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Chlorine and Hydrogen Chloride This report contains the collective views of an nternational group of experts and does not xcessarily represent the decisions or the stated 1 icy of the United Nations Environment Pro- '€mme, the International Labour Organisation, or the World Health Organization. Environmental Health Criteria 21 CHLORINE AND HYDROGEN CHLORIDE 'ublished under the joint sponsorship of Ic United Nations Environment Programme. the International Labour Organisation, and the World Health Organization / \r4 ( o 4 UI o 1 o 'T F- World Health Organization kz Geneva, 1982 The International Programme on Chemical Safety (IPCS) is a joint ven- ture of the United Nations Environment Programme. the International Labour Organisation, and the World Health Organization. The main objective of the IPCS is to carry out and disseminate evaluations of the environment. Supporting activities include the development of epidemiological, experi- mental laboratory, and risk assessment methods that could produce interna- tionally comparable results, and the development of manpower in the field of toxicology. Other relevant activities carried out by the IPCS include the development 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 154081 8 World Health Organization 1982 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 loto, 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 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 men- tioned. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. i'nirrrrrr IN PiNLArcn tin R.jrij i)iijn 01 iS .tTS 6 vi un 01 am San) -3- CONTENTS Page ENVIRONMENTAL HEALTH CRITERIA FOR CHLORINE AND HYDROGEN CHLORIDE ....................8 1. SUMMARY AND RECOMMENDATIONS FOR FURTHER STUDIES . . 11 1.1 Summary .................... 11 1.1.1 Sampling and analytical methods ..... 11 1.1.2 Sources and pathways of exposure . . 11 1.1.3 Experimental animal studies on the effects of chlorine .......... 12 1.1.4 Experimental animal studies on the effects of hydrogen chloride ..... 15 1.1.5 Controlled, clinical, and epidemiological studies on the effects of chlorine . 17 1.1.6 Controlled, clinical, and epidemiological studies on the effects of hydrogen chloride .............. 19 1.1.7 Evaluation of health risks ....... 20 1.2 Reconmendatioms for further studies ...... 20 1.2.1 Monitoring ............... 20 1.2.2 Human exposure ............. 20 1.2.3 Experimental animal studies ....... 21 1.2.4 Controlled, clinical, and epidemiological studies ........ 21 1.2.5 The significance of biological effects ................ 21 2. PROPERTIES AND ANALYTICAL METHODS .......... 22 2.1 Physical and chemical properties of chlorine and hydrogen chloride ............22 2.2 Sampling and analytical methods ........22 2.2.1 Chlorine ................22 2.2.2 Hydrogen chloride .............4 3. SOURCES OF CHLORINE AND HYDROGEN CHLORIDE IN THE ENVIRONMENT .....................26 3.1 Natural sources of chlorine and hydrogen chloride ...................26 -4- Page 3.2 Man-made sources of chlorine and hydrogen chloride ................... 26 3.2.1 Chlorine manufacture .......... 26 3.2.2 Hydrogen chloride manufacture ...... 27 3.2.3 Combustion of fuels ........... 27 3.2.4 Waste disposal ............. 28 3.2.5 Transportation ............. 28 3.3 Industrial consumption of chlorine and hydrogen chloride ................... 29 3.3.1 Chlorine ................ 29 3.3.1.1 Chemical industry ....... 29 3.3.1.2 Pulp and paper industry . 2 3.3.1.3 Water and waste treatment 29 3.3.2 Hydrogen chloride ............ 4. ENVIRONMENTAL TRANSFORMATIONS, LEVELS, AND EXPOSURE . 31 4.1 Exposure of the general population ....... 31 4.1.1 Air ................... 31 4.1.2 Water .................. 31 4.2 Occupational exposure ............. 32 4.2.1 Chemical industry ............ 32 4.2.1.1 Chlorine ............ 32 4.2.1.2 Hydrogen chloride ....... 32 4.2.2 Pulp and paper industry ......... fl 4.2.3 Water and waste treatment ........ 33 4.2.4 Miscellaneous .............. 33 5. EFFECTS OF CHLORINE AND HYDROGEN CHLORIDE ON SOME ELEMENTARY FORMS OF LIFE AND ON EXPERIMENTAL ANIMALS. 34 5.1 Chlorine .................... 34 5.1.1 Effects of chlorine on bacteria, viruses, and other elementary forms of life ............. 34 5.1.2 Effects of chlorine on experimental animals ................ 34 5.1.2.1 Qualitative toxicological and related effects ....... 35 5.1.2.2 Quantitative effects of short- term exposure ........ 37 5.1.2.3 Effects of repeated exposure to chlorine ......... 40 5.1.2.4 Multigeneration and reproductive studies ........... 44 5.1.2.5 Carcinogenicity ........ 45 5.1.2.6 Mechanisnis of action ...... 45 -5- Page 5.2 Hydrogen chloride ............... 46 5.2.1 Effects on experimental animals ..... 46 5.2.1.1 single exposure toxicity studies 46 5.2.1.2 Dermal toxicity studies . . . 51 5.2.1.3 Intrabronchial insufflation of hydrochloric acid ...... 51 5.2.1.4 Repeated exposure to hydrogen chloride ........... 51 5.2.1.5 Carcinogenicity ........ 53 5.2.1.6 Mechanisms of action ...... 53 6. EFFECTS IN MAN - CONTROLLED, CLINICAL, AND EPIDEMIOLOCICAL STUDIES ............... 54 6.1 Chlorine .................... 5 4 6.1.1 Controlled human studies ........ 54 6.1.1.1 Odour perception and irritation 54 6.1.1,2 Reflex neurological changes . 57 6.1.1.3 Respiratory diseases ...... 58 6.1.2 Clinical studies ............ 59 6.1.2.1 Immediate effects and sequelae of short-term exposures . 59 6.1.3 Effects of long-term (industrial) exposure - epidemiological studies . 69 6.1.4 Teratogenicity, mutagenicity, and carcinogenicity ............ 72 6.2 Hydrogen chloride ............... 72 6.2.1 Controlled human studies ........ 72 6.2.1.1 Odour perception threshold levels ............ 72 6.2.1.2 Reflex neurological changes . 73 6.2.1.3 Effects of hydrogen chloride in combination with chlorine . 74 6.2.2 Short-term exposures .......... 75 6.2.3 Long-term exposure ........... 75 6.2.4 Teratogenicity, mutagenicity, and carcinogenicity ............ 76 7. EVALUATION OF HEALTH RISKS TO MAN FROM EXPOSURE TO CHLORINE OR HYDROGEN CHLORIDE ............77 - 7.1 Exposure levels .................77 7.2 Experimental animal studies ...........78 7.3 controlled studies in man ............78 7.4 Field studies in man ..............79 7.5 Evaluation of health risks ...........80 REFERENCES .......................81 -6- NOTE TO READERS OF THE CRITERIA DOCUMENTS While every effort has been made to present information in the criteria documents as accurately as possible without unduly delaying their publication, mistakes might have occurred and are likely to occur in the future. In the interest of all users of the environmental health criteria documents, readers are kindly requested to communicate any errors found to the Division of Environmental Health, World Health Organization, Geneva, Switzerland, in order that they may be included in corrigenda which will appear in subsequent volumes. In addition, experts in any particular field dealt with in the criteria documents are kindly requested to make available to the WHO Secretariat any important published information that may have inadvertently been omitted and which may change the evaluation of health risks from exposure to the environ- mental agent under examination, so that the information may be considered in the event of updating and re-evaluation of the conclusions contained in the criteria documents. -7- WHO TASK GROUP MEETING ON ENVIRONMENTAL HEALTH CRITERIA FOR CHLORINE AND HYDROGEN CHLORIDE Members Professor M.C. Battigelli, School of Medicine, Department of Medicine, Department of Environnental Science & Engineering, University of North Carolina, NC, USA (Chairman) Dr D.P. Duffield, Medical Department, Inperial Chemical Industries, Nond Division, Cheshire, England Professor M. Ikeda, Department of Environmental Health, Tohokt University School of Medicine, Sendai, Japan ! Dr M. Muchtarova, Department of Industrial Toxicology and Chemistry, Institute of Occupational Health, Sofia, Bulgaris (Vice-Chairman) Professor N.H. Noweir, Occupational Health Department, High Institute of Public Health, University of Alexandria, Alexandria, Egypt Mr C. Satkunananthan, Additional Government Analyst (retired) Colonbo, Sri Lanka (Rapporteur) Dr V.V. Vashkova, Departnent of Coordination of Scientific - International Relations, Institute of General and Municiple Hygiene, Moscow, USSR Secretariat Dr R.R. Cook, Health & Environmental Sciences, Dow Chemical USA, Michigan, USA Dr N. Gavrilesco, Occupational Safety and Health Branch, International Labour Organization, Geneva, Switzerland
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