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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
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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