Toxicology of Insecticides

ISBN-13: 9781461344124 / Angielski / Miękka / 2011 / 504 str.

Fumio Matsumura

Opis

Why are books written? Since I have read many works by my colleagues with admiration, this question has always intrigued me. Further, writing a book takes a good deal of time and effort, and I had imagined that I would never undertake such a demanding task. A few unexpected events and circumstances have changed my mind. The first was the pleasant experience of editing Environmental Toxicology of Pesticides with Drs. Mallory Boush and Tomomasa Misato. This fine symposium volume occasioned many interesting responses, including a suggestion to prepare a more complete treatise on the grounds that such "proceedings" volumes, by their very nature, do not satisfactorily offer a complete and coherent description of the field, but cater chiefly to specialists. I myself prefer single-authored books for basic understanding of a scientific field. The second circumstance leading to the present volume was the avail ability of teaching notes from my course on the toxicology of insecticides. As the need to cultivate environmental awareness has increased, there has been a parallel increase in the enrolments of such courses both here and in other major institutions. Yet no comprehensive and up-to-date text has been available. The third factor which facilitated the effort was an especially pleasant sabbatical in Hawaii, where the availability of the excellent Hamilton Library at the University of Hawaii considerably eased my task."

Spis treści

1 Introduction.- 1.1. Toxicolog.- 1.2. General Patterns of Pesticide Us.- 1.3. Economic and Legal Aspects of Pesticide Us.- 1.4. Reference.- 2 General Principles of Insecticide Toxicology.- 2.1. Evaluation of Toxicity.- 2.1.1. Toxicity Tests Against Insects and Other Invertebrates.- 2.1.1a. Graphical Method for Estimating LD50.- 2.1.1b. Goodness-of Fit (x2 Test) and Confidence Limit.- 2.1.1c. Symptomatological Observation.- 2.1.2. Toxicological Evaluation in Higher Animals.- 2.1.2a. Selection of Test Animals.- 2.1.2b. Acute Toxicity Data.- 2.1.2c. Chronic Toxicity and Other Nonacute Toxicity Tests.- 2.1.2d. Observation of Toxic Symptoms.- 2.2. Analytical Methods for Insecticides.- 2.2.1. Chromatographic Analysis of Insecticide Residues.- 2.2.1a. Sampling, Extraction, and Cleanup.- 2.2.1b. Separation and Detection of Residues.- 2.2.2. Other Confirmatory Techniques for Residue Analysis.- 2.2.2a. Chemical Reactions.- 2.2.2b. Spectroscopic Methods.- 2.2.2c. Biological and Biochemical Assay.- 2.3. References.- 3 Classification of Insecticides.- 3.1. History and General Groupings of Insecticidal Compounds.- 3.2. Chlorinated Hydrocarbon Insecticides.- 3.2.1.DDT Analogue.- 3.2.2. Benzene Hexachloride.- 3.2.3. Cyclodiene Compound.- 3.3. Organophosphorus Insecticide.- 3.3.1. Pyrophosphates and Related Compounds.- 3.3.2. Phosphorohalides and Cyanides.- 3.3.3. Dialkylarylphosphates, Phosphorothioates, and Phosphorodithioates.- 3.3.4. Trialkylphosphates and Thiophosphates.- 3.4. Carbamate Insecticides.- 3.4.1. Naphthylcarbamates.- 3.4.2. Phenylcarbamates.- 3.4.3. Heterocyclic Dimethylcarbamates.- 3.4.4. Heterocyclic Methylcarbamates.- 3.4.5. Oximes.- 3.5. Thiocyanate Insecticides.- 3.6. Dinitrophenols.- 3.7. Fluoroacetate Derivatives.- 3.8. Acaricidal Chemicals: Sulfonates, Sulfones, Sulfides, and Nitrogen-Containing Compounds.- 3.9. Fumigants.- 3.10. Inorganic Insecticides.- 3.10.1. Arsenicals.- 3.10.2. Inorganic Fluorides.- 3.11. Botanical Insecticides.- 3.11.1. Nicotinoids.- 3.11.2. Rotenoids.- 3.11.3. Pyrethroids.- 3.11.3a. Pyrethrum.- 3.11.3b. Synthetic Pyrethroids.- 3.12. Synergists.- 3.13. References.- 4 Modes of Action of Insecticides.- 4.1. Introduction.- 4.2. Classification of Insecticides by Their Actions.- 4.3. The Nervous System.- 4.3.1. Mammalian Nervous System.- 4.3.1a. The Somatic System.- 4.3.1b. The Autonomic Nervous System.- 4.3.1c. The Electric (Axonic) Conduction of Nerve Impulses.- 4.3.1d. The Chemical Transmission of Nerve Impulses.- 4.3.2. Insect Nervous System.- 4.4. Chlorinated Hydrocarbon Insecticides.- 4.4.1. DDT and Its Analogues.- 4.4.1a. Symptomatology and Characteristics.- 4.4.1b. Action of DDT on Nerves and Theories of Its Mode of Action.- 4.4.1c. Theories of Structure-Toxicity Relationships.- 4.4.2. ?-BHC (Lindane).- 4.4.2a. Symptomatology.- 4.4.2b. Theories of Structure-Toxicity Relationships.- 4.4.3. Cyclodiene Insecticides.- 4.4.3a. Symptomatology.- 4.4.3b. Theories of Structure-Toxicity Relationships.- 4.5. Naturally Occurring Botanical Insecticides.- 4.5.1. Pyrethroids and Synergists.- 4.5.2. Nicotinoids.- 4.5.3. Rotenoids.- 4.6. Organofluorine Compounds: Fluoroacetate and Its Analogues.- 4.7. Anticholinesterases: Organophosphorus and Carbamate Insec ticides.- 4.7.1. Organophosphorus Compounds.- 4.7.1a. Symptoms.- 4.7.1b. Inhibition.- 4.7.1c. Recovery.- 4.7.1d. Aging.- 4.7.2. Carbamates.- 4.7.2a. Action.- 4.7.2b. Symptoms.- 4.8. Inhibitors of Respiratory Enzymes.- 4.8.1. Inhibitors of the Electron Transport System.- 4.8.2. Inhibitors of Oxidative Phosphorylation.- 4.9. Inhibitors of Mixed-Function Oxidases.- 4.10. Chlordimeform and Its Analogues.- 4.11. References.- 5 Metabolism of Insecticides by Animals and Plants.- 5.1. General Types of Metabolic Activities.- 5.2. Primary Metabolic Processes.- 5.2.1. Oxidation Through Mixed-Function Oxidase Systems.- 5.2.2. Reduction.- 5.2.3. Hydrolytic Processes: Metabolism of Esters and Ethers.- 5.2.4. Glutathione-Mediated Metabolism.- 5.2.4a. Glutathione-Catalyzed Metabolism.- 5.2.4b. Glutathione S-Transferases.- 5.3. Conjugation Systems: Secondary Metabolic Processes.- 5.3.1. Glucuronide or Glucuronic Acid Conjugation.- 5.3.2. Sulfate Conjugation or Ethereal Sulfate Synthesis.- 5.3.3. Glycine Conjugation or Hippuric Acid Synthesis.- 5.3.4. Cysteine Conjugation or Mercapturic Acid Synthesis.- 5.3.5. Histidine, Lysine, and Glutamine Conjugation.- 5.3.6. Glucoside Formation.- 5.3.7. Cyanide-Thiocyanate Detoxification.- 5.3.8. Methylation.- 5.3.9. Acetylation and Coupling with CoA.- 5.3.10. Glutathione Conjugations.- 5.3.11. Other Examples and Possibilities of Conjugations.- 5.4. Metabolic Reactions Characteristic of Each Group of Insecti- cidal Chemicals.- 5.4.1. Chlorinated Hydrocarbon Insecticides.- 5.4. la. Dehydrochlorination.- 5.4.1b. Reductive and Hydrolytic Dechlorination.- 5.4.1c. Oxidative Reactions.- 5.4.1d. Metabolism of Aliphatic Chlorinated Hydrocarbons: Fumigants and Metabolic Fragments.- 5.4.1e. Metabolism of Halogenated Aromatic Compounds.- 5.4.1f. DDT Metabolism.- 5.4. lg. Methoxychlor Metabolism.- 5.4.1h. BHC Metabolism.- 5.4. li. Aldrin and Dieldrin Metabolism.- 5.4. lj. Isodrin and Endrin Metabolism.- 5.4.1k. Metabolism of Heptachlor and Chlordane Analogues.- 5.4.1l. Endosulfan Metabolism.- 5.4.2. Metabolic Reactions Specific to Organophosphates.- 5.4.2a. General Reactions.- 5.4.2b. Enzyme Systems Involved in the Degradation of Organophosphates.- 5.4.2c. Schradan and Dimefox Metabolism.- 5.4.2d. Trichlorfon, Dichlorvos, and Naled Metabolism.- 5.4.2e. Bidrin, Azodrin, Phosphamidon, Mevinphos, and Ciodrin Metabolism.- 5.4.2f. Metabolism of Parathion and Analogues.- 5.4.2g. Diazinon, Chlorfevinphos, and Coumaphos Metabolism.- 5.4.2h. Demeton, Phorate, and Disulfoton: Oxidation of Thioether Side-Groups.- 5.4.2i. Metabolism of Malathion, Acethion, and Dimethoate: Degradation Through Hydrolytic Cleavage of Side-Chains.- 5.4.3. Metabolism of Carbamate Insecticides.- 5.4.3a. General Patterns.- 5.4.3b. Oxidative Metabolism of Carbamates.- 5.4.3c. Carbaryl Metabolism.- 5.4.3d. Substituted Phenylcarbamate.- 5.4.3e. Oxime Insecticide: Aldicarb Metabolism.- 5.4.4. Metabolism of Botanical and Other Insecticides.- 5.4.4a. Nicotine Metabolism.- 5.4.4b. Rotenone Metabolism.- 5.4.4c. Pyrethrin I, Allethrin, Dimethrin, and Phthalthrin Metabolism.- 5.5. References.- 6 Entry of Insecticides into Animal Systems.- 6.1. Penetration of Insecticides Through the Insect Cuticle.- 6.1.1. Morphology of the Insect Cuticle.- 6.1.2. Insect Cuticles as Membranes.- 6.1.3. Factors Influencing the Rate of Penetration: Chemical Nature of Insecticides.- 6.1.4. Factors Influencing Penetration of Insecticides : Effects of Cuticular Components.- 6.1.5. Effect of Carriers and Solvents.- 6.1.5a. Oil.- 6.1.5b. Detergents.- 6.1.5c. Dusts.- 6.2. Routes of Insecticide Entry into Insects.- 6.3. Routes of Insecticide Entry into Higher Animals.- 6.3.1. Penetration of Insecticides Through Mammalian Skin.- 6.3.2. Other Routes of Entry into Higher Animals.- 6.4. References.- 7 Dynamics of Insecticide Movement in the Animal Body.- 7.1. Total Intake-Elimination Dynamics.- 7.2. Transport of Insecticides by Blood and Body Fluid.- 7.3. Distribution and Redistribution Within the Animal Body.- 7.3.1. Distribution After Acute Administration.- 7.3.2. Distribution After Chronic Dosing and Dynamics of Redistribution.- 7.4. Factors Affecting Storage and Release.- 7.5. Penetration and Distribution into Vital Organs and Tissues.- 7.5.1. Nervous System.- 7.5.2. Transfer to Fetus and Reproductive Organs.- 7.6. Elimination of Insecticides: Excretion and Secretion.- 7.6.1. Biliary and Urinary Excretion.- 7.6.2. Secretion in Milk.- 7.7. References.- 8 Movement of Insecticides in the Environment.- 8.1. Introduction.- 8.2. Residues of Insecticides.- 8.2.1. General.- 8.2.2. Terrestrial Plants Including Agricultural Crops.- 8.2.3. Soils.- 8.3. Movement of Residues in the Environment.- 8.3.1. Water- and Air-Mediated Transport.- 8.3.2. Long-Range Transport.- 8.3.3. Mathematical Models for Insecticide Movement.- 8.4. References.- 9 Environmental Alteration of Insecticide Residues.- 9.1. Characteristics of Environmental Alteration.- 9.2. Characteristics of Microbial Metabolism.- 9.3. Metabolism of Chlorinated Hydrocarbon Insecticides by Microorganisms.- 9.3.1. DDT Analogues.- 9.3.2. BHC.- 9.3.3. Cyclodiene Insecticides.- 9.4. Metabolism of Organophosphate and Carbamate Insecticides by Microorganisms.- 9.5. Metabolism of Acaricidal Compounds by Microorganisms.- 9.6. Degradation by Sunlight and Other Physical Factors.- 9.6.1. Chlorinated Hydrocarbons.- 9.6.2. Aromatic Pesticides.- 9.7. References.- 10 Effects of Pesticides on Wildlife.- 10.1. General Survey of Residue Levels in Various Ecosystems.- 10.2. Hazards to Wildlife.- 10.2.1. Acute Toxicity.- 10.2.2. Chronic Toxicity.- 10.2.3. Factors Influencing Toxicity.- 10.2.3a. Age and Size.- 10.2.3b. Environmental Factors.- 10.2.4. Subtle Effects of Insecticides.- 10.2.4a. Birds.- 10.2.4b. Fish and Other Aquatic Organisms.- 10.3. Biological Transfer and Bioaccumulation.- 10.3.1. Route of Biological Transport.- 10.3.1a. General Pattern.- 10.3.1b. Aquatic Environments.- 10.3.1c. Terrestrial Environments.- 10.3.2. Bioaccumulation Through the Food Chain.- 10.3.2a. Aquatic Environments.- 10.3.2b. Terrestrial Environments.- 10.3.3. Factors Affecting the Degree of Bioaccumulation.- 10.3.3a. Physicochemical Characteristics of Insecticides.- 10.3.3b. Competition: “Biological Concentration” vs. “Biological Dilution”.- 10.3.3c. Rate of Food Consumption and Body Size.- 10.3.3d. Dynamics of Pesticide Bioaccumulation.- 10.4. References.- 11 Hazards to Man and Domestic Animals.- 11.1. Introduction.- 11.2. Acute Poisoning by Insecticidal Chemicals.- 11.2.1. Chlorinated Hydrocarbon Insecticides : General Group Characteristics and Method of Treatment.- 11.2.2. DDT Poisoning.- 11.2.2a. Animals.- 11.2.2b. Symptoms of DDT Poisoning in Animals.- 11.2.2c. Human Toxicology.- 11.2.3. BHC Poisoning.- 11.2.4. Aldrin and Dieldrin Poisoning.- 11.2.4a. Symptoms and Toxicity.- 11.2.4b. Autopsy Results on Dieldrin-Poisoned Animals.- 11.2.5. Organophosphate Poisoning.- 11.2.5a. Symptoms.- 11.2.5b. Cause of Death.- 11.2.5c. Example : Description of Malathion Poisoning.- 11.2.6. Carbamate Poisoning.- 11.2.6a. Symptoms and Treatment.- 11.2.6b. Example: Description of Carbofuran Poisoning.- 11.2.7. Botanical Insecticides.- 11.2.7a. Nicotine.- 11.2.7b. Rotenone.- 11.3. Chronic Toxicity and Studies on Subtle Effects.- 11.3.1. Studies on Occupational Exposure and Human Feeding Tests.- 11.3.1a. Chlorinated Hydrocarbon Insecticides.- 11.3.1b. Organophosphates and Carbamates.- 11.3.2. Nonfatal and Subtle Effects of Insecticides.- 11.3.2a. Pathological and Histological Changes.- 11.3.2b. Biochemical Changes.- 11.3.2c. Carcinogenicity-Tumorigenicity.- 11.3.2d. Mutagenicity and Teratogenicity.- 11.4. Insecticide Residues in Man.- 11.4.1. Geographical Variation in Residues Found in Man.- 11.4.2. Factors Influencing the Residue Levels in Man.- 11.4.3. The Meaning of Residues in Man.- 11.4.3a. Change in Residue Levels with Time.- 11.4.3b. Human Intake of Pesticides Through Residues.- 11.4.3c. Pharmacokinetics of Pesticide Residues in Man.- 11.4.3d. Assessment of Safety.- 11.5. References.- Author Index.