Some Inorganic Poisons
1919 — Harvard Medical School, Cambridge MA
OBSERVATIONS of industrial arsenical poisoning in the United States are scattered, and are not very detailed. Our most important arsenic industry is the manufacture of insecticides, Paris green (the acetoarsenite of copper), and lead arseniate. The two centres for this manufacture are Brooklyn and Chicago. While working for the New York State Division of Industrial Hygiene, Lester Roos examined fourteen men in two Paris-green factories and found three with inflamed eyes, two with ulcers, and four more with scars of old ulcers and furuncles, and two with marked anæmia. The Paris-green plants in Illinois employ a very fluctuating force of workmen, varying from about 12 in October to 561 in March. Few men remain in the work for long. It is one of the many industries in which a rapid labour turnover makes for the protection of the men against poisoning.
The reports of the Illinois Factory Inspection Department for the years 1912 to 1916 have several items on arsenical poisoning. These reports note that scrotal ulcers are pretty common among the men working in Paris green. Six cases of poisoning from Paris green and two from lead arsenate are noted one year; twenty cases another year from a force that varied between sixteen and 178. Two of these patients had ulceration; two, conjunctivitis and inflammation of throat and nose; the others, colic and constipation. I do not believe cases of poisoning from lead arsenate have ever been thoroughly enough worked up for one to say which element is the more important.
It is excessively hard to protect workers in Paris green. Two cases are on record of arsenical poisoning from the use of Paris green or arsenate of lead as a spray for fruit trees. The powder is very light and fluffy, and it has, so far, been impossible to carry out mechanical packing.
No protection can be worn which makes the skin perspire, for perspiration only increases the danger of ulceration. Respirators do this by pressing on the skin and making it soft and thin. The best procedure seems to be to plug the nostrils lightly with cotton, to plug the ears in the same way, and to smear the face over with some bland ointment. A full shower bath ought to be taken at the end of work, and the work clothes should be clean each day.
Wholesale poisoning by the fumes of arseniurretted hydrogen has been reported several times, the victims being always persons confined in ill-ventilated parts of a ship, carrying in the hold a cargo of an alloy of iron and silicon-ferrosilicon. It is made by fusing together silicon (sand and quartz), coke, and iron in an electric furnace. Arsenic may be present in the quartz or in the iron, and in the presence of the coke it is converted into calcium arsenide, which in moist air is partly changed to arseniurretted hydrogen. If the silicon is present in the alloy in the proportion of less than 30 per cent. or more than 70 per cent., this does not occur; the dangerous points are between 40 per cent. and 60 per cent. silicon. Formerly we imported our ferrosilicon from Germany, but of late years we have made it at Niagara Falls. The only instance of poisoning of this kind which can by any stretch be called American is that recounted by Kober as occurring on the Vaderland bound from Antwerp to New York with a cargo of ferrosilicon. Fifty steerage passengers came down with a mysterious sickness from which eleven died. The vessel was detained at quarantine under the suspicion of plague, but the discovery of the nature of the cargo explained the real cause of the sickness.
The fact that the symptoms of antimonial poisoning are so like those of lead poisoning, makes it very hard to discover how great a part antimony plays in any case of occupational disease which occurs in a man exposed to both metals, as printers are. I could not find any evidence of antimonial poisoning in an examination of printers in 150 different shops, unless it was responsible for two bad cases of eczema of the hands and forearms of men working at the stereotype kettles.
The same difficulty is encountered in the second industry in which large quantities of antimony are used –the manufacture of rubber. Golden and crimson sulphides of antimony (really mixtures of the penta-sulphide, the trisulphide, and the oxysulphide in different proportions) are used in great quantities and, so carelessly that one often sees men covered from head to foot with the reddish-brown powder. But these men, the compounders and those on the mixing mills, are also handling litharge and lead sulphate, and whatever symptoms they
suffer from are much more likely to be caused by lead. In fact, toxicologists in general seem to think the sulphides of antimony quite harmless, only Kobert believing that large quantities of the dust might cause poisoning in a workman. In order to throw some light on this question, the Bureau of Labour Statistics asked Professor A. J. Carlson, of the Physiological Department of the University of Chicago, to test the solubility of golden and crimson sulphides of antimony in human gastric juice. Dr. Carlson used commercial mixtures obtained from the B. F. Goodrich Co., of Akron. He found that about 8 per cent. of the antimony in the crimson and about 3 per cent. of the antimony in the golden sulphide were soluble in gastric juice, making it clear that these compounds are soluble in the human stomach. Dr. Carlson believes it to be probable that this solubility is sufficient to be a source of danger to men who are obliged to use these compounds in such a way as to expose them to a great deal of dust, or who handle food or tobacco when their hands are smeared with these sulphides of antimony.
Finally, antimony trisulphide is used in making fulminate caps, and, according to an expert of the Ordnance Department, some cases of possible antimonial poisoning were reported from that industry during the war, though it is impossible here also to separate the effects of the antimony from those of the fulminate. The symptoms enumerated by the ordnance expert — i.e., a local irritation of the skin and of the respiratory mucosa — might certainly be due to fulminate.
Two quite extensive investigations into industrial mercurial poisoning have been published in the United States. The first investigation was published in 1912, and led to the discovery of ninety-four cases. Over 18 per cent of these came from thermometer makers. These people have to seal the glass tubes of the thermometers with heat. The glass often bursts and the mercury volatilses. In the Bausch and Lomb factory they have this well arranged. The workman slips his arms through openings in the furnace in which the tubes are sealed, and there is an exhaust to keep the air in the furnace from escaping.
Four of the patients from the Civic Federation list were making incandescent lamps. The risk comes here from the use of the Sprengel vacuum pumps, which may break and scatter mercury. These pumps are now being gradually replaced by rotary pumps, which are much less likely to break, but which have to be cleaned, and therefore there is still risk of poisoning. The pumps used for making Röntgen-ray tubes have even more mercury.
Mercurial poisoning in the making of fulminate is rare. I have heard of but one case that developed during the war, though, of course, there may have been more.
Another industry that involves the use of mercury amalgam is the MacArthur-Forrest cyanide process for the recovery of precious metals. Mercury, according to Teleky, is sometimes used in the preliminary stage for this process, to form an amalgam with the gold and silver. Teleky has hear of no mercurial poisoning in this field, but of course we know that pretty widespread poisoning can go on in some of our more remote industrial centres where all the medical work is in the hands of company physicians, without the world at large knowing it. This problem would make an interesting subject of research.
But the most notorious mercury trade is the making of felt hats and the preparation of fur for felt hats. In 1914 Dr. Louis Harris, of the New York City Department of Health, made a thorough study of conditions in the furriers’ and hat-making trades in that city, and examined for mercurial poisoning large numbers of the employees. The men in the hatters’ fur trade treat rabbits’ fur with mercuric nitrate, a process known as carroting. Each person who subsequently handles the hairs is exposed to mercurial poisoning. Among 266 men in the New York shops, Harris found that 212 were exposed to mercurial poisoning in carroting the fur in drying it in ovens, in cutting hair from the skins, and in sorting out the long hairs and packing the fine ones. Basing his diagnosis on evidence of gingivitis and violent muscular tremors, Harris decided that there were at least forty clear cases of mercurialism among these 212 men, and probably twenty more. No fewer than ninety-one had muscular tremors, and they ere violent in seventeen.
It is interesting to note that the amounts of mercury used in felt-hat making are small, and that in the finished hat there is only 0.138 per cent. of mercury. Analysis of all the materials used, following them through the different stages, yielded as the highest content 0.17 per cent. The heat volatilizing the small quantities of the mercury used in ill-ventilated rooms is evidently largely responsible for the poisoning, and it is also evident that very small doses are enough to bring about serious results.
This is one of the trade poisons to the study of which Americans have made noteworthy contributions, though not in as great number as have the Germans, French, and British. This is not because of neglect in the United States, but because we do not use carbon disulphide in industry as much as do foreign countries. Caron disulphide is the substance which has made the rubber industry in Germany and France so notoriously dangerous, and though the British rubber industry seems to be carried on more like ours, still there are some quite shocking pictures of this kind of poisoning in British literature also.
In 1904, Jump and Cruice, of the University of Pennsylvania, published an interesting article on carbon-disulphide poisoning in artificial-silk workers. The history of one of these cases is so typical that it is worth quoting. The silk is made by treating cellulose first with caustic soda, then, in a closed tumbling vat, with carbon disulphide. At the completion of the reaction the carbon disulphide is largely, but not entirely driven out with a blast of air. When the contents of the vat are dumped to be again treated with Caustic soda, quite a little fume of carbon disulphide escapes. In cleaning these vats, too, the men are exposed to fumes. One of Jump and Cruice’s patients said that when we went to work in the morning he felt exhilarated and jolly, though when the fumes ere thick, as in cleaning a vat, he might be almost overcome and obliged to go out of doors. When he reached home in the evening he was morose and irritable, could eat nothing with pleasure because everything tasted of carbon disulphide. Presently he began to have sever headache, vertigo, weakness, first in the arms and then in the legs, until at last he could hardly climb stairs. He had muscular tremors, slight ataxia in the legs, a weakened grip, could not get up from his knees without help. His memory and his vision were impaired.
Hayhurst, in 1914, found only about 1 per cent. of the 30,000 rubber workers in Ohio exposed to carbon disulphide. This figure includes persons making rubber cement for the repair kits, to which carbon disulphide is commonly added.
Phosphorus poisoning is much the most conspicuous and dreaded of the industrial poisons, and has caused more agitation, first for control and later for abolition, than all the others put together. Yet phosphorus does not affect more than a small proportion of persons exposed to it, and its mortality is only 15 to 20 per cent. It is, however, exceedingly painful, and so disfiguring that everyone can see the effects. Moreover, the offensive character of the discharge makes life with the victim almost impossible. I remember Miss Jane Addams telling me that in 1888 she went to a great mass meeting in London to protest against conditions in the match industry, and that there were a number of girls with horribly deformed faces on the stage to show the audience just what the effect of phosphorus was. I often think that if lead poisoning did all of its work on the face we should have been rid of it long ago.
I think you probably all know how we got rid of white phosphorus — by the passage in 1912 of the Esch law, which placed a prohibitive tax on white phosphorus matches. In 1913 their importation became illegal, and in 1914 their export. At the same time the Diamond Match Co., which held the patents for the manufacture of sesquisulphide matches, threw open to the whole country the use of the process, thus making it possible for all to use the safe methods.
So far as I know, white phosphorus is used now very little in American industry. We do make phosphor bronzes, and an analysis of these bronzes shows that they contain from 0.068 per cent. to 0.813 per cent. of phosphorus. No case of poisoning has been reported from this industry in America, but it is well to bear it in mind. Kaup found a case in Austria, and, though the proportion of phosphorus in the bronze the man was working with was only 0.76 per cent., yet enough phosphuretted hydrogen was given off to poison him.
Ferrosilicon may give off phosphuretted hydrogen as well as arseniuretted, as reported by Glaister at the International Congress for Industrial Hygiene in 1910. We used white phosphorus last summer in the making of an incendiary projectile. I heard of no trouble from its use in this way, and probably it was not continued long enough for any cases of poisoning to develop. Occasionally one is told of phosphorus in connection with the manufacture of fireworks, a purpose for which it seems to be used in Italy.
Source: Chemical Trade Journal and Chemical Engineer, 1919, lxv, pp. 365-367.