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Paraquat and Diquat This report contains the collective views of an international group of experts and does not necessarily represent the decisions or the stated policy of the United Nations Environment Pro- gramme, the International Labour Organisa- tion. or the World Health Organization Environmental Health Criteria 39 PARAQUAT AND DIQUAT Published under the joint sponsorship of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization World Health Organization Geneva, 1984 The Internatfonal Programme on Chemical Safety (IPCS) is a joint venture of the United Nations Environment Programme, the Interna- tional Labour Organisation, and the World Health Organization. The main objective of the IPCS is to carry out and disseminate evaluations of the effects of chemicals on human health and the quality of the environment. Supporting activities include the development of epidemiological, experi- mental laboratory, and risk-assessment methods that could produce inter- nationally comparable results, and the development of manpower in the field of toxicology. Other activities carried out by IPCS include the devel- opment of know-how for coping with chemical accidents, coordination of laboratory testing and epidemiological studies, and promotion of research on the mechanisms of the biological action of chemicals. ISBN 92 4 154099 4 World Health Organization 1984 Publications of the World Health Organization enjoy copyright protec- tion in accordance with the provisions of Protocol 2 of the Universal Copy- right Convention. For rights of reproduction or translation of WHO publica- tions, in part or in tote, application should be made to the Office of Publica- tions, World Health Organization, Geneva, Switzerland. The World Health Organization welcomes such applications. The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the World Health Organization concerning the legal status of any country, territory, city or area or of its authorities, or con- cerning the delimitation of its frontiers or boundaries The mention of specific companies or of certain manufacturers' products does not imply that they are endorsed or recommended by the World Health Organization in preference to others of a similar nature that are not men- tioned. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. PRINTED IN FINLAND 845229 - VAMMALA - 5500 -3- CONTENT S Page ENVIRONMENTAL HEALTH CRITERIA FOR PARAQUAT AND DIQUAT PARAQUAT 1. SUMMARY AND RECOMMENDATIONS .............13 1.1 Summary ..................... 13 1.1.1 General properties ............ 13 1.1.2 Environmental distribution and tansformat ion - environmental effects . 13 1.1.3 Kinetics and metabolism ......... 14 1.1.4 Effects on experimental animals ..... 14 1.1.5 Effects on man .............. 15 1.2 Recommendations ................. 16 1.2.1 General ................. 16 1.2.2 Prevention and treatment ......... 16 1.2.3 Experimental york ............ 16 IDENTITY, PROPERTIES AND ANALYTICAL METHODS .....18 2.1 Identity .................... 18 2.2 Physical and chemical properties ........ 18 2.3 Analytical methods ............... 19 3. SOURCES IN THE ENVIRONMENT .............. 24 3.1 introduction .................. 24 3.1.1 Industrial technology .......... 24 3.1.2 Impurities ................ 24 3.2 Production and use ............... 25 3.3 Mechanism of the herbicidal effect ....... 28 4. ENVIRONMENTAL DISTRIBUTION AND TRANSPORTATION . 29 4.1 Photochemical degradation ............ 29 4.1.1 Photochemical degradation on plant surfaces ................. 29 4.1.2 Photochemical degradation of paraquat on soil and other mineral surfaces ..... 30 4.2 Microbial degradation .............. 3D 4.3 Environmental adsorption and transformation . 31 4.3.1 Soil ................... 31 4.3.2 Water .................. 34 4.3.3 Air ................... 36 -4- Page 4.3.4 Plants • 38 4.3.5 Animals ................. 40 5. BIOLOGICAL ACTiVITY OF RESIDUES ........... 42 5.1 Soil organisms ................. 42 5.2 Effect of residues on crop yields ........ 42 5.3 Effects on fish and aquatic organisms ...... 43 5.4 Effects on birds ................ 43 6. KINETICS AND METABOLISM ............... 45 6.1 Animal studies ................. 45 6.1.1 Absorption ................ 45 6.1.1.1 Oral absorption ......... 45 6.1.1.2 Pulmonary absorption ...... 45 6.1.1.3 Dermal absorption ........ 46 6.1.2 Distribution ............... 4€ 6.1.3 Metabolic transformation and excretion. 51 6.2 Observations on human beings .......... 52 6.2.1 Observations on paraquat poisoning after ingestion. non-fatal cases ........ 52 6.2.2 Observations on paraqtist poisoning after ingestion: fatal cases .......... 53 6.2.3 Significance of paraquat concentrations in cases of paraquat poisoning ....... 53 6.3 Biochemical mechanisms ............. 54 7. EFFECTS ON ANIMALS .................. 59 7.1 Effects on experimental animals ......... 59 7.1.1 Respiratory system ............ 59 7.1.1.1 Pathomorphological lung studies .59 7.1.1.2 Species differences in lung injury ............. 64 7.1.1.3 Functional lung studies ..... 65 7.1.2 Renal system ............... 6.5 7.1.3 Gastrointestinal tract and liver ..... 65 7.1.4 Skin and eyes .............. 66 7.1.5 Other systems .............. 67 7.1.6 Effects on reproduction, embryotoxicity, and teratogenicity ............ 67 7.1.6.1 Effects on reproduction ..... 67 7.1.6.2 Embryotoxicity and teratiogenicity 68 7.1.7 Mutagenicity ............... 68 7.1.8 Carcinogenicity ............. 69 7.2 Effects on farm animals ............. 69 -5- p ag e 7.3 Dose-effect of paraquat 70 7.4 Methods for decreasing paraquat toxicity . 71 7.5 Relation between age, sex, and toxicity .....72 8. EFFECTS ON MAN ....................74 8.1 Accidental and suicidal poisoning ........ 74 8.1.1 Case reports ............... 74 8.1.2 Distribution of cases of paraquat p oisoning ................ 74 8.1.3 Route of entry .............. 76 8.1.4 Formulations ............... 76 8.1.5 Dose ................... 76 8.1.6 Clinical and pathomorphological data relating to fatal paraquat poisoning . 78 8.1.6.1 Respiratory system ....... 78 8.1.6.2 Renal system .......... 79 8.1.6.3 Gastrointestinal system, the Liver, and the pancreas ..... 79 8.1.6.4 Cardiovascular system ...... 80 8.1.6.5 Central nervous system ..... 80 8.1.6.6 Adrenal glands ......... 80 8.1.6.7 Pregnancy ............ 80 8.1.7 Recovery from paraquat poisoning ..... 81 8.2 Occupational exposure .............. 83 8.2.1 Epidemiological studies and case reports 53 8.2.1.1 Spraying personnel ....... 83 8.2.1.2 Formulation workers ....... 86 8.2.2 Cases of occupational poisoning and local caustic effects ............. 87 8.2.2.1 Oral ingestion ......... 87 8.2.2.2 Derinal absorption ........ 88 8.2.2.3 Local skin and nail effects . 89 8.2.2.4 Ocular damage .......... 89 8.2.2.5 Inhalation ........... 90 8.3 Use of marijuana contaminated by paraquat 90 8.4 Guidelines for the treatment of paraquat p oisoning .................... 91 9. EvALUATION OF RISKS FOR HUMAN HEALTH AND EFFECTS ON THE ENVIRONMENT ...................93 9.1 Exposure ....................93 9.2 Poisoning by paraquat ..............95 9.2,1 Suicidal ingestion ............95 9.2.2 Accidental poisoning ...........95 9.2.3 Occupational poisoning ..........95 -6- Page 9.3 Occupational exposure 96 9.4 Effects 96 9.4.1 Paraquat toxicity in animals .......96 9.4.2 Paraquat determination in biological fluids and tissues ............97 9.5 Earlier evaluations by international bodies 97 9.6 Conclusions ...................97 REFERENCES........................99 M. Page DIQUAT )-. SUMMARY AND RECOMMENDATIONS . 131 1.1 Summary ..................... 131 1.1.1 General properties ............ 131 1.1.2 Environmental distribution and transformation - environmental effects 131 1.1.3 Kinetics and metabolism ......... 132 1.1.4 Effects on animals ............ 132 1.1.5 Effects on man .............. 133 1.2 Recommendations ................. 133 1.2.1 General ................. 133 1.2.2 Prevention and treatment ......... 133 1.2.3 Experimental work ............ 134 PROPERTIES AND ANALYTICAL METHODS .......... 135 2.1 Physical and chemical properties ........ 135 2.2 Analytical procedures ..............136 SOURCES IN THE ENVIRONMENT ..............138 3.1 Production and uses ............... 138 ENVIRONMENTAL DISTRIBUTION, LEVELS, AND EXPOSURE . 139 4.1 Photochemical and microbial degradation of diquat .................... 139 4.1.1 Photochemical degradation ........ 139 4.1.2 Microbial degradation .......... 140 4.2 Diquat adsorption, residue levels, and exposure in soil ................ 140 4.2.1 Diquat adsorption on soil particles . 140 4.2.2 Residue levels of diquat in soils . 141 4.2.3 Effect of resi6sa1 diquat on soil biological activity, and on plants and crop yields ............... 141 4.3 Diquat transformation, residue levels, and effects on aquatic organisms and crops ..... 142 4.3,1 Transformation and residue levels of diquat in water ............. 142 4.3.2 Effects of residual diquat on aquatic organisms and crops ........... 143 4.4 Diquat exposure and residue levels in plants and animals ................... 144 4.4.1 Plants .................. 144 4.4.2 Animals ................. 145 -8- 4.5 Diquat levels in air and exposure of workers . 146 5. KINETICS AND METABOLISM ............... 146 5.1 Animal studies ................. 148 .1.1 Absorption ...............
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