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Hamilton, Alice, . l-to- and Hardy, . - r.'.J-.'. Harriet L. Industrial Toxicology,, Harper, 1949 m Industrial Toxicblogtj Tiie study of poisoning from arsenic trioxido and copper ncetoarsenite (Paris green) in industry is largely a study of skin lesions, and these run all the way from inflammation, with or without ulcera tion, to scleroderma, melanoderma, warts, and a slowly developing cancerous degeneration which usually has a fairly benign course and does not give rise to metastases. (See page 438 ) Loss of hair and trophic changes in the hails are common. Some interesting cases have been reported due to the handling of paper dyed with arsenic green, as, for instance, one reported by Ayres (32) in the foreman of a paper works. This was a case of scleroderma, with arsenic in the urine. A similar case in the out-patient clinic at the Massachusetts General Hospital was traced to arsenic-containing paper which was pasted on skyrockets. The picture of generalized, arsenical poisoning from solid arsenic, as seen in exceptional cases in industry, rarely is severe. Neuralgic pains and multiple neuritis with motor palsy, slight in degree, are characteristic of these cases. Hie palsy is likely to affect the long ex tensors of fingers and toes, as does lead, but it is distinguished from the latter by the severe neuralgic pains and by the tendency toward a multiple, symmetrical neuritis. A very rare form of industrial poison inginvolving the optic nerve was reported by Molcen (338), who de scribed a case of skin lesions and double optic atrophy in a man using arsenical insecticides. L Of 135 patients having arsenic poisoning by solid compounds of i , arsenic, discussed by Legge (682) 38 hod gastric symptoms, 13 had l- tremors or muscular cramps, 6 had peripheral neuritis- pf the re .1t; mainder allhad lesions of the skin, in 6 of whom there were keratoses or epithelioma. Legge speaks of 3 cases of epileptiform seizures, a most unusual manifestation of such poisoning. !| There is, however, a general consensus that serious oases of injury from white arsenic or Paris green are extremely rare in industry. It is hard to explain the difference between Industrial arsenical poisoning and nonindustrial, but thcro is a difference am) it is noted in all Iho industrial countries. With hydrogen arsenide gas, the story is quite different. The lack of serious symptoms in industrial arsenic poisoning Is not to be explained on tho ground of slight exposure, for in the nrcul smelling works of tho West, iho lead works in Colorado, and t|io O k Soiirl Arsenic Compounds 129 copper works in Montana the ores eontain a high proportion of arsenic, which is volatilized in the furnaces -and carried in tire flues to be deposited in the hag-house and tunnels as while arsenic. Sotnetimes in Colorado smelting works as much as CO per cent of the flue dust is arsenic trioxide. This dust must be shoveled into trucks and transported for a second sublimation, after which the product, almost pure, must be handled and packed; yet the men carrying on this work almost never show any but local effects on skin anti mucous mem branes. Years ago, in 1912, a case of generalized polyneuritis came to light in a Montenegrin working in a western smelter when the arsenic content of the ore was high. There used to be also occasionally among Paris-green packers cases with gastrointestinal symptoms and neu ralgia and even one fatal case with fatty degeneration of the liver came to light. .Arsenic is given as the cause of 6 cases of poisoning and one death in England in 1924, all tho subjects being employed in making or handling sheep dip. One man, 44 years of age, suffered from epithelioma of the left side of the face, after employment in contact with arsenic for twenty-six years. The others had ulceration of the septum, dark pigmentation of tho skin around the neck and axillae, and irritation of the skin. The liistory of the fatal case is scanty, wo are told only that there was swelling of the eyelids, intense vomiting, and that arsenic was found in the organs. Among the unusual sources of arsenic poisoning are: in glass manu facture the emptying of sacks of white arsenic, adding it to the glass mixture; the stitching of window shades dyed with arsenic green; the mixing of arsenic with enamel for iron bathtubs, shot-blasting such enamel from defective ware (Australia); the handling of hides and bird skins that have keen treated with white arsenic. Of course it is impossible in these industries to protect the nostrils nud throat entirely from arsenic without putting each worker into a protective pressure mask, which Is not always practicable. However, tho skin ami eyes can ho protected against tho dust and every effort should be made lo do this; otherwise there will be painful ulceration, especially of tho skin of iho scrotum, tho lips, and the nostrils. Lend and Calcium Arsenate. A great deni of study has been de voted of late to the toxlo action of the arsenates, lead and calcium, V69Z00 .^ I ,-s'HT r- l"'", "i' n r T>i:iVTt M rtf > * Vi r-f u ixn im*. 132 Industrial Toxicology la mcdicclcgul cases. The early symptoms arc (hose of anoxemia; the later symptoms arc largely those caused by the effort of the body to excrete the debris of red cells which clog the liver and kidneys (Stadelmann [1122]). Thus tho acute symptoms will be followed In four to six hours by the passage of dark urine or bloody urine, and this is often the first symptom that alarms the victim. Later, in twenty four to forty-eight hours, jaundice appears, and a blood count shows a loss of red cells which may fall below two million. As the disease pro gresses, jaundice deepens and the urine grows scantier until just before death there is complete suppression (Jones [571]). The British industrial physicians report these cases under the head of toxic jaun dice. Arsenic can always be detected in the urine and may continue to be excreted for many weeks after the acute symptoms have disap peared (Wignall [1245]). The anemia is likely to persist even longer. : The source of this dangerous gas is always some process in industry ' which causes the formation of nascent hydrogen in the presence of arsenic; in other words, a process which reproduces the conditions of Marsh's test for the detection of arsenic, and there arc many industrial processes in which these conditions may be present. la making Marsh's test, zinc dust and hydrochloric acid are used far the produc tion of hydrogen. That Is die way hydrogen is produced for filling balloons, and many cases of poisoning have occurred in such work be cause zinc is very commonly contaminated with arsenic; in fact it is difficult to get arsenic-free zinc. Lead-burners who use an oxyliydrogen dame may have to produce their own hydrogen, and then they ' run this same risk. Most of the iron, lead, and antimony used in indus' . ry is likely to be contaminated with arsenic, as is also commercial sulphuric arid made by the ordinary chamber process mul the liytliro" chloric acid which is made from it. In the production of aniline dyes and coal-tar drugs, one of the most important processes is reduction by means of nascent hydrogen, which is produced from iron dust or zinc dust and hydrochloric acid, and here there is always a risk Uiat arsine may be formed. Five severe cases of this form of poisoning occurred in a New Jersey plant making dye intermediates during the `ft First World War. In ono of these the body of the victim was bronzed to a mahogany color, according to the physician's report. ,j: ,. The most frequent ennso of poisoning from arsine in this country is * *i * ' ij j, t t- Cuscous Arsenic 133 the cleaning out of tanks and tank cars that have contained a heavy . qcid, either hydrochloric or sulphuric. Strong acid docs not attack mm or steel (links, iuiYwcakncld docs. Therefore there is no trouble while the tank is full, but when it is emptied and Hushed out with water, weak acid is left iu the residue which is called "sludge," and when the laborer or lead-burner goes in to dipout the sludge or to make repairs, the arsine formed by the action of the weak acid on the nrscnic-containing iron rises and poisons him. Three men in a plant in New Jersey were sent into an acid tank to make repairs after it lmd been sup posedly well-flushed out. There was, however, about a bucketful of residue left at the bottom and this contained enough arsine to poison the men, two of whom died. In some cases it was the galvanized iron dipper that was responsible, and accordingly the great chemical works in Germany prohibit the use of zinc-covered vessels and make the men wear gas-masks while they work. There is a general belief in industry that pickling metal, l.e., treat. ing it In tanks of sulphuric or hydrochloric acid, hot or cold, is un- healthful work, and it seems probable that small amounts of arsine formed from time to time in such tanks may be responsible for this. Muehlbergcr, Loeveuhavt, and O'Malley (356) describe a case of arsenical poisoning, with multiple neuritis, in a man employed in pickling iron and steel. Legge reported 7 cases in 1002, the acid con taining 0.035 per cent of arsenic or 350 parts per million. In the Navy Yard at Puget Sound two men were severely poisoned by tho arsine evolved from a pickling tank. One died after thirteen days' exposure; the other had nephritis and anemia. The man who died was in a coma for four days, with anuria, hemoglobin under 40 per cent, red cells , about ono million, brownish pigment in the skin, edema of the lungs, eud albumin and blood in the urine. The acid in tho tank was used over and over again so that the content of arsenic rose from 0.0005 per cent to 0.05 per cent. The samo sort of accident is possible In the charging and the form: big departments in storage battery manufacture, where lead antimony ' grids are immersed in weak sulphuric acid. Epidemics of poisoning with arsine occurred during tho First World War in two Italian sub marines and ono English, and iu each the gas was traced to t|ic stor age batteries. It was found that tho acid had eaten into the lead anti- i I 142 hulustrlul Toxicology Phosphorus 1J3 exposures of two, eight, ami tilliteon yours respectively. Tliu result lit hud hud a denial exainluaUtm within one month of the onset of the dis the mint with only two ye;in' exposure was complete healing with no ease and hud been pronounced normal. deformity; in Ihe one with eiglil years', recovery hut loss of nil leeih of The match now made is the safety match, for which amorphous red the lower jaw and part of the left mandible with some facial de phosphorus is used, and the "strike anywhere" match, made with tho formity, Hie third case and tho ona slowest to develop was much sesquisulphido of phosphorus; neither of these has the poisonous more serious, hi tills man the upper jaw os well ns llio lower was in properties of white phosphorus. In a French match factory Nicolas volved, with loss of a large portion of the palate bone and the forma and his colleagues (878) found that there was a great deal of skin dis tion of fistulous tracts leading from the mouth to the nose and nasal ease due to the handling of phosphorus scsquisulphidc. There was a accessory sinuses. At the time of writing, eighteen months after the rapidly developing erythema with formation of vesicles or pustules onset, the condition was still active. accompanied by severe subjective sensations and, sometimes, by con Heinumn discusses methods of protection against the fumes of junctivitis. Creasy skins were most susceptible. An eruption was pro yellow (or white) phosphorus. The red allotrope docs not seem to be duced in volunteers by the use of the paste and also the powder. A poisonous. Since yellow phosphorus burns when exposed to the air, it wash of potassium permanganate and sodium bicarbonate caused Is always handled under water and is transpor ted from ono receptacle prompt recovery. to another in liquid molten form under water. At Uiis stage small par- Coses of phosphorus poisoning, however, have been reported from I! tides will separate from the flowing moss, rise to the surface and vola tilize (or bum). Local exhausts must be provided wherever this may other Industries, chiefly in the production of phosphorus, in the chem ical industry, in the manufacture of phosphor bronze, and in making Si occur. j lights for miners' lamps. In Great Britain most of the cases of phos A still more recent industry whidi carries with it the danger of phos phorus necrosis coming to the knowledge of the Factory Inspection h; phorus poisoning is the electrothermal process for the production of Department have occurred in persons employed in the production of elemental phosphorqs to be used in the preparation of phosphate fer phosphorus. Copper ores sometimes carry phosphorus. tr tilizer. Fleming Miller, and Swayne (327), of the Tennessee Valley A rare source of phosphorus poisoning is the accidental formation Authority, attempted to determine the threshold of physiologic toler of phosphoretted hydrogen (phosphine, Pi/.,), in the production of ance when white phosplunus, or its suboxldcs, are administered in small doses over a long period. They found significant changes`in die acetylene gas from carbide for use in autogenous welding. Several cases have been reported from Germany1 from this source and it is bones of animals given phospltorus by injection under the skin. Tho of course possible that cases have occurred in this country but have i limit of tolerance seemed to lie betwen 0.05 mg. of phosphorus per not been recognized because it is a poison unfamiliar to American kilogram of body weight and 0.8 mg. given daily. physicians. There is another source of poisoning from phosphoretted The practical impossibility of providing complete protection against hydrogen which may or may not bo of occupational character, that is the action of phosphorus is seen in the factory inspectors' reports front the escape of PII# from fcrrosilicon in the same way that the formation English and Ccrman match factories when yellow phosphorus was and escape of AsIIa occurs. Either or both of these gases may he usod. Workers had to be forbidden to keep a glass of water on the formed, but in tho larger number of instances it is the latter that has workbench, to chew gum or cat an apple, or put a finger in the mouth, been bold rosponsibla. Only analysis of tho fumes would settle this or pick the teeth; but in spite of the efforts of sanitary engfneers, question, although the absence of a hemolytic action would point to physicians, and dentists, cases persisted in appearing. j phosphorus. It is noteworthy that all three of the victims reported by 1-fc.imanu 1 Thiele. Zcntralb). f. Cewcrkehyg. 0: 0-1, 1621. ucc 002693 ' ' V f*` 1 1 1 - * 1 !" ' " ' - *t f '( " ! 5 T,` * l 't /. ?'j . [. ' s'. v y/_l, . ,,'l - " , . ,!lJ