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Emergency and Continuous Exposure Limits for Selected Airborne Contaminants, Volume 1 ARSINE BACKGROUND INFORMATION PHYSICAL AND CHEMICAL PROPERTIES: Structural formula: AsH3 Molecular weight: 77.9 Synonyms: Hydrogen arsenide, arsenuretted hydrogen CAS number: 7784–42–1 Physical state: Colorless gas Melting point: −116.3°C Boiling point: −55°C Density: 2.69 (air=1) Odor threshold: 1–10 ppm (garlic-like odor) Conversion factors: ppm=0.31 (mg/m3) mg/m3=3.23 (ppm) OCCURRENCE AND USE Arsine is not used industrially, but is formed whenever nascent (freshly formed) hydrogen comes into contact with a solution that contains inorganic arsenic (Sittig, 1979). Exposure to arsine gas may result from the action of acids on metals that contain arsenic or from the use of impure sulfuric or hydrochloric acid that contains arsenic (Patty, 1963). SUMMARY OF TOXICITY INFORMATION Arsine is the most acutely toxic form of arsenic. Its lethal capacity by inhalation suggested its use as a chemical-warfare agent (Gates et al., 1946). Its toxic manifestations are methemoglobinemia and hemolysis. Secondary effects resulting from hemolysis include renal and hepatic damage, hemoglobinuria, anuria, anoxia, jaundice, and hemolytic anemia. Results of acute toxicity studies are summarized in Tables 7 and 8. Little information on subchronic toxicity is available. Guinea pigs exposed to arsine at 0.5–2.0 ppm 1–3 h/d for up to 144 h showed evidence of decreases in red and white blood cell counts and hemoglobin concentration (Nau et al., 1944); there was also some evidence of peripheral nerve damage. There have been numerous cases of accidental arsine poisoning (mostly acute) in man; little information is available on the arsine concentrations involved. Arsine concentrations thought to produce physiologic effects in man are shown in Table 9. ACGIH has established a TLV of 0.05 ppm for occupational exposure. Similar values have been established in other countries (Table 10). Gates et al. (1946) estimated minimal disabling exposure to arsine for humans of 5.0 mg/L for 2 min and 0.2 mg/L for 30 min.
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Emergency and Continuous Exposure Limits for Selected Airborne Contaminants, Volume 1 COMMITTEE RECOMMENDATIONS EXPOSURE LIMITS Previous EEL and CEL recommendations made by the Committee (1961 and 1966) for arsine exposure are as follows: Concentrations, ppm Duration 1961 1966 1 h 1.0 1.0 8 h 0.05 — 24 h 0.01 0.1 90 d — 0.01 There is little additional information available for revising the 1966 recommendations and additional animal toxicity studies are necessary for the determination of an appropriate CEL. The Committee, thus, recommends that the 1-h and 24-h EELs be 1.0 and 0.1 ppm, respectively; these concentrations agree with the estimates provided by Gates et al. (1946) and Henderson and Haggard (1943). The Committee does not recommend a 90-d CEL because data are insufficient.
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Emergency and Continuous Exposure Limits for Selected Airborne Contaminants, Volume 1 TABLE 7 LD50 of Arsine after Intraperitoneal Injection (Levvy, 1946) Species LD50 mg/kg Mouse 3.0 Rabbit 2.5 Cat 2.0–2.5 Sheep 3.0 TABLE 8 Acute Toxicity of Arsine in Mice After Inhalation (Levvy, 1947)a Concentration Duration of Exposure Mortality,a % Estimated Duration for 50% Mortality mg/L ppm 2.5 783 0.50 min 93 0.40 min 0.33 min 20 1.0 313 1.25 min 57 1.18 min 0.83 13 0.50 157 10 min 100 2.4 min 5 min 93 2.5 min 57 1.7 min 0 0.25 78.3 15 min 70 12 min 9 min 33 0.10 31.3 70 min 100 50 min 50 min 50 0.025 7.8 30 h 100 24 h 27 h 50 24 h 50 21 h 50 18 h 0 15 h 0 aThirty mice in each experiment with arsine at 0.1 to 2.5 mg/L; six mice used in each experiment with arsine at 0.025 mg/L.
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Emergency and Continuous Exposure Limits for Selected Airborne Contaminants, Volume 1 TABLE 9 Effects of Various Concentrations of Arsine on Humans (Henderson and Haggard, 1943) Concentration, ppm Maximum concentration allowable for prolonged exposure 1 Slight symptoms after exposure of several hours 3–10 Maximum concentration that can be inhaled for 1 hour without serious consequences 6–30 Dangerous after exposure of 30–60 minutes 16–60 Fatal after exposure of 30 minutes 250 TABLE 10 Occupational Exposure Limits for Arsine Country Year MAC Reference United States 1974 0.05 ppm (0.2 mg/m3) Winnell, 1975 W. Germany 1974 0.2 mg/m3 " E. Germany 1973 0.2 mg/m3 " Sweden 1975 0.05 mg/m3 " Czechoslovakia 1969 0.2 mg/m3 " USSR 1972 0.3 mg/m3 (ceiling value) " Italy 1975 0.1 mg/m3 Soc. Ital. Med. Lav., 1975 Japan 1965 0.05 ppm (0.2 mg/m3) (Avg. cone. for a working day) Japan Assoc. Ind. Health, 1971
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Emergency and Continuous Exposure Limits for Selected Airborne Contaminants, Volume 1 REFERENCES Gates, M., Williams, J., and Zapp, J.A. 1946. Arsenicals. In Summary Technical Report of Division 9, NRDC. Vol. 1. Chemical Warfare Agents, and Related Chemical Problems. Part 1. Washington, DC.: Office of Scientific Research and Development, National Defense Research Committee, p. 83–114. Henderson, Y., and Haggard, H.W. 1943. Noxious Gases and the Principles of Respiration Influencing Their Action. 2nd ed. New York: Reinhold. [294 p.] Japan Association of Industrial Health. 1971. Recommendations for permissible concentrations, etc. Jpn. J. Ind. Health 13:475–484. Levvy, G.A. 1946. The toxicity of arsine administered by intraperitoneal injection. Brit. J. Pharmacol. 1:287–290. Levvy, G.A. 1947. A study of arsine poisoning. Quart. J. Exper. Physiol. 34:47–67. Nau, C.A., Anderson, W., and Cone, R.E. 1944. Arsine, stibine, and hydrogen sulfide. Ind. Med. 13:308. Patty, F.A. 1963. Industrial Hygiene and Toxicology. Vol. II. Second Edition. New York: John Wiley & Sons. p. 878. Sittig, M. 1979. Arsine. In Hazardous and Toxic Effects of Industrial Chemicals. Park Ridge, New Jersey: Noyes Data Corp. p. 39–41. Societa Italiana di Medicina del Lavoro 1975. Associazione Italiana degli Igienisti Industriali. Valori Limite Ponderati degli Inquinanti Chimici e Particolali degli Amiqienti di Lavoro Per Il. 1975. Med. Lav. 66:361–371. Winnell, M. 1975. An international comparison of hygienic standards for chemicals in the work environment. AMBIO 4:34–36.
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