_TPr~ JN.TFRNATIONAL PROGRAMME ON CHEMICAL SAFETY

~ ou 99 Health and Safety Guide No. 90 94AC c.2

[t ACETALDEHYDE HEALTH AND SAFETY GUIDE

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UNITED NATIONS INTERNATIONAL ENVIRONMENT PROGRAMME LABOUR ORGANISATION

~ ' · . . ~ ~ . rJ1 ?~ ' • WORLD HEALTH ORGANIZATION

WORLD HEALTH ORGANIZATION, GENEVA 1994 111? L

Other HEALTH AND SAFETY GUIDES available: (continued on inside back cover)

Acrolein (No. 67, 1992) Endrin (No. 60, 1991) Acrylamide (No. 45, 1991) ., Epichlorohydrin (No. 8, 1987) Acrylonitrile (No. I, 1986) •· Bhylene oxide (No. 16, 1988) Aldicarb (No. 64, 1991) Fenitrothion (No. 65, 1991) Aldrin and dieldrin (No. 21, 1988) Fc;pvalerate (No. 34, 1989) Allethrins (No. 24, 1989) Folpet (No. 72, 1992) Amitrole (No. 85, 1994) FormalcJtWyde (No. 57, 1991) Ammonia (No. 37, 1990) Heptachlor (No. 14, 1988) Arsenic compounds, inorganic, other lban Hexachlorobutadiene (No. 84, 1993) arsine (No. 70, 1992) Hexachlorocyclohexanes, alpha- lfnd Atrazine (No. 47, 1990) beta- (No. 53, 1991) Barium (No. 46, 19f!IJ) Hexachlorocyclopentadiene (No. 63, 1991) Benomyl (No. 81, l!)93) n-Hexane (No. 59, 1991) Bentazone (No. 48, "1990) ··:~­ Hydrazine (No. 56, 1991) Beryllium (No. 44, 1990) r' Isobenzan (No. 61, 1991) 1-Butanol (No. 3, 1987) Isobutanol (No. 9, 1987) 2-Butanol (No. 4, 1987) Kelevan (No.- 2, 1987) ten-Butanol (No. 7, 1987) Lindane (No. 54, 1991) Camphechlor (No. 40, 1990) Magnetic fields (No. 27, 1990) Captafol (No. 49, 1990) Methamidophos (No. 79, 1993) Captan (No. 50, 1990) Methyl bromide (Bromomethane) (No. 86, 1994) Carbaryl (No. 78, 1993) '*' .,~_ Methyl isobutyl ketone (No. 58, 1991) Carbendazim (No. 82, 1993) i Methyl parathion (No. 75, 1992) Chlordane (No. 13, 1988) l!4e.I,Jlylene chloride (No. 6, 1987) Chlordecone (No. 41, 1990) ~x (No. 39, 1990) Chloroform (No. 87, 1994) .. . · Mo~crotophos (No. 80, 1993) Cyhalothrin and lambda-cyhalothri~ (No. 38;,: · Nickel; nickel carbonyl, and some nickel 1990) compounds (No. 62, 1991) Cypermethrin (No. 22, 1988) Paraquat (No. 51, 1991) Deltamethrin (No. 30, 1989); Parathion (No. 74, 1992) 1,2-Dichloroethane (No. 55, 1991) '· Pentachlorophenol (No. 19, 1988) 1 ,3-Dichloropropene, I ,2-dichloi'ojltopane, · Permethrin (No. 33, 1989) and mixtures of 1 ,3-dichloropropene and Phenol (No. 88,1994) 1,2-dichloropropane (No. 76, 1992) d-Phenothrin (No. 32, 1989) 2,4-Dichlorphenoxyacetic acid (2,4-D) (No. 5, Phosphine (No. 28, 1989) 1987) · Phosphorus trichloride and phosphorus Dichlorvos (No. 18, 1988) oxychloride (No. 35, 1989) Dimethoate (No. 20, 1988) Polybrominated biphenyls (PBBs) (No. 83, 1993) Dimethyl sulfate (No. 29, 1989) Polychlorinated hiphenyls and polychlorinated Dimethylarsinic acid, methanearsonic acid, and terphenyls (PCBs and PCTs) (No. 68, 1992) salts (No. 69, 1992) Propachlor (No. 77, 1992) Dimethylformamide (No. 43, 1990) Propylene oxide (No. 15, 1988) Diquat (No. 52, 1991) Pyrrolizidine alkaloids (No. 26, 1988) Endosulfan (No. 17, 1988) Quintozene (No. 23, 1988) '

\ I 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

WHO Library Cataloguing in Publication Data

Acetaldehyde: health and safety guide.

(Health and safety guide; no. 90)

!.Acetaldehyde - adverse effects 2. Acetaldehyde - toxicity 3.Environmental exposure I.Series

ISBN 92 4 151090 0 (NLM Classification: QU 99) ISSN 0259-7268

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Health and Safety Guide No. 90

ACETALDEHYDE Ill HEALTH AND SAFETY GUIDE

This is a companion volume to Environmental Health Criteria 167: Acetaldehyde

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)

WORLD HEALTH ORGANIZATION, GENEVA 1994 CONTENTS

Page INTRODUCTION 5

1. PRODUCT IDENTITY AND USES 7 1.1 Identity 7 1.2 Physical and chemical properties 7 1.3 Composition . . . . 8 1.4 Analysis 8 1.5 Production and uses 8

2. SUMMARY 9 2.1 Identity, physical and chemical properties, and analytical methods ...... 9 2.2 Sources of human and environmental exposure . 9 2. 3 Environmental transport, distribution, and transformation ...... 9 2.4 Environmental levels and human exposure 10 2.5 Kinetics and metabolism ...... 10 2.5 .1 Absorption, distribution, and elimination 10 2.5.2 Metabolism ...... 11 2.5.3 Reaction with other components . 12 2.6 Effects on organisms in the environment 12 2.6.1 Aquatic organisms ...... 12 2.6.2 Terrestrial organisms . . . . . 12 2. 7 Effects on experimental animals and in vitro test systems ...... 13 2. 7.1 Single exposure ...... 13 2.7.2 Short- and long-term exposures .. 13 2. 7. 3 Reproduction, embryotoxocity, and teratogenicity ...... 13 2.7.4 Mutagenicity and related end-points 13 2. 7. 5 Carcinogenicity 14 2.7.6 Special studies 14 2.8 Effects on humans 14

3 CONTENTS

3. EVALUATION AND CONCLUSIONS 15

4. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION . 17 4.1 Human health hazards, prevention and protection, first aid 17 4.2 Advice to physicians ...... 17 4.3 Health surveillance advice ...... 17 4.4 Explosion and fire hazards, prevention 18 4.4.1 Explosion and fire hazards 18 4.4.2 Prevention . . . . . 18 4.4.3 Fire extinguishing agents 18 4.5 Storage 18 4.6 Transport 19 4. 7 Spillage 19

5. HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION 20

6. SUMMARY OF CHEMICAL SAFETY INFORMATION 21

7. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS 25 7.1 Exposure limits 25 7.2 Specific restrictions ...... 25 7.3 Labelling, packaging, and transport 25 7.4 Discharges, waste disposal 30

BIBLIOGRAPHY 32

4 INTRODUCTION

The Environmental Health Criteria (EHC) monographs 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 a Summary of Chemical Safety Information 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 Director International Programme on Chemical Safety World Health Organization 1211 Geneva 27 Switzerland

5 THE INFORMATION IN TIDS GUIDE SHOULD BE CONSIDERED AS A STARTING POINT TO A COMPREHENSNE HEALTH AND SAFETY PROGRAMME

6 1. PRODUCT IDENTITY AND USES

1.1 Identity Chemical formula: Chemical structure: H I H- C C-0 I H H

Common name: acetaldehyde Common synomyms: acetic aldehyde, acetylaldehyde, ethanal, ethylaldehyde, diethyl acetal, 1,1-diethoxy ethane CAS registry number: 75-07~ RTECS registry number: AB 1925000 Conversion factors: 1 ppm acetaldehyde = 1. 8 mg acetaldehyde/m3 air 1 mg acetaldehyde/m3 air= 0.56 ppm acetaldehyde at 25 °C and 101.3 kPa (760 mmHg).

1.2 Physical and Chemical Properties Acetaldehyde is a mobile liquid with a pungent suffocating odour that is somewhat fruity and pleasant in dilute concentrations. The odour threshold 3 for acetaldehyde in air is reported to be 0.09 mg/m (0.05 ppm).

7 PRODUCT IDENTITY AND USES

The compound is miscible in all proportions with water and most common organic solvents. The most important physical and chemical properties of acetaldehyde are presented in the Summary of Chemical Safety Information (page 21).

1.3 Composition Commercial acetaldehyde should contain at least 99% of the compound and the acidity (as acetic acid) should be maximal 0.1 %.

1.4 Analysis The most specific and sensitive method, widely used, is based on the derivatization of acetaldehyde (in most cases by 2,4-dinitro­ phenylhydrazine) and subsequent analysis of the hydrazone derivatives by high pressure liquid chromatography (HPLC) or gas chromatography (GC). Analytical methods are available for the detection of acetaldehyde in air, water, beverages, and blood.

1.5 Production and Uses In Japan, production was estimated to be 328 000 tonnes in 1981. In 1982, the total acetaldehyde production in the USA amounted to 281 000 tonnes while in Western Europe, production was 706 000 tonnes in 1983. Around 80% of the total production of acetaldehyde is made by liquid-phase oxidation of ethylene using a catalytic solution of palladium and copper chlorides. The remainder is produced by the oxidation of ethanol and the hydration of acetylene. The greater part of the acetaldehyde produced is used in the production of acetic acid. It is also used in flavourings, foods, beverages, perfumes, plastics, aniline dyes, synthetic rubber manufacturing, the silvering of mirrors, gelatin fibre hardening, and in the laboratory.

8 2.SUMMARY

2.1 Identity, Physical and Chemical Properties, and Analytical Methods Acetaldehyde is a colourless volatile liquid with a pungent suffocating 3 odour. The reported odour threshold is 0.09 mg/m . Acetaldehyde is a highly flammable and reactive compound that is miscible in water and most common solvents. Analytical methods are available for the detection of acetaldehyde in air (including breath) and water. The principal method is based on the reaction of acetaldehyde with 2,4-dinitrophenylhydrazine and the subsequent analy­ sis of the hydrazone derivatives using high-pressure liquid chromatography or gas chromatography.

2.2 Sources of Human and Environmental Exposure Acetaldehyde is a metabolic intermediate in humans and higher plants and a product of alcohol fermentation. It has been identified in food, beverages, and cigarette smoke. It is also present in vehicle exhaust and in ~astes from various industries. Degradation of hydrocarbons, sewage, and solid biological wastes produces acetaldehyde, as well as open burning and incineration of gas, fuel oil, and coal. More than 80% of acetaldehyde used commercially is produced by the liquid-phase oxidation of ethylene with a catalytic solution of palladium and copper chlorides. The annual emission of acetaldehyde from all sources in the USA is estimated to be 12.2 million kg.

2.3 Environmental Transport, Distribution, and Transformation Intercompartmental transport of acetaldehyde is expected to be limited because of its high reactivity. However, some transfer of acetaldehyde to air from water and soil is expected, because of its high vapour pressure and low sorption coefficient. It is suggested that the photo-induced atmospheric removal of acetaldehyde occurs predominantly via radical formation. Photolysis is expected to

9 SUMMARY

contribute another substantial fraction to the removal process. Both pro­ cesses cause a reported daily loss of about 80% of atmospheric acetaldehyde emissions. Reported half-lives of acetaldehyde in water and air are 1.9 h and 10-60 h, respectively. Acetaldehyde is readily biodegradable.

2.4 Environmental Levels and Human Exposure 3 Levels of acetaldehyde in ambient air generally average 5 p,g!m . Con­ centrations in water are generally less than 0.1 p,g/litre. Analysis of a wide range of foodstuffs in the Netherlands showed that concentrations were generally less than 1 mg/kg (1 ppm), but, occasionally, they ranged up to several 100 mg/kg, particularly in some fruit juices and vinegar. The principal source of exposure to acetaldehyde for the majority of the general population is through the metabolism of alcohol. Cigarette smoke is also a significant source of exposure. With respect to other media, the general population is exposed to acetaldehyde mainly from food and beverages and, to a lesser extent, from air. The amounts contributed to total intake from drinking-water are negligible. Available data are inadequate to determine the extent of exposure to acetaldehyde in the workplace. Workers may be exposed in some manu­ facturing industries and in alcohol fermentation where the principal route of exposure is most likely inhalation and possibly, dermal contact.

2.5 Kinetics and Metabolism

2.5.1 Absorption, distribution, and elimination Available studies on toxicity indicate that acetaldehyde is absorbed through the lungs and gastrointestinal tract, but no adequate quantitative studies have been identified. Absorption through the skin is probable. Following inhalation by rats, acetaldehyde is distributed to the blood, liver, kidney, spleen, heart, and other muscles. Low levels were detected in embryos after maternal i.p. injection of acetaldehyde (mouse) and following maternal exposure to ethanol (mouse and rat). Potential production of acetaldehyde has also been observed in rat fetuses and the human placenta in vitro.

10 SUMMARY

Distribution of acetaldehyde to brain interstitial fluid, but not to brain cells, has been demonstrated following intraperitoneal injection of ethanol. A high affinity, low-Km ALDH8 may be important in maintaining low levels of acetaldehyde in the brain during the metabolism of ethanol. In humans and the baboon, acetaldehyde is taken up by red blood cells following ethanol consumption and can, in vivo, reach intracellular levels that are 10 times greater than plasma levels. Following oral administration, virtually no unchanged acetaldehyde is excreted in the urine.

2.5.2 Metabolism The major pathway for the metabolism of acetaldehyde is by oxidation to acetate under the influence ofNAD-dependent ALDH.8 Acetate enters the citric acid cycle as acetyl-CoA. There are several isoenzymes of ALDH with different kinetic and binding parameters that influence acetaldehyde oxidation rates. ALDH activity has been localized in the respiratory tract epithelium (excluding olfactory epithelium) in the rat, in the renal cortex and tubules in the dog, rat, guinea-pig, and baboon, and in the testes in the mouse. Acetaldehyde is metabolized by mouse and rat embryonic tissue in vitro. Acetaldehyde crosses the rat placenta despite placental metabolism. Though there is some metabolism in human renal tubules, the liver is the most important site of metabolism of acetaldehyde. Several isoenzymic forms of ALDH have been identified in human liver and other tissues. There is polymorphism for the mitochondrial ALDH. Subjects who are homozygous or heterozygous for a point mutation in the mitochondrial ALDH corresponding gene have a low activity of this enzyme, metabolize acetaldehyde slowly, and are intolerant of ethanol. The metabolism of acetaldehyde can be inhibited by crotonaldehyde, dimethylmaleate, phorone, disulfiram, and calcium carbamide. a NAD = nicotinamide adenine dinucleotide. ALDH = aldehyde dehydrogenase.

11 SUMMARY

2.5.3 Reaction with other components Acetaldehyde forms stable and unstable adducts with proteins. This can impair protein function as evidenced by inhibition of enzyme activity, impaired histone-DNA binding, and inhibition of polymerization of tubulin. Unstable adducts of acetaldehyde of undetermined significance occur in vitro with nucleic acids. Acetaldehyde can react with various macromolecules in the body, preferentially those containing lysine residues, which can lead to marked alterations in the biological fimction of these molecules.

2.6 Effects on Organisms in the Environment

2.6.1 Aquatic organisms LCsos in fish ranged from 35 (guppy) to 140 mg/litre (species not specified). An ECs of 82 mg/litre and an ECso of 42 mg/litre were reported for an alga and Daphnia magna, respectively.

2.6.2 Terrestrial organisms Relatively low concentrations of acetaldehyde in air appear to be toxic for some microoganisms. Aphids were killed when exposed to acetaldehyde at a concentration of 0.36 p,g/m3 for 3 or 4 h. Median lethal values were 8.91 mg/litre per hand 7.69 mg/litre per h for the slug species, Arion hortensis andAgriolimax reticulatus, respectively. Inhibition of the seed germination of onion, carrot, and tomato by acetal­ dehyde (up to 1.52 mg/litre) was reversible, whereas inhibition of seed germination in Palmer amaranth, similarly exposed, was irreversible; acetaldehyde at 0.54 g/m3 damaged lettuce.

12 SUMMARY

2. 7 Effects on Experimental Animals and in vitro Test Systems

2.7.1 Single exposure On the basis of the LDsos in rats and mice and the LCsos in rats and Syrian hamsters, the acute toxicity of acetaldehyde is low. Acute dermal studies were not available.

2.7.2 Short- and long-term exposures In repeated dose studies by both the oral and inhalation routes, toxic effects at relatively low concentrations were limited principally to the sites of initial contact. In a 28-day study in which acetaldehyde was administered in the drinking-water to rats, effects were limited to slight focal hyperkeratosis of the forestomach at 675 mg/kg body weight (no-observed-effect level (NOEL): 125 mg/kg body weight). Following administration of a single dose level of 0.05% in the drinking-water for 6 months (estimated by the Task Group to be approximately 40 mg/kg body weight), acetaldehyde induced synthesis of rat liver collagen, an observation that was supported by in vitro data. Following inhalation, NOELs for respiratory effects were 275 mg/m3 in rats exposed for 4 weeks and 700 mg/m3 in hamsters exposed for 13 weeks. At lowest-observed-effect levels, degenerative changes of the olfactory 3 3 epithelium in rats (437 mg/m ) and trachea in hamsters (2400 mg/m ) were observed. Degenerative changes of the respiratory epithelium and larynx were observed at higher concentrations. No repeated dose dermal studies were available.

2.7.3 Reproduction, embryotoxicity, and teratogenicity In several studies, parenteral exposure of pregnant rats and mice to acetaldehyde induced fetal malformations. In the majority of these studies, maternal toxicity was not evaluated. No data on reproductive toxicity were identified.

2. 7.4 Mutagenicity and related end-points Acetaldehyde is genotoxic in vitro, inducing gene mutations, clastogenic effects, and SCEs in mammalian cells in the absence of exogenous metabolic activation, though negative results were reported in adequate tests on

13 SUMMARY

Salmonella. Following intraperitoneal injection, acetaldehyde induced SCEs in the bone marrow of Chinese hamsters and mice. However, acetaldehyde administered intraperitoneally did not increase the frequency of micronuclei in early mouse spermatids. There is indirect evidence from in vitro and in vivo studies to suggest that acetaldehyde can induce protein-DNA and DNA-DNA cross-links.

2. 7.5 Carcinogenicity Increased incidences of tumours have been observed in inhalation studies on rats and hamsters exposed to acetaldehyde. In rats, there were dose­ related increases in nasal adenocarcinomas and squamous cell carcinomas (significant at all doses), and, in hamsters, non-significant increases in nasal and laryngeal carcinomas. All concentrations of acetaldehyde administered in the studies induced chronic tissue damage in the respiratory tract.

2. 7.6 Special studies Adequate studies on the potential neuro- and immunotoxicity of acetal­ dehyde were not found.

2.8 Effects on Hwnans In limited studies on human volunteers, acetaldehyde was mildly irritating to the eyes and upper respiratory tract following acute exposure for very short periods to concentrations exceeding approximately 90 mg/m3 and 3 240 mg/m , respectively. Cutaneous erythema was also observed in patch testing with acetaldehyde, in twelve subjects of "oriental ancestry". One limited investigation has been reported in which the incidence of cancer was examined in workers exposed to acetaldehyde and other compounds. On the basis of indirect evidence, acetaldehyde has been implicated as the putatively toxic metabolite in the induction of alcohol-associated liver damage, facial flushing, and developmental effects.

14 3. EVALUATION AND CONCLUSIONS

The acute toxicity in animals of acetaldehyde administered by the inhalation or oral route is low. Acetaldehyde is mildly irritating to the eyes and the upper respiratory tract in humans following short exposures in air to concentrations exceeding 3 3 approximately 90 mg/m and 240 mg/m , respectively. Cutaneous erythema has been observed in patch testing of humans. Following oral administration of 675 mg/kg body weight per day to rats, a borderline increase in hyperkeratosis of the forestomach was observed (NOEL: 125 mg/kg body weight). In rats exposed to approximately 40 mg/kg body weight in the drinking-water for 6 months, there was an increase in collagen synthesis in the liver. In inhalation studies, the NOELs for respiratory effects were 275 mg/m3 in rats exposed for 4 weeks and 700 mg/m3 in hamsters exposed for 13 weeks. At concentrations that induce tissue damage in the respiratory tract, increased incidences of nasal adenocarcinomas and squamous cell carcinomas in the rat, and laryngeal and nasal carcinomas in the hamster have been observed. There is suggestive evidence that acetaldehyde causes genetic damage to somatic cells in vivo. Available data are inadequate for the assessment of potential reproductive, developmental, neurological, or immunological effects. On the basis of data on irritancy in humans, a tolerable concentration of 2 mg/m3 has been derived. Division of an effect level for irritancy in the respiratory tract of rodents by an uncertainty factor (1000), gave a tolerable concentration of

15 EVALUATION AND CONCLUSIONS

3 0.3 mg/m . On the basis of the estimation of lifetime cancer risk using the method of linear extrapolation, the concentrations associated with a 10-5 excess lifetime risk are 3 11-65 p.g/m . The limited data preclude definitive conclusions concerning the risks of acetaldehyde for environmental biota. However, considering the short half-lives of acetaldehyde in air and water and the fact that it is readily biodegradable, the toxicity of acetaldehyde for organisms in the aquatic and terrestrial environments is expected to be low, except, possibly, during industrial discharges and spills.

16 4. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION

4.1 Human Health Hazards, Prevention and Protection, First Aid The human health hazards associated with exposure to acetaldehyde, preventive and protective measures, and first aid measures are listed in the Summary of Chemical Safety Information in section 6. The substance can be absorbed into the body by inhalation of its vapour and by ingestion. Liquid acetaldehyde and fairly low levels of the vapour are irritating to the eyes, skin, and upper respiratory tract. Repeated exposure may result in dermatitis (rarely). Acute exposure to high levels of acetaldehyde vapour may result in pulmonary oedema, preceeded by excitement, followed by narcosis. Chronic effects due to acetaldehyde exposure seem unlikely, since inhalation of toxicologically significant levels of acetaldehyde are precluded by its irritant properties at fairly low levels.

4.2 Advice to Physicians Inhaled steroids will help to prevent lung damage and oedema. In the presence of wheezy breathing, the physician may consider the subcutaneous application of Ih-sympathomimetics, such as terbutaline sulfate (0.5 mg), followed, if necessary, by application of a suppository containing aminophylline (360 mg). In cases of suspected poisoning by acetaldehyde inhalation, attention should be paid to the lungs and upper respiratory tract for irritant effects. When a victim has breathing difficulties, 100% oxygen can be administered; if necessary, artificial respiration may be applied.

4.3 Health Surveillance Advice Workers frequently exposed to acetaldehyde should be examined periodi­ cally. Consideration should be given to the skin, eyes, and respiratory tract.

17 HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION

4.4 Explosion and Fire Hazards, Prevention

4.4.1 Explosion and fire hazards Acetaldehyde is highly flammable when exposed to heat or flame (flash­ point, closed cup -38 °C). Acetaldehyde in air can be explosive, explosion limits in air are4.5-60.5 vol%. The autoignition temperature is 185-193 °C. The vapour of acetaldehyde is heavier than air, and may spread along the ground and be ignited from a distance. Acetaldehyde can react violently with acid anhydrides, alcohols, ketones, phenols, Nib, HCN, H2S, halo­ gens, P, isocyanates, strong alkalis, and amines. Reactions with cobalt chloride, mercury(II) chlorate, or mercury (II) perchlorate form sensitive, explosive products. Acetaldehyde polymerizes violently in the presence of traces of metals and acids. Reaction with oxygen may lead to detonation. When heated to decomposition, it emits acid smoke and fumes.

4.4.2 Prevention Use ventilation, non-sparking tools, and closed and explosion-proof equipment and illumination sources. Do not smoke and do not use acetal­ dehyde near other sources of ignition. Avoid contact of acetaldehyde with oxidants. In case of fire, keep containers with acetaldehyde cool by spraying with water.

4.4.3 Fire extinguishing agents Fires can be extinguished with chemical powder, alcohol-resistant foams, carbon dioxide, or a lot of water.

4.5 Storage Acetaldehyde should be stored in the dark in tightly closed containers, under cool and fireproof conditions with the addition of an inhibitor. It must be stored away from substances with which it can react, such as halogens, oxidative substances, amines, organic substances, caustic solutions, con­ centrated sulfuric acid.

18 HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION

4.6 Transport In case of an accident, stop the engine. Remove all sources of ignition. Keep public away from danger area, mark the roads and keep upwind. Use non-sparking handtools and explosion-proof electrical equipment. Notify police and fire brigade immediately. In case of spillage or fire, follow advice given in sections 4.4 and 4.7, respectively. In case of poisoning, follow advice in the Summary of Chemical Safety Information (section 6).

4. 7 Spillage In case of spillage of acetaldehyde, remove all ignition sources and evacuate and ventilate the danger area. Ensure personal protection (protective clothing, safety goggles and/or breathing protection), and shut off leaks, if without risk. Collect the leaking liquid in sealable contamers. Absorb the spilt acetaldehyde in sand or an inert absorbent and remove to a safe place; DO NOT absorb in sawdust or other combustible absorbents. Remove vapour with fine water spray and flush contaminated area with plenty of water. Prevent the liquid from entering sewers and ditches. If acetaldehyde has entered a water course or sewer, or, if it has con­ taminated soil or vegetation, warn police.

19 5. HAZARDS FOR THE ENVIRONMENf AND THEIR PREVENTION

Acetaldehyde appears to be toxic, even at low concentrations and with short periods of exposure, to fungi. It can also inhibit the seed germination of several plants. Contamination of the environment can be minimized by proper methods of storage, handling, transport, and production, and by reducing the emission sources (such as open burning, incineration of gas, fuel oil, and coal). In case of spillage, apply methods recommended in section 4. 7.

20 6. SUMMARY OF CHEMICAL SAFETY INFORMATION

This summary should be easily available to all health workers concerned with, and users of, acetaldehyde. It should be displayed at, or near, entrances to areas where there is potential exposure to acetaldehyde, and. on processing equipment and containers. The summary should be translated into the appropriate language(s). · All persons potentially exposed to the chemical should also have the instructions in the summary clearly explained. Space is available for insertion of the National Occupational Exposure Limit, the address and telephone number of the National Poison Control Centre, and local trad£ names.

21 SUMMARY OF CHEMICAL SAFETY INFORMATION

ACETALDEHYDE CH3CHO; CAS Registry No.75-07-0

PHYSICAL PROPERTIES OTHER CHARACTERISTICS

Melting point -123.5 °C Acetaldehyde is a colourless liquid Boiling point at 101.3 kPa 20.2 °C with a pungent suffocating odour; Water solubility completely miscible in water the odour threshold in air is reported to N 3 N Specific density (20/4) 0.778 be 0.09 mg/m ; vapour is heavier than Relative vapour density 1.52 air and may spread along the ground and Vapour pressure (20 °C) 101.3 kPa be ignited from a distance; the compound Autoignition temperature 185-193 °C may polymerize violently under the Flash point, closed cup -38 °C influence of bases, with fire or explosion Relative molecular mass 44.1 hazards; acetaldehyde is a strong reducing Octanollwater partition agent and reacts violently with oxidants, coefficient (log Pow) 0.63 causing fire and explosion hazards HAZARD/SYMPTOM PREVENTION AND PROTECTION FIRST AID

SKIN: corrosive; redness, pain Wear plastic or synthetic rubber gloves, Remove soaked clothing, wash the skin with apron, and boots plenty of water; obtain medical attention immediately

EYES: corrosive; redness, pain, Wear safety goggles or face shield in Wash the eyes with plenty of water; remove blurred vision combination with breathing protection contact lenses if easily possible; obtain medical attention immediately

INHALATION: corrosive; sore throat, Apply ventilation, exhaust hood and/or Remove victim to fresh air and keep victim coughing, pulmonary oedema, un­ breathing protection quiet in half-upright position; obtain N consciousness and effects resembling medical attention immediately; subcutaneous c..l alcoholic intoxication application of 6-sympathomimetic substances

INGESTION: corrosive; abdominal Do not eat, drink, chew or smoke Rinse mouth; do not induce vomiting; pains, diarrhoea, vomiting, burning during work; do not keep food in areas obtain medical attention immediately sensation, dizziness, headache, with potential exposure; keep out of nausea, unconsciousness reach of children

ENVIRONMENT: toxic to micro­ Minimize contamination of water, soil organisms, inhibits seed germination and atmosphere by proper methods of in plants storage, handling, transport, and production, and by reduction of emission sources SUMMARY OF CHEMICAL SAFETY INFORMATION (continued)

SPILLAGE STORAGE FIRE AND EXPLOSION

Ensure personal protection; shut Store in fireproof, dark and cool Acetaldehyde is highly flammable; off leaks, if without risk; remove conditions with addition of an inhibi- avoid open fire or sparks; no smoking ignition sources; evacuate and tor; store separately from halogens, and no naked lights; no contact with ventilate area; collect leaking oxidative substances, amines, organic heated surfaces; in case of fire keep liquid in closed containers; substances, caustic solutions, concen- containers cool by spraying water; absorb spilt acetaldehyde in trated sulfuric acid extinguish fire with chemical powder, sand or inert absorbent; remove alcohol-resistant foams, carbon dioxide, a N vapour with fine water spray and large amount of water; acetaldehyde vapour ~ flush area with plenty of water; in air may be explosive; ventilate; use non- do not let run off into a sewer sparking tools, closed and explosion- proof equipment

WASTE DISPOSAL

Dissolve in a combustible solvent, such as alcohol or benzene, then spray the solution in the furnace with afterburner 7. CURRENT REGULATIONS, GUIDELINES, AND ·STANDARDS

7.1 Exposure Limits Some exposure limits are given in the table on pages 26-29.

7.2 Specific Restrictions In the USA, no power-operated truck may be used in atmospheres where a hazardous concentration of the substance is present. Current regulation of the EC: Warning signs: F Easily flammable Risk numbers: 12 Extremely flammable 36/37 Irritating to eyes and respiratory system Safety numbers: 9 Keep container in a well-ventilated place 16 Keep away from sources of ignition-no smoking 29 Do not empty into drains 33 Take precautionary measures against static discharges

7.3 Labelling, Packaging, and Transport United Kingdom In the United Kingdom, the labelling of road tankers containing acetal­ dehyde must be: "flammable liquid". Emergency action code: 2YE. For labelling and packaging methods, the United Kingdom refers to the EC (OJEC L.106,18,1982). Germany For labelling and packaging methods, Germany refers also to the EC (OJEC L.106, 18, 1982).

25 ,, ' ·'

.. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS

Exposure limit values

Medium Specification Country/ Exposure limit description a Value Effective organization date

AIR Occupational Argentina Maximum permissible concentration 1979 Time-weighted average (TWA) 180 mg/m3 Short-term exposure limit (STEL) 270 mg/m3 Australia Threshold limit value (TLV) 1985 (r) N 3 01 Time-weighted average (TWA) 180 mg/m Short-term exposure limit (STEL) 270 mg/m3 Belgium Threshold limit value (TLV) 1987 (r) Time-weighted average (TW A) 180 mg/m3 Short-term exposure limit 270 mg/m3 Canada Threshold limit value (TL V) 1980 Time-weighted average (TWA) 180 mg/m3 Short-term exposure limit (STEL) 270 mg/m3 Czechoslovakia Maximum acceptable concentration 1985 Time-weighted average (TWA) 200 mg/m3 Celing limit value (CL V) 400 mg/m3 Finland Maximum permissible concentration 1985 (r) 3 Time-weighted average (TWA) 90 mg/m Short-term exposure limit (STEL) 135 mg/m3 Germany (former Threshold limit value (TLV) 1987 (r) FRG) Time-weighted average (TWA) 90 mg/m3 Short-term exposure limit (STEL) 180 mg/m3 (5-min TWA) Germany (former Maximum acceptable concentration 1988 (r) 3 GDR) Short-term exposure limit (STEL) 100 mg/m Hungary Maximum acceptable concentration 1985 (r) 3 Time-weighted average (TWA) 50 mg/m 3 ~I Short-term exposure limit (STEL) 250 mg/m (30 min) 3 Italy Treshold limit value (TLV) 100 mg/m 1985 (r) Netherlands Maximum limit (MXL) 1987 (r) 3 Time-weighted average (TWA) 180 mg/m Poland Maximum permissible concentration 1985 (r) Time-weighted average (TWA) 5 mg/m3 Romania Maximum permissible concentration 1985 (r) 3 Time-weighted average (TWA) 100 mg/m Ceiling limit value (CLV) 200 mg/m3 CURRENT REGULATIONS, GUIDELINES, AND STANDARDS (continued)

Medium Specification Country/ Exposure limit description8 Value Effective organization date

AIR Occupational Sweden Hygienic limit value 1988 Time-weighted average (TWA) 45 mg/m3 Short-term exposure limit (STEL) 90 mg/m3 Switzerland Maximum work-site concentration 1987 (r) Time-weighted average (TWA) 90 mg/m3

N 00 United Kingdom Recommended limit (RECL) 1987 (r) Time-weighted average (TWA) 180 mg/m3 Short-term exposure limit (STEL) 270 mg/m3 USA Permissible exposure limit (PEL) 1987 (r) Time-weighted average (TWA) 360 mg/m3 USA(ACGIH) Threshold limit value (TLV) 1987 (r) Time-weighted average (TW A) 180 mg/m3 Short-term exposure limit (STEL) 270 mg/m3 former USSR Maximum acceptable concentration 1982 (r) Ceiling limit value (CL V) 5 mg/m3 1977 AIR Ambient, former USSR Maximum acceptable concentration 1984 background 1 x/day 0.01 mg/m3 average/day 0.01 mg/m3

Emission Germany (former Maximum limit (MXL) 0.15 mg/m3 1986 FRG)

Japan Maximum limit (MXL) 0.09-0.9 mg/m3 1982 (r) emmision standard because of offensive odour

WATER Surface former USSR Maximum acceptable concentration 0.2 mg/litre 1983

~I SOIL former USSR Maximum acceptable concentration 10 mg/kg 1985

a TWA = time-weighted average over one working day (usually 8 hours). CURRENT REGULATIONS, GUIDELINES, AND STANDARDS

The substance is classified as harmful to water (class 2). In order to protect water, appropriate security measures should be taken during storage, loading, and transport. United States ofAmerica In the USA, acetaldehyde, when carried in bulk, is classified as a "cargo of particular hazard" for purposes of regulations governing handling of dangerous cargoes in, or contiguous to, waterfront facilities. A permit is required for handling such cargo. Unless in compliance with a specified procedure, owners/operators of vessels, or on- or offshore facilities must notifY the US Government of any discharge of this substance in, or on, navigable waters, adjoining shorelines or the contiguous zone in an amount equal to, or greater than, 45 kg in any 24-h period. Such a discharge is a violation of the Federal Water Pollution Control Act. When certain specified vessels carrying acetaldehyde in bulk are bound for departure from the US ports, the captain of the port must be notified at least 24 h in advance. Canada Acetaldehyde is hazardous to the environment. The maximum amount per package that may be transported on a cargo aircraft: 30 litres.

7.4 Discharges, Waste Disposal In the USA, a permit is required for the discharge of any pollutant from any point source into US waters. The following must report quantitative data for the substance in their applications: every applicant who has reason to believe that the substance is contained in any of his outfalls inspection, monitoring and reporting requirements after the issue of the permit are specified. Even if not required in the permit, discharge of the substance must be reported if it exceeds the highest of the following levels: (a) 100 mg/litre, (b) 5 times the maximum concentration reported in the application, (c) the level established by the director of the Environmental Protection Agency. In the USA, acetaldehyde, including any isomers, hydrates, and solutions and mixtures containing the substance, is designated as a hazardous

30 CURRENT REGULATIONS~ GUIDELINES, AND STANDARDS substance for the purposes of discharge (including spilling, leaking, etc.) under the water pollution control act. Acetaldehyde, if it is a commercial chemical product, is identified in the USA as a "toxic waste" subject to regulation and notification requirements.

31 BIBLIOGRAPHY

CEFIC (1979) Transport Emergency Cards for Individual Products. CEFIC TEC(R)-620. London & Tonbridge, Whitefriars Press Ltd. The Association of the Dutch Chemical Industry (1989) [Chemical cards. Data for working safely with chemicals.] 5th ed. Alphen aan den Rijn, Samson HD Tjeenk Willink (in Dutch). Henschler D (1992) [Hazardous occupational materials. Toxicological basis of exposure limits.] Weinheim: VCH VerlagsgesellschaftmbH, pp 1-3 (in German). IARC (1985) Allyl compounds, aldehydes, epoxides and peroxides. Lyon, International Agency for Research on Cancer, pp 101-132 (IARC Monographs on the evaluation of carcinogenic risk of chemicals to humans, Vol. 36). IPCS/CEC (1990) International chemical safety card No. 0009: Acetaldehyde. Luxembourg, Commission of the European Communities. IRPTC (1992) Legal file 1992. Geneva, International Register of Potentially Toxic Chemicals/UNEP. Sittig M (1979) Hazardous and Toxic Effects of Industrial Chemicals. Park Ridge, Noyes Data Corporation, pp 1-3. WHO (in preparation) Environmental Health Criteria 167: Acetaldehyde. Geneva, World Health Organization.

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32 Other HEALTH AND SAFETY GUIDES available: (continued from inside front cover)

Resmethrins (No. 25, 1989) Rotenone (No.73, 1992) Tecnazene (No. 12, 1988) Tetrachloroethylene (No. 10, 1987) 'retradifon (No. 11, 1987) Tetramethrin (No. 31, 1989) Tri-allate (No. 89, 1994) Trichlorfon (No. 66, 1991) Trimeilitic anhydride (No. 71, 1992) Vallldiu~ (No. 42, 1990) Vinylidene ehloride (No. 36, 1989) ...... Price: Sw. fr. 5.- ISBN 92 4 151090 0 Price in developing countries: Sw. fr. 3.50