II. SMELTING OF METALS
LEAD (ZINC, SILVER)
OCCURRENCE OF INDUSTRIAL LEAD POISONING IN GENERAL
Chronic lead poisoning plays the most important rôle in industrial metallic poisoning, and indeed in industrial poisoning generally. The result everywhere where inquiry into industrial poisoning has been instituted has been to place the number of cases of lead poisoning at the top of the list; for one case of other forms of industrial poisoning there are twenty of lead.
In the last few years a very extensive literature and one not easily to be surveyed has grown up on the subject of chronic industrial lead poisoning. I cannot attempt as I have done with other forms of poisoning to do justice to all sources of literature on this subject.
As there is no obligation to notify industrial lead poisoning[B]—or indeed any form of industrial poisoning—in many countries, the most important source of information is wanting. Nevertheless more or less comprehensive inquiries as to the extent of the disease in general have been made in different countries and large cities which furnish valuable data.
An idea of the yearly number of cases of lead poisoning occurring in Prussia is given in the following statistics of cases treated in Prussian hospitals for the years 1895-1901:
| Year. | Males. | Females. | Total. |
|---|---|---|---|
| 1895 | 1120 | 43 | 1163 |
| 1899 | 1601 | 23 | 1624 |
| 1900 | 1509 | 14 | 1523 |
| 1901 | 1359 | 24 | 1383 |
The occupation of these cases was as follows:
| Year. | Metallic Lead. | White Lead. | Painters. |
|---|---|---|---|
| 1895 | 364 | 312 | 347 |
| 1899 | 551 | 310 | 460 |
| 1900 | 516 | 360 | 378 |
| 1901 | 498 | 282 | 339 |
About half the cases, therefore, are caused by use of white lead. The report of the sick insurance societies of the Berlin painters gives information as to the proportion treated in hospital to those treated at home, which was as 1:4.
The industries may be classified according to risk as follows[1] :
White lead workers, 33 per cent.; red lead workers, 32 per cent.; shot and lead pipe workers, 20 per cent.; painters, 7-10 per cent.; lead and zinc smelters, 8-9 per cent.; printers, 0·5 per cent.
In Austria through the Labour Statistical Bureau comprehensive information is being collected as to the occurrence of lead poisoning in the most dangerous trades, but is not yet published. The reports of the factory inspectors give a very incomplete picture; for example, in 1905 only fifteen cases are referred to. In the most recent report (1909) information of lead poisoning is only given for thirty works. Teleky has made a general survey of the occurrence of lead poisoning from the reports of the Austrian sick insurance societies.[2] From this we gather that in Vienna, with an average membership of 200,000, there were, in the five year period 1902-6, 634, 656, 765, 718, 772 cases of illness involving incapacity from mineral poisons, which Teleky assumes were practically all cases of lead poisoning. By circularising Austrian sick insurance societies outside Vienna with a membership of about 400,000, Teleky obtained information of 189 cases, which he considers too few.
In 1906-1908 inquiry was made by the sick insurance societies in Bohemia as to the extent of lead poisoning. With an average number employed of from 700,000 to 850,000 information was obtained of 91, 147, and 132 cases in the three years in question. The increase in 1907 was probably accounted for by the greater attention paid to the subject.[3] The number of ascertained cases of lead poisoning treated by the societies of Hungary was 225 in 1901 and 161 in 1902. Teleky again considers these figures too low, which is proved by Toth’s publications as to lead poisoning in Hungarian lead smelting works, and especially Chyzer’s on lead poisoning among Hungarian potters. Legge has reported fully in the second International Congress for Industrial Diseases in Brussels (September 1910) on occurrence of industrial lead poisoning in Great Britain in the years 1900 to 1909. During that period 6762 cases with 245 deaths occurred. The number of cases in the course of the ten years had diminished by 50 per cent. These figures appear remarkably small, but it has to be borne in mind that the statistics referred to related only to cases occurring in factories and workshops, and do not include cases among house painters and plumbers. The number of such cases which came to the knowledge of the Factory Department in 1909 was 241 (with 47 deaths) and 239 in 1908 (with 44 deaths).
LEAD, SILVER, AND ZINC SMELTING
Lead is obtained almost entirely from galena by three different processes. In the roast and reaction process galena is first roasted at 500°-600° C. and partially converted into lead oxide and lead sulphate: on shutting off the air supply and increase of temperature the sulphur of the undecomposed galena unites with the oxygen of the lead oxide and sulphate to form sulphur dioxide, while the reduced metallic lead is tapped. In the roast and reduction process the ore is completely calcined so as to get rid of sulphur, arsenic, and antimony. The oxides (and sulphates) formed are reduced by means of coke in a blast furnace. This process is generally applicable and is, therefore, that most in use. The precipitation process consists chiefly in melting galena with coke and iron flux, whereby the lead is partly freed from the sulphur, and, in addition to lead, iron sulphide is formed, which acts on the remaining lead sulphide, producing a lead matte which can be further treated.
Fig. 27.—Smelting Furnace, showing mechanical charging and exhaust ventilation applied to slag runs, &c. (Locke, Lancaster & W. W. & R. Johnson & Sons, Ltd. By permission of the Controller of H.M. Stationery Office.)
The roast and reaction process is carried out in specially constructed reverberatory furnaces; small furnaces with small amounts of ore and at as low a temperature as possible are the rule in the Kärntner process. In the English process large amounts of ore are melted in large furnaces at high temperatures so as to oxidise the material. The so-called Tarnowitz process combines these two—large amounts of ore are roasted in large furnaces at a moderate temperature. In the roast and reduction process it depends on the nature of the ore whether the roasting is done in reverberatory or blast furnaces. Generally the ore is in the form of powder—less often in pieces. Pyritic ore (ore with much sulphur) is almost always roasted in blast furnaces, and the sulphur dioxide evolved can be used in the manufacture of sulphuric acid. Open-hearth furnaces are rarely used now. Reverberatory furnaces are employed most frequently.
The lead thus obtained contains several other metals, especially silver, copper, arsenic, antimony, iron, zinc, bismuth, and tin. Lead containing silver (work-lead) is next de-silverised, after which follows refining to get rid of the other impurities. For de-silverising work-lead rich in silver (containing about 10 per cent.) cupellation is practised, in which the silver lead is melted and oxidised so that the lead is converted into litharge, metallic silver remaining behind. In a cupellation furnace the flame strikes on the top of the lead bath, and at the same time air under slight pressure is driven in; the litharge which forms is removed through suitable openings. The litharge that is first formed contains silver and is treated again; the remainder is ready for market. After the litharge has run off silver appears, containing still 5-10 per cent. of lead, and it is again submitted to an analogous refining process. Work-lead which does not contain enough silver to be cupelled at once is generally treated first by either the Pattinson or the Parkes’ process.
In the Pattinson crystallising process work-lead is melted in open semi-circular pots: as the pots cool crystals of lead poor in silver form on the surface and are transferred by a perforated ladle into the next pot: the silver collects in the small amount of molten lead remaining behind. Lead that has become enriched by repeated crystallisation contains a high percentage of silver and is cupelled. The Parkes’ process or zinc de-silverisation depends on the formation of a lead-zinc alloy which is less fusible than lead. Work-lead is melted and agitated with addition of pure zinc. The crust which first rises on cooling contains gold, copper, zinc, and lead, and is removed. Further addition of zinc is then made: the rich silver crust which separates is subsequently freed from lead by gradual heating in a reverberatory furnace, and from zinc, in a zinc distilling retort. Other impurities are got rid of by oxidising in reverberatory or other furnaces. Small quantities of antimony and arsenic are removed by stirring with fresh green sticks.
Zinc is obtained principally from blende (sulphide of zinc) and from calamine (carbonate of zinc). The process of zinc recovery depends on the production of zinc oxide and reduction of this by carbon to metallic zinc.
Conversion of the ore to zinc oxide is effected by roasting. Since the temperature at which reduction takes place is higher than the melting-point of zinc the latter is volatilised (distilled) and must be condensed in suitable condensers.
Calamine is calcined in a blast furnace. Blende was formerly roasted in reverberatory furnaces, but such nuisance arose to the neighbourhood from sulphur dioxide vapour that now Hasenclever-Helbig calcining furnaces are used. These furnaces furnish a gas so rich in sulphur dioxide that they serve at once for the production of sulphuric acid. The Hasenclever furnaces consist of muffles placed one above another: the finely ground ore is charged through hoppers above and then raked down from muffle to muffle.
Reduction is carried out in the Belgian or Silesian process by strongly heating calcined matte with coal in retorts. The zinc as it distils is caught in special condensing receptacles (prolongs). After distillation is complete the residue is raked out of the muffle and the furnace charged afresh. As zinc ores generally contain much lead, the work-zinc is therefore refined by remelting in a reverberatory furnace, during which process the impurities collect on the zinc as dross and are removed by agitation with sal-ammoniac or magnesium chloride.
Fig. 28.—Arrangement of Spelter Furnace showing Ventilating Hood.
Risk of Poisoning in Lead, Silver, and Zinc Smelting.—As the description of the manipulations in smelting processes shows, all involve risk of lead poisoning. As a matter of fact in lead smelting much lead passes into the atmosphere. In the smelting works at Tarnowitz yearly some 36,000 kilos of oxidised lead escape.
Estimations[4] of the amount of lead in air samples collected in lead smelting works have been made. Thus in a cubic metre of air immediately over the slag run from 0·0029 to 0·0056 g. of lead were found, so that a worker in a ten-hour day would inhale from 0·013 to 0·025 g. of lead. In a cubic metre of air immediately above the Parkes’ melting-pot from 0·0056 to 0·0090 g. were found, so that a worker would inhale daily from 0·0252 to 0·0405 g. if he kept constantly close to the pot. On the handles of a de-silveriser 0·112 g. were found. In Hungarian lead-smelting works the water in which the hands had been washed was found to contain 1·27 g. of lead per litre. The hands of litharge grinders and sifters showed the highest amounts.
Work carried on in lead-smelting works may be divided into five classes according to risk. Those most exposed to risk are the smelters at lead hearths and reverberatory furnaces, persons employed at the lead and slag runs, flue cleaners, and in crushing and packing flake litharge. Next come those employed at the refining furnaces, those breaking up the roasted ore, blast furnace workers, and those employed at the cupellation process. Attended with danger also is the removal of lead ashes and distillation of the zinc crust. Less dangerous are transport of material, crushing and mixing the ore, refining the work-lead and zinc crust, and work at the Pattinson and Parkes’ processes.
In zinc smelting risk of lead poisoning is great, no matter which process is in question, because of the high proportion of lead in the ore and work-zinc. Swedish blende contains as much as 9 per cent. of lead, and Upper Silesian 2½ per cent. or less. There is risk in calcination, but it is much less than in the distillation process.[5]
There are no quite satisfactory statistics as to the number of cases of lead poisoning in smelting works. Nevertheless, a number of recent publications give valuable data for certain smelting works in Germany, Austria, and Hungary.
From details[6] of lead poisoning at Tarnowitz it would appear that the conditions have materially improved since 1884, the cases having declined from 32·7 per 100 employed in 1884 to 6·2 in 1894 and 1895. The following figures show the proportion affected in the different processes in the years 1901 and 1902:
| Process. | Year. | No. Employed. | Cases. | Per Cent. | |
|---|---|---|---|---|---|
| Reverberatory Furnace | { | 1901 | 131 | 11 | 8·3 |
| { | 1902 | 111 | 4 | 3·6 | |
| Blast Furnace | { | 1901 | 152 | 47 | 30·9 |
| { | 1902 | 187 | 21 | 11·1 | |
| Cupelling Furnace | { | 1901 | 12 | 1 | 8·3 |
| { | 1902 | 12 | 1 | 8·3 | |
| De-silverising | { | 1901 | 32 | 10 | 31·2 |
| { | 1902 | 34 | 7 | 20·6 | |
| Other Employment | { | 1901 | 300 | 7 | 2·3 |
| { | 1902 | 350 | 2 | 0·6 | |
In one smelting works the percentage attack rate was 17·8 in 1901, and 27·1 in 1902. Here the number of workers had increased from 73 in 1901 to 129 in 1902, and the absolute and relative increase probably has relation to the well-known fact that newly employed untrained workers become affected. Similar incidence according to process can be given for the Friedrich’s smelting works during the years 1903-1905:
| Process. | Year. | No. Employed. | Cases. | Per Cent. | |
|---|---|---|---|---|---|
| Reverberatory Furnace | { | 1903 | 86 | 12 | 13·9 |
| { | 1904 | 87 | 8 | 9·2 | |
| { | 1905 | 83 | 11 | 13·3 | |
| Blast Furnace | { | 1903 | 267 | 59 | 22·1 |
| { | 1904 | 232 | 24 | 10·3 | |
| { | 1905 | 247 | 27 | 10·9 | |
| De-silverising | { | 1903 | 56 | 12 | 21·4 |
| { | 1904 | 73 | 4 | 5·5 | |
| { | 1905 | 75 | 4 | 5·3 | |
| Cupelling | { | 1903 | 16 | 4 | 25·0 |
| { | 1904 | 15 | 1 | 6·7 | |
| { | 1905 | 14 | 1 | 7·1 | |
| Other Employment | { | 1903 | 330 | 5 | 1·5 |
| { | 1904 | 309 | 4 | 1·3 | |
| { | 1905 | 347 | 7 | 2·0 | |
Among 3028 cases of lead poisoning treated between 1853 and 1882 in smelting works near Freiberg (Saxony) gastric symptoms were present in 1541, rheumatic pains in 215, cerebral symptoms in 144, paralysis in 58, and lead colic in 426.
The recent reports of the German factory inspectors point still to rather high incidence in many lead smelting works. Thus in the district of Aix la Chapelle in 1909 there were sixty cases involving 1047 sick days, as compared with 58 and 878 in 1908.
In a well-arranged smelting works near Wiesbaden fifty-two and forty-two cases were reported in 1908 and 1909 respectively, among about 400 persons employed. This relatively high number was believed to be closely connected with frequent change in the personnel. Introduction of the Huntingdon-Heberlein method is thought to have exercised an unfavourable influence.
Other smelting works in Germany appear to have a relatively small number of reported cases. Thus in 1909 among 550 workers employed in four smelting works in the Hildesheim district only four cases were reported, and in the district of Potsdam among 600 smelters only five were found affected on medical examination. There is no doubt that many of the cases described as gastric catarrh are attributable to lead. Full information as to the conditions in Austria is contained in the publication of the Imperial Labour Statistical Bureau. In this comprehensive work the conditions in smelting works are described. In the lead smelting works at Przibram the cases had dropped from an average of 38·2 among the 4000-5000 persons employed to twenty-two in 1894 and to six in 1903, but only the severer cases are included. No single case has occurred among the 350-450 persons engaged in mining the ore, as galena (lead sulphide) is practically non-poisonous. It was found, for example, that 50 per cent. of the furnace men had (according to their statement) suffered from lead colic. Of eight employed in the Pattinson process, seven stated they had suffered from colic. The lead smelting works in Gailitz showed marked frequency of lead poisoning—here the appointed surgeon attributed anæmia and gastric and intestinal catarrh to lead:
| Year. | No. Employed. | Lead Colic. | Illness of Saturnine Origin. | Total Lead Sickness. | Total Sickness. | Per Cent. due to Lead. | ||
|---|---|---|---|---|---|---|---|---|
| Anæmia. | Gastric Catarrh. | Intestinal Catarrh. | ||||||
| 1899 | 61 | 14 | 2 | 76 | 16 | 108 | 178 | 60·0 |
| 1900 | 57 | 6 | 2 | 16 | 5 | 29 | 80 | 36·2 |
| 1901 | 48 | 4 | 2 | 17 | 1 | 24 | 60 | 40·0 |
| 1902 | 47 | — | — | 24 | 6 | 30 | 56 | 53·5 |
| 1903 | 49 | — | 3 | 11 | 4 | 18 | 57 | 31·6 |
The diminution in the number of cases, especially of colic, is attributable to the efforts of the appointed surgeon.
At Selmeczbanya a diminution from 196 cases in 1899 (50·7 per cent.) to six (2·2 per cent.) in 1905 had taken place. These figures point clearly to the success of the hygienic measures adopted in the last few years.
In the large spelter works of Upper Silesia during the years 1896-1901, among 3780 persons employed, there were eighty-three cases of lead colic and paralysis, that is, about 2·2 per cent. each year. The following tables show the incidence among spelter workers in the works in question from 1902 to 1905:
Illness among Zinc Smelters
| Year. | Lead Colic and Lead Paralysis. | Kidney Disease. | Gastric Catarrh. | Anæmia. | Rheumatism. | No. Employed. |
|---|---|---|---|---|---|---|
| 1902 | 29 | 18 | 137 | 18 | 448 | 4417 |
| 1903 | 28 | 21 | 151 | 24 | 470 | 4578 |
| 1904 | 44 | 23 | 181 | 35 | 596 | 4677 |
| 1905 | 50 | 18 | 223 | 40 | 612 | 4789 |
| Average | 0·8% | 0·5% | 3·7% | 0·6% | 11·5% | 4615 |
Illness among Calciners
| Year. | Lead Colic and Lead Paralysis. | Kidney Disease. | Gastric Catarrh. | Anæmia. | Rheumatism. | No. Employed. |
|---|---|---|---|---|---|---|
| 1902 | — | — | 5 | 1 | 78 | 1149 |
| 1903 | — | — | 9 | — | 112 | 1087 |
| 1904 | 2 | — | 68 | 1 | 136 | 1140 |
| 1905 | 1 | 2 | 47 | 2 | 134 | 1159 |
| Average | 0·08% | 0·05% | 2·6% | 0·1% | 10·2% | 1134 |
In thirty-two spelter works in the district of Oppeln in the year 1905, among 4789 spelter workers proper, there were 50 cases of colic, 18 of kidney disease, 223 of gastric and intestinal catarrh, 40 of anæmia, and 612 of rheumatism, and among 1159 calciners 1 case of colic, 2 of kidney disease, 47 of gastric catarrh, 2 of anæmia, and 134 of rheumatism. Cases are much more numerous in spelter works where Swedish blende containing lead is worked. It is remarkable, however, that in large spelter works in Upper Silesia, where for years no cases of lead poisoning were reported, medical examination showed that 20·5 per cent. had signs of lead absorption.
White Lead and Lead Colours
Manufacture.—The primitive Dutch process consisted in placing lead grids in earthenware pots containing dilute acetic acid and covering them with tan bark. Fermentation ensued with evolution of carbonic acid gas and increase in temperature. The acetic acid vapour forms, with aid of atmospheric oxygen, first basic lead acetate, which, by the action of the carbonic acid gas, becomes converted into white lead and neutral lead acetate. The product is crushed, sieved, and dried. In the German or Austrian process thin sheets of metallic lead are hung saddle-wise in chambers. Acetic acid vapour and carbonic acid gas (produced by burning coke) are led in from below. The chamber is then sealed and kept so for a considerable time. When the chamber is ‘ripe’ the white lead that has formed is taken out, freed from uncorroded lead by spraying, dried, finely ground, and packed. White lead comes on the market either as a powder or incorporated with oil. Of the remaining lead colours, red lead (Pb₃O₄) is much used. It is produced by heating lead oxide in reverberatory furnaces with access of air and stirring.
Lead Poisoning in the Manufacture of White Lead and Lead Colours
The manufacture by the German process may be divided into three categories according to the degree of risk run:
1. The most dangerous processes are hanging the plates in the chambers, work at the filter press, drying, pulverising, and packing by hand.
2. Less dangerous are transport to the washer, washing, and grinding.
3. Relatively the least dangerous are casting the plates, transport of them to the chambers, drying, mechanical packing, and mixing with oil.
The number of cases of lead poisoning in white lead factories is often relatively great despite regulations. Casual labourers especially run the greatest risk. This is frequently brought out in the reports of the German factory inspectors, who connect the high proportion of cases directly with the large number of unskilled workers. Regulations are really only successful in factories with regular employment.
This has been found also in Great Britain, where the Medical Inspector of Factories showed that the cases among regular workers numbered 6 per cent. and among casual workers 39 per cent.
The following table gives particulars as to the occurrence of lead poisoning in the white lead factories in the district of Cologne in 1904, some of which have admirable hygienic arrangements:
| Place. | Manufacture. | No. Employed. | Cases of Lead Poisoning. | No. of Cases of Gastric Catarrh. | |||||
|---|---|---|---|---|---|---|---|---|---|
| Regular | Casual | Average | Regular | Casual | Total | ||||
| Cologne I. | White lead | { | 46 | 59 | 32 | 9 | 16 | 25 | 16 |
| { | 173 | 95 | 127 | 13 | 17 | 30 | 22 | ||
| ” I. | Litharge and red lead | { | 46 | 4 | 38 | 5 | 1 | 6 | 7 |
| { | 76 | 62 | 49 | 3 | 4 | 7 | 15 | ||
| Chromate | { | 14 | 2 | 11 | — | — | — | 5 | |
| { | 43 | 72 | 33 | — | — | — | 7 | ||
| Cologne II. | White lead, litharge, and red lead | { | 107 | 332 | 91 | 6 | 34 | 40 | 30 |
| { | 102 | 332 | 76 | 9 | 19 | 28 | 38 | ||
It is worth noting that cases of lead poisoning have been reported in the manufacture of zinc white, as, for example, in Bohemia in 1907 and 1908.
USE OF LEAD COLOURS AND PAINTS (HOUSE PAINTERS, DECORATORS, ETC.)
Use of lead colours, especially by painters and decorators, causes relatively much lead poisoning. Apart from ignorance of danger on the part of the worker, and lack of personal cleanliness, unsuitable methods of working add to the danger, especially dry rubbing of painted surfaces, which gives rise to much dust containing lead. Again, the crushing and mixing of lumps of white lead and rubbing lead colours with the hand are very dangerous.
The following German and Austrian figures enable conclusions to be drawn as to the frequency of lead poisoning among painters. In the sick insurance societies of Frankfurt-a-M. in 1903 of every 100 painters 11·6 suffered from an attack of lead poisoning. The similar sick insurance society of painters in Berlin has kept useful statistics which are given in the following table for the ten years 1900-9:
| Year. | No. of Members. | No. of Cases of Lead Poisoning. | Cases per 100 Members. |
|---|---|---|---|
| 1900 | 3889 | 357 | 9·18 |
| 1901 | 3616 | 335 | 9·26 |
| 1902 | 3815 | 308 | 8·07 |
| 1903 | 4397 | 470 | 10·69 |
| 1904 | 5029 | 516 | 10·26 |
| 1905 | 5328 | 471 | 8·84 |
| 1906 | 5355 | 347 | 6·48 |
| 1907 | 5173 | 379 | 7·32 |
| 1908 | 4992 | 298 | 5·97 |
| 1909 | 4781 | 285 | 5·96 |
| Average | 4637 | 376·6 | 8·11 |
This shows that lead poisoning among the painters of Berlin is happily diminishing, which may be attributed to recent regulations. The society, however, complains in its reports that not all cases of lead appear as such in their statistics, and believes that all diseases entered as rheumatism, gastric catarrh, nervous complaints, heart and kidney disease, should be regarded as associated with lead. The kinds of work in which painters suffer most are painting iron girders and machines, sheet metal and iron furniture, railway waggons, agricultural implements, coach painting, cabinet-making, shipbuilding, and the use of red and white lead. The use of lead colours, lead acetate, and lead chromate often give rise to lead poisoning. Colours containing lead are not infrequently used in the textile industry in dyeing, printing, and finishing. White lead has been used for weighting the weft.
Teleky has described cases of lead poisoning in which silk thread was weighted with acetate of lead. As a consequence a number of women engaged in sewing on fringes with the thread suffered. The English factory inspectors’ reports describe cases from manipulating yarn dyed with chromate of lead.[7]
Chromate of lead and white lead are used in colouring oil-cloth, artificial flowers, paper, rubber goods, pencils, penholders, socks, sealing-wax, candles, and stamps.
USE OF LEAD IN THE CHEMICAL INDUSTRY
Lead poisoning has been frequently observed in such branches of the chemical industry as require large leaden or lead-lined vessels and pipes: the persons affected are principally those engaged in lead burning.
Risk is considerable in manufacture of lead acetate. The most dangerous processes are drying and packing the crystals.
MANUFACTURE OF ELECTRIC ACCUMULATORS
The manufacture of accumulators begins with the casting of lead plates, which are then polished and dressed. Next follows ‘pasting,’ that is, smearing the negative plate with a paste of litharge, the positive plate being ‘formed’ by having an electric current passed through so that the lead is converted into spongy peroxide. The wooden boxes in which the plates are assembled are lead-lined.
The most dangerous processes are casting, wire-brushing, and pasting—the latter especially when done by hand.
In the years 1908 and 1909 among about 761 workers employed in the accumulator factories of Cologne there were fifty-six cases of lead colic and seventy-nine of gastric and intestinal catarrh. Further figures for German accumulator works show that in the two largest accumulator factories in the district of Potsdam employing 142 workers there were fifteen cases in 1904. In Great Britain, in the ten years 1900-1909, 285 cases were reported—an average of about thirty a year.
THE CERAMIC INDUSTRY
Risk is present in several branches of the ceramic industry. It is greatest in glazing earthenware, but not infrequent also in the porcelain and glass industries. It is impossible to deal with the extensive literature on this subject exhaustively. A comprehensive and detailed survey of lead poisoning in the ceramic industry on the Continent is that by Kaup. Distinction is made between leadless glazes which melt at high temperature and lead glazes which have the advantage of a low melting-point. Galena and litharge are used in the preparation of glazes for common earthenware and red and white lead for ware of better quality. Distinction has to be made between a lead silicious glaze for pottery ware, a lead and boric acid glaze for stoneware, and a lead and zinc oxide glaze for ordinary faience and stoneware. Seegar, the celebrated expert, praises the advantage of lead glaze and the use of lead in the ceramic industry—it is indeed practically indispensable—and speaks of the poisonous nature of lead as its only fault. The components of the glaze must have definite relation to the hardness or softness of the body. The higher the proportion of silicic acid in the glaze the harder the firing it will stand; the more the flux materials are in excess the lower will the melting point be.
The most important flux materials are, arranged in order of decreasing fusibility, lead oxide, baryta, potash, soda, zinc oxide, chalk, magnesia, and clay.
The glaze is made by first mixing the ingredients dry, and then either fritting them by fluxing in a reverberatory furnace and finally grinding them very finely in water or using the raw material direct. In the fritting process in the case of the lead glazes the soluble lead compounds become converted into less soluble lead silicates and double silicates.
The glaze is applied in different ways—dipping, pouring, dusting, blowing, and volatilising. Air-dried and biscuited objects are dipped; pouring the glaze on is practised in coarse ware, roofing-tiles, &c.; dusting (with dry finely ground glaze, litharge, or red lead) also in common ware; glaze-blowing (aerographing) and glaze dusting on porcelain. In these processes machines can be used. Bricks are only occasionally glazed with glazes of felspar, kaolin, and quartz, to which lead oxide is often added in very large quantity. Lead poisoning in brick works in view of the infrequent use of lead is not common, but when lead is used cases are frequent. Kaup quotes several cases from the factory inspectors’ reports: thus in three roof-tiling works examination by the district physician showed that almost all the workers were affected.
Coarse ware pottery is made of pervious non-transparent clay with earthy fracture—only a portion of this class of ware (stoneware) is made of raw materials which fire white. Such ware generally receives a colourless glaze. The clay is shaped on the potter’s wheel, and is then fired once or, in the better qualities, twice.
Grinding the ingredients of the glaze is still often done in primitive fashion in mortars. The glaze is usually composed of lead oxide and sand, often with addition of other lead compounds as, for example, in quite common ware, of equal parts of litharge, clay, and coarse sand. Sometimes, instead of litharge, galena (lead sulphide) or, with better qualities of ware, red lead or ‘lead ashes’ are used.
The grinding of the glazes in open mills or even in mortars constitutes a great danger which can be prevented almost entirely by grinding in ball mills. The glaze material is next mixed with water, and the articles are either dipped into the creamy mass or this is poured over them. In doing this the hands, clothes, and floors are splashed. The more dangerous dusting-on of glaze is rarely practised. Occasionally mechanical appliances take the place of hand dipping. Placing the ware in the glost oven is done without placing it first in saggars.
In the better qualities of pottery cooking utensils, which are fired twice, a less fusible fritted lead glaze is generally used. Coloured glaze contains, besides the colouring metallic oxides, 30-40 per cent. of litharge or red lead.
As Kaup shows, Continental factory inspectors’ reports make only isolated references to occurrence of lead poisoning in potteries. Insight into the conditions in small potteries is obtained only from the Bavarian reports. In Upper Bavaria ninety-three potteries employ 157 persons who come into contact with lead glaze. Eleven cases were known to have occurred in the last four years. Teleky found thirty-six cases of lead poisoning (mostly among glostplacers) in the records of the Potters’ Sick Insurance Society of Vienna.
Chyzer has described the striking conditions in Hungary. There there are about 4000 potters, of whom 500 come into contact with lead glaze. Chronic lead poisoning is rife among those carrying on the occupation as a home industry. Members of the family contract the disease from the dust in the living rooms. This dust was found to contain from 0·5 to 8·7 per cent. of lead.
In the china and earthenware factories in Great Britain, in the ten years 1900-9, 1065 cases with fifty-seven deaths were reported.
Manufacture of stove tiles.—The application of glaze to stove tiles is done in different ways. The two most important kinds are (1) fired tiles and (2) slipped tiles. In the production of fired tiles a lead-tin alloy consisting of 100 parts lead and 30-36 parts tin—so-called ‘calcine’—are melted together in fireclay reverberatory or muffle furnaces and raked about when at a dull red heat so as to effect complete oxidation. The material when cool is mixed with the same quantity of sand and some salt, melted in the frit kiln, subsequently crushed, ground, mixed with water, and applied to the previously fired tiles. In this process risk is considerable. Presence of lead in the air has been demonstrated even in well-appointed ‘calcine’ rooms. In unsuitably arranged rooms it was estimated that in a twelve-hour day a worker would inhale 0·6 gramme of lead oxide and that 3-8 grammes would collect on the clothes.
Slipped tiles are made in Meissen, Silesia, Bavaria, and Austria by first applying to them a mixture of clay and china clay. The glaze applied is very rich in lead, containing 50-60 parts of red lead or litharge. Generally the glaze is applied direct to the unfired tiles and fired once. Figures as to occurrence of poisoning in Germany are quoted by Kaup from the towns of Velten and Meissen. Among from 1748 to 2500 persons employed thirty-four cases were reported in the five years 1901-5. Thirteen cases were reported as occurring in the three largest factories in Meissen in 1906.
From other districts similar occurrence of poisoning is reported. In Bohemia in a single factory in 1906 there were fourteen cases with one death, in another in 1907 there were fourteen, and in 1908 twelve cases; eight further cases occurred among majolica painters in 1908.
Stoneware and porcelain.—Hard stoneware on a base of clay, limestone, and felspar has usually a transparent lead glaze of double earth silicates of lead and alkalis, with generally boric acid to lower the fusing-point; the lead is nearly always added in the form of red lead or litharge. The portion of the glaze soluble in water is fritted, and forms, when mixed with the insoluble portion, the glaze ready for use. The frit according to Kaup contains from 16 to 18 per cent. of red lead, and the added material (the mill mixing) 8-26 parts of white lead; the glaze contains from 13 to 28 parts of lead oxide. The ware is dipped or the glaze is sometimes aerographed on. Ware-cleaning by hand (smoothing or levelling the surface with brushes, knives, &c.) is very dangerous work unless carried out under an efficient exhaust. Colouring the body itself is done with coloured metal oxides or by applying clay (slipping) or by the direct application of colours either under or over the glaze. Some of the under-glaze colours (by addition of chrome yellow or nitrate of lead or red lead) contain lead and are applied with the brush or aerograph or in the form of transfers.
Plain earthenware is either not glazed or salt glazed; only when decorated does it sometimes receive an acid lead glaze.
Porcelain receives a leadless glaze of difficultly fusible silicate (quartz sand, china clay, felspar). Risk is here confined to painting with lead fluxes (enamel colours) containing lead. These fluxes are readily fusible glasses made of silicic acid, boric acid, lead oxide, and alkalis, and contain much lead (60-80 per cent. of red lead).
In the glass industry lead poisoning may occur from use of red lead as one of the essential ingredients. In Great Britain, in the years 1900-9, forty-eight cases were reported in glass polishing from use of putty powder.
LETTERPRESS PRINTING, ETC.
Type metal consists of about 67 per cent. lead, 27 per cent. antimony, and 6 per cent. tin, but sometimes of 75 per cent. lead, 23 per cent. antimony, and 2 per cent. tin.
The actual printer comes least of all in contact with lead. Use of lead colours (white lead, chromate of lead, &c.) may be a source of danger, especially in the preparation of printing inks from them and in cleaning the printing rolls. A further, if slight, danger arises from the use of bronze powder consisting of copper, zinc, and tin. The two last-named metals contain from 0·1 to 0·5 per cent. of lead, and in the application and brushing off of the bronze there is a slight risk.
The compositor is exposed to constant danger from handling the type and disturbing the dust in the cases. This dust may contain from 15 to 38 per cent. of lead. Blowing the dust out of the cases with bellows is especially dangerous, and want of cleanliness (eating and smoking in the workroom) contributes to the risk.
Type founders and persons engaged in rubbing and preparing the type suffer. Introduction of type-casting machines (linotype, monotype) has lessened the danger considerably.
No lead fumes are developed, as a temperature sufficiently high to produce them is never reached. In all the processes, therefore, it is lead dust which has to be considered.
The following figures of the Imperial Statistical Office as to occurrence of lead poisoning among printers in Vienna indicate the relative danger:
| Occupation. | Average No. of Members, 1901-1906. | Average No. of Cases, 1901-1906. | Percentage of Cases, 1901-1906. |
|---|---|---|---|
| Compositors | 3182 | 90·3 | 2·8 |
| Printers | 809 | 20·3 | 2·4 |
| Casters and Stereotypers | 241 | 15·8 | 6·6 |
| Females employed in casting | 74 | 8·17 | 10·8 |
In Bohemia there is reference to thirty-eight cases in letterpress printing in 1907 and twenty-seven in 1908.
Among 5693 persons treated for lead poisoning between the years 1898 and 1901 in hospitals in Prussia, 222 were letterpress printers.
Between 1900 and 1909 in Great Britain 200 cases of lead poisoning were reported.
VARIOUS BRANCHES OF INDUSTRY
The number of industries using lead is very large. Layet as long ago as 1876 enumerated 111. We, however, limit ourselves to those in which the risk is considerable.
Use of lead beds in file-cutting has given rise to many cases. Further, to harden the file it is dipped into a bath of molten lead. From 3 to 6 per cent. of lead has been found in the dust in rooms where hardening is done.
Of 7000 persons employed in file-cutting in the German Empire in the years 1901-5 on an average 30·5 or 0·43 per cent. were affected yearly. In Great Britain 211 cases were reported in the years 1900-9.
In polishing precious stones formerly many cases of lead poisoning occurred, the reason being that the polishers come into contact with particles of lead and fix the diamonds to be polished in a vice composed of an alloy of lead and tin. Danger is increased when the stones are actually polished on revolving leaden discs. In Bohemia granite polishing used to be done in this way, but is now replaced in many factories by carborundum (silicon carbide).
Musical instrument making in Bohemia in the years 1906-8 was found regularly to give rise to cases of lead poisoning from use of molten lead in filling them with a view to shaping and bending. In lead pipe and organ pipe works, lead burning, plumbing, &c., considerable risk is run.
Often the causes of lead poisoning are difficult to discover, and, when found, surprising. Thus shoemakers have suffered from holding leaden nails in the mouth. Again, cases in women have been reported from cutting out artificial flowers or paper articles with aid of lead patterns, or counting stamps printed in lead colours.[8]
MERCURY
As metallic mercury gives off vapour even at ordinary temperatures, poisoning can occur not only in the recovery of the metal from the ore, but also in all processes in which it is used.
Chronic industrial poisoning occurs principally in the preparation and use of mercury salts, in recovery of the metal itself and of other metals with use of an amalgam, in water gilding, from use of nitrate of mercury in the preparation of rabbit fur for felt hat making, from use of mercury pumps in producing the vacuum in electric filament lamps, and in making barometers and thermometers.
Preparation.—Mercury is obtained by roasting cinnabar (sulphide of mercury). When cinnabar is heated with access of air the sulphide burns to sulphur dioxide and the mercury volatilises and is subsequently condensed. Formerly the process was carried on in open hearths; now it is done usually in blast furnaces. The mercury is condensed in Idria in large chambers cooled with water, while at Almaden in Spain it is collected in a series of small earthenware receptacles (aludels), from small openings in which the mercury flows in gutters and collects. The mercury so recovered is usually redistilled.
On the walls of the condensers a deposit of sulphide and oxide of mercury collects, removal of which is one of the operations most attended with risk.
Recovery of silver or gold by amalgamation with mercury is carried on only in America. The metallic silver or gold is taken up by the mercury, from which it is recovered by distillation.
The conditions in the quicksilver mines of Idria in Austria have improved of late years. Thus in the five years prior to 1886 of 500 cases of illness more than 11 per cent. were due to chronic mercurial poisoning. In 1906, 209 persons were employed, of whom only one-third were permanent hands. Among these the sickness rate was very high (95-104 per cent.). Of 741 cases of illness among the miners there were six of mercury poisoning, and of 179 among persons employed in recovery of the metal, twelve cases.[1]
The conditions of employment in the cinnabar mines of Monte Amiata in Italy have recently been described in detail.[2] Here, although the recovery of the metal is carried out in modern furnaces, thus greatly reducing the danger, nevertheless nearly all the furnace workers suffer from chronic poisoning.
In silvering of mirrors the leaf of tinfoil was spread out on an inclined table; mercury was poured over it and the sheet of glass laid on the top with weights. The superfluous mercury was squeezed out and ran away owing to the sloping position of the table. Now this process, even in Fürth, is almost entirely replaced by the nitrate of silver and ammonia process. Years ago the number of cases of poisoning was very serious in places where, as in Fürth, the work was carried on as a home industry.
In the production of incandescent electric bulbs danger arises from breaking of the glass pipes of the pumps and scattering of mercury on the floor of the workrooms. Since there is a growing tendency to replace mercury pumps by air pumps such cases ought to become rare.
In water gilding—a process little employed now—the metal objects (military buttons, &c.) to be gilded, after treatment with a flux, are brushed over with the mercury amalgam, and subsequently fired to drive off the mercury. Unless careful provision is made to carry away the vapour chronic poisoning cannot fail to occur. Even sweeps have been affected after cleaning the chimneys of water gilders’ workshops. In Great Britain, between 1899 and 1905, six cases were reported among water gilders.
In the manufacture of barometers and thermometers mercury poisoning is not infrequent. Between 1899 and 1905 sixteen such cases were reported in England; during the same period there were seventeen cases among those putting together electrical meters.
Risk of mercurial poisoning is constantly present in hatters’ furriers’ processes and in subsequent processes in felt hat factories. The risk from use of nitrate of mercury is considerable to those brushing the rabbit skins with the solution (carotting), and subsequently drying, brushing, cutting, locking, and packing them. According to Hencke in 100 kilos of the carotting liquid there are 20 kilos of mercury. In England, in the years 1899-1905, thirteen cases of mercurial poisoning were reported in hatters’ furriers’ processes. Among eighty-one persons so employed the medical inspector found twenty-seven with very defective teeth as the result of the employment, and seventeen with marked tremor.
In the manufacture of mercurial salts poisoning occurs chiefly when they are made by sublimation, as in the manufacture of vermilion, of corrosive sublimate (when mercurous sulphate is sublimed with salt), and in the preparation of calomel (when sublimate ground with mercury or mercurous sulphate mixed with mercury and salt is sublimed). Between 1899 and 1905 in England seven cases were reported from chemical works. As to occurrence of mercury poisoning from fulminate of mercury, see the chapter on Explosives.
ARSENIC
Chronic industrial arsenical poisoning, both as to origin and course, is markedly different from the acute form.
The chronic form arises mainly from inhalation of minute quantities of metallic arsenic or its compounds in recovery from the ore, or from the use of arsenic compounds in the manufacture of colours, in tanyards, and in glass making. Acute industrial arseniuretted hydrogen poisoning is especially likely to occur where metals and acids react on one another and either the metal or the acid contains arsenic in appreciable amount. Further, arseniuretted hydrogen may be contained in gases given off in smelting operations and in chemical processes.
Recovery of Arsenic and White Arsenic.—Pure arsenic is obtained from native cobalt and arsenical pyrites by volatilisation on roasting the ore in the absence of air. After the furnace has been charged sheet iron condensing tubes are affixed to the mouths of the retorts, which project out of the furnace, and to these again iron or earthenware prolongs. Arsenic condenses on the sides of the sheet metal tubes and amorphous arsenic, oxides, and sulphides in the prolongs. After sublimation has been completed the contents of the prolongs are removed and used for production of other arsenic compounds; the (generally) argentiferous residues in the retorts are removed and further treated in silver smelting works; finally, the crusts of crystalline arsenic (artificial fly powder) are knocked out from the carefully unrolled sheet iron tubes.
As can be readily understood from the description opportunity of poisoning from volatilisation of arsenic and of arsenic compounds is considerable. Metallic arsenic is used for making hard shot, and for increasing the brilliancy and hardness of metal alloys (type metal, &c.).
White arsenic (arsenic trioxide) is obtained by roasting with access of air in reverberatory furnaces arsenical ores and smelting residues. The vapours of white arsenic sublime and are condensed as a powder in long walled channels or in chambers, and are resublimed in iron cylinders. White arsenic is used in making colours, in glass (for decolourising purposes), as an insecticide in the stuffing of animals, &c.
Industrial Arsenic Poisoning.—In the extraction of arsenic and preparation of arsenious acid danger is present. But reliable accounts in literature of poisoning among those engaged in arsenic works are wanting.
Those engaged in roasting operations and packing suffer much from skin affections. Similar poisoning is reported in the smelting of other arsenical ores—nickel, cobalt, lead, copper, iron, and silver, from arsenic compounds present in the fumes. This is especially the case in the smelting of tin, which generally contains arsenical pyrites.
Danger is present also in unhairing (i.e. removing the wool from sheep skins), since the skins imported from Buenos Aires and Monte Video are treated with a preservative which, in addition to sodium nitrate, soda, and potash, contains generally arsenious acid.
In tanneries a mixture of arsenic sulphide (realgar) and lime is used for unhairing. Arsenic is used also for preserving and stuffing animal furs; but although affections of the skin are described I cannot find reference to arsenical poisoning.
The inspector for East London in 1905 refers to severe eczematous eruptions on face, neck, and hands, affecting workers in a sheep dip works—mainly in the packing of the light powder in packets.
Formerly the use of arsenic in the manufacture of colours was great, especially of emerald (Schweinfurter) green. This is made by dissolving arsenious acid in potash with addition of acetate of copper. Drying and grinding the material constitute the main danger. Scheele’s green is another arsenical colour.
Use of arsenic colours is becoming less and less. But in colour printing of paper and colouring of chalk they are still employed. They are used, too, as mordants in dyeing, but cases of poisoning from these sources in recent years are not to be found.
The dust in many glass works contains, it is stated, as much as 1·5 per cent of white arsenic.
Despite the numerous opportunities for arsenical poisoning in industries it is rare or, at any rate, is only rarely reported.
Arseniuretted Hydrogen Poisoning.—Industrial poisoning from arseniuretted hydrogen is caused mostly by inhalation of the gases developed by the action on one another of acids and metals which contain arsenic. Hydrogen gas as usually prepared for filling balloons gives occasion for poisoning.
In Breslau in 1902 five workmen became affected, of whom three died from inhalation of arseniuretted hydrogen gas in filling toy balloons.[1]
Further, use of hydrogen in lead burning may expose to risk, and also preparation of zinc chloride flux.
Of thirty-nine recorded cases of arseniuretted hydrogen poisoning twelve were chemists, eleven workers filling toy balloons, seven aniline workers, five lead smelters, three balloonists, and in one the origin could not be traced. Nineteen of these proved fatal within from three to twenty-four days.[2]
Cases are recorded (1) in the reduction of nitroso-methylaniline with zinc and hydrochloric acid; (2) in the preparation of zinc chloride from zinc ashes and hydrochloric acid; (3) from manufacture of zinc sulphate from crude sulphuric acid and zinc dust; (4) in spelter works in the refining of silver from the zinc crust with impure hydrochloric acid; and (5) in the formation room of accumulator factories.
The English factory inspectors’ report describes in 1906 occurrence of three cases in an electrolytic process for the recovery of copper in which the copper dissolved in sulphuric acid was deposited at the cathode, and hydrogen at the lead anode. In the 1907 report mention is made of two cases, one affecting a chemist separating bismuth from a solution of bismuth chloride in hydrochloric acid, and the other (which proved fatal) a man who had cleaned a vitriol tank.
The poisoning resulting from ferro-silicon is in part referable to development of arseniuretted hydrogen gas.
ANTIMONY
It seems doubtful if industrial poisoning can really be traced to antimony or its compounds; generally the arsenic present with the antimony is at fault. Erben[1] considers that industrial antimony poisoning occurs among workmen employed in smelting antimony alloys in making tartar emetic through inhalation of fumes of oxide of antimony.
A case is cited of a workman in Hamburg engaged in pulverising pure antimony who was attacked with vomiting which lasted for several days, and the inspector of factories noted epistaxis (nose bleeding) and vomiting as following on the crushing of antimony ore.
Compositors in addition to chronic lead poisoning may suffer, it is alleged, from chronic antimony poisoning, showing itself in diminution in the number of white blood corpuscles and marked eosinophilia. These changes in the blood could be brought about experimentally in rabbits. Antimony was found by the Marsh test in the stools of those affected.
IRON
Pig iron is obtained by smelting iron ores in blast furnaces ([fig. 29]), through the upper opening of which charges of ore, limestone or similar material to act as a flux, and coke are fed in succession. The furnaces are worked continuously, using a blast of heated air; carbon monoxide is produced and effects the reduction of the ore to molten iron. The latter accumulates in the hearth and is covered with molten slag; this flows constantly away through an opening and is collected in slag bogies for removal, or is sometimes cooled in water.
The crude iron is tapped from time to time, and is led in a fluid condition into moulds called ‘pigs,’ in which it solidifies. Cast iron is occasionally used direct from the blast furnace for the purpose of making rough castings, but generally it is further refined before being used in a foundry by remelting with cast iron scrap in a cupola furnace.
Fig. 29.
a Hearth; b Bosh; c Shaft; d Gas uptake; e Down-comer; f Tuyères with water cooling arrangement; g Blast pipes; h Tapping hole; k Supporting columns; l Furnace bottom; m Charging hopper; n Bell with raising and lowering arrangement.
Wrought iron is made by treating pig iron in refinery and puddling furnaces; in these much of the carbon is removed as carbon monoxide, and from the puddling furnace the iron is obtained as a pasty mass which can be worked into bars, rods, or plates.
Steel is made in various ways. The Acid Bessemer process consists in forcing compressed air in numerous small streams through molten cast iron, in iron vessels (converters) which are lined with ganister, a silicious sandstone. These can be rotated on trunnions. Basic Bessemer steel is made in similar converters by the Thomas-Gilchrist or basic process, which can be applied to pig irons containing phosphorus. The latter is removed by giving the converter a basic lining of calcined magnesium limestone mixed with tar.
In the Martin process steel is obtained by melting together pig iron with steel scrap, wrought iron scrap, &c., on the hearth of a Siemens regenerative furnace with a silicious lining.
In iron smelting the most important danger is from blast furnace gas rich in carbonic oxide. Sulphur dioxide, hydrocyanic acid, and arseniuretted hydrogen gas may possibly be present.
When work was carried out in blast furnaces with open tops the workers engaged in charging ran considerable risk. But as the blast furnace gas is rich in carbonic oxide and has high heating capacity these gases are now always led off and utilised; the charging point is closed by a cup (Parry’s cup and cone charger) and only opened from time to time mechanically, when the workers retire so far from the opening as to be unaffected by the escaping gas. The gas is led away ([fig. 29]) through a side opening into special gas mains, is subjected to a purifying process in order to rid it of flue dust, and then used to heat the blast, fire the boilers, or drive gas engines.
Severe blast furnace gas poisoning, however, does occur in entering the mains for cleaning purposes. Numerous cases of the kind are quoted in the section on Carbonic oxide poisoning.
The gases evolved on tapping and slag running can also act injuriously, and unpleasant emanations be given off in granulating the slag (by receiving the fluid slag in water).
In the puddling process much carbonic oxide is present. Other processes, however, can scarcely give rise to poisoning.
The basic slag produced in the Thomas-Gilchrist process is a valuable manure on account of the phosphorus it contains; it is ground in edge runners, and then reduced to a very fine dust in mills and disintegrators. This dust has a corrosive action already referred to in the chapter on Phosphorus and Artificial Manures.
The poisoning caused by ferro-silicon is of interest. Iron with high proportion of silicon has been made in recent years on a large scale for production of steel. Some 4000 tons of ferro-silicon are annually exported to Great Britain from France and Germany. It is made by melting together iron ore, quartz, coke, and lime (as flux) at very high temperature in electrical furnaces. The coke reduces the quartz and ore to silicon and metal with the production of ferro-silicon. Certain grades, namely those with about 50 per cent. silicon, have the property of decomposing or disintegrating into powder on exposure for any length of time to the air, with production of very poisonous gases containing phosphoretted and arseniuretted hydrogen. The iron and quartz often contain phosphates, which in presence of carbon and at the high temperature of the electrical furnace would no doubt be converted into phosphides combining with the lime to form calcium phosphide; similarly any arsenic present would yield calcium arsenide. These would be decomposed in presence of water and evolve phosphoretted and arseniuretted hydrogen gas. In addition to its poisonous properties it has also given rise to explosions.
[In January 1905 fifty steerage passengers were made seriously ill and eleven of them died. In 1907 five passengers died on a Swedish steamer as the result of poisonous gases given off from ferro-silicon, and more recently five lives were lost on the steamer Aston carrying the material from Antwerp to Grimsby.[C] This accident led to full investigation of the subject by Dr. Copeman, F.R.S., one of the Medical Inspectors of the Local Government Board, Mr. S. R. Bennett, one of H.M. Inspectors of Factories, and Dr. Wilson Hake, Ph.D., F.I.C., in which the conclusions arrived at are summarised as follows:
1. Numerous accidents, fatal and otherwise, have been caused within the last few years by the escape of poisonous and explosive gases from consignments of ferro-silicon, which, in every instance, have been found to consist of so-called high-grade ferro-silicon, produced in the electric furnace.
2. These accidents, for the most part, have occurred during transport of the ferro-silicon by water, whether in sea-going vessels or in barges and canal-boats plying on inland waters.
3. These accidents have occurred in various countries and on vessels of different nationalities, while the ferro-silicon carried has, in almost every instance, been the product of a different manufactory.
4. Ferro-silicon, especially of grades containing from 40 per cent. to 60 per cent. of silicon, is invariably found to evolve considerable quantities of phosphoretted hydrogen gas, and, in less amount, of arseniuretted hydrogen, both of which are of a highly poisonous nature. A certain amount of the gas evolved is present, as such, in the alloy, being ‘occluded’ in minute spaces with which its substance is often permeated.
5. As the result of careful investigation, it has been shown that certain grades of ferro-silicon—notably such as contain about 33 per cent., 50 per cent., and 60 per cent. of silicon—even when manufactured from fairly pure constituents, are both brittle and liable to disintegrate spontaneously, this latter characteristic being apt to be specially marked in the case of the 50 per cent. grade.
All these grades are commonly employed at the present time.
6. In the event of disintegration occurring, the amount of surface exposed will, obviously, be greater than if the mass were solid.
7. Evolution of poisonous gases is greatly increased by the action of moisture, or of moist air, under the influence of which phosphoretted hydrogen is generated from calcium phosphide, which, in turn, is formed, in large part, at any rate, from the calcium phosphate present in anthracite and quartz, at the high temperature of the electric furnace. If spontaneous disintegration of the alloy also occurs, much larger quantities of gas would be given off from such friable and unstable material, other conditions being equal. The greater or less tendency of a given sample to evolve poisonous gases, and even a rough estimate of their probable amount may be arrived at by the use of test-papers prepared with silver nitrate.
8. There is no evidence that low-grade ferro-silicon (10 to 15 per cent.), produced in the blast-furnace, has ever given rise to accidents of similar character to those known to have been caused by the high-grade electrically produced alloy. Blast-furnace ferro-silicon does not evolve poisonous gases even in presence of moisture.
9. As regards ferro-silicon produced in the electric furnace, the evidence available goes to show that certain percentage grades are practically quite innocuous. This statement applies to grades of alloy of a silicon content up to and including 30 per cent., and probably also, though in considerably less degree, to those of 70 per cent. and over.
10. In view of the fact that the use of ferro-silicon of grades ranging between 30 per cent. and 70 per cent. apparently is not essential in metallurgical operations, with the possible exception of basic steel manufacture, it will be advisable that the production of this alloy of grades ranging between these percentages should be discontinued in the future.
11. The proprietors of iron and steel works making use of ferro-silicon will assist in the protection of their workpeople, and at the same time act for the public benefit by restricting their orders to grades of this material, either not exceeding 30 per cent., or of 70 per cent. and upwards, according to the special nature of their requirements.
12. But as, pending international agreement on the question, intermediate percentages of ferro-silicon will doubtless continue to be manufactured and sold, the issue, by the Board of Trade, of special regulations will be necessary in order to obviate, so far as may be possible, chance of further accidents during the transport of this substance.
Inter alia, these regulations should require a declaration of the nature, percentage, date of manufacture, and place of origin of any such consignment.
The suggested regulations are printed on p. [291].]
ZINC
Industrial poisoning from zinc is unknown. The chronic zinc poisoning among spelter workers described by Schlockow with nervous symptoms is undoubtedly to be attributed to lead.
COPPER: BRASS
Occurrence of brass-founder’s ague.—Opinion is divided as to whether pure copper is poisonous or not. Lehmann has at any rate shown experimentally that as an industrial poison it is without importance.
Occurrence, however, of brass-founder’s ague is undoubtedly frequent. Although neither pure zinc nor pure copper give rise to poisoning, yet the pouring of brass (an alloy of zinc and copper) sets up a peculiar train of symptoms. As the symptoms are transient, and medical attendance is only very rarely sought after, knowledge of its frequency is difficult to obtain.
Sigel,[1] who has experimented on himself, believes that the symptoms result from inhalation of superheated zinc fumes. In large well-appointed brass casting shops (as in those of Zeiss in Jena) incidence is rare.
Lehmann[2] very recently has expressed his decided opinion that brass-founder’s ague is a zinc poisoning due to inhalation of zinc oxide and not zinc fumes. This conclusion he came to as the result of experiments on a workman predisposed to attacks of brass-founder’s ague. Lehmann’s surmise is that the symptoms are due to an auto-intoxication from absorption of dead epithelial cells lining the respiratory tract, the cells having been destroyed by inhalation of the zinc oxide. He found that he could produce typical symptoms in a worker by inhalation of the fumes given off in burning pure zinc.
Metal pickling.—The object of metal dipping is to give metal objects, especially of brass (buckles, lamps, electric fittings, candlesticks, &c.), a clean or mat surface and is effected by dipping in baths of nitric, hydrochloric, or sulphuric acid. Generally after dipping in the dilute bath the articles go for one or two minutes into strong acid, from which injurious fumes, especially nitrous fumes, develop with occasionally fatal effect (see the chapter on Nitric Acid). Unfortunately, there are no references in the literature of the subject as to the frequency of such attacks.
Recovery of gold and silver has been already referred to in the chapters on Mercury, Lead, and Cyanogen.
Mention must be made of argyria. This is not poisoning in the proper sense of the word, as injury to health is hardly caused. Argyria results from absorption of small doses of silver salts which, excreted in the form of reduced metallic silver, give the skin a shiny black colour. Cases are most frequently seen in silverers of glass pearls who do the work by suction. Local argyria has been described by Lewin in silvering of mirrors and in photographers.