bp = 1740 C. CLP classi \201 cation and labeling \200 Lead alkyls: Repr (1A), acute tox (1), STOT/RE (2); H360Df, 330, 310, 300, 373 Other lead compounds (excluding azide, acetate and chromate): Repr (1A), acute tox (4), STOT/RE (2); H360Df, 332, 302, 373. Uses/occurrence \200 Extraction of lead from its ore (lead sulfide) and melting of scrap lead ( 2 smelting) Manufacture of lead acid batteries, lead compounds, and paints \200 Production of solder, ceramics, glass, pigments, and ammunition \200 Organic lead (alkyls) added to gasoline a s an anti-knocking agent \200 Exposure during blast removal, stripping and burning of lea d paint; hot cutting in demolition work; breaking and recycling lead batteries. Key health effects \200 Hematological: anemia, reticulocytosis, basophilic stippled red c ells \200 Encephalopathy, peripheral neuropathy \200 Renal toxicity (tubular damage and interstitial \201 brosis) \200 Effects on GI tract (colic) \200 Reduced fecundity in males, impaired fetal neurological development. Measurement \200 Pumped inhalable dust sample on \201 lter, acid digestion, analysis by \202 ame or electrothermal AAS (MDHS 6/3) or XRF (91) or ICP-AES (99). \200 Biological monitoring: lead (inorganic) \200\224blood, zinc protoporphyrin (ZPP), ALA. Lead (organic) \200\224urine (end of shift, end of working week). Further information L132. Control of lead at work. Control of lead at Work Regulations 2002 . ACoP and guidance, (3rd edn. ISBN 9780717625659. INDG305REV1. Lead and you (free). ISBN 9780717663873. Available at: M http://www.hse.gov. uk/pubns/indg305.pdf 02_Smedley_Chap02.indd 70 12/31/2012 8:44:06 PM MANGANESE 71 Manganese General substance information \200 CAS No. Manganese metal 7439 \200\22396 \200 \2235 \200 Occupational exposure limit: manganese and its inorganic compounds (as Mn) \200\224WEL, 8h TWA of 0.5mg/m 3 Physical properties: hard brittle gray-white metal found in mainly crystalline form, mp = 1244 C, bp = 1962 C. CLP classi \201 cation and labeling \200 Manganese dioxide: acute tox (4); H332, 302. \200 Manganese sulfate: STOT/RE (2); H373. Uses/occurrence \200 Major use: production of stainless and carbon steel \200 Manganese compounds have various uses in the production of batteries, fertilizers, ceramics, and glass Exposure occurs during re \201 ning of ore, smelting and fabrication operations \200 Welding (steel). Key health effects \200 Central nervous system effects associated with repeated exposure by inhalation; early signs include sleepiness and weakness in legs \200 Historically, effect s on lungs (pneumonitis) were associated with chronic exposure, although recent studies provide no evidence of this. Measurement Pumped inhalable dust sample on to \201 lter, analysis by XRF MDHS91) or ICP- AES (MDHS 99). 02_Smedley_Chap02.indd 71 12/31/2012 8:44:06 PM CHAPTER 2 Chemical hazards 72 Mercury General substance information \200 CAS No. 7439 \200\22397 \200\2236 \200 No WE L (EH40) \200 Biological monitoring guidance value: 20 mol mercury/mol creatinine in urine (random sampling) Physical properties: silver colored liquid metal, mp = \210\222 39 C, bp = 357 C. CLP classi \201 cation and labeling \200 Mercury (elemental): acute tox (3), STOT/RE (2) ; H331, 373 \200 Some organic and inorganic mercury compounds: acute tox (1), STOT/ RE (2); H330, 310, 300, 373. Uses/occurrence \200 Used as an electrode in the electrolytic production of chlorine from sodium hydroxide (chloro-alkali process). Widely used in thermometers, barometers, and batteries \200 Use in dental amalgam is in d ecline \200 Production of fungicides, biocides, and antifouling paints. Key health effects \200 Irritation of respiratory tract associated with short-term exposu re to Hg vapors Effects on central nervous system (psychomotor effects) \200 Renal toxicity (tubular dama ge). Treatment See b p. 804, Mercury poisoning, for management of acute poisoning. Measurement \200 MDHS 16/2 Sampling: mercury vapor \200\224passive (badge) sampling or pumped sampling on to sorbent tube particulate mercury \200\224pumped sampling on to \201 lter mounted in inhalable sampler ; back-up sorbent tube if vapor also present Analysis by cold vapor atomic absorption spectroscopy \200 Biological monitoring: usually based on measuring total inorganic mercury in urine (cumulative exposure) total inorganic mercury blood levels (acute exposure). 02_Smedley_Chap02.indd 72 12/31/2012 8:44:06 PM NICKEL 73 Nickel General substance information \200 CAS No. Nickel metal 7440 \200\22348 \200\2234 \200 Occupational exposure limit: nickel and its inorganic compounds. water-soluble compounds (as Ni): WEL, 8h TWA of 0.1mg/m 3 \200 metal and insoluble compou nds (as Ni), 8h TWA of 0.5mg/m 3 \200 Physical properties: hard ductile silvery metal, re sistant to corrosion, mp = 1453 C, bp = 2752 C Nickel tetracarbonyl is a gaseous metal compound. CLP classi \201 cation and labeling \200 Nickel: H351, 317 \200 Nickel oxides and sulf ides: H350, 317 \200 Nickel sulfate: H351, 302, 334, 317 \200 Nickel tetracarbonyl: Car c (2), Repr (1B), acute tox (3); H351, 360D, 330. Uses/occurrence \200 Used mainly in stainless steel alloys. Alloys with other metals incl ude copper, aluminum and silver Also used in electroplating, as a catalyst and in the production of nickel compounds, rechargeable batteries, and coins Exposure occurs when welding and grinding nickel containing metal alloys. Key health effects \200 Nickel metal and insoluble salts are retained in the lung \200 Soluble nickels salts may also be absorbed through the skin \200 Skin and respiratory sen sitization \200 Cancer of the lungs and nasal sinuses \200 Fibrosis of lungs, with loss of pulmonary function. Measurement Pumped inhalable dust sample on to \201 lter, acid digestion, analysis by \202 ame or electrothermal AAS (MDHS 42/2) or XRF (MDHS 91) or ICP-AES (MDHS 99). Further information INDG351. Nickel and You (free). Available at: M http:www.hse.gov.uk/pub ns/indg351.pdf Nickel and nickel alloy plating operations: controlling the risk of inhaling mist containing nickel . Available at: M www.hse.gov.uk/surfaceengineering/nickelinhalation.pdf EH60. Nickel and its inorganic compounds. health hazards and precautionary methods . ISBN 0717613420. 02_Smedley_Chap02.indd 73 12/31/2012 8:44:06 PM CHAPTER 2 Chemical hazards 74 Vanadium \200 Vanadium is an essential element \200 Inhalation is the main route of ent ry \200 Vanadium compounds are poorly absorbed through the GI system and rapidly excreted in the urine. General substance information \200 CAS No. Vanadium pentoxide 1314 \200\22362 \200\2231 \200 Occupational exposure limit. Vanadium pentoxide: WEL, 8h TWA of 0.05mg/m 3 Physical properties: soft ductile gray-white metal; good resistance to corrosion by acids and alkalis. CLP classi \201 cation and labeling Vanadium pentoxide M uta (2), Repr (2), STOT/RE (1), a cute tox (4), STOT/ SE (3); H341, 361d, 372, 332, 302, 335. Uses/occurrence \200 Vanadium occurs in different minerals such as patronite (VS 4 ) \200 Also present in carbon-containing deposits such as crude oil and oil shale. The ash f rom oils may be rich in vanadium and is a hazard for industrial furnace and boiler cleaners . Approximately 80% of vanadium produced is used as ferrovanadium, in the production of steel alloys Vanadium salts are used as catalysts in the manufacture of glass, dyes, inks, and pesticides Exposure also occurs during re \201 ning and manufacture of steel alloys. Key health effects \200 Effects include irritation of the eyes, skin, and respiratory tra ct, and GI disturbances Workers may complain of metallic taste and there may be a greenish discoloration of tongue (indication of exposure rather than toxicity) The key health effects of concern for vanadium pentoxide are mutagenicity and respiratory tract toxicity Measurement \200 Vanadium can be collected on a cellulose ester \201 lter and analyzed by ICP-AES (MDHS 99) Oxides of vanadium can be analyzed by XRD after collection (total inhalable fraction) on a PVC membrane \201 lter. 02_Smedley_Chap02.indd 74 12/31/2012 8:44:06 PM ZINC 75 Zinc General substance information \200 CAS No. Zinc metal 7440 \200\22366 \200\2236 \200 Occupational exposure limit: zinc chloride fume \200\224WEL, 8h TWA of 1mg/m 3 ; STEL of 2mg/m 3 \200 zinc distearate inhalable dust \200\224WEL, 8h TWA, 10mg/m 3 ; STEL, of 20mg/m 3 . Respirable dust: WEL 8h TWA, 4mg/m 3 Physical properties: hard, brittle, and lustrous bluish-white metal, mp = 420 C, bp = 907 C. CLP classi \201 cation and labeling \200 Zinc powder (stabilized): no classi \201 catio n for health effects \200 Zinc chloride fume: acute tox (4), skin corr (1B); H302, 314 \200 Zinc sulfate: acute tox (4), eye damage (1); H302, 318. Uses/occurrence \200 Major uses of zinc metal are in galvanizing and the production of batteries, die castings, and construction materials Many zinc alloys are of industrial importance, principally those with copper (brass), tin, lead, and aluminum Zinc chloride is used in soldering \202 ux, as a battery electrolyte, and in textiles, wood preservatives, and medical products Uses of zinc distearate include the manufacture of plastics and pharmaceuticals. Key health effects \200 Zinc is an essential trace element and effects may arise as a res ult of de \201 ciency Metal-fume fever, a transient acute condition associated with exposure to freshly formed fumes of zinc oxide (and some other metals); characterized by fever, chil ls, dyspnoea, nausea, and fatigue, which occur several hours after exposure. Measurement Pumped sampling on to \201 lter in inhalable/respirable sampling head, analy- sis by ICP-AES (MDHS 99). 02_Smedley_Chap02.indd 75 12/31/2012 8:44:06 PM CHAPTER 2 Chemical hazards 76 Acetone General substance information \200 CAS No. 67 \200\22364 \200\2231. Formula CH 3 COCH 3 \200 Occupational exposure limit: WEL, 8h TWA of 1210mg/m 3 (500ppm); STEL of 3620mg/m 3 (1500ppm) Physical properties: colorless liquid, water-soluble liquid, mp = \210\222 94 C, bp = 56 C. CLP classi \201 cation and labeling Eye irrit (2), STOT/SE (2); H319, 336. Uses/occurrence \200 Used in polymer synthesis in the plastics, textile, and pharmaceutic al industries Widely used as a solvent in manufacturing, in paint, inks, varnishes, and other coatings, and in cleaning materials Some use in consumer products, e.g. nail varnish remover. Key health effects \200 Irritation of eyes and respiratory tract \200 Central nervous s ystem (CNS) effects. Measurement \200 MDHS 96 Pumped solid sorbent tubes, solvent desorption, analysis by gas chromatography (GC) MDHS 72 Pumped sorbent tubes, thermal desorption, GC \200 MDHS 88 Diffusive sorbent sampl ers, solvent desorption, GC \200 Biological monitoring: acetone in urine (sampling time e nd of shift). 02_Smedley_Chap02.indd 76 12/31/2012 8:44:06 PM ACID ANHYDRIDES (CYCLIC ANHYDRIDES) 77 Acid anhydrides (cyclic anhydrides) General substance information \200 Phthalic anhydride : CAS No. 85 \200\22344 \200\2239 \200\224 formula C 8 H 4 O 3 \200 occupational exposure l imit \200\224WEL, 8h TWA of 4mg/m 3 ; STEL of 12mg/m 3 physical properties \200\224white crystalline solid, mp = 131 C, bp = 295 C \200 Trimellitic anhydride: CAS No. 552 \200\22330 \200\2237 \200\224formula C 9 H 4 O 5 \200 occupational exposure limit \200\224WEL, 8h TWA of 0.04mg/m 3 ; STEL of 0.12mg/m 3 physical properties \200\224white crystalline solid, mp = 165 \200\223169 C Acetic anhydride: CAS No. 108 \200\22324 \200\2237 \200\224formula (CH 3 CO) 2 O \200 occupational exposur e limit \200\224WEL, 8h TWA of 2.5mg/m 3 ; STEL of 10mg/m 3 physical properties \200\224colorless liquid with a pungent odor, mp = \210\222 73 C, bp = 138 \200\223140 C. CLP classi \201 cation and labeling \200 Phthalic anhydride: acute tox (4), STOT/SE (3), skin irrit (2), eye dam (1), resp/skin sens (1); H302, 335, 315, 318, 334, 317 Trimellitic anhydride: STOT/SE (3), eye dam (1), resp/skin sens (1); H335, 318, 334, 317 Acetic anhydride: acute tox (4), skin corr (1B); H332, 302, 314. Uses/occurrence Cyclic acid anhydrides are a group of reactive chemicals that are used as c uring agents and plasticizers in the production of epoxy resins, a range of polymers, chemi cals, dyes, and pesticides. At room temperature cyclic anhydrides are powders. The most abu ndant chemicals are listed here. Key health effects \200 Irritation of eyes and respiratory tract \200 Occupational asth ma and rhinitis \200 Sensitization of the skin. Measurement MDHS 62 Carboxylic acid anhydrides in dust and fume measured by pumped sampling on to a glass \201 bre \201 lter with a sorbent (tenax) back- up tube. During desorpti on, acid anhydrides are converted to the cor- responding acids, analysis by high-performanc e liquid chromatography (HPLC). 02_Smedley_Chap02.indd 77 12/31/2012 8:44:06 PM CHAPTER 2 Chemical hazards 78 Acrylamide General substance information \200 CAS No. 79 \200\22306 \200\2231: formula H 2 C=CHCON= H 2 \200 Occupational exposure limit: WEL, 8h TWA of 0.3mg/m 3 \200 Physical properties: white crystalline solid, soluble, mp = 84 \200\22385 C, bp = 125 C. CLP classi \201 cation and labeling Carc (1B), Muta (1B), Repr (2), acute tox (3), STOT/RE (1), eye/skin irrit (2), skin sens (1); H350, 340, 361f, 301, 372, 332, 312, 319, 315, 317 . Uses/occurrence Used in the synthesis of polyacrylamides which are used in the treatment of drinking water and waste water, paper industry, metal ore processing, dye, adhesive and te xtile manufacturing, as an oil recovery agent in the oil industry, and in construction. Health effects \200 Irritation of the skin \200 Neurotoxicity; symptoms include fatigue , muscle weakness, numbness of extremities, and other sensory effects \200 Possibility of cancer, based on animal stu dies \200 May cause adverse effects in offspring. Measurement MDHS 57 Acrylamide in air \200\224collection of pumped sample into a Midget Imp inger (containing water), analysis by HPLC. 02_Smedley_Chap02.indd 78 12/31/2012 8:44:07 PM ACRYLONITRILE 79 Acrylonitrile General substance information \200 CAS No. 107 \200\22313 \200\22301. Formu la H 2 C=CHCN \200 Occupational exposure limit: WEL, 8h TWA of 4.4mg/m 3 (2ppm). Limit values are currently under review by HSE Physical properties: colorless, soluble liquid, mp = \210\222 83 C, bp = 77 C. CLP classi \201 cation and labeling Carc (1B), acute tox (3), STOT/SE (3), skin irrit (2), eye dam (1), skin sens (1); H350, 331, 311, 301, 335, 315, 318, 317. Uses/occurrence \200 Major use in the synthesis of acrylic co-polymers in the textile ind ustry \200 Used in the manufacture of acrylonitrile-butadiene-styrene (ABS) rubber, plast ics, and in the production of acrylamide and other chemical intermediates. Key health effects \200 Acrylonitrile is a suspected carcinogen, based on animal studies \200 Dermatitis may result from prolonged or repeated skin contact \200 Central nervous system effects (headache, nausea, fatigue) \200 Diarrhea and jaundice \200 Respiratory tract irritation \200 Simultanous exposure to some other organic solvents may enhance acrylonitrile toxicity. Measurement \200 Pumped sorbent tubes, followed by either thermal or solvent desorption, analysis by GC (MDHS 96, MDHS 72) Diffusive sorbent samplers, followed by solvent or thermal desorption, analysis by GC (MDHS 80 and 88). 02_Smedley_Chap02.indd 79 12/31/2012 8:44:07 PM CHAPTER 2 Chemical hazards 80 Benzene General substance information \200 CAS No. 71 \200\22343 \200\2232: formula C 6 H 6 \200 Occupational exposure limit: WEL, 8h TWA of 1ppm \200 Physical properties: colo rless liquid, slightly soluble in water, mp = \210\222 6 C, bp = 80 C. The main natural source of benzene is crude oil. CLP classi \201 cation and labeling Carc (1A); Muta (1B), STOT/RE (1), Asp tox (1), eye/sk in irrit (2); H350, 340, 372, 304, 319, 315. Uses/occurrence \200 Used in the synthesis of other organic compounds (e.g. styrene, phenol, aniline) and the synthesis of polymers used in the manufacture of plastics, resins, and textiles Also used in tire and shoe manufacturing \200 Exposure occurs mainly in petroleum indust ry \200 Benzene also found in cigarette smoke 2 Benzene is no longer used as a general so lvent because of its high toxicity. Key health effects Effects on blood and blood-forming tissues (anemia, leukemia, and other blood disorders) (see b p. 330, Hematological malignancies). Measurement Air monitoring \200 Pumped sorbent tubes, followed by either thermal or solve nt desorption, analysis by GC (MDHS 96, MDHS 72) Diffusive sorbent samplers, followed by solvent or thermal desorption, analysis by GC (MDHS 80 and 88). Biological monitoring S-phenylmercapturic acid in urine (sample end of week). Further information INDG329. Benzene and You . M http://www.hse.gov.uk/pubns/indg329.pdf 02_Smedley_Chap02.indd 80 12/31/2012 8:44:07 PM CARBON DISULPHIDE 81 Carbon disulphide General substance information \200 CAS No. 75 \200\22315 \200\2230: for mula CS 2 \200 Occupational exposure limit: WEL, 8h of TWA of 32mg/m 3 (10ppm). Physical properties: colorless liquid, mp = \210\222 112 C, bp = 47 C. CLP classi \201 cation and labeling \200 Repr (2), STOT/RE (1), eye/skin irrit (2); H361 fd, 372, 319, 315. Uses/occurrence \200 Most important use is the production of viscose rayon and cellophane \200 Also used in the production of carbon tetrachloride and as a pesticide and fungicide Solvent for oils, resins and phosphorous. Key health effects \200 Irritation of skin, eyes, and respiratory tract \200 Repeated o r prolonged skin contact may cause dermatitis (see b p. 242, Dermatitis 1) Effects on nervous system (acute and chronic encephalopathy, peripheral and cranial polyneuropathy, central and peripheral nervous system dysfunction) Effects on cardiovascular system (coronary heart disease) \200 Possible effects on reprod uction, based on animal data. Measurement Environmental monitoring \200 MDHS 96 Pumped sorbent tubes, solvent desorptio n, analysis by GC \200 MDHS 88 Diffusive sorbent samplers, solvent or thermal desorption, analysis by GC (MDHS 80, 88). Biological monitoring: 2-thioxothia zolidine-4-carboxylic acid \200\224end of shift. 02_Smedley_Chap02.indd 81 12/31/2012 8:44:07 PM CHAPTER 2 Chemical hazards 82 Chloroform General substance information \200 CAS No. 67 \200\22366 \200\2233: formula CH Cl 3 \200 Occupational exposure limit: WEL, 8h TWA of 9.9mg/m 3 (2ppm) \200 Physical pr operties: colorless liquid, slightly soluble in water, volatile liquid mp = \210\222 64 C; bp = 62 C. CLP classi \201 cation and labeling Carc (2), acute tox (4), STOT/RE (2), skin irrit (2); H351, 302, 373, 315. Uses/occurrence \200 Major use is in the production of \202 uorocarbon 22, a refrigeran t and aerosol propellant Also used in the synthesis of polytetra \202 uoroethylene (PTFE) plastics and some dyes and pesticides. Key health effects \200 Brief exposure to high concentrations can result in CNS depressio n (dizziness, headaches, fatigue) Repeated exposure can cause renal toxicity and hepatotoxicity. Measurement MDHS96 Pumped sorbent tubes, solvent desorption, analysis by GC. MDHS 80, 88 D iffusive sorbent samplers, solvent or thermal desorption, analysis by GC. 02_Smedley_Chap02.indd 82 12/31/2012 8:44:07 PM 2, 2 \200\231-DICHLORO-4, 4-METHYLENE DIANILINE 83 2, 2 \200\231-Dichloro-4, 4-methylene dianiline General substance information \200 CAS No . 101 \200\22314 \200\2234: formula C (13) H (12) Cl (2) N (2) \200 Occupational exposure limit: WEL, 8h TWA of 0.005mg/m 3 ; BMGV, 15 mol total 2, 2 \200\231-dichloro-4, 4-methy lene dianiline (MbOCA)/mol creatinine in urine (post-shift) Physical properties: colorless to tan, odorless solid, slightly soluble in water, mp = 110 C. CLP classi \201 cation and labeling Carc (1B), acute tox (4); H350, 302. Uses/occurrence \200 MbOCA is used in the manufacture of polyurethane elastomers with many applications in industrial and consumer plastics Also used in adhesives. Key health effects \200 MbOCA is easily absorbed through the skin \200 Bladder cancer f ollowing inhalation, skin absorption or ingestion via food, drink or cigarettes Acute effects on the blood (formation of methaemoglobin). Measurement \200 Environmental monitoring: collection on pumped acid coated \201 lters, desorption and analysis by HPLC Biological monitoring: total MbOCA in urine (end of shift). Further information HSE Research Report 828 (2010). Occupational exposure to MbOCA and isoc yanates in polyurethane manufacture . Available at: M http://www.hse.gov.uk/research/rrpdf/rr828.pdf HSL (2007). Survey of MbOCA chemical exposure . Available at: M http://www.hse.gov.uk/resea rch/ hsl_pdf/2007/hsl0707.pdf 02_Smedley_Chap02.indd 83 12/31/2012 8:44:07 PM CHAPTER 2 Chemical hazards 84 Formaldehyde General substance information \200 CAS No. 50 \200\22300 \200\2230: formula HCHO \200 Occupational exposure limit: WEL, 8h and 15min TWA of 2.5mg/m 3 (2ppm) Physical properties: pungent colorless gas; soluble in water (formalin). CLP classi \201 cation and labeling Carc (2), acute tox (3), skin corr (1B), skin sens (1) ; H351, 331, 311, 301, 314, 317. Uses/occurrence \200 Main use is the production of resins, principally urea-formaldehyde and phenol-formaldehyde, which are used to make cores and molds for foundries; formaldehyde is given off when resins are heated \200 Formaldehyde has various other uses in agricult ure and medicine where it is used as a disinfectant, fungicide, fumigant, and preservative. Key health effects \200 Irritation of skin and upper respiratory tract \200 Severe irri tation of eyes \200 Allergic contact dermatitis resulting from skin contact \200 Suspec ted human carcinogen (nasopharyngeal cancer) based on animal and some human evidence Little evidence that formaldehyde induces asthma \200 Formaldehyde mixed with hydrochlori c acid can generate bis(chloromethyl)ether, a potent carcinogen. Measurement MDHS 102 Aldehydes in air (pumped sample) collected on to a chemical coated gla ss \201 bre \201 lter contained in a personal inhalable dust sampler, sampler solvent d esorbed (into acetonitrile), aldehydes derivatized and analyzed using HPLC. 2 Method is pri marily intended for measurement of formaldehyde but also suitable for measurement of other aldehydes including glutaraldehyde. Not applicable where formaldehyde is partly in the part iculate phase. Further information IAC (L) 88. Formaldehyde \200\224its safe use in foundries . Available at: M http://www.hse.gov.uk/pubns/ iacl88.htm 02_Smedley_Chap02.indd 84 12/31/2012 8:44:07 PM GLUTARALDEHYDE 85 Glutaraldehyde General substance information \200 CAS No. 111 \200\22330 \200\2238: formu la HCHO(CH 2 ) 3 CHO (used in aqueous solution) Occupational exposure limit: WEL, 8h and STEL of 0.2mg/m 3 (0.05ppm) \200 Physical proper ties: colorless liquid. CLP classi \201 cation and labeling Acute tox (3), skin corr (1B), resp/skin sens (1); H33 1, 301, 314, 334, 317. Uses/occurrence \200 Used as a sterilizing agent in medicine, mainly in endoscopy and oth er surgical procedures Used in leather tanning \200\224leather softening and to improve resistance to water and molds Minor uses in the production of resins and dyes \200 Biocide in the pulp and paper indust ry \200 Disinfect animal housing (sprays). Key health effects \200 Respiratory sensitization \200 Skin sensitization \200 Severe irritation of eyes \200 Irritation of skin and upper respiratory tract. Measurement See b p. 84, Formaldehyde MDHS 102. 02_Smedley_Chap02.indd 85 12/31/2012 8:44:07 PM CHAPTER 2 Chemical hazards 86 Isocyanates De \201 nition Isocyanates are a group of chemicals that contain the N=C=O gro up. Toluene 2,4-diisocyanate (TDI) and methylenebis(phenyl isocyanate) (MDI) are aromatic i socyanate monomers; 1,6-hexamethylenediisocynate (HDI) is an example of an aliphatic isocya nate. General substance information \200 CAS No. TDI, 584 \200\22384 \200\2239; MDI, 101 \200 \22368 \200\2238: formula TDI, CH 3 C 6 H 3 (NCO) 2 ; MDI, CH 2 (C 6 H 4 NCO) 2 Occupational exposure limit: WEL, 8h TWA of 0.02mg/m 3 (total isocyanates as NCO) Physical properties TDI: colorless to yellow solid, mp = 20 \200\22322 C, bp = 251 C. MDI: yellow solid, mp = 37 C, bp = 196 C. CLP classi \201 cation and labeling \200 TDI: Carc (2), acute tox (2), eye/skin irrit (2 ), resp/skin sens (1), STOT/SE (3); H351, 330, 319, 335, 315, 334, 317 MDI: acute tox (4), eye/skin irrit (2), STOT/SE (3), resp/skin sens (1); H332, 319, 335, 315, 334, 317. Uses/occurrence \200 Used in the manufacture of polyurethane foams and for a range of coatings ( \200\230one-pack \200\231, i.e. pre-reacted, or \200\230two pack \200\231, form ed in situ by the addition of a catalyst) Motor vehicle coating: spraying produces the highest exposure \200 Released when heating polyurethane products. Key health effects \200 Respiratory and skin sensitization (see b p. 198, Occupational as thma and rhinitis) Irritation of eyes and respiratory tract. Measurement \200 MDHS 25/3 Pumped sampling train with reagent coated \201 lters and absorbing solution, derivatization, HPLC Laboratories should compare total isocyanates with the WEL. \200 Biological monitoring: u rine sample (isocyanate derived diamine), at end of exposure. Further information INDG388 (REV1) Safety in motor vehicle repair \200\224working with isoc yanate paints . Available at: M http://www.hse.gov.uk/pubns/indg388.pdf Controlling isocyanates exposure in spray booths and spray rooms . Available at: M http://w ww.hse. gov.uk/pubns/web36.pdf Visiting premises spraying Isocyanates based paints \200\224a checklist for HSE staff . Ava ilable at: M http:// www.hse.gov.uk/mvr/priorities/isocyanates/checklist.pdf 02_Smedley_Chap02.indd 86 12/31/2012 8:44:07 PM METHYL ETHYL KETONE 87 Methyl ethyl ketone General substance information \200 CAS No. 78 \200\22393 \200\2233: f ormula C 2 H 5 COOH \200 Occupational exposure limit: WEL, 8h TWA of 600mg/m 3 (200ppm) \200 STEL of 899mg/m 3 (300ppm) \200 BMGV of 70 mol /l in urine (post-shift) Physical properties: colorless volatile liquid with a faint odor, moderately soluble in water, mp = \210\222 86 C, bp = 80 C. CLP classi \201 cation and labeling Eye irrit (2), STOT/SE (2); H319, 336. Uses/occurrence Widely used as a solvent in resins and coatings including paints, lacquers, varnishes, stains, and associated cleaning materials. Key health effects \200 Irritation of eyes and respiratory tract \200 Acute central ner vous system effects, with unconsciousness at high exposure levels Prolonged or repeated skin contact with liquid causes de-fatting of skin \200 Possible ef fects on reproduction (based on animal data). Measurement Environmental monitoring \200 MDHS 96, 72 Pumped sorbent tubes, solvent or th ermal desorption, analysis by GC Diffusive sorbent samplers, solvent desorption, analysis by GC (88). \200 Biological moni toring: MEK in urine (end of shift). 02_Smedley_Chap02.indd 87 12/31/2012 8:44:07 PM CHAPTER 2 Chemical hazards 88 n-Hexane General substance information \200 CAS No. 110 \200\22354 \200\2233: formula CH 6 (CH 2 ) 4 CH 3 \200 Occupational exposure limit: WEL, 8h TWA of 72mg/m 3 (20ppm) \200 Physical properties: colorless volatile liquid insoluble in water, faint odor, mp = \210\222 95 C, bp = 69 C. CLP classi \201 cation, and labeling Repr (2), Asp tox (1), STOT/RE (2), skin irrit (2), S TOT/SE (3); H361f, 304, 373, 315, 336. Uses/occurrence \200 Main use is as a solvent in edible oil extraction and polymerization processes and as a starting material in the production of other organic chemicals Also used as a degreasing agent in various manufacturing processes and as a cleaning agent in printing. Key health effects \200 Peripheral neuropathy, including subclinical effects such as electrophysiological changes in peripheral nerves Depression of central nervous system (e.g. drowsiness and vertigo). Measurement \200 MDHS 96, MDHS 72, NIOSH 1500 Pumped sorbent tubes, solvent or thermal desorption, analysis by GC MDHS 80, MDHS 88 Diffusive sorbent samplers, solvent or thermal desorption, analysis by GC. 02_Smedley_Chap02.indd 88 12/31/2012 8:44:07 PM This page intentionally left blank CHAPTER 2 Chemical hazards 90 Pesticides General substance information \200 Broad spectrum of biocidal agents used in a gricultural and non-agricultural industries. WELs (Tables 2.4 and 2.5) Biological monitoring value: lindane, 35nmol/l (10 g/l) in whole blood. Uses/occurrence \200 Main categories are organophosphate, organochlorine, and carbamate pesticides Exposure occurs mainly in agriculture, although pesticide use is very widespread Exposure arises through preparation (decanting, mixing, spillage), application (spraying, c oating, dipping), and through persons not directly engaged in application entering affected areas. Key health effects (see also b p. 298, Organophosphate poisoning) \200 Organochlorine pes ticides cause a range of neurological effects. acute effects include headache, dizziness, nausea, vomiting, fatigue, convulsions, stimulated respiration, tremors, ataxia chronic effects include intermittent muscle twitching, muscle weakness, tremors, ataxia, in coordination, slurred speech, visual impairment, memory loss, irritation, and depression Organophosphate pesticides act by inhibiting acetylcholinesterase activity, resulting in a range of neurological effects Bipyridylium herbicides (e.g. paraquat) may cause the following effects following ingestion: \200 severe in \202 ammation of mouth, throat, and GT tract \200 effects in the lungs (dyspnoea, anoxia, progressive \201 brosis) \200 necrotic damage t o liver, kidneys, and myocardial muscle \200 extensive hemorrhage, coma, and death. See b Chapter 39 for management of acute contamination and poisoning. Measurement MDHS 94 Inhalable dust/mists sample on to \201 lter with sorbent tube analy- sis by GC-MS. For dermal exposure use swabs (number and sites stipu- lated in MDHS), analys is by GC-MS. Further information Pesticides Safety Directorate. Available at: M http://www.pesticides.go v.uk/home.asp Guidance on storing pesticides for farmers and other professional users . Ava ilable at: M http://www. hse.gov.uk/pubns/ais16.pdf Sheep dipping \200\224advice for farmers and others involved in dipping sheep . Available a t: M http://www. hse.gov.uk/pubns/as29.pdf INDG141 Reporting incidents of exposure to pesticides and veterinary medicines . Available at: M http://www.hse.gov.uk/pubns/indg141.pdf HSE Pesticides Available at: M http://www.pesticides.gov.uk 02_Smedley_Chap02.indd 90 12/31/2012 8:44:07 PM PESTICIDES 91 Table 2.4 Risk phrases for pesticides in EH40/2005 (as amended 2007) CAS CLP Reg Class \200\231n H-statements Captan 133-06-2 Carc (2), Acute tox (3), Eye dam (1), Skin sens (1) H351, 331, 318, 317 Chlopyrifos 2921-88-2 Acute tox (3) H301 Endosulfan 115-29-7 Acute tox (3), Eye irrit (2) H311, 301, 319 Malathion 121-75-5 Acute tox (4) H302 Paraquat dichloride 1910-42-5 Acute Tox. (2), STOT/RE (1), H330, 311, 301, 372, 319, 335, 315 Eye irrit (2), STOT/SE (3), Skin irrit (2) Phorate 298-02-2 Acute tox (1) H310, 300 Pichloram 1918-02-1 Pyrethrum 8003-34-7 Pyrethrin (I and II) 121-21-1 121-29-9 Acute tox (4) H332, 312, 302 Rotenone 83-79-4 Acute tox (3), Eye irrit (2), STOT/SE (3), Skin irrit (2) H301, 319, 335, 315 Sulfotep 3689-24-5 Acute tox (1) H310, 300 02_Smedley_Chap02.indd 91 12/31/2012 8:44:08 PM CHAPTER 2 Chemical hazards 92 Table 2.5 Workplace exposure limits (WELs) for pesticides in EH40/2005 (as amended 2007) WEL (mg/m 3 ) Type 8h STEL Captan OC 5.0 15.0 Chlorpyrifos* OP 0.2 0.6 Sk Endsulfan* OC 0.1 0.3 Sk Malathion OP 10.0 \200\223 Sk Paraquat dichloride e Byp 0.08 _ Phorate OP 0.05 0.2 Sk Picloram 10.0 20.0 Rotenone Bo 5.0 10.0 Sulfotep OP 0.1 _ Sk OC, organochlorine; OP, organophosphate; Bot, botanical; Byp, bypiridylium; P, pyrethrin. 02_Smedley_Chap02.indd 92 12/31/2012 8:44:08 PM PHENOL 93 Phenol General substance information \200 CAS No. 108 \200\22395 \200\2232: formula C 6 H 5 OH \200 Occupational exposure limit: WEL, 8h TWA of 2ppm \200 Physical properties: c olorless or white crystalline solid, slightly soluble in water, mp = 43 C, bp = 182 C. CLP classi \201 cation and labeling Muta (2), acute tox (3), skin corr (1B), STOT/RE (2); H341, 311, 301, 373, 314. Uses/occurrence \200 Main use is in the manufacture of phenolic resins and plastics \200 Also as intermediates in nylon and epoxy resins \200 Phenol has a range of other uses i n production of fertilizers, paints, rubber, textiles, drugs, paper, soap, and wood preservatives Also used as a disinfectant. Key health effects \200 Phenol can be absorbed through the skin \200 Corrosive to eyes, skin, and respiratory tract \200 Dermal exposure can lead to effects on the central nerv ous system (tremors, convulsions, nausea, circulatory failure, bowel cramps, and unconsciou sness). Subsequent respiratory failure may result in death. See b p. 806, Phenol poisoning for acute poisoning with phenols. Measurement MDHS 96,72 Pumped sorbent tubes, solvent desorption, analysis by GC. 02_Smedley_Chap02.indd 93 12/31/2012 8:44:08 PM CHAPTER 2 Chemical hazards 94 Styrene General substance information \200 CAS No. 100 \200\22342 \200\2235: formula C 6 H 5 CH=CH 2 \200 Occupational exposure limit: WEL, 8h TWA of 430mg/m 3 (100ppm); STEL of 1080mg/m 3 (250ppm). Limit values are currently under review by HSE Physical properties: colorless liquid with oily odor, slightly soluble in water, mp = \210\222 31 C, bp = 145 C. CLP classi \201 cation and labeling Acute tox (4), eye/skin irrit (2); H332, 319, 315. Uses/occurrence \200 Major use is the production of polystyrene and as a copolymer in the production of styrene-butadiene rubber, styrene-acrylonitrile, and acrylonitrile-butadiene -styrene polymers and polyester resins Also used in the manufacture of reinforced plastics. Key health effects \200 Acute central nervous system depression \200 Eye irritation fol lowing exposure to liquid or vapor \200 Skin irritation following repeated exposure to li quid \200 Nasal irritation \200 Repeated exposure can result in central nervous system effects and ototoxicity. Measurement \200 MDHS 72,96 Pumped sorbent tubes, solvent /thermal desorption, analysis by GC MDHS 80,88 Diffusive sorbent samplers, solvent /thermal desorption, analysis by GC. Further information HSE (2003). Assessing and controlling styrene levels during contact mol ding of \201 bre-reinforced plastic (FRP) products . Available at: M http://www.hse.gov.uk/pubns/pps14.pdf 02_Smedley_Chap02.indd 94 12/31/2012 8:44:08 PM TETRACHLOROETHYLENE (PERCHLOROETHYLENE) 95 Tetrachloroethylene (perchloroethylene) General substance information \200 CAS No. 127 \200\22318 \200\2234: formula Cl 2 C=CCl 2 \200 Occupational exposure limit: WEL, 8h TWA of 345mg/m 3 (50ppm); STEL of 689mg/m 3 (100ppm) Physical properties: colorless liquid practically insoluble in water with an ether odor, mp = \210\222 22 C, bp = 121 C. CLP classi \201 cation and labeling Carc (2); H351. Uses/occurrence \200 Major use is as a dry cleaning agent \200 Used as a cleaning/degre asing agent in the automotive and other industries. Key health effects \200 Acute central nervous system effects (drowsiness, dizziness, with unconsciousness at high exposures; very high exposures may be fatal) Irritation of skin and respiratory tract \200 Liver and kidney toxicity \200 Evidence f rom animal studies indicates that tetrachloroethylene may cause cancer. Measurement \200 MDHS 72,96 Pumped sorbent tubes, solvent /thermal desorption, analysis by GC MDHS 88 Diffusive sorbent samplers, solvent desorption analysis by GC. 02_Smedley_Chap02.indd 95 12/31/2012 8:44:08 PM CHAPTER 2 Chemical hazards 96 Vinyl chloride General substance information \200 CAS No. 75 \200\22301 \200\2234: formul a H 2 C=CHCl \200 Occupational exposure limit: WEL, 8h TWA of 3ppm \200 Physical proper ties: colorless gas with a sweet odor, slightly soluble in water, mp = \210\222 154 C, bp = \210\222 14 C. CLP classi \201 cation and labeling Carc (1A); H350. Uses/occurrence Used as chemical intermediate in the production of polymers, mainly poly- v inyl chloride (PVC) and copolymer resins. Key health effects \200 Liver cancer (angiosarcoma) (see b p. 264, Hepatic angiosarcoma) \200 Other chronic effects include liver and spleen toxicity, bone deterioration, circulatory disorders affecting feet and hands, and soft tissue lesions Acute central nervous system effects (e.g. dizziness and disorientation). Measurement \200 MDHS 96 Pumped sorbent tubes, solvent desorption, GC \200 MDHS 88 Diff usive sorbent samplers, solvent desorption, GC \200 MDHS 80 Diffusive sorbent tubes, ther mal desorption, GC. 02_Smedley_Chap02.indd 96 12/31/2012 8:44:08 PM ARSINE 97 Arsine General substance information \200 CAS No. 7784 \200\22342 \200\2231: formula AsH 3 \200 Occupational exposure limit: WEL, 8h TWA of 0.16mg/m 3 (0.05ppm) \200 Physical p roperties: colorless gas, garlic-like odor but odorless at low concentrations, slightly sol uble in water, mp = \210\222 117 C, bp = \210\222 63 C. CLP classi \201 cation and labeling Acute tox (2), STOT/RE (2); H330, 373. Uses/occurrence \200 Generated by the action of acid on arsenic \200 Used as a doping a gent in the semiconductor industry \200 Minor use in the production of organic chemicals. Key health effects \200 Haemolysis is main acute effect, leading to haemolytic anemia, possible kidney damage, and jaundice Renal failure may subsequently occur, sometimes leading to death. Measurement MDHS 34 Withdrawn. 02_Smedley_Chap02.indd 97 12/31/2012 8:44:08 PM CHAPTER 2 Chemical hazards 98 Carbon monoxide General substance information \200 CAS No. 630 \200\22308 \200\2230: form ula CO \200 Occupational exposure limit: WEL, 8h TWA of 35mg/m 3 (30ppm); STEL of 232mg/m 3 (200ppm) Physical properties: colorless odorless gas, sparingly soluble in water, mp = \210\222 199 C, bp = \210\222 92 C. CLP classi \201 cation and labeling Repr (1A), acute tox (3), STOT/RE (1); H360D, 331, 372 . Uses/occurrence \200 Used in the production of hydrogen and acetic acid and in the production of hydrocarbons (Fischer \200\223Tropsch process) Also used as an industrial reducing agent \200 Produced as a ubiquitous by-product of inc omplete combustion. Key health effects Acute effects resulting from formation of carboxyhaemoglobin: \200 Asp hyxiation \200 Effects on the developing fetus \200 Cardiovascular effects (effects in subjects with pre-existing cardiovascular disease; exacerbation of exercise-induced angina; ventricular arrhythmia; ta chycardia) CNS effects (headache, dizziness, impaired \201 ne manual dexterity,