Chemical Pesticides: Mode of Action and Toxicology / Jørgen Stenersen
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CHEMICAL PESTICIDES MODE OF ACTION AND TOXICOLOGY ©2004 by Jørgen Stenersen CHEMICAL PESTICIDES MODE OF ACTION AND TOXICOLOGY Jørgen Stenersen CRC PRESS Boca Raton London New York Washington, D.C. ©2004 by Jørgen Stenersen Library of Congress Cataloging-in-Publication Data Stenersen, Jørgen. Chemical pesticides: mode of action and toxicology / Jørgen Stenersen. p. cm. Includes bibliographical references and index. ISBN 0-7484-0910-6 1. Pesticides--Toxicology. I. Title. RA1270.P4S74 2004 615.9'02--dc22 2004043568 This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage or retrieval system, without prior permission in writing from the publisher. The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for creating new works, or for resale. Specific permission must be obtained in writing from CRC Press LLC for such copying. Direct all inquiries to CRC Press LLC, 2000 N.W. Corporate Blvd., Boca Raton, Florida 33431. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation, without intent to infringe. Visit the CRC Press Web site at www.crcpress.com ©2004 by Jørgen Stenersen No claim to original U.S. Government works International Standard Book Number 0-748-40910-6 Library of Congress Card Number 2004043568 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper ©2004 by Jørgen Stenersen Dedication To Eira, my grandchild Without your inspiration, references from 2002 and 2003 would have been missing and the book already outdated! Although much wisdom can be extracted from Tomlin’s The Pesticide Manual, even more is found in The Norwegian Folk Tales and Astrid Lindgren’s Pippi Langstrømpe, which you for long periods gave me an excuse to concentrate upon. ©2004 by Jørgen Stenersen About the Author Jørgen H.V. Stenersen, Dr. Philos., is a professor in ecotoxicology at the Biological Institute, University of Oslo. He graduated as Cand. Real. in biochemistry in 1964 (University of Oslo) and subsequently worked at the Norwegian Plant Protection Institute on research related to possible side effects of pesticides. His first interests were the mechanisms behind insect resistance to insecticides, with emphasis on DDT resistance in stable flies. He was also engaged in studies of the extent of DDT contamination of soil, fauna, and humans as a result of DDT usage in orchards. During a one-year stay at the Agricultural Research Laboratory in Lon- don, Ontario, Canada, he became interested in the effects of pesticides on earthworms at the biochemical level. This became his research focus for some years. A stay at the Biochemical Institute of the University of Stockholm led to research in the comparative biochemistry of biotransformation enzymes (glutathione transferases). In 1985, Dr. Stenersen was a senior lecturer in ecotoxicology at the University of Oslo, becoming a professor in 1994. Since then he has been devoted to the education of environmental toxicologists. It is his opinion that the basic knowledge of health-oriented toxicologists and ecotoxicolo- gists should be the same, or at least overlap so they can compete in the same job market and “speak the same language.” He is a member of the Norwe- gian Committee for Approval of EUROTOX Registered Toxicologists and is responsible for the master’s and Ph.D. studies of toxicology at the Biological Institute, University of Oslo. The mode of action of pesticides, development of resistance, and their side effects are central topics in this pursuit. The present book is an enlarged revision of an earlier book written in Norwegian (Kjemiske plantevernmidler, 1988, Yrkeslitteratur as, Oslo, pp. 218), and is suited to introductory courses in general toxicology. Dr. Stenersen’s current research interest is the appli- cation of biochemical methods in terrestrial ecotoxicology. ©2004 by Jørgen Stenersen Acknowledgments I thank in particular Professor John Ormerod at the Department of Biology, University of Oslo; Senior Scientist Avi Ring at the Norwegian Defense Research Institute; and Senior Scientist Christian Thorstensen at the Norwe- gian Plant Protection Institute for reviewing the many chapters, correcting, and proposing rewriting. Thanks also go to Baard Johannessen for providing materials to the chapter about interaction. I also thank my students that had to hear and learn more about pesticides than they actually needed for their exams and future jobs. I also thank Catherine Russel at Taylor & Francis for her difficult job of correcting my English. ©2004 by Jørgen Stenersen Contents Chapter 1 Introduction 1.1 Motivation 1.2 Pesticides and opinion 1.2.1 The fly in the soup 1.2.2 Low-tech food production 1.2.3 Conclusion 1.3 A great market 1.3.1 The number of chemicals used as pesticides 1.3.2 Amounts of pesticides produced 1.3.3 Marketing 1.3.4 Dirty dozens 1.4 Nomenclature, definitions, and terminology 1.4.1 Toxicology, ecotoxicology, and environmental toxicology 1.4.2 Pesticides, biocides, common names, chemical names, and trade names 1.4.3 Chemical structures are versatile Helpful reading Biochemistry and cell biology General toxicology Insect biochemistry, plant physiology, and neurophysiology Pesticides Side effects of pesticides Chapter 2 Why is a toxicant poisonous? 2.1 Seven routes to death 2.1.1 Enzyme inhibitors 2.1.2 Disturbance of the chemical signal systems 2.1.3 Toxicants that generate very reactive molecules that destroy cellular components 2.1.4 Weak organic bases or acids that degrade the pH gradients across membranes 2.1.5 Toxicants that dissolve in lipophilic membranes and disturb their physical structure 2.1.6 Toxicants that disturb the electrolytic or osmotic balance or the pH ©2004 by Jørgen Stenersen 2.1.7 Strong electrophiles, alkalis, acids, oxidants, or reductants that destroy tissue, DNA, or proteins 2.2 How to measure toxicity 2.2.1 Endpoints 2.2.1.1 Endpoints in ecotoxicology and pest control 2.2.1.2 Endpoints in human toxicology 2.2.2 Dose and effect 2.2.3 Dose and response 2.2.3.1 Dose–response curves for the stable fly 2.2.3.2 Scatter in dose–response data 2.2.4 LD50 and related parameters 2.2.5 Acute and chronic toxicity 2.3 Interactions 2.3.1 Definitions 2.3.2 Isoboles 2.3.3 Mechanisms of interactions 2.3.4 Examples 2.3.4.1 Piperonyl butoxide 2.3.4.2 Deltamethrin and fenitrothion 2.3.4.3 Atrazine and organophosphate insecticides Chapter 3 Pesticides interfering with processes important to all organisms 3.1 Pesticides that disturb energy production 3.1.1 Anabolic and catabolic processes 3.1.2 Synthesis of acetyl coenzyme A and the toxic mechanism of arsenic 3.1.3 The citric acid cycle and its inhibitors 3.1.3.1 Fluoroacetate 3.1.3.2 Inhibitors of succinic dehydrogenase 3.1.4 The electron transport chain and production of ATP 3.1.4.1 Rotenone 3.1.4.2 Inhibitors of electron transfer from cytochrome b to c1 3.1.4.3 Inhibitors of cytochrome oxidase 3.1.4.4 Uncouplers 3.1.5 Inhibition of ATP production 3.1.5.1 Organotin compounds 3.1.5.2 Diafenthiuron 3.1.5.3 Summary 3.2 Herbicides that inhibit photosynthesis 3.2.1 Weak organic acids 3.2.2 Free radical generators 3.2.3 D1 blockers 3.2.3.1 Urea derivatives 3.2.3.2 Triazines ©2004 by Jørgen Stenersen 3.2.4 Inhibitors of carotene synthesis 3.2.4.1 Amitrole 3.2.4.2 Aclonifen 3.2.4.3 Beflubutamid 3.2.5 Protoporphyrinogen oxidase inhibitors 3.3 General SH reagents and free radical generators 3.3.1 Mercury 3.3.2 Other multisite fungicides 3.3.2.1 Perhalogenmercaptans 3.3.2.2 Alkylenebis(dithiocarbamate)s and dimethyldithiocarbamates 3.3.2.3 Fungicides with copper 3.4 Pesticides interfering with cell division 3.4.1 Fungicides 3.4.1.1 Benomyl 3.4.1.2 Thiofanate-methyl 3.4.1.3 Carbendazim 3.4.1.4 Thiabendazole 3.4.1.5 Diethofencarb 3.4.2 Herbicides 3.4.2.1 Trifluralin 3.4.2.2 Carbetamide 3.5 Pesticides inhibiting enzymes in nucleic acid synthesis 3.5.1 Sporulation-inhibiting fungicides 3.5.2 Inhibition of incorporation of uridine into RNA Chapter 4 Bacillus thuringiensis and its toxins 4.1 The mechanism of action of δ-endotoxins 4.2 Biotechnology 4.3 Engineered plants 4.4 Biology 4.5 Commercial products Chapter 5 Specific enzyme inhibitors 5.1 Inhibitors of ergosterol synthesis 5.1.1 Inhibition of HMG-CoA reductase 5.1.2 Inhibition of squalene epoxidase 5.1.3 DMI fungicides 5.1.4 Examples of DMI fungicides from each group 5.1.4.1 Azoles and triazoles 5.1.4.2 Pyridines and pyrimidines 5.1.4.3 Piperazines 5.1.4.4 Amines 5.1.4.5 Morpholines 5.1.5 Conclusions ©2004 by Jørgen Stenersen 5.2 Herbicides that inhibit synthesis of amino acids 5.2.1 The mode of action of glyphosate 5.2.2 Degradation of glyphosate 5.2.3 Selectivity 5.2.4 Mode of action of glufosinate 5.2.5 Inhibitors of acetolactate synthase 5.3 Inhibitors of chitin synthesis 5.3.1 Insecticides 5.3.2 Fungicides 5.4 Inhibitors of cholinesterase 5.4.1 Acetylcholinesterase 5.4.2 Organophosphates 5.4.2.1 Naturally occurring organophosphorus insecticides 5.4.3 Carbamates 5.4.3.1