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Toxic Manifestations of Osmium Tetroxide

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Toxic Manifestations of Osmium Tetroxide Br J Ind Med: first published as 10.1136/oem.3.3.183 on 1 July 1946. Downloaded from TOXIC MANIFESTATIONS OF OSMIUM TETROXIDE BY A. I. G. McLAUGHLIN, R. MILTON and KENNETH M. A. PERRY From the University of Sheffield and Factory Department, Ministry of Labour and National Service, and the Department for Research in Industrial Medicine (Medical Research Council), the London Hospital Osmium is one of the precious metals and was the vapours of osmic acid gave rise to a capillary discovered in 1803 by Tenant. It occurs naturally bronchitis from which he died. Necropsy revealed in close association with iridium. Osmiridium is a confluent broncho-pneumonia with a tendency to an exceptionally hard alloy with a high melting- suppuration and gangrene; there was also a fatty point (2700° C.) and for this reason it is used degeneration of the epithelium of the renal tubules. extensively for tipping fountain-pen nibs. It is Bardieux (1898) showed that the subcutaneous and also used for electrical contacts, as a catalyst in the intramuscular injection of a 1 per cent. solution of preparation of synthetic ammonia, and for measur- osmic acid produced no serious effect in animals ing the rapidity of explosion of gun-cotton. Before but that small quantities injected into the lungs the introduction of tungsten, electric lamp filaments were immediately fatal. Attempts have been made were sometimes made with it. Osmium is also to make use of the solution in treating diseases such used in the taking of finger-prints, and osmic acid as tuberculosis (Walbum, 1926), syphilis (Levaditi, which is a watery solution of osmium tetroxide is 1927; and Jahnel, 1937) and cancer (Kraus, 1931) used for activating solutions of chlorate of potas- but without success, though Fischl (1933) showed it sium; hardening and colouring certain prepara- possessed some spirochaetocidal properties in tions and in histology for the fixing and staining of experimentally infected mice Coca (1908) studied nerves and fat. The precious metals are likely to the effect of the substance on red blood cells, but be used increasingly in the future and it is felt that the most comprehensive study of the toxicological the possible health risks in the use of their deriva- properties of osmium tetroxide is by Brunot (1933). tives should be known at the outset. He exposed himself to some of the vapours and http://oem.bmj.com/ after 10 minutes he noticed a metallic taste in the Review of Literature mouth and found that smoking was unpleasant; Metallic osmium is innocuous but osmium after 30 minutes he noticed a smarting sensation in tetroxide is slowly formed on exposure of the spongy his eyes, lacrimation which was exaggerated by metal to air. The toxic properties of osmium efforts to read; 3 hours later reading was difficult, tetroxide were first noticed by Gmelin (1827) who he felt a definite constriction in the chest and found described the occurrence of vomiting when it was breathing also difficult; on going out into the street given by mouth. Intravenous injections in animals the lamps appeared to be surrounded by large on September 27, 2021 by guest. Protected copyright. caused serous exudate from the lungs, three such haloes as if there were a dense fog. He therefore injections producing paralysis and death. Vauquelin carried out animal experiments. Rabbits were (1814), Berzelius (1828) and Wohlea (1834) drew exposed for 30 minutes in a box of 190 litres capacity. attention to its corrosive action on the respiratory An ampoule containing 250 mg. of osmium tetroxide tract and eyes. Branell (1849) suggested that the was placed in it on a hot plate and a fan was used symptoms resulted from the oxidizing action of to distribute it throughout the atmosphere. During osmium tetroxide (OS04) which is reduced to the exposure the tetroxide was steadily reduced to osmium dioxide (OsO2), which is then hydrated the dioxide and metal so that at the end of the (OsO22H2O). Deville and Debray (1859, 1874) experiment only 10 per cent. was left. The muzzles described how one of them was rendered almost of the animals became blackened, the pelt changed blind for 24 hours when a current of air taking from white to dirty grey, and a brown film developed away vapour was thrown back unexpectedly on to over the sclera and cornea. After 4 days the him. It produced a sensation like a vigorous blow animals showed marked pulmonary embarrassment on the eye. Osmium tetroxide on the conjunctivae and when killed the lungs were voluminous and produced inflammation which continued to render did not float in water. They were dark red and sight troublesome for some weeks. The author solid with scattered irregular purple areas and the also developed mild asthmatic symptoms and a bronchi were filled with pus. The kidneys showed co-worker a painful skin eruption. Raymond cloudy swelling and granulation of the epithelium. (1874) reports the only fatal case in the literature. After exposure to 500 mg. and 1 g. the animals The patient was employed by Vulpain in Paris and became semi-comatose a few minutes after the 183 184 BRITISH JOURNAL OF INDUSTRIAL MEDICINE Br J Ind Med: first published as 10.1136/oem.3.3.183 on 1 July 1946. Downloaded from exposure, showed acute bronchial irritation and tively a measurement can be made using a colori- pulmonary embarrassment and died within 30 hours. meter if standard solutions of osmium are used in He also placed 1 drop of 1 per cent. osmium the comparison cell. Where very small quantities tetroxide in water into the conjunctival sacs of of osmium are encountered, a micro-technique may rabbits. After 24 hours- there was oedema and be employed, in which case the distillate may be swelling of the lids with profuse purulent discharge arranged so that the osmium is contained in 2 ml. and a metallic brown stain on all parts of the con- of liquid and colour development carried out as junctiva. After 48 hours the cornea was milky and above, making certain that the concentration of semi-opaque with superficial conjunctival ulcers. acid in the distilling solution is of the order of Ten days after the exposure the acute stage had 10 per cent. by volume. The colour is read in the subsided, but there was corneal opacity and a Spekker absorptiometer fitted with micro cups, or pannus began to form which after 1 month slowly in a microcolorimeter. This refinement was carried extended towards the centre of the cornea. out when the osmium present was appreciably lower than 100 ,ug. Recent Investigation We had the opportunity of observing the effect CALIBRATION CURVE of osmium tetroxide on seven men who were ,ug. osmium Spekker reading engaged in refining osmiridium. The findings 0 0 100 0-070 appeared worth reporting. The atmospheric con- 200 0-145 centration of osmium tetroxide to which the men 300 0 225 were exposed was estimated. This part of the 400 0 300 investigation is described first, the clinical findings 500 0 375 being given later. 600 0 450 1000 0 750 Environmental Study ATMOSPHERE SAMPLES In dissolving ores containing the precious metals (2-hour sample at 75 litres per hour= 150 litres) with aqua regia, osmium compounds are apt to 1. Osmium found=20,g. 133,ug per cu. metre. gain access to the surrounding atmosphere in the 2. Osmium found=70/tg. 467,ug per cu metre. fine spray which is given by the acid reaction. 3. Osmium found=96L&g. 640/g per cu. metre. Samples of the air near to the action pots were obtained by sucking the air through a cone-shaped Clinical Picture filter which was fitted with a low-resistance What- The men exposed to these concentrations had man filter paper. Suction was obtained by means symptoms similar to those described by Brunot of an injector pump attached to an air line, and in (1933). They had irritation of the eyes with pain the system was incorporated a flowmeter reading and lacrimation.. They saw large haloes round all http://oem.bmj.com/ up to 100 litres per hour. Three 2-hour samples lights, one man saying they were green in the centre were taken during the reaction and distillation and red round the outside. Mostly the symptoms processes and estimated by the following method. subsided within 24 hours. One of the men com- The paper containing the osmium in particulate plained of bronchial irritation which caused a form was gently boiled under reflux with 2 5 ml. of cough and thick sputum. The case histories of the concentrated nitric acid for half an hour. Water seven men are as follows: was then added to the macerate until the solution was 10 per cent. with regard to nitric acid, and the Case Histories on September 27, 2021 by guest. Protected copyright. volume was then about 25 ml. This solution was then transferred to an all-glass microdistillation Case 1. A. A., aged 33, had during the whole of his working life been an analytical chemist in contact with apparatus and gently distilled into a receiver con- osmiridium, for 12 years with one firm and for the last taining 3 ml. of concentrated hydrochloric acid 4 years at the firm where these observations were made. saturated with sulphur dioxide. When about a He said that when he was in contact with osmium fifth of the solution (5 5 ml.) has been distilled, the tetroxide, he notice his eyes were sore and ran freely and that if he looked at a light there was a large halo distillation was terminated as all the osmium was round it.
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