3 A TLV–TWA of 0.0002 ppm (0.0016 mg/m , as Acute 3 Os) and a TLV–STEL of 0.0006 ppm (0.0047 mg/m , (6) as Os) are recommended for occupational exposure Brunot found that rabbits exposed for 30 minutes to osmium tetroxide. These values are intended to to osmium tetroxide in concentrations estimated at > 3 minimize the potential for irritation of the eyes, 130 mg/m succumbed after 4 days from pulmonary mucous membranes, skin, and respiratory tract. edema. Rat and mouse 4-hour LC50 values for osmium 3 (7) Osmium tetroxide has a caustic action on skin and tetroxide of 40 ppm (400 mg/m ) were reported. has been reported to produce transient disturbances Toxic effects on the bone marrow in guinea pigs (4) of vision following brief, high exposures to the exposed to osmium tetroxide have also been reported. compound. Sufficient data were not available to The route of administration, dose, or duration was not recommend Skin, SEN, or carcinogenicity notations. described. Application of a drop of 1% solution of osmium tetroxide to a rabbit's eye caused severe corneal Chemical and Physical Properties damage, permanent opacity, and superficial (8) Osmium tetroxide is a noncombustible, colorless vacularization. to pale yellow solid, with a disagreeable chlorine-like odor. An odor threshold of 0.0019 ppm has been Human Studies (1) reported. Chemical and physical properties (4) include: (2,3) According to Hamilton and Hardy, workers Molecular weight: 254.20 have described the odor of osmium tetroxide as Specific gravity: 4.906 at 22°C "having the kick of a mule." Irritation of the nose and Melting point: 39.5°C to 41°C throat may persist at least 12 hours after cessation Boiling point: 130°C of exposure. Osmium tetroxide has a caustic action (4) Vapor pressure: 11 torr at 27°C on the skin that has produced dermatitis. (6) Solubility: soluble in water, alcohol, and ether Brunot, after a brief exposure to osmium Conversion factors at 25°C and 760 torr: tetroxide vapor from opening four 0.25-gram 3 3 1 ppm = 10.39 mg/m ; 1 mg/m = 0.096 ppm ampoules, experienced delayed lacrimation and (9) "halo" effects. According to Flury and Zernik, the highest concentration that can be tolerated for 6 Major Uses 3 hours without harmful effects is 0.001 mg/m . (10) The chief use of osmium tetroxide is as a biolog- McLaughlin et al. found concentrations of 3 ical stain for adipose tissues in histopathological osmium tetroxide ranging from 0.1 to 0.6 mg/m in laboratories. Other applications are in photography the air of a precious metal refining plant. The and as a catalyst in organic synthesis. workers suffered from lacrimation and vision Metallic osmium and most of its other disturbances such as a gritty feeling in the eyes and compounds are not considered highly toxic. Osmium the appearance of rings around lights. Some tetroxide is apparently formed quite readily from employees complained of headache, conjunctivitis, finely divided osmium metal by heating in air, or and cough. Exposure was not continuous, and (4) (5) even at room temperature. According to Fairhall, symptoms sometimes developed after inhaling osmium is the only element that forms definite osmium tetroxide for 2 hours. In most cases, octavalent compounds. The toxicities of substances recovery occurred within a few days. (10) such as osmium octafluoride and osmium McLaughlin et al. referred to a human fatality tetrasulfide had apparently not been investigated. resulting from inhalation of osmium tetroxide in
1874. The concentration of the vapor was not References reported. The osmium tetroxide vapor caused capillary bronchitis, which brought about the death of 1. Amoore, J.E.; Hautala, E.: Odor as an Aid to Chemical Safety: Odor Thresholds Compared with Threshold the worker. The autopsy revealed frank pulmonary Limit Values and Volatilities for 214 Industrial edema and other findings similar to those in animals Chemicals in Ai r and Water Dilution. J. Appl. Toxicol. exposed to the vapor of osmium tetroxide. 3(6):272–290 (1983). 2. Merck & Co., Inc.: Osmium Tetroxide. In: The Merck TLV Recommendation Index, 12th edition on CD-ROM, Version 12.1. S. Budavari, M. O'Neil, A. Smith, et al., Eds. Chapman & Osmium tetroxide is an irritant of the eyes, Hall, New York (1996). (4,6,10) mucous membranes, and the skin. Based on 3. Lide, D.R.; Frederikse, H.P.R. (Eds.): Osmium the report that irritation or other harmful effects did Tetroxide. In: Handbook of Chemistry and Physics, not occur in humans exposed to osmium tetroxide at 77th ed. CRC Press, Boca Raton, FL (1996). 3 concentrations up to 0.001 mg/m (0.0001 ppm) for 4. Hamilton, A.; Hardy, H.: Industrial Toxicology, 3rd ed., (9) 6 hours and on the report of transient vision distur- pp. 155–156. Publishing Sciences Group, Acton, MA 3 (10) bance at concentrations from 0.1 to 0.6 mg/m , a (1974). 3 TLV–TWA of 0.0002 ppm (0.0016 mg/m , as Os) 5. Fairhall, L.T.: Industrial Toxicology, p. 120, Williams & 3 and a TLV–STEL of 0.0006 ppm (0.0047 mg/m , as Wilkins, Baltimore (1949). Os) are recommended for osmium tetroxide. 6. Brunot, F.R.: The Toxicity of Osmium Tetroxide Sufficient data were not available to recommend (Osmic Acid). J. Ind. Hyg. 15:136–143 (1933). Skin, SEN, or carcinogenicity notations. 7. Shell Chemical Co.: Unpublished Report, p. 8. Shell Chemical Co., San Ramon, CA (1961). 8. Grant, W.M.: Toxicology of the Eye, 3rd ed., p. 682. Historical TLVs Charles C. Thomas, Springfield, IL (1986). 1962: Proposed: TLV–TWA, 0.0002 ppm 9. Flury, F.; Zernik, F.: Schadliche Gase, p. 253. J. 1963–present: TLV–TWA, 0.0002 ppm Springer, Berlin (1931). 1976–present: TLV–STEL, 0.0006 ppm 10. McLaughlin, A.; Milton, R.; Perry, K.: Toxic Manifestation of Osmium Tetroxide. Br. J. Ind. Med. 3:183–186 (1946).