Document jgvxz3qD9jwoNyGdnbJ5Jw54N

ucc 032102 ^ . Hinadmuisltotrnia, lATliocxeic, oalongd yH, aHrdayrd, eHr ar1r9i4e0t IL* 138 Industrial Toxicblogy Solid Arsenic Compounds 129 The study of poisoning from arsenic trioxido and copper aecto- copper works in Montana the ores contain a high proportion of arsenite (Paris green) in industry is largely a study of skin lesions, arsenic, which is volatilized in the furnaces and carried in the lines (o and these run all the way from inflammation, with or without ulcera tion, to scleroderma, melanoderma, warts, and a slowly developing V Jic deposited in the bag-house nud_Uinnc[s _as white arsenic. Some times in Coiorado_smc)ting works as much as 60 per cent of the flue cancerous degeneration which usually has a fairly benign course and dust is arsenic trioxide. Th:s dust must be shoveled into trucks and does not give rise to metastases. (See page 438.) Loss of hair and transported for a second sublimation, after which the product, almost trophic changes in the nails are common. Some interesting cases have pure, must be handled and packed; yet the men carrying on this work been reported due to the handling of paper dyed with arsenic green, almost never show any but local effects on skin and mucous mem as, for instanpc, one reported byAyres (83) in the foreman of a paper branes. Years ago, in 1912, a case of generalized polyneuritis came to works. This was a case of scleroderma, with arsenic in tire urine. A light in a Montenegrin working in a western smelter when the arsenic similar case in the out-patient clinic at the Massachusetts General content of the ore was high. There used to be also occasionally among Hospital was traced to arsenic-containing paper which was pasted on Paris-green packers cases with gastrointestinal symptoms and neu skyrockets. The picture of generalized, arsenical poisoning from solid arsenic, ralgia and even one fatal case with fatty degeneration of the liver came to light. as seen in exceptional cases in industry, rarely is severe. Neuralgic Arsenic is given as the cause of 6 cases of poisoning and one death pains and multiple neuritis with motor palsy, slight in degree, are in England in 1924, all tho subjects being employed in making or han characteristic of these cases. The palsy is likely to affect the long ex dling sheep dip. One man, 44 years of age, suffered from epithelioma tensors of fingers and toes, as does lead, but it is distinguished from of the left side of the face, after employment in contact with arsenic the latter by the severe neuralgic pains and by the tendency toward a for twenty-six years. The others had ulceration of the septum, dark multiple, symmetrical neuritis. A very rare form of industrial poison ing involving the optic norve was reported by Moleen (888), who de pigmentation of the skin around the neck and axillae, and irritation of the skin. The history of the fatal case is scanty, we arc told only that scribed a case of skin lesions and double optic atrophy in a man using arsenical insecticides. Of 135 patients having arsenic poisoning by solid compounds of 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 arsenic, discussed by Legge (632) 38 had gastric symptoms, 13 had facture the emptying of sacks of white arsenic, adding it to the glass tremors or muscular cramps, 8 had peripheral neuritis- of the re mixture; the stitching of window shades dyed with arsenic green; the mainder all had lesions of the skin, in 6 of whom there were keratoses mixing of arsenic with enamel for iron bathtubs, shot-blasting such or epithelioma. Legge speaks of 3 cases of epileptiform seizures, a enamel from defective ware (Australia); the handling of bides and most unusual manifestation of such poisoning. bird skins that have been treated with white arsenic. There is, however, n general consensus that serious cases of injury Of course it is impossible in these industries to protect the nostrils from white arsenic or Paris green arc extremely rare in industry. It ts and throat entirely from arsenic without putting each woikcr into n hard to explain the difference between industrial arsenical poisoning protective pressure mask, which is not always practicable. However, and nonindustrial, but there is a difference and it is noted in all lire tho skin and oyes can bo protected against Iho dust and every effort industrial countries. With hydrogen arsenide gas, the story is tjulte should be made to do this; otherwise there will be painful ulceration, different. The luck of serious symptoms in iinhishinl arsenic poisoning especially of tho skin of the scrotum, tho lips, and the nostrils. . b not to be explained on tho ground of slight exposure, fur in iho ureal Land and Cutcium Arsenate. A great deal of study has been de . smelting works of tho West, tlio lead works in Colorado, and ijic voted of )Ato to the toxlo action of the arsenates, lend and calcium, Jt "*t! V ft S'F' " .i ll i *; ' ii > i < li 11 i'jp mlit i V, / Ill ft"1 :\ t It t:y-! a 11* i ip* ucc 032103 Industrial Toxicology fit mcdicolcgol cases. The early symptoms are those ot anoxemia; (ho later symptoms are largely those caused by the elfort of the body to excrete the debris of red cells which clog the liver and kidneys (Stodclmann [JJ22]). Thus the 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, nnd a blood count shows a loss of red cells which may fall below two million. As the disease pro gresses, Jaundice deepens and dm urine grows scantier until just before death there is complete suppression f Jones [574]). The British industrial physicians report these cases under the head of toxic jaun dice. Arsenic can always be detected hi the urine and may continue to be excreted for many weeks after the acute symptoms have disap peared (Wignall [1245]). Hie 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 Marshs test forthe detection of arsenic, and there arc many industrial processes in which these conditions may bo present, in making Marsh's test, zinc dust and hydrochloric acid are used for the produc tion of hydrogen. That is the way hydrogen is produced for filling balloons, and manycases of poisoning have occurred in such work be- . cause zinc is very commonly contaminated with arsenic; in fact it is 1 . difficult to get arsenic-free zinc. Lead-burners who use an oxyhydro- - gen flame may have to produce their own hydrogen, and then they 1 run this same risk. Most of the iron, lead, and antimony used in indus- .' try is likely to be contaminated with arsenic, as is also commercial _ sulphuric acid made by the ordinary chamber process and the hydro 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 tliat arsine may be formed. Five severe cases of this form of poisoning occurred in a New Jersey plant making dye Intermediates during the V v,` First World War. In ono of these the body of the victim was bronzed /'to a mahogany color, according to the physicians report. . ,!' .tv;',, The most frequent enuso of poisoning from arsine in this country is if: !>. i; f .1 i v Caseous Arscnlo 133 the cleaning out of tanks nnd tank cars that have contained a heavy . ncid, cither hydrochloric or sulphuric. Strung acid docs not attack iron or sieLTlanks, lint weak acid docs. Therefore there is no trouble white the tank is full, but when it is emptied and Hushed out with water, weak acid is left in the residue which is called "sludge," and when the laborer orlead-burner goes tn to dipnut the sludge or to make repairs, the arsine formed by the action of the weak acid on the arsenic-con taining iron rises nnd poisons him. Three men in a plant in New Jersey were sent into an acid tank to make repairs after it had 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 tliat was responsible, and accordingly the great chemical works in Germany prohibit the use of zinc-covcrcd vessels and make the men wear gas-masks while they work. There is a general belief in industry that pickling metal, i.e., treat ing it in tanks of sulphuric or hydrochloric acid, hot or cold, is unhealthful work, and it seems probable that small amounts of arsine formed from time to time in such tanks may be responsible fer this. Mueblberger, Loevenhnrt, and O'Malley (856) 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 the arsine evolved from a pickling tank. One died after thirteen days' exposure; the other had nephritis nnd anemia. The man who died was in a coma for four days, with anuria, licmoglobin under 40 per cent, red cells . about one million, brownish pigment in the skin, edema of the lungs, and albumin nnd blood in the urine. The acid in the tank was used over and over again so that the content of arsenic rose from 0.0005 per cent to 0.05 per cent. Hie same sort of accident is possible in the charging nnd the form, lug departments in storngo battery manufacture, where lead antimony grids arc immersed in weak sulphuric acid, Epidemics of poisoning with nrsino occurred during (ho First World War in two Italian sub marines and ono English, and in each iho gas was traced to t|iu stor age batteries. It was found that Iho acid had oaten into the lend anti- 142 Industrial Toxicology exposures of two, eight, uml thirteen years respectively. Tho rodiifl In the roun witli only two years' exposure was complete healing with no deformity; in the one will* eight yenvs', recovery hut loss of nil teeth of (lie lower jaw and part of llu> left roimdiblo with some facial de formity. The third case and tho ono slowest to develop was much more serious. In tills man tho upper jaw as well ns tho lower was In volved, witli toss of a largo portion of the palate bono and the forma tion of fistulous tracts leading from the mouth to the nose and nasal accessory sinuses. At the time of writing, eighteen months after Die onset, the condition was still active. (Ieimann discusses methods of protection against the fumes of yellow (or white) phosphorus. Tho red allotrope docs not seem to be poisonous. Since yellow phosphorus burns when exposed to the air, it is always handled under water and is transported from one receptacle t6 another in liquid molten form under water. At this stage small par ticles will separate from the flowing mass, rise to the surface and vola tilize (or burn). Local exhausts must be provided wherever this may occur. I, A still more recent industry which carries with it the danger of phos phorus poisoning Is the electrothermal process for the production of elemental phosphorqs to be used In tlie preparation of phosphate fer tilizer. Fleming Miller, and Swayne (327), of the Tennessee Valley Authority, attempted to determine the threshold of physiologic toler ance when white phosphorus, or its suboxidcs, aro administered in small doses over a long period. They found significant changes in Die bones of animals given phosphorus by injection under the skin. The limit of tolerance sccmod to lie betwen 0.05 mg. of phosphorus per kilogram of body weight and 0.8 mg. given daily. ] The practical impossibility of providing complete protection against the action of phosphorus is seen in the factory inspectors' reports from English and German match factories when yellow phosphorus was used. Workers had to be forbidden to keep a glass of water on Die work Ircnch, to chew gum or eat an apple, or put a finger in the mouth, or pick the teeth; but In spite of the efforts of sanitary engjneers, physicians, and dentists, cases persisted in appearing. j . It Is noteworthy that all three of the victims reported by Hcmuuin ' 1`hosjthortts 143 had laid a dontill examination within one month of (he ousel of Die dis ease and laid been pronounced normal. The match now made is Die safely match, for which amorphous red phosphorus is used, and the "strike anywhere" match, made with tho scsquisulphidu of phosphorus; neither of these has the poisonous properties of white phosphorus. In a French match factory Nicolas and his colleagues (873) found that there was a great deal of skin dis ease due to Die handling of phosphorus scsqoisulphidc. There was a rapidly developing erythema with formation of vesicles or pustules accompanied by severe subjective sensations and, sometimes, by con junctivitis. Greasy skins were roost susceptible. An eruption was pro duced in volunteers by the use of the paste and also the powder. A wash of potassium permanganate and sodium bicarbonate caused prompt recovery. Cases of phosphorus poisoning, however, have been reported from ether industries, chiefly in the production of phosphorus, in the chem ical industry, in the manufacture of phosphor bronze, and in making lights for miners' lamps. In Croat Dritain most of the cases of phos phorus necrosis coming to the knowledge of the Factory Inspection Department have occurred in persons employed in the production of phosphorus. Copper ores sometimes carry phosphorus. A rare source of phosphorus poisoning is the accidental formation of phosphoretted hydrogen (phosphine, PIl;l), in the production of acetylene gas from carbide for use in autogenous welding. Several cases have been reported from Cermany1 from this source and it is of course possible that cases have occurred in this country but lravo not been recognized because it is n poison unfamiliar to American physicians. There Is another source of noisonimi from nhosnhorettcd hydrogen which may or may not bo of occupational character, that is the escape of Hlj, from fcrrosiflcon in the same way that the formation and escape of AsIIs occurs. Either or both of these gases may be formed, but in tho larger number of instances it is tho latter that has been hold responsible. Only analysis of tho fumes would scttlo this question, although the abscnco of a hemolytic action would point to phosphorus. * Hilda. Zcnlralbl, f. Cewerbehyg. 0: 01,1621.