dosing pumps, and timer controllers. The tunnels were built with “plug flow” hydraulic regime. In part of the channels, air diffusers will be added to enhance biological activity. In some of the channels bundles of plastic strips will be dipped to supply large surface area for the development of active biomass attached to the plastic strips. The view of the units is shown in Fig. 2a, b, respectively. Characteristics of the ITBFs and tunnel reactors are given in Table 1 and Table 2, respectively. In Table 3 average concentration and removal efficiencies of the two units in available WWTP were given, respectively. As seen from Table 3, these low efficiency results shoved that rehabilitation study of the WWTP was inevitable.

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a) ITBFs as simulation of FP

b) Tunnels as simulation of SR

Fig. 2 General view of the established pilot units Table 1 ITBFs units and design criteria Reactors #

Height of biofilter

Type of wood chips

Size of wood chips

Aeration

Retention time (day)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

2.5 2.5 2.5 1.5 1.5 1.5 2.5 2.5 1.5 1.5 2.5 2.5 2.5 1.5 1.5 1.5

Olive wood Olive wood Pine wood Olive wood Olive wood Pine wood Pine wood Pine wood Pine wood Pine wood Pine wood Pine wood Pine wood Pine wood Pine wood Pine wood

4`` 2`` 4`` 4`` 2`` 4`` 2`` 2`` 2`` 2`` 4`` 2`` 2`` 4`` 2`` 2``

− − − − − − − + − + + − + + + +

6 6 6 6 6 6 6 6 6 6 10 10 3 10 10 3

Table 2 Tunnel reactors and design criteria Reactors #

Reactor type

Fixed medium

Aeration

Retention time (day)

1 2 3

Rectengular Rectengular Rectengular

− + +

+ − +

60 60 60

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Table 3 Effluent concentration and removal rates of the units in the present WWTP Concentrations

Removal efficiency, %

Parameters

FP

SR

FP

SR

sCOD, mg/L NH3 -N, mg/L PO4 -P, mg/L TSS, mg/L

489 51.6 15.6 125.5

317.7 46.9 14.8 90.8

6.7 3.6 18.1 16.3

29.4 17.1 No reduction 13.2

During the monitoring of the effluent characteristics of the new two units, all the parameters such as sCOD, TSS, NH3 -N and PO4 -P were analyzed according to the APHA-AWWA-WPCF [3]. At the end of a-one year monitoring programme (April 2005–2006), removal efficiencies of two redesigned units were evaluated.

3 Results and Discussions After a-6 week start-up periods, the effluent water quality parameters such as sCOD, NH3 -N, PO4 -P and TSS of two units were analyzed. The total experimental period was 12 months. Each of the units includes different reactors which have special operating processes. Each of the reactors gives different removal efficiencies in their effluents. To determine the best reactor type in each of the units, the effluent pollution parameters in both ITBFs and tunnel system were monitored for 1 year. The results of the ITBFs study were given in Figs. 3, 4, 5 and 6, respectively for different initial concentrations. As seen in each of the figures, only two reactors which have maximum removal efficiencies were shown for different two heights. One of the two reactors expresses a-1.5 m height and the other one a-2.5 m height.

COD removal, %

100 95

h = 1.5m h = 2.5m

90 85 80 75 250 300 350 400 450 500 550 600 650 700

Fig. 3 sCOD removal efficiency

Initial COD, mg/L

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Fig. 4 TSS removal efficiency

TSS removal, %

100

h = 1.5m h = 2.5m

95

90

85 100

110

120

130

140

150

Fig. 5 NH3 -N removal efficiency

NH4-N removal, %

Initial TSS, mg/L

100 95 90 85 80 75 70 65 60 55

h = 1.5m h = 2.5m

38

41

44

47

50

53

56

59

62

65

Initial NH4-N, mg/L

h = 1.5 m h = 2.5 m

100

PO4-P removal, %

Fig. 6 PO4 -P removal efficiency

95 90 85 80 75 70 65 10

12

14

16

18

20

22

Initial PO4-P, mg/L

This determination study is the most important issue to rehabilitate FP unit of the available WWTP during the establishing full scale system. sCOD removal rates of the ITBF units decrease when the sCOD inlet concentrations increases. The maximum sCOD removal rates were determined at lowest sCOD inlet 300 mg/l. removal efficiencies of are as 81.4 and 87.7% in R-15 and R-8

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for the 1.5 and 2.5 m heights, respectively. As seen from Fig. 3, there are some main effective factors on having high ratio sCOD removal efficiency. The most effective factor is having aeration system of the reactors. The others are material size and retention time. It is easily said that the reactor with aeration, fine materials size and longer retention time gives better results on sCOD removals. In Fig. 4, TSS removal rates were shown. It is clearly said that TSS removal rate depends exactly on the material size and long retention time. The thinner material size gives the best result. From Fig. 4, R-15 and R-12 have the highest TSS removal rates with the value of 95.2 and 98.8% for a-1.5 and a-2.5 m height, respectively. The variation of NH3 -N concentration throughout the ITBF reactors is given in Fig. 5. As seen from Fig. 5, R-14 and 8 installed with aeration systems to capable of removing NH3 -N as expected as a result of nitrification process. The maximum NH3 -N removal rate was obtained at lowest NH3 -N initial concentration as 40.2 mg/l. R-14 and R-8 were determined having the highest removal rates as 79% as 87.9% for 1.5 and 2.5 m heights, respectively. During the experimental period, inlet pH values changed between 7.7 and 8.3 which were in the optimum range of nitrification process [4]. As nitrification process needs alkalinity, low pH values were determined in effluent at the end of the nitrification process as 5.7 and 6.2. As for the phosphorus removal in the reactors, Fig. 6 shows the performance of the reactors. As seen from Fig. 6, filters having without aeration have higher phosphorus removal capacities than the aerobic ones. This indicates that in the anaerobic conditions denitrifying consortium presents in these reactors so phosphate accumulation by this consortium is used in excess of the metabolic requirements [5]. As seen from Fig. 6, the highest PO4 -P removal level with a percentage of 89 and 89.3%, respectively in R-6 and R-12. According to the results, it is clear that anaerobic conditions have higher PO4 -P removal rates. At the end of the studies, a-2.5 m height ITBF reactor gives higher removal results when it is compared with a-1.5 m height. Establishing an ITBFs system to rehabilitate the available FP system, the effluent water pollution qualities of FP will be improved at high ratios. In tunnel systems, effluents quality parameters such as sCOD, TSS, PO4 -P and NH3 -N of the constructed tunnels were given in Fig. 7. As seen from Fig. 7, it is clearly seen that the R-3 including strips and aeration gives the best results. sCOD, TSS and phosphorus removal values are higher than the other two reactors with the values of it 86.5, 97.2 and 90.7%, respectively as maximum. The nitrification capacity of the all reactors was also tested during the measurement studies. According to the analyses results, changing of the nitrification capacity of the all reactors are shown in Fig. 8. As seen from Fig. 8, the best nitrification process occurred in R-3 having aeration system and strips. According to the figure, the effluent NH3 -N concentration was determined 0.8 mg/L. This value is rather low concentration for NH3 -N when it is compared with the available SR unit effluent. With the construction of R-3 the NH3 -N removal rate will be increased up to 98.3% as maximum.

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Fig. 7 sCOD, TSS and PO4 -P removals

TSS

100

sCOD

PO4-P

90 Removal rates, %

80 70 60 50 40 30 20 10 0 R-1

R-2

R-3

Reactors

70

Concentrations, mg/ L

Fig. 8 NH3 -N and NO3 -N changing in the reactors

NH3-N

NO3-N

60 50 40 30 20 10 0 R1

R2

R3

Reactors

At the end of the study it was seen that redesigned two units contribute at high removal ratios. The maximum removal rate results determined in the study were given in Table 4 for each unit. As seen from the Table 4, there are big differences between available and redesigned units.

Table 4 Comparison of the available and redesigned unit efficiency rates Removal efficiency of available WWTP, %

Removal efficiency of redesigned units, %

Parameters

FP

SR

FP

SR

sCOD, mg/L NH3 -N, mg/L PO4 -P, mg/L TSS, mg/L

6.7 3.6 18.1 16.3

29.4 17.1 No reduction 13.2

87.7 87.9 89.3 98.8

86.5 98.5 90.7 97.2

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4 Conclusion To increase the low removal efficiency of the FP and SR units, different ITBF and tunnel reactors were established as a pilot scale at the bank of the available WWTP. According to the evaluation of the results, it was observed that ITBFs and tunnel units contribute to reasonable removal capacity on sCOD, TSS, NH3 -N and PO4 -P parameters. When it is considered establishing a full scale treatment plant to rehabilitate FP and SR units of available WWTP, this study will be able to a guide for decision makers.

References 1. TAEQ (2002) Sakhnin Center as a Model for Environmental Education and International Cooperation on Advanced Wastewater Treatment (A-WWT) in Rural Areas, Life mid-report. The Towns Association for Environmental Quality-Agan Beit Natufa (TAEQ), Sakhnin, Israel 2. Avsar Y, Tarabeah H, Kimchie S, Ozturk I (2007) rehabilitation by constructed wetlands of available wastewater treatment plant in Sakhnin. Ecol Eng 29:27–32 3. APHA (1995) Standard methods for the examination of water and wastewater, 18th edn. American Public Health Organization, Washington, DC 4. EPA (2000) Wastewater Technology Fact Sheet Trickling Filter Nitrification. United States Environmental Protection Agency Office of Water, Washington, DC. EPA 832-F-00-015 Sep 2000 5. Barak Y, van Rijn J (2000) Biological phosphate removal in a prototype recirculating aquaculture treatment system. Aquacultural Eng 22:121–136

Removal of Mn(II) Ions from the Aqueous Solutions by Cotton Boll H. Duygu Ozsoy and Halil Kumbur

Abstract In this study, cotton boll was used as an adsorbent for the removal of the Mn (II) ions from the aqueous solutions. The adsorption process was carried out in a batch process and the effects of contact time (2–24 h), adsorbent dosage (1–20 g/l), initial pH (2.0–6.0), initial metal ion concentration (20–100 mg/l) and temperature (20–40◦C) on the adsorption were investigated. Maximum adsorption capacity was determined at pH 5.0 and adsorbed Mn(II) ion concentration was increased with increasing adsorbent concentration and contact time. The isothermal data of cotton boll could be well described by the Langmuir equations and the Langmuir monolayer capacity had a mean value of 5.20 mg/g. Experimental results indicated that the pseudo-second order reaction model provided the best description of the data with a correlation coefficient 0.9898. The results of the study indicate that cotton boll can use as an effective low-cost adsorbent for the removal of the Mn(II) ions from the aqueous solutions and also Mn(II)-contaminated waters and wastewaters. Keywords Adsorption · Cotton boll · Mn (II) · Langmuir isotherm model · Pseudo-second order kinetic model

1 Introduction Many industries, including the electroplating, metallurgical, tannery, metal finishing, mining, chemical manufacturing, produce heavy metal containing effluents, causing serious soil and water pollution [1]. The commonly used traditional methods for the treatment of metal-contaminated wastewater include chemical precipitation and filtration, chemical oxidation or reduction, electrochemical treatment, reverse osmosis, solvent extraction, ion exchange and evaporation, all show H.D. Ozsoy (B) Department of Environmental Engineering, Engineering Faculty, Mersin University, Mersin 33360, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_110,

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several disadvantages, such as high cost, incomplete metal removal, low selectivity, high energy requirements, the generation of toxic slurries that are difficult to be eliminated [2, 3]. Adsorption is expected to overcome such impediments, having a wide variety of applications. Of many sorbents, utilization of naturally occurring materials has been recognized as a way of reducing waste management cost [4]. In recent years, there has been considerable interest in the use of biological materials including, algae, bacteria, fungi, agricultural by-products and residues as adsorbents to remove toxic metals from aqueous solution by adsorption since they are cheap and have high efficiency adsorbents [5–9]. One of the agricultural byproducts from waste of cotton factory is cotton boll, which are an abundant, cheap and readily available residue. To our knowledge, they have not been used for Mn(II) ions removal from aqueous solutions. The purpose of the present study was investigate the possible use of cotton boll, which wasn’t used as an adsorbent material before, for removal of Mn(II) ions from aqueous solutions and also determine the effects of contact time, initial pH, initial metal ion concentration, temperature and different adsorbent dosage on adsorption efficiency.

2 Materials and Methods 2.1 Materials The cotton boll used in this study were supplied Cukurova Region, Turkey. Raw cotton boll were washed by about 2 l of distilled water and dried in an over for 24 h at 105◦ C. Materials were ground into appropriate particle size by a blender and then screened through a US standard 14-mesh sieve.

2.2 Chemicals The stock solution of Mn(II) was prepared in 1.0 g/l concentration using MnSO4 .H2 O and then diluted to appropriate concentrations. HNO3 and NaOH were obtained from Merck and used for pH value adjustment.

2.3 Adsorption Experiments Adsorption studies were performed in 100 ml erlenmeyer flasks by addition of adsorbent to 50 ml of metal solutions. The pH was adjusted with 1 M HNO3 and 1 M NaOH before the addition of adsorbents. In all experiments, the flasks were shaken at 150 rpm on a shaker. Contact time was 24 h except for the contact time experiments. After shaking, samples were filtered and the final metal concentration of the filtrate was determined by flame atomic absorption spectrometry (Perkin

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Elmer Analyst 700 Atomic Absorption Spectrophotometer). The same procedure was applied for different amount of adsorbent added to 50 ml of distilled water. They served as a control (blank). All experiments were performed in triplicate. The amount of adsorbed Mn(II) ions at equilibrium, qeq (mg/g) and the percent of adsorption (%) were calculated as follows [10]: [(C0 − Ceq )V] x C0 − Ceq Percent of adsorption (%) = x 100 C0 qeq =

(1) (2)

where C0 and Ceq are the initial and equilibrium concentrations of Mn(II) ions (mg/l), V volume of solution (l) and x the weight of sorbent (g).

2.4 Equilibrium Isotherms The Langmuir isotherm was used to describe observed sorption phenomena. The Langmuir isotherm applies to adsorption on completely homogenous surface with negligible interaction between adsorbed molecules [11, 12]. The linear form of the equation can be written as; Ceq Ceq 1 = + qeq bqmax qmax

(3)

where Ceq is the equilibrium concentration of Mn(II) ions, qeq is the amount of adsorption at equilibrium, qmax is the mono layer capacity, and b is an equilibrium constant of Langmuir. The Freundlich isotherm (empirical model adsorption in aqueous systems) was also tested with our experimental data. The linear form of the equation can be written as: ln qeq = ln Kf +

1 ln Ceq n

(4)

where Kf is the measure of sorption capacity, 1/n is sorption intensity.

2.5 Kinetics of Adsorption In order to analyse the sorption kinetics of Cu (II) ions, the pseudo-first order and pseudo-second order kinetic models were applied to data. A simple pseudo firstorder equation due to Lagergren was used by different researchers [13, 14]: log(qeq − qt )= log qeq −

kad . 2.303t

(5)

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where qeq and qt are the amount of adsorption at equilibrium and at time t respectively, and kad is the rate constant of the pseudo first-order adsorption process. Plot of log (qeq −qt) vs. t gives a straight line for first order adsorption kinetics, which allow computation of the adsorption rate constant, kad . Ho’s second-order rate equation which has been called pseudo-second order kinetic expression has also been applied widely [15, 16]. The linear form of the kinetic rate equations can be written as follows:

t 1 1 = + t qt qeq kqeq 2

(6)

where k is the rate constant of sorption (dm3/mg min), qeq is the amount of metal ion sorbed at equilibrium (mg/g), and qt is the amount of metal ion sorbet at time t (mg/g). The constants can be determined experimentally by plotting of t/qt against t.

3 Results and Discussion 3.1 The Effect of Contact Time Figure 1 shows the effect of contact time on adsorption of Cu (II) ions (100 mg/l) onto the cotton boll. Mn(II) ions biosorption capacity increases with the time during the first 18 h and than levels off toward the equilibrium biosorption capacity. However, 24 h contact time was used for the further experiments.

6.00

q (mg/g)

5.00 4.00 3.00 2.00 1.00 0.00 0

5

10

15 t (hour)

20

25

30

Fig. 1 The effect of contact time on adsorption of Mn (II) ions (100 mg/l) onto the cotton boll (Adsorbent dosage10 g/l; pH 5.0; 30◦ C)

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6.00

q (mg/g)

5.00 4.00 3.00 2.00 1.00 0.00 1

2

3

4 pH

5

6

7

Fig. 2 The effects of the initial pH on adsorption of Mn(II) ions (100 mg/l) onto the cotton boll (adsorbent dosage 10 g/l; 30◦ C)

3.2 The Effect of Initial pH Since the surface charge of an adsorbent could be modified by changing pH of the solution, pH is one of the most important parameters affecting the adsorption process of metal ions [17]. In order to determine the effects of the initial pH value on the adsorption efficiency of Mn(II) ions by cotton boll, the initial pH values was changed from 2.0 to 6.0. The results of pH experiments are presented Fig. 2. At low pH values, the active sites of the adsorbent are less available for the metal ions due to protonation of the active sites at higher H+ concentration. As the pH increased, the overall surface on the cotton boll became negative and adsorption increased.

3.3 The Effect of the Temperature The effect of temperature on the Mn(II) ions removal is illustrated in Fig. 3. While an increasing trend of adsorption was observed with increasing temperature from 20±1 to 30±1◦C, adsorption capacity of cotton boll was decreased with temperatures higher than 30±1◦C.

3.4 The Effect of Initial Metal Concentration The adsorption of Mn(II) by the cotton boll was studied at different Mn(II) ion concentrations in the range from 20 to 100 mg/l. Results are presented in Fig. 4. Although adsorption (%) decreased, equilibrium sorption capacity of the cotton boll increased with increasing initial Mn(II) ion concentration. The initial concentration provides an important driving force to overcome all mass transfer resistance

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Fig. 3 The effects of the temperature on adsorption of Mn(II) ions (100 mg/l) onto the cotton boll (adsorbent dosage 10 g/l; contact time 24 h; pH:5.0)

6.00

q (mg/g)

5.00 4.00 3.00 2.00 1.00 0.00 15

20

25

30 Sıcaklık

35

40

45

6.00 5.00

q (mg/g)

4.00 3.00 2.00 1.00 0.00 0

20 mg/L

5

10

40 mg/L

15 t (hour)

60 mg/L

20

80 mg/L

25

30

100 mg/L

Fig. 4 The effects of initial metal concentration on adsorption of Mn(II) ions onto the cotton boll (adsorbent dosage10 g/l; pH:5.0)

of Mn(II) ions between the aqueous and solid phases, hence a higher initial concentration of Mn(II) ions may increase the adsorption capacity.

3.5 The Effect of Adsorbent Concentration The removal of the Mn(II) ions from aqueous solutions was effected by adsorbent dosage (Fig. 5). The amount of removed Mn(II) ions per g adsorbent was decreased with increasing adsorbent dosage from 1 to 20 g/l. This result can be explain the flocculation of adsorbent in the medium and than decrease of active sites which is affective for adsorption of Mn(II) ions.

Removal of Mn(II) Ions from the Aqueous Solutions by Cotton Boll

1177

14.00 12.00 q (mg/g)

10.00 8.00 6.00 4.00 2.00 0.00

0

5

10 15 20 Adsorbent Dosage (g/L)

25

Fig. 5 The effects of adsorbent dosage on adsorption of Mn(II) ions onto the cotton boll (Co:100 mg/l; pH:5.0, 30◦ C)

3.6 The Equilibrium Isotherms and Kinetics of Adsorption In order to investigate the sorption isotherm for cotton boll, two equilibrium models were employed: The Langmuir and Freundlich isotherm equations. In this study Langmuir model was the best-fit isotherm for adsorption of Mn(II) to the cotton boll. Langmuir isotherm model parameters, qmax and b, were estimated from the intercept and slope of Ceq /qeq vs. Ceq , according to Eq. 3 and obtained as 5.20 (mg/g) and 0.49 (l/g), respectively. The correlation coefficient of Langmuir isotherm (R2 ) was 0.9932 (Fig. 6). The kinetics of Mn(II) ions adsorption on cotton boll was studied with 100 mg/l initial metal concentrations. Experimental results indicated that the pseudo-second order reaction model provided the best description of the data with a correlation coefficient 0.9898 (Fig. 7).

12.000 y = 0.1922x + 0.3915 R2= 0.9932

10.000

Ce/qe

8.000 6.000 4.000 2.000 0.000 0

10

20

30

40

50

60

Ce (mg/L)

Fig. 6 The Langmuir adsorption isotherms for Mn(II) adsorption on cotton boll (adsorbent dosage10 g/l; pH 5.0; initial metal concentration of 20–100 mg/l; 30◦ C)

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t/qt

250.0 200.0

y = 0.1383x + 77.96 R2 = 0.9898

150.0 100.0 50.0 0.0 0

500

1000

1500

2000

t (min)

Fig. 7 The plots of pseudo-second order kinetics with respect to different initial Mn(II) ion concentrations (adsorbent dosage 10 g/l; pH 5.0; 30◦ C)

4 Conclusions The adsorption of Mn(II) ions on to cotton boll was investigated as a function of contact time, initial pH, adsorbent dosage, temperature and initial metal ion concentration and determined the effects of these parameters on adsorption efficiency. Batch adsorption studies showed that based on the Langmuir coefficients, the total capacity (monolayer saturation at equilibrium) of the cotton boll for Mn(II) ions was 5.20 mg/g. A comparison of the kinetic models on the overall adsorption rate showed that the adsorption system was best described by the pseudo-second order rate model rather than by pseudo-first order rate model with a correlation coefficient 0.9898. The results indicate that cotton boll are an affective low-cost adsorbent for removal of Mn(II) ions from the aqueous solutions.

References 1. Benhammou A, Yaacoubi A, Nibou L,Tanouti B (2005) Adsorption of metal ions onto Moroccan stevensite kinetic and isotherm studies. J Colloid Interface Sci 282:320–326 2. Ozcan A, Ozcan AS, Tunali S, Akar T, Kiran I (2005) Determination of the equilibrium, kinetic and thermodynamic parameters of adsorption of copper(II) ions onto seeds of capsicum annuum. J Hazard Mater B124:200–208 3. Duygu Ozsoy H, Kumbur H (2006) Adsorption of Cu(II) ions on cotton boll. J Hazard Mater B136:911–916 4. Gotoh T, Matsushima K, Kikuchi K (2004) Adsorption of Cu and Mn on covalently crosslinked alginate gel beads. Chemosphere 55:57–64 5. Ozsoy HD, Kumbur H, Özer Z (2007) Adsorption of copper (II) ions to peanut hulls and Pinus brutia sawdust. Int J Environ Pollut 31(1–2):125–134 6. Ma W, Tobin JM (2004) Determination and modelling of effects of pH on peat biosorption of chromium, copper and cadmium. Biochem Eng J 18:33–40 7. Hanzlik J, Jehlicka J, Sebek O, Weishauptova Z, Machovic V (2004) Multi-component adsorption of Ag(I), Cd(II) and Cu(II) by natural carbonaceous materials. Water Res 38:2178–2184

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8. Garg VK, Gupta R, Kumar R, Gupta RK (2004) Adsorption of chromium from aqueous solution on treated sawdust. Bioresour Technol 92:79–81 9. Kadirvelu K, Kavipriya M, Karthika C, Radhika M, Vennilamani N, Pattabhi S (2003) Utilization of various agricultural wastes for activated carbon preparation and application for the removal of dyes and metal ions from aqueous solution. Bioresour Technol 87:129–132 10. Ozer A, Ozer D, Ozer A (2004) The adsorption of copper (II) ions on to dehydrated wheat bran (DWB): Determination of the equilibrium and thermodynamic parameters. Process Biochem 39:2183–2191 11. Ho YS (2004) Pseudo-isotherms using a second order kinetic expression constant. Adsorption 10:151–158 12. Yu B, Zhang Y, Shukla A, Shukla SS, Dorris KL (2001) The removal of heavy metals from aqueous solutions by sawdust adsorption-removal of lead and comparison of its adsorption with copper. J Hazard Mater B84:83–94 13. Ho YS, McKay G (1998) Sorption of dye from aqueous solution by peat. Chem Eng J 70: 115–124 14. Bhattacharyya KG, Sharma A (2005) Kinetics and thermodynamics of Methylene Blue adsorption on neem (Azadirachta indica) leaf powder. Dyes Pigm 65:51–59 15. Ho YS (2005) Effect of pH on lead removal from water using tree fern as the sorbent. Bioresour Technol 96:1292–1296 16. Ho YS, McKay G (2000) The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Water Res 34(3):735–742 17. Ucer A, Uyanik A, Aygun SF (2006) Adsorption of Cu(II), Cd(II), Zn(II), Mn(II) and Fe(II) ions by tannic acid immobilized activated carbon. Separation Purif Technol 47:113–118

Optimization of Electrochemical Oxidation of Textile Dye Wastewater Using Response Surface Methodology (RSM) Bahadır K. Körbahti

Abstract The electrochemical treatment of textile dye wastewater containing Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes was studied on iron electrodes in the presence of NaCl electrolyte in a batch electrochemical reactor. The wastewater was synthetically prepared in relatively high dye concentrations between 400 and 2,000 mg/L. The effects of initial dye concentration, electrolyte concentration and current density on dye removal, turbidity removal and pH change were studied at 28◦ C reaction temperature. In the study, complete dye removal and effective turbidity removal achieved; the rate of dye removal obtained as Levafix Yellow CA>Levafix Blue CA>Levafix Red CA at all reaction conditions. The flow pattern was analyzed, mass transfer coefficients and mass fluxes were evaluated. At optimized conditions, mean energy consumption were calculated as 8.3, 9.0 and 7.7 kWh/kg COD removed for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively. Keywords Electrochemical wastewater treatment · Electrolysis · Textile wastewater · Dye removal · Optimization · Response Surface Methodology (RSM) · Mass transfer · Energy consumption

1 Introduction Dyeing is the application of color to the textile material with some degree of colorfastness, and may take place at any of several stages in the manufacturing process with continuous and batch processes [1, 2]. Dyeing operations generate a large portion of the industry’s total wastewater and the major problems that face cotton dyers are water-use reduction and elimination of color and salt from dye wastewater [1]. B.K. Körbahti (B) Faculty of Engineering, Chemical Engineering Department, University of Mersin, Çiftlikköy, 33343 Mersin, Turkey e-mail: [email protected]

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The primary source of wastewater in dyeing operations is spent dyebath and rinsing processes which typically contains residual dye, salt and auxiliary chemicals, and generate about 125–150 l wastewater per kilogram of product [2]. Textile wastewater is well known with its high chemical oxygen demand, strong color, large amount of suspended solids, variable pH values, salt content and high temperature. Therefore, the treatment systems combined with physical, biological and chemical methods are inefficient for the effective treatment of industrial textile wastewater due to the variation of wastewater characteristics and heavy COD load [3–8]. Electrochemical oxidation is becoming an alternative wastewater treatment method and replacing the traditional processes, because many industrial processes produce toxic wastewaters, which are not easily biodegradable and requiring costly physical or physico-chemical pretreatments [9]. In this study, the electrochemical treatment of textile dye wastewater containing Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes was investigated, and the effect of operating parameters of current density, electrolyte concentration, initial dye concentration and electrolysis time on COD removal, dye removal and turbidity removal efficiency were analyzed to optimize the electrochemical treatment conditions in order to maximize the rates of dye removal and COD removal was aimed from batch runs using response surface methodology (RSM).

2 Materials and Methods Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes (DyStar) and sodium chloride (Merck) were obtained in extra pure grade and double distilled water was used for the preparation of synthetic textile dye wastewater. The textile dye wastewater was synthetically prepared for the standardization throughout the study. R glass having a volume The batch electrochemical reactor was made of Pyrex of 600 mL with a heating and cooling coil around. The three pairs of iron electrodes (OD=12 mm) were used as anode and cathode and placed 15 mm apart on R reactor cover. A glass stirrer with two blades 3 cm diameter impeller a Plexiglas was driven with a Heidolph-RZR 1 model mixer for homogenization at 750 rpm. The reaction temperature was monitored with a glass thermometer immersed. The reaction temperature was controlled with circulating water recycled from a temperature controlled water bath (New Brunswick, G-86). The current was applied by a constant voltage/current controlled DC power source, NETES NPS-1810D. COD, color and turbidity analysis was performed, and pH of the reaction medium was monitored during the electrochemical oxidation. The central composite design with five factors at five levels was applied using Design-Expert 6.0 (trial version) with the bounds of the factors (independent variables). Each independent variable was coded at five levels between −2 and +2 at the ranges determined by the preliminary experiments, where the independent variables

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were initial dye concentration, 400–2,000 mg/L; current density, 1.0–11 mA/cm2 ; electrolyte concentration, 0–4 g/L and reaction time, 0–40 min. In the study, maximum NaCl concentration was determined as 4 g/L, since in typical cotton dyeing operations 2–3 g/L NaCl electrolyte exist in the textile wastewater as a remaining dyebath additive [1]. The five factor designed experiments were augmented with six replications at the design center to evaluate the pure error and were carried in randomized order as required in many design procedures. Performance of the process was evaluated by analyzing the response of color and turbidity removal percents.

3 Results and Discussions In the first step of the study, the effect of operating variables on dye removal and turbidity removal was investigated using response surface methodology (RSM) according to central composite design (CCD). In the second step, the main objective was to select the current density and NaCl electrolyte concentration in order to achieve optimal COD removal, dye removal and turbidity removal. As a general trend, increase in current density and electrolyte concentration resulted in enhanced color and turbidity removal percents in all runs.

3.1 The Effect of Initial Dye Concentration The effect of initial dye concentration on dye removal at 28◦ C reaction temperature, 6 mA/cm2 current density and 2 g/L NaCl concentration is shown in Fig. 1. The Levafix CA dyes removed at rather long reaction durations as the initial dye concentration increased. In Fig. 1, the fastest dye removal obtained with Levafix Yellow CA dye at 400 mg/L initial concentration and the slowest with Levafix Red CA at 2,000 mg/L. At 1,200 and 2,000 mg/L initial dye concentrations, rapid Levafix Yellow CA dye removal obtained and followed by Levafix Blue CA and Levafix Red CA. More effective dye removal obtained with Levafix Yellow CA at 2,000 mg/L dye concentration than Levafix Red CA at 1,200 mg/L initial dye concentration. Dye removal obtained at 400 mg/L initial dye concentration as 95% for Levafix Blue CA and Levafix Red CA, and 97% for Levafix Yellow CA at 10 min reaction duration. The effect of initial dye concentration on turbidity removal is shown in Fig. 2. The turbidity removal could not obtained until 15 min reaction duration with 1,200 mg/L Levafix Red CA and until 30 min with 2,000 mg/L Levafix Red CA dye. The lowest turbidity removal obtained at 55% with 1,200 mg/L Levafix Blue CA dye and the highest obtained at 96% with 1,200 mg/L Levafix Yellow CA as shown in Fig. 2. The turbidity removal obtained after 40 min reaction duration at 400 mg/L initial dye concentration as 83, 89 and 91%, at 1,200 mg/L initial dye concentration as 60, 83, 94% and at 2,000 mg/L initial dye concentration as 74, 90, 96% for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively.

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Fig. 1 The effect of initial dye concentration on dye removal

Fig. 2 The effect of initial dye concentration on turbidity removal

3.2 The Effect of Electrolyte Concentration The effect of electrolyte concentration on dye removal at 28◦ C reaction temperature and 1,200 mg/L dye concentration is shown in Fig. 3. The potential difference stabled at 6 V in order to observe the effect of electrolyte concentration. The supplied current density was 1 mA/cm2 without NaCl, 6 and 11 mA/cm2 with 2 and 4 g/L NaCl, respectively. The increase in electrolyte concentration increased dye removal as shown in Fig. 3. The lowest dye removal obtained without NaCl after 40 min reaction duration as 7%, 2%, 22% for Levafix Blue CA, Levafix Red CA

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Fig. 3 The effect of electrolyte concentration on dye removal

and Levafix Yellow CA reactive dyes, respectively. In Fig. 3, the fastest dye removal obtained with Levafix Yellow CA dye at 4 g/L electrolyte concentration and the slowest at Levafix Red CA without NaCl. More effective dye removal obtained with Levafix Yellow CA at 2 g/L electrolyte concentration than Levafix Red CA at 4 g/L electrolyte concentration. The rate of dye removal obtained as Levafix Yellow CA>Levafix Blue CA>Levafix Red CA at all electrolyte concentrations, and complete dye removal obtained at 2 and 4 g/L electrolyte concentrations after 25 min reaction duration. Since in typical cotton dyeing operations 2–3 g/L NaCl electrolyte exist in the textile wastewater as a remaining dyebath additive [1], this investigated electrochemical treatment process could be employed to the real textile dye wastewater without any further electrolyte addition. The effect of electrolyte concentration on turbidity removal is shown in Fig. 4. The turbidity removal increased up to 5 min reaction duration by electrocatalytic effects without NaCl addition and then decreased due to insufficient formation of oxidizing agents. At the end of 40 min reaction, turbidity removal could not obtained in the runs without NaCl. Turbidity removal obtained at 2 g/L electrolyte concentration as 60, 83, 94% and at 4 g/L electrolyte concentration as 77, 74, 90% for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively. The turbidity removal could not obtained until 10 min reaction duration with 2 g/L NaCl and until 15 min with 4 g/L NaCl for Levafix Red CA dye.

3.3 The Effect of Current Density The effect of current density on dye removal at 28◦C reaction temperature, 1,200 mg/L dye concentration and 2 g/L electrolyte concentration is shown in Fig. 5.

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Fig. 4 The effect of electrolyte concentration on turbidity removal

Fig. 5 The effect of current density on dye removal

The increase in current density increased dye removal as shown in Fig. 5. In Fig. 5, the fastest dye removal obtained at 8 mA/cm2 current density with Levafix Yellow CA and the slowest at 4 mA/cm2 current density with Levafix Red CA dye. The rate of dye removal obtained as Levafix Yellow CA>Levafix Blue CA>Levafix Red CA at all applied current densities. More effective dye removal obtained with Levafix Yellow CA both at 4 and 6 mA/cm2 current densities than Levafix Red CA at 6 and 8 mA/cm2 current densities, respectively. Dye removal obtained at 4 mA/cm2 current density after 20 min reaction duration as 57, 3, 93% and 98, 81, 98% for

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Fig. 6 The effect of current density on turbidity removal

Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively. At 8 mA/cm2 current density complete dye removal obtained for all reactive dyes after 20 min reaction. In Fig. 5, the removal of Levafix Red CA dye improved from 3 to 81% with the increase in current density from 4 to 6 mA/cm2 . The effect of current density on turbidity removal is shown in Fig. 6. The turbidity removal could not obtain for Levafix Red CA dye until 15 min reaction duration at 6 and 8 mA/cm2 current densities and until 30 min at 4 mA/cm2 current density. The lowest turbidity removal obtained as 60% with Levafix Blue CA dye and the highest obtained as 94% with Levafix Yellow CA at 6 mA/cm2 current density as shown in Fig. 6. The turbidity removal obtained after 40 min reaction duration at 4 mA/cm2 current density as 69, 78, 91%, at 6 mA/cm2 current density as 60, 83, 94% and at 8 mA/cm2 current density as 76, 79, 79% for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively.

3.4 Experimental Optimization The batch runs were conducted in CCD designed experiments to visualize the effects of independent factors on responses and the results along with the experimental conditions. The experimental results were evaluated and approximating functions of dye removal were obtained in Eqs. 1–3. yb = 827.778 − 0.380x1 + 101.212x2 −189.927x3 −54.572x4 + 8.305x5 −9.50 · 10−6 x21 −0.556x22 −3.900x23 + 0.752x24 −0.094x25 −0.006x1 x2 +0.015x1 x3 + 0.013x1 x4 + 0.002x1 x5 −1.058x2 x3 −2.658x2 x4 −0.064x2 x5 +7.543x3 x4 − 0.718x3 x5 −0.074x4 x5 (1)

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yr = 580.286 − 0.392x1 + 100.236x2 −203.118x3 −44.088x4 + 8.061x5 −9.50 · 10−6 x21 −0.556x22 −3.900x23 + 0.752x24 −0.094x25 −0.006x1 x2 +0.015x1 x3 + 0.013x1 x4 + 0.002x1 x5 −1.058x2 x3 −2.658x2 x4 −0.064x2 x5 +7.543x3 x4 − 0.718x3 x5 −0.074x4 x5 (2) yy = 902.234 − 0.367x1 + 95.802x2 −178.510x3 −57.069x4 + 8.035x5 −9.50 · 10−6 x21 −0.556x22 −3.900x23 + 0.752x24 −0.094x25 −0.006x1 x2 +0.015x1 x3 + 0.013x1 x4 + 0.002x1 x5 −1.058x2 x3 −2.658x2 x4 −0.064x2 x5 +7.543x3 x4 − 0.718x3 x5 −0.074x4 x5 (3) In Eqs. (1), (2), and (3), y’s are Levafix CA reactive dye removal in which b, r and y indicates Levafix Blue CA, Levafix Red CA and Levafix Yellow CA, respectively; x1 , x2 , x3 , x4 , and x5 are corresponding to independent variables of initial dye concentration, current density, electrolyte concentration, reaction temperature and reaction time, respectively. ANOVA results of these quadratic models presented in Table 1 indicating that these quadratic models can be used to navigate the design space. SS, DF and MS terms in Table 1 are sum of squares, degrees of freedom and mean square, respectively. In Table 1, the Model F-values of 22.04 and 6.49 imply the models are significant for dye removal and turbidity removal, respectively. Adequate precision measures the signal to noise ratio and a ratio greater than 4 is desirable. Therefore, in the quadratic models of dye removal and turbidity removal, the ratios of 16.39 and 9.56 indicate adequate signals for the models to be used to navigate the design space. The values of Prob>F less than 0.0500 indicate model terms are significant, whereas the values greater than 0.1000 are not significant. For all models, Prob>F is less than 0.0001, indicating that terms are significant in all models. For Eqs. (1), (2), and (3), Lack of Fit F-values of 9,669.96 and 24,744.58 implies the significance for dye removal and turbidity removal, respectively.

Table 1 ANOVA results of the quadratic models of Levafix reactive dye removal and turbidity removal Source Dye removal (%)

Turbidity removal (%)

SS

DF

MS

F value

Model 119,652.40 32 3,739.14 22.04 Residual 9,670.00 57 169.65 Lack of Fit 9,669.96 50 193.40 27,970.95 Pure Error 0.0484 7 0.0069 R2 = 0.93, Radj 2 = 0.88, Adequate precision = 16.39 Model 89,591.22 32 2,799.73 6.49 Residual 24,746.06 57 434.14 Lack of Fit 24,744.58 50 494.89 2,327.49 Pure Error 1.488 7 0.2126 R2 = 0.78, Radj 2 = 0.66, Adequate precision = 9.56

Prob > F < 0.0001 (significant) < 0.0001 (significant)

< 0.0001 (significant) < 0.0001 (significant)

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The model adequacy checking is an important part of the data analysis procedure, which the approximating model would give poor or misleading results if it were an inadequate fit. The residual plots should always be examined for the approximating model [10, 11]. The quadratic models for dye removal percents well satisfied the assumptions of the analysis of variance (ANOVA) according to normal probability, studentized residuals and outlier-t residual plots, which are not shown here. The residual plots indicated a normal distribution, in which case there was no response transformation need and no apparent problem with normality. In the study, the outlier-t values lied below the interval of ±3.50 indicated that the approximation of the fitted model to the response surface was fairly good with no any data recording error. In this study, a cost driven approach was preferred at 28◦ C reaction temperature within 0–40 min of reaction time; current density and electrolyte concentration were to be minimized so as to save energy and electrolyte, whereas dye removal and turbidity removal percents were maximized at 2,000 mg/L textile dye concentration. Optimized conditions under specified constraints were obtained for the highest desirability at 6.7, 5.9 and 5.4 mA/cm2 current density and 3.1, 2.5 and 2.8 g/L NaCl concentration for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive textile dyes, respectively.

3.5 Mass Transfer Coefficients Mass transfer coefficient for a loaded reactor and stirred for a given time, during which the reaction occurs to a certain extent could be determined by Eq. 4 [12–14]:

xSBR = 1 − exp

−km A t VR

(4)

In Eq. (4), VR reaction volume of 400 mL, A electrode area in m2 , km mass transfer coefficient in m/s and t reaction time in s. The mass transfer coefficients calculated as 7.72×10−6, 9.05×10−6 and 7.81×10−6 m/s for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA, respectively. The convective mass flux could be determined by Eq. 5 [15]. JA = km (CAi − CAe )

(5)

In Eq. (5), JA is the mass flux in kg/m2.s, CAi and CAe inlet and exit COD concentrations in kg/m3 . The mass fluxes were calculated as 4.77×10−3, 4.61×10−3 and 3.79×10−3 kg/m2 .s for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA, respectively.

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3.6 Energy Consumption The mean energy consumption during the electrochemical treatment of textile dye wastewater in the stirred batch reactor was evaluated. The mean energy consumption at 28◦ C reaction temperature in 40 min reaction duration at optimum conditions were calculated as 8.3 kWh/kg COD removed, 9.0 kWh/kg COD removed and 7.7 kWh/kg COD removed for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA, respectively. The obtained mean energy consumption values are reasonable for electrochemical treatment of textile dye wastewater.

4 Conclusion The electrochemical treatment of Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes was investigated in textile dye wastewater using iron electrodes. The batch runs were conducted for the investigation of the effects of initial dye concentration, electrolyte concentration and current density on dye removal and turbidity removal of textile dye wastewater at 28◦C reaction temperature. The increase in current density and electrolyte concentration resulted in enhanced dye removal and turbidity removal in all runs. In the study, complete dye removal obtained and satisfactory turbidity removal achieved however turbidity values fluctuated due to the possible formation of low molecular weight complex by-products during the electrochemical treatment. The electrochemical treatment of textile dye wastewater was optimized using response surface methodology (RSM), and the optimized conditions were satisfied at 28◦ C reaction temperature with 6.7, 5.9 and 5.4 mA/cm2 current density and 3.1, 2.5 and 2.8 g/L NaCl concentration for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive textile dyes, respectively. Under specified cost driven constraints determined for highest desirability, COD removal obtained as 32.5, 36.9 and 32.8% for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively. In the study, the mass transfer coefficients calculated as 7.72×10−6, 9.05×10−6 and 7.81×10−6 m/s and the mass fluxes were evaluated as 4.77×10−3, 4.61×10−3 and 3.79×10−3 kg/m2 .s for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA, respectively. At optimized conditions, the mean energy consumption were evaluated at 28◦ C reaction temperature in 40 min reaction duration as 8.3 kWh/kg COD removed, 9.0 kWh/kg COD removed and 7.7 kWh/kg COD removed for Levafix Blue CA, Levafix Red CA and Levafix Yellow CA reactive dyes, respectively. In this study, a pilot plant electrochemical process was proposed achieving almost complete decoloration and satisfactory COD reduction requiring no further addition of supporting electrolyte. In the study, the rate of dye removal obtained as Levafix Yellow CA>Levafix Blue CA>Levafix Red CA at all reaction conditions. Since in typical cotton dyeing operations 2–3 g/L NaCl electrolyte exist in the textile wastewater as a remaining dyebath additive, such investigated electrochemical treatment process could be employed to the real textile dye wastewater.

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References 1. US EPA (1996) Best management practices for pollution prevention in the textile industry. EPA625R96004, USA 2. US EPA (1997) Profile of the textile industry. EPA310R97009, USA 3. Lin SH, Chen ML (1997) Textile wastewater treatment by enhanced electrochemical method and ion exchange. Environ Technol 18:739–746 4. Lin SH, Peng CF (1996) Continuous treatment of textile wastewater by combined coagulation, electrochemical oxidation and activated sludge. Water Res 30:587–592 5. Naumczyk J, Szpyrkowicz L, Zilio-Grandi F (1996) Electrochemical treatment of textile wastewater. Water Sci Technol 34:17–24 6. Szpyrkowicz L, Juzzolino C, Kaul SN (2001) A comparative study on oxidation of disperse dyes by electrochemical process, ozone, hypochlorite and Fenton Reagent. Water Res 35:2129–2136 7. Vlyssides AG, Loizidou M, Karlis PK, Zorpas AA, Papaioannou D (1999) Electrochemical oxidation of a textile dye wastewater using a Pt/Ti electrode. J Hazard Mater B70:41–52 8. Vlyssides AG, Papaioannou D, Loizidoy M, Karlis PK, Zorpas AA (2000) Testing an electrochemical method for treatment of textile dye wastewater. Waste Manag 20:569–574 9. Pulgarin C, Adler N, Péringer P, Comninellis Ch (1994) Electrochemical detoxification of a 1,4-benzoquinone solution in wastewater treatment. Water Res 28:887–893 10. Montgomery DC (1996) Design and analysis of experiments. Wiley, New York 11. Myers RH, Montgomery DC (2002) Response surface methodology: Process and product optimization using designed experiments. Wiley, New York 12. Rajeshwar K, Ibanez JG (1997) Environmental Electrochemistry. Academic, New York 13. Pickett DJ (1979) Electrochemical reactor design. Elsevier, Netherlands 14. Fogler HS (1992) Elements of chemical reaction engineering. Prentice-Hall, Englewood Cliffs, NJ 15. McCabe WL, Smith JC, Harriott P (2001) Unit operations of chemical engineering. McGrawHill, New York

Dynamic Modelling of Bioconversion of Domestic Wastewater Sludge for Cellulase Enzyme N.A. Kabbashi, Md. Zahangir Alam, and Khadijah B. Abdul Rahim

Abstract A mathematical modeling of bioconversion of domestic wastewater sludge for cellulase enzyme production was constructed based on the ideal batch mode. The mathematical models was based on the mass balance equation and focused particularly on the biomass, substrate and product rate of reaction. The biomass, substrate and product considered in this project were glucosamine, reducing sugar and cellulase enzyme respectively. The optimal conditions of pH, temperature, inoculum size, substrate concentration, co-substrate concentration and agitation speed were maintained during the simulation. The MATLAB simulation has been done by using modified Monod equation and modified kinetic equations for biomass, substrate and product. The results showed that higher product yields would be achieved when optimal conditions of parameters were held constant, the time constraints was 10 days and 95% of confidence level had been achieved which determined the range of validity of k’s values for these models. This study also involved the quantitative analysis and qualitative analysis graphically for validation of models. Keywords Bioconversion · Wastewater · Enzyme

1 Introduction Every year, Indah Water Konsortium (IWK) in Malaysia has produces around 3.8 million cubic meters of wastewater sludge in the wastewater treatment plants. The sludge volume is expected to increase to 7 million cubic meters by the year 2020 which contribute vast amount of money for management cost in the future approximately more than RM 1 billion [1]. N.A. Kabbashi (B) Bioenvironmental Engineering Research Unit (BERU), Department of Biotechnology Engineering, International Islamic University, Kuala Lumpur 50728, Malaysia e-mail: [email protected]

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It is believed that cellulose exists in the domestic sludge in few percentages but lignocellulosic components are very resistant to biodegradation [2]. Bioconversion of domestic wastewater sludge refers to biodegradation by specific microorganism for enzymes or other metabolite production which in this case, cellulose can be degrade for cellulase enzyme production by fungi called Trichoderma harzianum. Cellulase enzyme is recently used in the pulp, dye, paper, textile, and biodegradation of toxic wastes and in chemical industries. Thus, the cellulase production from the domestic wastewater sludge offers potentially low cost alternatives with the abundant availability of material source [3]. Mathematical modeling is an effective method used widely in science and engineering. The mathematical models and methods provide a rigorous, systematic, and quantitative description of various real-world phenomena such as physical, chemical and biological. The mathematical modeling helps to understand and analyses the important qualitative features of these phenomena, to organize and process data and to design and develop complex engineering system. A good model can identify possible future problem areas in engineering activity and predict the side effects of recommended engineering solutions in the long run [4]. Modeling in bioengineering is devoted to applied mathematical modeling in the rapidly growing field using biotechnology which industries can replaced chemical-based manufacturing processes with bioengineering processes that offers less expensive, faster and safer for the people and environment. This give advantages as biotechnology plays an essential roles in the food production such as yeast to make bread rise, bacteria used in yogurt and enzymes to make cheese. In addition, the biotechnology increasingly used to design a desirable protein or enzyme from the available natural source and can applied on a larger industrial scale [4]. However, the study of mathematical modeling of bioconversion of domestic wastewater sludge for ligninase and cellulase enzyme production is still new. Thus, this paper will propose a suitable mathematical modeling for a product-oriented process of bioconversion that enhanced the understanding of some mechanisms in studied process, to test the sensitivity of system parameters and to optimize system behaviour.

2 Methodology The model builds in this project mainly for batch mode operation of reactor. Batch reactors are simplest type of mode of reactor operation. In this mode, the reactor is filled with medium and the bioreactor is allowed to proceed. When the fermentation has finished, the contents are emptied for downstream processing. The reactor is then cleaned, re-filled, re-inoculated and the bioreactor process starts again. In a batch bioreactor process, the biomass will start growing from initial concentration (about zero) and often after a short lag period until the substrate will finish. According to the above description, the zero input and the zero output to the system characterize the batch process. Like many other operated reactors, volume of a batch

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reactor is usually kept constant. In order to build mathematical modeling that resemble with the actual phenomena or biological process, many assumptions have to be made to offer good models that can simulate the biological reaction within certain conditions or constraints. The construction of this model can be initiated from the simple microbial kinetics for batch fermentation process. In this project, each group members are assigned for mathematical models for production of different enzymes. The assigned project is to identify the mathematical models for the bioconversion of domestic wastewater sludge for cellulase enzyme production. MATLABTM is a software package used for high performance numerical computation and visualization to solve application of mathematical and computer modeling and simulation [5]. It provides an interactive environment with hundreds of built-in functions for technical computation, graphic and animation. It also provides easy extensibility with its own high-level programming language. The name MATLAB stands for MATrix LABoratory. In this study, MATLAB 7.0 was used to simulate specifically the rate of glucosamine, reducing sugar and cellulase activity by using module of ode45.

2.1 Modeling Procedure There are two method of model reduction which is the first situation when a number of different candidate models are available and the best model can be selected from them while the second situation occurs when a reference model available and the model could be simplified for certain purpose [6]. In this project, the first method has been selected where the model equation has been developed by available models that resemble the system of bioconversion of domestic wastewater sludge to produce enzyme cellulase.

2.2 Phases of Model According to Jeppsson [6], the modeling construction can be divided to three phases, which is Phase 1 for identification, Phase 2 for mathematical model formulation and construction and Phase 3 for verification and validation. Phase 1 has been subdivided to functional specification of the process, setting the modeling objectives and selected a model type and system characterization. The functional specification of the process refers to a quantitative understanding of the structure and the parameters describing the process are required. The modeling objectives are decided that may concern about model purpose, system boundaries, time constraints and accuracy of the model developed. While Phase 2, consist of mathematical model formulation and construction according to a generic modeling methodology where many attempts have been made to apply systems approach to the development of a modeling methodology, which have the major concern on system characterization

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and model construction. In Phase 3, the process involves with the verification and validation of model to obtain the appropriate model at the end of the project. It is clear that model verification and model validation are closely related and require an iterative procedure In this model development, analytical method of calculation for μmax , Ks , Yp/x and Yx/s were calculated by previous study using experimental data [3], which was held as constant parameters in the model. Even though the above-mentioned parameter was held constants in each run or trial of MATLAB coding, the values are within the range of boundaries that indicates validity of constant parameters (Figs. 1 and 2).

Functional specification of the process

Set modeling objectives & select a model type No

System characterization Yes Structure OK?

Mathematical model formulation

Verification /analysis

No Verification

Yes Model validation

No Validation

Yes Appropriate model

Fig. 1 A generic modeling methodology [6]

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System Input

Process (batch model)

Domestic Wastewater Sludge (Substrate: Reducing sugar)

Liquid State Bioconversion

Output

Fig. 2 Schematic diagram for cellulase enzyme production

2.3 Model Structures The available model which best describe the bioconversion of domestic wastewater sludge for cellulase enzyme was Monod equation and general kinetic models for biomass, substrate and product that has been modified where this system has been identified as closed system (batch mode reactor). Valid coefficients and parameters were added, which then compared to the experimental graph in order to indicate the appropriate modified Monod equation and kinetic models. 2.3.1 Monod Equation Based on the literature review on the cellulase activity that has been produced by Trichoderma harzianum in the batch mode operation [3], the mathematical reaction rate models that fitted the general characteristics of bioconversion process was known as Monod equation [7] was used as general model that undergone certain modification with boundaries as shown below: μ=

μmax S Ks + S

(1)

where μ = specific growth rate, μmax = maximum specific growth rate (h−1 ), S = limiting substrate concentration (g/l), Ks = saturation constant (equivalent to substrate concentration when μmax /2). 2.3.2 General Kinetic Model Until today, there have been no reports on mathematical modeling of the kinetics of cellulase production by Trichoderma harzianum in batch fermentations. It is logical to use the mathematical models that have been used to describe batch fermentations for process control as a basic equation and was modified to indicate the process control of liquid state bioconversion of domestic wastewater sludge for cellulase enzyme production. The series of equations describing a general kinetic system for cellulase production is as follows: Biomass X(t) :

dX =μ·X dt

(2)

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Product P(t) :

dP = μ · X · Ypx dt

(3)

μ·X dS =− dt Yxs

(4)

Substrate S(t) :

where μ = specific growth rate (h−1 ), X = biomass concentration (g/l), Ypx = moles of product formed per unit mole substrate consumed, Yxs = moles of biomass produced per unit mole of substrate consumed.

3 Results and Discussion 3.1 Mathematical Equation for Cellulase Enzyme Production by Liquid State Bioconversion The modified Monod equation and kinetic models of biomass, substrate and product described the liquid state bioconversion of domestic wastewater sludge to produce cellulase enzyme within valid range. The parameters were held constants while the dimensionless parameters (the k’s values) were varied to identify the best-fit models and pattern of graph. The following equations were modified Monod and kinetic models: 3.1.1 Modified Monod Equation

μ=

μmax .S.X Ks .X + S

(5)

where μ = specific growth rate (per day), μmax = maximum specific growth rate (per day), S = concentration of substrate (mg/ml), X = concentration of biomass (mg/ml), Ks = saturation constant of the substrate (mg/ml). 3.1.2 Modified Kinetic Models

dX = μ · X − K1 · X dt

K3 μ·X dS =− · K2 + dt Yxs S dP = μ · X · Ypx · K4 − K5 · X − K6 · P dt

(6) (7) (8)

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where μ = specific growth rate (per day), X = concentration of glucosamine (mg/ml), S = concentration of reducing sugar (mg/ml), P = concentration of cellulase activity (FPU/ml), Yxs = moles of biomass produced per unit mole of substrate consumed, Ypx = moles of product formed per unit mole of biomass formed, and Ki = dimensionless constants where i = 1, 2, 3, 4, 5, 6. The model equations have been developed according to the principles of mass balance. The following are assumptions developed in mathematical modeling formation: 1. Ideal batch mode operation is considered at steady state 2. Co-substrate are not considered in the mathematical modeling 3. The mathematical modeling was valid within range of the following physical parameters:

3.2 The Simulation Result The conditions for simulations such as μmax , Yxs , Ypx , Ks , the initial conditions and the constants were determined as shown in Table 1: According to the graph plotted for each trial, Trial 1 provides the most significant result as shown in Fig. 3 compared to Trial 2 which varies in constant parameters by using the lower range of k’s values and Trial 3 which varies in constant parameters by using the upper range of k’s values. The plot of Trial 1 resembles the rate of production of glucosamine, reducing sugar and cellulase activity which was simulated by modified Monod equation and kinetic models as shown before. The mathematical model developed was on the basis of general mass balance equation and one of the major objectives in this study was to achieve maximal production of cellulase enzyme as illustrated in Fig. 3. The Monod equation was used because it resembles the interaction of glucosamine, reducing sugar and cellulase activity in the bioreactor. As shown in Eq. (5), the specific growth rate was mainly influenced by the maximum specific growth rate, the concentration of biomass and substrate and the saturation constant of the substrate, which was determined from experimental data. As illustrated in Table 1 The values of parameters and constants that varied in Trial 1, Trial 2 and Trial 3 Initial conditions (mg/ml) Trial

μmax Yxs

Trial 1 0.12 Trial 2 0.12 Trial 3 0.12

Ypx

Ks

X

S

Constants P K1

K2

K3

K4

K5

K6

0.0119 5.9725 0.6 1.112 9.025 0 0.01 0.157 0.6 12.13 3.5 1.37 0.0119 5.9725 0.6 1.112 9.025 0 0.009 0.122 0.5 11.55 3.2 1.32 0.0119 5.9725 0.6 1.112 9.025 0 0.03 0.16 0.7 13.21 3.7 1.39

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Fig. 3 Graph of biomass, substrate and product in Trial 1

Fig. 3, the experimental plot was compared to the model plot. The formula used was shown in Eq. (6) to simulate the rate of cell growth or glucosamine within 10 days. Based on this equation, the constant, K1 was multiplied with biomass concentration and subtracted from the rate of cell growth. The constant applied in this formula indicates the kinetics of cell death where deactivation of the culture occurs over a finite period of time depending on the initial number of viable cells and the severity of the conditions imposed. The plotted model of biomass seems to increase within time as stated in the literature review that Trichoderma genus had capacities to adapt severe environmental constraints [8]. Thus, the model of rate of glucosamine concentration was confirmed by the experimental result from the previous study. The graph (Fig. 3) of substrate was plotted on the basis of Eq. (7) that indicates the rate of reducing sugar in the batch culture process. In this model, the substrate uptakes coincide with product formation. When products are formed in energy-generating pathways, product synthesis is an unavoidable consequence of cell growth and maintenance. The Eq. (7), illustrated the substrate taken up for product synthesis and to support growth and maintenance [9]. This statement supported by the addition of constant K2 and K3 for maintenance of cell growth and maximal production of cellulase enzyme. As shown in Fig. 3, the maximum synthesis of the cellulase enzyme in optimal conditions was on day 3 and the minimum substrate observed was on day 3 before reaches zero concentration of substrate. Therefore, the rate of reducing sugar concentration was confirmed by the experimental result from the previous study. Based on the Eq. (8), the rate of cellulase activity was influenced mostly by the biomass concentration. This explained that the higher the cell concentration, the higher the cellulase enzyme production. But, the cellulase enzyme formation decreased dramatically after day 3 because of inconsistency of pH that stated in the previous study [3]. Also, Eq. (8) was influenced by the product concentration, which indicates that there was other formation of metabolites, which

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simultaneously produced and inhibit the cellulase enzyme. Thus, the model of rate of cellulase activity was confirmed by the experimental result from the study.

3.3 Validation of Mathematical Model Each simulation of mathematical model according to the trial was compared with the experimental data. Combining the graph of both measured and predicted of each trial did the comparison. It can be observed that the Trial 1 gave the best result. The combination of each graph of Trial 1, illustrate least percentage error and the pattern of curve shape was approximately the same with the experimental graph. The best-fit conditions of these graphs validated by using optimal physical parameters, constant parameters and within time constraints of 10 days with 95% of accuracy level. The mathematical models after validation could be modify within the range of validity of k’s values and parameters such as Yxs and Ypx for future studies. The range of validity for Trial 1 is as follows (Table 2): Table 2 The range of validity for Trial 1 Yxs

Ypx

K1

K2

0.0119 ±0.0001

5.9725 0.01 0.157 ±0.0005 ±0.0002 ±0.001

K3

K4

K5

K6

0.6 ± 0.02

12.13 ±0.13

3.5 ±0.08

1.37 ±0.003

4 Conclusion Based on the mathematical model development of bioconversion of domestic wastewater sludge to produce cellulase enzyme, the model could be used as an indicator for prediction of maximum production of cellulase enzyme as illustrated before where the maximum cellulase enzyme formation was occurred on day 3. The development of mathematical model in this study was based on the batch culture mode and considered the general mass balance equation that results in modifying Monod equation and general kinetics model. The validity of the constructed mathematical model was bounded by several restrictions such as assumptions was done to simplified the complex reaction to the simplified model, the time constraints was 10 days and the accuracy of confidence level was at 95%. The final model developed in this study was modified Monod equation and modified kinetic models of biomass, substrate and product, which can be used to solve certain problem especially with the accumulation of sludge in the wastewater treatment. The model described the bioconversion process to convert the available source of sludge to give value-added material or substances, which in this case the production of cellulase enzyme for industrial usage in Malaysia. The advantages of model developed, it can reduce the accumulation of sludge cakes, the cost of wastewater treatment in Malaysia and the content of pollutant in the effluent treatment.

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References 1. Kadir MDA, Velayutham S (1999) The management of municipal wastewater sludge in Malaysia. Symposium on Sludge Management, University Technology Malaysia 2. Wen Z, Liao W, Chen S (2005) Production of cellulase by Trichoderma reesei from dairy manure. Appl Biochem Biotechnol 121–124:93–104 3. Wahid R (2005) Production of cellulase enzyme from sewage treatment plant sludge by liquid state bioconversion. 1–5 4. Hritonenko N, Yatsenko Y (2003) Applied mathematical modeling of engineering problems. Kluwer Academic Publishers, Dordrecht, The Netherlands 5. Moeller DPF (2004) MATLAB and simulink based books-mathemathics. University of Hamburg, http://www.mathworks.com 6. Jeppsson U (1996) Modelling aspects of wastewater treatment processes (pp. 15–47). Reprocentralen, Lund University, Lund, Sweden 7. Volesky B, Votruba J (1992) Modeling and optimization of fermentation processes. Elsevier Science Publishers, Amsterdam, The Netherlands, pp 3–11 8. Lilly VM, Barnett HL (1951) Physiology of the fungi, 1st edn. McGraw-Hill, New York 9. Doran PM (1994) Bioprocess engineering principles. Sydney, Australia, pp 277–289

Treatment of H-Acid Containing Wastewater by Wet Peroxide Oxidation Zhao Binxia, Li Hongya, Wang Jin, Bai Weili, Zhang Xiaoli, and Jin Qiting

Abstract The treatment of the H-acid containing in wastewater by wet peroxide oxidation (WPO) and catalytic wet peroxide oxidation (CWPO) was studied in a 0.5 L autoclave. It were investigated that the effects of temperature, pH, dosage of hydrogen peroxide and the types of catalyst on the oxidation process and the degradation efficiency. The results showed that H-acid which have stable structure at lower pressure and temperature can be degraded by WPO, and 62.0% of COD and 98.7% color removal were attained at the conditions of 110◦C, 0.5 MPa, initial pH = 5.0 and theoretical dosage of peroxide when the initial concentration of H-acid containing water was 10 g/L. With catalyst Cu/Ni, 92.0% of COD and 99.9% color removal were obtained in the CWPO process under the same reaction conditions. Keywords Wet peroxide oxidation · Dye wastewater · H-acid · Catalyst The effluents discharged from the production process of H-acid, an important intermediate of dye, frequently contain pollutants which have strong acidity and deep color as well as resistant to conventional wastewater treatments. Some scholars has already tried to use the photocatalytic oxidation [1] and the wet air oxidation [2] to treat the H-acid in dye wastewater, but the results indicate that the photocatalytic oxidation is only suitable for lower COD density (about 50 mg/L), and the COD removal of the wet air oxidation is no more than 50%. Yang Min [3], Du Hongzhang [4], etc. adopted catalytic wet air oxidation (CWAO) to deal with the wastewater, the COD removal was more than 88%, but the operating temperature was up to 200◦C and pressure was above 4.0 MPa, so the apparatus must be able to bear the severe conditions and the running cost is increased. Due to the shortcomings existed in the above-mentioned methods, it is necessary to seek a new kind of high-efficient method to treat this kind of wastewater.

Z. Binxia (B) College of Chemical Engineering, Northwest University, Taibai North Road No.229, Xi’an 710069, People’s Republic of China e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_113,

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Wet peroxide oxidation (WPO) is an advanced technology which was developed on the basis of WAO, has received the extensive concerns [5–7] in recent years. WPO process was developed in order to decrease the running cost of wet oxidation, which is efficient under severe temperature and pressure. In this study, the effects of important variables such as hydrogen peroxide dosage, initial pH, contact time and temperature on WPO and CWPO were examined.

1 Experimental 1.1 Materials and Procedures The reactions were carried out in a 0.5 L autoclave (manufactured by the automatic control kettle Co. Ltd. of Weihai, ShanDong Province) equipped with a gas sampling, a aqueous sampling, a magnetic stirrer and a cooling coil. In order to get rid of the interferer of impurity and to facilitate the studying, H-acid sodium salt, the representative of the dyestuffs intermediate of naphthalene, and the powder catalyst that prepared by the co-precipitation method were adopted in the tests. For each reaction, 300 ml of the certain concentration of H-acid sodium salt, the initial pH value of which was regulated by NaOH, was introduced into the reactor, then the reactor was closed and agitated. Once the designated temperature was reached, a certain amount of the 30% hydrogen peroxide was introduced with the high-pressure pump and regarded it as the zero moment, thereafter, liquid samples were withdrawn at equal time interval to analyze the COD and color removal. The composite oxides of Cu/Ni series catalysts were prepared by co-precipitation using the corresponding metal nitrate at different mole ratio and calcination temperature followed by calcinations at designated temperature for 16 h. The mole ratio of Cu/Ni was 2:1, 1:1 and 1:2 and the calcination temperature was 600, 700 and 800◦C, respectively. The COD was measured using the potassium dichromate law in the tests. The pH was measured by means of PHS-3B meter. The chroma was determined by 721# spectrophotometer. The catalyst was characterized by the D/max-3C X-ray diffraction.

2 Results and Discussion 2.1 Wet Peroxide Oxidation (WPO) 2.1.1 Influence of the Dosage of Hydrogen Peroxide The wet air oxidation uses oxygen or air as the oxidant. The amount of oxygen is generally 1.1–1.4 times of the theoretical demand, so its influence is often neglected in the dynamics studying. If hydrogen peroxide will be adopted as the oxidant, it is necessary to study and confirm the most suitable quantity because of its high cost.

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Fig. 1 Effect of H2 O2 dosage on the COD removal

Under the condition of 110◦C and pH = 5, after acting 2.0 h, the effect of hydrogen peroxide dosage (0.5, 1.0 and 2.0 times of the theoretical dosage) and contact time on the COD removal was shown in Fig. 1. As can be seen from the results that as the dosage of hydrogen peroxide increased, a higher COD removal was achieved. When the dosage increased to 1.0 times from 0.5 times of the theoretical demand, the COD removal increases from 32.3 to 62.0%, increased nearly 1 times. While the dosage doubled to 2.0 times, the COD removal increased from 62.0 to 65.3%. This indicates that when the dosage of hydrogen peroxide is lower than the theoretical demand, the insufficient makes the COD removal reduce. When the dosage is higher than that, the COD removal is improved slightly. It means that increasing the dosage of hydrogen peroxide excessively can not improve COD removal further, because the excessive hydrogen peroxide takes the following reaction: H2 O2 + HO• → HO2 + H2 O And HO2 • can react with the hydrogen peroxide further HO2 • + H2 O2 → H2 O + HO• Then the excessive HO• will consume hydrogen peroxide itself. 2.1.2 Influence of Temperature The effect of temperature was investigated in the range of 90–150◦C for the WPO of H-acid under the condition of P = 0.5 MPa and pH = 5 with the theoretical dosage of hydrogen peroxide. The results are shown in Figs. 2 and 3. As expected, by increasing the temperature, an obvious increase in COD and color removal are observed. When raised to

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Fig. 2 Effect of temperature on the COD removal

Fig. 3 Effect of temperature on the color removal

150◦C from 90◦ C, correspondingly, after 2.0 h reaction, the COD and color removal raised from 45.5 and 87.3% to 84.7 and 99.9% respectively. The COD removal increased more remarkably under low temperature (90–130◦C) than high temperature (more than 130◦C), because it could excite the hydrogen peroxide produce a large amount of HO• when raised temperature, but at higher temperature, hydrogen peroxide would decompose into oxygen and water. At the same temperature, color removal is greater than COD removal, for the color group of H-acid, which is unstable, may be degraded antecedently in the oxidation. 2.1.3 Influence of pH Under 110◦C and the theoretical dosage of hydrogen peroxide, the COD and color removal varied with contact time under different pH were investigated respectively.

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Figs. 4 and 5 depict that the pH value has obvious influence on WPO process. The COD and color removal is higher during the acid range than that above 7. Because lower pH prevents the useless consumption of HO• itself. But in neutral and alkaline solution, OH− will catch the HO• which hydrogen peroxide produced, thus accelerates the resolving of hydrogen peroxide and reduces the effect of oxidation. Fig. 4 Effect of initial pH on the COD removal

Fig. 5 Effect of initial pH on the color removal

2.2 The Catalytic Wet Peroxide Oxidation (CWPO) Catalytic wet peroxide oxidation is an efficient method that uses peroxide to catalytically destroy target pollutants contained in wastewater streams. The use of a

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solid catalyst not only allows to accomplish oxidative treatment under moderate severity, but also offers a versatile process wherein the catalyst may be conveniently recovered and eventually reused. A good result was attained for treating the simulation wastewater of H-acid by WPO, however it is not appropriate to get a better result by increasing the dosage of hydrogen peroxide or rising the operating temperature, so it seems important to develop a new-type and high-efficient catalyst. 2.2.1 Textural Properties Characterization The Cu/Ni series catalysts were prepared at different mole ratio and calcination temperature under the same calcination time, and they were named by D1 −D9 separately. When the dosage of hydrogen peroxide was equal to the theoretical demand, under the condition of T = 110◦C and pH = 5, 1 g D1 −D9 catalyst in the reactor, the influences of different catalyst on the COD removal were investigated, respectively. The result in Fig. 6 shows the COD removal increased with Cu/Ni mole ratio under the same calcination temperature. Therefore, catalysts with high copper content tend to exhibit high activity. However, the effects of calcination temperature on catalyst activity are not monotonous. The catalyst activity is the highest at calcination 700◦ C under the same metal ratio. It may be that this metal oxide crystal can not be deformed to form the mixed crystal structure, and the surface area is smaller, so it is not good at dealing with the wastewater during the lower calcination temperature. On the contrary, if calcination temperature is too high, catalysts may be sintered and crystal structure destroyed. The activity of D6 (Cu: Ni = 2:1, roast at 700◦C) is the highest.

Fig. 6 Comparison of different catalysts of Cu/Ni on COD removal

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Fig. 7 XRD of Cu/Mn catalyst D6

Figure 7 shows the powder XRD pattern of D6 , According to the main features of the pattern, Cu exists as CuO in the catalyst, and Ni exists in the form of compound oxide with Cu and Ni. Therefore, NiO enters into CuO and forms a mixed crystal structure, its molecular formula is Cu0.2 Ni0.8 O, then forms the Cu-Ni oxide solid solution, which structure accounts for 41% of the total amount. Because of the formation of this kind of structure, the crystal energy of the metal oxide has improved and the structure of the metal oxide becomes more steadily, which contribute to controlling the leaching of the active component. 2.2.2 Influence of Temperature The COD and color removal varied with time under different reaction temperature were investigated at the theoretical dosage of hydrogen peroxide, pH = 5 and 1 g D6 . The effect of temperature on COD and color removal are depicted in Figs. 8 and 9. D6 demonstrates higher activity. The COD and color removal are improved

Fig. 8 Effect of temperature on the COD removal with D6

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Fig. 9 Effect of temperature on the color removal with D6

greatly compared with WPO. When temperature was raised to 130◦ C from 90◦ C, COD and color removal increased from 87.5 and 99.4% to 95.0 and 99.9% respectively after 2.0 h. The use of D6 makes the final COD removal rise to 92.0% from 62.0% of WPO at 110◦C. Therefore, the introduction of the catalyst has achieved the purpose of getting higher COD and color removal under lower temperature and shorter reaction time. 2.2.3 Influence of Initial pH Figures 10 and 11 show the effects of initial pH on COD and color removal in CWPO. The conditions of experiments are: theoretical dosage of hydrogen peroxide, T = 110◦ C and 1 g D6 .

Fig. 10 Effect of pH value on COD removal with D6

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Fig. 11 Effect of initial pH on color removal with D6

Compared Fig. 4 with 10, it is clear that the regularity of the effects of initial pH on COD removal was different from that of WPO. COD removal did not increase with the decline of initial pH all the time, when the pH was lower than 5.0, COD removal declined instead. For example, when pH = 3.5, the final COD removal was 81.9%, it was lower than that of pH = 5.0 (92%). The reason is that the leaching amount of catalyst is increased and the catalyst activity is weakened with the reducing of pH value, so the COD removal is lower when pH = 3.5 than that pH = 5.0. Therefore, the appropriate initial pH is 5.0 to deal with the H-acid containing wastewater during the CPWO process.

3 Conclusions (1) It could get a better result to treat the H-acid dye wastewater by wet peroxide oxidation under the gentle condition: P = 0.5 MPa, T = 110◦C, pH = 5.0 and the theoretical dosage of hydrogen peroxide, the COD and color removal are up to 62.0 and 98.7%, respectively. (2) Among the Cu/Ni series catalyst D1 −D9 , the higher content of the copper is, the higher activation of the catalyst is. The calcination temperature is an important factor to influence the catalyst activation as well, and the suitable temperature is 700◦C. (3) The CWPO with D6 catalyst is compared with WPO, the COD and color removal are both improved. Put into 1 g catalyst, under P = 0.5 MPa, T =110◦C, pH =5.0 and the theoretical dosage of hydrogen peroxide, the COD and color removal are up to 92.0 and 99.9% respectively.

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References 1. Wanpeng Z, Li W (1996) Photocatalytic oxidation of H-acid in aqueous solution. Environ Sci (in Chinese) 17(4):7–10 2. Yongyi W, Zhihua Y (1996) Wet air oxidation of H-acid production waste liquor. Environ Sci (in Chinese) 17(1):31–33 3. Min Y, Ying S, Quanyi W (2003) Catalytic wet oxidation of H-acid wastewater over TiO2 supported Ru on catalyst. J Fudan Univ (in Chinese) 42(3):340–342 4. Hongzhang D, Xihai D, Bin W (2004) Treatment of H-acid industrial wastewater by catalytic wet oxidation. Ind Water Treat (in Chinese) 24(9):25–27 5. Akolekar DB, Bhargava SK, Shirgoankar I, Prasad J (2002) Degradation of azo dye acid red 14 in water. Appl Catal B Gen 157:255–262 6. Daneshvar N, Salari D, Khataee AR (2003) Photocatalytic investigation of the effect of operational parameters. J Photochem Photobiol A Chem 157:111–116 7. Neri G, Pistone A, Milone C, et al (2002) Wet air oxidation of p-coumaric acid over promoted ceria catalysts. Appl Catal B Environ 38:321–329

Ambient Ozone Levels in the Eastern Mediterranean Region and Assessment of Its Effect on the Forested Mountain Areas of Southern Turkey Evrim Akkoyunlu, Rukiye Tipirdamaz, Saime Ba¸saran, Halil Sariba¸sak, Dudu Özkum, and Gülen Güllü

Abstract Ambient ozone measurements were conducted from the beginning of May 2003 to the end of October 2004 in the forested areas of west Mediterranean mountains of Turkey. The ozone concentrations were estimated using a passive sampling method from the bottom of the valley (altitude 10 m) to the top of the mountain (1950 m) over 20 sites distributed all over the study area. Active continuous measurements of ozone were done at one of the monitoring site and helped to calibrate the concentrations of ozone obtained by passive method. The results indicated that ozone concentrations were in the range of 19−410 μg m−3 , the yearly average of ozone was 89.37±71.25 μg m−3 . Generally, maximum ozone concentrations were measured at high altitude stations (1950 amsl) during the spring and summer season, and minimum concentrations were measured at the locations near to the road traffic. The sypmtoms of probable ozone injury in the vicinity of passive ozone samplers were examined by collecting needle and leaf samples from the main native plants. According to the visual inspection of leaves and measurement of photosentetic pigments of control and symptomatic leaves, out of 41 species of native plants, 11 species were identified as potential bioindicators of ozone. Ozone concentrations in the west Mediterranean part of Turkey appear to be high enough and of sufficient duration to cause foliar injury on a wide variety of native plants. Keywords Ozone · Bioindicators · Forest · Mediterranean · Photosentetic pigment

1 Introduction Ozone has been proved to cause foliar injury in a variety of native forest species in different Southern European countries as a consequence of the particular air pollution chemistry and dynamics of this region. Due to high solar radiation, widespread emission of the precursors of photochemical oxidants (e.g. NOx, VOCs, NMHC)

D. Özkum (B) Near East University, Faculty of Pharmacy, Nicosia, Northern Cyprus, Mersin 10, Turkey e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_114,

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and prolonged drought periods, the Mediterranean forests become potentially sensitive to climatic fluctuations and changes [4]. Owing to the complex relationships existing between species sensitivity, ozone exposure and doses, length of the vegetative periods, the impact areas on the Mediterranean coastal areas have not been identified yet [2]. Among the Mediterranean countries, only in Spain, Israel and Greece, poor tree condition attributed to the action of ozone have been reported [9, 22]. Recent surveys carried out in southern Switzerland reported ozone-like symptoms on a variety of broadleaved species [3]. The results of a 7 year monitoring across a 16 × 16 km network in Southern Turkey, Antalya, show that defoliation is increasing [10]. During 1991 survey, 40% of the trees were in the moderately damaged class, whereas, in 1997 survey, it has been determined that 80% of the trees were in the moderately damaged class. According to the results of this study, as there is an extensive neutralization of acidity by local soil and long range trasported Saharan dust which are rich in carbonates, the reasons of forest decline in the study region cannot be attributed to the acidic precipitation [1, 10], acidic deposition could not been to be a significant factor contributing to forest health problems. From October 1994 to January 1996, a continuous hourly ozone sampling was performed on the Mediterranean coast of Turkey (30.34 ◦ E, 36.47 ◦ N). In this study, the ozone levels in the region show values over the critical level of 10 ppm.h which is the level accepted by European Community as a threshold for the forests [11]. As the measured ambient ozone levels higher than critical level, it has been proposed that ozone may be one of the antropogenic stress factor causing forest decline in Southern Turkey observed within this study. The main purpose of this study is to determine if ozone may contribute to forest decline in Southern Turkey. To accomplish this goal, ambient ozone concentrations were measured with passive and active monitors and vegetation near the passive samplers and active monitor was evaluated for probable ozone injury symptoms during May and early September. Native plants, growing in situ, are preferred for vegetation surveys. These established detector bioindicators visibly respond to ozone only when sufficient soil moisture and climatic conditions allow uptake of enough ozone for a sufficient time to allow inactivation of antioxidant defense mechanisms [6, 16].

2 Materials and Methods 2.1 Ozone Monitoring During three weekly sequences from May 2003 to October 2004, passive ozone samplers (Passam) and a continious active monitor (Environement 41 M-LCD) were used in forest condition monitoring sites in forested areas, along the the slopes of Toros mountains in Antalya (Fig. 1). Samplers were placed in open field stations within the forest area, at a height of 3 m above ground level. The samplers were provided with rain shelters that also protected them from the wind.

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MEDITERRANEAN SEA

Fig. 1 The southern Turkey, west Mediterranean research region, indication the relative position of the ozone passive and continuous monitoring sites and their altitudes

Co-located measurements of O3 with the photometric analyzer and passive samplers indicate good agreement between the two methods (p < 0.05, R2 = 0.891). Some data periods were excluded from the data set due to malfunctioning of the equipments.

2.2 Collection and Storage of Foliar Samples for Physiological Measurements In the vicinity of the location where the ozone passive sampler is installed, foliar samples for physiological measurements were collected from main tree species within 0.5 km of the ozone monitoring stations during late summer (September, 2003) for broadleaf species and spring (May, 2003) for conifers. Samples were taken from the upper sun exposed part of the crown, for conifers, second and third year of the foliar were sampled. Symptomatic leaf or needle material was collected for later analyses in the laboratory. Asymptomatic material was also sampled on the same individuals in a nearby branch for control. Samples were collected 1–2.5 m above ground from the sunlight, stored in paper bags at room temperature, and moistened three or four times daily. After identifying all tree, bush and perennial species growing inside the plots and along the edges and examining the foliage up to 2 m for ozone-like injury, symptomatic and asymptomatic branch and leaf samples were photographed with Canon Powershot SD600 digital camera and then dried in a plant press (herbarium).

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2.3 Symptom Identification and Injury Scoring Visible ozone like symptoms were identified according to the instructions given in Submanual for the Assessment of Ozone Injury on European Forest Ecosystems (http://www.icp-forests.org/Manual.htm). The identification of visible ozone injury was based on the examples given in the “Submanual”, on the current list of sensitive species [21]. The ozone injury criterion for coniferous species was the presence of photo bleaching and/or mottling on the light-exposed portion of the needles. Among angiosperm species, various symptoms were exhibited on the adaxial and light-exposed side of leaves. They included light-green or reddish to brownish stippling between leaf second-order veins, variable bronzing, whole leaf reddening or intercostal band necroses. Additional characteristics for discriminating between ozone injury and other abiotic stress factors were the increase in degree of injury with leaf age, with lower position on the branch, and with light exposure. Biotic origins of the symptoms were excluded by close examination of leaves and needles using a 12_ magnifying lens and looking for fungal fruit-bodies and for insect and mite individuals or evidence of them such as sucking injury, scats and eggs. If symptoms were found, the number of affected plants/species was determined and an estimate of severity of incidence was made, using a simple 0–4 scale, where 0 = no symptoms, 1 = 1–5%, 2 = 6–25%, 3 = 26−50%, and 4 = 50− 100%.

2.4 Quantification of Photosynthetic Pigments Chl a and b and Carotenoid concentrations were measured in leaf extracts with 100% acetone. The absorbance of the extracts was measured with a spectrophotometer at 662, 645 and 470 nm. The individual levels of Chl a, Chl b and Car(x + c) were calculated by means of Lichtenthaler equations [15].

2.5 Statistical Analyses An ANOVA analysis for each parameter and species was performed to evaluate O3 effects on plant health related parameters. Also, a combined analysis involving all the assessed species was performed to assess whether plant sensitivity to O3 exposure could be related to plant family and their location; therefore a three-way ANOVA analyses were carried out considering ozone exposure and family as factors. When significant differences (p < 0.05) were detected, the differences between means were assessed using the least significant difference (LSD) test. All statistical analyses were carried out using Statgraphics Plus v.3.1 software.

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3 Results and Discussion Across the study region, maximum ozone concentrations were observed during August, 2004, 410.90 μg m−3 , and minimum were observed December, 2003, 19.03 μg m−3 . Monthly average ozone concentrations show a marked seasonal variation with maximum concentrations occurring from July to November (Fig. 2). During this period the average ozone concentration generally exceeds 60 μg m−3 . In other months the average concentration is somewhat lower. Observed summer-time peak cycle is due to the effect of continental emissions causing an ozone reduction in winter by titration with NO and ozone excess in summer due to photochemical formation. Summer-time peak ozone cycle has an adverse effects on vegetation as the time of the ozone increase often coincides with the growing season. The diurnal variation is also pronounced at Antalya (Fig. 2). Here the mean of the hourly average concentrations for May 2003 to October 2004 show the concentration to increase from about 15 μg m−3 before sunrise to an average maximum of about 55 μg m−3 at 15:00. There after the concentration decreases rapidly to sunset 500

O3(μg m–3)

400 300 200 100 0

1

2

3

4

5

6 7 months

8

9

10

11

12

80

O3(μg m–3)

60 40 20

1:15 2:00 3:00 4:00 5:00 6:00 7:00 8:00 9:00 10:00 11:00 12.00 13:00 14:00 15:00 16:00 17:00 18:00 19:00 20:00 21:00 22:00 23:00 24:00

0

Fig. 2 Mean monthly ozone concentration at Antalya for 2003–2004 (top) and mean hourly concentrations in 2003–2004 (bottom)

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at about 19:00, it is followed by a more gradual decrease to the minimum at sunrise. The average concentration is above 40 μg m−3 for about 11 h. It is well-known that ozone concentrations are highly dependent on meteorological variables, increasing with higher air temperature and solar radiation and decreasing in cloudy and rainy periods [19]. There is a significant correlation between ozone and temperature (r = 0.745) and solar radiation (r = 0.877). Which revelated that warm and sunny weather enhances the ozone concentration because of the emission of volatile hydrocarbons increase with temperature, higher solar radiation increases photochemical processes, and high temperature results in more rapid chemical ozone formation [8]. It has been tested whether the ozone concenrations vaired between the geographical locations of the stations, their altitudes and closeness to roads. There is an statistically significant difference of ozone concentrations between the locations of stations closeness to road and their altitudes (p < 0.05). The maximum ozone concentrations were observed on the high altude stations. It has been found that ozone concentration increased gradually with an increase of altitude. Similar altitudinal gradients have been identified at a regional scale in rural areas of the Mediterranean, mountain–top locations [19]. When the closeness of the stations to roads is taken as a factor for ozone variation, it has been found that, as the distance to roads increases, the ozone concentrations also increases. The difference is more pronounced during summer season (April to September). From the previous studies, it has been known that eleveated NOx emission sources act as a local sink for ozone [12]. For this reason, in areas with heavy traffic as in town centres, ozone levels are usually lower than outside city areas. As can be seen in Table 1, due to the increase in the trafic activities during summer time in the study region, the ozone concentrations were lower at the stations near to raods. Our results indicate that concentrations of ozone in southern Turkey are similar and even higher to those measured in forested parts of Romanian and Ukranian Carpacian mountains and Sumava mountains [5] which all suffer from ozone phytotoxicity. With annual mean ozone, 89.37 μg m−3 (summer time mean ozone,

Table 1 Mean ozone concentrations over the region and at the stations far away and near to the roads during different seasons (μg m−3 )

Stations near to the roads Stations far away from the roads All ∗ Statistically

Mean annual ozone Mean ± std

Summer (April–September) Mean ± std

Winter (October–March) Mean ± std

85.59±62.78∗

101.69±63.49∗

61.32±53.65

100.59±75.09∗

122.68±76.74∗

62.65±54.36

89.37±71.25

113.25±71.68

62.00±53.79

significant difference P < 0.05 observed pairs

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113.25 μg m−3 ) the southern Turkey forested regions are under the influence of anthropogenic sources and chronic exposure to ambient ozone concentrations is probably one of the primary reasons for forest decline.

3.1 Relation Between Ozone Exposure and Plant Injury The most common method of assessing plant injury, induced by air pollutants, involves visual estimation of the percent leaf area that is injured and variation of chlorophyll content. Band shape of yellowing on the light-exposed upper side of the needles with increasing needle age is a characteristics symptom of ozone [20]. Based on visual injury damage percentages, it has been observed that, visual injury increases with needle age on the coniferous species. For the whole region, the percent of visual injury for 2nd class of severity index (6–25% injury) on symptomatic needles for the current year is around 37% as the previous year’s is around 50%. The most common coniferous specie all around the study region is P. brutia, apart from it, Pinus nigra, Pinus pinea, Abies cilicica, Cedrus libani, Cupressus sempervirens and Juniperus oxycedrus are also available in the study region. When the maximum ozone concentrations observed in the stations were compared with the visual injury damage of the previous year needles of P. brutia of the same station, it has been seen that, there is a statistical significant increases on the visual damage if the maximum ozone concentrations are higher than 60 μg m−3 (p = 0.015 < 0.05). There were 36 different natural decidiuous tree species throughout the study area; Amelonchier paruiflora, Berberis, Capparis ovata, Ceratonia siliqua, Cistus crateagus, Cotinus coggyria, Crataegus, Daphne mezereum, Daphne sericea, Ficus carica, Fontanesia phylliraeoides, Myrtus communis, Nerium oleander, Olea europea, Osyris alba, Paliurus spina- christi, Phillyrea latifolia, Pistacia lentiscus, Pistacia terebinthus, Platanus orientalis, Pyrus, Quercus, Quercus coccifera, Rhamnus, Rhus coriaria, Rosa, Ruscus oculeatus, Salvia, Smilax, Smilax aspera, Styrax officinalis, Thymelea tartonraira, Vitex agnus-castus. For whole deciduous species investigated in the study region, 26% of the trees do not show any visual damage, whereas 60% of them have 1–5% of the leaf area damage and the rest has more than 6% of the leaf area damage similar to current year needle visual damage. The change in chlorophyll content has been used in many studies investigating the effects of ozone on plants [7, 13, 14, 18]. The results, however, of such investigations do not always lead to the same conclusions concerning the pattern of effects. Knudson et al. [13] found higher reduction in chl a in ozone-exposed plants of Phaseolus vulgaris L., and Spinacia oleracea L. Robinson and Wellburn [18] also observed reduction in the chl a/b ratio in Picea abies L. plants, due to summer ozone exposures. Price et al. [17] found no differences in the relative reduction of chlorophylls a and b, although both chlorophyll forms decreased by 20–40% in barley exposed to 200 ppb of O3 .

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According to the results of chlorophyll content of the coniferous species, control groups has more than 18% Chl a, 22% Chl b, 17% Chl a+b and 10% Carotenoid content compared to symptomatic needles and changes from specie to specie. For deciduous species, the Chl a, Chl b and Chl a+b content of symptomatic foliars has less than 31, 34 and 32%, respectively compared to their control groups. For carotenoids, there is no significant difference observed for deciduous species. For the common coniferous species the chlorophyll content variation for symptomatic and control groups can be seen in Fig. 3. The difference between symptomatic and control group is significant for Pinus pinea and Cupressus sempervirens (p < 0.05). There is no difference observed for Pinus brutia and Pinus nigra and as there is no control group for Abies cilicica, Cedrus libani and Juniperus oxycedrus, the variation of pigment content could not be investigated. For different deciduous species, the variation of pigment content from symptomatic to control group foliars is high. The most significant reduction in Chl a content on the symptomatic leaves were observed for Vitex agnus castus, Paliurus spina cristii, Phillyrea latifolia, Thymelea tartonraira with 51, 44, 42 and 36% reduction, respectively. For the same species, the Chl b, Chl a+b reduction varies from 30 to 70% (Fig. 4). Although, for whole deciduous species there is no significant Carotenoid content variation, there is statistically significant carotenoid reduction for Crateagus, Quercus coccifera, Phillyrea latifolia and Vitex agnus-castus, 81, 65 55 and 36%, respectively. 1600 Chl a+b (mg g–1)

1400 1200 1000 800 600 400 200 0

Carotenoids (mg g–1)

300 250

Kontrol Semptom

1234567

200 150 100 50 0 P.Brutia

P.Pinea

P. Nigra

Abies Cedrus libani Cupres. cilicica Semp

Juniperus oxy.

Fig. 3 Variation of Chl a+b and Carotenoid content of symptomatic and control group of coniferous species

Chl a+b (mg g–1)

Ambient Ozone Levels in the Eastern Mediterranean Region

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800 700 600 500 400 300 200 100 0

Control Symp.

400 Control Symp.

Carotenoids (mg g–1)

350 300 250 200 150 100 50

is in

al

er of x tra

iu er

Sy

m

ol

fic

te

ea

ag

nd

us

ra fe ra N

ue

rc

us

C

co

ca Q

te

x

ag

nu

s

la ea

yl

lir Vi

ci

st

o tif

cr a Ph

us

lia

r is

nr in sp

lir

us

el Pa

ym

tii

ai

s Ta ea

re ia

te Th

ac

to

nt bi

m m co

s st Pi

itu yr M

ku

is un

cu is nt

le ia

ac st

Pi

Fa

nt

an

es

ia

ph

yl

lir

ae

oi

de

s

s

0

Fig. 4 Variation of Chl a+b and Carotenoid content of symptomatic and control group of decidious species

It has been observed that the reduction of chlorophyll content on foliars is increasing with increasing ozone concentration on the region. When the ozone concentrations is around 40–60 μg m−3 , the reduction of pigment content is 2–10% for coniferous species and 15% for deciduous species, whereas the reduction of pigment content increases 30% for coniferous, 45% for deciduous species as the ozone concentrations higher than 80 μg m−3 .

4 Conclusion The results of our study indicate that ambient ozone is prevalent in forested regions of southern Turkey at concentrations high enough to injure sensitive plants. With respect to ozone increase, visual injury and reduction of chlorophyll pigment content of the foliar samples were observed. Based on visual injury indexes and pigment

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losses, out of 41 investigated natural species, 11 of them has been identified as bioindicator for ozone injury: Vitex agnus castus, Palirus spina cristii, Phyllirea latifolia, Thymelea Tatonraira, Crateagus, Quercus cocifera, Salvia, Berberis, Ceratonia siliqua, Pinus pinea and Cupressus sempervires. Out of this identified sensitive species Crateagus, Berberis and Pinus pinea have already been identified as sensitive species to ozone on Europe. There is a clear need for development of long-term O3 monitoring networks in mountain forest of the southern Mediterranean Region. Such networks should consist of active and passive samplers. Acknowledgement We acknowledge financial support from the Scientific and Technological Research Council of Turkey (No. ˙IÇTAG-Ç062 102I049). We thank the many people we worked in the field for research colloboration, logistical support and friendship. Organizations and individuals include: Dr. Gürdal Tuncel, Middle East Technical University, Turkey, Yusuf Cengiz, Dr. Mehmet Ali Ba¸saran, West Mediterranean Forest Research Center, Antalya, Turkey.

References 1. Al-Momani IF, Aygün S, Tuncel G (1998) Wet deposition of major ions and trace elements in the eastern Mediterranean basin. J Geophys Res Atmospheres 103(D7):8287–8299 2. Barnes J, Gimeno B, Davison A, Dizengremel P, Gerant D, Bussotti F, Velissariou D (2000) Air pollution impacts on pine forests in the Mediterranean basin. In: Ne’eman G, Trabaud L (eds) Ecology, biogeography and management of pinus halephensis and P. brutia forest ecosystems in the mediterranean basin. Backhuys Publishers, The Netherlands, pp 391–404 3. Bussotti F, Ferretti M (1998) Air pollution, forests condition and forest decline in Southern Europe. Environ Poll 10:49–65 4. Butkovic V, Cvitas T, Klasinc L (1990) Photochemical Ozone in the Mediterranean. Sci Total Environ 99(1–2):145–151 5. Bytnerowicz A, Godzik B, Grodzinska K, Fraczek W, Musselman R, Manning W, Badea O, Popescu F, Fleisceher P (2004) Ambient ozone in forests of the Central and Eastern European mountains. Environ Poll 130:5–16 6. Davison AW, Barnes JD (1998) Effects of ozone on wild plants. New Phytol 139:135–151 7. Della Torre G, Ferranti F, Lupattelli M, Pocceschi N, Figoli A, Nali C, Lorenzini G (1998) Effects of ozone on morpho–anatomy and physiology of Hedera helix. Chemosphere 36:651–656 8. Fiala J, Cernikovsky L, de Leeuw F, Kurfuerst P (2003) Air pollution by ozone in Europe in summer 2003. Overview of exceedances of EC ozone threshold values during the summer season April–August 2003 and Comparison with previous years, European Environmental Agency, Copenhagen (EEA Topic Report 3/2003) 9. Gimeno BS, Penuelas J, Porcuna JL, Reinert RA (1995) Biomonitoring ozone phytotoxicity in eastern Spain. Water Air Soil Pollut 85:1521–1526 10. Güllü G, Sirin ¸ G, Örtel E, Tuncel G (2001) The effects of air pollution an crown and foliar conditions of forests in the Southern Turkey. 11th International Symposium on Environmental Pollution and Its Impact on Life in the Mediterranean Region, 6–10 Oct, Limmasol, Cyprus 11. Güllü G, Sirin ¸ G, Tuncel G (2003) Forest decline evidence in Southern Turkey and its possible dependence on ozone trends. Water Air Soil Pollut Focus 3(5–6):263–275 12. ICP Forests (International Co-operative Programmes and the Mapping Programme under the Working Group on Effects) (1996) Convention on long range transboundary air pollution “effects of O3 and NO2 ”

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13. Knudson LL, Tibbitts TW, Edwards GE (1977) Measurement of ozone injury by determination of leaf chlorophyll concentration. Plant Physiol 60:606–608 14. Köllner B, Krause GHM (2000) Changes in carbohydrates, leaf pigments and yield in potatoes induced by different ozone exposure regimes. Agric Ecosyst Environ 78:149–158 15. Lichtenthaler HK (1987) Chlorophylls and carotenoids: Pigments of photosynthetic biomembranes. Meth Enzymol 148:351–382 16. Manning WJ, Godzik B, Musselman R (2002) Potential bioindicator plant species for ambient ozone in forested mountain areas of central Europe. Environ Pollut 119:283–290 17. Price A, Young A, Beckett P, Britton G, Lea P (1990) The effects of ozone on plant pigments. In: Balscheffsky M (ed) Current research in photosynthesis, vol 4. Kluwer Academic Publishers, Dordrecht, pp 595–598 18. Robinson DC, Wellburn AR (1991) Seasonal changes in the pigments of Norway spruce, Picea abies (L.). Karst, and the influence of summer ozone exposures (trans). New Phytol 119:251–259 19. Sanz MJ, Calatayud V, Sanzhez-Pena G (2007) Measures of ozone concentrations using passive sampling in forests of South Western Europe. Environ Pollut 145(3):620–628 20. Schmieden U, Wild A (1995) The contribution of ozone to forest decline. Physiol Plant 94:371–388 21. Skelly JM, Innes JL, Snyder KR, Savage JE, Vanderheyden D, Zhang J, Sanz MJ (1999) Observation and confirmation of foliar ozone symptoms of native plant species of Switzerland and southern Spain. Water Air Soil Pollut 116:227–234 22. Vellissariou D, Gimeno BS, Badiani M, Fumigalli I, Davison AW (1996) Records of ozone visible injury in the ECE Mediterranean region. In: Kärenlampi L, Skärby L (eds) Critical levels for ozone in Europe: Testing and finalizing the concepts. UN/ECE workshop report. Department of ecology and environmental. University of Kuopio, Finland, pp 343–354

Physico-chemical Study of Bagasse and Bagasse Ash from the Sugar Industries of NWFP Pakistan and Remediation of Environmental Problems Caused by Refused Bagasse Ash Khurshid Ali, Noor-ul-Amin, Tahir Shah, and Saeed-ur-Rehman

Abstract Bagasse ash from the local sugar mills of NWFP (Pakistan) has been analyzed both physically and chemically. The moisture, ash contents, loss on ignition (LOI), volatile matter and calorific value have been determined. The qualitative and quantitative analysis was carried out by x-ray flourimeter (XRF) and carbon sulfur detector. The physical parameters were determined by thermogravemetric analyzer (TGA) and bomb calorimeter. The bagasse was also analyzed for ash and moisture contents which were found to be 3.66 and 9.47% respectively. The bagasse ash was found to consist of 86.69% ash, 13.45% loss on ignition (LOI) and 50 kcal/kg calorific value. The chemical constituents of bagasse ash were found to comprise of SiO2 , Al2 O3 , Fe2 O3 , CaO, MgO, Na2 O, K2 O, carbon and sulfur. Keywords Bagasse ash · Environmental pollution · Cement industry

1 Introduction Cement is the third most energy intensive material to produce on a per ton basis, after steel and aluminum. Cement industry consumes raw material rich in silica, alumina, iron and calcium. Therefore this industry has been actively involved in finding ways to use waste products in the manufacturing of cement both as secondary fuel and raw material. Fly ash is a pozzolan; a silica, alumina, and calcium based material which, in the presence of water, will chemically combine with the free lime contained in the fly ash and produces a cementitious material with excellent structural properties [1–8]. Ashes from combustion of coal are the major industrial by-products that are suitable for use as mineral admixtures in Portland cement. High carbon fly ash is also being utilized as both a source of fuel and raw material

K. Ali (B) Institute of Chemical Science, University of Peshawar, Peshawar, Pakistan e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_115,

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in the cement and construction material [9–11]. Fly ash is rich in all or some of these contents and can be used as a raw material. High carbon fly ash has the additional benefits of being a source of fuel. Environmentally, it provides a sound method for recycling non-hazardous waste and conserving natural resources [12– 15]. Economically, its use can replace some of the raw material, reduce the energy cost, and increasing revenues from the cement industry. In terms of the cement itself, benefits can include a decrease in alkali contents and improved burnability, resulting in energy savings and cement with better hydraulic properties [16]. Bagasse is fibrous residue of cornstalk that is obtained after the extraction of sugarcane juice by the milling process. The ready availability of bagasse, as a byproduct of sugar production, has always made it an attractive fuel for the sugar industry, and covers the energy requirements (electricity/ steam) of the industry, and leave 0.26% of residual ash. Thus it has been used as fuel in the boilers of the sugar factories since the beginning of the 20th century. Sugar manufacturing is the major agro industry in Pakistan [17]. In the year 2005 Pakistan produced about 54 million tons of sugarcane which was mainly used to produce sugar. Each ton of sugarcane generates approximately 26% of bagasse. Therefore, considering the production of 2005, about 0.5 million ton of residual ash become available in Pakistan per year. The residue after combustion presents a chemical composition with SiO2 , Al2 O3 , and Fe2 O3 as a major constituent. In Pakistan this ash founds no use and is discarded and dumped around the factory adjoining area. This unwise disposal causes environmental nuisance. The objective of this work is to characterize the bagasse ash produced by local sugar mills of North West Frontier Province (NWFP, Pakistan) in terms of its chemical composition, physical properties, and pozzolanic activity in order to undertake further study to evaluate how far it meets the existing specifications for Portland cement.

2 Experimental In this work both bagasse and bagasse ash from the local sugar mills have been analyzed for their physical and chemical properties. Samples of bagasse and bagasse ash were collected from three, randomly selected sugar mills, i.e. Premier Sugar Mill Mardan (PSM), Khazana Sugar Mill Peshawar (KSM) and Frontier Sugar Mill Thaktbhai Mardan (FSM). A number of samples of both the material were collected from different heaps inside the sugar mill and thoroughly mixed before final samples were taken from these mixed samples. Following this procedure three samples from each mill were collected. The sampling date was recorded on the plastic bags in which the samples were sealed and properly tagged for identification purpose. Bagasse was in the form of crushed pieces ranging in size from 0.5–10 mm which was ready for burning in the mill. These samples were taken to the laboratory for analysis.

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Moisture and ash contents, loss on ignition and amount of volatile matter in bagasse ash were determined by thermogravemetric analyzer (TGA 701 LECO Corporation). Calorific value of bagasse ash was determined by bomb calorimeter (AC-350 LECO Corporation). Carbon and sulfur was determined by carbon-sulfur analyzer (SC-144 DR Dual Range Sulfur and Carbon Analyzer 2001 LECO Corporation). The major and minor elements in the ash after complete loss on ignition were determined by XRF for which glass bead was formed from the ash. For this purpose one gram powdered ash was mixed with six gram of dilithium tetraborate (spectromelt, Merck) in a platinum crucible to which 0.001 g of lithium bromide (Merck) was also added. The ingredients were thoroughly mixed. The crucible was heated in a muffle furnace at 1150◦C for 15 min. Then the content of the crucible was transferred to a platinum mould inside the furnace and shaken to acquire the shape of the mould. The mould was cooled and the glass bead was obtained. After calibrating the XRF with certified standards, the sample bead was run in the machine and the analysis result was obtained.

3 Results and Discussion Bagasse may contain various amounts of sand or soil, especially in wet harvesting conditions, and may also vary in moisture content, depending upon the harvesting conditions and the conditions of the milling train. It consists of lignocellulose, insoluble inorganic matter (ash), water soluble material (brix) and water. The bagasse samples were analyzed for moisture and ash contents by thermogravemetric analyzer (TGA). The results are reported in Table 1 and graphically shown in Fig. 1 Moisture contents of bagasse samples range from 8.88 to 9.47. The average moisture present in these samples is 9.18%. This data indicate that there is not a considerable difference between the moisture contents in bagasse sample of these factories. On the other hand, the average percentage of ash is 3.47. As in the case of moisture, ash contents of different samples, also has very little variation from the average value. Table 1 Physical analysis of bagasse collected from sugar mills Sample no.

Moisture (%)

Ash (%)

S1 S2 S3 S4 S5 S6 S7 S8 S9

9.21 9.26 9.07 8.88 8.97 8.78 9.52 9.55 9.34

3.23 3.01 4.05 3.03 3.64 3.27 3.51 3.81 3.62

Average

9.18

3.46

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b

10 Ash (wt%)

moisture (wt%)

a

9.5 9 8.5 8 S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample numbers

5 4 3 2 1 0 S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample numbers

Fig. 1 (a) Moisture content; (b) ash content in bagasse (sugarcane) Table 2 Analysis of bagasse ash using of thermogravemetric analyzer Sampling station

Sample code

Moisture (%)

Ash (%)

Loss on ignition (%)

Premier sugar mill Mardan (PSM)

S1 S2 S3 S4 S5 S6 S7 S8 S9

2.25 2.35 2.36 2.95 2.76 3.02 3.56 3.68 3.46

85.58 85.21 85.95 88.47 88.62 88.75 85.85 85.66 86.14

14.45 14.80 14.20 11.60 11.40 11.52 14.25 14.44 14.38

2.93

86.69

13.45

Khazana sugar mill Peshawar(KSM) Frontier sugar mill Thakt-Bhai (Mardan) (FSM) Average

The results of bagasse ash analysis by TGA are given in Table 2 and graphically shown in Fig. 2(a–c). The percent moisture contents are 2.32, 2.91, and 3.57 for PSM, KSM and FSM respectively. The average value is 2.93%. The loss on ignition (LOI) of dry samples is 14.18, 11.15 and 14.36 with an average of 13.45%. The remaining residue after ignition i.e. the ash is 85.58, 88.61 and 85.88% for PSM, KSM and FSM respectively, with an average of 86.69%. The value of LOI (13.45%) is largely attributable to unburned carbon in the ash that can potentially result in significant fuel value. The calorific values of bagasse ash as determined by bomb calorimeter are shown in Table 3 and graphically shown in Fig. 3, the average values were found to be 50, 48.33, and 49.66 kcal/kg for the ash samples of the three factories respectively. The overall average valve was 49.33 kcal/kg. The percentages of sulfur in PSM, KSM and FSM samples were determined as 0.21, 0.17, and 0.23 respectively, while the average value is 0.21%. The percentage carbon contents were 16.33, 23.33, and 16.33 for PSM, KSM and FSM respectively with the average value of 18.67% as shown in Table 4 and Fig. 4 Fig.5. The appreciable amount of carbon content shows an incomplete burning of bagasse. About 16% carbon remains unburned in PSM and FSM while in KSM about 23% carbon remains unburned. It seems that the burning system has got

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4

b Ash (Wt%)

Moisture (wt%)

a

3.5 3 2.5 2 S1 S2

S3

S4 S5 S6

S7

90 89 88 87 86 85 84 83 S1 S2 S3 S4 S5 S6 S7 S8 S9

S8 S9

Sample numbers

Sample numbers

Loss on Ignition (wt%)

c 16 14 12 10 S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample numbers

Fig. 2 (a) Moisture content; (b) ash content; (c) loss on ignition of bagasse ash Table 3 Analysis of bagasse ash through bomb calorimeter Sampling station

Sample code

Calorific value (kcal/kg)

Premier Sugar Mill Mardan (PSM)

S1 S2 S3 S4 S5 S6 S7 S8 S9

50 50 50 48 49 48 50 49 50

Khazana Sugar Mill Peshawar (KSM) Frontier Sugar Mill Thakt-Bhai (Mardan) (FSM)

49.33

Calorific value (kcal/kg)

Average

Fig. 3 Calorific value of bagasse ash (kcal/kg)

52 50 48 46 44 42 40 S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample numbers

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K. Ali et al. Table 4 Analysis of bagasse ash through carbon-sulphur detector

Sampling station

Sample code

Sulfur (%)

Carbon (%)

Premier Sugar Mill Mardan (PSM)

S1 S2 S3 S4 S5 S6 S7 S8 S9

0.22 0.21 0.21 0.17 0.18 0.17 0.23 0.24 0.23

15 16 18 24 23 23 15 16 18

0.21

18.67

Khazana Sugar Mill Peshawar(KSM) Frontier Sugar Mill Thakt-Bhai (Mardan) (FSM) Average

b 0.25

sulphur (wt%)

Carbon (wt%)

a

26 24 22 20 18 16 14 12 10

0.23 0.21 0.19 0.17 0.15

S1 S2 S3 S4 S5 S6 S7 S8 S9

S1 S2 S3 S4 S5 S6 S7 S8 S9

Sample numbers

Sample numbers

Fig. 4 (a) Carbon content; (b) sulfur content in bagasse ash

some inherent problem which hamper complete burning of bagasse and this problem whatsoever is more pronounced in the case of KSM where the value of unburned carbon is about 23% vis-à-vis 16% in the other two cases.

4 Chemical Analysis The chemical analysis of bagasse ash was carried out by X-Ray fluorescence (XRF) method and carbon sulfur detector. The percentages of sulfur and carbon in bagasse ash samples are given in Table 5. The average amount of sulfur present in samples of PSM, KSM and FSM are 0.21, 0.17 and 0.23% respectively. The percentage of carbon was found to be 16.33, 23.33 and 16.33 respectively. The amount of carbon present in the ash indicates that the burning of bagasse in boilers of these mills is not very effective and some technical improvement in the burning process must be made to insure complete burning of bagasse. The results obtained from XRF analysis is given in Table 6. For this analysis the ash left after loss on ignition was used. The results show that the average amount of SiO2 in all the samples is 87.87% and is present as a major constituent in the ash.

Physico-chemical Study of Bagasse and Bagasse Ash

92 90 88 86 84 82 80

3 2 1 0

S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample identificaiton

S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample identification

Sample identification

Na2O Wt%

MgO wt %

S9

Sample identification e

2.5 2 1.5 1 0.5 0

f

0.3 0.25 0.2 0.15 0.1 0.05 0

S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample identification

S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample identification g

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

h

0.25 SO3 Wt%

K2O Wt%

S8

S1

S8 S9

S6 S7

S5

S4

S3

S2

S1

0

S7

1

S6

2

S5

3

S4

4

S3

CaO wt%

5

d

4 3.75 3.5 3.25 3 2.75 2.5 2.25 2 S2

c

6 Fe2O3 Wt%

b

4 Al2O3 Wt%

SiO2 wt %

a

1231

0.2 0.15 0.1 0.05 0

S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample identification

S1 S2 S3 S4 S5 S6 S7 S8 S9 Sample identification

Fig. 5 Variations of different element oxides in bagasse ash (a–h)

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K. Ali et al. Table 5 Analysis of bagasse ash through carbon-sulphur detector Sampling station

Sample code

Sulfur (%)

Carbon (%)

Premier sugar mill Mardan (PSM)

S1 S2 S3 S4 S5 S6 S7 S8 S9

0.22 0.21 0.21 0.17 0.18 0.17 0.23 0.24 0.23

15 16 18 24 23 23 15 16 18

0.21

18.67

Khazana Sugar Mill Peshawar (KSM) Frontier Sugar Mill Thakt-Bhai (Mardan) (FSM) Average

Table 6 Chemical analysis of bagasse ash collected from sugar mills of N.W.F.P Percent composition PSM

KSM

Analyte

S1

S2

SiO2 Al2 O3 Fe2 O3 CaO MgO Na2 O K2 O SO3

87.4 3.60 4.90 2.56 0.69 0.15 0.47 0.11

87.23 3.45 5.02 2.49 0.71 0.14 0.47 0.12

Total

99.88

99.63

S3

FSM

S4

S5

S6

S7

S8

S9

Average

90.09 1.77 2.65 2.68 0.66 0.28 0.32 0.16

89.89 1.84 2.71 2.75 0.72 0.27 0.35 0.15

88.36 1.72 2.82 2.65 0.62 0.25 0.32 0.12

85.65 2.15 4.82 3.39 1.98 0.11 0.58 0.23

86.25 1.99 4.75 3.25 2.02 0.11 0.57 0.21

87.32 2.02 4.56 3.35 1.87 0.1 0.41 0.20

87.87 2.47 4.05 2.86 1.10 0.17 0.44 0.16

100.54 98.61

98.68

96.86

98.91

99.15

99.83

99.12

88.65 3.65 4.26 2.64 0.63 0.154 0.45 0.11

Other minor constituents are Al2 O3 (2.47%), Fe2 O3 (4.05%), CaO (2.86%), MgO (1.10%), Na2 O (0.17%), K2 O (0.44%) and SO3 (0.16%). There were slight, but not considerable, variations in the percentages of these constituents in samples from the said mills. For a comparison, the analysis of different types of ashes of different countries along with the present one is presented in Table 7. The table contains analytical result of fly ash (FA), blast furnace slag (BFS) and bagasse ash. All of them may be used as pozzolan in cement manufacturing. The pulverized fuel ash or the so called fly ash (FA), emitted as a particulate matter in the effluent gas of coal based thermal power plants, is a pozzolanic material. The blast furnace slag (BFS) is a waste product, recovered in a granulated form, from the blast furnace manufacturing pig iron in steel plants. The use of these materials, as admixtures to cement, is based on long experience. As can be seen in Table 7, there is a significant difference in the oxide composition of FA and BFS and it also shows considerable regional variations.

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Table 7 Analysis of different types of ashes of different countries Chemical composition S/No

Country

SiO2

Al2 O3 Fe2 O3 CaO

MgO Na2 O K2 O

SO3

LOI

1

Coal fly ash

France UK Germany USA India Japan China

48.1 50.09 1.2 52.24 58.06 59.6 52.3

24.68 6.5 28.1 11.7 29.6 6.8 19.01 15.71 26.4 4.81 31.2 2.3 31.7 4.7

1.41 1.62 3.4 4.48 2.23 1.4 2.13

1.82 1.54 1.2 0.89 0.69 0.5 0.56

0.56 0.28 0.6 0.82 0.4 0.7 0.25

4.06 0.62 3.1 2.05 0.12 0.5 0.47

– – 0.5 1.34 0.28 0.2 0.51

11.7 1.27 3.3 0.92 5.39 – 4.5

2

Blast France furnace UK slag Germany USA India Japan

25 35 35 34 31.61 32.7

12 16 12 10 21.53 13.4

43 40 42 41 34.71 41.6

8 6 7 11 7.12 6.9

– – – – 0.49 0.2

– – – – 0.36 0.30

0.9 1.7 1.3 1.3 0.1 0.3

– – – – 0.72 0.6

3

Bagasse ash

1.65 1.10

0.12 0.17

3.46 0.44

– 0.16

0.42 13.45

Brazil 78.34 3.55 Pakistan 87.87 2.47 (Present work)

2.0 0.8 0.3 0.8 0.95 0.5

3.61 2.15 4.05 2.86

In Portland cement (PC), the close relationship between the chemical and the mineralogical composition generally holds. However, it is not so in case of mineral admixtures. It is only when the siliceous and the aluminous materials present in these pozzolanic admixtures hydrate at slow rate in alkaline medium, to furnish silica and alumina for the reaction with lime, that the formation of cementitious products take place. This characteristic of these substances give them a considerable importance in concrete formation. This is contrary to the hydration of Portland cement, where the principal silicates (C3 S and C2 S) and aluminte (C3 A), present essentially in the crystalline form, react with water to provide desired silica and alumina for the formation of cementitious compounds. Hence, while evaluating the suitability of mineral admixtures for blended cement, their mineralogical composition will has to be considered together with the chemical composition. Table 8 compares the chemical analysis of Portland cement with the analysis of bagasse ash made in the present study. A careful observation on Table 8 reveals that the bagasse ash contains all the ingredients those are present in cement, this strengthen the possibility of bagasse ash to be used as a part of cement admixture. However, there is one major problem in Table 8 Chemical analysis of portland cement and bagasse ash Admixtures

SiO2

Al2 O3

Portland cement Bagasse ash

21.55 5.69 87.87 3.60

Fe2 O3 3.39 4.90

CaO

MgO Na2 O K2 O SO3

64.25 0.85 2.56 0.69

0.33 0.15

0.59 0.47

2.47 0.11

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the present untreated samples of bagasse ash that they contain about 16% unburned carbon which may affect the cement strength. This problem can be overcome by adding the bagasse ash as a raw mix during the clinkering process. This can be advantageous in two ways; one the unburned carbon will supplement the energy requirement needed for clinkerization and secondly, it will render the bagasse ash free of carbon. The remaining residue will be an addition to the cement as a raw mix. Both of these advantages will entail in reduction in the cost of production of cement. However, since the composition of bagasse ash does not match with that of each corresponding constituent of the cement, therefore, a careful and intelligent raw mix designing must be made in order to make the addition of bagasse ash compatible to the cement composition without affecting the strength and quality of the cement. This needs an additional, carefully designed, experimental work which is underway in our laboratory.

5 Conclusion Bagasse ash analysis from sugar industry shows that it contains unburned carbon, and all constituents present in Portland cement. Thus, this ash can be added as a mix in cement manufacturing during the clinkerization. It will help to reduce the remediate the environmental pollution problem and reduce the cost of production of cement.

References 1. Valenti M (1995) Using fly ash for construction. Mech Eng 117(5):82–86 2. Al-Amoudi OSB, Maslehuddin M, Asi IM (1996) Performance and correlation of the properties of fly ash cement concrete. Cement Concrete Aggregate 18(2):71–77 3. British Standards Institution (1995) Specifications for pozzolanic pulverized fuel ash cement, BSI, Milton keynes, BS 6610 4. Saraswathy V, Muralidharan S, Thangavel K, Srinivasan S (2002) Activated fly ash cements: Tolerable limit of replacement for durable steel reinforced concrete. Adv Cement Res 14:9–16 5. Thomas MDA, Shehata MH, Shashiprakash SG (1999) The use of fly ash in concrete. Classification by composition. J Cement, Concrete and Aggregates. 12(2):105–110 6. Goni S, Guerrerl A, De Luxan MP, Macias A (2000) Dehydration of pozzolonic products hydro thermally synthesized from fly ashes, microstructure evolution. Materials Research Bulletin 7. Guerrero, A., Goni, S., Macias, A. (2000) Durability of new fly ash belite cements mortar in sulphated and chloride medium. Cement Concrete Res 30:1231–1238 8. Kameshwara Rao B, Arvind Kumar J (1998). The role of fly ash in minimizing cement content in concrete. Proceedings of National Seminar on Cement Content and Parameters for Durability of Concrete, organized by Maharashtra India 9. Bhatty JI, Gajda J, Miller FM (2001) Use of high-carbon fly ash in cement manufacture. Cement Americas May/June 32–34, 1, 2001 10. Bhatty JI, Gajda J, Miller FM (2000) Use of high-carbon Illinois fly ash in cement manufacturing demonstration phase ICCI project number: 99-1/2.1A-1 Nov 1, 1999 through Oct 31, 2000

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11. Bhatty JI, Gajda J, Miller FM (2002) High carbon fly ash in cement manufacturing. A commercial demonstration. 27th International technical conference on coal utilization & fuel systems, sheraton sand key, Clearwater, Florida, Mar 3–7, 2002 12. Shi C, Day RL (2001) Comparison of different methods for enhancing reactivity of Pozzolans. Cement Concrete Res 31(5):813–818 13. Waste treatment and recycling equipment ebara corporation 1-6-27, Konan, Minato-ku, Tokyo, Japan, 2001, 108–8480 14. Waste treatment and recycling equipment, Ebara Corporation, 1-27, Konan, Minato-ku, Tokyo, Japan, 2003 15. Shi C (2002) Activation of slag, fly ash and natural Pozzolan. Proceedings of 5th International Symposium on Cement and Concrete, vol. 2. Shanghai, China, Oct 28–Nov 31, 2002, pp 691–697 16. Wang R, Trettin V, Rudert R (2003) Umlauf recrystallization of granulated blast furnace slag and the significance for the hydraulic Reactivity. Institute for Building and Material Chemistry, Siegen University, Wilhelm Dyckerhoff Institute for Building Material Technology. Advances in Cement Research 15:29–33 17. Ali I (2004) Biomass: An ideal fuel for sugar mills for steam/power generation. Fuel Research Centre, PCSIR, Karachi, XVII(197), Dec

Adsorption of Different Reactive Dyes onto Surfactant-Modified Zeolite: Kinetic and Equilibrium Modeling Bulent Armagan, Mustafa Turan, and Dogan Karadag

Abstract This study deals with the kinetic and equilibrium modeling of adsorption of the commercially important reactive azo dyes, Black B (C.I. Reactive Black 5), Red 3BS (C.I. Reactive Red 239) and Yellow 3RS H/C (C.I. Reactive Yellow 176) onto a Turkish zeolite mineral. To increase the adsorption capacity of the zeolite, the surface of natural samples was modified with a typical quaternary amine surfactant hexadecyltrimethylammonium bromide (HTAB). A series of batch adsorption tests were carried out at 298 K and the pseudo-first–order, pseudo-second-order kinetic models and intraparticle diffusion model were used to evaluate the kinetic data. The pseudo-second-order model provided excellent kinetic data fitting (R2 > 0.997) for these three dyes. The free energy changes G for dye adsorption onto HTAB-zeolite were calculated. The negative values of G indicate that the adsorption process is spontaneous and thermodynamically favorable. The Freundlich and Langmuir equations were also applied to describe the equilibrium isotherms for three reactive dyes and isotherm constants were determined. The Langmuir model agrees very well with experimental data while the adsorption behavior of all reactive dyes is favorable (0< RL < 1). Keywords Adsorption capacity · Cationic surfactant · Kinetics · Reactive dye · Zeolite

1 Introduction The effluents of wastewater in the textile industry contain various kinds of synthetic dyestuffs. Reactive azo dyes are extensively used in dyeing processes in textile industry and as much as 40% of these dyes remain in the effluents [1]. A large B. Armagan (B) Environmental Engineering Department, Engineering Faculty, Harran University, 63300 Sanlıurfa, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_116,

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number of reactive dyes are azo compounds that are linked by an azo bridge. The dyes are therefore released into the environment in the form of colored wastewater. This can lead to acute effects on exposed organisms due to the toxicity of the dyes, abnormal coloration and reduction in photosynthesis because of the absorbance of light that enters the water. Since reactive dyes are water soluble, their removal from wastewater is difficult by conventional coagulation and the activated sludge processes [2, 3]. A variety of physicochemical methods have been proposed for the removal of colored and colorless organic pollutants from textile wastewater. Adsorption process is one of the effective methods ro remove dyes from wastewater by using suitable adsorbents [4, 5]. Activated carbon and polymer resins appear to be the best adsorbents for removing chemicals from relatively concentrated wastewater [6–9]. However, these adsorbents are not only high cost but they also have a rather low effect against some reactive dyes. Nevertheless, several investigators reported studies on cost-effective adsorbent systems. They included peat [10], chitosan [5, 11], fly ash [12], turba [13], wood chips [14], fruit wastes [15], sunflower stalk [16], shale oil ash [4], sugar beet [17], olive-mill wastes [18], dry active sludge [19], diatomita [20], and natural or modified minerals such as montmorillonite [21–23], zeolite [24–26], sepiolite [23, 27, 28], bentonite [29–31]. Zeolite mineral has a three dimensional crystal structure and its typical unit cell formula is given either as Na6 [(AlO2 )6 (SiO2 )30 ] 24H2O or (Na2 , K2 , Ca, Mg)3 [(AlO2)6 (SiO2 )30 ] 24H2 O [26]. The structure of zeolite contains channels which embody some ion exchangeable cations such as alkali (sodium, potassium, lithium and caesium) and/or alkaline earth (calcium, strontium, barium and magnesium). These exchangeable cations give rise to the ion-exchange properties of the material [32]. The goal of the present study is to explore the adsorption kinetic and isotherm of three reactive dyes namely Reactive Black 5, Red 239 and Yellow 176 onto natural and HTAB-zeolites. The adsorption rates were determined by using the pseudo-first–order (lagergren), pseudo-second-order kinetic models and intraparticle diffusion model. The Freundlich and Langmuir equations were used to fit the equilibrium isotherm.

2 Experimental 2.1 Adsorbent and Dyes A Turkish natural zeolite (clinoptilolite) sample used in the experiments was received from Manisa, Turkey. It was crushed, grounded, sieved below 63 μm and dried at 105◦C in an oven for 2 h before use. The zeolite have the following properties: cation exchange capacity of 1.9–2.2 eq/kg, pore diameter of 4×10−10 m, purity of 92%, bed porosity of 40%, density of 2150 kg/m3 , apparent density of 1300 kg/m3, and suspension pH of 7.5–7.8. The chemical analyses of the zeolite were summarized in Table 1 [24].

Adsorption of Different Reactive Dyes onto Surfactant-Modified Zeolite Table 1 Chemical properties of the zeolite [24]

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Parameter

Value

SiO2 , % CaO, % K2 O, % SO3 , % AI2 O3 , % MgO, % TiO2 , % P2 O5 , % Fe2 O3 , % Na2 O, % Loss of Ignition, %

70.0 2.5 2.3 0.01 14.0 1.15 0.05 0.02 0.75 0.2 9.02

Since the reactive dyes have negative sulfonate groups and zeolite sample surfaces were negatively charged, a quaternary amine, Hexadecyltrimethylammonium bromide (HTAB, C19 H42 BrN), was used for modifying the surface of zeolite. HTAB was purchased from SIGMA and specified to be of 99% purity with a molecular weight of 346.46 g [33]. The reactive dyes marketed by Everlight Chem. Ind. Corp. of Taipei are anionic azo dyes: Black B (C.I. Reactive Black 5), Red 3BS (C.I. Reactive Red 239) and Yellow 3RS H/C (C.I. Reactive Yellow 176). These three dyes are all known to contain anionic sulfonate groups to various degrees. The chemical structures of Reactive Black 5 and Reactive Red 239 were made available by the supplier, as illustrated in Fig. 1.

OH NaO3SOCH2CH2O2S

N=N

NH2 N=N

NaO3S

SO3Na (a)

(b)

Fig. 1 Chemical structures of (a) reactive black 5 and (b) reactive red 239

SO2CH2CH2OSO3Na

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2.2 Adsorption Experiments Adsorption kinetic experiments for natural and HTAB-zeolite were undertaken by a batch equilibrium technique by placing a known quantity of the adsorbent in a glass bottle containing 25 mg L−1 of an aqueous solution of zeliote with a predetermined concentration. After such solution preparation, the bottles were placed on an orbital shaker at 400 rpm at room temperature for 4 h followed by centrifugation at 4000 rpm for 10 min. The equilibrium concentrations of dyes were respectively determined at 592, 400, and 540 nm for Black 5, Yellow 176 and Red 239 dyes, respectively, using a visible spectrophotometer. The calibration curves for each dye at the respective wavelengths were established as a function of dye concentration. The reproducibility of the data varied in the range of ±1.5%. The adsorption capacity was calculated by the following formula: qe =

(Ci − Ce ).V m

(1)

where qe = Amount of dye adsorbed by adsorbent (mg g−1 ), Ci = initial dye concentration (mg L−1 ), Ce = equilibrium or residual dye concentration (mg L−1 ), V = the volume of the solution (L), and m = mass of adsorbent (g). Distilled and deionized water with a conductivity value of 2.10−6 mhos cm−1 was used in all experiments.

3 Results and Discussion 3.1 Adsorption of Different Dyes The effect of conditioning (contact) time on adsorption capacity of natural zeolite was studied in batch experiments at an initial dye concentration of 25 mg L−1 and adsorbents (solids) concentration of (50 g L−1 ) 5% for three reactive dyes. Figure 2 presents the dynamic adsorption of three different dyes onto natural zeolite. The adsorption capacity increases with increasing the contact time and then it approaches equilibrium after 240 min. For the different dyes, equilibrium adsorption is quite different. As seen from Fig. 2, the adsorption follows the order of Black 5 >Red 239 >Yellow 176 above equilibrium time while in the order of Yellow 176 > Red 239 >Black 5 below equilibrium time. The adsorption capacity of natural zeolite was changed between 0.164−0.180 mg g−1 in the range from 300 to 500 min (Fig. 2). The difference in adsorption for three dyes is probably ascribed to the varying molecular size and the exothermic process during the adsorption [5]. Since the reactive dyes have negative sulphonate groups, they are repelled by the negatively charged zeolite surface [24, 26]. This induces a relatively low adsorption capacity, as shown in Fig. 2. Therefore, to neutralizes the negative charges, the surface of natural zeolite was modified with hexadecyltrimethylammonium bromide (HTAB) which is a cationic surfactant. A comparison of natural and modified zeolites at 5% solids concentration indicated that modification of zeolite with HTAB

Adsorption of Different Reactive Dyes onto Surfactant-Modified Zeolite

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0,35

adsorption capacity, mg/g

0,3 0,25 0,2 0,15 0,1 Yellow Black Red

0,05 0

0

100

200

300 time, min.

400

500

600

Fig. 2 Adsorption capacities of reactive dyes versus time onto natural zeolite (solids concentration = 5%, Ci = 25 mg/l, natural pH 6.5)

substantially improves the adsorbability of reactive dyes. However, a precipitation formation was observed above Ce =10 mg L−1 dye concentration in HTAB–zeolite system [24]. Since no precipitation is formed at and below 0.1% solids concentration for all dye concentrations, kinetic and equilibrium studies of HTAB-zeolite were conducted at 0.1% solids concentration. Dye adsorption rate onto HTAB-zeolite is fast before 60 min and then it approaches equilibrium after 200 h (Fig. 3). It can be said that beyond this there is almost no further increase in the adsorption. The curve of dye adsorption appears smoother than that of natural one. The equilibrium adsorption for Red 239, Yellow 176 and Black 5 will be around 15, 14.50 and 14.16 mg/g, respectively (Fig. 3). Below and above equilibrium time, the adsorption capacity indicated different trend for different dyes. Below equilibrium time, Yellow dye showed more rapid increase than the others, thus, the adsorption follows the order of Yellow 176 > Red 239 > Black 5. Above equilibrium time, this order changed as Red 239 > Yellow 176 > Black 5. The slower the initial adsorption rate becomes, the longer the equilibrium time requires [5].

3.2 Kinetics of Dye Removal The mechanism of adsorption depends on the physical and/or chemical characteristics of the adsorbent as well as on the mass transport process. The pseudo-first-order, pseudo-second-order kinetic models and intraparticle diffusion model were used to find out the mechanism of adsorption. The pseudo-first-order kinetic model is given as

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adsorption capacity, mg/g

16 14 12 10 8 6 4

Black Red

2

Yellow

0 0

100

200

300 time, min.

400

500

600

Fig. 3 Adsorption capacities of reactive dyes versus time onto HTAB-zeolite (solids concentration = 0.1%, Ci = 25 mg/l, natural pH 6.5)

log (qe − qt ) = log qe −

k1 t 2.303

(2)

where qt is the amount of dye sorbed (mg g−1 ) at time t (min); qe is the amount of dye sorbed at equilibrium (mg g−1 ) and k1 is the equilibrium rate constant of pseudo-first-order adsorption (min−1 ). The slopes and intercepts of plots of log (qe −qt ) vs time were used to determine the first order rate constant k1 . This model was successfully used to describe the kinetics of many adsorption systems [10, 34]. The adsorption kinetics may also be described by the pseudo-second-order model [35, 36]. The linearized-integrated form of this model is

t 1 1 = + t qt k2 .q2e qe

(3)

where k2 is the rate constant of pseudo-second-order adsorption. The slopes and intercepts of plots of t/qt vs. t were used to calculate the second-order rate constant k2 and qe . The intraparticle diffusion model can be presented as follows [5] √ q t = kd t

(4)

−1 −1/2 ). where kd is the rate constant of intraparticle diffusion adsorption √ (mg g min The kd is the slope of straight line portions of plot of qt vs. t. The three models were applied to the adsorption of the three reactive azo dyes by natural zeolite; the results are presented in Figs. 4, 5, and 6, respectively. In order to quantify the applicability of each model, the correlation coefficient, R2 , were calculated from these plots. Table 2 lists the results of rate constant studies for

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three reactive dyes by pseudo-first–order, pseudo-second-order kinetic models and intraparticle diffusion model. As can seen from Table 2, the correlation coefficient, R2 are between 0.780 and 0.945 at the first order kinetic model. These results show that the R2 value of Red 239 is greater than that of the others. For the second order model, R2 values of three reactive dyes are higher than that of the first order model and intraparticle diffusion model. In other words, the dynamical data fitted well with the second order kinetic model because R2 is greather than 0.968. Besides, in 0 –1

log (qe-q)

–2 –3 –4 –5 –6

Black Red

–7 –8

Yellow

0

100

200

300 time, min.

400

500

Fig. 4 Dye uptake by natural zeolite according to the pseudo first order model

Fig. 5 Dye uptake by HTAB-zeolite according to the pseudo first order model

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Fig. 6 Pseudo-second-order kinetic plots for the adsorption of azo dyes onto natural zeolite

the pseudo-second-order model, the correlation coefficient, R2 of Black 5 is greater than that of the others. However, the equilibrium adsorption capacity, qe cal. for the pseduo-first-order kinetic model is close to the second order model [37]. The qe cal. values of the first order model are also decreased from 0.514 to 0.227 mg g−1 for Yellow 176, Red 239 and Black 5, respectively. However, there does not appear to be a general second best model to describe all the adsorption systems. The second best model to generate a good fit to the experiment is the intraparticle diffusion model, followed by the pseudo-first-order kinetic model for these reactive dyes. Adsorption capacities of HTAB-zeolite for the three dyes were also plotted in Figs. 7, 8, and 9 respectively. In order to quantify the applicability of each model, the correlation coefficient, R2 , was calculated from these plots (Table 2). The correlation coefficients, R2 , showed that the pseudo-second-order reaction model fitted better with the experimental data (R2 > 0.997) than the pseudo-first-order model (R2 is in the range of 0.873–0.988) and the intraparticle diffusion model (R2 is in the range of 0.888–0.931). However, the qe cal. values of the pseudo-first-order model were found negative and showed a desorption. In the pseudo-second-model, the values of the qe cal are changed from 14.79 to 16.05 mg g−1 for Yellow 176, Black 5 and Red 239, respectively. From the results, it is also seen that the equilibrium adsorption from the pseudo-second-order model are much close to the experimental data (Table 2, Fig. 3), suggesting the better application of the second order kinetics [5, 37]. While the intraparticle diffusion model showed a good fit to the experimental data better than the pseudo-first-order kinetic model for Red 239, the pseudo-first-order model has a better performance than the intraparticle diffusion model for Black 5 and Yellow 176.

Reactive Red 239 Reactive Yellow 176 Reactive Black 5 Reactive Red 239 Reactive Yellow 176 Reactive Black 5

Natural zeolite Natural zeolite

HTABZeolite

Natural zeolite HTABzeolite HTABzeolite

Adsorbant

Zeolite

0.227 −0.0313 −0.1480 −2.87×10−3 0.988

2.7×10−2

1.08 ×10−2

6.91×10−3

8.29×10−3

0.973

0.873

0.793

0.780

0.514

1.75×10−2

0.945

0.389

1.15×10−2

R2

1.38×10−3

3.84×10−3

1.972×10−3

7.78 ×10−2

4.79 ×10−1

9.9 ×10−2

15.40

14.79

16.05

0.206

0.166

0.195

0.997

0.999

0.999

0.998

0.968

0.986

R2

5.0×10−1

2.9×10−1

4.7×10−1

6.9×10−3

1.6×10−3

5.2×10−3

0.931

0.888

0.892

0.967

0.922

0.949

R2

kd (g mg−1 min−1 )

qe cal. (mg.g−1 )

k2 (g mg−1 min−1 )

k1 (g mg−1 min−1 ) qe cal. (mg g−1 )

Intraparticle diffusion model

Pseudo-second-order kinetic model

Pseudo-first-order kinetic model

Table 2 Comparison of the first-order, second-order adsorption and intraparticle diffusion rate constants with the calculated qe for Reactive Black 5, Reactive Red 239, Reactive Yellow 176

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Fig. 7 Pseudo-second-order kinetic plots for the adsorption of azo dyes onto HTAB-zeolite

0,25

(t)1/2 (min1/2)

0,2 0,15 0,1 Black Red Yellow

0,05 0 0,00

5,00

10,00 15,00 time, min.

20,00

25,00

Fig. 8 Diffusion model plots for the adsorption of azo dyes onto natural zeolite

On the other hand, to characterize the actual rate-controlling step involved in the dye sorption process, the sorption data were further analyzed using the kinetic expression given by Boyd et al. [38, 39]. F =1−

6 exp(−Bt) π2

(5)

where F is the fraction of solute adsorbed at time t and Bt is a mathematical function of F and given by

Adsorption of Different Reactive Dyes onto Surfactant-Modified Zeolite

1247

20 18 16

(t)1/2, (min 1/2)

14 12 10 8 6

Black

4

Red

2

Yellow

0

0

5

10

15

20

25

time, min.

Fig. 9 Diffusion model plots for the adsorption of azo dyes onto HTAB-zeolite

F=

qt qe

(6)

where, qt and qe represents the amount adsorbed (mg/g) at time t and at equilibrium, respectively. In this study, we take qe from the second-order kinetic model. Substituting Eq. 6 into Eq. 5, the kinetic expression becomes

qt Bt = −0.4977 − ln 1 − qe

(7)

Thus the value of Bt can be calculated for each value of F using Eq. 7. The calculated Bt values were plotted against time as shown in Fig. 10. The linearity of this plot will provide useful information to distinguish between external-transportand intraparticle-transport-controlled rates of adsorption. From Fig. 10, it was observed that the plots were linear and passed origin for Black 5 and Red 239. But the curve of Yellow 176 did not pass through the origin. If a plot of Bt vs time t is a straight line passing through the origin, then adsorption is governed by a particle-diffusion mechanism, otherwise it is governed by film diffusion. The free energy change (G) and equilibrium constant (Kc ) were determined by using the following equations [5, 29]: Kc = (

CAe ). Ce

G = −RT ln Kc

(8) (9)

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B. Armagan et al. 5 4,5 4 3,5

Bt

3 2,5 2 1,5 1 Black Red Yellow

0,5 0 – 0,5

0

50

100

150

200 250 time, min.

300

350

400

450

Fig. 10 Corelationship between Bt and t of various dye adsorption onto HTAB-zeolite Table 3 Free energy change and equilibrium constant for dye adsorption onto HTAB-zeolite at 298 K Adsorbate

KC , Equilibrium constant

G, (kJ mol−1 )

Reactive Red 239 Reactive Yellow 176 Reactive Black 5

1.50 1.40 1.31

−0.67 −1.01 −0.67

where KC is the equilibrium constant, CAe is the amount of dye (g) adsorbed on the adsorbent per dm3 of the solution at equilibrium, Ce is the equilibrium concentration (g/dm3) of the dye in the solution, T is the solution temperature of Kelvin (K) and R is the gas constant and is equal to 8.314 J mol−1 K−1 . The qe cal. of the pseudo-second-order model in Table 2 was used to obtain CAe = Ci −Ce . Kc and G were calculated from Eqs. (8) and (9) respectively and the results are listed in Table 3. The negative values of free energy changes G indicate that the adsorption of the three reactive dyes onto HTAB-zeolite is spontaneous and thermodynamically favorable. Besides, the change in free energy for physisorption is between −20 and 0 kJ mol−1 ; chemisorption has a range of −80 to −400 kJ mol−1 [9, 29]. The calculated G values were obtained to be between −0.67 and −1.01 kJ mol−1 for the there reactive dyes and this could be considered as physisorption.

˙ 3.3 Adsorption Isotherms Adsorption isotherm data of Reactive Black 5, Red 239 and Yellow 176 dyes were investigated to fit the models of Freundlich and Langmuir. The well-known

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expression of the Freundlich model describes adsorption in terms of the sorbate concentration and is given as $ qe = KF . [n]Ce

(10)

where KF and n are Freundlich constants as indicators of adsorption capacity and adsorption intensity, respectively. The following linearized form of the Freundlich isotherm model can be used to obtain the values of the Freundlich constant:

1 ln qe = ln KF + . ln Ce n

(11)

The intercept and the slope of the linear plot of ln qe versus ln Ce at given experimental conditions provide the values of KF and 1/n, respectively (Fig. 11). The Freundlich model is applied to describe heterogeneous systems and is not restricted to the formation of monolayers [29]. On the other hand, the capacity of HTAB-zeolite for the three types of reactive dyes is also analyzed according to the Langmuir equation as follows:

qe =

KL .b.Ce 1 + b.Ce

(12)

One of the linearized forms of Eq. 12 is:

Ce qe

1 = + KL

b KL

.Ce

(13)

6 5

Inqe

4 3 2 Black Red Yellow

1 0 –1

0

1

2

4

3

5

6

7

InCe

Fig. 11 Freundlich plots for the adsorption of three reactive dyes onto HTAB-zeolite

8

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B. Armagan et al. 18 16 14

Ce/qe, g/l

12 10 8 6 Yellow Black Red

4 2 0

0

200

400

600

800

1000

Ce, mg/l

Fig. 12 Langmuir plots for the adsorption of three reactive dyes onto HTAB-zeolite

where b = Langmuir constant and KL = qmax. .b= Langmuir constant. As seen from Fig. 12, when Ce /qe is plotted against Ce, the Langmuir model fits the data very well. While the value of (b/KL ) gives the slope of the line, (1/KL ) yields the intersection of the line with the Ce /qe axis. It should be noted that Langmuir model has two significant limitations such as the adsorbate and solvent molecules should be of the same size and the adsorbate layer is limited to a monolayer [24, 29]. Since no significant adsorption capacities were obtained for natural zeolite, therefore, isotherm studies were performed for HTAB-zeolite with high adsorptive capacity. In the Freundlich model, plots of ln qe vs ln Ce for the adsorption of three reactive dyes onto HTAB-zeolite was employed to generate the intercept value of KF and the slope of 1/n. On the other hand, the Langmuir model was applied to this HTAB-zeolite system and the values of qmax. , KL and b are calculated. The values of qmax. , KL , KF , b, 1/n and the correlation coefficients for Langmuir and for Freundlich are given in Table 4.

Table 4 Parameters of the Freundlich and Langmuir Isotherm for Three Reactive Dyes Langmuir constant Adsorbate Reactive Red 239 Reactive Yellow 176 Reactive Black 5

Freundlich constant KF (Lg−1 )

1/n (L mg−1 )

R2

0.833 0.98

1.74

1.45

0.86

0.008

0.526 0.97

1.62

1.52

0.78

0.036

0.816 0.99

3.10

1.90

0.84

qmax (mg g−1 )

KL (Lg−1 )

b (L mg−1 )

RL

111.11

0.919

0.009

88.50

1.364

60.61

0.458

R2

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The Langmuir model appear to fit the experimental data better than the Freundlich model as reflected with the correlation coefficients in the range of 0.97–0.99. The values of Freundlich constant, 1/n, are in the range of 1.45–1.90. If the value of 1/n is larger than 1, the adsorption bond becomes weak, unfavorable adsorption take place, as a result of the adsorption capacity decreases [29]. Besides, the area occupied by HTAB is found to be 1.96 nm2 /molecule and the cross-sectional area of an amine molecule reported as 3.782 nm2 /molecule, thus, the surface coverage (θ ) is found to be 2.0. However, the applicability of the Langmuir isotherm suggests a monolayer coverage; surface coverage as a bilayer rather than a monolayer has a strongly favorable influence on the dye uptake [27]. Consequently, the Langmuir equation agrees very well with the equilibrium isotherm for the three different dyes. The main properties of the Langmuir isotherm can be expressed in terms of dimensionless constant separation factor RL which is given as: RL =

1 1 + bCi

(14)

The value of RL indicates the type of the isotherm to be either unfavorable (RL > 1), linear (RL = 1), favorable (0< RL < 1), or irreversible (RL = 0). Under the same conditions, the adsorption capacity decreases in the following manner: Reactive Red 239> Reactive Black 5 > Reactive Yellow 176. The RL values reported in Table 4, show that the adsorption behavior of all reactive dyes was favorable (0< RL < 1).

4 Conclusions The results of present study indicate that HTAB-zeolite prepared low-cost natural zeolite is an effective adsorbent for reactive dye removal from aqueous solutions. HTAB-zeolite showed a higher adsorption capacity than natural one. For the different dyes, equilibrium adsorption is quite different. The adsorption capacity of HTAB-zeolite for three dyes follows an order of Red 239 >Yellow 176 >Black 5 above equilibrium time while in the order of Yellow 176 > Red 239 >Black 5 below equilibrium time. The pseudo-second-order model for HTAB-zeolite fitted better with the experimental data (R2 > 0.997) than the pseudo-first-order model (R2 < 0.988) and intraparticle diffusion model (R2 < 0.931). The sorption process is particlediffusion-controlled for Black 5 and Red 239, while film-diffusion controlled for Yellow 176. The calculated G values were obtained to be between −0.67 and −1.01 kJ mol−1 for the there reactive dyes and this could be considered as physisorption. The Langmuir model appear to fit the experimental data better than the Freundlich model as reflected with the correlation coefficients (R2 > 0.97). The

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applicability of the Langmuir model suggests a monolayer coverage, surface coverage as a bilayer rather than a monolayer has a strongly favorable influence on the dye adsorption.

Nomenclature aL = b= Bt = CAe = Ci = Ce = F= k1 = k2 = kd = KC KL = KF = m= qe = qt = V= = R= RL = T=

Langmuir isotherm constant (l/mg) Langmuir constant Mathematical function of F Amount of dye (g) adsorbed on the adsorbent per dm3 of the solution at equilibrium Initial dye concentration (mg L−1 ) Equilibrium concentration (g/dm3, mg L−1 ) of the dye in the solution Fraction of solute adsorbed Equilibrium rate constant of pseudo-first-order adsorption (min−1) Rate constant of pseudo-second-order adsorption (min−1) Rate constant of intraparticle diffusion adsorption (mg g−1 min−1/2) Equilibrium constant (l/g) Langmuir isotherm constant (l/g) Freundlich constants (l/g) mass of adsorbent (g) Equilibrium solid-phase concentration (mg/g) The amount of dye sorbed (mg g−1 ) Volume of solution (ml) Adsorption density (mg/g) Gas constant, 8.314 J mol−1 K−1 Dimensionless constant separation factor Solution temperature of Kelvin (K)

References 1. Allen SJ (1996) Types of adsorbents materials. In: McKay G (ed) Use of adsorbents for the removal of pollutants from wastewater. CRC, Boca Raton, FL, USA, pp 59–97 2. Al-Qodah Z (1998) Adsorption of methylene blue with diatomite. J Eng Technol 17:128–137 3. Al-Qodah Z (2000) Adsorption of dyes using shale oil ash. Water Res 34:4295–4303 4. Arbeloa FL, Arbeloa TL, Arbeloa IL (1997) Spectroscopy of rhodamine 6G adsorbed on sepiolite aqueous suspensions. J Colloid Interface Sci 187:105–112 5. Armagan B, Ozdemir O, Turan M, Celik MS (2003) The removal of reactive azo dyes by natural and modified zeolites. J Chem Technol Biotechnol 78:725–732 6. Arma˘gan B, Özdemir O, Turan M, Çelik MS (2003) Adsorption of negatively-charged azo dyes onto surfactant–modified sepiolite. J Environ Eng ASCE 129:709–715 7. Aksu Z (2001) Biyosorption of reactive dyes by dried activated sludge: Equilibrium and kinetic modelling. Bichem Eng J 7:79–84 8. Bousher A, Shen X, Edyvean RGJ (1997) Removal of colored organic matter by adsorption onto low-cost materials. Water Res 31:2084–2092

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9. Chaoa L, Zhaoyangb L, Aiminb L, Weib L, Zhenmaob J, Jinlongb C, Quanxingb Z (2005) Adsorption of reactive dyes onto polymeric adsorbents: effect of pore structure and surface chemistry group of adsorbent on adsorptive properties. Sep Purif Technol 44:91–96 10. Chiou MS, Li HY (2002) Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads. J Hazard Mater B 93:233–248 11. Chiou MS, Li HY (2003) Adsorption behaviour of reactive dye in aqueous solution on chemical cross-linked chitosan beads. Chemosphere 50:1095–1105 12. Englert AH, Rubio J (2005) Characterization and environmental application of a chilean natural zeolite. Int J Miner Process 75:21–29 13. Gharaibeh SH, Abu-el-sha’r WY, Kofihi MM (1998) Removal of selected heavy metals from aqueous solutions using processed solid residue of olive mill products. Water Res 32:498–502 14. Hasany S, Saeed M, Ahmed M (2000) Adsorption isotherms and, thermodynamic profile of Co(II)—SCN complex uptake on polyurethane foam. Sep Sci Technol 35:379–394 15. Haggerty GM, Bowman RS (1994) Sorption of chromate and other inorganic anions by organo-zeolite. Environ Sci Technol 28:452–458 16. Hermosin MC, Martin P, Cernejo J (1993) Adsorption mechanims of monobutyltin in clay minerals. Environ Sci Technol 27:2606–2611 17. Ho Y, Chinag C (2001) Sorption studies of acid dye by mixed sorbents. Adsorption 7:139 18. Hu QH, Qiao Z, Haghseresht F, Wilson MA, Lu GQ (2006) Adsorption study for removal of basic red dye using bentonite. Ind Eng Chem Res 45:733–738 19. Juang RS, Lin SH, Tsao KH (2002) Mechanism of sorption of phenols from aqueous solutions onto surfactant-modified montmorillonite. J Colloid Interface Sci 254:234–241 20. McKay G (1983) The adsorption of dyestuffs from aqueous solution using activated carbon: analytical solution for batch adsorption based on external mass transfer and pore diffusion. Chem Eng J 27:187–196 21. McKay G, Allen SJ, McConvey IF, Walters JHR (1984) External mass transfer and homogeneous solid-phase diffusion during the adsorption of dyestuffs. Ind Eng Chem Process Des Dev 23:221–226 22. McKay G, Ho YS (1999) The sorption of lead (II) on peat. Water Res 33:578–584 23. McKay G, Ho YS (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465 24. Nollet H, Roels M, Lutgen P, Meeren PVD, Vestraete W (2003) Removal of PBCs from wastewater using fly ash. Chemosphere 53:655–665 25. Nassar MM, Majdy YH (1997) Removal of different basic dyes from aqueous solutions by adsorption on palm-fruit bunch particles. Chem Eng J 66:223–339 26. Lin CC, Liu H (2000) Adsorption in a centrifugal field: Basic dye adsorption by activated carbon. Ind Eng Chem Res 39:161–167 27. Ozcan AS, Erdem B, Özcan A (2004) Adsorption of acid blue 193 from aqueous solutions onto Na-bentonite and DTMA-bentonite. J Colloid Interface Sci 280:44–54 28. Ozacar M, Sengil IA (2003) Adsorption of reactive dyes on calcined alunite from aqueous solutions. J Hazard Mater B98:211–224 29. Pearcea CI, Lloydb JT, Guthriea JT (2003) The removal of colour from textile wastewater using whole bacterial cells: A review. Dyes Pigments 53:179–196 30. Rytwo G, Nir S, Crepsin M, Margulies L (2000) Adsorption and interactions of methyl green with montmorillonite and sepiolite. J Colloid Interface Sci 222:12–19 31. Sun G, Xu X (1997) Sunflower stalks as adsorbents for color removal from textile wastewater. Ind Eng Chem Res 36:808–812 32. Turan M, Arma˘gan B, Özdemir O, Celik MS (2004) Mesoporous mineral columns for color removal from aqueous solutions. J Environ Sci Health A 39:2221–2228 33. Yıldız N, Gönül¸sen R, Koyuncu H, Çalımlı A (2005) Adsorption of benzoic acid and hydroquinone by organically modified bentonites. Colloids Surf A Physicochem Eng Asp 260:87–94

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Water Quality Index for Municipal Water Supply of Attock City, Punjab, Pakistan Humera Qasim Khan

Abstract Water Quality Index has been calculated in this paper for the municipal water of Attock city. This calculation was carried out using recent water quality data collected from thirty sampling station. For the calculation of water quality index, six parameters were taken in account pH, Total Dissolve Solids, Dissolved Oxygen, Electrical Conductivity, Nitrates and Sulphate. The calculated values of WQI for thirty sampling stations range from 109.2 to 142.1. The average value is found to be 127.56. The value of water quality index exceeds 100, the upper limit for drinking water at all sampling stations. It was due to high Total Dissolve Solids, Dissolved Oxygen and Nitrates in municipal water. The present study reveals that the municipal water of Attock City needs some treatment in order to get fit for the human consumption and also to avoid some health hazardous also. Keywords Groundwater · Pakistan · Water Quality Index

1 Introduction Water chemistry plays a vital role in interpretation of geological environment, source, direction, recharge, movement, climatic influence, presence of ore bodies and source of contamination (both anthropogenic and natural) for ground water. More important the determination of physical and chemical properties of water is essential for assessing the suitability of water for various uses like drinking, domestic, industrial and agricultural [1]. The quality of drinking water is of vital concern for human health and life. History reveals that drinking water caused water borne diseases, which wiped out entire population of the cities. The menace of the water borne disease and epidemic still looms large on the horizon on the developing

H.Q. Khan (B) National Center of Excellence in Geology, University of Peshawar, Peshawar, Pakistan e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_117,

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H.Q. Khan

countries. According to WHO survey, 60% diseases in the Asian countries are water borne. The major pollution sources are domestic and industrial waste from urban rural industrial areas, discharged into natural water bodies. The agricultural revolution has resulted in increased soil loss, erosion and downstream sedimentation. The study conducted by several agencies and available data that both highly toxic chemicals and microbiological organisms generally contaminate drinking water in Pakistan [2]. WHO recorded 315 case of water borne disease out of 100,000 in Pakistan [3, 4]. Ground water plays an important role in human development and is important natural resources. The hydrochemical characteristics of water determine usefulness for municipal, commercial, industrial, agricultural and domestic water supply. With urbanization, industrialization and rapid growth in world in world population, man has manipulated the natural hydrological cycle both quantitively and qualitatively. The study of water quality involves a description of occurrence of various constituents in water use. The growing awareness that chemical constituents are an integral part of hydrologic system has lead to greater emphasis on determining relationship between dissolves pollutants and other hydrologic parameters [5]. Water systems in Pakistani cities are often poorly maintained, and their pipes sometimes run near waste water outlets. Deaths from water contamination are common. Nearly half of Pakistan’s population about 160 million lack access to proper sanitation, and 40% of hospital beds are occupied by victims of waterborne diseases, according to a recent government study [6]. According to Pakistan Council of Research in Water Resources (PCRWR), Draft safe Drinking Water Act, “In Pakistan the most common water borne disease are Typhoid, Cholera, Hepatitis, Giardiasis, Dysentery and other intestinal disturbances ”. Globally 80% of the children deaths are attributed to water borne diseases. Nitrate is the upcoming pollutant in drinking water. Main contributors of this ion are Fertilizer use, leachates from refuse dumps; domestic effluents decayed vegetable and animal matter, industrial discharges, and atmospheric wash out. A maximum of 10 mg/l of Nitrate, Nitrogen is permissible. Higher level of Nitrate causes Methemoglobinemia, a pathological condition caused by chemical interference with the Oxygen transfer mechanism of the blood. It may be caused in infants by drinking water, high in Nitrate content. Symptoms of this disease are the infant looks blue and has shortness of breath.12.8% of the samples fall under this category [7]. Rapid urbanization especially in developing countries has affected the availability and quality of water a renewable resource – due to it’s all over exploitation and improper waste disposal, especially in urban areas. It is necessary therefore, to regularly monitor the quality of water and to advise ways and means to protect it [6]. Water quality index is one of the most effective ways to communicate information on the quality of water to concerned citizens and the policy makers. A water quality index may be defined as “a rating reflecting the composite influence of a number of water quality parameters on the overall quality of water”. Much efforts has been directed the formulation especially in developed countries, towards the definition of criteria for water quality and formulation of Water Quality Indices [8].

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2 Study Area In this paper, we investigated the quality of ground water of Attock City, situated at the distance of 15 km in southwestern direction of Rwp-Pesh GT road. The town lies from 33◦ 46 to 33◦ 49 N latitude and 72◦20 to72◦ 30 E longitude. The town is located on sandy plain in potohar plateau. The northern side of Attock is comprised of plain sandy area, where non-irrigated agricultural activity is predominant. Two important streams originated from north and enter into the town on eastern and western side. Haro River flow at a distance of 3–5 km in the southeast of the town. There are non-perennial torrents, fed up by monsoon rains. The average height of Attock is between 1150 and −1200 feet above mean sea level. The water table is generally too low. The total rainfall during last year has been recorded 311 mm or 12.25 in.. Generally the soil of the Attock town is sandy but it turned into alluvial in the southern part and continues up to Kalachitta range. The area between the town and Kalachitta is full of deep Georges, stream sediments termed as barani land. It is well known that quality of ground water is a function of the predominant type of rocks found in the region. The general texture of soil of Attock is light i.e. sandy loam. The ground water is one of the principal sources of the industrial, public and rural supplies in Attock regions. It is essential, either direct or indirect, to almost all activities of human beings. In addition to its use in household activities it is tremendous use for irrigational purposes.

3 Calculation of Water Quality Index In order to calculate the water quality index, 30 water samples of ground water were collected from Attock City. These samples were analyzed for six water quality parameters. To calculate the Water Quality Index the following parameters were analyzed i.e. pH, Total Dissolved Solids, Sulphate, Nitrates, Electrical Conductivity and Dissolved Oxygen. The results are given in Table 1. The above data was analysed by MINITAB 11 software and a statistical distribution is given below in the Table 2. Correlation coefficient is a commonly used measure to establish the relationship between two variables. It is simply a measure to exhibit how well one variable predicts the other. The correlation matrices for 6 variables were prepared and it illustrated that EC showed a good positive correlation with TDS. The other showed no significant correlation among the variables (Table 3). The drinking water standards for these six parameters recommended by World Health Organization (WHO) are given in the second column of Table 4 [9]. The method to be followed here for calculating the weighted arithmetic water quality index is as following: In the first place, the more harmful a given pollutant of water, the smaller in magnitude is its standards for drinking water, so the unit weight wI for the ith Parameter P1 is assumed to be inversely proportional to its recommended standards Si (i=1,2,3,4. . .n)

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H.Q. Khan Table 1 Results of municipal water samples

Sample IDs

pH

Conductivity

Nitrates

Sulphates

TDS

DO

1M 2M 3M 4M 5M 6M 7M 8M 9M 10 M 11 M 12 M 13 M 14 M 15 M 16 M 17 M 18 M 19 M 20 M 21 M 22 M 23 M 24 M 25 M 26 M 27 M 28 M 29 M 30 M

8.01 7.91 7.9 7.98 7.91 7.8 7.86 7.67 7.67 7.58 8 7.94 7.86 7.83 7.75 7.83 7.58 7.31 7.73 7.78 7.76 7.96 7.85 7.67 7.21 7.52 7.88 7.39 7.44 7.39

579 566 546 566 566 542 536 553 573 655 563 575 546 567 565 573 560 667 557 527 566 512 574 567 549 546 519 518 635 679

11.9 12.6 11.6 11.9 11.8 8.6 11.2 11.8 11.9 15.6 11.8 12.3 13.9 12.9 11.5 11.2 10.6 14.3 10.5 10.9 11.2 11.1 9.9 10.8 13.7 10 10 9.8 12.5 12.8

37.6 38 42.4 40.8 41.2 28.4 29.6 42.4 40.8 48.8 43.2 49.2 36.2 48 39.2 34 37.6 20 40.4 33.6 44.8 36.8 45.2 41.2 49.2 37.2 46 42 16 85.2

434.25 424.5 409.5 424.5 424.5 406.5 402 414.75 429.75 491.25 422.25 431.25 409.5 425.25 423.75 429.75 426.75 500.75 417.25 395.25 417 384 430.25 425.25 411.75 409.5 389.25 388.5 376.25 509.25

4.09 1.09 4.1 4.18 4.18 4.14 4.14 4.04 4.13 4.12 4.15 4.09 3.92 4.11 4.09 4.14 4.12 4.13 4.09 4.12 4.14 4.02 4.12 3.58 3.13 3.98 4.11 4.04 3.7 3.4

Table 2 Statistical distribution of observed data

pH Conductivity Nitrates Sulphates TDS DO

Mean

Median

St dev

Min

Max

Q1

Q2

7.732 568.23 11.687 40.5 422.81 3.913

7.79 566 11.7 40.8 423 4.11

0.217 40.74 1.473 11.46 30.42 0.586

7.21 512 8.6 16 376.25 1.09

8.01 679 15.6 85.2 509.25 4.18

7.58 546 10.75 36.65 408.75 4.01

7.902 573.25 12.525 44.9 429.75 4.133

n= no. of parameters (6 in this study) wi = k/Si = i/Si where k is the constant of proportionality and is equal to unity. The unit weight wI for the for the six water quality parameter are shown in Table 4.

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Table 3 Correlation of physicochemical parameter of municipal water

E.Conductivity Nitrates Sulphate TDS DO

pH

EC

Nitrates

Sulphate

TDS

−0.430 −0.247 −0.075 −0.287 0.111

0.621 0.205 0.819 −0.090

0.139 0.560 −0.218

0.442 −0.117

−0.050

Table 4 Water quality parameters their standards and unit weight Parameter (Pi)

Standards (Si)

Unit weight (wi )

pH Total dissolve solids Sulphates Nitrates Electrical conductivity Dissolve oxygen

7.0–8.5 500 mg/l 250 mg/l 10 mg/l 1000 3 mg/l

0.005 0.002 0.004 0.1 0.001 0.333

The relation gives the water quality rating qi for the ith Parameter P1, for all the parameters except pH qi = 100 (Vi/Si) where Vi is the observed value of the ith Parameter and Si is its recommended standards for drinking water. For pH, the quality rating qpH can be calculated from the relation qp H

= 100[(VpH 7.0)/1.5]

Finally, the water quality index can be calculated by taking the weighted arithmetic mean of the quality ratings qi , thus WQI = [ (qi.wi / wi )]

4 Results and Discussion The present study is aimed at the calculation of water quality index of ground water of Attock City. For this purpose 30 samples were collected from the area under study (Fig. 1). These 30 samples were analyzed in laboratory for 6 parameters (pH, TDS, DO, Nitrates, Sulphates and Electrical Conductivity) and the water quality index was calculated for all the 30 samples. A sample calculation for WQI for the first

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H.Q. Khan Table 5 Sample calculation of the water quality index for sample 1 M Parameters (Pi)

Average value (Vi)

Quality rating (qi ) Sub index (qi .wi )

PH TDS DO SO4 NO3 EC

7.73 568.23 11.68 40.5 422.80 3.913

2.67 86.85 136.3 15.04 119 57.9

Table 6 Water quality index for the municipal water supply of Attock city

2.67 0.173 45.399 0.060 11.9 0.0579

Sample IDs

WQI

1M 2M 3M 4M 5M 6M 7M 8M 9M 10 M 11 M 12 M 13 M 14 M 15 M 16 M 17 M 18 M 19 M 20 M 21 M 22 M 23 M 24 M 25 M 26 M 27 M 28 M 29 M 30 M

135.4 129.4 129.1 130.7 131.4 124.3 122.3 132.1 130.4 137.7 142.1 130.3 130.7 132.7 131.7 122.7 134.7 134.9 130.7 127.9 130.1 125.8 125.7 114.7 109.2 122.4 125.5 124.1 120.1 114.8

sample is shown in detail in Table 4. In this Table 6 quality parameters are listed in the first columns, while there average values are given in second column. The third column shows the quality rating qi for these parameters, while the last column gives

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Water Quality Index

160 150

Observed WQI

140 130 120 110 100 90 80 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Standard WQI

Fig. 1 Water quality index standard value verses samples results

the sub indices. The water quality index value for the first sample is 119.51. In the way, the WQI’s of Sambalpur was calculated using the recent data of Patnaik and co-workers [10]. WQI for all 30 sample of Attock city may be calculated. Result are shown in Table 5. WQI = [ (qi. wi / wi )] = 135.41

The numerical value of water quality index implies that the water under consideration is fit for human consumption if it is WQI < 100 and is unfit for drinking without treatment if it is WQI > 100. Moreover, the larger the value of WQI, the more polluted the water concerned. In the present study, keeping in view the properties of WQI, the study reveals interesting and important information about the quality of ground water in Attock City. The overall quality of the ground water of this town is reflected in the average value of WQI, which is found to be 127.56. It means that the water needs some treatment to make it fit human consumption. Secondly, the individual values of WQI range from a minimum value of 109.2 to maximum of 142.1. It is clear from the Table 6 that WQI exceeds 100 in all samples. The high values of the WQI are mainly due to high value of total dissolved solids, nitrates and DO in the ground water.

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5 Conclusion Clean and whole some drinking water is an essential requirement for a healthy life. There are many potential sources of contamination with pathogens and toxic chemicals and the control and treatment of drinking water has evolved to combat these threats. The complexity of water pollution in surface and ground water is due to several processes occurring simultaneously like variation in the nature and flow rate of effluents, chain of reactions and their products. In this study the concentration of nitrate ions were above the permissible level both for human and animal consumption level. The increasing concentration of these ions in water makes unsuitable not only for domestic purposes but also for aquatic animals in river. No appreciable contamination of sulfates was observed in bore, municipal and river water.

6 Recommendation On the basis of study carried out the following recommendations are made: • Municipal water must be thoroughly monitored physiochemical so that precise source of pollution can be sorted out. • Public awareness regarding water pollution must be carried out as a part of environmental education program. • Strict environmental laws are needed to implement.

References 1. Dara SS (1997) A text book of environmental chemistry and pollution control. S. Chand and Company, New Delhi 2. Nature power people citizen’s report on sustainable development (1995). Islamabad: Sustainable Development Policy Institute. p 67 3. Khan H, Khan HM, Sheikh IM (1999) Eng Horiz 135(19) 4. Yaseen M, Khan MS, Zaidi SS (1987) Sci Technol Develop 43(6) 5. Manivasakhan N (1997) Physiochemical examination of water, sewage and industrial effluents, 3rd edn, Meerut: Pragati, Pratashan 6. Tiwari TN, Kayak S (2000) Environ Pollut Res 5(2):97–101 7. Tariq S (2000) Environmental geochemistry of surface and subsurface water & soil in Peshawar basin. NWFP, Pakistan 8. Naih A, Naih PK (1997) Indian J Earth Sci 22(90) 9. WHO (1998) Guidelines for drinking water quality, Reference from URL, http://www.who.int/water-santation-health-GWQ.index.html 10. Patnaik A, Sinha BK, Sahoro HK (1997) Indian J Environ Protect 17:415

Reaction Kinetics of Spent Reactive Dye Bath Ozonation Process T. Ölmez, I. Kabda¸slı, and O. Tünay

Abstract Oxidation of a spent reactive dye bath containing a mixture of Remazol brand dyes as well as two main inorganic additives was carried out using ozone and decolorization was obtained in a relatively short time (10–30 min) and ozone utilizations were between 329 and 1609 mg. The spent dye bath oxidation could not be represented by any simple kinetics. Ozonation kinetics and decolorization character was evaluated using synthetic samples with dyes and assisting chemicals. Synthetic Dye Sample decolorization was achieved in 90 s with ozone utilization of 32 mg. NaCl addition decelerated the decolorization rate and increase the ozone utilizations. Na2 CO3 addition resulted in high pH and alkalinity and changed the mechanism of ozonation process as well as decolorization reactions yielding a better oxidation than that of the sample containing only NaCl. Keywords Color removal · Dye bath additives · Ozonation · Reactive dye bath · Textile finishing industry

1 Introduction Color in textile industry wastewaters has long been recognized as an environmental problem. However, little attention has been paid to color since it was considered only a problem of aesthetics. Color, depending on its origin, is not only a problem of aesthetics but may indicate toxicity and reduced biodegradability [4, 5, 15]. Although there are several physical-chemical methods applied for color removal such as adsorption and membrane processes. Chemical oxidation has become the method of choice due to its high efficiency and ease of operation. Ozone isone

T. Ölmez (B) Civil Engineering Faculty, Environmental Engineering Department, Istanbul Technical University, Ayaza˘ga Kampüsü, 34469, Maslak, Istanbul, Turkey e-mail: [email protected]

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of the most effective oxidant used for this purpose. Ozone oxidation of textile industry wastewaters, spent and simulated dye baths has been a focus of investigations [3, 6, 9, 10]. Mechanism and kinetics of ozonation of synthetic dye solutions were also extensively studied [11–13, 17]. Namboodri et al. [9, 10] studied ozonation of disperse dyes Red 13 and Blue 60. Complete decolorization of both dyes has been obtained between 40 and 60 s while more than 50% color removal was realised within first 20–30 s. It was noted that pH was lowered and conductivity was increased during ozonation. Namboodri et al. [9, 10] studied the effect of dyeing additives on oxidation of disperse Red 60. EDTA, levelling ester blends and organic defoaming agents were found to increase ozone requirement and to extend the ozonation time required to remove color. Perkins et al. [11] found the effect of pH between 4–10 insignificant on ozone oxidation of disperse dyes. Namboodri et al. [9, 10] found that 6 different direct dyes could be completely decolorized within 20 s. Gähr et al. [4] studied decolorization of 6 reactive dyes. They noted that color removal rates decreased as the dye concentration increased. They explained this tendency as the further oxidation of reaction intermediates. The authors also determined that alginate thickeners and urea did not affect the oxidation rate, while water glass accelerated the decolorization. The effect of pH was explained by the change in the oxidation mechanism. Actual dye baths involve the use of several assisting chemicals in addition to dyes. Basic chemicals used in reactive dyeing are NaCl, Na2 CO3 and sequestering agents. NaCl is used to facilitate diffusion of the dye to the fiber. Na2 CO3 mostly has a dual purpose: it helps the fixing of the dye and increasing and buffering the pH. Sequestering agents are chelate forming ligands that bind the metal ions such as Cu2+ , Fe2+ , and prevent their interference with dye. In this study, oxidation of a reactive dye bath of a mixture of three Remazol brand dyes and contained several organic and inorganic additives was carried out using ozone. The dye bath sample was synthetically prepared and the effect of NaCl and Na2 CO3 on ozonation kinetics and decolorization was experimentally evaluated.

2 Experimental Study 2.1 Experimental Approach The reactive dye bath samples (Spent Bath I and II), on which the experiments were conducted, reactive dyes and other additives of spent dye bath were provided from a local textile industry. The initial composition of dye baths are given in Table 1. The general structure of remazol brand reactive dyes is given in Fig. 1. The water solubilising group (ionic groups, often sulphonate salts), which has the expected effect of improving the solubility, since reactive dyes must be in solution for application to fibres. The bridging group links the cromophore group and the fibre-reactive group. Frequently the bridging group is an amino, −NH−, group. The fibre-reactive group

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Table 1 The composition of reactive dye baths

Bath volume Amount of fabric Supra Yellow 3R Remazol Red RB Remazol Black B Black HFGR Chikazol Orange 3R NaCl Na2 CO3 Acetic acid Chelating agent

Fig. 1 Structure of Remazol brand reactive dyes

Unit

Spent bath I

Spent bath II

l kg mg/l mg/l mg/l mg/l mg/l g/l g/l g/l g/l

300 20 130 213 320 – – 55 8 1.75 2

3000 150 – – – 2500 585 59 7.8 2.7 2

Water-solubilising Group

Bridging Group Cromophore Group

Fibre-reactive Group

is the only part of the molecule able to react with the fibre. Cromophore group have structures of azo, antraquinon and phtalocyanin. The Synthetic Dye Sample was the dye solution, which was prepared as per the initial composition of Spent Bath I and contained only a mixture of dyes. This solution was then diluted to obtain the color as Pt-Co Unit of the actual spent bath. Dye assisting chemicals of NaCl and Na2 CO3 were added to Synthetic Dye Sample one component at a time to reach the composition given in Table 1. Synthetic Dye Sample and the samples which were prepared by addition of NaCl and Na2 CO3 has been separately ozonated and kinetic evaluations were made. The data obtained from these experiments were utilized to characterize the mechanism and rate of spent dye bath ozonation process. In this evaluation spent Bath II sample was selected as a concentrated one having high initial color to facilitate the assessment of the course of reactions and their kinetics. Ozone feed rate was experimentally selected for both spent bath and synthetic samples and an optimum applied ozone dose between 64 and 72 mg/min was used for all experiments. Oxidation experiments of spent baths and synthetic dye samples were conducted at original pH of the samples. Color was measured by the method of Pt-Co unit. This method is quite useful in monitoring the decolorization particularly, through the end of the oxidation reaction, because at this stage most of the dyes exhibit a yellowish hue whose maximum absorbance fit well the reading absorbance wavelength (λ) of the Pt-Co method.

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3 Materials and Methods Ozone was provided using GL-1 brand PCI Model ozone generator that was fed with air at the capacity of 0.57 m3 /h. All connections in the experimental set up were made using Teflon fittings. The ozonation reactor was made of Pyrex glass with 4.5 cm internal diameter and 120 cm height. The ozone-air mixture was fed through the sintered glass diffusers placed at the bottom of the reactor. Off-gas ozone was trapped using two serially connected gas-washing bottles containing 2% KI solution. The sample volume was taken as one liter in all experiments. Color measurement was carried out on samples filtered through 0.45 μm Millipore membrane filters and was made using HACH-Dr-B model spectrophotometer. All analyses were made in accordance with Standard Methods [16].

4 Results and Discussion 4.1 Oxidation Applications Table 2 presents the results of Spent Bath I and II oxidations with ozone. As can be seen from the Table, 88% color removal was obtained in the first 5 minutes and almost complete decolorization was reached in 30 minutes for both samples. The amount of ozone utilized at the end of the experiment for Spent Bath I was 950 mg while it was 1609 mg for Spent Bath II sample. The amount of ozone fed for complete decolorization of dye baths was reported between 0.29–5.4 g/l [3, 4, 10, 12, 18]. The pH decreased during the course of the oxidation reaction as a result of formation of oxidation products such as carboxylic acids. However due to the high buffer capacity of the spent bath samples pH remained above 9.5 during the experiments. The results of Spent Bath I and II oxidation experiments could not be represented by any simple kinetics due to the complex matrix of the spent baths. However the results can be compared to oxidation studies conducted on samples containing the components of spent baths. Table 3 shows the results of ozone oxidation of Synthetic Dye Sample. 90% color removal was achieved in 60 s. The ozone required for this color removal was 28 mg. The oxidation experiment was conducted at the original pH of the sample. As can be seen from the results the pH decreased rapidly during the first 30 s. It can be said that the main reaction that caused decolorization was the direct attack of ozone molecule to the chromophore group of the dye at this pH. In ozonation applications where semi-batch reactors with ozone bubbling from the bottom of the reactor are used, the reaction takes place at the gas-liquid interface [12, 18]. The direct reaction of ozone is assumed to be first order with respect to the organic matter (dye) and ozone [1, 7, 18]. As the reactions occurred in acidic pH (3.0), the rate of decolorization, exclusively due to the direct reaction with ozone, can be expressed as follows:

11.66 11.33 11.21 11.08 – – 11.00

2500 280 60 35 − − 0

− 88 98 99 − − 100

− 359 720 1078 1438 1798 2158

– 221 329 424 – – 950

− 340 681 1021 − − 2044

− 358 661 893 1156 1361 1609

Utilized O3 (mg)

0 300 600 900 1200 1500 1800

Color removal (%)

Applied O3 (mg)

Color (Pt-Co unit)

Utilized O3 (mg)

Applied O3 (mg)

Time (s)

pH

Spent Bath II

Spent Bath I

Table 2 Results of spent bath I and II oxidation with ozone

11.64 11.77 11.37 10.75 10.26 10.04 9.88

pH

40000 5000 1200 600 350 120 90

– 88 97 98.5 99 99.7 99.77

Color Color removal (Pt-Co unit) (%)

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T. Ölmez et al. Table 3 Results of synthetic dye sample oxidation with ozone

Time (s)

Applied O3 (mg)

Utilized O3 (mg)

pH

Color (Pt-Co unit)

Color removal (%)

0 30 60 90 120 150

31 63 92 127 158

22 28 32 38 39

6.03 3.14 2.89 2.94 2.92 2.90

2500 900 250 60 35 30

– 64 90 98 99 99

r=−

d [C] = k [O3 ] [C] dt

(1)

where C is the color of the sample in Pt-Co unit, O3 is the ozone concentration in the liquid and k is the rate constant of the direct reaction. If ozone concentration is assumed to reach a stationary concentration at the bubble interface Eq. 1 becomes a pseudo first-order kinetic equation: r=−

d [C] = k [C] dt

(2)

where k = k [O3 ]

(3)

# Following integration of Eq. 2, a plot of −ln C C0 versus time gives a straight line where the slope of the line is k . Figure 2 shows the plot corresponding to the oxidation experiments of the Synthetic Dye Sample.

5.0 ln (C/C0) = - 0.0416t + 0.107

– ln(C/Co)

4.0

R2 = 0.9947

3.0 2.0 1.0

Fig. 2 Pseudo first-order reaction kinetic of synthetic dye sample

0.0 0

10

20

30

40

50 Time (s)

60

70

80

90

100

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Table 4 Results of NaCl added synthetic dye sample oxidation with ozone Time (s)

Applied O3 (mg)

Utilized O3 (mg)

pH

Color (Pt-Co unit)

Color removal (%)

0 30 60 90 120 150 600

− 32 64 97 130 162 651

− 12 33 44 50 51 301

6.21 4.48 3.98 4.12 4.04 3.97 4.03

2500 950 410 250 190 160 40

– 62 84 90 92 94 98

For the evaluation of the effect of NaCl and Na2 CO3 , a step by step addition of these assisting chemicals was made to Synthetic Dye Sample. The results of NaCl added Synthetic Dye Sample was given in Table 4. As can be seen from Table 4 oxidation duration and amount of consumed ozone were found different than those of Synthetic Dye Sample. The same percentage of color removal (90%) was achieved in 90 s and the amount of consumed ozone was 44 mg. After the first 30 s, the reaction rate became slower to an extent that the reaction was almost blocked as also indicated by ozone utilizations. NaCl added Synthetic Dye Sample oxidation experiment was also conducted at the original pH of the sample and similar to Synthetic Dye Sample pH decreased for the first 30 s. However the final pH of the sample was around 4.0 that is different than that of Synthetic Dye Sample. Graphical representation of pseudo first-order reaction kinetic of NaCl added Synthetic Dye Sample is given in Fig. 3. The data of first 90 s were used for the calculations because the deceleration in reaction rate was more pronounced after this oxidation duration. Gähr et al. [4] expressed that salt had a slight effect on oxidation of reactive dyes. However, higher ozone utilizations were obtained for the oxidation of NaCl added 5.0 ln (C/C0) = - 0.0258t – 0.1073

–ln(C/C0)

4.0

R2 = 0.981

3.0 2.0 1.0 0.0 0

10

20

30

40

50

60

70

80

90

Time (s)

Fig. 3 Pseudo first-order reaction kinetic of NaCl added synthetic dye sample

100

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Synthetic Dye Sample and this might be attributed to the higher ozone decomposition rate accelerated by the ionic strength. Sotelo and his co-workers [14] indicated that for a given pH, ozone decomposition kinetic rate constant decreased by increasing ionic strength. The decrease in the reaction rate of decolorization might be also attributed to the change of the chromophore group oxidation character of the dyes due to the solution pH. The next step was the addition of both NaCl and Na2 CO3 to Synthetic Dye Sample at concentrations corresponding to Spent Bath I. Oxidation results of this sample are given in Table 5. 90% percent color removal was obtained in 60 s by the utilization of 28 mg ozone similar to Synthetic Dye Sample. As can be also seen from the table after 90 s, the reaction rate became slower similar to NaCl added Synthetic Dye Sample. 50 Pt-Co unit color was obtained in 300 s and 124 mg ozone was utilized for NaCl and Na2 CO3 added synthetic dye sample oxidation experiment. It seems that when NaCl and Na2 CO3 combined, they cancelled their effect out on decolorization. This surprising effect also observed for ozone utilizations which were smaller than NaCl added synthetic dye sample oxidation. Due to the matrix of the solution (high pH and alkalinity) the mechanism of ozonation process as well as decolorization reactions may have changed. The reaction of ozone with substrate may involve both direct and OH• radical type reactions under high pH. The oxidation of a substrate during an ozonation process can be formulated as follows: −

d [C] = kO3 [C] [O3 ] + kOH [C] [OH• ] dt

(4)

where C is the substrate concentration, O3 is the ozone concentration in the liquid, OH• is the concentration of hydroxyl radical, kO3 and kOH are the rate constants for the reaction of C with ozone and hydroxyl radical, respectively. In an ozonation process inhibiting character of the water matrix should also be considered as an important parameter. It has been established that particularly bicarbonate (HCO3 − ) and carbonate (CO3 2− ) ions, which are frequently found in spent reactive dye bath, are among the strongest OH• scavengers (Eqs. 5 and 6) [2]. The contributing term of these substances to the inhibiting character of the water is due to the following reactions: Table 5 Results of NaCl and Na2 CO3 added synthetic dye sample oxidation with ozone Time (s)

Applied O3 (mg)

Utilized O3 (mg)

pH

Color (Pt-Co unit)

Color removal (%)

0 30 60 90 120 150 300 600

32 64 97 130 161 324 650

10 28 41 49 60 124 266

10.96 11.02 11.01 11.01 11.02 11.01 10.97 10.95

2450 1000 230 130 120 110 50 30

– 59 91 95 95 95 98 99

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6 −1 −1 −• • kc1=8.5×10 M s HCO− 3 + OH −−−−−−−−−−−→ CO3 + H2 O

(5)

−• − • kc2=3.9×108 M −1 s−1 CO−2 3 + OH −−−−−−−−−−−→ CO3 + OH

(6)

•

By defining # the ratio of the concentrations of OH (Rc = [OH• ] [O3 ]) Eq. 4 can be rewritten as follows: −

radicals and ozone

d [C] = kO3 + kOH Rc [C] [O3 ] dt

(7)

When ozone is present in excess and ozone concentration in the solution is stable at a certain level during the oxidation reaction, Eq. 7 may be assumed as a pseudo first-order kinetic equation: −

d [C] = ktotal [C] dt

(8)

where ktotal = kO3 + kOH Rc [O3 ]

(9)

Graphical representation of pseudo first-order reaction kinetic of NaCl and Na2 CO3 added Synthetic Dye Sample is given in Fig. 4. Present study is a step in the evaluation of spent bath oxidation responses through the analysis of its components and their vulnerability to oxidation. The first result, being the most important, is that the synthetic dye sample oxidation is a straight forward and a quite fast reaction as compared to spent bath oxidation. Ozone oxidation of the dye solution and combination of the dyes with the main inorganic elements 5.0 ln (C/C0) = - 0.0343t – 0.0077

–ln(C/C0)

4.0

R2 = 0.9751

3.0 2.0 1.0 0.0 0

10

20

30

40

50 60 Time (s)

70

80

90

100

Fig. 4 Pseudo first-order reaction kinetic of NaCl and Na2 CO3 added synthetic dye sample

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of reactive dye baths were observed to be well represented by first order kinetics and their rate constants although had different values found to be in the same order of magnitude. Addition of NaCl, an inert element reduced the rate of decolorization almost to the half of the that of Synthetic Dye Solution while the reaction pH was still acidic. Soda addition raised the pH thus introduced a new mechanism ie radical induced oxidation, although assumed to be significantly suppressed by the scavenging effect of carbonate ions, but the next result was the increase of the oxidation rate approaching to that of dye solution at the pH of spent bath oxidation. Kabda¸slı et al. [8] studied the effect of assisting chemicals in the dye bath on ozonation of dyestuffs. They found out that sequestering agents exerted a significant effect on the ozone oxidation of the dye by reducing the reaction rate and increasing the amount of ozone being used, while NaCl and Na2 CO3 had negligible effect on color removal.

5 Conclusions Results of the study indicated that ozone oxidation of spent dye bath was a complex process which cannot be directly simulated or compared with synthetic dye oxidation process results. Every additive had a different effect on the oxidation mechanism or on the rate of oxidation. Therefore, a wide range of studies conducted on synthetic dye samples, although quite useful, should not be assumed to reflect the dye bath responses to oxidation directly. Oxidation of single ingredients could be followed by simple kinetics. However the spent dye bath oxidation exhibited a more complex pattern that can be explained by interactions of the ingredients through the oxidation process. The effect of pH was also significant in determining the mechanism and rate and of the process. Further studies are required to reveal in a more detailed way the mechanism of spent bath oxidation and to be able to model the process more accurately.

References 1. Bertran FJ, Garcia-Araya JF, Acedo B (1994) Advanced oxidation of atrazine in water-I. Ozonation. Water Res 28:2153–2164 2. Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical-review of rate constants for reactions of hydrated electrons, hydrogen-atoms and hydroxyl radicals (.oh/.o-) in aqueoussolution. J Phys Chem Ref Data 17:513–886 3. Carrière J, Jones P, Broadbent AD (1993) Decolorization of textile dye solutions. Ozone Sci Eng 15:189–200 4. Gähr F, Hermanutz F, Oppermann W (1994) Ozonation – An important technique to comply with new German Laws for textile wastewater treatment. Water Sci Technol 30(3):255–263 5. Goronszy MC, Tomas H (1992) Characterization and biological treatability of textile dyehouse wastewater. In: Proceedings of the 47th Industrial Waste Conference, Purdue University, West Lafayette, Indiana, USA, pp 743–764 6. Grau P (1991) Textile industry wastewaters treatment. Water Sci Technol 24:97–103

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7. Hoigné J, Bader H (1976). The role of hydroxyl radical reactions in ozonation processes in aqueous solutions. Water Res 10:377–386 8. Kabda¸slı I, Ölmez T, Tünay O (2002) Factors affecting colour removal from reactive dye bath by ozonation. Water Sci Technol 45(12):261–270 9. Namboodri CG, Perkins WS, Walsh WK (1994) Decolorizating dyes with chlorine and ozone: Part I. Am Dyestuff Repor Mar 18–22 10. Namboodri CG, Perkins WS, Walsh WK (1994) Decolorizating dyes with chlorine and ozone: Part II. Am Dyestuff Repor Apr 17–26 11. Perkins WS, Judkins JF, Perry WD (1980) Renovation of dye bath water by chlorination or ozonation. Textile Chem Colorist 12(8):27/182–32/187 12. Perkins WS, Walsh WK, Reed IE, Namboodri CG (1995) A demonstration of reuse of spent dyebath water following color removal with ozone. Textile Chem Colorist 28(1):31–37 13. Snider EH, Porter JJ (1974) Ozone destruction of selected dyes in wastewater. Am Dyestuff Repor Aug 36–48 14. Sotelo JL, Beltran FJ, Benitez FJ, Beltran-Heredia J (1989) Henry’s law constant for the ozone-water system. Water Res 23:1239–1246 15. Stahr RW, Boepple CP, Knocke WR (1980) Textile waste treatment colour removal and solids handling characteristics. In: Proceedings of the 35th Industrial Waste Conference, Purdue University, West Lafayette, Indiana, USA, pp 187–199 16. Standard Methods for the Examination of Water and Wastewater (1998) (20th edn) American Public Health Association/American Water Works Association/Water Environment Federation, Washington DC, USA 17. Teramoto M, Imamura S, Yatagai N, Nishikawa Y, Teranishi H (1981) Kinetics of the self decomposition ozone and the ozonation of cyanide ion and dyes aqueous solutions. J Chem Eng Jpn 14(5):383–388 18. Whu J, Wang T (2001) Ozonation of aqueous azo dye in a semi-batch reactor. Water Res 35:1093–1099

Copper Adsorption from Aqueous Solutions by Usıng Red Mud – An Aluminium Industry Waste Semra Çoruh and Osman Nuri Ergun

Abstract Rapid inustriliazation and usage of heavy metals in industrial process have resulted in an unprecedented increase in the flux into groundwater and industrial effluents. The removal of heavy metal ions from industrial wastewaters using defferent adsorbents is currently of great interest. Adsorption by red mud is investigated as possible alternative to the conventional methods of copper removal from aqueous synthetic and industrial effluents. In this study, various factors such as particle size, red mud/solution ratio, contact time and initial concentration for copper removal using red mud are taken into account, and promising results are obtained. The results indicate that the red mud can be successfully employed for the removal of Cu2+ in a wide range concentrations. Keywords Copper removal · Adsorption · Red mud

1 Introduction The increasing levels of heavy metals in the environment represent a serious threat to human health, living resources and ecological systems. Although there are many sources of heavy metals, some industrial sectors, namely metal plating, minning, painting are at present those which contribute the most to environmental pollution with these toxic metals [1, 7]. Copper and zinc, for example, are higly toxic as they are carcinogens and mutagens in nature. Morover, high intakes of these metals can cause liver, kidney and pancreas damage. The maximum allowable limit for both metals in discharged water was set by the Environmental Protection Agency (EPA) to be 1.3 and 5 mg/l, respectively [6, 14, 18]. To attain these values different remediation techniques for treatment of wastewater can be applied. Among the many methods available to reduce heavy metal concentration from wastewater, S. Çoruh (B) Department of Environmental Engineering, Ondokuz Mayıs University, 55139 Samsun, Turkey e-mail: [email protected]

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the most common ones are chemical precipitation, ion-exchange, adsorption, membrane filtration, evaporation, electrolysis and reverse osmosis [9, 17]. The removal heavy metal pollutants at high concentrations from water can be readily accomplished by chemical precipitation or the elecktrochemical method. The chemical precipitation method is widely used for removal of heavy metal from wastewater because of its simplicity and low cost. However, this method has some disadvantages due to its production of a large volume of metallic sludge, which is costly and hazardous to dispose of. At low concentrations, removal of such pollutants is more effectively implemented by ion exchange or adsorption on solid sorbents such as activated carbon or coal fly ash. The use of activated carbon is stil very popular and different grades are available, but are quite expensive and the regeneration of the carbon is not always possible. Aconsiderable research work has been done in the search of inexpensive adsorbents especially developed from various industrial waste materilas i.e. fly ash, metal hyroxides, blast furnace slag, biomass, bagasse pith, bagasse fly ash, red mud, cement kiln dust, waste slurry and sawdust [3, 8, 10, 16]. Red mud is a waste material formed during the production of alumina when the bauxite ore is subjected to caustic leaching. It is a brick red colored highly alkaline (pH 10–12) sludge containing mostly oxides of iron, aluminum, titanium and silica. Red mud, due to its aluminum, iron and calcium content, has been suggested as a cheap adsorbent for removal of toxic metals (e.g., As, Cr, Cu, Zn, Pb, Cd) as well as for water or wastewater treatment. Addition, this material has been extensively investigated to decrease nutrient export, mainly P, to sensitive waterways and improve agricultural productivity [5, 12, 13]. In this study, copper removal from aqueous solutions was investigated by using red mud as an adsorbent. The effects of particle size, red mud/solution ratio, contact time and initial metal concentrations on adsorption capacity were experimentally studied.

2 Material and Methods 2.1 Materials Bauxite, one of the abundant minerals, mainly consists of aluminium and iron oxide and is widely processed for alumina production. During production in the Konya Seydi¸sehir Aluminium Plant, Turkey approximately 40% of the processed bauxite ore becomes waste with the major contents of Fe2 O3 , Al2 O3 , SiO2 , Na2 O, TiO2 , CaO as well as minor constitutions of V, Ti, Zr; Se, etc. The sample was sieved into the following particle sizes: −250+125, −125+90, −90+63, −63+45 and −45+20 μm. The chemical composition of red mud material is presented in Table 1. The mineralogical analysis conducted by means of SEM Fig. 1 indicated hematite, sodalite, cancrite, diaspore, boehmite, rutile and quartz.

Copper Adsorption from Aqueous Solutions Table 1 Chemical composition (wt.%) of the copper flotation waste, red mud and clinoptilolite

1277 Constituent

% (w/w)

SiO2 Fe2 O3 Al2 O3 a TiO2 CaO CO2 SO3 Na2 O P2 O5 LOIa

15.64 36.24 20.10 4.76 2.68 2.93 0.056 9.99 0.023 8.39

a Loss

on ignition

Fig. 1 Scanning electron microscopic (SEM) micrograph of red mud

2.2 Preparation of Metal Solution Metal ion solutions were prepared according to Standart Methods. Stock copper solutions were prepared by dissolving of CuCl2 .2H2 O analytical grade in distilled water APHA [2]. The samples collected at different stages of copper removal studies were acidified to pH 2 and analyzed on a UNICAM model 929 AAS for the copper removal efficiencies.

2.3 Experimetal Studies The influences of particle size, contact time, amount of material and initial metal concentration in solution were investigated. Experiments were conducted in 250 ml erlenmeyer flaks containing known Cu2+ synthetic solutions. The effect of the red mud amount, which provided the optimum removal efficiency for a constant red

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mud particle size, on Cu2+ removal was examined. The solution-red mud mixtures were stirred at 70 rpm at varying time intervals for 5, 15, 30, 60, 90, 120, 180 and 240 minutes to ensure equilibrium at 20±2◦C. The flaks were placed in a rotary mechanical shaker for a particular period of time and shaken gently. After the contact time, the flaks were taken from shaken and the contents filtered trough 0.45 μm membrane filter using a vacum pump and, the concentration of copper in the filtrate was determined using Atomic Absorption Spectrophotometry (AAS).

3 Results and Discussion 3.1 Effect of Particle Size on Copper Removal

Removal Efficiency (%)

Red mud samples with their different particle sizes were stirred with 100 ml of 100 mg/l Cu2+ solutions for 60 minutes. The removal efficiencies of red mud with respect to particle sizes are given in Fig. 2. Figure 2 indicates that decreasing the particle size results little increase in removal efficiency. The differences between the −250+125 μm and −45+20 μm values of the removal efficiencies for red mud were 1.61%, respectively. The initial pH values of the Cu2+ solution and red mud were 3.74 and 8.55, respectively, but, after stirring with red mud, it varied 5.82 and 6.18 for different red mud particle sizes. The literature studies show that decrease in grain size leads to an increase in adsorption capacity, whereas Levya-Ramos et al. [11] report that decreasing the particle size does not increase the adsorption capacity. It is clear from the results of this study that an increase in external surface area has little effect on the internal surface area, thus, it has little effect on copper removal efficiency.

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Fig. 2 Effect of particle sizes of red mud on Cu2+ removal (red mud/solution ration = 10 g/l)

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3.2 Effect of Red Mud/Solution Ratio on Cu2+ Removal At this stage, the removal studies related to different red mud/solution ratios were performed. Red mud samples were stirred with 100 ml of 100 mg/l Cu2+ solution for 60 minutes. The effect of red mud/solution ratios on adsorption of Cu2+ metal ion was investigated. For this purpose, red mud amount was taken between 5 and 40 g/l. The removal results for red mud indicate that removal percentage did not change much with increasing amounts of red mud (Fig. 3). The removal efficiencies for 5, 10, 20, 30 and 40 g/l red mud/solution ratios were found to be 80.94, 98.03, 99.11, 99.4 and 99.9%, respectively. The results show that 10 g/l of the ratio seems to be an optimum value to provide enough removal for 100 ml of the solutions. The pH values were increased by increasing red mud/solution ratios. Initially, the pH value of the Cu2+ solution was 3.75, but after contact with red mud, it varied from 6.43 to 8.12. Red mud is alkaline and contains solid phases to adsorb and fix metals. Therefore, both a pH effect and chemical adsorption/fixation may be involved in the reduction of metal mobility [12, 13, 4].

3.3 Effect of Contact Time Figure 4 shows the adsorption of Cu2+ ions of red mud (10 g/l) as a function of contact time by varying from 5 to 240 minutes for an initial concentration of 100 ml copper metal ion. As can be seen, the percentage of copper removal increases with the contact time up to 30 minutes. After this point there was considerable change in copper removal recovery. More than 95% of the removal was achieved in the first 15 minutes.

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Fig. 4 Effect of contact time on the removal of the copper ions (copper concentration : 100 mg/l, red mud/solution: 10 g/l)

˙ 3.4 Effect of Initial Copper Concentration

Removal efficiency (%)

Copper concentrations to determine the effect of the initial concentration were selected in the range of 12.5 to 200 mg/l for red mud. The effect of concentration on removal efficiency and adsorption capacity was investigated and the results are given in Fig. 5. As shown in Fig. 5, copper removal decreased with the increase in initial copper concentrations. When the initial copper concentration was increased from 12.5 to 200 mg/l, the removal for red mud decreased from 96 to 90%. The red mud exhibits great removal efficiency and adsorption capacity, probably because it contains large amounts of Fe and Al oxides and hydroxides, has large surface area and stabilises the pH at acceptable values [4, 15, 16].

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Fig. 5 Effect of initial copper concentration (red mud/solution ratio: 10 g/l; stirring time: 60 minutes, particle size: −125+90 mm)

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4 Conclusions Red mud, a solid waste material from the aluminum industry, is converted into an adsorbent, and the suitability of the red mud for copper removal from aqueous solution is investigated by batch experiment. The removal of metal ions by this adsorbent takes place by particle diffusion and the thermodynamic parameters reflect the feasibility of the process.. Almost 90–98% of copper adsorption from aqueous solution at an initial concentration of 12.5–200 mg/l was observed. The results indicate that the red mud can be successfully employed for the removal of Cu2+ in a wide range concentrations.

References 1. Alvarez-Ayuso E, Garcia-Sanchez A, Querol X (2003) Purification of metal electroplating waste waters using zeolites. Water Res 37:4855–4862 2. APHA; AWWA; WPCF, Standart Methods for the Examination of Water and wastewater (1985) 16th edn. American Public Health Association/American Water Works Association/Water Environment Federation, Washington, DC 3. Babel S, Kurniawan TA (2003) Low-cost adsorbents for heavy metals uptake from contaminated water: A review. J Hazard Mater B97:219–243 4. Bertocchi AF, Ghiani M, Peretti R, Zucca A (2006) Red mud and fly ash for remediation of mine sites contaminated with As, Cd, Cu, Pb and Zn. J Hazard Mater 134:112–119 5. Erdem E, Karapinar N, Donat R (2004) The removal of heavy metal cations by natural zeolites. J Colloid Interface Sci 280:309–314 6. Ergun ON, Bakan G, Gökbulut NG, Çoruh S (1998) Copper removal from wastewater using zeolitized tuffs, in The Kriton Curi International Symposium of Environmental Management in the Mediterranean Region, Antalya Turkey. Ed. Kocasoy G. Bo˘gaziçi University, vol 2, pp 653–662 7. Faur-Brasquet C, Reddah Z, Kadirvelu K, Cloirec PL (2002) Modelling the adsorption of metal ions (Cu2+ , Ni2+ , Pb2+ ) onto ACCs using surface complexation models. Appl Surface Sci 196:356–365 8. Gupta VK, Gupta M, Sharma S (2000) Process development for the removal of lead and chromium from aqueous solutions using red mud- an aluminium industry waste. Water Res 35(5):1125–1134 9. Hui KS, Cha CYH, Kot SC (2005) Removal of mixed heavy metal ions in wastewater by zeolite 4A and residual products from recycled coal fly ash. J Hazard Mater B127: 89–101 10. Kocaoba S, Akyüz T (2005) Effects of conditioning of sepiolite prior to cobalt and nickel removal. Desalination 181:313–318 11. Levya-Ramos R, Aguilar-Armenta G, Gonzales-Gutierrez LV, Guerrero-Coronado RM, Mendoza-Barron J (2004) Ammonia exchange on clinoptilolite from mineral deposits located in Mexico. J Chem Technol Biotechnol 79:651–657 12. Lombi E, Zhao FJ, Wieshammer G, Zhang G, McGrath SP (2002) In-situ fixation of metals in soils using bauxite residue: Biological effects. Environ Pollut 118:445–452 13. Lombi E, Zhao FJ, Zhang G, Sun B, Fitz W, Zhang H, McGrath SP (2002) In-situ fixation of metals in soils using bauxite residue: Chemical assessment. Environ Pollut 118: 435–443 14. Lopez E, Soto B, Arias M, Nunez A, Rubinos D, Barral MT (1997) Adsorbent properties of red mud and its us efor wastewater treatment. Water Res 12(4):1314–1322

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15. Pradhan J, Das SN, Thakur RS (1999) Adsorption of hexavalent chromium from aqueous solution by using actived red mud. J Colloid Interface Sci 217:137–141 16. Santona L, Castaldi P, Melis P (2006) Evaluation of the interaction mechanisms between red muds and heavy metals. J Hazard Mater 136:324–329 17. Sarioglu M, Atay ÜA, Cebeci Y (2005) Removal of copper from aqueous solutions by phosphate rock. Desalination 181:303–311 18. Shawabkeh R, Al-Harahsheh A, Al-Otoom A (2004) Copper and zinc sorption by treated oil shale ash. Sep Purif Technol 40:251–257

Global Warming: How Much of a Threat to Tropical Forests? Philip M. Fearnside

Abstract Tropical forests area key part of debates on climate change science and policy because of the prospect of large areas of Amazonian forest not surviving projected climate changes under “business as usual” scenarios, the substantial contributions that deforestation and other landscape modifications make to climate change, and the potential role of efforts to counter deforestation as part of a strategy to mitigate climate change in the coming decades. Because half of the dry weight of the trees in a tropical forest is carbon, either deforestation or forest die-off releases this carbon in the form of greenhouse gases such as carbon dioxide (CO2 ) and methane (CH4 ), whether the trees are burned or simply left to rot. Tropical forests are vulnerable to projected changes in precipitation and temperature. These changes could therefore threaten the biodiversity of these forests and the traditional peoples and others who depend upon the forests for their livelihoods. Also threatened are the environmental services supplied by the forests to locations both near and far from the forests themselves. Greenhouse-gas emissions provoked by forest die-off due to climate change are part of a potential positive feedback relationship leading to more warming and more die-off. The Amazon forest is a focus of concern both because of the particularly severe impacts of climate changes predicted for this area and because the vast extent of this forest gives it a significant role in either intensifying or mitigating future climate change (see: http://philip.inpa.gov.br). Keywords Amazon forest · Global warming · Tropical forests

P.M. Fearnside (B) National Institute for Reseach in Amazonia (INPA), C.P. 478, 69.011-970 Manaus-Amazonas, Brazil e-mail: [email protected] Contribution for: Conference on Environment: Survival and Sustainability, 19–24 February 2007, Near East University, Northern Cyprus.

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_120,

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1 Climate-Forest Interaction in Amazonia 1.1 Scenarios Modeled scenarios for future climate in tropical forest areas vary widely, creating corresponding uncertainty regarding both the impacts of climate change and the climatic benefits of keeping the forests standing. However, the wide range of possible outcomes can easily be misleading from a policy perspective for three reasons. First, the range of things that have ever been written or said about these predictions is always much wider than the true range of scientific doubt: studies become obsolete and their predictions of the future are discarded (even by the studies’ own authors), yet the ghost of these results can continue to haunt not only popular but also scientific discussion of the topic for years or decades (see Fearnside [14] for examples in the case of impacts of Brazilian deforestation). Second, there is a strong tendency to fall victim to the “Goldilocks fallacy,” where, when presented with a range of numbers, one naturally assumes that one in the middle will be “just right”; such an assumption is fallacious because it is the quality of the data and of the reasoning used to interpret the data that will determine which of various possible results is the best, and this may well be at either the high or the low end of a range of available estimates (see [22]). Third, the existence of uncertainty commonly provokes the response of “let’s wait and see what the experts decide,” when this uncertainty should instead lead to even more vigorous action based on the precautionary principle (e.g., [43]). At any moment in time, there is always one best value for each parameter in each calculation (together with an associated range of uncertainty), and we must act on the current information. Decisions must be based both the current best value and an allowance for avoiding risks of major impacts from the high ends of the uncertainty ranges. The case of predicted climate change and their impacts on Amazonian forest is a highly relevant example. In 2000, the Hadley Center model of the UK Meteorological office (UKMO) was updated to include various feedbacks that made it predict a catastrophic dieoff of Amazonian forest by the year 2080 under a business-as-usual scenario [11]. Other global climate models, which lacked the same feedbacks, did not indicate any such catastrophe (see review by Nobre [40]. Over the next 5 years, testing of the various models proceeded at Brazil’s Center for Research in Weather and Climate (CPTEC). In November 2005 the conclusion was reached that the Hadley Center’s Had3CM model provided the best fit to the current climate in Amazonia, lending strong support to this most catastrophic scenario as the most likely (J. Marengo, public statement, 2005). Global climate models contain substantially more uncertainty in their predictions of changes in rainfall than for temperature. For Amazonia, the key question is the establishment or not of a permanent El Niño. The disastrous consequences that severe El Niño conditions imply for tropical rainforests are evident from the observed effects of the 1982–1983 El Niño, which produced widespread fires in standing forest in Brazil and Indonesia [29], and these events were repeated on an even larger scale in the same countries during the 1997–1998 El Niño [4, 23].

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The first model to show a massive die-off of Amazonian forest as a result of predicted global warming was the Hadley Center model of the UK Meteorological Office [10, 11]. Under a business-as-usual scenario, the forest is essentially wiped out by the year 2080 (and replaced by a savanna). In 2005, most of the global climate models were revised to include feedbacks that had previously been restricted to the Hadley model, with the result that five out of seven models now show the climate locking into permanent “El Niño-like conditions”, meaning that surface water in the Pacific Ocean warms to levels characteristic of El Niño events today. However, only one model (the Hadley model) replicates the connection between these “El Niño-like conditions” and the actual consequences of an El Niño with reduced rainfall and increased temperature in Amazonia. Unfortunately, the connection between El Niño and Amazonian droughts is something that we know from direct observations, not something that depends on the results of computer models. In other words, when other models show the water in the Pacific warming and nothing happening in Amazonia, this indicates that there is something wrong with those models, not that Amazonia is less at risk. If a high climate sensitivity is assumed, the Hadley Center model indicates Amazonia as expecting an increase in average temperature of 14◦ C, far the greatest increase of any locality on the planet ([44], p. 405). This calculation assumed the equilibrium concentration of CO2 double the pre-industrial level, a mark that should be reached in approximately 2070 if there is no mitigation of the greenhouse effect. The increase in global mean temperature over pre-industrial levels at this CO2 concentration is what defines “climate sensitivity.” Projected temperature increases by 2100 are approximately 40% higher than the corresponding value for climate sensitivity (i.e. 3.5◦C as a “most likely” value in 2100 versus 2.5◦ C for climate sensitivity). A recent piece of good news is that an analysis of indicators of past climatic changes reduced the estimates for the probability of the true value of climate sensitivity being at the extreme high end of the range of possible values, the point that corresponds to a 95% margin of safety decreasing from 9.7 to 6.2◦C [26]. Proportionally, the 14◦ C increase in Amazonia in approximately 2070 under high climate sensitivity would fall to an increase of 8.3◦C, which would still be a catastrophe that threatens both the forest and the human population in the area. The temperatures indicated by Stainforth et al. ([45], p. 405) are now out-of-date as representations of the situation under high climate sensitivity in approximately 2070 (the time of doubled pre-industrial CO2 ). The revised probability density function for climate sensitivity makes the Stainforth et al. [45] temperatures a close match for what would be expected under high climate sensitivity in 2100. Assuming proportionality, under high climate sensitivity the global mean temperature in 2100 would be 8.7◦C above pre-industrial levels and the mean in Amazonia would be 14.7◦C above the same baseline. Establishment of a permanent El Niño would lead to the Amazon forest being killed by the joint effect of increased temperature and decreased rainfall in Amazonia (e.g., [4]). If a high climate sensitivity is assumed, the Hadley Center model indicates Amazonia as expecting by far the greatest temperature increase

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of any locality on the planet ([44], p. 405). In addition, when programmed with a model similar to that of the Hadley Center, the same result is shown by the Earth Simulator, including peak temperatures exceeding 50◦ C in Amazonia after 2050. The Earth Simulator is a gigantic array of interconnected computers in Yokohama, Japan that simulates global climate on a scale of 10 km, whereas normal climate models simulate the earth on scales of several hundred kilometers. Large carbon stocks would be lost if the “permanent El Niño” is allowed to form [27]. Fortunately, this catastrophic outcome only applies to a business-as-usual scenario, and restricting emissions to keep atmospheric CO2 concentrations from rising much above their current levels would avert this disaster [2]. Reducing emissions globally will require using every existing mitigation option, among which reducing tropical deforestation is one of the most cost effective [16, 17, 19, 21, 32, 42].

1.2 Synergisms Climate change is linked through synergisms to other processes that threaten tropical forests. Forest fires have become a major threat to forests both in Amazonia and in Southeast Asia. These forests are not adapted to fire, and the thin bark of the trees makes them more susceptible to mortality when fires do occur than is the case for trees such as those in savannas or coniferous forests. In Amazonia, fire entering surrounding forest from burning in agricultural clearings or in cattle pastures was practically unknown to most Amazonian residents prior to the 1982/1983 El Niño event. Nevertheless, severe El Niños in the past had resulted in forest burning as in the “big smoke” of 1926 [46] and in four “mega-El Niño” events over the last 2000 years when forest left charcoal in the soil [31]. But the 1982/1983 El Niño was a change, with substantial areas burning both in Amazonia and in Indonesia [29]. The frequency of El Niño is significantly higher since 1976 than it was prior to that year ([39], p. 165). Some evidence exists that the explanation for this change in frequency is due to global warming [48, 50], although the Intergovernmental Panel on Climate Change (IPCC) has not yet arrived at a consensus over the existence of such a connection. The “official” status of IPCC recognition of a causal connection between global warming and El Niño would have major policy implications, because El Niños have unambiguous and devastating consequences today, as opposed to predicted consequences at some future time. The 1982–1983 El Niño killed over 200,000 people in Ethiopia and neighboring countries. El Niño impacts include both human mortality in droughts and floods and the environmental losses of forest fires such as those in Roraima (in northern Brazil) and in Kalimantan (Indonesia) in 1997–1998 [4, 3]. Establishment of a “permanent El Niño” is the critical event in the Hadley Center model simulations that leads to reduced rainfall and greatly increased temperature in Amazonia after 2050 [10, 11]. Flammability of Amazonian forest is expected to increase under various climatic scenarios [7]. Current El Niño conditions already result in wide areas of the region becoming susceptible to fire [1, 34, 36]. The logical result of reducing

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rainfall and increasing temperature is to dry out the litter on the forest floor that serves as fuel for forest fires. Tree mortality increases the amount of litter available to burn, forming a positive feedback loop with fire occurrence [8, 9]. In addition, loss of forest both through deforestation and through dieback from climate change would lead to reduced evapotranspiration in the region, thereby cutting off part of the supply of water vapor needed to maintain large amounts of rainfall in the region— forming another positive feedback relationship leading to forest degradation and loss [13].

2 Feedbacks A positive feedback relationship exists between biomass carbon and global warming. Carbon in the biomass of standing Amazonian forests is released to the atmosphere during El Niño events (e.g., [41, 47]). These forests can subsequently reabsorb the carbon during La Niña and “normal” years, but the observed shift towards more frequent El Niños, together with the prediction of a permanent El Niño after the middle of the current century, suggest that carbon stocks will be steadly drawn down in the remaining forest. Forest degradation takes place under experimentally induced dry conditions in Amazonian forest that mimic conditions after the rainfall reductions foreseen by models such as that of the Hadley Center [37]. In these plots, where plastic sheeting intercepts 60% of the throughfall in the forest over an entire hectare as part of the Large-Scale Atmosphere Biosphere Project (LBA), large trees are the first to die, thus greatly increasing the release of carbon [38]. Mortality in trees > 30 cm diameter at breast height (DBH) was 9.47%/year in the dry plot, as compared to 1.74%/year in the wet (control) plot. The same occurs at forest edges, where microclimatic conditions are hotter and drier than in the interior of a continuous forest [33, 28]. The carbon released from such events would increase global warming and its effect on the “permanent El Niño”, thereby driving further carbon releases from Amazonian forest (e.g., [10, 11]). Drying and tree mortality in Amazonian forest are part of another very dangerous positive feedback relationship, this one between climate change and fire. Both reduced rainfall and higher temperatures would increase the flammability of Amazonian forest [36], leading to more forest fires in standing forest and greater emissions of greenhouse gases. Forest flammability is further increased by an interaction with logging, which greatly increases the risk of fire by its opening the canopy and by the logging operations killing many trees in addition to those that are harvested [3, 9, 35]. The disastrous potential of fires under a “permanent El Niño” is illustrated by the fires that occurred during recent El Niño events. The Great Roraima Fire of 1997–1998 burned 11.4–13.9 × 103 km2 of forest, releasing 17.7–18.0 × 106 t CO2 -equivalent C by combustion alone [4]. Unfortunately, fire risk is virtually never included in forest management plans, which invariably calculate sustainability under the simple assumption that the areas will never burn. Logging is rapidly spreading to formerly inaccessible areas of the

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forest. Forest management is foreseen as the use to which large areas of forest will be allocated outside of fully protected parks and reserves. Fire risk will increase both in the large areas subject to illegal logging, in legally managed areas on private land and in new areas of public land to be opened for forest management in accord with law enacted in January 2006 allowing 40-year concessions in up to 13 million hectares of “public forests.” An early model indicating the possibility of substantial loss of soil carbon in Amazonia was developed by Townsend et al. [49]. The temperature and vegetation changes foreseen by the Hadley Center model [10, 11] are much more severe than those assumed by Townsend et al. [49]. A series of simulations using the Hadley Center models and simpler models that represent the behavior of the Hadley Center models with several adjustments to best to represent the observed current values of important parameters, all indicate a dramatic loss of soil carbon [27]. By 2080 approximately two-thirds of the soil carbon is lost; although the authors do not indicate to what depth in the soil this result applies, it appears to represent the top 30 cm. The carbon stock in this layer drops from 60 to approximately 40 tC/ha over the 2000–2080 period, which corresponds to a loss of approximately 20 GtC over the period, or an average of 250 million tC/year. Soil carbon is not limited to the top 30 cm, and what becomes of carbon stocks at deeper levels could have substantial consequences. Carbon stocks in soil under Amazonian forest average 42.0 tC/ha for 0–20 cm depth, 52.0 tC/ha for 20–100 cm and 142.8 tC/ha for 100–800 cm [20]. The large carbon stocks in the deep soil undergo an appreciable turnover under present conditions [51]. Conditions altered by climate change could therefore turn these carbons stocks into a veritable timebomb. One factor that would decrease the speed of soil-carbon release in the tropics as compared to releases at higher latitudes is the discovery that carbon in highly weathered tropical soils is less sensitive to release from a given temperature increase than is carbon in many temperate and boreal soils [12]. The future role of soil carbon under global warming has recently become a worldwide concern with the publication of results from a detailed monitoring program in England and Wales [5]. This longitudinal study over the 1978–2003 period with four samplings at each of 2179 sampling locations indicated significant loss of soil carbon under both agriculture and undisturbed natural vegetation. This represents a potential positive feedback loop – a “runaway greenhouse effect” that could escape from human control. The more carbon that is released by the soil, the greater the temperature increase from global warming, leading to still more release of soil carbon. Unlike emissions from fossil fuels and deforestation, humans do not have the option of solving the problem by diminishing their own emission, since the magnitude of the soil emission potentially exceeds the fossil fuel emissions of the human population. The study in Britain raises the possibility that we may already have entered into the territory of the “runaway greenhouse,” but data from other parts of the world, such as Amazonia, are lacking to either confirm or contradict this. If the 2 trillion tons of carbon in the Earth’s soils were being released at the 0.6%/year average rate detected in Britain, the annual emission from this source today would be 12 GtC/year, or 50% more than the approximately 8 GtC/year emission today

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from fossil-fuel combustion and cement manufacture. Even deforestation, for which global estimates vary from 1.6 GtC/year for 1980–1989 ([42], p. 79; see review in [14]) to 2.4 GtC/year for 1990 [15], would not bring the anthropogenic total to this level, meaning that even complete elimination of anthropogenic emissions might be insufficient to avert a runaway greenhouse. This points to both the need for intensified research to quantify soil emissions under different climatic scenarios, and to take immediate action on a scale much larger than that agreed so far under the Kyoto Protocol in order to halt, or even reverse, global warming before damage worsens and escapes from control. The visible damage to Amazonian forests from the 2005 drought brought home to many the ease with which such large-scale processes can escape from human control.

3 Tropical Forests and “Dangerous” Climate Change The United Nations Framework Convention on Climate Change (UN-FCCC), signed by 155 countries at the 1992 “Earth Summit” in Rio de Janeiro, specifies its purpose as stabilizing the atmospheric concentrations of greenhouse gases at levels that avoid “dangerous” interference with the climate system [52]. However, what is “dangerous” is not defined by the UN-FCCC (Article 2), and negotiations to define such a level got off to at least a symbolic start in December 2005. In an illustration with a maximum temperature increase of 2.85◦C as the median value considered “dangerous,” available “conventional” climate-policy controls have been shown to be capable of significantly reducing the probability of reaching this level and incurring its consequences within the current century [30]. A wider range of mitigation options would need to be tapped if a lower value for maximum temperature rise (such as 2◦ C) is adopted as the definition of “dangerous.” The first version of the Hadley Center model indicated that stabilizing atmospheric CO2 concentration at 750 ppmv would stave off the demise of Amazonian forest (which dominates global vegetation dieback) by approximately 100 years beyond the 2080 crash indicated by simulations without mitigation, while limiting the concentration to 550 ppmv would postpone the disaster by over 200 years [2]. Limiting the rise in average global temperature to 2◦ C would be necessary to avoid substantial forest degradation in Amazonia and consequent carbon releases [27]. A global average temperature rise of 2◦ C is close to the amount of temperature increase that has been set in motion by emissions that have already occurred [25]. In March 2005 the European Union heads of government adopted 2◦ C as their goal for maximum amount by which global mean temperatures should be allowed to rise above pre-industrial levels. This would require holding the atmospheric concentrations of greenhouse gases to the equivalent of 400 ppmv of CO2 , or, as an alternative to facilitate negotiating such a definition of “dangerous” climate change, by allowing the concentration to overshoot this limit and rise to 420 ppmv, after which the concentration would be reduced to the 400 ppmv limit [25]. A 400 ppmv limit implies a risk of 2–57% (mean = 27%) that the 2◦ C would be overshot; at

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350 ppmv this risk would be reduced to 0–31% (mean = 8%) [25]. The concentration of CO2 passed the 380 ppmv mark in 2006, but the equivalent of approximately 40 ppmv of CO2 from the atmospheric loads of CH4 and N2 O mean that we have already entered into the age of “dangerous” climate change as defined by a 2◦ C ceiling on temperature increase. The vulnerability of tropical forests to climate change is evident from indications of biomass loss in standing forest from the changes in climate that have already occurred [18], combined with the modest amount of change so far relative to what is projected for the next century in a “business-as-usual” world. Global mean temperatures have so far increased by only 0.8◦C [24]. Acknowledgments The Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq: Proc. 470765/01-1) and the Instituto Nacional de Pesquisas da Amazônia (INPA: PPI 1-1005) provided financial support. A longer version of this discussion is expected to appear as a chapter in: Climate Change Science and Policy. Steven Schneider, Armin Rosencranz and Michael Mastrandrea (eds.) Island Press, Covelo, California.

References 1. Alencar AC, Solórzano LA, Nepstad DC (2004) Modeling forest understory fires in an eastern Amazonian landscape. Ecol Appl 14(4):S139–S149 2. Arnell NW, Cannell MGR, Hulme M, Kovats RS., Mitchell JFB, Nichols RJ., Parry ML, Livermore MTJ, White A (2002) The consequences of CO2 stabilisation for the impacts of climate change. Climatic Change 53(4):413–446 3. Barber CV, Schweithelm J (2000) Trial by fire: Forest fires and forestry policy in Indonesia’s era of crisis and reform. World Resources Institute, Washington, DC, USA, 76pp 4. Barbosa RI, Fearnside PM (1999). Incêndios na Amazônia brasileira: Estimativa da emissão de gases do efeito estufa pela queima de diferentes ecossistemas de Roraima na passagem do evento “El Niño” (1997/98). Acta Amazonica 29(4):513–534 5. Bellamy PH, Loveland PJ, Bradley RI., Lark RM, Kirk GJD (2005) Carbon losses from all soils across England and Wales 1978–2003. Nature 437:245–248 6. Betts RA, Cox PM, Collins M, Harris PP., Huntingford C, Jones CD (2004). The role of ecosystem-atmosphere interactions in simulated Amazonian precipitation decrease and forest dieback under global climate warming. Theor Appl Climatol 78:157–175 7. Cardoso M, Hurtt GC, Moore III B, Nobre CA, Prins EM (2003) Projecting future fire activity in Amazonia. Glob Change Biol 9(5):656–669 8. Cochrane MA (2003) Fire science for rainforests. Nature 421:913–919 9. Cochrane MA, Alencar A, Schulze MD, Souza Jr CM, Nepstad DC, Lefebvre P, Davidson EA (1999) Positive feedbacks in the fire dynamic of closed canopy tropical forests. Science 284:1832–1835 10. Cox PM, Betts RA, Collins M, Harris P, Huntingford C, Jones CD (2004) Amazonian dieback under climate-carbon cycle projections for the 21st century. Theor Appl Climatol 78:137–156 11. Cox PM, Betts RA, Jones CD, Spall SA, Totterdell IJ (2000) Acceleration of global warming due to carbon-cycle feedbacks in a coupled climate model. Nature 408:184–187 12. Davidson EA, Janssens IA (2006) Temperature sensitivity of soil carbon decomposition and feedbacks to climate change. Nature 440:165–173 13. Fearnside PM (1995) Potential impacts of climatic change on natural forests and forestry in Brazilian Amazonia. Forest Ecol Manag 78(1–3):51–70 14. Fearnside PM (2000) Effects of land use and forest management on the carbon cycle in the Brazilian Amazon. J Sustain Forestry 12(1–2):79–97

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The European Sea Level Service Information System for Coastal Activities Christoph J. Blasi

Abstract In coastal areas, nearly all kinds of engineering and other activities are dependent on information about the sea level. Furthermore, the sea level is one of the most important parameters for studying climate processes. There are many tide gauges along the European coasts which have been operated for long time. These tide gauges are usually part of a national tide gauge network and designed for national purpose. In Europe and many other regions of the world, a considerable proportion of the population lives and work at the coast or near the coast. Therefore the need for information on sea-level data has developed during the last decades both for scientific and non-scientific application. To overcome the problem of dealing with different national networks, the European Sea Level Service (ESEAS) was established in 2001. This paper describes the objectives, tasks and products of the ESEAS and the organisational structure of the European Sea Level Service. Moreover, the current activities and the relation to other organisation are discussed. Keywords GEOSS · Information network · Sea level

1 Introduction The sea level is one of the environmental parameters which are easily recognised and widely used in both scientific and non-scientific applications. It is established as one of the parameters in global observation systems. Sea level pays also attention in the Global Earth Observation System of Systems (GEOSS) as a parameter that needs to be observed continuously. In Europe, sea level is being observed and recorded in many coastal regions by roughly 450 tide gauges along the European coasts. Some stations have records over 200 years. It can be stated that the total data-base of European sea-level observation is likely to exceed 10,000 station-years so far C.J. Blasi (B) Federal Institute of Hydrology, D-56002 Koblenz, Germany e-mail: [email protected]

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[3]. All these tide gauges are administrated, maintained and organised by national authorities. As a consequence the users of sea level data will be faced with more than 50 national authorities or institutes involved in the operation of gauging station. The data themselves are stored in several databases governed by different data policies. Furthermore, the sampling and the processing of data may by different too. All these end up with various data bases with different quality controlled data. By this means there is no European inventory of sea level data.

2 The Aim of the European Sea Level Service “The European Sea Level Service (ESEAS) in an international collaboration of governmental and non-governmental organisation operating tide gauges along the European coast or providing sea-level related information originating from other sources such as satellite altimetry, GPS and absolute gravity measurements at tide gauges” This is the description of ESEAS in the Terms of References (ToR). The full ToR are available on the ESEAS home page at http//:www.eseas.org/. During the last decade and driven by various events there is a concentrated need on Earth System Science in both scientific and non-scientific areas. It is worth to mention that there is a growing demand for environmental information in societal areas. ESEAS focuses on sea-level as one of the climate-sensitive parameters which are used in many scientific studies and practical applications. The practical application of sea level is straight forward, it does not need conversation, explanation and further definition. The growing public interest might reflect this. One of the major objective of ESEAS is to enhance the exploitation of sea-level and related databases both scientific and non scientific applications. In order to achieve this, the ESEAS strives to identify and promote user requirements as well as requests and wishes made by users for specific products and to give access to quality-assured sea-level and sea-level related information on European waters (Plag 2004). Furthermore, ESEAS coordinates sea-level observations along European coasts, sets standards for sea-level observations, promotes the analysis of the observations and sets the focus on advanced analysis in order to derive more information from sea-level data. As mentioned before, the uses of sea-level and sea-level related information is both scientific and non-scientific; therefore a user-friendly interface to databases is another objective of ESEAS. The interface should also act as a “clearing house” in order to promote and stimulate research for improved observation and analysis of the sea-level. The ESEAS can be seen as a source of comprehensive information on sea-level with a wide range of products for nearly all kind of users, from the man in the street to environmental managers, engineers and scientists. It should also be mentioned here that the ESEAS is endorsed by the Global Sea-Level Observing System (GLOOS) Group of Experts as the regional densification of GLOSS [1] and in this function contributes to the three Global Observing System (G3OS). The major tasks of the ESEAS are to ensure the sufficient quantity, guarantee the quality, and improve the accessibility of sea-level information. To

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meet the requirements and specifications of a wide range of users is another task of the ESEAS. Following the ToR, the ESEAS should integrate their activities into the strategies of relevant on-going programmes or services such as GLOSS, MEDGLOSS, G3OS, EuroGOOS, IGS and EUREF, and more recently IGOPS and GEO. Moreover, the ESEAS has the task to set and maintain standards for observation of tide gauges and other ancillary observation infrastructure and to take appropriate measures to quality-assure data, products and information provided to users through the ESEAS. Another task to be mentioned is the establishment and maintenance of a comprehensive sea-level Website that provides general information and provides access to sea-level data and products. The ToR emphasise that the list of products to be developed and provided by the ESEAS has to oriented at user requirements. At the moment, this list includes near real-time access to tide-gauge data, hourly data from tide-gauge sites, including relative sea-level and meteorological parameters, monthly mean values of relative sea level, extreme sea-level estimates, long-term statistics and possibly predictions of extremes, long-term trends and perhaps predictions of means, routine maps of sea–surface topography over extended areas of the European coastal seas and the adjacent deep ocean, crustal vertical motion at locations the adjacent to the tide gauge, and absolute gravity values from sites close to tide gauges. ESEAS intends to provide these products, wherever possible, in close cooperation and coordination with existing services such us PSMSL and EUREF. In addition, the ESEAS aims to provide general information on sea-level related topics, contact addresses, bibliographies, as well as links to other relevant information sources.

3 The Structure and Organisation of the European Sea Level Service The ESEAS as a provider of information needs a structure and organisation to serve the users. The ESEAS can be divided into the physical network of observation sites, an application network providing access to data and data products as well as research results, and an institutional network of the authorities and institutes that own the physical and application networks and provide the required resources (see Fig. 1). The physical network is largely in place; tide gauges are located along all European coasts (see Fig. 2) and with much diversity in operational routines and quality assurance. Not all regions of there European coasts are covered evenly, what means there are geographical gaps in certain information aspects. The institutional network is represented through the Governing Board (GB), the Central Bureau (CB) and the Technical Committee (TEC). The Governing Board determines the policies of the ESEAS, adopts standards, and approves operational and scientific goals. The Board may initiate Working Groups for relevant topics. Detailed information about the Governing Board and its responsibilities are fixed in the ToR.

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Fig. 1 Organisational structure of the ESEAS. The ESEAS structure is composed of physical, application and institutional networks [2]

The Central Bureau is led by a Director, who is appointed by the Governing Board. The main tasks of the Central Bureau are the day-to-day operation of the ESEAS in the light of the guidelines and decisions of the Governing Board. The day-to-day operation of the CB is a broad business. It reaches from the updating of the mailing list and the web site to the submission of proposals for ESEAS Working Groups to the secretariat of the Governing Board and the Technical Committee.

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Fig. 2 The ESEAS network of observation sites

The Technical Committee and the ESEAS Working Groups are an appropriate platform for preparing proposals for standards, testing technologies and methodologies and the integration of new developments. These working groups are established by the Governing Board. There is also a permanent working group within in the ESEAS, called Technical Committee (TEC). The TEC has 12 members, who are elected on staggered terms of 4 years, so that each year three new members are elected. More details of the Working Groups and the TEC and how they have to work and act are specified in the ToR too.

4 The Coordination and Users of the European Sea Level Service The physical network is one of the main components of the ESEAS, because it provides the data for the service via the National Centres. The coordination of these centres is an elementary task and of high importance for the service. The Network Coordinator links together the physical network with the institutional network and is responsible for: – coordinating the operation of networks of Observing Sites, – coordinating the data archiving activities of ESEAS National Centres, – monitoring the quality of network operation,

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– assuring adherence to pertinent standards, – ensuring the accessibility of the data archived in the National Centres. As mention above and in accordance with the ToR, there is a list of products which is available for potential users. The products stem from the application network and the institutional network which need coordination. This is done by the Product Coordinator, who is responsible for: – coordinating the activities of the ESEAS Analysis and Supporting Centres, – monitoring the performance of the ESEAS Analysis and Supporting Centres, – provide a link between the ESEAS Analysis and Supporting Centres and the Central Bureau, – Maintaining a list of Products confirming with the user’s needs. Users of the ESEAS come from both scientific and non-scientific communities. Sea level is a sensitive environmental variable and is very important for studying climate processes with a coupled atmosphere-ocean system. As considerable proportion of the European population live near the coast, sea-level data and products are relevant for society. These data and products will be used for assessments of risks and safety in coastal regions. Extreme values, subsidence rates and increasing storminess are issues which play an important role for the coastal communities. During the last years and also driven by various events, the non-scientific demand of sea-level data has increased. Together with the scientific need, it can be stated that there is a large market for sea-level data.

5 Conclusion Since 2001, the ESEAS has achieved considerable issues like building up an active community with interdisciplinary knowledge transfer as well as an improvement of the observational and application networks. The achievements are also encouraged by the increased need for sea-level information by scientific and non-scientific users. The ESEAS has also worked for process standardisation of operational routines and access to data and products. Despite these achievements, there are a number of open issues which need to be addressed: Data-quality Information, Digital Object Identifier (DOI), Copyright Issues and Data Access Policy are only a few. At the moment there is no clear concept of how Data-quality Information can be made available to users together with the data. The ESEAS has to consider how the user can associated the data and products from different sources. “Copyright Issues” is also an important matter for the service. The ESEAS lives and relies on providing data and products of their members. Copyright Issues on ESEAS data and products would be an encouragement for most institutes and would ensure that their data and products are linked to their originators. Also the Data Access Policy needs to address more clearly to ensure that the requirements for data access are respected.

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References 1. IOC (1997) Global Sea Level Observing System (GLOOS) implementation plan. Intergovernmental oceanographic commission, Technical Series, vol 50. Plus Annexes, Technical report, 91 pp 2. Plag H-P (1999) Network implications for global change monitoring. In: Noll CE, Gowey KT, Neilan R (eds) Proceedings of IGS Network System Workshop, IGS/JPL, Pasadena, pp 69–76 3. Plag H-P, Axe P, Knudsen P, Richter B, Verstraeten J (eds) (2000) European sea level observing system (EOSS): Status and future developments, vol. EUR 19682. Office for Publication of the European Communities, Luxembourg 4. Plag HP (2004) The ESEAS data portal: principle contributions. In: Holgate S, Aurup T (eds) Workshop on technical developments in the sea and land level observing systems. UNESCO, Paris, pp 108–113

A Review on the Impact of the North Sea – Caspian Pattern (NCP) on Temperature and Precipitation Regimes in the Middle East H. Kutiel

Abstract An upper level atmospheric teleconnection between grid points: 0◦ , 55◦ N; 10◦ E, 55◦ N (North Sea) and 50◦ E, 45◦ N; 60◦ E, 45◦ N (northern Caspian) was identified. This teleconnection, referred as the North Sea-Caspian Pattern (NCP) is evident at the 500 hPa level. The NCP is more pronounced during winter and the transitional seasons. An index (NCPI) measures the geopotential heights differences between the two poles of the NCP. Time series of the NCPI are presented and analysed. A calendar of all months according to their belonging to NCP(−), NCP(+) or normal conditions during the analysis period (1958–1998) was prepared. The associated anomaly circulation during either NCP(−) or NCP(+) conditions was defined and their impact on the regional temperature and precipitation regimes in Greece, Turkey and Israel is analysed. At all stations and in all months, temperature values were significantly higher during the NCP (−) as compared with the NCP (+). Furthermore, apart from very few exceptions, the absolute monthly mean maximum and monthly mean minimum values were obtained during the NCP (−) and the NCP (+) phases, respectively. The maximum impact of the NCP on mean air temperature was detected in the continental Anatolian Plateau, where the mean seasonal differences are above 3.5◦C. This influence decreases westwards and southwards. The influence on the rainfall regime is more complex. Regions exposed to the southern maritime trajectories, in Greece and in Turkey, receive more rainfall during the NCP (−) phase, whereas in the regions exposed to the northern maritime trajectories, such as Crete in Greece, the Black Sea region in Turkey, and in all regions of Israel, there is more rainfall during the NCP (+) phase. The accumulated rainfall differences between the two phases may be over 50% of the seasonal average for some stations. Keywords North sea · Precipitation · Temperature · Telecommunity

H. Kutiel (B) Laboratory of Climatology, Department of Geography and Environmental Studies, University of Haifa, Haifa 31905, Israel e-mail: [email protected]

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1 Introduction Atmospheric teleconnections became a frequent issue in the study of the global or regional circulations and their influences on the temperature or precipitation regimes in their surroundings. Certainly, the most widely known teleconnection is the Southern Oscillation (SO) related with the El Niño effect and referred by the acronym ENSO. There is an enormous volume of studies relating the ENSO with many climatic consequences and their economic, societal and environmental effects, almost all around the world. Another widely studied and referred teleconnection is the North Atlantic Oscillation (NAO). This oscillation, between the Azores and Iceland, affects primarily the rainfall regime in northwestern Africa (Morocco) and northwestern Europe (e.g. [1, 9, 12, 23, 29–32, 35, 36]). The NAO has also an important role in determining the winter characteristics of wider regions in Europe. Other teleconnections were found and defined in that region. Kutiel and Kay [16], defined the Southern Europe-North Atlantic (SENA) index. Yin [38], collected and mapped many teleconnections’ action centers, published in the literature. Some of these teleconnections are at higher levels and not only at the sea level, e.g., the Eastern Atlantic pattern (EA) at the 700 hPa level, defined by Esbensen [8], the Scandinavian pattern (SCAND), Kutiel and Helfman, [15] the Central African-Caspian Oscillation (CACO), [33], the North African/Western Asia (NAWA), Hatzaki et al. [11] the Eastern Mediterranean Pattern (EMP) just to mention some. The role of these teleconnections, however, as influencing the climate of the Mediterranean in general, and of its eastern basin in particular, was seldom studied. Conté et al. [4], suggested the existence of a so-called Mediterranean Oscillation, at the 500 hPa level between the two extremes of the Mediterranean. Their suggestion was based on a seesaw effect they found between Alger and Cairo in mean annual geopotential heights at the 500 hPa level. They even tried to relate this oscillation with precipitation in Italy. Based on this concept of a Mediterranean Oscillation, a seesaw behaviour of other climatic parameters (temperatures, precipitation, circulation, etc.) between western and eastern Mediterranean were reported and attributed to this oscillation [7, 21, 26–28, 17, 18, 25]. In a series of recently published articles [2, 14, 19]. The existence of the North Sea – Caspian Pattern (NCP), an upper level atmospheric teleconnection that has a major and crucial effect on the temperature and precipitation regimes in the Eastern Mediterranean (EM) was demonstrated. The purpose of the present study is to review the identification process of that teleconnection, to illustrate its impact on the regional climate and to discuss its capabilities in a long-term forecast.

2 Data and Methodology Mean monthly geopotential heights at the 500 hPa at 66 grid points, 10◦ longitude by 10◦ latitude, in the region delimited by the 30◦W and 70◦ E meridians and 15◦ N

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and 65◦ N parallels, were used. Monthly Intrinsic Pressure Level phi Geopotential height grided data, for the period 1958–1998 were used. The data were obtained from NOAA NCEP-NCAR. Linear correlations between mean monthly geopotential heights at each grid point, with all other grid points, were calculated. A total of 2145 (66×65/2) correlations were calculated for each month. As one would expect, correlation coefficients of adjacent grid points showed high positive values, which decreased as the distance between the grid points, increased. However, as one of the main purposes of the study was to define the location of the poles having a seesaw like behaviour, only the significant negative correlations were retained. These were found at remote locations each other. In each month, each pair of grid points having a significant (p ≤ 0.05) negative correlation, was connected with a line. Figure 2 in Kutiel and Benaroch [14], illustrates the annual course of the number of significant negative correlations between pairs of grid points. One may observe a clear annual course with large numbers in winter (maximum in February) and a sharp decrease in summer (minimum in July). The maximum number of significant negative correlations accounts for about 7–8% of the total number of correlations in winter and drops to less than 1% in summer. This implies that the seesaw like behavior between different locations within the study area is much more pronounced during the winter. A GIS oriented software (ArcView), was used to differentiate between the various levels of the significant correlations. This was done to enable an easier location of the poles of the teleconnection. The definition of the teleconnection and its poles was based also on the persistency of the location as having a large number of negative correlations all (most) year around. According to this criterion, we were unable to find a teleconnection across the Mediterranean itself, but we spotted a different teleconnection located north of the Mediterranean. Two poles were defined at 0◦ , 55◦N; 10◦E, 55◦ N (North Sea) and 50◦ E, 45◦N; 60◦E, 45◦ N (northern Caspian). Therefore, we decided to refer to it, as the North Sea – Caspian Pattern or NCP hereafter, a name that well reflects the geographical extent of this teleconnection. An index defining the NCP intensity was calculated as follows: NCPI = gpm(0◦ , 55◦N; 10◦ E, 55◦N) − gpm(50◦E, 45◦N; 60◦ E, 45◦N) where, gpm (geo-potential metres) is the average height of the two grid points forming each of the two poles, respectively. This index enabled the calculation of monthly time series of the NCPI. For each month the data were then standardized as follows: zi = (NCPI i −NCPI)/σ where, NCPIi is the monthly NCPI in the year i; NCPI is the monthly long-term NCPI average and σ is its standard deviation.

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A month was defined to be in the Negative phase of NCP (NCP(−) hereafter) when: zi ≤ −0.5. Similarly, a month was defined to be in the Positive phase of NCP (NCP(+)) when: zi ≥ +0.5. Table 2 in Kutiel and Benaroch, [14], shows a calendar of all months during the analysis period and their belonging to NCP(−) or to NCP(+). Months belonging neither to NCP(−) nor to NCP(+), were considered as normal and remained blank in that Table. Monthly mean temperatures and monthly rainfall totals for the same period from 20 stations across Greece, 13 stations across Turkey representing the seven climatic regions of that country as defined by Türkes [34] and six from Israel, were used. For each station in each month, the averages of the mean temperatures and rainfall totals were calculated separately for all cases defined as the NCP (−) or the NCP (+), based on the above defined calendar (Table 2 in [14]). These values were compared with the long-term mean values calculated for the entire period. Significant departures (larger than 0.5 standard deviation, either positive or negative) are frequent during the period October–April, whereas in the period May–September, there are only few sporadic significant departures. These results fit the postulated that the NCP is mainly evident in autumn, winter and spring. Furthermore, recent studies on rainfall conditions associated with pressure patterns revealed that precipitation are well related to the regional circulation, mainly in winter and the transitional seasons (e.g., [18, 20]). Thus, the study is limited to the period October–April.

3 Results and Discussion The NCP(−) implies an increased counterclockwise anomaly circulation around its western pole and an increased clockwise anomaly circulation around its eastern pole and the opposite during NCP (+). This means that during NCP(−) we should expect an increased westerly anomaly circulation towards central Europe, an increased easterly anomaly circulation towards Georgia, Armenia and eastern Turkey resulting in an increased southwesterly anomaly circulation towards the Balkans and western Turkey. Similarly, during the NCP(+), it implies an increased northwesterly circulation towards eastern Europe, an increased northeasterly circulation towards the Black Sea resulting in an increased northeasterly anomaly circulation towards the Balkans (Figs. 6a and 6b in [14]). Based on the above scheme, one should expect to find the maximum differences between NCP(−) and NCP(+) to be exhibited over the Balkans and the Middle East.

3.1 Temperature Regime During the study period from October to April, monthly mean temperatures are considerably higher for all months at all stations during the NCP (−) phase as compared with the NCP (+) phase.

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3.1.1 Temperature Regime in Greece The mean seasonal temperature difference between the NCP (−) and the NCP (+) for the entire period is higher in the eastern parts of Greece and smaller in the western parts. At the stations of Alexandroúpoli and Mitilíni the differences are 2.6◦C and 2.5◦C, respectively. At the Ioanian islands these differences are the smallest. At the station of Kérkira (Corfu) and at Argostóli the differences are only 1.1◦C and 1.2◦ C, respectively. The mean differences in all the regions are the greatest in February, 2.7◦C, which are in a complete agreement with the distribution of monthly standard deviations of temperatures in Greece [24]. The largest mean differences in 1 month at one station are observed in February at Alexandroúpoli, 3.8◦ C (7.5◦C during the NCP (−) and 3.7◦C during the NCP (+)), at Kozáni, 3.5◦C (5.5◦C and 2.0◦C, respectively) and in October at Mílos, 3.4◦ C (20.8◦C and 17.4◦C, respectively). 3.1.2 Temperature Regime in Turkey In Turkey, we observe even larger temperature differences between the NCP (+) and the NCP (−) phases. The mean difference for the entire period is the highest in the Anatolian continental stations of Ankara and Erzurum, 3.4◦ C and 3.5◦C, respectively, and the smallest in the Mediterranean station of Mu˘gla, only 2◦ C. The mean differences in all the regions are greatest in January and February, 3.6◦ C and 3.5◦C respectively and the smallest in November, only 1.9◦C. The largest mean differences in 1 month at one station are observed in January at Erzurum, 5.5◦C (−6.7◦C during the NCP (−) and −12.2◦C during the NCP (+)), at Diyarbakir, 5.0◦C (3.8◦C and −1.2◦C, respectively) and at Ankara, 4.6◦C (2.4◦C and −2.2◦C, respectively). The reason that the maximum impact of the NCP on air temperatures has been found at the stations of the Anatolian Plateau is related with the physical geography of the Anatolian Plateau itself. The continental inner regions of the Anatolian Peninsula are geographically recognized as a high plateau. It is somewhat protected from the maritime effects of the Black Sea and the Mediterranean Sea by means of the high Northern Anatolian Mountains (highest peaks with elevations of over 3,500 m in the eastern section) and the Mediterranean Taurus Mountains and the South-eastern Taurus Mountains (highest peaks with elevations of over 3,500–4,000 m in the eastern section). These high mountain chains form a main part of the eastern section of the Palaeozoic and the Alpine originated Mediterranean fold belt that characterize the Turkish geomorphology. The Anatolian Plateau is affected mostly by the southerly and easterly anomaly circulation patterns during the NCP (−) phase, whereas it experiences mostly northeasterly anomaly circulation patterns during the NCP (+) phase. During the NCP (+) phase it does not benefit the humid and temperate effect of the Mediterranean air as much as in the western regions of Turkey, because the Taurus Mountains create an obstacle effect for the Mediterranean air to enter into the Anatolian Plateau. Thus, the larger mean monthly and seasonal temperature differences between the NCP (+) and the NCP (−) conditions occur over the continental Anatolian Plateau. Keeping in mind that each of the above figures represents an average of over ten Januarys, these differences are very impressive.

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Table 6 in Kutiel, and Türke¸s, [19] lists the average temperatures at the six Cappadocian stations during NCP(−) and NCP(+). These differences vary between 3.4◦ C at Kır¸sehir and 3.9◦ C at Nev¸sehir. The greatest differences at the seasonal scale, are observed in January and February, 5.9◦ C and 4.5◦C respectively, whereas, the smallest differences in November and March, 2.6◦C and 2.5◦C respectively. Figure 3 in Kutiel, and Türke¸s, [19] shows the spatial distribution of the temperature differences between NCP(−) and NCP(+). Figure 3a, presents the regional impact of the NCP on the temperature regime, Fig. 3b shows the differences in Turkey and Fig. 3c, focuses on the Cappadocian region. From this series of maps, one can conclude that the influence of the NCP on the temperature regime in Turkey is probably the most evident in the Middle East, In Turkey itself, the central Anatolian Plateau is more affected by the NCP than the coastal regions and finally, within central Anatolia, the Cappadocian region is probably the core of that influence. 3.1.3 Temperature Regime in Israel In Israel, due to its very limited geographical extent, there are no large spatial differences in the intensity of influence of both phases. However, at the coastal station of Tel-Aviv, the mean seasonal temperature difference between the two phases is only 1.2◦C, whereas, at the mountainous stations of Mt. Cnaan and Jerusalem, the difference is 2.2◦ C. The mean differences in all regions are the greatest in December and January, 1.6◦C. The largest mean difference in 1 month at one station is 2.6◦ C. These differences are observed at Mt. Cnaan in October (20.9◦C during the NCP (−) phase and 18.3◦C during the NCP (+) phase) and at Jerusalem, in February, (11.0◦C and 8.4◦C, respectively).

3.2 Rainfall Regime As assumed earlier, the impact of the NCP on the rainfall regime in the region is more complex and not as clear as with the temperature regime. This is probably due to the fact that rainfall, anywhere in the world, is affected more by local factors and the regional circulation is less reflected as compared with other meteorological parameters. Table 4 in Kutiel et al. [22], summarizes the differences in rainfall totals at the various stations for both phases. Figure 4 in Kutiel et al. [22], illustrates the annual course of the standardized rainfall anomalies for both phases. Figure 6 in Kutiel et al. [22], shows their spatial distribution. 3.2.1 Rainfall Regime in Greece In Greece, we may observe a NCP influence gradient from north to south. Northern Greece gets more rainfall during the NCP (−) phase while Crete gets more rainfall during the NCP (+) phase. In the Eastern Macedonia and Thrace region represented by the station of Alexandroúpoli, the mean accumulated difference in rainfall totals between the NCP (−) and the NCP (+) conditions is 232 mm or 55% of the total

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rainfall, in favour of the NCP (−) phase. In Epirus represented by the station of Ioánina, this surplus of the NCP (−) phase is 421 mm (50%) and in Western Greece represented by the station of Agrínio, 344 mm (45%). Other regions, in which there are more abundant rainfall amounts during the NCP (−), are the Peloponnesus and the Northern Aegean. In Crete represented by the stations of Chania and Iráklio (both located on the northern shore), there are surplus of 140 mm (25%) and 123 mm (27%) respectively during the NCP (+) phase. At Ierápetra, also in Crete, but located on the southern shore, the difference is less significant. 3.2.2 Rainfall Regime in Turkey In Turkey, we may observe a NCP influence gradient from southwest to northeast. The southwestern Mediterranean region represented by the station of Mugla gets the maximum influence of the NCP (−). The mean accumulated difference in rainfall totals at Mugla, between the NCP (−) and the NCP (+) conditions, is 444 mm, or 41% of the total rainfall, in favour of the NCP (−) phase. In the Mediterranean to Central Anatolia Transition region represented by the station of Usak, this surplus of the NCP (−) phase is only 115 mm (27%). In the eastern Black Sea sub-region, represented by the station of Giresun, we observe an opposite influence. The mean accumulated rainfall total during the NCP (+) is higher by 191 mm (23%) as compared with the NCP (−). In the other stations, there are only slight differences. However, in the two western stations (i.e., Göztepe and Ankara) there is more rainfall during the NCP (−) phase while in the two other eastern stations (Sarikamis and Diyarbakir) rainfall is more abundant during the NCP (+) phase, thus maintaining the east–west gradient. 3.2.3 Rainfall Regime in Israel In Israel, the role of the NCP on the rainfall regime is very clear. The rainfall accumulated during the NCP (+) phase is by far greater than that accumulated during the NCP (−) phase. Due to the small dimensions of the country, it is difficult to detect significant differences between the various regions. However it seems that the NCP effects on the rainfall regime increase from the northern parts of the country in the Upper Galilee to the southern parts of the Northern Negev. The mean accumulated difference in rainfall totals at Kfar Blum, between the NCP (−) and the NCP (+) phases is 224 mm, or 44% of the total rainfall, in favour of the NCP (+). This percentage increases to 54% at Be’er-Sheva and 56% at Tel-Aviv and Jerusalem.

3.3 Comparison Between the NCP, the NAO and the SO Recently, Kahya and Karabörk [13] tried to relate streamflows in two regions in Turkey with El Niño and La Niña signals. There are some indications that such a relationship may exist, but not statistically significant. Wibig [37], found a good

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relationship between precipitation in Western Europe and the NAO index but the correlation coefficients decreased to zero in the Balkans and the eastern Mediterranean. Delitala et al. [6], results confirmed the connection between precipitation in Sardinia and the NAO. Camuffo et al. [3], however, did not find any relationship between the ENSO or the NAO and sea storms in the Adriatic. Cullen and deMenocal [5], analysed the influence of the NAO on the Tigris-Euphrates stream flow. According to their findings a weak correlation exists between the NAO index and temperatures or precipitation in the eastern Mediterranean. Recently, Ben-Gai et al. [2] reported about a relationship between the NAO index and 5 years. smoothed cool season temperatures in Israel. Correlation coefficients are much more significant with temperatures or precipitation in western Mediterranean or Western Europe. A comparison of the capabilities of NCPI, NAO index and SOI to differentiate between below and above normal temperatures, was made. The analysis was done for seven stations of Turkey, 7 months and both phases, yielding a total of 98 values (7×7×2) for that comparison. Table 5 in Kutiel et al. [22], summarizes the main results. The SOI has failed completely in differentiating between below or above normal temperatures. For each phases, almost the same number of above or below normal cases are observed. Thus, it is impossible to state if above or below normal temperatures are associated either with SOI(+) or SOI(−). Furthermore, only in two cases out of 98, both during SOI(−), the standard scores are larger than 0.5 (|zi |>0.5). In all other cases the deviations from the long-term average are tiny and insignificant. These results, however, contradict a significant relationship between air temperatures at several locations in the eastern Mediterranean and ENSO as reported by Hasanean [10]. The performance of the NAO index is slightly better than that of SOI. However, while during most NAO(−) cases, monthly mean temperatures are above normal and the opposite during NAO(+), there are also some cases when below normal temperatures are measured during NAO(−) and vice versa. Only in seven cases out of 98, the standard scores are larger than 0.5. Thus, we can conclude that there is some tendency of above normal temperatures during NAO(−) and the opposite during NAO(+), but temperature differences between both phases are seldom considerable. These results placed the NCP as the leading teleconnection in its ability to differentiate between below or above normal temperatures in EM. First, during all NCP(−) cases, monthly mean temperatures are above normal and the opposite during NCP(+) without any exceptions. Furthermore, in 89 cases out of 98 the standard scores are larger than 0.5, and in many cases even larger than 1.0. Finally, the last column in Table 5 in Kutiel et al. [22], compares the averages of the seasonal (for 7 months) differences between temperatures in both phases (the negative minus the positive). The smallest difference between NCP(−) and NCP(+) has been obtained for the station of Mugla, 2.0◦ C. Even this figure is greater than the largest difference between NAO(−) and NAO(+) obtained for the station of Erzurum, 1.6◦ C. For the SO, values are much more smaller and not considerable. These performances of the NCP were recognized by Climatic Research Unit (CRU) at the University of East Anglia which updates constantly the NCP index in their website: http://www.cru.uea.ac.uk/~andrewh/ncp.html

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4 Conclusions The main conclusions of the present study may be summarized as follows: The NCP has a major impact on the mean air temperatures over the Balkans, the Anatolian Peninsula and the Middle East. The positive phase of this pattern (the NCP (+)) is associated with below normal temperatures, while the negative phase (the NCP (−)) is related with above normal temperatures. Negative temperature anomalies are caused by the increased north-easterly anomaly circulation during the NCP (+) phase in the region, resulting from the joint effect of an increased anticyclonic anomaly circulation pattern over the North Sea region and an increased cyclonic anomaly circulation pattern over the northern Caspian Sea region. On the other hand, positive temperature anomalies are related with the increased southerly and/or south-westerly anomaly circulation during the NCP (−) phase, arising from the joint effect of an increased cyclonic anomaly circulation pattern over the North Sea region and an increased anticyclonic circulation pattern over the northern Caspian Sea region. Among the three countries involved in the study, the impact on the air temperature is most severe in Turkey, due to its closer location to one of the poles of the NCP. The maximum impact on the temperatures is observed in the Continental Central Anatolia and the mountainous Continental Eastern Anatolia regions, and decreases westwards and southwards, Fig. 5 in Kutiel et al. [22]. In Greece there is a decreasing gradient of the impact westward. The impact of the NCP on air temperature in Israel is relatively small and more pronounced in the mountainous inland regions. The temperature differences are evident not only on the long-term monthly averages but also on particular extreme months either hotter or colder than normal. The impact of the NCP on rainfall is more complex. In the regions exposed to the southern maritime fluxes, such as Thrace, Epirus or the Peloponnesus in Greece and the Mediterranean or the Mediterranean to Central Anatolia Transition in Turkey, there is more rainfall amount during the NCP (−) phase. Whereas, in the regions exposed to the northern maritime fluxes, such as Crete in Greece, the Black Sea region in Turkey, and in all regions of Israel, there is more rainfall during the NCP (+) phase, Fig. 6 in Kutiel et al. [22]. It seems, that the impact on rainfall is less crucial in Turkey than in the two other countries. During the NCP (−) phase, western Turkey characterized with the southern maritime trajectories benefits from much above normal rainfall, whereas during the NCP (+) phase this is the case in eastern Turkey characterized with the northern maritime trajectories. In Greece larger parts of the country will benefit from more abundant rainfall during the NCP (+) than during the NCP (−). In central Turkey, however, the main impact is on the spatial structure of the rainfall and not on the annual amount. The impact on rainfall is the most crucial in Israel as during the NCP (−) not only the temperatures are higher but also there is a considerable reduce in the rainfall amounts in all parts of the country. Seasonal mean temperature differences greater than 1◦ C, 2◦ C or even 3◦ C, are as larger as any anticipated temperature change due to a global climatic change. Similarly, differences of hundreds of millimetres of rainfall, for the seasonal totals

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(which for some stations, represent almost all the annual rainfall) are also beyond any scenario regarding a possible modification of the rainfall regime. Furthermore, although the ENSO and the NAO have certainly a major role in affecting the rainfall and temperature regime in the southern hemisphere and the western Europe, respectively, their influences in the Eastern Mediterranean part of the northern hemisphere are very much reduced mainly in the rainfall regime. No clear simple causative explanation can be given for such apparent relationship found e.g., between the ENSO and rainfall in a certain region. The present study has provided not only very clear and significant results illustrating the major role of the NCP in determining the temperature and rainfall regime in that part of the world, but also an explanation for these results in terms of upper level atmospheric circulation. Thus, future studies aimed to downscale GCM scenarios to a regional scale and provide forecasts regarding eventual temperature and/or rainfall changes in this region, should prefer the use of the NCPI upon the NAO index or the SOI.

References 1. Barnston AG, Livezey RE, (1987) Classification, seasonality and persistence of low-frequency atmospheric circulation patterns. Mon Wea Rev 115:1083–1126 2. Ben-Gai T, Bitan A, Manes A, Alpert P, Kushnir Y (2001) Temperature and surface pressure anomalies in Israel and the North Atlantic oscillation. Theor Appl Climatol 69:171–177 3. Camuffo D, Secco C, Brimblecombe P, Martin-Vide J (2000) Sea storms in the Adriatic Sea and western Mediterranean during the last millennium. Climatic Change 46:209–213 4. Conté M, Giuffrida A, Tedesco S (1989) The Mediterranean oscillation. Impact on precipitation and hydrology in Italy. Conference on Climate Water, Publications of the Academy of Finland, Helsinki, Sep 11–15, pp 121–137 5. Cullen HM, deMenocal PB (2000) North Atlantic influence on Tigris-Euphrates streamflow. Int J Climatol 20:853–863 6. Delitala AMS, Cesari D, Chessa P, Ward MN (2000) Precipitation over Sardinia (Italy) during the 1946–1993 rainy seasons and associated large-scale climate variations. Int J Climatol 20:519–541 7. Douguédroit A (1998) L’oscillation Méditerranéenne: Le cas du printemps. Pub Assoc Int Climatol 11:383–390 8. Esbensen SK (1984) A comparison of intermonthly and interannual teleconnections in the 700 mb geopotential height field during the northern hemisphere winter. Mon Wea Rev 112: 2016–2032 9. Glowienka-Hense R (1990) The north Atlantic oscillation in the Atlantic-European SLP. Tellus 42A:497–507 10. Hasanean HM (2001) Fluctuations of surface air temperature in the Eastern Mediterranean. Theor Appl Climatol 68:75–87 11. Hatzaki M, Flocas HA, Asimakopoulos DN, Maheras P (2006) The eastern Mediterranean teleconnection pattern: Identification and definition. Int J Climatol DOI:10.1002/joc.1429 12. Hurrell JW, (1995) Decadal trends in the North Atlantic Oscillation: Regional temperatures and precipitation. Science 269:676–679 13. Kahya E, Karabörk MÇ(2001) The analysis of El Niño and La Niña signals in streamflows of Turkey. Int J Climatol 21:1231–1250 14. Kutiel H, Benaroch Y (2002) North Sea – Caspian Pattern (NCP) – An upper level atmospheric teleconnection affecting the Eastern Mediterranean: Identification and definition. Theor Appl Climatol 71:17–28

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15. Kutiel H, Helfman I (2004) The impact of central African-Caspian oscillation (CACO) on climate regime in the Red Sea region. In: Maos JO, Inbar M, Shmueli DF (eds) Contemporary Israeli Geography, Horizons in geography. Haifa: University of Haifa Press, pp 183–194 16. Kutiel, H., Kay, P.A. (1992) Recent variations in 700 hPa geopotential heights in summer over Europe and the Middle East, and their influence on other meteorological factors. Theoretical and Applied Climatology, 46, 99–108 17. Kutiel H, Maheras P (1998) Variations in the temperature regime across the Mediterranean during the last century and their relationship with circulation indices. Theor Appl Climatol 61:39–53 18. Kutiel H, Paz S (1998) Sea level pressure departures in the Mediterranean and their relationship with monthly rainfall conditions in Israel. Theor Appl Climatol 60:93–109 19. Kutiel H, Türke¸s M (2005) New evidences for the role of the North Sea – Caspian Pattern on the temperature and precipitation regimes in continental central Turkey. Geografiska Annaler Ser A 87:501–513 20. Kutiel H, Hirsch-Eshkol TR, Türke¸s M (2001) Sea level pressure patterns associated with dry or wet monthly rainfall conditions in Turkey. Theoretical and Applied Climatology 69:39–67 21. Kutiel H, Maheras P, Guika S (1996) Circulation indices over the Mediterranean and Europe and their relationship with rainfall conditions across the Mediterranean. Theoretical and Applied Climatology 54:125–138 22. Kutiel H, Maheras P, Türke¸s M, Paz S (2002) North Sea – Caspian Pattern (NCP) – An upper level atmospheric teleconnection affecting the eastern Mediterranean – Implications on the regional climate. Theor Appl Climatol 72:173–192 23. Lamb PJ, Peppler RA (1987) North Atlantic oscillation: Concept and an application. Bull Am Meteorol Soc 68:1218–1225 24. Maheras P (1983) Climatologie de la mer Egée et de ses marges continentals. Etude de climatologie descriptive et de climatologie dynamique, Thèse d’Etat, Atelier de reproduction de Lille III, 776p 25. Maheras P, Kutiel H (1999) Spatial and temporal variations in the temperature regime in the Mediterranean and their relationship with circulation during the last century. Int J Climatol 19:745–764 26. Maheras P, Kutiel H, Kolyva-Machera F (1997) Evolution de la pression atmospherique en Europe meridionale et en Mediterranée durant la dérnier période séculaire. Pub Assoc Int Climatol 10:304–312 27. Maheras P, Kutiel H, Vafiadis M (1998) Tendances spatiales et temporelles de la pression atmospherique de surface et des geopotentiels de 500 hPa en Europe meridionale et en Mediterranée durant la période 1950–1994. Pub Assoc Int Climatol 11:345–351 28. Maheras P, Xoplaki E, Kutiel H (1999) Wet and dry monthly anomalies across the Mediterranean basin and their relationship with circulation, 1860–1990 Theore Appl Climatol 64:189–199 29. Rogers JC (1984) The association between the north Atlantic oscillation and the southern oscillation in the northern hemisphere. Mon Wea Rev 112:1999–2015 30. Rogers JC (1990) Patterns of low-frequency monthly sea level pressure variability (1899– 1986) and associated wave cyclone frequencies. J Climate 3:1364–1379 31. Rogers JC, van Loon H (1979) The seasaw in winter temperatures between Greenland and northern Europe. Part II: Some oceanic and atmospheric effects in middle and high altitudes. Mon Wea Rev 107:1364–1379 32. Stephenson DB, Pavan V, Bojariu R (2000) Is the north Atlantic oscillation a random walk? Int J Climatol 20:1–18 33. Tourre YM, Paz S (2004) The North-Africa/Western Asia (NAWA) sea level pressure index: A Mediterranean signature of the Northern Annular Mode (NAM). Geophys Res Lett 31:L17209, doi:10.1029/2004GL025176 34. Türke¸s, M. (1996) Spatial and temporal analysis of annual rainfall variations in Turkey. Int J Climate 16:1057–1076

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35. van Loon H, Rogers JC (1978) The seasaw in winter temperatures between Greenland and northern Europe. Part I: General description. Mon Wea Rev 106:296–310 36. Wallace J, Gutzler D (1981) Teleconnections in the geopotential height field during the Northern Hemisphere winter. Mon Wea Rev 109:784–812 37. Wibig J (1999) Precipitation in Europe in relation to circulation patterns at the 500 hPa level. Int J Climatol 19:253–269 38. Yin ZY (1999). Winter temperature anomalies of the north China plain and macroscale extratropical circulation patterns. Int J Climatol 19:291–308

Wave Damping and Retardance by Emergent Vegeatation Oral Ya˘gci, Umut Türker, and M. Sedat Kabda¸sli

Abstract Although in the past great attention has been devoted to coastal stabilization, the effect of aquatic vegetation on wave characteristics (damping and retardance etc) is still not well known. In this context an experimental study was performed in an irregular wave flume to explore the effect of reeds (phragmites australis) on wave damping and retardance. Further for a given vegetated area the effect of wave characteristics (i.e. wave height, wave period and wave steepness) on wave damping and retardance were discussed. Real reeds (phragmites australis) with diameter less than 5 mm were employed throughout the experiments for the emergent case. A dimensionless number was introduced to characterize both the vegetated area magnitude and the effect of the vegetation on wave damping and retardance. Keywords Coastal stability · Vegetation · Wave · Wave damping ratio

1 Introduction Knowledge of the interaction between vegetation and incident waves helps a better understanding of ecological and geomorphological processes in coastal waters with particular respect to coastal defence management. In the literature the effect of different vegetation species (i.e. Laminaria hyperborea, mangrove forests) on wave propagation have been studied (e.g. [1, 7, 8, 10]). Kobayashi et al. [6] proposed an analytical expression for the submerged vegetation case and tested the expression using experimental data collected from experiments conducted in a wave tank roughened with artificial vegetation elements. Ostendrop [13] investigated the bio-

O. Ya˘gci (B) Civil Engineering Faculty, Division of Hydraulics, Istanbul Technical University, Maslak, Istanbul 34469, Turkey e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_123,

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mechanical resistance of lakeside Phragmites australis stands. While Coops et al. [2] explored the growth and distribution of this specie as well as Scirpus lacurtis. In current literature, it has been generally agreed that vegetation increases flow resistance, controls the mean and turbulent flow structure in channels and coastal regions and thus, modifies sediment transport and deposition [12, 15]. Several studies have already been performed to analyze the flow resistance of rigid emergent vegetation. In all those studies the vegetation was simulated by a group of cylinders of the same height and diameter at a regular spacing [9, 11]. In another approach, it was claimed that the flow resistance depends on the density of the vegetation as well as bending stiffness of the species. The density of vegetation is defined as the frontal area of submerged vegetation projected onto a plane perpendicular to the direction of flow per unit volume of flow [4]. Türker et al. [14] experimentally explored the protection performance of the emergent vegetation on the morphological changes of a costal zone. The list of wave parameters and beach erosion related functions were incorporated in relation to vegetation intensity in order to define coastal zone response. Knowledge of interaction between vegetation and incident waves helps a better understanding of ecological and geomorphological processes in coastal waters with particular respect to coastal defence management. The primary objective of the current study is to experimentally investigate and examine the effect of lakeside Phragmites australis on wave damping and retardance. Furthermore, for a given vegetated area magnitude the correlations between various representative wave characteristics (i.e. wave height, wave period and wave steepness) and wave damping were investigated.

2 Analysis and Records Characterizing of a vegetated area magnitude is necessary to explore damping and retardance by vegetation. Further it is also essential for the upscaling procedure by the data obtained from experimental study. For this purpose, a new dimensionless parameter is introduced below to characterize the vegetated area magnitude. In Fig. 1 a vegetated area is shown together the geometric characteristics of vegetative elements.

lx d ly Ly

Fig. 1 Definition of vegetation density

Lx

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Based on the nomenclature in Fig. 1 the dimensionless vegetated area magnitude is given by: λ=

Lx Ly (lx − d)(ly − d)

(1)

The wave transmission coefficient is given below (Eq. 2) and this parameter is utilized through the description of the wave damping ratio (Eq. 3). The wave damping ratio gives the damping percentage of the incident wave through the vegetated area: Ct =

Ht Hi

DR = 1 − Ct

(2) (3)

where Ct =transmission coefficient; Ht =transmitted representative wave height; Hi =incident representative wave height; DR =wave damping ratio in terms of percentage. In a similar way the retardance ratio (or ratio of wave period retardance) is described: RR =

Tt −1 Ti

(4)

where RR =wave period retardance ratio in terms of percentage; Tt =transmitted representative wave period; Ti =incident representative wave period. At the stage of analysing the experimental data variations of DR and RR versus λ, L, H/L, H were computed and plotted. The experimental results and analyses are presented later in the Sect. 4.

3 Experimental Set-Up and Technique The laboratory experiments were performed in a wave flume 24 m long, 1 m wide and 1 m in height. The water depth was 60 cm during the experiments. Irregular waves were generated using a wave generator jointed to the bottom of the flume and attached to a hydraulic shaft at an upper part of the flume. A computer controlled the wave maker. The wave flume was divided into two parts, one side was vegetated and the other side was smooth and unvegetated. A sand slope of 1 V/5H was placed behind the vegetated area in order to dissipate the wave energy and to overcome wave reflection problems. 61 irregular wave series (P-M spectrum) in the irregular wave flume were applied to the vegetated and unvegetated areas simultaneously. The duration of the each irregular wave series was 5 minutes. A wave monitor amplifier, which was connected to A/D converter card in the computer and three resistance type wave electrodes connected to wave monitor amplifier were utilized for wave data collection both in the vegetated and non-vegetated zone simultaneously. One wave electrode was positioned 10 cm behind the vegetated area and

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another one was located at an identical position in the unvegetated zone. Further, a wave electrode was positioned at an offshore location. The location of this electrode was in the centreline of flume cross-section and 1 m away from the vegetated zone. In order to check the validity of the experimental irregular wave data, ratios between obtained (measured and analysed) wave height statistics were compared with ratios between wave height statistics derived from Rayleigh distribution [3, 5]. Ratios between wave height statistics showed that the generated waves in the flume fitted Rayleigh distribution properly. Real reeds (phragmites australis- without foliage), with diameter less than 5 mm were employed throughout the experiments for the emergent case. The spacing between each vegetative element was 20 mm in the cross-streamwise and 20 mm in the wave direction. 7, 15, 30, 45 and 60 rows (in the wave direction) of reed were tested in the experiments and a total of 61 irregular wave series were applied to the vegetated area. A wooden array system was utilized to mount the vegetative elements.

4 Experimental Results The variation of damping ratio “DR ” with respect to dimensionless vegetated area magnitude λ is presented in Fig. 2. As it may be seen from the Fig. 2, with the increasing of the vegetated area magnitude, wave damping ratio increases. The determination coefficient (R2 =0.95) show that the correlation between these two parameters is quite high and this result point out that the λ parameter is defines well the vegetated area magnitude. Further, for the lower values of λ, the gradient of the curve is steeper compared to higher λ values and also for the highest λ values, the gradient tends to go to asymptote. In other words, increasing the number of

0.6 0.5

y = – 7E-12x3 + 6E-08x2 – 4E-05x + 0.151 R2 = 0.95

DR (–)

0.4 0.3 0.2 0.1 0.0 0

2000

4000

6000

λ(–) Fig. 2 The variation of wave damping ratio “DR ” with respect to vegetated area magnitude “λ”

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λ = 622.22 λ = 1333.33 λ = 2666.67 λ = 4000.00 λ = 5333.33

0.5 0.4

DR (–)

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R2 = 0.98 2 R = 0.43

0.3 R2 = 0.81

0.2

2 R = 0.01

R2 = 0.46

0.1 0.0 0.8

1.0

1.2

1.4

1.6 L (m)

1.8

2.0

2.2

2.4

Fig. 3 DR –L variation for different vegetation magnitudes

vegetative elements for the low vegetated area magnitudes is more efficient in terms of wave damping compared to higher λ values. In Fig. 3 the variation between wave damping ratio “DR ” and wave length “L” is presented for the different vegetated area magnitudes. The wave length was computed using small amplitude wave theory and “Tm ” mean wave period values were utilized through the computations. As it may be seen from the Fig. 3, there is a considerable correlation between those two parameters and with the increasing of wave length, the wave damping ratio tends to decrease for a given vegetated area magnitude. The experimental data in Fig. 4, which give the relationship between “representative wave height statistic” and “wave damping ratio”, showed that there is a weak correlation between those two parameters. As a representative wave parameter, (Hrms )i was chosen to characterize the incident wave height since in a way it represents the wave energy as well. Based on the experimental data in Fig. 4 it may be judged that with the increasing values of representative wave height parameter, the wave damping ratio decreases. The same conclusion was obtained for the other representative wave height parameters (i.e. Hm , Hs , H1/10, H1/30 and Hmax ) however not to repeat the similar results here those graphs were not presented here. The variations of wave damping ratio “DR ” with respect to wave steepness “H/L” is illustrated in Fig. 5 for five different vegetated area magnitudes. During the computation of wave steepness, significant wave height values “Hs ” were utilized as the representative wave height parameter and mean wave period values “Tm ” were used through the calculation of wave length as it is stated above. As can be seen from the Fig. 5, there is a weak correlation between “H/L” and “DR ”. Also from the same figure it may be concluded that with the increasing of wave steepness “H/L”, wave damping ratio “DR ” increases for the all vegetated area magnitudes except λ=622.22.

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λ = 622.22 λ = 1333.33 λ = 2666.67 λ = 4000.00 λ = 5333.33

0.5

R2 = 0.40

DR(–)

0.4

R2 = 0.22

0.3 R2 = 0.14

0.2

R2 = 0.05 R2 = 0.52

0.1 0.0 3

6

9

12

(Hrms)i (cm)

Fig. 4 Wave damping ratio “DR ” versus representative wave height statistic “Hrms ” for different λ values

0.6 0.5

DR (–)

0.4

λ = 622.22 λ = 1333.33 λ = 2666.67 λ = 4000.00 λ = 5333.33

R2 = 0.97 R2 = 0.13 R2 = 0.12

0.3 0.2

R2 = 0.39 2

0.1 0.0 0.025

R = 0.15

0.050 H/L (–)

0.075

Fig. 5 The variation of wave damping ratio “DR ” with respect to wave steepness “H/L” for five different vegetated area magnitudes “λ”

The variations of wave period retardance ratio “RR ” with respect to vegetated area magnitude “λ” is given in Fig. 6. During the computation of “RR ” parameter, mean wave period values “Tm ” was used for both incident and transmitted waves. As it can be seen from the Fig. 6 for the higher values of “vegetated area magnitudes”, “wave period retardance ratio” increases.

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0.30 0.25

RR (–)

0.20 0.15 R2 = 0.36 0.10 0.05 0.00 0

2000

4000

6000

λ (–) Fig. 6 The variation of wave period retardance ratio “DR ” with respect to vegetated area magnitude “λ”

5 Conclusion This paper presents an analysis of effect of lakeside Phragmites australis stands on wave damping and retardance phenomenon for the emergent case. In summary, the following conclusions were drawn based on the experimental data. It was seen that there is s strong correlation between introduced “vegetated area magnitude” (λ) and “wave damping ratio” (DR ). This result confirms that the introduced “λ” parameter represent well the vegetated area magnitude. However it should be considered that in this study only the “Lx ” parameter was varied in the λ parameter during the experiments. Therefore it is necessary to vary the other parameters (i.e. Ly , lx , ly and d) in λ to test the λ parameter further. It was seen that there is a considerable correlation between “wave damping ratio” and “wave length” for a given vegetated area. Also it was found that with the increasing of wave length, wave damping ratio decreases. The experimental data which gives the relationship between “representative wave height parameter” and “wave damping ratio” showed that for a given vegetated area, wave damping ratio tends to decrease with the increasing of representative wave height. Experimental data showed that there is a weak correlation between “wave damping ratio” and “wave steepness”. Based on these data it was also concluded that with increasing of wave steepness, wave damping ratio increases. Based on the experimental data it was found that, with the increasing of “vegetated area magnitude”, “wave period phase retardance” increases. This increment is more drastic for the lower values of λ. Acknowledgements The authors would like to present their thanks to Dr. Catherine A.M.E. Wilson from Cardiff University, Environmental Water Management Research Centre for her valuable contributions.

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References 1. Andersen KH, Mork M, Nilsen JEO (1996) Measurement of the velocity profile in and above a forest of Laminaria hyperborean. Sarsia 81:193–196 2. Coops H, Geilen N, Gerard VDV (1994) Distribution and growth of the helophyte species Phragmites Australis and Scirpus lacustris in water depth gradients in relation to wave exposure. Aquat Bot 48:273–284 3. Dean RG, Dalrymple RA (1991) Water wave mechanics for engineers and scientists. World Scientific, Prentice-Hall Inc. Singapore, p 353 4. Dudley SD, Bonham CD, Abt SR, Fischenich JC (1998) Comparison of methods for measuring woody riparian vegetation density. J Arid Environ 38:77–86 5. Goda Y (2000) Random sea and design of maritime structures, 2nd edn. World Scientific, Prentice-Hall Inc. Singapore, pp 464 6. Kobayashi N, Raichle AW, Asano T (1993) Wave attenuation by vegetation. J Waterway, Port, Coastal Ocean Eng ASCE 119(1):30–48 7. Lovas SM, Torum A (2001) Effect of kelp Laminaria hyperborea upon sand dune erosion and water particle velocities. Coastal Eng 44:37–63 8. Massel SR, Furukawa K, Brinkman RM (1999) Surface wave propagation in mangrove forests. Fluid Dyn Res 24(4):219–249 9. Meijer D, Van Velzen EH (1999) Prototype-scale flume experiments on hydraulics roughness of submerged vegetation. Proceedings of 28th international association for hydraulic research (IAHR) conference. IAHR, Graz, Austria 10. Mork M (1996) The effect of kelp in wave damping. Sarsia 80:323–327 11. Nepf HM (1999) Drag, turbulence and diffusion in flow through emergent vegetation. Water Resour Res 35:479–489 12. Nepf HM, Vivoni ER (2000) Flow structure in depth-limited, vegetated flow. J Geophys Res 105(C12):28547–28557 13. Ostendrop W (1995) Estimation of mechanical resistance of lakeside Phragmites stands. Aquat Bot 51:87–101 14. Türker U, Yagci O, Kabda¸sli S (2006) Analyses of coastal damage of a beach profile under the protection of emergent vegetation. Ocean Eng 33(5–6):810–828 15. Yen BC (2002) Open channel flow resistance. J Hydraul Eng 128:20–39

The Effect of Sludge History on Aerobic Sludge Stabilization Efficiency G. Insel, H. Gökçeku¸s, S. Sözen, E. Dulekgurgen and D. Orhon

Abstract This paper evaluated the effect of sludge history on the efficiency of aerobic sludge stabilization. The fate of excess sludge in activated sludge systems is closely related to the nature of biomass sustained in the system. The composition of biomass greatly affects stabilization performance. In this study, the impact of sludge history was investigated for different sludge ages in the range of 1–35 days in a system treating typical domestic sewage. A biochemical model was adopted to define particulate COD components for selected sludge ages. For each selected sludge age, the progress of aerobic stabilization was evaluated in terms of the same parameters for a period of 30 days. Model simulation indicated that the active fraction of the biomass (XH ) varied between 0.13–0.40 depending on the sludge age of the systems at the beginning of the stabilization period. It also showed that the nature of the biomass corresponding to a selected sludge age was a key factor determining the stabilization efficiency. Keywords Activated sludge · Aerobic sludge stabilization · COD fractionation · Domestic sewage · Modelling · Process kinetics · Sludge age

1 Introductıon Within the waste and wastewater management, sludge stabilization is gaining more interest and concern over the last decade with the enforcement of European Union (EU) environmental legislation which intends to achieve a higher degree of waste treatment for the increasing population to safeguard human health and the environment against hazards arising from waste material (EEC, 1986) Stabilization is in principle controlled decomposition of easily degradable organic matter resulting in a significant reduction of volatile solids content D. Orhon (B) Environmental Engineering Department, Faculty of Civil Engineering, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey e-mail: [email protected]

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(McFarland, 2001). Aerobic stabilization is now a viable alternative especially for medium-size and smaller activated sludge treatment plants. Aerobic stabilization of activated sludge process is preferred in an increasing number of treatment plants. As in all biological processes, temperature plays an important role in aerobic digestion. When an aerobic process is used at ambient temperatures; the degradation rate is reported as about 30–40% at sludge retention time (SRT) of over 25 days. On the other hand, in the thermophilic range, much higher rates for VSS reduction were reported (Pehlivano˘glu et al., 2007; Roš and Zupancic, 2002). In wastewater treatment plants (WWTPs) where extended aeration process is employed (SRT > 20–30 days) stabilization of sludge may be almost complete in the aeration tank; whereas in plants having a SRT of less than 10 days, an additional sludge treatment will be necessary (ATV, 2003). The process itself, the operational conditions and wastewater characteristics directly indicate the characteristics of the sludge produced in the system. Aerobic stabilization of biological sludge reflects further biodegradation of the organic content through endogenous respiration. Hence, if the treatment plant is not welldesigned, it is probable that there will be some particulate sludge component (Xs ) present, which has to be considered in the hydrolysis process. In this context, the objective of the study was to evaluate the effect of sludge history on the efficiency of aerobic sludge stabilization. The sludge age of the activated sludge system generating excess sludge was selected as the indicative design parameter. Model simulation was used to assess stabilization efficiency.

2 Materials and Methods In this study, the efficiency of aerobic sludge stabilization was determined for a typical domestic sewage with characteristics given in Table 1. The schematic representation of the activated sludge plant generating excess sludge was illustrated Table 1 Wastewater characterization and parameters used in design Parameter Total suspended solids Volatile suspended solids Fixed solids (TSS-VSS) Chemical oxygen demand (COD) Biochemical oxygen demand (BOD5 ) Influent soluble COD COD fractions Soluble inert COD Particulate inert COD Readily biodegradable COD Slowly biodegradable COD Total Kjeldahl nitrogen (TKN) Design process temperature a ammonia

nitrogen, NH4 –N=0.70·TKN

mg/L mg/L mg/L mgO2 /L mgO2 /L mgO2 /L – mgO2 /L mgO2 /L mgO2 /L mgO2 /L mgN/L ◦C

Notation Concentration

% Fraction CT

TSS VSS FS CT BOD5 ST

455 250 205 680 330 210

– – – – 48 31

SI XI SS XS TKN ◦C

35 86 174 385 52a 20

5 13 25 57 – –

The Effect of Sludge History on Aerobic Sludge Stabilization Efficiency Influent

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Aerobic

Effluent

WAS

Fig. 1 Wastewater treatment plant configuration Table 2 Kinetic and stoichiometric relationships of processes for Aerobic Stabilization as defined in ASM1 Component Process

SS

XS

Growth Hydrolysis Decay

–1/YH 1

–1

XH

XP

SP

1 –1

fEX

fES

S0

Process rate ML–3 T–1

–(1∗ YH )/YH

μH ·SS /(KS +SS ) XH S /XH Kh (KXX+X XH S /XH ) bH XH

–(1–fEX –fES )

in Fig. 1. The model adopted for the evaluation included the basic template of Activated Sludge Model No.1 – ASM 1 (Henze et al., 1987), modified for endogenous respiration (Orhon and Artan, 1994). The model utilized the part of the modified model which was relevant for aerobic stabilization, as shown in the matrix format in Table 2.

3 Results and Discussion Many studies presented in the literature have used synthetic sludge to represent biological sludge which allows a well-controlled system by elimination of various problems for modeling (Ormeci and Vesilind, 2000). On the other hand, characterization of domestic wastewater was also helpful for determination of model coefficients. Therefore, model calibration was performed by using the kinetic coefficients of domestic wastewater close to data provided by Orhon et al. (2002) Simulations using the adopted model were executed using BIOWIN 3.1 computer program. Values of model parameters used in the study are given in Table 3. Sludge productions were calculated as defined by Orhon and Artan (1994) for each particulate component respect to influent characteristic of domestic wastewater plant. Calculated sludge production assumed to represent the influent sludge characteristic of aerobic stabilization plant. Results of model calibration studies were compared with the VSS efficiency calculation according to Tchobanoglous et al. (2003). Since the model calibration and calculations were suitable, design of the aerobic stabilization were completed with the calculation of oxygen requirements and appropriate flow of waste sludge. Figure 2 reflects the simulation results on the

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Parameter

Unit

Value

Heterotrophic yield coefficient, YH Endogenous decay rate for XH , bH Maximum growth rate for XH, μHmax Half saturation constant for growth of XH, KS Half saturation constant of oxygen for XH , KOH Maximum hydrolysis rate for XS1 , kh Hydrolysis half saturation constant for XS , KX Soluble inert COD fraction of biomass, fes Particulate inert COD fraction of biomass, fex

gcellCOD/gCOD 1/day 1/day mgCOD/L mgO2 /L 1/day gCOD/gcellCOD – –

0.60 0.20 3.5 5 0.2 1.5 0.02 0.05 0.15

fate of different particulate COD components during aerobic stabilization started with excess sludge generated from an activated sludge plant operated at a sludge age of 10 days. Obviously, the operating conditions of the activated sludge plant play a decisive role on the characteristics of excess sludge as well as the performance of the plant itself. The selected sludge age sets the value of the other significant operation parameter, the hydraulic retention time (HRT), and also the carbonaceous oxygen uptake rate (OURc ). Table 4 gives the variation of the operating parameters of the activated sludge plant as well as the level of effluent COD with the selected sludge age. The selected sludge history (the sludge age) also sets the nature of the biomass sustained in the activated sludge plant. Model evaluation allows defining the nature of the biomass in terms of its composition, i.e. the relative magnitude of the active heterotrophic biomass together with other significant particulate COD fractions in the mixed liquor. Table 5 summarizes the results of model simulation determining the composition of the biomass as a function of the operating sludge age.

X_H

Particulate Components (mg COD/l)

400

X_P

350

X_S

300

X_T

250

X_I

200 150 100 50 0 −50

0

5

10

15

20

25

30

Time (day)

Fig. 2 Fate of particulate COD components of excess sludge for a sludge age of 10 days

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Table 4 Effect of sludge age on the operating parameters of the activated sludge plant (Qinfluent =1 m3 /day) SRT

HRT

Plant effluent quality

Oxygen uptake rate for Carbon, OURC

ORc/Q

days 1 5 15 20 35

days 0.14 0.55 1.50 2.30 3.20

mgCOD/L 39.5 44.0 49.0 48.0 50.0

g/m3 .h 75 27 12 10 6

gO2 /m3 252 356 432 552 461

Table 5 Mixed liquor composition depending upon solids retention time (MLSS:4500 mg/L) Active heterotrophic biomass∗ , XH

Endogenous microbial products∗ , XP

Particulate ınert COD∗ , XI

SRT

Fixed solids, XF

Slowly hydrolysable COD∗ , XS

days 1 5 15 25 35

mg/L 1731 2173 2394 2600 2650

mgCOD/L 1851 1520 852 594 450

mgCOD/L 82 313 506 613 644

mgCOD/L 607 773 852 930 940

mgCOD/L 294 20 5.0 2.5 1.7

1 g COD ≈ 1 gTSS

The performance level of aerobic stabilization obviously depends on the active ingredient of the sludge to be stabilized, i.e. the active heterotrophic biomass component which would be responsible for removing any available particulate substrate in the sludge and also, on the endogenous respiration process, which will be sustained during the stabilization process, again a function of the active biomass. Therefore, this parameter is crucially important for the success of stabilization. Consequently, analysis based on modeling, assessing the fraction of active biomass depending on the operating conditions of the plant generating excess sludge becomes a valuable instrument for the success of stabilization. Figure 3 outlines the initial active biomass fraction of the sludge to be stabilized as a function of the sludge age and shows that the XH fraction changes from around 40% at a sludge age of 1.0 days, down to 10% at a sludge age of 35 days. The same figure also indicates the level of VSS reduction to be achieved for the sludge age range tested in the simulation. Model simulations performed with excess sludge corresponding to the tested range of sludge ages indicate that the expected efficiency of aerobic stabilization changes as a function of sludge history. Table 6, which outlines the simulation results, shows that the VSS removal at the end of the selected stabilization period drops from more than 50% at a sludge age of 1.0 days down to 28% when the sludge age is increased to 15 days. It also indicates that the stabilization period is an important parameter affecting VSS reduction.

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Fig. 3 The effect of sludge age on (a) the active biomass fraction, (b) VSS/TSS ratio in the mixed liquor (MLSS) Table 6 Simulation results for aerobic digestion Activated sludge SRT days 1

5

15

Stabilization SRT days

XH /MLSS ratio %

VSS removal %

5 10 30 5 10 30 5 10 30

33 24 12 19 13 7 10 7 4

40 52 65 24 32 42 16 21 28

References 1. EEC (1986) Council Directive 86/278/EEC, 12 June 1986 on the protection of the Sewage Sludge Directive. http://ec.europa.eu/environment/waste/sludge/index.htm 2. ATV (2003) German ATV-DVWK Rules and Standards, Advisory Leaflet, ATV-DVWK-M 368E, Biological Stabilization of Sewage Sludge April, Germany 3. Henze M, Grady CPL Jr, Gujer W, Marais GVR, Matsuo T (1987) Activated sludge model No. 1. IAWPRC Scientific and Technical Report No. 1, IAWPRC, London, UK 4. McFarland MJ (2001) Biosolids engineering. McGraw Hill, New York, ISBN 0-07-047178-9 5. Orhon D, Okutman D, Insel G (2002) Characterization and biodegradation of settleable organic matter for domestic wastewater. Water SA 28(3):299–305 6. Ormeci B, Vesilind PA (2000) Development of an improved synthetic sludge: a possible surrogate for studying activated sludge dewatering characteristics. Water Res 34(4):1069–1078 7. Pehlivanoglu E, Okutman Tas D, Insel G, Aydin E, Ubay Cokgor E, Gorgun E, Orhon D (2007) Evaluation of municipal and industrial wastewater treatment sludge stabilization for environmental hazard in Istanbul. Clean 35(6):558–564 8. Ros M, Zupancic GD (2002) Thermophilic aerobic digestion of waste activated sludge. Acta Chim Slovenica 49(4):931–939 9. Tchobanoglous G, Burton FL, Stensel HD (2003) Wastewater enginnering: treatment and Reuse. Metcalf and Eddy

Morphological and Physiological Features of an Aerobic Granular EBPR Biomass Fed with Propionate Ebru Dulekgurgen, Nazik Artan and Derin Orhon

Abstract The current study is an attempt to link the morphological and EBPRrelated physiological traits of a propionate-fed aerobic granular biomass with the EBPR performance of the system. A lab-scale SBR was started up by the aerobic granular EBPR biomass taken from an acetate-fed SBR and the inoculum was acclimated to propionate as the sole C-source. Mechanical-mixing applied during 2-h of anaerobiosis at the head of the cycle was the main source of shear (vSMix ; 7.6 cm/s), thus hydraulic selection pressure, and feeding the system under anaerobic conditions for 1 h at the head of the cycle, as well as supplying ortho-P in the influent (COD:P=12.8 mg COD/mgPO4 -P) were the main metabolic-selection pressures ensuring the dynamic formation, maintenance, and stability of the aerobic semi-granular EBPR biomass (dgra ; 1.41 mm) with superior settling properties and compactness (SVI≤50 mL/g), and promoting the selection of anaerobically C-storing (>95% anaerobic COD-removal), aerobically slowly growing and Premoving organisms –the PAOs- in the system, resulting in an acceptable level of EBPR performance (78% EBPR efficiency). The biomass was considerably diverse with various morphotypes being present (rods, filaments, tetrads/sarcina-like cells, coccoid-clusters, diplo-coccoids, and elongated rod-shaped cells unique for the system). Phenotypic characterization via chemical-staining and conventional lightmicroscopy revealed the presence of the PAOs cycling their intracellular poly-P and PHB inclusions between the anaerobic and aerobic phases. Tetrads/sarcina-like cells (TFOs) resembled the GAOs morphologically but not phenotypically. Elongated rod-shaped cells (PUBs), which had the ability to anaerobically utilize propionate and store it as PHB, were speculated to be either GAOs or functionally less efficient PAOs. Microbiological observations were qualitative, rather than quantitative, yet they found to correlate to an extend with the observed biochemical performance of the system.

E. Dulekgurgen (B) Faculty of Civil Engineering, Environmental Engineering Department, Istanbul Technical University, Maslak, Istanbul, 34469, Turkey e-mail: [email protected]

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Keywords Enhanced biological phosphorus removal (EBPR) · Selection pressure · Aerobic granular biomass · Morphology · Poly-phosphate accumulating organisms (PAOs) · Tetra-forming organisms (TFOs)

1 Introduction Various lab- and pilot-scale studies, carried out extensively in recent years to enlighten the fundamental microbiological and biochemical aspects of Enhanced Biological Phosphorus Removal (EBPR), have significantly contributed to understanding the basics of this exclusive biological phenomenon. Yet the structure of EBPR being complicated due to reliance of the essential steps of the metabolism on anaerobic-aerobic cycling of intracellular storage polymers dictates further need for research on microbiological and/or physiological aspects of this phenomenon [17]. Upon introduction and accelerated use of the advanced molecular techniques in the field of environmental science and engineering, information on microbial diversity of EBPR communities and phylogenetic identity of significant populations in well-performing and deteriorated EBPR systems has been well documented [4, 5, 14, 27]. On the other hand, classification of microorganisms as PAOs (Phosphate Accumulating Organisms) and non-polyP bacteria or GAOs (Glycogen Accumulating Organisms) is a functional categorization, rather than a phylogenetic one, and co-existence of these two functional groups in EBPR systems complicates evaluation of the systems in terms of carbon-, phosphorus-, and energy-budgets. Besides, knowing that the term “PAOs” refers to a functional microbial group with phylogenetically scattered members, phylogenetic evaluation of EBPR biomass to describe community structure and diversity, needs to be supported by biochemical performance analyses, as well as by morphological and phenotypic characterizations to accurately identify the populations of the microflora contributing to the observed conversion processes, and to estimate the extent of contribution from different populations. This can be realized by performing a combined set of experiments. After recognition of granulation in anaerobic systems in the 1970s, numerous full-scale treatment plants with anaerobic granular biomass, providing superior supernatant-biomass separation, high mixed liquor suspended solid (MLSS) concentrations, and ability to meet high loading rates or to treat more wastewater in smaller volumes due to the compact structure of granular biomass, have been in act world-wide [24]. Moreover, during the last decade, research has focused on carbon and/or nitrogen removal by aerobic granular biomass in lab-scale sequencing batch reactors (SBRs). Yet, studies on EBPR with aerobic granular biomass still remain in a limited number [6, 7], and evaluation of such systems in terms of microbiological and phenotypic traits is even more scarce [8]. With this insight, this study attempts to couple the morphological and EBPRrelated physiological traits of an aerobic granular biomass fed with propionate and cultivated in a lab-scale SBR, with the EBPR performance of the system. For that purpose the morphological and phenotypic characteristics assessed

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via chemical-staining and conventional light-microscopy were evaluated together with the EBPR performance of the lab-scale system determined via conventional chemical analyses.

2 Materials and Methods 2.1 Experimental Set-Up and Operation A lab-scale SBR, with an internal diameter of 14 cm and a working height of 24.7 cm (HW /D ratio of 1.8), was operated at a sequential anaerobic/aerobic mode with the following operational conditions: 2 h of anaerobic phase followed by 3 h 15 min of aerobic phase; 15 min of settling (TS ), 30 min of effluent withdrawal and idle phase; thus total of 6 h per cycle (TC ) and 4 cycles per day. Initial volume (V0 ) was 1.8 L and filling volume (VF ) was 2 L, resulting in a V0 /VF ratio of 0.90, an exchange ratio of 53%, and an HRT of 11.4 h. The system was fed under anaerobic conditions during the first hour of each cycle and mechanical mixing was employed ◦ during 2 h of anaerobiosis. A 2-blades pitched (60 ) impeller and a 4-blades square pitched propeller were present on the shaft of the mechanical mixing device. The power number (NP ) and the flow number (NQ ) of the impeller were 1.2 and 0.85, respectively, and those of the propeller were 0.4 and 0.55, respectively. The diameter of the impeller was 0.052 m and that of the propeller was 0.068 m. Speed of the mechanical mixer was 300 rpm. Using the characteristics of the impeller and the propeller, as well as the mixing speed, the pump discharge capacity of the mechanical mixer (Qi ) was calculated as 0.69 L/s [16]. The theoretical air flow rate (Qair ) was 130 L/h -maximum capacity of the air compressor-, yet this was considered to decrease by 20% due to an efficiency loss to occur while transferring the motor/compressor power to power in water. The volumetric COD-loading rate was 1.35 kg/m3 .d and the influent composition was 642 mg COD/L (from propionate as the sole carbon source), 50 mg PO4 -P/L, 45 mg NH4 -N/L, resulting in a C:P ratio of 12.8 mg COD/mg PO4 -P. Biomass withdrawal from the system on a daily basis resulted in a sludge retention time (SRT) of 10.9 d, and an effective SRT of 9.5 d. pH in the system was monitored online and maintained at 7.0±0.5 via acid/base addition controlled by dosing pumps connected to a pH-controller. The double-jacketed configuration of the reactor enabled ◦ maintaining the temperature at 20 C.

2.2 Analytical Measurements Samples collected by the end of the aerobic periods of two subsequent cycles (effluent samples; E1 and E2) and by the end of the first and second hours of the anaerobic period (end of anaerobic filling and end of anaerobic mixing samples; F and M respectively) were filtered and subjected to COD, PO4 -P and NOX -N measurements.

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MLSS and MLVSS measurements were carried out on mixed liquor samples collected right before the end of the aerobic phase. 1 L of mixed liquor, sampled 30 min before the end of the aerobic phase, was used to determine the SVI of the biomass. C-, P-, and N-contents of the feed were determined via COD, total phosphorus (TP), and TKN measurements. Total phosphorus content of the biomass (BPC) was determined in the mixed liquor sample which was collected right before the end of the aerobic period and subjected to sulfuric-acid nitric-acid digestion followed by stannous chloride method. All measurements, except for SVI, were carried out in duplicates in accordance with the Standard Methods [1], except for COD. For the latter, measurements were carried out in duplicates via following the closed-reflux method described in the International Standard ISO 6060 [10].

2.3 Microbiological Measurements To assess the general texture of the EBPR biomass cultivated in the propionate-fed reactor, several mixed liquor samples were collected and transferred to petri dishes at the day of sampling. Macro-structure of the aerobic granular EBPR biomass was observed with a light microscope (Olympus BX60) and micrographs were captured with a diagnostic camera (SPOT RX) mounted on the microscope and connected to a PC. Digital images were processed with an image analysis software (ImagePro Plus, V4.0, Media Cybernetics) to determine the mean diameter of each granule and the average dgra value for each biomass sample (a fictive value representing the arithmetic average of the mean diameters of all the granules measured in a biomass sample). Since the EBPR phenomenon is characterized by cycling of the intracellular storage materials between the anaerobic and aerobic periods, thus resulting in significantly different amounts of stored polymers by the end of these periods, several mixed liquor samples were collected both from the end of the anaerobic- and from the end of the aerobic-periods to qualitatively evaluate the propionate-fed aerobic granular EBPR biomass in terms of morphological and phenotypic traits characteristic for the EBPR phenomenon. For detection and visualization of the intracellular storage materials, chemical staining procedures were applied to thin smear samples fixed on glass microscope slides. The thin smear samples were gently but quickly fixed by heat-treatment to avoid consumption and/or production of storage polymers prior to staining reactions [13]. Although not specific for poly-P, but has been widely used for microscopic evaluation of EBPR biomass, Neisser’s staining (Methylene Blue and Crystal Violet for staining, and Bismark Brown for counter-staining) was applied for determination of the intracellular metachromatic, volutin poly-P granules. To visualize the lipophilic cellular inclusions, mainly the PHBs (polyhydroxy-butyrate), samples were treated with Sudan Black B (staining PHB), and then with Safranin O (counter-staining). Gram-staining was also applied to some of the samples. The recipes used and the staining procedures followed for all chemical staining reactions were adopted from those provided by Jenkins et al. [11]. Digital

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images of the stained samples were captured with the diagnostic camera mounted on the light-microscope and connected to a PC, processed initially with the SPOT Advanced Software, then in Adobe Photoshop.

3 Results and Discussions 3.1 Aerobic Granulation and EBPR Performance The reactor was started up by a semi-granular EBPR biomass taken from an acetatefed lab-scale SBR and the inoculum was acclimated to propionate as the sole C-source. The acetate-fed parent reactor had a stable and complete EBPR performance and the biomass was determined not only to be enriched with PAOs, but also to be at a pseudo steady-state during which formation of aerobic granules followed a repetitive pattern of growing in size, then breaking into smaller granules, and starting to grow in size again. EBPR performance of the parent reactor and the macro-structure of the acetate-fed aerobic granular EBPR biomass were previously described in Dulekgurgen et al. [8], together with a detailed evaluation of the biomass in terms of morphological and phenotypic characteristics. Hydraulic- and metabolic-selection pressures-related parameters determined to evaluate the system with regard to aerobic granulation were as follows: Minimum settling velocity (vmin) dictated by the operationally set settling time (TS ; 15 min) and the effluent extraction height (Hmin ; 13 cm) was 0.87 cm/min and this was significantly lower than those (i.e., minimum of 8–11 cm/min) reported in the literature for aerobic granular biomass systems [12, 15, 19, 20], and the references therein). Superficial upflow air velocity (vSair ) has been the most frequently reported and almost the only quantitatively determined component of hydrodynamic shearing conditions in aerobic granular biomass systems. The vSair value for the propionate-fed SBR was 0.19 cm/s, and this was also markedly lower than the values (2–2.5 cm/s) repeatedly reported in the literature [2, 3, 23, 24, 26]. On the other hand, aeration was not the only hydrodynamic shear-causing factor in the system since the propionate-fed reactor was operated at a sequential anaerobicaerobic mode and mechanical mixing was employed during 2 h of anaerobiosis at the head of each cycle. Hence, it was required to determine the hydrodynamic shearing rate due to mechanical mixing (vSMix ) via taking into account the pumping input (Qi ) of the mechanical mixing device and the cross-sectional area of the reactor [16]. Hydrodynamic shear rate originating from mechanical mixing (vSMix ) and being valid for the first 2 h of the total react time (TReact ; 5.25 h) during each cycle was calculated as 7.6 cm/s. As apparent from the above calculations, although the hydraulic selection pressure-related parameters of minimum settling velocity (vmin ) and superficial upflow air velocity (vSair ) − in other words aeration-related shear rate − were significantly relaxed when compared to the levels reported in the aerobic granular biomass literature in general, the system was under a considerable shearing effect due to mechanical mixing, and the mixing-related hydrodynamic

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shear rate (vSMix ) was considered as the main hydraulic selection pressure ensuring the dynamic formation and maintenance of the aerobic granular biomass in the propionate-fed SBR. Operating the reactor with a 2-h anaerobic period prior to the 3.25-h aerobic phase, feeding the system under anaerobic conditions for 1 h at the beginning of each cycle, and supplying ortho-P to the system, not only served as strategies for securing the continual selection and dominance of the PAOs for an acceptable EBPR performance, but also functioned as the metabolic selection pressures ensuring the stability of the aerobic granular biomass via slowing down the system through the absolute elimination of an aerobic feast phase of rapid growth and selection of these anaerobically C-storing, aerobically slowly growing and P-removing organisms in the system. The amount of phosphorus in the influent was increased from 30 to 40, then to 50 mg PO4 -P/L during the course of the study. The corresponding C:P ratios were 21.4, 16.1, and 12.8 mg COD/mg PO4 -P, respectively. The influent composition and the applied operational characteristics, translating into the abovementioned hydraulic- and metabolic-selection pressures assured the dynamic formation and maintenance of a semi-granular EBPR biomass in the system. SVI of the propionatefed semi-granular EBPR biomass was less than 50 mL/g, pointing out to a biomass with superior settling properties. A typical mature granule from the propionate-fed reactor, surrounded by young granules, can be seen in Fig. 1 panel A, and size distribution of the semi-granular EBPR biomass after 1-year of operation is presented in panel B. Average granule diameter at the time of sampling was determined as 1.41 mm. Conventional biomass characteristics determined after 1 year of operation are given in Table 1, together with the influent composition valid for the time of the study. PO4 -P, COD, and NOX -N values measured by the end of subsequent cycles

(A)

Size distribution of the propionate-fed semi-granular EBPR biomass

(B)

% of objects

16 12 8 4 0 0.2 0.4 0.5 0.6 0.7 0.8 1.2 1.5 2 2.5 3 Mean dgra (mm)

4

5

Fig. 1 Macro-structure of the propionate-fed semi-granular EBPR biomass. Panel A: A typical mature granule surrounded by young granules; Panel B: Size distribution in terms of mean dgra (granule diameter) values after 1 year of operation

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Table 1 Characteristics determined for the propionate-fed SBR Week 53: 78% P-removal with propionate-fed semi-granular EBPR biomass Influenta

COD (mg/L) TP (mg/L) TKN (mg/L)

Biomass T 642 50 45

M 540 50 45

MLSS (mg/L) MLVSS (mg/L) MLVSS/MLSS SVI (mL/g)

Measured (mg/L)

5000 3360 67% 50

Sampleb E1 F M E2

PO4 -P 9 120 136 11

COD 26 23 20 29

NOX -N 5 0 0 4

a Theoretical

(T) and measured (M) values. b E1: end of aerobic phase of previous cycle; E2: end of aerobic phase of investigated cycle; F: end of 1-h anaerobic feeding; M: end of 2-h anaerobic mixing

and at the end of 1-h of anaerobic feeding and 2-h of anaerobic mixing are also provided in Table 1. As apparent from the reported values, overall COD removal efficiency of the system was around 96% and all of the externally supplied propionate was consumed under anaerobic conditions (most of it within the first hour), leaving no propionate available for the subsequent aerobic phase. NOX -N measurements indicated that nitrification occurred to some extent, resulting in approximately 5 mg NOX -N/L in the effluent. The NOX -N recycled from the previous cycle was totally depleted at the beginning of the investigated cycle through denitrification, during which a minor amount of externally supplied propionate was consumed. Anaerobic C-uptake value by the end of anaerobic mixing was 10.32 C-mmole/L. These results suggested an apparent C-storage mechanism operating under anaerobic conditions, which is typical both for the PAO- and the GAO-phenotypes. Despite an average of 10 mg PO4 -P/L was recorded in the effluent, bulk liquid ortho-P values recorded by the end of 1-h of anaerobic feeding and 2-h of anaerobic mixing (120 and 136 mg PO4 -P/L, respectively) indicated that the propionate-fed semi-granular EBPR biomass exhibited a P-metabolism typical for the PAO-phenotype, with a pronounced anaerobic P-release (3.40 P-mmole/L) followed by a significant aerobic P-uptake (4.03 P-mmole/L). Corresponding Puptake/P-release ratio of the semi-granular EBPR biomass was 1.19 (P-mol/P-mol), P-release/C-uptake ratio was 0.33 (P-mole/C-mole), and the EBPR efficiency was 78%. The MLVSS/MLSS ratio of the biomass was as low as 67%, suggesting a significant contribution from the inorganic constituents (i.e., poly-P inclusions). Total P-content of the biomass by the end of the aerobic period was determined as 107 mg PO4 -P/gTSS.

3.2 Morphological and Phenotypic Traits Results of the chemical staining reactions combined with light-microscopy for visualization of intracellular storage materials are presented in Fig. 2. The propionate-fed semi-granular EBPR biomass was considerably diverse with various morphotypes being present: 1–2μm rod-shaped cells (panels A, B, D, F, G, H), straight filaments 20–40 μm in length (panels A, B, E, G, I, J, K), tetrad-forming

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Fig. 2 Morphological and phenotypic characterization of the semi-granular EBPR biomass fed with propionate: Panels [A] to [D]: end of anaerobic period. Panels [E] to [H]: end of aerobic period. Panels [A], [B], [E], and [F]: Neisser-staining; dark blue-violet cells with and brown cells without intracellular poly-P granules. Panels [C], [D], [G], and [H]: staining with Sudan Black B; dark violet cells with and pink cells without PHB inclusions. Panels [I], [J], and [K]: Gramstaining; end of anaerobic period. Interpretations of these micrographs are summarized in Table 2

cells or sarcina-like packed organisms with overall diameter of 3.5–4 μm (panels E, F, H, I, J, K), huge coccoid-clusters resembling the staphylococci morphology or seemed to be the gatherings of individual coccoids with diameters in the range of 1.3–1.8 μm (panels G, H), large coccoids/diplococci (panels A, B, E, F, G, H, I, J, K). All of those morphotypes had also been detected in the biomass samples collected from the acetate-fed parent reactor [8], yet were present at different abundances. There were less rod-shaped cells and more diplo-coccoids in the propionate-fed biomass than in the acetate-fed one, and more filaments in the former than in the latter. The abundancy of the filamentous organisms in the propionate-fed SBR was determined as 2 in accordance with the subjective-scoring suggested by Jenkins et al. [11]. In addition to these, the most significant difference between the acetate-fed parent reactor and the propionate-fed one was the presence of elongated rod-shaped cells in the latter (panels A, B, C, E, G, H, K), which were different than the other rod-shaped cells common for both SBRs. These elongated rod-shaped Gram(+) cells (see panel K for Gram-reaction), which were 3–4 μm in length, scattered all around the other morphotypes, and present in significant quantities, were unique for the propionate-fed reactor. The rod-shaped cells were definitely and strongly PHB(+) by the end of the anaerobic phase (panel D), indicating that these organisms had the ability to consume the externally supplied propionate and convert it into intracellular PHB

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inclusions under anaerobic conditions; a trait common both for the PAO- and the GAO-phenotypes. These cells were partly PHB(+) by the end of the aerobic phase (panels G, H), and the significant difference in the level of PHB-related staining responses between the anaerobic and aerobic samples was considered as a visual evidence of consumption of intracellular PHB pools as carbon and energy sources for growth under aerobic conditions. The same morphotypes were not totally but mostly Neisser(−) by the end of the anaerobic period (panel B) and were not totally but weakly Neisser(+) by the end of the aerobic phase (panels E, F). These results were speculated to point to an incomplete anaerobic P-release and a concomitant incomplete aerobic P-uptake by these organisms, as revealed by weak Neisser-reactions rather than the expected definite/strong anaerobic (−) and aerobic (+) responses, respectively. Yet, the difference between the levels of responses to Neisser-staining reaction was considered to be apparent enough to address the difference between the anaerobic and aerobic samples as an indication of intracellular poly-P storage under aerobic conditions. Considering that the rod-shaped cells fit to the known morphology of the PAOs [17], and combining the results from the chemical staining reactions, these organisms were considered to function as the PAO-phenotype, but with an efficiency lower than the expected level; not in terms of anaerobic PHB-production, but especially in terms of aerobic poly-P storage. Remembering that the EBPR efficiency of the system was 78% despite of a complete COD-removal under anaerobic conditions, the abovementioned microbiological data was considered to be reasonable and in line with the biochemical performance of the system. The staining-responses of the elongated rod-shaped cells were similar to those of the rod-shaped cells with some differences in the level of responses. The elongatedcells, unique for the propionate-fed reactor, were also definitely PHB(+) by the end of the anaerobic period (panel C), and were almost totally PHB(−) by the end of the aerobic period (panels G, H); together suggesting an operative mechanism of anaerobic PHB-storage and almost complete exhaustion of the intracellular PHB pools under aerobic conditions. The differences were that although both morphotypes were definitely PHB(+) by the end of anaerobiosis, the elongated rod-shaped cells seemed to be less efficient in anaerobic PHB-production than their rod-shaped neighbors (compare panels C and D), and they exhausted all of their PHB pools under aerobic conditions (compare panels G and H). Responses of these organisms to Neisser-staining reaction were similar to those of the rod-shaped cells summarized above. These elongated rod-shaped cells, unique for the propionate-reactor, were also weakly Neisser(+) both by the end of the anaerobic- and aerobic-periods, and the difference was even less apparent than that for the rod-shaped cells. Thus, it was not possible, with the presented data, to decide whether they were organisms with any contribution to the observed EBPR efficiency, thus were members of a low efficiency PAO-phenotype with an unusual morphology, or were cells with the ability of anaerobic PHB-storage without causing any change in the bulk liquid ortho-P budget, thus were the GAOs which did not fit to the proposed GAO-morphology. Moreover, since they did not fit to the accepted/observed morphology of the PAOs [17], or the proposed/observed morphology of the GAOs [5, 17], and apparently did not fit to the morphological description of the Tetra Forming Organisms −TFOs-

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[25], but were determined to produce PHB from propionate under anaerobic conditions, they were addressed as Propionate Utilizing Bacteria (PUBs) within the framework of this study. Most of the tetrad/sarcina-like cells gave Neisser(+) responses both by the end of the anaerobic- and aerobic-periods (Fig. 2, panels E, F), yet they were determined to be strongly Neisser(+) only on their cell walls, but not in their cytoplasm. Mino and his colleagues, who reviewed and summarized the literature on microbiological characteristics of the populations observed in EBPR systems, described the PAOs as containing strongly stain-positive intracellular granules, whereas a Gram(−) “so called GAO” isolate was determined to gave Neisser(+) response only on its cell wall ([17] and references therein). Some microorganisms are also known to demonstrate a bi-phasic poly-P distribution [22], with majority of the poly-P being present in the cytoplasm packed in the form of intracellular volutin granules, and some of the poly-P being associated with the outer membrane or being present in the periplasm [18, 21], the latter not being involved in the anaerobic P-release and consequent aerobic P-uptake processes, describing the EBPR phenomena [9]. Based on these, the tetrad/sarcina-like cells detected in this current study were considered not to be recycling poly-P between anaerobic- and aerobic-phases, thus were discarded to be PAOs contributing to the observed EBPR performance. In fact, the tetrad/sarcina-like cells resembled the GAO-morphotype in general. Yet, all the tetrads were determined to be PHB(−) at all times; both by the end of the anaerobicand aerobic-periods (Fig. 2, panels D, and G, H, respectively), despite that the system was operated with a considerably high influent propionate concentration (642 mg COD/L). Hence, it was deduced that the tetrads resembled the GAOs morphologically, but not phenotypically, especially with respect to the eco-physiological characteristic of anaerobic PHB-storage. Taking into account the morphological features of the tetrad/sarcina-like cells and their responses to poly-P and PHB staining reactions, they were addressed as Tetra Forming Organisms (TFOs; after [25]), rather than GAOs. The Gram-staining reactions revealed that some of the TFOs were Gram(−) (Fig. 2, panels I, K), and the other were Gram(+) (Fig. 2, panel I). Similar to the TFOs, the dense coccoid-clusters (CCs) were also determined to be definitely PHB(−) in all cases; both at the end of the anaerobic phase (Fig. 2, panel D) and at the end of the aerobic period (panels G, H). As evident from their PHB(−) response by the end of the anaerobic period, these cells were not storing the externally supplied propionate in the form of intracellular lipophilic PHB inclusions under anaerobic conditions, thus not showing the GAO-phenotype under the applied operational conditions. Rather, they were initially speculated to be either ordinary heterotrophs (OHO), or ordinary denitrifiers (but not denitrifying PAOs), or nitrifiers. Considering the data summarized in Table 1, possibility of these organisms being OHOs was quickly ruled out: as mentioned above, all of the propionate supplied to the system was removed from the bulk liquid at the head of the cycle under anaerobic conditions leaving no externally supplied carbon source available in the presence of oxygen. Under such circumstances, strictly aerobic OHOs, who did not posses the capability of anaerobic C-storage, were expected to be diluted from the system. On the other hand, the biochemical data on nitrogen species was

PHB(−−−) D

Gram(−) I, J

P(−−+) A, B

eP(++−)

Gram(+) I

Elongated rod-shaped cells

Tetrads/sarcinalikea (mostly)

Panel

Panel

Panel

PHB(+++) C

PHB(+++) D

P(−−+) A, B

Rod-shaped cells

Panel

End of anaerobic period

Morphology

Figure 2

eP(++−) E, F

P(++−)? E

P(++−) E, F

PHB(−−−) G, H

PHB(−−−) G, H

PHB(−++) G, H

End of aerobic period

Abbreviation

PAOs − Fit to known morphology of PAOs − Behave as PAOs, though; − incomplete anaerobic P-release, concomitant incomplete aerobic P-uptake together with incomplete aerobic PHB-consumption − 78% EBPR efficiency PUBs − Able to utilize propionate anaerobically and store it as PHB − Able to utilize PHB aerobically − Either GAOs? or low efficiency PAOs? TFOs − Fit to proposed morphology of GAOs − Neisser(+) only on their cell walls − PHB(−) at all times − Not behaving as GAOs

Comments

Table 2 Morphological and EBPR-related physiological traits of propionate-fed semi-granular EBPR biomass

Morphological and Physiological Features 1337

Thin/Thick filaments

P(+++) E, F

PHB(−−−) G, H

PHB(−−−) G, H

End of aerobic period

Poly-P(−) and PHB(−) in all cases; Gram (−) or Gram (+)

Gram(−) K

Diplococcoids

P(+++) A

PHB(−−−) D

End of anaerobic period

Coccoid-clusters

Morphology

Abbreviation

− PHB(−) at all times CCs − Not behaving as GAOs − Neisser(+) at all times − − Need further research − Abundancy recorded − as 2

Comments

responses of the tetrads/sarcina-like cells to the Neisser-staining reactions were abbreviated as eP(++−) to emphasize that these were stained strongly only on their cell walls, exerting very dark envelopes, surrounding the cells

a The

Panel

Panel

Panel

Figure 2

Table 2 (continued)

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not sufficient for assigning the coccoid-clusters to, or discarding them as, either the nitrifiers or the denitrifiers, thus this was left out of the scope of this current study. Another significant morphotype in the system was the diplococcoids. These organisms were definitely Neisser(+) not only at the end of the aerobic phase, but also at the end of the anaerobic period, and the difference between the level of responses was not apparent enough to state whether they were involved in the observed EBPR performance or not. These Gram(−) organisms (Fig. 2, panel K) were determined to be PHB(−) by the end of the aerobic phase (Fig. 2, panel G). Interpretation of the chemical staining reactions, visually presented in Fig. 2, is summarized in Table 2 with respect to the key morphological and physiological features of the propionate-fed semi-granular EBPR biomass. Results are summarized in the table by using a simple scaling approach ((+++) for strong, (++−) for moderate, (−−+) for weak, (−−−) for no response) to address the relative quantities of the storage polymers observed in the cells.

4 Conclusions • Chemical and microbiological data revealed that the propionate-fed semigranular EBPR biomass, which demonstrated superior settling properties and compactness (SVI<50 mL/g, MLSS=5000 mg/L), also exhibited a P-metabolism typical for the PAO-phenotype: a pronounced anaerobic P-release followed by a significant aerobic P-uptake, together translating into an EBPR efficiency of 78%. Moreover, anaerobic and overall COD removal efficiencies were >90% and the former suggested an apparent C-storage mechanism operating under anaerobic conditions; a trait typical both for the PAO- and the GAO-phenotypes. • Hydraulic selection pressure in terms of minimum settling velocity (vmin ) and aeration-related shear rate (vSair ) was significantly relaxed when compared to the levels reported in the literature, yet the system was under a considerable shearing effect originating from mechanical mixing (vSMix ), and this was considered as the main hydraulic selection pressure promoting formation and maintenance of the propionate-fed aerobic granular biomass. • Application of 2 h of anaerobiosis at the beginning of the cycle, feeding the system during the first hour of the anaerobic phase, and supplying ortho-P in the influent helped selection and dominance of the PAOs in the system, and also served as the metabolic selection pressures contributing to the stability of the aerobic granular biomass by eliminating the occurrence of an aerobic feast phase of rapid growth and helping the selection of the anaerobically C-storing, aerobically slowly growing and P-removing organisms − the PAOs − in the system. • The propionate-fed semi-granular EBPR biomass was considerably diverse with various morphotypes being present: rod-shaped cells, straight filaments, tetrads/sarcina-like cells, coccoid-clusters, diplo-coccoids, and elongated rodshaped cells unique for the system. • Presence of elongated rod-shaped bacteria (tentatively named as PUBs) in the system, and their weak response to Neisser-staining, together with their ability

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to consume propionate under anaerobic conditions, to convert it into intracellular C-storage materials, and to cycle the intracellular PHB-inclusions between anaerobic and aerobic phases are concluded to be encouraging for further research to determine whether they are morphologically different GAOs or morphologically different and functionally less efficient PAOs. • The tetrads/sarcina-like cells resemble GAOs morphologically, yet their definite negative response to PHB-staining by the end of the anaerobic period suggests that they do not behave as GAOs under the applied operational conditions. They were addressed as Tetra Forming Organisms (TFOs) − a term referring to morphological differentiation − rather than GAOs − the term used for functional categorization dictated by phenotypic traits. Some TFOs being Gram(−) and the others Gram(+), and some possessing dense poly-P layers associated with their cell walls/membranes/periplasm indicate the need for further research. • Results dictated that, to clarify the identity, function, and contribution of different microbial groups in EBPR biomass, such systems are required to be assessed in terms of morphological and eco-physiolocigal aspects, as well as with regard to the biochemical conversion processes. • As a conclusive remark, despite the microscopic observations were qualitative, rather than quantitative, they seemed to correlate to an extend to the observed EBPR performance of the system, which was a lab-scale example of the Aerobic Granular EBPR Technology; a promising alternative combining the operational flexibility provided by the SBR configuration and the superior settling properties of granular biomass, as well as enhanced biological phosphorus removal.

References 1. APHA, WEF, AWWA (1998) Standard methods for the examination of water and wastewater. In: Clesceri LS„ Greenberg AE, Eaton AD (eds), 20th edn. American Public Health Association, Washington, DC, USA 2. Beun JJ, van Loosdrecht MCM, Heijnen JJ (2000) Aerobic granulation. Water Sci Technol 41(4–5):41–48 3. Beun JJ, van Loosdrecht MCM, Heijnen JJ (2002) Aerobic granulation in a sequencing batch airlift reactor. Water Res 36(3):702–712 4. Crocetti GR, Hugenholtz P, Bond PL, Schuler A, Keller J, Jenkins D, Blackall LL (2000) Identification of polyphosphate-accumulating organisms and design of 16S rRNA-directed probes for their detection and quantitation. Appl Environ Microbiol 66:1175–1182 5. Crocetti GR, Banfield JF, Keller J, Bond PL, Blackall LL (2002) Glycogen-accumulating organisms in laboratory-scale and full-scale wastewater treatment processes. Microbiology 148(11):3353–3364 6. de Kreuk MK, van Loosdrecht MCM (2004) Selection of slow growing organisms as a means for improving aerobic granular sludge stability. Water Sci Technol 49:9–17 7. Dulekgurgen E, Ovez S, Artan N, Orhon D (2003) Enhanced biological phosphate removal by granular sludge in a sequencing batch reactor. Biotechnol Lett 25:687–693 8. Dulekgurgen E, Yesiladali K, Ovez S, Tamerler C, Artan N, Orhon D (2003) Conventional morphological and functional evaluation of the microbial populations in a sequencing batch reactor performing EBPR. J Environ Sci Health A A38(8):1499–1515

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9. Florentz M, Granger P, Hartemann P (1984) Use of 31 P nuclear magnetic resonance spectroscopy and electron microscopy to study phosphorus metabolism of microorganisms from wastewaters. Appl Environ Microbiol 47(3):519–525 10. International Organization for Standardization (1986) International Standard ISO 6060: Water quality – Determination of the chemical oxygen demand, Reference No. ISO 6060–1986(E), Technical Committee ISO/TC 147, ISO, Switzerland 11. Jenkins D, Richard MG, Daigger GT (1993) Manual on the causes and control of activated sludge bulking and foaming, 2nd edn. Lewis Publishers Inc., Boca Raton, USA 12. Kim SM, Kim SH, Choi HC, Kim IS (2004) Enhanced aerobic floc-like granulation and nitrogen removal in a sequencing batch reactor by selection of settling velocity. Water Sci Technol 50(6):157–162 13. Levantesi C, Serafim LS, Crocetti GR, Lemos PC, Rossetti S, Blackall LL, Reis MAM, Tandoi V (2002) Analysis of the microbial community structure and function of a laboratory scale enhanced biological phosphorus removal reactor. Environ Microbiol 4(10):559–569 14. Liu W-T, Nielsen AT, Wu J-H, Tsai C-S, Matsuo Y, Molin S (2001) In situ identification of polyphosphate- and polyhydroxyalkanoate-accumulating traits for microbial populations in a biological phosphorus removal process. Environ Microbiol 3:110–122 15. Liu Y, Wang Z-W, Tay J-H (2005) A unified theory for upscaling aerobic granular sludge sequencing batch reactors. Biotechnol Adv 23(5):335–344 16. Metcalf, Eddy (2003) Wastewater engineering: Treatment, disposal, and reuse, 4th edn. McGraw-Hill, Inc., New York 17. Mino T, van Loosdrecht MCM, Heijnen JJ (1998) Microbiology and biochemistry of the enhanced biological phosphate removal process. Water Res 32:3193–3207 18. Ohtake H, Takahashi K, Tsuzuki Y, Toda K (1985) Uptake and release of phosphate by a pure culture of Acinetobacter calcoaceticus. Water Res 19(12):1587–1594 19. Qin L, Liu Y, Tay J-H (2004) Effect of settling time on aerobic granulation in sequencing batch reactor. Biochem Eng J 21(1):47–52 20. Qin L, Tay J-H, Liu Y (2004) Selection pressure is a driving force of aerobic granulation in sequencing batch reactors. Process Biochem 39(5):579–584 21. Streichan M, Golecki JR, Schon G (1990) Polyphosphate-accumulating bacteria from sewage plants with different processes for biological phosphorus removal. FEMS Microbiol Ecol 73:113–124 22. Suresh N, Warburg R, Timmerman M, Wells J, Coccia M, Roberts MF, Halvorson HO (1985) New strategies for the isolation of microorganisms responsible for phosphate accumulation. Water Sci Technol 17(11–1):99–111 23. Tay JH, Liu QS, Liu Y (2001) The effects of shear force on the formation, structure and metabolism of aerobic granules. Appl Microbiol Biotechnol 57(1–2):227–233 24. Tay JH, Liu QS, Liu Y (2004) The effect of upflow air velocity on the structure of aerobic granules cultivated in a sequencing batch reactor. Water Sci Technol 49:35–40 25. Tsai CS, Liu WT (2002) Phylogenetic and physiological diversity of tetrad-forming organisms in deteriorated biological phosphorus removal systems. Water Sci Technol 46:179–184 26. Zheng Y-M, Yu H-Q, Sheng G-P (2005) Physical and chemical characteristics of granular activated sludge from a sequencing batch airlift reactor. Process Biochem 40(2):645–650 27. Zilles JL, Peccia J, Kim M-W, Hung C-H, Noguera DR (2002) Involvement of Rhodocyclusrelated organisms in phosphorus removal in full-scale wastewater treatment plants. Appl Environ Microbiol 68:2763–2769

Part VIII

Integrated Water Resources Management

Water Quality Variation in a Tank Cascade Irrigation System: A Case Study from Malagane Cascade, Sri Lanka Kushani Mahatantila, Rohana Chandrajith, H.A.H. Jayasena, and Sampath Marasinghe

Abstract Tank cascade irrigation system (TCIS) is a water management practice developed in order to match the nature of the rainfall and landscape in the dry zone of Sri Lanka. The series of interconnected tanks in this system serves multiple functions, including irrigation. This study was carried out to investigate the water quality variation in a tank cascade system and study the role of hydrophytes found in the upper periphery (Thaulla). The Malagane Tank in the northwestern intermediate zone of Sri Lanka was selected for the study. Fairly high levels of nutrients and metal concentrations were recorded in the upstream paddy fields and main inflow of the tank. The concentrations of most of the chemical parameters were showed a decreasing trend while passing the thaulla area which is one of the most important hydrologic regime in a tank system. However, the runoff from the either sides of the tank has polluted the lake water particularly during the rainy season. The hydrophytes in the thaulla area play a major role in the hydrology of the tank system. Keywords Hydrophytes · Irrigation · Water quality

1 Introduction The artificial lakes or reservoirs called “tanks” created a remarkable hydraulic system, which was the basis of the Dry Zone prosperity in ancient Sri Lanka. Because of the highly variable nature of rainfall both between seasons and within seasons and paucity of readily accessible to shallow groundwater in the hard rock region of the area, the small tank storage systems provided the lifeblood for human existence in the Dry Zone of Sri Lanka. The Land and water management practices that were perfected through several centuries in order to match the nature of rainfall with the special geomorphological attributes of the landscape had led to a system of irrigation development described as a “cascading system” [3]. These small K. Mahatantila (B) Department of Geology, University of Peradeniya, Peradeniya, Sri Lanka e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_126,

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tank cascade systems were constructed in ancient times could be considered as unique irrigation systems with distinctive assemblage of land uses and agricultural attributes [1]. A cascade is a “connected series of tanks organized within the microcatchments of the dry zone landscape, storing, conveying and utilizing water from an ephemeral rivulet” (Maddumabandara, 1985). Cascade systems provide multiple functions including to irrigation and domestic supply of water, water for livestock and subsurface water for perennial cropping. They seems to be adherence to: Having adequate volume of water in every tank of settled villages in a cascading valley even in a year of low average rainfall; instituting a regulated flow of water from one tank to another downstream, avoiding a sudden influx of large volumes of water in order to minimizing risk to the tank bund breaking [4]. Water is passing from one tank to another in downstream, while it is utilized. All the agricultural and domestic pollutants in the particular water divide entered to the waterway, and accumulate in the end member of the cascade. Plant debris and animal manure as a source of nitrogenous fertilizer had been used for the cultivation since early days. Buffalo wallows and buffalo resting grounds might be contributed to the addition of excess nutrients to the small tank irrigation systems. The use of grazing cattle during the dry season contributes to the high levels of nutrients in the tank. Even though, there is a high possibility to enter excess nutrients to the water from the agricultural fields, eutrophication of these tanks have not been recorded. The recent field observation indicated that the tank cascade irrigation system consists of a water purification system in its path. It is hypothesized that the plants in the upper periphery of the tank may act as a constructed wetland (locally called Thaulla) and remove excessive nutrients which drains to the tank. The main objectives of the study are to identify the water quality variation in a tank cascade system with respect to the functions of constructed wetland in the system. The Deduru Oya is the fourth largest river basin in Sri Lanka having a total area of 2,622.5 km2 [5]. In hydrological point of view Malagane cascade is located in the Maguru Oya catchment, which is a tributary of Deduru Oya. Maguru Oya consists of five meso-catchments and a drainage area of 231.2 km2 . The cascade is consists of seven members and Malagene tank is the end member of that particular cascade (Fig. 1). Climatologically, the study area lies within the intermediate zone of Sri Lanka where the average annual rainfall is in between 1,250 and 1,900 mm. The average annual rainfall of the study area is 1,890 mm [5].

2 Materials and Methods 2.1 Analysis of Chemical Parameters and Data Modeling Water samples from the tank, inflow stream and outflow streams were collected twice a month from May to December 2005. pH, water temperature, electrical conductivity, Nitrate-nitrogen (NO3 − -N), nitrite-nitrogen (NO2 − -N), reactive

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Fig. 1 Map showing the studied cascade and the surrounding land use

phosphorus (PO4 3− ), sulphate (SO4 2− ) and metal ions such as Na, K, Ca, Mg were analyzed using standard methods of water analysis. In order to interpolate the spatial distribution of nitrate, nitrite and phosphate Universal Kriging in Arc GIS software was used. The Kriging needs a point interpolation which requires a point map as input and returns to a raster map with estimations and optionally an error map. The weighted averaged input point values were estimated which is similar to the Moving Average operation. The weight factors in Kriging are determined by using a user-specified semi-variogram model (based on the output of the spatial correlation), the distribution of input points, and

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are calculated in such a way that they minimize the estimation error in each output pixel. The estimated or predicted values are thus a linear combination of the input values and have a minimum estimation error. The optional error map contains the standard errors of the estimates. Kriging from raster can be seen as a raster interpolation which requires a raster map as input, returns a raster map with estimations and optionally an error map. The estimations or predictions are calculated as weighted averages of known input pixel values, similar to the Moving Average operation.

3 Results and Discussion A classification method of small tank cascade has been proposed by Sakthivadivel et al. [4] based on their topology, i.e. on the form and size class of the cascade. The Malagane tank cascade irrigation system is a linear cascade with the form index (the ratio of the overall area of the cascade to its overall length) of 1.85. This cascade belongs to small size class (meso-catchment area is less than 2,500 acres), which comprises of a meso-catchment area with 3.7 km2 area. Eighteen percent of the meso catchment is used for paddy cultivation (Fig. 1) and the other main crop of the area is coconut. The inflow of the tank passes ˜1.0 km2 of the paddy on its way toward the Malagane tank. However, before entering the tanks it passes a wetland located at the upper periphery of the tank. The wetland consists of various kinds of shrubs and herbaceous plants including Typha sp., Nymphs sp. and Terminelia arjuna. The surface area of the tank is 0.2 km2 (Fig. 1) and Thaulla covers approximately 10% of the surface area of the tank. The average depth of the tank is 1.75 m when it is in its full capacity. While water passes the Thaulla, it may undergo three main processes, eliminating of pollutant by absorption of nitrogen and phosphorus i.e. roots of the hydrophytes absorbed nitrogen and phosphorus as nutrients, eliminating nutrient by denitrification and adsorption, sedimentation by contact with stem [6]. When the flowing water contacts stems, pollutants are settled and deposited. Therefore the intra tank variations of some chemical parameters are discussed in this paper. The intra tank variations of the selected parameters over the tank in the studied period of time are given in Fig. 2. Metals show a higher variation compared to the anionic parameters. The concentration of Na varies from 10 to 18 mg/l, K from 2.6 to 3.6 mg/l, Ca varies from 5.3 to 11.0 mg/l while Mg varies from 10.5 to 14.0 mg/l. Among anions, nitrate-nitrogen shows the highest intra tank variation from 0.8 to 1.9 mg/l.

3.1 Nitrate–Nitrite Variation During the study period, the nitrate-nitrogen concentration decreased towards the tank bund, indicating the purification activity of thaulla. The highest nitrate

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Concentration (mg/l)

20

10

0

NO3– –N NO2– –N PO43– Na+

K+

Ca2+

Mg2+

Fig. 2 Box plots showing the arithmetic range of physicochemical parameters in the tank water

Fig. 3 Variation of nitrate concentration after the rain

concentration was recorded in the thaulla area where the lowest were recorded near the tank bund (Fig. 3). After heavy rain occurred in October (700 mm), the nitrate distribution was changed. During this period the higher nitrate concentration was recorded in the middle of the tank than the thaulla area and closer to tank bund (Fig. 4). During the rainy period a heavy surface runoff was observed from the near by settlements and paddy fields beside the tank, which might caused the different nitrate variation pattern compared to the dry season. The data modeling indicates that there is a nitrate input by the either sides of the lake (Fig. 5) rather than the inflow stream.

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NO3– –N (mg/l)

0.95 0.90 0.85 0.80 0.75 Towards the tank bund

Fig. 4 Nitrate distribution towards the tank bund in dry period

Fig. 5 Intra tank variation of nitrate-nitrogen

Nitrite concentration of the tank ranged from 0.026 to 0.036 mg/l. This shows a similar trend before and after the rain. The concentration of nitrite from the paddy field, main inflow, thaulla and right below the thaulla were showing a decreasing trend; 0.27, 0.175, 0.27, 0.12 mg/l, respectively. Data modeling indicates that the nitrite concentration in the tank is low at the middle of the tank, high in the eastern edges and towards the tank bund (Fig. 6).

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Fig. 6 Intra tank variation of nitrite-nitrogen

3.2 Soluble Reactive Phosphorus The soluble reactive phosphorous (SRP) concentration in the tank varies from 0.05 to 0.14 mg/l. The SRP concentrations were shown a decreasing trend from the paddy field (0.26 mg/l) towards thaulla, where the concentration was lowest (0.06 mg/l). However, it was observed that the phosphorus concentration increases towards the tank bund from thaulla (Fig. 7). Covey et al. [2] has obtained increase in SRP from

Fig. 7 Intra tank variation of SRP

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Fig. 8 Distribution of metals in tank water

the inflow to out flow while passing through a wetland and noted due to the release of SRP from sediments and decaying of vegetation when the wetland first was inundated rather than mineralization of deposited particulate organic phosphate (POP) from the inflow. The metal ion concentrations of the tank water are decreased from thaulla to the tank bund while pH of the tank water increases (Fig. 8). The pH varies from 6.8 to 7.4 and lowest pH occurs at thaulla and highest at closer to tank bund. The results prove that the hydrophytes in thaulla act as a constructed wetland and reduce the nutrient and metal ion concentration. The absence of hydrophytes in either sides of the tank has led to the increase of nutrients in tank systems, which might cause eutrophication. Most of the recent development activities centered in ancient tank systems in Sri Lanka destroy this hydrologically important constructed wetlands in tanks. Therefore establishment of hydrophytes in these inflow areas and proper conservation is essential for the sustainability of the tank cascade irrigation systems in Sri Lanka. Acknowledgment Authors express their sincere acknowledgement to the National Science Foundation of Sri Lanka for the financial support given through the research grants RG/2004/GMR/01. Ms. Meththika and villagers of the Malagane are acknowledging for their numerous support given during the study.

References 1. Abeyratne E (1956) Dry farming in Ceylon. Trop Agric 112:191–229 2. Convey MF, Stites DL, Lowe EF, Battoe LE, Conrow R (2002) Nutrient removal from eutropic lake water by wetland filtration. Ecol Eng 19:141–159 3. Madduma Bandara CM (1991) Heritage in natural resource management in natural resources of Sri Lanka: Conditions and trends. Natural Resources, Energy and Science Authority of Sri Lanka, Colombo

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4. Sakthivadivel R, Fernando N, Pannabokke CR, Wijayaratna CM (1996) Nature of small tank cascade systems and frame work for rehabilitation of tanks within them. International Irrigation Management Institute, Sri Lanka 5. Somarathne PG, Jinapala K, Perera LR, Ariyaratne BR, Bandaragoda DJ, Makin IW (2003) Developing effective institutions for water resources management: a case study in the Deduru oya basin, Sri Lanka, 58. IWMI, Sri Lanka 6. Stottmeister U, Wiessner A, Kuschk P, Kappelmeyer U, Kästner M, Bederski O, Müller RA, Moorrmann H (2003) Effects of plats and microorganisms in constructed wetlands for wastewater treatment. Biotechnol Adv 22:93–117

Investigation of Flood Event Possibility over Iran Using Flood Index Kazem Nosrati, Mohsen Mohseni Saravi, and Afsaneh Shahbazi

Abstract Focusing on the problem of forecasting flood, the goal of this study is to investigate Flood Index (FI) during flood events. Such a flood index based on effective precipitation is utilized to estimate flood index from two floods over Fars province from October 25 to November 15 in 1986 and December 20 to January 20 in 1992–1993. Daily precipitation on Shiraz station from January 1975 to December 2002 is examined to calculate indices and to compare with result. FI is calculated by considering precipitation and produces the Available Water Resources Index (AWRI) by precipitation. Comparisons of validation results from FI and AWR with observed flood over two events are purposes. This study reveals FI to be promising tool for warning flood. Keywords Flood · Flood index · Available water resources index

1 Introduction Modeling of flood occurrence from a catchment subjected to rainfall is of prime importance in water resources management and design activities such as flood control and management. Flood disaster prediction includes three aspects such as danger, vulnerability, and extent predictions on flood disaster [6]. Accurate forecasting of flood event is necessary for, among others: (1) optimal design of drainage networks; and (2) management of extreme events, such as floods and droughts. During the past few decades, a great deal of research has been devoted to the modeling and forecasting of flood. In such cases, the hydrologist is faced with the difficult task of estimating flood event magnitudes from catchment properties and regional climatology. Despite

K. Nosrati (B) Faculty of Natural Resources, University of Tehran, Tehran, Iran e-mail: [email protected]

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many advances in weather forecasting over the last decades, the need for accurate flood forecasting remains as one of the most elusive challenges in operational hydrology structure. The incorporation precipitation in flood warning systems has been acknowledged to play a key role, which may enable a more timely implementation of flood control. At the research of the cause of flood, the systems to prevent flood should be considered not only precipitation and topography characteristics, but also water resources amounts at present. Current flood control systems are only computed by short-term accumulated rainfall data with subjective decision and long-term accumulated water resource amounts is not considered. Moreover, if flood events occur at particular regions with no water management systems, the objective and decisive flood standardization is hardly defined. In addition, it is impossible to compare with intensity of flood on each station because of different standards. In case of statistical research, the precipitation effluence model and precipitation intensity model are very useful not a long-term research but a short-term research and, on the contrary, Palmer Drought Severity Index (PDSI) is useful not a shortterm research but a long-term research because minimum analysis period is only a week. Byun and Wilhite [3] developed a new Flood Index (FI) that is different from previous flood indices. FI is calculated by considering precipitation at a station, produces the available water resources by precipitation, and computes the standardized index on the intensity of flood by comparing with maximum amounts of available water resources. This is able to produce not only long-term results but also shortterm results. However, our current flood control systems considered by Kim et al. [5] in South Korea. They resulted that FI is established a good indicator of the danger of flood. In this study, through the past flood events, the accuracy of FI will be investigated.

2 Material and Methods 2.1 Data Collection Study station is Shiraz in Fars province having 1488-m elevation and is limited to 29.33 northern latitude and 52.36 eastern longitude. Long-term mean precipitation of this station is 344.2 mm and is located in south of Iran. To calculate flood index and available water resources from two floods over Fars province from October 25 to November 15 in 1986 and December 20 to January 20 in 1992–1993 daily precipitation on Shiraz station from January 1975 to December 2002 is examined.

2.2 Flood Index (FI) and Available Water Resources Index (AWRI) Byun and Jung [2], Byun and Wilhite [3] and Kim et al. [5] suggested solutions to overcome the problems how much the gathered precipitation is; and how the daily

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depletion of the water resources can calculate. To assess the accumulated precipitation, the daily depletion of water resources is considered which can be calculated according to the following equation: ⎡

⎤

N

Pm ⎥ D ⎢ ⎢ m=1 ⎥ E= ⎥ ⎢ ⎣ N ⎦

(1)

N=1

where, E = Accumulative Effective Precipitation D = Duration of Summation Pm = Precipitation of m days before N = the number of the day Equation 1 is derived from the concept that the precipitation of m-days before is added to total water resources as form of average precipitation of m-days. D is the number of the days which precipitation is summed for calculation of AWR. A dummy value of 365 was chosen, because one year is the most dominant precipitation cycle worldwide. E365 can be a representative value of the total available water resources or stored for a long period. Accumulated precipitation calculated from Eq. (1) is converted into daily precipitation by Eq. (2). W=

D

E

N=1

(2)

1 N

where W is the AWRI. Therefore, if W is larger than normal, it means that the water resources are abundant [4]. FI is calculated by considering precipitation at a station, produces the available water resources by precipitation, and computes the standardized index on the intensity of flood by comparing with amounts of available water resources. FI is proposed by Eq. (3). FI = (E − EPmax)/ST

(3)

where, EPmax= the mean value of the annual maximum effective precipitation on a station ST= denotes the standard deviation If FI value increases more and more, it means that water resources reach the average maximum water level and the probability of flood event is increased.

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3 Results To verify the accuracy of FI, two flood events were selected over shiraz city. One flood is occurred in October 25–November 15 in 1986 and another is occurred in December 20–January 20 in 1992–1993 [1]. Figure 1 shows daily precipitation and FI of 1986 at shiraz station. The maximum daily precipitation occurred on the Nov. 2 with 99 mm. In addition, maximum FI occurred on the Nov. 4. Therefore, the increaser in accumulated effective precipitation the increaser in accumulated water resources. When analyzing the other cases it also reach same conclusion (see Fig. 2). With the help of Fig. 2, the trend of hydrological situation change can be detected. Detecting the starting and the ending date of rapid increase of AWRI is easy at Fig. 2. The maximum of the AWRI is on the Nov. 4 with 273 mm. Figure 3 shows daily precipitation and FI of 1992–1993 at shiraz station which calculate the accumulated effective precipitation. As Fig. 3, maximum daily precipitation occurred on Dec. 21 with 75 mm, but maximum FI occurred on the Jan. 10. With the help of Fig. 4 maximum AWRI occurred on the Jan 10. The result shows that FI affected by AWRI. There are daily precipitations on Dec. 20–Jan. 20, that causing increase available water resource. The increasing in available water resources causes increase in flood index. The results indicate that there is no significant difference between FI and precipitation. If FI variation has same phase with precipitation then the use of FI is meaningless. To reflect the relationship between FI and precipitation, accumulated precipitation has been examined (see Table 1). As the results from Table 1, FI values 120

1.2 1

100

80

0.6 0.4

60 0.2 40

0 – 0.2

20 – 0.4 – 0.6

19

86

/ 19 10/ 86 25 / 19 10/ 86 26 / 19 10/ 86 27 / 19 10/ 86 28 / 19 10/ 86 29 /1 19 0/ 86 30 / 19 10/ 86 31 / 19 11/ 86 01 / 19 11/ 86 02 / 19 1/0 86 3 / 19 11/ 86 04 / 19 11/ 86 05 / 19 11/ 86 06 / 19 11/ 86 07 / 19 11/ 86 08 / 19 11/ 86 09 / 19 11/ 86 10 / 19 11/ 86 11 / 19 11/ 86 12 / 19 11/ 86 13 / 19 11/ 86 14 /1 1/ 15

0

Date Precipitation

Flood Index

Fig. 1 Time series of precipitation and FI over Shiraz from Oct. 25 to Nov. 15 in 1986

Flood Index

Precipitation(mm)

0.8

19 9 19 2/1 9 2/ 19 2/1 20 9 2/ 19 2/1 21 9 2/ 19 2/1 22 9 2/ 19 2/1 23 9 2/ 19 2/1 24 9 2/ 19 2/1 25 9 2/ 19 2/1 26 9 2/ 19 2/1 27 9 2/ 19 2/1 28 9 2/ 19 2/1 29 9 2/ 19 2/1 30 9 2/ 19 3/0 31 9 1/ 19 3/0 01 9 1/ 19 3/0 02 9 1/ 19 3/0 03 9 1/ 19 3/0 04 9 1/ 19 3/0 05 9 1/ 19 3/0 06 9 1/ 19 3/0 07 9 1/ 19 3/0 08 9 1/ 19 3/0 09 9 1/ 19 3/0 10 9 1/ 19 3/0 11 9 1/ 19 3/0 12 9 1/ 19 3/0 13 9 1/ 19 3/0 14 9 1/ 19 3/0 15 9 1/ 19 3/0 16 9 1/ 19 3/0 17 9 1/ 19 3/0 18 93 1/1 /0 9 1/ 20

Precipitation(mm)

Flood Index

80 0.5

70 0.4

60

50

0.1

40

0

30

– 0.1

20

10

– 0.4

0

– 0.5

Precipitation(mm)

Flood Index

86 19 /10 86 /25 19 /10 86 /26 19 /10 86 /27 19 /10 86 /28 19 /10 86 /29 19 /10 86 /30 19 /10 86 /31 19 /11 86 /01 19 /11 86 /02 19 /11 86 /03 19 /11 86 /04 19 /11 86 /05 19 /11 86 /06 19 /11 86 /07 19 /11 86 /08 19 /11 86 /09 19 /11 86 /10 19 /11 86 /11 19 /11 86 /12 19 /11 86 /13 19 /11 86 /14 /1 1/ 15

19

FI(100 unites) and AWR(mm)

Investigation of Flood Event Possibility over Iran 1359

300

250

200

150

100

50

0

– 50

– 100

Date

AWRI

Fig. 2 Daily variation of AWRI and FI at Shiraz from Oct. 25 to Nov. 15 in 1986

0.3

0.2

– 0.2

– 0.3

Date

Flood Index

Fig. 3 Time series of precipitation and FI over Shiraz from Dec. 20 to Jan. 20 in 1992–1993

are different from precipitation although it has been prepared from precipitation. It means that even if precipitation is strong, FI dose not increase sharply when water resources are not sufficient. In other words, the differences come from the consideration of available water resources in the index.

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FIv(100 unites) and AWR(mm)

250 200 150 100 50 0 – 50

19

9 19 2/1 9 2/ 19 2/1 20 9 2/ 19 2/1 21 9 2/ 19 2/1 22 9 2/ 19 2/1 23 9 2/ 19 2/1 24 9 2/ 19 2/1 25 9 2/ 19 2/1 26 9 2/ 19 2/1 27 9 2/ 19 2/1 28 9 2/ 19 2/1 29 9 2/ 19 2/1 30 9 2/ 19 3/0 31 9 1/ 19 3/0 01 9 1/ 19 3/0 02 9 1/ 19 3/0 03 9 1/ 19 3/0 04 9 1/ 19 3/0 05 9 1/ 19 3/0 06 9 1/ 19 3/0 07 9 1/ 19 3/0 08 9 1/ 19 3/0 09 9 1/ 19 3/0 10 9 1/ 19 3/0 11 9 1/ 19 3/0 12 9 1/ 19 3/0 13 9 1/ 19 3/0 14 9 1/ 19 3/0 15 9 1/ 19 3/0 16 9 1/ 19 3/0 17 9 1/ 19 3/0 18 93 1/1 /0 9 1/ 20

– 100

Date Flood Index

AWRI

Fig. 4 Daily variation of AWRI and FI at Shiraz from Dec. 20 to Jan. 20 in 1992–1993

Table 1 The rank of AWRI and FI on Shiraz between Jan. 1975 and Dec. 2002 Rank

Year

Month

Day

Rainfall

AWRI

FI

1 2 3 4 5 6 7

1977 1976 1978 1977 1980 1985 2000

3 12 1 10 9 1 12

26 22 5 30 3 3 26

39 35 4 32 17.5 52 44

41 27 60 25 120 323 29

–0.69 –0.8 –0.55 –0.81 1.31 1.39 –0.78

4 Conclusion After selecting the flood events over Fars province in Iran, flood index was compared and verified. FI was successfully represented the danger of flood and FI variation was different from precipitation because of calculation of available water resources. Available water resources index that is the accumulated precipitation value in which daily reduction (by runoff, evapotranspiration, etc.) of water are taken into account quantitively was used. The big value of AWRI indicates plenty of water resource available and the small value its deficiency. A reasonable prediction of flood not only provides useful information for management of water resources, but also reduces losses to life and property caused by extreme events.

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References 1. Ahmadi H (2002) Applied geomorphology, desert-wind erosion, vol 2. Tehran University Publication, Iran, 570 pp (In Persian) 2. Byun HR, Jung JS (1998) Quantified diagnosis of flood possibility by using effective precipitation index. J Korean Water Res Assoc 31(6):657–665 3. Byun H-R, Wilhite DA (1999) Objective quantification of drought severity and duration. J Climate 12(9):2747–2756 4. Han SU, Byun H-R (2006) The existence and the climatological characteristics of the spring rainy period in Korea. Int J Climatol 26:637–654 5. Kim KH, Byun HR, Park SJ (2004) The verification of flood events over South Korea using flood index. Proceedings of ICHWC (International Conference on High-impact Weather and Climate), March 22–24, Seoul, South Korea, pp 68–471 6. Wei YM, Jin JL (1997) The general system for analysis and evaluation of flood disaster, vol 1. Proceedings of IEAS and IWGIS 97, Beijing, pp 841–847

Analysis of First-Flush Load from Urban Catchment in Isfahan, Iran Afsaneh Shahbazi, Kazem Nosrati, and Mohsen Mohseni Saravi

Abstract Large amount of raining water is transferred to reception resources in urban areas due to the increased impermeable surfaces. Urban catchments water is that produced by precipitating or snow melting considered as one the most important non-point source pollutants. Good management of treatment works requires an understanding of the First-Flush phenomenon of wet weather in urban drainage systems. In this study, having discrete sampled the output drainage of 13 precipitation events in one of Isfahan catchments during autumn/winter, 2002/2003, 10 qualitative/quantitative parameters were measured assessing general quality and the First-Flush curves were drown for each pollutant parameters. The results showed that primary elution much occurred for nitrates, biological oxygen demand and chemical oxygen demand in comparison to other pollutants and the major pollution amount can be eradicated through controlling the primary drainage volume. Keywords First-flush · Urban runoff · Non-point source pollutant

1 Introduction The extent and nature of water pollution during wet weather is usually related to technical control measures in urban drainage systems, including storage and infiltration facilities, and combined sewage over flows and separators [7]. One control measure often recommended is the incorporation of storage tanks (control and detention retention basins) in order to provide additional volume for attenuation and control of both flow and pollution. To assess the first flush, researchers usually use curves of the cumulative fraction of total pollutant mass vs. the fraction of total cumulative runoff volume for the event [5]. A. Shahbazi (B) Department of Environment, Faculty of Natural Resources and Marine Sciences, Tarbiat Madares University, Iran e-mail: [email protected]

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Geiger defined a first flush as occurring when such curves have an initial slope greater than 45%, and used the point of maximum divergence from the 45% slope to quantify the first flush [4]. Gupta and Saul [6] used a very similar definition, as did Ashley et al. [2]. French researchers suggested a very strict definition of the phenomenon; they defined a first flush as occurring when at least 80% of the pollution load is transferred in the first 30% of the runoff volume. Other researchers have defined the phenomenon in terms of the pollution load in the first 25% of the event volume [3]. In recent work published by Sansalone and Buchberger [8] a non-restrictive criteria is used; the first flush is perceived if a mass cumulative curve of a pollutant is above the runoff volume curve. Gupta and Saul [6] showed that, in combined sewers, the first flush load of total suspended solids correlated well with the peak rainfall intensity, the storm duration, and the antecedent dry weather period. In their study, 109 recorded events from two urban catchments were analyzed using the multiple regression method. In contrast, in the French study mentioned above, no correlation was found between the shape of cumulative load curves and catchments characteristics (area, time concentration, and average slope), or any rainfall characteristic (rainfall depth, maximum intensity and antecedent dry weather period) [3]. In this study, some qualitative/quantitative parameters were measured in one of Isfahan catchments and the first-flush curves were drown for each pollutant parameters.

2 Material and Methods Isfahan city is located in central of Iran and it have arid and semiarid climate. One of the most important permanent rivers of Iran is Zayandehrood that is passing through Isfahan city and at the end arrive to Gavkhooni wetland. Gavkhooni wetland is one of the international wetland and controlling amounts of pollutant that are discharge to it, is very important. So investigation the pollution load that discharge to Zayandehrood is the most important goal to access to this controlling. Good management of treatment works requires an understanding of the first flush phenomenon of wet weather in urban drainage systems. The data used in this study were collected at one small urban catchments, located in Iran, Isfahan. Storm runoff from catchment was monitored for water quality. The size of the catchment is 600 hectares. The measuring equipment was installed at catchment’s outlet to river. Rainfall intensity, overland flow rate, runoff depth, act., and four water quality (nitrate, suspended solid, chemical oxygen demand and biologic oxygen demand) were measured by Discrete Sampling at 10 minutes intervals throughout an event. From September 2002 to November 2003, 13 rainfall events were observed in Isfahan. The first flush is the percentage of total event pollution load transported by the first 20% of storm runoff volume [3]. Cumulative curves were constructed for all measured water quality characteristics were drown vs. cumulative runoff percentage following Eq. 1 [5].

Analysis of First-Flush Load from Urban Catchment

⎛

1365

⎞ Q t i i⎟ ⎜ ⎜ i=1 ⎟ i=1 =f⎜ ⎟=f N N ⎝ ⎠ Ci Qi ti Qi ti j

Ci Qi ti

i=1

j

⎛

⎞ V i⎟ ⎜ ⎜ i=1 ⎟ ⎜ N ⎟ ⎝ ⎠ Vi

i=1

j

(1)

i=1

where, concentration of each pollutant (mg/l) discharge (m3 /s) time interval of sampling (s) pollutant parameter (NO3 , COD, BOD5 , TSS)

100

Cummulative load of BOD/ Total

Cummulative load of NO3/ total load

Ci : Qi : ti : i:

80 60 40 20 0 0

20

40

60

80

80 60 40 20 0 40

60

80

60 40 20 0 0

100

Cummulative runoff / Total volume

20

40

60

80

100

Cummulative runoff / Total volume

Cummulative load of COD / Total load

Cummulative of TSS / Total load

100

20

80

100

Cummulative runoff / total volume

0

100

100 80 60 40 20 0 0

20

40

60

80

100

Cummulative runoff / Total runoff

Fig. 1 Cumulative curves of nitrate (NO3 ), biologic oxygen demand (BOD), total of suspended solids (TSS) and chemical oxygen demand (COD)

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3 Results The cumulative curves were calculated using Eq. (1). Cumulative load curves (mass curves) for all measured water quality characteristics are presented in Fig. 1. According to Fig. 1, first flush appear in all parameters. The most intensity of first flush occurred in COD. So 100% of pollution load is discharged to river by 30% of initial runoff. First flush important for NO3 , too. So we can release about 95% of pollution loaded by treating 40% of initial runoff. The figure shows that it is less likely for the Suspended Solids and only 40% of it control by controlling 20% of initial runoff. From the conclusions listed above, it is obvious that a strong first flush effect at the end of a drainage system is not very likely to be caused by a first flush of pollution input into the system. The phenomenon may rather be caused by pollutant transformations and transport processes in the drainage system [1]. It is also clear that variations in the first flush load of surface runoff could not be calculated using a universal set of climate, rainfall and runoff characteristics, or universal types of regression curves.

4 Conclusion Data collected in one almost asphalt-covered urban catchment were analyzed and cumulative curves for prediction of the first flush load were drown for urban drainage systems. A strongly first flush appear in Chemical Oxygen Demand (COD) and it is weakest in suspended solids. The phenomenon was observed at all parameters. The first flush was not a regular feature for parameters. This study showed that we can release the large amount of pollutant parameter from urban runoff by controlling and treating initial runoff volumes. By this work, we can conserve surface water and management it appropriately. Further studies of the first flush phenomenon should be performed at the outfalls of drainage systems. The main aim should be to find the critical amount of runoff volume, which is able to flush away available pollution, rather than to determine the pollution load during the first part of each storm event.

References 1. Adams Barry J, Papa F (2000) Urban storm water management planning with analytical probabilistic models. Wiley, New York 2. Ashley RM, Wotherspoon DJJ, Coghlan BP, McGregor I (1992) The erosion and movement of sediment and associated pollutants in combined sewers. Water Sci Technol 25(8):101–114 3. Deletic A (1998) The first flush load of urban surface runoff. Water Res 32(8):2462–2470 4. Geiger W (1987) Flushing effects combined sewer systems. In Proceeding of 4th international conference on urban storm drainage. Lausanne, Switzerland, pp 40–46 5. Griffin DM (1999) Efficient design of storm water holding basins use for water quality protection. Water Environ Res 71(2):241–250 6. Gupta K, Saul Adrian J (1996) Specific relationships for the first flush load in combined sewer flows. Water Res 30(5):1244–1252

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7. Novotny V, Olem H (1994) Water quality, prevention, identification and management of diffuse pollution. Van Nostrand Reinhold, New York 8. Sansalone JJ, Buchberger SG (1997) Partitioning and first flush of metals in urban roadway storm water. J Environ Eng 123(2):134–143

Assesment of Ecological Flow for Mountain Rivers of the Kura Basin Rovshan Abbasov

Abstract Development of an irrigation farming and intensive water use in water catchments areas of Kura basin river of Azerbaijan has increased consumption to fresh water, which is supplied only by small mountain rivers. Most of water resources of small mountain rivers of Kura basin are completely consumed by the enterprises of industry and agriculture. Waste of the water resources of small rivers bring to the “loss of rivers” as an element of landscape in the Small Caucasus region. In lower part of Kura river basin within the Azerbaijan during the shallow season of year the river flow is completely absent. To prevent such condition on the mountain rivers needs to reserve a part of the river flow, that is to say, reserve “ecological flow” in the riverbeds. Ecological flow is such a quantity and condition of the flow, in which is vital for aquatic organisms, quarantines increase for them, sufficient for transporting all solid materials and sediments. In other words, the ecological flow maintains the river ecosystem as a part of an environment. To quarantine of these conditions are needed enough quantity, quality and strong watercourse speed in the riverbeds. The complex assessment of the ecological flow needs systematical and complex hydrological, biological and ecological investigations and stationary observations on the watersheds. As a result of long-term investigations, new methodic, which gives a possibility to calculate ecological flow for mountain rivers is proposed. For sufficient situation of hydroecological safety, ecological flow is needed to estimate for points of concentration of rivers. Points of concentration in many small rivers are situated very far from the river mouthes and consequently, stationary hydrological observations do not reflect hydroecological situations in the mountain rivers. By the offered methodic it is possible to estimate ecological flow for all year period. By this methodic the ecological runoff is estimated not only for water gauge stations, but also for a mouthes of small rivers. The index of a relativity of a ecological flow is developed. It has been revealed, that the interrelation between recordable and ecological flows defines an ecological situation in river ecosystem. R. Abbasov (B) Hydrometeorolgy Scientific Research Institute (HSRI) A2 1073, Baku, B. Agayev St. 100(A), Azerbaijan e-mail: [email protected]

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Such interrelation may be called relative hydroecological factor of flow (CREF). Relative ecological factor of the water is an indicator of ecological situation in the river for any period. If the CREF value is higher than the unit is, then the danger of ecological crises in the river ecosystem does not exist, because, for an exchange of substances and energy in the river there is enough water. If CREF value is lower than the unit, then insufficient water flow is observed in the river. Keywords Ecology · Environment · Hydroecology · River

1 Introduction At present the extremely undesirable ecological situation is observed in the basins of small rivers of Azerbaijan, where the irrigation farming is very developed. As a result of intensive river intake, water flow of the some small rivers of Azerbaijan completely is lost. Sharp decrease in water content of river leads to disappearance of a flowage; in result the sanitary-biological condition in the river ecosystem worsens. In many small rivers of the Kura basin within the Azerbaijan Republic during a shallow season of the year in the lower part of the rivers the natural runoff is completely absent. The rivers often desiccation below water reservoirs, which one are constructed with the purposes of irrigation. For example, in the lower part of the river Terterchay, after construction Serseng water reservoir the natural runoff completely is absent. Kura basin region of Azerbaijan Republic has enough dense rivers set (Fig. 1). On this region the river flow is formed due to thawed snow and rain waters. Ground waters also have a great role in the feed of the rivers. The primary phase of water regime of the rivers is high flow, caused by intensive snowmelt and constant rains. High flow is being observed in April–June, and 50–60% of the volume of annual river flow is being observed during this time. The rivers of this territory have high water content, however, water catchments areas of the rivers are not very large and the average annual water flow not above 15–20 m3 /s.

Georgia

Russia

Caspian sea

Armenia

Iran

Fig. 1 Kura basin within the area of Azerbaijan Republic

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Irrigation farming and intensive water use and in mountain and foothill areas of Small Caucasus has increased consumption to fresh water, which supplied only from small mountain rivers. In this region of Azerbaijan water resources most of small mountain rivers were completely consumed by the industry, agriculture and municipal objects. Full consumption of water resources of small mountain rivers has resulted to full absence of a river flow in the river mouth part. In result, waste of the water resources of small rivers bring to the “loss of rivers” as an element of landscape in the Kura basin region. To prevent such condition on the mountain rivers needs to reserve part of the river flow in the riverbeds, that is to say, reserve “ecological flow” in the riverbeds. Ecological flow is such a quantity and condition of the flow, in which is vital for aquatic organisms, quarantines increase for them, sufficient for transporting all solid materials and sediments. In other words, ecological flow enables to protect river as an element of a landscape. For quarantines these conditions is needed sufficient quantity, quality, temperature and strong speed of the water in the riverbeds [1].

2 The Basic Conditions for Existence of the Ecological Flow 2.1 History of Basic Researches and the Experiences In spite of the fact, that researchers are engaged in research of an ecological flow since 70th years of the last century, up to these it was not accepted the standardized term, for concept an “ecological flow”. Therefore, instead of the term “ecological flow” various researchers use various terms such as: “sanitary river flow”, “reserve runoff” “reserved flow”, “minimally residual runoff” “minimally acceptable flow”, “minimally remaining flow” etc. [2]. Fashevsky considers, that the term should be used as an “ecological flow” and this term does not mean economic approach [3, 4]. On the other hand there were no standard principles for an estimation of ecological flow. For example, according to recommendations of Gatillo and Filipovich, quantity of the minimally residual flow is accepted equal 75–80% from the minimal monthly water flow [5]. Shahov I.S. recommends calculating minimal ecological flow on specific energy of a stream [6]. On Imanov F.A., value of an ecological flow should be equal to such value, at which a river ecosystem is already existed in natural conditions [7]. With this purpose Imanov F.A. suggests to study a natural perennial flow regime of river and only after that to estimate a ecological flow. Propositions of Imanov support Vladimirov A.M., Orlov V.G., and Sakovich V.M., specifying on their correctness. Simultaneously, as authors mark, it is impossible to accept the minimal base flow for extensive territories [8]. In the different countries various manuals for definition of quantity of the ecological flow are being used. In Germany, Austria and Poland the ecological flow is defined in percents from the minimal daily average or else average annual flow. In Norway and England such approach is defined in each concrete event depending on local features. In Greece

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quantity of ecological flow must be at least 1/3 of the average summer flow rate of the river, In Portugal its quantity must be equal or higher than 1/10 of the average inter-annual flow rate. In Scotland it is accepted that quantity of ecological flow must be equal or higher than 45% of the average inter-annual flow rate [9].

2.2 Basic Conditions As it has been noted above, qualitative and quantitative infringement of the ecological flow may be observed in following situations: 1. In river medium there is no enough water for a full exchange of energy and community metabolism. The quantity of water in a riverbed defines all vital processes in a river ecosystem. Consequently, the ecological flow is quantity of water, which must be left always in the riverbeds for protection of an environment in the river ecosystem. 2. In the river sufficient quantity of water is being observed, but pollution by some pollutants above a maximum concentration limit (Mcl). At pollution by chemicals and biological wastes, in the rivers happens “a general pollution of an environment”, so that, for aquatic organisms character of relations with an environment is distinctive for duration, indissolubility and interference. 3. In the river there is no sufficient speed of a watercourse for transition of river sediments. For transition river sediments and some wastes of an anthropogenic origin speed of a watercourse in the river mismatches natural conditions. In some cases anthropogenic impacts lead to reduction of a watercourse speed, occurs a silting of riverbeds; therefore occurs vital changes in the inhabitations of the water organisms. For maintenance of a ecological flow in riverbeds should be realized in following conditions: 1. Concentration of the pollutant, which has a highest concentration in the river, must be below from the maximum concentration limit (Mcl), i.e. realization of a following condition is necessary: C ≤1 Mcl where are, C − is concentration of the pollutant, which has a highest concentration, Mcl− limit of an admissible concentration for the same pollutant. 2. For maintenance of energy exchange and metabolism, for satisfaction of any needs of aquatic organisms in the river should be enough quantity of water. Water quantity in the rivers should be at such level, at which the river ecosystem has already existed in natural conditions.

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3. For satisfactory transition of the river sediments, for prevention silting of the riverbed, watercourse velocity in the river should be at the sufficient level. Normally, in natural conditions, speed of a watercourse minimally provides transition of fluvial sediments and other hard materials. 4. Water temperature of a river stream should not exceed a limit of natural measures. 5. Quantity of the ecological flow cannot be invariable for perennial period and depends on water content of year. This requirement considers perennial variation of a river flow, so that water content of river can vary with agency of climatic oscillations. For the complex estimation of the ecological flow, there is a need to systematical and complex hydrological, biological and ecological investigations on the water catchments areas. But, such complex investigations for each small mountain river are practically impossible and require great material expenses.

3 Estimation of the Ecological Flow As specifies some authors, ecological flow in the riverbeds takes into consideration all phases of water regime [5] and depends from the water content of the calendaring interval [2] (season, month, week), minimal water flow for that interval, from the concentration of soiled ingredients: Qec = f (Qqu , Qmin , C)

(2)

where, Qec − ecological flow m3 /s, Qqu − water content of the period for which minimal water flow is needed to be estimated m3 /s, Qmin − is natural minimal water flow for estimating period m3 /s, C− concentration of pollutants. For simplification of calculations as a computational interval it is possible to take calendar months. For any calendar month interval ecological flow may be estimated by under mentioned formula: Qec = kQmin

(3)

where, k − is the empirical coefficient, which depends from the water content of calendaring period, Qmin − minimal average annual flow of lowest duration, which was recorded during perennial instrumental observation. For definition of the average annual minimal flow, a statistical number of longterm stationary observations above a minimal monthly flow should be divided into two periods − the natural and disturbed regime. Then, on a natural regime is defined Qmin , as a flow of lowest duration, which was recorded.

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In this case, the length of stationary observations above flow parameters should be not less than 30th years. Such condition enables to estimate ecological flow at which a river ecosystem already existed in natural conditions. If stationary instrumental observations have no sufficient prolongation, then value of Qmin it is possible to take equal to a water flow of 95% duration. As a rule, value of the coefficient k strongly depends on water content of the computational period. In high-water period always value of k above than in shallow period. For the months, abounding in water, value of the coefficient K may be changed from 0.75 to 0.25, for the periods. For dry months, when is observes luck of water, value of the coefficient K may be changed from 0.75 to 0.98. Reduction of value K may be caused to increase the water intake from the rivers. Extension of the value K may decrease water intake. For any calendar month value of the k may be estimated by this formula: W1 k =1− W2

(4)

volume for estimated period (in our concrete case where, − W1 − is the runoff month flow) m3 or km3 , W2 − is the annual runoff volume, m3 or km3 . Offered formula may be used for calculating of ecological flow in small mountain rivers for calendaring months. At the Fig. 2 is shown minimal ecological flow for river Terterchay at the water gauge station Serseng (point of concentration), which is situated in Kura river basin within the limits of Azerbaijan Republic. The constructed graph well represents, how many waters do not suffice, for normal functioning of river ecosystem in different calendaring months. As it is shown from the graph, and as was expected, luck of water in the small mountain river Terterchay is being observed for the low flow periods. In other words, in dry months, river intake for various needs there is more than norm. It is related by an intensive water-fence during the summer and autumn periods, when in nearby territories, Terterchay becomes a unique water source for an irrigation. Apparently from the

Q, m3/s. 35

30 25

observed flow preserved flow

20 15 10 5 0 1

2

3

4

5

6

7

8

9

10

11

12 months

Fig. 2 Allocation on months ecological and recorded flows

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graph, that in spring months in this river luck of water is not observed, so that a feed of the river is provided with melt-waters of Small Caucasus Mountains and during this period Terterchay has a high water. In high flow periods the quantity of the ecological flow always less than observed water and ecological situation in the riverbeds is normally. As a rule in shallow water months ecological conditions in the river Terterchay worsens as a result of shortage of water in river ecosystem. In these months, especially the condition of spawning of sturgeon fishes worsens, which have great economic and aesthetic value for Azerbaijan.

3.1 Estimation of Ecological Flow in Case of Polluting As it has noted above, in case of pollution by chemical pollutants, quantity of a ecological flow should be proportionally increased for diluting ingredients. However at such increase Eq. (1) inequality should be considered. If there is pollution by chemicals and biological pollutants, then quantity of a ecological flow should be proportionally increased for diluting of pollutant ingredients [10]. In this case increasing quantity of water should occur proportionally to quantity of all pollutants that the concentration of any pollutant did not exceed a maximum concentration limit (Mcl). In other words, Eq. (1) inequality should be satisfied. Therefore in case of pollution by chemicals, the quantity of the ecological flow may be calculated under the following formula: Qec =

C kQmin Mcl

(5)

Where, C − is the concentration of pollutant, which has a high concentration at the moment of observations, Mcl − maximum concentration limit for that pollutant. However, it is clear, that in natural conditions quantity of the ecological flow never should be more than observable water flow or any recorded flow. In other words, for satisfactory hydroecological situation in mountain rivers there is must be gratification of following inequality [2]: Qrec − Qec ≥ 0

(6)

where, Qrec − is the recorded water flow, m3 /s. If to consider value Qpre from the Eq. 5 in an inequality Eq. (6) then we shall receive: Qrec −

C kQmin ≥ 0 Mcl

Qrec C ≥0 − kQmin Mcl

(7) (8)

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C Qrec ≥ kQmin Mcl

(9)

Last inequality shows, that in case of chemical pollution, the ration of recordable C flow to ecological flow should be more or equal to the ration Mcl . After definition value of ecological flow, capacity of the river intake may be estimated by this formula: Qri = Qrec − Qec

(10)

where, Qri − is the river intake. If pollution is taking place below water-intaking construction, capacity of the river intake should be decreased proportionally to capacity of pollutants. In other words in the case of pollution, capacity of water intake may be estimated by undermentioned formula: Qri = Qrec −

C kQmin Mcl

(11)

3.2 Estimation of Ecological Flow for River Mouthes For sufficient situation of hydroecological safety, ecological flow needed to be estimated for river mouthes. Ecological condition of river mouthes has a great importance for all river ecosystems. In the mouthes of Kura basin rivers occurs a spawning of valuable sturgeon fishes, which after spawning returns to Caspian sea. The riverbeds of the Kura basin rivers are a unique spawning area for sturgeons. Simultaneously, the mouthes of small rivers are an irreplaceable dwelling place of some living organisms. River mouthes of many Kura basin rivers is situated very far from the points of concentrations and other water gauge stations, so stationary hydrological observations do not reflect hydroecological situations in the rivers. Therefore, ecological flow must be estimated for river mouthes and capacity of the ecological flow may be estimated with the help of this dependence: Qec = f (F)

(12)

where, F is the water catchments areas of rivers. According to dependence Eq. (12), ecological flow may be estimated for river mouthes. Such relations can be constructed not only for the separate rivers, but also for whole regions. Practice shows, that between a ecological flow and the water catchments areas always is a close relation. Coefficient of correlation of such relations always are not below than 0.7. On such associations it is possible to calculate value of a ecological flow for river mouthes of investigated territory.

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3 3

Qec, m /sec

2.5 2 1.5 1 0.5 0 100

F, km2 300

500

700

900

1100

1300

1500

1700

Fig. 3 Dependence of ecological flow on water catchments area of right-bank rivers of Kura basin for January

In the Fig. 3 is shown relation between ecological flow and water catchments areas of some right-bank rivers of Kura basin for January month. On this association it has been calculated value of the ecological flow for the mouthes of right bank rivers. However, this method for the rivers of arid territories gives the overestimated value for the ecological flow. Such values are gained when the river mouthes is very far from a point of concentration, simultaneously between the point of concentration and a river mouth flow formation does not occurs. In such cases the quantity of the ecological flow can be calculated under the following formula:

Qpre − mouth =

Qmouth Qpre − po Qpo

(13)

where, Qmouth − perennial flow in the mouth, Qpo − perennial flow in the point of concentration, which is estimated as a result of perennial stationary hydrological observations, Qpre−po − ecological flow in the point of concentration, witch is calculating by the formula Eq. (3). The value of Qmouth is calculated on well-known dependence: q = f (H)

(14)

Where, q − is a modulus of flow l/s·km2 , H − is a average height of a water catchments area, m.

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4 CREF From an inequality Eq. 6 becomes obvious, that satisfaction of an ecological situation in the river ecosystem strongly depends on the relation of the recorded and ecological flows. For effective existence of a river ecosystem quantity of the ecological flow in the river always should be more than recorded flow or equal to it. If the observable water flow a lesser amount of the ecological flow, there is a crisis at the river ecosystem. In other words, the hydroecological situation in the river grows out belowmentioned factors: 1. Quantity of ecological flow in the river; 2. Quantity of observed flow; 3. Ration of the observed flow to ecological flow; There is no direct connection between the first and second factors, though as an independent factor the interrelationship between them determines the formation of ecological situation in the river. Such interrelations may be called relative hydroecological factor of flow. The coefficient of relative ecological factor of the flow (CREF) is computed on the following formulation: CREF =

Qrec Qpre

(15)

where, CREF − is coefficient of relative ecological factor of the water. Relative ecological factor of the water is a main indicator of ecological situation in the river for any period. 2 CREF

1

0 1

2

3

4

5

6

7

8

9

10

11 months

Fig. 4 Change CREF in time

12

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In other words, CREF is the result of dissymmetry between recorded and ecological flows. The principle of dissymmetry is successfully applied by A.N. Kondratyev in riverbed study. Exploring dissymmetry between transporting ability of the flow and silt entry from the upper measurement point he made the following conclusion: “Dissymmetry between silt entry and transporting ability of the riverbed is the reason for the change of the form of riverbed and the type of riverbed processes”. The author calls such a dissymmetry relative transporting ability of the flow [11]. For example, in the Fig. 4 is illustrated distribution in time of the coefficient of CREF at the water gauge station of Serseng on Terterchay river. The shaded field on the graph illustrates the period of ecological trouble. Apparently from the schedule, during the shallow period on the river Terterchay, on the water gauge station Serseng sharp shortage of water is observed. The ecological condition of the river Terterchay becomes even worse in the lower part, where the year round river flow almost is absent.

References 1. Abbasov RK (2005) The model of hydroecological safety of flatland rivers. Theoretical and applied problems of geology. Materials from 2nd International Scientific Conference, Minsk, pp 77–79 2. Imanov FA (2000) Minimal water flow of Caucasus rivers. Nafta-Press, Baku, 298p 3. Fashchevsky BV (1996) Bases of ecological hydrology. Minsk, Ecoinvest, 240p 4. Fashchevsky B, Fashchevskaya T (2003) Water management budget as a basis for assessment water priorities, vol 1. Proceedings of the 1st international conference on hydrology and water resources in Asia Pacific Region, Kyoto, Japan, pp 357–360 5. Gatillo PD, Filipovich IM (1971) Questions of assessment of minimally necessary water flows of the rivers. Problems of use of water resources. The collection of scientific works. Meteoizdat, Minsk, pp 26–42 6. Shahov IS (1980) Methodic for calculating minimally ecological flow for the rivers of Urals Mountains, vol 11. Proceedings of the Ural Institute of the Water Management, Sverdlovsk, pp 27–37 7. Imanov FA (1995) Minimum discharges of the Caucasian rivers. Abstracts of International Symposium on Runoff Computations for Water Projects, Saint-Petersburg, Russia, p 71 8. Vladimirov AM, Orlov VG, Sakovich VM (1997) Ecological aspects of consumption and water resources protection. Hydrometeoizdat, Saint-Petersburg, 125p 9. Abbasov RX (2001) Estimation of ecological flow for river mouthes. International conference on Fresh-water, Baku 10. Mamedov MA, Abbasov RX (2004) Problems of studying of hydroecological safety of the rivers of Azerbaijan. Proceedings of the 3rd international conference on environmental security of the mountain regions, Tbilisi, pp 67–72 11. Kondratyev AN (1999) Relation of transporting ability of the stream to the sediment flow as a condition of riverbed formation. Geomorphology 3:14–18

Effictiveness of Water Resources Use in Aral Sea Basin and Lower Reaches of the Amu Darya River M. Ikramova, A. Khodjiev, and K. Misirkhonov

Abstract Natural-climatic conditions of Uzbekistan, the limited area of lands suitable for cropping and limited water resources force to search more effective and useful ways of water-land resources usage. An anthropogenic desertification brings to complication of the problem above. About 15% of a crop is lost because of a unsuccessful ameliorative condition of the lands. This situation is more serious in the lower reaches of the Amu Darya river. Efficiency of the irrigated lands in Karakalpakstan 4.5 times lower than in the country, in the Khorezm area – 1.4 times. The parameters of disease connected to water quality have grown and there is a sanitary-and-epidemiologic condition get worse frequently. Alongside with the general problems, situation can be complicated with water shortage and a drought. Hydrological mode of the Amu Darya River is not stability. Extreme situations such as flood (1994, 1995 is observed, 2003–2004) and dry become more frequent (2000, 2001). In the Amu Darya river basin limited water division is carried out to manage of water distribution taking into account water quality. The structure of water consumption in a lower reaches of Amu Darya is various. In the Khorezm area the agriculture consumes 97.5% from the taken water, for municipal services − 1.8, fish economy − 0.7%. We have developed an information-program complex which includes: • Model of water resources management • A database • User interface The model allows calculating various scenarios of the Amu Darya river water resources management considering its quantity and quality in imitation and optimization modes.

M. Ikramova (B) Central Asian Research Institute of Irrigation (SANIIRI), Karasu-4, 11, Tashkent 700187, Uzbekistan e-mail: [email protected]

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Keywords Flood · Agriculture · Water resources

1 Introduction A lot of attention being given to the problem of the ecological crisis in zone of Aral sea not only in Uzbekistan and Central-Asian republics, but also by international public, research and financial institutes. However, crisis is intensified, dried up bottom of the sea turned into extensive sandy desert, became a powerful source of release of dust and salt. Appeared real threat to residence of the people in this zone is aggravated by periodically repeated water shortages. For the last 40 years water arrival in Aral Sea strongly shortened (Fig. 1). The sea level fell more then on 17 m which has brought disastrous social-economic consequences for population of the Aral Sea basin which number is about 5 million people. An area of the dry bottom that being left forms 36 thousand km. It is being reported that 150 thousands of tons to salt and sand, infected by remainder pesticides, is carried to the other regions annually, moreover situation is aggravated by widening frequency and power of sand-storms/16/. Intensive water use on irrigation in upper and middle levels of a river and water pollution collector-drainage water from irrigated lands has vastly worsened the quality of water in the source of the water-supply in lower levels of the Amudarya river. Variability of the water flow, appeared in recent years contradictions in requirements on water use between hydroenergetics and irrigated agriculture has complicated the water situation in Amudarya river basin which was particularly reflected in its lower flow. At years of the shortage of water arrival to a delta of Amudarya its amount forms about 40% from annual averages, brings to a depletion of reservoirs, reduction and stop of water supply to channels and feeders. The main part of lenses of fresh underground water also is hydraulically connected with activity of irrigation channels, absence of water in which brings in many places to sharp reduction of horizons of underground water sources. Because of extreme insufficiency of irrigation water in Karakalpakstan, sowings of the agricultural cultures shortened 1500 1000 General

P1

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Sirdarya

km3

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Fig. 1 Graphs of the Aral Sea volume change and water arrival

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55 50 River flow, km3

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Annual flow, km3

15

Forecast

2010

2008

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Fig. 2 Annual water runoff of Amudarya River on years of observations (Darganata post)

in 2 times, about 70–80 thousands of people of the able-bodied population remain out of job. The results of a numerical calculation on forecast of Amudarya water content in nearest and remote prospect (till 2010 and 2025) show that shallow years are seasonally repeated each 4–5 years (Fig. 2). Hydrological features of lower current approach show that maximum arrival of the river sewer was in 1992 and has formed 53.6 km3 , but minimum annual arrival of the sewer was in 2001 and has formed 12.95 km3 . During 21 years of observations 5 years were abounding in water, 10 years − average, 6 years − shallow i.e. approximately 28–30% fall into category of shallow. The Tuyamuyun hydrosystem`s complex of buildings (TMGU) plays the essential role economies of Karakalpakstan and Horezm areas of Uzbekistan and Tashauz area of Turkmenistan and consequently, efficient use of hydrosystem and its serviceability has a big importance at solving of the above-mentioned problems. Analysis of a mode of the influx into Tuyamuyun for period from 1981 to 2004 shows (Fig. 2) that influx of water into fold of TMGU changes in significant limits: “ in shallow years − 20−25 milliard m3 ” in abounding in water years − 45−65 milliard m3 in years of average water content influx forms the value of the 30–35 milliard km3 that 4–5 milliard km3 more then volume of the required by lower levels with provision for all losses that forms 25–27 milliard km3 .

2 Present Water Use Situation in Lower Levels of the Amudarya River In a hydrological mode of the Amudarya river there are clearly stand out two phase periods: lowest water level with big share of the underground flow and high water, when in flow dominate melting water a glacier and seasonal snow. With standpoint

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of purpose and problems of this work most of interest is the phase of the high water, more so that at period of the high water river will wear out more than 80% of annual flow. With reference to a lower Amudarya parameters of the high water basically define Vahsh and Pyandzh rivers while role of other influxes of river reveals weakly and only with such important factor as big length of the main stem of Amudarya river (more than 1500 km). This factor defines certain spreading of high waters, as a result of which its length at the input in Tyuyamuyun reservoir equals to 160–180 days in interval during April–September. The maximum water discharges are, as a rule, observed in the first- second decades of the July (Fig. 3). Systematic observations of flow mode in a lower levels are conducted in following alignments: Darganata, Tuyamuyun, Beruniy, Kipchak, Samanbay. For analysis of the flow and mineralization of water of Amudarya is used data of hydrological yearbooks, GMS, expeditions of SANIIRI and others. Analyzed results of the perennial observations (for 1981–2003) of the flow change in a lower level of Amudarya show that average annual water discharges near Darganata hydropost changed from 580 m3 /s (1986) to 2000 m3 /s (1969), while average annual water discharge is 37.0 km3 /year. Observations have shown that in Tuyamuyun area average annual water discharges changed within 531 m3 /s (1986) − 1640 m3 /s (1992.). At average monthly maximum discharges were 1417 m3 /s (VII-89) − 3970 m3 /s (VII-92), but minimum discharges varied within 22 m3 /s (I87) − 490 m3 /s (III-93). Accordingly, annual volume of the flow changed from 54, 1 km3 (1968) till 16.7 km3 (1986) at average annual value in this period 30.07 km3 .

Q, m3/s 6000

1989 1990 1991

5000

1992 1993 1994 1995

4000

1996 1997 1998

3000

1999 2000 2001

2000

2002 2003 2004 2005

1000

2006 2007 2008

0 Jan

Feb

Mar

Apr

May

Jun

Jul Aug

Sep

Fig. 3 Average monthly water discharges on Darganata post

Oct

Nov

Dec

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In Kipchak alignment flow changes from 9.02 km3 (1986) to 52.2 km3 (1969.). The maximum discharges were within 750–2530 m3 /s, but minimum − 55−220 m3 /s. For Tahiatash hydrosystem (in Samanbay alignment) Amudarya flow changes within 0.34 km3 (1982) − 24.2 km3 (1992.). During some months of the shallow years arrival not existed at all (1981, 1985, 1986). Maximum and minimum discharges were accordingly within 50–1700 m3 /s and 0.3–16 m3 /s. Maximum annual volume of the arrival in delta of Amudarya river for this period was fixed in 1988 − 16.0 km3 . A flow into Aral sea was observed only in waterabundant years in volume 3–5 km3 , but in shallow – is absent.

2.1 Alluvial Mode and Mineralization Alluvial features on approach to Tuyamuyun hydro system varies within: in shallow years 30–40 million tones; in average years − 70−90 million tones; in water-abundant years 150–170 million tones. With starting TMGU in a lower level became to enter lightened water, and in channel reservoir occurs postponing an alluvium. On condition on the end 2003 total volume of deposits has formed 1100 mln. m3 . The turbidity of the flow decreased to 0.03–0.20 kg/m3 (tenfold). At channel reservoir drawdown below 118 m mark in lower level enters the flow with saturation alluvium 1.2–1.3 kg/m3 . Average annual of the turbidity of water below dams were 0.11–0.20 kg/m3, but during vegetation period varies within 0.40–0.55 kg/m3 that in 7.5 times less then average. The weighted alluvium forms flow of 4–10 millions of tones. The measurements of mineralization in TMGU area are conducted on coast posts: alignment Darganata − 90 km above dams, in alignment 0.2 km above dams and in alignment 0.5 below dams. In autumn-winter period (October–January) water mineralization varies within 0.8–1.2 g/l. The growing water mineralization exists since January, which lasts before the second decade of March and reaches 1.9 g/l. Starting from the middle of March, water mineralization gradually falls and by the end of August comes to 0.6 g/l. Water mineralization in lower stream has a vital importance not only for irrigation, but also for drinking water-supply, since are at present realized water-scoop of water from channel with installation of cleaning devices.

2.2 Water Distributions into Irrigational Canals Distribution of irrigation water in lower lands of Amudarya river depends on water level of an year, technical restrictions, as level of water and reception capacity of canals and is realized on the following system irrigation channel. Distribution of river water in Karakalpakstan is realized from channel reservoir of Tyuyamuyun hydrosystem (TMGU) through right-side canal, as well as by means of water-fences, located alongside the river below TMGU – from republican canals (the Pahta-Arna,

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2000

m3/s

Jan 350 300 250 200 150 100 50 0

Feb

Mar

Apr

May

m3/s

Jun

Jul

Aug

Sep

Oct

Nov

Dec

Jul

Aug

Sep

Oct

Nov

Dec

Jul

Aug

Sep

Oct

Nov

Dec

Jul

Aug

Sep

Oct

Nov

Dec

Jul

Aug

Sep

Oct

Nov

Dec

Jul

Aug

Sep

Oct

Nov

Dec

2001

Jan

Feb

Mar

Apr

May

Jun 2002

m3/s 500 400 300 200 100 0 Jan 2000

Feb

Mar

Apr

May

m3/s

Jun 2003

1500 1000 500 0 Jan

Feb

Mar

Apr

May

m3/s

Jun 2004

1500 1000 500 0 Jan 2000

Feb

Mar

Apr

May

m3/s

Jun 2005

1500 1000 500 0 Jan

Feb

Mar

Apr

Dashkhous (Turkmenistan)

May

Jun

Khorezm (Uzbekistan)

Fig. 4 Water abstraction from the Amudarya River in lower reaches

Karakalpakstan (Uzbekistan)

Effictiveness of Water Resources Use in Aral Sea Basin

1387

Nayman, Kyzketken, Suenli and others) and interstate canals (Klychbay, KinchakBozsu). The Lands of Horezm area (Uzbekistan) are irrigated from left-bank main channel (TMGU), interstate main channel (with Turkmenistan) and regional channel (Tashsaka, Pitnyak- Arna, Urgench- Arna, Dariyalyk- Arna and others.). Water distribution to Tashauz (Turkmenistan) is realized through network of canals (Shavat, Gazavat, Klychbay, Kipchak-Bozsu, Khan-yab, Dzhumabaysaka), main water-fences which are located on territory of Uzbekistan, in transit through Horezm area and Karakalpakstan. Water selection into canals from channel reservoir TMGU into LMK, PMK, Tashauz is realized duly. However, limits on water selection are fixed by ICWC, which not are always provided because of lack of water. Total average monthly water selections are presented on Fig. 4 in lower lands for the last 6 years. Hydrographs distinctly show the difference between actual water supply and established limit. For lower streams of Amudarya today and particularly in the future exists need to organize firm guaranteed water supply, minimizing loss of water, for the reason warning negative consequence in condition of the shortage of water and social damage, ensuring the ecological requirements to river flow increasing productivity of lands.

3 Mode of Work of Tuyamuyun Hydro-system 3.1 The Main Indexes of the Work of Tuyamuyun (TMGU) The Construction of TMGU on the Amudarya river was finished in 1981–1983. It provides guaranteed water-supply for irrigation on lower lands on area of 1.2 million hectars. TMGU includes 4 reservoirs − 1 channel and 3 fluid: Kaparas, Sultansandzhar and Koshbulak. Channel and Kaparas have entered in usage in 1981–1982, and Sultansandzhar and Koshbulak − in 1983–1984. Reservoirs are interconnected between themselves. The total capacity of reservoirs forms 7.8 km3 , but useful capacity − 5.27 km3 . About 40% of full capacity of flow reservoirs forms a dead volume. The complex of the buildings is projected and built so that reservoirs can be filled and operate in a pair: channel through regulator with Kaparas, Sultansandzhar with Koshbulakom. Filling of flow reservoirs is realized through channel capacity. Supply of water into Sultansandzhar reservoirs is realized through building with 500 m3 /s discharge. Into Koshbulak reservoir water comes from Sultansandzhar through canal with 24 km length, reception capacity- 100 m3 /s. Leveling of flow chalices is produced through channel of lightened water and siphon, into the river or through channel lightened water and floodgate-regulator into irrigation network. First of all turns on itself attention that fact that mode of the filling and leveling of the TMGU capacities depends on water content not only current, but also preceding year. The volume of filling and leveling of the Kaparas and channel capacities in a water-abundant year has a more low amplitude of the fluctuations while at shallow years channel capacity being devastated almost completely at period of leveling,

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Channel

Kaparas

Sultansandjar

Koshbulak

132 130 128 126 124 122 120 118 116 114 112 110 1/1/1997

1/1/1998

1/1/1999

1/1/2000

12/31/2000

12/31/2001

12/31/2002 Date

Fig. 5 Regime of work of reservoirs of TMGU in 1997–2002, flow: in 1997 − 23.0 km3 ; 1998 – 53.5 km3 ; 1999 − 32.1 km3 ; 2000 − 15.5 km3 ; 2001 − 12.95 km3 ; 2002 – 33.7 km3

but at period of the accumulation of water its maximum volume reaches not more than 50% from the total volume. For instance (Fig. 5), in abounding in water 1998 level of water during this year varied slightly: in channel capacities from 130 to 126 m, and in Kaparas from 129 to 124 m. In shallow year (2001) it is seen deep minimum water level (and volumes), formed already at the beginning of spring and is saved whole year term up to renewing the capacities of low flow at the beginning of autumn. At the same time fluctuations of water levels in channel capacity reached 10 m, and in Kaparas 9 m. Silting of reservoir in abounding in water 1998 has formed 108 mln. m3 , in mean 1999 − 44 mln. m3 , in strongly shallow 2000–2001 has occurred the erosion which formed 110 million m3 .

3.2 Mathematical Model of Tuyamuyun Hydro-system The mathematical model of the TMGU`s work enables to develop a scenario of water amount and quality change in a down stream of the Amudarya river depending on annual water content and its working regime. Input data for calculation of the water balance are values of the surface inflow and fault, reservoir levels and value of the evaporation and precipitations. Values of the inflow and outflow of reservoir water are taken from Exploitation department of TMGU. For channel reservoir inflow is defined based on Darganata hydrological post data, outflow – based on Tyuyamuyun hydrological post data and water scoops on

Effictiveness of Water Resources Use in Aral Sea Basin

1389

right-bank and left-bank canals. For Kaparas reservoir inflow-outflow is defined on exchange between Kaparas and channel reservoir and scoop of water by pumping station. For Sultandzhar reservoir inflow-outflow is defined according to exchange between Sultandzhar and channel reservoir and water-scoop of lightened water from canal. For Koshbulak reservoir inflow-outflow is defined according to change level in reservoir, considering precipitation and evaporations. The System of the equations of the water balance for TMGU`s reservoirs look as follows: Q −Qc −QB ± QPK ± P + QPC −Qf −E + W + S = 0

(1) – Channel

±QPK −Qf −QB E + P + W + S = 0

(2) – Kaparas

±QCK −Qφ −E + P + W + S = 0

(4) – Koshbulak

±QPK ± QCK −Qf −E + P − QB + W + S = 0

(3) – Sultansandzhar

where Qp − a surrface inflow in reservoir, mln. m3 , P − precipitations, Qs − a surrface outflow from reservoir, Qv − water scoop from reservoir, QRS − water exchange with Sultansandzhar, QRK − water exchange with Kaparas, Qf − underground water exchange of reservoir, E − an evaporation, W − a change of volume of water in reservoir for accounting period, S − equation’s discrepancy for the reservoir water balance, QRK − water exchange with Kaparas, QRS − water exchange with channel reservoir, QSK − water exchange with Koshbulak, QSK − water exchange with Sultansandzhar. The water balance of Tuyamuyun hydrosystem is calculated for a month. An evaporation from water surface and precipitations from reservoir surface is calculated as layer of the evaporation or precipitation, defined by meteorological service, multiplied by area of reservoirs. The area of reservoirs in turn is calculated on reservoir level on base of bathymetric curves. Change of volumes of reservoirs is defined on condition of the value of the reservoir volumes for beginning and the end of the accounting period, which is in turn defined also on reservoirs level by means of bathymetric curves. Bathymetric curve for channel reservoir is built for each year of the TMGU usage. This is explained by big amount of weighted feculences, entering in reservoir with river water. Their deposition brings to a silting of channel reservoir. The underground inflow in reservoir is formed in zone of backwater. Underground outflow from reservoir occurs basically because of the filtering in body of the dam and partly in reservoir’s banks. In case of quick filling of reservoir, the level of underground water turns out to be below reservoir’s level. Occurs water outflow from reservoir. During sharp reservoir drawdown its level becomes below level of underground water adjoining to territory of reservoir. It occurs the inflow of water into reservoir. For this reason it was made calibration of model.

3.3 Balance Model of Lower Stream of the Amudarya River The Equation of the water balance of the accounting river area for a given time interval (days, decades, months) has a following type:

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W1 + W2 − Wdrawdown − WB − WII − W = S

(5)

Where W1 − an arrival of water resources on area, mln. m3; W2 − an inflow k.d.s.; W drawdown − drawdown in closing alignment ; Wv − water scoop on area; Wp- loss of outflow on area; W − a volume of channel regulation; S − balance discrepancy. Channel losses of the outflow are defined on formula (mln. kub. m): W = Wisp − W about + W f .p. − W f .pr.

(6)

where Pisp − a losses on evaporation; Po − an arrival of water to account of the precipitation; Pf.p. − a filtration losses; Pf.pr. − a filtration inflow on area. At calculation of the volume of channel regulation and losses of the sewer were used dependencies of H. Ismagilov/3/, for determination of the turbidities of the flow were used empirical dependencies, designed in SANIIRI for lower stream. The surface outflow is defined using values of account of the flow of river on hydro-posts Tuyamuyun and Samanbay, water scoops and revocable drains were identified as of data of operational hydrometrics. According to above mentioned methods were made calculations of water-saline balance of the Amudarya and are organized numerical experiments for two scenarios, allowing to evaluate the modes of the sharing of the flow: scenario 1 − a modes under existing requirement on water, existing scheme of the sharing the flow and water draining; the scenario 2 − a possible modes with change of requirements on water with provision for water saving, increasing to productivity of the lands, stop of outflow of collector-drainage water and observance of ecological drawdowns and standards on water quality. On the first scenario deficit in irrigated agriculture at the average on basin has formed 2.5% from quota, with maximum value 10% at separate years. The average annual flow of Amudarya changed: in Darganata alignment- 32.0 km3 , Samanbay − 7.5 km3, accordingly average annual water mineralization- from 1.00 g/l in Darganata and 1.2 g/l in Samanbay. The inflow in delta of Amudarya varies from 1.6 to 12.5 km3 during vegetation and 0.8–8.5 km3 during intervegetation period. Average seasonal mineralization in Samanbay changes from 0.8 g/l to 2.8 g/l. The ecological requirements for Amudarya are endured in water abounding years. On the second scenario deficit in irrigated agriculture practically is absent. The average annual runoff of Amudarya changing: in Darganata alignment − 34.5 km3 , Samanbay − 12.0 km3. Average annual water mineralization changing within 0.9 g/l in Darganata and 0.6- 1.4 g/l in Samanbay. In condition of the full stopping of collector water runoff water mineralization in lower reaches does not exceed 0.7 g/l. Ecological requirements for Amudarya (sanitary discharge on channel and water supply into system of delta’s lakes) are endured in volume of 7–8 km3/year.

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3.4 Recommendations on Increasing of Efficiency of Tuyamuyun (TMGU) Work The usage regime of TMGU depends basically from hydrological, hydro-chemical and alluvial modes of river, initial filling of reservoirs and mode of the requirements on water of lower reaches of Amudarya. The rational state of TMGU reservoirs work were designed on base of the optimization of scenarios taking into account interests of irrigation (the amount), drinking water-supply (the quality), as well as technical condition of channel reservoirs (silting) and minimization of the wasteful losses. In condition of water shortage reserves of river runoff for reservoirs filling will be available only in November–January. That is why in this period it is necessary to transfer through the TMGU not more than 100 m3 /s (sanpopuski+losses+others), but rest runoff, with approximate volume 2140 mln. m3 to regulate in TMGU reservoirs for economic and drinking purposes from Kaparas. It Is recommended to fill all reservoirs at least till 124 m including Sultansandzhar and Koshbulak: (1) it is recommended to begin reservoir drawdown in the following sequence: – channel: February−April till 118 m for lands washing; – Kaparas: February−April till 118 m for drinking and for waterings; (2) at the following period, namely in June−August, it is necessary: On the one hand, a part of river runoff to use for filling of channel and Kaparas reservoirs till 126 m minimum, and on the other hand − realize the leveling of Sultansandzhar and Koshbulak before dead volume mark (116 m) through channel by lightened water and alignment. In specified length of time total filling volume of reservoir will form approx. 1000 mln. m3 , but leveling volume − about 1200 mln. m3 ; (3) hereinafter, in September−October, accumulated spare water in channel reservoir in volume approx. 650 mln. m3 possible to use for irrigation of the lands and other economic necessities. An advisable mode for reservoirs usage of Tyuyamuyun hydroscheme in condition of the shortage of water is shown on Fig. 6 and is only appropriate since allows to limit the damage at vegetation period considering interests of irrigation and at the same time to fill Kaparas by the most qualitative river water for drinking. Calculations on increasing of usage efficiency of TMGU were compared with materials of field studies and data of hydroscheme`s Exploitation Department on real working state of reservoirs in different water content years and theoretical elaborations earlier conducted by research fellows of SANIIRI, on reservoirs silting calculations (V.LAPSHENKOV, V.SKRYLINIKOV, O.KAYUMOV, A.SOROKIN). Values of rivers runoffs are accepted as an average for abounding, mean, and shortage in water years accordingly. Coefficient of water lightening is included in all calculations of the volumes of the alluvium postponing in reservoirs (designed by SANIIRI /11/) depended level of water mark in reservoir for accounting length of time.

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M. Ikramova et al. Wet year 130

Water level, m

128 126 124 122 120 118 116

real (1998)

calculated

1-Jan 11-Jan 21-Jan 31-Jan 10-Feb 20-Feb 2-Mar 12-Mar 22-Mar 1-Apr 11-Apr 21-Apr 1-May 11-May 21-May 31-May 10-Jun 20-Jun 30-Jun 10-Jul 20-Jul 30-Jul 9-Aug 19-Aug 29-Aug 8-Sep 18-Sep 28-Sep 8-Oct 18-Oct 28-Oct 7-Nov 17-Nov 27-Nov 7-Dec 17-Dec 27-Dec

114

calculated

real (1999)

1-Jan 11-Jan 21-Jan 31-Jan 10-Feb 20-Feb 2-Mar 12-Mar 22-Mar 1-Apr 11-Apr 21-Apr 1-May 11-May 21-May 31-May 10-Jun 20-Jun 30-Jun 10-Jul 20-Jul 30-Jul 9-Aug 19-Aug 29-Aug 8-Sep 18-Sep 28-Sep 8-Oct 18-Oct 28-Oct 7-Nov 17-Nov 27-Nov 7-Dec 17-Dec 27-Dec

Water level, m

Average water year 130 128 126 124 122 120 118 116 114

Dry Year

130 Water level, m

128 126 124 122 120 118 116

calculated

real (2001)

1-Jan 11-Jan 21-Jan 31-Jan 10-Feb 20-Feb 2-Mar 12-Mar 22-Mar 1-Apr 11-Apr 21-Apr 1-May 11-May 21-May 31-May 10-Jun 20-Jun 30-Jun 10-Jul 20-Jul 30-Jul 9-Aug 19-Aug 29-Aug 8-Sep 18-Sep 28-Sep 8-Oct 18-Oct 28-Oct 7-Nov 17-Nov 27-Nov 7-Dec 17-Dec 27-Dec

114

Fig. 6 Actual and recommended modes of state of Tuyamuyun’s reservoirs work

An intensity of channel reservoir silting during high and mean water years can vastly be reduced by usage in non-support regime from the end of the March and till passing of high water. Herewith main mass (about 70% of annual runoff) of suspended alluvium by transit enters in lower reach of hydroscheme. Use of reservoirs during shallow years on proposed mode will reduce the tension of water-management system situations in region, despite to some expenses connected to channel reservoir silting. The amount of the alluvium on a bed of the reservoir are determined on proposed and actual modes of hydroscheme`s exploitation taking into account water content. Practically all alluviums transported by river settle in channel reservoir which work

Effictiveness of Water Resources Use in Aral Sea Basin

1393

under practiced usage mode during high and mean water years. On proposed mode main mass alluvium enter the transit lower reach. The calculated values of the transported from reservoir alluvium volumes and alluvium erosion in a channel reservoir for different variants, are shown on Fig. 7. As can be seen from table, percent of alluvium from reservoir in wet year under actual mode forms 6%, and on proposed mode amount of suspended and washed away alluvium removed from reservoir has formed − 70%, accordingly for mean year − 38%, and 52%, and for shallow year 74%, and 43%. A conducted analysis shows that realization of proposed by us mode of the TMGU usage will allow to adjust clearest water resource management, their rational use in consumers interests, will reduce the intensity of the deterioration of the ecological situation in Aral basin region. Comparison of results on loss and water mineralization values in a channel reservoir (Fig. 7) shows that recommended mode allows to reduce water mineralization on 13–30% depending on year’s water content. Recommendations on state of reservoirs work are conditioned that in wet and mean years, when excess of the flow exceed the total useful volume of reservoir optimum for both variant will be a mode, under which in the first half of the year to moment of the growth of the expenses of reservoir water achieve harmony in work − a May–June, but at the first period of the passing of the high water − is filled − a June–August, and hereinafter level of water are supported near normal level of support before the end of the year. And leveling and filling must be such: in the beginning channel, then Kaparas and finally Sultansandzhar and Koshbulak reservoirs. Full satisfaction of the requirements of lower reaches on water is provided under such mode and maximum possible filling of all reservoirs. Besides, high water is regulated, filling of reservoirs by river water with the least mineralization is realized, as well as certain channel reservoir’s silting reduction is reached due to washing during spring leveling of this capacities. Water-regulating building influences on the following factors: satisfactory quality of drinking water for the whole year is provided, in comparison with period of 5–7 months; water mineralization decreased in 1.4–1.6 times in Kaparas; silting volume decreased on 1.0–1.5 mln. m3 per annum; water turbidity in lower reach increased on 0.05 kg/m3. At shallow years, according to calculation, Tuyamuyun hydro-system under blank reservoirs must be used so that leveling was minimum, and filling − maximum at any time of excess water appearance. The changes of values of the losses on filtering and evaporation depending on flow is shown on Fig. 8. Comparison between actual and recommended level and volume reservoir characteristics with provision for uncertainty, values of mineralization for conditions and state of working for 1998–2002 are submitted in Fig. 9 (the picture of the conclusion results to models on screen PC).

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Sediment volume, thous.ton

50000 45000 40000 35000 30000 25000 20000 15000 10000 5000 0 1

2

3

4

5

6

7

8

9

10

11

12 Months

8

9

10

11

12 Months

8

9

10

11

12 Months

Wet Year

Sediment volume, thous.ton

14000 12000 10000 8000 6000 4000 2000 0

1

2

3

4

5

6

7

Average water year

Sediment volume, thous.ton

12000 10000 8000 6000 4000 2000 0 1

2

3

4

5

6

7

Dry year Inflow of sediments (calculated) Volume of precipitation sediments (calculated) Volume transit sediments (calculated) Inflow of sediments (real) Volume of precipitation sediments (real) Volume transit sediments (real)

Fig. 7 Amounts of alluvium and erosion in channel reservoir

Effictiveness of Water Resources Use in Aral Sea Basin Loss, Mio m3

real

3500

Salinity, g/l

calculated

1

1818.3

2000

2092.7

1000

761 606

761 606

500

606 353

606 304

2000

2001

0.78

0.74

0.68

0.72

0.64

0.57

0.6

1212.2

0.86

0.85

0.8

1789.1

1436.1

1500

calculated

1.02

2424.4

2500

real

1.2

3030.5

3000

1395

0.52

0.4

744 606

0.2

0

0

1998

1999

2002

1998

1999

2000

2001

2002

Fig. 8 Comparison on filtering and evaporation loss and mineralization: (a) Water loss volume dynamics in the channel reservoir at the recommended operation terms; (b) Kaparas water salinity comparison (a)

Capacity, Mio m3

1500 Real operation

1300

Recommended operation

1100 900 700 500 300

2034

2032

2030

2028

2026

2024

2022

2020

2018

2016

2014

2012

2010

2008

2006

2004

2002

2000

1998

1996

100

water level, real Water volume at 130m, real

Jul-03

Jan-03

Jul-02

Jan-02

Jul-01

Jan-01

Jul-00

Jan-00

Jul-99

Jan-99

Jul-98

Jan-98

Jul-97

Jan-97

Jul-96

1565 1365 1165 965 765 565 365 165

Volume, Mio m3

130 128 126 124 122 120 118 116

Jan-96

Water level, m

(b)

Water level, calculated Water volume at 130m, calculated

Fig. 9 Calculations results on fluid and hard inflow into Tuyamuyun hydro-system

4 Conclusion Lower reaches water complex’s work must be directed considering increasing quality water resources and management efficiency and that expects, first of all, full satisfaction of the requirements on drinking water-supply and irrigation, withstanding standard on quality of water, lands productivity increasing, reduction of the wasteful losses. The reduction of the water deficit in lower reaches

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can be reached due to checking of limits on water scoop, withstanding state of Tuyamuyun hydro-system’s work, minimizing loss of water in reservoir and in lower reaches. Perfect quality of river water at lower reaches possible to reach by partly limiting of unsets of the revocable flow at the average current yard. Given action most effectively in the event of absence of the deficit (the reduction of the revocable flow on 20–30% can bring to mineralization reduction in river on 10–15%). At waterland resources productivity one of the main factors, which has to be taken into account is distribution of water and irrigational management at lower reaches of Amudarya.

References 1. Navruzov ST (1986) Calculation rules of irrigation-energy water reservoirs management. Acad Sci USSR 22 2. Ikramova MR, Kayumov OA (1997) Affect of the Tuyamuyun hydro complex in to the river bed process and the water intake conditions in the lower parts of the Amudarya river. Uzbekistan Agric 2:6 3. Ikramova MR, Khodjiev A (1998) Tuyamuyun hydro complex operation regime characteristics. Uzbekistan Agric 4;29–30 4. Ikramova M (2001) Using water transfers to provide safe drinking water in the Aral region – Uzbekistan. US Committee on Irrigation and Drainage, 24–28 May, Denver, CO, 11p 5. Sorokin D, Sorokin A (2001) Report on the work conducted for the application of the hydrological model towards the assessment of scenarios of the Aral Sea basin development. UNDP and SIC ICWC, Tashkent 6. Ikramova MR, Kayumov OA (2004) Development of the operative measures for fighting with water shortage in the lower part of the Amudarya river. Global change, sustainable development and environmental management in the Central Asia. UNDP International Seminar, Tashkent, 20–22 Jan 7. Ikramova MR, Sorokin A, Khodjiev A, Misirkhanov K, Karomov B (2004) Quality drinking water to population. Uzbekistan Agric 12:5–6 8. Prihodko VG, Engorn FY (2004) Water resources prospect development in the Central Asia on the Aral Sea Basin model. SIC IWIC proceedings, #8, Tashkent 9. Chub VE (2002) Meteorological and hydrological monitoring of the Central Asian water resources. Water resources of the Central Asia. SIC IWIC conference proceedings, Almata, 20–22 Feb, pp 87–91 10. Kurbanbaev E (2002) Water shortage in the Amudarya basin and ecological problems of the Aral Sea. Water resources of the Central Asia. SIC IWIC conference proceedings, Almata, 20–22 Feb, pp 309–344

Uncertainties in the Water Budget Computations of Develi Closed Basin in Turkey Ibrahim Gurer and F. Ebru Yildiz

Abstract Develi Closed Basin is located at the south-western side of Erciyes Mountain, in the Central Anatolia. Sultansazligi Wetland is located in Develi Closed Basin, which is one of the seven important wetlands of Turkey and the second important bird habitat of Turkey. Sultansazligi is also known as one of the most important wetlands of the Eastern Europe and the Middle East. In the recent years, this wetland faced with the water shortage and salinity, due to the climatic change and irrigation return flow with the high salt content. There is an intensive irrigation around the marsh with abundant use of water due to the wild flooding. In this study, the water budget of Develi Closed Basin is computed and the uncertainties faced during the water budget computations are introduced. Uncertainties of the Develi Closed Basin water budget computations; can be summarized as the unknown hydrological parameters such as missing flow data, infiltration index of the soil, evapotranspiration from the reedfield, insufficient flow and precipitation data. Keywords Sultansazligi · Develi closed basin · Water budget · Surface water groundwater interaction · Wetlands

1 Introduction There are three types of main errors which are causing uncertainties in the water budget calculations. These are: (1) Measurement errors from imperfect instrumentation, inadequate data and data collection method. (2) Spatial interpolation techniques from point data cause interpolation errors. I. Gurer (B) Engineering and Architecture Faculty, Civil Engineering Department, Gazi University, Celal Bayar Bulvari Maltepe, Ankara, Turkey e-mail: [email protected]

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(3) Model errors which had been caused by inaccurate conceptual modeling of the water mass system. For example; not including important discharge in the mass balance equation, can be given as this type of error [6]. In this study, classical water budget computation of Develi Closed Basin in Turkey is presented with the uncertainties in the water budget calculations. There are inadequate and missing data so some estimations and interpolations (first and second type of errors as shown above) cause uncertainties within the water budget computations. Develi Closed Basin is located in the Central Anatolia in Turkey. Total area of Develi Plain is approximately 800 km2 and watershed area of Develi Closed Basin is 3190 km2 . Sultansazligi Wetland Area is located in the middle of Develi Closed Basin. There are Yay Lake, Çöl Lake, North and South reedfield areas in Sultansazligi Wetland Region. Coordinates of Sultansazligi Wetland are 38◦ 05 –38◦40 North and 35◦ 00 –35◦35 East. Sultansazligi is located at the center of Develi, Ye¸silhisar and Yahyali towns. This wetland area is a conservation area protected by International Ramsar Agreement. The reedfield, Yay Lake and Çöl Lake are entirely dry during irrigation period because there is no inflow to feed the reedfield and the evaporation is very high. Figure 1 shows the location of the project area.

2 Classical Water Budget Calculations of Develi Closed Basin The basic uncertainty in the water budget computation of Develi Closed Bain was the relationship between the surface water of Sultansazligi Wetland and groundwater. For the solution of this uncertainty problem; C14 , H2 , O18 and H3 isotope studies have been utilized to define the relationship between surface water at wetland and groundwater under, during 2003–2005 time period. Figure 2 shows the conceptual model showing the interrelation among the water components of surface and subsurface water. (No conceptual modeling error (3rd type of water budget error) in Develi Closed Basin water budget studies). Precipitation measurement and the density of gage network affect the reliability and representativity of the precipitation data [13]. There are many missing precipitation data for Develi Closed Basin. For example Akköy meteorology station had been closed since 1999, so regression is used to fill out these missing data. Groundwater and surface water budgets are prepared for four different type of long term average precipitation conditions; 390 mm/year to represent the “wet period”, 330 mm/year for the “dry period”, 345 and 363 mm/year for the “below average” and “average precipitation” periods. Classical water budget of the Develi Closed Basin is computed both for the surface and groundwater.

Uncertainties in the Water Budget Computations BLACK SEA

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Reservoir area

District

Marshland

Lake area

Kayseri Irrigation area MES TERRANEAN SEA INCESU Çalbalma Tunnel Erciyes M.

Çöl Lake Northern Marshland Güzel River

YE LH SAR

Akköy Dam Karapınar Derivation

Özdere River.

DEVELI Yay Lake

Southern Marshland

Zamantı Tunnel

Kovalı Dam

A ca ar Dam

SCALE : 1 / 350 000

Zamantı River

YAHYALI

Fig. 1 Develi closed basin (modified after [9])

2.1 Groundwater Budget of the Develi Closed Basin Maximum value of surface runoff discharge is: Q= where: Q: C: i: A:

CiA 3.6

Runoff disharge (m3 /s) Runoff coefficient (dimensionless) Rainfall Intensity (mm/h) Drainage area (km2)

(1)

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Akköy Dam

Karapınar Derivatiion Kovalı Dam

Kovalı Irrigation Area

Ag ca ar Agca ar Dam Irrigation Area YAHYALI

N

¸ YESiLHiSAR

Irrigation Return Lake and Flow Marshland Area

Çalbalma Tunnel**

? DEVEL CLOSED BAS N

DEVEL

? Zamantı Tunnel*

Precipitation

Springs

Evaporation

N

S.Marshland

Irrigation Return Flow

N.Marshland

YAY LAKE

LAKE & MARSHILAND

ÇÖL LAKE

Groundwater Feeding Spring Water

N

Surface water Feeding GROUNDWATER AQUIFER

Fig. 2 The conceptual model showing the interrelation among the water components of surface and subsurface water. PS: ∗ Zamantı Tunnel is under construction, there is no inflow yet, ∗∗ There is no excess water in the basin so there is no outflow from Çalbalma Tunnel (modified after [12])

There is uncertainty about the runoff coefficient of Develi Closed Basin. Since Develi Closed Basin (3190 km2 ) is a sub-basin of Kızılırmak Basin (78646 km2 ) and the runoff coefficient of Kızılırmak Basin is 0.17 [3], the runoff coefficient C for Develi Closed Basin is also assumed to be 0.17, although there is a big difference in geomorphological parameters between Develi and Kızılırmak Basins. Drainage area of Develi Closed Basin except the drainage area of the reservoirs is Ad =2625 km2 and the average annual precipitation height is Pav =363 mm so the surface runoff is:

161.989 × 106 m3 /year

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There is no lysimeter in Develi Closed Basin, therefore the average infiltration index of the soil is not exactly known According to the lithology of the basin, percentage volume of deep percolation into the aquifer is assumed as 15% of the surface runoff [8] so the percolated water from surface runoff into the groundwater is; V1 = 24.298 × 106 m3 /year The plain area of Develi is approximately 800 km2 . About 100 km2 of this plain is lake and about 60% of the lake surface is covered by the reedfield. Additionally 150 km2 of the plain is covered by the clay formation so it can be accepted that, the precipitation can only directly infiltrate into the aquifer in area of 550 km2 . 20% is assumed as direct infiltration ratio [8]. If the precipitation is Pav =363 mm; direct infiltration volume of the precipitation into the aquifer is: V2 = 39.93 × 106 m3 /year There is also uncertainty in the real transmissibility values of the project area. It is accepted that at the eastern part of the basin, water is discharged from the tuff formations of the aquifer at Develi town, at the southern and the southwestern part of the basin; water is discharged from the Paleozoic limestone at Yahyali town and at the western part of the basin; water is discharged from alluvial cone at Yesilhisar town [8]. It is thought that at the northern side, there is no groundwater inflow from the Erciyes Mountain. According to the available DSI well logs [11], the average soil transmissibility values are computed as shown in the Table 1. Darcy law states the inflow discharge as: Q=G×T ×i

(2)

where; Q: i: T: G:

Groundwater flow (m3 /day) Hydraulic gradient (m/m) Transmissibility (m2 /day), Aquifer width (m)

The total volume of groundwater inflow V3 can be computed by using the transmissibility values given in Table 1. Table 1 Average transmissibility values according to each region

Region name

T (m2 /day)

Develi (East) Yahyali (South) Southwest Yesilhisar (West)

552 2574 1000 1115

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V3 = VEAST + VSOUTH + VSOUTHWEST + VWEST

(3)

Hydraulic gradient of each aquifer is computed by using piezometric water level map and the total groundwater inflow volume is calculated as: V3 = 90.585 × 106 m3 /year Total groundwater aquifer recharge volume: V = V1 + V2 + V3 For the annual precipitation as 363 mm; V = 154.813 × 106m3 /year. V is shown in Table 2 for the four different annual precipitation heights. Another uncertainty is observed in aquifer discharge. Because the total number of the private deep wells is unknown. There are many illegally drilled private wells in the basin. Farmers use surface water from reservoirs during normal irrigation season, but during the dry period, they use the groundwater from their private wells. Even the total number of the private wells is known, it is impossible to know the total abstraction exactly from private wells. It varies every irrigation season according to the climatic conditions. But according to DSI report [11]; the reliable average groundwater abstraction is estimated as 65×106 m3 /year.

2.2 Surface Water Budget of Develi Closed Plain Human factors in streamflow measurement and recording equipment errors cause streamflow errors [13]. There are many missing streamflow data for Develi Closed Basin, so regression is used to fill these gaps. Also there is uncertainty about spring water amount flowing through Sultansazligi Wetland. There are many springs in the basin but almost all spring water is used for irrigation during irrigation period so springs can feed the wetland during winter but this water amount is unknown. The estimation errors in evapotranspiration computations can be listed as: model errors, propagated error due to the meteorological parameters. Evapotranspiration from farmlands is calculated by using Blaney Criddle Method and the total irrigation water requirement is found as 400×106 m3 /year. Penman and Penman-Monteith Methods do not give reliable results for the irrigation water requirement calculations. Since these methods require more meteorological parameter than Blaney Criddle Method, however there is lack of meteorological parameter such as solar radiation, humidity, wind velocity etc. Because of the economical restrictions; Ye¸silhisar and Yahyalı meteorological observation stations had been

Table 2 Total groundwater aquifer recharge volume Annual precipitation Pav (mm)

V(×106 )m3 /year

330

345

363

390

152.604

153.608

154.813

156.621

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closed in 1994, there is only one station at Develi Town to represent Develi Closed Basin operated by Turkish State of Meteorological Organization. Evapotranspiration from the reedfields is also another source of uncertainty; there is no former study on the evapotranspiration of the reedfield plants in Sultansazligi Wetland. According to [2], Phragmites is the main reedfield plant in Sultansazligi Wetland. Phragmites reedfield plant is shown at Fig. 3. Abtew and Obeysekera [1], Burba et al. [4] and Choi and Harvey [6] used Penman-Monteith Method to estimate the evapotranspiration from reedfield plants. So Penman-Monteith Method is used in order to estimate the annual average evapotranspiration from Phragmites at Sultansazlı˘gı reedfield area and annual average evapotranspiration from Phragmites is estimated as 1576 mm. Regression equations are used to estimate the meteorological parameters such as temperature, relative humidity and wind velocity at the reedfield area. Reedfield area covered by Phragmites at the Southern and Northern Marshland is approximately 60 km2 [14]. No evaporation measurement is done at Develi meteorology station but there are Class A evaporation pans at Agcasar, Kovali, Yenihayat (Yay Lake) and Musahacılı Stations. Figure 4 shows Class A Type Evaporation Pan. These stations are being

Fig. 3 Phragmites plant at the reedfield (http://aquat1.ifas.ufl.edu/phraus. html)

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Fig. 4 Class A evaporation pan [7]

operated by Turkish State of Hydraulic Works (DSI). But class A evaporation pan correction coefficient is not known. [15] used Penman Method to estimate the evaporation from free water surface of Brokopondo Lake at Surinam, then Penman evaporation results were compared with Class A Pan evaporation results and it was found that Class A Pan evaporation values and Penman evaporation values were close to each other. In order to estimate pan coefficient at Develi Closed Basin; first Penman Method is used to estimate the evaporation from free water surface of Sultansazligi Wetland, then evaporation from free water surface values are divided by pan evaporation values and pan coefficient is estimated as 0.65. Yenihayat (Yay Lake) station is close to the wetland so pan evaporation data of this station is used. Both Penman and Penman-Monteith Methods require some meteorological data, such as solar radiation, wind velocity, relative humidity, average air temperature etc. However there is no meteorology station which is measuring these parameters at Sultansazlı˘gı Wetland Region, so linear regression is used to estimate these parameters for Sultansazlı˘gı. On the other hand, Thornwhite Method requires only average air temperature for evaporation calculations. In order to control the sensitivity of Penman Evaporation values; Thornwhite Method is additionally used to determine Class A Pan coefficient at Develi Closed Basin. First evaporation from free water surface of Sultansazlı˘gı Wetland is estimated by using Thornwhite Method, then evaporation from free water surface values are divided by pan evaporation values and pan coefficient is estimated as 0.67. Pan coefficients, estimated by using Penman (pan coefficient:0.65) and Thornwhite Method are close to each other, so 0.65 can be used as Class A Pan coefficient for Develi Closed Basin. A˘gca¸sar, Kovalı and Akköy dams are located in the basin, their average reservoir areas and annual average evaporation from free water surface of these reservoirs are shown in Table 3. According to the pan evaporation data; annual average evaporation from Sultansazligi Wetland Area (Yay Lake and reedfield area) is 1458 mm.

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Table 3 Evaporation from free water surface of the reservoirs Name of dam

Reservoir area (km2 )

Pan evaporation from free water surface (mm)

A˘gca¸sar Kovalı Akköy

4.17 1.67 0.92

849 912 1020

It is necessary to remind that pan is under operation on April, May, June, July, Agust, September and October. There is also evaporation on the other months from free water surface but this evaporation is not measured, so this factor causes an error at the evaporation calculations. When the free water surface elevation is 1071 m then total free water surface area of Yay Lake and reedfield area is computed as 52 km2 by using “Volume-Elevation-Area Curves” for the reedfield and Yay Lake [10]. 1071 m is the average free water surface elevation for Sultansazligi Wetland. Surface water budget computation of Develi Closed Basin is given in Table 4. Surface runoff is the runoff volume over total drainage area (3190 km2 ) of the basin. Net storage water volume is not sufficient for the irrigation because total irrigation water is estimated as 400×106 m3 /year, therefore the rest of the irrigation water is abstracted from the groundwater. Table 5 shows the surface water budget only for Sultansazlı˘gı Wetland (reedfield area and Yay Lake). Since Çöl Lake is entirely dry; there is a thick mud cover at Çöl Lake area, so this lake is disregarded in water budget calculations. There is no direct relationship between the groundwater and wetland water so infiltration parameter is neglected at the wetland water budget calculations. Evaporation from free water surface and evapotranspiration from reedfield area which is covered by Phragmites, are very high so there will be a continious need of water at Sultansazligi Wetland as shown at Table 5. (−) sign shows the water need.

Table 4 Surface water budget for Develi closed basin Annual prepicitation Pav (mm) Surface runoff (×106 )m3 /year Infiltration (×106 ) m3 /year Direct precipitation over free water surface (×106 )m3 /year Evaporation from free water surface (×106 ) m3 /year Evapotranspiration from reedfield (×106 ) m3 /year Net Storage (×106 ) m3 /year

330 178.956 22.089 19.390

345 187.09 23.093 20.27

363 196.855 24.298 21.330

390 211.497 26.105 22.920

53.180

53.18

53.180

53.180

94.560

94.560

94.560

94.560

28.517

36.53

46.147

60.572

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Annual prepicitation Pav (mm) Direct precipitation over free water surface (×106 )m3 /year Evaporation from free water surface (×106 ) m3 /year Evapotranspiration from reedfield (×106 ) m3 /year Drainage water feeding the wetland (×106 )m3 /year Water storage in the reedfield and lake (×106 )m3 /year

330 17.160

345 17.940

363 18.876

390 20.280

49.280

49.280

49.280

49.280

94.560

94.560

94.560

94.560

40

40

40

40

−86.68

−85.90

−84.964

−83.56

3 Conclusion The irrigation water requirement within the project area is too high, because of large irrigation areas and high irrigation water loss due to wild flooding. Drip irrigation use is recommended for the optimum use of irrigation water. The irrigation return flow with high salt content must not be diverted directly to the reedfield, because of the high salt and pesticide problem. The number of all private deep wells must be directly determined and excess groundwater discharge must be avoided. Unknown parameters in water budget calculations should be minimized. Pumping tests at some locations of the project area are needed to follow up groundwater and aquifer parameters. The floating evaporation pan is strongly recommended to measure the evaporation from the free water surface of the reedfield. As an integrated water resources management of Develi Closed Basin, an automatic hydrometeorological network comprising reservoir water level observations, groundwater level variation observations, meteorology stations and stream gaging stations should be set up for real time data collection at an operation center. So more efficient use of groundwater and less uncertainties in water budget computations can be achieved.

References 1. Abtew W, Obeysekera J (1995) Lysimeter study of evaporation of cattails and comparison of three estimation methods. Trans ASCE 38(1):121–129 2. Akçakaya R, Bari¸s S, Bilgin C (1983) Final report of Sultansazlı˘gı conservation project. Middle East Technical University, Ankara, Turkey 3. Bayazıt M (1979) Hydrology. ˙Istanbul Technical University Publication, ˙Istanbul, Turkey 4. Burba GG, Verma SB, Kım J (1999) Surface energy fluxes of phragmites Australis in Prairie Wetland. Agr Forest Meteorol 94(1):31–51 5. Center of Aquatic and invasive plants (2007) University of Florida, IFAS. Web page: On Line. http://aquat1.ifas.ufl.edu/phraus.html 6. Choi J, Judson WH (2000) Quantifying time-varying groundwater discharge and recharge in wetlands of the Northern Florida Everglades. Wetlands 20(3):500–511 7. DMI (2005) Turkish state of meteorology service presentation CD, Ankara 8. DSI (1970) Hydrogeological investigation report of Develi-Yesilhisar Plain, Ankara, Turkey

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9. DSI (1988) Kayseri develi irrigation project, first stage irrigation, (in Turkish). DS˙I 12th Regional Directorate, Kayseri (brochure) 10. DSI (1993) Water balance study related with the solutions of the environmental effects of Develi project, 1st Report. Report of general directorate of state hydraulic works, Groundwater Division, Ankara, 61–64 (In Turkish) 11. DSI (1995) Revised hydrogeologic investigation report of Kayseri Develi-Yesilhisar Plain, Kayseri, 12th Regional Directorate, Kayseri, Turkey 12. Gürer I, Yildiz FE (2004) Surface and groundwater interaction in wetlands case study: ASAR, MERIS Satellite Data Use in Sultan Reedfields, Kayseri, Turkey. Proceeding for 22nd Conference of the Danubian Countries, Brno, Czech Republic 13. Joe SN (2004) Quantifying errors in large scale water balance. Unprinted M.Sc. Thesis, USA 14. Karadeniz N (1995) Sultansazli˘gi Örne˘ginde Islak Alanlarin Çevre Koruma Açisindan Önemi Üzerine Bir Ara¸stirma, Yayinlanmami¸s Doktora Tezi, Ankara Üniversitesi 15. Weert RVD, Kamerling GE. (1974) Evapotranspiration of water hyacinth (Eichhornia crassipes). J Hydrol 22: 201–212

Impacts Assessment of Newly Constructed Highways via Spatial Information Sciences H. Demirel, M. Çetin, and N. Musaoglu

Abstract This paper presents a comprehensive framework for determining the interaction between transport, land-use and environmental impacts, where the developed concepts were tested using a case study. Two bridges, connecting Europe in Asia and their peripheries, and one of the alternatives of the newly planned third bridge at the Istanbul Metropolitan area were selected. The constructed transportation infrastructures had drastically changed the land-use profile and still have negative impacts on environment. After exploring the interaction systematically, possible impacts of the new bridge were investigated in this study. In order to detect changes and to predict the potential impacts, former land-use, transport infrastructure data were integrated with satellite images retrieved in 1963, 1987, 1992, and 2002. A four kilometers band was created referencing the center-line of the highway and this process was repeated for all satellite data. The land-use classes for exploring the interaction were settlement, transportation infrastructure, green land and forest, water and barren land. Within this range, the images were classified and results were compared statistically, in order to analyze the impact of transportation infrastructure. In order to explore the interaction between transport, land-use and environment, a spatio-temporal conceptual data model was designed to project the impacts of the newly planned third bridge. The results show that, easy accessibility caused by the development in transportation infrastructures created an attraction in this region and urban areas expanded rapidly. In year 1987, where the construction of the second bridge was recently begun, the 23% of the selected band was determined as settlement. In the year 1992, after the second bridge was full in operation, the percentage of the settlements was increased 12% only within a period of 5 years. In order to estimate the impacts of third bridge to the study area, the second bridge feet at the Asian side was selected. According to the classification results of the year 1963, the settlement class retrieved showed an increase of 339.5%, where 44.2% decrease was detected in the green areas. By means of the shortly described H. Demirel (B) Faculty of Civil Engineering, Geodesy and Photogrammetry Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey e-mail: [email protected]

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methodology and achieved results, integrated data collection and analysis was highly emphasized and the new proposed framework might be used effectively for aiding authorities and decision-makers to better understand the main causes of interaction, to inform them of the changing conditions and monitoring similar projects elsewhere. Keywords Impact assessment · Environmental monitoring · Transport · Land-use · Remote sensing · Spatial data modeling

1 Introduction The interaction between transport, land -use and their impacts to the environment is prioritized at the research agenda, since the necessity of integrated policies for sustainable development is highly emerged [10, 11, 7, 12, 9, 5, 15, 6]. Transport system creates new accessibility levels that encourage changes in land use patterns. Changes in land use system, on the other hand, can modify the travel demand patterns and induce changes in the transportation system. The adverse affects of transportation on environment can be listed as air pollutant emissions, greenhouse gas emissions, noise, and diverse affects on habitat, ecosystems, endangered species. Additionally, it affects water quality through consumption and causes fragmentation and replacement of natural cover with impervious surfaces. In parallel, the urban form affects travel behavior, resulting air pollution, global climate change and noise. Residential and commercial development was indirectly effected including the distribution of employment opportunities. The transportation options available to link residential and commercial locations influence household travel behavior, including trip frequency, trip lengths, and mode of choice. Vehicle travel, in turn, generates air pollutant emissions, greenhouse gas emissions and noise [14]. The complexity and variety of different components making up the urban environment, and the interactions among them, are the most pronounced in the mega cities. In this context, it is important to develop integrated frameworks and systems in order to detect changes and monitor dynamics, where looking at one component of change in isolation could lead to decisions being taken on the basis of insufficient information. The integration will certainly be facilitated be new technologies, tools, and expertise as landuse/cover changes are quite difficult to grasp as they occur incrementally [8]. Since the interaction between transport, land-use and environment has spatial and temporal characteristic, Spatial Information Sciences, involving Photogrammetry, Remote Sensing and Geographic Information Systems (GIS), provide mature solutions for integrated policies. In order to emphasize the efficiency of Spatial Information Sciences for integrated policies, spatial and temporal analyses were conducted in the Istanbul, which was selected as the case study area. The Istanbul Metropolitan Area is the only mega-city in the world that sits astride two continents – Europe and Asia, where the transportation system has been unable to keep pace with the rapid growth and changing urban structure. Two bridges connect Europe and Asia, the Bosphorus

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Bridge (1973, part of the inner-city traffic ring) and the Fatih Sultan Mehmet Bridge (1988, part of the outer-city traffic ring) span the Bosphorus. The city proper covers an area of 2,000 km2, while the metropolitan area occupies 5,700 km2 . The study area was illustrated in Fig. 1. The Istanbul Metropolitan area had a population about 4.1 Million according to 1980 census data which has more than doubled and reached about 10 millions in only two decades. According to the estimations performed by State Statistical Institute, population of Istanbul may reach about 20 million in 2032 [4]. The growth rate in Istanbul has had a significant negative effect on the remaining green area. The urbanization effort with the lack of proper and sufficient infrastructure brought together many environmental problems among which the land-use change are of utmost importance. Rapid motorization is generating serious congestion and air pollution in Istanbul due to the high population density and the lack of supporting infrastructure. According to the State Statistical Institute reports, in 2006, every fifth citizen of Istanbul owns a vehicle. Rapid motorization is generating serious congestion and air pollution in Istanbul due to the high population density and the lack of supporting infrastructure. Emissions caused by the road traffic in Istanbul were rapidly increased between years of 1990 and 2000, where the increase in CO2 , CO, NOx , SO2 , particulates, VOC and NMVOC were 52.6, 50.1, 62.5, 55.7, 82.5, 51.3 and 51.2% respectively. In order to diminish the problem, since 80’s the infrastructure of the town is under constant renovation, new roads, motorways are build, bridges laid, under-ground line is under construction. This unfortunately could not solve the problem of congestion and some negative side effects were observed, such as valuable agricultural lands and forest were cut through new routes [3]. Dense urbanization along the transportation network was settled. The proposal for a third highway bridge by the Ministry of Public Works has been heavily criticized by transportation and city planners and non-governmental organizations. This strong opposition have resulted evaluation of other alternatives, such as railway tunnel,

Fig. 1 The study area – The Istanbul metropolitan area

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however the proposal of constructing a third highway bridge is still on the agenda of policy- makers. The main objective of the study arc to discuss and evaluate the land-use changes which may be attributed to transport and monitoring the affects on environment. In order to achieve these goals, the objective of this study is to develop a comprehensive spatial data model for detecting the relationship, where the main focus will be (i) to characterize the major spatial-temporal changes of land use, which may be attributed to transportation activities, (ii) to identify the interactions among the transport system and land use with the contribution of continuous and extendable spatial data model, (iii) impacts of transport and land-use on environment at a local scale.

2 Methodology The interaction between transport, land-use and environment is a dynamic process that involves changes over spatial and temporal dimensions between the three systems. Transportation, land use and environment interaction involves the time element (when), the location element (where) and the attribute element (what) that are interrelated with each other. The critical dimensions of the designed framework were the consistent definition of spatial information and time. Effects of transportation system changes on other systems and vice versa, occur at varying spatial and temporal scales. A highway construction project may introduce a traffic increase shortly after its completion and lead to some land-use changes in its immediate vicinity. However, its impacts on the land-use patterns at the regional scale may be insignificant in both short and long-terms, due to the relatively small changes to the accessibility levels on other parts of the metropolitan area. In order to model this spatio-temporal interaction Spatial Information Technologies were used including digital image processing of satellite images and spatial data modeling, spatial analysis, information presentation and dissemination on both spatial and time domain. The methodology of this work is constituted upon Spatial Information Sciences, where photogrammetry, remote Sensing and GIS forms the components. The great strength of remote sensing is that it can provide spatially consistent data sets that cover large areas with both high detail and high temporal frequency, including historical time series and remote sensing data provide a means of monitoring change in urban land cover over time [6]. GIS are composition of tools and methods for collecting, storing, retrieving at will, transforming, and displaying spatial data for a particular set of purposes. Given the spatial nature of many environmental impacts, GIS can have a wide application in all Environmental Impact Assessment (EIA) stages, acting as an integrative framework for the entire process, from the generation, storage, and display of the thematic information relative to the vulnerability/sensitivity of the affected resources, to impact prediction and finally their evaluation for decision [1]. The designed framework for exploring the interaction is presented in Fig. 2. In the designed framework, the contribution of the spatial information sciences to the decision-making process was marked in grey.

Impacts Assessment of Newly Constructed Highways via Spatial Information Sciences

Data acquisition & retrieval

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Remote sensing, photogrammetry, existing spatial databases, surveying, maps having various scales

Integrated

Integration of transport, land-use and environmental

framework

data&methodologies on spatial bases

Analyze the problem Spatial, temporal analyses, recognizing common indicators and identifying criteria

Developing Scenarios, Selecting Alternatives

Visualization of scenarios, analyze, assessing the impacts

Implementing the selected alternative

Reduced risks, reliable and quantitative evaluation

Monitoring & Evaluation

Information Dissemination

Remote Sensing, Photogrammetry, GIS

Web based GIS, Location Based Services

Fig. 2 The designed framework

The frame-work involves data acquisition, analyses, assessment, monitoring and information to the public, where the integrated policies for transport, land-use and environment were emphasized. This will ensure the integration of currently loosely coupled information and increase the efficiency of the decision making process. In this study various spatial information were retrieved from satellite images, aerial photographs and orthophoto maps. Satellite sensor images acquired in 1963, 1987, 1992 and 2002, were used to monitor the development of transportation infrastructures and their impacts to the land-cover/use. The image used for the year 1963 was retrieved from CORONA, where it was scanned and sampled by 5 m and transformed into raster format. Landsat 5 TM image belonging to September 1987 and 1992 were acquired and used in the analysis, after processing. The Landsat 5 TM data have spatial resolutions of 30 m in visible, near and mid infrared bands, and 120 m in the thermal infrared band. For the year 2002, Spot-5 image, which was

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acquired on May, was used. The Spot-5 pan-sharpened data have spatial resolutions of 2.5 m. Since the remote-sensing data are distorted by the Earth’s curvature, relief displacement and the acquisition geometry of the satellites, satellites images should be rectified before classification process performed. During this process 1:25000 scaled topographic maps were used, where the achieved accuracy was 05 pixel root mean square (RMS). The first degree polynomial transformation and nearest neighborhood method were used. In order to detect the dynamics of the interaction, digital land cover classification was performed. The purpose was to establish the link between the spectral characteristics of the image to a meaningful information class value. In this study, the Iterative Self Organizing Data Analysis Technique (ISODATA) unsupervised classification algorithm was used [13]. From satellite images retrieved 1987 and 1992 for the Istanbul Metropolitan area the Trans European Motorway (TEM) which was being constructed in 1987 was retrieved and from the centerline of the highway a band having a width of 4 km was created, which was illustrated in Fig. 3. The reason for creating a band was to determine the impacts of transportation infrastructure to land-use and environment. The same process was performed for the year 1992, where the construction of TEM involving the Second Bridge was finished. Since the aim of the study is to explore the interaction between transport, land-use and environment, five spectrally separable, land cover classes identified by ISODATA were; (i) settlements (involving impervious surfaces such as urban area, road and industrial areas), (ii) barren land, (iii) green area (involving forest areas, semi-natural vegetation etc.), (iv) water and (v) mining area. The classification accuracy for the year 1987 image was 82%, where for the year 1992 the accuracy of 84% was achieved. The data integration, second stage, is utilized upon spatial data bases via implementing spatial information technologies. After extracting geographic information of transportation infrastructures and land use patterns from satellite images, the information was stored in a designed conceptual data model using Unified Modeling Language (UML). The data model was designed involving four distinct components namely, geometry, topology, “interaction”, being non-spatial information, and metadata. Incorporating the metadata component, object temporal requirements,

Fig. 3 The band around the TEM, 1987

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land use detection and development of transportation infrastructures, were modeled. Transaction log approach was adopted here [2]. During the establishment of external schema, a progressive approach appropriate to the conceptual data modeling requirements of an integrated management system was reflected on. Within the system designed, it is possible to answer questions such as; when did major land developments take place with a four-kilometer zone of a new highway transit line after its completion?, where were the areas that experienced land value increases/decreases after the completion of a new belt with a determined period? What were the traffic volumes on the highway in each census tract with an annual population growth rate over 2.5% from 1987 to 1992.

3 Results and Discussion The developed frame-work was used to monitor the changes experienced in 1963, 1987, 1992 and 2002 within the study area. For the study area, urban areas sharply increase between 1987 and 1992, likewise the increase in the total length of road network. Hence, development of transportation infrastructures created an attraction in this region and urban areas expanded rapidly. At the satellite image of 1987 the construction site of the Trans European Motorway, which connects the European and Asian side, can he detected. At the satellite image of 1992, it can be observed that, TEM was completed and new roads were constructed in order to access TEM. However, the complete network begins to enlarge with new branches, which helps people to access the main network easily. The development is mainly observed at the northern side. Impact of developing infrastructures to the environment was analyzed

Fig. 4 Classification results of the selected band

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by means of classification results of the satellite images. As a result of easy accessibility caused by the development in transportation infrastructures, several industries have moved to these areas and resulting unplanned and uncontrolled expansion in urban area. The spatial and temporal distribution of the introduced classes namely; settlements, barren land, green area, water and mining area were presented in Fig. 4. The total area classified was 51,740 ha where in 1987, 23% of the area was determined as settlements. From Table 1, it is seen that between years 1987–1992, the urban land was 11,698 ha in 1987 and an extra 6,283 ha has been gained by year 1992, only within 5 years period. In contrast, crop and bare soil areas decreased 12%, indicated as barren lands in Table 1. No significant change was observed at the green areas, where some of them are zones under-protection such as watershed and forest zones. The regulations allow no permanent settlements or industrial activities in the absolute and short-range of such zones. The classification results and the comparison between years 1987 and 1992 were presented in Table 1 and Fig. 5. From Fig. 5, it is seen that between years 1987–1992, 6,100 ha of barren land is converted to urban. According to the analyze results, there is a tendency of conversion of barren land to settlement and green area to barren land. The achieved classification results between years 1963–2002, support the recognized tendency clearly. The proposed framework enlightened the task of evaluation of the alternatives for the third bridge. Six alternative routes are being publicized, where within this study only one of them is going to be examined. The chosen alternative is at the northern part of the Istanbul Metropolitan Area, presently detected form the satellite images as condense forestry area, illustrated in Fig. 6. In order to estimate the impact and the interaction between transport, land-use and environment, the second bridge and the new alternative bridge foot locations were examined. Since the alternative routes are currently not declared, a circle having a 4 km radius was created in order to estimate the impact. The Corona satellite image pertaining 1963 and the Spot-5 image pertaining 2002 were compared. The second bridge foot and the alternative bridge foot and their peripheries at the Asian side of Istanbul were classified and compared. According to the classification results of the year 1963 for the second bridge, the area of settlements and barren lands was 306 ha, where in 2002 the classification

Table 1 Classification results Year Class

1987

%

1992

%

Barren land (ha) Settlements (ha) Green area (ha) Mining area (ha) Water (ha) Total (ha)

28,903 11,698 9,236 211 1,693 51,740

56 23 18 0.2 2.8 100

22,742 17,981 8,772 245 2,000 51,740

44 35 17 0.2 3.8 100

Impacts Assessment of Newly Constructed Highways via Spatial Information Sciences

30000

25000

1417

28903

22742

17981

20000

87(Ha.)

15000

11698

92(Ha.) 9236

10000

8772

5000

1693 2000

0 Barren Land

Settlements

Green Area

Water

Fig. 5 Classification results between 1987 and 1992 Fig. 6 Current status, II. Bridge and the alternative for the III. Bridge

N Planned III. Bridge

II. Bridge

results showed that the same class was increased to 1,345 ha which was illustrated in Fig. 7. The incensement ratio was 339.5%. For the same area, green areas were 2,098 ha in 1963, where in 2002 the green area class was detected as 1,169 ha. There is a 44.2% decrease in the green areas. There was a dense forest area in 1963, where

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Fig. 7 The comparison between 1963 and 2002 for the second bridge

it was divided by the newly constructed highway, which can be observed at 2002. The rapid expansion of urban areas was continued in 2002. The alternative location for the third bridge was also investigated following the same procedure. The images of 1963 and 2002 were compared, where the classification results were illustrated in Fig. 8. According to the classification results of this alternative, in year 1963 the area for settlements and barren areas were detected as 74 ha, where for the same class the area was 178 ha. The green areas were 2,095 ha, where in year 2002 the green areas

Fig. 8 The comparison between 1963 and 2002 for the third bridge alternative

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were detected as 2,209 ha. Green areas were increased 5%. According to the classification results no significant change was detected, since the compared time was 40 years. The results for the year 1963 of the second bridge and the third bridge alternative are quite similar, where there is huge difference between the results of 2002. These results illustrated that development of transportation infrastructures created an attraction in the region and urban areas expanded rapidly. With the selected case study area, further studies are going to be conducted. A three-dimensional city model along the transportation infrastructures is going to be integrated into the system, in order to determine the interaction between urban class retrieved from satellites and transportation. In order to support strategic planning the data model will involve analyses for studying impacts and estimate further years interaction between transport, land-use and environment. Results will be simulated and visualized, in order to increase the awareness on the interaction and support sustainable policies.

4 Conclusion Spatial information sciences served quite well in detecting the interaction between transport, land-use and environment. The spatial and temporal analyses indicated the rapid conversion of forest areas and bare land to urban areas, where transportation activities increase. The distribution of infrastructure in the transport system creates opportunities for spatial interactions and can be measured as accessibility. As consequence, the distribution of accessibility in space influences location decisions and therefore results in changes of the land use. The interaction of the land-use system and the transport system generates a feedback cycle, and adversely affects environment. At the local scale the efforts of connecting Europe to Asia, which is inevitable, contributed to the drastic affects on urban development and environment. There is a tendency that urbanization sprawl will continue. The study aims to aid managers and decision makers by informing them of past and current land-use/cover changes, to influence transparent integrated policies for transport, land-use and environmental policies. The research results indicate how spatial information technologies can be utilized for detecting the dynamic changes in urban and environment, which may be attributed to transport.

References 1. Antunes P, Santos R, Jorda L (2001) The application of geographical information systems to determine environmental impact significance. Environ Impact Asses Rev 21 511–535 2. Demirel H (2004) A dynamic Multi-dimensional conceptual data model proposal for the transportation applications. ISPRS J Photogrammetry Remote Sens 58:301–314 3. Demirel H (2006) A novel approach for determining the impacts of road transportation on air quality. Fresenius Environ Bull 15(8b): 891–897 4. DIE (2006) State Statistical Institute, Turkey. http://www.die.gov.tr Accessed 10 July 2006

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5. Geurs KT, Wee B (2004) Accessibility evaluation of land-use and transport strategies: Review and research directions. J Transport Geogr 12:127–140 6. Kaya S, Curran P J (2006) Monitoring urban growth on the European side of the Istanbul metropolitan area: a case study. Int J Appl Earth Obs Geoin 8:18–25 7. Kitwiroon N, Sokhi R S, Luhana L, Teeuw, R M (2002) Improvements in air quality modelling by using surface boundary layer parameters derived from satellite land cover data. Water Air Soil Pollut: Focus 2:29–41 8. Musaoglu N, Gurel M, Ulugtekin, N, Tanik A, Seker D Z (2006) Use of remotely sensed data for analysis of land-use change in a highly urbanized district of mega city, Istanbul. J Environ Sci Health Part A 41:2057–2069 9. Parsons B, Salter, L F (2003) air quality effects of traffic in a canyon-like street (Falmouth, U.K.). Environ Monit Assess 82:63–73 10. Rajaram B, Nagarajan R, Khire M V (2001) Synergistic use of orbital satellite image and ground-based information in environmental monitoring of railway alignment construction a case study. Int J Remote Sens 22(16):3187–3201 11. Rodier C J, Johnston R A, Abraham J E (2002) Heuristic policy analysis of regional land use, transit, and travel pricing scenarios using two urban models. Transp Res Part D 7:243–254 12. Shaw S, Xin X (2003) Integrated land use and transportation interaction: a temporal GIS exploratory data analysis approach. J Trans Geogra 11:103–115 13. Tou J T, Gonzalez R C (1974) Pattern recognition principles. Addision – Wesley, Reading, MA 14. United States Environmental Protection Agency (EPA) (2001) Our built and natural environments, a technical review of the interaction between land-use, transportation and environmental quality. EPA 231 R-01-002. http://www.smartgrowth.org/library/built.html Accessed 10 July 2006 15. Wang X (2005) Integrating GIS, simulation models, and visualization in traffic impact analysis. Comput Environ Urban Syst 29:471–496

Water Resources in the Slovak Republic and Their Protection Jozef Kriš, Faško Martin, and Škultétyová Ivona

Abstract Water supply resources are groundwater and surface water bodies currently used or intended for prospective use. Water used from identified water bodies shall meet relevant qualitative objectives and resulting requirements on water quality and quantity according to its purpose of use. Water resources protection should be viewed as a integrated protection of quality and quantity of sustace and ground water, including natural curative springs and minerals waters. For water resources protection the protection zones with limited agricultural use and other activities are designated according to the valid legislation. The paper deals with issues relating to water quality and quantity protection. Keywords Water sources · Surface water · Groundwater · Protection of water sources · Protection of water quality · Vulnerable areas

1 Surface Water Quality Surface water quality assessment is based on the Summarization of the classification results under the Slovak Technical Standard (STS) 75 7221 – As the Slovak Hydrometeorological Institute(SHMI) have not submitted the results of analyses for 2004 due to unallocated funds of the Ministry of Environment for this works, the Slovak Water Management Enterprise has conducted the review of surface water quality assessment for 2004 using own result of physical, chemical, biological and microbiological analyses carried out for the purpose of surface watercourses and reservoirs quality monitoring. This assessment was performed within the operational monitoring of the administrator of important water management watercourses [7, 13]. In 2004 the water quality monitoring was carried out in 182 profiles of the national surface water monitoring network including 20 profiles of transboundary J. Kriš (B) Department of Sanitary and Environmental Engineering, Faculty of Civil Engineering, Slovak University of Technology Bratislava, Radlinského 11, 813 68 Bratislava, Slovak Republic e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_133,

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rivers, 8 water supply reservoirs and other 309 monitoring sites at streams and 73 water reservoirs that are monitored within the operational monitoring performed by the administrator of important watercourses [11, 12]. The network of basic and additional profiles is located at important water management watercourses and reservoirs throughout Slovakia [4]. Surface water quality monitoring and assessment have been conducted under the Slovak Technical Standard No. 75 7221 “Surface Water Quality” [15], which recognize 8 groups (A to H) of important water management watercourses monitored surface water quality 12 times in 300 quality of 214 streams in Slovakia with length about 3,695 river kilometers. A number of regime, basic physical-chemical parameters, nutrients and microbiological parameters) were monitored at 464 sampling sites and biological parameters (group D) at 146 sampling sites, micro-pollutants (group E) at 96 sites and radioactivity (group H) at 108 sampling sites. A general assessment points out negative classification of surface water caused mostly by microbiological parameters of group E, in which 326 sites are classified into the quality categories IV and V. In groups A, B, C, and D the most of sampling sites is classified into the category III. In selected sites of the Danube river basin the toxicity (group H) tests were carried out proving the quality category I. Surface water quality in the Slovak streams is primarily affected by wastewater discharged from the point sources of pollution. The 2003 and 2004 data proved slight downward trend in pollution production. Despite the increase in identified pollution source amount of wastewater discharged into surface water has decreased in a range from 4 to 8% and thus the recompenses for wastewater discharge has been decreased. The general assessment points out a negative classification of surface water mainly due to microbiological parameters of group E in which 326 sampling sites are classified into the quality categories 4 and 5 for 2004. The most of sampling sites from the A, B, C and D quality groups are classified into the quality category 3. In selected areas of the Danube River Basin the toxicity tests have been performed (group G) and proved the 1st quality category.

2 Groundwater Quality In 2004, groundwater quality was monitored in 26 important water management regions (especially in alluvial deposits, mezozoic and neovolcanic complexes) at objects of the Slovak Hydrometeorlogical Institute’s network added by wells and used or unused springs [3]. The monitoring network consists of 333 points with monitoring frequency of two times a year. The groundwater of the “Žitný ostrov” region forms separate part of groundwater quality monitoring in four regions with frequency of 2 up to 12 times a year [2]. Previous monitoring has proved that there is a problem with unfavorable oxidation-reduction network in Slovakia. In 2004, the groundwater quality was monitored at 46 monitoring objects conditions indicated by frequently present

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higher concentrations of Fe, Mn and NH4 . The pollution caused by organic substances indicated by frequent exceeding of limit values for concentrations of nonpolar extractable substances (NELuv) and phenols remains the same as in previous years. The dominant character of land use in monitored areas results in relatively frequent higher concentrations of oxidized and reduced forms of nitrogen in waters. From the trace elements, higher concentrations were mostly observed in the aluminium concentrations, but together with other parameters they have only local character. The following groundwater quality parameters measured in situ in the region of “Žitný ostrov” almost at all measuring objects did not meet limit concentrations: dissolved oxygen, in some objects also water temperature (33 measurements), conductivity (9 measurements) and pH (3 measurements). From the group of basic physical-chemical analysis the following parameters had higher concentrations: iron, manganese, ammonium ions, nitrides, nitrates, chlorides, chemical consumption of oxygen with permanganate and fluoranthene as well as phenols and NELuv . Natural groundwaters are the most important resources of drinking water on the Slovak territory. They represent one of the basic elements of ecosystems. They are used in industry and agriculture. Therefore, it is very important to know their quality within the monitoring of groundwater regime. In addition to quantitative characteristics, the objective of groundwater monitoring is also focused on: • • • • •

assessment of the current state of groundwater quality description of ground water quality trends providing water management authorities and other entities with basic data for decision making process application of results to research and expertise activities

Systematic groundwater monitoring within the frame of the National monitoring programme runs since 1982. At the present time, 26 significant water management regions are monitored (alluvial deposits, mezozoic and neovolcanic complexes). For fulfilment of requirements on gathered information about water quality development in regions without considerable anthropogenic effects also pre-quaternary structures were included in monitoring programme [8]. In 2004, 333 objects were monitored − 208 wells of the SHMI basic network, 36 used and 19 unused wells (exploration wells), 47 used and 23 unused springs. In 2004, the groundwater samples were taken only one time in the autumn. The results of laboratory analyses were evaluated according to the Decree of the Ministry of Health of the Slovak Republic No. 126/2006 Coll. on requirements on drinking water and control of drinking water quality by comparing the measured and limit values for all analysed parameters [5]. The results are annually published in the “Groundwater quality in Slovakia” Yearbook. In 2004, the values of acceptable concentration (the highest acceptable concentration) were more often exceeded

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by the following parameters: Mn (144 times), total Fe (148 times) and NELuv (63 times) from the total number of 333 measurements. The unfavorable oxidation-reduction conditions indicated by frequently present higher concentrations of Fe, Mn and NH4 + pose currently the most significant problem within the groundwater quality assessment process. As in previous years, the pollution by organic substances indicated by frequent exceeding of the nonpolar extractable substance limit concentrations (NELuv and chemical consumption of oxygen with permanganate) still prevails. In some monitored regions the number of exceeded NELuv concentrations has increased compared to previous periods. The dominant character of land use in monitored areas results in relatively frequent higher concentrations of oxidized and reduced forms of nitrogen in water (nitrides − 35 times, nitrates − 9 times). As far as trace elements are considered, the most frequent higher concentrations were observed for As (19 times), Al (13 times), Ni (1 times), Pb (1 time) and Hg (1 time). The pollution by specific organic substance has only local character.

3 Water Resources Protection 3.1 Protection of Water Quantity The major objective of water utilities is to maximize usage of the stored water resource [9]. In the period between 1989 and 1991, the impact of environmentally uncontrolled exploitation of water-deficit regions was highly adverse, ultimately resulting in the depletion of ground water resources by using the accumulated reserves. As a consequence, water managers, in addition to qualitative water resource protection, began to pay closer attention to quantitative protection, i.e. protection of the volume of water reserves. The water resources protection in Slovakia is considered as an integrated protection of groundwater and surface water quality and quantity, including springs and mineral waters. Quantitative protection is based on accumulation ability and management of particular region with respect to abstracted or pumped water. This is the reason why the limit for surface water use is determined by so-called ecological limit (MWeko ), which has no effect on a habitat in river basin. The quantitative protection of the yield of ground water was introduced in 1993. At the same time, the Methodology of Establishing Ecological Limits of Ground Water Resource Utilization was developed and applied in the General Protection and Rational Water Utilization. The methodology defines how to establish usable volumes of ground water resources while ensuring sustainable development of the land by defining general ecological limits for the entire watershed – a hydrogeological zone or hydrogeological structure, as well as local ecological limits for particular sources that are being used (springs and wells). Previous experience shows a decrease in the volume of continuously used springs Qmin and wells Qrec of 15–20% and 20–30%, respectively.

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Qualitative protection plays significant role in water resource quality protection. The pollution comes from population, industry and agriculture through various types of contamination. Legislation determines obligations and responsibilities for wastewater discharge and manipulation with chemicals in order to avoid deterioration of surface and ground water resources.

3.2 Protection of Water Quality One of the key roles of water protection in terms of water quality is to resolve the problems relating to sources of pollution. Pollution sources, which have a negative impact on water quality, are broken down into two categories based on the type and severity of their impact: point sources of pollution and non-point sources of pollution. The most significant point sources of pollution are wastewater discharges from industrial and agricultural facilities and from residences. Even though the volume of discharged wastewater has been declining since 1990, in order to ensure active water quality protection, the portion of population connected to the sewage system has to be increased and measures relating to wastewater treatment have to be taken. Legally, the polluter is in charge of drainage water and sewerage treatment and obliged to monitor the quantity and quality of discharged wastewater. The validity of monitoring results depends on the precision of the sampling procedure and the level of expertise of laboratories providing wastewater analyses. The currently operated wastewater treatment plants represent a specific problem, because they are overloaded (both hydraulically and from a load point of view) and the wastewater treatment technology does not comply with legal regulation standards any more. Protected areas are determined according to the Act No. 184/2002 Coll: 1. 2. 3. 4. 5. 6. 7. 8.

Protected water management areas (PA) Protection zones of water supply resources (PZ) Sensitive areas (SA) Vulnerable areas (VA) Areas containing surface water intended for drinking water abstraction Bathing water areas Areas with water suitable for life and reproduction of indigenous fish species Protected areas and their protection zones under the article 17, Act. No. 543/2002 Coll on Nature and Landscape Protection

3.3 Protected Water Management Areas The protected water management areas are defined as areas where, due to favorable natural conditions, surface and ground water are accumulated. This is why the Government may declare them as the protected water management areas. All activities in protected water management areas can be planned and performed only if a broad protection of surface and ground water will be assured.

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J. Kriš et al. Table 1 Protected water management areas in Slovakia [14] Available water resources

No. 1. 2. 3.

4. 5. 6. 7. 8.

9. 10. Total:

Name Beskydy – Javorníky Žitný ostrov Nízke Tatry (a) western part (b) eastern part Strážovské vrchy Vel’ká Fatra Upper river basin of Ipel’, Rimavica and Slatina Vihorlat Slovak karst (a) Plešivská planina (b) Horný vrch Muránska planina Upper river basin of Hnilec

Area (km2 ) 1856 1400 1290 358 805 757 644 375

Surface (m3 s−1 )

Ground (m3 s−1 )

Total (m3 s−1 )

1.84 –

0.69 18.00

2.53 18.00

– 2.33 – 0.97 1.09

2.50 2.43 2.33 2.98 0.11

2.50 4.76 2.33 3.95 1.20

225 209 57 152 205 108

0.08

0.43

0.51

– – – 0.16

0.55 1.97 1.40 1.10

0.55 1.9 1.40 0.26

6, 942

6.47

33.49

39.96

The protection of water production, occurrence as well as transport and other interests shall be in accordance with requirements set for protected water management areas within the processing of development conceptions and regional planning documentation. Today, there are ten designated protected water management areas in Slovakia covering area of 6, 942 sq km that represents 14,16% of the entire Slovak territory. Basic characterization of designated protected water management areas are listed in Table 1.

3.4 Protection Zones of Water Supply Resources Protection zones of water supply resources (see Tables 2 and 3) are designated by the state water authorities with aim to protect their yield, quality and safety [10, 16]. Protection zones of water supply resources are divided into the protected zone of the 1st degree serving for its protection in direct vicinity of water abstraction points or capture devices and the 2nd degree protection zone serves for protection of water supply resource against risks coming from more distant sites. For enhanced protection the water authority is allowed to establish also the 3rd degree protection zone. Protection Zone 1 serves to protect water supply resource in the immediate vicinity of the water intake or water collector. Protection Zone 2 serves to protect water supply resource against contamination from farther resources.

Sub-basin

Váh

Hron

Bodrog Hornád

2.

3.

4. 5.

Váh incl. Nitra Hron Ipel’ Slaná Bodrog Hornád

Morava

Dunajec a Poprad

Total (Slovakia):

1.

Dunajec a Poprad

International virtual river basin

Danube

1.

International Danube river basin

No.

River basin district

49014

1950

5465 3649 3217 7272 4414 858

2282 1138 18769

Sub-basin areas (km2 )

1138

50

124 49 71 207 140 31

39 31 396

Ground water

Number

73

13

7 1 5 15 1 7

0 0 6

Surface water

356.280

15606

55123 8360 16371 6760 19865 7818

13901 7375 205101

Ground water

505.139

14023

9316 7872 17703 335272 67890 9024

0 0 44.038

Surface water

Area of protection zones (ha)

Table 2 Number and areas of protection zones in Slovakia [10]

8614.2

296.3

644.4 162.3 340.7 3420.3 877.6 168.4

139,0 73,8 2491.4

Total area (km2 )

17.6

15.2

11.8 4.4 10.6 47.0 19.9 18.6

6,1 6,5 13.3

% of basin area

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J. Kriš et al. Table 3 The water supply protection zones in Slovakia for water reservoirs [9]

No.

Name of water reservoir

1. 2. 3. 4. 5. 6. 7. 8. Total:

Bukovec Hriˇnová Klenovec Málinec Nová Bystrica Rozhund Starina Turˇcek

Total (km2 )

Agricultural land (km2 )

Forest area (km2 )

52.9 71.04 92.12 78.72 59.32 3.42 120.45 28.96 506.93

5.12 9.61 26.90 33.46 5.39 0.47 4.99 − 85.94

45.91 60.97 65.22 44.17 53.13 2.89 115.46 28.96 416.71

Protection Zone 3 can be established to improve the overall protection of water supply resource. If conditions in the locality of the 1st degree protection zone provide sufficient protection of water resource yield, quality and safety, further degrees of protection zones will not be designated. Designated protected zones serve simultaneously specific regulations. According to 2002 data there are about 1138 PZ groundwater resources in Slovakia. A single PZ, especially the 2nd degree PZ, may comprise several water resources, e.g. the entire spring line or group of wells, etc. In Slovakia there are 73 protection zones designated for the need of surface water abstraction for drinking purposes, 8 of which are designated for the abstraction from water supply reservoirs and 65 for the direct water abstraction from surface streams that are mostly situated in the East Slovakia Region. In Slovakia there are 73 PZ intended for surface drinking water abstraction, of which 8 are related to abstraction from water supply reservoirs and 65 PZ are designated to direct abstraction from surface streams that are situated mostly in the East Slovakia Region. The above-mentioned data indicate high percentage of the area covered by protection zones in Slovakia − 17.56% (Table 2). It is important to note that the areas of protection zones of some water supply resources arte often overlapping. Therefore, the area of 17,75% does not represent the total area of protection zones in Slovakia, but it is a sum of all individual protection zone areas without mutual overlapping. After consideration of the zone overlapping, the area of all protection zones covers 3 113 sq km in total, i.e. 6,36% of the Slovak territory.

3.5 Sensitive Areas Sensitive areas are surface water bodies, water quality of which is or can be threatened by increased nutrient concentrations; which are or can be used as water supply

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resources as well as water bodies requiring a higher level of discharged wastewater treatment with regard to advanced water protection interests. From 2003, the Governmental Regulation specifying designation of sensitive and vulnerable areas came into force. All surface water bodies in Slovakia. It means that all area of Slovakia have been declared as sensitive areas.

3.6 Vulnerable Areas Vulnerable zones under the Water Act are agriculturally used areas where rainfall water flows into a surface water or infiltrates to groundwater resources in which the nitrate concentration is higher that 50 mg l−1 or can be exceeded in the near future. Plots agriculturally used in particular cadastral territories listed in the Governmental Regulation have been designated as vulnerable zones. In particular, it relates to all lowland areas of Slovakia, alluvial plains of larger rivers as well as lower situated valleys with agriculturally used land. Sensitive and vulnerable area identification is being re-evaluated every 4 years under the coordination of the Ministry of Environment of the Slovak Republic. The Regulation accepts the possibility to not declare the 3rd or even 2nd degree PZ of water supply resource, if there exist other type of area protection, e.g. vulnerable area. In practice it means that such protection can substitute the function of the 3rd degree PZ and in specific cases even the 2nd degree PZ.

3.7 Surface Water Resources Intended for Drinking Water Abstraction Water supply streams and their river basins can be considered as protected areas with surface water intended for drinking water abstraction under the Decree No. 211/2005 Coll. Setting the list of important water management rivers and water supply streams [6]. There are 102 identified water supply streams in Slovakia. According to Article 7 of the Water Act water supply streams are water supply resources of surface water [1]. Ground water supply resources are groundwater bodies used for drinking water abstraction or groundwater bodies supplying more than 50 person or allowing water abstraction in average of more than 10 m3 a day in natural status or after treatment.

3.8 Bathing Water In 2004 Water Administration Authority of the Ministry of Environment together with the Public Health Office identified 39 nature localities with water suitable for bathing in Slovakia. The listed localities are situated mostly in proximity of water reservoir and gravel pits.

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3.9 Water Suitable for Life and Reproduction of Indigenous Fish Species Protected areas with water suitable for life and reproduction of indigenous fish species have not been designated by 2004.

3.10 Implementation of Protected Areas in Slovak Republic The European System of Protected Areas – NATURA 2000 is applied for protection of animal and plant species of Slovakia. It is confirmed in the Act. No. 543/2002 Coll. on Nature and Landscape Protection. NATURA 2000 us a system of the EU member states protected the most rare and endangered plant and animal species as well as natural habitants and through this preserve biological diversity throughout the European Union. The system of NATURA 2000 consists of the two types of protected areas: – Special Protection Areas – Special Areas of Conservation The national system of protected areas is created in conformity with the Act No. 543/2002 Coll. on Nature and Landscape Protection. It divides the Slovak territory in to five levels of protection. The higher level of protection is established the wider range of measures is applied. The areas not included in any protection category are classified into the first level of protection under the act mentioned above. In particular, it concerns the following categories of protection areas and protection levels: – Protected Landscape Area (2nd protection level) – National Park (3rd protection level) and its protection zone (2nd protection level) – Protected Range (3rd to 5th protection level) – Nature Monument and National Nature Monument (4th to 5th protection level) – Protected Landscape Element (2nd to 5th protection level) At the present time there is designated 23 large protected areas in Slovakia comprising 9 National Parks and 14 Protected Landscape Areas covering an area of 1 113 565 ha including protection zones. The number of small protected areas is 1101 inclusive of 385 Natural Reserves, 239 Nature Monuments, 60 National Nature Monuments and 189 protected Ranges covering the total area of 111 062 ha including their protection zones.

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3.11 Special Type of Protection Areas – Wetlands Wetlands are areas of marshes, fens, peat lands or water, whether natural or artificial, including habitats dependent on aquatic environment. Wetland protection is provided at national and international levels. International wetland protection is included in the Convention on Wetlands, signed in Ramsar, Iran in 1971 and known as the Ramsar Convention. The Convention provides the framework for national action and international cooperation for the conservation and wise use of wetlands and their resources. The Slovak Republic signed the Ramsar Convention in 1990, which obliged Slovakia to meet requirements on wetland protection in its territory. The fulfilment of obligations resulting from the Ramsar Convention are managed and coordinated through the Slovak Ramsar Committee. Wetland mapping in Slovakia is coordinated by the Wetland Mapping Centre, headquartered in Prievidza. The Centre keeps records of the following categories and numbers of wetlands: – 13 wetlands of international importance included in the List of Wetlands of International Importance, i.e. Ramsar sites with area of 39 337 ha. (Another four sites with area of 1 007 ha are proposed for the List of Wetlands of International Importance.) – 72 wetlands of national importance – 179 wetlands of regional importance – 1050 wetlands of local importance

3.12 Pecuniary Damages/Loss In connection with pecuniary damages compensation in protected areas due to limited economic activities it is important to distinguish between protected areas designated under the Act No. 543/2002 Coll. on Nature and Landscape Protection and protected areas designated under the Act No. 364/2004 Coll [1].

4 Conclusion Monitoring of water resources qualitative parameters has a long-standing tradition in Slovakia. Issued legislative regulations define parameters and character of quality monitoring as well as number of analyses in relevant monitoring periods. The above results indicate that quality of our water resources becomes slightly better. However, there exist some water resources with water unsuitable for long-term drinking water abstraction. Protected areas it is important to note that individual components of landscape protection shall be integrated within the frame of integrated approach to the institutes of landscape protection as a whole.

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Acknowledgement The paper has been written with the support of the Grant Research Tasks VEGA No. 1/0854/08 and VEGA No. 1/0559/10 dealt with at the Department of Sanitary and Environmental Engineering of the Faculty of Civil Engineering of the Slovak University of Technology Bratislava.

References 1. Act nop. 364/2004 Coll. of May 13, 2004 on waters and amendments to the Act of the National no. 372/1990 Coll. On offences as amended by later regulations (water Act) 2. Božíková J, Mikita M (2005) “Žitný ostrov” region and use of its drinking water resources potential, Project and Construction, I, Vol. 1, No. 2, Bratislava, The Slovak Chamber of Civil Engineers, pp. 8–11, ISSN 1336 – 6327 3. Decree no. 29/2005 of the Ministry of Environment of the Slovak Republic of the February, 2005 on details for identification of water supply protection zones and measures for water protection 4. Decree no. 100/2005 of the Ministry of Environment of the Slovak Republic determining the details on handling of hazardous substances, on requirements of emergency plan and managing enormous water quality deterioration 5. Decree of the Ministry of Heath No 126/2006 Coll. Drinking water quality 6. Decree no. 211/2005 of the Ministry of Environment of the Slovak Republic establishing the list of significant water management rivers and water supply streams 7. Decree no. 221/2005 of the Ministry of Environment of the Slovak Republic determining the details on identification, assessment and monitoring of surface water and groundwater, on water resources inventory and water balance 8. Decree no. 457/2005 of the Ministry of Environment of the Slovak Republic determining the details on requirements of hydraulic structure operating regulations 9. Hanzel V, Melioris L. Groundwater of Slovakia – its share of population supply. Groundwater SAH 2(96):5–11 10. Kriš J (1996) Water and life (Regulation of the Government of the Slovak Republic no. 249/2003 of June 26, 203 designating sensitive and vulnerable areas). Vodohospodársky spravodajca XXXIX:4–5 11. Report on Water Management in the Slovak Republic (2004) (Green Report) The Ministry of Environment SR, Bratislava, 2005 12. Report on the State of Environment in the Slovak Republic, the Ministry of Environment SR, Bratislava 2004 13. Regulation of the Government of the Slovak Republic no. 296/2005 establishing requirements for surface water quality and quantity, limit values of wastewater and specific water pollution parameters 14. Regulation of the Government of the Slovak Republic no. 249/2003 of June 26, 2003 designating sensitive and vulnerable areas 15. STS 757221 surface water quality classification 16. Tóthová K, Mahríková I (2006) Securite of water supply and sewerage systems in Slovakia – present state. Security of water supply systems: From source to tap. The NATO programme for security through science. NATO security through science series – C: Environmental security. Springler, pp 155–167. ISBN 1-4020-4563-8, ISSN 1871-4668

E-Waste Management Santosh M. Avvannavar, Ravi Kiran Mutnuru, and S. Shrihari

Abstract E-waste is a new term coined in the market of hazardous substances. It has taken a new bourgeoning route since the boom of IT. The problems regarding the transportation, handling and disposable have to be tackled at the earliest else it might cause detrimental effects on environment. Presently in India there is no distinct and lucid regulation(s) regarding e-waste management. We are looking for one stop solution! In the present paper, we have put forth some of the Technical and E-Management Strategies that can be implemented by adopting 3 R’s policy – reduce, recovery and recycle. Keywords E-waste · 3 R’s policy · E-Management

1 Introduction IT industry is an inviting platform for many young job seekers. IT such as telecommunication, electronic goods etc., has made our life easier and lethargic to certain extent by providing the information at our finger tips. It is no doubt that vast resource utilization by the fastest growing manufacturing industry is electronic industry [1]. The electronic industry generates enormous amount of waste, which is not properly handled, and is just dumped.

1.1 Definition of E-Waste Electronic goods that become “outdated” or approaching “end life”, due to the changes in standard of living, new technologies can be termed as E-waste.

S.M. Avvannavar (B) Department of Chemical Engineering, Technische Universiteit, Eindhoven, The Netherlands e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_134,

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1.2 Sources of E-Waste in India E-waste is generated by three major sectors • Individual and small business • Large business, institutions and governments • Original Equipment Manufacturers

1.3 Hazards in E-Waste Most of the chemical compounds are found in E-waste are hazardous in nature and if not handled properly can cause many problems. As such electronic goods are not harmful; but its handling in crude way such as open burning, acid operation etc, can cause many problems. It has been reported that more than 8,000 chemical compounds are found in E-waste [3].

2 Source Visit Visit to IT “Top Notch” organization to get the information regarding handling left us bare hand. Most of leading IT domain don’t have EHS department. Most of the companies have a storeroom for dumping the E-waste. They discard the electronic goods by segregating the essential component(s) such as hard disk and remaining components are stored in the store room. Usually most of the corporate call for a tender through newspapers or have common retailers or vendors who purchase at a low-price. These are not aware of the problems associated with E-waste. Added to this there are no standards put forth to regulate the E-nuisance [1]. General Invoice can be as shown below (Table 1). Table 1 Categories and prices per ton for general invoices Categories

Price/ton

Hard disks, batteries, tube light, table fan cables etc. Monitors, PCBs, CDs, Floppy etc. Photocopy machine, mouse, keyboard

R1 R2 R3

R1, R2, R3 indicate the cost in Rs/ton

2.1 General Commitment That All the Organization Must Follows About EH and S • Provide products and services that are environmentally sound throughout their lifecycles • Conduct its operations in an environmentally friendly manner

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• Create health and safety work practices that enable employees to work injury-free • Ensure the security of work force, places and assets

2.2 Awareness • General public should be made aware of hazards of E-waste • Unorganized sectors should be banned and organized sector should be encouraged • Awareness programs for government sectors, IT hub/Park, and individuals • Educating world-wide by use of media

3 E-Waste Regulations Put Forth by Various Countries • Rapid innovation in the electrical and the electronic equipment division is continuing to shorten product lives and accelerate the replacement process. As a result of this heaps of e-waste, this has become unmanageable. These products consist of various hazardous chemical substances such as lead, mercury etc. • In order to grab the on going increase of E-waste the legislative should enforce the Directive on waste electrical and electronic equipment (WEEE Directive) and Directive on the restriction of certain hazardous substances in electrical and electronic equipment (RoHS Directive). • Basel Action Network (BAN) should be enforced in developing countries due to the health pertaining problems. • Exim code for trade in second-hand computers should be implemented in order to avoid the easy dumping of E-waste from developed countries or other sources. • By making individual responsible (manufacturer responsible) and Collective responsible (other organized park or manufacturer and consumers)

4 R’s Policy

E-Waste Reduce-Reuse-RecycleRecover Disposal

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User

Organization

Materials Park and Operations

EHS&S

ETP

Reduce • • • •

Smart purchasing and proper maintenance can extend the life of your equipment When possible, upgrade your equipment Lease equipment so you can trade it Protect your equipment by using a surge protector and keeping covered Reuse

• Equipment that does not meet the users current needs may be perfect for someone else • Purchase used equipment if it is available and meets your needs • Donate unwanted equipment to local charities or organization to be used for teaching centers or technical training houses Recycle • Most electronic equipment can be recycled, but not necessarily in local areas • Contact the local recycling park or organized sector

3.1 Different Chemical Process for Recovery and Reuse of E-Waste According to the literature survey it is revealed that the recovery and recycling of various metals such as Cu, Hg, Ag etc., plastics, glass is still in an elementary stage. R&D work is carried out worldwide in this area. Some of the examples- The extraction of copper chemically such as copper recovery from waste printed circuit board by using leaching process and the electro deposition process. Glass-ceramics obtained by the recycling of end of life cathode ray tubes glasses. Glasses are melted at a temperature of about 1500◦C and transformed into glassceramics by different thermal treatments. By using the evaluation of thermal, mineralogical and micro structural data it has been pointed out that a good degree of crystallization is reached at about 1000◦C and with a high proportion of waste glass (50–75%) if 40–45% of CaO and MgO bearer is introduced. In this way alkaline and

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alkaline earth silicate and aluminosilicate mainly develop probably with a surface mechanism. Closed-Loop recycling of Ni, Co and rare-earth metals from spent Ni-Metal Hydride-Batteries. Ni and Co are obtained by recycling from Lithium-ion batteries by electrochemical processes. The process is the combination of mechanical, pryometallurgical and hydrometallurgical processes. Metal recovery from multimetal pressure sulphide concentrates (CuFeS2 -PbSZnS): combination of thermal process and leaching. Reuse of ground glass as aggregate for mortars. The study reveals that the possible reuse of waste glass from crushed containers and building demolition as aggregate for preparing mortars and concrete. At present, this kind of reuse is still not common due to the risk of alkali-silica reaction between the alkalis of cement and silica of the waste glass. This expansive reaction can cause great problems of cracking and consequently. It can be extremely deleterious for the durability of mortar and concrete. However that if the waste glass is finely ground, under 75 Micrometer, this effect does not occur and mortar durability is guaranteed. And also No reaction (between waste glass and cement paste in mortars) has been detected with particle size up to 100 Micrometer thus indicating the feasibility of the waste glass reuse as fine aggregate in mortars and concrete. In addition, waste glass seems to positively contribute to the mortar micro-structural properties resulting in an evident improvement of its mechanical performance.

4 Recommendations for Action Rapid product obsolescence in the electronic industry has created a waste crisis that is out of control. The answer to the looming e-waste crisis lies not in finding new downstream hiding places for this waste; it lies not in exporting it to the desperately poor, but in moving upstream to prevent the problem at its manufacturing source. Today it is frequently cheaper and more convenient to buy a new machine to accommodate the latest software and hardware technology and their increasing demands for more speed, memory, and power, than it is to upgrade the old. Yet, this “trash and buy” cycle comes with a monumental price that we are just beginning to pay. We need to change the dominant paradigm that has prevailed over the past three decades. The lust for faster, smaller and cheaper must be governed by a new paradigm of sustainability that demands that our products are cleaner, long-lived, up gradable, and recyclable [3]. It is time to strengthen the call for sustainable production, environmental justice, corporate and government accountability in order to achieve these goals. 1. 2. 3. 4.

Ban hazardous waste imports Make the producer responsible Inform the consumer Design for recycling

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5 Conclusion The e-waste disposal methods prevalent in the advanced countries today are heavily dependent on the non-recyclable parts being dumped into the developing countries. In developing countries, the disposal and recycling systems suffer from an inherent lack of proper regulations and monitoring systems. A sustainable solution for ewaste disposal and recycling systems should take into account the interests of all the stakeholders. An end of lifecycle service approach, which has become popular in the recent past, offers a close to sustainable solution, if integrated with environment friendly product designs and marketing methods. Acknowledgement We thank E-Parisarra Pvt Ltd., for providing the training and details regarding E-waste and most of the top notch organizations, local vendors, and Law College, Bangalore.

References 1. Various IT Organizations, Bangalore 2. Discussion with Prof.Subramainyam, University Law College, Bangalore, India 3. www.toxiclinksgropu.com, Toxic links Groups, Chennai

Extreme Rainfall Events and Uncertainty in the Mediterranean Basin Hadas Reiser and Haim Kutiel

Abstract The Most Expectable Rainfall Regime- MERR in a certain region is composed of various parameters regarding the rainfall regime in that region. Two stations in the Mediterranean basin, Valencia and Larnaca, were used as an example of the diversity of the rainfall regime and its extremes. The present study examines several parameters of the MERR, such as: the rainfall TOTAL, the Date of Accumulated Percentage- DAP, the Rainy Season Length- RSL, the Number of rainspells- NRS, the Rain-spells Yield- RSY, the ratio between the Average rainfall and its Median- AMED and the relationship between the precipitation and number of the rain-spells. The study shows that Larnaca’s rainfall regime is less extreme as compared with the regime in Valencia. In addition, the rainfall regime in Larnaca suits the definition of a Mediterranean climate better than that of Valencia. Therefore the Rainfall Regime Uncertainty- RRU is higher there. Keywords Mediteranean · MERR · Rain spell

1 Introduction Many efforts were made during the recent years in studying climatic changes. The main aim, of those studies, was to find indications to variability from the known climatic patterns, and to understand the reasons for their occurrence. To do so, it is essential to find what is the “typical” rainy season, or in other words what is the Most Expectable Rainfall Regime − MERR, in a given region. Rainfall Regime is a term that comprises many components including: mean and other statistical measures of annual rainfall TOTAL, temporal distribution of the rainfall, length of a rainy season, distribution of rain-spells and their yields, distribution of dry spells and so on. The MERR, in a certain location, combines all of these parameters [14]. H. Reiser (B) Laboratory of Climatology, Department of Geography and Environmental Studies, University of Haifa, Haifa 31905, Israel e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_135,

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Once the MERR is defined, it is then possible to calculate how much a season or a period of time, varies from the MERR and to quantify the extreme values of its various components. In other words, to quantify the degree of the Rainfall Regime Uncertainty- RRU. Uncertainty in climate refers to the inability to accurately determine when, where and how intense a climatic phenomenon occurs. Following the definition of the RRU, it is possible to analyze time-series of this variability and to estimate whether the RRU has changed over a given period of time [14]. Many studies on rainfall in the Mediterranean basin or in parts of it, deal with the spatial and temporal rainfall distributions, mostly by characterizing the annual or seasonal rainfall (e.g. [1, 3, 5, 6, 7, 10, 12, 16, 17, 18]). Only some analyze the dry spells in order to understand the nature of the rainy season [2, 4, 9, 10, 11]. A typical characteristic of the rainfall regime in the Mediterranean climate is a long dry period along the summer. A widely accepted definition for Mediterranean climate states that in winter months (Dec, Jan & Feb) rainfall is at least three times greater than in summer months (Jun, Jul & Aug) [13, 19]. Even in areas, were there is hardly any rain in summer, either at the beginning of the rainy season and at its end, we may observe some sporadic rainfall events of minute amounts followed (at the beginning of the season) or preceded (at the end of the season) by long dry spells. Thus, if we consider the Rainy Season Length- RSL as the period elapsed from the first rainy day until the last one; we may obtain a very long RSL consisting mainly of long dry spells. Most of the sporadic rainfall at the beginning and at the end of the rainy season is of a minute value for most purposes. According to one definition, a rainy season is the time elapsed between the first and the last days with rainfall amounts that equal or exceed a specified threshold [3]. The objective is to maintain the continuity of the rainy period and to separate the rainy season at the dry period. Therefore, the hydrological year is used rather than the calendar year and the Rainy Season Beginning Date- RSBD is set to the 1st day of the month on which the RSL is averagely the shortest. In the southern part of the Mediterranean basin, rainfall starts usually around October and ends close to May, so the RSBD is set from the 1st of July to the 30th of June of the following year. In the northern part, where there is rain almost all year round, RSBD is set from the 1st of February to the 31st of January the flowing year [15].

2 Data and Methodology The present research focuses on the Mediterranean basin (excluding the North African Coasts). The main aims are to quantify the different components of the MERR, in order to describe the rainfall regimes; to analyze their time-series and to emphasis some of the components’ extreme values. This study practices the methodology approach which is presented in Paz and Kutiel [14] (Fig. 1). The rainfall data used for the analyses are daily rainfall totals from 40 stations obtained from the European Climate Assessment & Dataset- ECA&D, [8]. For at least 41 years between 1947 and 2003.

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Fig. 1 Research station location map

R The research data were statistically analyzed using Microsoft Excel based software named Rainfall Uncertainty Model- RUM2005 developed at the Laboratory of Climatology, Department of Geography and Environmental Studies, at the University of Haifa. RUM2005 uses daily rainfall data as input to calculate all the components of the MERR for any desired daily rainfall threshold (from 0.1 mm and above), and their time-series for the entire, or any desired period of the available dataset. In the present study, a daily threshold of 1.0 mm was used. The following parameters are some of the components of the MERR, the first three deals with the annual rainfall and its distribution:

1. TOTAL(d) – Average accumulated rainfall [mm] from all rain-spells of a given duration [days]. 2. DAP(k) – The temporal rainfall distribution is quantified by the median Date of an Accumulated Percentage (k = 10, 20, . . . ,90) of the annual rainfall (in days, since 1st of July on the southern stations or 1st of February on the northern ones). For example, DAP(10) is the date when 10% of the annual rainfall was accumulated. Therefore, DAP(50) , is the date of the middle of the season, or the date on which half of the annual rainfall was accumulated. 3. RSL – Rainy Season Length [days] from the date when 10% of the annual rainfall amount until the date of 90% were accumulated, RSL=DAP(90)−DAP(10) . The next two MERR parameters deal with rain-spells: 4. NRS(d) – The Number of Rain-spells of a given duration [days], and their Relative Contribution. Dividing TOTAL(d) by NRS(d) yields: TOTAL(d)/NRS(d) =RSY(d) 5. RSY(d) - Rain-spell Yield [mm]. The average rainfall accumulated during all rainspells of a given duration [days] and their daily amount- RSY/day.

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The following ratios are used to analyze extreme values of rain-spells: 6. AMED(d) − A ratio between the average rainfall of a given rain-spell length and its median [mm] ratio. AMED(d) =(Average(d)−Median(d) )× 100/Median(d). For a symmetrical distribution this parameter equals 0. High values of this ratio indicate a positively skewed distribution caused by few extreme cases. 7. 50%P/50%S(d) − A ratio between the 50% of Precipitation and the 50% of rainspells of a given length. A perfect fit, when this ratio equals 1, indicates that all rain-spells yield exactly the same amount of rain. High values of this ratio imply that a very small number of rain days contribute most of the rainfall. This parameter deals with dry spells: 8. DSD(j,r,p) − Dry Spells Distribution calculates the time [days] elapsed from the last rainy day. A dry spell is calculated for each Julian day for any given daily rainfall threshold and any desired probability. The following examples from Valencia and Larnaca reflect the variety of MERR parameters and the extent of the uncertainties demonstrated by the extreme values. It should be made clear that similar analyses were obtained also in other stations.

3 Results and Discussion The TOTAL in Valencia is 430.5 mm; the maximum value recorded in the research period was 879.4 mm, measured in 1989/1990 and is nearly 7 times higher than the minimum, 126.2 mm in 1954/1955. The TOTAL in Larnaca is 328.5 mm; the max rainfall amount, 629.4 mm in 1991/1992, is 4.5 times higher than the min amount recorded in 1972/1973, 138.4 mm (Fig. 2). In Valencia, 90% of the annual rainfall was accumulated as early as 26th of November in 1982, a month earlier than the date when only 10% of the annual Larnaca - Accumulated Rainfall per Year [TOTAL] - 1947 - 1999 900

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rainfall was accumulated in 1981 (26 of December). This reflects the inconsistency of the temporal distribution within the rainy season. In Larnaca, the earliest date on which 90% of the annual rainfall was accumulated was on the 1st of February 1985, while the latest date of accumulating 10% of the annual rainfall was 25th of December 1980. (Fig. 3). As said above, the RSL is defined as the time [days] elapsed from the accumulation of 10% of the annual rainfall until 90% is accumulated. Therefore, the median RSL in Valencia consists 221 days (7 months). The shortest season was 1969/1970 and consisted only 94 days. On the other hand, the longest rainy season (1954/1955) is 1.5 times the median (344 days) and 3.6 times the shortest season. In Larnaca, the median rainy season consists only 130 days (4.3 months). Consequently, 80% of the precipitation in Larnaca is concentrated in a very short period of time, compared to Valencia. The difference between the shortest season (91 days in 1977/1978) and the longest season (207 days in 1985/1986) is smaller compared with Valencia (ratio of 2.2 compared with 3.6) (Fig. 4). Another example deals with the contributions of the rain-spells. As expected, the NRS decreases as the rain-spell length increases. The median NRS/yr of all durations sums up to 27 rain-spells in Valencia, and 23 in Larnaca. Note that the NRS/yr of 1 day in both stations is extremely high (Fig. 5). Larnaca - Time Series of DAP's - 1947 – 1999 26/06

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Valencia - RSY/day - 1938 – 2004

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Fig. 7 Distribution of RSY and RSY/day for Larnaca

The RSY and the RSY/day are differently distributed compared with the NRS. That is to say, i.e. the longer the rain-spell is, the greater its yield (Figs. 6 and 7). The major differences between these two stations are in the distributions and extreme events of the rain-spells. In Valencia, rain-spells of 2 days, for example, contribute almost 29% of the total annual rainfall (Fig. 8). During the analysis period, 436 rain-spells of 2 days were recorded. 9 cases yielded over 100 mm, one of them yielded the extreme amount of 285.3 mm, whereas more than 400 two-day

Extreme Rainfall Events and Uncertainty in the Mediterranean Basin Valencia - Relative Contribution - 1938 – 2004

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0.0

1 2 3 4 5 6 7 8 9 101112131415 1617181920 21222324 2526 27282930 3132333435

0.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.00.0

1

3

5

7

9

11 13

15 17

19 21 1

23 25 27

29 31

33 35

Rainspell Length (days)

Rainspell Length (days)

Fig. 8 Relative contribution for Valencia and Larnaca

200 150 100

1 NRS 1

2

3

250 Rainfall (mm)

Rainfall (mm)

2

NRS 2

S

R

N

250

NRS 3

300

Larnaca - Rainspell Distribution - 1947 – 1999 300

NRS 11

NRS 3

Valencia - Rainspell Distribution - 1938 – 2004

200 150 100 50

50 0

0 0

200

400 600 800 1000 1200 1400 Total Number of Rainspells

NRS 1

NRS 2

0

NRS 3

200

400 600 800 1000 1200 1400 Total Number of Rainspells

NRS 1

NRS 2

NRS 3

Fig. 9 Rain-spells distribution for Valencia and Larnaca

rain-spells yielded less than 50 mm (Fig. 9). Similarly, in Larnaca, rain-spells of 2 days contribute 30% of the annual rain (Fig. 8), but their distribution is much smaller i.e. 299 out of 306 two-day rain-spells recorded during the analysis period, yielded less then 50 mm. There are two events with more than 70 mm and one of 100 mm (Fig. 9). Thus, in Valencia, the precipitation of rain-spells of 2 days is more diverse compared with Larnaca, where the precipitation is more constant. These extreme distributions can be demonstrated also in another way. In Valencia, 50% of the total precipitation accumulated by rain-spells of 2 days, were produced by 82.2% of the rain-spells, whereas, the remaining 50% by only 17.8% of the events. On the other hand, 50% of the rain-spells of 2 days produced 18.2% of the rainfall amount while the remaining 50% of the rain-spells yielded 81.8% of the rain. Consequently, the 50%P/50%S ratio is 4.5 (Table 1). In Larnaca, the proportions between the precipitation and the rain-spells are more constant, so this ratio is smaller, only 3.6 (Table 1). Figure 10 demonstrates the relations between the precipitation percentage and the rain-spells of 1, 2 and 3 days. As the rain-spells’ durations get longer this ratio gets even more skewded.

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Table 1 50%P, 50%S, and their ratio for rain-spells of 2 days for Valencia and Larnaca

100 90 80 70 60 50 40 30 20 10 0

50%S

Ratio: 50%P/50%S

82.2 77.5

18.2 21.7

4.5 3.6

Valencia - Percipitartion % & Rain Spells % Relationships for 1, 2, 3, Days − 1938− 2004

Larnaca - Percipitation % & Rain Spells % Relationships for 1, 2, 3, Days - 1947 - 1999

%Rainfa ll

%Rainfa ll

Valencia Larnaca

50%P

0

10 20 30 40 50 60 70 80 90 100 NRS 1 NRS 2 NRS 3 %Days

100 90 80 70 60 50 40 30 20 10 0

0

10 20 30 40 50 60 70 80 90 100 %Days NRS 1 NRS 2 NRS 3

Fig. 10 Precipitation % and rain-spells % relationship for rain-spells of 1, 2, 3 days for Valencia and Larnaca

The last parameter that emphasizes the differences between these two rainfall regimes, in Valencia and in Larnaca, and their extreme values, is the annual course of the dry spells. In Valencia, the dry period is between June and September, however, there are still some sporadic rains. Larnaca has a longer and rainless dry period that lasts throughout the summer, from May until late September. In this sense, the definition of the Mediterranean climate is suited to Larnaca more than to Valencia (Fig. 11). Extreme values are evident also when the distribution of dry spells is analyzed. The longest dry spell recorded in Valencia during the analysis period, consisted 119 days, from 21st of June until 27th of October 1977. This duration is 30 times longer than the median dry spell duration, in the same period, that lasts for Larnaca - Annual Course of Dry Spells - 1947 – 1999

140

140

120

120

100

100 Dry spells (days)

Dry spells (days)

Valencia - Annual Course of Dry Spells - 1938 – 2004

80 60

80 60 40

40

20

20

0

0 01.07

01.08

01.09 01.10

01.11 01.12

01.01

01.02 01.03

01.04 01.05 01.06

01.07 01.08 01.09 01.10 01.11 01.12 01.01 01.02 01.03 01.04 01.05 01.06

Dates

Fig. 11 The annual course of the dry spells in Valencia and Larnaca

Dates

Extreme Rainfall Events and Uncertainty in the Mediterranean Basin

1447

only 26 days. In Larnaca, the longest dry period consisted 200 days, from 29th of April until the 14th of November 1977. This dry spell is 1.6 times longer then the median one, in the same period, which lasted 125 days. These parameters mentioned above demonstrate that the two so-called Mediterranean stations, Valencia and Larnaca, have a different rainfall regime, although they are both classified under the same climatic definition. In addition, from the observation of the extreme values in different parameters of the MERR one can detect that Valencia has a more extreme rainfall regime compared to that in Larnaca.

4 Conclusions The parameters, that compose the Most Expectable Rainfall Regime, are a useful tool to understand the different rainfall regimes in a region. The classic definition of a Mediterranean climate limits the ability to track minor changes in the rainfall regime, while the details that these parameters present, show the diversity. According to the MERR, the two Mediterranean climate stations show different distributions in some of the parameters. In Valencia, the rainfall regime has an extreme character; the rainy season’s precipitation can be 7 times higher or 0.3 smaller than the TOTAL. It can be 1.5 times longer or 2.3 times shorter than the median RSL and very inconsistent in its temporal distribution. The distribution of the rain-spells is very skewed; the precipitation of a rain-spell of 2 days, for example, can be as little as 2.4 mm or as much as 285.3 mm and the ratio, between the rain-spells’ precipitation and their occurrences, is high. Finally, the distribution of a dry spell can be up to 30 times longer than the median one. In Larnaca, the rainfall regime is less extreme; the rainy season’s precipitation can be 1.9 times higher or 0.4 smaller than the TOTAL. It can have a RSL of 1.5 times more or 0.7 times less than the median and it has more consistent temporal distribution. The distribution of the rain-spells is more constant; the accumulation rainfall in a 2 days rain-spell, for example, can range between 2.5 and 100 mm; the ratio between the rain-spells’ precipitation and the amount of the 2-day rain-spells is not as high. Eventually, a dry spell distribution is only 1.6 times longer than the median one. Larnaca demonstrates a typical Mediterranean rainfall regime. In Valencia conditions are much more extreme and therefore the uncertainty is higher than in Larnaca.

References 1. Alpert P, Ben-Gai T, Baharad A, Benjamini Y, Yekutieli D, Colacino M, Diodato L, Ramis C, Homar V, Romero R, Michaelides S, Manes A (2002) The paradoxical increase of Mediterranean extreme daily rainfall in spite of decrease in total values. Geophys Res Lett 29:1–4

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2. Anagnostopoulou C, Maheras P, Karacostas T, Vafiadis M (2003) Spatial and temporal analysis of dry spells in Greece. Theor Appl Climatol 74:77–91 3. Aviad Y, Kutiel H, Lavee H (2004) Analysis of beginning, end, and length of the rainy season along a Mediterranean- Arid climate transect for geomorphic purposes. J Arid Environ 59:189–204 4. Ceballos A, Martínez-Fernández J, Luengo-Ugidos MÁ (2004) Analysis of rainfall trends and dry periods on a pluviometric gradient representative of Mediterranean climate in the Duero Basin, Spain. J Arid Environ 58:215–233 5. Esteban-Parra MJ, Rodrigo FS, Castro-Diez Y (1998) Spatial and temporal of precipitation in Spain for the period 1880–1992. Int J Climatol 18:1557–1574 6. Gonzalez-Hidalgo JC, De-Luis M, Raventós J, Sánchez JR (2001) Spatial distribution of seasonal rainfall trends in a Western Mediterranean area. Int J Climatol 21:843–860 7. Houssos EE, Bartzokas A (2006) Extreme precipitation events in NW Greece. Adv Geosci 7:91–96 8. Klein T et al (2004) Online. http://www.knmi.nl/samenw. 13 March, 2006 9. Kutiel H (1985) The multimodality of the rainfall course in Israel, as reflected by the distribution of dry spells. Arch Meteorol Geophys Bioclimatol 36:15–27 10. Maheras P, Anagnostopoulou C (2003) Circulation types and their influence on the interannual variability and precipitation changes in Greece. In: Bolle JH (ed) Mediterranean climate. Springer, Germany, pp. 215–239 11. Martin-Vide J. Gomez L (1999) Regionalization of peninsular Spain based on the length of dry spells. J Climatol 19:537–555 12. Norrant C, Douguédoit A (2005) Monthly and daily precipitation trends in the Mediterranean (1950–2000). Theor Appl Climatol 83:89–106 13. Palutikof JP, Wigley TML (1992) Developing climate change scenarios for the Mediterranean region. In: Jeftic L, Keˇckeš S, Pernetta JC (eds) Climatic change and the Mediterranean. Edward Arnold, London, pp 27–54 14. Paz S, Kutiel H (2003) Rainfall regime uncertainty (RRU) in an Eastern Mediterranean region a methodological approach. Isr J Earth Sci 52:47–63 15. Reiser H, Kutiel H (2006) Rainfall uncertainty in the Mediterranean: 1-Definition of the rainy season. Theoretical and Applied Climatology 94(1):35–49 16. Steinberger EH, Gazit-Yaari N (1996) Recent changes in the spatial distribution of annual precipitation in Israel. J Climate 9:3328–3336 17. Tomozeiu R, Lazzeri M, Cacciamani C (2002) Precipitation fluctuations during the winter season from 1960 to 1995 over Emilia–Romagana, Italy. Theor Appl Climatol 72:221–229 18. Türke¸s M (1996) Spatial and temporal analysis of rainfall variations in Turkey. Int J Climatol 16:1057–1076 19. Wigley TML (1992) Future climate of the Mediterranean basin with particular emphasis on changes in precipitation. In: Jefitic L, Milliman JD, Sestini G (eds) Climatic changes and the Mediterranean. Edward Arnold, London, pp 15–42

Part IX

Pesticides in the Environment and Food Commodities

An Investigation of Pesticide Transport in Soil and Groundwater in the Most Vulnerable Site of Bangladesh Anika Yunus and A.H.M. Faisal Anwar

Abstract We investigate the behaviour and fate of pesticides in soil and groundwater in one of the most vulnerable site of Bangladesh, name Rangpur sadar thana. Leaching Potential Index (LPI) of sixty nine sites is calculated and one most vulnerable site is selected. Six soil samples are collected from different depths of soil and analysed for pesticide residues using Gas Chromatograph (GC) and High Performance Liquid Chromatograph (HPLC). Tests are carried out for most recently used pesticide fenitrothion as well as other pesticides of organophosphorous, carbamate and organochlorine group. No peak is detected in chromatograms which resembles to the retention time of these pesticides. The transport behaviour of pesticides for the chosen site is also investigated by MODFLOW to forecast on the contamination potential of different pesticides. Simulation results reveal that low persistent pesticides fenitrothion and malathion are environment friendly, as percentage remaining is very small in different depths. In contrast diazinon, chlorpyrifos, cypermethrin of organophosphorous; carbofuran and carbaryl of carbamate; and heptachlor and endosulfan of organochlorine pesticides could reach groundwater because their percentage remaining in the groundwater level is high. However, this study revealed that due to the general use of low persistent organophosphorous pesticides there is no significant contamination in soil and groundwater of Rangpur sadar thana. Keywords Contamination · Groundwater · Pesticide

1 Introduction The quality of groundwater is very important factor for agriculture, domestic, municipal and industrial uses. Soil and groundwater pollution by pesticides resides a major environmental concern due to extensive use in agriculture and public health. A. Yunus (B) Department of Water Resources Engineering, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_136,

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The potential of pesticides to contaminate groundwater depends on a number of soil and pesticides properties that affect the mobility and persistence of the pesticides in the soil environment [20, 22]. It has been reported that pesticide residues from nonpoint sources have the potential to contaminate groundwater [6, 7]. As a result there has been a significant concern about pesticide contamination in soil and groundwater in recent years [2–4, 17]. Barlas et al. [5] analysed water and sediment samples collected from the Uluabat Lake, Turkey. It was found that the Uluabat Lake was contaminated by organochlorine pesticides and their residues were more accumulated in sediment samples. Singh [21] determined organochlorine pesticides residues in soil and groundwater samples collected from different locations of Agra, India. The results showed that the concentration of α-BHC, DDT, α-Endosulfan, aldrin was much higher than the limit specified by WHO (World Health Organisation) at almost all locations. Pesticide fate and transport in soil and groundwater have also been studied by various analytical and numerical models during the last three decades [8, 10, 19]. Bangladesh is an agricultural country and has been using pesticides since 1950 where insecticides constitute more than 90% of the consumption of pesticides. Due to ignorance and low literacy rate (10% rural literacy) farmers in Bangladesh depend quite heavily on variety of pesticides to control pest with other agricultural inputs. Talukder [24] reported that different insecticides in Bangladesh are generally three classes; organophosphorous, carbamate and organochlorine. Gain [9] reported that a huge quantity of inferior quality Indian pesticides is smuggled into Bangladesh from markets bordering India. While extremely hazardous pesticides, namely “Dirty Dozen” organochlorines are prohibited in Bangladesh, because of high illiteracy, farmers sometimes use these hazardous pesticides. As a result it is suspected that soil and ground water contamination might have arisen from deep percolation under irrigated areas in Bangladesh as well. There have been no reports to date on the possible contamination of organophosphorus, carbamate and in particular organochlorine pesticides as they leach to the greater depth of soil in the terrains of high pesticide use in Bangladesh. In this paper we report the behaviour and fate of different pesticides in different depth of soil and groundwater in one of the most vulnerable site of Bangladesh. Rangpur sadar thana is chosen as the study area because of having relatively shallow unconfined aquifers, high pesticide use, and availability of study support materials. Gas Chromatograph (GC) and High Performance Liquid Chromatograph (HPLC) observations of collected soils from different depths show no peak which resembles to the retention time of organochlorine as well as carbamate and organophosphorous pesticides. A simulation of the transport behaviour of these pesticides is also performed by invoking the physical properties of the soil, chemical properties and recommended dose of the different pesticides at the chosen site. It is found that there is no significant contamination in soil and groundwater of Rangpur sadar thana from organochlorine as well as other pesticides.

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2 Material and Methods 2.1 LPI Methodology Information on the soil characteristics of Rangpur sadar thana is taken from a report of the Physical Properties of Soil and the Teesta River Flood Plain and Barind Tract of Bangladesh [12]. Depending on soil characteristics, Rangpur sadar thana is divided into sixty nine sites and the susceptibility of groundwater contamination by pesticide leaching in each site is evaluated by calculating Leaching Potential Index (LPI), [15]. LPI =

1000 V Rλz

(1)

where, V = soil water velocity, R = retardation factor, λ = decay rate and z = groundwater depth. The soil water velocity is obtained by dividing the recharge rate by the field capacity of the soil. The recharge rate is taken as the annual fluctuation in the depth of groundwater table [13]. Depth of groundwater is taken from the observation-well data in Rangpur sadar thana. The percent organic matter at sixty nine sites of this thana are extracted from Land and Soil Resources Use Guidebook [23]. Percent organic carbon content is calculated as 0.5263 times of percent organic matter for a specific site [16]. Based on higher LPI values, one most vulnerable site is chosen.

2.2 Soil Sampling Procedure and Analysis Six soil samples are collected from the ground surface and 5 feet, 10 feet, 15 feet, 20 feet, and 25 feet below the surface on 1st June 2004. Samples are collected in a 500 gram pre-cleaned glass bottles, dried and extracted with n-hexane in a Soxhlet for 4 hours. The extracts are cleaned up with florisil and dried fully by N2 gas blower. Concentration of organophosphorous and carbamate pesticide is measured using High performance Liquid Chromatograph (HPLC) with Ultra Violet detector and Gas Chromatograph (GC) with Electron Capture Detector is used for determining the concentration of organochlorine pesticides.

2.3 Application of MODFLOW To forecast on the contamination potential of different pesticides in Rangpur sadar thana, the transport behaviour of pesticides is simulated by the groundwater flow and transport modelling system MODFLOW [14]. The solute transport program

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A. Yunus and A.H.M.F. Anwar Table 1 The physical properties of soil in the most vulnerable Site

Soil type

Sandy loam

Sandy loam

Loam

Loam

Sand

Layer (feet) Field capacity, θ (cm3 /cm3 ) Hydraulic conductivityK(m/day) Bulk density, ρb (Kg/m3 )

1(0–5) 0.4025 0.372 1350

2(5–10) 0.42 0.372 1410

3(10–15) 0.41 0.0127 1390

4(15–20) 0.41 0.0127 1310

5(20–25) 0.42 1.15 1270

MT3D [25] is used to investigate the remaining percentage of different pesticides at different depth of soil after 2 months period. The chosen site is divided into five layers and physical properties of the soil, chemical properties and recommended dose of different pesticides are invoked in the MT3D program. Table 1 shows physical properties of the soil in different depths of the chosen site [12]. Chemical properties of different pesticides are available in the literature [10, 11, 18, 19] and presented in Table 2. Recommended dose of various pesticides are taken from Department of Agricultural Extension (DAE), Rangpur sadar thana.

3 Results and Discussion 3.1 Estimation of LPI Organophosphorous (Diazinon, Chlorpyrifos, Cypermethrin, Fenitrothion and Malathion), carbamate (Carbofuran and Carbaryl) and organochlorine (Heptachlor and Endosulfan) pesticides are chosen to compute LPI for sixty nine sites. The numerical ranks of computed LPI for these pesticides are grouped by quantiles into very high, high, moderate, low and very low categories as presented in Table 3. This categorization is designed to facilitate the identification of areas susceptible to groundwater contamination in the study area. The assigned leaching category and quantiles and number of sections in the study area in each category are also presented in Table 3. Of the 69 sites, 7 are ranked very high, 9 are high, 21 are moderate, 21 are low and 11 are very low. Based on this ranking, one site from the very highly susceptible category is selected.

3.2 Pesticide Residue Analysis Figure 1 shows standard chromatograms for known organophosphorous and carbamate pesticides. The retention time of diazinon, cypermethrin, malathion, carbaryl, carbofuran, fenitrothion, and chlorpyrifos is found to be 0.105, 0.132, 1.808, 2.451, 3.705, 4.5, and 5.095 minutes respectively. So from standard chromatogram it can be said that organophosphorous and carbamate pesticides can be detected before retention time of 6 minutes. Figure 2 shows the HPLC results of soil samples collected from the surface and from 5 feet (below groundwater level), and 25 feet below the surface. Comparing the test results (Fig. 2) with the standard chromatogram (Fig. 1)

6070

30 2 ml/l

Diazinon

1000

40 2 ml/l

Chemical name

Organic carbon partition coefficient, KOC (cm3 /g) Half life, t1/2 (days) Recommended dose 1 2 ml/l

1800

Chlorpyrifos Malathion

Values for pesticides

Parameters

30 1.7 ml/l

100000 8 2 ml/l

2000

10 3.44 g/l

300

Cypermethrin Fenitrothion Carbaryl

Table 2 Chemical properties of different pesticides

50 0.99 g/m2

22

Carbofuran

250 0.2 g/m2

24000

Heptachlor

50 10 μg/l

12400

Endosulfan

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A. Yunus and A.H.M.F. Anwar Table 3 LPI distributions of different pesticides for the study area

LPI category

Very high

High

Moderate

Quantile range Diazinon Malathion

Fenitrothion

≥ 90 0.47–1.27 0.00066– 0.00177 0.059–0.16 0.0036– 0.0096 0.047–0.1274

75–90 0.3–0.47 0.00042– 0.00066 0.038–0.059 0.0023– 0.0036 0.03–0.047

50–75 0.16–0.3 0.00022– 0.00042 0.0197–0.038 0.0012– 0.0023 0.01596–0.03

Carbofuran Carbaryl

24.55–57.8 0.392–1.05

16.05–24.55 0.252–0.392

Heptachlor Endosulfan No. of section Percent of study area

0.12–0.33 0.053–0.129 7 10

0.08–0.12 0.032–0.053 9 13

Chlorpyrifos Cypermethrin

Low

25–50 0.08–0.16 0.00011– 0.00022 0.01–0.0197 0.00061– 0.0012 0.0081– 0.01596 8.79–16.05 4.51–8.79 0.1327–0.252 0.0674– 0.1327 0.04–0.08 0.02–0.04 0.024–0.032 0.009–0.024 21 21 30 30

Very low ≤2 5 0.033–0.08 0.0000458– 0.00011 0.004–0.01 0.000247– 0.00061 0.0033– 0.0081 1.86–4.51 0.0274– 0.0674 0.009–0.02 0.0033–0.009 11 16

Fig. 1 High performance liquid chromatogram of standard organophosphorus and carbamate pesticides

it is found that none of the pesticides of this group are present in the samples. In general organophosphorous and carbamate pesticides degrade very rapidly in the natural environment because of their low to moderate persistence. In the field survey, it is found that low persistent organophosphorous pesticides are usually used in Rangpur sadar thana and Sumithion (50 EC), chemical group of fenitrothion was applied on that site 2 months before the soil sample collection. As fenitrothion is a

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Fig. 2 High performance liquid chromatograms for soil samples collected from (a) surface, (b) 5 feet and (c) 25 feet below the surface

low persistent organophosphorous insecticide, it might be degraded or washed out during 2 months period. That is why there is no trace of fenitrothion as well as other organophosphorous and carbamate pesticides in the test results. Similar results are found for samples collected from 10 feet, 15 feet and 20 feet below the surface. Figure 3 shows the standard chromatogram for “Dirty Dozen” organochlorine pesticides by Gas Chromatograph (GC). The retention time of different pesticides can be found from this figure and is presented in the figure inset. Figure 4a–e show chromatograms of soil samples collected from the surface and 5 feet (below groundwater level), 10 feet, 20 feet and 25 feet below the surface. No peak is detected which corresponds to any known organochlorine pesticides. For samples collected from the surface and 5 feet, 10 feet, 20 feet and 25 feet below the surface as shown in Fig. 4a– e, a peak is found at around 2.5 minutes retention time which does not resemble to any one of the tested organochlorine pesticides. This peak corresponds to the retention time of hexane, the solvent used in the test which is shown in Fig. 4 f. For samples collected from 20 feet and 25 feet below the surface as shown in Fig. 4d and e another peak is detected at around 12.422 minutes retention time and a peak can also be found at around 19.404 minutes retention time for samples collected from the surface (Fig. 4a) which also do not correspond to the retention time of any one of the tested organochlorine pesticides. These can be attributed to unknown living organisms undergoing reactions. Contaminants entering living organisms undergo metabolic alternations by enzyme systems [1]. These alternations, which use a series of biochemical processes, give rise to compounds and hence unknown peaks are

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Fig. 3 Gas Chromatogram of standard organochlorine pesticides

Fig. 4 Gas chromatograms of soil samples collected from (a) surface, (b) 5 feet, (c) 10 feet, (d) 20 feet, (e) 25 feet below the surface. The chromatogram of used solvent Hexane is presented in Fig. 4(f)

found in the chromatogram. In summary, the results of Fig. 4a–e imply that there is no contamination in different depths of soil by organochlorine pesticides in Rangpur sadar thana. Similar result is also found for the sample collected from 15 feet below the surface.

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3.3 Simulation Results Figure 5 illustrates the simulation result of MODFLOW showing the remaining percentage of fenitrothion and diazinon in different depths of soil after 2 months where the groundwater level is around 1.35 meter from the surface. For fenitrothion as shown in Fig. 5 (a), it can be observed that a very negligible amount (<2×10−4%) remain in the surface and different depths of soil. As it is a low persistent pesticide with half-life of 8 days (Table 2), it breaks down completely within 2 months and hence percentage remaining is very small. Similar result is also found for malathion of organophosphorous group indicating that low persistent pesticides like malathion and fenitrothion (half life < 10 days) have no contamination possibility for Rangpur sadar thana. For diazinon as shown in Fig. 5 (b) around 24% and 7% remain in the surface and groundwater level respectively. As diazinon has a similar recommended dose of fenitrothionin (Table 2), these results imply that diazinon has more contamination potential than that of fenitrothion. Simulation is also done for chlorpyrifos, cypermethrin of organophosphorous; carbofuran, carbaryl of carbamate; and heptachlor, endosulfan of organochlorine group. Table 4 summarizes the result. From Table 2 and 4, it can be seen that significant amount of pesticides remain both in surface (≥24%) and ground water level (≥ 5%) for pesticides with high persistence (>30 days). As a result these pesticides have the potential of transporting into the groundwater level and hence, have the possibility of groundwater contamination. However this would also depend on the sorptivity of pesticides and the groundwater depth. In general high sorptivity pesticides have the characteristics to be confined within the surface level and hence extensive use of low sorptivity and high persistence pesticides would be expected to have more contamination potential for groundwater than that of high sorptivity pesticides with a similar persistence. As a result even though there is a possibility of using hazardous organochlorines, general habit of using low persistent organophosphorous pesticides explains the absence of peak in chromatograms for Rangpur sadar thana.

Fig. 5 Remaining percentage of fenitrothion and diazinon in different depths of soil after 2 months

Diazinon

24 7

Chemical Name

Surface (meter) Groundwater level (meter)

15 2.5

Chlorpyrifos

Remaining percentage of different pesticides (%) Cypermethrin 15 2.2

Malathion 1×10−23 <1×10−23

1.25×10−4 <6×10−5

Fenitrothion 0.33 0.05

Carbaryl

Table 4 Remaining percentage of different pesticides after 2 months

33 6

Carbofuran

86 20

Heptachlor

33 5

Endosulfan

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4 Conclusion We have investigated the behaviour and fate of pesticides in soil and groundwater in one of the most vulnerable site of Bangladesh, name Rangpur sadar thana. The GC and HPLC observations of collected soils from different depths showed no peak which resembles to the retention time of organochlorine as well as carbamate and organophosphorous pesticides. From the experimental and modelling results it is revealed that possibility of contamination of soil and groundwater from malathion and fenitrothion is very low unless heavy rain and irrigation occur soon after pesticide application. Model results also showed that diazinon, chlorpyrifos, cypermethrin, of organophosphorous; carbofuran and carbaryl of carbamate; and heptachlor and endosulfan of organochlorine pesticides could contaminate groundwater because of having potential of transporting into the groundwater level. Based on this study, no significant contamination in the soil and groundwater of Rangpur sadar thana is expected due to the conventional use of low persistent organophosphorus pesticides. Acknowledgement The authors acknowledge the support from Soil Resources Development Institute (SRDI), Department of Agriculture Extension (DAE), and Atomic Energy Commission of Bangladesh for conducting this research.

References 1. Alexander M (1977) Introduction to soil microbiology. Wiley, New York 2. Ayaˆs Z, Barlas NE, Kolankaya D (1997) Determination of organochlorine pesticide residues in various environments and organisms in Göksu delta, Turkey. Aquat Toxicol 39:171–181 3. Badach H, Nazimek T, Kaminski R, Turski WA (2000) Organochlorine pesticide concentration in the drinking water from regions of extensive agriculture in Polland. Ann Agric Environ Med 7:25–28 4. Barlas NE (2002) Determination of organochlorine pesticide residues in water and sediment samples in inner anatolia in Turkey. Bull Environ Contam Toxicol 69:236–242 5. Barlas NE, Cok I, Akbulut N (2006) The contamination levels of organochlorine pesticides in water and sediment samples in Uluabat lake, Turkey. Environ Monit Assess 118(1–3): 383–391 6. Beitz H, Schmidt H, Herzel F (1994) Occurrence, toxicological and ecotoxicological significance of pesticides in groundwater and surface water. In: Borner H (ed) Pesticides in groundwater and surface water. Chemistry of plant protection, vol 9. Springer, Berlin, pp 1–56 7. Cohen SZ, Eiden C, Lorber MN (1986) Monitoring groundwater for pesticides. ACS Symp Ser 315:170–196 8. Di HJ, Kookana RS, Aylmore LAG (1995) Application of a simple model to assess the groundwater contamination potential of pesticides. Aust J Soil Res 33:1031–1040 9. Gain P (1993) State of pesticide Business and use in Bangladesh. An investigation report of society for environment and human development. The Report was partially financed by Proshika, Dhaka, February, 1993 10. Hantush MM, Marino MA, Islam MR (2000) Models for leaching of pesticides in soil and groundwater. J Hydrol 227:66–83 11. Hornsby AG (1995) How contaminants reach groundwater. Soil science fact sheet, SL-48, Institute of Food and Agriculture Sciences, University of Florida, Gainesville, FL

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12. Joshua WD, Rahman M (1983) Physical properties of soils on the Teesta river floodplain and barind tract of Bangladesh. Soil Research and Development Institute, Dhaka 13. Karim MA (1984) Upazilla-wise groundwater recharge conditions of Bangladesh. Groundwater Investigation Circle, Bangladesh Water Development Board, Dhaka, May, 1984 14. McDonald MG, Harbaugh AW (1988) A modular three-dimensional finite difference ground water flow model, book 6, chap A1. USGS 15. Meeks YJ, Dean JD (1990) Evaluating groundwater vulnerability to pesticides. J Water Resour Plann Manage 116(5):693–707 16. Mercer JW, Waddell RK (1992) Contaminant transport in groundwater . In: Maidmaint DR (ed) Handbook of hydrology, chap 6. McGraw Hill, New York 17. Mukherjee I, Gopal M (2001) Organochlorine insecticide residues in drinking and ground water in and around Delhi. Environ Monit Assess 76:185–193 18. Olesen T, Gamst J, Moldup P, Komatsu T, Rolston DE (2001) Diffusion of sorbing organic chemicals in the liquid and gaseous phases of repacked soil. Soil Sci Soc Am J 65:1585–1593 19. Pang XP, Letey J (1998) Pesticide leaching sensitivity to irrigation, salinity and N application: model simulation. Soil Sci J 164:922–929 20. Pennel KD, Hornsby AG, Jessup RE, Rao PSC (1990) Evaluation of five simulation models for predictiong aldicarb and bromide behavior under field conditions. Water Resour Res 26:2679–2693 21. Singh RP (2001) Comparison of organochlorine pesticide levels in soil and groundwater of Agra, India. Bull Environ Contam Toxicol 67;126–132 22. Singh R, Gerritse RG, Aylmore LAG (1989) Adsorption-desorption behavior of selected pesticides in some Western Australian soils. Aust J Soil Res 28:227–243 23. Soil Resources and Development Institute (SRDI) (1990) Land and soil resources use guidebook. Rangpur Sadar Thana, Rangpur District. Ministry of Agriculture, Published by Government of Bangladesh 24. Talukder ABMA (1995) Use of insecticides in agricultural production. Sachitra, Bangladesh, pp 34–36, 16th October,1995 25. Zheng C (1992) MT3D: a modular three-dimensional model for simulation of advection, dispersion, and chemical reactions of contaminants in ground water systems, version 1.5. S.S. Papadopulos and Associates, Bethesda, MD

Conservation of Beneficial Insects for Sustainable Agriculture M. Anjum Suhail, M. Arshad, Jalal Arif, and M. Dildar Gogi

Abstract Insects are the most diverse group of organisms and are 3/4th of all described forms of life. Potentially they are highly indicative of environmental change through close adaptation to their environment. Migratory insect species are at the verge of extinction owing to increasing trend in global warming. Insect fauna also represent the majority of links in the community food chain and they likely have the largest biomass of the terrestrial animals. While the positive values of the insect fauna is remarkably more than that of their negative values. They act as pollinators and bio-control agents in the agro-ecosystem and have batter impact for the development of sustainable agriculture. Thus, knowledge about them is fundamental to study the environment. One to three million insects species are identified worldwide while 2,000 from Pakistan. Out of which more than 954 species from 10 orders are identified/explored by the “Insect Biodiversity and Biosystematics Lab”, Department of Agri-Entomology, University of Agriculture, Faisalabad, Pakistan. Of the described species in the order Orthoptera (Grasshoppers, Crickets, 279), Odonata (Dragonflies, 130), Lepidoptera (Moths and Butterflies, 82), Diptera (Syrphids, Fruitflies, Clypterate species 187), Homoptera (Aphids, Whiteflies, 65), Thysanoptera (Thrips, 52), Neuroptera (Antlion, Chrysopids, 42), Dictyoptera (Mantids, 32), Hemiptera (Reduviid & Anthocorid Bugs, 11) and Hymenoptera (Braconids, 17). The abundance of bee forage plants throughout the year determines the growth of honey bee colonies and hence the productivity of bee farming. Pakistan is endowed with more than700 plant species. Out of which entomophilous crops cover 7.3 million hectares of land and forest more than 10 million hectares which can support 0.4–0.5 million honey bee colonies. Despite fairly abundant floral sources and quite suitable climatic conditions for keeping bees in the country, honey production (1000 tonnes) from 3,00,000 colonies is much below to its

M.A. Suhail (B) Department of Agricultural Entomology, Insect Biodiversity and Biosystematics Research Laboratory, University of Agriculture, Faisalabad, Pakistan e-mail: [email protected]

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exploitable potential. All of this work has been completed by students M.Sc/Ph.D theses research and many students are working on different groups of insect fauna and their biodiversity. Eleven species of scrabid beetles (Coleoptera) have been identified recently on molecular level by DNA characterization. Many other identified species specimens, are placed in the departmental insectarium, which are not mentioned in this report. Keywords Agriculture · Insects · Sustainability

1 Introduction The main focus of biodiversity and biosystematics studies are the exploration of insect fauna on different regions (crop, agro-forestry, geographical) of Pakistan; insect faunal richness and evenness and their significance. Studies are also being introduced on the molecular characterization of insects, being conducted to devise better management strategies. Unfortunately, insect fauna always claimed as pest fauna only, otherwise of the total insect fauna, pest constitute only 38% while rest includes beneficial/useful like bio-control agents (Chrysoperla carnea, Coccinella spp, Brumus spp. Bracon spp. Trichogramma spp., Apenteles spp), pollinators, silkworm, scavengers, decomposers, competitor etc. It has been estimated that 140 plants and animal species are lost everyday in the world and loss of one plant means the extinction of 30 insects + other animal species. This awesome situation can only be avoided by strengthen the efforts to explore the insect faunal diversity and to conserve the beneficial insects in the country. Because most of our farmers control the pest insects by using insecticides which are harmful for beneficial insects as well as his own life is under the hazards of insecticidal residues. Now a day’s biological disturbance and loss of biodiversity is one of the major reasons of the insecticidal use. The migratory species of pollinators especially honeybees have been disturbed by the use of such agrochemicals which cause mortality. Pollinators have declined considerably in recent decades in the world [2, 3, 14, 16]. One reason for pollinators decline is linked to the intensification of farming practices, which has resulted in a loss of their habitat. The other one is urbanization, which causes habitat fragmentation and ultimately the surrounding urban matrix influences the remaining habitat patches. This habitat fragmentation impacts species richness and abundance of a wide diversity of taxa. Rare plants tend towards extinction in habitat fragments [15]. The biodiversity of insects are also be changed due to the change of environmental and agro-ecosystem. Biodiversity is a common thread that runs through our work, drawing together scientific disciplines and research collaboration and binding to the farmers they serve. Of course, insect Biodiversity is also a subject of impassioned debate and IBB research group has a seat in the Department, too, contributing to the lively discussion. Out of 30 insect orders only ten orders are incompletely explored in following 700 species

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• 1. Odonata: Out of 130 species 35 species from AJ&K 27 species from Gilgit andBaltistan 20 species from Punjab 14 species from Balochistan 34 species (Zygoptera)from Pakistan. • 2. Orthoptera: Out of 279 species 146 species (Acridoids) from Pakistan. 80 species (Gryllids) from Pakistan. 53 species (Acridides) from AJ&K 03 families need to be explored • 3. Dictyoptera: Out of 32 species 32 species (Mantids) from Punjab Blattids need to be explored. • 4. Hamiptera: Out of 11 species 11 species (reduviids & anthocorids) from Punjab 09 families need to be explored. • 5. Homoptera: Out of 130 species 34 species (Aphids) from Punjab 31 species (Whiteflies) from Punjab. 11 families need to be explored. • 6. Thysanoptera: 52 species from Pakistan • 7. Neuroptera: 42 species from Punjab • 8. Lepidoptera: Out of 82 species 67 species (Butterflies) from Pakistan. 15 species (Sphingids)from Punjab. 09 families need to be explored. • 9. Diptera: Out of 187 species 42 species (Syrphids)from Pakistan. 36 species (fruitflies)from Pakistan. 11 families need to be explored. • 10. Hymenoptera: Out of 130 species 17 species (Braconids) from Punjab. Many families need to be explored. • 11. Coleoptera: 57 species (Scarab beetles) from Punjab. Many families need to be explored.

2 Pollinators Threats to pollinators and the services they provide are perceived to be increasing around the world and are largely man-made in origin. Declines in pollinators have

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been reported in several regions of Europe and same the case is in Pakistan. Some common species of pollinators found in abundant are: 1. 2. 3. 4. 5. 6. 7. 8. 9.

Adrena: Andrena floridula Anthophora: Anthophora confuse, Anthophora niveocincta Apis: Apis dorsata, Apis florae, Apis indica Bombus: Bombus festivus, Bombus flavescens, Bombus eximius Ceratina: Ceratina beata Halictus: Halictus rugolatus Megachile: Megachile hera Melecta: Melecta himalayana, Melecta shakeenae Psithyrus: Psithyrus jafari

3 Entomophagous Insects Ghani [6] reported 11 species of primary parasites and 7 secondary from the Punjab. The important parasites include Apenteles spp., Chelonus spp. Etc. Habib [8] had listed 161 species of parasites, 55 predators and 10 pathogens of Helicoverpa armigera in the world and parasites that were recorded from Pakistan include Netelia ocellaris, Campoletus chlorideae, Apanteles sp., Bracon hebator, Trchogramma chilonis and Exorista xanthaspis etcSurvey of entomophagous insects of scale insect of mango [7, 10] Aphytis melinus (Aphilinidae:Hymenoptera) is reported parasitizing the Aonidiella destructor, Aonidiella orientalis and Aonidiella citrina (Diaspididae; Chilocorus nigritus (Coccinelidae: Coleoptra) is a predator of Aonidiella orientalis and paralatoria sp.(Diaspididae), Cybocephalis semiflavus on Chloropulvinaria sp. (Coccidae), Aonidiella citrina and Aonidiella orientalis from from Murree and Rawalpindi, Pakistan. Cheema et al. [4] recorded twenty-three species of predators from cotton fields in Multan area consisting of four arachnids, ten Coccinellids, Chrysopids, lygaeid, anthocorid and three formicids. Cheema et al. [5] reported about 28 species of parasites and 63 species of the pink bollworm from Pakistan. Habib and Muhyuddin [9] had reported 27 species of parasites in Pakistan. The important parasites reported include Elasmus johnstoni Ferr. (Elasmidae); Bracon greeni Ash., Rogas restaceus Spinola (Braconidae) and Gorryphus nursci Cam. (Ichneumonodae). Mohyuddin and Muhammad [13] reported that the Trichogramma chilonis (Bhii) is a gregarious parasitoid in Pakistan. Mohyuddin et al. [11] listed 11 Aphelinid prasitoids associated to Bemisia tabaci from Pakistan. Out of these, Encarsia spp. C and E, Eretmocerus aligarhensis and E. mundus had been the most commonly associated with Bemisia tabaci. Mohyuddin and Mahmood [12] reported that mango fruit are attacked in central Punjab in July with maximum in August by fruit fly which is parasitised by Ostereslongi caudatus in Pakistan. Survey of parasitoids of fruit flies was carried out Haripur(NWFP), Multan, Sheikhupura and Sargoda(Punjab). Mohyuddin

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and Mahmood [12] reported the survey of entomophagous of leaf hopper the egg Parasitiods Gonatoceus spp.and the adult ecto parasitoid Epipyrops fuliginosa in Pakistan. Attique [1] reported that population dynamics of predators and parasitoids of Bemisia tabaci, Encarsia spp. and Eretmocerus spp. were the most common parasitoids of nymphs and pupae. Predators recorded from the different plant species were Brumoids suturalis (E) Coccinelids, Scymunus spp., Paederus fuscipes Curtis, Chrysoperla carnea Steph., Orius spp., Geocoris spp. and spiders. The collection we made in 2004–2006 and found different numbers of predators and parasitoids i.e., Robber fly, Hover fly, Orius, Assassin bug, Dragonfly, Damselfly, Lady Bird Beetle (Coccinella spp.), Rove beetle, Yellow wasp, Red wasp, Carpenter Ant, Ant, Nabis bug, Menochilus sp., Chrysopa sp., Bracon sp., Cotesia flavipes, Cotesia ruficrus Trichogramma sp. Telenomus sp., Chlaenius sp., Nemorilla maculosa, Brachymeria sp, Chlaenius sp., Apanteles sp., Tachinids, Brumiodes suturalis, Epiricalia melanoleuca, Elasmus sp., Encarsia sp., Eretmocerus sp., Amitus sp. While in laboratory predators., Chrysoperla carnea, Coccinella spp. are being reared for the release against aphids on cotton, maize and wheat, whereas parasitoids Bracon hebector, Trichgramma chilonis are being reared for the control of some lepidopterous pests in cotton, rice, sugarcane crops.

References 1. Attique MR, Rafiq M, Ghaffar Z, Mohyuddin AI (2001) Role of natural enemies for the control of Bemisia tabaci (Gennadius) (Homoptera: Aleyrodidae) in the Punjab. Pak Cottons 44:29–37 2. Banaszak J (1996) Ecological bases of conservation of wild bees. In: Matheson A, Buchmann SL, O’Toole C, Westrich P, Williams IH (eds) The conservation of bees. Academic, London, pp 55–62 3. Buchmann SL, Nabhan GP (1996) The forgotten pollinators. Island Press/Shearwater Books, Washington, DC 4. Cheema MA, Muazaffar N, Ghani MA (1980) Biology, host range and incidence of parasites of Pectinophora gossypiella in Pakistan. Pak Cotton 24:37–73 5. Cheema MA, Muazaffar N, Ghani MA (1980) Investigation on phenology, distribution, host range and evaluation of predators of Pectinophora gossypiella in Pakistan. Pak Cotton 24:139– 176 6. Ghani MA (1960) Sylepta derogata and possibilities of its biological control in Pakistan. Commonwealth Agricultural Bureau, Slough, pp 1–42 7. Ghani MA, Muzaffar N (1974) Relations between the parasites-predators complex and host plants of scale insects in Pakistan. Misc Publ Commonw Inst Biol Control 5:1–92 8. Habib R. (1973) Memorandom on possibilities of biological control of Heliothis armigera (Hb.). Common Inst. Boil Control, Ann. Report, 18 9. Habib R, Mohyuddin AI (1981) Possibilities of biocontrol of some pests of cotton in Pakistan. Biologia 27:107–113 10. Mahmood R, Mohyuddin AI, Kazami SK (1980) Rastrococcus spinosus robinson (Homoptera: Pseudococcidae) and its natural enemies in Pakistan. Proceedings of 1st Pakistan Congress of Zoology, Lahore, Pakistan, pp 291–294

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11. Mohyuddin AI, Khan AG, Goraya AA (1989) Population dynamics of cotton whitefly Bemisia tabaci (Gennadius) (Homoptera: Aleyrodidae) and its natural enemies in Pakistan. Pak J Zool 21(3):273–288 12. Mohyuddin AI, Mahmood R (1993) Integrated control of mango pests in Pakistan. Acta Horticult 341:467–483 13. Mohyuddin AI, Muhammad A (1985) Invasion of Gurdaspur borer Acigona steniellus (Hampson) (Lepidoptera: Pyralidae) in NWFP, Pakistan and its biological control. Proceedings of 21st annual Convention of Pakistan society of sugar technologists, Rawalpindi, pp 82–85, 19–21 September, 1985 14. Rasmont P (1995) How to restore the apoid diversity in Belgium and France? Wrong and right ways, or the end of protection paradigm! In: Banaszak J(ed) Changes in fauna of wild bees in Europe. Pedagogical University, Bydgoszcz, pp 53–64 15. Tscharntke T, Steffan-Dewenter I, Kreuss A, Thies C (2002) Characteristics of insect populations on habitat fragments, amini review. Ecol Res 17:229–239 16. Williams PH (1986) Environmental change and the distribution of British Bumblebees (Bombus Latr.). Bee World 67:50–61

Organochlorine Pesticides in Soil and Sediment from an Urban Zone of Novi Sad, Serbia Nataša Ðuriši´c-Mladenovi´c, Biljana Škrbi´c, and Jelena Cvejanov

Abstract The content of 16 organochlorine pesticides (OCPs) was determined in the surface zone (0–5 cm) of soil and sediment samples, taken from different locations in the city of Novi Sad, capitol of Vojvodina Province (North of the Serbia) covering residential and commercial area, recreational and arable zone. The total organochlorine pesticides concentration in soil varied from 2.63 to 31.78 μg/kg dry matter, while the level in sediment was 10.35 μg/kg dry matter. Maximum content of identified individual organoclorine pesticide in soil samples was 10.40 μg/kg dry matter for p,p-DDE in the market garden and 6.31 μg/kg dry matter for p,p’-DDT in sediment of the Danube River, although their application is restricted in Serbia. Data were compared with the ones found for soils and river sediments throughout the world, and with limit values set by soil and sediment quality guidelines. Also, correlation between the levels of certain pesticides and soil characteristics (organic matter, pH and clay content) was investigated. Keywords Pesticide · Sediment · Soil

1 Introduction Pesticides play a very important role in the control of pests and thus the maintenance of high agricultural production, in mosquito control in tropical countries and against termites. Because of high toxicity of these compounds most industrialized countries have led restrictions on the use of pesticides and regulations in the production, distribution, application and disposal of these chemicals. However, agricultural soils are suspected to be an important emission source of old organochlorine pesticides because of the large quantities that were applied. Although these residues have degraded to some extend, it is likely that a significant portion exists in the soil. These compounds also be washed in run-off from the land into watercourse and

B. Škrbi´c (B) Faculty of Technology, University of Novi Sad, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia e-mail: [email protected] H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_138,

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emitted into atmosphere through volatilization, which indirectly resulted in water and atmospheric contamination. Atmospheric transport may significantly affect the level of pesticides even at locations for away from agricultural regions. According to the Stockholm Convention on Persistent Organic Pollutants nine organochlorine pesticides (aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, mirex, hexachlorobenzene and toxaphene) are scheduled for worldwide elimination. On the basis of literature data, endosulfan and lindane are still in use in the world [1, 7, 20, 23, 28]. Endosulfan, a mixture of α- and β-isomers, is an organochlorine insecticide used for the control of sucking and chewing insects on fruits and vegetables, while lindane is a broad spectrum organochlorine insecticide and fumigant which has been used on a wide range of soil-dwelling and plant eating insects. In Canada, lindane is one of the 10 top insecticides used for protection of livestock, cropseed and poultry [21]. In China, technical HCH was replaced by the purified active isomer γ-HCH (lindane) in 1991; while chlordane as a broad-spectrum contact pesticide is still being extensively used against termites [27]. Although DDT has been banned in developed countries, it is still used in developing countries. Additional release of DDT into the environment occurs due to the impurity of some other pesticides being used such as dicofol [24, 25]. Due to their hydrophobicity, organochlorine pesticides are persistent to the degradation process in the environment, and they are ubiquitous contaminants in soil, water, air, and food. Therefore, they have become a major issue of environmental research in order to investigate level of their occurrence, biochemical and toxic effects, human exposure and health risk assessment and have been subjected to national and international regulations and controls. Commonly analyzed OCPs in environmental samples are hexachlorocyclohexane isomers (α-, β-, γ-, δ-HCH), DDT and its metabolites (DDE, DDD), hexachlorobenzene (HCB), and pesticides from cyclodiene group (endrin, aldrin, dieldrin, chlordane, heptachlor, endosulfan). The aim of the paper was investigation of OCPs in surface soil and sediment samples in the city of Novi Sad, the capitol of the Vojvodina Province (the north part of Serbia). This study was of a limited, local scale, but to date no survey exists for Novi Sad area concerning the levels of these compounds in these types of samples. In addition, the data were compared with the ones found in other areas throughout the world and with limit values set by soil and sediment quality guidelines.

2 Material and Methods 2.1 Description of the Investigated Site With 300,000 inhabitants, Novi Sad is the second largest city in Serbia. It is located on the Danube River, approximately 70 km northwest of Belgrade, in the Province of Vojvodina. It is a commercial and industrial center of the Province with intense traffic and wide range of industrial activities, and a crossroad of major land and water ways.

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The soil sampling sites were chosen in order to cover the whole city area: downtown, outskirts, and the districts of the city where the motorway and Flour Milling industry are located. Sediment was sampled on the left bank of the Danube River in the vicinity of the Oil Refinery and infiltration galleries used for water supply of inhabitants of Novi Sad. The infiltration galleries are located some hundred meters downstream of the Novi Sad Oil refinery. The quality of abstracted groundwater is closely linked that of the Danube River as well as to the quality of the groundwater located within the catchment area of infiltration galleries. Thereby the quality of the abstracted groundwater is also closely linked to potential sources of contamination located upstream of the river and within the catchments of the infiltration galleries.

2.2 Soil and Sediment Sampling The samples were collected during 1 day with stable weather conditions at the beginning of April 2002. Surface soils (0–5 cm) were taken from representative areas. Four soil samples (∼250 g) for each sampling site were collected from a rectangular area of approximately 20×50 m. The sampling was designed to investigate OCPs concentrations in representative soils: residential and commercial area, park – school backyards (No. 1 and No. 2 in the downtown of the city and outskirts, respectively), market garden (No. 3), industrial area (No. 4) and roadside arable fields (No. 5). The locations of the sampling sites are shown in Fig. 1.

Fig. 1 The study area 1–6 sampling locations; DTD Danube-Tisa-Danube Canal; E-75 motorway; FMI flour milling industry; IG infiltration galleries, OR oil refinery; PP power plant

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Also, four sediment subsamples along the left bank of the Danube River were taken to obtain the composite sediment sample (No. 6). The distance between sampling sites was approximately 30 m that is distance between water wells located in the coastal area of the Danube River. The collected samples were stored in prewashed glass bottles and immediately transported to the laboratory. The four samples from each location were mixed together and sieved through a steel mesh (∼2 mm) to remove large particles and organic debris, creating six composite samples (∼1 kg) which were stored in closed ◦ amber glass beaker at the temperature about 4 C for not more then 10 days prior to analysis.

2.3 Chemicals Organic solvents (HPLC grade) and anhydrous sodium sulphate were purchased from Promochem (Wesel, Germany); Florisil 60-100/PR and copper powder from Sigma Aldrich Chemie Gmbh (Steinheim, Germany); EPA 608 Pesticides Calibration Mix standard containing 20 μg/mL each component (α-, β-, γ-, δ-HCH, p,p’-DDT, p,p’-DDE, p,p’-DDD, aldrin, dieldrin, endrin, endrin adehyde, endosulfan I and II, endosulfan sulfate, heptachlor, heptachlor epoxide) in hexane/toluene mixture was purchased from Supelco (Bellefonte, PA, USA). Distilled water used in the extraction procedure was previously extracted with n-hexane. Florisil was heated ◦ ◦ at 150 C during 12 h before use, while anhydrous sodium sulphate at 600 C for 6 h in a furnace to remove impurities. Copper powder was activated with concentrated HCl and washed with water, methanol, methylene chloride and hexane, then was stored in hexane. The laboratory glassware was washed with detergent, rinsed with ◦ distilled water and acetone and then heated to 130 C overnight prior to use.

2.4 Soil and Sediment Characterization The soil and sediment organic matter was determined as percentage mass loss after ◦ the ignition of approximately 5 g of air-dried sample at 500 C for 2 h [19]. Particle size analysis of the samples was determined by the sedimentation method [5]. Percentage and diameter of the particles was determined according to the Stocks’ law by means of nomogram. pH measurements were carried out in deionized water (50 mL) after stirring the sample portion of 20 g for an hour. Water content of the samples necessary for the expression of OCPs content per dry matter was obtained ◦ after drying of homogenized samples at 105 C to the constant mass. Results are presented as mean value of duplicate analysis.

2.5 Analysis Sample extraction and cleanup were carried out according to the EPA methods 3540C, 3660B, and 3620C [10]. Soil and sediment samples (about 20 g) were

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extracted in a Soxhlet apparatus with hexane/acetone (1:1) for 12 h. After the extract washing and acetone removal, sulphur and water in the extracts were removed with copper powder and anhydrous sodium sulphate, respectively. The extracts were concentrated by rotary evaporator and cleanup through a chromatographic column filled with activated Florisil. The column was eluted with 6%, 15% and 50% ethyl ether in hexane to obtain OCP fractions. The eluates were concentrated by a rotary evaporator, transferred to vials and dried under nitrogen to the near dryness. Finally the residues were redissolved in 1 mL n-hexane and analysed by GC. Sample analysis was carried out using HP 6890 gas chromatograph equipped with HP-5 fused silica column (60 m × 0.32 mm i.d., film thickness 0.25 μm) coupled to electron capture detector (ECD). Temperature program was as follows: ◦ ◦ ◦ initial temperature 120 C, held 2 min, with 10 C/min to 180 C, then with the run ◦ ◦ of 5 C/min to 290 C. Helium was used as the carrier gas with nominal initial flow through column of 2.2 mL/min. The injector and detector temperatures were main◦ tained at 290 and 310 C, respectively. A 1 μL of extracts was injected into GC systems in splitless mode with purge time of 0.75 min. The OCPs identification was performed by comparison of their retention time with those of standard mixture. The quantitative analysis was done by the external standard method. Five calibration standards were prepared. Quality control consisted of analysis of blank, spiked and duplicate samples. The detection limits of the applied method for individual components were 0.05 and 0.1 ng/g. The fortified samples were prepared by adding known volume of mixed OCPs standard solutions. They were stored (for equilibrium) and then analysed as previously described. The recoveries of analytes were in the range of 69–90% (relative standard deviation, RSD, less than 12%), that is acceptable [11] the residue data were not adjusted on the basis of these recoveries. Obtained results were blank corrected and presented as mean value of the duplicates.

3 Results and Discussion 3.1 Soil and Sediment Characteristics Organic content and physical parameters of the soil and sediment such as pH(H2O), water content and particle size distribution are given in Table 1. The range of organic matter in the investigated soil samples was 4.23–8.09%, while the level for sediment was 0.55%. Soil samples of park-schoolyard in outskirt (sample 2), roadside arable area (sample 5) and market garden (sample 3) had similar organic content (5.82%, 6.01% and 6.19%, respectively) while minimum and maximum values for organic content were observed in soil samples from industrial area (sample 4) and park-school backyard in the downtown of the city (sample 1), respectively. The clay content was ranged from 4 to 9%. A small change in clay content can significantly affect soil characteristics like the cation exchange capacity, because of the much higher surface area to volume ratio for clay size particles

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Table 1 Analysis of organic matter, particle size distribution, pH and water content of investigated soil and sediment samples from Novi Sad areas (April 2002) Location

Soil characteristics

Parkschool backyard, city

Parkschool backyard, outskirts

Market garden

Roadside Industrial arable area fields Sediment

Organic matter, % Loss of ignition

8.09

5.82

6.19

4.23

6.01

0.55

6

5

9

4

5

0

49

55

45

27

56

0

45

40

46

69

39

100

7.80 18.6

8.02 20.4

7.90 16.6

7.95 15.4

8.10 17.3

8.12 30.2

Particle size distribution, % Clay (<0.002 mm) Dust (0.002– 0.05 mm) Sand (0.05–2 mm) pH (H2 O) Water content, %

as opposed to sand size particles. Sand was predominant component of sample 4, while the sediment sample 6 was consisted of sand. Variation of soil pH was very low due to the calcareous nature of the soil.

3.2 Organochlorine Pesticides in Soil The obtained levels of pesticides based on the standard mixture of 16 OCPs in the investigated soil samples are presented in Table 2. Non-detectable samples were assigned as zero in calculating the total organochlorine pesticides concentrations. This value in soil varied from 2.63 μg/kg dry matter for roadside arable area (sample 5), see Fig. 1, to 31.78 μg/kg dry matter for sample from park-school backyard in the downtown of the city (sample 1). OCP-load in the soils could be rated as follows: school backyard in the downtown of the city>grassland from industrial area>market garden>school backyard in outskirts>arable field. The minimum total content of HCHs of 1.35 μg/kg dry matter was obtained in sample 3 (market garden) followed by 3.61 μg/kg in sample 1 (backyard in the downtown) and 11.36 μg/kg in sample 4 (grassland from industrial area), while in samples from outskirts (Nos. 2 and 5) none of the HCH isomers were detected. High content of HCHs in sample 4, preferentially because of pronounced level of γ-HCH, could be attributed to the usage of lindane due to protection of wheat grains against diseases during the storage for Flour Milling industry (see Fig. 1). In the samples 1 and 4 the following rank was observed: γ-HCH>δ-HCH>βHCH; in the sample 3, δ-HCH was not detected while the content of γ-HCH was again higher than β-HCH. Of all analysed HCH isomers α-HCH was not identified in any of the samples.

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Table 2 Mean content of organochlorine pesticides (OCPs) (μg/kg dry matter), in surface soil samples from the urban area of Novi Sad (April 2002) Location

Compound α-HCH β-HCH δ-HCH γ-HCH p,p -DDT p,p -DDE p,p -DDD Aldrin Dieldrin Endrin Endrin aldehyde Endosulfan I Endosulfan II Endosulfan sulfate Heptachlor Heptachlor epoxide HCH DDT OCP

Park-school backyard, city

Park-school backyard, outskirts

Market garden

Industrial area

Roadside arable fields

<0.1 0.21 1.50 1.90 6.30 3.50 <0.1 0.64 0.95 4.70 3.20

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.05 <0.05 1.90 2.90

<0.1 0.15 <0.1 1.20 <0.1 10.40 <0.1 <0.05 <0.05 0.59 1.23

<0.1 0.35 2.91 8.10 1.98 1.10 <0.1 <0.05 0.15 2.23 1.46

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.05 <0.05 2.22 0.41

0.59 0.36 6.00

<0.05 <0.05 <0.05

<0.05 <0.05 <0.05

1.00 0.87 <0.05

<0.05 <0.05 <0.05

1.10 0.83

<0.05 <0.05

0.50 <0.05

4.30 0.53

<0.05 <0.05

3.61 9.80 31.78

<0.1 <0.1 5.40

1.35 10.40 14.07

11.36 3.08 24.98

<0.1 <0.1 2.63

The highest total DDT content was observed in market garden (sample 3) due to high level of p,p -DDE (10.40 μg/kg), while in samples 2 and 5 DDT and its metabolites were not identified as in the case of HCHs. p,p -DDD was not detected in any of the samples. DDT was identified in samples 1 and 4 (grasslands in the down town of the city and industrial area) with 3-fold concentration in former than in later sample. In these samples value of p,p -DDT/p,p-DDE ratio was 1.8. A small value of the p,p DDT/p,p -DDE ratio (<1) is indicative of aged (microbially degraded) DDT. Thus obtained ratio value may suggest the latest use/deposition from the atmosphere [12]. Total level of cyclodiene insecticides were in the range from 2.32 to 18.37 μg/kg dry matter. Endrin and endrin aldehyde were presented in all the samples. Endosulfan (I and II) was detected in samples 1 and 4, while endosulfan sulfate was found only in sample 1 with maximum level of cyclodiene insecticides (6.00 μg/kg). Heptachlor was observed in the samples 1, 3 and 4, while its breakdown product was presented in the samples 1 and 4. Contents of certain OCPs in soil of some countries are presented in Table 3. The levels of HCHs in soil of Novi Sad were in the range of literature data but contents of DDTs were almost close to the lower values which were determined for the soils

<0.1 <0.1–0.15 <0.1 <0.1–1.20 <0.1 <0.1–10.40 <0.1 <0.05 <0.05 0.59–2.22 0.41–1.23 <0.05 <0.05 <0.05 <0.05–0.50 <0.05

<0.02–0.121

<0.02–23.8

<0.02–1.07 <0.02–367 <0.02–112 <0.02–21.0

<0.02–2.36

Harner et al. [15] (agricultural soil core, 0–8 cm)

b range

are presented as in the article of mean values nd – not detected c MPC-maximum permissible concentration d sum of o,p - and p,p -isomers

a figures

α-HCH β-HCH δ-HCH γ-HCH p,p -DDT p,p -DDE p,p -DDD Aldrin Dieldrin Endrin Endrin aldehyde Endosulfan I Endosulfan II Endosulfan sulfate Heptachlor Heptachlor epoxide HCH DDT

Compound

Present work (agricultural surface soil, 0–5 cm)

Source

8.3–112.2

6.4

1.1–37.6 nd

1.0–36.0 6.2–121.8

2.8–102.0

Jiries et al. [17] (agricultural surface soil, 0–25 cm)

0.10–1490

<0.1–17

<0.05–0.24 0.1–365 0.10–1300 <0.01–8.7

<0.05–0.47

Bidleman and Leone [3] (farmland core soil, 0–8 cm)

nd-8.96 nd-94.07

nd-1.10 nd-2.67 nd-3.93 nd-1.37 nd-5.84 nd-44.82 nd-7.54

Zhang et al. [30] (farmland surface soil, 10–20 cm)

0.14–42.31 7.60–831.32

0.04–4.10 0.04–19.76 0.03–7.01 0.01–11.45 2.18–777.71 1.98–144.59 0.54–21.75

Chen et al. [8] (vegetable surface soil, 0–20 cm)

5.72–7.64 0.13–1.85

nd nd

0.02 0.02 1.73 0.05

0.14 6.37

Zhang et al. [31]b (farm land, surface soil, 0–10 cm)

1.0 10d 13d 21d 38 43 0.95

310 101

The Netherland, new proposal MPCc

Table 3 Content of organochlorine pesticides (OCPs) in soil samples in the area of Novi Sad, the literature dataa , range, ng/g dm, residue limit according to Dutch legislation [26]

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Organochlorine Pesticides in Soil and Sediment

1477

in the world. Also, the maximum concentration of individual pesticide obtained for p,p -DDE (10.40 μg/kg) in sample 3 was similar with lower limit of the results taken from the literature (Table 3). As well as, the concentrations of all the detectable OCPs in the agricultural soils of Novi Sad were preliminary compared with the corresponding target value according to Dutch value due to shortage of national standard for identifying soil pollution. The contents of OCPs in the investigated soil samples were much lower than maximum acceptable concentration (MAC) set by the new proposal of the Dutch legislation [26] except of γ-HCH for sample 3 (MAC is 1 μg/kg) and endrin for sample 5 (MAC is 0.95 μg/kg) (Table 3).

3.3 Correlation Analysis The intensity of OCP degradation depends upon several environmental factors, temperature, soil type and pH, redox potential, moisture and organic carbon content [9, 16], although substance specific parameters, such as water solubility, vapor pressure and Henry’s law often play a dominant role. These parameters affect both the current concentration in the soil system as well as possible adsorption onto various soil components. In order to get a rough estimate of OCP behavior in area of Novi Sad, Pearson correlation between several soil geochemical factors and soil OCP concentration was applied. For correlation significance, the criteria value of probability (p<0.05) was used. Correlation of the soil pH with organic content matter resulted in a negative variation (r = −0.54), it could be speculated that source of soil acidity is from organic matter decomposition [17]. Significant correlations of the soil pH with total DDT and total OCP were found, r = −0.89 and r = −0.88, respectively, which indicated that the source of soil acidity is causing the reduction of total DDT and total OCP investigated. This is in the accordance to the finding of Bollag and Loll [4] and Carter and Suffet [6] who showed that in alkaline solutions carboxylic and phenolic functional groups on the humic polymer are probably dissociated and pesticides may attach to it cation exchange. Several researchers [2, 18] note that the molecular configuration of humic acid changes with pH, shifting from a stretched formation at neutrality to a coiled one at lower pH. Khan [18] uses this phenomenon as an explanation for differences in the adsorption of paraquat and diquat by humus. Of the investigated pesticides only positive and significant correlation was obtained for clay and p,p -DDE (r = 0.95) indicating the adsorption of p,p -DDE by ion exchange and by weaker physicochemical processes in soils having an organic matter content lower than 6%. In this case clay may compete with humic materials for binding p,p -DDE [4]. As well as, positive and significant correlations were found for soil samples from site 1 and site 4 (r = 0.84), and site 2 and site 5 (r = 0.95), indicating similarity between them concerning OCP content. Former samples belonged to the urban area, while the later ones to the outskirts. Different level of pesticides could be attributed to latest use. Around Novi Sad, agricultural regions supply the inhabitants of the city with agricultural products, especially crops and vegetables. Except agricultural

<0.1 <0.1 <0.1 <0.1 6.31 0.52 0.91 <0.05 0.43 0.51 0.52 0.23 0.51 0.41 <0.05 <0.05 <0.1 7.74

Compound

α-HCH β-HCH δ-HCH γ-HCH p,p -DDT p,p -DDE p,p -DDD Aldrin Dieldrin Endrin Endrin aldehyde Endosulfan I Endosulfan II Endosulfan sulfate Heptachlor Heptachlor epoxide HCH DDT 19.1–90.0 72.7–81.5 56.0–177.0 1.9–110.0 1.3–47.7 0.8–70.2 0.6–60.0 1.5–100.0 1.9–92.0

36.7–184.0

nd-1.9 1.3–50 0.8 0.6–25 1.5–80 1.9–92

1.2

Fatoki and Awofolu [13], (Buffalo River, South Africa, 0–5 cm)

1.8–30 0.8–134 1.5

Fatoki and Awofolu [13] (London harbor, (0–5 cm) 0.01–0.13 nd-0.06 nd-0.08 0.02–0.16 nd-0.011 0.11–3.78 nd-0.008 nd-0.084 nd-8.83 nd-0.002 nd-0.06 nd-0.07 0.01–0.18 nd 0.22–3.98 nd-0.01 0.06–0.38 0.11–3.78

Zhang et al. [29] (Tonghui River of Beijing, 0–1 cm)

nd-15.0 nd-1.17

7

0.6

2.85 2.67

1.42d 3.54d

44 9.8d 5.8d 3.9d 9.2 10 2.6

nd-0.71 nd-70.0 nd-13.0 nd-4.33

The Netherland, new proposal MPCb 310 11

0.94

MacDonald et al. [22], TELa

nd-0.20

Pazou et al. [23] (Queme River, Benin, 0–10 cm)

are presented as in the article nd – not detected a TEL – threshold-effect level represents the concentration below which adverse effects are expected to occur only rarely b MPC – maximum permissible concentration d sum of o,p – and p,p -isomers

e figures

Present work, Danube River, Serbia (0–5 cm)

Source

Table 4 The mean content of organochlorine pesticides (OCPs) in surface sediment of the Danube River, ng/g dm, the literature datae , range, ng/g dm, and residue limits according to MacDonald et al. [22] and Dutch legislation [26]

1478 N. Ðuriši´c-Mladenovi´c et al.

Organochlorine Pesticides in Soil and Sediment

1479

soils, potential pesticides emission source can be destruction of unwanted vegetation along transportation routes (railway, highways).

3.4 Organochlorine Pesticides in Sediment In sediment sample, total level of OCPs was 10.35 μg/kg dry matter. Nine OCPs compounds were determined with dominant level of p,p -DDT (6.31 μg/kg); these can be arranged in descending order as follow: total DDT>total cyclediene insecticides, while HCHs were not found (Table 4). Similar order was obtained for the sediments samples (given as mean values) taken along the bank of the Ebro River (Spain) [14], which passes through agricultural areas like the Danube River: DDTs (3.076 μg/kg)>cycledienes (0.421 μg/kg)>HCHs (0.007 μg/kg). Comparison with literature data (Table 4) revealed that the levels of identified OCPs in Danube River sediment were similar with the lower values of the ones determined for sediments from East London harbor (which receives domestic and industrial effluents from city sewage works) and Buffalo River, South Africa (which passes through agricultural areas) [13] and for sediment of Queme River [23] which drains the largest part of Benin cotton belt. However, contents of identified OCPs in Danube River sediment were slightly higher than values given for Tonghui River of Beijing [29]. In addition, the results obtained for the Danube River sediment were compared with sediment quality guidelines (Table 4). It could be seen that the concentrations of the analyzed OCPs were much lower than the maximum acceptable concentration set by the Dutch legislation [26] for the protection of aquatic environment and below threshold-effect level (TEL), which represents the concentration below which adverse effects are expected to occur only rarely [22].

4 Conclusion Five species of Stockholm Convention pesticides (DDT, aldrin, dieldrin, endrin, heptachlor) were detectable in the soils and three (DDT, dieldrin, endrin) in the river sediment of Novi Sad. In addition, HCH isomers were determined in the samples from park – school backyard in the downtown of the city, market garden, and industrial area. On the basis of comparison of the obtained OCPs contents with literature data and limit values defined by soil and sediment quality guidelines, it could be revealed that the presence of these compounds in soil and sediment samples from Novi Sad was not pronounced. Significant correlation of the soil pH with total DDT and with total OCP, as well as of clay content with p,p -DDE were found. Acknowledgements This work was supported by the Serbian Ministry of Science and Environmental Protection as a part of the Project BTN-321004B.

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References 1. Barr DB, Needham LL (2002) Analytical methods for biological monitoring of exposure to pesticides: a review. J Chromatogr B Analyt Technol Biomed Life Sci. 778:5–29 2. Best JA, Weber JB, Weed SB (1972) Competitive Adsorption of Diquat2+, Paraquat2+, and Ca2+ on Organic Matter and Exchange Resins. Soil Sci 114:444–450 3. Bidleman TF, Leone AD (2004) Soil-air exchange of organochlorine pesticides in the Southern United States. Environ Pollut 128:49–57 4. Bollag J-M, Loll MJ (1983) Incorporation of xenobiotics into soil humus. Experientia 39:1221–1231 5. Bouyoukos GJ (1962) Hydrometer method improved for making particle size analysis of soils. Agron J 54:464–465 6. Carter CW, Suffet IH (1982) Binding of DDT to dissolved humic materials. Environ Sci Technol 16:735–740 7. Castro J, Sanchez-Brunete C, Rodriguez JA, Tadeo JL (2002) Persistence of chlorpyrifos and endosulfan in soil. Fresen Environ Bull 11:578–582 8. Chen L, Ran Y, Xing B, Mai B, He J, Wei X, Fu J, Sheng G (2005) Contents and sources of polycyclic aromatic hydrocarbons and organochlorine pesticides in vegetable soils of Guangzhou, China. Chemosphere 60:879–890 9. Cousins IT, Bondi G, Jones KC (1999) Measuring and modeling the vertical distribution of semivolatile organic compounds in soils. I: PCH and PAH soil core data. Chemosphere 39:2507–2518 10. Environmental Protection Agency (1986) Test methods for evaluating solid wastephysical/chemical methods – EPA publication SW-846, Method 3620, Method 3540, Method 3660. Office of Solid Waste and Emergence Response, Washington, DC 11. European Commission (2000) SANCO/825/00, rev. 6. Directorate general health and consumer protection, section 4, Part A of annex II, and section 5, part A of annex III of Council directive 91/414/EEC 12. Falandysz J, Brudnowska B, Kawano M, Wakimoto T (2001) Polychlorinated biphenyls and organochlorine pesticides in soils from the southern part of Poland. Arch Environ Contam Toxicol 40:173–178 13. Fatoki OS, Awofolu RO (2003) Methods for selective determination of persistent organochlorine pesticides residues in water and sediments by capillary gas chromatography and electron capture detector. J Chromatogr A 983:225–236 14. Fernandez MA, Alonso C, Gonzalez MJ, Hernandez LM (1999) Occurrence of organochlorine insecticides, PCBs, and PCB congeners in waters and sediments of the Ebro River (Spain). Chemosphere 38:33–43 15. Harner T, Wideman JL, Jantunen LMM, Bidleman TF, Parkhurst WJ (1999) Residues of organochlorine pesticides in Alabama soils. Environ Pollut 106:323–332 16. Hitch RK, Day HR (1992) Unusual persistence of DDT in some western USA soils. Bull Environ Contam Toxicol 48:259–264 17. Jiries AG, Al Nasir FM, Beese F (2002) Pesticide and heavy metals residue in wastewater, soil and plants in wastewater disposal site near Al-Lajoun valley, Karak/Jordan. Water, Air Soil Pollut 133:97–107 18. Khan SU (1974) Adsorption of bihyridylium herbicides by humic acid. J Environ Qual 3:202– 206 19. Krumgalz B, Fainshtein G (1989) Trace metal contents in certified reference sediments determined by nitric acid digestion and atomic absorption spectrometry. Anal Chim Acta 218:335–340 20. Lorenzatti E, Altahus R, Lajmanovich R, Peltzer P (2004) Residues of endosulfan in soy plants in Argentina croplands. Fresen Environ Bull 13:89–92 21. Ma J, Daggupaty S, Harner T, Blanchard P, Waite D (2004) Impacts of lindane usage in the Canadian Prairies on the Great Lakes ecosystem. 2. Modeled fluxes and loadings to the Great Lakes, Environ Sci Technol 38:984–990

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22. MacDonald DD, Ingersoll CG, Berger TA (2000) Development and Evaluation of ConsensusBased Sediment Quality Guidelines for Freshwater Ecosystems. Arch Environ Contam Toxicol 39:20–31 23. Pazou EYA, Boko M, van Gestel CAM, Ahissou H, Laleye P, Akpona S, van Hattum B, Swart K, van Straalen NM (2006) Organochlorine and organophosphorus pesticide residues in the Ouémé River catchment in the Republic of Bénin. Environ Int 32:616–623 24. Qiu X, Zhu T, Zhu T, Li J, Pan H, Li Q, Miao G, Gong J (2004) Organochlorine pesticides in the air around the Taihu Lake, China. Environ Sci Technol 38:1368–1374 25. Tao S, Guo LQ, Wang XJ, Liu WX, Ju TZ, Dawson R, Cao J, Xu FL, Li BG (2004) Sci Total Environ 320:1–9 26. Verbruggen EMJ, Posthumus R, van Wezel AP (2001) Ecotoxicological serious risk concentrations for soil, sediment and (ground) water: updated proposal for first series of compounds. National Institute of Public Health and the Environment (RIVM), Bilthoven, The Netherlands, Report No. 711701020 27. Xu D, Zhong W, Deng L, Chai Z, Mao X (2004) Regional distribution of organochlorinated pesticides in pine needles and its indication for socioeconomic development. Chemosphere 54:743–752 28. Yeo HG, Choi M, Chun MY, Sunwoo Y (2003) Gas/particle concentrations and partitioning of PCBs in the atmosphere of Korea. Atmos Environ 37:3931–3839 29. Zhang Z, Huang J, Yu G, Hong H (2004) Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China. Environ Pollut 130:249–261 30. Zhang H, Lu Y, Dawson RW, Shi Y, Wang T (2005) Classification and ordination of DDT and HCH in soil samples from the Guanting Reservoir, China. Chemosphere 60:762–769 31. Zhang HB, Luo YM, Zhao QG, Wong MH, Zhang GL (2006) Residues of organochlorine pesticides in Hong Kong soils. Chemosphere 63:633–641

Conversion of Agricultural Wastes into Value Added Product with High Protein Content by Growing Pleurotus ostreatus Ahmad Al-Momany and Kholoud Ananbeh

Abstract An experiment was conducted to examine the ability of Oyster mushroom to grow on tomato tuff mixed with wheat straw. Six treatments were examined including the control, which contained 90% wheat straw with the fixed additives (wheat bran and gypsum). After inoculation and incubation, transparent plastic bags were used for cultivation. Three days were needed for pinheads to start appearing, and then between 3–7 days were needed for the maturity of the basidiomete. Several growth parameters were examined including incubation, primordial induction and fructification period, earliness, average weight of individual basidiomata, average yield for each treatment, diameter of the pileus, Biological Efficiency (BE%). In addition, proximate analyses for protein, crude fat, crude fiber, ash, carbohydrates, minerals and moisture were performed. The best performance was obtained by adding 30% tomato tuff to the basal growing medium which gave the highest yield (417–478 g/bag), average weight (21–29 g/cap), average cap diameter (9.2–10 cm/cap) and BE% (84–96%). Carbohydrates and protein content were high in Pleurotus basidiomete, fiber was high too but not as high as carbohydrates and proteins. Ash content was moderate, while fat content was low. For mineral contents in mushrooms, the trend was the same in all treatments. Both macroelements K and P were high in their concentrations when compared with other minerals in all treatments. Sodium was moderate in its concentration, while both Mg and Ca were found at low concentrations, but Mg was relatively higher than Ca. For microelements, both Fe and Zn were relatively high compared with other minerals like Cu and Mn, which were found at very low concentrations. Keywords Mushroom · Pleurotus ostreatus · Fungus · Biological efficiency · Tomato tuff · Cultivation · Agricultural wastes

A. Al-Momany (B) Faculty of Agriculture, University of Jordan, Amman, Jordan e-mail: [email protected]

H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_139,

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1 Introduction The Oyster mushroom Pleurotus sp. is known by this name because of typical shape of pileus resembling to Oyster shell [17]. It is a wood destroying saprophytic fungus [5, 6], sometimes appearing as a parasite and is wide spread in the temperate zone. It is a cosmopolitan genus [5] which was commercially grown in the far east countries and the USA several years ago [13]. German scientists were the first who studied the need of this fungus [8]. For both mycelial growth and fruit body development on lignin, and cellulose; materials such as corn cobs, all grain straws, paper wood shavings, sawdust, nutshells and vegetable wastes are sufficient. They are commonly found in forests and wood land, where they grow on fallen branches, dead tree stumps and fallen logs [6]. Pleurotus sp. is characterized by their rapid growth and high saprophytic colonization ability of the mycelium [1, 2, 9, 10]. Sporophores may develop as white mycelium with cream-colored pilei, brownish brown, dark brown, black brown, gray, dark gray, blue gray or black gray ones. The individual speciemens often grow in layers on top of each other [9, 18]. The higher price for fresh Oyster mushroom reflects, in part, the less developed and less reliable technology available to growers for cultivating these important species [15]. The objective of this study was to decrease the cost of mushroom production by finding other suitable substrates for Oyster mushroom cultivation mainly from agricultural wastes.

2 Materials and Methods 2.1 Fungal Culture The basidiomycetous fungus Pleurotus ostreatus (Jacquin: Fries) P. Kummer was obtained from the White Button Establishment in Al-Salt, near Amman, Jordan. The strain used was P015; it was obtained as ready spawn grown on wheat seeds. Later, the spawn was prepared from a pure culture of the starin which was isolated on Malt Extract Agar (MEA) media.

2.2 Experimental Design The experiment was carried out in a glass house. Six treatments were used including the control treatment. Completely Randomized Design (CRD) was used with four replicates. Data were statistically analyzed, and treatments were compared using Waller Duncan multiple range test [16]. The additives used were 5% wheat bran and 5% gypsum. The control growth medium was composed of 90% straw, 5% gypsum and 5% wheat bran. The percentages used for each medium were similar, the conducted treatments were prepared on a dry weight basis, and those were: Control: 90% straw: 5% wheat bran: 5% gypsum; Tomato tuff 1: 80% straw: 10% tomato

Conversion of Agricultural Wastes into Value Added Product

1485

tuff: 5% wheat bran: 5% gypsum; Tomato tuff 2: 70% straw: 20% tomato tuff: 5% wheat bran: 5% gypsum; Tomato tuff 3: 60% straw: 30% tomato tuff: 5% wheat bran: 5% gypsum; Tomato tuff 4: 50% straw: 40% tomato tuff: 5% wheat bran: 5% gypsum; Tomato tuff 5: 90% tomato tuff: 5% wheat bran: 5% gypsum.

2.3 Substrate Preparation Each treatment was mixed with the additives and placed in a cloth bag, then completely submerged in a water bath inside a large drum at 100◦C for 1–2 hours. This was done to eliminate insects and pathogens that may be found in the medium. The working area was disinfected using diluted house hold bleach, or alcohol to avoid contamination. Then the material was removed from the water bath and allowed to drain, and was cooled at about 30–40◦C, which was suitable for cultivation. Then it was placed in large plastic bags in order to allow the manipulation of mixing the spawn with the substrate by manual shaking. Bags were then tied at the top by a nylon thread and punctured by a clean nail or fork in a form of (+) shape for ventilation purposes [3].

2.4 Substrate Inoculation, Incubation and Culture Conditions After pasteurization, substrates were placed inside plastic bags and inoculated with spawn at a rate of 5% of their dry weight, and then were placed inside incubators at 20–25◦C under humid conditions between 80 and 95% with complete darkness during the first days of incubation until the compost was completely colonized by the mycelium. After that, the colonized substrates were exposed to a cold shock at around 4–5◦C for 1–2 days to improve induction of the first flush. During the fruiting period, ventilation was very important, so the bags’ upper parts were opened and air was allowed to enter. Temperature was recorded by using a thermograph (it was around 18–25◦C in average), and relative humidity was between 80 and 90%. It was obtained by watering the bags twice daily, and spraying water on the floor. Relative humidity was measured by using a hygrograph.

2.5 Harvesting and Measurement of Parameters Mushrooms were harvested when the pilei were fully mature and before they started to curl up. Remnants of the substrate attached to the stipes were removed, and the mushroom clusters were weighed and photographed. After mushroom harvesting, several parameters were evaluated to test the suitability of tomato tuff as substrate for the cultivation of Oyster mushroom. These included: length of production cycle (incubation, primordial induction and fructification), earliness, defined as the time elapsed between the day of inoculation and the day of the first harvest, the

1486

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average weight of individual basidiomata determined as the quotient of the total weight of fresh mushrooms harvested by their total number, the average yield for each treatment, diameter of the pilei and color. Biological Efficiency (BE %) was calculated as the percentage yield of fresh mushroom over the dry weight of the substrate.

2.6 Proximate and Mineral Analysis Proximate analysis was conducted according to the guidelines of the Association of Official Analytical Chemists for protein, crude fiber, ash, carbohydrates, minerals and moisture. Mineral analysis was performed by the wet ashing procedure; iron, zinc, calcium, magnesium, cupper and manganese were determined by using an atomic absorption spectrophotometer, while sodium and potassium were determined by flame photometry [4], and phosphorous was determined by using Olsen’s method [12].

3 Results and Discussion 3.1 Effect of Different Rates of Tomato Tuff on Growth Parameters of P.ostreatus Including Incubation Period, Primordial Induction, Earliness, Yield, Average Weight, Average Diameter and Biological Efficiency Pleurotus mycelium didn’t spread completely in tomato tuff media (tomato tuff 5), and so no parameters were taken on this treatment at all. As shown in Table 1, the incubation period was the highest in tomato tuff 4, where 40% of tomato tuff was Table 1 Effect of different rates of tomato tuff substrate amendments on incubation period, primordial induction, earliness, yield, average weight, average diameter and Biological Efficiency (BE %) of P. ostreatus Treatments

Inc.per. (Days)

Prim.Ind. (Days)

Earl. (Days)

Yield (g/0.5 kg)

A.wt. (g/cap)

A.D. (cm/cap) BE%

Control Tomato tuff 1 Tomato tuff 2 Tomato tuff 3 Tomato tuff 4

13b∗ 12c 12c 12c 14a

30.30a 25.00b 28.75a 28.00a 29.50a

37.50a 34.25a 36.50a 37.50a 37.75a

413.05a 478.23a 416.75a 456.33a 313.90b

20.7a 20.9a 25.8a 28.6a 20.6a

8.44ab 9.16a 9.28a 10.10a 7.20b

82.6a 95.6a 83.4a 91.3a 62.8b

Inc.per. = incubation period, Prim.Ind. = primordial induction, Earl. = earliness, A.wt. = average weight, A.D. = average diameter, BE% = Biological Efficiency ∗ = Means followed by the same letter within each column were not significantly different according to Duncan’s multiple range test (P= 0.05)

Conversion of Agricultural Wastes into Value Added Product

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used, it reached 2 weeks. The control treatment came in the second level, where it differs by 1 day from the highest and the lowest value. Tomato tuff 1, tomato tuff 2 and tomato tuff 3 came in the third level with no significant differences among them; they were the lowest in their value, and that was considered better for early cropping. Primordial induction time increased when tomato tuff percentage was increased in the substrate. It was the lowest in tomato tuff 1, and the highest in tomato tuff 4 but with no significant differences from control, tomato tuff 2 and tomato tuff 3. Earliness took about 37 days, with no significant differences among the whole treatments. Table 1 showed that there were no significant differences among the whole treatments in yield obtained except for that of tomato tuff 4 in which the increase in yield reached 40%, where it was 314 g. The other treatments had a yield value which varied from 413 to 478 g. Average cap weight ranged between 20.6 and 28.6 g/cap, but with no significant differences among the whole treatments. Average cap diameter ranged from 7.2 to 10.1 cm. It was the highest in tomato tuff 3 (10.1 cm), but there were no significant differences between them and the control. Tomato tuff 4, which had the lowest average diameter, didn’t differ significantly from the control treatment. It was safe to add tomato tuff to the growth medium up to 30%. Table 1 showed that BE% was not significantly different among control, tomato tuff 1, tomato tuff 2 and tomato tuff 3, but all of them were significantly different from tomato tuff 4, which had the lowest BE% which reached 63%. The Biological Efficiency (BE) was positively correlated with the yield.

3.2 Effect of Different Rates of Tomato Tuff on Proximate Analysis of P. ostreatus Including Protein, Fat, Ash, Fiber, Carbohydrates and Energy Table 2 showed that protein content was increased when tomato tuff content increased. This may be due to the high protein content in tomato tuff itself. It was Table 2 Effect of different rates of tomato tuff substrate amendments on proximate composition of P. ostreatus Treatments

Protein %

Fat %

Ash %

Fiber %

CHO %

Energy Kcala

Control Tomato tuff 1 Tomato tuff 2 Tomato tuff 3 Tomato tuff 4

25.57c∗ 32.6ab 35.23a 30.29b 34.68a

0.77ab 0.59b 0.70ab 0.91a 0.70ab

6.71a 5.87a 6.34a 6.34a 5.69a

20.2a 20.26a 17.02b 20.27a 18.03b

46.76a 40.68b 40.73b 42.19b 40.91b

296.2b 298.4b 310.1a 298.1b 308.6a

∗ = Means followed by the same letter within each column were not significantly different according to Duncan’s multiple range test (P= 0.05). a Energy: calculated by using proximate analysis values and by using the values: 4, 9, and 4 Kcal/100 g for soluble carbohydrates, fat and protein, respectively

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the highest in tomato tuff 1, tomato tuff 2 and tomato tuff 4, but they didn’t differ significantly from each other. Protein content in tomato tuff 3 was high too but not like the previous treatment, and it was not significantly different from tomato tuff 1. The lowest protein value was found in the control treatment where it reached 25.6%. Fat content was l‘ess than 1% and ranged between 0.5 and 0.9%. Tomato tuff 3 showed the highest fat content, and was not significantly different from the control, tomato tuff 2 and tomato tuff 4. Tomato tuff 1 had the least fat content where it was 0.59%. Table 2 showed no significant differences among the whole treatments in their ash content, and its value ranged from 5.9 in tomato tuff 1 to 6.7% in the control. Table 2 showed that fiber content was the highest in control, tomato tuff 1 and tomato tuff 3 where it reached 20%. Both tomato tuff 2 and tomato tuff 4 came in the second level where the values of their fiber content were 17 and 18% respectively. Carbohydrates content was lower than 45% starting from tomato tuff 1. It was 46% in the control treatment, where this value was the highest compared with the rest treatments, and it was significantly different from all treatments. Tomato tuff 1, tomato tuff 2, tomato tuff 3 and tomato tuff 4 were not significantly different from each other and the values of their carbohydrates content ranged from 40 to 42%. Tomato tuff 2 and tomato tuff 4 had the highest energy level; 310 and 308 Kcal respectively. Control, tomato tuff 1 and tomato tuff 3 came next in their energy content where there were no significant differences among them as shown in Table 2. Proximate analysis for Oyster mushroom obtained in this study resembled those recorded by [3, 7, 11, 14]).

3.3 Effect of Different Rates of Tomato Tuff on Mineral Contents Table 3 showed that K concentration was the highest in the control treatment which was significantly different from the other treatments. Phosphorus concentration was high in tomato tuff 1 with no significant differences from tomato tuff 3 and tomato tuff 4. The control treatment didn’t differ significantly from tomato tuff 2, tomato tuff 3 and tomato tuff 4 in its phosphorus concentration. Sodium had the highest concentration in both the control and tomato tuff 1. The rest treatments didn’t differ Table 3 Effect of different rates of tomato tuff substrate amendments on mineral contents (ppm) of P.ostreatus Treatments

K

P

Na

Ca

Mg

Zn

Fe

Cu

Mn

Control Tomato tuff 1 Tomato tuff 2 Tomato tuff 3 Tomato tuff 4

2973a∗ 2211b 2095b 2061b 1804b

1837bc 2066a 1732c 1999ab 1912abc

92.3a 88.3a 79b 78b 77b

1.7bc 1.94ab 2.14a 1.44c 0.79d

29.6a 17.52a 19.53a 21.38a 23.93a

1.03ab 1.26ab 0.91b 1.33a 0.97ab

1.78a 1.77a 1.85a 1.94a 1.63a

0.18a 0.16a 0.17a 0.16a 0.25a

0.18a 0.21a 0.18a 0.16a 0.24a

∗ = Means followed by the same letter within each column were not significantly different according to Duncan’s multiple range test (P= 0.05)

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significantly from each other. For calcium, tomato tuff 2 had the highest amount, but it didn’t differ significantly from tomato tuff 1 which in turn didn’t differ significantly from the control. Tomato tuff 3 didn’t differ significantly form the control. Tomato tuff 4 had the lowest Ca concentration. There were no significant differences among the whole treatments in their magnesium content, but it was the highest in the control treatment compared to the other treatments. Zinc had the highest concentration in tomato tuff 3 with no significant differences from the control, tomato tuff 1 and tomato tuff 4. Tomato tuff 2 had the lowest Zn concentration. Iron, cupper and manganese didn’t differ significantly in their concentrations among the whole treatments.

References 1. Alian A, Madbouly F, Gadallah A (1989) Cultivation of Pleurotus columbinus on cannery wastes. 2nd conference of food science and technology for Mediterranean countries, Cairo 2. Al-Shimi MM, Alian AM, Madbouly FH, Raouf MS (1990) Cultivation and processing of mushrooms. 2- drying and freeze-drying of Pleurotus ostreatus. Cairo University, Egypt 3. Ananbeh KM, Almomany AR (2005) Production of Oyster mushroom Pleurotus ostreatus on olive cake agro waste. Dirasat 32(1):64–70 4. Association of Official Analytical Chemists (AOAC) (1995) Official methods of analysis of the association of official analytical chemists, 16th edn. Publishing Association of Official Analytical Chemists, Arlington, VA 5. Chang ST, Hayes WA (1978) The biology and cultivation of edible mushrooms, 1st edn. Academic, London 6. Croan SC (2000) Conversion of wood waste into value added products by edible and medicinal Pleurotus (Fr.) P. Karst. species (Agaricales s.I., Basidiomycetes). Int J Med Mushrooms 2:73–80 7. Guler M, Axoxlu YS (1999) Comparison of composition elements on different substrates of Oyster mushrooms (Pleurotus sp.) growing under plastic sheet. XI world forestry congress, vol. 3. Topic 15. Antalya, Turkey 8. Guler M, Muh YZ (1988) Kayin Mantari Yetistirme Teknigi. Yayin No. 669, series No. 16. Arastirma planlama ve koordinasyon dairesi baskanligi, Ankara 9. Hoglov J (1999) Pleurotus flabellatus culturing on water hyacinth, Eichhornia crassipes. M.Sc. Thesis, University of Daresalaam, Tanzania, Stockholm 10. Madbouly FH (1987) Some studies on cultivation and preservation of mushroom. Ph.D. Thesis, Cairo University, Egypt 11. Oei P (1991) Manual on mushroom cultivation. Techniques, species and opportunities for commercial application in developing countries. Transfer of technology for development (Amsterdam) and Technical Center for Agricultural and Rural Co-operation (Wageningen) 12. Olsen SR, Dean LA (1965) Phosphorus. In: Black CA (ed) Methods of soil analysis, part 2. Agronomy 9:1035–1049, American Society of Agronomy, Madison, WI 13. Royse DJ, Schisler LC (1987) Yield and size of Pleurotus ostreatus and P. sajor-caju as affected by delayed release nutrients. Appl Microbiol Biotechnol 26:191–194 14. Sanjust E, Pompel R, Rescigano A, Rinaldi A, Ballero M (1991) Olive milling wastewater as a medium for growth of four Pleurotus species. Appl Biochem Biotechnol 31:223–235 15. Sharadqah WSN (2000) Lignin biodegradation during the process of biological conversion of olive mill byproduct (Jift). M.Sc. Thesis, Jordan University of Science and Technology, Jordan

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16. Steel RGD, Torrie JH (1980) Principles and procedures of statistics, 2nd edn. McGraw-Hill, NewYork 17. Wani PV, Sawani DM (1998) Oyster-A mushroom of broad adaptability: an overview. J Maharashtra Agric Univ 23(3):230–237 18. Wood DA, Smith JF (1988) The cultivation of mushroom (part II). Mushroom J 188:665–674

Plants as a Source of Biopesticides for Pest Control: A New Perspective E. Hassan and D. Prijono

Abstract Rhizome extract of “C” and seed extract of “N” were tested in the laboratory for their effects on feeding, development, mortality, reproduction and oviposition of Crocidolomia pavonana (Fabricus) (Lepidoptera; Pyrallidae) on broccoli. Antifeedant activity of “C” and “N” biopesticides were tested against fourth instar C. pavonana larvae in leaf-disc choice and no-choice tests. The results show that under the choice condition, the treatment with 1% and 1.25% “C” biopesticide for 24h or 48h, reduced feeding by the test larvae on broccoli leaves by more than 90%. Under the same condition, reduction in feeding after 24h caused by treatment with 0.12% and 0.2% “N” biopesticide was recorded as 86.7% and 95.8% respectively. In the no-choice test, the treatment with 1% and 1.25% “C” biopesticide reduced feeding by 61.8% and 74.2% respectively after 24h and by 70.6% and 77.7% after 48H. Under no-choice conditions “N” biopesticide at concentrations from 0.025% to 0.2% was not effective in deterring the test larvae from feeding on treated leaves. In the testing to evaluate the effects of test biopesticides on reproduction and longevity of C. pavonana, fourth instar larvae were offered treated leaves for 48 h, then their development was followed until adult emergence. The duration of fourth instar and pupal period of the survivors, as well as the fecundity and longevity of the resulting adults, were recorded. Oviposition-deterring activity on C. pavonana of “C” and “D” biopesticides was tested against gravid females of C. pavonana (5-8 days post emergence) on broccoli seedlings in choice and no-choice tests. Keywords Biopesticides · Pest · Rhizome

E. Hassan (B) Integrated Crop Management, School of Agronomy and Horticulture, University of Queensland, GATTON 4343 QLD, Australia e-mail: [email protected] Note: Please note that it is beyond the scope of this paper to provide information of the insect rearing methodology and the extraction methods of bio-pesticides from “C” and “N” and their fractionation of compounds. This is commercial in confidence. H. Gökçeku¸s et al. (eds.), Survival and Sustainability, Environmental Earth Sciences, C Springer-Verlag Berlin Heidelberg 2011 DOI 10.1007/978-3-540-95991-5_140,

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1 Introduction Arthropod pests are responsible for huge annual losses in crop production throughout the world and for transmitting a number of life threatening diseases for both humans and livestock. The control of such pests is therefore, of the utmost importance. Insecticides have become an indispensable tool in modern agricultural practices and will continue to play an important role in pest management programs in the foreseeable future. However, intensive use of synthetic insecticides during the past several decades has led to several negative effects such as resistance, accidental killing of non-target organisms including beneficial organisms, and an adverse effect on human health and the environment. It is generally realized that the current agricultural productivity level would be hard to envisage without the use of insecticides. Extensive and injudicious use of insecticides however, may lead to a number of undesirable side effects including the development of insect resistance to insecticides [3, 16], resurgence of primary pests and outbreak of secondary pests [4, 14, 15]. Resistance in the target insect is the most common problem related to the application of synthetic insecticides. From the first case of insecticide resistance to lime sulphur which was detected in a scale insect in 1905, then grew to 14 cases in the 1940s and reached 490 in 1986 [7], there has been a steady increase in the incidence of resistance and by the year 2000, 533 arthropod species have been reported to be resistant to one or more insecticide substances [17]. Plants produce chemical compounds in their tissues with a variety of functions including as anti-herbivore agents. The main plant chemicals that have been implicated as anti-herbivore agents are terpinoids, alkaloids and phenolics. The main advantage of using bio-pesticides in insect control is that they are in general, relatively safe for non-target organisms due to their low persistency in the environment. In the present research, the insect control properties of the rhizome extract of “C” and “N” seed extracts were tested in the laboratory against the cabbage cluster caterpillar Crocidolomia pavonana (Fabricius) (Lepidoptera : Pyralidae).

2 Test Insect The cabbage cluster caterpillar is a major pest of cruciferous crops in tropical and subtropical parts of Africa, Asia, Australia and the Pacific Islands [2, 6, 8, 13, 18, 19]. Young larvae feed in clusters on the underside of the leaves. Mature caterpillars often defoliate the plants and in cabbage and broccoli they frequently destroy the head completely. In Queensland (Australia), this insect becomes a major constraint in the production of brassica crops mainly in late summer and early autumn [9]. Brassica growers normally rely heavily on the use of insecticides to control

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this pest and other brassica crop pests, since other control methods cannot suppress the pest population adequately. As a consequence of intensive insecticide application brassica crop pests have developed resistance to a large variety of insecticides. Availability of an alternative to synthetic insecticides therefore, is highly desirable in brassica pest management. The research was conducted at the Plant Protection Laboratory at the University of Queensland Gatton Campus. The temperature in the laboratory during the study varied from 25◦ C to 28◦ C and the relative humidity ranged from 40 to 70%. Broccoli plants grown under pesticide free conditions in a glasshouse served as a source of the larval diet. Broccoli seeds were sown on a mixture of vermiculite and peat and supplemented with a slow-release fertilizer. A laboratory colony of C. pavonana was established from larvae collected from cabbage plants in the field. The larvae were maintained on broccoli leaves in plastic boxes (ca. 28 cm × 20 cm × 7.5 cm) with gauzed-windowed lids. Mature larvae were transferred to clean boxes provided with a sterilized mixture of soil and sand (ca. 2 cm deep) as a pupation medium. One week after all larvae had entered the soil, the pupae in their earthen cells were transferred to wooden-framed gauze cages (ca 40 cm × 40 cm × 40 cm). Upon emergence, the adults were provided with a 10% honey solution in cotton swabs and 3–4 leaf stage broccoli seedlings were placed in the cages as repositories for eggs. Seedlings with eggs were removed from the cages every other day and kept in gauze cages (ca 30 cm × 30 cm × 30 cm) until the eggs hatched. Newly emerged larvae were transferred to plastic boxes as above and fed broccoli leaves to start subsequent breeding cycles. During the rearing studies of the life cycle of this insect, it was found that the larval stages passed through four instars during its development.

3 Extraction Extraction from both plant material was performed according to a number of different methods and it would take too long to mention each of these in this paper. However, both plant extractions were prepared with a mixture of ethanol and diethyl ether (3:1 V/V). The extracts were kept in a refrigerator (<4◦ C) until use. In all cases, traces of solvents were removed under nitrogen prior to use.

4 Preparation of Test Extract Emulsions In all tests, extracts were applied as freshly prepared emulsions of their ethanolic solutions in water. Known amounts of particular extracts were dissolved in ethanol to obtain 10% (W/V) stock solutions. Various concentrations of extract emulsions were prepared by diluting appropriate volumes of stock solutions in a small volume of ethanol and then the diluted solutions were emulsified in distilled water containing Triton X-100 0.1% and Agral 600 0.1% as an emulsifier and a sticker respectively.

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5 Leaf Disc Choice Bioassay All assays were performed using a leaf-dip feeding method. In each assay, the extract was evaluated at four to six concentration levels. The feeding assay was performed using procedures adapted from those described by Jeremy et al. [12]. Leaf discs were punched out of broccoli leaves using a cork borer (inner diameter 3 cm). Each leaf disc was submersed in an appropriate extract emulsion for 3–5 seconds, the excess of liquid was blotted on towel paper, and leaf disc was mounted on insect pins and air dried. Control (untreated) leaf discs were dipped in water containing ethanol and surfactants. Two treated and two control leaf discs were arranged alternatingly around the periphery of a plastic container (11 cm diameter and 5 cm high) provided with high density polystyrene foam pad at the bottom. The container was covered with a lid having a gauze-covered circular window (ca. 3 cm diameter) at the centre. Moist filter paper was placed on top of the pad and the leaf discs on pins were fixed to the pad. Two fourth-instar (1-day old) were released into each container (5 container in total) and allowed to feed for 24 h. The remaining leaves were replaced with fresh, treated or control discs and the feeding assay was run for another 24 h. The leftover discs were secured on a piece of paper by means of an adhesive tape and then were photocopied. Image areas were measured using an image analyzer “Optimax V”. Each treatment was replicated 10 times, in particular concentrations, the area of treated leaves consumed after 24 h and 48 h was compared with that of their respective controls using paired t-test [22].

6 Leaf Disc and NO Choice Bioassay This assay was done using the same procedure as in leaf-disc choice bioassay, but in this test the treated and control leaf discs were placed in separate containers [1, 10, 11]. In each container, three treated or control leaf discs were pinned on the foam-pad around the edge of a plastic container and then two fourth instar (1-day old) were released into the container.

7 Results and Discussion All experiments were arranged in a completely randomized design with 10 replications. Analysis of variance [21] was performed to compare the effects of extract concentrations on leaf consumption (based on leaf area data) and means between concentrations were separated using Duncan’s new multiple range test [5]. Analysis was done using SAS program [20]. The results showed that under choice condition. The treatment with 1 and 1.25% “C” extract reduced feeding by the test larvae on broccoli leaves by more than 90%,

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both after 24 h and 48 h of feeding. Under the similar condition, reduction in feeding after 24 h caused by the treatment with 0.12 and 0.2% “N” extract were 86.7 and 95.8% respectively, and those after 48 h were 83.3 and 94.0% respectively. In the no-choice test, the treatment with 1.0 and 1.25% “C” extract reduced feeding by 61.8 and 74.2%, respectively, after 24 h and by 70.6 and 77.7%, respectively, after 48 h. Under no-choice test condition “N” extract at concentrations from 0.025 to 0.2% was not effective in deterring the test larvae from feeding on treated leaves. Irrespective of feeding duration, in the treatment with 0.025, 0.04% “N” extract C. pavonana larvae consumed treated leaves as much as untreated (control) ones, and at these concentrations feeding reduction was negligible. Leaf consumption over 24 h and 48 h was only slightly decreased by the treatment with 0.2% extract. In experiments to asses the effects of test extracts on development and mortality of cabbage cluster caterpillar (C. pavonana) third and fourth (final) instar were fed for 24 h and 48 h, respectively, broccoli leaves treated with “N” and “C” extract. In the tests with the third instar, test larvae were observed daily until pupation and the daily larval mortality, the duration of the surviving third-and fourth instar and any metamorphic defects resulting from the treatment were recorded. In the test with the fourth instar, larval development was followed until adult emergence and records were kept with regard to the daily larval mortality and the number of malformed and dead pupae and of malformed adults. The results showed that the treatment with 0.75% “C” extract induced a slight delay in the development of the third instar, but no significant difference was recorded in the treatments with 0.35–0.6% extract as compared with control. The extract at 0.45–0.75% some what prolonged the duration of the fourth instar but at 0.35% did not. “C” extract at concentrations of 0.25 to 1.25% did not exert immediate kills in the third – or fourth instar. Mortality in the test larvae was first observed 2 days from treatment. The last occurrence of larval death in the third and fourth instar was noted 12 and 7 days from treatment respectively. Treatments with 0.175–0.35% and 0.025–0.14% with “N” extract with third instar fed treated leaves and its development observed to the fourth instar resulted in a marked developmental delay and severe metamorphic disturbances in the test insects. Time duration was 24 h and 48 h. Results from this study suggest that the action of the active substance(s) in “N” extract is associated with the molting processes. The fecundity of females developing from larvae fed leaves treated with 0.4% and 0.65% of “C” extract was reduced by 54.1 and 71.0% respectively. The decreases in fecundity resulting from the treatment with 0.0325 and 0.4% “N” extract were 63.0 and 73.1% respectively. The treatment with 0.65% of “C” extract reduced the longevity of the resulting females and males significantly, where as that with 0.4% did not. The treatment with 0.0325 and 0.04% “N” extract significantly shortened the life span of the females but not the males.

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Fig. 1 Effects of “C” and “N” extracts on fecundity of Crocidolomia pavonana. Vertical bars represent standard errors of means

Oviposition deterring activity of “C” and “N” extracts (Fig. 1) was tested against gravid females of C. pavonana (5–8 days post-emergence) on broccoli seedlings in choice and no-choice tests. The results showed that in choice test, the treatment with 0.75% “C” extract and 0.2% “N” extract significantly reduced oviposition by test insects. The effects of “C” and “N” N extracts on oviposition were more pronounced in no-choice than in choice tests. Oviposition reduction caused by the treatment with 0.75% “C” extract in the no-choice test was almost 80.0% as compared to about 50.0% in the choice test. In the no-choice test the result for the treatment with “N” extract was consistent in that the reduction in oviposition increased with the increase in extract concentration, whereas in the choice test the result was inconsistent. Oviposition reduction under no-choice condition caused by the treatment with 0.2 and 0.4% “N” extract were 26.5 and 52.6%, respectively (Table 1). Table 1 Effects of “C” and “N” extract on oviposition by Crocidolomia pavonana on Broccoli seedlings over 4 days (No-choice test) Extract

Concentration (%)

Mean no. eggs1) per oviposition unit

C.

0 0.50 0.75

219 a (21) 124 b (46) 45 b (21)

43.4 79.5

0 0.20 0.40

253 a (50) 186 ab (22) 120 b (26)

26.5 52.6

N

1)

Oviposition reduction2) (%)

Means within extract followed by the same letter are not significantly different √ [Duncan’s (1955) multiple range test, α = 0.05]; data were transformed to x (N extract) √ or (x + 0.5) (C. extract) prior to analysis; figures in parentheses denote standard errors of means. Each oviposition unit contained two treated or control seedlings and two pairs of adults. 2) Mean oviposition reduction (%) = (1 − mean treated/mean control) × 100.

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Table 2 Effects of “C” extract on feeding of fourth instar of Crocidolomia pavonana (No-choice test) Feeding duration (hours) 24

48

Concentration (%)

Mean (S.E.)1) leaf area (cm2 ) consumed

Feeding reduction (%)

Control 0.25 0.50 1.00 1.25

18.56 a (0.62) 17.47 a (0.58) 12.49 b (0.72) 7.09 c (0.70) 4.78 d (0.66)

5.87 32.7 61.8 74.2

Control 0.25 0.50 1.00 1.25

31.79 a (0.81) 26.75 v (1.52) 20.20 c (0.98) 9.35 d (1.14) 7.32 d (1.08)

15.9 36.5 70.6 77.7

1)

S.E.: standard error Within feeding duration category, means followed by the same letter are not significantly different [Duncan’s (1955) multiple range test, α = 0.05]

Under no-choice conditions, the larvae initially rejected the treated leaves, moving from one leaf disc to another, and then remained idle on the underside of the leaf discs for some time before they started feeding. “C” extract at 0.25% did not significantly affect the feeding by fourth-instar of C.pavonana during the first 24 h of feeding (Table 2). After 48 h, however, the same treatment caused a slight reduction in feeding. In the treatment at higher concentrations, i.e. 0.5%; 1.0% and 1.25%, the amount of treated leaves consumed over 24 h and 48 h was significantly less than that of control. For the two feeding periods the percentage of feeding reduction increased with the increase in extract concentration. At particular concentrations, the reduction in feeding over 48 h was slightly higher. Than that over 24 h. The crude “C” extract or fraction “Cur2.3” at concentrations of 0.25–1.25% did not exert immediate kills in the third or fourth-instar of C.pavonana. Mortality in the test larvae was first observed at 2 days from the beginning of the feeding treatment (Fig. 2a,b). The duration of the feeding treatment in the third and fourth-instar were 24 h and 48 h, respectively. In general, the mortality level increased gradually until all the affected larvae died. In the treatment with the crude extract of “C” at the highest concentration (1.25%) against the fourth-instar, there was a steep increase in the mortality level between 2 and 3 days from the treatment. The mortality level using “N” extract was relatively constant during the normal duration of the fourth-instar stadium, i.e. between 3 and 7 days from treatment, and then it increased steadily until all the affected larvae died. The progression of mortality level in the treated fourth-instar (Fig. 3) exhibited a similar pattern to that in the third instar.

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Fig. 2 Cumulative mortality (%) of third instar of Crocidolomia pavonana as affected by (a) “C” and (b) by fractionation of “C”. Observation was made until all the survivors pupated or all the affected larvae died, whichever was the later. Arrows indicate the time of molting to the fourth instar (M) and pupation (P) in the control larvae

Fig. 3 Cumulative mortality (%) of fourth-instar of Crocidolomia pavonana as affected by “N”. No larval mortality was observed in control. The arrow indicate the time of pupation in the control

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8 Conclusion Extract of “C” rhizomes at a concentration range of 0.25–1.25% exhibited concentration-dependent antifeedant and insecticidal effects and a moderate growth inhibitory effect in the larval stage of C.pavonana. Under no-choice condition “C” extract was less active antifeedant against C.pavonana larvae than under choice condition. The extract at 0.4–0.65% possessed a moderate to strong fitness-reducing activity in the adults C.pavonana given the treatment as the final instars, and that at 0.5–0.75% exerted a weak to moderate oviposition repellent effect in the females C. pavonana. The insecticidal, growth inhibitory and fitness-reducing effects of “C” extract could result from a combination of the antifeedant effect and inherent toxicity of the extract, since the concentrations of the extract needed to induce those effects were within the range of those required for antifeedant activity. “N” extract at concentrations as low as 0.05% possessed strong antifeedant, growth inhibitory and fitness-reducing activities against C. pavonana. “N” extract at much higher concentrations (0.2–0.4%), however, exhibited only a weak to moderate oviposition repellent effect. At a concentration range of 0.025–0.2%. the antifeedant effect of “N” extract was observed only under choice condition, but not under no-choice condition. Unlike in “C” extract, feeding inhibition did not appear to contribute appreciably to the growth inhibitory and fitness-reducing effects of “N” extract because the concentrations of “N” extract that could yield these effects were lower than those necessary for antifeedant activity (under no-choice). The pattern of growth inhibitory activity of “N” extract against C. pavonana larvae it indicates that this extract contain some chemical that regulates insect growth.

References 1. Bhuiyan KR, Hassan E, Isman MB (2001) Growth inhibitory and lethal effects of some botanical insecticides and potential synergy by dillopiol in Spodoptera litura (Fab.) (Lepidoptera Noctuidae). J Plant Dis Prot 108(1):82–88 2. Brown JD, Hargraves JR (1979) Control of cabbage pests. Qld Agric J 105:222–228 3. Brown AWA, Pal R (1971) Insecticide resistance in arthropods. WHO, Geneva 4. Dittrich V (1987) Resistance and hormoligosis as driving forces behind pest outbreaks. In: Brent KJ, Athin RK (eds) Rational pesticide use. Cambridge University Press, Cambridge, pp 169–181 5. Duncan DB (1955) Multiple range and multiple F test. Biometrics 11:1–42 6. Fullerton RA (1987) Use of synthetic phyrethroids fenvalerate and cypermethrin to control diamondback moth (Plutella xylostella L.) and the large cabbage moth (Croccidolomia binotalis Zeller) in Rarotonga, Cook Is. Fiji Agric J 41:49–51 7. Georghiou GP (1987) Insecticides and pest resistance; the consequences of Abuse. 36th annual faculty research lecture. University of California, Riverside, CA 8. Gunn D (1925) The large cabbage moth, Crosidolomia binotalis Zell. J Dept Agric Union S Afr 11:233–239 9. Hassan E (1977) Major insect and mite pests of Australian crops. Ento Press, Gatton, QLD 10. Hassan E (1998) Insecticidal toxicity off neem seed kernel extract on Bactrocera tryoni (Frogg) (Diptera; Tephritidae) and repellency on persimmon fruit. J Plant Dis Prot 105(4):411–416

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11. Hassan E (1999) The insecticidal effects of neem seed kernel extract on eggs and larvae of Helicoverpa armigera (Hubner). J Plant Dis Prot 106(5):523–529 12. Jeremy T, Hassan FE, Dethier VG (1868) Induction of specific food preferences in lepidoptera larvae. Ent Exp Appl 11:211–230 13. Kalshoven LGE (1981) Pests of Crops in Indonesia (revised and trans: Van Der Laan PA). Ichtiar Baru-Van Hoeve, Jakarta Indonesia 14. Luck RL, Van Der Bosch R, Garcia R (1977) Chemical insect control- a troubled insect control strategy. Bioscience 27:606–611 15. Metcalf RL (1982) Insecticides in pest management. In: Metcalf RW, Luckman WH (eds) Introduction to insect pest management, 2nd edn. Willey, New York, pp 217–277 16. Metcalf RL (1989) Insect resistance to insecticides. Pestic Sci 26:333–358 17. Mota-sanchez D, Bills PS, Whallon ME (2002) Arthropod resistance to pesticides: status and overview. In: Wheeler WB (ed) Pesticides in agriculture and environment. Marcel Dekker, New York, pp 241–272 18. Ooi PCA, Keldermen W (1979) The biology of three common pests in Cameroon highlands, Malaysia. Malays Agric J 52:85–100 19. Rai PS, Chandra BKN (1976) Bionomics of the cabbage leaf-webbing in caterpillar, Croccidolomia binotalis Zeller. Indian J Ent 38:233–235 20. SAS Institute (1985) SAS user’s guide: statistics, version 5th edn. SAS Institute, Cary, NC 21. Stell RGD, Torrie JH (1980) Principles and procedures of statistics: a biometrical approach, 2nd edn. McGraw-Hill, New York 22. Walpole RE (1974) Introduction to statistics, 2nd edn. Macmillan, New York

Study of Some Factors of Variation of intake on Course by Dairy Ewes T. Najar, Aziza-Guesmi Boubaker, A. Rigueiro-Rodríguez, and M.R Mosquera-Losada

Abstract The quantity of herbage intake by sicilo-sarde dairy ewes, under a rotational grazing system, was determined by the method of count bite. Measurements were taken on a mountainous area of Béja (northern west of Tunisia) being the pasture mainly constituted by herbaceous species, especially of the graminaceous ones, its composition as well as bite weight and rate were estimated. Grazing time was around 7 h per day. Average ewes dairy production was around 0.8 kg per day (0.4–1.3 kg). All ewes were supplemented by avena hay ad labitum, and 0.35–0.70 kg of concentrate. Concentrate feed consisted of a mixture of barley, wheat bran, and soybean meal. The results obtained show that biting rate varies between dairy ewes according to their milk production, and pasture availability. The average pasture consumption varied between 420 and 640 g/day. Pasture consumption increases with the level of production and concentrate in the diet. Individual intake variability was also observed, and can be related to other zootechnical factors such as age and weight of the animals. Keywords Dairy ewes · Grazing behaviour · Intake

1 Introduction In ruminant herbivores, most studies on the behavioural and mechanistic adjustment of grazing have been carried out in rather simplified conditions [8, 24]. Animal behavior at natural pasture and the plant animal interactions are important to improve our understanding of the behavior of the herbivores when selecting food from heterogeneous vegetation. This stage is of primary importance to define a strategy of management of the pastures. In literature several studies are related to animal

T. Najar (B) Institut National Agronomique de Tunis, 42, Av Charles Nicolle, 1082 Tunis, Tunis e-mail: [email protected]

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feed behaviour since along time [2, 3, 13, 27]. Only a few results are published on ingestive behaviour in heterogeneous pasture of animals receiving mixed rations. In Tunisia natural pastures represent an important resource for and sheep and goats, but there is only a very limited number of studies on this topic. The aim of this study is to evaluate of intake and the variation of the intake behaviour of dairy ewes on natural pasture of dairy ewes and to study the relationships between intake and animal production.

2 Material and Methods The study was conducted on a natural and mountainous private rangeland in Beja (North West of Tunisia) of 6 ha. Twelve sicilo-sarde dairy ewes average weight 48 ± 3.4 kg were used in the experimental trials. The ewes lambing period spreads from September at end of November. The general stocking rate during the experiment was 2 dairy ewes per hectare in continous grazing system..The soil is clay and chalky with a average slope of 10–20%. Pasture production measurements were realized during the period of herbage growth. Twelve squares of 2 m × 2 m distributed on the whole plot were enclosed by barbed wire in order to prevent from ewes grazing. Biomass production and intake measurements were carried out at two periods, the first one in February, and the second in April. Before this date, the farmers do not exploit the pasture because of the weak forage production, the low temperatures and the high humidity of this region. The minimal, maximal temperatures and the middle humidity are respectively of 5◦ C, 14◦ C and 75% in February, and of 9◦ C, 22◦ C and 69% in April. In each period, half of each six squares were clipped at approximately 1.0 cm above ground level. Samples were oven dried for 24 h at 105◦C and weighed to determine total biomass and protein and NDF analysis. Nitrogen was determined by the AOAC method 990.03 [5]. Neutral detergent Fiber (NDF) was determined using the procedure of Van Soest and Wine [30]. The height of the grass has been measured on 5 samples of every square by a millimeter rule. Herbage intake measurements were carried out by the count bite method as described by Bryant et al. [9], Penning and Hooper [21], and Mc Innis et al. [17] Meuret et al. [18] based on direct and individual observations of ingestive behaviour of the twelve ewes. Bite number were ocularly measured during three short periodes of 10 min each one, during three consecutive days. Timing was interrupted when ewes stop grazing or when they walked with heads raised. Each period was recorded using a camera for additional checks and counting. Ewes used for these observations were accustomed during 1 week to being handled and observed and were apparently undisturbed by the observer. The weighed of the mean bite was estimated in the enclosed squares, by differences between total harvested biomass in each half of the square, before and after a short grazing period (three times of 7 min each), and divided by the number of bites during this period. The accuracy of this method is better to the simulation of the intake behavior of the animal [22]. The grazing time was the same for all of the

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ewes, and equal to 7 h per day, divided on two periods (4 h in the morning and 3 h in the afternoon). The daily intake can be calculated using the following formula: Daily Intake (g/d) = Bite weight (g) × Bite rate (bites/min) × Grazing time (min). Bite rate (bites/min) = [Bite number/Time spent biting (sec)] × 60 The ewes grazing were supplemented, with oat hay ad libitum, and a fixed quantity of concentrate of approximately 550 g/d and 450 g/d for February and April, respectively. The reduction in the supplemented concentrate was related to the advance of the stage of lactation of the ewes. Ewes were milked twice per day, The daily production is measured and the average quantity of milk produced during the experimental period was calculated. Student test [10] was used to compare differences in biting rate and pasture intake Regression analysis [26].

3 Results and Discussion 3.1 Pasture Characteristics Pasture composition was predominantly gramineous species (more than 50%), mostly Bromus madritensis, Lolium rigidum and Phalarys trunculata. Less leguminous species proportion species was observed, especially Lotus creticus, Lolium regidum and Medicago ciliaris. Other species was found than as Sonchus oleraceus and Cardus pycrocephalus. Pasture composition was different between the two evaluated periods (Table 1), the amount of graminous species increased from February to April, and the proportion of leguminous species decreased in the same period. This seasonal variation in pasture composition was reported by several authors [15, 19]. This fact could explain the reduction of pasture crude protein percentage and the increase of the pasture NDF proportion. High level of fiber determines the turnover rate in the digestive tract and can become a constraining factor for the digestibility of the herbage compounds [6, 13, 14]. Table 1 Herbage production and characteristics Period Species/characteristic

February

April

Mean production (t/ha) Graminous (%) Leguminous (%) Other (%) Mean grass height (cm) Dry matter (%) Crude protein (% DM) NDF (% DM)

2.8 51 36 13 6.6 27.1 15.7 42.5

4.7 57 28 15 28.4 34.7 13.1 56.4

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The average height of grass varied from 2 to 10 cm during the first period and from 15 to 35 cm during the second period. A significant heterogeinity is observed in each plot, according to relief and to soil characteristics. This increase in the height of the vegetation stimulates ingestion in the ruminants [8]. The increase of available forage affects the grazing time and biting rate [1, 25, 22].

3.2 Mean Count Bite and Dry Matter Intake Biting rates of individual animals were significantly different between the two periods (p = 0.011). During period 1, biting rates ranged from 24.3 to 39 and averaged 29.2 bites/min. Biting rate was increased in April by approximately 28.7%, and ranges from 27.3 to 46.8 with and average of 37.6 bites/min. These bite rate increment can be related to the increase in herbage availability between the two periods. The bite mass increases of 95–125 gr between the two measured periods. This result agrees with those reported in literature for sheep [27], but appear contradictory to the report of Scarnecchia et al. [25], who observe greater biting rate when forage availability decreased. Also, this result is different of that reported by Gong et al. [11] relating to the variation of the bite rate between legumes and grasses grazing monoculture pasture. Indeed, the reduction of bite mass when herbage availability increases is not observed when very low grass levels are offered, which constitute in this case a limiting factor for the animal behaviour [1, 12] reported that when forage height is below 6 cm, behavioural mechanisms are unable to compensate for changes in bite size; being intake rate reduced. Concentrate and hay supplementation to animals and herbage quality variability can also explain the observed results. The values of the total quantity of food intake show a lower of hay, and more significant consumption of pasture in April compared to February. (Table 2). This decrease of hay intake between the two periods can be related to associative effects and modifications in dry matter digestibility and rumen fermentations [7]. The higher proportion of grass in the pasture caused a substitution of hay by grass, being this substitution more important when hay of low quality is given. Bargo [4] reported that different forms and amounts of hay supplementation reduced pasture intake, hay supplementation resulted in a substitution rate from 0.81 to 0.97 kg pasture/kg hay. In this study, the simultaneously use of concentrate and Table 2 Mean intake and some behaviour parameters of ewes in the two periods February

Pasture intake (g/d) Hay intake (g/d) Concentrate intake (g/d) Bite rate (bite/min) Bit mass (g)

April

Mean

SD

Mean

SD

221.2 548 478 29.2 0.125

36.9

428.7 453 396 37.6 0.095

86.9

4.9

6.5

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Fig. 1 Relationship between pasture intake and milk production in dairy ewes

hay makes difficult the estimation the pasture/hay substitution ratio. However, it has been suggested that forage supplementation decreases pasture matter intake more than concentrates [16]. In addition, pasture dry matter intake (PDMI, g/day) was related to ewes milk production (MP, g/day). The following relationships were determined between the two parameters: February: PDMI = 106.111 + 178.856MP, R2 = 0.53 April: PDMI = 239.491 + 240.286MP, R2 = 0.545 Even if correlation coefficients were not significant, the observed relations show the tendency that higher ingestion in the ewes is positively related to higher milk production (Fig. 1). The low number of animals used for these measurements as well as the important individual variations could explain the lack of significant results. In addition, these results agree with those reported by Owen et al. [20] in which ewes intake on pasture increased with milk yield. Other factors can also affect forage intake and milk production relationship in dairy ewes, particularly the nursing mode (single or twin) as discussed by Ramsey et al. [23]. The type of supplement could also have an influence on substitution rate and animal performance [29].

4 Conclusion Mean bite rate and intake are better when forage production increase. Dairy ewes behaviour in natural pasture is affected by pasture composition, supplementation level and type. Ewes decrease their hay intake when pasture production becomes more available. Level of concentrates, nursing mode and milk yield could affect pasture intake by dairy ewes.

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References 1. Agreil C, Fritz H, Meuret M (2005) Maintenance of daily intake through bite mass diversity adjustment in sheep grazing on heterogeneous and variable vegetation. Appl Anim Behav Sci 91:35–56 2. Allden WG (1962) Rate of herbage intake and grazing time in relation to herbage availability. Proc Aust Soc Anim Prod 4:163–l71 3. Arnold GW (1960) The effect of the quantity and quality of pasture available to sheep on their grazing behaviour. Aust J Agric Res 11:1034–1043 4. Bargo F, Muller LD, Kolver ES, Delahoy JE (2003) Production and digestion of supplemented dairy cows on pasture. J Dairy Sci 86:1–42 5. Bellomonte G, Costantini A, Giammarioli S (1987) Comparison of modified automatic Dumas method and the traditional Kjeldahl method for nitrogen determination in food. J Assoc Off Anal Chem 70:227–229 6. Belovsky GE (1986) Optimal foraging and community structure: implications for a guild of generalist grassland herbivores. Oecologia 70:35–52 7. Bhatta R, Vaithiyanathan S, Singh NP, Shinde AK, Verma DL (2005) Effect of feeding tree leaves as supplements on the nutrient digestion and rumen fermentation pattern in sheep grazing on semi-arid range of India. Small Rumin Res 60:273–280 8. Black JL, Kenney PA (1984) Factors affecting diet selection by sheep: 2. Height and density of pasture. Aust J Agric Res 35:551–563 9. Bryant FC, Kothmann MM, Merrill LB (1980) Nutritive levels in sheep, goat, and whitetailedeer diets on excellent condition rangeland in Texas. J Range Manage 33:410–414 10. Dagnelie P (1980) Théories et méthodes statistiques. Les Presses Agronomiques de Gembloux, Belgique, 463p 11. Gong Y, Hodgson J, Lambert MG, Gordon IL (1996) Short-term ingestive behaviour of sheep and goats grazing grasses and legumes 1. Comparison of bite weight, bite rate, and bite dimensions for forages at two stages of maturity. NZ J Agric Res 39:63–73 12. Gordon IJ (1994) Animal-based measurement techniques for grazing ecology research: a review. In: Gordon IJ, Rubino R (eds) Grazing behaviour of goats and sheep. CIHEAMIAMZ, Zaragoza, pp 13–28. (Cahiers Options Méditerranéennes; v. 5), Séminaire du Projet CCE-CAMAR 8001-CT90-0021, 1991/11/11-13, Bella (Italy) 13. Gordon IJ, Illius AW, Milne JD (1996) Sources of variation in the foraging efficiency of grazing ruminants. Funct Ecol 10:219–226; Hodgson J (1982) Ingestive behaviour.In: Leaver JD (ed) Herbage intake handbook. The British Grassland Society, Hurley, pp 113–138 14. Illius AW, Gordon IJ (1991) Prediction of intake and digestion in ruminants by a model of rumen kinetics integrating animal size and plant characteristics. J Agric Sci 116:145–157 15. Ledda L, Caredda S, Porqueddu C, Sulas L (1995) Sward characterization and grazing value of a hilly Mediterranean natural pasture. In Sylvopastoral systems. Environmental, agricultural and economic sustainability. CIHEAM-IAMZ, Zaragoza, 280 p. (Cahiers Options Méditerranéennes; v. 12). 143–146 16. Mayne CS, Wright IA (1988) Herbage intake and utilization by the grazing dairy cow. In: Garnsworthy PC (ed) Nutrition and lactation in the dairy cow. Butterworths, London, p 280 17. Mc Innis ML, Vavra M, Krueger WC (1983) A comparison of four methods used to determine the diets of large herbivores. J Range Manage 36:302–306 18. Meuret M, Bartiaux-Thill N, Bourbouze A (1985) Feed intake of dairy goats on woody rangelands: direct observation of biting method; chromic oxide method. Ann Zootech 34:159–180 19. Munöz F, Andueza JD, Delgado I, Ochoa MJ (2000) Chemical composition and in vitro digestibility of browse plants in a semi-arid region of spain. In fodder shrub development in arid and semi arid zones. Proceedings of the workshop on native and exotic fodder shrubs in arid and semi arid zones, Hammamet Tunisia, 27 October–2 November 1996

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20. Owen JB, Miller EL, Bridge PS (1968) Voluntary food intake in lactating ruminants. J Agric Sci 70:223 21. Penning PD, Hooper GE (1985) An evaluation of the use of short term weight changes in grazing sheep for estimating herbage intake. Grass Forage Sci 40:79–84 22. Prache S, Peyraud JL (1997) Préhensibilité. de l’herbe pâturée chez les bovins et les ovins. INRA Prod Anim 10:377–390 23. Ramsey WS, Hatfields PG, Wallace JD, Southward GM (1994) Relationships among ewe milk production and ewe and lamb forage intake in Targhee ewes nursing single or twin lambs. J Anim Sci 72:811–816 24. Reeves M, Fulkerson WJ, Kellaway RC, Dove H (1996) A comparaison of three techniques to determine the herbage intake of dairy cows grazing kikiyu (Pennisitum clandestinum) pasture. Aust J Exp Agric 36:23–30 25. Scarnecchia DL, Nastis AS, Malechek JC (1985) Effects of forage availability on grazing behavior of heifers. J Range Manage 38:177–180 26. Snedecor CW, Cochran WC (1971). Statistical methods. The lowa State University Press, Ames, Iowa 27. Stobbs TH (1974) Rate of biting by Jersey cows as influenced by the yield and maturity of pasture swards. Trop Grassl 881–886 28. Stockdale CR (2000) Levels of pasture substitution when concentrates are fed to grazing dairy cows in northern Victoria. Aust J Exp Agric 40:913–921 29. Van Soest PJ, Wine RH (1967) Use of detergents in the analysisof fibrous feeds. IV. Determinations of plant cell wall constituents. J Assoc Off Anal Chem 50:50–55

Index

A Acidity, 201, 294, 856, 1070, 1072, 1098–1099, 1103, 1203, 1214, 1477 Activation, 512–514, 517–519, 626, 834–835 Adsorption, 140, 832, 834–837, 852–856, 899–904, 907–915, 918–919, 978–979, 1046–1052, 1065–1084, 1097–1105, 1109, 1172–1178, 1237–1251, 1275–1281, 1348, 1477 Aerobic, 9, 239, 481, 582, 823, 842–844, 946, 1012, 1118, 1140, 1321–1323, 1327–1339 Africa, 311, 330, 373–374, 377, 436, 439–440, 452, 471–479, 536, 641–642, 644–645, 722, 806, 1302, 1478–1479, 1492 Agriculture, 24, 153, 166, 170, 173, 277, 320, 329–330, 337, 355–356, 364–366, 368–369, 373, 387, 402, 404, 406, 408–409, 415–417, 457, 508, 568, 600, 726, 745, 786, 801, 809, 863, 986–987, 1163, 1288, 1371, 1382, 1390, 1423, 1425, 1451, 1463–1467 Air, 29, 31, 153, 196, 201, 218, 226–227, 232, 257, 260, 282, 284, 290–291, 298, 312, 348, 354, 365–366, 427, 429, 434–436, 440, 443, 478, 481–482, 494, 502–504, 507, 512, 518, 526, 537, 546, 557–563, 594, 600, 626, 628, 646, 665–672, 862, 907–915, 920, 922, 925, 931, 933–936, 938–939, 958, 986, 1023–1035, 1047, 1056, 1058, 1141, 1163, 1203–1204, 1213, 1218–1219, 1266, 1305, 1308, 1329, 1331, 1404, 1410–1411, 1470, 1472, 1485, 1494 Algea, 945, 959, 963–964 Anaerobic, 492, 494, 842, 886, 1006–1012, 1060–1061, 1087–1095, 1162, 1167, 1328–1340

Antibiotic, 363, 608–609, 943–946, 948–950, 1087–1089 Antioxidant, 535–542, 1024, 1214 Arboviruses, 641, 646 Architecture, 179–186, 201, 226–229, 377 Aromatic, 93–95, 97–99, 440, 667, 670–671, 886, 900, 956, 962, 1073–1074, 1157 Arsenic, 290, 354, 356–357, 671 Ash, 504, 513, 853, 901, 932–934, 986, 1225–1234, 1238, 1276, 1466, 1486–1488 B Backwash, 917–928 Bacteria, 146–148, 153, 156, 159, 363, 383, 481, 503, 560, 562, 582–583, 585–586, 589, 607, 653, 667, 818, 877, 886, 918, 944, 1060, 1088, 1140–1142, 1162, 1172, 1194, 1328, 1336, 1339 Beech, 82, 103–115 Bentonite, 1097–1105, 1238 Biodegradability, 341, 842–843, 944, 947, 949, 951, 956–957, 962, 1118, 1120, 1124, 1140–1141, 1263 Biodiversity, 16–17, 22, 26, 30, 51–60, 86, 91–100, 154–158, 165, 236, 260, 325, 330, 372, 375, 461, 477, 500, 508, 688, 727, 786, 1026 Biofuel, 276, 436, 499–509 Bioidentification, 967–971 Bioreactor, 502, 842, 917–928, 947, 958, 961–962, 1006, 1194, 1199 Bioremediation, 361, 995, 1003 Biosurfactant, 841–848 Biotechnology, 361–369, 752, 876–877, 947, 956, 986, 1089, 1194 Biotypes, 129–136 Boron, 290–291, 1127–1137

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1510 C Cadmium, 355–357, 832, 1037–1038, 1040–1041 Cancer, 354–356, 358, 553, 563, 604, 636, 666–669, 671–672, 974 Capsicum annuum L., 137–141 Catalyst, 191, 305, 436, 655, 877, 908, 911–912, 1046, 1204, 1208–1211 Catastrophe, 383–388, 754–755, 1284–1285 Cellulase, 877–882, 1193–1201 Cellulose, 146–148, 516, 856, 876–879, 881–882, 901, 956, 1149–1158, 1194, 1484 Chain, 31, 117–127, 304, 307–310, 331, 343, 351, 354–355, 363, 374, 376–377, 436, 591, 608, 733, 838, 956, 996, 1016, 1305 Chemical oxygen demand (COD), 918, 1090, 1152, 1182, 1322, 1364–1366 Chitin, 853, 856–857 Chitosan, 853, 856–857, 1238 Chromatography, 292, 877–879, 881–882, 894 Chromium, 290, 306, 595–596, 671, 832, 974, 978, 985–993, 1117 Climate, 39, 86, 92, 151–159, 180, 182, 188, 195–205, 224, 227, 232, 334, 348, 372, 427, 435, 500, 568, 645, 745, 827, 863, 879, 908, 933, 1060, 1284–1290, 1294, 1298, 1302, 1364, 1366, 1410, 1440, 1446 Clinoptilolite, 832–839, 1238, 1277 Coast, 56–57, 62, 182, 191–192, 198, 204, 374, 377, 392, 476, 478, 724, 763, 786, 796, 864, 869, 1214, 1294, 1298, 1385 Coastal, 51–52, 55–62, 182, 208, 211, 235–240, 280, 334–336, 407, 568, 786, 795–803, 806, 812, 1214, 1293–1298, 1306, 1313–1314, 1472 Combustion, 354, 441, 456, 461, 493–494, 496, 500, 511–519, 521, 560–562, 666–668, 672, 931–940, 1013, 1225–1226, 1287, 1289 Composting, 815–824, 1006–1007, 1009, 1012–1013, 1056, 1060–1061, 1089 Consumption, 23, 25, 94, 167, 172, 228, 236, 238, 262, 277, 304, 341, 343, 346, 372, 426–428, 432–436, 438, 440–441, 452–454, 456, 458, 472, 474–476, 481–488, 500–502, 506–507, 536, 578, 601–602, 636, 657, 660, 691, 707, 731–732, 761, 919, 932–933, 986, 1010–1012, 1089, 1119, 1190, 1207,

Index 1261, 1330, 1335, 1337, 1371, 1410, 1423–1424, 1452, 1494–1495, 1504 Contaminant, 118, 355, 512, 559, 562, 582, 591, 600, 639, 667, 842, 974, 996, 1000–1002, 1108, 1457, 1470 Contamination, 8, 11, 145, 354–355, 357–358, 500, 553–554, 559, 582, 585, 589, 592, 594, 600, 639, 667, 826, 832, 862–864, 866–868, 986, 996, 1002, 1006, 1024, 1039, 1255–1256, 1425–1426, 1452–1454, 1458–1459, 1470–1471, 1485 Conventional, 53, 98, 165–166, 237, 316, 366, 427–428, 432, 438, 440–442, 458, 499–509, 743, 852, 918, 944, 947, 974, 1045, 1097, 1108, 1117–1120, 1128, 1150, 1162, 1203, 1238, 1289, 1329, 1332 Copper, 32, 34, 290–291, 354, 484, 522, 524, 527, 569–571, 574, 576–578, 597, 831–839, 908, 911–914, 974, 1022, 1024, 1037, 1098, 1208, 1275–1281, 1436, 1472–1473 Corchorus olitorius L., 535–542 Cotton, 899–905, 956–957, 1171–1178, 1181, 1183, 1185, 1466–1467, 1479, 1493 Cyanide, 907–915 Cyprus, 223–233, 236–237, 353–358, 536–537, 644, 779–780, 1015–1016, 1018, 1020, 1128 D Damage, 3, 53, 69, 76, 141, 195–205, 232, 259, 273, 283, 386, 392, 395–396, 398, 455, 494, 507, 582, 650, 669, 687, 703, 745, 753, 782, 852, 919–920, 1219, 1275, 1289, 1387, 1391 Dangerous, 248, 289–300, 554, 1287, 1289–1290 Decolourization, 885–891 Delta, 608, 791, 795–803, 806, 812, 1382, 1385, 1390 Desalination, 239, 456–458, 1127–1137 Desertification, 38, 188, 477–478 Digestion, 492, 594, 617–618, 844, 1005–1013, 1039, 1087–1094, 1109, 1322, 1326, 1330 Directive, 16, 196, 237, 290, 303–313, 351, 445, 500, 509, 707–708, 711–712, 714, 1006–1007, 1435 Disinfection, 551–552, 584, 589, 1066, 1150 Dissolved, 29, 120, 122–124, 292, 300, 481, 484, 538, 582, 825–829, 843–844, 852, 879, 894, 900, 911, 918, 946, 1002,

Index 1069, 1108, 1118, 1130, 1141, 1153, 1157, 1257, 1261, 1423, 1493 Diversity, 18–19, 23–25, 41, 51–55, 60, 68, 85–89, 92, 95–97, 145, 167–168, 189–190, 228, 246, 286, 319, 331, 348, 375, 419, 453, 536, 604, 683–684, 700, 702, 721–725, 727, 743, 842, 1034, 1295, 1328, 1430, 1464 Dump, 270, 546, 552, 554, 732, 816, 1055–1063, 1226, 1256, 1433–1435 E Earthquake, 207, 211, 383–388, 392–394, 396–399, 733 Ecology, 18, 104, 166, 188, 321, 347, 688–689, 700–701, 755–756 Ecotourism, 53, 371–380, 405 Efflux, 153–154, 158–159 Electrolysis, 1182, 1276 Emergency, 38, 245–251 Endemic, 56–57, 67–72, 88, 92, 95–96, 319–320, 569, 572, 574–575, 578–579, 642, 723, 786 Environmental impact assessment (EIA), 692, 695, 702, 761, 764–766, 1412 Enzyme, 6, 141, 363, 365, 369, 626, 877–881, 1024, 1142, 1193–1201, 1457 Erosion, 37–38, 93, 95–96, 196, 201, 224, 286, 333, 335, 402, 408, 477, 797–798, 800–801, 803, 826, 1256, 1314, 1388, 1393–1394 Eutrophication, 117, 236, 1346, 1352 Evolution, 43, 192, 236, 296, 298, 349, 407, 411, 453, 625–627, 700, 722–723, 770, 774–775, 910, 1256 Exploitation, 47, 59–60, 85–89, 95, 254–255, 258, 418, 448, 459, 491, 1256, 1294, 1388, 1391–1392, 1424 F Facultative, 1162–1163 Farm, 16, 23–24, 130–131, 165–174, 331, 333, 339, 385, 387, 411, 616, 1090, 1476 Fecal coliform, 582 Fertilization, 145–148 Flood, 154, 197, 201, 384, 387, 478, 595, 644–646, 693, 722, 813, 1286, 1355–1360, 1453 Fluid, 526, 546, 563, 1000, 1387, 1395 Fouling, 917–928, 1134, 1137, 1150 Fungal, 6, 11, 151–159, 203, 1033, 1216, 1484

1511 G Geotechnics, 384 Germination, 67–72, 130, 986–988 GIS, 317, 322–323, 326, 333, 710, 714, 788, 790, 799, 810, 1303, 1347, 1410, 1412–1413 Global warming, 152–153, 455, 500, 504, 506, 558, 646, 753, 931–932, 1283–1290 Glucose, 5, 536, 843, 877–878, 880–882, 946–947, 958, 961–962, 1141, 1143 Groundwater, 8, 383–384, 813, 852, 995–1003, 1056, 1128, 1345, 1389, 1398–1402, 1405, 1422–1424, 1428–1429, 1451–1461, 1471 H Habitualization, 772–773 Heavy, 3–11, 24–25, 29–35, 55, 68, 197, 201–202, 237, 353–358, 386, 392, 397, 437, 442, 472, 477, 500, 504, 591, 596–597, 646, 713, 828, 831–834, 836, 838, 862–864, 866–871, 968–970, 974, 987–988, 992–993, 1023–1024, 1026, 1033, 1037–1042, 1056–1057, 1060, 1062, 1107–1108, 1115, 1171, 1182, 1218, 1275–1276, 1349 Herbicides, 130–136, 145–148, 354, 842, 996 Heritage, 15–26, 92, 175, 179–186, 188–190, 192, 195–205, 220–221, 229, 231–232, 376–377, 393, 461, 764 Highland, 85–89, 405, 409, 411, 414–415, 477 Household, 23, 404, 406, 408, 410–411, 418, 426–427, 433, 472, 475–476, 591, 630–631, 633, 636, 639, 653–672, 822, 876, 1257, 1410 Housing, 226, 326, 395–396, 398, 425–434, 668, 691 Hydrophobic, 918, 996–997, 1001, 1066, 1088, 1149–1150, 1157, 1470 Hydrophytes, 1348, 1352 I Influenza, 623–633, 646, 666 Inhibition, 72, 504, 538, 540–541, 944–946, 950–951, 963, 988, 1142, 1145–1146 Insecticides, 649, 1463–1467, 1470, 1492–1493 Insects, 856, 1216, 1464, 1466, 1492–1494, 1499 Institution, 23, 55, 93, 98, 169, 172–173, 239, 316, 347–348, 402, 417–418, 451, 569, 632, 684, 688, 703–704, 711, 770–773, 779, 1434

1512 Instrument, 171, 181, 253–265, 305, 342, 351, 419, 512, 546, 553, 680, 732, 821, 1039, 1046, 1066, 1070, 1090–1091, 1098–1099, 1103, 1325 Intake, 355, 358, 616–620, 1370, 1374, 1376, 1426, 1501–1505 Invertebrate, 1023–1035 Irrigation, 75–82, 237, 411–412, 429–430, 582–583, 592, 646, 826, 933, 1013, 1108, 1162–1163, 1257, 1345–1352, 1370–1371, 1374, 1382, 1385–1387, 1391, 1398–1400, 1402, 1405 Island, 51, 182, 208, 224–226, 229, 232, 235–237, 239, 353–354, 356–357, 1305, 1492 Isotherm, 853–855, 904, 914, 976–980, 1047–1052, 1067–1069, 1078–1081, 1098–1099, 1104, 1173, 1177, 1238, 1248–1251 L Lagoon, 55–60, 796, 801 Land agricultural, 24, 274, 330–331, 406–407, 1428 barren, 1414, 1416–1417 complex, 719–727 Landfill, 305–306, 310, 312, 434, 554, 691–696, 816, 823, 1006–1009, 1012, 1055–1058 Landsat, 42, 404, 785–792, 797–799, 803, 1413 Landscape cultural, 188–190, 207–221 rural, 17–18, 24–25, 745 Leaching, 8, 290, 292–293, 296–300, 355, 457, 538–541, 893–897, 1209, 1211, 1216, 1276, 1436–1437, 1453–1454 Lead, 34–35, 354–358, 865–866, 871, 1041, 1109 Legislation, 20, 24, 53, 196, 228–229, 239, 246, 257, 263, 304–305, 307–308, 310–311, 342, 348, 350, 406–407, 546, 555, 708, 711, 949, 1321, 1425, 1476–1479 Lignosulphonates, 955–956 Liquid, 435–445, 894, 1091, 1198–1199, 1452–1453 Local, 22–23, 39, 55, 64, 99, 187–193, 229, 284, 372, 374, 378, 417, 459, 552, 554, 626, 631, 684, 711, 713, 762

Index M Maize, 145–148, 337 Marketing, 311, 341–351, 821 Media, 729–738, 1330, 1442 Medical, 245–251, 545–555, 561, 571, 601, 637, 1058 Mediterranean, 39, 56–57, 59, 187–193, 208, 211, 216, 221, 224, 237, 642, 763, 786, 792, 796, 806, 812, 1018, 1130, 1213–1222, 1302–1303, 1305, 1307–1308, 1439–1447 Membrane, 917–928, 1127–1137, 1149–1158 Metal, 3–11, 29–35, 353–358, 591–597, 866, 876, 1037–1042, 1109, 1175–1176, 1277, 1348, 1437 Methemoglobinemia, 635–640, 1256 Methylene, 899–905, 1097–1105, 1330 Microalgea, 945, 963–964 Microbiological, 201, 581–590, 1256, 1327–1328, 1330–1331, 1335–1336, 1421–1422 Mining, 267–278, 693, 695, 726, 831, 1022, 1171, 1414, 1416 Monitoring, 54, 196, 326, 561, 608, 632, 668, 785–792, 987, 1214–1215, 1413 Morphology, 1337–1338 N Nature, 16, 18, 95, 700, 752, 754, 756–758, 1425, 1430–1431 Network, 61–66, 172–173, 305, 809–810, 1297, 1435 Neurology, 354, 642, 646–649 Nitrate, 120, 123–124, 600, 635–640, 894, 1256–1259, 1346, 1348–1351 Nitrogen, 122–123, 145–148, 504, 609, 669–670, 826, 934, 1061–1062, 1070, 1098, 1142, 1256, 1502 Noise, 226, 260, 271, 348, 667, 787, 1188, 1410 Nutrient, 117–126, 1008, 1109 O Optimization, 919, 1181–1190 Organic, 5, 8–9, 122, 165–175, 300, 355, 358, 670, 816–819, 876, 893, 1005–1013, 1055–1062, 1089, 1455, 1470, 1472–1474 Osmosis, 1127–1137 Oxidation, 907–914, 1181–1190, 1203–1211, 1266–1272 Oxide, 558, 931, 935–936, 1046, 1071, 1100, 1208–1209, 1232, 1276

Index Ozonation, 908, 944–945, 947–951, 955–964, 1263–1272 P Park, 68, 154–158, 315–326, 377, 431, 1024–1027, 1031–1034, 1430, 1435–1436, 1474–1475 Pathogens, 583, 589, 646, 656, 918, 1466, 1485 Peroxide, 886, 908, 912, 1203–1211 Pest, 1491–1499 Pesticides, 562, 600, 1469–1479 Phosphorus, 123, 1328, 1351–1352, 1488 Phytoplankton, 118–119, 121 Phytoremediation, 987, 1107–1108, 1113 Pigment, 831, 1033, 1216, 1220–1221 Plan, 174, 211–213, 215, 217, 219–220, 224, 272, 318–321, 324–325, 357, 368–369, 377, 379, 393, 407–408, 459, 629, 747–748, 757, 760, 762, 764–766, 780–781, 789, 802, 1007, 1057 Policy, 17–19, 21–23, 98–99, 167, 268, 343–345, 762, 1435 Political, 16, 18, 683–684, 777–782 Pretreatment, 43, 138–140, 852, 877, 879–880, 900, 943–952, 957, 1010, 1117, 1144, 1146–1147, 1150, 1152, 1154–1155, 1182 Property, 17, 23, 153, 221, 224, 231, 257–258, 264, 276, 316, 378, 402, 406–407, 411–412, 414, 418, 448, 568, 650, 670, 735, 752, 771, 956, 1157, 1360 Psychological, 282–283, 684, 726, 736 Pump, 276, 293, 476, 478, 526, 609, 736, 842, 919–920, 996, 1002–1003, 1039, 1091, 1130, 1152, 1163, 1204, 1278, 1329, 1331, 1389, 1424 Q Quercus castaneifolia, 75–82 R Radionuclide, 615, 1065–1084 Radiotracer, 1066–1067, 1070 Rangeland, 86–87, 1502 Reconstruction, 19, 212, 223, 226, 394, 751–758 Recovery, 18, 20, 22, 68, 304–307, 309–313, 411, 427, 440, 443–444, 504, 821, 838, 908, 974, 1006, 1011–1013, 1016–1017, 1058, 1066, 1092, 1115, 1150, 1279, 1436–1437

1513 Recreation, 17, 19, 24, 225, 282–283, 285, 431, 701, 725–726 Reform, 26, 257, 401, 404, 406–408, 449 Regulation, 68, 237, 305, 347, 350, 699, 701, 704, 708, 752, 761, 775 Regulator, 373, 1387 Rehabilitation, 220, 233, 418, 1161–1169 Reinforcement, 393–399, 578 Remediation, 3–11, 851–857, 886, 987, 995–1003, 1107–1108, 1113, 1115, 1225–1234 Remote sensing, 38, 48, 317, 326, 692–695, 787–788, 795–803, 1410, 1412–1414 Residues, 236, 408, 457, 476, 495, 600, 607–612, 876, 944, 1059, 1088, 1113, 1172, 1452, 1464, 1469, 1473 Respiration, 118–119, 121–125, 133, 152, 154–159, 618, 947, 1322–1325 Retention, 334, 377, 616–619, 827, 842, 845–846, 848, 918, 980, 1118, 1141, 1164, 1167, 1322, 1324–1325, 1329, 1363, 1452, 1454, 1457, 1473 Reverse, 47, 108, 114, 304–310, 314, 349, 388, 455, 838, 868, 1089, 1097, 1127–1137, 1171, 1276, 1289 Rhizobacteria, 4 Rhizome, 95, 1492, 1499 Rock, 29, 108, 154, 191, 213–214, 276, 334, 354–355, 358, 384, 386–388, 591–592, 833, 1046, 1257, 1345 S Satellite, 38, 41–43, 48, 317, 322, 324, 335, 693–694, 786–789, 797–802, 1294, 1412–1419, 1413–1416, 1413 Scarcity, 236–237, 239, 451, 455, 457, 461, 654, 823, 832, 932, 1006, 1162 Seedling, 6, 10–11, 75–82, 76–82, 409, 987, 1493, 1496 Segregation, 245–251, 546, 1117 Shading, 75–82, 503 Shoreline, 797, 799–803 Slope, 41, 68, 71, 75, 191, 217, 294, 296, 298, 333, 403–419, 484, 513–514, 561, 694–695, 805–813, 924, 979, 997, 1048, 1068–1069, 1076, 1090, 1103, 1177, 1241–1242, 1249–1250, 1268, 1315, 1364, 1502 Solubilization, 4, 996–1002, 1067, 1069, 1073–1074 Stability, 68, 159, 168, 228, 380, 396, 418, 436, 444, 1006, 1009, 1076, 1080, 1083, 1150, 1332, 1339

1514 Strategy, 21, 193, 220, 227, 236–240, 342, 350–351, 358, 367–368, 379–380, 452, 467, 500, 560, 630–633, 655, 684, 701, 743–747, 751–758, 944, 1006–1007, 1009, 1026, 1056, 1501 Surface water, 568, 656, 662, 832, 872, 996, 1088, 1285, 1366, 1398, 1400, 1402–1406, 1421–1424, 1429 Surfactant, 842–843, 996–1002, 1039, 1237–1251 T Terrain, 805–812, 826, 1452 Textile, 345, 347, 852, 876, 885–891, 955–964, 974, 986, 1045, 1097, 1181–1190, 1194, 1237–1238, 1263–1264 Thermodynamics, 448, 526, 1067, 1081, 1281 Tide, 61–66, 1293–1295 Topography, 43, 86, 92, 192, 198, 226, 405, 723, 806, 1057, 1295, 1356 Toxicity, 11, 30, 348, 429, 558, 831, 841, 845, 848, 899, 907, 944–945, 950–952, 955–964, 968–971, 987–988, 1108, 1117, 1140–1142, 1263, 1422, 1469 Trace, 20, 24, 32, 118, 181, 213, 221, 290, 591–592, 597, 632, 657, 701, 826, 832, 834, 862, 918, 1017, 1018–1022, 1037–1038, 1066–1067, 1070, 1090, 1153, 1328, 1330, 1333–1336, 1423–1424, 1457 Traffic, 24, 226, 233, 270, 428, 639, 665, 691, 773, 862–864, 868–871, 1024, 1034, 1042, 1218, 1411–1412, 1415, 1470 Treatment sludge, 492, 1139–1147, 1322 wastewater, 239, 481–482, 582, 843, 852, 857, 899, 918, 949, 1006–1008, 1046, 1108, 1118, 1139–1141, 1144, 1146, 1150, 1161–1168, 1182, 1193, 1201, 1203, 1276, 1322–1323, 1425, 1429 U Ultrasound, 886, 888, 890 Urbanization, 56, 96, 321–325, 397, 645, 691, 786, 790–792, 828, 1256, 1411, 1419, 1464

Index V Vegetable, 170, 277, 337–338, 355, 429, 535–536, 539, 542, 572–573, 581–590, 600, 636 Vernacular, 201, 208, 219–221, 223–233, 392–393, 398–399 Vulnerable, 52–54, 60, 88, 95–96, 202, 380, 394, 398, 503, 723, 1425, 1429, 1451–1461 W Waste solid, 815–823, 1005–1013 water, 117–1124, 235–239, 429, 481–482, 496, 582–583, 596, 713, 827, 831–832, 842–844, 852, 857, 888, 893–896, 900, 919–920, 924, 944, 949, 951, 957–959, 974, 1007–1008, 1010–1012, 1046, 1097, 1108, 1115, 1139–1147, 1150, 1157, 1161–1168, 1171, 1181–1190, 1193–1201, 1203–1211, 1263–1264, 1275, 1321, 1322–1323 Wave, 65, 214, 388, 450, 483, 561, 608, 612–613, 774, 853, 865, 886, 894, 975, 1046, 1073, 1099, 1103, 1152, 1240, 1265, 1313–1319 Weeding, 75–82 Wells, 214, 276, 504, 636, 639, 656, 893, 897, 1119, 1402, 1406, 1422–1424, 1428, 1472 Wetland, 320, 475, 644, 710, 785–792, 799, 801, 1108, 1352, 1431 Wildlife, 19, 21, 192, 282, 284, 291, 319, 325, 476, 600, 786, 792 Wood, 76–77, 95, 105, 114, 169, 171, 191–192, 198, 204, 276, 290–300, 330, 354, 376, 391, 394, 409, 412, 471–472, 475–477, 511–519, 561, 659–660, 667, 745–748, 876, 936, 955, 986, 1163–1164, 1238, 1316, 1484, 1493 X Xenobiotics, 967–971, 1140 Z Zeolite, 831–839, 1237–1252 Zooplankton, 118–125