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A Review of the Toxicity and Environmental Behaviour

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A Review of the Toxicity and Environmental Behaviour w w w.environment-agency.gov.uk A Review of the Toxicity and Environmental Behaviour of Bromine in Air The Environment Agency is the leading public body protecting and improving the environment in England and Wales. It’s our job to make sure that air, land and water are looked after by everyone in today’s society, so that tomorrow’s generations inherit a cleaner, healthier world. Our work includes tackling flooding and pollution incidents, reducing industry’s impacts on the environment, cleaning up rivers, coastal waters and contaminated land, and improving wildlife habitats. This report is the result of research commissioned and funded by the Environment Agency’s Science Programme. Published by: Author(s): Environment Agency, Rio House, Waterside Drive, Aztec West, P Coleman, R Mascarenhas and P Rumsby Almondsbury, Bristol, BS32 4UD Tel: 01454 624400 Fax: 01454 624409 Dissemination Status: www.environment-agency.gov.uk Publicly available ISBN: 1844323536 Keywords: bromine, inhalation toxicity, air quality, exposure © Environment Agency January 2005 Research Contractor: All rights reserved. This document may be reproduced with prior Netcen, Culham Science Centre, Culham, Abingdon, permission of the Environment Agency. Oxfordshire, OX14 3ED WRc-NSF Ltd, Henley Road, Medmenham, Marlow, Bucks, The views expressed in this document are not necessarily SL7 2HD those of the Environment Agency. Tel: 0870 190 6437 Fax: 0870 190 6608 Website: www.netcen.co.uk. This report is printed on Cyclus Print, a 100% recycled stock, which is 100% post consumer waste and is totally chlorine free. Environment Agency’s Project Manager: Water used is treated and in most cases returned to source in Dr Melanie Gross-Sorokin from January 2003 to May 2004 and better condition than removed. Miss Jackie Maud from May 2004 onwards. Further copies of this report are available from: Science Project Number: The Environment Agency’s National Customer Contact Centre SC020104 by emailing [email protected] or by Product Code: telephoning 08708 506506. SCHO0105BIMU-E-P ii SCIENCE REPORT A Review of the Toxicity and Environmental Behaviour of Bromine in Air Science at the Environment Agency Science underpins the work of the Environment Agency, by providing an up to date understanding of the world about us, and helping us to develop monitoring tools and techniques to manage our environment as efficiently as possible. The work of the Science Group is a key ingredient in the partnership between research, policy and operations that enables the Agency to protect and restore our environment. The Environment Agency’s Science Group focuses on five main areas of activity: • Setting the agenda: To identify the strategic science needs of the Agency to inform its advisory and regulatory roles. • Sponsoring science: To fund people and projects in response to the needs identified by the agenda setting. • Managing science: To ensure that each project we fund is fit for purpose and that it is executed according to international scientific standards. • Carrying out science: To undertake the research itself, by those best placed to do it - either by in-house Agency scientists, or by contracting it out to universities, research institutes or consultancies. • Providing advice: To ensure that the knowledge, tools and techniques generated by the science programme are taken up by relevant decision-makers, policy makers and operational staff. Professor Mike Depledge Head of Science SCIENCE REPORT A Review of the Toxicity and Environmental Behaviour of Bromine in Air iii EXECUTIVE SUMMARY Bromine is an oxidising acidic gas with a noxious odour. The principal sources are associated with bromine production and use in the chemical industry. As a result, releases are often of short duration due to batch operations. A number of measurement methods have been published for bromine but while most are insufficiently sensitive to be of use in other than an occupational setting, some offer the potential for short-term sensitive measurements. These methods are not used routinely and are generally regarded as research methods suitable for short-term campaigns rather than continuous measurement networks. However if cost was not a significant barrier then it is likely that these measurements could be so used. No UK measurements of bromine in ambient air have been identified. The atmospheric lifetime of bromine is short during day light hours as a result of photodissociation. Bromine is a volatile liquid that gives off suffocating vapours, is corrosive to the skin, and may cause severe gastroenteritis if ingested. Inhalation of bromine vapours and/or direct contact of bromine liquid or vapour with the skin and mucous membranes will produce direct tissue injury. There is usually a delay in the appearance of clinical signs after exposure. The injury may occur at various levels of the respiratory tract depending on the concentration and duration of exposure. Target organs associated with bromine exposure include the upper and lower respiratory tract, skin, and eyes. Toxicological reviews for bromine, which include the inhalation route, have been published by the World Health Organization’s International Programme on Chemical Safety (ICPS) and the American Conference of Governmental Industrial Hygienists (ACGIH). A review for bromine published by the United States Environmental Protection Agency (US EPA) focuses primarily on the oral route. This discussion on bromine is largely based on these reviews. Particular mention is made of those studies that have been used to derive the inhalation limits. While there are no reported human volunteer studies, occupational and accidental exposure suggest that exposure to approximately 0.2 ppm (1.3 mg/m3) and above may be associated with eye and respiratory tract irritation. Case reports of accidental and occupational exposure to bromine vapours describe skin and eye irritation and damage, some of which is not apparent upon initial medical examination. The upper airway irritation caused by inhalation of bromine vapours is thought to be due to its water solubility. Bromine reacts with the water present in mucous membranes to liberate nascent oxygen or oxygen free radicals, which are capable of producing tissue damage. Acute animal studies have reported LC50 values in mice of approximately 240 ppm (1600 mg/m3; 2 hour exposure)-750 ppm (5000 mg/m3; 7 min exposure). Pulmonary oedema, pseudomembranous deposits on the trachea and bronchi, and haemorrhage of the gastric mucosa were observed after guinea pigs and rabbits inhaled bromine vapours at 300 ppm (2000 mg/m3) for 3 hours. Bronchopneumonia and iv Science Report A Review of the Toxicity and Environmental Behaviour of Bromine in Air evidence of functional disturbances in the central nervous system were observed in animals that died several days after the exposure. Rats, mice, and rabbits inhaling 0.2 ppm (1.3 mg/m3) of bromine for four months developed disturbances in the respiratory, nervous, endocrine systems. No adverse effects were observed at 0.02 ppm (0.13 mg/m3). In several early studies ranging from three months to one year the effects of oral administration of bromine or sodium bromide in laboratory animals were a reduction in relative prostate weight and secretory activity in males and reduced “thyroid activation” in females. A variety of behavioural effects were observed at higher doses. Rats fed 0.01 mg/kg bw/day bromine for 6 months experienced changes in their conditioned reflexes and several blood indexes. A No Observed Adverse Effect Level (NOAEL) for sodium bromide of >40 mg/kg-day was identified from a one-year feeding study in rats and 100 mg/kg bw/day from a one-year feeding study in dogs. Science Report A Review of the Toxicity and Environmental Behaviour of Bromine in Air v Contents EXECUTIVE SUMMARY i 1 Introduction 1 1.1 Anthropogenic Sources of Bromine 2 1.2 Atmospheric Chemistry of Bromine 3 1.2.1 Diatomic Bromine 3 1.3 Deposition Mechanisms 4 1.4 Methods of Measurement 4 1.4.2 Bubbler Methods 4 1.4.3 Sorbent Tube Sampling 4 1.4.4 Electronic Gas Detectors 4 1.4.5 DIAL 5 1.4.6 DOAS 5 1.4.7 DLSIOS 5 1.5 Ambient Air Measurements 5 2 Introduction to Toxicology of Bromine 6 3 Animal Studies 8 3.1 Introduction 8 3.2 Summary 8 3.3 Absorption, Distribution, Metabolism, and Excretion 9 3.4 Acute Toxicity 9 3.5 Chronic toxicity/Carcinogenicity studies 10 3.6 Genotoxicity 10 3.7 Neurotoxicity 11 3.8 Reproductive/Developmental Toxicity 11 4 Human Studies 12 4.1 Summary 12 4.2 Absorption, Distribution, Metabolism and Excretion 12 4.3 Mechanism of toxicity 12 4.4 Acute toxicity in humans 13 4.5 Occupational studies 14 4.6 Chronic toxicity /Carcinogenicity 15 4.7 Genotoxicity 15 4.8 Neurotoxicity 15 4.9 Reproductive/Developmental Toxicity 15 5 Evaluations and Recommendations by other Organisations 17 5.1 Summary 17 6 Conclusions 20 REFERENCES 22 vi Science Report A Review of the Toxicity and Environmental Behaviour of Bromine in Air List of Figures 26 List of Tables 26 Appendix A – Key References 27 Appendix B – Literature Search Strategy 28 Appendix C - Dispersion of Bromine from a Low Level Release 29 Appendix D – Equilibrium of bromate formation from the dissolution of bromine at the lung surface 34 Appendix E – Medical Glossary 36 Appendix F – Glossary of Terms and Acronyms 40 Science Report A Review of the Toxicity and Environmental Behaviour of Bromine in Air vii 1 INTRODUCTION The Environment Agency of England and Wales is responsible for the authorisation of releases of a wide range
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