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Flame Retardants: Tris(2-Butoxyethyl) Phosphate, Tris(2-Ethylhexyl) Phosphate and Tetrakis(Hydroxymethyl) Phosphonium Salts

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Flame Retardants: Tris(2-Butoxyethyl) Phosphate, Tris(2-Ethylhexyl) Phosphate and Tetrakis(Hydroxymethyl) Phosphonium Salts 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 Programme, the International Labour Organisation, or the World Health Organization. Environmental Health Criteria 218 FLAME RETARDANTS: TRIS(2-BUTOXYETHYL) PHOSPHATE, TRIS(2-ETHYLHEXYL) PHOSPHATE AND TETRAKIS(HYDROXYMETHYL) PHOSPHONIUM SALTS Please note that the layout and pagination of this web version are not identical with the printed document First draft prepared by Dr G.J. van Esch, Bilthoven, the Netherlands Published under the joint sponsorship of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization, and produced within the framework of the Inter-Organization Programme for the Sound Management of Chemicals. World Health Organization Geneva, 2000 The International Programme on Chemical Safety (IPCS), established in 1980, is a joint venture of the United Nations Environment Programme (UNEP), the International Labour Organisation (ILO), and the World Health Organization (WHO). The overall objectives of the IPCS are to establish the scientific basis for assessment of the risk to human health and the environment from exposure to chemicals, through international peer review processes, as a prerequisite for the promotion of chemical safety, and to provide technical assistance in strengthening national capacities for the sound management of chemicals. The Inter-Organization Programme for the Sound Management of Chemicals (IOMC) was established in 1995 by UNEP, ILO, the Food and Agriculture Organization of the United Nations, WHO, the United Nations Industrial Development Organization, the United Nations Institute for Training and Research, and the Organisation for Economic Co-operation and Development (Participating Organizations), following recommendations made by the 1992 UN Conference on Environment and Development to strengthen cooperation and increase coordination in the field of chemical safety. The purpose of the IOMC is to promote coordination of the policies and activities pursued by the Participating Organizations, jointly or separately, to achieve the sound management of chemicals in relation to human health and the environment. WHO Library Cataloguing-in-Publication Data Flame retardants : tris(2-butoxyethyl) phosphate, tris(2-ethylhexyl) phosphate, tetrakis(hydroxymeth yl) phosphonium salts. (Environmental health criteria ; 218) 1.Organophosphorus compounds – toxicity 2.Phosphoric acid esters – toxicity 3.Flame retardants – toxicity 4.No-observed-adverse-effect level 5.Environmental exposure 6.Occupational exposure I.Series ISBN 92 4 157218 3 (NLM Classification: QU 131) ISSN 0250-863X The World Health Organization welcomes requests for permission to reproduce or translate its publications, in part or in full. Applications and enquiries should be addressed to the Office of Publications, World Health Organization, Geneva, Switzerland, which will be glad to provide the latest information on any changes made to the text, plans for new editions, and reprints and translations already available. ©World Health Organization 2000 Publications of the World Health Organization enjoy copyright protection in accordance with the provisions of Protocol 2 of the Universal Copyright Convention. All rights reserved. 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 concerning 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 mentioned. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. CONTENTS ENVIRONMENTAL HEALTH CRITERIA FOR FLAME RETARDANTS: TRIS(2-BUTOXYETHYL) PHOSPHATE, TRIS(2-ETHYLHEXYL) PHOSPHATE, TETRAKIS- (HYDROXYMETHYL) PHOSPHONIUM SALTS PREAMBLE xi ABBREVIATIONS xix PART A: TRIS(2-BUTOXYETHYL) PHOSPHATE (TBEP) 1 A1. SUMMARY, EVALUATION AND RECOMMENDATIONS 2 A1.1 Summary 2 A1.2 Evaluation 3 A1.3 Recommendations 5 A2. IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES, AND ANALYTICAL METHODS 6 A2.1 Identity 6 A2.2 Physical and chemicals properties 7 A2.3 Conversion factors 8 A2.4 Analytical methods 8 A2.4.1 Air 8 A2.4.2 Water 8 A2.4.3 Sediment 9 A2.4.4 Soils and foodstuffs 9 A2.4.5 Biological media 9 A3. SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE 11 A3.1 Natural occurrence 11 A3.2 Anthropogenic sources 11 iii EHC 218: Flame Retardants: TBEP, TEHP and THPS ______________________________________________________ A3.2.1 Production levels and processes 11 A3.2.2 Uses 11 A4. ENVIRONMENTAL TRANSPORT, DISTRIBUTION AND TRANSFORMATION 12 A4.1 Transport and distribution between media 12 A4.2 Biodegradation 12 A4.2.1 Migration 13 A5. ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE 14 A5.1 Environmental levels 14 A5.1.1 Air 14 A5.1.2 Water (drinking-water and surface water) 15 A5.1.3 Soils and sediment 16 A5.1.4 Aquatic organisms 16 A5.2 Human tissue levels 17 A5.3 Food 17 A5.4 Occupational exposure 19 A6. KINETIC AND METABOLISM IN LABORATORY ANIMALS AND HUMANS 20 A7. EFFECTS ON LABORATORY MAMMALS AND IN VITRO TEST SYSTEMS 21 A7.1 Single exposure 21 A7.1.1 Oral and dermal 21 A7.1.2 Inhalation 21 A7.2 Short-term repeated exposure 22 A7.2.1 Oral 22 A7.2.2 Dermal 23 A7.3 Skin and eye irritation; sensitization 24 A7.4 Reproductive toxicity, embryotoxicity and teratogenicity 24 A7.5 Mutagenicity and related end-points 25 A7.6 Carcinogenicity 25 A7.7 Special studies 25 A7.7.1 Neurotoxicity 25 iv ______________________________________________________ A7.7.1.1 Acute administration 25 A7.7.1.2 Repeated oral administration 27 A7.7.1.3 Effects on esterase activity 29 A8. EFFECTS ON HUMANS 30 A9. EFFECTS ON OTHER ORGANISMS IN THE LABORATORY AND FIELD 31 A9.1 Laboratory experiments 31 A9.1.1 Aquatics organisms 31 A9.1.1.1 Invertebrates 31 A9.1.1.2 Vertebrates 31 PART B: TRIS(2-ETHYLHEXYL) PHOSPHATE (TEHP) 32 B1. SUMMARY, EVALUATION AND RECOMMENDATIONS 33 B1.1 Summary 33 B1.2 Evaluation 35 B1.3 Recommendations 36 B2. IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES, AND ANALYTICAL METHODS 37 B2.1 Identity 37 B2.2 Physical and chemical properties 38 B2.3 Conversion factors 38 B2.4 Analytical methods 39 B2.4.1 Air 39 B2.4.2 Water 39 B2.4.3 Sediment 40 B3. SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE 41 B3.1 Natural occurrence 41 B3.2 Anthropogenic sources 41 v EHC 218: Flame Retardants: TBEP, TEHP and THPS ______________________________________________________ B3.2.1 Production levels and processes 41 B3.2.2 Uses 41 B4. ENVIRONMENTAL TRANSPORT, DISTRIBUTION AND TRANSFORMATION 42 B4.1 Biodegradation 42 B4.2 Bioaccumulation 43 B5. ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE 44 B5.1 Environmental levels 44 B5.1.1 Air 44 B5.1.2 Surface water 44 B5.1.3 Drinking-water 45 B5.1.4 Effluents 45 B5.1.5 Sediment 46 B5.1.6 Food 46 B6. KINETICS AND METABOLISM IN LABORATORY ANIMALS 49 B7. EFFECTS ON LABORATORY MAMMALS AND IN VITRO TEST SYSTEMS 50 B7.1 Single exposure 50 B7.2 Repeated exposure 50 B7.2.1 Oral 50 B7.2.2 Dermal 51 B7.2.3 Inhalation 52 B7.3 Skin and eye irritation; sensitization 53 B7.4 Reproductive toxicity, embryo toxicity and teratogenicity 54 B7.5 Mutagenicity 54 B7.5.1 In vitro assays 54 B7.5.2 In vivo assays 55 B7.6 Carcinogenicity 55 B7.7 Special studies 56 B7.7.1 Neurotoxicity 56 vi ______________________________________________________ B8. EFFECTS ON HUMANS 59 B9. EFFECTS ON OTHER ORGANISMS IN THE LABORATORY AND FIELD 60 B9.1 Laboratory experiments 60 B9.1.1 Microorganisms 60 B9.1.2 Aquatic organisms 60 B9.1.2.1 Vertebrates 60 B9.1.3 Terrestrial organisms 60 PART C: TETRAKIS(HYDROXYMETHYL) PHOSPHONIUM SALTS 61 C1. SUMMARY AND EVALUATION 62 C1.1 Summary 62 C1.2 Evaluation 64 C2. IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES, AND ANALYTICAL METHODS 65 C2.1 Identity 65 C2.1.1 Tetrakis(hydroxymethyl) phosphonium chloride (THPC) 65 C2.1.2 Tetrakis(hydroxymethyl) phosphonium sulfate (THPS) 66 C2.1.3 Tetrakis(hydroxymethyl) phosphonium chloride-urea condensate (THPC-urea) 67 C2.2 Physical and chemical properties 68 C2.2.1 Technical products 68 C2.3 Conversion factors 68 C2.4 Analytical methods 68 C3. SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE 71 C3.1 Natural occurrence 71 C3.2 Anthropogenic sources 71 vii EHC 218: Flame Retardants: TBEP, TEHP and THPS ______________________________________________________ C3.2.1 Production levels and processes 71 C3.2.2 Uses 71 C4. ENVIRONMENTAL TRANSPORT, DISTRIBUTION AND TRANSPORTATION 73 C4.1 Transport and distribution between media 73 C4.2 Transformation 73 C4.2.1 Biodegradation 73 C4.2.2 Abiotic degradation 74 C4.3 Migration from textiles 74 C5. ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE 76 C6. KINETICS AND METABOLISM IN LABORATORY ANIMALS 77 C7. EFFECTS ON LABORATORY MAMMALS AND IN VITRO TEST SYSTEMS 78 C7.1 Single exposure 78 C7.1.1 Oral 78 C7.1.2 Dermal 78 C7.1.3 Inhalation 79 C7.2 Repeated exposure 79 C7.2.1 Oral 79 C7.2.1.1 THPC 79 C7.2.1.2 THPS 80 C7.2.2 Dermal 82 C7.3 Long-term exposure 83 C7.3.1 THPC 83 C7.3.2 THPS 84 C7.4 Skin and eye irritation; sensitization 84 C7.4.1 Skin irritation 84 C7.4.1.1 THPS 84 C7.4.1.2 THPC-urea 85 C7.4.2 Eye irritation 85 C7.4.3 Skin sensitization 85 C7.4.3.1 THPS 85 C7.4.3.2 THPC-urea 85 viii ______________________________________________________ C7.5 Reproductive toxicity, embryotoxicity and teratogenicity 86 C7.5.1 THPS 86 C7.5.2 THPC-urea 86 C7.6 Mutagenicity and related end-points 87 C7.6.1 THPC-urea 87 C7.6.1.1 In vitro studies 87 C7.6.1.2 In vivo studies 87 C7.6.2 THPC 87 C7.6.3 THPS 89 C7.6.4 THPO 90 C7.6.5 Treated fabrics 90 C7.7 Carcinogenicity 90 C7.7.1 Oral studies 90 C7.7.1.1 Mice 90 C7.7.1.2 Rats 91 C7.7.2 Dermal studies: initiation and promotion 91 C7.8 Special studies 91 C8.
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