An Ecotoxicological Perspective ORGANIC POLLUTANTS Second Edition © 2009 by Taylor & Francis Group, LLC CRC Press is an imprint of the Taylor & Francis Group, an informa business Boca Raton London New York An Ecotoxicological Perspective C. H. Walker ORGANIC POLLUTANTS Second Edition With contribution from Charles Tyler © 2009 by Taylor & Francis Group, LLC CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2009 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-13: 978-1-4200-6258-8 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher can- not assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copy- right.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that pro- vides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Walker, C. H. (Colin Harold), 1936- Organic pollutants : an ecotoxicological perspective / Colin H. Walker. 2nd ed. p. cm. Includes bibliographical references and index. ISBN 978-1-4200-6258-8 (alk. paper) 1. Organic compounds Toxicology. 2. Organic compounds Environmental aspects. 3. Environmental toxicology. I. Title. RA1235.W35 2009 615.9’5 dc22 2008030227 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com © 2009 by Taylor & Francis Group, LLC v Contents Preface to First Edition xiii Preface to Second Edition xv Acknowledgments in First Edition xvii 1PART Basic Principles 1Chapter Chemical Warfare 3 1.1 Introduction 3 1.2 Plant–Animal Warfare 4 1.2.1 Toxic Compounds Produced by Plants 4 1.2.2 Animal Defense Mechanisms against Toxins Produced by Plants 8 1.3 Toxins Produced by Animals and Microorganisms 10 1.3.1 Toxins Produced by Animals 10 1.3.2 Microbial Toxins 11 1.4 Human-Made Chemical Weapons 13 1.5 Summary 15 Further Reading 15 2Chapter Factors Determining the Toxicity of Organic Pollutants to Animals and Plants 17 2.1 Introduction 17 2.2 Factors That Determine Toxicity and Persistence 19 2.3 Toxicokinetics 21 2.3.1 Uptake and Distribution 21 2.3.2 Metabolism 24 2.3.2.1 General Considerations 24 2.3.2.2 Monooxygenases 26 2.3.2.3 Esterases and Other Hydrolases 36 2.3.2.4 Epoxide Hydrolase (EC 4.2.1.63) 40 2.3.2.5 Reductases 41 2.3.2.6 Conjugases 42 2.3.2.7 Enzyme Induction 48 2.3.3 Storage 50 2.3.4 Excretion 51 2.3.4.1 Excretion by Aquatic Animals 52 2.3.4.2 Excretion by Terrestrial Animals 52 © 2009 by Taylor & Francis Group, LLC vi Contents 2.4 Toxicodynamics 54 2.5 Selective Toxicity 60 2.6 Potentiation and Synergism 62 2.7 Summary 64 Further Reading 65 3Chapter Inuence of the Properties of Chemicals on Their Environmental Fate 67 3.1 Properties of Chemicals That Inuence Their Fate in the Gross Environment 68 3.2 Models of Environmental Fate 70 3.3 Inuence of the Properties of Chemicals on Their Metabolism and Disposition 71 3.4 Summary 72 Further Reading 73 4Chapter Distribution and Effects of Chemicals in Communities and Ecosystems 75 4.1 Introduction 75 4.2 Movement of Pollutants along Food Chains 75 4.3 Fate of Pollutants in Soils and Sediments 81 4.4 Effects of Chemicals upon Individuals—the Biomarker Approach 84 4.5 Biomarkers in a Wider Ecological Context 89 4.6 Effects of Chemicals at the Population Level 90 4.6.1 Population Dynamics 90 4.6.2 Population Genetics 93 4.7 Effects of Pollutants upon Communities and Ecosystems—the Natural World and Model Systems 96 4.8 New Approaches to Predicting Ecological Risks Presented by Chemicals 97 4.9 Summary 98 Further Reading 98 2PART Major Organic Pollutants 5Chapter The Organochlorine Insecticides 101 5.1 Background 101 5.2 DDT [1,1,1,-trichloro-2,2-bis (p-chlorophenyl) ethane] 102 5.2.1 Chemical Properties 102 5.2.2 Metabolism of DDT 104 5.2.3 Environmental Fate of DDT 105 © 2009 by Taylor & Francis Group, LLC Contents vii 5.2.4 Toxicity of DDT 109 5.2.5 Ecological Effects of DDT 112 5.2.5.1 Effects on Population Numbers 112 5.2.5.2 Effects on Population Genetics (Gene Frequencies) 115 5.3 The Cyclodiene Insecticides 116 5.3.1 Chemical Properties 116 5.3.2 The Metabolism of Cyclodienes 117 5.3.3 Environmental Fate of Cyclodienes 119 5.3.4 Toxicity of Cyclodienes 122 5.3.5 Ecological Effects of Cyclodienes 124 5.3.5.1 Effects on Population Numbers 124 5.3.5.2 Development of Resistance to Cyclodienes 130 5.4 Hexachlorocyclohexanes 131 5.5 Summary 132 Further Reading 132 6Chapter Polychlorinated Biphenyls and Polybrominated Biphenyls 133 6.1 Background 133 6.2 Polychlorinated Biphenyls 134 6.2.1 Chemical Properties 134 6.2.2 Metabolism of PCBs 136 6.2.3 Environmental Fate of PCBs 140 6.2.4 The Toxicity of PCBs 143 6.2.5 Ecological Effects of PCBs 146 6.2.5.1 Physiological and Biochemical Effects in the Field 146 6.2.5.2 Population Effects 146 6.2.5.3 Population Genetics 149 6.3 Polybrominated Biphenyls 149 6.4 Summary 150 Further Reading 150 7Chapter Polychlorinated Dibenzodioxins and Polychlorinated Dibenzofurans 151 7.1 Background 151 7.2 Origins and Chemical Properties 151 7.3 Metabolism 153 7.4 Environmental Fate 153 7.5 Toxicity 154 7.6 Ecological Effects Related to TEQs for 2,3,7,8-TCDD 158 7.7 Summary 160 Further Reading 161 © 2009 by Taylor & Francis Group, LLC viii Contents 8Chapter Organometallic Compounds 163 8.1 Background 163 8.2 Organomercury Compounds 163 8.2.1 Origins and Chemical Properties 163 8.2.2 Metabolism of Organomercury Compounds 165 8.2.3 Environmental Fate of Organomercury 166 8.2.4 Toxicity of Organomercury Compounds 168 8.2.5 Ecological Effects of Organomercury Compounds 170 8.3 Organotin Compounds 172 8.3.1 Chemical Properties 172 8.3.2 Metabolism of Tributyltin 173 8.3.3 Environmental Fate of Tributyltin 173 8.3.4 Toxicity of Tributyltin 174 8.3.5 Ecological Effects of TBT 176 8.4 Organolead Compounds 177 8.5 Organoarsenic Compounds 178 8.6 Summary 179 Further Reading 180 9Chapter Polycyclic Aromatic Hydrocarbons 181 9.1 Background 181 9.2 Origins and Chemical Properties 182 9.3 Metabolism 183 9.4 Environmental Fate 185 9.5 Toxicity 187 9.6 Ecological Effects 189 9.7 Summary 191 Further Reading 191 1Chapter 0 Organophosphorus and Carbamate Insecticides 193 10.1 Background 193 10.2 Organophosphorus Insecticides 194 10.2.1 Chemical Properties 194 10.2.2 Metabolism 197 10.2.3 Environmental Fate 200 10.2.4 Toxicity 202 10.2.5 Ecological Effects 208 10.2.5.1 Toxic Effects in the Field 208 10.2.5.2 Population Dynamics 209 10.2.5.3 Population Genetics 211 10.3 Carbamate Insecticides 212 10.3.1 Chemical Properties 212 10.3.2 Metabolism 213 © 2009 by Taylor & Francis Group, LLC Contents ix 10.3.3 Environmental Fate 213 10.3.4 Toxicity 215 10.3.5 Ecological Effects 217 10.4 Summary 218 Further Reading 218 1Chapter 1 Anticoagulant Rodenticides 219 11.1 Background 219 11.2 Chemical Properties 219 11.3 Metabolism of Anticoagulant Rodenticides 221 11.4 Environmental Fate 222 11.5 Toxicity 224 11.6 Ecological Effects 226 11.6.1 Poisoning Incidents in the Field 226 11.6.2 Population Genetics 228 11.7 Summary 228 Further Reading 229 1Chapter 2 Pyrethroid Insecticides 231 12.1 Background 231 12.2 Chemical Properties 231 12.3 Metabolism of Pyrethroids 232 12.4 Environmental Fate of Pyrethroids 234 12.5 Toxicity of Pyrethroids 236 12.6 Ecological Effects of Pyrethroids 237 12.6.1 Population Dynamics 237 12.6.2 Population Genetics 238 12.7 Summary 238 Further Reading 239 3PART Further Issues and Future Prospects 1Chapter 3 Dealing with Complex Pollution Problems 243 13.1 Introduction 243 13.2 Measuring the Toxicity of Mixtures 244 13.3 Shared Mechanism of Action—an Integrated Biomarker Approach to Measuring the Toxicity of Mixtures 245 13.4 Toxic Responses That Share Common Pathways of Expression 250 13.5 Bioassays for Toxicity of Mixtures 251 13.6 Potentiation of Toxicity in Mixtures 253 13.7 Summary 254 Further Reading 254 © 2009 by Taylor & Francis Group, LLC x Contents 1Chapter 4 The Ecotoxicological Effects of Herbicides 257 14.1 Introduction 257 14.2 Some Major Groups of Herbicides and Their Properties 258 14.3 Impact of Herbicides on Agricultural Ecosystems 258 14.4 Movement of Herbicides into Surface Waters and Drinking Water 261 14.5 Summary 263 Further Reading 264 1Chapter 5 Endocrine-Disrupting Chemicals and Their Environmental Impacts 265 R. M. Goodhead and C. R. Tyler 15.1 Introduction 265 15.2 The Emergence of Endocrine Disruption as a Research Theme 266 15.3 Modes of Action of Endocrine-Disrupting Chemicals 266 15.4 Case Studies of Endocrine Disruption in Wildlife 270 15.4.1 DDT (and Its Metabolites) and Developmental Abnormalities in Birds and Alligators 270 15.4.2 TBT and Imposex in Mollusks 272 15.4.3 Estrogens and Feminization of Fish 273 15.4.4 Atrazine and Abnormalities in Frogs 275 15.4.5 EDCs and Health Effects in Humans 276 15.5 Screening and Testing for EDCs 276 15.6 A Lengthening List of EDCs 278 15.6.1 Natural and Pharmaceutical Estrogens 279 15.6.2 Pesticides 279 15.6.3 PCBs 279 15.6.4 Dioxins 280 15.6.5 Polybrominated Diphenyl Ethers 280 15.6.6 Bisphenols 281 15.6.7 Alkylphenols 281 15.6.8 Phthalates 282 15.6.9 Natural EDCs 283 15.7 Effects of Mixtures 283 15.8 Windows of Life with Enhanced Sensitivity 284 15.9 Species Susceptibility 286 15.10 Effects of EDCs on Behavior 288 15.11 Lessons Learned from Endocrine Disruption and Their Wider Signicance in Ecotoxicology 290 15.12 Summary 292 Further Reading 292 © 2009 by Taylor & Francis Group, LLC Contents xi 1Chapter 6 Neurotoxicity and Behavioral Effects of Environmental Chemicals 293 16.1 Introduction 293 16.2 Neurotoxicity and Behavioral Effects 295 16.3 The Mechanisms of Action of Neurotoxic Compounds 296 16.4 Effects on the Functioning of the Nervous System 302 16.4.1 Effects on the Peripheral Nervous System 302 16.4.2 Effects on the Central Nervous System 305 16.5 Effects at the Level of the Whole Organism 306 16.6 The Causal Chain: Relating Neurotoxic Effects at Different Organizational Levels 308 16.6.1 Chemicals Sharing the Same Principal Mode of Action 308 16.6.2 Effects of Combinations of Chemicals with Differing Modes of Action 310 16.7 Relating Neurotoxicity and Behavioral Effects to Adverse Effects upon Populations 311 16.8 Concluding Remarks 313 16.9 Summary 316 Further Reading 317 1Chapter 7 Organic Pollutants: Future Prospects 319 17.1 Introduction 319 17.2 The Adoption of More Ecologically Relevant Practices in Ecotoxicity Testing 321 17.3 The Development of More Sophisticated Methods of Toxicity Testing: Mechanistic Biomarkers 323 17.4 The Design of New Pesticides 324 17.5 Field Studies 326 17.6 Ethical Questions 328 17.7 Summary 328 Further Reading 329 Glossary 331 References 337 © 2009 by Taylor & Francis Group, LLC [...]... Evolutionary Distance 2.0 Prokaryotic 10 2 51 0 0 200 400 600 800 10 00 12 00 14 00 Million Years Ago FIGURE 1. 2 An abbreviated version of the P450 phylogenetic tree compared with an evolutionary timescale (Lewis 19 96) The dashed line represents a plot of evolutionary distance (Nelson and Strobel 19 87) © 2009 by Taylor & Francis Group, LLC 10 Organic Pollutants: An Ecotoxicological Perspective, Second Edition This... represents an adaptation of herbivorous/omnivorous animals to life on land, where survival became dependent upon the ability to detoxify lipophilic toxins produced by plants 2.5 10 1 11 A 2E 2C 2B 2D 2 1 4A1 4A4 Microbiota 4 Soft-bodied fauna Primates Rodents 0.5 3 Mammals Reptiles Amphibia Insects Lungfish Agnatha Fish 1. 0 Eukaryotic 17 21 Mollusks 1. 5 P450 gene 11 11 B Birds Evolutionary Distance 2.0 Prokaryotic... giving due attention to the top-down approach—considering adverse changes at the levels of population, community, and ecosystem, and relating them to the effects of both organic and inorganic pollutants The present text gives a much more detailed and focused account of major groups of organic pollutants, and adopts a bottomup approach The fate and effects of organic pollutants are seen from the point... Group, LLC 14 Organic Pollutants: An Ecotoxicological Perspective, Second Edition Chemical warfare agents came to be used on the battlefield during the 19 14 19 18 war These included mustard gas (yperite) and lewisite More toxic compounds, the organophosphorous nerve gases, were produced later, during the Second World War (19 39 19 45), although they were not actually used in combat Organophosphorous anticholinesterases... from Harborne (19 93), Eldefrawi and Eldefrawi (19 90), Ballantyne and Marrs (19 92), Brooks, Pratt, and Jennings (19 79), Salgado (19 99), Copping and Duke (2007) Copping and Duke 2007) Sabadilla was used by the native people of South and Central America as an insecticide for many years Physostigmine (eserine) is a carbamate found in the calabar bean (Physostigma benenosum), which acts as an anticholinesterase... natural pyrethrins (Chapter 12 ) More widely, many detoxication mechanisms are relatively nonspecific, operating against a wide range of compounds that 3 © 2009 by Taylor & Francis Group, LLC 4 Organic Pollutants: An Ecotoxicological Perspective, Second Edition have common structural features (e.g., benzene rings, methyl groups, or ester bonds) Thus, they can metabolize both human-made and natural xenobiotics... Many of the compounds produced by plants known to be toxic to animals are described in Harborne and Baxter (19 93); Harborne, Baxter, and Moss (19 96); Frohne and Pfander (2006); D’Mello, Duffus, and Duffus (19 91) ; and Keeler and Tu (19 83) The development of new pesticides using some of these compounds as models has been reviewed by Copping and Menn (2000), and Copping and Duke (2007) Information about... Sabadilla is an insecticidal preparation derived from this source, which also contains another alkaloid, cevadine Further, pp -DDT and pyrethroid have similar effects to veratridine but evidently bind to different sites on the sodium channel (Eldefrawi and Eldefrawi 19 90, © 2009 by Taylor & Francis Group, LLC 6 Organic Pollutants: An Ecotoxicological Perspective, Second Edition TABLE 1. 1 Some Toxins... resistance of this type evolved in nature long before the appearance of commercial insecticides 1. 3 TOXINS PRODUCED BY ANIMALS AND MICROORGANISMS 1. 3 .1 TOXINS PRODUCED BY ANIMALS Animals use chemical weapons for both defense and attack Considering defensive tactics first, bombardier beetles (Brachinus spp.) can fire a hot solution of irritant © 2009 by Taylor & Francis Group, LLC Chemical Warfare 11 quinones... has also been used in human medicine Insecticidal carbamates are structurally related to it and also act as anticholinesterases (Ballantyne and Marrs 19 92) Dicoumarol is found in sweet clover and can cause hemorrhaging in cattle because of its anticoagulant action It acts as a vitamin K antagonist and has served as a model for the development of warfarin and related anticoagulant rodenticides Strychnine . 98 2PART Major Organic Pollutants 5Chapter The Organochlorine Insecticides 10 1 5 .1 Background 10 1 5.2 DDT [1, 1 ,1, -trichloro-2,2-bis (p-chlorophenyl) ethane] 10 2 5.2 .1 Chemical Properties 10 2 5.2.2. Rodenticides 219 11 .1 Background 219 11 .2 Chemical Properties 219 11 .3 Metabolism of Anticoagulant Rodenticides 2 21 11. 4 Environmental Fate 222 11 .5 Toxicity 224 11 .6 Ecological Effects 226 11 .6 .1 Poisoning. Populations 311 16 .8 Concluding Remarks 313 16 .9 Summary 316 Further Reading 317 1Chapter 7 Organic Pollutants: Future Prospects 319 17 .1 Introduction 319 17 .2 The Adoption of More Ecologically Relevant