IPCS INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY Health and Safety Guide No. 29 DIMETHYL SULFATE HEALTH AND SAFETY GUIDE UNITED NATIONS ENVIRONMENT PROGRAMME INTERNATIONAL LABOUR ORGANISATION WORLD HEALTH ORGANIZATION WORLD HEALTH ORGANIZATION, GENEVA 1989 This is a companion volume to Environmental Health Criteria 48: Dimethyl Sulfate Published by the World Health Organization for the International Programme on Chemical Safety (a collaborative programme of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization) 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 ISBN 92 4 154350 7 ISSN 0259-7268 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. (c) World Health Organization 1989 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 INTRODUCTION 1. PRODUCT IDENTITY AND USES 1.1. Identity 1.2. Physical and chemical properties 1.3. Analytical methods 1.4. Production and uses 2. SUMMARY AND EVALUATION 2.1. Human exposure to dimethyl sulfate 2.2. Fate of dimethyl sulfate 2.3. Uptake, metabolism, and excretion 2.4. Effects on organisms in the environment 2.5. Effects on animals and human beings 3. CONCLUSIONS AND RECOMMENDATIONS 4. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION 4.1. Main human health hazards, prevention and protection, first aid 4.1.1. Advice to physicians 4.1.2. Health surveillance advice 4.2. Explosion and fire hazards 4.3. Storage 4.4. Transport 4.5. Spillage and disposal 5. HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION 6. INTERNATIONAL CHEMICAL SAFETY CARD 7. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS 7.1. Exposure limit values 7.2. Specific restrictions 7.3. Labelling, packaging, and transport BIBLIOGRAPHY INTRODUCTION The Environmental Health Criteria (EHC) documents produced by the International Programme on Chemical Safety include an assessment of the effects on the environment and on human health of exposure to a chemical or combination of chemicals, or physical or biological agents. They also provide guidelines for setting exposure limits. The purpose of a Health and Safety Guide is to facilitate the application of these guidelines in national chemical safety programmes. The first three sections of a Health and Safety Guide highlight the relevant technical information in the corresponding EHC. Section 4 includes advice on preventive and protective measures and emergency action; health workers should be thoroughly familiar with the medical information to ensure that they can act efficiently in an emergency. Within the Guide is an International Chemical Safety Card which should be readily available, and should be clearly explained, to all who could come into contact with the chemical. The section on regulatory information has been extracted from the legal file of the International Register of Potentially Toxic Chemicals (IRPTC) and from other United Nations sources. The target readership includes occupational health services, those in ministries, governmental agencies, industry, and trade unions who are involved in the safe use of chemicals and the avoidance of environmental health hazards, and those wanting more information on this topic. An attempt has been made to use only terms that will be familiar to the intended user. However, sections 1 and 2 inevitably contain some technical terms. A bibliography has been included for readers who require further background information. Revision of the information in this Guide will take place in due course, and the eventual aim is to use standardized terminology. Comments on any difficulties encountered in using the Guide would be very helpful and should be addressed to: The Manager International Programme on Chemical Safety Division of Environmental Health World Health Organization 1211 Geneva 27 Switzerland THE INFORMATION IN THIS GUIDE SHOULD BE CONSIDERED AS A STARTING POINT TO A COMPREHENSIVE HEALTH AND SAFETY PROGRAMME 1. PRODUCT IDENTITY AND USES 1.1 Identity Chemical formula: (CH3)2SO4 Common synonyms: sulfuric acid dimethyl ester; methyl sulfate; dimethyl monosulfate; CAS registry number:77-78-1 RTECS number: WS8225000 United Nations number: 1595 Conversion factors: 1 ppm = 5 mg/m3 and 1 mg/m3 = 0.2 ppm, approximately, depending on temperature and pressure 1.2 Physical and Chemical Properties Dimethyl sulfate is a colourless oily liquid with a very faint onion odour at room temperature and normal atmospheric pressure. Its odour is mild and it produces no sensory irritation, so few people can detect the presence of the vapour in air. It is readily soluble in alcohol, sparingly soluble in very cold water, but it dissolves readily in water at 18°C with hydrolysis to form methanol, the monoester, and sulfuric acid. Hydrolysis is particularly rapid in alkaline solutions which are therefore used for decontamination. It is used as a methylating agent in organic syntheses. Technical dimethyl sulfate contains small amounts of acid impurities, e.g., the monoester. 1.3 Analytical Methods Sensitive analytical techniques are available to determine low levels of dimethyl sulfate. Gas or liquid chromatography, in the latter case of a derivative, can be used, followed by an appropriate method of detection, such as mass spectrometry or a flame ionization detector for gas chromatography, and ultraviolet or visible spectrometry for liquid chromatography. The lowest reported detection limit using gas chromatography is 0.026 mg/m3 (0.005ppm) for a 1-litre sample, and for liquid chromatography a detection limit of 0.05 mg/m3 (0.01 ppm) has been obtained. 1.4 Production and Uses Dimethyl sulfate has been produced for some 60 years. It can be made in a continuous process by the reaction of dimethyl ether with sulfur trioxide or by reacting methanol with oleum and distilling under vacuum. Manufacture is concentrated in relatively few companies in Europe and North America, but no information on the magnitude of total production is available. It is extensively used as a methylating agent, particularly in the dye industry and in the manufacture of organic chemicals, such as fabric softeners, and of pharmaceuticals. For all the processes in which it is used there are alternative methylating agents, and no estimate of the amounts of dimethyl sulfate produced can be made from the quantities of these products. 2. SUMMARY AND EVALUATION 2.1 Human Exposure to Dimethyl Sulfate Exposure of the skin and eyes, or the respiratory tract, to dimethyl sulfate may occur and the main effect is severe local inflammation that develops without sensory irritation at the moment of contact. Because of this and its severe systemic toxicity, exposure of workers is controlled to a low level in industrial environments and there is virtually no exposure of the general population. Designated occupational exposure limits range from 0.05 to 5 mg/m3 and these usually relate to skin exposure. Those at the lower end of the range reflect concern about the possible carcinogenicity of the chemical. In general, the substance is handled in closed systems, and it is usual for operators to wear impervious suits and self-contained breathing apparatus for operations involving the transfer of dimethyl sulfate, where there is the possibility of greater exposure. 2.2 Fate of Dimethyl Sulfate Dimethyl sulfate released into the atmosphere eventually hydrolyses. The resulting sulfuric acid is deposited in rain and the methanol is oxidized to carbon dioxide and water or is deposited in rain. The quantities released are likely to be so small that the contribution of these end-products to atmospheric levels of carbon dioxide and to acid rain is insignificant. Spillages on the ground will evaporate and will hydrolyse in a similar way. When vessels containing dimethyl sulfate are vented to the atmosphere, an alkaline scrubber is usually incorporated to prevent any emission. Spillages treated with ammonia or soda ash hydrolyse rapidly in situ. 2.3 Uptake, Metabolism, and Excretion Dimethyl sulfate is absorbed readily through mucous membranes, the intestinal tract, and the skin. It is rapidly metabolized in mammalian tissues and when injected intravenously into rats is undetectable in the plasma after 3 minutes. It is possible that the hydrolysis of dimethyl sulfate and the subsequent methylation of component molecules of the cells and tissues, including DNA, are responsible for its local effects, systemic toxic effects, and possible carcinogenicity. On the eye, dimethyl sulfate produces toxic effects similar to those of methanol and it is probable that its toxicity is in part a direct result of the dissolved methanol moiety of the molecule as well as being a result of alkylation reactions. The ultimate metabolites in the human body are sulfate and carbon dioxide, and these are excreted by the kidneys and released by the lungs, respectively. 2.4 Effects on Organisms in the Environment Dimethyl sulfate hydrolyses fairly rapidly in damp environments at temperatures above about 20°C. High concentrations are therefore unlikely to persist following accidental contamination. The 96-h LC50 values for aquatic species are generally in the range 100-10 mg/litre. The LC50 values for bluegill sunfish (Centrarchidae) and tidewater silversides (Atherinidae) are 7.5 mg/litre and 15 mg/litre, respectively. 2.5 Effects on Animals and Human Beings Dimethyl sulfate is toxic for all cells. It causes severe inflammation of the eye, respiratory epithelium, and skin that commences minutes or hours after the exposure; there is little initial discomfort but severe functional disturbances follow. In addition, it is readily absorbed and produces systemic toxic effects, principally on the nervous system, heart, liver, and kidneys. Dimethyl sulfate is mutagenic and is a suspected human carcinogen. In short-term studies on experimental mammals, oral LD50 values of 205 and 440 mg dimethyl sulfate/kg body weight (rat) and 140 mg/kg body weight (mouse) have been found; and a subcutaneous LD50 of 100 mg/kg body weight has been demonstrated in the rat. Rats inhaling a concentration of 75 mg dimethyl sulfate/m3 (15 ppm) for 4 hours survived, but rats inhaling 150 mg/m3 (30 ppm) for the same period died. Other work with rats showed that with exposure for 4 hours the lowest observed lethal concentration was 150 mg/m3 (30 ppm), and that mean survival times for mice and guinea-pigs exposed to 375 mg/m3 (75 ppm) were 17 and 24 minutes, respectively. Because of the delayed effects, concentrations producing eventual death after short exposures are likely to be a better guide to the toxicity of dimethyl sulfate than the time to death with continuous exposure at a particular concentration. Dimethyl sulfate is mutagenic in several in vitro test systems. It has produced tumours of the nasal epithelium and the nervous system when fed to pregnant rats, and single injections resulted in malignant tumours of the nervous system in their offspring. Inhalational exposure of rats for 1 hour per day, 5 days per week, for 130 days, to calculated concentrations of 55 mg/m3 (10 ppm) and 17 mg/m3 (3 ppm) resulted at 643 days in 5 of the 15 survivors at the higher dosage and 3 of the 20 at the lower dosage having tumours. Most tumours were of the nasal epithelium or the central nervous system. The effects on man have been well described and the acute effects of vapour exposure are uniform. The initial symptoms are headache, giddiness, and burning of the eyes, which reach a maximum intensity between 2 and 10 hours after exposure. Epithelial irritation follows, not merely of the exposed respiratory epithelium but also of the intestinal and urinary tracts. Thus, there is soreness of the nose and throat with hoarseness of the voice, cough, tightness of the chest, breathing difficulty, difficulty in swallowing, and also vomiting and diarrhoea and painful urination. These symptoms may persist for up to 2 weeks. The role of secondary infection of the damaged epithelia is not clear. In severe cases, there may be exudative pulmonary oedema, which can be fatal. The cardiotoxicity may lead to circulatory collapse. Biochemical tests have remained abnormal for periods of years following acute exposure and permanent changes in colour vision and visual field changes have been described. The clinical effects of chronic exposure have been reported to involve liver function and vision in particular. These, like the exposure, are likely to go unnoticed unless monitored. Human carcinogenicity was suggested by a study of a small group of workers in an environment where acute toxic effects were not uncommon. This study showed that 4 out of 10 workers had died of bronchogenic carcinoma. However, epidemiological studies among the work-forces of two major producers have failed to show an elevated cancer incidence and occupational exposure at 5 mg/m3 appears to be below the threshold for a demonstrable carcinogenic risk for man. 3. CONCLUSIONS AND RECOMMENDATIONS Dimethyl sulfate is a particularly dangerous chemical because of its systemic and local toxicity and because there is no warning of exposure. While the carcinogenic risk appears not to be significant under good industrial conditions, the reported high incidence of lung cancer in a small, highly exposed work-force, and the animal data, indicate that there may be a carcinogenic hazard for man. Exposure to high concentrations even for short periods should therefore be avoided. In addition to the acute effects of acute exposure, there is a risk of permanent or long-term damage to the liver and retina. These organs also appear to be the most sensitive to the effects of chronic exposure. The toxicity of dimethyl sulfate is such that it should be handled only within organizations having the resources and ability to carry out the engineering controls, workplace monitoring, sophisticated personal protection, occupational health surveillance, and emission treatment and control necessary to protect the work-force, the community, and the environment. 4. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION 4.1 Main Human Health Hazards, Prevention and Protection, First Aid The main hazard for man is unperceived exposure, which could lead to severe or lethal acute effects, and also to long-term health effects including possible carcinogenesis. High levels of engineering and process control are required to ensure that the possibility of emissions is remote. Flange joints between plant components should be avoided and welded joints should be used instead. Factory areas containing dimethyl sulfate should be enclosed by bunds and staff should have the necessary materials and equipment to treat spillages immediately with alkaline solutions or soda ash so that the dimethyl sulfate is rapidly hydrolysed. Vents should discharge through an alkaline scrubber. Continuous atmospheric monitoring for dimethyl sulfate levels is desirable so that immediate warning is given of significant workplace concentrations. The filling of storage tanks or reactors from drums, tankers, or tank cars should be undertaken only by experienced operators who are fully protected by impervious suits and by positive-pressure, demand, breathing apparatus supplied with respirable air from a cylinder or a remote source. Fully protected employees may deal with any small spillages that occur during transfers but they should be strictly instructed not to attempt to deal with larger spillages. Nearly all accidents with dimethyl sulfate have been the result of hasty and uninformed cleaning-up operations. Such spillages should be dealt with by specially trained and fully protected personnel. 4.1.1 Advice to physicians In the event of suspected inhalation of vapour, even in the absence of any symptoms, patients should be kept resting quietly under clinical observation for at least 12 hours. The eyes should be irrigated, even if apparently unaffected, with a 2% solution of sodium bicarbonate for a full 15 minutes. Eye irrigation should be repeated if any redness develops. Oxygen may be administered if there is breathing difficulty. Arrangements should be made for the possibly affected patient to be transferred to the nearest centre equipped for the treatment of pulmonary oedema, the support of patients with major organ failure, and circulatory collapse. No specific antidote is known. In the case of contamination of the body surface, irrigate affected eyes and skin burns with a 2% solution of sodium bicarbonate in water and treat conventionally. Hydrocortisone or other steroid drops may be useful. With inhalation exposure, the administration of high doses of methyl prednisolone (30 mg/kg body weight, by slow intravenous injection) or the administration of other steroids (e.g., beclometasone dipropionate) by metered-dose aerosol has been reported to reduce the incidence of exudative pulmonary oedema and subsequent pulmonary fibrosis. The prophylactic use of steroids after exposure, but before any signs and symptoms appear, may be of value in reducing pulmonary damage by dimethyl sulfate. An early chest X-ray may be useful for comparison with a later film in the event of the development of pulmonary oedema. Oral or aerosol bronchodilators (e.g., salbutamol) may be of value if there is bronchospasm. Oxygen and humidification are the main lines of treatment for mild pulmonary oedema; diuretics, opiates, and theophyllines do not have a role, since the condition is exudative rather than transudative. In extreme cases, intermittent positive-pressure ventilation may be necessary. Prophylactic antibiotics are generally indicated, since secondary bacterial infection of the airways often occurs. If there is oesophageal, ophthalmic, or urinary tract pain, analgesics may be given, but those that are respiratory depressants or topical irritants should be avoided. Oral medication should be avoided if there is nausea or upper abdominal pain. Heart rate, blood pressure, fluid balance, arterial blood gases, and liver and renal function should be monitored, and support should be given on general lines if there are signs of circulatory, liver, or renal failure. A detailed neurological and ophthalmological assessment should be made as early as possible and during the recovery phase. Where no symptoms or signs have appeared within 12 hours, the patient may be discharged from observation, but should be warned to return if any symptoms develop. As dimethyl sulfate can be metabolized to methanol, there is the theoretical possibility of superadded methanol poisoning, although this has never been reported in human poisoning cases. If methanol poisoning is suspected, the serum methanol level can be determined and metabolic acidosis corrected with sodium bicarbonate. Specific treatment for methanol poisoning should be given if indicated. A particularly difficult situation may arise when symptoms that could be a result of dimethyl sulfate exposure, but could equally well be an incipient upper respiratory tract infection or conjunctivitis, occur in workers in the plant without a history of exposure. Such people may seek advice because they know that exposure may be imperceptible. In such situations, the correct course of action will depend on a careful history of the presenting complaints, of the occurrence of similar symptoms in other members of the household or work-group, of the timing of the onset of symptoms in relation to the last work-period, and of any abnormal conditions or events in the plant that could have led to exposure. Medical and nursing staff who know their employees may also be able to take personality factors into account. 4.1.2 Health surveillance advice It may be advisable for persons with pre-existing respiratory or liver disease to be excluded from work with dimethyl sulfate. Preplacement examinations should also document the visual fields and the colour vision status of the employee or recruit. Wherever measured exposures are close to the occupational exposure limit or there is dependence on personal protection to limit exposure, it is wise to undertake regular health surveillance, including tests of liver and pulmonary function, colour vision, and visual fields. 4.2 Explosion and Fire Hazards Dimethyl sulfate represents a moderate fire hazard, but does not explode. Firefighters should wear full protective clothing and use compressed-air breathing apparatus. Water, foam, dry powder, or carbon dioxide are suitable firefighting media. 4.3 Storage Dimethyl sulfate should be stored in the suppliers' drums, properly sealed and labelled, or in a suitable bulk container. These should be housed in a cool, dry, well-ventilated place. Handle drums carefully to avoid puncturing. 4.4 Transport In case of a road transport accident, stop the motor and remain up-wind. If a vapour cloud drifts towards an inhabited area, warn the inhabitants and evacuate areas close to the spillage, if this can be done without risking exposure. 4.5 Spillage and Disposal Spillage should only be dealt with by trained personnel wearing full protective clothing, a full-face mask, and positive-pressure breathing apparatus. Soda ash or 3% ammonia solution may be applied to liquid spills. Sprays of 3% ammonia solution may be used to "knock down" the vapour over spillages. After complete neutralization, spillages may be washed away to a drain or sewer. If dimethyl sulfate has entered a watercourse or sewer, or contaminated soil or vegetation, advise the police and public authorities. For the treatment and disposal of waste, the recommended methods are alkaline hydrolysis, incineration, and landfill. Do not use open burning (e.g., as a boiler fuel) or evaporation for waste disposal. For incineration, dimethyl sulfate should be dissolved in a combustible solvent and sprayed into a furnace with an afterburner and an alkali scrubber. Dimethyl sulfate may be decomposed by adding a dilute alkaline solution; the mixture should be stirred and then allowed to settle. The resulting solution is then neutralized by acid or alkali as appropriate and drained into a sewer. When rapid decomposition is needed the waste may be warmed. It may also be adsorbed on vermiculite, packed in drums, buried and covered immediately. 5. HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION There are no hazards for the environment from the controlled transport and use of dimethyl sulfate. Spillages will cause local damage, but rapid hydrolysis of the material will prevent persistent or widespread effects, particularly in temperate conditions. 6. INTERNATIONAL CHEMICAL SAFETY CARD This card should be easily available to all health workers concerned with, and users of, dimethyl sulfate. It should be displayed at, or near, entrances to areas where there is potential exposure to dimethyl sulfate, and on processing equipment and containers. The card should be translated into the appropriate language(s). All persons potentially exposed to the chemical should also have the instructions on the chemical safety card clearly explained. Space is available on the card for insertion of the National Occupational Exposure Limit, the address and telephone number of the National Poison Control Centre, and for local trade names. DIMETHYL SULFATE Chemical formula: (CH3)2SO4) CAS Registry No.77-78-1 RTECS No. WS8225000 PHYSICAL PROPERTIES OTHER CHARACTERISTICS Melting point -32°C Dimethyl sulfate is a colourless, oily liquid with Boiling point 188°C (decomposes) a faint onion-like odour; it is readily soluble in Water solubility (18°C) 28 g/litre (readily soluble) alcohol and aromatic solvents, but is only sparingly Relative density (20-24°C) 1.332 soluble in cold water; it hydrolyses in water to the Relative vapour density 4.4 monoester, sulfuric acid, and methanol; hydrolysis is Vapour pressure (20°C) 67 Pa (0.5 mmHg) more rapid in alkaline solutions; it is combustible Flash point 83°C but not explosive Relative molecular mass 126.13 HAZARDS/SYMPTOMS PREVENTION AND PROTECTION FIRST AID Vapour EYES: severe delayed inflammation Meticulously engineered, totally Prompt irrigation with 2% sodium without initial irritation; high enclosed plant is required, with bicarbonate solution for at least acute exposures and chronic alkaline scrubbers for vents to 15 minutes, even if there is no irritation; exposures may cause visual field atmosphere; ideally there should obtain medical advice defects and colour vision changes, be continuous monitoring for but this may be a systemic effect concentrations in the workplace atmosphere; complete impervious suits and full-face positive pressure demand compressed-air breathing apparatus should be available for operations in which dimethyl sulfate is not contained, and for clean-up of spillages DIMETHYL SULFATE (cont'd) HAZARDS/SYMPTOMS PREVENTION AND PROTECTION FIRST AID INHALATION: no warning smell See above Keep under observation for at least or irritation; severe delayed 12 hours after possible exposure, even if irritation of the whole of the there are no symptoms; keep at rest; respiratory epithelium may result; administer oxygen if there is breathing the consequence is exudative difficulty; refer to hospital or a doctor pulmonary oedema, which may be fatal Liquid SKIN: delayed skin burns and Measures effective against Wash skin thoroughly with a 2% solution systemic absorption leading to respiratory exposure will be of sodium bicarbonate in water; remove serious, possibly fatal, effects effective against skin exposure any contaminated clothing (using gloves); on the nervous system, liver, send to a hospital or doctor; treat burns kidneys, and heart; there may be conventionally; observe for systemic convulsions, visual disturbance, effects pain on voiding the bladder, pain on swallowing, and vomiting INGESTION: Severe, possibly Do not eat, drink, or smoke Do not induce vomiting; give nothing delayed, effects on the mouth, where chemicals are handled by mouth; send patient immediately to throat, and oesophagus would hospital or to a doctor for treatment be expected with severe systemic effects 7. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS The information given in this section has been extracted from the International Register of Potentially Toxic Chemicals (IRPTC) legal file. The reader should be aware that regulatory decisions about chemicals taken in a certain country can only be fully understood in the framework of the legislation of that country.a When no effective date appears in the IRPTC legal file, the year of the reference from which the data are taken is indicated by (r). 7.1 Exposure Limit Values Some exposure limit values are given in the following table. 7.2 Specific Restrictions In the USA, dimethyl sulfate is designated as a hazardous waste. Any solid waste (except domestic waste) containing dimethyl sulfate is subject to regulations as regards handling, transport, treatment, storage, and disposal. Commercial dimethyl sulfate products are designated toxic waste and subject to similar regulations. 7.3 Labelling, Packaging, and Transport In the countries of the European Economic Community, dimethyl sulfate is classified as very toxic and a possible carcinogen. The label on a container must read: Very toxic; may cause cancer; also toxic if swallowed; also very toxic by inhalation; causes burns; avoid exposure - obtain special instructions before use. In case of contact with eyes, rinse immediately with plenty of water and seek medical advice. Take off immediately all contaminated clothing. In case of accident or if you feel unwell seek medical advice immediately (show the label where possible). In Czechoslovakia, dimethyl sulfate is subject to labelling requirements. In Sweden, it is labelled as a carcinogen and a very hazardous product with the symbol "T". In Japan, it is a designated deleterious substance for labelling purposes. In the United Kingdom, road tankers transporting dimethyl sulfate must be labelled "Toxic Substance". a The regulations and guidelines of all countries are subject to change and should always be verified with the appropriate regulatory authorities before application. For transport, the United Nations classifies dimethyl sulfate as a "poisonous substance", and for packing as a "very dangerous substance". For marine transport, the International Maritime Organization uses the same classifications. EXPOSURE LIMIT VALUES Medium Specification Country/ Exposure limit description Value Effective organization date AIR Occupational Australia Threshold limit value (TLV) 1985 (r) - Time-weighted average (TWA) 5 mg/m3 (carcinogen) (skin absorption) Belgium Threshold limit value 1987 (r) - Time-weighted average 0.5 mg/m3 (carcinogen) (skin absorption) Brazil Acceptable limit 0.4 mg/m3 1982 (r) - 48 h/week (hazardous degree: maximum) Canada Threshold limit value 1980 - Time-weighted average 0.5 mg/m3 (carcinogen) Czechoslovakia Maximum allowable concentration (MAC) 1985 - Time-weighted average 0.05 mg/m3 - Ceiling value (CLV) 0.1 mg/m3 Finland Maximum permissible concentration (MPC) 1985 (r) - Time-weighted average 5 mg/m3 (carcinogen) (skin absorption) German Maximum allowable concentration 1985 (r) Democratic - Time-weighted average 5 mg/m3 Republic - Short-term exposure limit (STEL) 5 mg/m3 (skin absorption) EXPOSURE LIMIT VALUES (cont'd) Medium Specification Country/ Exposure limit description Value Effective organization date AIR Occupational Germany, Technical reference concentration 1987 (r) Federal - Time-weighted average; 1 year 0.1 mg/m3 Republic of - Carcinogenic working material proven (production) in animal experiments. No maximum 0.2 mg/m3 (use) work-site concentration established (cutaneous absorption) Hungary Maximum allowable concentration 1985 (r) - Time-weighted average 5 mg/m3 - Short-term exposure limit 5 mg/m3 (30 minutes) (skin absorption) (sensitizer) Italy Threshold limit value (TLV) 1985(r) - Time-weighted average 0.05 mg/m3 (carcinogen) (skin absorption) Japan Maximum allowable concentration 1986 - Time-weighted average 0.5 mg/m3 (carcinogen) (skin absorption) Netherlands Maximum limit 1987 (r) - Ceiling value 0.5 mg/m3 (skin absorption) Poland Maximum permissible concentration 1985 (r) - Ceiling value 1 mg/m3 EXPOSURE LIMIT VALUES (cont'd) Medium Specification Country/ Exposure limit description Value Effective organization date AIR Occupational Romania Maximum permissible concentration 1985 (r) - Time-weighted average 3 mg/m3 - Ceiling value 8 mg/m3 (skin absorption) Sweden No exposure limit established Carcinogenic 1985 substance Switzerland Maximum work-site concentration 1987 (r) - Time-weighted average 0.1 mg/m3 (carcinogen) (skin absorption) United Recommended limit 1987 (r) Kingdom - Time-weighted average 0.5 mg/m3 - Short-term exposure limit 0.5 mg/m3 (10-minutes time-weighted average) (skin absorption) USA Threshold limit value 1987 (ACGIH) - Time-weighted average 0.5 mg/m3 (suspected carcinogen) (skin absorption) USA (OSHA) Permissible exposure limit (PEL) 1974 - Time-weighted average 5 mg/m3 (skin absorption) USSR Maximum allowable concentration 1983 - Ceiling value 0.1 mg/m3 EXPOSURE LIMIT VALUES (cont'd) Medium Specification Country/ Exposure limit description Value Effective organization date AIR Occupational Yugoslavia Maximum allowable concentration 1985 (r) - Time-weighted average 5 mg/m3 (skin absorption) BIBLIOGRAPHY ACGIH (1986) Documentation of the threshold limit values and biological exposure indices. Cincinnati, American Conference of Governmental Industrial Hygienists. CLAYTON, G.D. & CLAYTON, F.E. (1981) Patty's industrial hygiene and toxicology. Vol. 2A. New York, Wiley - Interscience, John Wiley & Sons. DUTCH ASSOCIATION OF SAFETY EXPERTS (1980) Handling chemicals safely. 2nd ed. Dutch Chemical Industry Association, Dutch Safety Institute. GOSSELIN, R.E., et al. (1976) Clinical toxicology of commercial products. 4th ed. Baltimore, Maryland, Williams and Wilkins Company. IRPTC (1988) Data profile (legal file, waste disposal file, treatment of poisoning file), Geneva, International Register of Potentially Toxic Chemicals. SAX, N.I. (1984) Dangerous properties of industrial materials. New York, Van Nostrand Reinhold Company. US NIOSH (1976) A guide to industrial respiratory protection. Cincinnati, Ohio, US National Institute for Occupational Safety and Health. US NIOSH/OSHA (1985) Pocket guide to chemical hazards. Washington DC, US National Institute for Occupational Safety and Health, Occupational Safety and Health Association (Publication No. 85.114). US NIOSH/OSHA (1981) Occupational health guidelines for chemical hazards. 3 vol. Washington DC, US National Institute for Occupational Safety and Health, Occupational Safety and Health Association, (Publication No. 01.123). WHO (1988) Dimethyl sulfate. Geneva, World Health Organization. (Environmental Health Criteria 48).
See Also: Toxicological Abbreviations Dimethyl sulfate (EHC 48, 1985) Dimethyl sulfate (ICSC) Dimethyl Sulfate (IARC Summary & Evaluation, Volume 71, 1999)