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diff --git a/old/60605-0.txt b/old/60605-0.txt deleted file mode 100644 index 826ca2c..0000000 --- a/old/60605-0.txt +++ /dev/null @@ -1,15476 +0,0 @@ -The Project Gutenberg EBook of Industrial Poisoning, by Joseph Rambousek - -This eBook is for the use of anyone anywhere in the United States and most -other parts of the world at no cost and with almost no restrictions -whatsoever. You may copy it, give it away or re-use it under the terms of -the Project Gutenberg License included with this eBook or online at -www.gutenberg.org. If you are not located in the United States, you'll have -to check the laws of the country where you are located before using this ebook. - -Title: Industrial Poisoning - From Fumes, Gases and Poisons of Manufacturing Processes - -Author: Joseph Rambousek - -Translator: Thomas M. Legge - -Release Date: November 1, 2019 [EBook #60605] - -Language: English - -Character set encoding: UTF-8 - -*** START OF THIS PROJECT GUTENBERG EBOOK INDUSTRIAL POISONING *** - - - - -Produced by Suzanne Lybarger, Brian Janes and the Online -Distributed Proofreading Team at http://www.pgdp.net - - - - - - - - - - -INDUSTRIAL POISONING - -FROM FUMES, GASES AND POISONS OF MANUFACTURING PROCESSES - - BY THE SAME AUTHOR - - LEAD POISONING AND LEAD ABSORPTION: - - THE SYMPTOMS, PATHOLOGY AND PREVENTION, WITH SPECIAL REFERENCE - TO THEIR INDUSTRIAL ORIGIN AND AN ACCOUNT OF THE PRINCIPAL - PROCESSES INVOLVING RISK. - - By THOMAS M. LEGGE M.D. (Oxon.), D.P.H. (Cantab.), H.M. Medical - Inspector of Factories; Lecturer on Factory Hygiene, University - of Manchester; and KENNETH W. GOADBY, D.P.H. (Cantab.), - Pathologist and Lecturer on Bacteriology, National Dental - Hospital. Illustrated. viii+308 pp. 12s. 6_d._ net. - - LONDON: EDWARD ARNOLD. - - - - - INDUSTRIAL POISONING - - FROM FUMES, GASES AND POISONS - OF MANUFACTURING PROCESSES - - BY - DR. J. RAMBOUSEK - PROFESSOR OF FACTORY HYGIENE, - AND CHIEF STATE HEALTH OFFICER, PRAGUE - - TRANSLATED AND EDITED BY - THOMAS M. LEGGE, M.D., D.P.H. - H.M. MEDICAL INSPECTOR OF FACTORIES - JOINT AUTHOR OF ‘LEAD POISONING AND LEAD ABSORPTION’ - - WITH ILLUSTRATIONS - - LONDON - EDWARD ARNOLD - 1913 - - - - -TRANSLATOR’S PREFACE - - -I undertook the translation of Dr. Rambousek’s book because it seemed to -me to treat the subject of industrial poisons in as novel, comprehensive, -and systematic a manner as was possible within the compass of a single -volume. Having learnt much myself from Continental writings on industrial -diseases and factory hygiene, I was anxious to let others also see how -wide a field they had covered and how thorough were the regulations for -dangerous trades abroad, especially in Germany. A praiseworthy feature of -Dr. Rambousek’s book was the wealth of references to the work of foreign -writers which is made on almost every page. To have left these names -and references, however, in the text as he has done would have made the -translation tedious reading, and therefore for the sake of those who -desire to pursue inquiry further I have adopted the course of collecting -the great majority and placing them all together in an appendix at the -end of the volume. - -Dr. Rambousek as a medical man, a chemist, and a government official -having control of industrial matters, is equipped with the very special -knowledge required to describe the manufacturing processes giving rise -to injurious effects, the pathology of the lesions set up, and the -preventive measures necessary to combat them. In his references to work -done in this country he has relied largely on abstracts which have -appeared in medical and technical journals published on the Continent. I -have only thought it necessary to amplify his statements when important -work carried out here on industrial poisoning,—such as that on nickel -carbonyl and on ferro-silicon—had been insufficiently noted. Such -additions are introduced in square brackets or in footnotes. - -In his preface Dr. Rambousek says ‘the book is intended for all who -are, or are obliged to be, or ought to be, interested in industrial -poisoning.’ No words could better describe the scope of the book. - -The work of translation would never have been begun but for the -assistance given me in Parts II and III by my sister, Miss H. Edith -Legge. To her, and to Mr. H. E. Brothers, F.I.C., who has been to the -trouble of reading the proofs and correcting many mistakes which my -technical knowledge was insufficient to enable me to detect, my best -thanks are due. - -I am indebted to Messrs. Davidson & Co., Belfast, for permission to use -figs. 46 and 48; to Messrs. Locke, Lancaster & Co., Millwall, for fig. -27; to Mr. R. Jacobson, for figs. 30, 33, 37, 38, and 43; to Messrs. -Siebe, Gorman & Co., for figs. 32, 39, and 40; to Messrs. Blackman & Co. -for fig. 47; to Messrs. Matthews & Yates for fig. 54; to H.M. Controller -of the Stationery Office for permission to reproduce figs. 52, 53, and -54, and the diagrams on p. 284; and lastly to my publisher, for figs. 41, -42, 43, and 49, which are taken from the book by Dr. K. W. Goadby and -myself on ‘Lead Poisoning and Lead Absorption.’ - - T. M. L. - -HAMPSTEAD, _May 1913_. - - - - -CONTENTS - - - PAGE - - INTRODUCTION xiii - - Part I.—Description of the industries and processes attended - with risk of poisoning: incidence of such poisoning - - CHEMICAL INDUSTRY 1 - Sulphuric acid industry (sulphur dioxide): use of sulphuric acid 4 - Its effects on health 9 - Hydrochloric acid, saltcake and soda industry 14 - Their effects on health 20 - Use of sulphate and sulphide of soda 22 - Ultramarine 22 - Sulphonal 22 - Diethyl sulphate 23 - Chlorine, chloride of lime and chlorates 23 - Their effect on health 26 - Other chlorine compounds and their use as well as bromine, - iodine and fluorine 29 - Chlorides of phosphorus 30 - Chlorides of sulphur 31 - Zinc chloride 32 - Rock salt 32 - Organic chlorine compounds 32 - Carbon oxychloride (phosgene) 32 - Carbon chlorine compounds (aliphatic) 33 - Methyl chloride 33 - Methylene chloride 34 - Carbon tetrachloride 34 - Ethyl chloride 34 - Monochloracetic acid 34 - Chloral 34 - Chloroform 34 - Chloride of nitrogen 35 - Cyanogen chloride 35 - Chlorobenzene 35 - Benzo trichloride, benzyl chloride 35 - Nitro- and dinitro-chlorobenzene 35 - Iodine and iodine compounds 36 - Bromine and bromine compounds 36 - Methyl iodide and methyl bromide 36 - Fluorine compounds 37 - Hydrofluoric and silicofluoric acids 38 - Manufacture and uses of nitric acid 39 - Its effect on health 40 - Nitric and nitrous salts and compounds 44 - Barium nitrate 44 - Ammonium nitrate 44 - Lead nitrate 44 - Mercurous and mercuric nitrate 44 - Silver nitrate 45 - Sodium nitrite 45 - Amyl nitrite 45 - Manufacture of explosives and their effects 45 - Fulminate of mercury 46 - Nitro-glycerin 46 - Dynamite 47 - Gun cotton 48 - Collodion cotton, smokeless powder 48 - Manufacture of phosphorus and lucifer matches and their effects 49 - Other uses of phosphorus and compounds of phosphorus 52 - Phosphor-bronze 52 - Sulphide of phosphorus 52 - Phosphoretted hydrogen 52 - Superphosphate and artificial manure 53 - Basic slag 54 - Chromium compounds and their uses 55 - Sodium and potassium bichromate 55 - Lead chromate and chrome colours 55 - Their effect on health 56 - Manganese compounds and their effects 58 - Mineral oil industry and the use of petroleum and benzine 59 - Chemical cleaning 61 - Their effect on health 61 - Recovery and use of sulphur 64 - Its effect on health 65 - Sulphuretted hydrogen and its effect 65 - Preparation and use of carbon bisulphide in vulcanising, &c. 68 - Its effect on health 69 - Preparation of illuminating gas 71 - Its effect on health 74 - Coke ovens and risk from them 77 - Other kinds of power and illuminating gas 80 - Producer gas 80 - Blast furnace gas 82 - Water gas 82 - Dowson and Mond gas 82 - Suction gas 83 - Acetylene (calcium carbide) 85 - Their effect on health 87 - Ammonia and ammonium compounds 90 - Use of ammonia and its effects 92 - Cyanogen compounds 93 - Use of cyanide, and their effects 95 - Coal tar and tar products 96 - Their effects on health 101 - Artificial organic dye stuffs (coal tar colours) 107 - Their effects on health 112 - RECOVERY AND USE OF METALS 120 - Lead poisoning in general 120 - Lead, silver and zinc smelting 122 - Spelter works 125 - Lead poisoning in lead smelting and spelter works 126 - White lead and other use of lead colours 131 - Lead poisoning in the manufacture and use of white lead - and lead paints 132 - Manufacture of electric accumulators 134 - The ceramic industry 135 - Coarse ware pottery 136 - Manufacture of stove tiles 137 - Stoneware and porcelain 138 - Lead poisoning in letterpress printing 138 - Lead poisoning in filecutting, polishing precious stones, - musical instrument making, &c. 140 - Mercury (poisoning in its recovery and use) 141 - Mercurial poisoning in water-gilding, coating mirrors, in - felt hat making, &c. 142 - Arsenic (poisoning in its recovery and in use of arsenic and - arsenic compounds) 143 - Recovery of arsenic and white arsenic 143 - Poisoning by arseniuretted hydrogen gas 145 - Antimony 146 - Extraction of iron 146 - Ferro-silicon 149 - Zinc 151 - Copper, brass (brassfounders’ ague) 151 - Metal pickling 152 - OTHER INDUSTRIES 153 - Treatment of stone and earths; lime burning, glass 153 - Treatment of animal products 154 - Preparation of vegetable foodstuffs 154 - Poisonous woods 154 - Textile industry 156 - - Part II.—Pathology and treatment of industrial poisoning - - INDUSTRIAL POISONS IN GENERAL 157 - Channels of absorption, classification, susceptibility, - immunity 158 - Fate of poisons in the body—absorption, cumulative action, - excretion 162 - General remarks on treatment 163 - INDUSTRIAL POISONS IN PARTICULAR 169 - Group: mineral acids, halogens, inorganic halogen compounds, - alkalis 169 - Hydrochloric acid 170 - Hydrofluoric and silico-fluoric acids 171 - Sulphur dioxide and sulphuric acid 171 - Nitrous fumes, nitric acid 172 - Chlorine, bromine, iodine 173 - Chlorides of phosphorus, sulphur and zinc 174 - Ammonia 175 - Alkalis 176 - Group: Metals and metal-compounds 176 - Lead and its compounds 177 - Zinc and its alloys 182 - Mercury and its compounds 183 - Manganese and its compounds 184 - Chromium and its compounds 185 - Nickel salts (nickel carbonyl) 186 - Copper 188 - Silver and its compounds 188 - Group: Arsenic, Phosphorus 189 - Arsenic and its oxides 189 - Phosphorus 190 - Phosphoretted hydrogen 191 - Group: Sulphuretted hydrogen, carbon bisulphide, and cyanogen - (nerve poisons) 192 - Sulphuretted hydrogen 192 - Carbon bisulphide 193 - Cyanogen compounds 195 - Group: Arseniuretted hydrogen and carbonic oxide (blood - poisons) 197 - Group: Hydrocarbons of the aliphatic and aromatic series and - their halogen and hydroxyl substitution products 202 - Sub-group: Hydrocarbons of mineral oils and their distillation - products (benzine, paraffin, &c.) 202 - Sub-group: Hydrocarbons of the aromatic series 204 - Benzene and its homologues 204 - Naphthalene 208 - Sub-group: Halogen substitution products of the aliphatic - series (narcotic poisons) 208 - Sub-group: Halogen substitution products of the benzene - series 209 - Sub-group: Hydroxyl substitution products of the fatty - series 210 - Group: Nitro- and amido-derivatives of the aliphatic and - aromatic series 211 - Sub-group: Nitro-derivatives of the aliphatic series 212 - Sub-group: Nitro- and amido-derivatives of the aromatic - series 212 - Turpentine, pyridene, alkaloids, nicotine, poisonous woods 215 - - Part III.—Preventive measures against industrial poisoning - - GENERAL PREVENTIVE MEASURES 217 - International action, notification of poisoning, schedules - of poisons 218 - Special preventive measures for workers—selection, periodical - medical examination, co-operation of workers, &c. 226 - Rescue appliances 230 - Washing accommodation and baths 237 - Removal of dust and fumes by exhaust ventilation 242 - PREVENTIVE MEASURES IN PARTICULAR INDUSTRIES 256 - Sulphuric acid industry 256 - Hydrochloric acid and soda industries 257 - Chlorine, bleaching powder, chlorine compounds 259 - Manufacture of nitric acid and explosives 260 - Artificial manures, basic slag 261 - Chromium and its compounds 265 - Petroleum, benzine 267 - Phosphorus, lucifer matches 268 - Bisulphide of carbon 271 - Illuminating gas, tar production 275 - Gas power plant 276 - Acetylene gas installations 278 - Ammonia 279 - Cyanogen, cyanogen compounds 280 - Coal tar, tar products 280 - Organic dye-stuffs, coal tar colours 285 - Recovery and use of metals 288 - Iron 289 - Lead 292 - Lead smelting 299 - Electric accumulators 305 - White lead and lead colours 310 - Letterpress printing 316 - Ceramic industry 319 - File cutting 321 - Other uses of lead 322 - Zinc smelting 323 - Brass casting, metal pickling 325 - Recovery and use of mercury 326 - Arsenic and its compounds 328 - Gold and silver 329 - PREVENTIVE MEASURES IN OTHER TRADES 329 - Manufacture and use of varnishes 330 - Production of vegetable foods 332 - Wood working 335 - Paper manufacture 336 - Textile industries 336 - - APPENDIX 339 - - INDEX 355 - - - - -INTRODUCTION - - -The attempt to systematise from the scientific standpoint the mass of -material that has been collected about poisons is a very heavy task, even -for the toxicologist who desires to treat his subject comprehensively. -How much greater is the difficulty of writing a systematic book on -industrial poisoning keeping practical application in the forefront! - -Technical considerations which are decisive in the causation and -prevention of industrial poisoning are here of especial moment, and must -naturally influence classification of the subject-matter when the object -is to assist those concerned in factory hygiene. - -Bearing this in mind, I have divided the subject into three parts. The -arrangement of the first, which gives as complete a statement as possible -of the occurrence of industrial poisoning, into industries and processes -was determined on technical grounds. The second, which amplifies the -first, attempts to summarise the pathology or symptoms of the various -forms of poisoning. The references to the literature of the particular -subjects—as exhaustive as I could make them—will lighten further study. -To these two parts, following on knowledge of causation and symptoms, the -third, in which preventive measures are outlined, is linked. - -The apparent drawback in use of the book is that one form of poisoning -has often to be referred to in three places. But, I hope, this is more -than counterbalanced by the completeness of the scheme which results from -the subdivision of the subject. - -The pathology of industrial poisoning necessitates frequent repetition -when describing the branches of industry giving rise to the -intoxication, as one and the same form can occur in the most varied -processes. The numerous instances of actual cases of poisoning quoted -must therefore be regarded as conforming to the same pathological type. -Similarly, preventive measures require separate systematic treatment in -order to avoid constant repetition which would otherwise obscure the -general survey. Quite a number of means of prevention apply equally -to several industries in which the same cause is at work. The success -attained by thus simplifying the issues is the greater because such -common measures are the easier to carry through and to supervise. - -The method therefore has been adopted only after serious reflection and -has been directed mainly by practical considerations. - -Recent cases which have either been reported or come to the knowledge -of the author have been given, with particulars as exact as possible. -Cases dating back some time have been omitted intentionally so as to -exclude everything which did not correspond with the present conditions -of industry and trade. Historical facts only receive consideration in so -far as they are fundamentally important and necessary for the sake of -completeness. - -The details given in Part I of actual instances will supply material for -fresh efforts, renewed investigation, and new points of attack. - - - - -INDUSTRIAL POISONING - - - - -PART I - -_DESCRIPTION OF THE INDUSTRIES AND PROCESSES ATTENDED WITH RISK OF -POISONING; INCIDENCE OF SUCH POISONING_ - - - - -I. THE CHEMICAL INDUSTRY - - -GENERAL CONSIDERATIONS AS TO INCIDENCE OF INDUSTRIAL POISONING - -The chemical industry offers naturally a wide field for the occurrence of -industrial poisoning. Daily contact with the actual poisonous substances -to be prepared, used, stored, and despatched in large quantity gives -opportunity for either acute or chronic poisoning—in the former case -from sudden accidental entrance into the system of fairly large doses, -as the result of defective or careless manipulation, and, in the latter, -constant gradual absorption (often unsuspected) of the poison in small -amount. - -The industry, however, can take credit for the way in which incidence -of industrial poisoning has been kept down in view of the magnitude and -variety of the risks which often threaten. This is attributable to the -comprehensive hygienic measures enforced in large chemical works keeping -abreast of modern advance in technical knowledge. A section of this -book deals with the principles underlying these measures. Nevertheless, -despite all regulations, risk of poisoning cannot be wholly banished. -Again and again accidents and illness occur for which industrial -poisoning is responsible. Wholly to prevent this is as impossible as -entirely to prevent accidents by mechanical guarding of machinery. - -Owing to the unknown sources of danger, successful measures to ward it -off are often difficult. The rapid advance of this branch of industry, -the constant development of new processes and reactions, the frequent -discovery of new materials (with properties at first unknown, and for a -long time insufficiently understood, but nevertheless indispensable), -constantly give rise to new dangers and possibilities of danger, of which -an accident or some disease with hitherto unknown symptoms is the first -indication. Further, even when the dangerous effects are recognised, -there may often be difficulty in devising appropriate precautions, as -circumstances may prevent immediate recognition of the action of the -poison. We cannot always tell, for instance, with the substances used -or produced in the processes, which is responsible for the poisoning, -because, not infrequently, the substances in question are not chemically -pure, but may be either raw products, bye-products, &c., producing -mixtures of different bodies or liberating different chemical compounds -as impurities. - -Hence difficulty often arises in the strict scientific explanation -of particular cases of poisoning, and, in a text-book such as this, -difficulty also of description. A rather full treatment of the technical -processes may make the task easier and help to give a connected picture -of the risks of poisoning in the chemical industry. Such a procedure may -be especially useful to readers insufficiently acquainted with chemical -technology. - -We are indebted to Leymann[1] and Grandhomme[2] especially for knowledge -of incidence of industrial poisoning in this industry. The statistical -data furnished by them are the most important proof that poisoning, at -any rate in large factories, is not of very frequent occurrence. - -Leymann’s statistics relate to a large modern works in which the number -employed during the twenty-three years of observation increased from -640 in the year 1891 to 1562 in 1904, giving an average of about 1000 -yearly, one-half of whom might properly be defined as ‘chemical workers.’ -The factory is concerned in the manufacture of sulphuric, nitric, and -hydrochloric acids, alkali, bichromates, aniline, trinitro-phenol, -bleaching powder, organic chlorine compounds, and potassium permanganate. - -These statistics are usefully complemented by those of Grandhomme drawn -from the colour works at Höchst a-M. This large aniline works employs -from 2600 to 2700 workers; the raw materials are principally benzene and -its homologues, naphthalene and anthracene. The manufacture includes the -production of coal-tar colours, nitro- and dinitro-benzene, aniline, -rosaniline, fuchsine, and other aniline colours, and finally such -pharmaceutical preparations as antipyrin, dermatol, sanoform, &c. Of the -2700 employed, 1400 are chemical workers and the remainder labourers. - -These two series of statistics based on exact observations and covering -allied chemical manufacture are taken together. They seek to give the -answer to the question—How many and what industrial poisonings are found? - -The figures of Leymann (on an average of 1000 workers employed per annum) -show 285 cases of poisoning reported between the years 1881 and 1904. Of -these 275 were caused by aniline, toluidine, nitro- and dinitro-benzene, -nitrophenol, nitrochloro and dinitrochloro benzene. Three were fatal -and several involved lengthy invalidity (from 30 to 134 days, owing to -secondary pneumonia). Included further are one severe case of chrome -(bichromate) poisoning (with nephritis as a sequela), five cases of lead -poisoning, three of chlorine, and one of sulphuretted hydrogen gas. In -the Höchst a-M. factory (employing about 2500 workers) there were, in the -ten years 1883-92, only 129 cases of poisoning, of which 109 were due to -aniline. Later figures for the years 1893-5 showed 122 cases, of which 43 -were due to aniline and 76 to lead (contracted mostly in the nitrating -house). Grandhomme mentions further hyperidrosis among persons employed -on solutions of calcium chloride, injury to health from inhalation of -methyl iodide vapour in the antipyrin department, a fatal case of benzene -poisoning (entering an empty vessel in which materials had previously -been extracted with benzene), and finally ulceration and perforation of -the septum of the nose in several chrome workers. - -The number of severe cases is not large, but it must be remembered that -the factories to which the figures relate are in every respect models -of their kind, amply provided with safety appliances and arrangements -for the welfare of the workers. The relatively small amount of poisoning -is to be attributed without doubt to the precautionary measures taken. -Further, in the statistics referred to only those cases are included -in which the symptoms were definite, or so severe as to necessitate -medical treatment. Absorption of the poison in small amount without -producing characteristic symptoms, as is often the case with irritating -or corrosive fumes, and such as involve only temporary indisposition, are -not included. Leymann himself refers to this when dealing with illness -observed in the mineral acid department (especially sulphuric acid), and -calls attention to the frequency of affections of the respiratory organs -among the persons employed, attributing them rightly to the irritating -and corrosive effect of the acid vapour. Elsewhere he refers to the -frequency of digestive disturbance among persons coming into contact -with sodium sulphide, and thinks that this may be due to the action of -sulphuretted hydrogen gas. - -Nevertheless, the effect of industrial poisons on the health of workers -in chemical factories ought on no account to be made light of. The -admirable results cited are due to a proper recognition of the danger, -with consequent care to guard against it. Not only have Grandhomme -and Leymann[A] rendered great services by their work, but the firms -in question also, by allowing such full and careful inquiries to be -undertaken and published. - - -SULPHURIC ACID (SULPHUR DIOXIDE) - -MANUFACTURE.—Sulphur dioxide, generally obtained by roasting pyrites in -furnaces of various constructions, or, more rarely, by burning brimstone -or sulphur from the spent oxide of gas-works, serves as the raw material -for the manufacture of sulphuric acid. Before roasting the pyrites is -crushed, the ‘lump ore’ then separated from the ‘smalls,’ the former -roasted in ‘lump-burners’ or kilns (generally several roasting furnace -hearths united into one system), and the latter preferably in Malétra and -Malétra-Schaffner shelf-burners (fig. 1) composed of several superimposed -firebrick shelves. The pyrites is charged on to the uppermost shelf and -gradually worked downwards. Pyrites residues are not suitable for direct -recovery of iron, but copper can be recovered from residues sufficiently -rich in metal by the wet process; the residues thus freed of copper and -sulphur are then smelted for recovery of iron. - -[Illustration: FIG. 1.—Pyrites Burner for Smalls (_after Lueger_)] - -Utilisation for sulphuric acid manufacture of the sulphur dioxide given -off in the calcining of zinc blende (see Spelter works), impracticable in -reverberatory furnaces, has been made possible at the Rhenania factory by -introduction of muffle furnaces (several superimposed), because by this -means the gases led off are sufficiently concentrated, as they are not -diluted with the gases and smoke from the heating fires. This method, -like any other which utilises the gases from roasting furnaces, has -great hygienic, in addition to economical, advantages, because escape -of sulphur dioxide gas is avoided. Furnace gases, too poor in sulphur -dioxide to serve for direct production of sulphuric acid, can with -advantage be made to produce liquid anhydrous sulphur dioxide. Thus, the -sulphur dioxide gas from the furnaces is first absorbed by water, driven -off again by boiling, cooled, dried, and liquefied by pressure. - -The gaseous sulphur dioxide obtained by any of the methods described is -converted into sulphuric acid either by (_a_) the chamber process or -(_b_) the contact process. - -In the _lead chamber process_ the furnace gases pass through flues in -which the flue dust and a portion of the arsenious acid are deposited -into the Glover tower at a temperature of about 300° C., and from there -into the lead chambers where oxidation of the sulphur dioxide into -sulphuric acid takes place, in the presence of sufficient water, by -transference of the oxygen of the air through the intervention of the -oxides of nitrogen. The gases containing oxides of nitrogen, &c., which -are drawn out of the lead chambers, have the nitrous fumes absorbed -in the Gay-Lussac tower (of which there are one or two in series), by -passage through sulphuric acid which is made to trickle down the tower. -The sulphuric acid so obtained, rich in oxides of nitrogen, and the -chamber acid are led to the Glover tower for the purpose of denitration -and concentration, so that all the sulphuric acid leaves the Glover -as Glover acid of about 136-144° Tw. Losses in nitrous fumes are best -made up by addition of nitric acid at the Glover or introduction into -the first chamber. The deficiency is also frequently made good from -nitre-pots. - -The lead chambers (fig. 2) are usually constructed entirely—sides, -roof, and floor—of lead sheets, which are joined together by means of a -hydrogen blowpipe. The sheets forming the roof and walls are supported, -independent of the bottom, on a framework of wood. The capacity varies -from 35,000 to 80,000 cubic feet. The floor forms a flat collecting -surface for the chamber acid which lutes the chamber from the outer air. -The necessary water is introduced into the chamber as steam or fine water -spray. - -The Glover and Gay-Lussac towers are lead towers. The Glover is lined -with acid-proof bricks and filled with acid-proof packing to increase -the amount of contact. The Gay-Lussac is filled with coke over which -the concentrated sulphuric acid referred to above flows, forming, after -absorption of the nitrous fumes, nitro-sulphuric acid. - -[Illustration: FIG. 2A.—Lead Chamber System—Section through X X (_after -Ost_) - -FIG. 2B.—Lead Chamber System—Plan - - A Pyrites Burner - B Glover Tower - C Draft Regulator - D, D´ Lead Chambers - E Air Shaft - F, F,´ F,´´ F´´´ Acid Reservoirs - G Acid Egg - H Cooler - J Gay-Lussac Tower] - -As already stated, two Gay-Lussac towers are usually connected together, -or where there are several lead-chamber systems there is, apart from the -Gay-Lussac attached to each, a central Gay-Lussac in addition, common -to the whole series. The introduction of several Gay-Lussac towers -has the advantage of preventing loss of the nitrous fumes as much as -possible—mainly on economical grounds, as nitric acid is expensive. But -this arrangement is at the same time advantageous on hygienic grounds, as -escape of poisonous gases containing nitrous fumes, &c., is effectually -avoided. The acids are driven to the top of the towers by compressed air. -The whole system—chambers and towers—is connected by means of wide lead -conduits. Frequently, for the purpose of quickening the chamber process -(by increasing the number of condensing surfaces) Lunge-Rohrmann plate -towers are inserted in the system—tall towers lined with lead in which -square perforated plates are hung horizontally, and down which diluted -sulphuric acid trickles. - -To increase the draught in the whole system a chimney is usual at -the end, and, in addition, a fan of hard lead or earthenware may be -introduced in front of the first chamber or between the two Gay-Lussac -towers. Maintenance of a constant uniform draught is not only necessary -for technical reasons, but has hygienic interest, since escape of -injurious gases is avoided (see also Part III). - -The chamber acid (of 110°-120° Tw. = 63-70 %) and the stronger Glover -acid (of 136°-144° Tw. = 75-82 %) contain impurities. In order to obtain -for certain purposes pure strong acid the chamber acid is purified and -concentrated. The impurities are notably arsenious and nitrous acids -(Glover acid is N free), lead, copper, and iron. Concentration (apart -from that to Glover acid in the Glover tower) is effected by evaporation -in lead pans to 140° Tw. and finally in glass balloons or platinum stills -to 168° Tw. (= 97 %). The lead pans are generally heated by utilising the -waste heat from the furnaces or by steam coils in the acid itself, or -even by direct firing. - -Production of sulphuric acid by the _contact method_ depends on the fact -that a mixture of sulphur dioxide and excess of oxygen (air) combines -to form sulphur trioxide at a moderate heat in presence of a contact -substance such as platinised asbestos or oxide of iron. The sulphur -dioxide must be carefully cleaned and dried, and with the excess of air -is passed through the contact substance. If asbestos carrying a small -percentage of finely divided platinum is the contact substance, it is -generally used in the form of pipes; oxide of iron (the residue of -pyrites), if used, is charged into a furnace. Cooling by a coil of pipes -and condensation in washing towers supplied with concentrated sulphuric -acid always forms a part of the process. A fan draws the gases from the -roasting furnaces and drives them through the system. The end product -is a fuming sulphuric acid containing 20-30 per cent. SO₃. From this by -distillation a concentrated acid and a pure anhydride are obtained. From -a health point of view it is of importance to know that all sulphuric -acid derived from this anhydride is pure and free from arsenic. - -The most important _uses_ of sulphuric acid are the following: as chamber -acid (110°-120° Tw.) in the superphosphate, ammonium sulphate, and alum -industries; as Glover acid (140°-150° Tw.) in the Leblanc process, i.e. -saltcake and manufacture of hydrochloric acid, and to etch metals; as -sulphuric acid of 168° Tw. in colour and explosives manufacture (nitric -acid, nitro-benzene, nitro-glycerine, gun-cotton, &c.); as concentrated -sulphuric acid and anhydride for the production of organic sulphonic -acids (for the alizarin and naphthol industry) and in the refining of -petroleum and other oils. Completely de-arsenicated sulphuric acid -is used in making starch, sugar, pharmaceutical preparations, and in -electrical accumulator manufacture. - -EFFECTS ON HEALTH.—The health of sulphuric acid workers cannot in general -be described as unfavourable. - -In comparison with chemical workers they have, it is said, relatively -the lowest morbidity. Although in this industrial occupation no -special factors are at work which injure in general the health of the -workers, there is a characteristic effect, without doubt due to the -occupation—namely, disease of the respiratory organs. Leymann’s figures -are sufficiently large to show that the number of cases of diseases -of the respiratory organs is decidedly greater in the sulphuric acid -industry than among other chemical workers. He attributes this to the -irritating and corrosive effect of sulphur dioxide and sulphuric acid -vapour on the mucous membrane of the respiratory tract, as inhalation -of these gases can never be quite avoided, because the draught in the -furnace and chamber system varies, and the working is not always uniform. -Strongly irritating vapours escape again in making a high percentage -acid in platinum vessels, which in consequence are difficult to keep -air-tight. Of greater importance than these injurious effects from -frequent inhalation of small quantities of acid vapours, or employment -in workrooms in which the air is slightly charged with acid, is the -accidental sudden inhalation of large quantities of acid gases, which may -arise in the manufacture, especially by careless attendance. Formerly -this was common in charging the roasting furnaces when the draught in the -furnace, on addition of the pyrites, was not strengthened at the same -time. This can be easily avoided by artificial regulation of the draught. - -Accidents through inhalation of acid gases occur further when entering -the lead chambers or acid tanks, and in emptying the towers. Heinzerling -relates several cases taken from factory inspectors’ reports. Thus, in a -sulphuric acid factory the deposit (lead oxysulphate) which had collected -on the floor of a chamber was being removed: to effect this the lead -chambers were opened at the side. Two of the workers, who had probably -been exposed too long to the acid vapours evolved in stirring up the -deposit, died a short time after they had finished the work. A similar -fatality occurred in cleaning out a nitro-sulphuric acid tank, the -required neutralisation of the acid by lime before entering having been -omitted. Of the two workers who entered, one died the next day; the other -remained unaffected. The deceased had, as the post mortem showed, already -suffered previously from pleurisy. A fatality from breathing nitrous -fumes is described fully in the report of the Union of Chemical Industry -for the year 1905. The worker was engaged with two others in fixing a fan -to a lead chamber; the workers omitted to wait for the arrival of the -foreman who was to have supervised the operation. Although the men used -moist sponges as respirators, one of them inhaled nitrous fumes escaping -from the chamber in such quantity that he died the following day. - -Similar accidents have occurred in cleaning out the Gay-Lussac towers. -Such poisonings have repeatedly occurred in Germany. Fatal poisoning is -recorded in the report of the Union of Chemical Industry, in the emptying -and cleaning of a Gay-Lussac tower despite careful precautions. The -tower, filled with coke, had been previously well washed with water, and -during the operation of emptying, air had been constantly blown through -by means of a Körting’s injector. The affected worker had been in the -tower about an hour; two hours later symptoms of poisoning set in which -proved fatal in an hour despite immediate medical attention. As such -accidents kept on recurring, the Union of Chemical Industry drew up -special precautions to be adopted in the emptying of these towers, which -are printed in Part III. - -Naturally, in all these cases it is difficult to say exactly which of the -acid gases arising in the production of sulphuric acid was responsible -for the poisoning. In the fatal cases cited, probably nitrous fumes -played the more important part. - -Poisoning has occurred in the transport of sulphuric acid. In some of -the cases, at all events, gaseous impurities, especially arseniuretted -hydrogen, were present. - -Thus, in the reports of the German Union of Chemical Industry for the -year 1901, a worker succumbed through inhalation of poisonous gases in -cleaning out a tank waggon for the transport of sulphuric acid. The tank -was cleaned of the adhering mud, as had been the custom for years, by a -man who climbed into it. No injurious effects had been noted previously -at the work, and no further precautions were taken than that one worker -relieved another at short intervals, and the work was carried on under -supervision. On the occasion in question, however, there was an unusually -large quantity of deposit, although the quality of the sulphuric acid was -the same, and work had to be continued longer. The worker who remained -longest in the tank became ill on his way home and died in hospital -the following day; the other workers were only slightly affected. The -sulphuric acid used by the firm in question immediately before the -accident came from a newly built factory in which anhydrous sulphuric -acid had been prepared by a special process. The acid was Glover acid, -and it is possible that selenium and arsenic compounds were present -in the residues. Arseniuretted hydrogen might have been generated in -digging up the mud. Two similar fatalities are described in the report of -the same Union for the year 1905. They happened similarly in cleaning out -a sulphuric acid tank waggon, and in them the arsenic in the acid was the -cause. Preliminary swilling out with water diluted the remainder of the -sulphuric acid, but, nevertheless, it acted on the iron of the container. -Generation of hydrogen gas is the condition for the reduction of the -arsenious acid present in sulphuric acid with formation of arseniuretted -hydrogen. In portions of the viscera arsenic was found. Lately in the -annual reports of the Union of Chemical Industry for 1908 several cases -of poisoning are described which were caused by sulphuric acid. A worker -took a sample out of a vessel of sulphuric acid containing sulphuretted -hydrogen gas. Instead of using the prescribed cock, he opened the -man-hole and put his head inside, inhaling concentrated sulphuretted -hydrogen gas. He became immediately unconscious and died. Through -ignorance no use was made of the oxygen apparatus. - -Another fatality occurred through a foreman directing some workers, -contrary to the regulations against accidents from nitrous gases, to -clean a vessel containing nitric and sulphuric acids. They wore no air -helmets: one died shortly after from inhalation of nitrous fumes. Under -certain circumstances even the breaking of carboys filled with sulphuric -acid may give rise to severe poisoning through inhalation of acid gases. -Thus a fatality[1] occurred to the occupier of a workroom next some -premises in which sulphuric acid carboys had been accidentally broken. -Severe symptoms developed the same night, and he succumbed the next -morning in spite of treatment with oxygen. A worker in the factory became -seriously ill but recovered. - -A similar case is described[2] in a factory where concentrated sulphuric -acid had been spilt. The workers covered the spot with shavings, -which resulted in strong development of sulphur dioxide, leading to -unconsciousness in one worker. - -The frequent observation of the injurious effect of acid gases on the -teeth of workers requires mention; inflammation of the eyes of workers -also is attributed to the effects of sulphuric acid. - -Leymann’s statistics show _corrosions and burns_ among sulphuric acid -workers to be more than five times that among other classes. Such burns -happen most frequently from carelessness. Thus, in the reports of the -Union of Chemical Industry for 1901, three severe accidents are mentioned -which occurred from use of compressed air. In two cases the acid had been -introduced before the compressed air had been turned off; in the third -the worker let the compressed air into the vessel and forgot to turn off -the inlet valve. Although the valves were provided with lead guards, -some of the acid squirted into the worker’s face. In one case complete -blindness followed, in a second blindness in one eye, and in the third -blindness in one eye and impaired vision of the other. - -Besides these dangers from the raw material, bye-products, and products -of the manufacture, _lead poisoning_ has been reported in the erection -and repair of lead chambers. The lead burners generally use a hydrogen -flame; the necessary hydrogen is usually made from zinc and sulphuric -acid and is led to the iron by a tube. If the zinc and sulphuric acid -contain arsenic, the very dangerous arseniuretted hydrogen is formed, -which escapes through leakages in the piping, or is burnt in the flame to -arsenious acid. - -Further, the lead burners and plumbers are exposed to the danger of -chronic lead poisoning from insufficient observance of the personal -precautionary measures necessary to guard against it (see Part III). -Those who are constantly engaged in burning the lead sheets and pipes of -the chambers suffer not infrequently from severe symptoms. Unfortunately, -the work requires skill and experience, and hence alternation of -employment is hardly possible. - -Finally, mention should be made of poisoning by _arseniuretted hydrogen -gas_ from vessels filled with sulphuric acid containing arsenic as an -impurity, and by sulphuretted hydrogen gas in purifying the acid itself. -In the manufacture of liquid _sulphur dioxide_, injury to health can -arise from inhalation of the acid escaping from the apparatus. The most -frequent cause for such escape of sulphur dioxide is erosion of the walls -of the compressor pumps and of the transport vessels, in consequence of -the gas being insufficiently dried, as, when moist, it attacks iron. - -Sulphur dioxide will come up for further consideration when describing -the industrial processes giving rise to it, or in which it is used. - - -HYDROCHLORIC ACID, SALTCAKE, AND SODA - -MANUFACTURE.—The production of hydrochloric acid (HCl), sodium sulphate -(Na₂SO₄), and sodium sulphide (Na₂S) forms part of the manufacture of -soda (Na₂CO₃) by the Leblanc process. The products first named increase -in importance, while the Leblanc soda process is being replaced more and -more by the manufacture of soda by the Solvay ammonia process, so much so -that on the Continent the latter method predominates and only in England -does the Leblanc process hold its ground. - -Health interests have exercised an important bearing on the development -of the industries in question. At first, in the Leblanc process the -hydrochloric acid gas was allowed to escape into the atmosphere, being -regarded as a useless bye-product. Its destructive action on plant -life and the inconvenience caused to the neighbourhood, in spite of -erection of high chimneys, demanded intervention. In England the evils -led to the enactment of the Alkali Acts—the oldest classical legislative -measures bearing on factory hygiene—by which the Leblanc factories were -required to condense the vapour by means of its absorption in water, and -this solution of the acid is now a highly valued product. And, again, -production of nuisance—inconvenience to the neighbourhood through the -soda waste—was the main cause of ousting one of the oldest and most -generally used methods of chemical industrial production. Although every -effort was made to overcome the difficulties, the old classical Leblanc -process is gradually but surely yielding place to the modern Solvay -process, which has no drawback on grounds of health. - -We outline next the main features of the _Leblanc soda process_, which -includes, as has been mentioned, also the manufacture of hydrochloric -acid, sodium sulphate and sulphide. - -The first part of the process consists in the production of the sulphate -from salt and sulphuric acid, during which hydrochloric acid is formed; -this is carried out in two stages represented in the following formulæ: - - 1. NaCl + H₂SO₄ = NaHSO₄ + HCl. - 2. NaCl + NaHSO₄ = Na₂SO₄ + HCl. - -The first stage in which bisulphate is produced is carried out at a -moderate heat, the second requires a red heat. The reactions, therefore, -are made in a furnace combining a pan and muffle furnace. - -This saltcake muffle furnace is so arranged that the pan can be shut -off from the muffle by a sliding-door (D). The pan (A) and muffle (E) -have separate flues for carrying off the hydrochloric acid developed (B, -F). First, common salt is treated with sulphuric (Glover) acid in the -cast-iron pan. When generation of hydrochloric acid vapour has ceased, -the sliding-door is raised and the partly decomposed mixture is pushed -through into the muffle, constructed of fire-resisting bricks and tiles, -and surrounded by the fire gases. While the muffle is being raised to -red heat, the sulphate must be repeatedly stirred with a rake in order, -finally, while still hot and giving off acid vapour, to be drawn out at -the working doors into iron boxes provided with doors, where the material -cools. The acid vapour given off when cooling is drawn through the top of -the box into the furnace. - -[Illustration: FIG. 3.—Saltcake Muffle Furnace—Section _(after Ost_) - -A Pan; B, F Pipes for hydrochloric acid vapour; D Shutter; E Muffle, O -Coke fire.] - -Mechanical stirrers, despite their advantage from a health point of view, -have not answered because of their short life. - -The valuable bye-product of the sulphate process, _hydrochloric acid_, is -led away separately from the pan and the muffle, as is seen, into one -absorption system. The reason of the separation is that the gas from the -pan is always the more concentrated. The arrangement of the absorbing -apparatus is illustrated in fig. 4. - -[Illustration: FIG. 4A.—Preparation of Hydrochloric Acid—Plan (_after -Lueger_) - - A, A´ Earthenware pipes - B, B´ Sandstone cooling towers - C, C Series of Woulff’s bottles - D, E Condenser wash towers - -FIG. 4B.—Elevation] - -The gases are led each through earthenware pipes or channels of stone -pickled with tar (A´), first into small towers of Yorkshire flags (B), -where they are cooled and freed from flue dust and impurities (sulphuric -acid) by washing. They are next led through a series (over fifty) of -Woulff bottles (bombonnes) one metre high, made of acid-resisting -stoneware. The series is laid with a slight inclination towards the -furnace, and water trickles through so that the gases coming from the -wash towers are brought into contact with water in the one case already -almost saturated, whilst the gas which is poorest in hydrochloric acid -meets with fresh water. From the bombonne situated next to the wash tower -the prepared acid is passed as a rule through another series. The last -traces of hydrochloric acid are then removed by leading the gases from -the Woulff bottles up two water towers of stoneware (D and E), which are -filled partly with earthenware trays and partly with coke; above are -tanks from which the water trickles down over the coke. The residual -gases from both sets of absorbing apparatus now unite in a large Woulff -bottle before finally being led away through a duct to the chimney stack. - -Less frequently absorption of hydrochloric acid is effected without use -of Woulff bottles, principally in wash towers such as the Lunge-Rohrmann -plate tower. - -In the purification of hydrochloric acid, de-arsenicating by sulphuretted -hydrogen or by barium sulphide, &c., and separation of sulphuric acid by -addition of barium chloride, have to be considered. - -Another method for production of sulphate and hydrochloric acid, namely, -the Hargreaves process, is referred to later. - -We return now to the further working up of the sodium sulphate into -sulphide and soda. The conversion of the sulphate into soda by the -Leblanc method is effected by heating with coal and calcium carbonate, -whereby, through the action of the coal, sodium sulphide forms first, -which next with the calcium carbonate becomes converted into sodium -carbonate and calcium sulphide. - -The reactions are: - - Na₂SO₄ + 2C = Na₂S + 2CO₂ - Na₂S + CaCO₃ = Na₂CO₃ + CaS - CaCO₃ + C = CaO + 2CO. - -The reactions are carried out in small works in open reverberatory -furnaces having two platforms on the hearth, and with continuous raking -from one to the other which, as the equations show, cause escape of -carbonic acid gas and carbonic oxide. - -Such handworked furnaces, apart from their drawbacks on health grounds, -have only a small capacity, and in large works their place is taken by -revolving furnaces—closed, movable cylindrical furnaces—in which handwork -is replaced by the mechanical revolution of the furnace and from which a -considerably larger output and a product throughout good in quality are -obtained. - -The _raw soda_ thus obtained in the black ash furnace is subjected to -lixiviation by water in iron tanks in which the impurities or tank -waste (see below) are deposited. The crude soda liquor so obtained is -then further treated and converted into calcined soda, crystal soda, or -caustic soda. In the production of calcined soda the crude soda liquor is -first purified (‘oxidised’ and ‘carbonised’) by blowing through air and -carbonic acid gas, pressed through a filter press, and crystallised by -evaporation in pans and calcined, i.e. deprived of water by heat. - -[Illustration: FIG. 5.—Revolving Black Ash Furnace—Elevation (_after -Lueger_) - -A Firing hearth; B Furnace; C Dust box.] - -_Crystal soda_ is obtained from well-purified tank liquor by -crystallising in cast-iron vessels. - -Caustic soda is obtained by introducing lime suspended in iron cages into -the soda liquor in iron caustic pots, heating with steam, and agitating -by blowing in air. - -The resulting clear solution is drawn off and evaporated in cast-iron -pans. - -As already mentioned, the _tank waste_ in the Leblanc process, which -remains behind—in amount about equal to the soda produced after -lixiviation of the raw soda with water—constitutes a great nuisance. -It forms mountains round the factories, and as it consists principally -of calcium sulphide and calcium carbonate, it easily weathers under -the influence of air and rain, forming soluble sulphur compounds and -developing sulphuretted hydrogen gas—an intolerable source of annoyance -to the district. - -At the same time all the sulphur introduced into the industry as -sulphuric acid is lost in the tank waste. This loss of valuable material -and the nuisance created led to attempts—partially successful—to recover -the sulphur. - -The best results are obtained by the Chance-Claus method, in which the -firebrick ‘Claus-kiln’ containing ferric oxide (previously heated to -dull redness) is used. In this process calcium sulphide is acted on by -carbonic acid with evolution of gas so rich in sulphuretted hydrogen that -it can be burnt to sulphur dioxide and used in the lead chambers for -making sulphuric acid. Sulphur also as such is obtained by the method. - -These sulphur-recovery processes which have hardly been tried on -the Continent—only the United Alkali Company in England employs the -Chance-Claus on a large scale—were, as has been said, not in a position -to prevent the downfall of the Leblanc soda industry. Before describing -briefly the Solvay method a word is needed as to other processes for -manufacture of sulphate and hydrochloric acid. - -_Hargreaves’ process_ produces sodium sulphate (without previous -conversion of sulphur dioxide into sulphuric acid) directly by the -passage of gases from the pyrites burners, air and steam, through salt -blocks placed in vertical cast-iron retorts, a number of which are -connected in series. A fan draws the gases through the system and leads -the hydrochloric acid fumes to the condenser. - -Sodium sulphate is used in the manufacture of glass, ultramarine, &c. -Further, the sulphate is converted into Glauber’s salts by dissolving the -anhydrous sulphate obtained in the muffle furnace, purifying with lime, -and allowing the clear salt solution to crystallise out in pans. - -A further use of the sulphate is the preparation of sodium sulphide, -which is effected (as in the first part of the Leblanc soda process) by -melting together sulphate and coal in a reverberatory furnace. If the -acid sulphate (bisulphate) or sulphate containing bisulphate is used much -sulphur dioxide gas comes off. - -The mass is then lixiviated in the usual soda liquor vats and the lye -either treated so as to obtain crystals or evaporated to strong sodium -sulphide which is poured like caustic soda into metal drums where it -solidifies. - -In _Solvay’s ammonia soda process_ ammonia recovered from the waste -produced in the industry is led into a solution of salt until saturation -is complete. This is effected generally in column apparatus such as is -used in distillation of spirit. The solution is then driven automatically -by compressed air to the carbonising apparatus in which the solution -is saturated with carbonic acid; this apparatus is a cylindrical tower -somewhat similar to the series of vessels used for saturating purposes in -sugar factories through which carbonic acid gas passes. In this process -crystalline bi-carbonate of soda is first formed, which is separated -from the ammoniacal mother liquor by filtration, centrifugalisation, -and washing. The carbonate is then obtained by heating (calcining in -pans), during which carbonic acid gas escapes, and this, together with -the carbonic acid produced in the lime kilns, is utilised for further -carbonisation again. The lime formed during the production of carbonic -acid in the lime kilns serves to drive the ammonia out of the ammoniacal -mother liquor, so that the ammonia necessary for the process is recovered -and used over and over again. The waste which results from the action of -the lime on the ammonium chloride liquor is harmless—calcium chloride -liquor. - -The _electrolytic_ manufacture of soda from salt requires mention, in -which chlorine (at the anode) and caustic soda (at the cathode) are -formed; the latter is treated with carbonic acid to make soda. - -EFFECTS ON HEALTH.—Leymann’s observations show that in the department -concerned with the Leblanc soda process and production of sodium -sulphide, relatively more sickness is noted than, for example, in the -manufacture of sulphuric and nitric acids. - -In the preparation of the sulphate, possibility of injury to health or -poisoning arises from the fumes containing hydrochloric or sulphuric acid -in operations at the muffle furnace; in Hargreaves’ process there may be -exposure to the effect of sulphur dioxide. Hydrochloric and sulphuric -acid vapours can escape from the muffle furnace when charging, from -leakages in it, and especially when withdrawing the still hot sulphate. -Large quantities of acid vapours escape from the glowing mass, especially -if coal is not added freely and if it is not strongly calcined. Persons -employed at the saltcake furnaces suffer, according to Jurisch, apart -from injury to the lungs, from defective teeth. The teeth of English -workers especially, it is said, from the practice of holding flannel in -their mouths with the idea of protecting themselves from the effect of -the vapours, are almost entirely eroded by the action of the hydrochloric -acid absorbed by the saliva. Hydrochloric acid vapour, further, can -escape from the absorbing apparatus if this is not kept entirely -sealed, and the hydrochloric acid altogether absorbed—a difficult -matter. Nevertheless, definite acute industrial poisoning from gaseous -hydrochloric acid is rare, no doubt because the workers do not inhale it -in concentrated form. - -Injury to the skin from the acid absorbed in water may occur in filling, -unloading, and transport, especially when in carboys, but the burns, -if immediately washed, are very slight in comparison with those from -sulphuric or nitric acids. Injury to health or inconvenience from -sulphuretted hydrogen is at all events possible in the de-arsenicating -process by means of sulphuretted hydrogen gas. At the saltcake furnace -when worked by hand the fumes containing carbonic oxide gas may be -troublesome. In the production of caustic soda severe corrosive action on -the skin is frequent. Leymann found that 13·8 per cent. of the persons -employed in the caustic soda department were reported as suffering from -burns, and calls attention to the fact that on introducing the lime -into the hot soda lye the contents of the vessel may easily froth over. -Heinzerling refers to the not infrequent occurrence of eye injuries in -the preparation of caustic soda, due to the spurting of lye or of solid -particles of caustic soda. - -The tank waste gives rise, as already stated, to inconvenience from the -presence of sulphuretted hydrogen. In the recovery of the sulphur and -treatment of the tank waste, sulphuretted hydrogen and sulphur dioxide -gases are evolved. According to Leymann, workers employed in removing -the waste and at the lye vats frequently suffer from inflammation of -the eyes. Further, disturbance of digestion has been noted in persons -treating the tank waste, which Leymann attributes to the unavoidable -development of sulphuretted hydrogen gas. - -In the manufacture of sodium sulphide similar conditions prevail. Leymann -found in this branch relatively more cases of sickness than in any other; -diseases of the digestive tract especially appeared to be more numerous. -Leymann makes the suggestion that occurrence of disease of the digestive -organs is either favoured by sodium sulphide when swallowed as dust, or -that here again sulphuretted hydrogen gas plays a part. Further corrosive -effect on the skin and burns may easily arise at work with the hot -corrosive liquor. - -In the Solvay ammonia process ammonia and carbonic acid gas are present, -but, so far as I know, neither injury to health nor poisoning have been -described among persons employed in the process. Indeed, the view is -unanimous that this method of manufacture with its technical advantages -has the merit also of being quite harmless. As may be seen from the -preceding description of the process there is no chance of the escape of -the gases named into the workrooms. - - -USE OF SULPHATE AND SULPHIDE - -_Ultramarine_ is made from a mixture of clay, sulphate (Glauber’s -salts), and carbon—sulphate ultramarine; or clay, sulphur, and -soda—soda ultramarine. These materials are crushed, ground, and burnt -in muffle furnaces. On heating the mass in the furnace much sulphur -dioxide escapes, which is a source of detriment to the workmen and the -neighbourhood. - -_Sulphonal_ (CH₃)₂C(SO₂C₂H₅)₂, diethylsulphone dimethylmethane, -used medically as a hypnotic, is obtained from mercaptan formed by -distillation of ethyl sulphuric acid with sodium or potassium sulphide. -The mercaptan is converted into mercaptol, and this by oxidation with -potassium permanganate into sulphonal. The volatile mercaptan has a most -disgusting odour, and clings for a long time even to the clothes of those -merely passing through the room. - -_Diethyl sulphate_ ((C₂H₅)₂SO₄).—Diethyl sulphate obtained by the -action of sulphuric acid on alcohol has led to poisoning characterised -by corrosive action on the respiratory tract.[1] As the substance in -the presence of water splits up into sulphuric acid and alcohol, this -corrosive action is probably due to the acid. It is possible, however, -that the molecule of diethyl sulphate as such has corrosive action. - -Contact with diethyl sulphate is described as having led to fatal -poisoning.[2] - -A chemist when conducting a laboratory experiment dropped a glass flask -containing about 40 c.c. of diethyl sulphate, thereby spilling some over -his clothes. He went on working, and noticed burns after some time, -quickly followed by hoarseness and pain in the throat. He died of severe -inflammation of the lungs. A worker in another factory was dropping -diethyl sulphate and stirring it into an at first solid, and later -semi-liquid, mass for the purpose of ethylating a dye stuff. In doing -so he was exposed to fumes, and at the end of the work complained of -hoarseness and smarting of the eyes. He died of double pneumonia two days -later. Post mortem very severe corrosive action on the respiratory tract -was found, showing that the diethyl sulphuric acid had decomposed inside -the body and that nascent sulphuric acid had given rise to the severe -burns. The principal chemist who had superintended the process suffered -severely from hoarseness at night, but no serious consequences followed. - -It is stated also that workmen in chemical factories coming into contact -with the fumes of diethyl sulphate ester suffer from eye affections.[3] - - -CHLORINE, CHLORIDE OF CALCIUM, AND CHLORATES - -MANUFACTURE.—The older processes depend on the preparation of chlorine -and hydrochloric acid by an oxidation process in which the oxidising -agent is either a compound rich in oxygen—usually common manganese -dioxide (pyrolusite)—or the oxygen of the air in the presence of heated -copper chloride (as catalytic agent). The former (Weldon process) is -less used now than either the latter (Deacon process) or the electrolytic -manufacture of chlorine. - -In the _Weldon process_ from the still liquors containing manganous -chloride the manganese peroxide is regenerated, and this so regenerated -Weldon mud, when mixed with fresh manganese dioxide, is used to initiate -the process. This is carried out according to the equations: - - MnO₂ + 4HCl = MnCl₄ + 2H₂O - MnCl₄ = MnCl₂ + Cl₂. - -[Illustration: FIG. 6.—Preparation of Chlorine—Diaphragm Method (_after -Ost_)] - -Hydrochloric acid is first introduced into the chlorine still (vessels -about 3 m. in height, of Yorkshire flag or fireclay), next the Weldon -mud gradually, and finally steam to bring the whole to boiling; chlorine -comes off in a uniform stream. The manganous chloride still liquor is run -into settling tanks. The regeneration of the manganous chloride liquor -takes place in an oxidiser which consists of a vertical iron cylinder in -which air is blown into the heated mixture of manganous chloride and milk -of lime. The dark precipitate so formed, ‘Weldon mud,’ as described, is -used over again, while the calcium chloride liquor runs away. - -The _Deacon process_ depends mainly on leading the stream of hydrochloric -acid gas evolved from a saltcake pot mixed with air and heated into a -tower containing broken bricks of the size of a nut saturated with -copper chloride. Chlorine is evolved according to the equation: - - 2HCl + O = 2Cl + H₂O. - -[Illustration: FIG. 7.—Preparation of Chlorine—Bell Method (_after Ost_)] - -The _electrolytic production_ of chlorine with simultaneous production -of _caustic alkali_ is increasing and depends on the splitting up of -alkaline chlorides by a current of electricity. The chlorine evolved at -the anode and the alkaline liquor formed at the cathode must be kept -apart to prevent secondary formation of hypochlorite and chlorate (see -below). This separation is generally effected in one of three ways: (1) -In the diaphragm process (Griesheim-Elektron chemical works) the anode -and cathode are kept separate by porous earthenware diaphragms arranged -as illustrated in fig. 6. The anode consists of gas carbon, or is made -by pressing and firing a mixture of charcoal and tar; it lies inside the -diaphragm. The chlorine developed in the anodal cell is carried away by -a pipe. The metal vessel serves as the cathode. The alkali, which, since -it contains chloride, is recovered as caustic soda after evaporation -and crystallisation, collects in the cathodal space lying outside the -diaphragm. (2) By the Bell method (chemical factory at Aussig) the -anodal and cathodal fluids, which keep apart by their different specific -weights, are separated by a stoneware bell; the poles consist of sheet -iron and carbon. The containing vessel is of stoneware. (3) In the -mercury process (England) sodium chloride is electrolysed without a -diaphragm, mercury serving as the cathode. This takes up the sodium, -which is afterwards recovered from the amalgam formed by means of water. - -If _chlorate_ or _hypochlorite_ is to be obtained electrolytically, -electrodes of the very resistant but expensive platinum iridium are used -without a diaphragm. Chlorine is developed—not free, but combined with -the caustic potash. The bleaching fluid obtained electrolytically in this -way is a rival of bleaching powder. - -_Bleaching powder_ is made from chlorine obtained by the Weldon or Deacon -process. Its preparation depends on the fact that calcium hydrate takes -up chlorine in the cold with formation of calcium hypochlorite after the -equation: - - 2Ca(OH)₂ + 4Cl = Ca(ClO)₂ + CaCl₂ + 2H₂O. - -The resulting product contains from 35 to 36 per cent. chlorine, which is -given off again when treated with acids. - -The preparation of chloride of lime takes place in bleaching powder -chambers made of sheets of lead and Yorkshire flagstones. The lime is -spread out on the floors of these and chlorine introduced. Before the -process is complete the lime must be turned occasionally. - -In the manufacture of bleaching powder from Deacon chlorine, Hasenclever -has constructed a special cylindrical apparatus (fig. 8), consisting of -several superimposed cast-iron cylinders in which are worm arrangements -carrying the lime along, while chlorine gas passes over in an opposite -direction. This continuous process is, however, only possible for the -Deacon chlorine strongly diluted with nitrogen and oxygen and not for -undiluted Weldon gas. - -_Liquid chlorine_ can be obtained by pressure and cooling from -concentrated almost pure Weldon chlorine gas. - -_Potassium chlorate_, which, as has been said, is now mostly obtained -electrolytically, was formerly obtained by passing Deacon chlorine into -milk of lime and decomposing the calcium chlorate formed by potassium -chloride. - -Chlorine and chloride of lime are used for bleaching; chlorine further -is used in the manufacture of colours; chloride of lime as a mordant in -cloth printing and in the preparation of chloroform; the chlorates are -oxidising agents and used in making safety matches. The manufacture of -organic chlorine products will be dealt with later. - -[Illustration: FIG. 8.—Preparation of Bleaching Powder. Apparatus of -Hasenclever (_after Ost_) - -A Hopper for slaked lime; W Worm conveying lime; Z Toothed wheels; -K Movable covers; C Entrance for chlorine gas; D Pipe for escape of -chlorine-free gas; B Outlet shoot for bleaching powder] - -EFFECTS ON HEALTH.—In these industries the possibility of injury to -health and poisoning by inhalation of chlorine gas is prominent. Leymann -has shown that persons employed in the manufacture of chlorine and -bleaching powder suffer from diseases of the respiratory organs 17·8 per -cent., as contrasted with 8·8 per cent. in other workers: and this is -without doubt attributable to the injurious effect of chlorine gas, which -it is hardly possible to avoid despite the fact that Leymann’s figures -refer to a model factory. But the figures show also that as the industry -became perfected the number of cases of sickness steadily diminished. - -Most cases occur from unsatisfactory conditions in the production of -chloride of lime, especially if the chloride of lime chambers leak, if -the lime is turned over while the chlorine is being let in, by too early -entrance into chambers insufficiently ventilated, and by careless and -unsuitable methods of emptying the finished bleaching powder. - -The possibility of injury is naturally greater from the concentrated gas -prepared by the Weldon process than from the diluted gas of the Deacon -process—the more so as in the latter the bleaching powder is made in -the Hasenclever closed-in cylindrical apparatus in which the chlorine -is completely taken up by the lime. The safest process of all is the -electrolytic, as, if properly arranged, there should be no escape of -chlorine gas. The chlorine developed in the cells (when carried out on -the large scale) is drawn away by fans and conducted in closed pipes to -the place where it is used. - -Many researches have been published as to the character of the skin -affection well known under the name of _chlorine rash_ (chlorakne). -Some maintain that it is not due to chlorine at all, but is an eczema -set up by tar. Others maintain that it is due to a combined action of -chlorine and tar. Support to this view is given by the observation that -cases of chlorine rash, formerly of constant occurrence in a factory -for electrolytic manufacture of chlorine, disappeared entirely on -substitution of magnetite at the anode for carbon.[1] The conclusion -seems justified that the constituents of the carbon or of the surrounding -material set up the condition. - -Chlorine rash has been observed in an alkali works where chlorine was -not produced electrolytically, and under conditions which suggested that -compounds of tar and chlorine were the cause. In this factory for the -production of salt cake by the Hargreaves’ process cakes of rock salt -were prepared and, for the purpose of drying, conveyed on an endless -metal band through a stove. To prevent formation of crusts the band -was tarred. The salt blocks are decomposed in the usual way by sulphur -dioxide, steam, and oxygen of the air, and the hydrochloric acid vapour -led through Deacon towers in which the decomposition of the hydrochloric -acid into chlorine and water is effected by metal salts in the manner -characteristic of the Deacon process. These salts are introduced in small -earthenware trays which periodically have to be removed and renewed; -the persons engaged in doing this were those affected. The explanation -was probably that the tar sticking to the salt blocks distilled in the -saltcake furnaces and formed a compound with the chlorine which condensed -on the earthenware trays. When contact with these trays was recognised as -the cause, the danger was met by observance of the greatest cleanliness -in opening and emptying the Deacon towers. - -Leymann[2] is certain that the rash is due to chlorinated products which -emanate from the tar used in the construction of the cells. And the -affection has been found to be much more prevalent when the contents of -the cells are emptied while the contents are still hot than when they are -first allowed to get cold. - -Lehmann[3] has approached the subject on the experimental side, and is of -opinion that probably chlorinated tar derivatives (chlorinated phenols) -are the cause of the trouble. Both he and Roth think that the affection -is due not to external irritation of the skin, but to absorption of the -poisonous substances into the system and their elimination by way of the -glands of the skin. - -In the section on manganese poisoning detailed reference is made to the -form of illness recently described in persons employed in drying the -regenerated Weldon mud. - -Mercurial poisoning is possible when mercury is used in the production of -chlorine electrolytically. - -In the manufacture of chlorates and hypochlorite, bleaching fluids, &c., -injury to health from chlorine is possible in the same way as has been -described above. - - -OTHER CHLORINE COMPOUNDS. BROMINE, IODINE, AND FLUORINE - -Chlorine is used for the production of a number of organic chlorine -compounds, and in the manufacture of bromine and iodine, processes -which give rise to the possibility of injury to health and poisoning by -chlorine; further, several of the substances so prepared are themselves -corrosive or irritating or otherwise poisonous. Nevertheless, severe -poisoning and injurious effects can be almost entirely avoided by -adoption of suitable precautions. In the factory to which Leymann’s -figures refer, where daily several thousand kilos of chlorine and organic -chlorine compounds are prepared, a relatively very favourable state of -health of the persons employed was noted. At all events the preparation -of chlorine by the electrolytic process takes place in closed vessels -admirably adapted to avoid any escape of chlorine gas except as the -result of breakage of the apparatus or pipes. When this happens, however, -the pipes conducting the gas can be immediately disconnected and the -chlorine led into other apparatus or into the bleaching powder factory. - -As such complete precautionary arrangements are not everywhere to be -found, we describe briefly the most important of the industries in -question and the poisoning recognised in them. - -_Chlorides of phosphorus._—By the action of dry chlorine on an excess -of heated amorphous phosphorus, trichloride is formed (PCl₃), a -liquid having a sharp smell and causing lachrymation, which fumes -in the air, and in presence of water decomposes into phosphorous -acid and hydrochloric acid. On heating with dry oxidising substances -it forms phosphorus oxychloride (see below), which is used for the -production of acid chlorides. By continuous treatment with chlorine -it becomes converted into phosphorus pentachloride (PCl₅), which also -is conveniently prepared by passing chlorine through a solution of -phosphorus in carbon bisulphide, the solution being kept cold; it is -crystalline, smells strongly, and attacks the eyes and lungs. With excess -of water it decomposes into phosphoric acid and hydrochloric acid: -with slight addition of water it forms phosphorus oxychloride (POCl₃). -On the large scale this is prepared by reduction of phosphate of lime -in the presence of chlorine with carbon or carbonic oxide. Phosphorus -oxychloride, a colourless liquid, fumes in the air and is decomposed by -water into phosphoric acid and hydrochloric acid. - -In the preparation of chlorides of phosphorus, apart from the danger of -chlorine gas and hydrochloric acid, the poisonous effect of phosphorus -and its compounds (see Phosphorus) and even of carbon disulphide (as -the solvent of phosphorus) and of carbonic oxide (in the preparation of -phosphorus oxychloride) have to be taken into account. - -Further, the halogen compounds of phosphorus exert irritant action on -the eyes and lungs similar to chloride of sulphur as a result of their -splitting up on the moist mucous membranes into hydrochloric acid and an -oxyacid of phosphorus.[4] - -Unless, therefore, special measures are taken, the persons employed -in the manufacture of phosphorus chlorides suffer markedly from the -injurious emanations given off.[5] - -Leymann[6] mentions one case of poisoning by phosphorus chloride as -having occurred in the factory described by him. By a defect in the -outlet arrangement phosphorus oxychloride flowed into a workroom. -Symptoms of poisoning (sensation of suffocation, difficulty of breathing, -lachrymation, &c.) at once attacked the occupants; before much gas had -escaped, the workers rushed out. Nevertheless, they suffered from severe -illness of the respiratory organs (bronchial catarrh and inflammation of -the lungs, with frothy, blood-stained expectoration, &c.).[7] - -_Chlorides of sulphur._—Monochloride of sulphur (S₂Cl₂) is made by -passing dried, washed chlorine gas into molten heated sulphur. The oily, -brown, fuming liquid thus made is distilled over into a cooled condenser -and by redistillation purified from the sulphur carried over with it. -Sulphur monochloride can take up much sulphur, and when saturated is used -in the vulcanisation of indiarubber, and, further, is used to convert -linseed and beetroot oil into a rubber substitute. Monochloride of -sulphur is decomposed by water into sulphur dioxide, hydrochloric acid, -and sulphur. By further action of chlorine on the monochloride, sulphur -dichloride (SCl₂) and the tetrachloride (SCl₄) are formed. - -In its preparation and use (see also Indiarubber Manufacture) the -injurious action of chlorine, of hydrochloric acid, and of sulphur -dioxide comes into play. - -The monochloride has very irritating effects. Leymann cites an industrial -case of poisoning by it. In the German factory inspectors’ reports for -1897 a fatal case is recorded. The shirt of a worker became saturated -with the material owing to the bursting of a bottle. First aid was -rendered by pouring water over him, thereby increasing the symptoms, -which proved fatal the next day. Thus the decomposition brought about by -water already referred to aggravated the symptoms. - -_Zinc chloride_ (ZnCl₂) is formed by heating zinc in presence of -chlorine. It is obtained pure by dissolving pure zinc in hydrochloric -acid and treating this solution with chlorine. Zinc chloride is -obtained on the large scale by dissolving furnace calamine (zinc -oxide) in hydrochloric acid. Zinc chloride is corrosive. It is used -for impregnating wood and in weighting goods. Besides possible injury -to health from chlorine and hydrogen chloride, risk of arseniuretted -hydrogen poisoning is present in the manufacture if the raw materials -contain arsenic. Eulenburg considers that in soldering oppressive zinc -chloride fumes may come off if the metal to be soldered is first wiped -with hydrochloric acid and then treated with the soldering iron. - -_Rock salt._—Mention may be made that even to salt in combination with -other chlorides (calcium chloride, magnesium chloride, &c.) injurious -effects are ascribed. Ulcers and perforation of the septum of the nose in -salt-grinders and packers who were working in a room charged with salt -dust are described.[8] These effects are similar to those produced by the -bichromates. - - -Organic Chlorine Compounds - -_Carbon oxychloride_ (COCl₂, carbonyl dichloride, phosgene) is produced -by direct combination of chlorine and carbonic oxide in presence of -animal charcoal. Phosgene is itself a very poisonous gas which, in -addition to the poisonous qualities of carbonic oxide (which have to be -borne in mind in view of the method of manufacture), acts as an irritant -of the mucous membranes. Commercially it is in solution in toluene and -xylene, from which the gas is readily driven off by heating. It is used -in the production of various colours, such as crystal violet, Victoria -blue, auramine, &c. - -A fatal case of phosgene gas poisoning in the report of the Union of -Chemical Industry for 1905 deserves mention. The phosgene was kept in a -liquefied state in iron bottles provided with a valve under 2·3 atm. -pressure. The valve of one of these bottles leaked, allowing large escape -into the workroom. Two workers tried but failed to secure the valve. The -cylinder was therefore removed by a worker, by order of the manager, -and placed in a cooling mixture, as phosgene boils at 8° C. The man in -question wore a helmet into which air was pumped from the compressed air -supply in the factory. As the helmet became obscured through moisture -after five minutes the worker took it off. A foreman next put on the -cleaned mask, and kept the cylinder surrounded with ice and salt for -three-quarters of an hour, thus stopping the escape of gas. Meanwhile, -the first worker had again entered the room, wearing a cloth soaked in -dilute alcohol before his mouth, in order to take a sack of salt to the -foreman. An hour and a half later he complained of being very ill, became -worse during the night, and died the following morning. Although the -deceased may have been extremely susceptible, the case affords sufficient -proof of the dangerous nature of the gas, which in presence of moisture -had decomposed into carbonic acid and hydrochloric acid; the latter had -acutely attacked the mucous membrane of the respiratory passages and set -up fatal bronchitis. Further, it was found that the leaden plugs of the -valves had been eroded by the phosgene. - -Three further cases of industrial phosgene poisoning have been -reported,[9] one a severe case in which there was bronchitis with -blood-stained expectoration, great dyspnœa, and weakness of the heart’s -action. The affected person was successfully treated with ether and -oxygen inhalations. Phosgene may act either as the whole molecule, or is -inhaled to such degree that the carbonic oxide element plays a part. - -In another case of industrial phosgene poisoning the symptoms were those -of severe irritation of the bronchial mucous membrane and difficulty of -breathing.[10] The case recovered, although sensitiveness of the air -passages lasted a long time. - -_Carbon chlorine compounds_ (_aliphatic series_).—_Methyl chloride_ -(CH₃Cl) or chlormethane is prepared from methyl alcohol and hydrochloric -acid (with chloride of zinc) or methyl alcohol, salt, and sulphuric acid. -It is prepared in France on a large scale from beetroot _vinasse_ by dry -distillation of the evaporation residue. The distillate, which contains -methyl alcohol, trimethylamine, and other methylated amines, is heated -with hydrochloric acid; the methyl chloride so obtained is purified, -dried and compressed. It is used in the preparation of pure chloroform, -in the coal-tar dye industry, and in surgery (as a local anæsthetic). In -the preparation of methyl chloride there is risk from methyl alcohol, -trimethylamine, &c. Methyl chloride itself is injurious to health. - -_Methylene chloride_ (CH₂Cl₂, dichlormethane) is prepared in a similar -way. It is very poisonous. - -_Carbon tetrachloride_ (CCl₄, tetrachlormethane) is technically -important. It is prepared by passing chlorine gas into carbon bisulphide -with antimony or aluminium chloride. Carbon tetrachloride is a liquid -suitable for the extraction of fat or grease (as in chemical cleaning), -and has the advantage of being non-inflammable. Carbon tetrachloride, so -far as its poisonous qualities are concerned, is to be preferred to other -extractives (see Carbon Bisulphide, Benzine, &c.); for the rest it causes -unconsciousness similar to chloroform. - -When manufactured industrially, in addition to the poisonous effect of -chlorine, the poisonous carbon bisulphide has also to be borne in mind. - -_Ethyl chloride_ (C₂H₅Cl) is made in a way analogous to methyl chloride -by the action of hydrochloric acid on ethyl alcohol and chloride of zinc. -It is used in medicine as a narcotic. - -_Monochloracetic acid._—In the preparation of monochloracetic acid -hydrochloric acid is developed in large quantity. From it and anthranilic -acid artificial indigo is prepared (according to Heuman) by means of -caustic potash. - -_Chloral_ (CCl₃CHO, trichloracetaldehyde) is produced by chlorinating -alcohol. Chloral is used in the preparation of pure chloroform and (by -addition of water) of chloral hydrate (trichloracetaldehyde hydrate), the -well-known soporific. - -_Chloroform_ (CHCl₃, trichlormethane).—Some methods for the preparation -of chloroform have been already mentioned (Chloral, Methyl Chloride). -Technically it is prepared by distillation of alcohol or acetone with -bleaching powder. The workers employed are said to be affected by the -stupefying vapours. Further, there is the risk of chlorine gas from use -of chloride of lime. - -_Chloride of nitrogen_ (NCl₃) is an oily, volatile, very explosive, -strongly smelling substance, which irritates the eyes and nose violently -and is in every respect dangerous; it is obtained from the action of -chlorine or hypochlorous acid on sal-ammoniac. The poisonous nature of -these substances may come into play. Risk of formation of chloride of -nitrogen can arise in the production of gunpowder from nitre containing -chlorine. - -_Cyanogen chloride_ (CNCl).—Cyanogen chloride is made from hydrocyanic -acid or cyanide of mercury and chlorine. Cyanogen chloride itself is an -extremely poisonous and irritating gas, and all the substances from which -it is made are also poisonous. According to Albrecht cyanogen chloride -can arise in the preparation of red prussiate of potash (by passage of -chlorine gas into a solution of the yellow prussiate) if the solution is -treated with chlorine in excess; the workers may thus be exposed to great -danger. - -_Chlorobenzene._—In his paper referred to Leymann cites three cases of -poisoning by chlorobenzene, one by dinitrochlorobenzene, and, further, -three cases of burning by chlorobenzene and one by benzoyl chloride -(C₆H₅COCl). The last named is made by treating benzaldehyde with -chlorine, and irritates severely the mucous membranes, while decomposing -into hydrochloric acid and benzoic acid.[11] Benzal chloride (C₆H₅CHCl₂), -benzo trichloride (C₆H₅CCl₃), and benzyl chloride (C₆H₅CH₂Cl) are -obtained by action of chlorine on boiling toluene. The vapours of these -volatile products irritate the respiratory passages. In the manufacture -there is risk from the effect of chlorine gas and toluene vapour (see -Benzene, Toluene). - -Leymann[12] describes in detail six cases of poisoning in persons -employed in a chlorobenzene industry, of which two were due to -nitrochlorobenzene. Symptoms of poisoning—headache, cyanosis, fainting, -&c.—were noted in a person working for three weeks with chlorobenzene.[13] - -In Lehmann’s opinion chlorine rash, the well-recognised skin affection -of chlorine workers, may be due to contact with substances of the -chlorbenzol group.[14] - -_Iodine and iodine compounds._—Formerly iodine was obtained almost -exclusively from the liquor formed by lixiviation of the ash of seaweed -(kelp, &c.); now the principal sources are the mother liquors from -Chili saltpetre and other salt industries. From the concentrated liquor -the iodine is set free by means of chlorine or oxidising substances -and purified by distillation and sublimation. Iodine is used for the -preparation of photographic and pharmaceutical preparations, especially -iodoform (tri-iodomethane, CHI₃), which is made by acting with iodine and -caustic potash on alcohol, aldehyde, acetone, &c. - -Apart from possible injurious action of chlorine when used in the -preparation of iodine, workers are exposed to the possibility of chronic -iodine poisoning. According to Ascher[15] irritation effects, nervous -symptoms, and gastric ulceration occur in iodine manufacture and use. -He considers that bromide of iodine used in photography produces these -irritating effects most markedly. Layet and also Chevallier in older -literature have made the same observations. - -The Swiss Factory Inspectors’ Report for 1890-1 describes two acute -cases of iodine poisoning in a factory where organic iodine compounds -were made; one terminated fatally (severe cerebral symptoms, giddiness, -diplopia, and collapse). - -_Bromine and bromine compounds._—Bromine is obtained (as in the case of -iodine) principally from the mother liquors of salt works (especially -Stassfurt saline deposits) by the action of chlorine or nascent oxygen -on the bromides of the alkalis and alkaline earths in the liquors. They -are chiefly used in photography (silver bromide), in medicine (potassium -bromide, &c.), and in the coal-tar dye industry. - -The danger of bromine poisoning (especially of the chronic form) is -present in its manufacture and use, but there is no positive evidence of -the appearance of the bromine rash among the workers. On the other hand, -instances are recorded of poisoning by methyl bromide, and the injurious -effect of bromide of iodine has been referred to. - -_Methyl iodide and methyl bromide._—Methyl iodide (CH₃I), a volatile -fluid, is obtained by distillation of wood spirit with amorphous -phosphorus and iodine; it is used in the production of methylated -tar colours and for the production of various methylene compounds. -Grandhomme describes, in the paper already referred to, six cases, some -very severe, of poisoning by the vapour of methyl iodide among workers -engaged in the preparation of antipyrin, which is obtained by the action -of aceto-acetic ether on phenyl hydrazine, treatment of the pyrazolone -so obtained with methyl iodide, and decomposition of the product with -caustic soda. A case of methyl iodide poisoning is described in a factory -operative, who showed symptoms similar to those described for methyl -bromide except that the psychical disturbance was more marked.[16] - -Three cases of methyl bromide (CH₃Br) poisoning are described in persons -preparing the compound.[17] One of these terminated fatally. There -is some doubt as to whether these cases were really methyl bromide -poisoning. But later cases of methyl bromide poisoning are known, and -hence the dangerous nature of this chemical compound is undoubted. Thus -the Report of the Union of Chemical Industry for 1904 gives the following -instance: Two workers who had to deal with an ethereal solution of methyl -bromide became ill with symptoms of alcoholic intoxication. One suffered -for a long time from nervous excitability, attacks of giddiness, and -drowsiness. Other cases of poisoning from methyl bromide vapour are -recorded with severe nervous symptoms and even collapse. - -_Fluorine compounds._—_Hydrogen fluoride_ (HFl) commercially is a watery -solution, which is prepared by decomposition of powdered fluorspar by -sulphuric acid in cast-iron vessels with lead hoods. The escaping fumes -are collected in leaden condensers surrounded with water; sometimes to -get a very pure product it is redistilled in platinum vessels. - -Hydrogen fluoride is used in the preparation of the fluorides of -antimony, of which antimony fluoride ammonium sulphate (SbFl₃(NH₄)₂SO₄) -has wide use in dyeing as a substitute for tartar emetic. It is produced -by dissolving oxide of antimony in hydrofluoric acid with addition of -ammonium sulphate and subsequent concentration and crystallisation. -Hydrofluoric acid is used for etching glass (see also Glass Industry). - -In brewing, an unpurified silico-fluoric acid mixed with silicic acid, -clay, oxide of iron, and oxide of zinc called Salufer is used as a -disinfectant and preservative. - -_Hydrofluoric acid and silicofluoric acid_ (H₂SiFl₆) arise further -in the superphosphate industry by the action of sulphuric acid on the -phosphorites whereby silicofluoric acid is obtained as a bye-product -(see also Manufacture of Artificial Manure). Hydrofluoric acid and its -derivatives both in their manufacture and use and in the superphosphate -industry affect the health of the workers. - -If hydrogen fluoride or its compounds escape into the atmosphere they -attack the respiratory passages and set up inflammation of the eyes; -further, workers handling the watery solutions are prone to skin -affections (ulceration). - -The following are examples of the effects produced.[18] A worker in an -art establishment upset a bottle of hydrofluoric acid and wetted the -inner side of a finger of the right hand. Although he immediately washed -his hands, a painful inflammation with formation of blisters similar to a -burn of the second degree came on within a few hours. The blister became -infected and suppurated. - -A man and his wife wished to obliterate the printing on the top of -porcelain beer bottle stoppers with hydrofluoric acid. The man took a -cloth, moistened a corner of it, and then rubbed the writing off. After a -short time he noticed a slight burning sensation and stopped. His wife, -who wore an old kid glove in doing the work, suffered from the same -symptoms, the pain from which in the night became unbearable, and in -spite of medical treatment gangrene of the finger-tips ensued. Healing -took place with suppuration and loss of the finger-nails. - -Injury of the respiratory passages by hydrofluoric acid has often been -reported. In one factory for its manufacture the hydrofluoric acid vapour -was so great that all the windows to a height of 8 metres were etched -dull. - -Several cases of poisoning by hydrofluoric acid were noted by me when -examining the certificates of the Sick Insurance Society of Bohemia. In -1906 there were four due to inhalation of vapour of hydrofluoric acid in -a hydrofluoric acid factory, with symptoms of corrosive action on the -mucous membrane of the respiratory tract. In 1907 there was a severe case -in the etching of glass.[19] - - -NITRIC ACID. - -MANUFACTURE AND USES.—_Nitric acid_ (HNO₃) is obtained by distillation -when Chili saltpetre (sodium nitrate) is decomposed by sulphuric acid in -cast-iron retorts according to the equation: - - NaNO₃ + H₂SO₄ = NaHSO₄ + HNO₃. - -Condensation takes place in fireclay Woulff bottles connected to a -coke tower in the same way as has been described in the manufacture of -hydrochloric acid. - -[Illustration: FIG. 9.—Preparation of Nitric Acid (_after Ost_)] - -Lunge-Rohrmann plate towers are also used instead of the coke tower. -Earthenware fans—as is the case with acid gases generally—serve to -aspirate the nitrous fumes. - -To free the nitric acid of the accompanying lower oxides of nitrogen -(as well as chlorine, compounds of chlorine and other impurities) air -is blown into the hot acid. The mixture of sodium sulphate and sodium -bisulphate remaining in the retorts is either converted into sulphate by -addition of salt or used in the manufacture of glass. - -The nitric acid obtained is used either as such or mixed with sulphuric -acid or with hydrochloric acid. - -Pure nitric acid cannot at ordinary atmospheric pressure be distilled -unaltered, becomes coloured on distillation, and turns red when exposed -to light. It is extremely dangerous to handle, as it sets light to straw, -for example, if long in contact with it. It must be packed, therefore, in -kieselguhr earth, and when in glass carboys forwarded only in trains for -transport of inflammable material. - -Red, _fuming nitric acid_, a crude nitric acid, contains much nitrous -and nitric oxides. It is produced if in the distillation process less -sulphuric acid and a higher temperature are employed or (by reduction) if -starch meal is added. - -The successful production of nitric acid from the air must be referred -to. It is effected by electric discharges in special furnaces from which -the air charged with nitrous gas is led into towers where the nitric -oxide is further oxidised (to tetroxide), and finally, by contact with -water, converted into nitric acid. - -Nitric acid is used in the manufacture of phosphoric acid, arsenious -acid, and sulphuric acid, nitro-glycerin and nitrocellulose, smokeless -powder, &c. (see the section on Explosives), in the preparation of -nitrobenzenes, picric acid, and other nitro-compounds (see Tar Products, -&c.). The diluted acid serves for the solution and etching of metals, -also for the preparation of nitrates, such as the nitrates of mercury, -silver, &c. - -EFFECTS ON HEALTH.—Leymann considers that the average number of cases and -duration of sickness among persons employed in the nitric acid industry -are generally on the increase; the increase relates almost entirely to -burns which can hardly be avoided with so strongly corrosive an acid. The -number of burns amounts almost to 12 per cent. according to Leymann’s -figures (i.e. on an average 12 burns per 100 workers), while among the -packers, day labourers, &c., in the same industry the proportion is only -1 per cent. Affections of the respiratory tract are fairly frequent (11·8 -per cent. as compared with 8·8 per cent. of other workers), which is no -doubt to be ascribed to the corrosive action of nitrous fumes on the -mucous membranes. Escape of acid fumes can occur in the manufacture of -nitric acid though leaky retorts, pipes, &c., and injurious acid fumes -may be developed in the workrooms from the bisulphate when withdrawn from -the retorts, which is especially the case when excess of sulphuric acid -is used. The poisonous nature of these fumes is very great, as is shown -by cases in which severe poisoning has been reported from merely carrying -a vessel containing fuming nitric acid.[1] - -Frequent accidents occur through the corrosive action of the acid or -from breathing the acid fumes—apart from the dangers mentioned in the -manufacture—in filling, packing, and despatching the acid—especially -if appropriate vessels are not used and they break. Of such accidents -several are reported. - -Further, reports of severe poisoning from the use of nitric acid are -numerous. Inhalation of nitrous fumes (nitrous and nitric oxides, &c.) -does not immediately cause severe symptoms or death; severe symptoms tend -to come on some hours later, as the examples cited below show. - -Occurrence of such poisoning has already been referred to when describing -the sulphuric acid industry. In the superphosphate industry also -poisoning has occurred by accidental development of nitric oxide fumes on -sodium nitrate mixing with very acid superphosphate. - -Not unfrequently poisoning arises in pickling metals (belt making, -pickling brass; cf. the chapter on Treatment of Metals). Poisoning by -nitrous fumes has frequently been reported from the action of nitric acid -on organic substances whereby the lower oxides of nitrogen—nitrous and -nitric oxides—are given off. Such action of nitric acid or of a mixture -of nitric and sulphuric acid on organic substances is used for nitrating -purposes (see Nitroglycerin; Explosives; Nitrobenzol). - -Through want of care, therefore, poisoning can arise in these industries. -Again, this danger is present on accidental contact of escaping acid with -organic substances (wood, paper, leather, &c.), as shown especially by -fires thus created.[2] - -Thus, in a cellar were five large iron vessels containing a mixture of -sulphuric and nitric acids. One of the vessels was found one morning to -be leaking. The manager directed that smoke helmets should be fetched, -intending to pump out the acid, and two plumbers went into the cellar -to fix the pump, staying there about twenty-five minutes. They used -cotton waste and handkerchiefs as respirators, but did not put on the -smoke helmets. One plumber suffered only from cough, but the other died -the same evening with symptoms of great dyspnœa. At the autopsy severe -inflammation and swelling of the mucous membrane of the palate, pharynx -and air passages, and congestion of the lungs were found. - -Two further fatal cases in the nitrating room are described by Holtzmann. -One of the two complained only a few hours after entering the room of -pains in the chest and giddiness. He died two days later. The other died -the day after entering the factory, where he had only worked for three -hours. In both cases intense swelling and inflammation of the mucous -membrane was found. - -Holtzmann mentions cases of poisoning by nitrous fumes in the heating of -an artificial manure consisting of a mixture of saltpetre, brown coal -containing sulphur, and wool waste. Fatalities have been reported in -workers who had tried to mop up the spilt nitric acid with shavings.[3] -We quote the following other instances[4]: - -(1) Fatal poisoning of a fireman who had rescued several persons from a -room filled with nitrous fumes the result of a fire occasioned by the -upsetting of a carboy. The rescued suffered from bronchial catarrh, the -rescuer dying from inflammation and congestion of the lungs twenty-nine -hours after the inhalation of the gas. - -(2) At a fire in a chemical factory three officers and fifty-seven -firemen became affected from inhalation of nitrous fumes, of whom one -died. - -(3) In Elberfeld on an open piece of ground fifty carboys were stored. -One burst and started a fire. As a strong wind was blowing the firemen -were little affected by the volumes of reddish fumes. Soon afterwards at -the same spot some fifty to sixty carboys were destroyed. Fifteen men -successfully extinguished the fire in a relatively still atmosphere in -less than half an hour. At first hardly any symptoms of discomfort were -felt. Three hours later all were seized with violent suffocative attacks, -which in one case proved fatal and in the rest entailed nine to ten days’ -illness from affection of the respiratory organs. - -The Report of the Union for Chemical Industry for 1908 describes a -similar accident in a nitro-cellulose factory. - -Of those engaged in extinguishing the fire twenty-two were affected, and -in spite of medical treatment and use of the oxygen apparatus three died. - -From the same source we quote the following examples: - -In a denitrating installation (see Nitro-glycerin; Explosives) a man was -engaged in blowing, by means of compressed air, weak nitric acid from a -stoneware vessel sunk in the ground into a washing tower. As the whole -system was already under high pressure the vessel suddenly exploded, and -in doing so smashed a wooden vat containing similar acid, which spilt on -the ground with sudden development of tetroxide vapours. The man inhaled -much gas, but except for pains in the chest felt no serious symptoms at -the time and continued to work the following day. Death occurred the next -evening from severe dyspnœa. - -A somewhat similar case occurred in the nitrating room of a dynamite -factory in connection with the cleaning of a waste acid egg; the vessel -had for several days been repeatedly washed out with water made alkaline -with unslaked lime. Two men then in turn got into the egg in order to -remove the lime and lead deposit, compressed air being continuously blown -in through the manhole. The foreman remained about a quarter of an hour -and finished the cleaning without feeling unwell. Difficulty of breathing -came on in the evening, and death ensued on the following day. - -In another case a worker was engaged in washing nitroxylene when, through -a leak, a portion of the contents collected in a pit below. He then -climbed into the pit and scooped the nitroxylene which had escaped into -jars. This work took about three-quarters of an hour, and afterwards he -complained of difficulty of breathing and died thirty-six hours later.[5] - -A worker again had to control a valve regulating the flow to two large -vessels serving to heat or cool the nitrated liquid. Both vessels were -provided with pressure gauges and open at the top. Through carelessness -one of the vessels ran over, and instead of leaving the room after -closing the valve, the man tried to get rid of the traces of his error, -remaining in the atmosphere charged with the fumes,[6] and was poisoned. - - -Nitric and Nitrous Salts and Compounds - -When dissolving in nitric acid the substances necessary for making the -various nitrates, nitric and nitrous oxides escape. In certain cases -nitric and hydrochloric acids are used together to dissolve metals such -as platinum and gold and ferric oxides, when chlorine as well as nitrous -oxide escapes. Mention is necessary of the following: - -_Barium nitrate_ (Ba(NO₃)₂) is prepared as a colourless crystalline -substance by acting on barium carbonate or barium sulphide with nitric -acid. Use is made of it in fireworks (green fire) and explosives. In -analogous way strontium nitrate (Sr(NO₃)₂) is made and used for red fire. - -_Ammonium nitrate_ (NH₄NO₃), a colourless crystalline substance, is -obtained by neutralising nitric acid with ammonia or ammonium carbonate, -and is also made by dissolving iron or tin in nitric acid. It is used in -the manufacture of explosives. - -_Lead nitrate_ (Pb(NO₃)₂), a colourless crystalline substance, is made by -dissolving lead oxide or carbonate in nitric acid. It is used in dyeing -and calico printing, in the preparation of chrome yellow and other lead -compounds, and mixed with lead peroxide (obtained by treatment of red -lead with nitric acid) in the manufacture of lucifer matches. Apart from -risk from nitrous fumes (common to all these salts) there is risk also of -chronic lead poisoning. - -_Nitrate of iron_ (Fe(NO₃)₂), forming green crystals, is made by -dissolving sulphide of iron or iron in cold dilute nitric acid. The -so-called nitrate of iron commonly used in dyeing consists of basic -sulphate of iron (used largely in the black dyeing of silk). - -_Copper nitrate_ (Cu(NO₃)₂), prepared in a similar way, is also used in -dyeing. - -_Mercurous nitrate_ (Hg₂(NO₃)₂) is of great importance industrially, and -is produced by the action of cold dilute nitric acid on an excess of -mercury. It is used for ‘carotting’ rabbit skins in felt hat making, for -colouring horn, for etching, and for forming an amalgam with metals, in -making a black bronze on brass (art metal), in painting on porcelain, &c. - -_Mercuric nitrate_ (Hg(NO₃)₂) is made by dissolving mercury in nitric -acid or by treating mercury with excess of warm nitric acid. Both the -mercurous and mercuric salts act as corrosives and are strongly poisonous -(see also Mercury and Hat Manufacture). - -_Nitrate of silver_ (AgNO₃) is obtained by dissolving silver in nitric -acid and is used commercially as a caustic in the well-known crystalline -pencils (lunar caustic). Its absorption into the system leads to -accumulation of silver in the skin—the so-called argyria (see Silver). -Such cases of chronic poisoning are recorded by Lewin.[7] Argyria occurs -among photographers and especially in the silvering of glass pearls owing -to introduction of a silver nitrate solution into the string of pearls by -suction. In northern Bohemia, where the glass pearl industry is carried -on in the homes of the workers, I saw a typical case. The cases are now -rare, as air pumps are used instead of the mouth. - -_Sodium nitrite_ (NaNO₂) is obtained by melting Chili saltpetre with -metallic lead in cast-iron vessels. The mass is lixiviated and the -crystals obtained on evaporation. The lead oxide produced is specially -suitable for making red lead. Cases of lead poisoning are frequent and -sometimes severe. Roth[8] mentions a factory where among 100 employed -there were 211 attacks in a year. - -_Amyl nitrite_ (C₅H₁₁NO₂) is made by leading nitrous fumes into iso-amyl -alcohol and distilling amyl alcohol with potassium nitrite and sulphuric -acid. It is a yellowish fluid, the fumes of which when inhaled produce -throbbing of the bloodvessels in the head and rapid pulse. - -For other nitric acid compounds see the following section on Explosives -and the section on Manufacture of Tar Products (Nitro-benzene, &c.). - - -Explosives - -Numerous explosives are made with aid of nitric acid or a mixture of -nitric and sulphuric acids. Injury to health and poisoning—especially -through development of nitrous fumes—can be caused. Further, some -explosives are themselves industrial poisons, especially those giving off -volatile fumes or dust. - -The most important are: - -_Fulminate of mercury_ (HgC₂N₂O₂) is probably to be regarded as the -mercury salt of fulminic acid, an isomer of cyanic acid. It is used -to make caps for detonating gunpowder and explosives, and is made by -dissolving mercury in nitric acid and adding alcohol. The heavy white -crystals of mercury fulminate are filtered off and dried. Very injurious -fumes are produced in the reaction, containing ethyl acetate, acetic -acid, ethyl nitrate, nitrous acid, volatile hydrocyanic acid compounds, -hydrocyanic acid, ethyl cyanide, cyanic acid; death consequently can -immediately ensue on inhalation of large quantities. The fulminate is -itself poisonous, and risk is present in filtering, pressing, drying, -and granulating it. Further, in filling the caps in the huts numerous -cases of poisoning occur. Heinzerling thinks here that mercury fumes are -developed by tiny explosions in the pressing and filling. In a factory in -Nuremburg 40 per cent. of the women employed are said to have suffered -from mercurial poisoning. Several cases in a factory at Marseilles are -recorded by Neisser.[9] In addition to the risk from the salt there is -even more from nitrous fumes, which are produced in large quantity in the -fulminate department. - -_Nitro-glycerin_ (C₃H₅(O—NO₂)₃, dynamite, explosive -gelatine).—Nitro-glycerin is made by action of a mixture of nitric and -sulphuric acids on anhydrous glycerin. The method of manufacture is as -follows (see fig. 10): glycerin is allowed to flow into the acid mixture -in leaden vessels; it is agitated by compressed air and care taken that -the temperature remains at about 22° C., as above 25° there may be risk. -The liquid is then run off and separates into two layers, the lighter -nitro-glycerin floating on the top of the acid. The process is watched -through glass windows. The nitro-glycerin thus separated is run off, -washed by agitation with compressed air, then neutralised (with soda -solution) and again washed and lastly filtered. The acid mixture which -was run off is carefully separated by standing, as any explosive oil -contained in it will rise up. The waste acid freed from nitro-glycerin is -recovered in special apparatus, being denitrified by hot air and steam -blown through it. The nitrous fumes are condensed to nitric acid. The -sulphuric acid is evaporated. - -_Dynamite_ is made by mixing nitro-glycerin with infusorial earth -previously heated to redness and purified. - -_Blasting gelatine_ is made by dissolving gun cotton (collodion wool, -nitro-cellulose) in nitro-glycerin. Both are pressed into cartridge shape. - -Nitro-glycerin itself is a strong poison which can be absorbed both -through the skin and from the alimentary canal. Kobert describes a case -where the rubbing of a single drop into the skin caused symptoms lasting -for ten hours. Workmen engaged in washing out nitro-glycerin from the -kieselguhr earth, having in doing so their bare arms immersed in the -liquid, suffered. Although it be granted that nitro-glycerin workers -become to a large extent acclimatised, cases of poisoning constantly -occur in explosives factories referable to the effect of nitro-glycerin. - -Persons mixing and sieving dynamite suffer from ulcers under the nails -and at the finger-tips which are difficult to heal. Further, where the -apparatus employed is not completely enclosed nitrous fumes escape and -become a source of danger. Formerly this danger was constantly present -in the nitrating house where nitration was effected in open vessels. -Now that this is usually done in closed nitrating apparatus with glass -covers the danger is mainly limited to the acid separating house, wash -house, and especially the room in which denitration of the waste acids is -effected. - -[Illustration: FIG. 10.—Preparation of Nitro-glycerin. Nitrating Vessel -(_after Guttmann_) - -A Glycerine reservoir; C Fume flue; D Acid supply pipe; E, G Compressed -air supply; H, J Cooling coil.] - -A fatal case in a nitro-glycerin factory was reported in 1902 where, -through carelessness, a separator had overflowed. The workman who tried -to wash away the acid with water inhaled so much of the nitrous fumes -that he succumbed sixteen hours later. - -Other cases of poisoning by nitrous fumes occurring in the denitrating -department are described in detail in the section on the use of nitric -acid. - -One of these occurred to a man forcing dilute nitric acid from an -earthenware egg by means of compressed air into a washing tower. The egg -burst and broke an acid tank. The workman died on the following day. - -A fatal case occurred in a dynamite factory in cleaning out a storage -tank for waste acid in spite of previous swilling and ventilation. - -_Gun cotton_ (_pyroxyline_) and its use.—Pyroxyline is the collective -name for all products of the action of nitric acid on cellulose (cotton -wool and similar material); these products form nitric acid ester of -cellulose (nitro-cellulose). - -Gun cotton is formed by the action of strong nitric acid on cellulose -(cotton wool). A mixture of sulphuric and nitric acids is allowed to act -on cotton wool (previously freed from grease, purified, and dried), with -subsequent pressing and centrifugalising. In the nitrating centrifugal -machine (in the Selvig-Lange method) both processes are effected at the -same time. - -The interior of this apparatus is filled with nitric acid, cotton wool is -introduced, the acid fumes exhausted through earthenware pipes, and the -remainder of the acid removed by the centrifugal machine; the nitrated -material is then washed, teazed in teazing machines, again washed, -neutralised with calcium carbonate, again centrifugalised, and dried. -Since drying in drying stoves is a great source of danger of explosion, -dehydration is effected with alcohol, and the gun cotton intended for -the production of smokeless powder carried directly to the gelatinising -vessels (see Smokeless Powder). - -Gun cotton, apart from its use for smokeless powder, is pressed in prisms -and used for charging torpedoes and sea mines. - -_Collodion cotton_ is a partially nitrated cellulose. It is prepared -generally in the same way as gun cotton, except that it is treated with -a more dilute acid. It is soluble (in contradistinction to gun cotton) -in alcohol-ether, and the solution is known as collodion (as used in -surgery, photography, and to impregnate incandescent gas mantles). Mixed -with camphor and heated collodion forms celluloid. - -In Chardonnet’s method for making artificial silk collodion is used by -forcing it through fine glass tubes and drawing and spinning it. The -alcohol-ether vapours are carried away by fans and the spun material is -de-nitrated by ammonium sulphide. - -_Smokeless powder_ is a gun cotton powder—that is gun cotton the -explosive power of which is utilised by bringing it into a gelatinous -condition. This is effected by gelatinising the gun cotton with -alcohol-ether or acetone (sometimes with addition of camphor, resin, -&c.). A doughy, pasty mass results, which is then rolled, washed, dried, -and pressed into rods. Nobel’s nitroleum (artillery powder) consists half -of nitro-glycerin and half of collodion cotton. In the production of gun -cotton and collodion cotton the workers are affected and endangered by -nitric and nitrous fumes unless the nitrating apparatus is completely -airtight. - -Erosion of the incisor teeth is general, but use of the new nitrating -apparatus, especially of the nitrating centrifugal machines already -described, has greatly diminished the evil. In making collodion, -celluloid and artificial silk, in addition to the risks referred to -in the production of gun cotton, the vapour from the solvents, ether, -alcohol, acetone, acetic-ether, and camphor, comes into consideration, -but there is no account of such poisoning in the literature of the -subject. - -Other explosives which belong to the aromatic series are described in the -chapter on Tar Derivatives, especially picric acid. - - -PHOSPHORUS AND PHOSPHORUS MATCHES - -The total production of _phosphorus_ is not large. Formerly it was -prepared from bone ash. Now it is made from phosphorite, which, as -in the super-phosphate industry, is decomposed by means of sulphuric -acid, soluble phosphate and calcium sulphate being formed; the latter -is removed, the solution evaporated, mixed with coal or coke powder, -distilled in clay retorts, and received in water. - -Phosphorus is also obtained electro-chemically from a mixture of -tricalcium phosphate, carbon, and silicic acid, re-distilled for further -purification, and finally poured under water into stick form. - -_Red phosphorus_ (amorphous phosphorus) is obtained by heating yellow -phosphorus in the absence of air and subsequently extracting with carbon -bisulphide. - -_Phosphorus matches_ are made by first fixing the wooden splints in -frames and then dipping the ends either into paraffin or sulphur which -serve to carry the flame to the wood. Then follows dipping in the -phosphorus paste proper, for which suitable dipping machines are now -used. The phosphorus paste consists of yellow phosphorus, an oxidising -agent (red lead, lead nitrate, nitre, or manganese dioxide) and a binding -substance (dextrine, gum); finally the matches are dried and packed. - -_Safety matches_ are made in the same way, except that there is no -phosphorus. The paste consists of potassium chlorate, sulphur, or -antimony sulphide, potassium bichromate, solution of gum or dextrine, -and different admixtures such as glass powder, &c. These matches are -saturated with paraffin or ammonium phosphate. To strike them a special -friction surface is required containing red phosphorus, antimony -sulphide, and dextrine. In the act of striking the heat generated -converts a trace of the red phosphorus into the yellow variety which -takes fire. - -Danger to health arises from the poisonous gases evolved in the -decomposition of the calcined bones by sulphuric acid. When phosphorus is -made from phosphorite the same dangers to health are present as in the -production of super-phosphate artificial manure, which is characterised -by the generation of hydrofluoric and fluosilicic acids. In the -distillation of phosphorus phosphoretted hydrogen and phosphorus fumes -may escape and prove dangerous. - -Industrial poisoning from the use of white phosphorus in the manufacture -of matches has greater interest than its occurrence in the production -of phosphorus itself. Already in 1845 chronic phosphorus poisoning -(phosphorus necrosis) had been observed by Lorinser, and carefully -described by Bibra and Geist in 1847. In the early years of its use -phosphorus necrosis must have been fairly frequent in lucifer match -factories, and not infrequently have led to death. This necessitated -preventive measures in various States (see Part III); cases became fewer, -but did not disappear altogether. - -Especially dangerous is the preparation of the paste, dipping, and -manipulations connected with drying and filling the matches into boxes. -According to the reports of the Austrian factory inspectors there are -about 4500 lucifer match workers in that country, among whom seventy-four -cases of necrosis are known to have occurred between the years 1900 and -1908 inclusive. - -Teleky[1] considers these figures much too small, and from inquiries -undertaken himself ascertained that 156 cases occurred in Austria -between 1896 and 1906, while factory inspectors’ reports dealt with only -seventy-five. He was of opinion that his own figures were not complete, -and thinks that in the ten years 1896 to 1905 there must have been from -350 to 400 cases of phosphorus necrosis in the whole of Austria. Despite -strict regulations, modern equipment of the factories, introduction of -improved machinery, and limitation of the white phosphorus match industry -to large factories, it has not been possible to banish the risk, and the -same is true of Bohemia, where there is always a succession of cases. -Valuable statistics of phosphorus necrosis in Hungary are available.[2] -In 1908 there were sixteen factories employing 1882 workers of whom -30 per cent. were young—children even were employed. The industry is -carried on in primitive fashion without hygienic arrangements anywhere. -It is strange that, notwithstanding these bad conditions, among a large -number of the workers examined only fourteen active cases were found, in -addition to two commencing, and fifteen cured—altogether thirty-one cases -(excluding fifty-five cases in which there was some other pathological -change in the mouth). Altogether ninety-three cases since 1900 were -traced in Hungary, and in view of the unsatisfactory situation preventive -measures, short of prohibition of the use of white phosphorus, would be -useless. - -In England among 4000 lucifer match workers there were thirteen cases -in the years 1900 to 1907 inclusive. Diminution in the number was due -to improved methods of manufacture and periodical dental examination -prescribed under Special Rules. - -Phosphorus necrosis is not the only sign of industrial phosphorus -poisoning, as the condition of fragilitas ossium is recognised.[3] -From what has been said it is evident that preventive measures against -phosphorus poisoning, although they diminish the number, are not able to -get rid of phosphorus necrosis, and so civilised States have gradually -been driven to prohibit the use of white phosphorus (for the history of -this see Part III). - -Use of chrome salts (especially potassium bichromate) in the preparation -of the paste causes risk of poisoning in premises where ‘Swedish’ -matches are made. Attention has been called to the frequency of chrome -ulceration.[4] The paste used consists of 3-6 per cent. chrome salt, so -that each match head contains about ½ mg. Wodtke found among eighty-four -workers early perforation of the septum in thirteen. Severe eczema also -has been noted. - -It is even alleged that red phosphorus is not entirely free from danger. -Such cachexia as has been noted may be referable to the absorption of -potassium chlorate. - - -Other Uses of Phosphorus and Compounds of Phosphorus - -Isolated cases of phosphorus poisoning have been observed in the -manufacture of phosphor-bronze. This consists of 90 parts copper, 9 parts -tin, and 0·5 to 0·75 phosphorus. - -_Sulphides of phosphorus_ (P₂S₅, P₄S₃, P₂S₃) are made by melting together -red phosphorus and sulphur. They make a satisfactory substitute for the -poisonous yellow phosphorus and are considered non-poisonous, but the -fact remains that they give off annoying sulphuretted hydrogen gas. - -_Phosphoretted hydrogen gas_ (PH₃) rarely gives rise to industrial -poisoning. It may come off in small amounts in the preparation of -acetylene and in the preparation of, and manipulations with, white -phosphorus. It is stated that in acetylene made of American calcium -carbide 0·04 per cent. of phosphoretted hydrogen is present, and in -acetylene from Swedish calcium carbide 0·02 per cent.; Lunge and -Cederkreutz found an acetylene containing 0·06 per cent. These amounts -might cause poisoning if the gas were diffused in confined spaces. -Poisoning, in part attributable to phosphoretted hydrogen gas, is brought -about through ferro-silicon (see under Ferro-silicon). - - -Superphosphate and Artificial Manure - -_Superphosphate_, an artificial manure, is prepared from various -raw materials having a high proportion of insoluble basic calcium -phosphate (tricalcium phosphate), which by treatment with sulphuric -acid are converted into the soluble acid calcium phosphate (monocalcium -phosphate) and calcium sulphate. Mineral substances such as phosphorites, -coprolites, guano, bone ash, &c., serve as the starting-point. Chamber -acid, or sometimes the waste acid from the preparation of nitro-benzene -or purification of petroleum, are used in the conversion. The raw -materials are ground in closed-in apparatus, under negative pressure, -and mixed with the sulphuric acid in wooden lead-lined boxes or walled -receptacles. The product is then stored until the completion of the -reaction in ‘dens,’ dried, and pulverised in disintegrators. - -In the manufacture of bone meal extraction of the fat from the bones with -benzine precedes treatment with acid. - -A further source of artificial manure is _basic slag_—the slag left in -the manufacture of steel by the Gilchrist-Thomas method—which contains -10-25 per cent. of readily soluble phosphoric acid. It requires, -therefore, only to be ground into a very fine powder to serve as a -suitable manure. - -Owing to the considerable heat generated by the action of the sulphuric -acid when mixed with the pulverised raw materials (especially in the -conversion of the phosphorites) hydrofluoric and silicofluoric acid -vapours are evolved in appreciable amount, and also carbonic and -hydrochloric acid vapours, sulphur dioxide, and sulphuretted hydrogen -gas. These gases—notably such as contain fluorine—if not effectually -dealt with by air-tight apparatus and exhaust ventilation—may lead to -serious annoyance and injury to the persons employed. Further, there is -risk of erosion of the skin from contact with the acid, &c. - -A case is described of pustular eczema on the scrotum of a worker engaged -in drying sodium silicofluoride, due probably to conveyance of irritating -matter by the hands. After the precaution of wearing gloves was adopted -the affection disappeared. - -A marked case of poisoning by nitrous fumes even is recorded in the -manufacture of artificial manure from mixing Chili saltpetre with a very -acid superphosphate. - -Injurious fumes can be given off in the rooms where bones are stored and, -in the absence of efficient ventilation, carbonic acid gas can accumulate -to an amount that may be dangerous. - -The fine dust produced in the grinding of _basic slag_ has, if inhaled, a -markedly corrosive action on the respiratory mucous membrane attributed -by some to the high proportion (about 50 per cent.) in it of quicklime. -As a matter of fact numerous small ulcers are found on the mucous -membranes of basic slag grinders and ulceration of the lung tissue has -been observed. The opinion is expressed that this is due to corrosive -action of the dust itself, and not merely to the sharp, jagged edged -particles of dust inhaled. And in support of this view is cited the -frequency with which epidemics of pneumonia have been noted among -persons employed in basic slag works. Thus in Nantes thirteen cases of -severe pneumonia followed one another in quick succession. And similar -association has been noted in Middlesbrough, where the action of the -basic slag dust was believed to injure the lung tissue and therefore to -provide a favourable soil for the development of the pneumonia bacillus. -Statistics collected by the Imperial Health Office showed that in the -three years 1892, 1893, and 1894, 91·1 per cent., 108·9 per cent., and -91·3 per cent. respectively of the workers became ill, the proportion -of respiratory diseases being 56·4 per cent., 54·4 per cent., and 54·3 -per cent. respectively. A case of severe inflammation of the lungs is -described in a labourer scattering basic slag in a high wind which drove -some of it back in his face. - -Lewin has described a case in which a worker scattering a mixture of -basic slag and ammonium superphosphate suffered from an eczematous -ulceration which, on being scratched by the patient, became infected and -led to death from general blood poisoning. Lewin regarded the fatal issue -as the sequela of the scattering of the manure. - -Inflammation of the conjunctiva and of the eyelids has been recorded. - - -CHROMIUM COMPOUNDS AND THEIR USES - -Chrome ironstone, lime, and soda are ground and intimately mixed. They -are next roasted in reverberatory furnaces, neutral _sodium chromate_ -being formed. This is lixiviated and converted into sodium bichromate -(Na₂Cr₂O₇) by treatment with sulphuric acid. Concentration by evaporation -follows; the concentrated liquor is crystallised in cast-iron tanks. The -crystals are centrifugalised, dried, and packed. _Potassium bichromate_ -may be made in the same way, or, as is usually the case, out of sodium -bichromate and potassium chloride. - -The bichromates are used in the preparation and oxidation of chrome -colours, but their principal use is in dyeing and calico printing, -bleaching palm oil, purifying wood spirit and brandy, in the preparation -of ‘Swedish’ matches, in the manufacture of glass, in photography, in -dyeing, in tanning, and in oxidation of anthracene to anthraquinone. - - -Lead Chromate and Chrome Colours - -_Chrome yellow_ is neutral lead chromate (PbCrO₄). It is obtained by -precipitating a solution of potassium bichromate with lead acetate or -lead nitrate, or by digesting the bichromate solution with lead sulphate, -and is used as a paint and in calico and cloth printing. With Paris or -Berlin blue it forms a _chrome green_. _Chrome orange_, i.e. basic lead -chromate (PbCrO₄Pb(OH)₂) is made by adding milk of lime to lead chromate -and boiling. - -_Chromium_ and _chromic acid salts_ are widely used in dyeing and -printing, both as mordants and oxidising agents and as dyes (chrome -yellow, chrome orange). In mordanting wool with potassium chromate the -wool is boiled in a potassium chromate solution to which acids such as -sulphuric, lactic, oxalic, or acetic are added. - -In dyeing with chrome yellow, for instance, the following is the process. -Cotton wool is saturated with nitrate or acetate of lead and dried, -passed through lime water, ammonia, or sodium sulphate, and soaked in a -warm solution of potassium bichromate. The yellow is converted into the -orange colour by subsequent passage through milk of lime. - -_Chrome tanning._—This method of producing chrome leather, first patented -in America, is carried out by either the single or two bath process. - -In the two bath process the material is first soaked in a saturated -solution of bichromate and then treated with an acid solution of -thiosulphate (sodium hyposulphite) so as to reduce completely the chromic -acid. The process is completed even with the hardest skins in from two to -three days. - -In the single bath method basic chrome salts are used in highly -concentrated form. The skins are passed from dilute into strong -solutions. In this process also tanning is quickly effected. - -EFFECTS ON HEALTH.—Among the persons employed in the bichromate factory -of which Leymann has furnished detailed particulars, the number of sick -days was greater than that among other workers. - -Further, _erosion of the skin_ (_chrome holes_) is characteristic of -the manufacture of bichromates. These are sluggish ulcers taking a long -time to heal. This is the main cause of the increased general morbidity -that has been observed. The well-known perforation of the septum of the -nose without, however, causing ulterior effects, was observed by Leymann -in all the workers in the factory. This coincides with the opinion of -others who have found the occurrence of chrome holes, and especially -perforation of the septum, as an extraordinarily frequent occurrence. -Many such observations are recorded,[1] and also in workers manufacturing -‘Swedish’ matches. Thus of 237 bichromate workers, ulcers were present -in 107 and perforation in 87. According to Lewin, who has paid special -attention to the poisonous nature of chromium compounds, they can act in -two ways: first, on the skin and mucous membrane, where the dust alights, -on the alimentary tract by swallowing, and on the pharynx by inhalation. -Secondly, by absorption into the blood, kidney disease may result. - -The opinion that chromium, in addition to local, can have constitutional -effect is supported by other authorities. Leymann describes a case -of severe industrial chrome poisoning accompanied by nephritis in a -worker who had inhaled and swallowed much chromate dust in cleaning -out a vessel. Regulations for the manufacture of bichromates (see Part -III) have no doubt improved the condition, but reports still show that -perforation of the septum generally takes place. - -It must be borne in mind that practically all chromium compounds are not -alike poisonous. Chrome ironstone is non-poisonous, and the potassium -and sodium salts are by far the most poisonous, while the neutral -chromate salts and chromic oxide are only slightly so. Pander found that -bichromates were 100 times as poisonous as the soluble chromium oxide -compounds, and Kunkel is of opinion that poisonous effect shown by the -oxides is attributable to traces of oxidation into chromic acid. - -Lewin, on the other hand, declares in a cautionary notice for chrome -workers generally that all chromium compounds are poisonous, and -therefore all the dyes made from them.[2] - -In the manufacture of bichromates, chance of injury to health arises -partly from the dust, and partly from the steam, generated in pouring -water over the molten mass. The steam carries particles of chromium -compounds with it into the air. In evaporating the chromate solutions, -preparation of the bichromate, breaking the crystals, drying and packing, -the workers come into contact with the substance and the liquors. Chrome -ulceration is, therefore, most frequently found among those employed in -the crystal room and less among the furnace hands. - -From 3·30 to 6·30 mg. of bichromate dust have been found in 1 c.m. of air -at breathing level in the room where chromate was crushed, and 1·57 mg. -where it was packed. Further, presence of chromium in the steam escaping -from the hot chrome liquors has been proved.[3] - -Poisoning from use of chrome colours is partly attributable to lead, as, -for example, in making yellow coloured tape measures, yellow stamps, and -from the use of coloured thread. Gazaneuve[4] found 10 per cent. of lead -chromate in such thread, in wool 18 per cent., and in the dust of rooms -where such yarn was worked up 44 per cent. - -Use of chrome colours and mordants is accompanied by illness which -certainly is referable to the poisonous nature of the chrome. In France -use of chromic and phosphoric acid in etching zinc plates has caused -severe ulceration. - -Bichromate poisoning has been described among photographers in Edinburgh -in the process of carbon printing, in which a bichromate developer is -used.[5] - -There is much evidence as to occurrence of skin eruptions and -development of pustular eczema of the hands and forearms of workers in -chrome tanneries.[6] In a large leather factory where 300 workers were -constantly employed in chrome tanning nineteen cases of chrome ulceration -were noted within a year. Injury to health was noted in a chrome tannery -in the district of Treves, where the two bath process was used, from -steam developed in dissolving the chromate in hot water. - -Finally, I have found several records in 1907 and 1908 of perforation of -the septum in Bohemian glass workers. - - -MANGANESE COMPOUNDS - -The raw material of the manganese industry is _hausmannite_ (manganese -dioxide, MnO₂). This is subjected to a crushing process, sorted, sieved, -finely ground, washed, and dried. The pure finely ground manganese -dioxide is much used in the chemical industry, especially in the -recovery of chlorine in the Weldon process and in the production of -_potassium permanganate_, which is obtained by melting manganese dioxide -with caustic soda and potassium chlorate or nitre, lixiviation and -introduction of carbonic acid, or better by treatment with ozone. - -Manganese is also used in the production of colours: the natural and -artificial umbers contain it; in glass works it is used to decolourise -glass, and also in the production of coloured glass and glazes; in the -manufacture of stove tiles, and in the production of driers for the -varnish and oil industry. Manganese and compounds of manganese are -dangerous when absorbed into the system as dust. - -Already in 1837 nervous disorders had been described in workmen who -ground manganese dioxide.[1] The malady was forgotten, until Jaksch[2] -in Prague in 1901 demonstrated several such cases in persons employed -in a large chemical factory in Bohemia, from the drying of Weldon mud. -In the same year three similar cases were also described in Hamburg.[3] -In 1902 Jaksch observed a fresh case of poisoning, and in the factory -in question described a condition of manganophobia among the workers, -obviously hysterical, in which symptoms of real manganese poisoning were -simulated. In all some twenty cases are known. Jaksch is of opinion that -it is manganese dust rich in manganese protoxide that is alone dangerous, -since, if the mud has been previously treated with hydrochloric acid, by -which the lower oxides are removed, no illness can be found. The most -dangerous compounds are MnO and Mn₃O₄. - - -PETROLEUM - -OCCURRENCE AND USES.—Crude petroleum flows spontaneously from wells in -consequence of high internal pressure of gas or is pumped up. In America -and Russia also it is conveyed hundreds of miles in conduits to the ports -to be led into tank steamers. - -The crude oil is a dark-coloured liquid which, in the case of -Pennsylvanian mineral oil, consists mainly of a mixture of hydrocarbons -of the paraffin series, or, in Baku oil, of those of the naphtha series. -There are in addition sulphur compounds, olefines, pyridin, &c. The -crude oil is unsuitable for illuminating purposes and is subjected to a -distillation process. It is split up into three fractions by a single -distillation, namely, (_a_) benzines (boiling-point 150° C.), (_b_) -lighting oil (boiling-point 150°-300° C.); at a temperature of 300° C. -the distillation is stopped so that (_c_) the residuum boiling above 300° -C. remains. Distillation is effected (in America) in large stills, in -which periodically benzine and lighting oil up to 300° C. is distilled -and the residuum run off. In Baku continuously working batteries of -so-called cylindrical boilers are used, into which the crude oil -streams. In the first set of boilers, the temperature in which rises to -150° C., the benzine is distilled off, and in the succeeding ones, heated -to 300° C., the illuminating petroleum oils (kerosine), the residuum -flowing continually away. - -The _mineral oil residues_ are used as fuel. Heating by this means, -tried first only in Russia, is spreading, especially for the heating of -boilers, in which case the liquid fuel is blown in generally as a spray. -The combustion if rightly planned is economical and almost smokeless. - -The American oil residuum, rich in paraffin, is distilled, the distillate -is cooled and separated by pressure into solid paraffin and liquid oil. -The latter and the Russian mineral oil residues which are free from -paraffin are widely used as lubricants. In the production of lubricants -the residues are distilled at low temperature (in vacuo or by aid of -superheated steam) and separated into various qualities by fractional -cooling, are then purified with sulphuric acid, and finally washed with -caustic soda solution. - -In the preparation of vaseline the residum is not distilled, but purified -only with fuming sulphuric acid and decolourised with animal charcoal. - -The _illuminating oil_ is next subjected to a purifying process -(refining); it is first treated with sulphuric acid and well agitated -by means of compressed air. The acid laden with the impurities is drawn -off below, and the oil freed from acid by washing first with caustic -soda and subsequently with water. It is then bleached in the sun. For -specially fine and high flash point petroleum the oil undergoes a further -distillation and purification with acid. - -The fractions of crude petroleum with low boiling-point (under 150° C.) -are known commercially as raw _benzine_ or _petrol naphtha_. It is used -for cleaning, in extraction of fats and oils, and for benzine motors. - -Frequently raw benzine is subjected to a purifying process and to -fractional distillation. Purification is carried out by means of -sulphuric acid and soda liquor and subsequent separation into three -fractions and a residue which remains in the retort—(_a_) _petroleum -ether_ (called gasoline, canadol, and rhigoline), which comes over -between 40° and 70° C., and serves for carburetting water gas and other -similar gases, as a solvent for resin, oil, rubber, &c.; (_b_) _purified -benzine_ (70°-120° C.) is used as motor spirit and in chemical cleaning; -(_c_) _ligroine_ (120°-135° C.), used for illuminating purposes; and -(_d_) the _residual oil_ (above 135° C.) serves for cleaning machinery -and, especially, as a solvent for lubricating oil, and instead of -turpentine in the production of lacquers, varnishes, and oil colours. - -In _chemical cleaning_ works benzine is used in closed-in washing -apparatus, after which the clothes are centrifugalised and dried. In -view of the risk of fire in these manipulations, originating mainly from -frictional electricity, various substances are recommended to be added -to the benzine, of which the best known is that recommended by Richter, -consisting of a watery solution of oleate of sodium or magnesium. - -EFFECTS ON HEALTH.—Industrial poisoning in the petroleum industry is -attributable to the gases given off from crude petroleum or its products -and to inhalation of naphtha dust. Poisoning occurs principally in -the recovery of petroleum and naphtha from the wells, in storage and -transport (in badly ventilated tanks on board ship, and in entering -petroleum tanks), in the refinery in cleaning out petroleum stills and -mixing vessels, and in emptying out the residues. Further cases occur -occasionally from use of benzine in chemical cleaning. - -In addition to poisoning the injurious effect of petroleum and its -constituents on the skin must be borne in mind. Opinion is unanimous -that this injurious action of mineral oil is limited to the petroleum -fractions with high boiling-point and especially petroleum residues. - -Statistics officially collected in Prussia show the general health of -petroleum workers to be favourable. These statistics related to 1380 -persons, of whom forty-three were suffering from symptoms attributable -to their occupation. Of these forty-three, nine only were cases of -poisoning, the remainder being all cases of petroleum acne. - -The conditions also in French refineries from statistics collected in -the years 1890-1903 seem satisfactory. Eighteen cases of petroleum acne -were reported, eleven of which occurred at the paraffin presses, five in -cleaning out the still residues, and two were persons filling vessels. - -The conditions are clearly less favourable in the Russian petroleum -industry.[1] - -The workers at the naphtha wells suffer from acute and chronic affections -of the respiratory organs. Those suffer most who cover the wells with -cast iron plates to enable the flow of naphtha to be regulated and led -into the reservoirs. In doing this they inhale naphtha spray. - -Lewin[2] describes cases of severe poisoning with fatal issue among -American workers employed in petroleum tanks. One man who wished to -examine an outlet pipe showed symptoms after only two minutes. Weinberger -describes severe poisoning of two workers engaged in cleaning out a -vessel containing petroleum residue. - -Interesting particulars are given of the effect of petroleum emanations -on the health of the men employed in the petroleum mines of Carpathia, -among whom respiratory affections were rarely found, but poisoning -symptoms involving unconsciousness and cerebral symptoms frequently. -These experiences undoubtedly point to differing physiological effects of -different kinds of naphtha. - -This is supported by the view expressed by Sharp in America that -different kinds of American petroleum have different effects on the -health of the workers, which can be easily credited from the different -chemical composition of crude naphthas. Thus in Western Virginia, where a -natural heavy oil is obtained, asphyxia from the gas is unknown, although -transient attacks of headache and giddiness may occur, whereas in Ohio, -where light oils are obtained, suffocative attacks are not infrequent. -And it is definitely stated that some naphtha products irritate the -respiratory passages, while others affect the central nervous system.[3] - -The authors mentioned refer to occurrence of cases of poisoning in the -refining of naphtha from inhalation of the vapour of the light oils -benzine and gasoline. Fatal cases have been recorded in badly ventilated -workrooms in which the products of distillation are collected. Workers -constantly employed in these rooms develop chronic poisoning, which is -reported also in the case of women employed with benzine. Intoxication is -frequently observed, it is stated, among the workmen employed in cleaning -out the railway tank waggons in which the mineral oils and petroleum are -carried. - -Foulerton[4] describes severe poisoning in a workman who had climbed into -a petroleum reservoir, and two similar cases from entering naphtha tanks -are given in the Report of the Chief Inspector of Factories for 1908. Two -fatal cases are reported by the Union of Chemical Industry in Germany -in 1905 in connection with naphtha stills. Such accidents are hardly -possible, except when, through insufficient disconnection of the still -from the further system of pipes, irrespirable distillation gases pass -backwards into the opened still where persons are working. Ordinary cocks -and valves, therefore, do not afford sufficient security. Thus, several -workers engaged in repairing a still were rendered unconscious by gases -drawn in from a neighbouring still, and were only brought round after -oxygen inhalation. - -Gowers describes a case of chronic poisoning following on frequent -inhalation of gases given off from a petroleum motor, the symptoms -being slurring speech, difficulty of swallowing, and weakness of the -orbicularis and facial muscles. Gowers believed this to be petroleum -gas poisoning (from incomplete combustion), especially as the symptoms -disappeared on giving up the work, only to return on resuming it again.[5] - -Girls employed in glove cleaning and rubber factories are described as -having been poisoned by benzine.[6] Poisoning of chauffeurs is described -by several writers.[7] - -Recent literature[8] tends to show marked increase in the number of -cases of poisoning from greater demand for benzine as a motive power for -vehicles. Such cases have been observed in automobile factories, and are -attributable to the hydrocarbons of low boiling-point which are present -as impurities in benzine. - -A worker in a paraffin factory had entered an open benzine still to -scrape the walls free of crusts containing benzine. He was found -unconscious and died some hours later. It appeared that he had been in -the still several hours, having probably been overcome to such an extent -by the fumes as to be unable to effect his escape. - -Attempt to wipe up benzine spilt in the storage cellar of a large -chemical cleaning works resulted in poisoning. - -A night worker in a bone extracting works having turned on the steam, -instead of watching the process fell asleep on a bench. In consequence -the apparatus became so hot that the solder of a stop valve melted, -allowing fumes to escape. The man was found dead in the morning. In a -carpet cleaning establishment three workers lost consciousness and were -found senseless on the floor. They recovered on inhalation of oxygen. - -One further case reported from the instances of benzine poisoning -collected recently[9] is worth quoting. A worker in a chemical factory -was put to clean a still capable of distilling 2500 litres of benzine. -It contained remains of a previous filling. As soon as he had entered -the narrow opening he became affected and fell into the benzine; he -was carried unconscious to the hospital, his symptoms being vomiting, -spastic contraction of the extremities, cyanosis, weak pulse, and loss of -reflexes, which disappeared an hour and a half later. - -The occurrence of skin affections in the naphtha industry has been noted -by several observers, especially among those employed on the unpurified -mineral oils. Eruptions on the skin from pressing out the paraffin and -papillomata (warty growths) in workers cleaning out the stills are -referred to by many writers,[10] Ogston in particular. - -Recent literature refers to the occurrence of petroleum eczema in a -firebrick and cement factory. The workers affected had to remove the -bricks from moulds on to which petroleum oil dropped. An eczematous -condition was produced on the inner surface of the hands, necessitating -abstention from work. The pustular eczema in those employed only a short -time in pressing paraffin in the refineries of naphtha factories is -referred to as a frequent occurrence. Practically all the workers in -three refineries in the district of Czernowitz were affected. The view -that it is due to insufficient care in washing is supported by the report -of the factory inspector in Rouen, that with greater attention in this -matter on the part of the workers marked diminution in its occurrence -followed. - - -SULPHUR - -RECOVERY AND USE.—Sulphur, which is found principally in Sicily (also in -Spain, America, and Japan), is obtained by melting. In Sicily this is -carried out in primitive fashion by piling the rock in heaps, covering -them with turf, and setting fire to them. About a third of the sulphur -burns and escapes as sulphur dioxide, while the remainder is melted and -collects in a hole in the ground. - -The crude sulphur thus wastefully produced is purified by distillation in -cast-iron retorts directly fired. It comes on the market as stick or roll -sulphur or as flowers of sulphur. - -Further sources for recovery of sulphur are the Leblanc soda residues -(see Soda Production), from which the sulphur is recovered by the -Chance-Claus process, and the gas purifying material (containing up to 40 -per cent.), from which the sulphur can be recovered by carbon bisulphide -(see Illuminating Gas Industry). - -The health conditions of the Sicilian sulphur workers are very -unsatisfactory, due, however, less to the injurious effect of the -escaping gases (noxious alike to the surrounding vegetation) than to the -wretched social conditions, over exertion, and under feeding of these -workers. - -Of importance is the risk to health from sulphuretted hydrogen gas, -from sulphur dioxide in the recovery of sulphur from the soda residues, -and from carbon bisulphide in the extraction of sulphur from the gas -purifying material. - - -SULPHURETTED HYDROGEN GAS - -Sulphuretted hydrogen gas is used in the chemical industry especially -for the precipitation of copper in the nickel and cobalt industry, in -de-arsenicating acid (see Hydrochloric and Sulphuric Acids), to reduce -chrome salts in the leather industry, &c. In addition it arises as a -product of decomposition in various industries, such as the Leblanc soda -process, in the preparation of chloride of antimony, in the decomposition -of barium sulphide (by exposure to moist air), in the treatment of gas -liquors, and in the preparation of carbon bisulphide: it is present -in blast furnace gas, is generated in mines (especially in deep seams -containing pyrites), arises in tar distillation, from use of gas lime -in tanning, and in the preparation and use of sodium sulphide: large -quantities of the gas are generated in the putrefactive processes -connected with organic sulphur-containing matter such as glue making, -bone stores, storage of green hides, in the decomposition of waste water -in sugar manufacture and brewing, in the retting of flax, and especially -in sewers and middens. - -Both _acute_ and _chronic_ poisoning are described. - -The following case is reported by the Union of Chemical Industry in 1907: -Three plumbers who were employed on the night shift in a chemical factory -and had gone to sleep in a workroom were found in a dying condition two -hours later. In the factory barium sulphide solution in a series of large -saturating vessels was being converted into barium carbonate by forcing -in carbonic acid gas; the sulphuretted hydrogen gas evolved was collected -in a gasometer, burnt, and utilised for manufacture of sulphuric acid. In -the saturating vessels were test cocks, the smell from which enabled the -workers to know whether all the sulphuretted hydrogen gas had been driven -out. If this was so the contents of the retort were driven by means of -carbonic acid gas into a subsidiary vessel, and the vessel again filled -with barium sulphide liquor. From these intermediate vessels the baryta -was pumped into filter presses, the last remains of sulphuretted hydrogen -gas being carried away by a fan into a ventilating shaft. The subsidiary -vessel and ventilating shaft were situated in front of the windows of -the repairing shop. On the night in question a worker had thoughtlessly -driven the contents out of one saturating vessel before the sulphuretted -hydrogen gas had been completely removed, and the driving belt of the fan -was broken. Consequently, the sulphuretted hydrogen gas escaping from -the subsidiary vessel entered through the windows of the workshop and -collected over the floor where the victims of the unusual combination of -circumstances slept. - -In another chemical works two workers suffered from severe poisoning -in the barium chloride department. The plant consisted of a closed vat -which, in addition to the openings for admitting the barium sulphide -liquor and sulphuric acid, had a duct with steam injector connected -with the chimney for taking away the sulphuretted hydrogen gas. Owing -to a breakdown the plant was at a standstill, as a result of which the -ventilating duct became blocked by ice. When the plant was set in motion -again the sulphuretted hydrogen gas escaped through the sulphuric acid -opening. One of the workers affected remained for two days unconscious.[1] - -The report of the Union of Chemical Industry for 1905 cites a case -where an agitating vessel, in which, by action of acid on caustic -liquor, sulphuretted hydrogen gas was given off and drawn away by a fan, -had to be stopped to repair one of the paddles. The flow of acid and -liquor was stopped, and the cover half removed. The deposit which had -been precipitated had to be got rid of next in order to liberate the -agitator. The upper portion of the vessel was washed out with water, -and since no further evolution of sulphuretted hydrogen was possible -from any manufacturing process, the work of removing the deposit was -proceeded with. After several bucketfuls had been emptied the man inside -became unconscious and died. The casualty was no doubt due to small -nests of free caustic and acid which the spading brought into contact -and subsequent developement of sulphuretted hydrogen afresh. A case -is reported of sulphuretted hydrogen poisoning in a man attending to -the drains in a factory tanning leather by a quick process. Here, when -sulphurous acid acts on sodium sulphide, sulphuretted hydrogen is given -off. In cleaning out a trap close to the discharge outlet of a tannery -two persons were rendered unconscious, and the presence of sulphuretted -hydrogen was shown by the blackening of the white lead paint on a house -opposite and by the odour.[2] - -In the preparation of ammonium salts Eulenberg[3] cites several cases -where the workers fell as though struck down, although the processes were -carried on in the open air. They quickly recovered when removed from the -spot. - -Oliver cites the case where, in excavating soil for a dock, four men -succumbed in six weeks; the water contained 12 vols. per cent. of -sulphuretted hydrogen. - -Not unfrequently acute poisoning symptoms result to sewer men. Probably -sulphuretted hydrogen gas is not wholly responsible for them, nor for -the chronic symptoms complained of by such workers (inflammation of the -conjunctiva, bronchial catarrh, pallor, depression). - -In the distillation processes connected with the paraffin industry -fatalities have been reported. - - -CARBON BISULPHIDE - -MANUFACTURE.—Carbon bisulphide is prepared by passing sulphur vapour over -pure coal brought to a red heat in cast-iron retorts into which pieces of -sulphur are introduced. The crude carbon bisulphide requires purification -from sulphur, sulphuretted hydrogen, and volatile organic sulphur -compounds by washing with lime water and subsequent distillation. - -Use is made of it principally in the extraction of fat and oil from bones -and oleaginous seeds (cocoanut, olives, &c.), for vulcanising, and as a -solvent of rubber. It is used also to extract sulphur from gas purifying -material and for the preparation of various chemical substances (ammonium -sulphocyanide, &c.), as well as for the destruction of pests (phylloxera -and rats). - -Fat and oil are extracted from seeds, bones, &c., by carbon bisulphide, -benzine, or ether, and, to avoid evaporation, the vessels are as airtight -as possible and arranged, as a rule, for continuous working. - -_Vulcanisation_ is the rendering of rubber permanently elastic by its -combination with sulphur. It is effected by means of chloride of sulphur, -sulphide of barium, calcium, or antimony, and other sulphur-containing -compounds, heat and pressure, or by a cold method consisting in the -dipping of the formed objects in a mixture of carbon bisulphide and -chloride of sulphur. The process of manufacture is briefly as follows: -The raw material is first softened and washed by hot water and kneading -in rolls. The washed and dried rubber is then mixed on callender -rolls with various ingredients, such as zinc white, chalk, white -lead, litharge, cinnabar, graphite, rubber substitutes (prepared by -boiling vegetable oils, to which sulphur has been added, with chloride -of sulphur). In vulcanising by aid of heat the necessary sulphur or -sulphur compound is added. Vulcanisation with sulphur alone is only -possible with aid of steam and mechanical pressure in various kinds of -apparatus according to the nature of the article produced. In the cold -vulcanisation process the previously shaped articles are dipped for a few -seconds or minutes in the mixture of carbon bisulphide and chloride of -sulphur and subsequently dried in warm air as quickly as possible. - -In view of the poisonous nature of carbon bisulphide, benzine is much -used now. In the cold method use of chloride of sulphur in benzine can -replace it altogether. - -Instead of benzine other solvents are available—chlorine substitution -products of methane (dichlormethane, carbon tetrachloride). In other -processes _rubber solvents_ are largely used, for instance, acetone, oil -of turpentine, petroleum benzine, ether, and benzene. Rubber solutions -are used for waterproofing cloth and other materials. - -Similar to the preparation and use of rubber is that of guttapercha. But -vulcanisation is easier by the lead and zinc thiosulphate process than by -the methods used in the case of rubber. - -EFFECTS ON HEALTH OF CS₂ AND OTHER DANGERS TO HEALTH IN THE RUBBER -INDUSTRY.—In the manufacture of carbon bisulphide little or no danger is -run either to health or from fire. - -In the rubber trade the poisonous nature of _benzine_ and _chloride of -sulphur_ have to be borne in mind, and also the considerable risk of -_lead poisoning_ in mixing. Cases of plumbism, especially in earlier -years, are referred to.[1] - -_Benzine_ poisoning plays only a secondary part in the rubber industry. -No severe cases are recorded, only slight cases following an inhalation -of fumes. - -Cases of poisoning are recorded in a motor tyre factory in Upsala.[2] -Nine women were affected, of whom four died. Whether these cases were due -to benzene or petroleum benzine is not stated. It is remarkable that two -such very different substances as benzene and benzine should be so easily -confused. - -But that in the rubber industry cases of benzene poisoning do actually -occur is proved by the following recent cases: Rubber dissolved in benzol -was being laid on a spreading machine in the usual way. Of three men -employed one was rendered unconscious and died.[3] - -In a rubber recovery process a worker was rendered unconscious after -entering a benzol still, also two others who sought to rescue him. Only -one was saved. - -Cases of aniline poisoning are reported where aniline is used for -extracting rubber.[4] - -_Chloride of sulphur_, by reason of its properties and the readiness -with which it decomposes (see Chloride of Sulphur), causes annoyance to -rubber workers, but rarely poisoning. - -Much importance attaches to _chronic carbon bisulphide poisoning_ in the -rubber industry. Many scientists have experimented as to its poisonous -nature (see especially on this Part II, p. 194). - -Lehmann’s[5] experiments show that a proportion of 0·50-0·7 mg. of CS₂ -per litre of air causes hardly any symptoms; 1·0-1·2 mg. slight effects -which become more marked on continued exposure; 1·5 mg. produces severe -symptoms. About 1·0 mg. per litre of air is the amount which may set up -chronic effects. In vulcanising rooms this limit may easily be exceeded -unless special preventive measures are adopted. - -Laudenheimer[6] has made several analyses of the proportion of CS₂ in -workrooms. Thus 0·9-1·8 mg. per litre of air were found in a room where -pouches were vulcanised; 0·5-2·4 mg. were aspirated one-half metre -distant from the dipping vessels; and 0·18-0·27 mg. in the room for -making ‘baby comforters.’ - -In analyses made some years ago proportions of 2·9-5·6 mg. were obtained. - -Although literature contains many references to CS₂ poisoning, too -much importance ought not to be attached to them now in view of the -arrangements in modern well-equipped vulcanising premises. Laudenheimer -has collected particulars of 31 cases of brain, and 19 of nervous, -diseases among 219 persons coming into contact with CS₂ between 1874 -and 1908, all of whom had been medically attended. In the last ten -years, however, the psychical symptoms were seven times less than in the -preceding period. Between 1896 and 1898 the average proportion of brain -disease in the vulcanising department was 1·95 per cent., and of nervous -diseases 0·22 per cent., as compared with 0·92 per cent. and 0·03 per -cent. in the textile. Moreover, he maintains that practically all workers -who come at all into contact with CS₂ must be to some extent affected -injuriously by it. - -Studies on the injurious nature of CS₂ date from the years 1851-60, when -the French writers Pazen, Duchenne, Beaugrand, Piorry, &c., came across -cases from the Parkes’ process (cold vulcanisation by means of CS₂ and -SCl₂). Delpech[7] published in 1860 and 1863 details of twenty-four -severe cases in rubber workers, some of which were fatal, and at the -same time described the pitiable conditions under which the work was -carried on. - -In Germany Hermann, Hirt and Lewin, and Eulenberg dealt with the subject, -but their work is more theoretical in character; and in Laudenheimer’s -work referred to the histories of several cases are given in detail. - -Mention should be made of the injury caused to the skin by the fluids -used in extraction of fat and in vulcanising—especially by benzine -and carbon bisulphide. Perrin considers the effect due partly to the -withdrawal of heat and partly to the solvent action on the natural -grease, producing an unpleasant feeling of dryness and contraction of the -skin. - - -ILLUMINATING GAS - -Illuminating gas is obtained by the dry distillation of coal. The -products of distillation are subjected on the gasworks to several -purifying processes, such as condensation in coolers, moist and dry -purifying, from which valuable bye-products (such as tar, ammonia, -cyanogen compounds) are obtained. The purified gas is stored in gas -holders containing on an average 49 per cent. hydrogen, 34 per cent. -methane, 8 per cent. carbonic oxide, 1 per cent. carbon dioxide, 4 -per cent. nitrogen, and about 4 per cent. of the heavy hydrocarbons -(ethylene, benzene vapour, acetylene, and their homologues) to which the -illuminating properties are almost exclusively due. - -The most important stages in its preparation will be shortly described. -_Distillation_ is effected in cylindrical, usually horizontal, fireclay -retorts placed in a group or setting (fig. 11), which formerly were -heated by coke but in modern works always by gas. Charging with coal and -removal of the coke takes place about every four hours, often by means of -mechanical contrivances. - -Iron pipes conduct the products of distillation to the _hydraulic main_. -This is a long covered channel extending the entire length of the stack -and receiving the gas and distillate from each retort. In it the greater -part of the tar and of the ammoniacal water condense and collect under -the water which is kept in the main to act as a seal to the ends of the -dip pipes, to prevent the gas from passing back into the retort when -the latter is opened. While the liquid flows from the hydraulic main -into cisterns, the gas passes into _coolers_ or _condensers_, tall iron -cylinders, in which, as the result of air and water cooling, further -portions of the tar and ammoniacal liquor are condensed. To free it still -more from particles of tar the gas passes through the _tar separator_. - -[Illustration: FIG. 11.—Manufacture of Illuminating Gas. Horizontal -fireclay retorts placed in a setting and heated by gas(_after Ost_)] - -The tar which remains behind flows through a tube to the cistern. From -the tar separator the gas goes through _scrubbers_ (fig. 12), where the -gas is washed free of ammonia and part of the sulphuretted hydrogen and -carbon dioxide with water. The scrubbers are tower-like vessels filled -with coke or charcoal through which the gas passes from below upwards, -encountering a spray of water. Several scrubbers in series are used, so -that the water constantly becomes richer in ammonia. Mechanical scrubbers -are much used, so-called standard washers; they are rotating, horizontal -cylinders having several chambers filled with staves of wood half dipping -in water. In them the same principle of making the gas meet an opposing -stream of water is employed, so that the last traces of ammonia are -removed from the gas. - -The various purifying apparatus through which the gas has to pass cause -considerable resistance to its flow. Escape in various ways would occur -had the gas to overcome it by its own pressure, and too long contact of -the gas with the hot walls of the retorts would be detrimental. Hence an -exhauster is applied to the system which keeps the pressure to the right -proportion in the retorts and drives on the gas. - -[Illustration: FIG. 12.—Washer or Scrubber] - -After purification in the scrubbers _dry purification_ follows, having -for its object especially removal of compounds of sulphur and cyanogen -and carbon dioxide. To effect this several shallow receptacles are -used, each having a false bottom upon which the purifying material is -spread out. The boxes are so arranged that the gas first passes through -purifying material which is almost saturated and finally through fresh -material, so that the material becomes richer in sulphur and cyanogen -compounds. The _gas purifying material_ formerly used was slaked lime, -and it is still frequently used, but more generally bog iron ore or -artificially prepared mixtures are used consisting mostly of oxide of -iron. The saturated purifying material is regenerated by oxidation on -spreading it out in the air and turning it frequently. After having been -thus treated some ten times the mass contains 50 per cent. sulphur, and -13 to 14 per cent. ferrocyanide. - -[Illustration: FIG. 13.—Manufacture of Illuminating Gas. Diagrammatic -view (_after Lueger_) A Retort setting and hydraulic main; B Condensers -and coolers; C Exhauster; D Well; E Water tank; F Tar extractor; -G Scrubber; H Purifier; I Station meter; K Gas holder; L Pressure -regulator.] - -The _naphthalene_ in illuminating gas does not separate in the condenser, -and therefore is generally treated in special apparatus by washing the -gas with heavy coal tar. - -The gas purified, as has been described, is measured by a meter and -stored in gasometers. These are bells made up of sheet iron which hang -down into walled receptacles filled with water to act as a water seal, -and are raised by the pressure of the gas which streams into them. The -gas passes to the network of mains by pressure of the weight of the -gasometer, after having passed through a pressure regulating apparatus. - -As to recovery of bye-products in the illuminating gas industry, see the -sections on Ammonia, Cyanogen Compounds, Tar, Benzene, &c. - -EFFECT ON HEALTH.—Opinions differ as to the effect on health which -employment in gas works exerts. This is true of old as well as of modern -literature. - -Hirt[1] maintains that gas workers suffer no increase in illness because -of their employment. They reach, he says, a relatively high age and their -mortality he puts down at from 0·5 to 1 per cent. (my own observations -make me conclude that the average mortality among persons insured in sick -societies in Bohemia is 1 per cent., so that Hirt’s figure is not high). - -Layet[2] agreed with Hirt, but was of opinion that gas workers suffered -from anæmia and gastro-intestinal symptoms attributable to inhalation of -injurious gases. The sudden symptoms of intoxication, ‘exhaustion and -sinking suddenly into a comatose condition,’ which he attributes to the -effect of hydrocarbons and sulphuretted hydrogen gas, may well have been -the symptoms of carbonic oxide poisoning. - -Goldschmidt[3] in recent literature considers manufacture of illuminating -gas by no means dangerous or unhealthy, and speaks of no specific -maladies as having been observed by him. Nevertheless, he admits with -Layet that the men employed in the condensing and purifying processes are -constantly in an atmosphere contaminated by gas, and that the cleaning -and regeneration of the purifying mass is associated with inflammation of -the eyes, violent catarrh, and inflammation of the respiratory passages, -since, on contact of the purifying mass with the air, hydrocyanic acid -gas, sulphocyanic acid gas, and fumes containing carbolic, butyric, and -valerianic acids are generated. - -Other writers[4] refer to the injurious effects from manipulating the -purifying material. In general, though, they accept the view, without -however producing any figures, that work in gas works is unattended with -serious injury to health and that poisonings, especially from carbonic -oxide, are rare. Such cases are described,[5] but the authors are not -quite at one as to the healthiness or otherwise of the industry. The one -opinion is based on study of the sick club reports for several years of -a large gas works employing some 2400 workers (probably Vienna).[6] The -average frequency of sickness (sickness percentage), excluding accidents, -was 48·7 per cent. The conclusion is drawn that the health conditions -of gas workers is favourable. It is pointed out, however, that diseases -of the respiratory and digestive organs (12·8 and 10·16 per cent. of -the persons employed) are relatively high, and that the mortality (1·56 -per cent.) of gas-workers is higher than that of other workers. This -is attributed to the constant inhalation of air charged with injurious -gases. Work at the retorts, coke quenching, and attending to the -purifying plant are considered especially unhealthy. - -The other figures relate to the Magdeburg gas works; they are higher -than those quoted. The morbidity of the gas workers was found to be 68·5 -per cent., of which 18 per cent. was due to disease of the digestive -system, 20·5 per cent. to disease of the respiratory organs, and 1 per -cent. to poisoning. No details of the cases of poisoning are given. -Carbonic oxide poisoning is said to be not infrequent, the injurious -effect of cleaning the purifiers is referred to, and poisoning by -inhalation of ammonia is reported as possible. - -Still, no very unfavourable opinion is drawn as to the nature of the -work. The sickness frequency in sick clubs is about 50 per cent., and -even in well-managed chemical works Leymann has shown it to be from 65 to -80 per cent. The recently published elaborate statistics of sickness and -mortality of the Leipzig local sickness clubs[7] contain the following -figures for gas workers: Among 3028 gas workers there were on an -average yearly 2046 cases of sickness, twenty deaths, and four cases of -poisoning. The total morbidity, therefore, was 67·57 per cent., mortality -0·66 per cent., and the morbidity from poisoning 0·13 per cent. Diseases -of the respiratory tract equalled 10·63 per cent., of the digestive -tract 10·87 per cent., of the muscular system 13·10 per cent., and from -rheumatism 11·10 per cent. These figures, therefore, are not abnormally -high and the poisoning is very low. - -Still, industrial cases of poisoning in gas works are recorded. Of these -the most important will be mentioned. Six persons were employed in a -sub-station in introducing a new sliding shutter into a gas main, with -the object of deviating the gas for the filling of balloons. A regulating -valve broke, and the gas escaped from a pipe 40 cm. in diameter. Five -of the men were rendered unconscious, and resuscitation by means of -oxygen inhalation failed in one case. In repairing the damage done two -other cases occurred.[8] In emptying a purifier a worker was killed from -failure to shut off the valve. - -Besides poisoning from illuminating gas, industrial poisoning in gas -works is described attributable, in part at least, to ammonia. Thus the -report of the factory inspectors of Prussia for 1904 narrates how a -worker became unconscious while superintending the ammonia water well, -fell in, and was drowned. - -A further case is described in the report of the Union of Chemical -Industry for 1904. In the department for concentrating the gas liquor -the foreman and an assistant on the night shift were getting rid of the -residues from a washer by means of hot water. The cover had been removed, -but, contrary to instructions, the steam had not been shut off. Ammonia -fumes rushed out and rendered both unconscious, in which condition there -were found by the workmen coming in the morning.[9] - -In the preparation of ammonium sulphate, probably in consequence of -too much steam pressure, gas liquor was driven into the sulphuric acid -receiver instead of ammonia gas. The receiver overflowed, and ammonia gas -escaped in such quantity as to render unconscious the foreman and two men -who went to his assistance.[10] - -The use of illuminating gas in industrial premises can give rise to -poisoning. Thus the women employed in a scent factory, where so-called -quick gas heaters were used, suffered from general gas poisoning.[11] - -In Great Britain in 1907 sixteen cases of carbonic oxide poisoning from -use of gas in industrial premises were reported. - - -COKE OVENS - -Coke is obtained partly as a residue in the retorts after the production -of illuminating gas. Such _gas coke_ is unsuitable for metallurgical -purposes, as in the blast furnace. Far larger quantities of coal are -subjected to dry distillation for metallurgical purposes in coke ovens -than in gas works. Hence their erection close to blast furnaces. In the -older form of coke oven the bye-products were lost. Those generally used -now consist of closed chambers heated from the outside, and they can be -divided into coke ovens which do, and those which do not, recover the -bye-products. These are the same as those which have been considered -under manufacture of illuminating-gas—tar, ammonia, benzene and its -homologues, cyanogen, &c. In the coke ovens in which the bye-products are -not recovered the gases and tarry vapours escaping on coking pass into -the heating flues, where, brought into contact with the air blast, they -burn and help to heat the oven, while what is unused goes to the main -chimney stack. - -[Illustration: FIG. 14.—Distillation Coke Oven (_after Lueger_) - -A, A´ Coal to be coked; B, B´ Standpipes; C Hydraulic main; D Condensing -apparatus; E Purified gas: F, F´ Air inlets; G G,´ G´´ Combustion -chambers.] - -In the modern _distillation ovens_ with recovery of the bye-products the -gases escaping from the coal are led (air being cut off as completely as -possible) through ascending pipes into the main collector, where they are -cooled, and the tarry ingredients as well as a part of the ammonia are -absorbed by water; subsequently the gases pass through washing apparatus -with a view to as complete a recovery of the ammonia and benzene as -possible. The purified gases are now again led to the ovens and burnt -with access of air in the combustion chambers between two ovens. -Generally these ovens are so constructed as to act as non-recovery ovens -also (especially in starting the process). - -The coal is charged into the ovens through charge holes on the top -and brought to a level in the chambers either by hand or mechanically. -Removal of the coke block after completion of the coking operation is -done by a shield attached to a rack and pinion jack. Afterwards the coke -is quenched with water. - -Recovery of the _bye-products_ of coke distillation ovens is similar to -the method described for illuminating gas, i.e. first by condensation -with aid of air or water cooling, then direct washing with water -(generally in scrubbers), whereby tar and ammonia water are recovered. -_Recovery of benzene_ and its homologues (see Benzene later) depends on -the fact that the coke oven gases freed from tar and ammonia are brought -into the closest possible contact with the so-called wash oils, i.e. coal -tar oils with high boiling-point (250-300° C.). For this purpose several -washing towers are employed. The waste oil enriched with benzene is -recovered in stills intermittently or continuously and used again. - -EFFECTS ON HEALTH.—Injury to health from work at coke ovens is similar -to that in the manufacture of illuminating gas. There is the possibility -of carbonic oxide poisoning from escape of gas from leakage in the -apparatus. As further possible sources of danger ammonia, cyanogen and -sulpho-cyanogen compounds, and benzene have to be borne in mind. - -In the distillation of the wash oil severe poisoning can arise, as in a -case described, where two men were fatally poisoned in distilling tar -with wash oil.[1] - -The details of the case are not without interest. The poisoning occurred -in the lavatory. The gases had escaped from the drain through the -ventilating shaft next to the closet. The gases came from distillation of -the mixture of tar and wash oil, and were driven by means of air pumps -in such a way that normally the uncondensed gases made their way to the -chimney stack. On the day of the accident the pumps were out of use, and -the gases were driven by steam injectors into the drain. Analysis showed -the gases to contain much sulphuretted hydrogen. When this was absorbed, -a gas which could be condensed was obtained containing carbon bisulphide -and hydrocarbons of unknown composition (? benzene). Only traces of -cyanogen and sulpho-cyanogen compounds were present. Physiological -experiment showed that poisoning was attributable mainly to sulphuretted -hydrogen gas, but that after this was removed by absorption a further -poisonous gas remained. - - -Other Kinds of Power and Illuminating Gas - -_Producer gas_ or _generator gas_.—Manufacture of producer gas consists -in dealing separately with the generation of the gas and the combustion -of the gases which arise. This is effected by admitting only so much air -(primary air supply) to the fuel as is necessary to cause the gases to -come off, and then admitting further air (secondary supply) at the point -where the combustion is to take place; this secondary supply and the gas -formed in the gas producer are heated in regenerators before combustion -by bringing the gases to be burnt into contact with _Siemens’s heaters_, -of which there are four. Two of these are always heated and serve to heat -the producer gas and secondary air supply. - -[Illustration: FIG. 15.—Horizontal Regenerative Grate (_after Lueger_)] - -A producer gas furnace, therefore, consists of a gas producer, a gas main -leading to the furnace hearth, the heater, and the chimney. - -[Illustration: FIG. 16.—Step Regenerative Grate (_after Lueger_)] - -The gas producer is a combustion chamber filled with coal in which -the coal in the upper layer is burnt. Generators may have horizontal -or sloping grate (see figs. 15 and 16). The _Siemens’s_ heaters or -regenerators are chambers built of, and filled loosely with, fireclay -bricks and arranged in couples. Should the gas producers become too hot, -instead of the chambers subdivided air heaters are used, whereby the hot -furnace gases are brought into contact with a system of thin-walled, -gastight fireclay pipes, to which they give up their heat, while the -secondary air supply for the furnace is led beside these pipes and so -becomes heated indirectly. Previous heating of the producer gas is here -not necessary; no valves are needed because the three streams of gas all -pass in the same direction. - -[Illustration: FIG. 17A.—Siemens’s Regenerative Furnace - -L Air; G Gas - -FIG. 17B.—Siemens’s Regenerative Furnace] - -Such air heating arrangements are used for heating the retorts in gas -works, for melting the ‘metal’ in glass works, and very generally in -other industries, as they offer many technical and hygienic advantages. -Generator gas from coke contains 34 per cent. carbonic oxide, 0·1 per -cent. hydrogen, 1·9 per cent. carbon dioxide, and 64 per cent. nitrogen. - -_Blast furnace gas._—Blast furnace gas is formed under the same -conditions as have been described for generator gas; it contains more -carbon dioxide (about 10 per cent.). (Further details are given in the -section on Iron—Blast Furnaces.) - -_Water gas._—Water gas is made by the passage of steam through -incandescent coal, according to the equation: - - C + H₂O = CO + 2H. - -The iron gas producer, lined with firebrick, is filled with anthracite -or coke and heated by blowing hot air through it. This causes producer -gas to escape, after which steam is blown through, causing water gas to -escape—containing hydrogen and carbonic oxide to the extent of 45-50 per -cent., carbon dioxide and nitrogen 2-6 per cent., and a little methane. - -The blowing of hot air and steam is done alternately, and both kinds of -gas are led away and collected separately, the water gas being previously -purified in scrubbers, condensers, and purifiers. It serves for the -production of high temperatures (in smelting of metals). Further, when -carburetted and also when carefully purified in an uncarburetted state, -it serves as an illuminant. The producer gas generated at the same time -is used for heating purposes (generally for heating boilers). - -_Dowson gas._—Dowson gas is obtained by collecting and storing together -the gases produced in the manner described for water gas. Under the -grating of the wrought-iron gas producer (lined with firebrick and -similarly filled with coke or anthracite) a mixture of air and steam, -produced in a special small boiler, is blown through by means of a -Körting’s injector. - -Before storage the gas is subjected to a purifying process similar to -that in the case of water gas. The mixed gas consists of 1 vol. water gas -and 2-3 vols. producer gas, with about 10-15 vols. per cent. H, 22-27 -vols. per cent. CO, 3-6 per cent. CO₂, and 50-55 per cent. N. It is an -admirable power gas for driving gas motors (fig. 18). - -_Mond gas_ similarly is a mixed gas obtained by blowing much superheated -steam into coal at low temperature. Ammonia is produced at the same time. - -[Illustration: FIG. 18.—Power Gas Installation (_after Lueger_) - - A Steam boiler - a Steam injector - B Furnace - b Charging hopper - c Cover g - d Valve C - e Cock D - f Vent pipe - g Steam Pipe - C Washer - D Coke tower - E Sawdust purifier] - -_Suction gas._—In contradistinction to the Dowson system, in which air -mixed with steam is forced into the producer by a steam injector, in the -suction gas plant the air and steam are drawn into the generator by the -apparatus itself. The whole apparatus while in action is under slight -negative pressure. A special steam boiler is unnecessary because the -necessary steam is got up in a water container surrounding or connected -with the cover of the generator. The plant is set in motion by setting -the fire in action by a fan. - -[Illustration: FIG. 19.—Suction Gas Plant (_after Meyer_)] - -Fig. 19 shows a suction gas plant. B is the fan. Above the generator -A and at the lower part of the feed hopper is an annular vessel for -generating steam, over the surface of which air is drawn across from -the pipe e, passing then through the pipe f into the ash box g, and -then through the incandescent fuel. The gas produced is purified in the -scrubber D, and passes then through a pipe to the purifier containing -sawdust and to the motor. - -_Carburetted gas._—Gas intended for illuminating purposes is carburetted -to increase its illuminating power, i.e. enriched with heavy -hydrocarbons. Carburetting is effected either by a hot method—adding the -gases distilled from mineral or other oils—or by a cold method—allowing -the gas to come into contact with cold benzol or benzine. Coal gas as -well as water gas is subjected to the carburetting process, but it -has not the same importance now in relation to illuminating power, as -reliance is more and more being placed on the use of mantles. - - -ACETYLENE - -_Calcium carbide._—Acetylene is prepared from calcium carbide, which on -contact with water gives off acetylene. - -_Calcium carbide_ is prepared electro-chemically. A mixture of burnt lime -and coke is ground and melted up together at very high temperature in an -electric furnace, in doing which there is considerable disengagement of -carbonic oxide according to the equation: - - CaO + 3C = CaC₂ + CO. - -The furnaces used in the production of calcium carbide are of different -construction. Generally the furnace is of the nature of an electric arc, -and is arranged either as a crucible furnace for intermittent work or -like a blast furnace for continuous work. - -Besides these there are resistance furnaces in which the heat is created -by the resistance offered to the passage of the current by the molten -calcium carbide. - -The carbonic oxide given off in the process causes difficulty. In many -furnaces it is burnt and so utilised for heating purposes. The calcium -carbide produced contains as impurities silicon carbide, ferro-silicon, -calcium sulphide, and calcium phosphide. - -_Acetylene_ (C₂H₂), formed by the decomposition of calcium carbide by -means of water (CaC₂ + 2H₂O = Ca(OH)₂ + C₂H₂), furnishes when pure an -illuminating gas of great brilliancy and whiteness. Its production is -relatively easy. Used for the purpose are (1) apparatus in which water -is made to drop on the carbide, (2) apparatus in which the carbide dips -into water and is removed automatically on generation of the gas, (3) -apparatus in which the carbide is completely immersed in water, and (4) -apparatus in which the carbide in tiny lumps is thrown on to water. These -are diagrammatically represented in figs. 20A to 20D. - -[Illustration: FIG. 20A. - -FIG. 20B. - -FIG. 20C. - -FIG. 20D. - -Acetylene Apparatus—diagrammatic (_after Lueger_) A Dripping; B Dipping; -C Submerging; D Throwing in] - -The most important impurities of acetylene are ammonia, sulphuretted -hydrogen gas, and phosphoretted hydrogen. Before use, therefore, it -is subjected to purification in various ways. In Wolf’s method the -gas is passed through a washer (with the object of removing ammonia -and sulphuretted hydrogen gas) and a purifying material consisting -of chloride of lime and bichromate salts. In Frank’s method the gas -passes though a system of vessels containing an acid solution of copper -chloride, and also through a washer. Chloride of lime with sawdust is -used as a purifying agent. Finally, the gas is stored and thence sent to -the consumer (see fig. 21). - -[Illustration: FIG. 21.—Acetylene Gas Apparatus (_after Lueger_)] - -EFFECTS ON HEALTH.—Almost all the poisoning caused in the industries in -question is due to carbonic oxide gas, of which water gas contains 41 per -cent., generator gas 35 per cent., and suction and Dowson gas 25 per cent. - -That industrial carbonic oxide poisoning is not rare the reports of the -certifying surgeons in Great Britain sufficiently show. In the year 1906 -fifty-five persons are referred to as having suffered, with fatal issue -in four. In 1907 there were eighty-one, of which ten were fatal. Of the -1906 cases twenty resulted from inhalation of producer, Mond, or suction -gas, sixteen from coal gas (in several instances containing carburetted -water gas), seventeen from blast furnace gas, and one each from charcoal -fumes from a brazier, and from the cleaning out of an oil gas holder. - -As causes of the poisoning from suction gas were (1) improper situation -of gas plant in cellar or basement, allowing gas to collect or pass -upward; (2) defective fittings; (3) starting the suction gas plant by the -fan with chimney valve closed; (4) cleaning out ‘scrubbers’ or repairing -valves, &c.; (5) defective gasometer. In the seventeen cases due to blast -furnace gas six were due to conveyance of the gas by the wind from a flue -left open for cleaning purposes into an engineering shed, two to charging -the cupola furnace, two to entering the furnace, and four to cleaning the -flues. - -The following are instances taken from recent literature on gas -poisoning[1]: Several cases of poisoning by _water gas_ occurred in a -smelting works. The poisoning originated when a blowing machine driven -by water gas was started. Owing to premature opening of the gas valve -two men employed in a well underneath the machine were overcome. The -attendant who had opened the valve succeeded in lifting both from the -well; but as he was trying to lift a third man who had come to his -assistance and fallen into the well he himself fell in and was overcome. -The same fate befell the engineer and his assistant who came to the -rescue. All efforts to recover the four men by others roped together -failed, as all of them to the number of eight were rendered unconscious. -With the aid of rescue appliances (helmets, &c.) the bodies were -recovered, but efforts at artificial respiration failed. - -A workman was killed by _suction gas_ while in the water-closet. It -appeared that some time previously when the plant was installed the -ventilating pipe between the purifier and motor, instead of being led -through the roof, had been led out sideways on a level with the floor -immediately above the closet. - -In another case the suction gas attendant had taken out the three-way -cock between the generator and motor for repairs and had not reinserted -it properly, so that when effort was made to start the motor this -failed, as gas only and no air was drawn in. The motor was thought to -be at fault, and the fan was worked so vigorously that the gas forced -its way out through the packing of the flange connections and produced -symptoms of poisoning in the persons employed. - -More dangerous than suction gas plants, in which normally no escape -takes place, are installations depending on gas _under pressure_. Such -an installation was used for heating gas irons in a Berlin laundry. The -arrangements were considered excellent. The gas jets were in stoves -from which the fumes were exhausted. The gas was made from charcoal -and contained 13 per cent. of hydrogen. No trace of carbonic oxide was -found in the ironing room on examination of the air. After having been -in use for months the mechanical ventilation got out of order, with the -result that twelve women suffered severely from symptoms of carbonic -oxide poisoning, from which they were brought round by oxygen inhalation. -The laundry reverted to the use of illuminating gas. The conclusion -to be drawn is that installations for gas heating are to be used with -caution.[2] - -Industrial poisoning from _blast furnace gas_ is frequent. Two fatal -cases were reported[3] in men employed in the gas washing apparatus. They -met their death at the manhole leading to the waste-water outlet. In -another case a workman entered the gas main three hours after the gas had -been cut off to clear it of the dust which had collected. He succumbed, -showing that such accumulations can retain gas for a long time. Steps had -been taken three hours previously to ventilate the portion of gas main in -question. - -A fatal case occurred in the cleaning out of a blast furnace flue which -had been ventilated for 1½ hours by opening all manholes, headplates, &c. -The foreman found the deceased with his face lying in the flue dust; both -he and a helper were temporarily rendered unconscious. - -Cases of poisoning by _generator gas_ are described.[4] A workman who had -entered a gasometer containing the gas died in ten minutes, and another -remained unconscious for ten days and for another ten days suffered from -mental disturbance, showing itself in hebetude and weakness of memory. - -_Acetylene_ is poisonous to only a slight extent. Impurities in it, such -as carbon bisulphide, carbonic oxide (present to the extent of 1-2 per -cent.), and especially phosphoretted hydrogen gas, must be borne in mind. - -American calcium carbide[5] yields acetylene containing 0·04 per cent. of -phosphoretted hydrogen; Lunge and Cederkreutz have found as much as 0·06 -per cent. in acetylene. - - -AMMONIA AND AMMONIUM COMPOUNDS - -PREPARATION.—Ammonia and ammonium salts are now exclusively obtained as -a bye-product in the dry distillation of coal, from the ammonia water in -gas works, and as a bye-product from coke ovens. - -The ammonia water of gas works contains from 2-3 per cent. of ammonia, -some of which can be recovered on boiling, but some is in a non-volatile -form, and to be recovered the compound must be decomposed. The volatile -compounds are principally ammonium carbonate and, to a less extent, -ammonium sulphide and cyanide; the non-volatile compounds are ammonium -sulphocyanide, ammonium chloride, sulphate, thiosulphate, &c. Other -noteworthy substances in ammonia water are pyridine, pyrrol, phenols, -hydrocarbons, and tarry compounds. - -Decomposition of the non-volatile compounds is effected by lime. Hence -the ammonia water is distilled first alone, and then with lime. The -distillate is passed into sulphuric acid, ammonium sulphate being formed. -Distillation apparatus constructed on the principle usual in rectifying -spirit is used, so that continuous action is secured; the ammonia water -flows into the apparatus continuously and is freed of the volatile -compounds by the steam. At a later stage milk of lime is added, which -liberates the ammonia from the nonvolatile compounds. - -Of the ammonium salts there require mention: - -_Ammonium sulphate_ ((NH₄)₂SO₄), which serves for the production of other -ammonium salts. It is usually centrifugalised out from the sulphuric acid -tank previously described. - -_Ammonium chloride_ (sal-ammoniac, NH₄Cl) is formed by bringing the -ammonia fumes given off in the process described in contact with -hydrochloric acid vapour. The crude salt so obtained is recrystallised or -sublimed. - -_Ammonium phosphate_ ((NH₄)₂HPO₄) is made in an analogous manner by -leading ammonia into phosphoric acid. It is useful as an artificial -manure. - -_Ammonium carbonate_ is made either by bringing together ammonia vapour -and carbonic acid or by subliming ammonium sulphate with calcium -carbonate. It is very volatile. The thick vapour is collected and -purified in leaden chambers. - -[Illustration: FIG. 22.—Preparation of Ammonia. Column Apparatus of -Feldman (_after Ost_) - -A, B, C Columns; D Saturator; (a) Settling tank and regulator for flow of -ammonia; (b) Economiser; (f) Milk of lime; (g) Pump] - -_Caustic ammonia_ is prepared either from gas liquor or, more usually, -from ammonium sulphate by distillation with caustic alkali in a -continuous apparatus. - -USE OF AMMONIA.—Ammonia is used in laundries and bleaching works in -dyeing and wool washing. It is used especially in making ammonium salts, -in the preparation of soda by the Solvay process (see Soda Manufacture), -and in making ice artificially. - -It is used also in the preparation of indigo, in lacquers and colours, -and the extraction of chloride of silver, &c. - -EFFECTS ON HEALTH.—Industrial ammonia poisoning is rare. It occurs -most frequently in gas works and occasionally in its use, especially -the manufacture of ammonium salts. Those engaged in subliming ammonium -carbonate incur special risk, but often it is not the ammonia vapour so -much as the escaping evil-smelling gases containing carbon bisulphide and -cyanogen compounds which are the source of trouble. - -Occasionally in the production of ice through leakage or by the breaking -of carboys of ammonia accidental poisoning has occurred. - -Some cases are cited from recent literature: - -A worker was rendered unconscious and drowned in an ammonia water -well.[1] Two workers were poisoned (one fatally) in the concentration of -gas liquor. Three workers were gassed (one fatally) in the preparation -of ammonium sulphate in a gas works. Probably as the result of excessive -steam pressure gas water was driven over with the ammonia into the -sulphuric acid vessel.[2] - -Eulenberg[3] reports the occurrence of sulphuretted hydrogen gas -poisoning in the production of ammonium salts. The workers succumbed as -though shot, although work was being carried on in the open air. They -recovered when removed from the poisonous atmosphere. - -In a large room of a chemical factory phosphoric acid was being saturated -with ammonia gas water in an iron lead-lined vessel. Carbonic acid gas -and hydrogen gas were evolved, but not to such extent as to be noticeable -in the large room. A worker not employed in the room had to do something -close to the vessel, and inhaled some of the fumes given off. A few -yards from the vessel he was found lying unconscious, and although -removed into the open air failed to respond to the efforts at artificial -respiration.[4] - -Lewin, in an opinion delivered to the Imperial Insurance Office, -describes poisoning in a man who during two days had been employed -repairing two ammonia retorts in a chemical factory. On the evening of -the second day he suffered from severe symptoms of catarrh, from which -he died five days later. Lewin considered the case to be one of acute -ammonia poisoning.[5] - -Ammonia is frequently used in _fulling_ cloth, the fumes of which collect -on the surface after addition of sulphuric acid to the settling vats. -This is especially liable to occur on a Monday, owing to the standing -of the factory over the Sunday, so that entrance into the vats without -suitable precautions is strictly forbidden. Despite this, a worker did -go in to fetch out something that had fallen in, becoming immediately -unconscious. A rescuer succumbed also and lost his life. The first worker -recovered, but was for long incapacitated by paralytic symptoms. - -Cases of poisoning in _ice factories_ and refrigerator rooms from -defective apparatus are reported. - -Acute and chronic poisoning among sewer men are due mainly to -sulphuretted hydrogen gas and only partly to ammonia. The more ammonia -and the less sulphuretted hydrogen sewer gases contain the less poisonous -are they. - - -CYANOGEN COMPOUNDS - -TREATMENT OF THE MATERIALS USED IN GAS PURIFYING.—Cyanogen compounds -are still sometimes prepared by the original method of heating to -redness nitrogenous animal refuse (blood, leather, horn, hair, &c.) with -potash and iron filings; potassium cyanide is formed from the nitrogen, -carbon, and alkali, and this with the sulphur and iron present is easily -converted into potassium ferrocyanide (yellow prussiate of potash, -K₄FeC₆N₆) by lixiviation of the molten mass. It crystallises out on -evaporation. - -Cyanogen compounds are obtained in large quantity from the material -used in purifying the gas in gas works. This saturated spent material -contains, in addition to 30-40 per cent. of sulphur, 8-15 per cent. of -cyanogen compounds and 1-4 per cent. of sulphocyanogen compounds. - -By lixiviation with water the soluble ammonium salts are extracted from -the purifying material. This solution furnishes _sulphocyanide of -ammonium_, from which the remaining unimportant sulphocyanide compounds -are obtained (used in cloth printing). The further treatment of the -purifying material for potassium ferrocyanide is rendered difficult -because of the sulphur, which is either removed by carbon bisulphide -and the ferrocyanide obtained by treatment with quicklime and potassium -chloride, or the mass is mixed with quicklime, steamed in closed vessels, -lixiviated with water, and decomposed by potassium chloride; ferrocyanide -of potassium and calcium separates out in crystals, and this, treated -with potash, yields potassium ferrocyanide. - -The well-known non-poisonous pigment Prussian blue is obtained by -decomposing ferrocyanide of potash with chloride or oxide of iron in -solution. - -_Potassium cyanide_ (KCN) is prepared from potassium ferrocyanide by -heating in absence of air, but it is difficult to separate it entirely -from the mixture of iron and carbon which remains. All the cyanogen is -more easily obtained in the form of potassium and sodium cyanide from -potassium ferrocyanide by melting it with potash and adding metallic -sodium. - -The very poisonous _hydrocyanic acid_ (prussic acid, HCN) is formed by -the action of acids on potassium or sodium cyanide; small quantities -indeed come off on mere exposure of these substances to the air. The -increasing demand for potassium cyanide has led to experimental processes -for producing it synthetically. - -One method consists in the production of potassium cyanide from potash -and carbon in a current of ammonia gas. Small pieces of charcoal are -freed from air, saturated with a solution of potash, dried in the absence -of air, and heated in upright iron cylinders to 100° C., while a stream -of ammonia gas is passed through. - -Again, sodium cyanide is prepared from ammonia, sodium, and carbon by -introducing a definite amount of sodium and coal dust into melted sodium -cyanide and passing ammonia through. The solution is then concentrated in -vacuo and sodium cyanide crystallises out on cooling. - -USE OF CYANIDES.—Potassium cyanide is principally used in the recovery -of gold, in gold and silver electroplating, in photography, for -soldering (it reduces oxides and makes metallic surfaces clean), for -the production of other cyanogen compounds, for the removal of silver -nitrate stains, &c. Hydrocyanic acid gas is given off in electroplating, -photography, in smelting fumes, in tanning (removing hair by gas lime), -&c. - -EFFECTS ON HEALTH.—Industrial cyanogen poisoning is rare. Weyl[1] states -that he could find no case in any of the German factory inspectors’ -reports for the twenty years prior to 1897, nor in some twenty-five -volumes of foreign factory inspectors’ reports. I have found practically -the same in my search through the modern literature. - -Of the very few references to the subject I quote the most important. - -A case of (presumably) chronic hydrocyanic acid poisoning is described in -a worker engaged for thirteen years in silver electroplating of copper -plates.[2] The plates were dipped in a silver cyanide solution and then -brushed. After two years he began to show signs of vomiting, nausea, -palpitation, and fatigue, which progressed and led to his death. - -A case of sudden death is described[3] occurring to a worker in a sodium -cyanide factory who inhaled air mixed with hydrocyanic acid gas from a -leaky pipe situated in a cellar. The factory made sodium cyanide and -ammonium sulphate from the residue after removal of the sugar from -molasses. This is the only definite case of acute cyanogen poisoning in a -factory known to me. I believe that under modern conditions, in which the -whole process is carried on under negative pressure, chance of escape of -cyanogen gases is practically excluded. - -It should be mentioned that hydrocyanic acid vapour is given off in the -burning of celluloid. In this way eight persons were killed at a fire in -a celluloid factory.[4] - -Skin affections are said to be caused by contact with fluids containing -cyanogen compounds, especially in electroplating. It is stated that -workers coming into contact with solutions containing cyanides may -absorb amounts sufficient to cause symptoms, especially if the skin -has abrasions. Such cases are described.[5] In electroplating, further, -in consequence of the strong soda solutions used, deep ulceration and -fissures of the skin of the hand can be caused. - - -COAL TAR AND TAR PRODUCTS - -Of the products of the illuminating gas industry tar has considerably the -most importance. Coal tar as such has varied use in industry, but far -greater use is made of the products obtained by fractional distillation -from it such as benzene, toluene, naphthalene, anthracene, carbolic acid, -pyridine, and the other constituents of tar, a number of which form the -starting-point in the production of the enormous coal-tar dye industry. -Especially increasing is the consumption of benzene. In Germany alone -this has increased in ten years from 20 to 70 million kilos. This is -partly due to the need of finding some cheap substitute for benzine, the -consumption and cost of which has increased, and it has in many respects -been found in benzene. - -Besides benzene and its homologues, toluene, anthracene, and naphthalene -are valuable. Anthracene is used in the manufacture of alizarine and -naphthalene in that of artificial indigo and of the azo-colours. Carbolic -acid (phenol) and the homologous cresols serve not only as disinfectants -but also in the manufacture of numerous colours and in the preparation -of picric acid and salicylic acid. Further, a number of pharmaceutical -preparations and saccharin are made from the constituents of tar. - -The important _constituents of tar_ are: - -1. Hydrocarbons of the methane series: paraffins, olefines; hydrocarbons -of the aromatic series: benzene and its homologues, naphthalene, -anthracene, phenanthrene, &c. - -2. Phenols (cresols, naphthols). - -3. Sulphides: sulphuretted hydrogen, carbon bisulphide, mercaptan, -thiophene. - -4. Nitrogen compounds: ammonia, methylamine, aniline, pyridine, &c. - -5. Fifty to sixty per cent. of tar consists of pitch constituting a -mixture of many different substances which cannot be distilled without -decomposition. - -_Crude tar_, i.e. tar which separates in the dry distillation of coal, -is employed as such for preserving all kinds of building materials, -for tarring streets, as plastic cement, as a disinfectant, in the -preparation of roofing paper or felt, lampblack, briquettes, &c. - -_Brattice cloth_ and _roofing felt_ are made by passing the materials -through hot tar and incorporating sand with them; in doing this heavy -fumes are given off. - -_Lampblack_ is made by the imperfect combustion of tar or tar oil by -letting them drop on to heated iron plates with as limited an air supply -as possible; the burnt gases laden with carbon particles are drawn -through several chambers or sacks in which the soot collects. - -[Illustration: FIG. 23.—Tar Still (_after Krämer_)] - -_Briquettes_ (patent fuel) are made by mixing small coal (coal dust) with -tar or pitch and then pressing them in moulds. - -The separation and recovery of the valuable ingredients is effected by -_fractional distillation_. This is carried out by heating the tar at -gradually increasing temperature in a wrought-iron still, the bottom -of which is arched and having a cast-iron still head, or in horizontal -boilers by direct fire. Before commencing the distillation the tar is -freed as far as possible of water by storage. On gradual increase of -temperature the volatile constituents, the so-called ‘light oil,’ and -later the heavier volatile constituents come over. The constituents are -liberated in a gaseous state and are collected in fractions. The pitch -remains behind in the still. Considerable quantities of coal tar are not -distilled for pitch. Often the light oils and a portion of the heavy oils -are collected, when soft pitch remains, or, if the light oils and only -a very small portion of the heavy oils are collected, _asphalt_ remains -behind, this residue being used as a basis for the manufacture of roofing -felt. The vapours are condensed in iron coils round which cold water -circulates. The receivers in which the distillate is caught are changed -at definite times as the temperature gradually rises. If five fractions -have come over they are called (1) first runnings, (2) light oil to 170° -C., (3) middle oil (carbolic oil to 230° C.), (4) heavy oil to 270° C., -and lastly (5) anthracene oil, which distills at over 270° C.; the pitch -remaining behind is let out of the still by an opening at the bottom. - -We will briefly sketch the further treatment and use of these fractions, -so far as a knowledge of the most important processes is necessary for -our purpose. - -1. The _light oils_ (including first runnings) coming over up to 170° C. -are again distilled and then purified with sulphuric acid in lead-lined -cast-iron or lead-lined wooden tanks. The dark-coloured acid used for -purifying after dilution with water, which precipitates tarry matters, -is treated for ammonium sulphate; the basic constituents of the light -oils extracted with sulphuric acid and again liberated by lime yield -_pyridine_ (C₅H₅N) and the homologous pyridine bases, a mixture of which -is used for denaturing spirit. After the light oils have been washed -with dilute caustic soda liquor, whereby the phenols are removed, they -are separated by another fractional distillation into (_a_) crude benzol -(70°-130° C.) and (_b_) solvent naphtha (boiling-point 130°-170° C.). - -_Crude benzol_ (70°-140° C.) consists chiefly of benzene and toluene -and is separated into its several constituents in special rectifying -apparatus. For this production of pure benzene (boiling-point 80°-82° C.) -and pure toluene (boiling-point 110° C.) fractionating apparatus is used -(fig. 24). - -The _commercial products_ in use which are obtained from the fractional -distillation of the light oil are: - -(_a_) _Ninety per cent. benzol_, so called because in the distillation 90 -per cent, should come over at a temperature of 100° C. It is made up of -80-85 per cent. benzene, 13-15 per cent. toluene, 2-3 per cent. xylene, -and contains, as impurities, traces of olefines, paraffins, sulphuretted -hydrogen, and other bodies. - -(_b_) _Fifty per cent. benzol_ contains 50 per cent. of constituents -distilling at 100° C. and 90 per cent. at 120° C.; it is a very mixed -product, with only 40-50 per cent. of benzene. - -(_c_) _Solvent naphtha_, so called because it is largely used for -dissolving rubber, is free from benzene, but contains xylene and its -homologues and other unknown hydrocarbons. - -[Illustration: FIG. 24.—Column Apparatus of Hickman for Distillation of -Benzene (_after Ost_) - -A Still body; B Analysing column; C Cooler; D Condenser for pure -distillate.] - -Benzol is widely used. Ninety per cent. benzol is largely used in -the chemical industry, serving for the preparation of dye stuffs, -pharmaceutical preparations, scents, &c. In other industries it took the -place of benzine and also of turpentine oil, especially in the paint -industry, since it evaporates quickly and readily dissolves resins. -Hence it is used in the preparation of quick drying ship’s paints, as a -protection against rust, and as an isolating lacquer (acid proof colours) -for electrical apparatus, in the production of deck varnishes, and as a -solvent of resins. - -This use of benzol in the paint industry is by no means unattended with -danger, as benzol is poisonous. Far less harmful, if not altogether -without risk, is use of benzol free solvent naphtha—but this evaporates -only slowly and hence cannot take the place of benzol. - -Benzol serves further for fat extraction from bones in manure factories -and of caffein from coffee beans. - -Again, it is used as a motive power in motor vehicles. - -The solvent naphtha above mentioned with boiling-point above 140° C. and -all the light oils are employed in chemical cleaning and for dissolving -indiarubber (see Indiarubber). - -These are known in the trade erroneously as ‘benzine,’ which -unfortunately often leads to confusion with petroleum benzine (see -Petroleum) and to mistakes in toxicological accounts of poisoning. - -2. Between 150° and 200° C. the _middle oil_ comes over, from which on -cooling _naphthalene_ (C₁₀H₈) crystallises out, and is subsequently -washed with caustic soda liquor and with acid; it is re-distilled and -hot pressed. The remaining liquor yields, when extracted with caustic -soda, _phenol_ (carbolic acid, C₆H₅OH), which, on addition of sulphuric -acid or carbonic acid, separates from the solution and then—generally in -special factories—is obtained pure by distillation and special purifying -processes. - -From the sodium salt of carbolic acid (sodium phenolate) _salicylic -acid_ (C₆H₄OH.COOH) is obtained by combination with compressed CO₂ at a -temperature of 150° C. _Picric acid_ (trinitrophenol, C₆H₂OH.(NO₂)₃) is -obtained by treating phenol with a mixture of sulphuric and nitric acids -(nitration). The yellow crystals of this explosive which separate are -carefully washed, recrystallised, centrifugalised, and dried. - -3. The _heavy oils_ which come over between 200° and 300° C. containing -cresols, naphthols, naphthaline, quinoline bases, fluid paraffins, &c., -are seldom separated further. The disinfectants lysol, sapocarbolic, &c., -are obtained from such fractions. - -The heavy oils are much in use for _impregnating wood_ (piles, railway -sleepers, &c.), to prevent rotting. This is done in special creosoting -installations. The wood is first freed from moisture under vacuum and -lastly the heavy oil forced in. This is a better means of preserving -timber than the analogous method by means of chloride of zinc. - -4. _Anthracene oil_ or ‘green oil’ comes over between 300° and 400° C. -and contains the valuable anthracene which crystallises out, is separated -from the oil in filter presses, or dried in centrifugal machines. -_Alizarin_ dyes are made from it. Raw anthracene oil further is used -commercially as a paint under the name of carbolineum for preserving wood. - -5. The _pitch_ remaining behind in the still serves (like tar) for -making varnishes, patent fuel, &c. For our purpose use of pitch in -the preparation of iron varnishes which adhere to metals and protect -them from oxidation have interest. Pitch and the heavy oils are melted -together or, if for thin varnishes, dissolved in solvent naphtha. The -volatile constituents evaporate after the coat has been applied. - -EFFECTS ON HEALTH.—Severe injury to health or poisoning cases scarcely -arise through manipulations with or use of tar. Inhalation, however, of -large quantities of tar vapour is without doubt unpleasant, as a number -of poisonous substances are contained in the fumes. And the ammonia water -which separates on standing can give off unpleasantly smelling odours -from the sulphur compounds in it, especially if it comes into contact -with waste acids, with consequent development of sulphuretted hydrogen -gas. - -I could not find in the literature of the subject references to any -clearly proved case of poisoning from tar emanations. But deserving of -mention in this connection are the _effects on the skin_ caused by tar. - -Workers coming into contact with tar suffer from an inflammatory -affection of the skin, so-called tar eczema, which occasionally takes -on a cancerous (epithelioma) nature similar to chimney-sweep’s cancer, -having its seat predominantly on the scrotum. In lampblack workers who -tread down the soot in receptacles the malady has been observed to affect -the lower extremities and especially the toes. - -In tar distillation and in the _production_ and _use_ of _benzene_ -industrial poisoning frequently occurs. Many cases are recorded, but in -several the immediate exciting cause is doubtful, and consequently it is -often difficult to classify the cases. - -Most frequently the manufacture and use of benzene come in question. -Besides this, in tar distillation poisoning may be caused by other -substances, such as sulphuretted hydrogen gas, carbonic oxide gas, &c. In -the production of antipyrin, aspirin, &c., and in the preparation and use -of anthracene injury to health is recognised. - -From the list of recognised cases of these forms of poisoning the most -characteristic are chosen from the recent literature on the subject. - -The Prussian factory inspectors’ reports for 1904 describe the following: -In cleaning out a tar still two workers were killed by inhalation of gas. -The nature of the gas was not ascertained. But what probably happened was -that the cock on the foul gas pipe collecting the gases from the stills -leaked and allowed fumes to pass over from one still to another. - -A foreman and worker were rendered unconscious on entering a receiver -for heavy oil for cleaning purposes. On treatment with oxygen gas they -speedily recovered. - -_Industrial benzene poisoning_ is especially frequent now in view of the -increasing use to which it is put. Several cases have proved fatal. - -A worker, for instance, forgot to open the cock for the water to cool the -condenser, so that some of the benzene vapour remained uncondensed. The -case proved fatal. - -The Report of the Union of Chemical Industry for 1905 stated that a -worker on night duty, whose duty it was to regulate the introduction -of steam and the cooling of the benzol plant, was found lying dead in -front of the building. Inquiry showed that he had not opened the valve -for running the distillate into the appropriate receiver. Eight thousand -litres overflowed. - -In an indiarubber extracting factory a worker was rendered unconscious -while inspecting a benzol still; before entering he had omitted to -observe the instructions to drive steam through and have a mate on watch -at the manhole. Two other workmen were similarly affected who went to the -rescue without adoption of precautions. Only one survived. - -In a further accident (already mentioned under ‘Coke Furnaces’) two -workmen were killed. In the factory in question the thick tar from the -coke ovens was being distilled under slight pressure. The air pumps, -however, were out of order, and temporary use was being made of Körting’s -injectors, whereby the steam and tar constituents were cooled and led -into the drain in front of the closet, near to which was a ventilating -shaft. Probably, in addition to benzene and its homologues, sulphuretted -hydrogen and cyanogen compounds were present in the poisonous gases. - -In cleaning out a benzene extracting apparatus a workman was killed by -the stagnant fumes in it. - -A similar case of benzene poisoning occurred in a naphthalamine works -through inspecting an extracting vessel which had contained benzene -and naphthalamine and had to be cleaned. The vessel had been empty for -twenty-two hours and had been washed and ventilated, but through a -leaking pipe benzene had dropped down into it. The workman engaged was -rendered unconscious inside the retort, but was rescued by an engineer -equipped with a breathing helmet. Others who without such apparatus tried -to effect a rescue were overcome, and one who had entered the retort -succumbed.[1] - -Benzene poisoning has often occurred in the cleaning of tanks, &c., for -the transport and storage of the substance. The following examples are -taken from the Reports of the Union of Chemical Industry. - -A worker during the pause for breakfast had, unknown to his employer, -cleaned out an empty truck for crude benzol. Later he was with difficulty -removed unconscious through the manhole and could not be resuscitated. -Only a short time previously a similar occurrence had taken place in the -same factory. - -Two further fatal cases were reported in 1908 in the cleaning out of -railway tank waggons. The tank had previously been thoroughly sprayed -with water. The partition plates which are required in such tanks -increase the difficulty of cleaning from the manhole. After the foreman -had tested the air by putting his head inside and considered it free from -danger, a man entered to clean out the deposit; another man on watch -outside had evidently gone in for rescue purposes. Resuscitation in both -cases failed. - -A worker died and several were affected in the cleaning out of a benzol -storage tank in a tar distillery. The tank had had air blown through it -several weeks before, and had been thoroughly cleaned by steam and water. -Also in the inspection the greatest care was taken in only permitting -work for short spells. This shows that, notwithstanding great care, the -last traces of benzol cannot be entirely removed and that quite small -quantities are sufficient to cause severe and even fatal poisoning. -Workers should only clean out tanks, therefore, when properly equipped -with helmets. - -In the German factory inspectors’ reports for 1902 a case of intoxication -is described in a man who was engaged painting the inside of an iron -reservoir with an asphalt paint dissolved in benzol. - -Of special interest is a fatal case from inhalation of benzol fumes in -a rubber factory. Rubber dissolved in benzol was being rubbed into the -cloth on a spreading machine in the usual way. The cloth then passes -under the cleaning doctor along the long heated plate to the end rolls. -Of the three men employed at the process one was found to be unconscious -and could not be brought round again. - -The cases described[2] of poisoning with impure benzol in a pneumatic -tyre factory in Upsala are, perhaps, analogous. Here nine young women had -severe symptoms, four of whom died. - -In reference to the cases which occurred in rubber factories it is -conceivable that carbon bisulphide played a part, since in such factories -not only are mixtures of benzol and carbon bisulphide used, but also -frequently the ‘first runnings’ of benzol, which, on account of the high -proportion (sometimes 50 per cent.) of carbon bisulphide in them, make an -excellent solvent for rubber. - -From some coke ovens crude benzol was collected in two large iron -receivers. They were sunk in a pit projecting very little above the -ground. To control the valves the workmen had to mount on the receiver, -the manholes of which were kept open during filling. The pit was roofed -over and two wooden shafts served both for ventilation and as approaches -to the valves. One summer day benzol had been blown in the usual way -into a railway truck and a worker had entered the space to control the -valves. Some time afterwards he was found in a doubled-up position on -the receiver, grasping the valves, from which later he fell off down to -the bottom of the pit. Three rescuers entered, but had to retire as they -became affected. A fourth worker, in the presence of the manager, was let -down by a rope, but succumbed immediately and was dragged up a corpse. -Finally, equipped with a smoke helmet, a rescuer brought up the lifeless -body of the first man. It was believed that the benzol had distilled -over warm and had evaporated to such an extent as to fill with fumes the -unsuitably arranged and inadequately ventilated space. Possibly other -volatile compounds were responsible for the poisoning.[3] - -A similar though less serious accident occurred to a foreman who forgot -to set the cooling apparatus at work at the commencement of distillation, -and became unconscious from the escaping fumes, as also did a rescuer. -The latter was brought round by oxygen inhalation, but the former, -although alive when recovered, succumbed despite efforts at artificial -respiration. - -A fatal case occurred in an aniline factory where benzol fumes had -escaped owing to faulty arrangement of the valves. The worker, although -ordered at once to leave the room, was found there ten minutes later dead. - -Interesting are the following cases of accidents due to use of paints -containing benzol. - -In painting a retort with an anti-corrosive paint called ‘Original -Anti-corrosive,’ unconsciousness followed on completion of the painting, -but by prompt rescue and medical assistance life was saved. The accident -was attributed to benzol fumes from the paint insufficiently diluted by -the air coming in at the open manhole. A similar case arose from use -of a rust-preventing paint—‘Preolith’—and only with difficulty was the -man using it pulled out from the inside of the steam boiler. Although -resuscitated by oxygen inhalation, he was incapacitated for eight days. -Crude benzol was a constituent of ‘Preolith.’ Obviously use of such -paints in closely confined spaces is very risky. - -The frequency of such poisonings caused Schaefer,[4] Inspector of -Factories in Hamburg, to go fully into the question. He lays stress on -the dangerous nature of paints containing a high proportion of benzol, -but considers use of unpurified constituents with boiling-point between -130°-170° C., such as solvent naphtha, as free from risk (cf. in Part II -the experiments on benzene and the commercial kinds of benzol). Schaefer -mentions that in 1903 and 1904 cases of unconsciousness from painting -the inside of boilers were numerous. The proportion of benzol in the -paints was 20-30 per cent. In 1905 and 1906 the cases were attributable -rather to inhalation of hydrocarbons in cleaning of apparatus. Use of -‘Dermatin’ affected two painters. One case in 1906 happened to a man -painting the double bottom of a ship in Hamburg harbour with ‘Black -Varnish Oil’ through the manhole, in doing which he inhaled much of the -fumes. This paint consisted of coal-tar pitch in light coal-tar oil, the -latter constituent (distilling at 170° C.) amounting to 31-33 per cent. -Investigation showed further that the bulk of the tar oil volatilised at -ordinary temperatures and so quickly dried. Sulphuretted hydrogen gas was -given off on slight warming. The person after using it for some time felt -poorly, and then became ill with severe inflammation of the respiratory -passages, which proved fatal after twenty-four days. - -Several similar cases occurred in 1908 and 1909. Painting the inside -of a boiler with ‘Auxulin’ caused unconsciousness in four persons, -of whom three were rescuers. A fatal case was due to use of a patent -colour containing 30-40 per cent. benzol in an entirely closed-in space -(chain-well), although the worker was allowed out into fresh air at -frequent intervals. - -A case of chronic industrial xylene poisoning is described in a worker -using it for impregnating indiarubber goods. The symptoms were nervous, -resembling neurasthenia. - -Some of the cases of poisoning, especially when severe and fatal, in -the production of distillation constituents of coal tar are doubtless -attributable to _sulphuretted hydrogen gas_. Thus in England, in the -years 1901-3, there were eleven fatal and as many other severe cases -reported from tar distilleries, of which the majority were due to -sulphuretted hydrogen gas. - -One case of _carbonic oxide_ poisoning in coal-tar distillation is -described.[5] In cleaning out pitch from a still fourteen days after the -last distillation a workman succumbed to carbonic oxide poisoning. This -is at all events a rare eventuality, since no other case is to be found -in the literature of the subject, but it is a proof that in the last -stage of coal-tar distillation carbonic oxide plays a part. - -Mention must be made of the frequent occurrence of severe skin affections -in _anthracene workers_; they take the form of an eruption on the hands, -arms, feet, knees, &c., and sometimes develop into cancer. - -Observations in a chemical factory since 1892 showed that of thirty thus -affected in the course of ten years twenty-two came into contact with -paraffin. - - -Artificial Organic Dye Stuffs (Coal-tar Colours) - -MANUFACTURE.—The starting-points for the preparation of artificial -coal-tar dyes are mainly those aromatic compounds (hydrocarbons) -described in the preceding section. Besides these, however, there are the -derivatives of the fatty series such as methyl alcohol (wood spirit), -ethyl alcohol, phosgene, and, latterly, formaldehyde. - -The _hydrocarbons of the benzene series_ from tar distillation are -delivered almost pure to the colour factory. Of these benzene, toluene, -xylene, naphthalene, anthracene, and the phenols, cresols, &c., have to -be considered. - -Further treatment is as follows: - -1. Nitration, i.e. introduction of a nitro-group by means of nitric acid. - -2. Reduction of the nitrated products to amines. - -3. Sulphonation, i.e. conversion to sulphonic acids by means of -concentrated sulphuric acid. - -4. The sulphonic acids are converted into phenols by fusing with caustic -soda. - -5. Introduction of chlorine and bromine. - -_Nitro-derivatives_ are technically obtained by the action of a mixture -of nitric and concentrated sulphuric acids on the aromatic body in -question. The most important example is _nitrobenzene_. - -Benzene is treated for several hours in cylindrical cast-iron pans with -nitric and concentrated sulphuric acids. The vessel is cooled externally -and well agitated. A temperature of 25° C. should not be exceeded. - -[Illustration: FIG. 25.—Preparation of Intermediate Products in the -Aniline Colour Industry (Closed Apparatus), showing Arrangement for -Condensation (_after Leymann_)] - -On standing the fluid separates into two layers: the lower consists of -dilute sulphuric acid in which there is still some nitric acid, and -the upper of nitrobenzene. The latter is freed of remains of acid by -washing and of water by distillation. _Toluene_ and _xylene_ are nitrated -in the same way. _Dinitro products_ (such as metadinitrobenzene) are -obtained by further action of the nitro-sulphuric acid mixture on the -mononitro-compound at higher temperature. - -For conversion of phenol into _picric acid_ (trinitrophenol) the use of a -nitro-sulphuric acid mixture is necessary. - -The _aromatic bases_ (aniline, toluidine, xylidine) are obtained by -reduction of the corresponding nitro-compound by means of iron filings -and acid (hydrochloric, sulphuric, or acetic). Thus in the case of -_aniline_ pure nitrobenzene is decomposed in an iron cylindrical -apparatus, provided with agitators and a condenser, and avoidance of a -too violent reaction, by means of fine iron filings and about 5 per cent. -hydrochloric acid. After completion of the reaction the contents are -rendered alkaline by addition of lime and the aniline distilled over. -Manufacture of _toluidine_ and _xylidine_ is analogous. - -_Dimethylaniline_ is obtained by heating aniline, aniline hydrochloride, -and methyl alcohol. - -_Diethylaniline_ is prepared in an analogous way with the use of ethyl -alcohol. - -By the action of nitrous acid (sodium nitrite and hydrochloric acid) on -the acid solution of the last-named compound the _nitroso compounds_ are -formed. - -_Sulphonic acids_ arise by the action of concentrated or fuming sulphuric -acid on the corresponding bodies of the aromatic series: benzene -disulphonic acid from benzene and fuming sulphuric acid, &c. - -_Phenols_ and _cresols_ are obtained pure from tar distillation. The -remaining hydroxyl derivatives (resorcin, α- and β-naphthol, &c.), are -generally obtained by the action of concentrated caustic soda on aromatic -sulphonic acids. - -The most important aromatic aldehyde, _benzaldehyde_, is obtained from -toluene; on introducing chlorine at boiling temperature benzyl chloride -is first formed, then benzal-chloride and finally benzo-trichloride. In -heating benzal-chloride with milk of lime (under pressure) benzaldehyde -is formed (C₆H₅COH). - -_Picric acid_ and _naphthol yellow_ belong to the _nitro dyestuffs_; the -last named is obtained by sulphonating α-naphthol with fuming sulphuric -acid and by the action of nitric acid on the sulphonated mixture. - -Nitroso derivatives of aromatic phenols yield (with metal oxides) the -material for production of nitroso dyestuffs. To these belong naphthol -green, &c. - -The most important _azo dyestuffs_ technically are produced in principle -by the action of nitrous acid on the aromatic amines. The amido compound -is converted into the diazo salt by treatment with sodium nitrite in -acid solution. Thus diazo-benzene is made from aniline. Diazo compounds -are not usually isolated but immediately coupled with other suitable -compounds—amido derivatives, phenols—i.e. converted into azo compounds. - -[Illustration: FIG. 26.—Nitrating Plant (_after Leymann_) - - I Nitric acid - II Balance - III Storage tank - IV Nitrating pan - V Waste acid tank - VI Acid egg - VII Hydrocarbon - VIII Balance - IX Storage tank - X Washing vessel - XI Centrifugal machine - XII Egg - - - - Exhaust ventilation pipe.] - -The combination of the two constituents takes place at once and -quantitatively. The colour is separated from the aqueous solution by -salting-out, and is then put through a filter press. The reactions -are carried out generally in wooden vats arranged in stages. Besides -a second, a third constituent can be introduced, and in this way -naphthol—and naphthylamine sulphonic acids yield a large number of -colouring matters. A very large number of azo dyestuffs can thus be -produced by the variation of the first component (the primary base) with -the second and again with the third component, but it would carry us too -far to deal further with their preparation. - -_Anthracene colours_—yielding so-called direct dyes—are prepared -from anthracene, which is converted into anthraquinone by the action -of bichromate and dilute sulphuric acid when heated; the crude -‘quinone’ is purified with concentrated sulphuric acid and converted -into anthraquinone monosulphonic acid to serve in the preparation of -_alizarin_, which is made from it by heating for several days with -concentrated caustic soda to which sodium chlorate is added. The process -is carried on in cast-iron pans provided with agitators. - -_Alizarin_ is the starting-point for the alizarin dyes, but of their -production we will not speak further, as they, and indeed most of the -coal-tar dyes, are non-poisonous. - -_Indigo_ to-day is generally obtained by synthesis. It is prepared from -phenylglycine or phenylglycine ortho-carboxylic acid, which on heating -with sodamide becomes converted into indoxyl or indoxyl carboxylic -acid. These in presence of an alkali in watery solution and exposure to -the oxygen of the air immediately form indigo. The necessary glycine -derivatives are obtained by the action of monochloracetic acid on aniline -or anthranilic acid, which again are derived from naphthalene (by -oxidation to phthalic acid and treatment of phthalimide with bleaching -powder and soda liquor). - -_Fuchsin_ belongs to the group of triphenylmethane dyestuffs, with the -production of which the epoch of coal-tar colour manufacture began, from -the observation that impure aniline on oxidation gave a red colour. The -original method of manufacture with arsenic acid is practically given up -in consequence of the unpleasant effects which use and recovery of large -quantities of arsenic acid gave rise to. The method consisted in heating -a mixture of aniline and toluidine with a solution of arsenic acid under -agitation in cast-iron cylinders. The cooled and solidified mass from the -retorts was boiled, and from the hot solution, after filtration, the raw -fuchsin was precipitated with salt and purified by crystallisation. - -Now by the usual nitrobenzene process, aniline, toluidine, nitrobenzene, -and nitrotoluene are heated with admixture of hydrochloric acid and some -iron protochloride or zinc chloride. Further treatment resembles the -arsenic process. - -By alkylation, i.e. substitution of several hydrogen atoms of the -amido-groups by ethyl, &c., through the action of alkyl halogens -and others, it was found possible to convert fuchsin into other -triphenylmethane colours. But it was soon found simpler to transfer -already alkylated amines into the colours in question. Thus, for example, -to prepare _methyl violet_ dimethyl aniline was heated for a long time -with salt, copper chloride, and phenol containing cresol in iron mixing -drums. The product is freed from salt and phenol by water and calcium -hydrate, subsequently treated with sulphuretted hydrogen or sodium -sulphide, and the colour separated from copper sulphide by dissolving in -dilute acid. - -Mention must be made, finally, of the _sulphur dyes_ obtained by heating -organic compounds with sulphur or sodium sulphide. For the purpose -derivatives of diphenylamine, nitro- and amido-phenols, &c., serve as the -starting-point. - -EFFECTS ON HEALTH.—From what has been said of the manufacture of coal-tar -dyes it is evident that poisoning can arise from the initial substances -used (benzene, toluene, &c.), from the elements or compounds employed -in carrying out the reactions (such as chlorine, nitric acid, sulphuric -acid, arsenious acid, sodium sulphide, and sulphuretted hydrogen gas), -from the intermediate bodies formed (nitro and amido compounds, such as -nitrobenzene, dinitrobenzene, aniline, &c.), and that, finally, the end -products (the dyes themselves) can act as poisons. It has already been -said that most of the dyes are quite harmless unless contaminated with -the poisonous substances used in their manufacture. - -We have seen that many of the raw substances used in the manufacture -of coal-tar dyes are poisonous, and we shall learn that several of the -intermediate products (especially the nitro and amido compounds) are so -also. - -According to Grandhomme,[1] of the raw materials benzene is the one -responsible for most poisoning. He describes two fatal cases of benzene -poisoning. In one case the worker was employed for a short time in a room -charged with benzene fumes, dashed suddenly out of it, and died shortly -after. In the other, the workman was employed cleaning out a vessel in -which lixiviation with benzene had taken place. Although the vessel -had been steamed and properly cooled, so much benzene fume came off in -emptying the residue as to overcome the workman and cause death in a -short time. - -Grandhomme describes no injurious effect from naphthalene nor, indeed, -from anthracene, which he considered was without effect on the workers. - -Similarly, his report as to nitrobenzene was favourable. No reported case -of poisoning occurred among twenty-one men employed, in some of whom -duration of employment was from ten to twenty years. Aniline poisoning, -however, was frequent among them. In the three years there was a total -of forty-two cases of anilism, involving 193 sick days—an average of -fourteen cases a year and sixty-four sick days. None was fatal and some -were quite transient attacks. - -In the fuchsin department no cases occurred, and any evil effects in the -manufacture were attributable to arsenic in the now obsolete arsenic -process. Nor was poisoning observed in the preparation of the dyes in -the remaining departments—blues, dahlias, greens, resorcin, or eosin. In -the manufacture of methylene blue Grandhomme points out the possibility -of evolution of arseniuretted hydrogen gas from use of hydrochloric acid -and zinc containing arsenic. Poisoning was absent also in the departments -where alizarine colours and pharmaceutical preparations were made. - -Among the 2500-2700 workers Grandhomme records 122 cases of industrial -sickness in the three years 1893-5, involving 724 sick days. In addition -to forty-two cases of anilism there were seventy-six cases of lead -poisoning with 533 sick days. Most of these were not lead burners, but -workers newly employed in the nitrating department who neglected the -prescribed precautionary measures. Lastly, he mentions the occurrence of -chrome ulceration. - -The frequency of sickness in the Höchst factory in each of the years -1893-5 was remarkably high: 126 per cent., 91 per cent., and 95 per -cent. Much less was the morbidity in the years 1899-1906—about 66 per -cent.—recorded by Leymann[2]—probably the same Höchst factory with 2000 -to 2200 employed. And the cases of industrial poisoning also were less. -He cites only twenty-one in the whole of the period 1899-1906. Of these -twelve were due to aniline, involving thirty sick days, only five to lead -poisoning, with fifty-four sick days, one to chrome ulceration, one to -arseniuretted hydrogen gas (nine sick days), and one fatal case each from -sulphuretted hydrogen gas and from dimethyl sulphate. In 1899, of three -slight cases of aniline poisoning one was attributable to paranitraniline -(inhalation of dust), and the two others to spurting of aniline oil on -to the clothing, which was not at once changed. Of the four cases in -1900, one was a plumber repairing pipes conveying aniline and the others -persons whose clothes had been splashed. - -In 1903 a worker employed for eleven and a half years in the aniline -department died of cancer of the bladder. Such cancerous tumours have -for some years been not infrequently observed in aniline workers, and -operations for their removal performed. Leymann thinks it very probable -that the affection is set up, or its origin favoured, by aniline. This -view must be accepted, and the disease regarded as of industrial origin. -Three slight cases in 1904 and 1905 were due partly to contamination of -clothing and partly to inhalation of fumes. Of the five cases of lead -poisoning three were referable to previous lead employment. Perforation -of the septum of the nose by bichromate dust was reported once only. A -fatal case from sulphuretted hydrogen gas and a case of poisoning by -arseniuretted hydrogen gas occurred in 1906, but their origin could not -be traced. - -In large modern aniline dye factories, therefore, the health of the -workers is, on the whole, good and industrial poisoning rare. Comparison -of the two sets of statistics show that improvement in health has -followed on improved methods of manufacture. Such cases of aniline -poisoning as are reported are usually slight, and often accounted for by -carelessness on the part of the workers. - -Data as to the health of workers in factories manufacturing or using -nitro compounds are given in the English factory inspectors’ reports -for 1905. Even with fortnightly medical examination in them, more than -half the workers showed signs of anæmia and slight cyanosis. Two men in -a factory employing twelve men in the manufacture of nitro compounds -were treated in hospital for cyanosis, distress of breathing, and general -weakness. One had only worked in the factory for nine days. In another -badly ventilated factory, of twenty persons examined fourteen showed -bluish-grey coloration of the lips and face, ten were distinctly anæmic, -and six showed tremor and weakness of grasp. - -Nitrobenzene poisoning arises from the fumes present in aniline and -roburite factories. Acute and chronic poisoning by nitro compounds of -the benzene series are described, brought about by accident (fracture -of transport vessels) and by carelessness (splashing on to clothes). -Cases of optic neuritis (inflammation of the optic nerve) as a result of -chronic nitrobenzene poisoning are described. - -Dinitrobenzene and other nitro and dinitro compounds are present -in safety explosives. Thus roburite and bellite consist of -metadinitrobenzene and ammonium nitrate; ammonite of nitronaphthalene and -ammonium nitrate; securite of the materials in roburite with ammonium -oxalate in addition. In roburite there may be also chlorinated nitro -compounds. - -Leymann,[3] describing accidents in the preparation of nitrophenol -and nitrochloro compounds, mentions four fatal cases occurring in the -manufacture of black dyes from mono- and di-nitrophenols as well as -mono- and di-nitrochlorobenzene and toluene. In three of the cases -dinitrophenol was the compound at fault owing to insufficient care in -the preparation,—the result of ignorance until then of risk of poisoning -from mono- and tri-nitrophenol. One of the men had had to empty a washing -trough containing moist dinitrophenol. He suddenly became collapsed, with -pain in the chest, vomiting, fever, and convulsions, and died within -five hours. Another suffered from great difficulty of breathing, fever, -rapid pulse, dilatation of the pupils, and died within a few hours in -convulsions. Two further cases of nitrochlorobenzene poisoning are -referred to, one of which was fatal. Four chlorobenzene workers after a -bout of drinking were found unconscious in the street, and only recovered -after eight to ten hours in hospital. The symptoms were grey-blue colour -of the skin, pallor of mucous membranes, lips, nose, and conjunctivæ, -and peculiar chocolate-coloured blood. - -Many cases of poisoning from roburite are recorded.[4] In the Witten -roburite factory it is stated that during the years 1890-7 almost all -the workers had been ill.[5] Only three looked healthy—all the others -suffered from more or less pallor, blue lips, and yellowish conjunctivæ. - -A case of chlorobenzene poisoning was reported with symptoms of headache, -cyanosis, fainting attacks, difficulty of breathing, &c., in a man who -had worked only three weeks with the substance.[6] - -In the nitrotoluene department of an explosives factory a number of -the workmen suffered from symptoms of distress in breathing, headache, -&c., of whom two, employed only a short time, died. The poisoning was -attributed, partly to nitrotoluene and partly to nitrous fumes. As a -contributing cause it was alleged that in view of shortage of hands -unsuitable persons were engaged who neglected precautions.[7] - -Nitronaphthalene is said to cause inflammation and opacity of the -cornea,[8] attributable either to long-continued exposure (four to eight -months) to nitronaphthalene vapour or to spurting of the liquid into the -eye. - -I could not find reference in literature to actual cases of poisoning by -picric acid. They are referred to in a general way only as causing skin -affections. - -Aniline poisoning arises generally from inhalation, but absorption -through the skin and less frequently inhalation of dust of aniline -compounds cause it. We have already laid stress on the frequently severe -cases resulting from carelessness in spilling on to or splashing of, -clothes without at once changing them, breaking of vessels containing it, -and entering vessels filled with the vapour. In literature of old date -many such cases have been described, and it was stated that workers were -especially affected on hot days, when almost all showed cyanosis. Such -observations do not state fairly the conditions to-day in view of the -improvements which Grandhomme and Leymann’s observations show have taken -place in aniline factories. Still, cases are fairly frequent. Thus in a -factory with 251 persons employed, thirty-three cases involving 500 days -of sickness were reported. - -The Report of the Union of Chemical Industry for 1907 cites the case of a -worker who was tightening up the leaky wooden bung of a vessel containing -aniline at a temperature of 200° C. He was splashed on the face and arms, -and although the burns were not in themselves severe he died the next day -from aniline absorption. - -Cases of anilism are not infrequent among dyers. The reports of the -Swiss factory inspectors for 1905 describe a case where a workman worked -for five hours in clothes on to which aniline had spurted when opening -an iron drum. Similar cases are described in the report of the English -factory inspectors for the same year. Aniline black dyeing frequently -gives rise to poisoning, and to this Dearden[9] of Manchester especially -has called attention. - -Typical aniline poisoning occurred in Bohemia in 1908 in a cloth presser -working with black dyes. While crushing aniline hydrochloride with -one hand, he ate his food with the other. That the health of persons -employed in aniline black dyeing must be affected by their work is shown -by medical examination. For instance, the English medical inspector of -factories in the summer months of 1905 found among sixty persons employed -in mixing, preparing, and ageing 47 per cent. with greyish coloration of -lips and 57 per cent. characteristically anæmic. Further, of eighty-two -persons employed in padding, washing, and drying, 34 per cent. had grey -lips, 20 per cent. were anæmic, and 14 per cent. with signs of acute or -old effects of chrome ulceration. Gastric symptoms were not infrequently -complained of. The symptoms were worse in hot weather. - -Use of aniline in other industries may lead to poisoning. Thus in the -extraction of foreign resins with aniline seventeen workers suffered -(eleven severely). Interesting cases of poisoning in a laundry from use -of a writing ink containing aniline have been recorded.[10] - -Reference is necessary to tumours of the bladder observed in aniline -workers. The first observations on the subject were made by Rehn of -Frankfurt, who operated in three cases. Bachfeld of Offenbach noticed in -sixty-three cases of aniline poisoning bladder affections in sixteen. -Seyberth described five cases of tumours of the bladder in workers -with long duration of employment in aniline factories.[11] In the -Höchst factory (and credit is due to the management for the step) every -suspicious case is examined with the cystoscope. In 1904 this firm -collected information from eighteen aniline factories which brought to -light thirty-eight cases, of which eighteen ended fatally. Seventeen were -operated on, and of these eleven were still alive although in three there -had been recurrence. - -Tumours were found mostly in persons employed with aniline, -naphthylamine, and their homologues, but seven were in men employed with -benzidine. - -Cases of benzene and toluidine poisoning in persons superintending tanks -and stills have been described. - -Industrial paranitraniline poisoning has been described, and a fatal case -in the Höchst dye works was attributed by Lewin (as medical referee) to -inhalation of dust. Before his death the workman had been engaged for -five hours in hydro-extracting paranitraniline. - -Paraphenylene diamine leads not unfrequently to industrial poisoning -from use of ursol as a dye. It produces skin eruptions and inflammation -of the mucous membrane of the respiratory passages.[12] No doubt the -intermediate body produced (diimine) acts as a powerful poison. - -A case of metaphenylene diamine poisoning is quoted in the Report of the -Union of Chemical Industry for 1906. A worker had brought his coffee and -bread, contrary to the rules, into the workroom and hidden them under a -vessel containing the substance. Immediately after drinking his coffee he -was seized with poisoning symptoms, and died a few days later. Some of -the poison must have dropped into his coffee. - -Few instances of poisoning from pure aniline colours are recorded. - -At first all tar colours were looked upon as poisonous, but as they were -mostly triphenylmethane colours they would contain arsenious acid. When -the arsenic process was given up people fell into the other extreme -of regarding not only the triphenylmethane colours but all others as -non-poisonous, until experience showed that production and use of some of -the tar colours might affect the skin. - -Finally, mention must be made of inflammation of the cornea caused by -methyl violet dust. The basic aniline dyes are said to damage the eye. -As opposed to this view is the fact that methyl violet and auramine are -used as anti-bactericidal agents, for treatment of malignant tumours, and -especially in ophthalmic practice. - - - - -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. - -[Illustration: 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. - -[Illustration: 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: - - Illness of Saturnine Origin. - Year. No. Lead Colic. Per Cent. - Employed. Anæmia. Intestinal Catarrh. due to - Gastric Total Lead Total Lead. - Catarrh. Sickness. Sickness. - 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 - - Lead Colic - Year. and Kidney Gastric Anæmia. Rheumatism. No. - Lead Paralysis. Disease. Catarrh. 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 - - Lead Colic - Year. and Kidney Gastric Anæmia. Rheumatism. No. - Lead Paralysis. Disease. Catarrh. 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: - - +-----------+--------------+-----------------+---------------+--------+ - | | | No. Employed. |Cases of Lead | | - | | | |Poisoning. | | - | | +-----------------+---------------+ No. of | - | Place. | Manufacture. |Regular |Regular |Cases of| - | | | |Casual | |Casual |Gastric | - | | | | |Average | |Total|Catarrh.| - +-----------+--------------+-----+-----+-----+----+----+-----+--------+ - |Cologne I. | White lead {| 46 | 59 | 32 | 9 | 16 | 25 | 16 | - | | {| 173 | 95 | 127 | 13 | 17 | 30 | 22 | - | ” I. | Litharge and{| 46 | 4 | 38 | 5 | 1 | 6 | 7 | - | | red lead {| 76 | 62 | 49 | 3 | 4 | 7 | 15 | - | | Chromate {| 14 | 2 | 11 | — | — | — | 5 | - | | {| 43 | 72 | 33 | — | — | — | 7 | - |Cologne II.| White lead, {| | | | | | | | - | | litharge, {| 107 | 332 | 91 | 6 | 34 | 40 | 30 | - | | and red lead{| 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: - - +--------+----------+------------+--------------+ - | | | No. | | - | | No. of | of Cases | Cases per | - | Year. | Members. | of Lead | 100 Members. | - | | | Poisoning. | | - +--------+----------+------------+--------------+ - | 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.|Average No.|Percentage| - | |of Members,| of Cases, | of Cases,| - | |1901-1906. |1901-1906. |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. - -[Illustration: 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. - - - - -III. OCCURRENCE OF INDUSTRIAL POISONING IN VARIOUS INDUSTRIES - - -The most important facts have now been stated as to the occurrence of -poisoning in industry, and there remain only a few gaps to fill in and to -survey briefly the risks in certain important groups of industry. - - -TREATMENT OF STONE AND EARTHS - -Lime Burning: Glass Industry - -Lead poisoning in the ceramic industry (earthenware, porcelain, glass, -polishing of precious stones, &c.) has been dealt with in detail in the -chapter on Lead. There is further the possibility of chrome-ulceration, -of arsenic poisoning, and conceivably also of manganese. Further, -poisoning by _carbonic oxide_ and carbon dioxide may occur from the -escape of furnace gases where hygienic conditions are bad. In charging -lime kilns poisoning by carbonic oxide has occurred. The report of the -Union of Chemical Industry in 1906 describes the case of a workman who -was assisting in filling the kiln with limestone. As the furnace door -was opened for the purpose gas escaped in such amount as to render him -unconscious. He was picked up thirty minutes later, but efforts at -resuscitation failed. - -Carbonic oxide poisoning, again, may arise from the use of Siemens -regenerative furnaces, especially glass furnaces: details are given in -the chapter on Illuminating Gas. - -_Hydrofluoric acid_ is present as an industrial poison in _glass etching_ -(see Fluorine Compounds). Persons employed in this process suffer from -inflammation of the respiratory tract and ulceration of the skin of the -hands. I could not find any precise statement as to the frequency of the -occurrence of such injuries. Use of sand-blasting to roughen the surface -of glass has to some extent taken the place of etching by hydrofluoric -acid. - - -TREATMENT OF ANIMAL PRODUCTS - -In _tanning_ use of arsenic compounds for detaching the wool from skins -and of gas lime for getting rid of hair may cause injury to health. With -the latter there is possibility of the action of cyanogen compounds (see -the chapters on Arsenic and Cyanogen). - - -PREPARATION OF VEGETABLE FOOD STUFFS AND THE LIKE - -In _fermentation_ processes as in breweries and the sugar industry -accumulations of carbonic acid gas occur, and suffocation from this -source has been repeatedly described. Mention in this connection -should be made of the use of salufer containing some 2 per cent. of -silicofluoric acid as a preservative and antiseptic in beer brewing. In -the _sulphuring_ of hops, wine, &c., the workers may run risk from the -injurious action of sulphur dioxide. _Arsenic_ in the sulphuric acid -used for the production of _dextrine_ may set up industrial poisoning. -Poisoning from _ammonia_ gas can occur in _cold storage_ premises. -Industrial poisoning from tobacco is not proved, but the injurious effect -of the aroma and dust of tobacco—especially in women—in badly arranged -tobacco factories is probable. - - -WOOD WORKING - -_Injurious woods._—In recent literature there are several interesting -references to injury to health from certain poisonous kinds of wood—skin -affections in workers manipulating satinwood, and affections of the heart -and general health in workers making shuttles of African boxwood. Details -of these forms of poisoning are reported from England and Bavaria. The -wood used for making the shuttles was West African boxwood (Gonioma -Kamassi). It appears that the wood contains an alkaloidal poison which -affects the heart’s action. The workers suffered from headache, feeling -of sleepiness, lachrymation, coryza, difficulty of breathing, nausea, and -weakness. Four workers had to give up the work because of the difficulty -in breathing. Inquiry was made by Dr. John Hay of Liverpool in 1908 and -by the medical inspector of factories in 1905. The following table shows -the symptoms found: - - +----------------------+-----------------------------------+ - | | Persons Examined. | - | +-----------------+-----------------+ - | Symptoms. | 1905. | 1907-1908. | - | +-------+---------+-------+---------+ - | |Number.|Per cent.|Number.|Per Cent.| - | (1) | (2) | (3) | (4) | (5) | - +----------------------+-------+---------+-------+---------+ - |Headache | 27 | 24·1 | 18 | 22·8 | - |Feeling of somnolence | 10 | 9·0 | 17 | 21·5 | - |Running of eyes | 13 | 11·6 | 9 | 11·3 | - |Running of nose | 28 | 25·0 | 20 | 28·0 | - |Breathing affected | 34 | 30·4 | 13 | 16·4 | - |Nausea or sickness | 13 | 11·6 | 3 | 3·8 | - |Faintness or weakness | 11 | 9·6 | 1 | 1·2 | - +----------------------+-------+---------+-------+---------+ - -The later inquiry shows considerable diminution in the amount of -complaint as to respiratory trouble. This may have been due to the -improved conditions of working, freely acknowledged by the men. Men were -examined who had complained of the effects of the wood in 1905, and had -continued uninterruptedly at the same kind of work during the interval -without any obvious further injury to their health, although they -preferred working on other woods. - -East Indian boxwood had to be discarded in the shuttle trade owing to -its irritant action on the eyes. Sabicu wood from Cuba was stated to -give off ‘a snuffy dust under the machine and hand planes, the effect of -which upon the worker is to cause a running at the eyes and nose, and a -general feeling of cold in the head. The symptoms pass off in an hour or -so after discontinuance of work.’ Reference was made in the report for -1906 to eczematous eruptions produced by so-called Borneo rosewood, a -wood used owing to its brilliant colour and exquisite grain in fret-saw -work. The Director of the Imperial Institute experimented with this wood, -but failed to discover injurious properties in it. At the same time -experiments with the wood and sawdust of East and West Indian satinwood -were undertaken, but also without result. - -From inquiries subsequently made it appeared that much confusion existed -as to the designation ‘satinwood,’ as under this name were classed both -East and West Indian satinwood and also satin walnut. The evidence was -clear that East Indian satinwood was more irritating than West Indian. -Satin walnut wood is apparently harmless. In the shipbuilding yards of -East London, Glasgow, and Bristol affections of the skin were recognised, -but susceptibility to the wood varied. One man asserted that merely -laying a shaving on the back of his hand would produce a sore place. The -injurious effects here seem to disappear quickly. Exhaust ventilation is -applied, but there is a tendency to give up the use of the wood. - -Isolated cases of illness have been ascribed to working teak and olive -wood. In Sheffield the following are held to be irritating: ebony, -magenta rosewood, West Indian boxwood, cocos wood. Some kinds of mahogany -are said to affect the eyes and nose. - -Use of methylated spirit in polishing furniture is said to lead to injury -to health although not to set up actual poisoning. Lead poisoning can -occur from the sand-papering of coats of paint applied to wood. - -In impregnating wood with creosote and tar the effects on the skin noted -in the chapter on Tar are observed. - - -TEXTILE INDUSTRY - -In getting rid of the grease from animal wool carbon bisulphide or -_benzine_ may be used. - -The process of _carbonising_ in the production of shoddy may give rise to -injury to health from acid fumes. Lead poisoning used to be caused by the -knocking together of the leaden weights attached to the Jacquard looms. -This is a thing of the past, as now iron weights are universal. - -Opportunity for lead poisoning is given in the weighting of -yarn—especially of silk with lead compounds. - -In _bleaching_ use of chlorine and sulphur dioxide has to be borne in -mind. - -In _chemical cleaning_ poisoning by benzine may occur. - -In _dyeing_ and _printing_ use of poisonous colours is lessening, as -they have been supplanted by aniline colours. On occurrence of aniline -poisoning in aniline black dyeing see the section on Aniline. Use of lead -colours and of chromate of lead are dealt with in special sections. - - - - -PART II - -_THE SYMPTOMS AND TREATMENT OF INDUSTRIAL POISONING_ - - -In this section the most important diseases and symptoms of industrial -poisoning will be described. In doing this—considering the mainly -practical purpose of this book—theoretical toxicological details and any -full discussion of disputed scientific points will be omitted. - - - - -I. INTRODUCTORY - - -Hitherto in this book we have intentionally followed the inductive -method, from the particular to the general: we began by citing a -number of important instances of industrial poisoning, but only now -will endeavour be made to give a definition of the terms ‘poison’ and -‘poisoning.’ - -Attempts at such definitions are numerous; every old and new text-book -of toxicology contains them. A few only hold good for our purpose. It -is characteristic that Lewin, after attempting a definition of the -conception ‘poisoning,’ himself rejects it and declares that he can see -no practical disadvantage in the impossibility of defining this notion, -because deductions based upon the knowledge of undoubted cases can never -be dispensed with, even if a definition were possible: one justification -the more for our inductive method. - -But we will not quite dispense with a definition. - -_Poisons are certain substances which are able chemically to act on an -organism in such a way as to effect a permanent or transient injury to -its organs and functions; an injury consequently to the health and -well-being of the person affected; this injury we call poisoning._ - -In the present book we have refrained from including industrial -infections among industrial poisonings, and the subject has been limited -to poisoning in the restricted and current sense of the word. - -An industrial poison is a poison employed, produced, or somehow -occasioned in industrial occupation, which is brought about -inadvertently, and consequently against the will of the person poisoned. - -From a simple survey of the action of industrial poisons in general we -may group them as follows: - - 1. Poisons which act _superficially_, i.e. which cause in the - organs which they touch gross anatomical lesions (irritation, - corrosion, &c.)—so-called contact-effect. To this class belong - especially irritant and corrosive poisons. - - 2. _Blood_ poisons, i.e. poisons which are absorbed by the - blood and change it; this change can affect either the blood - colouring-matter, with which certain poisons form chemical - compounds, or the blood corpuscles themselves can be altered or - destroyed (for instance, poisons having a hæmolytic action). - - 3. Poisons with definite _internal_ action, so-called remote or - specific effect. To this class belong the poisons which, after - being absorbed into the system, act upon definite organs or - tissues in a specific manner (nerve poisons, heart poisons, &c.). - -It is indeed possible for one and the same poison to display two or all -three of these modes of action. - -The effect of poison depends upon an interaction of the poison and the -organism, or its single organs. Selection as regards quality and quantity -is a property of the organism as well as of the poison: the nature and -amount of the poison taken in are determining factors on the one side, -and on the other the constitution, size, and weight of the affected -organism. The chemical constitution of the poisonous substance determines -the qualitative property of the poison. - -Further, certain physical properties of the poison determine its action, -especially its form, solubility in water, and its power of dissolving -fat. These affect its susceptibility to absorption, to which point we -shall return shortly; the hygroscopic capacity of a poison produces a -highly irritant and corrosive action. - -Industrial poisons can be absorbed (1) as solid substances, (2) as -liquids, and (3) as gases. Since industrial poisoning, as defined -above, is of course neither desired nor intended by the sufferer, who -unsuspectingly takes into his system poison used or developed in the -factory, solid substances in finely divided condition—in the form of -dust—can be considered as industrial poisons. Accordingly, industrial -poisons can be classed as due to dust, gases, and liquids. - -The poison may be introduced into the body through the functional -activity of the organism by the lungs or alimentary tract, or it may -penetrate the uninjured or injured surface of the skin. - -Industrial poisons which contaminate the air of the factory are -inhaled—these are consequently either poisonous dusts or gases and -vapours. - -As a rule, only industrial poisons in a liquid form enter through the -skin, which may be either intact or wounded; gaseous poisons seldom do; -poisons in the form of fat or dust can only pass through the skin after -they have been first dissolved by the secretions of the skin or of a -wound, so that they come to be absorbed in solution. Most frequently -those liquid poisons which are capable of dissolving the fat of the skin -are thus absorbed, and next, such liquids as have a corrosive effect, -breaking down the resistance of the skin covering and producing an -inflamed raw surface. But such poisons much more easily enter through the -mucous membrane, as this naturally offers a much weaker resistance than -the skin. - -From a quantitative point of view it is especially the amount of poison -actively assimilated which determines the effect. Every poison is without -effect if assimilated in correspondingly small quantities. There is -consequently a minimum poisonous dose, after which the poison begins to -act; but this minimum dose can only be ascertained and specified when the -qualitative properties and the weight of the organism are also taken -into consideration; it has therefore a relative value. The strongest -effect which a poison is able to produce is the destruction of the life -functions of the organism, the fatal effect. This fatal dose, however, -can only be determined relatively to the qualities of the organism in -question. - -Not only is the absolute quality of the poison of decisive significance, -but the degree of concentration often influences its action, that is -to say, the greater or less amount of effective poison contained in -the substance conveying it into the organism; concentration plays an -important part in many industrial poisons, especially, as is obvious, in -corrosive poisons. - -A further important point is the time which it takes to absorb the -poison. The action of the poison—the whole expression of the symptoms of -poisoning—is essentially influenced by this fact. - -Usually gradual and repeated absorption of small quantities produces slow -onset of symptoms, while sudden absorption of larger quantities of poison -brings about rapid onset of illness. In the former case the poisoning -is called _chronic_, in the latter, _acute_. Acute industrial poisoning -is sometimes so sudden that the affected person cannot withdraw himself -in time from the influence of the poison, nor prevent its entrance in -considerable quantities into his system; this is often caused by the -fact that the effect of the poison is so rapid that he is often suddenly -deprived of power to move or of consciousness, and remains then exposed -to the action of the poison until help comes. Such accidents are mostly -caused by poisonous gases. Occasionally also considerable quantities of -poison enter quite unnoticed into the body, such as odourless poisonous -gases in breathing, or poisonous liquids through the skin. In chronic -industrial poisoning unsuspected accumulation of poison takes place, -until symptoms of illness ultimately reveal themselves; as the first -stages of poisoning are not recognised in time by the person affected, -he continues exposed to the influence of the poison for weeks, months, -even years, until the chronic effect has reached its full development and -becomes obvious. Such insidious industrial poisoning arises through the -continual absorption into the lungs or stomach of small quantities of -poisonous dust, gases, and vapours, during constant or frequent work in -an atmosphere containing such gases; poisonous liquids also, by soiling -hands and food, or by penetrating the skin, can produce slow industrial -poisoning. - -Industrial poisoning which in respect of its duration stands midway -between acute and chronic is called sub-acute poisoning. This usually -means that more frequent absorption of greater quantities of poison has -taken place, though not in doses large enough to produce an immediately -acute effect. This is important legally because industrial poisonings -caused through the sudden absorption of poison in sufficient quantity -to act immediately or to bring about subsequent symptoms of poisoning, -are reckoned as accidents. Thus acute and many sub-acute industrial -poisonings are accounted accidents. Chronic industrial poisonings, -acquired gradually, count as illnesses. But as in certain cases it -cannot be decided whether sudden or gradual absorption of the industrial -poison is in question, this distinction is an unnatural one. It is also -unnatural in the legal sense, for there is often no material reason for -regarding as legally distinct cases of chronic and acute industrial -poisoning. To this we shall refer later in discussing the question of -insurance against industrial poisoning. - -We have from the outset assumed that the effect of the poison depends -not only on the nature of the poison itself, but also on that of the -organism, considered both quantitatively and qualitatively. - -Significant in a quantitative respect is the body weight of the organism, -and the fatal dose of the poison must be ascertained and stated in -connection with the body weight, calculated as a rule per kilo of the -live weight. - -The qualitative point of view must reckon with the differing -susceptibility of organisms for poison. This varying susceptibility to -the action of poison, the causes of which are very obscure, is called -disposition. - -Different species (of animals and men) exhibit often very different -degrees of susceptibility towards one and the same poison; the -differences in this respect are often very considerable, and one cannot -simply transfer the experience experimentally gained from one species of -animal to man or another species of animal, without further experiment. -Besides disposition, sex, and still more age, often determine within the -same species marked difference of susceptibility to a poison. Further, -there is an individual disposition due to qualities peculiar to the -individual, which makes some persons more than usually immune and others -specially susceptible. Individuals weakened by illness are particularly -susceptible to poisoning. Two diseases, in especial, favour the operation -of poison, influencing disastrously the capacity for assimilating -food, and reducing the general resisting power of the body; of these -tuberculosis stands first. - -Individual disposition plays in industrial poisoning a part which must -not be under-estimated; it determines the possibility of acclimatisation -to a poison; some individuals capable of resistance habituate -themselves—often comparatively easily—to a poison, and become, up to a -certain limit, immune against it, that is, they can tolerate a quantity -which would be injurious to others not so accustomed. With other -individuals, however, the opposite effect is apparent. Repeated exposure -to the action of the poison leads to an increased susceptibility, so -that acclimatisation is not possible. Innate hyper-sensitiveness of the -individual towards a poison is called idiosyncrasy. Frequently, for -example, this quality shows itself as hyper-sensitiveness of the skin -towards the harmful action of certain poisons. A marked lowering in the -sensitiveness, innate or acquired, of the organism towards a poison is -called immunity. - -The possibility of the absorption and action of a poison -presupposes—speaking generally—its solubility, and indeed its solubility -in the body juices. - -In general, poison can be absorbed at very different points of the body; -so far as industrial poisons are concerned, these are the mucous membrane -of the respiratory passages, the mucous membrane of the digestive tract, -and the skin, intact or broken. The rapidity of absorption depends on the -nature of the poison, of the individual, and the channel of absorption. -Of industrial poisons gases are relatively the most quickly absorbed; -sometimes indeed so swiftly that the effect follows almost immediately. - -Elimination of industrial poisons is effected principally by the -kidneys, the intestinal canal, the respiratory organs, and, more rarely, -the skin. Rapidity of elimination also depends on the nature of the -poison and of the person poisoned. - -If elimination is insufficient, or absorption takes place more quickly -than excretion, the poison accumulates in the body, and has a cumulative -effect which in chronic industrial poisonings plays a very important -rôle. Under certain circumstances poisons are not thrown off, but stored -up—fixed—in the body. - -The poison absorbed in the body can act unchanged from the place where it -is stored. A number of poisons, however, undergo in the organism chemical -change through which the action of the poison is partly lessened, -rarely increased. Among such changes and weakening of the poison are: -oxidation, as, for example, of organic poisons into their final products -(carbonic acid, water, &c.), oxidation of benzene into phenol, oxidation -of sulphur dioxide into sulphuric acid, &c.; reduction in the case of -metals, peroxides, &c.; neutralisation of acids by alkaline juices; -chemical union (for instance, of aromatic compounds with sulphuric acid). -The splitting up of albuminous bodies is not of importance in regard to -industrial poisons. - - -GENERAL REMARKS ON THE TREATMENT OF INDUSTRIAL POISONINGS - -Although in industrial poisoning the importance of treatment is small in -comparison with that of preventive measures, in discussing particular -forms of poisoning, full weight must be given to it; and in order to -avoid repetition, certain points will be brought forward here. - -Of the treatment of chronic industrial poisonings not much in general can -be said; unfortunately, special treatment has often little chance. It -will usually be of advantage to maintain the activity of the excretory -organs. So far as there is question of poisons affecting metabolism and -injuriously influencing the general state of nutrition, treatment aiming -at improving the general health and strength offers hope of success. -For nervous symptoms, especially paralysis, disturbance in sensation, -&c., treatment generally suitable to nervous diseases can be tried -(electro-therapeutics, baths, &c.). In treatment of acute industrial -poisonings, which often demand the prompt intervention of laymen, ‘first -aid’ is more hopeful. - -The most important general rules of treatment arise in reference to -irritant poisons which produce ulceration of the skin, and further in -regard to those poisons which cause unconsciousness, especially blood -poisons. - -When an irritant poison is acting on the skin, the first object to be -aimed at is naturally the immediate removal of the cause of corrosion -by water, or, better still, neutralisation by an alkaline solution (for -example, soda solution) in the case of corrosive acids, and weak acids -(organic acids, acetic acid, citric acid) in the case of caustic action -by alkalis. Such remedies must be at hand in factories as part of the -equipment for first aid, where irritant poisonings can occur. - -In those industrial poisonings which result in loss of consciousness, -arrest of respiration and suffocation, attempts at resuscitation should -at once be made. In these attempts at resuscitation, _artificial -respiration_ is of the greatest importance; of course the sufferer must -first be withdrawn from the influence of the poison, i.e. be brought into -fresh air. Great care must be taken, especially where it is necessary to -enter places filled with a poisonous atmosphere, to prevent the rescuers, -as is often the case, themselves falling victims to the influence of the -poison. They should be provided with suitable smoke helmets or breathing -apparatus. - -We will not describe the methods of resuscitation and artificial -respiration universally enjoined; they can be found in every first-aid -handbook. - -Emphasis is laid on the great importance of _treatment by oxygen_ in -cases of industrial poisoning through gaseous blood poisons, as this -treatment is attended with good results. Apparatus for the administration -of oxygen should be kept wherever there exists the possibility of such -poisoning, especially in mines, smelting works, chemical factories, and -chemical laboratories. - -Oxygen treatment rests on the fact that by raising the pressure of the -oxygen from 113 mm., as it is generally in ordinary air, to 675 mm., -which is reached in presence of pure oxygen, the quantity of oxygen -absorbed in the blood rises from 0·3 to 1·8 per 100 c.c. Further, -the saturation of the hæmoglobin, the colouring matter of the blood, -undergoes an increase of 2·4 per cent. This increase of oxygen in the -blood can save life in cases where through poisoning a deficiency of -oxygen has resulted. - -The introduction of oxygen is done by special apparatus which acts -essentially on the principle that during inhalation oxygen is pressed -into the lungs which are below normal physiological pressure, while -exhalation is effected by a deflating arrangement when the poisoned -individual no longer breathes of his own accord. When natural breathing -begins, the introduction of oxygen without special apparatus generally -suffices. - -[Illustration: FIG. 30.—Dräger’s Oxygen Box - -I Oxygen cylinder; A Valve on cylinder; B Manometer; C Key for opening -and closing the flow of oxygen; F Economiser; H Facepiece.] - -Dräger’s _oxygen apparatus_ (fig. 30) consists of a small oxygen cylinder -provided with a closing valve, a small manometer, a so-called ‘automatic’ -reducing valve with an arrangement for opening and closing the oxygen -supply, a bag to act as a receiver or economiser, a breathing mask, and -a metal tube connecting the breathing mask with the other parts of the -apparatus. The oxygen cylinder, when filled, contains about 180 litres of -oxygen, and the manometer allows the manipulator to control at any time -whatever oxygen it still contains. The automatic arrangement not only -reduces the pressure but at the same time controls the supply of oxygen. -This dose is fixed at three litres of oxygen per minute, so that the -apparatus with the same oxygen cylinder will last for sixty minutes. The -oxygen is not inhaled pure, but is mixed with atmospheric air according -to need, and in order to make this possible the breathing mask is -provided with a small hole through which atmospheric air finds entrance. - -[Illustration: FIG. 31.—Oxygen Inhaling Apparatus] - -[Illustration: FIG. 32.—Showing apparatus in use (_Siebe, Gorman & Co._)] - -As the oxygen flows continuously from the cylinder waste during -exhalation is prevented by the economiser, in which, during exhalation, -the inflowing oxygen accumulates, to be absorbed again in inhalation. A -small relief valve in the screw head of the bag prevents the entrance -into it of exhaled air. - -[Illustration: FIG. 33.—Dräger’s Pulmotor (_R. Jacobson_)] - -Another oxygen inhaling apparatus for resuscitating purposes, that of -Siebe, Gorman & Co., is illustrated in figs. 31 and 32. - -Dräger also constructs an apparatus called the ‘Pulmotor’ which -simultaneously accomplishes the introduction of oxygen and artificial -respiration. - -Inflation and deflation are effected by an injector driven by compressed -oxygen; this alternately drives fresh air enriched with oxygen into the -lungs and then by suction empties them again. While with the mechanical -appliances of resuscitation belonging to older systems the hand of the -helper regulated the rate of breathing, in the case of the Pulmotor -the lungs, according to their size, automatically fix the rate of -breathing; as soon as the lungs are filled the apparatus of its own -accord marks the moment for ‘deflation,’ and as soon as they are emptied -of ‘inflation.’ This automatic reversal is effected by a little bellows -which is connected with the air tubes. During inflation the same pressure -is exerted in the bellows as in the lungs. As soon as the lungs are -filled, the pressure in the bellows increases and it expands, its forward -movement causing the reversal to deflation. When the lungs are emptied -the bellows contracts, and through this contraction results the reversal -to inflation. - -If, in an exceptional case, the breathing for some reason does not act -automatically, the hand of the helper can manipulate it by means of a -backward and forward movement of a lever. According to choice, either a -nose-mask or a mask covering both mouth and nose can be worn. - -Combined with the regular apparatus for resuscitation is an ordinary -apparatus for the inhalation of oxygen; by the simple altering of a -lever, either the one or the other can be employed. - - - - -II. INDUSTRIAL POISONING IN PARTICULAR INDUSTRIES - - -After the foregoing general remarks we may now consider various points of -view in regard to classification of industrial poisonings into groups: - - (1) Toxicological, based on the action of the poisons. - - (2) Chemical, based on the chemical composition of the poisons. - - (3) Physical, based on the varying density of the poisons. - (Division into solid (in form of dust), gaseous, and liquid - poisons.) - -To which may be added: - - (4) Classification according to the source of the poisoning and - therefore according to industry, upon which Part I is mainly - based. - -In this section (Part II) a system is adopted which takes into -consideration as far as possible all the principles of division mentioned -above, in order to classify industrial poisonous substances in such a -manner that general practical conclusions can be clearly drawn, and -supervision rendered easy. - - -_GROUP: MINERAL ACIDS, HALOGENS, INORGANIC HALOGEN COMPOUNDS, ALKALIS_ - -Common to this group is a strong corrosive and irritant effect, varying -however in degree; as gases this group corrode or inflame the mucous -membrane of the respiratory passages, and in liquid form or in solution, -the skin. - -Besides this superficial effect single members of this group, especially -those containing nitrogen, produce a remote effect upon the blood. - -After absorption of the acids a decrease in the alkalinity of the blood -can take place and in its power to take up carbonic acid, thus vitally -affecting the interchange of gases in the body, and producing symptoms of -tissue suffocation. - -As regards treatment in the case of acids and alkalis, neutralisation -has been already mentioned; further, oxygen treatment may be recommended -in cases where the blood has been injuriously affected. In cases of -poisoning through breathing in acid vapours, inhalation of extremely -rarefied vapour of ammonia or of a spray of soda solution (about 1 per -cent.) is advisable. - - -MINERAL ACIDS - -=Hydrochloric Acid= (HCl) is a colourless, pungently smelling gas which -gives off strong white fumes. Experiments on animals, carefully carried -out by Leymann, produced the following symptoms. - -Even in a concentration of 2-5 per thousand clouding of the cornea -ensues, and after about an hour inflammation of the conjunctiva, violent -running from every exposed mucous membrane with marked reddening, and -frequently inflammation (necrosis) of the septum of the nose; the lungs -are distended with blood, here and there hæmorrhages occur in the -respiratory and also in the digestive tracts. The animal dies of œdema -(swelling) of the lungs and hæmorrhage into the lungs if exposed long -enough to the action of HCl, even though (according to Lehmann) there may -not be accumulation of HCl in the blood; the chief effect is the irritant -one; 1·5-5 per thousand parts HCl in the air suffices, after three or -four hours’ exposure, to affect smaller animals (rabbits) so much that -they die during the experiment or shortly after it. Man can tolerate an -atmosphere containing 0·1 to 0·2 per thousand HCl; a somewhat greater -proportion of HCl produces bronchial catarrh, cough, &c. - -The solution of hydrochloric acid in water is about 40 per cent. Simply -wetting the skin with concentrated solution of hydrochloric acid does not -generally have an irritant effect unless persisted in for some time; the -action of the acid, when continued, has a marked effect upon the mucous -membranes and upon the eyes. - -The same treatment already recommended in the introductory remarks on -poisoning by inhalation of acid fumes in general applies. - -=Hydrofluoric Acid= (HFl), a pungently smelling, colourless gas, causes -even in weak solutions (0·02 per cent.) irritant symptoms (catarrh of the -mucous membrane of the respiratory organs, lachrymation, &c.). Stronger -solutions set up obstinate ulcers, difficult to heal, in the mucous -membrane and the skin. - -=Silico-fluoric Acid= (H₂SiFl₆) produces an analogous though somewhat -less marked corrosive action. - -As regards treatment the reader is again referred to the introductory -sentences on this group. - -=Sulphur Dioxide= (SO₂) is a colourless, pungently smelling gas which, -acting in low concentration or for a short period, causes cough and -irritation of the mucous membrane of the respiratory passages and of the -eyes; acting for a longer period, it sets up inflammation of the mucous -membrane, bronchial catarrh, expectoration of blood, and inflammation of -the lungs. - -As Ogata and Lehmann have proved by experiments—some of them made on -man—a proportion of 0·03-0·04 per thousand of sulphur dioxide in the air -has a serious effect on a person unaccustomed to it, while workmen used -to this gas can tolerate it easily. - -As sulphur dioxide probably does not affect the blood, treatment by -oxygen inhalation is useless. Otherwise the treatment spoken of as -applying to acid poisonings in general holds good. - -=Sulphuric Acid= (H₂SO₄). Concentrated sulphuric acid occasionally -splashes into the eye or wets the skin, causing severe irritation and -corrosion, unless the liquid is quickly washed off or neutralised. If the -action of the acid persists, the corrosive effect becomes deepseated and -leads to disfiguring scars. - -=Nitrous Fumes, Nitric Acid.=—Nitric oxide (NO) oxidises in the air -with formation of red fumes composed of nitrogen trioxide (N₂O₃) and -nitrogen peroxide (NO₂). These oxides are contained in the gases evolved -from fuming nitric acid and where nitric acid acts upon metals, organic -substances, &c. - -Industrial poisoning by nitrous fumes is dangerous; unfortunately it -frequently occurs and often runs a severe, even fatal, course; sometimes -numerous workers are poisoned simultaneously. The main reason why nitrous -fumes are so dangerous is because their effect, like that of most other -irritant gases, is not shown at once in symptoms of irritation, such -as cough, cramp of the glottis, &c., which would at least serve as a -warning to the affected person; on the contrary, generally no effect at -all is felt at first, especially if the fumes are not very concentrated. -Symptoms of irritation usually appear only after some hours’ stay in -the poisonous atmosphere. By this time a relatively large quantity of -the poisonous gas has been absorbed, and the remote effect on the blood -induced. - -The first symptoms of irritation (cough, difficulty of breathing, -nausea, &c.) generally disappear when the affected person leaves the -charged atmosphere, and he then often passes several hours without -symptoms, relatively well. Later severe symptoms supervene—often rather -suddenly—difficulty of breathing, fits of suffocation, cyanosis, and -copious frothy blood-stained expectoration with symptoms of inflammation -of the bronchial tubes and lungs. These attacks may last a longer or -shorter time, and in severe cases can lead to death; slight cases end in -recovery, without any sequelæ. - -In poisoning by nitrous acid fumes, oxygen inhalation, if applied in -time, undoubtedly holds out hope of success, and should always be tried. -Chloroform has been repeatedly recommended as a remedy. Probably its -inhalation produces no actual curative effect, but only an abatement of -the symptoms through the narcosis induced. - -Nitric acid (HNO₃) in solution has an irritant corroding action if, when -concentrated, it comes into contact with the skin or mucous membrane. - - -THE HALOGENS (CHLORINE, BROMINE, IODINE) - -Chlorine (Cl) is a yellow-green, pungently smelling gas, Bromine (Br) a -fuming liquid, and Iodine (I) forms crystals which volatilise slightly at -ordinary temperatures. - -According to Lehmann’s experiments on animals the effect of chlorine -gas and bromine fumes is completely similar. Lehmann and Binz assume -that chlorine has a twofold effect: (1) narcotic, paralysing the outer -membrane of the brain, and (2) the well-known irritant action upon the -mucous membrane, producing a general catarrh of the air passages, and -inflammation of the lungs; it is, however, only the latter which causes -menace to life. Other writers do not mention the narcotic effect upon -the brain and assume that the halogens when brought into contact with -the mucous membrane are quickly converted into halogen hydrides, and, -as such, produce a corrosive effect. According to Lehmann, even 0·01 -per thousand Cl or Br in the air is injurious, even 0·1 per thousand -produces ulceration of the mucous membrane, and one or two hours’ -exposure to the poison endangers life. Lehmann has further tested (on -dogs) acclimatisation to chlorine, and finds that after a month the power -of resistance to chlorine appears to be increased about ten times. In a -further series of experiments the same author has proved that even the -smallest quantities of chlorine present in the atmosphere are completely -absorbed in breathing. - -Continued or frequent action of chlorine upon the organism produces -symptoms which have been described as chronic chlorine poisoning—such as -anæmia and indigestion, in addition to catarrhal and nervous symptoms. -Further, in factories where chlorine is produced by the electrolytic -process, workers were found to be suffering from the so-called chlorine -rash (first observed by Herxheimer). This skin disease consists in an -inflammation of the glands of the skin, with occasional development of -ulcers and scars. Severe cases are accompanied by digestive disturbance. -Bettmann, Lehmann, and others maintain that it is not caused by chlorine -alone, but by chlorinated tar products, which are formed in the -production of chlorine and hydrochloric acid. - -In acute cases of chlorine poisoning oxygen treatment should be tried, -but in any case the patient should have free access to pure air. -Approved remedies are inhalation of soda spray or very dilute ammonia, -or of a vapourised solution of sodium hypochlorite. If the patient is in -great pain, he may be allowed to inhale cocaine solution (0·2 per cent.). - -The administration of arsenic (solutio arsenicalis) is recommended, -especially in cases of acne. In general the usual treatment for diseases -of the skin is followed; salicylic acid lotions, sulphur baths, and -sulphur ointments may be made use of. - -=Chlorides.=—_Chlorides of Phosphorus_, _Phosphorus-trichloride_ (PCl₃), -and _Phosphorus oxychloride_ (POCl₃), are strong-smelling liquids, -fuming in the air, and when brought into contact with water decomposing -into phosphorous acid and hydrochloric acid. These halogen compounds -of phosphorus have a violently irritant action upon the respiratory -organs and the eyes, in that they decompose on the mucous membrane into -hydrochloric acid and an oxyacid of phosphorus. Inhalation of the fumes -of these compounds causes cough, difficulty of breathing, inflammation of -the respiratory passages, and blood-stained expectoration. - -Treatment is similar to that for acid poisoning in general and -hydrochloric acid in particular. - -Similar to that of the chlorides of phosphorus is the action of -_chlorides of sulphur_, of which _sulphur monochloride_ (S₂Cl)₂ is of -industrial hygienic importance as it is employed in the vulcanising of -indiarubber. It is a brown, oily, fuming liquid, which, mixed with water -or even in damp air, decomposes into sulphur dioxide and hydrochloric -acid. The fumes of sulphur monochloride have therefore a marked irritant -effect, like that of hydrochloric acid and sulphur dioxide. The action of -sulphur chloride was thoroughly studied by Lehmann. Industrial poisoning -by sulphur chloride is mentioned by Leymann and also in the reports of -the Prussian factory inspectors for 1897. The latter case ended fatally -owing to the ignorance of the would-be rescuers: a workman had spilt -trichloride of phosphorus upon his clothes, and the by-standers, not -knowing its dangerous action when combined with water, poured water on -him. - -Treatment is similar to that of poisoning from hydrochloric acid or -sulphur dioxide. - -_Chloride of zinc_ (zinc chloride, ZnCl₂) likewise has corroding and -irritant action upon the mucous membrane of the respiratory organs. - - -AMMONIA - -Ammonia (NH₃) is a colourless, pungent-smelling gas which dissolves -to the extent of about 33 per cent. in water. Inhaled, it first -produces violent reflex coughing, then irritation and corrosion of the -mucous membrane of the respiratory organs, and finally death through -suffocation (spasm of the glottis) if exposure to its action has lasted -a sufficiently long time. Microscopic sections exhibit a diphtheritic -appearance of the mucous membrane, and inflammation of the lungs. The -effects upon the central nervous system (irritation of the medulla -and spinal cord) which are peculiar to ammonia compounds need not be -considered, as the corrosion of the respiratory passage is sufficient -alone to cause death. When the action of the gas is less intense, the -patient rallies from the first stage, but often severe symptoms come on -later affecting the lungs. - -Lehmann in experiments upon himself could tolerate as much as 0·33 per -thousand NH₃ for thirty minutes; he found in gas works (with fairly -marked odour) hardly more than 0·1 per thousand NH₃ in the atmosphere, -and considers 0·5 per thousand distinct evidence of excess. He found -that he could produce in dogs acclimatisation up to 1·0 per thousand -NH₃ (five times as much as could at first be borne). About 88 per cent. -of the ammonia contained in the air is absorbed in breathing; ammonia -is said to exercise also a reducing action upon the oxygen of the blood -(oxyhæmoglobin). - -Chronic poisoning by ammonia can hardly be said to occur. In those who -clean out sewers and drains, the inflammation of the eyes and digestive -disturbance attributed partly to ammonia are probably due more to the -action of sulphur compounds—ammonium sulphide and sulphuretted hydrogen. -Irritation due to solution of ammonia does not come into account in -industrial employment. - -As regards treatment, fresh air or administration of oxygen is most -likely to be successful. Inhalation also of very dilute acetic acid -vapour, steam, or spray of sodium carbonate is advocated. - - -ALKALIS - -The alkaline hydroxides (potassium and sodium hydroxide, KOH, NaOH) -have an albumen-dissolving and therefore caustic effect. Industrially -it occurs in the caustic action of concentrated (often hot) lyes upon -the skin or upon the eye—through splashing. Quicklime (CaO) has also a -caustic action, producing inflammation of the skin or eyes (especially in -those engaged in the preparation of mortar). - -Under this head comes also the effect upon the respiratory -passages—described by several authors—caused in the production of -artificial manure discussed at length in Part I. - -As regards treatment of the irritant effect of alkalis, what has been -said as to corrosives in general applies here (rinsing with water or weak -organic acids), and in inflammation of the eye caused by lime a drop of -castor oil is recommended. - - -_GROUP: METALS AND METAL-COMPOUNDS_ - -The various substances of this group differ markedly in their action. -Under this heading come principally chronic metal poisonings, -characterised by a general, often very intense, disturbance of nutrition, -which justifies their delineation as ‘metabolic poisons’; among these -poisons also are included certain others which produce chronic poisoning -accompanied by severe disturbance of the peripheral and central nervous -system. - -The corrosive action common to the metal oxides (when acting in a -concentrated condition), attributable to the formation of insoluble -albuminates, need not, in industrial poisoning, be taken so much into -account. The corrosive effect is characteristic only of the compounds, -especially of the acid salts of chromium, which, as an acid-forming -element, may be classed in the preceding group. Disturbance of health -in workmen handling nickel compounds are also ascribed to the corrosive -action of these substances. - - -LEAD, LEAD COMPOUNDS - -Lead poisoning is the most frequent and important chronic industrial -poisoning; the symptoms are very varied and associated with the most -different groups of organs. We shall describe the typical course of a -case of industrial lead poisoning, laying stress, however, on the fact -that numerous cases follow an irregular course, in that special symptoms -or complications of symptoms are in some especially accentuated, while in -others they become less marked or are absent altogether. - -A premonitory indication of chronic lead poisoning is a blue line -on the gum, indicated by a slate gray or bluish black edging to the -teeth, the appearance of which is usually accompanied by an unpleasant -sweetish taste in the mouth. The cause of this blue line was for some -time disputed. It is obviously due to the formation and deposit of -sulphide of lead through the action of sulphuretted hydrogen arising from -decomposition in the mouth cavity. At the same time a general feeling of -malaise and weakness often comes on, occasionally accompanied by tremor -of the muscles and disinclination for food, at which stage the sufferer -consults the doctor. Frequently he complains also of pains in the -stomach, not difficult to distinguish from the lead colic to be described -later. Usually the patient already exhibits at this stage general -emaciation and marked pallor. - -The blue line was formerly considered a characteristic early indication -of lead poisoning; but it has now been proved that occasionally it is -absent even in severe attacks. But although the blue line may fail as -an ‘initial symptom,’ it will nevertheless be a valuable aid to the -practitioner in the recognition of lead poisoning. It is worth while -to mention the fact that other metallic poisons produce a very similar -‘line,’ especially mercury, also iron and silver (as in the case of -argyria); it has been stated that the blue line can be simulated by -particles of charcoal on the gum. The pallor of the patient at the -commencement of lead poisoning drew attention to the condition of the -blood. The diminution in the amount of hæmoglobin often met with, which -under certain circumstances is accompanied by diminution of the red -blood cells, offers nothing characteristic. On the other hand, structural -changes in the red blood cells—presence of basophil granules in them—are -asserted by a number of writers to be characteristic of the first stages -of lead poisoning. The basophil granules are believed to be due to -regenerative changes in the nucleus. But these changes are also found in -pernicious anæmia, cancer, leucæmia, anæmia, tuberculosis, &c.; also in a -number of poisonings such as phenylhydrazine, dinitrobenzene, corrosive -sublimate, and others; they are therefore the less characteristic of -chronic lead poisoning, as occasionally they cannot be found in actual -lead poisoning, a point upon which I have convinced myself in the case -both of men and animals. Still, the appearance of much basophilia in the -red blood cells is a valuable aid to diagnosis, especially as the method -of staining to demonstrate them is simple. - -Other anomalies of the blood observed in lead poisoning may here be -mentioned. Glibert found a striking diminution in the elasticity of the -red blood corpuscles, and experiments I have made point to the fact that -the power of resistance of the red blood corpuscles to chemically acting -hæmolytic agents, such as decinormal soda solution, is considerably -reduced. - -The pulse is generally hard and of high tension, especially during the -attacks of colic. Further, cramp of the bloodvessels (also in the retinal -arteries) has been observed. To these functional disturbances in the -circulation are added sometimes definite changes in the vessel wall. -Later, obliterative arteritis comes on (in the brain arteries), and -arteriosclerosis. - -The most important symptom of fully developed lead poisoning is colic, -which is usually preceded by the initial symptoms described (especially -the gastric symptoms), but not always so, as occasionally colic sets in -without any warning. The colic pains often set in with marked vehemence. -They radiate from the navel on all sides, even through the whole body; -the abdomen is contracted and as hard as a board. Pressure on the -lower part diminishes the pain somewhat, so that the sufferer often -involuntarily lies flat on his stomach. During the attack the pulse is -often remarkably slow. Constipation occurs, and often does not yield -to purgatives. The attacks last sometimes for hours, occasionally for -days, or the pains can (with remissions) even distress the patient for -weeks. The frequency of attacks is also very variable. Occasionally one -attack follows another, often there are intervals of weeks, even years, -according to the severity of the poisoning and duration of exposure. -If the patient is removed from the injurious action of lead, as a rule -recovery soon ensues. - -[Illustration: FIG. 34.—Paralysis of the Ulnar Nerve in Lead Poisoning] - -[Illustration: FIG. 34A.—Different Types of Paralysis of the Radial Nerve -in Hungarian Potters poisoned by Lead (_after Chyzer_)] - -Often with the colic, or at any rate shortly after it, appear lead -tremor and arthralgia, paroxysmal pain mostly affecting the joints, but -occasionally also the muscles and bones. They are often the precursor of -severe nervous symptoms which affect the peripheral and central nervous -system. In a lead poisoning case running a typical course the predominant -feature is the peripheral motor paralysis of the extensors of the -forearms. Next the muscles supplied by the radial and ulnar nerves are -affected. Often the progress of the paralysis is typical; it begins with -paralysis of the extensor digitorum communis, passes on to the remaining -extensors, then to the abductor muscles of the hand; the supinator -longus and triceps escape. Sometimes the shoulder muscles are attacked; -also paralysis in the region supplied by the facial nerve and of the -lower extremities is observed. It appears plausible that overstrain of -single groups of muscles plays a decisive part; this seems proved by -the fact that paralysis first affects, among right-handed people, the -right hand (especially of painters), but in the case of left-handed, -the left hand; and among children the lower extremities are often -attacked first. Disturbance of sight increasing to amaurosis is often -an indication of severe brain symptoms. The view of some writers that -the cause of the sight disturbance lies in vasomotor influences (cramp -of the bloodvessels) is very probable, and supports the view that the -brain symptoms are entirely due to diseases of the arteries (arteritis). -These symptoms are distinguished by the collective name of saturnine -encephalopathy; they include apoplexy, hemiplegia, epilepsy, delirium, -and mania. The brain symptoms may cause death. - -As later symptoms of lead poisoning may be mentioned lead gout and kidney -disease (lead nephritis). The genesis of both these diseases is much -disputed. It seems to be proved that the gout is true gout (with presence -of tophi) and that the contracted kidney is indistinguishable from -ordinary chronic Bright’s disease. - -The kidney symptoms suggest that a regular excretion of lead through the -urine takes place which, if it were a fact, would have been an important -aid to diagnosis. But often analysis of urine for presence of lead is -negative. Excretion of lead by the skin is scarcely to be credited, -although occasionally affirmed. Elimination of lead is effected mainly -through the intestines (probably for the most part as sulphide of lead). - -All lead compounds more or less are to be regarded as poisonous, although -the intensity of the action depends on the amount absorbed. For this its -solubility in water or in weak acids (hydrochloric acid of the gastric -juice) is the simplest test. According to this acetate of lead, lead -chloride, carbonate of lead (white lead), oxide of lead (lead dross), -minium (red oxide of lead) are relatively the most poisonous. Lead -sulphate and lead iodide are to be regarded as relatively less poisonous, -although by no means innocuous. The least poisonous, if not altogether -innocuous, is sulphide of lead, because it is an insoluble lead compound. - -Treatment of lead poisoning ought to aim first and foremost at the -elimination of lead from the body. But unfortunately such attempts have -had little success. Treatment of symptoms is all that for the most -part is possible. Administration of iodide of potassium to assist the -excretion of lead has not been found the success which many anticipated. -This remedy however, can be tried; better results are to be expected -from careful regulation of the bowels by means of purgatives. During -colic administration of opium or morphia may be advisable to relieve pain -and overcome the probable cramp of the intestinal muscles. The cautious -administration of atropine (occasionally with cocaine) also serves -the same purpose. Hot compresses and mustard plasters may be applied, -and liquid diet should be given. Lead cachexia must be treated by -strengthening diet. Electrical treatment for lead paralysis is advocated. -From baths (sulphur baths) nothing more is to be expected than a bracing -effect—elimination of lead through increased diaphoresis is hardly to be -hoped for. - - -ZINC (ZINC ALLOYS) - -Zinc (Zn) melts at 412° C. and distills at about 900° C.; exposed to -the air it burns, when heated, into zinc oxide. Older writers, when -investigating gastric and intestinal diseases and affections of the -nervous system observed in zinc smelters, regarded them as the result of -chronic zinc poisoning; but it may now be accepted as certain that these -symptoms are due to the lead always present in the zinc. - -On the other hand so-called _brass-founders’ ague_ may be regarded as -a form of acute industrial zinc poisoning. Brass-founders’ ague occurs -exclusively in brass casters, and not in zinc workers. Sigel and Lehmann -have shown that founders’ ague is also caused by pure zinc if this is -heated so strongly that it burns. - -Premonitory symptoms often occur before the onset of the disease; usually -they appear early, soon after casting has begun. The workman has general -malaise accompanied by slight cough, nausea, throat irritation, &c., but -these symptoms mostly disappear, returning again after a few hours with -renewed violence, often in the evening before going to bed. Frequently, -trembling sets in rather suddenly, often accompanied by headache, nausea, -and muscular pains, and soon develops into a pronounced shivering fit, -lasting generally about a quarter of an hour, but in severe cases for -several hours (with intervals). At the same time the breathing is hurried -and the heart’s action quickened (asthma and palpitation). Often the -temperature rises as high as 104° F. The attack ends with profuse -perspiration, and the patient sinks exhausted to sleep, awaking in the -morning generally quite restored or with but slight signs of fatigue; -only rarely is he unable to resume work. - -It is noteworthy that some workmen are extraordinarily susceptible to -brass-founders’ ague, and are attacked again and again, while others -remain completely immune, so that idiosyncrasy and immunity both play -a part. Workmen who are susceptible to the disease, yet without marked -disposition (idiosyncrasy) towards it, can become acclimatised to the -poison. Lehmann has succeeded in artificially producing an attack in -a brass-caster who was highly susceptible. The symptoms in him were -the result of work with pure zinc in a burning condition. The proof, -therefore, is clear that brass-founders’ ague is due to zinc, and not, as -some authors have supposed, to copper or the simultaneous action of both -metals. The symptoms are produced through inhalation of zinc oxide, not -zinc fumes. - -Lehmann conjectures that brass-founders’ ague may be a secondary fever -due to absorption into the system of the remains of cells in the -respiratory tract that have been killed by the action of the zinc. - -The treatment can only be symptomatic; as the attack is so transient, -medical attendance is hardly necessary. - - -MERCURY, MERCURY COMPOUNDS - -Mercury (Hg), on account of its volatility, is classed among industrial -poisons. Although boiling at 360° C. it is volatile even at ordinary -temperature. Industrial mercurial poisoning is caused by the frequent -inhalation of small quantities of vapour, sometimes, but more rarely, of -dust containing mercury, and assumes usually a chronic form. - -Industrial mercurial poisoning often begins with inflammation of the -mucous membrane of the mouth and gums. There is increased flow of saliva, -a disagreeable metallic taste in the mouth, and foul breath. This may be -limited to a simple inflammation of the gum, or go on to ulceration with -falling out of teeth, or even to gangrene of the gum and mucous membrane -inside the mouth. Gastric attacks also occur in the early stages; -occasionally, however, they are absent. - -The main symptoms of chronic mercurial poisoning are nervous and -psychical derangement, to which in severe cases are added general -disturbance of digestion and loss of strength. - -Sometimes, after repeated attacks, more or less severe, a cachectic -condition is induced, showing itself in general emaciation, decrease -of strength, atrophy of the muscles, anæmia, and disturbed digestion, -which—often intensified by some intercurrent disease, such as -tuberculosis—lead to death. Slight cases of mercurialism recover, leaving -no evil results, if the patient is removed in time from the influence of -the poison. - -The treatment of chronic mercury poisoning is symptomatic. To allay the -inflammation of the mucous membrane of the mouth the patient should use -a mouth wash of potassium chlorate and peroxide of hydrogen; the general -condition should be raised by strengthening, unstimulating food; for the -nervous symptoms baths and electricity should be tried; and for very -marked erythism and tremor recourse to narcotics may be necessary. - -Industrial mercurial poisoning is produced not only by metallic mercury -but also by many compounds, of which industrially the oxides are the -most important. Nitrate of mercury (Hg₂(NO₃)₂) comes into account in the -treatment of fur. Mercury cyanide (HgCy₂) deserves mention, as small -quantities cause mercurial and large quantities cyanogen poisoning. - - -MANGANESE, MANGANESE COMPOUNDS - -Manganese (Mn) or manganese compounds are used industrially in fine -powder; continuous absorption of dust containing manganese produces -chronic manganese poisoning. Instances of such poisoning are not very -numerous; altogether about twenty cases have been described. Recent -publications agree in asserting that only the dust rich in manganese -protoxide is dangerous. - -Industrial manganese poisoning runs its course extraordinarily slowly, -and resembles chronic poisoning by other heavy metals, such as lead and -mercury, in that nervous and psychical symptoms, rather than digestive, -are prominent. Sometimes—but not always—the disease is introduced or -accompanied by psychical symptoms, both of excitement and depression -(hilarity, laughing, or depression and weeping). In the course of the -disease nervous disturbances arise, deafness, tingling, paralysis and -paræsthesia, in the arms and legs, giddiness, difficulty of walking, -tremor, increased knee-jerks and difficulty in speech. Often at the same -time swelling of the lower extremities (œdema) and loss of strength -(cachexia, marasmus) come on. Slight cases make a good recovery. An -interesting case of illness is described by Jaksch as manganophobia, in -which the symptoms were simulated, and were brought on solely by the fear -of manganese poisoning. - -As regards treatment, electricity, massage, and baths are advocated to -allay the nervous symptoms, as in the case of chronic metal poisoning and -suitable strengthening food. - - -CHROMIUM, CHROME COMPOUNDS - -Chromium trioxide (CrO₃) dissolves in water, forming chromic acid -(H₂CrO₄); of the salts of chromic acid the neutral and acid alkaline -salts concern our inquiry. These are normal and acid sodium or potassium -chromate (K₂CrO₄ and K₂Cr₂O₇). Chromate of lead (PbCrO₄) can cause lead -poisoning. - -Poisoning can be produced by dust and by alkaline chromates, the -latter, when hot, giving off steam which, as has been proved, contains -excessively fine chrome particles. Chrome compounds attack especially the -surface of the body, the skin and the mucous membrane. - -The bichromate and chromate dust produce ulcers where slight injuries -to the skin already exist. The ulcers develop slowly, and have a -smooth, heaped-up, undermined edge; deep-seated, they can even pierce -to the bone; they heal with great difficulty. Naturally they occur most -frequently on the uncovered parts of the body, especially on the arms -and hands. Characteristic also is an analogous ulceration attacking -the mucous membrane of the nose, from which hardly any chrome worker -(especially if brought into contact with chromate dust) is free. -Perforation and destruction of the cartilaginous septum of the nose is -very common. Ulcers on the mucous membrane at the entrance of the throat -(on tonsils and palate or in the larynx) have been occasionally observed. - -Absorption of small quantities of chrome compounds into the body are said -to cause disturbances of digestion of an inflammatory character, and -especially inflammation of the kidneys. - -The treatment of chrome ulcers is similar to that of other chronic -ulcers. An antidote for industrial chrome poisoning is not known. - - -OTHER METALS AND METAL COMPOUNDS - -=Nickel Salts.=—Of late years in nickel-plating establishments an -eczematous inflammation of the skin has been described affecting -first of all the hands, and occasionally spreading over the arms and -even the whole body. The skin becomes inflamed, and vesicles appear -on the affected part. Some persons are extraordinarily susceptible -to this disease, others only become so after having worked for years -quite unaffected, and are then obliged to give up their occupation. -Probably the action of nickel salts (especially nickel sulphate) used -in electrolytic baths causes the disease. But it was in fact traced by -several writers to contact with benzene, petroleum, and lime by the -workmen. The simultaneous action of these substances upon the skin -would no doubt encourage its appearance. The application to the skin of -vaseline or cream is recommended. Careful cleanliness and attention to -the skin is on the whole by far the most reliable protection. - -[=Nickel carbonyl= (Ni(CO)₄).—Mond, Langer, and Quincke in 1890 -discovered that, on passing a current of carbon monoxide over finely -divided (pyrophoric) metallic nickel, a gaseous compound of nickel and -carbon monoxide was formed. When heated to 150° C. the gas decomposes -into its constituents and metallic nickel is deposited. - -Nickel carbonyl is a clear, pale straw-coloured liquid, volatilising -at room temperature. It has a peculiar soot-like smell detectable when -present to the extent of about 1 vol. in 2,000,000, while the Bunsen -flame becomes luminous when nickel carbonyl is present in the air to the -extent of 1 vol. in 400,000—two facts of great importance in detecting -escape of the gas in the manufacture of pure nickel by the Mond process. - -_Occurrence of poisoning by nickel carbonyl._—At the first introduction -of the process about 1902, before the dangerous properties of the gas had -been sufficiently recognised, some twenty-five men were poisoned, of whom -three died. Poisoning only occurred when, as a result of the breakdown -of the automatic working of the plant, hand labour took the place of -machinery. - -This very rare form of poisoning has been very fully investigated by -H. W. Armit (_Journ. of Hygiene_, 1907, p. 526, and 1908, p. 565). The -symptoms in man, he says, were transient headache and giddiness and at -times dyspnœa, quickly passing off on removal to fresh air. After from -twelve to thirty-six hours the dyspnœa returned, cyanosis appeared, and -the temperature began to be raised. Cough with more or less blood-stained -sputum appeared on the second day. The pulse rate became increased, but -not in proportion to the respiratory rate. The heart remained normal. -Delirium of varying types frequently occurred. Death took place in the -fatal cases between the fourth and eleventh days. The chief changes -found post mortem were hæmorrhages in the lungs, œdema of the lungs, and -hæmorrhages in the white matter of the brain, while some doubt exists as -to whether any blood changes were present. - -Precisely analogous results were found in experiments on animals -(rabbits, cats, and dogs). - -The points Armit investigated experimentally were (1) Is the carbon -monoxide of the compound wholly or partly responsible for the symptoms, -or (2), is nickel carbonyl absorbed as such, or (3), is it the nickel -of the compound which produces the symptoms? His conclusions are that -the poisonous effects of nickel carbonyl are entirely due to the nickel -of the compound. The peculiar toxicity is due to the fact that, being -introduced in a gaseous form, the nickel is deposited as a slightly -soluble compound in a very fine state of subdivision over the immense -area of the respiratory surface. Nickel carbonyl when mixed with air -cannot be absorbed as such by an animal as it becomes split up into the -nickel containing substance (possibly hydrated basic carbonate of nickel) -and carbon monoxide before or soon after reaching the alveoli of the -lungs. The nickel is dissolved from the respiratory surface by the tissue -fluids and is then taken up by the blood. The hæmorrhages found after -death follow as the result of fatty degeneration of the vessel walls -which is the specific pathological change set up by nickel.] - -=Copper.=—Symptoms which have been described by some writers as chronic -industrial copper poisoning are probably due to admixtures of other -poisonous metals, especially lead and arsenic. Although some copper -workers, especially those careless of cleanliness, exhibit hair and teeth -coloured by the action of copper compounds (green tinge on hair and edge -of teeth), symptoms of illness traceable to copper are not demonstrable. - -_Brass-founders’ fever_, which by some earlier writers was ascribed to -copper or combined copper and zinc action, is traceable to zinc (see -Zinc). - -=Ferro-silicon.=—The illnesses due to this are phosphoretted or -arseniuretted hydrogen poisoning (see pp. 191 and 197). - -=Silver and Silver Compounds.=—Gradual absorption of small quantities -of a solution of silver may produce industrial argyria, often beginning -with the appearance of a black edge to the gums and darkening of the hair -and nails, followed by black spots on the skin which in severe cases -coalesce, so that the whole or almost the whole surface of the body -becomes black and glossy. - -Argyria is due to the absorption of silver compounds into the -circulation, and subsequent deposition of the reduced silver in the body -(liver, kidneys, spinal cord, &c.). The black colouring of the skin is -caused by the action of light. - -No interference with health worth mentioning is observed. - - -_GROUP: ARSENIC, PHOSPHORUS_ - -The poisons (gradually absorbed) belonging to this group are mainly such -as affect metabolism; they impair the processes essential to metabolism -(in especial the oxidation processes) and cause severe damage to the -cells, through destruction of albumen. The poisons of this group also -have a paralysing effect upon the central nervous system. - -Generally speaking the effects produced by the poisons of this group vary -considerably. Among the arsenic compounds arseniuretted hydrogen, which -is supremely a blood poison, must be excluded from the group and included -among the blood poisons. - - -ARSENIC, OXIDES OF ARSENIC - -Pure _metallic arsenic_ (As) is considered innocuous. _Oxides of arsenic_ -especially are held to be industrial poisons such as arsenic trioxide -(As₂O₃), the anhydride of arsenious acid (H₃AsO₃), a white powder, which -is known under the name of white arsenic; _arsenic acid_ (H₃AsO₄), which -forms crystals easily soluble in water, and the salts of these acids, -especially copper arsenite, formerly employed in the production of dyes, -and also _arsenic chloride_ (arsenic trichloride, AsCl₃). _Arseniuretted -hydrogen_ will be treated separately as it has a completely different -poisonous effect from that of the oxidic compounds of arsenic. _Arsenic -sulphides_ (realgar, AsS₂, and orpiment, AsS₃) are regarded as innocuous -in consequence of their insolubility in a pure state. But it may be -remarked that arsenic sulphides (sulphur arsenic ores) which are used -industrially, and even metallic arsenic, are to be considered poisonous, -as they contain oxidic arsenic compounds in great quantity. - -Chronic arsenical poisoning is caused by gradual absorption through the -respiratory or digestive tracts of small quantities of the oxidic arsenic -compounds either in solution or as dust or fumes. - -The disease usually begins with digestive derangement which shows -itself in more or less severe gastric and intestinal catarrh (loss of -appetite, vomiting and diarrhœa); sometimes there are severe affections -of the respiratory tract,—pharyngeal and bronchial catarrhs; often the -illness is accompanied by skin affections of various kinds, rashes, -pustular eczema, loosening of the nails, abscesses, dark pigmentation -of particular parts of the skin, and other symptoms. The nervous -symptoms vary much according to the severity of the disease; first of -all, deafness and feeling of pins and needles, or loss of sensation -(paræsthesia and anæsthesia) of the extremities. Further, rheumatic -joint pains, weakness of the extremities and characteristic symptoms of -paralysis occur, with accompanying atrophy of the muscles, and gradual -loss of energy leading to total incapacity for work. Severe cases end in -general exhaustion and loss of strength, with signs of severe injury to -the central nervous system, such as epileptic fits, mental hebetude, &c. - - -PHOSPHORUS - -_Phosphorus_ (P) is polymorphic; red (amorphous) phosphorus is innocuous, -while white or yellow is poisonous. Phosphorus at various stages of -oxidation is little if at all poisonous. White phosphorus is volatile -and fumes in the air—the fumes consisting of phosphorus, phosphoric and -phosphorous acids. - -Chronic industrial phosphorus poisoning is produced by continued -inhalation of the fumes of white phosphorus resulting in inflammation -of the periosteum of the bone, with which necrosis and formation of new -bone are associated. It attacks especially the lower jawbone (ossifying -periostitis). The inflammation begins with increased flow of saliva, -painful swelling of the gums, which, as it increases, brings about the -death of the jawbone (necrosis, phosphorus necrosis). This becomes -covered again with newly formed bone substance from the periosteum. The -process ends with the formation of a fistula (a passage filled with pus), -which discharges outwards, and through which the dead bone (sequestrum) -is eventually cast off. Occasionally the process attacks the upper jaw, -rarely other bones. - -With these characteristic symptoms of phosphorus necrosis, derangement of -nutrition together with anæmia, indigestion and bronchial catarrh, may -be associated. Further, a general brittleness of the bones (fragilitas -ossium) is observed with the result that the long bones of the leg or arm -sometimes break at relatively small exertion of force; such cases from -Bohemia came lately under my notice. - -Some authorities regard caries of the teeth as the pre-disposing cause of -phosphorus necrosis; according to this view the carious teeth constitute -the means of entrance for the poison. Opposed to this so-called ‘local’ -theory is the view that chronic phosphorus poisoning is a ‘general’ one. -The truth may lie midway. On the one hand phosphorus necrosis probably -arises partly from the general poisonous action of the phosphorus, and on -the other from local inflammation which leads to the occurrence of local -symptoms. The general symptoms of chronic phosphorus poisoning described -above support this view, especially the effect observed on the bones of -the skeleton. This view is also strengthened by the fact that workmen -with perfectly sound teeth, who had been exposed to phosphorus fumes for -many years, were attacked by necrosis only when traumatic inflammation -produced by chance injury was set up. - -The treatment of phosphorus necrosis is surgical. Formerly the treatment -recommended was to wait for formation of new bone and exfoliation of the -dead bone (expectant treatment); the necrosed portions of bone were then -extracted through the fistula. Recently early operative interference has -succeeded in preserving the periosteum which enabled the new bone to form. - - -Phosphoretted Hydrogen - -Industrial poisoning by gaseous phosphoretted hydrogen (PH₃) calls for -attention in connection with the preparation and employment of calcium -carbide (acetylene) and also of ferro-silicon. - -Phosphoretted hydrogen is a dangerous poison. Even 0·025 per cent. in -the air is harmful to animals after a time; 0·2 per cent. PH₃ in the air -quickly causes death. - -The poison produces changes in the lungs, though without injuring the -respiratory passages by corrosion, and finally has a paralysing effect -upon the central nervous system. It has no effect upon the blood. An -autopsy on a person who has died of phosphoretted hydrogen poisoning -reveals as a rule no characteristic sign, except centres of inflammation -in the lungs. - -The symptoms of phosphoretted hydrogen poisoning are—difficulty of -breathing, cough, fainting fits, noises in the ears, and nausea; -in severe cases coma and death. Slight cases soon recover without -after-effects. - - -_GROUP: SULPHURETTED HYDROGEN, CARBON BISULPHIDE, AND CYANOGEN (NERVE -POISONS)_ - -In this group are comprised industrial poisons the principal effect of -which is upon the nervous system, especially the central nervous system. -The chemical composition of the separate members of the group differs -much. - - -SULPHURETTED HYDROGEN - -Industrial poisoning by pure sulphuretted hydrogen (SH₂), the well-known -colourless, nauseous-smelling gas, occurs comparatively rarely. Poisoning -is generally acute, but chronic illness in workers has been traced back -to inhalation of the gas. - -This poison exerts a paralysing action upon the central nervous system -and is slightly irritating to the mucous membranes and respiratory organs. - -Its action can be described as follows: When absorbed into the blood -union of the poison with the alkaline constituents takes place with -formation of an alkaline sulphide. Presence of only slight quantities -of sulphuretted hydrogen in the air acts injuriously. Lehmann has shown -that about 0·15 to 0·2 per thousand sulphuretted hydrogen is not without -effect, and that prolonged inhalation of 0·5 per thousand becomes -dangerous. Continued exposure to the poison seems only to increase -susceptibility to its action. An almost complete absorption of the whole -of the sulphuretted hydrogen present in the air breathed takes place. - -Continued inhalation of small quantities of sulphuretted hydrogen -produces irritation of the mucous membrane, cough, and lacrymation; -headache, giddiness, nausea, and mental dulness soon ensue; occasionally -also symptoms of intestinal catarrh follow; if at this stage—or after -a longer exposure to the action of a smaller amount—the patient is -withdrawn from its further influence, there still continue for some time -symptoms of irritation of the mucous membrane (such as inflammation of -the conjunctiva and of the respiratory passages). - -Further exposure or absorption of greater amounts induces general -discomfort and passes on to a second stage of convulsions and delirium. - -Inhalation of a large dose of sulphuretted hydrogen causes almost -instantaneous death; the affected person falls dead—often without -a sound—as if struck by a blow; occasionally a short stage of -unconsciousness, with symptoms of suffocation, precede death. - -This acute form often occurs, especially in acute sewer gas poisoning. -Besides this, a sub-acute form of sewer gas poisoning is recognised -which is attributable, in part at least, to the action of sulphuretted -hydrogen, the prominent symptoms being irritation of the mucous membranes -and of the intestinal canal. In other severe cases symptoms of the -central nervous system preponderate (headache, giddiness, and delirium). -These forms of poisoning can be caused not only by sulphuretted hydrogen, -but also by other poisonous gases which are found in drains or sewers. - -As regards treatment, continued inhalation of oxygen, supported by -artificial respiration, is often, in serious cases, effective. In severe -poisonings also saline injections and bleeding may be advocated. Other -symptoms (catarrh, &c.) must be treated symptomatically. - - -CARBON BISULPHIDE - -Pure carbon bisulphide (CS₂) is a colourless, peculiar-smelling liquid -which boils at 46° C. - -As Lehmann has shown, even 1·5 to 3·0 mg. CS₂ per litre of air produces -distress—with acute symptoms of poisoning (congestion, giddiness, -sickness, &c.). - -Industrial carbon bisulphide poisoning is, however, chronic in nature and -induced by continuous inhalation of small quantities of the fumes. To -understand the action of carbon bisulphide, its capacity for dissolving -fats and fatty substances must be taken into account. Its injurious -effect extends to the nerve tissues (central and peripheral nervous -system) and the glandular tissues. - -Throughout chronic industrial carbon bisulphide poisoning, which has -been described fully by Delpech, Laudenheimer, and others, nervous and -psychical symptoms predominate, together with severe chronic digestive -derangement. - -The patient after exposure for some time suffers from violent headache, -giddiness, and sickness; he has sensations of cold, pains in the -limbs, a feeling of ‘needles and pins,’ and itching in different parts -of the body. Gradually a condition of general excitement develops. -Sleeplessness, cramps, and palpitation set in. At the same time the -nervous system becomes involved—hypersensitiveness, loss of sensation -or complete numbness of some parts of the skin, diminution of muscular -power, disturbances of movement, twitching, violent trembling, wasting -of the muscles, and paralysis; the sight also is sometimes affected. -The stage of excitement, in which the patient often becomes strikingly -loquacious without cause, passes gradually, as the nervous symptoms -develop, into the stage of depression; sometimes this takes weeks and -months; excitement and gaiety give place to deep depression; other -symptoms appear—weakness of memory, mental dulness, and difficulty in -speaking. The powers of sensation become affected, paralysis increases, -and digestive disturbances, anæmia, and general loss of strength are -manifest. Occasionally definite mental disease (psychosis, mania, -melancholia, dementia, &c.) develops. - -Certain cases of chronic carbon bisulphide poisoning in indiarubber -workers have come under my notice, and some remarks concerning them -may be of interest. The characteristic symptoms are essentially as -follows: the invalid appears in the consulting-room in a bent position, -leaning upon a stick with head and hands shaking. The gait is clumsy -(spastic-paralysis) so that the patient ‘steps’ rather than walks. When -seated, the tremor ceases to some extent, but in purposive movements -increases rapidly, involving the whole body, so that an exact systematic -examination becomes impossible, and the invalid sinks back into the -chair exhausted and bathed in perspiration. He complains of cold in -the extremities. He looks pale; the skin of the upper extremities is -totally without feeling, as also is the upper part of the feet; the skin -of the head is hypersensitive; the muscular strength of the arms is -almost lost; testing the strength brings on marked shaking, followed by -a fainting-fit caused by exhaustion. The extremities of the patient are -cyanotic (livid); the knee jerks are exaggerated. The patient suffers -from indigestion, constipation, headache, and giddiness; he is irritable, -and depressed; his memory is weak; mental derangement cannot be proved. - -Chronic carbon bisulphide poisoning is rarely fatal. Slight cases end in -recovery after more or less long continuance; in severe cases improvement -occasionally takes place, but serious nervous disturbance (paralysis, -weakness of the muscles, deterioration of intellect) usually persists. - -Treatment is symptomatic, aiming especially at relieving the nervous -symptoms and improving the state of nutrition. If psychical disturbances -are prominent, treatment in an institution is necessary. - - -CYANOGEN AND CYANOGEN COMPOUNDS (CYANOGEN GAS, PRUSSIC ACID, CYANIDES) - -Industrial cyanogen poisoning is not frequent. _Cyanogen gas_ (C₂N₂, -existing in small quantities in furnace gas, illuminating gas, and other -kinds of gas) and especially _hydrocyanic acid_ (CNH, prussic acid) are -considered industrial poisons; the latter is a very unstable, colourless, -pungent-smelling liquid, boiling at 27° C. Among the cyanides employed -industrially and having an effect similar to that of prussic acid must be -mentioned _cyanide of potassium_ and _cyanide of sodium_ (KCN and NaCN), -_cyanide of silver_ (AgCN) and _cyanide of mercury_ (Hg[CN]₂). - -Cyanogen and cyanogen compounds are extraordinarily powerful poisons. The -minimum dose lies, as Lehmann has proved by experiments on animals, at -about 0·05 per thousand of hydrocyanic acid in the atmosphere breathed; -1-5 mg. per kg. weight is fatal to animals; to man about 60 mg. would be -fatal. - -The poisonous action of cyanogen and cyanogen compounds depends upon -their power of preventing absorption of oxygen from the blood by the -tissues with the result that the venous blood flowing to the heart -retains the bright red colour which otherwise only arterial blood -exhibits. This effect is due to cessation of the gaseous exchange in the -body, and results in tissue suffocation. At the same time these poisons -have at first an exciting and then a paralysing effect upon the central -nervous system. In severe poisoning the nerve effect is masked by the -effect upon the exchange of gases in the blood, since this quickly leads -to death. - -Most of the cases of industrial poisoning under this heading result from -inhalation; absorption of liquid cyanogen compounds through the skin can -rarely come into consideration. - -If large quantities of hydrocyanic acid have been inhaled, death ensues -very quickly. The person affected falls down suddenly, breathes with -difficulty, the pulse soon becomes imperceptible, and after a more or -less long stage of deep unconsciousness (coma) life becomes extinct. - -In slight cases of poisoning the patient feels a sensation of irritation -in the throat, giddiness, sickness, and difficulty in breathing; -occasionally such disturbances persist for some time. - -Some writers have described symptoms in workers manipulating prussic -acid and cyanides, which they believe to be due to chronic prussic -acid poisoning. Complaint is made of oppression of the chest, throat -irritation, giddiness, difficulty in breathing, palpitation, hebetude, -exhaustion, and nausea and vomiting; in certain instances the attack, -aggravated by exhaustion and weakness, culminates in death. It is a -question whether such poisonings are chronic in the true sense of the -word. In view of the mode of action of hydrocyanic acid, such cases -of sickness should rather be accounted acute or sub-acute poisonings -through repeated action of small quantities of the poison. - -It may be mentioned that in persons working with alkaline cyanides -(especially in electro-plating) skin affections occasionally occur; these -are traceable to the caustic effect of alkaline cyanides. - -Treatment by oxygen inhalation with simultaneous artificial respiration -holds out most prospect of success. This holds good for acute poisoning -by the other poisons belonging to this group. Besides this, saline -injections and bleeding are recommended, and also the administration of -an infusion of sodium thiosulphate solution. - - -_GROUP: ARSENIURETTED HYDROGEN AND CARBONIC OXIDE (BLOOD POISONS)_ - -Included in this group, as in the former one, are substances chemically -very different from each other, but of which the action is especially -on the blood. Besides this common effect, these substances also produce -various other effects, such as local irritation, effect on the nervous -system, &c. The industrial blood poisons, which according to their -chemical constitution are classed among the aliphatic and the aromatic -series of organic compounds, will, for the sake of clearness, be -discussed in the following chapters. - - -ARSENIURETTED HYDROGEN - -Acute arseniuretted hydrogen poisoning, produced by inhalation of -relatively very small quantities of arseniuretted hydrogen gas (AsH₃) -is in most cases industrial in origin. The absorption of an amount -corresponding to about 0·01 mg. arsenic suffices to produce severe -poisoning symptoms. The poisonous effect results chiefly from action upon -the red blood corpuscles, which are dissolved (hæmolysis). Arseniuretted -hydrogen is therefore a genuine blood poison. The effect upon the -blood, if not immediately fatal to life, is to cause the dissolved -blood-colouring matter to pass into the tissues where, though some is -deposited, most goes to, and acts injuriously on, the organs, especially -the liver, spleen, and kidneys. In cases running at once a fatal course, -the impoverishment of the blood caused by the lack of colouring matter -necessary to internal respiration produces tissue suffocation, which is -therefore the primary cause of death. In cases not immediately fatal, the -injury to the functions of the organs alluded to (for instance, cessation -of the functions of the kidneys, &c.) may lead to death secondarily. - -Symptoms of the disease appear often only some time after the poisoning -has set in, and begin with general malaise, sickness, collapse, fainting -fits, and difficulty of breathing; after some hours the characteristic -signs follow—the urine becomes dark red to black, containing quantities -of blood colouring matter and dissolved constituents of the blood, and -later also bile colouring matter, so that a coppery jaundice comes on if -the illness is prolonged. The region of the liver, spleen, and kidneys -is painful. Severe cases often end fatally during the first stage of -the illness, more rarely later, with increased difficulty of breathing; -sometimes death occurs after a preceding comatose stage marked by -convulsions and delirium. In slighter poisoning cases the symptoms abate -in a few days and recovery follows. - -The treatment of arseniuretted hydrogen poisoning is similar to that -adopted in the case of all other blood poisonings: in addition, if -possible, direct transfusion of blood from the artery of the giver into -the vein of the receiver, liquid nourishment, saline injections, and, -above all, prolonged oxygen inhalation. - - -CARBONIC OXIDE (CO) - -Carbonic oxide (CO) is a colourless, odourless gas which frequently -causes both acute and, it is said, chronic industrial poisoning. - -Carbonic oxide is a very poisonous gas; even as little as 0·5 per -thousand in the atmosphere breathed has a poisonous effect; about 2-3 per -thousand can be dangerous to life. - -Its poisonous effect results from its power of combining with the -blood-colouring matter or hæmoglobin to form carboxy-hæmoglobin; the -affinity of carbonic oxide for the hæmoglobin of the blood is more than -200 times greater than that of oxygen, so that, however small the amount -of carbonic oxide in the air, it is inevitably absorbed by the blood and -retained. The blood so altered, assumes a cherry-red colour, is unable to -effect the necessary exchange of gases for internal respiration, and in -consequence of the lack of oxygen suffocation ensues. - -Without doubt, however, carbonic oxide has also an immediate effect -upon the central nervous system (first excitation, followed quickly -by paralysis). It is maintained also that besides the action upon the -hæmoglobin it favours coagulation of the blood through the disintegration -of the blood corpuscles. The last-mentioned action is thought to account -for the sequelæ of carbonic oxide poisoning, but they can also naturally -be accounted for by the direct effect of the poison. - -Onset of symptoms is very sudden if a large quantity of pure carbonic -oxide is inhaled. The affected person immediately falls down unconscious -and succumbs after drawing a few breaths with difficulty. - -In less acute cases the illness begins with premonitory symptoms, -generally headache, sickness, giddiness, sleepiness, though in cases -of fairly rapid absorption these are absent, and are naturally absent -also when the poisoning creeps upon the affected persons while asleep, -as occasionally happens in cabins, &c., in factories. If the poisoning -continues, increasing mental dulness, accompanied by nausea and vomiting, -leads sometimes to a short stage of seemingly drunken excitement, which -preludes deep unconsciousness during which there is often a convulsive -stage, followed by complete loss both of sensation and of reflex action; -the breathing becomes shallow and intermittent, the pulse small and -irregular, and finally death ensues. Occasionally in the stage of -unconsciousness, death is hastened by entrance of vomited matter into the -respiratory passages. Bright red patches are seen on the body after death. - -If persons affected by severe carbonic oxide poisoning are withdrawn -from the poisonous atmosphere after having reached the stage of -unconsciousness, they may recover, but often with difficulty; not -infrequently—in spite of suitable treatment—death occurs some -considerable time later from the symptoms described above. Still, in many -cases, under the influence of right treatment, gradual recovery has been -brought about, even after long unconsciousness accompanied by repeated -convulsions. In the rescued the symptoms described as characteristic of -the first stage often continue for at least a day. Further, they are -liable to a number of serious after effects, such as severe inflammation -of the lungs due to infection by the entrance of vomited matter into the -air passages, skin affections (rashes), and especially severe nervous and -mental affections. Frequently these develop from centres of softening -in the brain or from inflammation of the peripheral nerves (neuritis); -occasionally the poisoning may really only be the predisposing cause for -the outbreak of an existing psychical disease. It is not our task to -enumerate all the extremely varied disturbances which are observed after -carbonic acid gas poisoning. Neuralgias and paralyses have been described -as associated with the peripheral nerve symptoms over areas supplied -by different nerves; various forms of diseases of the brain and spinal -cord (poliomyelitis, paralysis, sclerosis, &c.); and finally a series of -psychoses (neurasthenia, melancholia, mania, &c.), occasionally passing -into dementia and imbecility. Glycosuria (sugar in the urine) has also -been noted as a sequela. - -Chronic carbonic oxide poisoning, arising from continued inhalation of -small quantities of the gas, sets in usually with symptoms similar to -those of acute carbonic oxide poisoning; if the worker continues exposed -to danger, severe symptoms may arise which point to marked alteration of -the blood and later also of the digestion and bodily functions. Under -certain circumstances severe nervous and mental affections are said -to occur similar to those which we have mentioned as sequelæ of acute -carbonic oxide poisoning (convulsions, disturbances of mental activity, -symptoms which resemble progressive muscular atrophy, &c.). - -In acute carbonic oxide poisoning oxygen inhalation indefatigably -continued and supported by artificial respiration is often successful. -The serious danger from this form of poisoning renders it very necessary -that in all premises where there is risk provision should be made for -the administration of oxygen. The sequelæ can of course only be treated -symptomatically. - - -OXYCHLORIDE OF CARBON (PHOSGENE) - -Oxychloride of carbon (COCl₂), also called phosgene, is, at the ordinary -temperature, a colourless gas with a disagreeable smell. This decomposes -in moist air into carbonic oxide, hydrochloric acid, or chlorine, and -produces a strongly irritant local effect upon the mucous membranes. -Industrial poisoning by phosgene is characterised by great difficulty -in breathing and inflammation of the respiratory tract (bronchitis and -bloodstained expectoration). - -Several cases have been treated successfully by oxygen inhalation. - - -NICKEL CARBONYL - -The effects of nickel carbonyl are described on pp. 186-8. - - -CARBONIC ACID - -Carbonic acid (CO₂), a colourless gas, is heavier than air (specific -weight, 1·526), and therefore, wherever it collects, sinks to the ground. -Carbonic acid is only very slightly poisonous; about 10 per cent. -carbonic acid in the air causes asphyxia. The extinguishing of a candle -flame will serve as an indication that the amount of carbonic acid in -the atmosphere has reached this point. Cases of industrial carbonic acid -asphyxia are sudden; they do not occur frequently. - -The gradual action of the gas when mixed with air produces first a -tingling sensation on the surface of the body, reddening of the face, -irritation of the mucous membrane and the respiratory organs, after -which succeed difficulty in breathing, palpitation, fainting, and -unconsciousness. - -Sudden and fatal poisoning occurs industrially. Upon entering places -filled with carbonic acid gas the affected person falls down dead almost -immediately. These are cases of asphyxia, in which the lack of oxygen -certainly plays the greatest part. If those affected by acute carbonic -acid poisoning are removed in time out of the dangerous atmosphere they -usually recover quickly. - -Oxygen inhalations and artificial respiration are to be applied in -severer cases. There are no sequelæ. - - -_GROUP: HYDROCARBONS OF THE ALIPHATIC AND AROMATIC SERIES AND THEIR -HALOGEN AND HYDROXYL SUBSTITUTION PRODUCTS_ - -The industrial poisons comprised in this group have as their principal -general effect injurious action upon the functions of the central -nervous system (paralysis or causing excitation) which is prominent in -most of the cases of industrial poisoning caused by these substances. -This effect is most marked in the case of the readily volatile (low -boiling) hydrocarbons, while those less volatile and boiling at a higher -temperature often have collateral effects (such as local irritation). -The characteristic poisonous effect caused by the chlorine and -hydroxyl-substitution products (chloroform and alcohol group) is also -mainly on the central nervous system (narcosis). - - -HYDROCARBONS OF MINERAL OIL - -BENZINE, LIGROINE, PETROLEUM, PARAFFIN, VASELINE - -_Mineral oil_ (crude petroleum) has, according to its origin, differing -composition. Thus in American mineral oil hydrocarbons of the methane -series preponderate; in the Russian, hydrocarbons of the aromatic series. -Reference has been made in Part I. to this point, as well as to the -separation of crude petroleum into its different fractions. - -The injury to health produced by crude petroleum and its derivatives is -of two kinds. Direct contact with liquid petroleum and the semi-liquid -and solid deposit after distillation (paraffin) cause local injury to the -skin. Inhalation of the volatile constituents of raw petroleum causes -symptoms affecting mainly the central nervous system. They have moreover -a markedly irritating effect upon the mucous membrane of the respiratory -organs. These substances clearly exhibit the characteristic we have -referred to, namely, that the hydrocarbons boiling at low temperature act -as nerve poisons, whereas those boiling at a higher temperature produce a -local irritant effect. - -The skin affections take the form of inflammation of the hair follicles -(acne), eruptions with characteristic formation of vesicles, and -pimples and pustules which precede the deep-seated formation of ulcers, -abscesses, &c. - -In paraffin workers the acne-like skin inflammations are known as -‘paraffin eczema.’ They develop sometimes into cancer of the skin (warty -and epitheliomatous growths). - -In the general poisoning produced by inhalation of petroleum fumes the -effect upon the central nervous system is all the more plainly and -clearly marked when the irritant effect of the hydrocarbons boiling at -higher temperature is slight or absent; that is, in the case of poisoning -which arises solely from industrial products of low boiling hydrocarbons; -among these benzine is included. - -Acute poisoning from inhalation of benzine fumes begins with headache, -sickness, and attacks of giddiness resembling alcoholic intoxication. If -very much has been inhaled, the patient quickly becomes unconscious, with -occasionally muscular tremors, convulsions, difficulty in breathing, and -cyanosis. - -In cases of poisoning by inhalation of fumes of crude petroleum, these -symptoms may be complicated by coughing, intense inflammation of the -mucous membrane of the respiratory organs—congestion, bronchitis, -bloodstained expectoration, and inflammation of the lungs. In workers -who frequently remain long in an atmosphere filled with benzine fumes, -further symptoms of chronic benzine poisoning show themselves—mental -hebetude, pains in the limbs, trembling, weakness of the muscles, and -other disturbances of the nervous system; in such cases these may really -be signs of continued attacks of acute or sub-acute poisoning; many -benzine workers are anæmic. - -The treatment of acute benzine poisoning consists in oxygen inhalation, -with simultaneous artificial respiration. Treatment of chronic -derangement of health is symptomatic. - - -HYDROCARBONS OF THE AROMATIC SERIES - -BENZENE AND ITS HOMOLOGUES - -_Benzene_ (C₆H₆) is a characteristically smelling (aromatic) liquid which -boils at 80·5° C. Acute benzene poisoning, which plays an important part -as an industrial poisoning, is caused by inhalation of benzene fumes. The -various kinds of benzol used commercially contain, besides benzene, alkyl -benzenes, especially _toluene_ (methylbenzene, C₆H₅.CH₃, boiling-point -111° C.); _xylene_ (dimethylbenzene, C₆H₄[CH₃]₂, boiling-point 140° -C.); _pseudocumene_ and _mesitylene_ (tri-methylbenzene, C₆H₃[CH₃]₃, -boiling-point 169° or 163° C.); the regular presence of _thiophene_ -(C₄H₄S, boiling-point 84° C.) in commercial benzol must also be taken -into account. Industrial benzol poisoning arises, therefore, as a rule, -not from the action of pure benzene vapour, but from fumes which contain -a mixture of the compounds mentioned. - -The course run by industrial benzol poisoning is often very acute, if -large quantities are inhaled—death occurring suddenly, after a short -illness with symptoms of vertigo. Gradual inhalation of lesser quantities -gives rise to headache, giddiness, malaise, then twitchings appear -which develop into convulsions, and lastly unconsciousness. In order to -ascertain in what manner the various substances contained in commercial -benzol share in the poisonous effect, experimental research seemed to me -to be indispensable, especially as published statements so far gave no -accurate data. - -Two cases of industrial benzol poisoning have given rise to close -experimental research upon the poisonous nature of benzene. - -Lewin undertook experiments on animals; which he confined under bells -and caused to inhale fumes of chemically pure and impure benzene. He -mentions that even at comparatively low concentration poisoning results, -and indeed more readily and certainly from the action of impure than pure -benzene. Lewin found that when air was made to flow slowly first through -benzene and then into the bell, symptoms of paralysis, convulsions, -and unconsciousness showed themselves in from four to six minutes. -After-effects by this means could not be observed. Lewin maintains, -however, that in man even slight acute action of benzene can be followed -by after-effects (giddiness, sickness, headache, distress in breathing, -and oppression of the heart). - -Santesson made researches upon the poisonous action of benzene in -connection with occurrence of certain cases of poisoning through ‘impure -benzol’ (coal-tar benzene) in a rubber tyre factory. In the factory -mentioned nine young women were poisoned, of whom four died. The symptoms -shown were lassitude, anæmia, giddiness, headache, vomiting, and fever. -Post mortem, hæmorrhages and fatty degeneration of the endothelium of the -bloodvessels and various organs were found. Experimental research showed -that commercial benzol and chemically pure benzene had the same effect. -Santesson did not succeed in his experiments on animals in producing -chronic poisoning by inhalation of benzine and of benzene fumes (which -two completely different poisons he does not distinguish strictly from -each other, as is the case, unfortunately, with many other writers). My -experimental researches upon the poisonous effect of pure benzene, pure -toluene, cumene, thiophene, and the most important kinds of commercial -benzol gave the following results: - -For rabbits the limit of toxicity is a proportion of 0·015 to 0·016 per -thousand pure benzene in the air, that is 0·015 to 0·016 c.c. benzene -vapour per litre of air. - -A concentration of 0·056-0·057 per thousand pure benzene in the air -causes in rabbits at once—after one minute—twitching of the muscles; -after eight minutes, convulsions; after ten minutes, deep narcosis; and -after twenty-five minutes, coma. If the animal is taken out of the bell -in time, even if it has shown marked symptoms, it recovers very quickly -(in two to ten minutes) without manifesting any after effects. Even in -animals repeatedly exposed to the poison sequelæ were not observed. - -Dogs are somewhat more susceptible to pure benzene than rabbits; 0·024 -per thousand causes after ten minutes severe convulsions, which after -twenty minutes become continuous; 0·042 per thousand kills after twenty -minutes (sudden death in a state of tetanus). - -Cats are less sensitive than dogs and more sensitive than rabbits; -0·03-0·04 per thousand causes after ten minutes attacks of cramp and, -after twenty minutes, convulsions; 0·05 per thousand at once brings on -poisoning symptoms. As regards the character of the symptoms (cramps, -convulsions, quick recovery, no after effects) the above statements apply -to all three kinds of animals (rabbit, dog, and cat). - -Chloral hydrate completely checks the convulsions and enables animals to -tolerate higher concentrations of benzene for a longer time. - -Benzene is thus to be counted among nerve irritant poisons. The -convulsions are probably provoked by excitement of the motor centres in -the brain. - -In view of the fact that thiophene in a concentration of 0·03-0·05 per -thousand in the air was borne by animals for an hour without producing -any symptoms of poisoning, the proportion of thiophene in commercial -benzol must be looked upon as practically non-injurious. - -The so-called 90 _benzol_—a commercial benzol of which 90 per cent. -distils at 100° C.—has naturally a somewhat weaker action, although, in -respect of the poisoning symptoms produced, it is similar to that of pure -benzene. - -_Pure toluene_ (boiling-point 111° C.) and purified toluol (commercial -product, boiling-point 109°-112° C.) produce, when inhaled, gradually -increasing narcosis in the three kinds of animals referred to; they -produce no symptoms of convulsions or spasms. - -After the animals have been taken out of the bell, recovery is not so -rapid as after benzine inhalation, but takes from half an hour to one -hour. In rabbits and cats 0·046-0·05 per thousand produces after fifteen -minutes staggering and paresis; after thirty minutes deep narcosis. The -dog is again somewhat more susceptible, as little as 0·034 per thousand -causing these symptoms in the same time. - -‘Purified toluol’ (commercial product) acts somewhat less rapidly -than pure toluene, but this small difference in effect need hardly be -considered. - -Other poisons were also investigated:— - -_Solvent naphtha I_, a commercial product, of which 90 per cent. -comes over at 160° C.; it contains little toluene, chiefly xylene, -pseudocumene, and cumene. - -_Solvent naphtha II_, of which 90 per cent. comes over at 175° C, it -contains besides xylene, chiefly pseudocumene, mesitylene, cumene, &c. - -The fumes of solvent naphtha I cause, when inhaled by rabbits, dogs, and -cats, gradual narcosis, although not nearly so quickly as toluene at -similar concentrations; recovery usually takes over an hour after the -deeply narcotised animals have been removed from the bell. Rabbits and -cats are affected in about equal degree. The dog is the more sensitive. -Rabbits and cats can tolerate about 0·012-0·013 per thousand of the -fumes of solvent naphtha I in the atmosphere for a long time without any -symptoms. Only after breathing for fifty minutes air containing 0·0536 -per thousand do they become narcotised. In the dog 0·036 per thousand -causes narcosis only after thirty minutes. - -With the fumes of solvent naphtha II I could not affect rabbits at all. -The cat also, in spite of long inhalation of the heavy fumes, showed no -marked symptoms of poisoning. In the dog gradual narcosis came about only -after an hour’s inhalation of 0·048 per thousand. - -The fumes of pure _xylene_ caused narcosis in rabbits after forty -minutes’ inhalation of 0·05 per thousand in the atmosphere; after being -taken out of the bell the animals recovered slowly (after half an hour to -one hour). - -_Cumene_ causes no symptoms after one hour’s inhalation in a -concentration of 0·06 to 0·07 per thousand. This explains the effects of -solvent naphtha I (in which xylene preponderates) and solvent naphtha II -(in which pseudocumene, cumene, &c., preponderate). After effects were -not observed. - -Benzol and toluol fumes, and particularly those of solvent naphtha, -exercise a distinctly irritant effect upon the mucous membrane, which, -however, passes off without after effects. - -Pure benzene, therefore, proved the most poisonous of the substances -under investigation. When inhaled its effect (convulsions, with quick -recovery) differs essentially from that of toluene, solvent naphtha, -xylene, and cumene (gradual narcosis, slow recovery). The fumes of the -various kinds of commercial benzol (solvent naphtha) boiling at a higher -temperature are practically non-poisonous (solvent naphtha II). Pure -benzene fumes are, however poisonous, even in very small quantities in -the air. The limit for animals lies at 0·015-0·016 per thousand. - -Lehmann has shown in a recent work that man, exposed to a mixture of -benzene and air, absorbs 80 per cent. of the benzene. - -Treatment of acute industrial benzene poisoning consists in severe cases -of artificial respiration, with simultaneous administration of oxygen; in -slight cases it is sufficient to bring the patient into fresh air. - -_Naphthalene._—Naphthalene, which is insoluble in water, has irritant -effect upon the mucous membrane and upon the skin when brought into -contact with it. - -Long continuance in an atmosphere containing naphthalene as dust or fumes -causes headache, nausea, giddiness, &c. - - -HALOGEN SUBSTITUTION PRODUCTS - -ALIPHATIC SERIES (NARCOTIC POISONS) - -The halogen substitution products of the aliphatic series are not of -much account as industrial poisons. They have generally a narcotic -effect, that is, a paralysing effect upon the central nervous system, -usually preceded by a short stage of excitement. This effect shows itself -typically on inhalation of chloroform (methanetrichloride, CHCl₃), which -however plays no part as an industrial poison. The narcotic effect of -the other alkyl chlorides is less than that of chloroform. With carbon -tetrachloride (CCl₄) the narcotic effect is only half that of chloroform; -it causes, however, a more violent excitation; inhaling the fumes brings -on nausea, coughing, sickness, headache, &c. - -_Methylchloride_ (CH₃Cl) has a less narcotising effect. On the other hand -it has a stronger local irritant action, which is indeed present also in -chloroform, though not so apparent. This gas, as is well known, is used -as a local anæsthetic in medicine. - -Pure _methylene chloride_ (CH₂Cl₂) similarly is much less powerful than -chloroform. Severe poisoning, alleged to have resulted from methylene -chloride was caused by a mixture, called indeed methylene chloride, but -composed of methylalcohol and chloroform. - -Of the remaining halogen substitution products of methane, _methyl -bromide_ (CH₃Br) and _methyl iodide_ (CH₃I) have given rise to industrial -poisoning. - -These poisons also act in the same way as the alkyl chlorides, but the -excitement accompanying the narcosis is more marked—so far as the scanty -observations allow conclusions to be drawn. The symptoms first show -themselves in sickness, giddiness, hebetude, slowing of respiratory -movements and of the heart’s action; convulsions or delirium ensue. - -Treatment consists in artificial respiration or promotion of breathing -by a plentiful supply of fresh air or oxygen; in pronounced narcosis -stimulating remedies should be applied. - - -BENZENE SERIES - -_Chlorobenzene_, and _nitro-_ and _dinitro-chlorobenzene_ and -_benzoylchloride_, have given rise to industrial poisoning. - -To chlorobenzene similar action is attributed as to benzene (headache, -fainting, rapid breathing, cyanosis); changes in the blood (methæmoglobin -formation) have also been observed. - -Nitro- and dinitro-chlorobenzene are active poisons; the effect -corresponds in general to that of nitro- and dinitrobenzene, but in -addition the fumes or dust have markedly irritant action on the skin -(dermatitis). - -_Benzoylchloride_ (C₆H₅COCl), a colourless, pungent-smelling liquid, -produces a violently irritant effect upon the mucous membrane, -decomposing into hydrochloric acid and benzoic acid. - -Treatment is analogous to that of benzene poisoning, and in cases of -benzoyl chloride poisoning to that by hydrochloric acid. - -It may be mentioned that chlorine rash is attributed to the action of -chlorinated tar products (chlorobenzene compounds). - - -HYDROXYL SUBSTITUTION PRODUCTS - -FATTY SERIES (ALCOHOLS) - -The hydroxyl substitution products of the fatty series belong mainly -to the narcotic poisons; the greater the molecular weight of the -alcohol, the more marked is usually the narcotic effect. According to -this propylalcohol is eighteen times as poisonous as ethylalcohol; -butylalcohol and amylalcohol have from 36 to 120 times as great a -narcotic effect as methylalcohol. - -_Methylalcohol_ (wood spirit, CH₃OH) plays relatively the greatest part -among alcohols as an industrial poison, because it is employed as a -means of denaturing spirit. Its poisonous nature is relatively great, -being very persistent. Industrial poisoning by methylalcohol is due to -inhalation of the vapour and is rarely of a severe nature. The fumes -have a strongly irritant effect upon the mucous membrane, giving rise to -throat irritation, cough, hoarseness, and in severe cases bronchitis and -inflammation of the conjunctiva of the eye. In addition inhalation of -methylalcohol vapour causes headache, giddiness, nausea (inclination to -vomit), and occasionally also twitchings and tremor. - -The _higher alcohols_ (propyl-, butyl-, amyl-alcohol, C₃H₇.OH, C₄H₉.OH, -and C₅H₁₁.OH) occur in fusel oil. They cause but slight (if any) -industrial poisoning. Cases of more severe industrial poisoning through -amylalcohol fumes have been described (in factories for smokeless -powder), with symptoms of sickness, headache, giddiness, with fatal -issue in some cases, preceded by severe nervous symptoms (convulsions or -delirium). - -Beyond speedy removal out of the dangerous atmosphere, probably no -special treatment is needed in these cases of industrial poisoning from -alcoholic vapour. - - -_GROUP: NITRO AND AMIDO COMPOUNDS OF THE ALIPHATIC AND AROMATIC SERIES -(BLOOD POISONS WHICH FORM METHÆMOGLOBIN)_ - -Characteristic of the nitro and amido compounds of the aliphatic and -aromatic series of the organic substances is their action upon the -blood. The normal oxyhæmoglobin (blood-colouring matter) is changed -into methæmoglobin, with which the oxygen is so firmly combined that -the internal exchange of gases necessary to life becomes impossible. -Methæmoglobin has a dark chocolate-brown colour and a clearly defined -characteristic spectrum. - -Of the poisons belonging to this group several are important. In so -far as these substances are volatile—and this is generally the case -with those causing industrial poisoning—effects are due to inhalation -of fumes, but it is proved that the poisons of this group in liquid -form can be absorbed by the intact skin, and this channel of absorption -is characteristic of industrial poisoning. Severe poisoning results -especially from wetting the skin by spilling on the clothes, &c. - -The grey-blue discoloration of the mucous membrane, especially of the -lips, is characteristic; sometimes also the skin is altered in colour. -This discoloration is often noticed by others before the patient feels -unwell. Soon the person affected has general nausea, vomiting, headache, -giddiness, severe nervous symptoms, feeling of anxiety, and difficulty -of breathing; in severe cases unconsciousness comes on, and death occurs -with increasing cyanosis (lividity). - -Treatment is naturally that which has been emphasised in the introductory -words to Part II, which hold for all blood poisonings. In mild cases -oxygen treatment has given good results. In all factories where such -poisoning can occur provision should be made for immediate oxygen -treatment. Besides this, the workers must be adequately instructed as to -the danger and symptoms of poisoning, especially of the characteristic -premonitory skin discoloration, in order to be able to assist their -fellows. - - -NITROCOMPOUNDS - -ALIPHATIC SERIES - -_Nitro-glycerin_ (triple nitric acid ester of glycerin, C₃H₅.[NO₃]₃), -the well-known oily explosive liquid, has also an irritant local effect. -When absorbed into the body, in addition to methæmoglobin formation, it -causes dilatation of the bloodvessels, slowing of the respiration and -heart’s action, and attacks of suffocation. The general remarks upon this -group apply here, but symptoms referable to central paralysis occur as -the methæmoglobin formation is slow. Industrial poisoning arises through -inhalation of gases containing nitro-glycerin and also by absorption -through the skin. Statements as to its poisonous nature are very varied. -Under certain conditions moistening the skin with small quantities of -nitro-glycerin suffices to produce symptoms. Probably the susceptibility -of different persons varies greatly. - -_Amylnitrite_ (nitric acid amyl ester, C₅H₁₁NO₂), a characteristically -smelling liquid, acts similarly. The fumes of amylnitrite, even when -inhaled in small quantities, cause marked dilatation of the bloodvessels, -through paralysis of the muscular walls of the bloodvessels, thus causing -marked flushing of the face; the pulse becomes quick, then weak and slow. - - -NITRO AND AMIDO COMPOUNDS - -AROMATIC SERIES - -The substances of this group are important. - -_Nitrobenzene_ (C₆H₅NO₂, named oil of mirbane), a yellowish liquid of -characteristic smell, induces especially the formation of methæmoglobin -in the blood; the effect upon the central nervous system (first -excitation, then depression) is often absent. The description of the -disease in general in the introductory words of this whole group is -characteristic. Occasionally signs of asphyxia show themselves; sometimes -there are twitchings, disturbance of the power of sensation, and -convulsions; early discoloration of the mucous membrane and the skin, -which assume a blue to grey-black colour, is characteristic. - -Chronic poisoning is also attributed to nitrobenzene, showing itself in -lassitude, headache, malaise, giddiness, and other disturbances of the -nervous system. - -_Nitrotoluene_ (C₆H₄CH₃NO₂), of which the ortho-compound acts most -powerfully, and also _nitroxylene_ (C₆H₃[CH₃]₂NO₂) have similar but less -marked effect. - -The _dinitrobenzenes_ (C₆H₄[NO₂]₂) are stable bodies. Meta-dinitrobenzene -inhaled as dust or otherwise, can produce marked poisoning symptoms -essentially the same as those described. Especially characteristic is the -early dark discoloration of the skin. - -Symptoms resembling nitrobenzene poisoning in general are caused by -_nitrophenols_ (C₆H₄.OH.NO₂), of which paranitrophenol is the most -toxic; also by _dinitrophenols_ (C₆H₃[NO₂]₂OH), solid crystalline -substances which melt at different temperatures, and the _mono-_ and -_di-nitrochlorobenzenes_ (C₆H₄.Cl.NO₂ and C₆H₃.Cl[NO₂]₂). In cases of -industrial poisoning by dinitrophenol, observed by Leymann, the workers -were taken suddenly ill, with symptoms of collapse, pains in the chest, -vomiting, distress of breathing, rapid pulse, and convulsions, and died -within a few hours. At the autopsy a yellow substance was found with -picric acid reaction which appeared to be di- or tri-nitrophenol. In -other cases, some fatal, of industrial nitrochlorobenzene poisoning, also -observed by Leymann, the typical grey-blue discoloration of the skin -was obvious, and the chocolate-brown colour of the blood produced by -methæmoglobin. - -_Trinitrophenol_ (picric acid, C₆H₂[NO₂]₃OH) is a yellow crystalline -compound with bitter taste; poisoning by this substance exhibits clearly -strong local irritant action (upon skin, mucous membrane, and intestinal -canal, and especially upon the kidneys), besides effect on the blood and -central nervous system. Prolonged action of picric acid upon the skin -causes inflammation. Absorption of picric acid dust causes inflammation -of the mucous membrane of the respiratory passages and symptoms of -gastric and intestinal catarrh as well as inflammation of the kidneys. - -A jaundice-like discoloration of the skin and darkening of the urine are -also characteristic; sometimes picric acid poisoning produces a rash -resembling that of measles and scarlet fever. - -_Nitronaphthalene_ (C₁₀H₇[NO₂]) and _nitronaphthol_ (C₁₀H₆.NO₂.OH) in -addition to methæmoglobin formation have an irritant action. It is stated -also that dulness of the cornea is produced. - -_Azobenzenes_ also, which are to be considered as intermediate between -nitrobenzene and aniline, form methæmoglobin (azobenzene, C₆H₅N = NH₅C₆). - -_Aniline_ (amidobenzene, C₆H₅.NH₂), a colourless, oily liquid of aromatic -smell, has only slight local irritant effect. In the frequent cases -of industrial poisoning by ‘aniline oil’ or aniline hydrochloride, in -which the aniline enters through the skin or is inhaled in the form -of fume, there appear the typical symptoms common to this group, of -the action upon the blood through methæmoglobin formation: headache, -weakness, cyanosis, difficulty in breathing, &c., to which are added -nervous symptoms such as convulsions and psychical disturbance, although -these play a subordinate part in industrial poisoning. In severe cases -the typical symptoms of air hunger are shown. Occasionally recovery -only takes place gradually, and signs of irritation of the kidneys -and inflammation of the urinary organs are seen. These symptoms occur -only rarely in acute industrial poisoning, but are, however, in so far -worthy of notice because of the frequent occurrence of tumours in the -bladder among aniline workers. It is possible that here the irritant -action of the urine which contains aniline plays a part. The tumours -in the bladder operated upon, in some cases with success, were many of -them non-malignant (papillomata), but some were carcinomata (cancerous -new growths) running a malignant course, and recurring after operation. -In the urine the aniline combines with sulphuric acid, and is partly -excreted as paramidophenol sulphuric acid. - -The treatment of aniline poisoning is the same as that for all the -poisons of this group. In view of the occurrence of tumours of the -bladder in aniline workers, they should be instructed to seek medical -aid on the first indications of trouble, so that a careful cystoscopic -examination may be made. - -_Toluidine_ (C₆H₄.CH₃.NH₂), which is mixed with aniline for industrial -use, produces the same symptoms with marked irritation of the renal -organs. - -Of the _nitroanilines_ (C₆H₄.NH₂.NO₂) _paranitroaniline_ is the most -poisonous. Characteristic of the action of this compound is methæmoglobin -formation, central paralysis and paralysis of the heart’s action. - -Of the _benzenediamines_, _paraphenylene diamine_ (C₆H₄[NH₂]₂) may be -regarded as an industrial poison. The irritant action of this substance -is prominent; it induces skin affections, inflammation of the mucous -membranes, more especially of the respiratory organs, and sometimes -inflammation of the kidneys. They have been noted in workers using ursol -as a dye; here, doubtless, the action of diimine (C₆H₄.NH.NH.) must be -taken into account, which arises as an intermediate product and exercises -a markedly irritant action. Further, the general effect of paraphenylene -diamine is an irritant one upon the central nervous system. - - -_APPENDIX_ - -TURPENTINE, PYRIDINE BASES, ALKALOIDS - -_Turpentine oil._.—Turpentine oil is a peculiar-smelling, colourless -liquid of the composition C₁₀H₁₆; different reactions show that -turpentine oil contains the aromatic nucleus (cymene). It is used in -the manufacture of varnish, and thus can cause industrial poisoning -by inhalation of fumes. Even from 3 to 4 mg. of vapour of turpentine -oil per litre of air brings on severe symptoms. Turpentine oil acts as -a local irritant, and when absorbed into the system has an exciting -effect upon the central nervous system. Inhalation of large quantities -of turpentine vapour cause rapid breathing, palpitation, giddiness, -stupor, convulsions, and other nervous disturbances, pains in the chest, -bronchitis, and inflammation of the kidneys. The last-mentioned symptom -also arises from the chronic action of turpentine vapours. - -_Pyridine._—Pyridine (C₅H₅N), a colourless liquid of peculiar odour, is -employed as well as methylalcohol in denaturing alcohol. The disturbance -of health observed in workers occupied with the denatured spirit are -probably mainly due to the inhalation of fumes of methylalcohol. Pyridine -is comparatively innocuous. Eczema, from which persons suffer who -come into contact with denatured spirit, is ascribed to the action of -pyridine. Larger doses produce a paralysing effect, but this need not be -considered in its industrial use. - -_Nicotine, tobacco._—According to various published statements, effects -among tobacco factory workers are attributed to the nicotine contained -in tobacco dust and to the aroma which fills the air. Nicotine in large -doses has at first an exciting followed by a paralysing effect upon the -central nervous system; it causes moreover contraction of the unstriped -muscles and has a local irritant effect. - -The symptoms of illness ascribed to nicotine are: conjunctivitis, catarrh -of the air passages, palpitation, headache, want of appetite, and, -particularly, tendency to abortion and excessive menstruation. Severe -industrial poisoning due to nicotine has only been observed in workers -who chewed tobacco leaves. - -_Poisonous wood._—The symptoms of disease noticed in workers who -manipulate certain kinds of wood are attributed by some writers to the -presence of alkaloids. Such knowledge as we have of the illness due to -them—they are evidently of the nature of poisoning—is referred to at the -end of Part I. - - - - -PART III - -_PREVENTIVE MEASURES AGAINST INDUSTRIAL POISONING_ - - - - -I - -_GENERAL MEASURES_ - - -In discussing preventive measures against industrial poisoning the -deductive method from the general to the particular will be followed. The -numerous instances of poisoning mentioned in Part I afford a practical -basis on which to formulate general rules before passing on to describe -special measures. Technical details will be omitted, as they must be left -to the technical expert whose business it is to draw up the plans as a -whole and to modify them according to the requirements of individual -cases. - -In the effort to control industrial poisoning and disease it is necessary -to insist absolutely on the concerted action of all concerned. In this -co-operation every one is called who through his knowledge and sphere of -activity is in a position to assist. - -The medical man comes in with his special knowledge of the action of -poisons as toxicologist, as practising physician (especially as works -surgeon and doctor of the sick insurance society), and also in an -official capacity as appointed surgeon or medical officer of health; the -technical expert comes in as engineer, as manager, as foreman, and as -factory inspector. But above all the interest and active co-operation of -employers and employed are needed as well as the organisations of both. -That the workers should understand and co-operate is essential for the -success of preventive measures, and subsequently it will be shown in what -direction this co-operation is most necessary. - -To make possible such co-operation interest must be aroused and -suitable information and teaching supplied to the parties concerned. -Medical men and practical workers require to receive instruction in -industrial hygiene, and teaching on this subject should be arranged -for in secondary and technical schools. Medical men and others who, as -officials and insurance doctors, are brought constantly into touch with -industrial workers should have opportunity—by means of special courses -and lectures—to keep pace with advancing knowledge in this direction. -Beside these there are, as educative organisations, special Institutes -of Industrial Hygiene and special hospitals for treatment of diseases -of occupation which bring together the patients and the teaching staff -and so facilitate pursuit of knowledge and research. A beginning of -this kind has already been made by the Industrial Hygiene Institute, -Frankfurt a.-Main, and the hospital for diseases of occupation at Milan, -showing that the ideas are attainable. International agencies which unite -all circles interested in the subject irrespective of profession or -nationality in common interchange of thought and discussion are of great -significance for uniform development of needful preventive measures; -international congresses, often in connection with exhibitions, have -given valuable stimulus and have been the starting-point of permanent -international societies, unions, and organisations. The significance -for our inquiry of these international efforts will be more closely -considered in the following pages. - - - - -II - -_GENERAL CONSIDERATIONS ON SOCIAL AND LEGISLATIVE MEASURES_ - -INTERNATIONAL PREVENTIVE MEASURES, NOTIFICATION OF INDUSTRIAL POISONING, -LISTS AND SCHEDULES OF INDUSTRIAL POISONS - - -Experience and inquiry in the field of industrial poisoning led to a -series of demands which, supported as they were by a general movement -for the protection of workers, were soon followed by regulations and -legislative action. For a long time efforts have been directed to treat -industrial disease and poisoning in the same way as has been done in -the case of industrial accidents. The question, however, is attended -with much greater difficulty. On the other hand, uniform international -regulation of questions affecting prevention of disease is called for -both on humanitarian and economic grounds. - -The idea of international legislation for the protection of workers -was first mooted about the year 1870. The possibility and need of such -intervention was much discussed and interest in it kept constantly alive, -especially in Switzerland, until the organisations of the workers took -up the idea. Several attempts failed. In France in 1883 a proposal of -the Socialist party aiming at international agreement on the subject -of protection of the workers was rejected. In 1885 (in opposition -to Hertling) Prince Bismarck expressed himself strongly against the -possibility of such international protection. But the stone, once set -rolling, could not be stayed. In the years 1886, 1887, and 1888 the -French and English trade unions, as well as the Swiss Federal Council, -took up the question afresh. These endeavours at last took tangible shape -in the first International Conference for the protection of workers held -in Berlin in March 1890. This date remains a landmark in the history of -the subject, but not until ten years later—1900—did the Congress held -in Paris for the international legal protection of workers lead to the -establishment of what had been repeatedly urged, namely, creation of an -International Bureau. This was inaugurated at Basle in 1901 and forms the -headquarters of the National Associations for Labour Legislation called -into being in various countries. - -This International Association meets regularly in conference, as in -Cologne (1902), Berne (1905), Lucerne (1908), Lugano (1910), and Zurich -(1912). The questions raised in the International Labour Bureau, -which receives financial aid from a number of States, are fully and -scientifically discussed with the object of finding a basis on which to -bring into agreement the divergent laws of the different countries. A -further task of this strictly scientific institution is the collection -and publication of literature bearing on the protection of workers in -one and another country, distribution of information, and the editing of -reports and memoranda. The question of prevention of industrial poisoning -has always taken a foremost place in the programme of the International -Association and in the agenda of the International Labour Bureau. At its -first meeting a resolution was adopted advocating the prohibition of the -use of white phosphorus and white lead, and the Labour Bureau in Basle -was instructed to take the necessary steps. Special, if not prohibitive, -economical considerations foreshadowed difficulties—all the greater -because the matter at issue concerned prohibition of articles playing -a part in the markets of the world. Just on that account international -treatment of such questions is necessary, since a peaceful and orderly -solution can only be arrived at on such lines. International effort -endeavours here to press with equal weight on the countries competing -with one another commercially, so that in the protection of the workers -economic adjustment is sought in order that efforts based on humanitarian -grounds shall not at the same time cause economic disadvantages, the aim -being to produce general welfare and not merely protection of one class -at the expense of another. - -Through these international agreements between various countries success -in the direction aimed at is hopeful, and indeed to a certain extent—as -in the phosphorus and lead questions—actually attained. Thus, for -example, Germany and Italy were in a position to enforce prohibition of -the use of white phosphorus early, while their neighbour Austria, on -account of commercial and political considerations and the conditions of -the home lucifer match industry, has only recently decided on prohibition. - -As international agreement for the protection of workers is advisable -on economic grounds, so also is it reasonable and just from purely -humanitarian reasons that workers, without reference to civil condition -or nationality, should be equally protected. On this point it is proposed -to take a vote and to press only for those reforms which are thoroughly -sound and recognised as necessary. - -The first step in such a comprehensive attack is precise knowledge of -the extent and source of origin of the particular forms of industrial -poisoning and disease and the collection of reliable statistics. This -suggested the obligation to notify such cases to the proper authorities -in the same way as is now done in the case of infectious disease. A -motion to this effect had already been passed at the Conference of the -International Association for Labour Legislation held in Basle, and a -request was made to the Labour Bureau to prepare a list of the diseases -and poisonings in question. To them we shall refer later, but a schedule -is necessary as a basis to work upon. Yet even when this is done there -are obviously great difficulties to be overcome in carrying out the -requirement of notification when the aim is kept in mind of collecting -complete statistical data for controlling the conditions giving rise -to industrial disease. The proposal of the International Association -seeks to make notification obligatory on the part both of the medical -practitioner in attendance and the occupier, and in connection with -this to secure the co-operation of the Sick Insurance Society.[D] The -proposal to require the appointed surgeons and surgeons of the Insurance -Society to notify all cases is hardly feasible in view of their dependent -position. Nor can the obligation on the occupiers lead to the desired -result because of their lack of medical knowledge and the fact that -by notifying they might be forced to act to their own disadvantage. A -successful effort in this direction is recorded in Saxony, where lead -poisoning was first made a notifiable disease, and later the general duty -of notification of industrial poisoning was prescribed by Order dated -March 4, 1901. - - +-----------------------+-----------------------------------------------+ - | | Reported Cases.[E] | - | Disease and Industry. +-------+-------+-------+-------+-------+-------+ - | | 1912. | 1911. | 1910. | 1909. | 1908. | 1907. | - | (1) | (2) | (3) | (4) | (5) | (6) | (7) | - +-----------------------+-------+-------+-------+-------+-------+-------+ - |Lead Poisoning |587 (44|669 (37|505 (38|553 (30|646 (32|578 (26| - | 1. Smelting of metals| 56 (7| 48 (3| 34 (5| 66 (5| 70 (2| 28 (2| - | 2. Brass works | 5 | 9 (1| 7 | 5 | 6 | 9 (1| - | 3. Sheet lead and | | | | | | | - | lead piping | 6 | 12 | 4 | 9 (2| 14 | 6 | - | 4. Plumbing and | | | | | | | - | soldering | 35 (5| 37 (2| 25 (1| 28 | 27 | 20 (2| - | 5. Printing | 37 | 32 (2| 33 (4| 21 (1| 30 (2| 26 (3| - | 6. File cutting | 13 | 18 (2| 9 (1| 8 | 9 (2| 10 | - | 7. Tinning | 15 (11| 13 | 17 | 22 | 10 | 25 | - | 8. White lead | 23 | 41 (2| 34 (1| 32 (2| 79 (3| 71 | - | 9. Red lead | 3 | 13 (1| 10 | 10 | 12 | 7 | - | 10. China and | | | | | | | - | earthenware | 80 (14| 92 (6| 77 (11| 58 (5|117 (12|103 (9| - |10a. Litho-transfers | 1 (1| 1 | 1 | 1 | 2 | 10 | - | 11. Glass cutting and | | | | | | | - | polishing | 1 (1| 5 | — | 4 (2| 3 (1| 4 | - | 12. Vitreous | | | | | | | - | Enamelling | 5 | 19 (1| 17 | 7 | 7 | 6 | - | 13. Electric | | | | | | | - | accumulators | 38 (1| 24 (1| 31 | 27 (2| 25 (1| 21 | - | 14. Paints and colours| 19 | 21 | 17 (1| 39 (2| 25 | 35 (1| - | 15. Coach building | 84 (7|104 (5| 70 (6| 95 (6| 70 (3| 70 (3| - | 16. Ship building | 34 (2| 36 (6| 21 (2| 27 (1| 15 | 22 (1| - | 17. Paint used in | | | | | | | - | other industries| 48 (3| 56 (1| 51 (3| 42 | 47 (1| 49 (2| - | 18. Other industries | 84 (2| 88 (4| 47 (3| 52 (2| 78 (5| 56 (2| - | | | | | | | | - |Phosphorus Poisoning | — | — | — | 3 | 1 | 1 (1| - | | | | | | | | - |Arsenic Poisoning | 5 | 10 (1| 7 | 4 | 23 (1| 9 (2| - | | | | | | | | - |Mercurial Poisoning | 17 | 12 | 10 (1| 9 | 10 | 7 | - | | | | | | | | - |Anthrax | 47 | 64 (11| 51 (9| 56 (12| 47 (7| 58 (11| - | Wool | 31 (6| 35 (10| 28 (3| 28 (3| 18 (3| 23 (3| - | Horsehair | 7 | 8 (1| 6 (1| 8 (2| 10 | 17 (4| - | Handling of hides and | | | | | | | - | skins | 8 | 20 | 14 (3| 18 (6| 13 (1| 12 (2| - | Other industries | 1 | 1 | 3 (2| 2 (1| 6 (3| 6 (2| - +-----------------------+-------+-------+-------+-------+-------+-------+ - - +--------------+-------+-------+-------+-------+-------+-------+--------+ - | | 1906. | 1905. | 1904. | 1903. | 1902. | 1901. | 1900. | - | | (8) | (9) | (10) | (11) | (12) | (13) | (14) | - +--------------+-------+-------+-------+-------+-------+-------+--------+ - |Lead |632 (33|592 (23|597 (26|614 (19|629 (14|863 (34|1058 (38| - | 1. | 38 (1| 24 (1| 33 (1| 37 (2| 28 | 54 (3| 34 (1| - | 2. | 11 | 5 (1| 10 (1| 15 | 5 | 6 (1| 3 | - | 3. | 7 | 9 | 7 | 11 | 12 | 17 | 17 (1| - | 4. | 16 (4| 24 (2| 21 (3| 26 | 23 (1| 23 | 9 | - | 5. | 16 (2| 19 (4| 15 | 13 (2| 19 | 23 (1| 18 (2| - | 6. | 15 | 12 | 20 (4| 24 (2| 27 (1| 46 (7| 40 (3| - | 7. | 18 (1| 14 (1| 10 | 14 | 11 | 10 | 5 | - | 8. |108 (7| 90 |116 (2|109 (2|143 (1|189 (7| 358 (6| - | 9. | 6 | 10 | 11 | 6 | 13 | 14 | 19 | - | 10. |107 (4| 84 (3|106 (4| 97 (3| 87 (4|106 (5| 200 (3| - | 10a. | 5 | 5 | 3 | 3 | 2 | 7 | 10 | - | 11. | 4 (1| 3 | — | 4 | 8 (2| 11 (3| 7 | - | 12. | 4 | 2 | 3 | 4 | 3 (1| 9 | 11 | - | 13. | 26 | 27 (1| 33 | 28 | 16 (1| 49 (1| 33 | - | 14. | 37 | 57 (1| 32 (1| 39 (1| 46 | 56 | 56 (1| - | 15. | 85 (7| 56 (3| 49 (4| 74 (5| 63 (1| 65 (4| 70 (5| - | 16. | 26 (1| 32 (2| 48 | 24 (1| 15 (1| 28 (1| 32 (2| - | 17. | 37 (3| 49 (2| 27 (3| 46 (1| 44 (1| 61 | 50 (5| - | 18. | 66 (2| 70 (1| 53 (3| 40 | 64 | 89 (1| 86 (4| - | | | | | | | | | - |Phosphorus | — | 3 (1| 1 (1| — | 1 (2| 4 | 3 | - | | | | | | | | | - |Arsenic | 5 | 1 | 5 | 5 | 5 | 12 (1| 22 (3| - | | | | | | | | | - |Mercurial | 4 | 8 | 3 | 8 | 8 | 18 | 9 | - | | | | | | | | | - |Anthrax | 67 (22| 59 (18| 50 (10| 47 (12| 38 (9| 39 (10| 37 (7| - | Wool | 24 (8| 34 (12| 12 (1| 20 (5| 12 (2| 6 (4| 9 (2| - | Horsehair | 10 (4| 7 (1| 12 (4| 7 (1| 10 (2| 9 (1| 12 (3| - | Hides | 19 (7| 17 (4| 18 (3| 12 (1| 11 (5| 20 (5| 9 (1| - | Other | 14 (3| 1 (1| 8 (2| 8 (5| 5 | 4 | 7 (1| - +--------------+-------+-------+-------+-------+-------+-------+--------+ - -My own experience does not lead me to expect much in elucidation of -industrial diseases from the Sick Insurance Societies. In Austria they -make a statistical return as to the causation of illness to the central -authorities. I have myself—in my capacity as an official of the State -Central Board—examined these in order to try and gain knowledge of -the extent of industrial disease in Bohemia. In spite of the returns -drawn up by the district surgeon who visits the factories in question, -it was impossible for me to obtain a complete picture of the extent -of industrial sickness. The reports only give valuable data on which -to base action in particular cases, and from this standpoint I do not -under-estimate their value. But so far as the expressed wish of the -International Association is concerned they appear to fulfil it, inasmuch -as for specially dangerous trades special reports are issued, the -Austrian law for sick insurance requiring such industries to institute -separate sick insurance funds with separate statistics. Hence, under -present conditions, I do not see how the duty of notification will be -effective. There remains the endeavour to secure insurance and the -right to claim compensation for industrial disease in the same way as -is provided for accidents. This point was fully discussed at the eighth -International Congress for Workmen’s Insurance held in Rome in 1908. -There is no valid ground for granting compensation only for _sudden_ -disturbance of health arising in the course of employment by accident or -acute poisoning, and withholding it in the case of _gradual_ disturbance -of health caused equally by the trade, as the effects of such chronic -indisposition weigh often no less heavily on the sufferer. Inclusion -of industrial disease in the same category as accident insurance, as -indeed has been done in France, Switzerland and Great Britain, has, -apart from the fact that it is dictated by fairness and humanity, the -advantage of removing existing hardship and of solving doubtful cases. -Correct statistics, further, would thus be obtainable for the first -time, and the employer by insurance would be freed from the legal -proceedings now frequently brought against him for injury due to chronic -industrial poisoning. And it seems the more right and just course to -institute a general scheme of insurance against industrial disease than -to have recourse to an Employer’s Liability Act in this or that case, -particularly as the question often arises in regard to a disease which -develops gradually—In whose employment was the disease contracted? - -Clearly in such a scheme of insurance against both accident and -industrial disease only specific industrial diseases would be included, -i.e. diseases in which the connection with the industry can be clearly -established as due to causes inherent in the industry, and traceable to -definite materials used. Such diseases as tuberculosis and the effects -of dust inhalation (bronchitis, &c.), which as industrial diseases occur -only too often, cannot be called specific, because they arise outside -the industry and make decision impossible as to whether or not in a -particular case the disease owed its origin to the occupation. In order -to determine what should be regarded as specific industrial poisons it -was deemed necessary to draw up a schedule. For one such list Sommerfeld -(in collaboration with Oliver and Putzeys) is responsible, Carozzi of -Milan for a second, and Fischer[F] for a third, published in 1910. Those -by Sommerfeld and Fischer are constructed in similar fashion—enumeration -of (1) the poisonous substance, (2) the industries in which it is made -or used, (3) the channel of absorption, and (4) the symptoms produced. -Sommerfeld enumerates the poisons in alphabetical order, noting against -each the requisite preventive measures, while Fischer adopts a chemical -classification, confining himself to general introductory remarks as to -prevention. - -Sommerfeld proposes to limit notification to poisoning sharply -defined as to the symptoms set up, such as lead, phosphorus, mercury, -arsenic, chromium, carbonic oxide, aniline, benzene, nitrobenzene, -carbon bisulphide, and nitrous fumes. This simplifies the obligation -to notify, but does not dissipate the fears expressed above as to the -difficulty, because in the present development of the chemical industries -new substances involving new danger to the persons handling them are -constantly being discovered, and thus there can be no finality as to -which industrial poisonings should entitle to compensation. And if -recourse were had from time to time to additions of new substances to -the schedule, reliance would have to be placed on experience with regard -to each substance added, and thus the actual individual who had suffered -would not benefit. Fischer, indeed, acknowledges that any schedule must -be incomplete, and emphasises the fact that continual additions would -be necessary; otherwise it would be better to refrain altogether from -publication of a list. Such lists may be valuable guides, but no sure -foundation for insurance legislation. The only possible way to do this -is to give as far as possible a correct definition of the industrial -diseases entitling to compensation and, in isolated cases, to leave the -decision to the expert opinion of competent judges. - -Extension of workmen’s insurance to cover chronic industrial poisoning -is, however, most desirable in the interest of employers and employed, -and also of science. The German accident insurance legislation is -especially suited to do this, since the trade organisations direct their -attention not only to the prevention of accidents but of industrial -diseases also. - - - - -III - -_SPECIAL PREVENTIVE MEASURES FOR WORKERS_ - -SELECTION, CHOICE OF TRADE, ALTERNATION OF EMPLOYMENT, MEDICAL CONTROL, -SAFETY APPLIANCES, INSTRUCTION AND CO-OPERATION OF WORKERS, CLOTHING, -ATTENTION TO CLEANLINESS, FOOD, GENERAL WELFARE - - -As a practical measure in protection against trade risk selection of -those capable of resisting danger has to be considered. It is obviously -desirable to select for employment in a dangerous trade persons -possessing powers of resistance, because predisposition and resistance -to the action of poisons differ markedly in individuals. To some extent -such a selection comes of itself, as those who are very susceptible -are obliged by repeated attacks to give up the work. The social and -physical misery, undeserved loss of employment, illness, and perhaps -early death following on this kind of selection might be checked by -timely medical examination so as to weed out the unfit. But medical -examination prior to admission into a dangerous trade (actually practised -in many industries involving risk of poisoning) inflicts hardship on -those seeking employment, and recruits the ranks of the unwillingly -unemployed. It would be much better were it possible to meet the need -of selection by pertinent direction and guidance in choice of calling. -There should be insistence in technical schools especially on the -dangers inherent in certain industries, school medical examination as to -physical qualifications for certain industries, and careful note made of -individual suitability in labour bureaus, apprentice agencies, and the -like. - -Young female workers, naturally less able to resist, should be excluded -from work involving risk of poisoning—a principle which has been acted on -in the legislation of civilised countries. - -Further, workers engaged in industries involving risk should not be -exposed to the pernicious influence for too long a time. Hence the -hours of employment should be shortened in occupations proved to be -injurious to health. An important aid in this respect is alternation of -employment. Change of occupation is particularly recommended where the -nature of the poisoning of which there is risk is cumulative in action, -because in the intervals from the work the system will rid itself of the -accumulated store. In this way a number of skilled resistant workers, -familiar with the risk and knowing how to meet it, will be maintained. -Casual labour works in a vicious circle—increase of fresh workers -increases the danger and the number of cases of poisoning, and, _vice -versa_, these augment again the need of change in the personnel, so that -the number of cases of poisoning rises very high. Thus the industry -itself may be endangered, since its prosperity depends mainly upon the -existence of a skilled staff of workers. In dangerous trades, therefore, -Hermann Weber’s words, ‘Change of work instead of change of workers,’ -have much force. - -Periodical medical examination in these industries cannot well be omitted -in order to weed out the physically unfit, and to suspend from work those -who show early symptoms. Note should be kept of the state of health of -the workers, the results of the periodical medical examination, the -duration of symptoms, and the treatment of any illness that occurs. -Medical supervision presupposes special training and experience in the -medical man entrusted with the task. - -Further, in some industries in which poisonous materials are used, -especially such as set up acute sudden poisoning, there should be a -trained staff competent to recognise the first symptoms of poisoning and -to render first aid, and having at its disposal adequate means of rescue. - -Apart from the rescue appliances generally needed in dangerous trades, -stress must be laid on the value of oxygen apparatus as a means of -saving life. In addition to what is needed for the sufferer there must -be defensive apparatus at hand for the rescuers (breathing helmets, -&c.), to facilitate and make safe their rescue work when in a poisonous -atmosphere. Without such defensive equipment rescuers should never -venture into gas conduits, or into any place where presumably a poisonous -atmosphere is to be met with. It hardly requires to be said that in -dangerous industries medical aid should be within easy reach; in large -works actual medical attendance may be necessary. - -In acute as well as in chronic cases of poisoning early medical -intervention is advisable. Hence medical aid should be sought on the -earliest appearance of symptoms, and the worker, therefore, should -know the nature and action of the poison with which he comes into -contact. This brings us to the subject of the education of the worker -and particularly observance of all those rules and regulations in which -his co-operation is necessary. This co-operation of the workers is -indispensable; it is the most important condition of effective defence. -The best regulations and preventive measures are worthless if the worker -does not observe them. He must be taught their aim, the way of using the -means of defence; he must be admonished to use them, and, if necessary, -compelled to do so. The co-operation of workmen’s organisations in this -matter can avail much, since a workman most readily follows the advice of -a fellow-worker. - -Teaching of the kind suggested can be done in different ways. Apart from -lectures and practical courses, concise instructions, either in the -form of notices or as illustrated placards, should be posted up in the -workrooms or handed in the form of leaflets particularly to the newly -employed. Distribution of such leaflets might well be placed as a duty on -the employer. - -Of preventive measures applying to the individual those are of prime -importance which serve to protect the worker, as far as is practicable, -from coming into contact with the poison. Protection of this kind is -attained by wearing suitable clothing, use of respirators, and careful -cleanliness—especially before partaking of food. It cannot be too -strongly urged that these precautions are a very potent defence against -the danger of industrial poisoning, especially of the chronic forms, -and in teaching workers their importance must be insisted on. It is not -sufficient merely to put on overalls over the ordinary clothes. The -ordinary clothes must be taken off before the commencement of work, and -working suits put on, to be taken off again before the principal midday -meal and before leaving work. They should be made of smooth, durable, -washable material, and be properly washed and dried not less often than -once a week. They must be plainly cut without folds or pockets. - -Direct handling of the poisonous substances is to be avoided, but where -this is necessary impervious gloves may have to be worn, especially in -the case of poisons which can be absorbed through, or act injuriously on, -the skin. If there is risk of splashing or spilling of poisonous liquids -on to the clothes, impermeable or partly impermeable overalls (aprons, -&c.) should be worn. The obligation of providing the overalls or working -suits falls naturally on the employer in industries where poisonous -substances are used, and there is equally obligation on the employee to -use the articles provided. - -Suitable cloakroom accommodation is essential, by which is meant room not -only to change clothes with cupboards or hooks on one side for clothing -taken off on commencement of work and on the other the working suits, -but also ample washing accommodation. These cupboards should be double, -that is, be divided by a partition into two parts, one serving for the -ordinary and the other for the working clothes. - -[Illustration: FIG. 35.—Aluminium Respirator] - -Protection of the respiratory organs can to some extent be obtained by -so-called respirators worn over the mouth and nose. Often they consist -simply of a moist sponge or folds of cloth, or again may be complicated -air-proof affairs enclosing mouth and nose, or the whole face like a -mask, or even the head like a helmet; they fit close, and the aperture -for respired air is provided with filtering material (cotton wool, &c.) -placed between two layers of wire gauze. The outer layer of the gauze -moves on a hinge, so that the filtering material can be renewed after -each time that it has been used. The construction of respirators is -extraordinarily varied. One form is illustrated. They must be light, and -in order not to obstruct breathing seriously they are often provided -with valves—closing during inspiration and opening during exhalation. -Generally the respirators in common use do not quite satisfactorily -fulfil the conditions required. After a time the pressure becomes -irksome, the face becomes hot, breathing more difficult, and discomfort -from wearing them unbearable. - -Respirators are only to be regarded in the light of secondary aids and -for occasional use. - -During temporary exposure to an atmosphere charged with poisonous dust -the wearing of an efficient apparatus—preferably one protecting the -head—is very desirable. - -[Illustration: FIG. 36.—Smoke Helmet, Flexible Tubing, and Foot Bellows -(_Siebe, Gorman & Co._)] - -Respirators afford no protection, or a very imperfect one, against -dangerous gases or fumes. If soaked with an absorbing or neutralising -fluid they can scarcely be worn for any length of time. - -In an atmosphere charged with poisonous gas recourse should be had either -to a smoke helmet with flexible tubing and bellows or to an oxygen -breathing apparatus so constructed that the workman carries the necessary -supply of oxygen with him in a knapsack on his back. In the latter case -oxygen from a compressed cylinder of the gas is conveyed to the breathing -mask, so that respiration is independent of the surrounding atmosphere. - -[Illustration: FIG. 37.—Diagram of Draeger 1910-11, Pattern H (_R. -Jacobson_) - -P Alkali cartridges; K Cooler; C Aspirating pipe; L₁ Purified air; L₂ -Expired air.] - -The mode of working is represented diagrammatically in figs. 37 and 40. -After putting on the helmet, the bag is first filled with fresh air, the -air valve is then closed, and the valve of the oxygen cylinder unscrewed -so as to permit of the flow of the oxygen which, mixes with the air in -the bag, and begins to circulate; the expired air passes through the -caustic potash pellets P, which free it of carbonic acid gas, so that, -with a fresh supply of oxygen from the cylinder through the pipe C, it -is regenerated and made fit for breathing again. The pressure in the -cylinder is measured by a manometer, which indicates also when the supply -of oxygen gives out. - -[Illustration: FIG. 38.—Showing the Potash Cartridge No. 2 with Change -Mechanism X; No. 2 Oxygen Cylinder with Spanner V; and on the Left a -Hexagonal Socket U, for unscrewing the Locking Nuts of Reserve Cylinders -(_R. Jacobson_)] - -[Illustration: FIG. 39.—‘Proto’ patent self-contained breathing apparatus -(_Siebe, Gorman & Co._)] - - Another apparatus—the ‘Proto’ patent self-contained breathing - apparatus (Fleuss-Davis patents)—is also illustrated in fig. - 39. Illustration 40 gives a diagrammatic view of the principle - upon which it is designed. The instructions for using the - ‘Proto’ apparatus are as follows: - - _The oxygen cylinders_ (B, B), having been charged with oxygen - through the nipple at (H) to a pressure of 120 atmospheres - (about 1800 lbs. per square inch), are to be re-attached to - the belt as shown, and the reducing valve, with its tubes, - &c., is to be connected to the nipple at (H). This supply is - sufficient for fully two hours. - - _Charging the breathing bag._—Put 4 lbs. of stick caustic - _soda_ into the bag (D), i.e. 2 lbs. into each compartment, - and immediately fasten the mouth of the bag by means of the - clamps and wing nuts (O). If the apparatus is not to be used - at once, but is to be hung up for use at some future time, the - indiarubber plug which is supplied with the apparatus should be - tightly fitted into the mouthpiece in order to prevent access - of air to the caustic soda, and to preserve it until required - for use. - - See that the inlet and outlet valves (T and S) and the - connection (N) are screwed up tightly. - - The small relief valve (K) is only to be opened (by pressing - it with the finger) when the bag becomes unduly inflated - through excess of oxygen. This may occur from time to time, - as the reducing valve is set to deliver more than the wearer - actually requires. - - _Equipment._—The whole apparatus is supported upon a broad belt - which is strapped round the body. The bag is also hung by a - pair of shoulder braces. - - The wearer having put the equipment over his shoulders, fastens - the belt and takes the plug out of the mouthpiece. The moment - the mouthpiece is put into the mouth or the mask is adjusted, - the main valve (H) is to be opened not more than one turn and - the necessary supply of oxygen will then flow into the bag. It - is advisable to open the by-pass (I) to inflate partially the - breathing bag (D) for a start, but this valve should again be - screwed up quite tight and not touched again, except in the - case of emergency as previously described should the bag become - deflated. Breathing will then go on comfortably. - - Should the by-pass (I) on the reducing valve (C) get out of - order then the wearer should turn on the by-pass (I) from time - to time to give himself the necessary quantity of oxygen, but, - as stated above, this is only to be done in case of deflation - of the bag. The best guide as to the quantity of oxygen to - admit _in the above circumstances_ is the degree of inflation - of the breathing bag. It will be found to be quite satisfactory - if the bag be kept moderately distended. - - _After using the apparatus._—The caustic soda should _at once_ - be thrown away, but if it is neglected and the soda becomes - caked, it must be dissolved out with warm water before putting - in a fresh supply. Caustic soda will not damage vulcanised - indiarubber, but it will damage canvas and leather, and will - burn the skin if allowed to remain upon it. - - If the apparatus is to be used again at once, it can be - recharged with caustic soda at once, but if it is only to be - charged ready for use at some future time the indiarubber bag - should be thoroughly washed out with warm water and dried - inside with a cloth or towel. - - When emptying or recharging the rubber bag with caustic soda, - it must always be removed from the canvas bag. After use each - day, it is advisable to wash the rubber mouthpiece (or mask, - as the case may be) with yellow soap and water. This acts as a - preservative to the indiarubber. - - Every man who is to use the apparatus should have his own - mouthpiece and noseclip, or mask, as the case may be, under - his own special care, both for sanitary reasons and so that he - may shape and adjust the mask to fit himself comfortably and - air-tightly, to such an extent that if the outlets are stopped - up by the hands while the mask is held in position by its bands - no breath can pass in or out. - -[Illustration: FIG. 40.—‘Proto’ Patent Self-breathing Apparatus (_Siebe, -Gorman & Co._)] - -[Illustration: FIG. 41.—Arrangement of Cloak-room, Washing and Bath -Accommodation, and Meal-room in a White Lead Factory] - -Where poisonous substances giving off dust or fumes are used, regular -washing and rinsing the mouth (especially before meals and on leaving) -is of great importance. Naturally the washing conveniences (basins, -soap, brushes, towels) must be sufficient and suitable, and the workers -instructed as to the importance of cleanliness by the foreman. They -should be urged to bath in rotation, and time for it should be allowed -during working hours. - -The taking of meals and use of tobacco in the workrooms must be -prohibited. Meal rooms should be so arranged as to be contiguous to the -cloakroom and washing accommodation, the worker gaining access to the -meal room through the cloakroom and bathroom. The arrangement described -is illustrated in fig. 41. The meal room serves also the purpose of a -sitting-room during intervals of work, and it goes without saying that -cloakroom and lavatory accommodation are as necessary in small as in -large premises. - -Simple lavatory basins of smooth impervious surface fitted with a waste -pipe and plug, or tipping basins, are recommended in preference to -troughs which can be used by several persons at once. Troughs, however, -without a plug, and with jets of warm water, are free from objection. - -The douche bath has many advantages for workmen over the slipper bath. -The initial cost is comparatively small, so that it can be placed at the -disposal of the workers at very small outlay. Maintenance and cleanliness -of douche baths are more easily secured than of other kinds, where -changing the water and keeping the bath in good order involve time and -expense. A dressing-room should form part of the douche or slipper bath -equipment. Walls and floors must be impervious and, preferably, lined -with smooth tiles or cement. It is better that the shower bath should be -under the control of the worker by a chain rather than be set in motion -by means of mechanism when trodden upon. The arrangement of baths is -illustrated in fig. 43. In many large works large bath buildings have -been erected. Fig. 44 is a plan of the splendid bath arrangements at the -colour works of Messrs. Lucius, Meister & Brüning of Höchst a.-M. - -[Illustration: FIG. 42.—Good Washing and Bath Accommodation in a Lead -Smelting Works] - -[Illustration: FIG. 43.—Washing Trough, Douche Baths, and Clothes -Cupboards, Type common on the Continent] - -[Illustration: FIG. 44A.—Baths in the Höchst Aniline Works (_after -Grandhomme_)] - -[Illustration: FIG. 44B.—Ground Floor] - -[Illustration: FIG. 44C.—First Floor. _a_, _c_, Baths (slipper and -douche) for workmen; _b_, Washing accommodation for workmen; _d_, _e_, -Baths for officials; _g_, Attendant’s quarters; _f_, Hot air (Turkish) -baths; _i_, Warm water reservoir.] - -Naturally maintenance of the general health by good nourishing diet is -one of the best means of defence against onset of chronic industrial -poisoning. Over and over again it has been noticed that ill-fed workers -speedily succumb to doses of poison which well-nourished workers can -resist. It is not our province here to discuss fully the diet of a -working-class population. We merely state that it is a matter of vital -importance to those employed in dangerous trades. The question of a -suitable drink for workers to take the place of alcohol calls for special -attention, as, when complicated with alcoholism, both acute and chronic -poisonings entail more serious results than they otherwise would do. -Over-indulgence in alcohol, owing to its effect on the kidneys, liver, -digestion, nervous system, and power of assimilation generally, requires -to be checked in every way possible. Apart from good drinking water, -milk, coffee, tea, fruit juices and the like, are excellent. Milk is -especially recommended, and should be supplied gratis to workers in -dangerous trades, notably where there is risk of lead poisoning. - -Lastly, other features such as games and exercise in the open air, -which help to strengthen bodily health, must not be forgotten. In this -connection much good work has already been done by employers’ and -workers’ organisations. - - - - -IV - -_GENERAL REMARKS ON PREVENTIVE MEASURES_ - -GENERAL PRINCIPLES, SUBSTITUTES FOR DANGEROUS MATERIALS, CLEANLINESS OF -WORKROOMS, CUBIC SPACE, VENTILATION, REMOVAL OF DUST AND FUMES - - -Preventive measures against industrial poisoning aim at an unattainable -goal of so arranging industrial processes that employment of poisonous -substances would be wholly avoided. Such an ideal must be aimed at -wherever practicable. Prohibition of direct handling of poisonous -substances is also sometimes demanded, which presupposes (although it is -not always the case) that this is unnecessary or can be made unnecessary -by suitable mechanical appliances. We have to be contented, therefore, -for the most part, with removal of injurious dust and fumes as quickly -as possible at the point where they are produced, and regulations -for the protection of workers from industrial poisoning deal mainly -with the question of the prevention of air contamination and removal -of contaminated air. Substitution of non-injurious for injurious -processes is only possible in so far as use of the harmless process -gives technically as good results as the other. If such a substitute -can be found let it be striven for. Mention has already been made of -international prohibition of certain substances, and attention has been -drawn to economical considerations affecting this point. - -Prohibition obviously may paralyse branches of industry and hit heavily -both employers and employed. The skilled trained workers are just the -ones to suffer, since they are no longer in a position to take up another -equally remunerative trade. - -Judgment has to be exercised before enforcing new regulations in order -that good and not harm may follow. If a satisfactory substitute be -discovered for methods of work injurious to health, then ways and -means will be found to make the alteration in the process economically -possible. It may, however, demand sacrifice on the part of employers and -employed, but the progress is worth the sacrifice. - -The following are instances of substitution of safe processes for those -involving risk: generation of dust can sometimes be avoided by a ‘wet’ -method (watering of white lead chambers, grinding pulp lead with oil, -damping of smelting mixtures, &c.); the nitrate of silver and ammonia -process has replaced the tin and mercury amalgam used in silvering of -mirrors; electroplating instead of water gilding (coating objects with -mercury amalgam and subsequently volatilising the mercury); enamelling -with leadless instead of lead enamels; use of air instead of mercury -pumps in producing the vacuum in incandescent electric lamps. - -Dealing further with the sanitation of the factory and workshop after -personal cleanliness, the next most important measure is cleanliness of -the workroom and purity of the air. Workrooms should be light and lofty; -and have floors constructed of smooth impervious material easily kept -clean. The walls should be lime-washed or painted with a white oil paint. -Angles and corners which can harbour dirt should be rounded. Cleansing -requires to be done as carefully and as often as possible, preferably by -washing down or by a vacuum cleaner. Saturation of the floor with dust -oil is recommended by some authorities in trades where poisonous dust is -developed and is permitted as an alternative to the methods described. I -refrain from expressing an opinion on this method of laying dust, since -by adoption of the practice insistence on the need for removal of the -poisonous material from the workrooms loses its force—a thing, in my -opinion, to be deprecated. - -The necessity of keeping the atmosphere of workrooms pure and fresh -makes it essential that there should be sufficient cubic space per -person and that proper circulation of the air should be maintained. The -minimum amount of cubic space legally fixed in many countries—10-15 -cubic metres—is a minimum and should be greatly exceeded where possible. -Natural ventilation which is dependent upon windows, porosity of building -materials, cracks in the floors, &c., fails when, as is desirable for -purposes of cleanliness, walls and floors are made of smooth impermeable -material, and natural ventilation will rarely supply the requisite cubic -feet of fresh air quickly enough. Ordinarily, under conditions of natural -ventilation, the air in a workroom is renewed in from one to two hours. -Artificial ventilation therefore becomes imperative. Natural ventilation -by opening windows and doors can only be practised in intervals of work -and as a rule only in small workrooms. During work time the draught and -reduction of temperature so caused produce discomfort. - -_Artificial ventilation_ is effected by special openings and ducts -placed at some suitable spot in the room to be ventilated and arranged -so that either fresh air is introduced or air extracted from the room. -The first method is called propulsion, the latter exhaust ventilation. -Various agencies will produce a draught in the ventilating ducts, namely, -difference of temperature between the outside and inside air, which can -be artificially strengthened (_a_) by utilising the action of the wind, -(_b_) by heating the air in the exhaust duct, (_c_) by heating apparatus, -and (_d_) by mechanical power (use of fans). - -Where advantage is taken of the action of the wind the exit to the -ventilating duct must be fitted with a cowl. - -The draught in pipes is materially increased if they are led into furnace -flues or chimneys; in certain cases there is advantage in constructing -perpendicular ventilating shafts in the building extending above the roof -and fitted with cowls. Combination of heating and ventilation is very -effective. - -[Illustration: FIG. 45.—Steam Injector (_after Körting_), showing steam -injector and air entry] - -In workrooms, however, where there is danger of poisoning by far the -most effective method of ventilation is by means of fans driven by -mechanical power. All the means for securing artificial ventilation -hitherto mentioned depend on a number of factors (wind, difference of -temperature, &c.), the influence of which is not always in the direction -desired. Exact regulation, however, is possible by fans, and the quantity -of air introduced or extracted can be accurately calculated beforehand -in planning the ventilation. In drawing up such a plan, detailing the -arrangement, proportions of the main and branch ducts, expenditure of -power, &c., a ventilating engineer should be consulted, as it is his -business to deal with complicated problems of ventilation depending -entirely for success on the design of the ventilation. - -Injectors are usually only employed for special technical or economical -reasons. A jet of steam or compressed air which acts on the injector -creates a partial vacuum and so produces a powerful exhaust behind. Fig. -45 shows the mechanism of an injector. They are used for exhausting acid -fumes which would corrode metal fans and pipes, and for explosive dust -mixtures where fans are inadmissible. - -[Illustration: FIG. 46.—Propeller Fan coupled to Electromotor (_Davidson -& Co., Ltd._)] - -In the industries described in this book fans are most commonly used. -These are, in the main, wheels with two or more wing-shaped flattened -blades. Some are encased, others are open and fitted by means of annular -frames in the ducts according to the intended effect and kind of fan. -Fans are of two kinds, propeller and centrifugal, and, according to the -pressure they exert, of low, medium, or high pressure. They are now often -driven electrically, in which case there is advantage in coupling them -directly with the motor. - -_Propeller fans_ have curved screw-shaped blades and are set at -right angles in the duct upon the column of air in which they act by -suction. The air is moved in the direction of the axis of the fan, and -generally it is possible, by reversing the action, to force air in -instead of extracting it. The draught produced is a low-pressure one -(generally less than 15 mm. of water). The current of air set in motion -travels at a relatively slow speed, yet such fans are capable, when -suitably proportioned, of moving large volumes of air. Propeller fans -are specially suitable for the general ventilation of rooms when the -necessary change of air is not being effected by natural means. - -[Illustration: FIG. 47.—The Blackman (Belt-driven) Fan.] - -_Centrifugal_ or _high-pressure fans_ (see figs. 48A and 48B) are always -encased in such a way that the exhaust ducts enter on one or both sides -of the axis. The air thus drawn in is thrown by the quickly rotating -numerous straight blades to the periphery and escapes at the outlet. -The centrifugal fan travels at a great speed, and the air current -has therefore great velocity and high pressure. When the pressure is -less than 120 mm. it is described as a medium, and when greater, a -high-pressure fan. For the former a galvanised iron casing suffices; -for the latter the casing requires to be of cast iron. Medium pressure -centrifugal fans are used to exhaust dust or fumes locally from the point -at which they are produced. They play a great part in industrial hygiene. - -[Illustration: FIG. 48A.—‘Sirocco’ Centrifugal Fan] - -[Illustration: FIG. 48B.—Showing exhaust aperture and fan blades] - -High-pressure fans are used mainly for technical purposes, as, for -example, the driving of air or gas at high pressure. Localised -ventilation is needed to limit diffusion of dust and fumes, which -is attained in a measure also by separation of those workrooms in -which persons come into contact with poisonous materials from others. -Separation of workrooms, however, is not enough, as it is the individual -who manipulates the poison for whom protection is desired. To enclose or -hood over a dusty machine or fume-producing apparatus completely, or to -close hermetically a whole series of operations by complicated technical -arrangements, is only possible when no opening or hand feeding is -required. Dangerous substances can only be wholly shut in by substitution -of machinery for handwork. - -[Illustration: FIG. 49.—Localised Exhaust Ventilation in a Colour Factory -(_Sturtevant Engineering Co., Ltd._)] - -[Illustration: FIG. 50A. - -FIG. 50B. - -Ball Mills] - -Where, however, absolute contact is unavoidable the dust or fume must -be carried away at its source. This is done by exhaust ventilation, -locally applied, in the following manner: A suitable hood or air guide -of metal or wood is arranged over the point where the dust is produced, -leaving as small an opening as possible for necessary manipulations. The -hood is connected with a duct through which the current of air travels. -An exhaust current dependent upon heat will only suffice in the case -of slight development of dust or fumes. As a rule exhaust by a fan is -necessary. Where exhaust ventilation has to be arranged at several -points all these are connected up by branch ducts with the main duct -and centrifugal fan. Where the ducts lie near the floor it is advisable -to fix adjustable openings in them close to the floor to remove the -sweepings. - -[Illustration: FIG. 51.—Ventilated Packing Machine (_after Albrecht_) - -_A_ Worm; _B_ Collector; _D_ Fan; _E_ Filter bag; _J_, _F_ Movable -shutters; _H_ Jolting arrangement] - -It is important for the exhaust system of ventilation to be designed -in general so that the dust is drawn away from the face of the worker -downwards and backwards. Many horrible arrangements are found in which -the dust is first aspirated past the mouth and nose before it is drawn -into a hood overhead. The proportions of the branch pipes to the main -duct require to be thought out, and friction and resistance to the flow -must be reduced as far as possible by avoidance of sharp bends. Branch -pipes should enter the main duct at an angle of thirty degrees. A -completely satisfactory system requires very special knowledge and often -much ingenuity when the apparatus is complicated. - -Disintegrators and edge runners can generally be covered in and the cover -connected with an exhaust. Ball mills, when possible, are best as the -rotating iron cylinder containing the steel balls and the material to be -pulverised is hermetically closed. - -Powdered material can be carried mechanically from one place to another -by worms, screws, endless bands, or be driven in closed pipes by means -of compressed air. The inevitable production of dust in packing can be -avoided by the use of ventilated packing machines, which are especially -necessary in the case of white lead, bichromates, basic slag, &c. - -[Illustration: FIG. 52.] - -The difficulty is great in preventing dust in sieving and mixing, since -this is mainly done by hand. Still here, for example, by use of cases -with arm-holes and upper glass cover, injury to health can be minimised. -Benches with a wire screen and duct through which a downward exhaust -passes are useful in sorting operations (fig. 52). - -Fig. 53 illustrates a grinding or polishing wheel fitted with localised -exhaust. - -[Illustration: FIG. 53.—Removing Dust from Bobs and Mops (_James Keith -& Blackman Co., Ltd. By permission of the Controller of H.M. Stationery -Office_)] - -To prevent escape of injurious gases all stills and furnaces must be kept -as airtight as possible and preferably under a slight negative pressure. -Agitators must be enclosed and should be fitted with arrangements for -carrying on the work mechanically or by means of compressed air and, if -necessary, exhaust ventilation applied to them. The aim should be to -enclose entirely drying and extracting apparatus. - -[Illustration: FIG. 54.—‘Cyclone’ Separator (_Matthews & Yates, Ltd._)] - -An important question remains as to what shall be done with the dust and -fumes extracted. In many cases they cannot be allowed to escape into -the atmosphere outside, and in the interests of economy recovery and -utilisation of the waste is the thing to aim at. This vital subject can -only receive barest mention here. The dust or fumes extracted require to -be subjected to processes of purification with a view to recovery of the -often valuable solid or gaseous constituents and destruction of those -without value. - -[Illustration: FIG. 55A. FIG. 55B. - -Dust-filter of Beth-Lübeck (_after Albrecht_)] - -[Illustration: FIG. 56.—Dust-filter of Beth-Lübeck—Detail] - -Collection of dust may take place in settling chambers as in a cyclone -separator in which the air to be purified is made to travel round the -interior of a cone-shaped metal receptacle, depositing the dust in its -passage (see fig. 54). - -[Illustration: FIG. 57.—Arrangement for Precipitating Dust (_after -Leymann_) - -_A_ Entry of dust laden air; _B_ Fan; _C_ Purified air; _D_ Pipe carrying -away water and last traces of dust; _E_ Worm carrying away collection of -dust.] - -The most effective method, however, is filtration of the air through -bags of canvas or other suitable fabric as in the ‘Beth’ filter (see -figs. 55 and 56). In the ‘Beth’ filter a mechanical knocking apparatus -shakes the dust from the bag to the bottom of the casing, where a worm -automatically carries it to the collecting receptacle. In the absence of -mechanical knocking the filtering material becomes clogged and increases -the resistance in the system. Contrivances of the kind unintelligently -constructed become a source of danger to the workers. Dust of no value -is usually precipitated by being made to pass through a tower down which -a fine spray of water falls. If the gases and fumes can be utilised they -are either absorbed or condensed—a procedure of the utmost importance for -the protection of the workers. - -Condensation of the gases into a liquid is effected by cooling and is -an essential part of all processes associated with distillation. The -necessary cooling is effected either by causing the vapours to circulate -through coils of pipes surrounded by cold water or by an increase in the -condensing surface (extension of walls, &c.), and artificial cooling of -the walls by running water. - -Absorption of gases and fumes by fluids (less often by solid substances) -is effected by bubbling the gas through vessels filled with the absorbing -liquid or conducting it through towers (packed with coke, flints, &c.), -or chambers down or through which the absorbent flows. Such absorption -towers and chambers are frequently placed in series. - -The material thus recovered by condensation and absorption may prove to -be a valuable bye-product. Frequently the gases (as in blast furnace gas, -coke ovens, &c.) are led away directly for heating boilers, or, as in the -spelter manufacture, to make sulphuric acid. - - - - -V - -_PREVENTIVE REGULATIONS FOR CHEMICAL INDUSTRIES_ - - -Sulphuric Acid Industry - -(See also pp. 4-14 and 171) - -Danger arises from escape of acid gases or in entering chambers, towers, -containers, &c., for cleaning purposes. The whole chamber system, -therefore, requires to be impervious and the sulphur dioxide and nitrous -gases utilised to their fullest extent—a procedure that is in harmony -with economy in production. The pyrites furnace must be so fired as to -prevent escape of fumes, which is best attained by maintenance of a -slight negative pressure by means of fans. The cinders raked out of the -furnace because of the considerable amount of sulphur dioxide given off -from them should be kept in a covered-in place until they have cooled. -Any work on the towers and lead chambers, especially cleaning operations, -should be carried out under strict regulations. Such special measures -for the emptying of Gay-Lussac towers have been drawn up by the Union -of Chemical Industry. Before removal of the sediment on the floor they -require a thorough drenching with water, to be repeated if gases are -present. Perfect working of the Gay-Lussac tower at the end of the -series of chambers is essential to prevent escape of acid gases. In a -well-regulated sulphuric acid factory the average total acid content of -the final gases can be reduced to 0·1 vol. per cent. Under the Alkali -Works Regulation Act of 1881 the quantity was limited to 0·26 per cent. -of sulphur dioxide—and this should be a maximum limit. - -_Entering and cleaning out chambers and towers_ should only be done, if -practicable, by workmen equipped with breathing apparatus, and never -without special precautionary measures, as several fatalities have -occurred at the work. Towers, therefore, are best arranged so as to allow -of cleaning from the outside; if gases are noticed smoke helmets should -be donned. The same holds good for entering tanks or tank waggons. After -several cases of poisoning from this source had occurred in a factory the -following official regulations were issued: - - The deposit on the floor of waggons or tanks shall be removed - either by flushing with water without entering the tank itself, - or if the tank be entered the deposit is to be scooped out - without addition of water or dilute soda solution. - - Flushing out shall only be done after the workmen have got out. - - Workmen are to be warned every time cleaning is undertaken that - poisonous gases are developed when the deposit on the floor is - diluted. - - Acid eggs, further, are to be provided with a waste pipe and - manhole to enable cleaning to be done from outside. - -The poisoning likely to arise is partly due to arsenic impurity -(development of arseniuretted hydrogen gas) in the sulphuric acid used. -Unfortunately arsenic free acid is very difficult to obtain. - - -Hydrochloric Acid—Saltcake and Soda Industries - -(See also pp. 15-23 and 170) - -Preventive measures here depend upon observance of the general principles -already discussed. - -The _saltcake pan_ and reverberatory furnace require to be accurately and -solidly constructed and the process carefully regulated. Regulations -indeed were drawn up at an early date in England as to their working -to prevent escape of gases when adding the acid, raking over in the -reverberatory furnace, and withdrawal of the still fuming saltcake. - -The following are the most important of these recommendations: - - The saltcake pan must not be charged when overheated. - - Sulphuric acid shall be added only after all the salt has been - charged and the door shut. - - If hydrochloric acid fumes escape at the door when the Glover - acid flows in the flow must be interrupted. - - All doors must be closed while work is in progress. - - Definite times shall be fixed for withdrawal of the saltcake in - order to try and ensure that it be not still fuming, but should - this be the case cold sulphate of soda shall be sprinkled over - it. - -The general principle should be observed of maintaining a slight negative -pressure in the furnace by insertion of a fan in the gas conduit so as to -avoid possible escape of gas. The fuming saltcake is best dealt with by -depositing it at once to cool in ventilated receptacles or chambers. - -On grounds of economy and hygiene as complete an absorption as possible -of the hydrochloric acid gas developed in the saltcake and soda ash -process is to be aimed at, by conveying it through impervious conduits -to the bombonnes and lofty absorption tower filled with coke or flints -down which water trickles. The entire loss of hydrochloric acid should -not amount to more than 1·5 per cent. of the whole. Under the Alkali Act -at first 5 per cent. was allowed, but this is excessive now in view of -improved methods of condensation. - -In the _Leblanc_ process the revolving furnace is on health grounds to -be preferred to the hand furnace. Such a furnace occupies the space -of but three hand furnaces and can replace eighteen of them. The vast -accumulation of waste, consisting mainly of calcium sulphide, and -generating sulphuretted hydrogen gas in such amount as to constitute -a nuisance, is only partially prevented by the Chance-Claus and other -methods of recovery, and makes it most desirable to adopt the Solvay -ammonia process. - -_Note._—_Sulphonal, Oxalic acid, Ultramarine, Alum._—The production of -_sulphonal_ is intensely unpleasant owing to the disagreeable smell (like -cats’ excrement) of the mercaptan developed. All work therefore must be -carried on in air-tight apparatus under negative pressure and careful -cooling. Any escaping fumes must be absorbed in solution of acetone and -fine water spray. - -Preparation of _oxalic acid_ unless carried on in closed-in vessels gives -rise to injurious and troublesome fumes. If open pans are used, hoods and -ducts in connection with a fan should be placed over them. - -Grinding of _ultramarine_ and _alum_ requires to be done in closed-in -mills, and any dust drawn away by locally applied ventilation and -filtered. The gases given off in the burning process contain 3 per cent. -of sulphur dioxide, which requires to be absorbed—a procedure most easily -effected in towers where the upstreaming gas comes into contact with a -dilute solution of lime or soda. - - -Chlorine, Bleaching Powder, Chlorine Compounds - -(See also pp. 23-9 and 173) - -What has been said as to imperviousness of apparatus, negative pressure -maintained by the tall chimney stack or earthenware or fireclay fan, -&c., applies equally here. The exhaust ventilation is also required to -aspirate the gas into the bleaching chambers. - -At the end of the system there must be either a tower packed with -quicklime to absorb the last traces of chlorine or such a number of -bleach chambers into which the gas can be led that no chlorine escapes. -Production of chlorine gas electrolytically is to be preferred to other -processes on hygienic grounds. - -Careful cleanliness is the best prophylactic against occurrence of -_chlorine rash_ among persons employed in the electrolytic production of -chlorine. In some factories attempt has been made to use other substances -(magnetite) instead of carbon for the anode, and the success attending -their adoption is further proof that the tar cement at the anode helped -to cause the acne. - -In the _Weldon_ process care must be taken that the water lutes are -intact, and the stills must not be opened before the chlorine has been -drawn off. All processes in which manganese dust can arise (grinding -of manganese dioxide and drying of Weldon deposit) should be done -under locally applied exhaust. The _bleaching powder_ chambers must be -impervious and care taken that they are not entered before the chlorine -has been absorbed. Usually the number of lime chambers connected up with -each other is such that no chlorine escapes free into the air. Emptying -of the finished product should not be done by hand, as considerable -quantities of chlorine escape and make the work extremely irksome. -Mechanical methods of emptying should be adopted in substitution for hand -labour, and of these the Hasenclever closed-in apparatus is the best. - - -Nitric Acid and Explosives - -(See also pp. 39-49 and 172) - -In the production of _nitric acid_ complete imperviousness of the system -and as complete condensation of the gases as possible by means of -tourilles, cooling condensers, and the requisite number of towers are -necessary. The method suggested by Valentine of manufacture of nitric -acid in apparatus under a partial vacuum has advantages from a hygienic -standpoint. Earthenware fans are used to force the nitric acid gases -onwards and have the advantage of creating a negative pressure. Great -care is needed in handling, emptying, packing, conveying, and storing the -acid in consequence of the danger from breaking or spilling. The bottles -used must be in perfect condition and must be well packed. No greater -stock of nitric acid should be allowed in a room than is absolutely -necessary, and care must be exercised in the event of a carboy breaking -that the spilt acid does not come into contact with organic substances, -as that would increase development of nitrous fumes. - -Workers must be warned not to remain in rooms in which acid has been -spilt. They are only to be entered by workers equipped with breathing -apparatus (smoke helmets). - -Among the special regulations on the subject may be mentioned those -of the Prussian Ministerial Decree, dated January 8, 1900, concerning -nitrous fumes and means of protection for workers employed with the acid. -What has been said on p. 257 in regard to the transport of sulphuric acid -applies equally to nitric acid. - -In the _nitrating_ process in the manufacture of explosives (see p. -47) it is essential that the apparatus is hermetically closed, that -agitation is done mechanically, or better still by means of compressed -air, and that any fumes developed are exhausted and condensed. In the -preparation of _nitro-glycerin_ (see p. 46) the gases developed in the -nitration of the waste acid require to be carefully condensed. Contact -of nitro-glycerin with the skin has to be avoided and the attention -of the workers drawn to the danger. Preparation of _gun cotton_ (see -p. 48) takes place in machines which are at the same time nitrating -and centrifugalising machines. The apparatus is first filled with -the nitrating acid and the cotton added; the fumes are drawn off by -earthenware ducts and fans, and lastly the bulk of the acid is removed by -centrifugal action. Such machines carry out effectually the principles of -industrial hygiene. - -In the preparation of _fulminate of mercury_ nitrous fumes, cyanogen -compounds, and acetic acid compounds are developed by the action of -the nitric acid on mercury, and require to be dealt with by exhaust -ventilation.[G] - - -Artificial Manures, Fertilizers - -(See also pp. 53 and 54) - -In grinding phosphorite and superphosphates, corrosive dust is produced. -All grinding operations must, therefore, be carried out automatically -in closed apparatus (ball mills, disintegrators, &c.). In making the -phosphorite soluble by treatment with sulphuric acid, and subsequent -drying of the product, corrosive hydrofluoric acid gas is developed, -which requires to be carried away by an acid proof exhaust fan, and -condensed in a tower by water (see fig. 58). The modern revolving drying -machines are especially serviceable. - -[Illustration: FIG. 58.—Washing tower for hydrofluoric acid (_after -Leymann_.)] - -In the production of _basic slag_ corrosive dust is given off, causing -ulceration of the mucous membrane. Grinding and other manipulations -creating dust must be carried on in apparatus under local exhaust -ventilation. The following—somewhat shortened—are the German Imperial -Regulations, dated July 3, 1909, for basic slag factories. - - BASIC SLAG REGULATIONS - - 1. Workrooms in which basic slag is crushed, ground, or stored - (if not in closed sacks) shall be roomy and so arranged as to - ensure adequate change of air. Floors shall be of impervious - material allowing of easy removal of dust. - - 2. Preliminary breaking of the slag by hand shall not be done - in the grinding rooms, but either in the open air or in open - sheds. - - 3. Slag crushers, grinding mills, and other apparatus shall be - so arranged as to prevent escape of dust as far as possible - into the workrooms. They shall be provided with exhaust - ventilation and means for collecting the dust if this cannot be - done in the absence of dust. - - 4. Arrangements shall be made whereby barrows conveying - material to the grinding mills shall be emptied directly into - partially hooded hoppers provided with exhaust ventilation so - as to prevent escape of dust into the workrooms. - - 5. The casing and joints of the grinding mills, ducts, dust - collectors and sieves shall be airtight; if leaks are noticed - they must be repaired forthwith. - - 6. Ducts, dust collectors and sieves shall be so arranged as to - enable periodical cleansing to be undertaken from the outside. - - 7. Repairs of the plant mentioned in Para. 5 in which workers - are exposed to inhalation of slag dust shall be entrusted by - the occupier only to such workers as wear respirators supplied - for the purpose or other means of protecting mouth and nostrils - such as wet sponges, handkerchiefs, &c. - - 8. Emptying of slag powder from the grinding mills and dust - collectors and transference to the store rooms shall only - be done in accordance with special regulations designed to - minimise dust. - - 9. Filling slag powder into sacks from the outlets of the - mills, elevating and discharging it into receptacles shall only - be done under efficient exhaust ventilation. - - 10. Sacks in which the powder is transported and piled in heaps - shall be of a certain defined strength to be increased in the - case of sacks to be piled in heaps more than 3½ metres in - height. Special rooms separated from other workrooms shall be - provided for storage of slag powder in sacks. Only the sacks - representing the previous day’s production may be stored in the - grinding rooms. - - Basic slag in powder and not in sacks shall be kept in special - storage rooms shut off entirely from other workrooms. No person - shall enter such storage rooms when they are being filled or - emptied. Discharging the contents of the sacks into them shall - be done under exhaust ventilation. - - 11. The floors of the workrooms described in Para. 1 shall be - cleaned before the commencement of each shift or in an interval - during each shift. No person except those engaged in cleaning - shall be present during the operation. If cleaning is effected - by sweeping, the occupier shall require the persons doing it to - wear the respirators provided or other protection for the mouth - and nose. - - 12. The occupier shall not permit the workers to bring spirits - into the factory. - - 13. A lavatory and cloakroom and, separated from them and in - a part of the building free from dust, a meal room shall be - provided. These rooms shall be kept clean, free from dust, and - be heated during the winter. - - In the lavatory and cloakroom water, soap, and towels shall be - provided and adequate arrangements shall be made for keeping - the clothing taken off before commencing work. - - The occupier shall give the persons employed opportunity to - take a warm bath daily before leaving work in a bathroom - erected inside the factory and heated during the winter. - - 14. No woman or male young person under eighteen years of age - shall work or remain in a room into which basic slag is brought. - - Persons under eighteen years of age shall not be employed in - beating sacks which have contained basic slag. - - 15. No person employed in breaking or grinding, emptying, - packing, or storing basic slag, shall work more than ten hours - daily. - - There shall be intervals during working hours amounting in the - aggregate to two hours, one of them lasting at least an hour. - If duration of employment daily is limited to seven hours with - never longer than four hours’ work without an interval, only - one interval of at least one hour is required. - - 16. For work mentioned in Para. 15 no person shall be employed - without a certificate from an approved surgeon stating that he - is free of disease of the lungs and not alcoholic. The occupier - shall place the supervision of the health of the workers under - a surgeon who shall examine them at least once a month for - signs of disease of the respiratory organs and alcoholism. - Workers engaged in the operations mentioned in Para. 15 shall - be suspended from employment when the surgeon suspects such - illness or alcoholism. Those showing marked susceptibility to - the effect of basic slag dust shall be permanently suspended. - - 17. A health Register shall be kept in which shall be entered - the precise employment, duration of work, and state of health - of the persons employed. - - 18. The occupier shall obtain a guarantee from the workers that - no alcohol or food shall be taken into the workrooms. - - -Preparation of Hydrofluoric Acid - -(See also pp. 37 and 171) - -The fumes given off in the preparation of hydrofluoric acid require to be -collected in leaden coolers and vessels; that which escapes requires to -be absorbed by a water spray in towers. The apparatus must be impervious -and kept under a slight negative pressure. - - -Chromium Compounds - -(See also pp. 55-8 and 185) - -The German Imperial Decree, dated May 16, 1907, contains the preventive -measures necessary in bichromate factories. According to this, workers -suffering from ulceration of the skin (chrome holes, eczema) are not to -be employed except on a medical certificate that they are free from such -affections, and daily examination for signs of ulceration is enjoined, -so that those affected may receive prompt treatment. Further, periodical -medical examination of the workers is required at monthly intervals. -Respirators (for work in which dust cannot be avoided), with lavatory, -cloakroom, and meal room accommodation, are to be provided, and also -baths. In handling bichromates wearing of impervious gloves may be -necessary, and smearing the hands and face with vaseline is recommended. -In addition diffusion of dust and fumes must be minimised; machines -in which mixing, crushing, and grinding are done must be impervious, -and provided with exhaust ventilation. Charging of the furnaces, where -possible, should be effected mechanically and the fumes developed both in -manipulation of the furnaces and from hot bichromate liquor removed by an -exhaust. - -A leaflet containing directions for workers coming into contact with -chromium compounds in chemical factories, dyeing, tanning, wood staining, -calico printing, wall paper printing, painting, &c., has been drawn up by -Lewin. It contains a list of the poisonous chrome compounds and of the -industries in which chrome poisoning occurs, information as to the action -of chrome upon the skin and mucous membrane, and the preventive measures -necessary. Among the last named are: smearing the skin with oil, use of -impervious gloves, respirators in work where dust arises, necessity of -cleanliness, and periodical medical examination. - -For the _chrome tanning industry_ the following leaflet was drawn up -by the Imperial Health Office in Berlin, which succinctly states the -measures against chrome poisoning in these industries and contains much -practical information for the workers: - - In chrome tanning by the two bath process, the first bath - containing potassium bichromate and hydrochloric acid has a - corroding effect upon broken surfaces of the skin (scratches, - chapped hands, eruptions, &c.). In consequence, they develop - into round ulcers (chrome holes) with hard raised edges which - are difficult to heal and go on increasing in size unless work - at the process is temporarily given up. In persons with very - sensitive skin, even though the surface may be intact, handling - the liquor brings on sometimes an obstinate rash (eczema) on - the hands and forearms. - - The solution used in the one bath process has no corrosive - action, but it is a strong poison, just as is the solution of - potassium bichromate of the two bath process. If swallowed, the - solutions cause vomiting, diarrhœa, kidney trouble, and even - death. Chromium compounds can also enter the body through skin - wounds and cause illness. - - _Prevention._—In order to prevent the occurrence of chrome - ulceration, workers employed with chrome or chrome solutions - must be especially careful in avoiding injury to the skin of - the hands or forearms. This applies especially to workers who - carry the vessels containing bichromate, who weigh and dissolve - the potassium bichromate, or who come into contact with the - tanning liquor or with undressed skins and hides which have - lain in the liquor. - - If, in spite of precautions, eruptions, rashes, or ulceration - occur, all work necessitating contact with corrosive tanning - liquors should be suspended until they are healed. - - In order to reduce risk of action of the liquor on the skin, - workers employed in the process described would do well if, - before commencing work, they carefully smeared hands and - forearms with unsalted lard, vaseline, or the like, and during - work avoided, as much as possible, soiling the bare hands and - arms with the liquor. - - If, nevertheless, a worker has contracted a chrome hole, or - eruption, he should consult a medical man, informing him at the - same time of the nature of his work. - - To avoid internal absorption of chrome, workers preparing the - baths must carefully avoid inhaling the dust of chromium salts. - These and all other workers engaged with the liquors containing - chromium must not take food and drink while at work. Working - suits should be taken off and face and hands washed with soap - before eating or drinking, and before leaving the factory. - - -Petroleum, Benzine - -(See also pp. 59-64 and 222-4) - -As crude petroleum and the higher fractions first distilled from it -affect the skin injuriously, wetting the skin should be avoided, and -careful cleanliness on the part of the workers enjoined. Workers exposed -to the influence of gases escaping from naphtha springs and wells should -be equipped with breathing apparatus (smoke helmets); this applies to -those who have to enter stills and other apparatus connected with the -distillation of petroleum. - -In the preparation of petroleum by sulphuric acid sulphur dioxide in -great quantity is developed, constituting a distinct danger to the -workers. This process, therefore, should be carried on in closed vessels -furnished with mechanical stirrers or compressed air agitators. The most -suitable apparatus is that illustrated in fig. 13. - -Petroleum tanks must be thoroughly aired before they are cleaned and -should be entered only by workers equipped with breathing apparatus. -Apparatus containing petroleum and benzine requires, as far as possible, -to be closed in and air tight (as, for example, in the extraction of fat -from bones and oil seed, in the rubber industry, and in chemical cleaning -establishments); where benzine fumes develop they should be immediately -drawn away by suitably applied exhaust ventilation. This is necessary, on -account of the danger of fire, in chemical cleaning establishments where -purification is effected by means of benzine in closed drums. - -Regulations for benzine extraction plants are contained in the Prussian -Ministerial Decree, dated January 5, 1909, for benzine extraction -works, and also in that of August 3, 1903, for dry-cleaning premises, -to which last were added ‘Directions for safety,’ containing important -regulations as to risk from fire. From our standpoint the following -points are of interest: care is to be taken to provide and maintain -exhaust ventilation directly across the floor. The air, however, must -not be allowed to pass near any fire. Drying rooms especially are to be -lofty and airy, and separated from other workrooms. In factories with -mechanical power the authorities may require provision of artificial -ventilation for the drying rooms. Washing machines, centrifugalising -machines, and benzine rinsing vessels should be furnished with -well-fitting covers to be removed only for such time as is absolutely -necessary for putting in and taking out the articles to be cleaned, -shaken, or rinsed. The vessels named are to be examined as to their -imperviousness at least once every quarter by a properly qualified -person. The condition in which they are found is to be noted in a book to -be shown to the Factory Inspector and police authorities on demand. - -Lastly, substitution for benzine of other less poisonous substances such -as carbon tetrachloride has been urged. - - -Phosphorus, Lucifer Matches - -(See also pp. 49-53 and 190) - -In view of the danger of the lucifer match industry, measures were -taken at an early date in almost all civilised states to guard against -phosphorus poisoning, and in many countries have led to the prohibition -of the use of white phosphorus. Complete prohibition of its manufacture -and use was first enacted in Finland (1872) and in Denmark (1874). -Prohibition was decreed in Switzerland in 1879 (in January 1882 this was -revoked, but again enacted in 1893), and in the Netherlands in 1901. In -Germany the law prohibiting the use of white phosphorus came into force -in January 1908, and runs as follows: - - 1. White or yellow phosphorus shall not be employed in the - production of matches and other lighting substances. Lighting - substances made with white phosphorus shall not be kept for - sale, or sold, or otherwise brought on the market. Provided - that this shall not apply to ignition strips which serve for - the lighting of safety lamps. - - 2. Persons wilfully infringing this law shall be punished - by a fine of 2000 marks. If the infringement occurs through - ignorance the fine shall consist of 150 marks. - - In addition to the fine, all prohibited articles produced, - imported, or brought into the trade shall be confiscated, - as well as the implements used in their production, without - reference to whether they belong to the person convicted or - not. If prosecution or conviction of the guilty party cannot be - brought home, confiscation nevertheless is to be carried out - independently. - -Roumania and France have a state monopoly of matches; in these states -no white phosphorus matches have been produced since 1900 and 1898 -respectively. France, by the Law of December 17, 1908, signified -concurrence with the International Convention in regard to the -prohibition of the use of white phosphorus. - -In Sweden and Norway the prohibition of white phosphorus is in force -only for the home trade. A Swedish Decree, dated December 9, 1896, -permitted factories carrying on the manufacture for export to use white -phosphorus, and almost precisely similar provisions are contained in the -Norwegian Decree. The Swedish Decree, dated March 30, 1900, permits white -phosphorus matches to be exported, but not to be sold in the country. In -Austria difficulties in regard to prohibition of white phosphorus arose -owing to trade conditions (especially in the East), and the attitude of -the states competing in the lucifer match trade, particularly Italy and -Japan. Austria, therefore, made agreement with international prohibition -of white phosphorus, dependent on the attitude of Japan; since Japan did -not concur, the decision of Austria fell through. When, however, Italy in -the year 1906 joined the Convention, the difficulties were also overcome -in Austria, and by a law similar to that of Germany, dated July 13, 1909, -prohibition of the manufacture and sale of white phosphorus matches dates -from the year 1912.[H] - -Belgium has refrained from prohibition of white phosphorus, but on the -other hand has passed a series of enactments relating to the match -manufacture, of which the most essential are here cited, since they -characterise the measures which come into consideration for factories in -which white phosphorus is still employed. - - _Royal Decree, dated March 25, 1890, modified by the Royal - Decree, dated February 12, 1895, and November 17, 1902, - concerning employment in lucifer match factories._ - - 1. In match factories where white phosphorus is used, mixing - the paste and drying the dipped matches shall be carried on in - a place specially set apart for the purpose. - - 2. Mixing the paste shall be carried on in an entirely closed - vessel or in one connected with an efficient exhaust draught - locally applied. - - The proportion of white phosphorus in the paste shall not - exceed in weight 8 per cent. of the total material, not - including water. - - 3. Hoods and ducts communicating with an exhaust draught shall - be installed at the level of the plates for dipping white - phosphorus matches, and over the vessels containing the paste. - - 4. Drying rooms for white phosphorus matches, if entered by the - workers, shall be mechanically ventilated. - - 5. Rooms in which phosphorus fumes can arise shall be lofty and - well ventilated, preferably by an exhaust at the level of the - work benches, communicating with the main chimney stack. - - The workrooms shall be kept clean. No food or drink shall be - taken in them. - - 6. In every match factory the workers shall have at their - disposal a special cloak room and suitable and sufficient - washing accommodation, so as to be able to change clothes - before commencing, and at the end of, work, and to wash the - hands and face on leaving. - - Cleanliness will be obligatory upon the workers manipulating - phosphorus paste or matches. - - 7. Workers coming into contact with phosphorus paste or matches - shall be examined monthly by a surgeon appointed by the - Minister of Industry, who shall be paid by the occupier. - - Workers having decayed, unstopped teeth, or exhibiting symptoms - of gingivitis or stomatitis, or in poor health at the time of - examination, shall be temporarily suspended from work. - - The surgeon shall enter the results of his monthly examinations - in a prescribed register. - - This register shall be shown to the Factory Inspector on demand. - -These decrees are supplemented by further orders regarding the taking of -samples of paste in match factories and store houses (Royal Orders of -March 25, 1890; February 12, 1895; April 18, 1898; November 17, 1902). - -As is evident from the Belgian enactment, in states where prohibition of -white phosphorus is not in force, palliative measures only are possible -and even then they can only be enforced in large factories when automatic -machinery is used to eliminate hand labour in dangerous operations. In -this respect the introduction of closed, ventilated, mechanical mixing -apparatus provided with mechanical stirrers, closed and ventilated -mechanical dipping and drying apparatus, are especially important. -Certain modern American machines carry through the whole complicated -process of the phosphorous match industry automatically. Seeing that -prohibition of white phosphorus is an accomplished fact and that matches -free from risk in their manufacture answer every purpose, the universal -enforcement of the prohibition of white phosphorus should be striven for -in civilised states. - - -Carbon bisulphide - -(See also pp. 68-71 and 193-5) - -Use of carbon bisulphide in the vulcanising of indiarubber goods by -dipping them into the liquid and subsequently drying them (usually in -a current of hot air) causes development of carbon bisulphide fumes in -considerable quantity, especially if the articles to be dried are laid -on shelves or hung up in the workroom, a procedure which should never be -permitted. Drying must be carried out under local exhaust ventilation. - -All vessels holding carbon bisulphide used for dipping can be placed in -a wooden channel above the dipping vessels, provided with openings for -manipulation, and connected with an exhaust system. - -The following are the German Imperial Regulations, dated March 1, 1902, -for vulcanising of indiarubber by means of carbon bisulphide: - - VULCANISING BY MEANS OF CARBON BISULPHIDE - - (Notice concerning the erection and management of industrial - premises in which indiarubber goods are vulcanised by means of - carbon bisulphide or chloride of sulphur.) - - The following regulations shall apply in accordance with - paragraph 120 (_e_) of the Industrial Code: - - 1. The floor of such rooms as are used for the vulcanising - of indiarubber goods by means of carbon bisulphide shall not - be lower than the surrounding ground. The rooms shall have - windows opening into the outer air, and the lower halves shall - be capable of being opened so as to render possible sufficient - renewal of air. - - The rooms shall be ventilated by fans mechanically driven. With - the approval of the higher authorities permission to dispense - with mechanical draught may be allowed, provided that in other - ways powerful change of air is secured. With the approval of - the higher authorities special ventilating arrangements can be - dispensed with if the fumes of carbon bisulphide are removed - immediately, at the point where they are produced, by means - of a powerful draught, and in this way purity of the air be - secured. - - 2. The vulcanising rooms shall not be used as a dwelling, or - for sleeping in, or for preparing food in, or as a store, - or drying room, nor shall other processes than those of - vulcanising be carried on in them. No persons, except those - engaged in vulcanising processes, shall be allowed in the rooms. - - There shall be at least 20 cubic meters (700 cubic feet) of air - space allowed for each person employed therein. - - 3. Only such quantities of carbon bisulphide shall be brought - into the vulcanising rooms as shall serve for the day’s supply. - Further storage shall be made in a special place separate from - the workrooms. Vessels to hold the vulcanising liquid shall be - strongly made, and when filled and not in use shall be well - covered. - - 4. Vulcanising and drying rooms shall be warmed only by steam - or hot-water pipes. - - These rooms shall be lighted only by means of strong - incandescent electric lamps. - - Exceptions from paragraphs 1 and 2 may be allowed by the higher - authorities. - - 5. Machines intended for vulcanising long sheets of cloth shall - be covered over (_e.g._, with a glass casing) so as to prevent - as far as possible the entrance of carbon bisulphide fumes into - the workrooms, and from the casing the air shall be drawn away - effectually by means of a fan mechanically driven. Entrance to - the space which is enclosed shall only be allowed in case of - defects in the working. - - In cases where a covering of the machine is not practicable - for technical reasons the higher authorities can, if suitable - means of protection are used (especially when the machine is - placed in an open hall, and provided that no person works at - the machine for more than two days a week), allow of exception - to the above arrangement. - - 6. Vulcanising of other articles (not mentioned in par. 5), - unless carried out in the open air, shall be done in covered-in - boxes into which the worker need only introduce his hands, and - so arranged as to keep the fumes away from the face of the - worker. - - The air must be drawn away from the box by means of a powerful - draught. - - 7. Rule 6 shall apply in vulcanising both the outside and - inside of indiarubber goods. In vulcanising the inside no - worker shall be allowed to suck the fluid through with the - mouth. - - 8. The goods after their immersion in the vulcanising fluid - shall not lie open in the room, but shall either be placed - under a ventilated cover or at once be carried into the drying - chamber. - - The drying chamber or drying rooms in which the wares are - exposed to artificial heat immediately after vulcanising - shall be so arranged that actual entrance into them for the - putting in or taking out of the vulcanised goods shall not - be necessary. No person shall be allowed to enter the drying - chamber while work is going on. The higher authorities can - permit of exceptions to this rule in the case of the drying of - long rolls if sufficient protecting arrangements are made. - - 9. When vulcanisation is effected by means of chloride of - sulphur the vessels or chambers used for holding it shall be so - arranged that escape of the fumes is prevented. - - No person shall enter the vulcanising chamber until the air in - the chamber has been completely changed; it shall not be used - for purposes other than vulcanising. - - 10. Employment in vulcanising with carbon bisulphide or in - other work exposing the workers to carbon bisulphide vapour - shall not be allowed without a break for more than two hours - and in no case for more than four hours in one day; after two - hours a pause of at least one hour must be allowed before - resumption. - - No person under 18 years of age shall be employed. - - 11. The occupier shall provide all workers employed in work - mentioned in paragraph 10 with proper and sufficient overalls. - By suitable notices and supervision he shall see that when not - in use they are kept in their proper place. - - 12. Separate washing accommodation and dressing-rooms for each - sex shall be provided, distinct from the workrooms, for all - persons employed as stated in paragraph 11. - - Water, soap, and towels and arrangements for keeping the - clothes put off before the commencement of work shall be - provided in sufficient amount. - - 13. The occupier shall appoint a duly qualified medical - practitioner (whose name shall be sent to the Inspector of - Factories) to supervise the health of those exposed to the - effects of carbon bisulphide. He shall examine the workers once - every month with a view to the detection of poisoning by carbon - bisulphide. - - By direction of the medical practitioner workers showing signs - of carbon bisulphide poisoning shall be suspended from work - and those who appear peculiarly susceptible shall be suspended - permanently from work in processes mentioned in paragraph 10. - - 14. The occupier shall keep a book, or make some official - responsible for its keeping, of the changes in the personnel in - the processes mentioned in paragraph 10 and as to their state - of health. The book shall contain— - - (1) The name of the person keeping the book; - - (2) The name of the appointed surgeon; - - (3) Surname, Christian name, age, residence, date of first - employment, and date of leaving of every worker mentioned in - paragraph 10, and the nature of the employment; - - (4) The date of any illness and its nature; - - (5) Date of recovery; - - (6) The dates and results of the prescribed medical examination. - - 15. The occupier shall require the workers to subscribe to the - following conditions:— - - No worker shall take food into the vulcanising rooms; - - The workers shall use the protection afforded in paragraphs 5-7 - and use the overalls in the work named; - - The workers shall obey the directions of the occupier given in - accordance with Rule 5, paragraphs 1 and 2, Rule 8, paragraphs - 1 and 2, and Rule 9, paragraph 2. Workers contravening these - orders shall be liable to dismissal without further notice. - - If in a factory regulations already exist (paragraph 134(a) of - the Industrial Code) the above shall be included. - - 16. In the vulcanising rooms mentioned in Rule 1 there shall be - posted up a notice by the police stating— - - (_a_) The cubic capacity of the rooms; - - (_b_) The number of workers who may be employed. - - Further, in every vulcanising room there shall be posted up in - a conspicuous place and in clear characters Rules 1-15 and the - conditions in paragraph 15. - -Reference should be made also to the Prussian Ministerial Decree, dated -February 23, 1910, on the preparation, storing, and manufacture of carbon -bisulphide, and to the French Ministerial Circular, dated January 20, -1909 (Manufacture of Indiarubber). - -Employment of benzine and chloride of sulphur for vulcanising is, from a -hygienic standpoint, to be preferred to that of the much more dangerous -carbon bisulphide. The same applies also to the process of the extraction -of fat. - -In the references made to general arrangements for the protection of -workers dealing with poisons, stress was laid on the complete enclosing -of extraction apparatus. This applies, of course, to extraction by means -of carbon bisulphide, both on grounds of economy, health, and risk from -fire. - -On account of the risk to health, efforts have been made to substitute -other means of equal efficiency, free from danger. Such a substitute may -be found in _carbon tetrachloride_. This extracts well, and dissolves -grease spots (like benzine), is not explosive, is scarcely inflammable, -and is less poisonous than the substances commonly used for extraction. -Its employment is to be recommended on hygienic grounds, but the -relatively high price may stand in the way of its use. - - -Illuminating Gas Industry. Production of Tar and Coke - -(See also pp. 71-90 and 199) - -In illuminating gas factories imperviousness of the whole working system -is especially important from an economical and hygienic standpoint, -since only in this way can danger to the working staff be avoided. This -applies especially to the retorts, from which no gas should be allowed -to escape. If the exhaust is working satisfactorily this should not be -possible, as the pressure of the gas in the retorts during distillation -will be a negative one. Correct regulation of pressure is thus of the -greatest importance in the prevention of poisoning in gas works. - -Further, special precaution is necessary in operations with gas purifying -material containing cyanogen, since otherwise the workers suffer from the -gases developed from the gas lime. - -Work with gas purifying material should be so arranged that injurious -gases are carried away by suitable ventilating arrangements. -Consideration for the neighbourhood forbids their discharge into the open -air, and forbids also operations with the gas purifying material in the -open air; therefore non-injurious removal of these gases is necessary. - -Quenching of the coke also should, on account of the annoyance to the -working staff and to lessen nuisance to the neighbourhood, be carried out -so that the fumes are drawn into the main chimney stack. - -In coke ovens escape of tarry constituents and of poisonous emanations -are prevented by imperviousness of the apparatus, by sufficiency of the -exhaust draught, and especially by passing the products of distillation, -which cannot be condensed, under a fire, or by absorbing them either with -water or oil. - -Special precautionary measures are needed further in the distillation of -the washing oil, and generally escape of poisonous emanations must be -prevented by the greatest possible imperviousness of the distillation -system and corresponding regulation of pressure. - - -Gas Motors (Power Gas Stations) - -(See also pp. 80-5) - -The following points, taken from an Austrian Ministerial Decree (dated -December 2, 1903), for the prevention of poisoning in power gas works, -may be useful: - - POWER GAS INSTALLATIONS - - In mixed gas installations (Dowson, water gas) of the older - system, the way in which the gas is produced causes the whole - apparatus and pipes to be under slight negative pressure, - because the steam required for the process must be blown into - the generator. In these works, therefore, a small special steam - boiler is required and a gas receiver to store the gas. - - In more modern suction generator gas installations the piston - is used to suck in steam and air as well as the gases arising - in the generator and to draw them into the motor cylinder. Thus - the whole system is kept in a condition of slight negative - pressure during the process. While the suction generator gas - system is working, only so much gas is produced as the motor - uses for the time being, so that with this system there is no - greater store of gas than is requisite. - - In such an installation the following rules should be borne in - mind: - - 1. All the apparatus (gas pipes, valves, &c.) must be - constructed and maintained in a completely impervious - condition. Any water seals especially which may be in use must - receive attention. - - 2. Precautions must be taken to prevent the gases from the - generator passing into the coolers and purifiers when the - engine is at rest. - - 3. Care is to be taken when the apparatus is at rest to prevent - any possible subsequent escape of gas into the room where the - apparatus is installed. - - 4. The return of explosive gas out of the gas engine into the - gas pipe by failure to ignite or other accident, must be made - impossible. - - 5. The apparatus through which the generator is charged must - possess a tightly fitting double valve to prevent escape of gas - into the room during charging. - - 6. The pipes for conducting away the unpleasantly smelling - bituminous constituents in the water mixed with sulphuretted - hydrogen from the scrubbers must not communicate with the - workroom. - - 7. Precautions must be taken to minimise the danger during the - cleaning of the generator (removal of ashes and slag). - - 8. All stop-cocks and valves are to be so arranged that their - position at any time (open or shut) is clearly visible from - outside. - - 9. Purifiers with a capacity greater than two cubic meters - must be provided with appliances which make possible thorough - removal of the gas before they are opened. - - 10. The gas washing and cleaning apparatus and pipes are to be - fitted with gauges indicating the pressure existing in them at - any moment. - - 11. When a suction gas plant is first installed and also at - times when there is no gas in the pipes and plant between the - generator and the engine, gas must be blown in until all air is - expelled before the engine is set going. - - 12. During the cleaning of apparatus and pipes which, when in - action, contain gas, the rooms must be thoroughly ventilated. - - 13. Rooms in which suction gas plant is installed must be of - such a height that all the plant and its connections can be - easily reached for cleaning, &c., and be capable of such free - ventilation as to render impossible an accumulation of gas. - - 14. These rooms must be separated from living rooms by a wall - without any openings in it. Emanations also must be prevented - as far as possible from entering into living or working rooms - situated over the gas engine. - - 15. Erection of apparatus for generating and purifying suction - gas in cellars shall only be allowed if specially effective - ventilation is provided by natural or mechanical means. - -Other Regulations are those of the Prussian Ministerial Decree, dated -June 20, 1904, as to the arrangement and management of suction gas -premises. - - -ACETYLENE GAS INSTALLATIONS - -(See also pp. 85-7) - -The following regulations for the protection of workers in acetylene gas -installations are taken from the Prussian Ministerial Decree, dated 2 -November, 1897: - - 1. Preparation and condensation of acetylene on the one hand, - and liquefaction on the other, must be carried on in separate - buildings. - - 2. If the pressure employed for condensation of the gas exceeds - eight atmospheres, this work must take place in a room set - apart for the purpose. - - 3. Rooms in which acetylene is prepared, condensed, or - liquefied shall not be used as, nor be in direct connection - with, living rooms. They must be well lighted and ventilated. - - 4. The carbide must be kept in closed watertight vessels, so - as to ensure perfect dryness and only such quantities shall - be taken out as are needed. The vessels must be kept in dry, - light, well-ventilated rooms; cellar rooms may not be used for - storage purposes. - - 5. Crushing of carbide must be done with the greatest possible - avoidance of dust. Workers are to be provided with respirators - and goggles. - - 6. Acetylene gasometers must be fitted up in the open air or in - a well-ventilated room, separated from the gas generator. Every - gas receiver must have a water gauge showing the pressure in - the receiver. - - 7. Between the gasometer and receiver a gas purifier must be - provided so as to remove impurities (phosphoretted hydrogen, - arseniuretted hydrogen, carbon bisulphide, ammonia, &c.). - - 8. Condensation of acetylene gas at a pressure exceeding ten - atmospheres shall only be done in combination with cooling. - - -DISTRIBUTION AND USE OF POWER AND ILLUMINATING GAS - -The Austrian Gas Regulations (of July 18, 1906) contain general -provisions as to impermeability and security of the gas pipes and the -precautions to be observed in their installation. Special directions -follow as to main flues, material, dimensions, branches, and connections, -valve arrangements, testing of the pipes against leakage, directions -for discovering leaks, and other defects; also the nature of the branch -pipes (dimensions and material), valves, cocks, syphons, water seals, and -pressure gauges. In addition there are directions as to testing pipes and -how to deal with escape of gas, freezing of pipes, and other mishaps. - - -Ammonia - -(See also pp. 90-3 and 175) - -In the production of ammonia and ammonium salts (ammonium sulphate) -combination of the ammoniacal vapour with the sulphuric acid is -accompanied with the formation of volatile dangerous gases containing -sulphuretted hydrogen and cyanogen compounds, which produce marked -oppression and sometimes endanger the health of the workers. Drawing-off -these fumes into the furnace (practised sometimes in small industries) -is not advisable, as the sulphuretted hydrogen is burnt to sulphur -dioxide; if it is burnt absorption of the sulphur dioxide should follow, -or working it up into sulphuric acid (Leymann). Often these gases are -freed from cyanogen compounds and sulphuretted hydrogen by means of gas -purifying materials, such as are used in gas works. The whole apparatus -must be impervious. Where liquids containing ammonia are used exhaust -ventilation is necessary. - - -Cyanogen, Cyanogen Compounds - -(See also pp. 93-5 and 195-7) - -Processes in which cyanogen gas can develop, require to be done under a -powerful exhaust draught. - -In the production of cyanogen compounds possibility of the escape of -hydrocyanic acid (prussic acid) has to be borne in mind. Such escape is -possible in its production from raw animal products. - -The most careful cleanliness and observance of general measures for -personal hygiene are necessary in factories in which cyanogen compounds -are manufactured or handled. In crushing cyanide of potassium the workers -should wear indiarubber gloves and respirators. The products should be -stored in closed vessels in dry store rooms set apart for the purpose. - -Modern cyanide of potassium factories which work up molasses, from which -the sugar has been removed, and also residuary distillery liquors, so -far conform with hygienic requirements that all the apparatus is under -negative pressure, so that poisonous gases cannot escape into the -workrooms. - - -Coal Tar, Tar Products - -(See also pp. 96-119) - -Care must be taken for the removal of injurious gases developed in the -manipulation and use of tar (tar distillation) and in the processes -of cleaning connected therewith. This can be most effectively done by -carrying on the processes in closed apparatus. Hofmann describes such -a factory where all mixing vessels in which the distillation products -are further treated are completely closed in, so that even in mixing and -running off, no contact is possible with the material. - -The vessels for holding tar, tar-water, &c., must be impervious and -kept covered. Only the cold pitch and asphalt should be stored in open -pits. The cooling of the distillation products and residues, so long as -they give off poisonous and strongly-smelling fumes, should be carried -out in metal or bricked receivers. Such directions find a place in the -‘Technical Instructions’ appended to the German Factory Code. Without -doubt, tar is, because of its smell and for other reasons, unpleasant to -handle, and the danger to health from contact with it is not a matter -of indifference. Spilling of small quantities of tar during transport -and other manipulations can hardly be avoided. Careful cleanliness, -therefore, on the part of workers is strongly urged. It may be mentioned -that if tar is covered with a layer of tar-water, treatment with acid -fluids develops sulphur and cyanogen compounds, which may affect the -workers. Tar water should, therefore, be separated carefully from the tar -and used for the preparation of ammonia. - -The same remarks as to cleanliness, &c., apply in the manufacture of -felt, lamp-black, and briquettes, with use of tar. Saturation of felt, -and manufacture of tar plaster should be done in closed apparatus. -In the production of lamp-black, even with a great number of soot -chambers, there is escape of soot causing nuisance to workers and the -neighbourhood. Complete avoidance of this seems to be difficult, so that -measures for personal hygiene must be assured. In briquette factories it -has been found useful to heat the tar by means of steam instead of by -direct fire, which renders possible the use of a closed apparatus and -mechanical stirring. - -In the distillation of tar, during the first distillation period (first -runnings) unpleasant and injurious gases containing ammonia and sulphur -escape from the stills. These should (according to Leymann) be carried -away through closed pipes branching off from the lower end of the -running-off pipe, either into the furnace (in doing which a possible back -flash of flame is to be guarded against) or be subjected to purification -by lime or oxide of iron (similar to that in the case of illuminating -gas) with a view to recovery of ammonia and sulphur. The lower end of the -distillation pipes should be U-shaped so as to form a liquid seal—the -pipes for the drawing off of the gases branching off before the curve. In -the later stages of distillation risk can be checked by careful cooling -and imperviousness of the apparatus. - -Very unpleasant yellow fumes develop in great quantity when pitch is run -off from the hot still. Hence hot pitch should not be run off into open -pitch receptacles, but be cooled first in closed receptacles. - -The crude products obtained by distillation (light oil, creosote oil) -are subjected to purification consisting in treatment on the one hand -with alkali and on the other with acid and followed by fractional -distillation. In these processes injurious fumes may develop, therefore -they must—as already mentioned—be carried on in closed vessels provided -with means of escape for fumes and appliances for mechanical stirring; -the fumes drawn off must be led into the chimney stack. - -In the distillation of brown coal, of tar, and of resin, it is necessary, -as in the distillation of coal tar, to insist above all on careful -cooling and condensation, and thorough absorption of uncondensed gases -in washing towers. Special precautionary rules are necessary to guard -against the danger of entering tar stills for cleaning purposes. Such -directions were approved in Great Britain in 1904 in view of accidents -which occurred in this way: - - TAR DISTILLING - - The following directions[I] are approved by the Home Office - and are applicable to factories in which is carried on the - distillation of tar for the production of naphtha, light oil, - creosote oil, and pitch. - - 1. During the process of cleaning, every tar still should - be completely isolated from adjoining tar stills either by - disconnecting the pipe leading from the swan neck to the - condenser worm, or by disconnecting the waste gas pipe fixed - to the worm end or receiver. Blank flanges should be inserted - between the disconnections. In addition, the pit discharge pipe - or cock at the bottom of the still should be disconnected. - - 2. Every tar still should be ventilated and allowed to cool - before persons are allowed to enter. - - 3. Every tar still should be inspected by the foreman or other - responsible person before any workman is allowed to enter. - - 4. The inspecting foreman on first entering any tar still - or tank, and all persons employed in tar stills or tanks in - which there are no cross stays or obstructions likely to cause - entanglement, should be provided with a belt securely fastened - round the body with a rope attached, the free end being left - with two men outside whose sole duty should be to watch and - draw out any person appearing to be affected by gas. The belt - and rope should be adjusted and worn in such a manner that the - wearer can be drawn up head foremost and through the manhole - and not across it. - - 5. A bottle of compressed oxygen, with mouthpiece, should be - kept at all times ready for use; and printed instructions as - to the use of this bottle, and the method to be employed for - resuscitation by means of artificial respiration should be kept - constantly affixed. A draft of such instructions is appended. - - 6. A supply of suitable chemical respirators properly charged - and in good condition should be kept ready for use in case - of emergency arising from sulphuretted hydrogen or certain - poisonous gases. (Granules of carbon saturated with a solution - of caustic soda readily absorb sulphuretted hydrogen and may be - used for charging respirators.) - - 7. The use of naked lights should be strictly prohibited in - any portion of the works where gas of an inflammable nature is - liable to be given off. - - 8. Each still should be provided with a proper safety valve, - which should at all times be kept in efficient working - condition. - - -GASSING - - _Symptoms._—The first symptoms are giddiness, weakness in the - legs, and palpitation of the heart. If a man feels these he - should at once move into fresh warm air, when he will quickly - recover if slightly affected. He should avoid exposure to cold. - He should not walk home too soon after recovery; any exertion - is harmful. - - _First Aid._—Remove the patient into fresh warm air. Send for - the oxygen apparatus. Send for a doctor. Begin artificial - breathing at once if the patient is insensible and continue it - for at least half-an-hour, or until natural breathing returns. - Give oxygen[J] at the same time and continue it after natural - breathing returns. - - _Artificial Breathing_ (_Schäfer Method_).—Place the patient - face downwards as shown in the diagrams. - - Kneel at the side of the patient and place your hands flat in - the small of his back with thumbs nearly touching, and the - fingers spread out on each side of the body over the lowest - ribs (_see_ Diagram 1). - - [Illustration: DIAGRAM 1] - - Then promote artificial breathing by leaning forward over the - patient and, without violence, produce a firm, steady, downward - pressure (_see_ Diagram 2). Next release all pressure by - swinging your body backwards without lifting your hands from - the patient (_see_ Diagram 1). - - [Illustration: DIAGRAM 2] - - Repeat this pressure and relaxation of pressure without any - marked pause between the movements, _about 15 times a minute_, - until breathing is established. - -In my opinion as expressed in the general discussion, use of breathing -apparatus (smoke helmets) with oxygen is strongly advisable; these -implements must be put on before entering the still. - -In creosoting wood, opening the apparatus and taking out the steeped -wood should only be done when the apparatus is sufficiently cooled, as -otherwise injurious fumes escape. - -In heating asphalt unpleasant fumes arise which should be drawn off into -a furnace, or absorbed by a condenser charged with oil (Leymann); open -pans should be avoided, as injurious to workers. - - -Organic Dye-stuffs, Coal-Tar Colours. - -(See also pp. 107-19 and 204-15) - -The hygienic measures to be adopted for the prevention of industrial -poisoning in coal-tar colour factories are chiefly concerned with the -poisonous nature on the one hand of the raw material (benzene, toluene, -&c.) and on the other of the intermediate products (nitrobenzene, -aniline, toluidine, &c.) and the subsidiary substances (chlorine, acids, -especially nitric acid, &c.,) used. - -The most important measures are as follows: - -In purifying the raw materials (benzene, &c.) the distillation requires -to be done under effective cooling and in impervious apparatus. If -injurious solvents are employed (such as pyridine in the production of -anthracene) the manipulations should be performed in closed apparatus -if possible, under negative pressure. The fumes exhausted should be -carefully condensed by cooling or absorbed by a spray of water or oil. - -In view of the poisonous nature of benzene, the apparatus, stills, -receivers, tanks, tank waggons, &c., should only be entered for the -purpose of cleaning or repairing after preliminary thorough removal of -all residue of benzene, complete isolation from all similar apparatus -near, and thorough ventilation. Workers entering the stills, &c., -should always be equipped with breathing apparatus (smoke helmets) and -with a supply of oxygen. Other aids, such as safety belts which are held -by helpers, are not here advocated in view of the often sudden fatal -poisoning, especially as the rescuer is easily induced to spring to the -assistance of his unfortunate mate without the necessary equipment. The -frequency of such accidents calls urgently for the use of breathing -apparatus. - -In the manufacture of _diazo-_ and _nitroso-compounds_ and generally in -nitrating operations poisonous nitrous fumes are developed. By reduction -in an acid solution, acid fumes and singularly pungent-smelling compounds -can be given off. If reduction by means of tin is practised, the arsenic -in the tin can cause evolution of the extremely poisonous arseniuretted -hydrogen gas. In sulphonating, sulphur dioxide can develop; and -sulphuretted hydrogen gas on heating with sulphur or sulphide of sodium. - -All manipulations should take place in tightly closed-in apparatus -provided with exhaust, and the gases drawn off should be absorbed or -effectively carried away. In the case of many injurious gases it is -not sufficient merely to conduct them into the flue; they ought to -be condensed and got rid of. Thus acid fumes (nitrous fumes, sulphur -dioxide, hydrochloric acid vapour, chlorine gas) are neutralised by water -or milk of lime, or a solution of soda; ammonia or alcohol by water; -sulphuretted hydrogen and arseniuretted hydrogen by lime and oxide of -iron; aniline, &c., by dilute acids. - -Production of _nitrobenzene_, by nitrating benzene requires to be done in -closed apparatus, provided with mechanical agitators. In the subsequent -separation of the nitrating acids from the resulting nitro-compounds, -escape of vapourised nitro-compounds can scarcely be avoided even if -closed apparatus is used. Provision, therefore, must be made for abundant -ventilation of the workrooms. The reduction of the nitro-compounds -(nitrobenzene, nitrotoluene) to aniline (toluidine) must similarly take -place in closed agitating vessels. Introduction of the iron filings and -sulphuric or hydrochloric acids, also the subsequent saturation with -lime, and driving over of the aniline, &c., with steam, and collection -of the distillate, must take place in completely closed apparatus. -Nevertheless, escape of small quantities of aniline is very difficult to -prevent unless ample ventilation is provided. - -In the production of _fuchsin_ by heating aniline hydrochloride -(toluidine, red oil) with nitrobenzene (formerly arsenic acid) in closed -vessels, furnished with mechanical stirring apparatus the aniline -remaining unconverted after the melting escapes in the form of steam -carrying aniline fumes, even with careful condensation, so that thorough -ventilation and the other general measures for the protection of workers -set forth on pp. 242 _et seq._ are required. - -Marked injury to health and distress to workers through acid fumes are -sometimes caused by the denitration of the waste mixture of sulphuric -and nitric acids in the nitrating process, that is, by the separation of -nitric acid from the acid mixture. This denitration takes place usually -in the Glover towers of the lead chamber system which is often associated -with the manufacture of aniline. The mixed nitro-compounds of the waste -acids, however, are often not completely condensed, but pass through the -chambers and Gay-Lussac towers and escape into the air, whence arises -the constant smell of nitrobenzene in aniline factories (Leymann). In -the production of _naphthylamine_ and recovery of chlorinated products, -escaping chlorine should be led into chloride of lime chambers, -hydrochloric acid fumes into towers to be absorbed by water and milk of -lime or a solution of soda. - -In aniline factories danger can scarcely be wholly avoided, as the -workers, on the one hand, come into contact with poisonous substances, -nitrobenzene, aniline, &c., and on the other hand, in spite of all -technical hygienic measures, can hardly help breathing in some of the -aniline. Apart from the technical regulations, therefore, there must -be insistence on cleanliness of the workrooms, personal cleanliness on -the part of the workers (washing, baths, working suits, cloak-rooms, -&c.). Besides this, contact with aniline, nitrobenzene, &c., wetting of -the body and clothes with these substances, and, especially spilling, -splashing, and scattering these fluids must be carefully avoided. -The workers require to be suitably instructed as to the symptoms of -nitrobenzene and aniline poisoning, and the right steps to take, if -poisoned. The oxygen apparatus must always be at hand, ready for use; the -workers must be instructed how to use it. Further, workers, especially -those newly employed, must be under supervision in order that assistance -may be rendered them on the first signs of poisoning; medical assistance -ought to be within easy reach. Workers also should know of the tendency -of aniline to cause cancer of the bladder. - -Precautions against the poisonous nitro-derivatives of benzene -(nitrophenol, picric acid, &c.), which are in the form of poisonous dust, -must take the form of entirely closed-in grinding and packing apparatus, -or, at all events, removal of the dust at its source. - -Among official regulations may be mentioned the Prussian Ministerial -Edict, dated December 18, 1908, as to purification and storage of -benzene, and further the Regulations dated December 13, 1907, and -December 30, 1908, in force in Great Britain for the manufacture -of nitro- and amido-derivatives of benzene, and the manufacture of -explosives with use of dinitrobenzene or dinitrotoluene. - - - - -VI - -_PREVENTIVE REGULATIONS—THE EXTRACTION OF METALS (SMELTING WORK IN -GENERAL)_ - - -Danger is incurred when the furnace leaks, a condition which generally -occurs in the course of time, or if gases escape during the necessary -manipulations through the working doors. This can be avoided by -maintaining the walls in as air-tight a state as possible; but as very -small leakages are almost unavoidable the best course is to so regulate -the draught in the furnace (by means of fans) that a slight negative -pressure always exists in it. Naturally, poisonous gases escaping from -the furnace such as sulphur dioxide, carbonic oxide, carbon dioxide, -and hydrocarbons require to be drawn away and rendered harmless. This -can often be done by merely conducting them into the main flue. Gases -containing carbonic oxide possess high heating capacity, and their -escape can usually be prevented by suitable cupola bells. They can be -led away in impervious conduits and utilised for heating purposes or -for driving gas engines. Entering the flues for cleaning or repairing -purposes is especially dangerous; and as it is difficult to isolate one -portion entirely from another, such operations might well be carried on -by persons equipped with breathing apparatus (smoke helmets or oxygen -apparatus). - -In roasting operations handwork can be largely replaced by furnaces -worked mechanically. If the gases generated are rich in sulphur dioxide -they can be utilised for the manufacture of sulphuric acid or for -the production of liquid sulphur dioxide either directly or after -concentration; if not, they must be rendered harmless by treatment with -milk of lime in absorption towers. Other methods of rendering the sulphur -dioxide (unsuited for manufacture of sulphuric acid) harmless depend on -treatment with minerals containing calcium carbonate, or magnesium or -aluminium hydrate, sodium sulphide, &c. Sometimes the sulphurous gases -are led into blast furnaces containing oxide of iron and coal (so as to -form sulphide of iron) or are absorbed by means of moist scraps of sheet -iron or brown coal or peat briquettes. - -Use of chlorine compounds in the extraction of metals from ores (silver, -copper) causes evolution of chlorine and hydrochloric acid vapour. These -should be dealt with in absorption towers. Metallic fumes are collected -by suitable condensing arrangements. Flue dust is retained in flue dust -chambers, but in the cleaning of such condensing flues and chambers -danger to the workers is considerable and they should be equipped with -respirators, working suits, &c. Personal hygiene must be insisted on. - - -Iron - -(See also pp. 146-51) - -In blast furnace work, industrial poisoning occurs mainly from escaping -gases rich in carbonic oxide. They may also contain sulphur dioxide and -cyanogen compounds. The high proportion of carbonic oxide, however, makes -these gases valuable and serviceable, because of their great heating -value. They are, therefore, now led away and utilised, the furnace being -closed by a cupola bell only opened by means of a mechanical contrivance -when charging is necessary; while this is being done the ignited blast -furnace gases pour out, and the workers retire from the opening, so -that danger to them is avoided. The construction of a blast furnace -with a cupola bell can be seen in fig. 29. The blast furnace gases are -conducted away by an opening in the side, and pass along special pipes -to be utilised, after having gone through a purifying process mainly for -the removal of flue dust, &c. The gases serve partly for the heating of -the blast for the furnace itself, and partly for driving the gas engines -which serve the electrical power apparatus, electric lighting, &c., in -the works. Through the rational utilisation of the blast furnace gases, -the workers are protected from their injurious action during the working -of the furnace. Serious gas poisoning, however, occurs not infrequently -to workers who have to enter the gas mains for cleaning purposes. -Workers, therefore, should only be permitted to enter the flues, &c., -a considerable time after the process has been stopped and after as -complete and thorough a ventilation of the system as is possible. - -Any portion of the gas system which is to undergo cleaning must be -completely isolated. Ventilation is best effected by the introduction of -compressed air. Thus a foundry (in the Duisburg district) has provided -all its cellars and passages, through which gas pipes pass, and which -must be entered during repairs, with compressed air pipes. It is, -however, advisable that gas conduits should only be entered by workers -equipped with breathing apparatus and oxygen supply. Naturally adequate -instruction of workers and training in first aid are necessary, as well -as a sufficient supply of oxygen in constant readiness. - -Injurious gases can escape from the furnace during tapping and slag -running; poisonous gases with a disagreeable odour, from presence of -sulphuretted hydrogen, also arise in granulating the slag, that is, when -the fluid slag is led into water for subsequent use in preparation of -cement. These gases should be collected by hoods, and be carried away as -far as possible. - -In the manufacture of _steel_ by the _Bessemer_ or _Thomas-Gilchrist_ -process, the dark smoke arising out of the converter during the blowing -operation should be drawn off (led into flues), as it is injurious to -health. In the _Martin_ furnaces poisoning may occur, especially when -the gas flues are entered after cessation of work. In letting out the -gas in order to stop the furnaces, the gas and air valves must first be -closed and the outlet valves for gas be opened only after the pipes have -been filled with steam. Steam is to be driven through until the pipes -are quite free from gas, and the system only entered after it has become -thoroughly cooled. If need arises for entering portions of the system -while neighbouring parts are still filled with gas, the workers employed -require to be provided with breathing apparatus and smoke helmets. - -In the transport of _ferro-silicon_ several cases of poisoning have -occurred. Cautionary regulations, therefore, relating to this work have -been found necessary. - -Such directions are contained in the police regulations of the Prussian -Minister of Trade and Industry respecting the transport on the Rhine of -corrosive and poisonous substances (dated September 29, 1910). - -It is prescribed: (1) that ferro-silicon be packed in strong watertight -cases of wood or metal; (2) that on the cases be inscribed, legibly and -indelibly, the notice ‘Ferro-silicon. To be kept dry! With care!’ (3) -that the substance be delivered dry and in dry cases; (4) that the cases -be stored in airy places on the deck of the ship in such a manner that -they are protected from wet. - -Further, care is to be taken that the storage on ships is done in such a -way that possible damage to the material in which it is packed entails no -risk. The harbour authorities where loading or landing takes place can -deal with special cases as they think fit. - -International regulation as to transport of ferro-silicon in the spirit -of the above regulations would be most desirable in view of the oversea -trade in this substance.[K] - - -Lead - -(See also pp. 120-40 and 177-82) - -For protection against lead poisoning, the most widely spread of the slow -industrial poisonings, all those measures are of moment which we have -described in our general discussion on protection against danger from -poison in industries, both personal and general. - -Personal hygiene, especially careful washing after work, prohibition of -eating in workrooms, suitable working clothes, provision of cloak rooms, -meal rooms, baths, &c., are important and effective measures for the -protection of workers against industrial lead poisoning. - -The worker should naturally be adequately instructed as to the risk. -Appropriate printed notices are especially adapted for this purpose. - -Further, selection of workers should be made under medical supervision. -Workers who suffer from specific disease which, if associated with lead -poisoning, may prove dangerous, should be excluded from all contact -with lead. Among such illnesses must be reckoned tuberculosis in all -its forms, alcoholism, epilepsy, tendency to mental disease (nervous -disposition, hysteria, neurasthenia, &c.), rheumatism, and disease of the -kidneys. - -Overtime work undoubtedly increases risk; therefore working hours should -be shortened as much as possible, and handwork replaced by machine work -where possible. Young persons and women especially should be excluded -from work in lead. Alternation of employment also is beneficial and -essential in very dangerous lead work, because the poison accumulates in -the body and only during intervals wherein absolutely no poison can be -absorbed has it time to be eliminated. - -Periodical medical examination by a surgeon is of great value with -systematic entry of the results of examination in a health register. As -bearing on this, early diagnosis is of the greatest importance, so that -workers in whom the first signs of lead poisoning appear may at once be -suspended or transferred to other work. - -Lead workers should take suitable nourishing food and avoid particularly -alcoholic excess. - -When the danger is due to fumes or dust in the air the measures -prescribed on pages 242-55 apply, particularly those which aim at keeping -the workrooms and the air in the factories free of them by locally -applied exhaust ventilation. - -In order to replace or reduce the use of lead we strongly advocate the -use of non-poisonous, or at any rate less poisonous, substances, where -this can be done without technical difficulties, as, for instance, -carborundum discs instead of lead in polishing of precious stones, -leadless glaze in pottery for lead glaze (so far as this is possible, -as to which see page 319), beds free of lead (in different industries) -for lead beds. In a number of cases, however, such substitution is -impracticable on technical grounds or can only partially be carried out, -as, for example, in letterpress printing and in the paint and colour -industry, in which the prohibition of lead has often been repeatedly -urged. So far, unfortunately, it must be admitted that repeated attempts -to find a non-poisonous substitute for lead colours, especially for -white lead, of equal value technically, have not succeeded. Endeavours -have been made to substitute for lead, zinc preparations (zinc white, -lithopone, &c.), but hitherto (in regard to durability, opacity, &c.) -with incomplete success. - -Mention must be made of the measures based upon the relatively -non-poisonous nature of lead sulphide. Lead sulphide is, in spite of -various assertions to the contrary, practically non-poisonous; a fact -attributable to its insolubility in water and weak acids. As lead -sulphide is the only non-poisonous lead compound it is a duty to take -advantage of this fact for purposes of lead prophylaxis. - -Attempts with this end in view were made by the introduction of sulphur -soaps in lead factories. Soaps containing in large quantity soluble -alkaline sulphides convert lead compounds adhering to the skin into -black lead sulphide. The lead compounds are in this way made harmless, -and besides this the worker is impelled to remove the staining by -washing. Such a sulphur soap has been brought into the market under the -name of akremnin soap, but does not enjoy special popularity with the -workmen on account of its unpleasant smell. - -The struggle against the risks of lead employment has been going on ever -since efforts for the protection of workers were commenced. - -The International Association for Labour Legislation has made valuable -inquiries in this direction. The question of lead poisoning had been -repeatedly discussed by this Association and its branches in various -countries. The International Labour Bureau also took up the issue and -in 1906—supported by the Institute for General Welfare in Frankfurt -a-M.—offered a prize for the best treatise on the prevention of -industrial lead poisoning. The outcome of this competition was the volume -compiled by Leymann, ‘Die Bekämpfung der Bleigefahr in der Industrie’ -(published by Fischer, Jena, 1908). - -In connection with the resolution adopted at the third Congress of the -International Association for Labour Legislation the Union of Social -Reform (as the German branch is called) addressed the Federal Council on -the white lead question, the chief points insisted upon being the need -for: (1) regulations for the house painting industry in pursuance of -Section 120 of the Factory Code; (2) report by the Imperial Health Office -on the practicability of substitutes for lead; (3) exclusion of lead -colours from use in the painting of public buildings; and (4) treatment -of lead poisoning by the State Insurance Office as an accident entitling -to compensation. - -These demands were supported by the central office of the Society for -Promoting the Welfare of Workers, which had as far back as its seventh -conference in 1898 occupied itself with the question of dangerous trades -and especially, at its conference in 1905, taken up the subject of the -protection of workers against industrial poisoning. - -In Germany these efforts resulted in the passage of a number of Imperial -Regulations for separate lead industries. - -In other countries similar action was set on foot. In Austria, where the -subject is of special importance in view of the part played by lead in -the home industries, the Government undertook to improve the conditions -in industries attended with risk of lead poisoning. For this purpose -the Statistical Office of the Ministry of Commerce and Labour has, -since 1904, carried out extensive inquiries into lead and zinc smelting -works, paint and colour factories, the painting and varnishing trades, -letterpress printing, and the ceramic industry. The results are contained -in the volume ‘Lead Poisoning in Smelting Works and Industries Generally’ -(published by Hölder, Vienna). - -As in Germany and Austria, so also in Great Britain, France, Switzerland, -Belgium, and the Netherlands, regulations in various lead industries were -enforced after previous official inquiry and report. - -A general code, however, affecting all lead industries has only been -published in one or two states. And yet this would, in my opinion, be -of very great practical value as it is hardly possible to regulate each -single branch of industry. - -In Germany the Regulations dated May 26, 1903, dealing with lead colours -are certainly comprehensive, but relate primarily to paint factories, and -are not, therefore, a general Order in the sense indicated. In Saxony the -decree of June 27, 1901, made notification of lead poisoning compulsory, -and in the subsequent decree of April 16, 1909, prescribed general -measures against lead poisoning. In Switzerland single cantons have made -general regulations. In France, by a decree dated April 23, 1908 (in -pursuance of the general law of June 12, 1893), all industries attended -with risk of lead poisoning were brought under Regulation. - -We give the provisions of this interesting decree, as it is a good -example of the kind of Regulations we have in mind. - - DECREE OF THE PRESIDENT OF THE FRENCH REPUBLIC (APRIL 23, 1908) - RELATING TO CERTAIN INDUSTRIES IN WHICH LEAD IS USED - - 1. In the lead industries hereinafter mentioned, viz.: - smelting, cupellation of argentiferous lead, manufacture - of accumulators, glass-making, manufacture and use of lead - enamels, manufacture of pottery, decoration of porcelain - or faience, ceramic chromo-lithography, manufacture of - lead alloys, oxides, salts and colours—employers, directors - or managers are required, apart from the general measures - prescribed by the Decree of 29 November, 1904, to take special - measures for protection and health as set forth in the - following sections. - - 2. Lead melting pots shall be erected in an airy place - separated from the other workrooms. - - Hoods or other means for the effectual removal of fumes shall - be provided:— - - (_a_) Over the openings for the run of lead and slag in lead - smelting. - - (_b_) Before the furnace doors in the manufacture of lead - oxides. - - (_c_) Above the pots for melting lead or its alloys, in the - other industries enumerated in Section 1. - - 3. All work with oxides and other compounds of lead capable of - producing dust shall be done as far as possible when in a damp - condition. - - When this work cannot be done in the presence of water or other - liquid, it shall be carried out by mechanical means, in covered - air-tight apparatus. - - If it is impossible to conform to the requirements of either - of the first two paragraphs of this section, the work shall - be done under a strong draught so arranged that the harmful - products may be intercepted by apparatus suitably placed. - - Finally, if none of these systems is possible the workmen shall - be supplied with respirators. - - 4. Oxides and other compounds of lead, whether dry or damp, - in suspension or solution, shall not be handled with the bare - hand. The employer shall at his own expense provide the workers - in these operations with either gloves made of impervious - material such as indiarubber, or suitable appliances, and shall - cause them to be kept in good repair and frequently cleaned. - - 5. Tables on which these products are handled shall be covered - with some impervious material, kept in a perfectly water-tight - condition. - - The same requirement applies to the floors of the workrooms, - which shall also be kept damp. - - The floor shall be slightly sloped towards a water-tight - receptacle for collecting the lead substances which are washed - down. - - The work shall be so arranged that there shall be no - splashing. The tables, floors and walls shall be washed at - least once a week. - - 6. Without prejudice to the requirements of section 3, the - grinding and mixing of lead products, and the use of them - in dusting shall be effected in special places with active - ventilation. - - If the materials cannot be damped, the workers shall be - provided with respirators. - - 7. Pottery shall not be dipped with bare hands in solutions - containing litharge, red lead, galena or white lead in - suspension. - - 8. No food or drink shall be brought into the works. - - 9. Employers shall, at their own expense, provide and maintain - for the use of the workers, overalls or clothing for use during - work only, in addition to gloves and respirators. - - 10. In a part of the building separated from the workrooms, - there shall be provided for the use of the workers exposed to - lead dust or fumes, a cloak room and lavatory kept in good - order, provided with basins or taps in sufficient number, a - plentiful supply of water, soap and a towel for each worker - replaced at least once a week. - - The cloak rooms shall be provided with cupboards or drawers - with locks or padlocks, the ordinary clothing being kept apart - from the working clothes. - - 11. A warm bath or shower bath shall be provided each week for - the workers exposed to lead dust or fumes. - - A warm bath or shower bath shall be provided every day after - work, for each worker employed, either in emptying or cleaning - the condensing chambers and flues, in repairing furnaces in - lead works, in carrying lead corrosions from the beds in white - lead factories, in packing red lead, in grinding lead enamels - and in dry dusting. - - 12. Employers are required to exhibit, in a conspicuous - position in the works, regulations imposing on the workers the - following obligations:— - - To use the appliances, gloves, respirators, and working clothes - placed at their disposal. - - Not to bring into the works either food or drink. - - To pay great care, before each meal, to the cleanliness of the - mouth, nose, and hands. - - To take the baths weekly or daily as provided in section 11. - - 13. The Minister of Labour may, by Order made with the advice - of the Consultative Committee for Arts and Manufactures, exempt - an establishment for a specified period, from all or part of - the requirements of Regs. 2ᵃ, 2ᵇ, 2ᶜ, 5² and 6¹ in any case - where it is found that observance of these requirements is - practically impossible, and that the health and safety of the - workers are assured by conditions at least equivalent to those - prescribed in the present Order. - - 14. Subject to additional postponements which may be granted - by the Minister in pursuance of Section 6 of the Act of 12th - June, 1893 (as amended by that of 11th July, 1903), the delay - required for the carrying out of the alterations necessitated - by the present Decree is limited to one year from the date of - its publication. - - 15. The Ministry of Labour is charged with the administration - of this Decree. - -This decree was supplemented by further noteworthy additions requiring -medical supervision in lead industries as follows: - - DECREE OF DECEMBER 28, 1909, ORGANISING MEDICAL SERVICE IN - INDUSTRIES EXPOSING THE WORKERS TO RISK OF LEAD POISONING - - 1. In premises in which the processes enumerated in Regulation - 1 of the Decree of April 23, 1908, are carried on medical - attendance as prescribed below shall be provided. - - 2. A surgeon appointed by the occupier shall examine the - workers and enter the results of examination required in - Regulations 3 and 4. The examinations shall be paid for by the - occupier. - - 3. No person shall be employed in work mentioned in Regulation - 1 of the Decree of April 23, 1908, without a certificate from - the surgeon stating that he is free from symptoms of lead - poisoning and of illness which might render him specially - susceptible. - - 4. No worker shall remain at the same employment unless - the certificate is renewed one month after commencement of - employment and subsequently at quarterly intervals. - - In addition to the periodical examination the occupier shall - give an order on the surgeon to every workman declaring himself - to be ill from his employment or who desires to undergo medical - examination. - - 5. A special Register open to the Factory Inspector shall be - kept containing the following particulars of each worker: - - (1) Dates and duration of absence on account of illness of any - kind; - - (2) Dates of medical certificates for such illness, the notes - made by the surgeon and the name of the surgeon furnishing them; - - (3) Instructions given by the appointed surgeon in pursuance of - Regulations 3 and 4 above. - - -Lead Smelting Works - -(See also pp. 122-31) - -As the fumes in lead smelting works contain a high proportion of lead, -all apparatus, especially furnaces and working doors, should be provided -with efficient exhaust ventilation and all flues, furnaces, and other -apparatus be as airtight as possible. Where lead dust is created exhaust -ventilation locally applied is necessary. Two of the most important -preventive measures are personal cleanliness and alternation of -employment. Dust arising in the furnaces and borne along by the furnace -gases together with arsenical fumes and dust must be deposited in flues -or chambers. - -In view of the importance of proper instruction of smelters as regards -the danger we quote the warning note prepared by the Institute for -Industrial Hygiene, Frankfurt a.-M., which deserves wide circulation. - - LEAD LEAFLET FOR SMELTERS - - _How does Lead Poisoning arise?_ - - The danger of lead poisoning in lead, spelter and other - smelting premises can be avoided if due care is observed. - - Lead poisoning occurs when lead enters the system. This takes - place by breathing dust and fume containing lead, or by eating - and drinking, smoking, snuff taking and tobacco chewing if food - or tobacco is taken into the mouth with dirty hands and dirty - face and beard. - - No one is immune from lead. Lead accumulates in the body of - careless persons and he who is not sick to-day can be so - to-morrow or after weeks or months. - - _How can Plumbism be avoided?_ - - All smelters must observe cleanliness. In this respect they - should see to the following points: - - 1. It is to their interest to see that the exhaust ventilation - is kept in order and that the Special Rules or Regulations are - exactly followed. Further, special clothing should be worn, the - mouth and nose should be covered, and the floors sprinkled. - - 2. It is especially important that in intervals and at the - close of work the mouth, face, beard, and hands should be - carefully cleaned. Food should not be eaten or the premises - left without putting on fresh clothes and thoroughly washing - or, still better, bathing. When drinking, the edge of the - drinking glass should not be fingered with dirty hands. - Especially important is it that the teeth should be cleaned and - the mouth washed out. - - 3. During work smoking, snuff taking, and tobacco chewing, - which invariably convey lead into the mouth, should be - given up, as it is impossible to prevent the hands getting - contaminated with lead. Lighting the pipe with glowing lead - ashes is in the highest degree dangerous from the risk of - inhaling lead fume. The body must be strengthened to withstand - the action of lead. Moderation in drinking, especially - avoidance of spirits, should be observed. Alcoholic subjects - succumb to lead poisoning much more readily than the temperate. - - Food should be abundant and rich in fat, for example milk and - bacon. Thick soups are excellent before work. Work should never - be begun on an empty stomach. And lastly as much fresh air as - possible. Walking, athletics, work in the garden and field will - help to keep off many an attack. If anyone thinks that he is - suffering from lead poisoning he should at once in his own and - his family’s interest see the doctor of his sick club. - -The following are the - - GERMAN IMPERIAL REGULATIONS FOR LEAD SMELTING WORKS, DATED JUNE - 16, 1905 - - _General Regulations_ - - 1. Workrooms in which lead ores are roasted, sintered, or - smelted, pig lead produced and submitted to further treatment, - distillation of rich lead (bullion cupellation) litharge, red - lead, or other oxides of lead prepared, ground or sieved, - stored or packed, or zinc skimmings distilled, shall be roomy, - high, and so arranged that a sufficient constant exchange of - air takes place. They shall be provided with a level and solid - floor to allow of easy removal of dust by a moist method. - - The walls shall be smooth so as to prevent collection of dust; - they shall be either washed down or lime washed at least once a - year. - - Provided that this shall not apply in the case of calcining - sheds with wooden walls. - - 2. An abundant supply of good drinking water, protected against - contamination from dust, shall be provided for the workers on - the furnaces and smelting pots, and in such close proximity to - them, that they can obtain it at any time without having to go - into the open air. - - Arrangements for sprinkling the floors shall be provided near - the furnaces. The floors of the rooms mentioned in paragraph 1 - shall be wet cleansed at least once daily. - - 3. Prepared (i.e. concentrated) lead ores and leady smelting - products, unless moist, shall not be crushed except in an - apparatus so arranged as to prevent as far as possible - penetration of dust into the workrooms. - - Provided that this shall not apply to calcined material from - converters. - - Sacks in which lead ores and materials containing lead have - been packed shall not be freed from dust and cleaned except in - a dust-proof apparatus or by washing. - - 4. Materials containing lead for charging the blast-furnaces, - if they are oxides and form dust, shall be damped before they - are mixed with other materials, stocked on the feeding floor, - or charged into the blast-furnaces. - - Provided that this shall not apply in the case of calcined - material from converters. - - 5. Dust, gases, and lead fumes, escaping from furnaces, and - converters, tapping spouts, tapping pots, drain sump, slag - pots, slag cars, or slag channels, and from glowing residues - taken from the furnaces, shall be caught as near as possible to - the point of origin and removed harmlessly. - - Dust collecting chambers, flues, as well as furnaces which - have been ‘blown down,’ shall not be entered by workmen unless - sufficiently cooled and ventilated. - - _Special Regulations for such parts of a factory where lead - colours are prepared_ - - 6. In grinding, sieving and packing dry leady materials, in - charging, and emptying litharge and red lead furnaces, in - collecting the red lead and similar operations in which leady - dust is developed, exhaust arrangements shall be provided for - preventing the entrance of dust into the workrooms. - - 7. Apparatus producing leady dust, if their construction and - manner of use does not effectually prevent evolution of dust, - shall have all cracks protected by thick layers of felt or - woollen material, or by similar means, so as to prevent the - entrance of dust into the workrooms. - - Apparatus of this character shall be provided with arrangements - for preventing compression of air in them. They shall only be - opened when the dust in them shall have completely settled, and - they are absolutely cool. - - _Special arrangements in force for the distillation of zinc - skimmings_ - - 8. Proposed new furnaces for the distillation of zinc skimmings - (for which according to pars. 16 and 25 of the Industrial Code - a special permission is required) shall be so arranged that (1) - there shall be at least a clear space of 10 feet in front of - the charging opening; (2) any passages under the distillation - rooms shall be roomy, at least 11½ feet high in the centre, - light and airy. - - 9. Dust, gases, and fumes arising from the zinc skimmings - distillation furnaces shall be collected as near as possible to - the point of origin, and carried outside the smelting room. - - The entrance of gases from the fires into the smelting room - shall be prevented as far as possible by suitable arrangements - for drawing them off. - - 10. Sieving and packing of by-products obtained in the - distillation of zinc skimmings (poussière, flue dust) shall - not be done except in a special room separated from the other - workrooms, and complying with the requirements of Reg. 1. - - Sieving shall only be done in an apparatus so constructed that - dust shall not escape. - - _Employment of workers._ - - 11. Women and young persons shall not be employed or permitted - in rooms mentioned in Reg. 1, in flue dust chambers, or dust - flues, or in the removal of flue dust. - - 12. No person shall be newly employed in rooms mentioned - in Reg. 1, in flue dust chambers, or dust flues, or in the - transport of flue dust, without a certificate of fitness from - the surgeon appointed by the higher authorities. - - These certificates shall be collected and shown to the Factory - Inspector and Appointed Surgeon on request. - - 13. No person shall be employed in charging blast furnaces, - apart from mere labouring work on the floors, for more than - eight hours daily. The same shall apply in the case of workmen - employed in the inside of furnaces when cool, or in emptying - flue dust chambers, or dust flues which contain wet flue dust. - - No person shall be employed in cleaning out, from inside, flue - dust chambers, or dust flues containing dry flue dust for more - than four hours daily; and including emptying and work of - transport of this kind altogether no longer than eight hours - daily. - - Other workers in rooms specified in Reg. 1 shall not work more - than 10 hours in 24, exclusive of mealtimes. - - Exception to this is allowed in the case of those workers who - are employed for the purpose of a weekly change of shift, and - for whom exception as to Sunday employment is permitted by - Imperial Decree. - - _Clothing, overalls, lavatory accommodation, &c._ - - 14. The occupier shall provide for all persons employed in - cleaning out flue dust chambers, dust flues, repairing of - cooled furnaces, grinding, sieving and packing of litharge, red - lead, or other lead colours, complete suits of working clothes, - including caps and respirators. - - 15. Work with lead salts in solution shall not be done except - by workers who either grease their hands or are provided with - impermeable gloves. - - 16. The suit of clothes, or overalls, provided in Regs. 14 and - 15, respirators and gloves, shall be provided in sufficient - amount and in proper condition. The occupier shall see that - they are always suitable for their purpose, and are not worn - except by those workers for whom they are intended; and that - they, at stated intervals (the overalls at least once a week, - the respirators and gloves prior to use), are cleaned, and - during the time that they are not in use are kept in a place - specially reserved for each article. - - 17. A lavatory and cloak room shall be provided for the use of - the workmen in a part of the building free from dust. Separate - from it there shall be a dining-room. These rooms must be kept - free from dust and be warmed during the winter. - - In a suitable place provision shall be made for warming the - workers’ food. - - Water, soap, and towels, and arrangements for keeping separate - the overalls from other clothing taken off before the - commencement of work shall be provided in sufficient amount in - the lavatory and cloak room. - - The occupier shall afford opportunity for persons engaged in - cleaning out flue dust chambers, dust flues, and the cooled - furnaces, to take a bath daily after the end of the work, and - for those handling oxides of lead, at least once a week, during - working hours inside the works. The bathroom shall be warmed - during the winter. - - 18. The occupier shall place the supervision of the health of - the workers in the hands of a surgeon, appointed by the higher - authorities for this purpose, whose name shall be sent to the - Inspector of Factories. The surgeon shall examine the workers - at least once a month in the factory, with a view to the - detection of symptoms of lead poisoning. - - The occupier shall not employ persons suspected by the surgeon - of having contracted lead poisoning in the processes mentioned - in Reg. 1 or in cleaning out flue dust chambers, dust flues, or - furnaces when cold, or transport of the flue dust, until they - are quite well. Those who appear peculiarly susceptible shall - be permanently suspended from working in these processes. - - 19. The Health Register shall be shown to the Factory Inspector - and Appointed Surgeon on demand. (Similar to Reg. 15 of Spelter - Regulations.) - - 20. The occupier shall require the workers to subscribe to the - following conditions:— - - (1) Food must not be taken into the workrooms. Meals may only - be taken outside the workrooms. - - (2) Workmen must only enter the meal room to take their meals - or leave the factory, after they have taken off their overalls - and carefully washed their face and hands. - - (3) Workmen must use the overalls, respirators and gloves in - those workrooms and for the particular processes for which they - are given them. - - (4) Cigar and cigarette smoking during work is forbidden. - - (5) A bath in the factory must be taken every day at the close - of their work by those engaged in the emptying and cleaning of - flue dust chambers, flues, and furnaces when cold, and by those - employed on oxides of lead once a week. - - Provided that this shall not apply in the case of workmen - exempted by the appointed surgeon. - - Workers contravening these orders will be liable to dismissal - without further notice. - - 21. In every workroom, as well as in the cloak room and - meal room, there shall be posted up by the occupier, in a - conspicuous place and in clear characters, a notice of these - regulations. - - The occupier is responsible for seeing that the requirement - of Reg. 20 (1) is obeyed. He shall make a manager or foreman - responsible for the precise carrying out of Reg. 20 (1) (2) and - (5). The person thus made responsible shall see to the carrying - out of the regulations and for the exercise of necessary care - as prescribed in par. 151 of the Factory Act. - - 22. No work in a lead smelting works shall be commenced until - notice of its erection has been sent to the Factory Inspector. - After receipt of the notice he shall personally visit to - see whether the arrangements are in accordance with these - regulations. - - 23. These regulations come into force on 1st January, 1906. - Where structural alterations are necessary for the carrying out - of Regs. 1, 5 (1), 6, 9, 10 and 17, the higher authorities may - allow an extension of time to a date not later than January - 1st, 1908. - - If it seems necessary on strong grounds of public interest, the - Council (Bundesrath) may extend the time in particular works - until 1st January, 1913, and until then allow exceptions from - the regulations as regards Reg. 13 (1) and (2). - - -Accumulator Factories - -[Dr. Rambousek gives a very brief synopsis of the German Imperial -Regulations in force for this industry and mentions that in Great Britain -the Regulations of the Secretary of State dated 1903 are similar. We -have printed these, as the code is fairly representative of the English -Regulations for (1) smelting of metals; (2) paints and colours; (3) -tinning of hollow ware; (4) yarn dyed with chromate of lead; (5) vitreous -enamelling; and the special rules for (6) white lead and (7) earthenware: - - REGULATIONS DATED NOVEMBER 21, 1903, MADE BY THE SECRETARY OF - STATE FOR THE MANUFACTURE OF ELECTRIC ACCUMULATORS - - Whereas the manufacture of electric accumulators has been - certified in pursuance of Section 79 of the Factory and - Workshop Act, 1901, to be dangerous; - - I hereby, in pursuance of the powers conferred on me by that - Act, make the following regulations, and direct that they shall - apply to all factories and workshops or parts thereof in which - electric accumulators are manufactured. - - _Definitions._—In these Regulations ‘lead process’ means - pasting, casting, lead burning, or any work involving contact - with dry compounds of lead. - - Any approval given by the Chief Inspector of Factories in - pursuance of these Regulations shall be given in writing, and - may at any time be revoked by notice in writing signed by him. - - _Duties of Occupier_ - - 1. _Ventilation._—Every room in which casting, pasting or lead - burning is carried on shall contain at least 500 cubic feet of - air space for each person employed therein, and in computing - this air space, no height above 14 feet shall be taken into - account. - - These rooms and that in which the plates are formed shall be - capable of through ventilation. They shall be provided with - windows made to open. - - 2. _Separation of processes._—Each of the following processes - shall be carried on in such manner and under such conditions as - to secure effectual separation from one another and from any - other process: - - (_a_) Manipulation of dry compounds of lead; - - (_b_) Pasting; - - (_c_) Formation, and lead burning necessarily carried on - therewith; - - (_d._) Melting down of old plates. - - Provided that manipulation of dry compounds of lead carried on - as in Regulation 5 (b) need not be separated from pasting. - - 3. _Floors._—The floors of the rooms in which manipulation - of dry compounds of lead or pasting is carried on shall be - of cement or similar impervious material, and shall be kept - constantly moist while work is being done. - - The floors of these rooms shall be washed with a hose pipe - daily. - - 4. _Melting pots._—Every melting pot shall be covered with a - hood and shaft so arranged as to remove the fumes and hot air - from the workrooms. - - Lead ashes and old plates shall be kept in receptacles - especially provided for the purpose. - - 5. _Manipulation of dry compounds of lead._—Manipulation of - dry compounds of lead in the mixing of the paste or other - processes, shall not be done except (_a_) in an apparatus so - closed, or so arranged with an exhaust draught, as to prevent - the escape of dust into the work room: or (_b_) at a bench - provided with (1) efficient exhaust draught and air guide so - arranged as to draw the dust away from the worker, and (2) a - grating on which each receptacle of the compound of lead in use - at the time shall stand. - - 6. _Covering of benches._—The benches at which pasting is done - shall be covered with sheet lead or other impervious material, - and shall have raised edges. - - 7. _Prohibition of employment._—No woman, young person, or - child shall be employed in the manipulation of dry compounds of - lead or in pasting. - - 8. (_a_) _Appointed Surgeon._—A duly qualified medical - practitioner (in these Regulations referred to as the - ‘Appointed Surgeon’) who may be the Certifying Surgeon, shall - be appointed by the occupier, such appointment unless held by - the Certifying Surgeon to be subject to the approval of the - Chief Inspector of Factories. - - (_b_) _Medical examination._—Every person employed in a lead - process shall be examined once a month by the Appointed - Surgeon, who shall have power to suspend from employment in any - lead process. - - (_c_) No person after such suspension shall be employed in a - lead process without written sanction entered in the Health - Register by the Appointed Surgeon. It shall be sufficient - compliance with this regulation for a written certificate to - be given by the Appointed Surgeon and attached to the Health - Register, such certificate to be replaced by a proper entry in - the Health Register at the Appointed Surgeon’s next visit. - - (_d_) _Health Register._—A Health Register in a form approved - by the Chief Inspector of Factories shall be kept, and shall - contain a list of all persons employed in lead processes. The - Appointed Surgeon will enter in the Health Register the dates - and results of his examinations of the persons employed and - particulars of any directions given by him. He shall on a - prescribed form furnish to the Chief Inspector of Factories - on the 1st day of January in each year a list of the persons - suspended by him during the previous year, the cause and - duration of such suspension, and the number of examinations - made. - - The Health Register shall be produced at any time when required - by H.M. Inspectors of Factories or by the Certifying Surgeon or - by the Appointed Surgeon. - - 9. _Overalls._—Overalls shall be provided for all persons - employed in manipulating dry compounds of lead or in pasting. - - The overalls shall be washed or renewed once every week. - - 10. _Cloak and dining rooms._—The occupier shall provide and - maintain: - - (_a_) a cloak room in which workers can deposit clothing put - off during working hours. Separate and suitable arrangements - shall be made for the storage of the overalls required in - Regulation 9. - - (_b_) a dining room unless the factory is closed during meal - hours. - - 11. _Food, &c._—No person shall be allowed to introduce, keep, - prepare or partake of any food, drink, or tobacco, in any room - in which a lead process is carried on. Suitable provision shall - be made for the deposit of food brought by the workers. - - This regulation shall not apply to any sanitary drink provided - by the occupier and approved by the Appointed Surgeon. - - 12. _Washing._—The occupier shall provide and maintain for the - use of the persons employed in lead processes a lavatory, with - soap, nail brushes, towels, and at least one lavatory basin for - every five such persons. Each such basin shall be provided with - a waste pipe, or the basins shall be placed on a trough fitted - with a waste pipe. There shall be a constant supply of hot and - cold water laid on to each basin. - - Or, in the place of basins the occupier shall provide and - maintain troughs of enamel or similar smooth impervious - material, in good repair, of a total length of two feet - for every five persons employed, fitted with waste pipes, - and without plugs, with a sufficient supply of warm water - constantly available. - - The lavatory shall be kept thoroughly cleansed and shall be - supplied with a sufficient quantity of clean towels once every - day. - - 13. Before each meal and before the end of the day’s work, at - least ten minutes, in addition to the regular meal times, shall - be allowed for washing to each person who has been employed in - the manipulation of dry compounds of lead or in pasting. - - Provided that if the lavatory accommodation specially reserved - for such persons exceeds that required by Regulation 12, the - time allowance may be proportionately reduced, and that if - there be one basin or two feet of trough for each such person - this Regulation shall not apply. - - 14. _Baths._—Sufficient bath accommodation shall be provided - for all persons engaged in the manipulation of dry compounds - of lead or in pasting, with hot and cold water laid on, and a - sufficient supply of soap and towels. - - This rule shall not apply if in consideration of the special - circumstances of any particular case, the Chief Inspector - of Factories approves the use of local public baths when - conveniently near, under the conditions (if any) named in such - approval. - - 15. _Cleaning._—The floors and benches of each workroom shall - be thoroughly cleansed daily, at a time when no other work is - being carried on in the room. - - _Duties of Persons Employed_ - - 16. _Medical examination._—All persons employed in lead - processes shall present themselves at the appointed times for - examination by the Appointed Surgeon as provided in Regulation - 8. - - No person after suspension shall work in a lead process, in - any factory or workshop in which electric accumulators are - manufactured, without written sanction entered in the Health - Register by the Appointed Surgeon. - - 17. _Overalls._—Every person employed in the manipulation of - dry compounds of lead or in pasting shall wear the overalls - provided under Regulation 9. The overalls, when not being worn, - and clothing put off during working hours, shall be deposited - in the places provided under Regulation 10. - - 18. _Food, &c._—No person shall introduce, keep, prepare, or - partake of any food, drink (other than any sanitary drink - provided by the occupier and approved by the Appointed - Surgeon), or tobacco in any room in which a lead process is - carried on. - - 19. _Washing._—No person employed in a lead process shall - leave the premises or partake of meals without previously and - carefully cleaning and washing the hands. - - 20. _Baths._—Every person employed in the manipulation of dry - compounds of lead or in pasting shall take a bath at least once - a week. - - 21. _Interference with safety appliances._—No person shall in - any way interfere, without the concurrence of the occupier - or manager, with the means and appliances provided for the - removal of the dust or fumes, and for the carrying out of these - Regulations. - - These Regulations shall come into force on the 1st day of - January, 1904. - - -White Lead - -(See also pp. 131 and 132) - -In the manufacture of white lead processes which create dust are -specially dangerous, namely, emptying the corrosion chambers, drying and -grinding, transport of the material in the form of powder, and packing. -The following measures are called for: emptying the chambers should only -be done by men wearing respirators or equipped with breathing helmets -after preliminary damping of the corrosions by means of a spray. Use -of a vacuum cleaning apparatus suggests itself. Drying should be done -as far as possible in stoves charged mechanically, the temperature in -which can be watched from the outside; grinding must be done in closed -and ventilated mills; transport of the dried material should be effected -by mechanical means or vacuum apparatus, and packing should be done in -mechanical packing machines. Further, cleanliness and strict discipline -are essential. Alternation of employment is advisable. The question of -substitutes for white lead is referred to on p. 293. - -Manufacture of red lead calls for precisely similar preventive measures. -Charging and emptying the oxidising furnaces should be done under -efficient exhaust ventilation. Conveyance, sifting, and grinding of the -cooled material requires to be done in the same way as has been described -for white lead. - -In the production of chrome colours (lead chromates) besides the danger -from lead the injurious action of chrome has to be borne in mind. - -Regulations for white lead factories have been made in Germany, Belgium, -and Great Britain. We give below the German Imperial Regulations dated -May 26, 1903. - - REGULATIONS FOR MANUFACTURE OF LEAD COLOURS AND LEAD PRODUCTS - - (1) The following regulations apply to all premises in which - lead colours or other chemical lead products (white lead, - chromate of lead, masicot, litharge, minium, peroxide of lead, - Cassel yellow, English yellow, Naples yellow, lead iodide, lead - acetate, &c., are manufactured), or in which mixtures of lead - are prepared as the principal or as a subsidiary business. - They shall not apply to lead smelting works, even though - processes named in paragraph (1) are carried on. - - Neither shall they apply to workplaces in which manufactured - colours are intimately mixed or ground in oil or varnish in - connection with another industry. - - (2) The workrooms in which the materials mentioned in paragraph - 1 are prepared or packed shall be roomy, lofty, and so arranged - that sufficient and constant exchange of air can take place. - - They shall be provided with a solid and smooth floor permitting - of easy removal of dust by a moist method. The floor, unless - for purposes of manufacture, shall be kept constantly wet, and - shall be wet cleansed at least once daily. - - The walls, when not of a smooth washable surface or painted - with oil, shall be whitewashed at least once a year. - - (3) The entrance of lead dust, or fumes, into the workrooms - shall be prevented by suitable means as far as possible. Rooms - which cannot be thus protected must be so separated from other - rooms that neither dust nor fumes can enter them. - - (4) Lead melting pots shall be covered with a hood and shaft - communicating directly or by a chimney with the open air. - - (8)[L] Grinding, sieving, and packing dry lead compounds, - emptying litharge and minium furnaces, and other operations in - which lead dust is generated, shall not be done except under an - exhaust draught, or other efficient means for preventing the - entrance of dust into the workrooms. - - In the packing of colours containing only a little lead, in - small amounts, or in small packages for retail purposes, - exception to these regulations can be allowed by the higher - authorities. - - (9) Machines generating lead dust and not efficiently protected - by their construction or method of use against the escape of - dust, shall have all cracks occluded by means of thick layers - of felt or similar material, so as to prevent the entrance of - dust into the workrooms. - - Machines of this kind shall be provided with arrangements - preventing pressure of the air inside. They shall not be opened - until they are cool, and until the dust generated has settled. - - (10) Women shall not be employed in factories in which the - colours specified in paragraph (1) are prepared except in work - which does not expose them to the action of lead dust or fumes. - Young persons shall not be employed nor be allowed on the - premises in factories concerned exclusively or in great part - with the preparation of lead colours or other lead compounds. - - (11) No person shall be employed in rooms where the processes - specified in paragraph (1) are carried on who is not provided - with a certificate from a qualified surgeon stating that he is - physically fit and free from disease of the lungs, kidneys, - and stomach, and that he is not addicted to alcohol. This - certificate shall be kept and produced on demand to the Factory - Inspector or Appointed Surgeon. - - (12) No person shall be employed in packing lead colours or - mixtures containing lead or other lead compounds in a dry - state, or with the coopering of the filled casks for more - than eight hours daily. This regulation shall not apply where - the packing machines are provided with effectual exhaust - arrangements, or so constructed and used as effectually to - prevent the escape of dust. - - No person under 18 years of age shall be employed in the - process mentioned in the above paragraph, but exception can - be allowed in the packing of colours containing lead in - small amount, or in small packages for retail purposes, on - application to the higher authorities. - - For the rest, no person coming into contact with lead or lead - compounds shall be employed for more than 10 hours within the - space of 24 hours. - - (13) The occupier shall provide overalls and head-coverings for - all persons coming into contact with lead or lead compounds, - and suitable footwear for those emptying the oxidising chambers. - - (14) The occupier shall not allow work involving exposure - to dust to be performed except by workers provided with - respirators or moist sponges covering the nose and mouth. - - (15) The occupier shall not allow work involving contact with - soluble salts of lead to be done except by workers provided - with waterproof gloves or by those whose hands have previously - been smeared with vaseline. - - (16) The occupier shall provide the overalls, respirators, &c., - mentioned in paragraphs (13) (14) and (15) for each one of the - workers in sufficient number and in good condition. He shall - take care that they are used only by the workers to whom they - are severally assigned, and that in the intervals of work and - during the time when they are not in use they shall be kept in - their appointed place. Overalls shall be washed every week, and - the respirators, sponges, and gloves before each time that they - are used. - - (17) Lavatories and cloak rooms, and, separate from these, - a mess room, shall be provided for the workers coming into - contact with lead or lead compounds in a part of the works free - from dust. These rooms shall be kept in a cleanly condition, - free from dust, and shall be heated during the cold seasons. In - the meal room or in some other suitable place there shall be - means for warming food. The lavatories and cloak rooms shall - be provided with water, vessels for rinsing the mouth, nail - brushes for cleaning the hands and nails, soap, and towels. - Arrangements shall also be made for keeping separate clothes - worn during work from these taken off before the commencement - of work. The occupier shall give facilities for all persons - employed in emptying the oxidizing chambers to have a warm - bath daily after the end of the work, and for those persons - coming into contact with lead or lead compounds, twice weekly. - The time for this shall be during the hours of work, and in - the cold season the bath room, which must be on the factory - premises, shall be heated. - - (18) The occupier shall appoint a duly qualified medical - practitioner, whose name shall be sent to the Inspector of - Factories and to the Health Authority. He shall examine the - workers at least twice every month with a view to the detection - of symptoms of lead poisoning. The occupier shall not employ - workers suspected of symptoms of lead poisoning in occupations - exposing them to lead or lead compounds until they have - completely recovered. Those who appear peculiarly susceptible - shall be suspended permanently from work. - - (19) The occupier shall keep a book, or make some official - responsible for its keeping, recording any change in the - personnel employed in lead or lead compounds and as to their - state of health. He shall be responsible for the completeness - and correctness of the entries except those made by the surgeon. - -The remaining regulations as to entries in the Health Register, &c., are -similar to those already given in the Regulations for lead smelting works -on p. 300. - - -Use of Lead Colours - -(See also pp. 132-4) - -As explained on pp. 132-134 use of lead in the painting and varnishing -trades frequently causes lead poisoning. This has led to regulations in -various countries having for their object partly hygienic measures and -partly also limitation of colours containing lead, such as prohibition of -the use of lead paints in the interior of buildings or in the painting of -public buildings and of ships, &c. - -The details of such regulations are seen in the German Imperial -Regulations dated June 27, 1905: - - ORDER OF THE IMPERIAL CHANCELLOR RELATING TO THE PROCESSES - OF PAINTING, DISTEMPERING, WHITEWASHING, PLASTERING, OR - VARNISHING. JUNE 27, 1906 - - I.—_Regulations for carrying on the Industries of Painting, - Distempering, Whitewashing, Plastering, or Varnishing._ - - _Regulation 1._—In the processes of crushing, blending, mixing, - and otherwise preparing white lead, other lead colours, or - mixtures thereof with other substances in a dry state, the - workers shall not directly handle pigment containing lead, - and shall be adequately protected against the dust arising - therefrom. - - _Regulation 2._—The process of grinding white lead with oil or - varnish shall not be done by hand, but entirely by mechanical - means, and in vessels so constructed that even in the process - of charging them with white lead no dust shall escape into - places where work is carried on. - - This provision shall apply to other lead colours. Provided that - such lead colours may be ground by hand by male workers over 18 - years of age, if not more than one kilogram of red lead and 100 - grains of other lead colours are ground by any one worker on - one day. - - _Regulation 3._—The processes of rubbing-down and - pumice-stoning dry coats of oil-colour or stopping not clearly - free from lead shall not be done except after damping. - - All _débris_ produced by rubbing down and pumice-stoning shall - be removed before it becomes dry. - - _Regulation 4._—The employer shall see that every worker who - handles lead colours or mixtures thereof is provided with, - and wears, during working hours, a painter’s overall or other - complete suit of working clothes. - - _Regulation 5._—There shall be provided for all workers - engaged in processes of painting, distempering, whitewashing, - plastering, or varnishing, in which lead colours are used, - washing utensils, nail brushes, soap and towels. If such - processes are carried on in a new building or in a workshop, - provision shall be made for the workers to wash in a place - protected from frost, and to store their clothing in a clean - place. - - _Regulation 6._—The employer shall inform workers, who handle - lead colours or mixtures thereof, of the danger to health - to which they are exposed, and shall hand them, at the - commencement of employment, a copy of the accompanying leaflet - (not printed with this edition), if they are not already - provided with it, and also a copy of these Regulations. - - II.—_Regulations for the Processes of Painting, Distempering, - Whitewashing, Plastering, or Varnishing when carried on in - connection with another Industry._ - - _Regulation 7._—The provisions of paragraph 6 shall apply to - the employment of workers connected with another industry - who are constantly or principally employed in the processes - of painting, distempering, whitewashing, plastering, or - varnishing, and who use, otherwise than occasionally, lead - colours or mixtures thereof. The provisions of paragraphs 8-11 - shall also apply if such employment is carried on in a factory - or shipbuilding yard. - - _Regulation 8._—Special accommodation for washing and for - dressing shall be provided for the workers, which accommodation - shall be kept clean, heated in cold weather, and furnished with - conveniences for the storage of clothing. - - _Regulation 9._—The employer shall issue regulations which - shall be binding on the workers, and shall contain the - following provisions for such workers as handle lead colour and - mixtures thereof: - - 1. Workers shall not consume spirits in any place where work is - carried on. - - 2. Workers shall not partake of food or drink, or leave the - place of employment until they have put off their working - clothes and carefully washed their hands. - - 3. Workers, when engaged in processes specified by the - employer, shall wear working clothes. - - 4. Smoking cigars and cigarettes is prohibited during work. - - Furthermore, it shall be set forth in the regulations that - workers who, in spite of reiterated warning, contravene the - foregoing provisions may be dismissed before the expiration of - their contract without notice. If a code of regulations has - been issued for the industry (par. 134a of the G.O.) the above - indicated provisions shall be incorporated in the said code. - - _Regulation 10._—The employer shall entrust the supervision of - the workers’ health to a duly qualified medical man approved of - by the public authority, and notified to the factory inspector - (par. 139b of the G.O.), and the said medical man shall examine - the workers once at least in every six months for symptoms - indicative of plumbism. - - The employer shall not permit any worker who is suffering from - plumbism or who, in the opinion of the doctor, is suspected of - plumbism, to be employed in any work in which he has to handle - lead colours or mixtures thereof, until he has completely - recovered. - - _Regulation 11._—The employer shall keep or shall cause to be - kept a register in which shall be recorded the state of health - of the workers, and also the constitution of and changes in - the staff; and he shall be responsible for the entries being - complete and accurate, except in so far as they are affected by - the medical man. - -Then follow the regulations as to entries in the Register, as to which -see the Regulations as to lead smelting works, p. 300. - - -Type Founding and Compositors’ Work - -(See also pp. 138 and 139) - -Fumes which may carry up lead dust are generated in the casting of -letters. Dust arises also in setting the type. General hygienic measures -are especially called for such as healthy conditions in the workrooms. -Much can be done by exhaust ventilation locally applied to the type cases -and to letter (mono- and linotype) casting machines. Vacuum cleaning of -printing workshops and type cases is strongly advised. - -As some lead poisoning in printing works is attributable to lead colours -or bronze powder containing lead their use should be limited as much as -possible. - -The German Imperial Regulations for printing works and type foundries are -as follows: - - ORDER OF THE FEDERAL COUNCIL OF JULY 31ST, 1897, REGULATING - LETTERPRESS PRINTING WORKS AND TYPE FOUNDRIES, IN PURSUANCE OF - SECTION 120_E_ OF THE INDUSTRIAL CODE - - I. In rooms in which persons are employed in setting up type - or manufacture of type or stereotype plates the following - provisions apply: - - 1. The floor of workrooms shall not be more than a half a meter - (1·64 feet) below the ground. Exceptions may only be granted by - the higher administrative authority where hygienic conditions - are secured by a dry area, and ample means of lighting and - ventilating the rooms. - - Attics may only be used as workrooms if the roof is provided - with a lathe and plaster ceiling. - - 2. In workrooms in which the manufacture of type or stereotype - plates is carried on, the number of persons shall not exceed - such as would allow at least fifteen cubic meters of air space - (529·5 cubic feet) to each. In the rooms in which persons are - employed only in other processes, there shall be at least - twelve cubic meters of air space (423·5 cubic feet) to each - person. - - In cases of exceptional temporary pressure the higher - administrative authority may, on the application of the - employer, permit a larger number in the workrooms, for at the - most 30 days in the year, but not more than will allow ten - cubic meters of air space (353 cubic feet) for each person. - - 3. The rooms shall be at least 2·60 meters (8· feet) in height - where a minimum of fifteen cubic meters are allowed for each - person, in other cases at least 3 meters (9·84 feet) in height. - - The rooms shall be provided with windows which are sufficient - in number and size to let in ample light for every part of the - work. The windows shall be so constructed that they will open - and admit of complete renewal of air in workrooms. Workrooms - with sloping roof shall have an average height equal to the - measurements given in the first paragraph of this section. - - 4. The rooms shall be laid with close fitting impervious - floor, which can be cleared of dust by moist methods. Wooden - floors shall be smoothly planed, and boards fitted to prevent - penetration of moisture. All walls and ceilings shall, if - they are not of a smooth washable surface or painted in oil, - be limewashed once at least a year. If the walls and ceilings - are of a smooth washable surface or painted in oil, they shall - be washed at least once a year, and the oil paint must, if - varnished, be renewed once in ten years, and if not varnished - once in five years. - - The compositors’ shelves and stands for type boxes shall be - either closely ranged round the room on the floor, so that no - dust can collect underneath, or be fitted with legs, so that - the floor can be easily cleaned of dust underneath. - - 5. The workrooms shall be cleared and thoroughly aired once at - least a day, and during the working hours means shall be taken - to secure constant ventilation. - - 6. The melting vessel for type or stereotype metal shall be - covered with a hood connected to an exhaust ventilator or - chimney with sufficient draught to draw the fumes to the outer - air. - - Type founding and melting may only be carried on in rooms - separate from other processes. - - 7. The rooms and fittings, particularly the walls, cornices, - and stands for type, shall be thoroughly cleansed twice a year - at least. The floors shall be washed or rubbed over with a damp - cloth, so as to remove dust once a day at least. - - 8. The type boxes shall be cleansed before they are put in use, - and again as often as necessary, but not less than twice at - least in the year. - - The boxes may only be dusted out with a bellows in the open - air, and this work may not be done by young persons. - - 9. In every workroom spittoons filled with water and one at - least for every five persons shall be provided. Workers are - forbidden to spit upon the floor. - - 10. Sufficient washing appliances, with soap and at least one - towel a week for each worker, shall be provided as near as - possible to the work for compositors, cutters, and polishers. - - One wash-hand basin shall be provided for every five workers, - fitted with an ample supply of water. - - The employer shall make strict provision for the use of the - washing appliances by workers before every meal and before - leaving the works. - - 11. Clothes put off during working hours shall either be kept - outside the workroom or hung up in cupboards with closely - fitting doors or curtains, which are so shut or drawn as to - prevent penetration of dust. - - 12. Artificial means of lighting which tend to raise the - temperature of the rooms shall be so arranged or such - counteracting measures taken that the heat of the workrooms - shall not be unduly raised. - - 13. The employer shall draw up rules binding on the workers - which will ensure the full observance of the provisions in - sections 8, 9, 10, and 11. - - II. A notice shall be affixed and a copy sent to the local - police authority shewing: - - (_a_) The length, height, and breadth of the rooms. - - (_b_) The air space in cubic measure. - - (_c_) The number of workers permitted in each room. - - A copy of Rules 1 to 13 must be affixed where it can be easily - read by all persons affected. - - III. Provides for the method of permitting the exceptions - named above in sections 2 and 3, and makes it a condition of - reduction in cubic air space for each person employed as type - founder or compositor that there shall be adequate mechanical - ventilation for regulating temperature and carrying off - products of combustion from workrooms. - - -Ceramic Industry - -(See also pp. 135-8.) - -A complete substitute for lead in glazes seems as yet impossible on -technical grounds, as glaze containing lead has qualities which cannot -be obtained without its use. In small works the technique necessary -for the production of leadless glazes (special kinds of stoves) cannot -be expected, especially as those carrying on a small industry lack the -necessary knowledge of how to be able to dispense with the use of lead -glazes and substitute leadless materials without complete alteration -in their methods of manufacture. And yet discontinuance or the utmost -possible limitation of the use of lead glazes and colours is most -urgently needed in all small ceramic workshops, as they are not in a -position to put in localised exhaust ventilation, &c., which is possible -in large factories. Observance of even the simplest hygienic measures can -scarcely be obtained. Consequently very severe cases of lead poisoning -are met with in small works. An effort in the direction of discontinuance -of lead glazes was made in Bohemia, where (at the cost of the State) -technical instruction was given by an expert on the preparation of -leadless glazes especially in districts where the industry was carried -on in the homes of the workers. This procedure, extension of which is -expected, had good results. - -Many have demanded, in view of the possibility of substituting leadless -for lead glazes, the total prohibition of lead. Such is the view of the -Dutch inspector De Vooys; Teleky and Chyzer share the view expressed so -far as the small industry is concerned, since the practicability of the -change has been demonstrated. - -English authorities (Thorpe, Oliver) propose diminution of the lead in -the glaze in such a way that on shaking with weak acid not more than a -specified small quantity shall be dissolved (Thorpe test). In my opinion -such a measure is hardly enough for the small industry. I do not expect -much good from obligatory use of fritted glazes. - -In addition to earthenware, manufacture of tiles and bricks leads not -infrequently to cases of lead poisoning from use of lead glaze. - -The following measures apply to the larger ceramic works. Since risk -is considerable, not only in glost placing but also in grinding, -ware-cleaning, &c., closed ball mills in grinding and locally applied -exhaust ventilation in ware-cleaning operations, &c., must be arranged. -Personal cleanliness and proper equipment of a factory in all the -essentials insisted on on pp. 226-9 are important, but nothing can take -the place of efficient locally applied ventilation. - -Vitreous enamelling of household utensils, baths, gas stoves, signs, -&c., is an analogous process as enamels containing lead may be used. -Sieving on the dry powder and brushing off superfluous glaze often cause -poisoning. Here generally the same preventive measures apply. - -[In Great Britain the china and earthenware industry is placed under -Regulations dated January 2, 1913, which supersede the previous Special -Rules. These Regulations—thirty-six in number—provide, among other -usual provisions, (1) for efficient exhaust ventilation in (_a_) -processes giving rise to injurious mineral dust (fettling and pressing -of tiles, bedding, and flinting, brushing and scouring of biscuit) -and (_b_) dusty lead processes (ware cleaning, aerographing, colour -dusting, litho-transfer making, &c.); and (2) monthly periodical medical -examination of workers in scheduled lead processes.] - -In the Netherlands, in consequence of lead poisoning in porcelain works, -committees were appointed to inquire into the subject in 1901, 1902, and -1903. - - -File Cutting - -(See also p. 140) - -In file cutting the file is cut on a lead bed or a bed of an alloy of -zinc and lead. The same source of poisoning occurs in other industries -such as amber working. Lead poisoning among file cutters is pronounced. -The best preventive measure is substitution of a bed of pure zinc for -lead. The German Imperial Health Office have issued a ‘Warning notice’ -for file-cutters. - - LEAFLET FOR FILE-CUTTERS - - The use of lead beds or of alloys of lead with other metals - has repeatedly brought about lead poisoning in file-cutters. - The beds also supposed to be made of zinc usually contain a - considerable proportion of lead, and are thus dangerous to - health. - - Among file-cutters lead poisoning arises from absorption of - the metal in small quantities by means of dirty hands, eating, - drinking, smoking or chewing of tobacco. The consequences of - this absorption are not at once noticeable. They appear only - after weeks, months, or even years, according to the extent to - which the lead has accumulated in the system. - - _How does lead poisoning show itself?_—The first sign is - usually a bluish-grey line on the gums called the blue line, - associated with anæmia or pallor. Later symptoms are very - varied. Most frequently lead colic comes on, the affected - person suffering from violent cramplike pains starting from the - navel; the stomach is hard and contracted; very often vomiting - and constipation ensue, or, very occasionally, diarrhœa. In - some cases paralysis shows itself—generally in those muscles - which extend the fingers, usually affecting both arms. In - exceptional cases other muscles of the arms and legs are - affected. Sometimes lead poisoning manifests itself in violent - pains in the joints—generally the knee, more rarely in the - shoulder and elbow. In specially severe cases brain trouble - supervenes—violent headache, convulsions, unconsciousness or - blindness. Finally lead poisoning may set up disease of the - kidneys—Bright’s disease and gout. - - Women suffering from lead poisoning frequently miscarry. - Children born alive may, in consequence of lead poisoning, die - in their first year. Children fed at the breast are poisoned - through the milk. - - Apart from severe cases complicated with brain trouble, - which are often fatal, persons suffering from lead poisoning - generally recover if they withdraw from further contact. - Recovery takes place after a few weeks, but in severe cases - only after months. - - The most effective preventive measures are cleanliness - and temperance. Persons who, without being drunkards, are - accustomed to take spirits in quantity are more likely to - succumb than the abstemious. Spirits should not be taken - during working hours. In regard to cleanliness, file-cutters - using lead beds should be especially careful and observe the - following rules: - - 1. Since soiling the hands with lead cannot be entirely - avoided, smoking and chewing tobacco during work should be - given up. - - 2. Workers should only take food and drink or leave the works - after thoroughly washing the hands with soap—if possible with - pumice stone; if drinking during work cannot be wholly given up - the edges of the drinking vessels ought not to be touched by - the hands. - - If a file-cutter falls ill in spite of precautions with - symptoms pointing to lead poisoning he should, in his own and - his family’s interest, at once consult a doctor, telling him - that he has been working with a lead bed. - - -Other Industries in which Lead is used - -In cutting _precious stones_ with use of lead discs lead poisoning -frequently occurs, especially where this trade, as in some parts of -Bohemia, is carried on as a home industry. The authorities have required -substitution of carborundum (silicon carbide) for lead discs. As, -therefore, an efficient substitute is possible, use of lead should be -prohibited. Similarly, use of lead in the making of musical instruments -should, if possible, be discontinued. Brass pipes in _musical instrument_ -making are filled with lead to facilitate hammering and bending, and in -this way poisoning has occurred. In numerous other industries where the -use of lead cannot be avoided, and where consequently the danger must -be present, as, for instance, in _lead melting_, _soldering_, _lead -rolling_, _stamping_, _pressing_, &c., in the manufacture of _lead -piping_, _shot_, _wire_, _bottle capsules_, _foil_, _toys_, and many -other articles, general preventive measures should be carefully carried -out. _Melting of lead_ and _lead alloys_ should be carried out only under -efficient exhaust ventilation. In larger works where dust is generated -this should be drawn away at the point where it is produced. This applies -also to processes in the chemical industries where lead or lead compounds -are used, seeing that no substitute is possible. - - -Zinc, Brass-casting, Metal Pickling, Galvanising - -(See also pp. 151 and 182) - -In zinc smelting account has to be taken of fumes which may contain -lead, zinc, arsenic, sulphur dioxide, and carbonic oxide. Metallic fumes -require to be condensed—a procedure in harmony with economic interests. -This is effected in a technically arranged condensing system, consisting -of a condenser and prolong, in which the fumes are given as large a -space as possible in which to condense and cool. In order to prevent -the entry of fumes into the shed when removing distillation residues, -hoods should be arranged over the front of the furnace through which -the gases can be conducted into the main chimney stack or be drawn away -by a fan; in addition the residue should fall into trolleys which must -either be covered at once or placed under a closely fitting hood until -the fuming contents are cool. As the mixing of the materials for charging -and the sifting and packing of the zinc dust (poussière) may cause risk, -these processes require to be carried out mechanically with application -of local exhaust. Such an arrangement is shown in fig. 59 below. The -material which is fed in is carried by the elevator to the sifting -machine, falls into the collecting bin, and is then packed. The points at -which dust can come off are connected with the exhaust and carried to the -dust collector; fans carry the filtered air to the outside atmosphere. - -[Illustration: FIG. 59.—Arrangement for Sieving and Packing Zinc Dust -(poussière). - -_a_ Charging hopper; _b_ Distributor; _c_ Elevator; _d_ Sieve; _e_ -Collector; _f_ Packing machine; _g_ Exhaust pipe; _h_ Worm; _i_ Dust -Collector; _k_ Motor] - -Only paragraphs 3-8 of the German Imperial Regulations dated February 6, -1900, for Spelter Works are quoted, as the remainder are on precisely -similar lines to those for lead smelting works given in full on p. 300. - - 3. Crushing zinc ore shall not be done except in an apparatus - so arranged as to prevent penetration of dust into the workroom. - - 4. The roasting furnaces as well as the calcining furnaces - shall be provided with effective exhaust arrangements for the - escaping gases. The occupier shall be responsible for their - efficiency during the time the furnace is at work. - - 5. To avoid dust, ores intended for charging distillation - furnaces shall not be stacked in front of or charged into - the furnace, or mixed with other material, except in a damp - condition. - - This regulation shall not apply to large so-called Silesian - - Retorts when in use in the zinc smelter; yet in the case of - them also the Higher Authorities may require damping of the - charging material if specially injurious to health. - - 6. Dust, gases and vapours escaping from distillation furnaces - shall be caught as near as possible to the point of origin by - efficient arrangements and carried out of the smelting rooms. - The entrance of the gases from the fires into the smelting room - shall be prevented as far as possible by suitable arrangements - for drawing them off. - - 7. Residues shall not be drawn into the smelting room; they - shall be caught in closed channels under the furnaces and - emptied from these channels at once into waggons placed in - passages beneath the distillation rooms. - - This regulation (where the Higher Authorities approve) shall - not apply to existing plants, should it be impossible to make - the arrangements mentioned in Reg. 1, or where such additions - could only be added by rebuilding at a prohibitive cost. - - 8. Sieving and packing of by-products obtained by the - distillation of zinc (poussière, flue dust) shall not be done - except in a special room separate from other workrooms, in - accordance with Reg. 1. - - Sieving shall only be done in an apparatus so arranged as to - prevent escape of dust. - -In _brass casting_, in order to prevent occurrence of brass-founders’ -ague, it is necessary that the zinc oxide fumes evolved should be -effectively drawn away from the crucible by locally applied exhaust -ventilation. General ventilation merely of the room is almost useless, as -in casting the fumes rise up into the face of the pourer. Seeing that -casting is carried on in different parts of the foundry, it is advisable -to connect up the hoods over the moulds by means of metal piping with the -exhaust system, or to arrange a flexible duct which can be moved about as -occasion requires. - -Dangerous acid fumes (notably nitrous fumes) are evolved in metal -pickling, especially of brass articles (such as harness furniture, -lamp fittings, church utensils, &c.), for the purpose of giving them a -shiny or dull surface by immersion in baths of nitric, hydrochloric, or -sulphuric acid. As severe and even fatal poisoning has occurred in these -operations they should be conducted in isolated compartments or channels -under exhaust ventilation. If the ventilation provided is mechanical an -acid proof earthenware fan or an injector is necessary. The following -description applies to one large works: The pickling troughs are placed -in a wooden compartment closed in except for a small opening in front. -To this compartment a stoneware pipe leading to a stoneware fan is -connected. The nitrous fumes are drawn through the pipe and led into -the lower part of an absorption tower filled with cone-shaped packing -material through which water trickles from a vessel placed at the top. -The greater part of the acid fumes are absorbed as they pass upwards -and the water collects in a receiver below, from which it is blown by -compressed air into the vessel above for utilisation again until it -becomes so charged with acid that it can be used for pickling purposes. - -In _galvanising_ and _tinning_ acid fumes, injurious acroleic vapour, and -metallic fumes can arise as the metal articles (iron, copper, &c.) first -require to be cleaned in an acid bath and then dipped into molten fat -or molten zinc or tin. Here also the fumes should be drawn away in the -manner described. - - -Recovery and Use of Mercury - -Escape of mercury vapour and development of sulphur dioxide seriously -endanger workers engaged in smelting cinnabar. The danger can be -minimised by proper construction of furnaces preventing escape as far -as possible of fumes and most careful condensation of the mercury in -impervious and sufficiently capacious chambers and flues. - -Continuous furnaces are to be preferred to those working intermittently. -The system of condensing chambers and flues must offer as long a passage -as possible to the fumes, and care must be taken to keep them thoroughly -cool. Removal of the deposit rich in mercury from the flues is especially -fraught with danger. This work should only be carried on after efficient -watering by workers equipped with respirators, working suits, &c. - -_Use of mercury._—Mirror making by coating the glass with mercury used -to be one of the most dangerous occupations. Now that a fully adequate -substitute for mercury has been found in the nitrate of silver and -ammonia process, use of mercury should be prohibited. As a home industry -especially mirror coating with mercury should be suppressed. Fortunately -the dangerous mode of production is rapidly being ousted. - -The following requirements are contained in a decree of the Prussian -Government dated May 18, 1889: - -(1) Medical certificate on admission to employment in mirror making with -use of mercury; - -(2) restriction of hours to six in summer and in winter to eight daily, -with a two hours’ mid-day interval; - -(3) fortnightly examination of the workers; - -(4) air space per person of 40 cubic meters in the coating room and 30 in -the drying room, and, in both, introduction of 60 cubic meters of air per -head per hour; - -(5) Work to cease if the temperature of the room in summer reaches 25° C. - -Measures are necessary to prevent occurrence of mercury poisoning in -hatters’ furriers’ processes (preparation of rabbit fur for felt hats) -in consequence of the use of nitrate of mercury. Danger arises chiefly -in cutting the hair, in dressing and drying, in sorting, and also in -the subsequent stages of hard felt hat manufacture. Aspiration of the -dust and fluff at its point of generation, isolation of the drying -rooms and prohibition of entry into them while drying is going on, are -necessary. In dressing (commonly known as ‘carotting’), the nitric acid -vapour requires to be drawn away. In addition strict personal hygiene, -especially of the teeth, is very important. Processes involving _water -gilding_ (nowadays practised on a very small scale) should only be -carried on in stoves provided with exhaust ventilation. Electroplating, -fortunately, has almost entirely taken its place. - -As cases of mercury poisoning have been reported from use of mercurial -pumps in producing the vacuum inside _electric incandescent bulbs_, air -pumps should be substituted for them whenever possible. - -_Barometer_ and _thermometer_ makers may and do suffer severely if care -is not taken to draw away the fumes and ensure good ventilation of the -workrooms. Careless handling and the dropping of mercury on the benches -make it difficult to prevent some volatilisation. Personal hygiene and -especially a proper hygiene of the mouth are of the greatest importance -in this class of work. - -Preparation of mercury compounds in chemical factories, especially the -dry processes (sublimation), as in production of cinnabar, corrosive -sublimate and calomel mixing, grinding, and sublimation, require to be -carried on in closed apparatus. Preparation of the substances named above -in solution involves much less risk than subliming. From our point of -view, therefore, the former is to preferred. - - -Arsenic, Arsenic Compounds, Arseniuretted Hydrogen - -For arsenic works imperviousness of the system and as complete -condensation as possible are necessary to prevent escape of fumes. - -Respirators should be worn in manipulations with white arsenic, and -such work as packing done under conditions of locally applied exhaust -ventilation. - -Industrial use of arsenic compounds, in view of the risk attaching to -them, should be reduced as much as possible. This has sometimes been -achieved by technical improvement in processes of manufacture. Thus in -the colour industry, where formerly colours containing arsenic played -an important rôle, coal-tar colours have taken their place, and use -of arsenic even in these (as in the manufacture of fuchsin) has been -replaced by nitrobenzene. - -As the danger from arseniuretted hydrogen gas is especially great in -processes in which acid acts on metal and either one or both of them -contain arsenic, the materials, should be as free from arsenic as -possible, in the production, for example, of hydrogen for soldering, in -extracting metals by means of acids, in galvanic elements, in accumulator -works, in the storage and transport of acids in metal vessels, and in -galvanising. - -In any case the workers in these industries should be warned of the -danger and instructed in case of emergencies. For soldering exclusive use -of hydrogen produced electrolytically and procurable in steel cylinders -is advisable. - - -Extraction and Use of Gold and Silver - -In the extraction of gold and silver by amalgamation and subsequent -volatilisation of mercury there is risk of mercurial poisoning. The -preventive measures necessary are similar to those for poisoning in the -recovery of mercury (see p. 327). - -_Argyria_ in pearl bead blowers can be avoided by using pumps to blow the -silver solution into the beads instead of the mouth. - -In electroplating the possibility of poisonous fumes arising from the -baths must be guarded against because hydrocyanic (prussic) acid, though -only in minute quantities, may be evolved; care must be taken that the -workrooms are well ventilated or the baths hooded. Careful personal -hygiene is essential, for the prevention of skin diseases from which -workers in electroplating often suffer. - - - - -VII - -_PREVENTIVE MEASURES IN OTHER TRADES_ - - -Ceramic Industry - -In the glass industry use of lead, chrome, and arsenic compounds should -be restricted as much as possible or allowed only under suitable -precautions (exhaust ventilation, personal hygiene, &c.). - -_Etching on glass_ by means of hydrofluoric causes almost inevitably -injury to the workers. Rendering the surface of glass opaque should -preferably be done by sand blast. When a bath of hydrofluoric acid for -etching on glass is used the fumes require to be drawn away by hoods over -the baths and the work-rooms well ventilated. - -Further precautionary measures are called for in view of industrial -poisoning by furnace gases in various ceramic industries, as, for -example, cement works, glass works, and tile works. - -The following suggestions are made in the technical introduction to the -Germany Factory Act for prevention of poisoning from carbonic oxide, -carbon dioxide, and sulphur dioxide: - -(1) Even the fixing of benches which might be used for sleeping on near -the furnaces should be strictly forbidden; - -(2) All furnaces which are roofed over should be provided with adequate -side and roof ventilation; - -(3) All gas pipes and cocks must be maintained in an impervious condition. - - -Manufacture and Use of Varnishes and Drying Oils - -Unpleasant fumes are given off on boiling linseed oil with oxidising -substances, which should be prevented by closely fitting covers and -condensation of the fumes in cooling apparatus. In heating and dissolving -resin for the production of varnishes the fumes evolved require to be -dealt with in a similar way. - -Preventive measures must be taken also in the use of quick-drying paints -on ships and inside steam boilers as, owing to the rapid evaporation of -the poisonous solvents—benzene, benzine and turpentine—fatalities have -occurred. As a result of elaborate investigation by the inspectors of -factories in Hamburg the following instructions were issued: - - Quick-drying paint for ships and for preventing rust should - only be used under the supervision of a person conversant with - the danger to health and risk from fire. - - They should only be allowed for the painting of interior - surfaces after adoption of adequate precautions—free - ventilation, use of smoke helmets with air conducting - apparatus, and no naked lights, &c. Since use of quick-drying - paints cannot easily be prohibited and the fumes from the - substitutes for turpentine—benzene and other light tarry - oils—exert injurious effect on man, precautionary measures are - called for. Regulation of working hours is as important as - provision of adequate ventilation. Workers, therefore, should - be allowed proper intervals from work. - - Confined spaces in the interior of ships should be adequately - ventilated before, after, and during work; all persons who use - the paints should have opportunity for washing given them at - their work places, and should be compelled to avail themselves - of these facilities; indulgence in alcohol and smoking should - be prohibited; receptacles in which quick-drying paints are - sold should be provided with an air-tight cover and with a - warning notice as to the danger of the contents. - - Paints made from petroleum fractions of low boiling-point, - light coal-tar oils, turpentine oil, carbon bisulphide, and - similar substances, are to be regarded as injurious to health. - - Persons under eighteen, and women, should not be allowed to - work with quick-drying paints. - - Obligatory notification of cases of poisoning by hydrocarbons - and other similar poisonings would have a good effect. - -Schaefer (Inspector of Factories in Hamburg) has drawn up the following -leaflet for painters, varnishers, workers in dry docks, and others -engaged in painting with quick drying paints and oils: - - All quick-drying paints and oils are more or less injurious - to health and very inflammable, as they contain volatile - substances such as benzine (naphtha, petrol ether), benzene, - turpentine oil, carbon bisulphide, &c. These paints are mostly - used in painting interiors of ships, boilers, machinery, - apparatus, &c., and come on the market under various - names, such as Black Varnish Oil, Solution, Patent Colour, - Anti-corrosive, Dermatin, Acid-proof Paint, Apexior, Saxol, &c. - - Even at ordinary temperatures the volatile fluids used - as mediums for dry paint powders, or as a first coating, - evaporate. Air filled with the fumes is not only harmful to - health, but liable to explosion. Working with these paints and - oils in the interior of ships, or steam boilers and the like, - has repeatedly led to explosions and fatal poisoning. - - _Danger of Poisoning._—All persons are exposed to the danger of - poisoning who use quick-drying paints in the interior of rooms - or receptacles, or otherwise manipulate the paints. The warmer - the room and the less ventilation there is before and during - the painting, the greater the danger of poisoning. On the other - hand, use of these paints in the open air is generally without - effect. - - Poisoning arises from inhaling the fumes of hydrocarbons. - The symptoms are oppression, headache, inclination to vomit, - cough, hiccough, giddiness, noises in the ears, drunken-like - excitement, trembling and twitching. Inhalation of larger - quantities brings on, quite suddenly and without previous - warning, unconsciousness, which may last many hours and is - often fatal. Except in severe cases the symptoms generally - soon disappear, if the affected person withdraws from further - contact with the fumes. The most effective protection therefore - against poisoning is fresh air and temperance. In so far as - painting with quick-drying materials is necessary in workrooms, - interiors of ships, water and ballast tanks, double bottoms, - bunkers, bilges, cabins, boilers and receptacles, care must - be taken to ensure thorough ventilation before, after, and - while the work is going on. Where no sufficient ventilation - is possible these paints ought not to be used. Frequent - intermission of work by a short stay in the open air is useful. - When working in spaces not easily accessible, the worker should - be roped. - - Speaking, singing, or whistling during work favours inhalation - of the fumes and is, therefore, to be avoided. Indulgence in - spirits, especially during working hours, increases the danger - of poisoning. Habitual drinkers should not be allowed to work - at all with quick-drying paints and oils. - - At the first signs of discomfort work should be stopped. An - immediate stay in the open air will then usually dispel the - poisonous symptoms. - - If, notwithstanding this, severe symptoms develop, oxygen - inhalation should be commenced forthwith and medical aid called - in. - - -Production of Vegetable Foods and Luxuries - -(See also p. 154) - -Measures for the prevention of industrial poisoning have to be thought of -in connection with drying processes (by smoke gases, carbon dioxide, and -carbonic oxide), many processes of preserving (use of sulphur dioxide, -&c.), and fermentation (accumulation of carbonic acid). - -In breweries the use of kilns allowing fire gases to enter the -drying-rooms formerly caused carbonic oxide and carbonic acid poisoning. -The general introduction of hot air kilns provided with mechanical -malt-turning apparatus should be insisted on, and is in keeping with -progress in technical methods. - -The accumulation of carbonic acid in the malting cellars can be prevented -in the same way as in a distillery. - -If ammonia is used for _refrigeration_, precautions are necessary so -that, in the event of leakage or bursting of pipes, the workers may -escape. Naturally the imperviousness of the freezing system must be -guaranteed. - -Oppression and danger to the health of the workers is occasionally caused -by the development of gases in the coating of barrels with pitch, partly -preventable by the use of pitching machines. - -In the production of _spirits_ carbonic acid poisoning can occur from -accumulation of carbonic acid in the fermentation cellars. These should -be thoroughly ventilated and in view of the heaviness of the gas, -openings for ventilation should always be located at the floor level. - -In the _sulphuring of malt_ the following recommendations were made by -the Austrian inspectors: - -During the sulphuring process the room ought not to be entered (for -the turning over of the malt). When the sulphur has been burnt, the -drying-room must be ventilated from the outside, by opening the windows -and letting in cold currents of air, until the sulphur dioxide has -completely dispersed, which can be tested by holding a strip of moistened -blue litmus paper at the half-opened door. If it does not turn red, -turning over of the malt may be proceeded with. - -As the _sulphuring of hops_ in hop districts is done in primitive little -kilns, in which the hops are spread out on a kind of gridiron and sulphur -burnt below in iron pans, development of sulphur dioxide may affect the -workers. The following regulations are therefore suggested for work in -these kilns: - - The rooms in which sulphuring takes place must be airtight, - capable of being locked, and provided with arrangements which - make it possible to remove the sulphur dioxide fumes before - the room is entered. This can usually be done by a strong - coke fire, maintained in the chimney place, which creates the - necessary draught. If fans are used, it must be remembered that - iron is affected and destroyed by acid gases; stoneware fans - are therefore advisable. - -In the production of _vinegar_, air escapes laden with acetic acid -vapour, alcohol, lower oxidation products of alcohol, aldehyde, acetic -ether, &c. Their escape can be avoided if the whole process is carried on -in a closed self-acting apparatus with the advantage also that no loss -occurs. - -In premises for _drying agricultural products_ (fruit, chicory, turnips) -the persons employed in the drying-room are exposed to the danger of -carbonic oxide poisoning from direct firing. - -The following recommendations for work in drying-rooms with direct firing -are taken from an Austrian decree of 1901: - - The lower drying chambers, in which the real drying process - is effected, should be so arranged that the objects dried in - them can be removed by means of long-handled implements through - a passage shut off from the drying-room. The separation of - this passage can be effected by loose tin plates which can be - removed as required for the work of turning or removal of the - dried products, so that the worker need not come into contact - with the gases. - - Open fires should be so arranged that if required they can - be shut off, by simple arrangements, from the drying-rooms - in which the workers are temporarily occupied in carrying - in, and turning, the objects to be dried, transferring the - partly dried products to hotter hurdles, and emptying them - when finished, in such a way that the entrance of combustion - gases into the drying chambers can be completely prevented. In - order, however, to prevent a back draught, arrangements must be - made for simultaneous removal of the gases by pipes connected - with a chimney or smoke flue. The places from which the fires - are charged should, in addition, be furnished with suitably - arranged openings for ventilation leading into the outer air, - in order to neutralise, in case of need, any back draught from - the furnaces into the rooms. - - The windows of the drying chambers should be so arranged as to - open both from within and without. - - The floor of the roof space, or attic, which forms at the same - time the ceiling of the upper drying-room, should be kept - perfectly airtight, as also the openings into it through which - the steam pipes pass. For this purpose the floor should be a - double one and the openings or boxes into which material is - thrown should have a double cover above and below. Further, - situated in the highest point of the ceiling of the roof space, - there should be a suitable number of openings topped by louvred - turrets. In the roof space no work should be done except - manipulations necessary for the charging of the hurdles with - the goods to be dried. Use of the roof floor as a sleeping or - living room is not permissible. - - Before the workers enter the drying chambers for the purpose of - turning the materials, the stove should be shut off, the gases - drawn from the furnace into the chimney or flue, and at the - same time the doors and windows of the drying rooms opened. - - Entering of drying chambers for working purposes should only be - done after a sufficient time has elapsed for removal of the air - by ventilation. - - Charging of the furnaces should be so arranged that they burn - as low as possible before the removal of the dried materials - and before subsequent work in the drying chambers. Seeing that - chicory and turnip drying is done intermittently by night, a - special sleeping or waiting room with free ventilation should - be provided. The regulations concerning the ventilation of the - workrooms are to be made known to the workers. - - -Cigar Industry - -In order to prevent injury to health to tobacco workers the dust and -fumes, especially at cutting and sifting machines, require to be drawn -away by locally applied exhaust ventilation. The workrooms, moreover, -must conform to hygienic requirements, especially as to cleanliness. -Washing accommodation and baths are desirable, but are only likely to be -provided in large works. - - -Wood Working - -(See also p. 154) - -Risk from poisonous woods can be avoided by exhaust ventilation applied -to the wood-working machinery. - -To lessen the danger to health in the use of methylated spirits in the -polishing of wood adequate ventilation of the workrooms is necessary; -drawing off the fumes by local ventilation is often impossible. - - -Production of Wood-pulp (Cellulose) and Paper. - -In the _sulphite cellulose_ process, sulphur dioxide may escape from -the sulphur stoves or from the boilers; escape of sulphur dioxide is -also possible through defective gas pipes and condensers. Gas pipes and -condensers require to be quite impervious and condensation or absorption -as complete as possible. The fumes escaping from the boilers should be -led through pipes into closed boilers for condensation purposes; the -gases not condensed here are to be led into absorption towers. - -In the manufacture of _paper_ with use of chloride of lime for bleaching -chlorine can be given off in considerable quantity, requiring removal of -the gases from the apparatus. - -The use of poisonous colours containing lead or arsenic, and addition of -lead-containing substances to the paper pulp, is now very rare. - - -Textile Industries. - -(See also p. 156) - -In the textile industry only a few manipulations are associated with -serious risk of poisoning. Those engaged in carbonising are exposed -to acid fumes; closed and ventilated apparatus, therefore, as far as -possible, require to be used and the acid gases escaping from them should -be absorbed. These requirements are fulfilled by carbonising stoves which -are ventilated and connected with coke condensers. It is especially urged -that only arsenic free acid be employed, as otherwise danger of poisoning -by arseniuretted hydrogen may be incurred. - -In the making of _artificial silk_, according to the Chardonnet-Cadoret -process, the precautionary measures recommended in nitrating together -with careful exhaustion of the ether and camphor fumes apply. - -The combustion gases (containing carbonic oxide) developed in the -process of singeing are harmful and require to be led away at their -source. - -Poisonous metallic salts, especially lead and lead-containing zinc, are -used as weighting materials, in dressing or finishing, and sometimes -cause symptoms among the workers. Apart from the danger to those occupied -in spinning and weaving, the workers who handle these products (in the -clothing trade) also run a risk from lead. - -Precautionary measures are necessary in the _varnishing of woven -materials_, as the substances employed may contain volatile poisonous -solvents. If these poisonous solvents cannot be replaced by others less -poisonous, carefully applied exhaust ventilation must be provided. -The same holds good when carbon bisulphide, benzene, and benzine are -used as solvents in the production of woven materials impregnated with -indiarubber. - -Employment of lead salts and other poisonous metallic salts in the -glossing of woven materials, or in order to render them non-inflammable, -is to be deprecated. - -Cases of lead poisoning have occurred in the working-up of asbestos, as -lead wire is sometimes used in the process of weaving. - -To protect workers in _chlorine_ and _sulphur bleaching_ from poisoning -by chlorine or sulphur dioxide the gases arising from the bleaching -liquids should be drawn away. Use of closed bleaching apparatus, as is -the case in large works, reduces the danger to a minimum. Bleaching-rooms -should be connected with a powerful stoneware fan, so that they may be -thoroughly aired before they are entered. - - -Dye Works - -Industrial poisoning by dyes is, in general, rare, as the natural dyes -(wood and tar dyes) are almost without exception non-poisonous. Further, -the dyes are generally only used in diluted solution. Formerly the -arsenic in many tar dyes caused poisoning, but now it is usually the -mordants which have harmful effect. To this class belong chromic acid -salts and mordants containing arsenic, antimony (tartar-emetic), and -also chloride of tin. In the scraping off of layers of paint containing -arsenic, arsenic dust may arise. In Turkey red dyeworks, especially -sodium arsenite is used for fixing the tar dyes. - -Orpiment dyes which may give off poisonous arseniuretted hydrogen gas -are becoming less and less used; from the point of view of industrial -hygiene, the utmost possible avoidance of the use of arsenic-containing -preparations in dye works is to be recommended. Where this is not -possible, strict personal hygiene must be enforced (as, for instance, -application of vaseline to the skin). - - - - -FOOTNOTES - - -[A] Leymann has dealt with the conditions of health in a large aniline -factory in a later work which is referred to in detail in the section on -the aniline industry. - -[B] Poisoning by lead, phosphorus, and arsenic contracted in a factory or -Workshop has been notifiable in Great Britain and Ireland since 1895. - -[C] ‘On the Nature, Uses, and Manufacture of Ferro-silicon,’ 1909, Cd. -4958. - -[D] In Great Britain section 73 of the Factory and Workshop Act, 1901, -requires every medical practitioner attending on or called in to visit -a patient whom he believes to be suffering from lead, phosphorus, -arsenical or mercurial poisoning, or anthrax, contracted in any factory -or workshop, to notify the Chief Inspector of Factories, and a similar -obligation is placed on the occupier to send written notice of every case -to the inspector and certifying surgeon of the district. - -The table on p. 222 shows the number of reports included in returns for -the years 1900-12. - -Cases of acute poisoning in factories and workshops are reportable to -the Inspector and certifying surgeon, under the Notice of Accidents Act, -1906, when (_a_) causing loss of life or (_b_) due to molten metal, hot -liquid, explosion, _escape of gas_ or steam, and so disabling any person -as to cause absence throughout at least one whole day from his ordinary -work. - -The following table gives indication of the relative frequency of cases -of poisoning from gases and fumes, although some were reported as -accidents the result of the unconsciousness induced: - - +-------------------------------+-------+------+------+------+------+ - | Nature of Gas or Fumes. | 1912. | 1911.| 1910.| 1909.| 1908.| - | (1) | (2) | (3) | (4) | (5) | (6) | - +-------------------------------+-------+------+------+------+------+ - |Carbon monoxide |91 (14 |64 (6 |53 (9 |53 (6 |55 (5 | - | (_a_) Blast furnace |33 (5 |16 (2 |19 (7 |16 |26 (3 | - | (_b_) Power (suction, | | | | | | - | producer, Mond, Dowson). |19 (4 |31 (1 |25 |25 (4 |19 (2 | - | (_c_) Coal |29 (2 | 6 (2 | 4 |11 (1 | 9 | - | (_d_) Other |10 (3 |11 (1 | 5 (2 | 1 (1 | 1 | - |Sulphuretted hydrogen | 6 | 8 (2 | 2 | 5 (2 | 8 (1 | - |Carbon dioxide | 3 (2 | 1 (1 | 2 (1 | 2 (2 | 4 (3 | - |Ammonia | 1 | 1 (1 | 2 | 1 | 1 | - |Chlorine and hydrochloric | | | | | | - | acid fumes | 3 | 5 (1 | 3 | 1 | 1 | - |Nitrous fumes |12 (1 |18 (2 |11 |12 (2 | 3 (1 | - |Nitro and amido derivatives of | | | | | | - | benzene | 9 (1 |21 |18 | 4 | 2 | - |Naphtha and benzene | 3 (1 | 1 (1 | — | 1 (1 | 2 | - |Other (Sulphur dioxide, &c.) | 7 (2 | 4 | 4 | 4 | 3 | - +-------------------------------+-------+------+------+------+------+ - -The principal figures are those of all cases, fatal and non-fatal; the -small figures relate to fatal cases. - -Transcriber’s Note: The ‘small figures’ are given here in brackets e.g. -(1. - -[E] The principal numbers relate to cases, the small figures to deaths. -Fatal cases not reported in previous years are included as both cases and -deaths. - -Transcriber’s Note: The ‘small figures’ are given here in brackets e.g. -(1. - -[F] Fischer adopts a chemical basis in his classification. His two -main subdivisions are (1) inorganic and (2) organic poisons. The -sub-divisions of the inorganic poisons are (_a_) non-metallic—chlorine, -calcium chloride, hydrochloric acid, potassium chlorate, hydrofluoric -acid, carbonic oxide, phosgene, carbon dioxide, cyanogen compounds, -ammonia, nitrous fumes, phosphorus, phosphoretted hydrogen, arsenic -compounds, antimony compounds, sulphur dioxide, sulphuric acid, -sulphuretted hydrogen, carbon bisulphide, chloride of sulphur; and -(_b_) metallic—chromic acid and chromates, manganese dioxide, sulphate -of nickel, mercury and lead. The sub-divisions of (2) the organic -substances are into (_a_) the unsaturated carbon compounds—benzene, -petroleum, methyl-, ethyl-, amyl-, and allyl-alcohol, oxalic acid, -formal- and acetaldehyde, acrolein, acetone, methyl-bromide and -iodide, nitro-glycerin, dimethyl-sulphate and amyl acetate, and -(_b_) the aromatic series benzene, nitro-, chloro-nitro-, dinitro-, -chloro-dinitro-benzene, phenol, picric acid, phenyl-hydrazine, aniline, -and certain aniline colours, para-nitraniline, pyridine, naphthalene, -nitro-naphthalene, naphthlyamine, naphthol, benzidine, acridine, -turpentine, and nicotine. - -[G] A Prussian Ministerial Decree, dated March 31, 1892, deals with the -preparation of nitrate of mercury. - -[H] In Great Britain and Ireland the White Phosphorus Matches Prohibition -Act became operative from January 1, 1910. In the United States of -America a Prohibition Act became operative on July 1, 1913. - -[I] Reprinted by permission of the Controller of H.M. Stationery Office. - -[J] _Use of Oxygen Cylinder._—Open the valve gradually by tapping the -lever key (which must first be extended to its full length) with the -wrist, until the oxygen flows in a gentle stream from the mouthpiece into -the patient’s mouth. The lips should not be closed round the mouthpiece. -The nostrils should be closed during breathing in, and opened during -breathing out. - -If the teeth are set, close the lips and one nostril. Let the conical end -of the mouthpiece slightly enter the other nostril during breathing in, -and remove it for breathing out. - -[K] The suggested regulations made after his inquiry (see p. 149) by Dr. -Copeman are: - -1. Ferro-silicon should not be sent out from the works immediately after -manufacture, but after being broken up into pieces of the size in which -it is usually sold, should be stored under cover, but exposed to the air -as completely as possible, for at least a month before being despatched -from the works. - -2. Manufacturers should be required to mark in bold letters each barrel -or other parcel of ferro-silicon with the name and percentage grade -(certified by chemical analysis) of the material; the name of the works -where it is produced; the date of manufacture; and date of despatch. - -3. The carriage of ferro-silicon on vessels carrying passengers should -be prohibited. When carried on cargo boats it should, if circumstances -permit, be stored on deck. If it be considered necessary to store it -elsewhere, the place of storage should be capable of being adequately -ventilated, and such place of storage should be cut off by airtight -bulkheads from the quarters occupied by the crew of the vessel. - -4. This regulation should apply to the transport of ferro-silicon on -river or canal barges as well as on sea-going vessels. - -5. Storage places at docks or at works where ferro-silicon is used should -have provision for free access of air, and should be situated at a -distance from work-rooms, mess-rooms, offices, &c. - -[L] Regulations 5-7 contain precautions to be observed in the corroding -chambers. - - - - -APPENDIX - -REFERENCES - - - - -PART I - -PROCESSES OF MANUFACTURE AND INSTANCES OF POISONING - - -GENERAL SURVEY OF POISONING IN CHEMICAL INDUSTRIES - -[1] Leymann, _Concordia_, 1906, Nos. 7, 8 and 9; [2] Grandhomme, _Die -Fabriken der Farbwerke zu Höchst a. M._, Verlag Mahlau, 4th edition. - - -SULPHURIC ACID INDUSTRY - -[1] _Zeitschr. für. Gewerbe-Hygiene_, 1907, p. 230; [2] Bath, _Zeitschr. -f. Angew. Chemie_, 1896, p. 477. - - -HYDROCHLORIC ACID AND SALTCAKE MANUFACTURE - -[1] _Zeitschr. f. Gewerbe-Hygiene_, 1906, p. 562; [2] _Zeitschr. f. -Gew.-Hyg._ 1902, p. 62; [3] Walther in Weyl’s _Arbeiterkrank-keiten_, p. -666. - - -CHLORINE AND BLEACHING POWDER - -[1] _Zeitschr. für. Gew.-Hyg._, 1906, p. 280; [2] _Concordia_, 1906, -No. 8; [3] _Arch. f. Hyg._, vol. 46, p. 322; [4] Egli, _Unf. b. Chem. -Arb._, Zurich, 1902, p. 40; [5] Vaubel, _Chemiker Zeitung_, 1903; [6] -_Concordia_, 1907, No. 7; [7] Rumpf, _D. Med. Wochenschr._, 1908, vol. -34, p. 1331; [8] Müller, _Vierteljahrsschr. f. Ger. Med. ü öffentl. -Sanitätsw._, vol. ix., p. 381; and Roth, _Komp. d. Gewerbekrankh_, p. -205; [9] Klocke-Bochum, _Zeitschr. f. Gew.-Hyg._, 1906, p. 563; [10] -Sury Bienz, _Vierteljahrsschr. f. Ger. Med._, 1907, vol. 34, p. 251; -[11] Erben, _Handb. d. ärztl. Sachverst_, 1910, vol. ii. p. 266; [12] -_Concordia_, 1902, No. 5., and _Vierteljahrsschr. f. öff. Ges. Pfl._, -1902, Suppl. p. 371; [13] Mohr, _D. Med. Wochenschr_., 1902, vol. 28, p. -73; [14] ‘Über Chlorakne,’ _Archiv. f. Dermatol._, 1905, vol. 77, p. 323; -[15] Dammer, _Handb. d. Arb. Wohlf._, vol. i. p. 433; [16] _D. Arch. f. -Klin. Med._, 1901, vol. 71, p. 370; [17] Schuler, _D. Vierteljahrsschr. -f. öffentl. Ges. Pfl._, vol. 31, p. 696; [18] Egli, _Unf. b. Chem. Arb._, -Zurich, 1902, pp. 22, 45; [19] Rambousek, _Concordia_, 1910, No. 6. - - -MANUFACTURE AND USE OF NITRIC ACID AND ITS COMPOUNDS - -[1] Schmitz, _Berl. Klin. Wochenschr._, 1884, vol. 21, p. 428, and -Becker, _Aerztl. Sachv. Ztg._, 1899, vol. v. p. 277; [2] _Concordia_, -1908, No. 23, p. 498; [3] Schmieden, _Zentralbl. f. Klin. Med._, 1892, -No. 11; Kockel, _Vierteljahrsschr. f. Ger. Med._, 1898, vol. 15; [4] -Egli, _Unf. b. chem. arb._, 1903, p. 52; [5] _Chem. Industrie_, 1905, p. -444; [6] _Chem. Industrie_, 1905, p. 445; [7] _Berl. Klin. Wochenschr._, -1886, vol. 23, p. 417; [8] _Komp. d. Gewerbekrankheiten_, p. 62; [9] -_Intern. Uebers. über Gew.-Hyg._, 1907, p. 76. - - -PHOSPHORUS AND LUCIFER MATCH MANUFACTURE - -[1] _Die Phosphornekrose, ihre Verbreitung in Oesterreich_, Wien, 1907; -[2] Friedrichs, in _Arb. d. Ung. Ver. f. ges. Arbeiterschutz_ 1908, -vol. 4, pp. 1-176; [3] v. Jaksch, _Handb. d. ärztl. Sachv.-Tät._, 1909, -vol. 7, p. 239; and Lévai, _W. Klin. Rundsch._, 1900, vol. 14, p. 33, -and Dearden, _Brit. Med. Journ._, 1899, vol. 1, p. 92; [4] Wodtke, -_Vierteljahrsschr. f. ger. Med. und öffentl. Sanitätsw._, vol. 18, p. 325. - - -CHROMIUM COMPOUNDS - -[1] Hermanni, _Münch med. Wochenschr._, 1901, No. 14, and Wodtke, _loc. -cit._, p. 325; [2] _Zeitschr. f. Gew.-Hyg._, 1908, p. 161; [3] Wutzdorff -und Heise, _Arb. a. d. Kais. Ges. Amt._, vol. xiii.; [4] _Zeitschr. f. -öffentl. Ges. Pfl._, 1894; [5] Burns, _Ann. Rept. of C. I. of F._, 1903; -[6] Neisser, _Intern. Uebers. über Gew.-Hyg._, 1907, p. 92. - - -MANGANESE COMPOUNDS - -[1] Couper, _Journ. de Chimie_, vol. 3, series ii.; [2] _Münch. med. -Wochenschr._, 1901, p. 412; [3] Embden, _D. med. Wochenschr._, vol. 27, -p. 795. - - -PETROLEUM AND BENZINE INDUSTRY - -[1] Berthenson, _D. Vierteljahrsschr. f. öffentl. ges.-Pfl._, 1898, vol. -30, p. 315; [2] _Virchow’s Archiv_, vol. 112, p. 35; [3] Felix, _D. -Vierteljahrsschr. f. öffentl. ges.-Pfl._, 1872; [4] _Lancet_, 1886, p. -149; [5] _Ramazzini_, 1908, vol. 2, p. 226; [6] Dorendorf, _Zeitschr. -f. Klin. Med._, 1901, p. 42; [7] _Brit. Med. Journ._, 1903, p. 546, and -_ibid._, 1908, p. 807; [8] _Zeitschr. f. Gew.-Hyg._, 1907, p. 157; [9] -Wichern, _Zeitschr. f. Gew.-Hyg._, 1909, Nos. 3 and 4; [10] Mitchell, -_Med. News_, iii., p. 152; _Ann. d’Hyg. publ._, vol. 24, p. 500; Arlidge, -_Dis. of Occupation_; _Revue d’Hygiène_, 1895, p. 166; Neisser, _Intern. -Uebers. f. Gew.-Hyg._, 1907, p. 96. - - -SULPHURETTED HYDROGEN GAS - -[1] _Chem. Ind._, 1908, p. 323; [2] Pfeiler, _D. Vierteljahrsschr. f. -öffentl. Ges.-Pfl._, 1904; [3] _Lehre v. d. schädl. u. gift. Gasen_, p. 274. - - -CARBON BISULPHIDE - -[1] _Archiv f. Hyg._, vol. 15, pp. 125-141; [2] Santesson, _Archiv f. -Hyg._, vol. 31, p. 336; [3] _Chem. Ind._, 1905, p. 442; [4] _Zeitschr. -f. Gew.-Hyg._, 1908 and 1909; [5] _Arch. f. Hyg._, xx., p. 74; [6] _Die -Schwefelkohlenstoffvergiftung der Gumniarbeiter_, Leipzig, Veit & Comp., -1899; [7] _Ann. d’Hyg. publ._, 1863. - - -ILLUMINATING GAS - -[1] _Krankheiten des Arbeiter_, 1871; [2] _Gewerbepathologie_, 1877; -[3] _Weyl’s Handb. d’Hyg._, 1894, vol. 8; [4] Sprenger and Albrecht: -Albrecht’s _Gewerbehygiene_, 1896; [5] Jehle, ‘Hygiene der Gasarbeiter,’ -_Zeitschr. f. Gew.-Hyg._, 1901, pp. 245 and 261; [6] Schütte: -‘Krankheiten der Gasarbeiter,’ Weyl’s _Arbeiterkrankheiten_, 1908, p. -239; [7] Heymann’s Verlag, 1910; [8] _Zeitschr. f. Gew.-Hyg._, 1909, No. -12; [9] _Chem. Ind._, 1905, p. 442; [10] Egli, _Über d. Unf. b. Chem. -Arb._, Zurich, 1903; [11] _Gewerb. techn. Ratgeber_, 1906, p. 96. - - -COKE OVENS - -[1] Hesse, _Concordia_, 1909. - - -POWER GAS, SUCTION GAS, &C. - -[1] _Zeitschr. f. Gew.-Hyg._, 1906, p. 250; 1909, p. 297; 1906, p. -19; [2] _Gewerbl. techn. Ratgeber_, 1906, p. 297; [3] Nottebohm, -_Socialtechnik_, 1907, vol. 7, p. 80; [4] Finkelstein, _Jahr. d. Peych._, -1897, vol. 15, p. 116; [5] Jokote, _Arch. f. Hyg._, 1904, vol. 49, p. 275. - - -AMMONIA - -[1] _Ber. pr. Gew. Insp._, 1904; [2] Egli, _loc. cit._, No. 2, p. 48; -[3] _Lehre v. d. schädl. u. gift. Gasen_, p. 274; [4] _Zeitschr. f. -gew.-Hyg._, 1909, p. 242; [5] _Berl. Klin. Wochenschr._, 1908. - - -CYANOGEN COMPOUNDS - -[1] _Handb. d. Hyg._, vol. 8, p. 897; [2] Merzbach, _Hyg. Rundsch._, -1899, No. 1; [3] _Zeitschr. f. Med. Beamte_, 1907, vol. 20, p. 825; [4] -Kockel, _Vierteljahrsschr. f. ger. Med._, 1903, vol. 26; [5] Erben, -_Vergiftungen_, ii. p. 204. - - -TAR AND ITS DERIVATIVES - -[1] Lewin, _Münchn. med. Wochenschr._, 1907; [2] Santesson, _Skand. Arch. -f. Physiol._, 1900, vol. 10, pp. 1-36; [3] _Concordia_, 1901, p. 287 -Jahresber. d. Staatl. Aufsichtsbeamten über Unfallverbütung, 1909; [4] -Arb. d. Hamb. Gewerbeinspektoren, 1909; [5] Greiff, _Vierteljahrsschr. f. -ger. Med._, 1890. - - -COAL TAR COLOURS - -[1] _Die Fabriken der Farbwerke vorm. Meister Lucius & Brüning zu Höchst -a. M._, 1896; [2] _Concordia_, 1910, p. 355; [3] _Vierteljahrsschr. -f. öffentl. Ges.-Pfl._, Supplem. pro 1902, p. 371; [4] Schröder, -_Vierteljahrsschr. f. ger. Med._, 1903, p. 138; Rump, _Zeitschr. f. -Med. Beamte_, 1903, p. 57; [5] Brat, _D. med. Wochenschr._, 1901, Nos. -19 and 20; [6] Mohr, _D. med. Wochenschr._, 1902; [7] _Zeitschr. f. -Gew.-Hyg._, 1908, p. 383; [8] Hanke, _W. Klin. Wochenschr._, 1899, vol. -12, p. 725; Frank, _Beiträge zur Angenheilk._, 1898, vol. 31, p. 93; -Silex, _Zeitschr. f. Angenheilk._, 1902, p. 178; [9] Dearden, _Brit. Med. -Journ._, 1902, vol. 2, p. 750; [10] _Ann. Rept. of C. I. of F._, 1905, p. -165; [11] _Münch, med. Wochenschr._, 1907; [12] Erdmann, _Arch. f. exp. -Path._, 1905, vol. 53, p. 401. - - -FERRO-SILICON - -_Nature, Uses and Manufacture of Ferro-silicon_, by S. M. Copeman, S. R. -Bennett, and H. W. Hake. London. 1909. Cd. 4958. - - -LEAD AND ITS COMPOUNDS - -Legge and Goadby, _Lead Poisoning and Lead Absorption._ Edward Arnold. -1912. - -[1] Wächter, _Die gewerbliche Bleivergiftung im Deutschen Reich_, 1908, -p. 36; [2] _XIV. Intern. Kongr. f. Hyg. und Dem._, 1907, vol. 2, p. -746; [3] Rambousek, _Concordia_, 1910; [4] Müller, _Die Bekämpfung -der Bleigefahr in Bleihütten_, Fischer, 1908, 156; [5] Frey, _Die -Zinkgewinning und ihre Hygiene_, Hirschwald, Berlin, 1907; [6] Wächter, -_Die gew. Bleivergiftung_, 1908, Braun, Karlsruhe; [7] Clayton, _Brit. -Med. Journ._, 1906, vol. 1, p. 310; [8] _Bericht an die Intern. -Vereinigung für Arbeiterschutz_, 1908. - - -MERCURY AND ITS COMPOUNDS - -[1] Laureck, _Weyl’s Arbeiterkr._, p. 62; [2] Giglioli, Ramazzini, 1909, -vol. 3, p. 230. - - -ARSENIC AND ITS COMPOUNDS - -[1] _Zeitschr. f. Gew.-Hyg._, 1902, p. 441; [2] Prölss, _Friedreich’s Bl. -f. ger. Med._, 1901, p. 176. - - -ANTIMONY - -[1] _Vergiftungen_, vol. ii. p. 285. - - -BRASS - -[1] _Vierteljahrsschr. f. ger. Med._, 1906, p. 185; [2] _Arch. f. Hyg._, -1910, vol. 72, p. 358. - - - - -PART II - -PATHOLOGY AND TREATMENT - - -OXYGEN INHALATION IN INDUSTRIAL POISONING - -Brat, ‘Bedeutung der Sauerstofftherapie in der Gewerbehygiene, _XIV. -Intern. Kongr. f. Hyg. u. Dem._ und _Zeitschr. f. Gew.-Hyg._ 1908, Heft -13, S. 305; Dräger, ‘Zur Physiologie des Rettungsapparates mit komprim. -Sauerstoff, _I. Intern. Kongr. f. Rett.-Wes., Frankfurt a. M._ 1908, -und _Fabrikfeuerwehr_ 1908, Heft 19, S. 74; Klocke, ‘Die Bedeutung -der Sauerstoffinhalationen in der Gewerbehygiene,’ _Zeitschr. f. -Gew.-Hyg._ 1906, Heft 20, S. 559; Dräger, ‘Neue Untersuchungen über die -Erfordernisse eines zur Arbeit brauchbaren Rettungsapparates,’ _Zeitschr. -f. Gew.-Hyg._ 1905, S. 49; Klocke, ‘Sauerstoffrettungsapparate,’ _Soz. -Techn._ 1908, Nr. 14, S. 272. - - -HYDROFLUORIC ACID POISONING - -Egli, _Unf. b. chem. Arb._, I, S. 23, und II, S. 45; Rambousek, -‘Gewerbekrankh. in Böhmen,’ _Concordia_ 1910, Heft 6, und _Amtsarzt_ -1910, Heft 7. - - -SULPHURIC ACID AND SULPHUR DIOXIDE - -Ogata, _Arch. f. Hyg._, Bd. 2; Lehmann, _Arch. f. Hyg._, Bd. 18, S. 180 -ff; Klocke ‘(SO₂-Vergiftung und O-Inhal.),’ _Zeitschr. f. Gew.-Hyg._ -1906, S. 562 und 617; ‘SO₂-Absorption beim Atemprozess,’ Chem. Ztg. -1909, S. 246; ‘Tod durch Einatmung von Schwefelsäuredampf,’ _Zeitschr. -f. Gew.-Hyg._ 1907, S. 430; ‘Schwefel-dioxydvergiftung in England,’ -_Concordia_ 1909, Heft 5, S. 105; ‘Schwefels.-Vergiftung, _Chem. Ind._ -1909 _(Ber. d. Berufsgen. f. chem. Ind. pro_ 1908, S. 26); Egli, _Unf. b. -chem. Arb._, ii, S. 52. - - -NITRIC ACID AND NITROUS FUMES - -‘Verg. durch nitrose Gase in einer Zellulosefabrik,’ _Zeitschr. f. -Gew.-Hyg._ 1908 Heft 24, S. 565; ‘Behandlung von Nitrosevergiftungen -durch Sauerstoffinhalationen,’ _Zeitschr. f. Gew.-Hyg._ 1908, Heft 20, S. -560; ‘Behandlung durch Chloroform,’ _Zeitschr. f. Gew.-Hyg._ 1904, Heft -10, S. 226, und 1907, Heft 8, S. 183; ‘Vergiftungen durch nitrose Gase -(Zusammenfassung),’ Holtzmann, _Concordia_, 1908, Nr. 23, S. 498. - - -CHLORINE, BROMINE, AND IODINE - -Leymann, _Arch. f. Hyg._, Bd. 7, S. 231; Binz, _Arch. f. exp. Path._, -Bd. 13; _Vierteljahrsschr. f. ger. Med._ 1888, S. 345; Lehmann, _Arch. -f. Hyg._, Bd. 34, S. 302, und _Arch. f. Hyg._, Bd. 17, S. 336; _Arch. f. -exp. Path. u. Ph._ 1887, S. 231; Egli, _Unf. b. chem. Arb._, II, S. 51; -Chlorverg., _Chem. Ind._ 1907, S. 347, 1908, S. 325; Neisser, _Intern. -Uebers. über Gew.-Hyg._, I, S. 94; ‘Chlorverg. in England,’ _Concordia_ -1909, S. 105. - -_Literatur Über Chlorakne._—Herxheimer, _Münchn. med. Wochenschr._ 1899 -S. 278; Bettmann, _D. med. Wochenschr._ 1901, S. 437; Lehmann, _Arch. -f. Dermatol._ 1905, S. 323; Leymann, ‘Erk.-Verh. der chem. Grossind.,’ -_Concordia_ 1906, Nr. 7-9; Holtzmann, _D. Vierteljahrsschr. f. öffentl. -Ges.-Pfl._ 1907, Bd. 39, S. 258. - - -CHLORIDES OF PHOSPHORUS - -Vaubel, _Chem. Ztg._ 1903; Leymann, _Concordia_ 1906, Nr. 7; Egli, _Unf. -b. chem.-Arb._ 1902, S. 49; Rumpf, _D. med. Wochenschr._ 1908, Bd. 34, S. -1331. - - -CHLORIDE OF SULPHUR - -Lehmann, _Arch. f. Hyg._ 1894, Bd. 20, S. 26; Leymann, _Concordia_ 1906, -Heft 7. - - -AMMONIA - -Lehmann, ‘Verauche über die Wirkung,’ _Arch. f. Hyg._, Bd. 5; ‘Vers. -über die Resorption,’ _Arch. f. Hyg._, Bd. 17 u. 67; ‘Versuche über die -Gewöhnung,’ _Arch. f. Hyg._, Bd. 34; Lewin, ‘Tödl. Ammoniakverg. in -einer chem. Fabrik, Berl. klin. Wochenschr. 1908; ‘Tödl. Ammoniakverg.,’ -_Zeitschr. f. Gew.-Hyg._ 1909, Wr. 9, S. 242; ‘Ammoniakverg. in der -Kälte-Ind.’ - - -LEAD POISONING - -‘Vorkommen der Bleivergiftung. Bleierkrankungen in der Bleihütte -Braubach,’ _Zeitschr. f. Gew.-Hyg._ 1909, S. 291; _Bleivergiftungen -in gewerbl. u hüttenmänn. Betrieben_ (_Oesterreichs_), herausgegeben -vom k. k. Arbeitsstat. Amt: I. Erhebungen in Blei- und Zinkhütten; -II. Erhebungen in Bleiweiss- und Bleioxydfabriken; III. Expertise, -betreffend die Blei- und Zinkhütten; IV. Expertise, betreffend die -Bleiweiss- und Bleioxydfabriken; V. Erhebungen in Farbenfabriken und -Betrieben mit Anstreicher-, Lackierer- und Malerarbeiten; VI. Expertise -hierzu; VII. Erhebungen und Expertise in Buch- und Steindruckereien -und Schriftgisseereien (alle Teile erschienen bei Alfr. Hölder, Wien -1905-1909). Frey, _Zinkgewinnung im oberschles. Industriebezirk_, -Berlin 1907, Verlag Hirschwald; Leymann, _Die Bekämpfung der Bleigefahr -in der Industrie_, Verlag Fischer, Jena 1908; Müller, _Die Bekämpfung -der Bleigefahr in Bleihütten_, Verlag Fischer, Jena 1908; Wächter, -_Die gewerbl. Bleiverg. im Deutschen Reich_, Verlag Braun, Karlsruhe -1908; Chyzer, _Les intoxications par le plomb se présentant dans la -céramiquen en Hongrie_, Schmidl, Budapest 1908; Kaup, _Bleiverg. in der -keramischen Ind._, als Manuskript gedruckt, D. Sekt. Ges. f. Soziale -Reform; Teleky, ‘Beitrag z. H. d. Erzeug. v. ord. Töpferware usw. in -Oesterr.,’ _Arbeiterschutz_, 1908, Nr. 19, 20; De Vooys, _Bleiverg. in -der niederl. keram. Ind._ (Nederl. Vereen. voor wettelijke Beseherming -van arbeiders 1908); Kaup, _Bleiverg. in österr. Gew.-Betrieben_, -Schriften des österr. Vereines für Arbeiterschutz 1902, Heft 3; -Sommerfeld, ‘Zur Bleiweissfrage,’ _Soz. Praxis_ 1902, Nr. 8; Friedinger, -‘Sanit. Verh. in d. Buchdr.,’ _Soz. Praxis_ 1902, Nr. 9; Wutzdorff, -_Bleiverg. in Zinkhütten_, Arb. a. d. Kais. Ges.-Amte, Bd. 17, S. 441; -Blum, _Unters. über Bleiverg._, Frankfurt a.M. 1900, _Vierteljahrsschr. -f. öffentl. Ges.-Pfl._, Suppl. 32, S. 630; Panwitz, _Bleiverg. in -Buchdruckereien_, Veröff. d. Kais. Ges.-Amtes 1897, S. 503; Teleky, -‘Bleiverg. bei Fransenknüpferinnen,’ Ref. _Zeitschr. f. Gew.-Hyg._ 1907, -Nr. 1, S. 13; ’ Bleierkrankung und Bekämpfung ders., Literatursammlung,’ -_Zeitschr. f. Gew.-Hyg._ 1904, Nr. 6, S. 131; Teleky, ‘Die gewerbl. -Bleiverg. in Oesterreich,’ _Soz. Techn._ 1909, Nr. 17, S. 333; Bleiverg. -(Legge), Verh. d. II. Intern. Kongr. f. Gewerbekrankh. in Brüssel 1910; -Bleiverg. in Böhmen (Rambousek), Concordia 1910, Nr. 7, Amtsarzt 1910, -Nr. 6; Abelsdorff, Statistik d. Bleiverg., Concordia 1910, Heft 17, S. -359; Wutzdorff, ‘Bleiverg. in Akkumulatoreniabr.,’ _Arb. a. d. Kais. -Ges.-Amte_ 1898, Bd. 15, S. 154; Rasch, ‘Ueber Bleiverg. d. Arb. in -Kachelfabr.,’ _Arb. a. d. kais. Ges.-Amte_ 1898, Bd. 14, S. 81. - - -GENERAL LITERATURE ON PATHOLOGY AND TREATMENT OF LEAD POISONING - -Jores, ‘Die allg. pathol. Anatomie der chron. Bleiverg. des Kaninchens,’ -_Beiträge z. path. Anat. u. allg. Path._ 1902, Bd. 31, S. 183; Glibert, -_Le saturnisme experimental, extrait d. rapp. ann. de l’insp. du travail -en 1906_, Bruxelles, 1907. Rambousek, ‘Die Pathol. d. Bleiverg.’ in -Leymann’s _Bekämpfung d. Bleigef._, S. 15, Velag Fischer, Jena 1908; -_Die Verhütung d. Bleigefahr_, Verlag Hartleben 1908; Blum, ‘Unters. -über Bleiverg., Frankfurt a.M. 1900,’ _Vierteljahrsschr. f. öffentl -Ges.-Pfl._, Suppl. 32, S. 630; Elschnig, ‘Sehstörungen b. Bleiverg.,’ -Ges. d. Aerzte, Wien, Sitzung v. 15. April 1898, und _Wiener med. -Wochenschr._ 1898, S. 1305; ‘Neuere Forschungen über Bleiverg.,’ -_Zeitschr. f. Gew.-Hyg._ 1909, S. 629; Seeligmüller, ‘Einfl. d. Bleies -auf den Frauenorganismus usw.,’ _Berl. klin. Wochenschr._ 1901, S. 842; -Bernhardt, ‘Zur Pathol. d. Bleilähmung,’ _Berl. klin. Wochenschr._ -1900, S. 26; Rambousek, ‘Die Bleierkrankung,’ _Zeitschr. f. ärztl. -Fortbildung_ 1909, Nr. 7; Israel, ‘Obd.-Befund b. Bleiverg.,’ _Berl. -klin. Wochenschr._ 1895, S. 575; Gumpertz, Bernhardt, ‘Anom. d. elektr. -Erregb. b. Bleiverg.,’ _Berl. klin. Wochenschr._ 1894, S. 372 u. S. -284; Jolly, ‘Sekt.-Befund b. Bleilänmung, Entart. d. Gangl.,’ _Berl. -klin. Wochenschr._ 1893; Miura, ‘Ueber die Bedeutung des Bleinachweises -auf der Haut Bleikranker,’ _Berl. klin. Wochenschr._ 1890, S. 1005; -Mattirolo, ‘Behandlung d. Bleikolik mit Erythroltetranitrat,’ _Wiener -med. Presse_ 1901, _Wiener med. Wochenschr._ 1901, S. 2171; Oddo und -Silbert, ‘Ausscheidung des Bleis,’ _Revue med._ 1892, Nr. 4, und _Wiener -med. Presse_ 1892, S. 1182; Mosse, ‘Veränderungen d. Gangl. coeliac. bei -exper. Bleikolik,’ _Wiener klin. Wochenschr._ 1904, S. 935; Escherich, -‘Zwei Fälle v. Bleilähmung b. Kindern (Peroneuslähmung.),’ _Wiener klin. -Wochenschr._ 1903, S. 229; Variot, ‘Ein Fall v. Bleilähmung b. einem -Kinde (Peroneuslähmung),’ _Gaz. des Hôp._ 1902, S. 482, und _Wiener klin. -Wochenschr._ 1902; Sorgo, ‘Progress. Muskelatrophie nach Bleiverg.,’ -_Weiner med. Wochenschr._ 1902, S. 919; Variot, ‘Bleiverg. b. einem -Kinde, Parese d. unt. Extrem.,’ _Wiener med. Wochenschr._ 1902, S. 2056; -Rome, ‘Bleiverg. b. Kindern,’ _La trib. med._ 1902, Nr. 39, und _Wiener -med. Wochenschr._ 1902, S. 2391; Layal, Laurencon, Rousel, ‘Erscheinungen -der Pylorusstenose b. Bleiverg.,’ _Wiener med. Wochenschr._ 1897; -Macfairlain, ‘Chloroformbehandlung bei Bleikolik,’ _Wiener med. -Wochenschr._ 1895; Bechtold, ‘Spast. Spinalparalyse b. Bleiverg.,’ _Med. -chir. Zentralbl._ 1904, Nr. 40; Oliver, ‘Lead-poisoning, &c.,’ _Lancet_, -1891, S. 530; Heymann, ‘Lähmungen d. Kehlkopfmuskeln b. Bleiverg.,’ -_Arch. f. Laringol._ 1896, S. 256; Clayton, ‘Ind. lead-poisoning,’ -_Brit. med. journ._ 1906, S. 310; Taylor, ‘Bleiamblyopie,’ _Lancet_ -1898, S. 742; Seeligmüller, ‘Zur Pathol. d. chron. Bleiverg.,’ _D. -med. Wochenschr._ 1902, S. 317; Lewin, ‘Puls b. Bleiverg.,’ _D. med. -Wochenschr._ 1897, S. 177; Walko, ‘Erkr. d. Magens b. chron. Bleiverg.,’ -_Münchn. med. Wochenschr._ 1907, S. 1728; Tielemanns, _Parotiserkr. -b. Bleiverg._, Monogr., Paris 1895; Borgen, ‘Blutdruckbestimmungen b. -Bleikolik,’ _D. Arch. f. klin. Med._ 1895, S. 248; Klieneberger, ‘Intox. -saturn. und Nephritis sat.,’ _München. med. Wochenschr._ 1904, S. 340; -Bach, ‘Augenerkr. b. Bleiverg.,’ _Arch. f. Augenheilk._ 1893, S. 218; -Redlich, ‘Tabes und chron. Bleiverg.,’ _Wiener med. Wochenschr._ 1897, -S. 801; Seifert, ‘Kehlkopfmuskellähmung b. Bleiverg.,’ _Berl. klin. -Wochenschr._ 1884, S. 555. - - -LITERATURE ON BLOOD CHANGES IN LEAD POISONING - -Schmidt, ‘Die Bleiverg. und ihre Erkennung,’ _Arch. f. Hyg._ 1907, Bd. -63, Heft 1; Galperin-Teytelmann, _Die basophilen Granula der roten Blutk. -b. Bleairbeitern, Ing. Diss._, Bonn 1908; Carozzi, _Reperti ematol. e -loro valore statistico nel saturn. prof. Corr. sanitar._ 1909, Bd. 20, -Nr. 5 u. 6; Gilbert, _Le saturnisme exp._, Bruxelles, 1907; Rambousek, -‘Beitrag z. Pathol. d. Stoffw. und d. Blutes b. Bleiverg., _Zeitschr. f. -exp. Path. und Therap._ 1910, Bd. 7; Moritz, ‘Beziehungen der basophilen -Granula zu den Erythrozyten,’ _Münchn. med. Wochenschr._ 1901, Nr. 5; -_St. Petersburger med. Wochenschr._ 1901, Nr. 26, 1903, Nr. 50; _Verh. d. -I. Intern. Kongr. f. Arb.-Krankh. in Mailand_ 1906, _Atti del congresso_, -S. 601-607; Trautmann, ‘Blutunters. b. Bleiverg.,’ _Münchn. med. -Wochenschr._ 1909, S. 1371; Grawitz,’Ueber die körn. Degenerat. d. roten -Blutkörperchen,’ _D. med. Wochenschr._ 1899, Nr. 44; ‘Die klin. Bedeutung -und exp. Erzeugung körn. Degener. in den roten Blutkörperchen,’ _Berl. -klin. Wochenschr._ 1900, Nr. 9; Hamel, ‘Ueber die Beziehungen der körn. -Degener. der roten Blutkörperchen zu den sonst. morph. Veränd. des Blutes -mit besonderer Berücks. d. Bleiintox.,’ _D. Arch. f. klin. Med._ 1900, -Bd. 67; Frey, ‘Beitrag zur Frühdiagnose v. chron. Bleiverg.,’ _D. med. -Wochenschr._ 1907, Nr. 6; Grawitz, _Klin. Pathol. des Blutes_, Leipzig -1906, S. 120 ff.; Naegeli, ‘Ueber die Entstehung der basoph. gek. roten -Blutk.,’ _München. med. Wochenschr._ 1904, Nr. 5; Schmidt, ‘Zur Frage -d. Entstehung d. basoph. Körner,’ _D. med. Wochenschr._ 1902, Nr. 44; -_Exp. Beiträge z. Pathol. d. Blutes_, Jena 1902; ‘Ein Beitrag. z. Frage -d. Blutregen.,’ _Münchn. med. Wochenschr._ 1903, Nr. 13; Erben, ‘Chem. -Zusammensetzung d. Blutes b. Bleiverg.,’ _Zeitschr. f. Heilkunde_, 1905, -S. 477. - - -LITERATURE ON CHANGES IN METABOLISM IN LEAD POISONING - -Preti, ‘Beitrag z. Kenntn. d. Stickstoffums. b. Bleiverg.,’ 1909, -S. 411; Rambousek, ‘Beitrag z. Pathol. d. Stoffw. und d. Blutes,’ -_Zeitschr. f. exp. Path. und Ther._ 1910, Bd. 7; ‘Pathol. d. Bleiverg.’ -in Leymann’s _Bekämpfung d. Bleigefahr_, Fischer, Jena 1909; Minkowski, -_Die Gicht_, Wien, 1903, Holders Verlag.; Schittenhelm und Brugsch, ‘Zur -Stoffwechselpathol. d. Gicht,’ _Zeitschr. f. exp. Path. und Ther._, Bd. -4, S. 494-495. - - -LITERATURE ON TOXICITY OF VARIOUS LEAD COMPOUNDS - -Blum, ‘Unters. über Bleiverg., Frankfurt a. M. 1900,’ _Vierteljahrsschr. -f. öffentl. Ges.-Pfl._, Suppl. 32, S. 630; Rambousek, _Die Verhütung der -Bleigefahr_, Verlag Hartleben 1908; Biondi und Rambousek, ‘Polemik über -die Ungiftigkeit d. Bleisulfids,’ _I. Intern. Kongr. f. Gew.-Krankh. in -Mailand_ 1906, _Atti del congresso_, S. 617-622; Lehmann, ‘Hyg. Unters. -über Bleichromat,’ _Arch. f. Hyg._ 1893, Bd. 16, S. 315. - - -ZINC - -Schlockow, ‘Ueber ein eigenartiges Rückenmarksleiden bei -Zinkhüttenarbeitern,’ _D. med. Wochenschr._ 1879, S. 208; Tracinsky, ‘Die -oberschlesische Zinkindustrie usw.,’ _D. Vierteljahrsschr. f. öffentl. -Ges.-Pfl._ 1888, Bd. 20, S. 59; Seiffert, ‘Erkr. d. Zinkhüttenarb. usw.,’ -_ibidem_ 1897, Bd. 31, S. 419; Lehmann, ‘Beiträge z. hygien. Bedeutung -d. Zinks,’ _Arch. f. Hyg._ 1897, Bd. 28, S. 300; Neuere Arbeiten: Frey, -_Die Zinkgew. im oberschl. Industriebez.-usw._,’ Verlag Hirschwald-Berlin -1907 und _Zeitschr. f. Gew.-Hyg._ 1907, Nr. 16, S. 376; Sigel, ‘Das -Giesserfieber u. seine Bekämpfung,’ _Vierteljahrsschr. f. ger. Med._ -1906, Bd. 32, S. 173; Lehmann, ‘Giess- oder Zinkfieber,’ _Arch. f. Hyg._ -1910, Bd. 72, S. 358. - - -MERCURY - -Schönlank, _Fürther Spiegelfabriken_ 1888 (Monogr.); Wollner, -‘Quecksilberspiegelfabrik in Fürth,’ _Vierteljahrsschr. f. öffentl. -Ges.-Pfl._, Bd. 19, 3, S. 421, und _Münchn. med. Wochenschr._ 1892, Bd. -39, S. 533; Stickler, ‘Hutfabrikation, 1886,’ _Revue d’Hygiène_, VIII, S. -632; Charpentier, ‘Spiegelfabrik,’ _Annal. d’hyg. publ._, avril 1885, S. -323; Henke, _Quecksilberverg. in Hutfabriken_, Knauer, Frankfurt 1889; -Wittzack, ‘Quecksilberverg. b. d. Spiegelbel. usw.,’ _Vierteljahrsschr. -f. öffentl. Ges.-Pfl._ 1896, S. 216; Donath, ‘Quecksilberverg. in -Gluhlampenfabriken,’ _Wiener med. Wochenschr._ 1894, 8. 888; Renk, -’ Quecksilberverarbeitung,’ Arb. a. d. Kais. Ges.-Amte, Bd. 5, Heft -I; Letulle, ‘Hasenhaarschneiderei,’ _Revue d’Hyg._, XI, S. 40; Ueber -Hasenfellbeize, _Zeitschr. f. Gew.-Hyg._ 1909, S. 821; _Sozialtechn._ -1910, S. 39; ‘Quecksilberverg. in d. Glühlampenind.,’ _Zeitschr. -f. Gew.-Hyg._ 1908, S. 469; ‘Quecksilberverg. in Amiata in Italien -(ausführliche Schilderung der Symptome schwerer Quecksilberverg.),’ -Giglioli, im _Ramazzini_ 1909, Bd. 3, S. 230, und ‘Demonstration am -II. Ital. Kongr. f. Arbeiterkrankh. in Florenz 1909,’ ref. _Zeitschr. -f. Gew.-Hyg._ 1909, S. 289, und _Chem. Ztg._, Repert., 1909, S. 411; -‘Quecksilberverg. in Hutfabriken in Italien,’ _Ramazzini_, 1909, S. 230; -Laureck, in Weyls _Handb. d. Arb.-Krankh._ 1909, S. 62. - - -MANGANESE - -Couper, _Journ. de chim._, 1837, Bd. 3, S. 2; Jaksch, _Münchn. med. -Wochenschr._ 1901, S. 602; Embden, _D. med. Wochenschr._, Bd. 27, -S. 795, u. _Münchn. med. Wochenschr._ 1901, S. 1852; Jaksch, ‘Ueber -Manganintoxikationen u. Manganophobie,’ _Münchn. med. Wochenschr._ 1907, -Bd. 54, S. 969; Hauck, ‘Manganismus.’ Vortrag auf dem XIV. Intern. Kongr. -f. Hyg. u. Dem., Berlin 1907, Bd. 4, S. 337; Friedel, D. med. Wochenschr. -1909, S. 1292. - - -CHROMIUM - -Delpech et Hillaret, _Annal. d’Hyg. publ._ 1876; Viron, _Contrib. à -l’étude phys. et tox. de quelques prép. chromés_, Paris, 1885; Burghardt, -‘Chromverg. in der Zündhölzchenindustrie,’ _Charité Annalen_, XXIII, -1898, S. 189; Wutzdorff, ‘Die in den Chromatfabriken beobachteten -Gesundheits-schädigungen.’ - - -NICKEL - -Nickelkrätze: ‘Jahresberichte d. preuss. Reg.- u. Gewerberäte für das -Jahr 1907,’ _Zeitschr. f. Gew.-Hyg._ 1908, Nr. 8, S. 185, u. 1909, Nr. -14, S. 374; Klocke, _Soz. Med. u. Hyg._ 1910, Bd. 5, Nr. 2. - - -NICKEL CARBONYL - -H. W. Armit: _Journ. of Hygiene_, 1907, p. 524, and 1908, p. 565; Vahlen, -_Arch. exp. Pathol. u. Ph._ 1902, Bd. 48, S. 117; Mittasch, _Arch. f. -exp. Path._ 1903, Bd. 49, S. 367; Langlois, _Compt. rend. de la soc. de -Biol._ 1891, S. 212. - - -SILVER (ARGYRIA) - -Schubert, ‘Argyrie bei Glasperlenversilberern,’ _Zeitschr. f. Heilk._ -1895, Bd. 16, S. 341; Lewin, ‘Lokale Gewerbeargyrie,’ _Berl. klin. -Wochenschr._ 1886, S. 417; Blaschko, _Arch. f. mikr. Anatomie_, Bd. 27, -S. 651. - - -ARSENIC - -‘Arsenverg. in der Delainage,’ _Zeitschr. f. Gew.-Hyg._ 1906, Nr. 3, S. -71; ‘Arsenikverg. in der Ind.,’ _Zeitschr. f. Gew.-Hyg._ 1907, S. 353, -und 1903, S. 476; ‘Arsenikverg. in England, nach den Ber. der engl. -Gew.-Insp.,’ _Concordia_ 1909, Nr. 5, S. 105; Egli, _Unf. b. chem. Arb._, -II, S. 51. - - -PHOSPHORUS - -Lorinser, _Med. Jahrb. d. österr. Staates_, 1845, Bd. 51, S. 257; und -_Zeitschr. d. Gesellsch. d. Aerzte in Wien_, 1851, Bd. 55, S. 22; -Geist u. Bibra, _Die Krankh. d. Arb. in der Phosphorzündholzfabrik_, -Erlangen 1847; Wegner, _Virch.-Arch._ 1872, Bd. 55, S. 11; Magitot, -_Revue d’Hygiène_, 1895, Bd. 17, S. 201; Kollin, ‘Oberkiefernekrose,’ -_Zentralbl. f. inn. Med._ 1889, S. 1279; Dearden, ‘Osseous fragilit. am. -workers in luc. match fet.,’ _Brit. Med. Journ._ 1899, S. 92; Lévai, -‘Ueber Phosphornekrose,’ _Wiener klin. Rundsch._ 1900, S. 33; ‘Ein Fall -von Phosphornekrose 19 Jahre nach der Arbeit in Zündhölzchenfabriken,’ -_Wiener klin. Rundsch._ 1896, Nr. 29, S. 503; Stockman, _Brit. Med. -Journ._ 1899; Stubenrauch, _Arch. f. klin. Chir._ 1899, Heft 1, und -_Samml. klin. Vortr._ 1901, Nr. 303; Röpke, _Zeitschr. d. Zentralst. -f. Arb.-Wohlf.-Einr._ 1901, Nr. 1; ‘Phosphorverg. in England (nach den -Berichten der engl. Gew.-Insp.),’ _Concordia_, 1909, Nr. 5, S. 105; -Teleky, ‘Die Phosphornekrose in Oesterreich,’ _Schriften der Oesterr. -Gesellsch. f. Arbeiterschutz_, Heft 12, Verlag Deuticke 1907; Friedrich, -‘Die Phosphorverg. in Ungarn’ (in ungar. Sprache), _Schriften der Ungar. -Gesellsch. f. Arbeiterschutz_, Heft 4, Budapest 1908. - - -PHOSPHORETTED HYDROGEN - -Schulz, _Arch. f. exp. Path. u. Phys._ 1890, Bd. 27, S. 314; Dietz, -‘Phosphorwasserstoffverg. bei einem Phosphorfabrikarb.,’ _Arch. f. Hyg._ -1904, Bd. 49. - -Spezielle Literatur über Phosphorwasserstoffvergiftung durch -Ferrosilizium: Bahr, Lehnkering, ‘Phosphorverg. durch Ferrosiliz.,’ -_Vierteljahrsschr. f. ger. Med._ 1906, S. 123; _Jahresber. d. engl. -Gew.-Insp. f. d. J._ 1907 (vgl. _Soz. Techn._ 1908, Bd. 7, S. 689 und -690); Oliver, _Diseases of Occupation_, 1908; H. Le Chatelier, _Ann. -Min._ 1909, Bd. 15, S. 213; vgl. ferner _Zeitschr. f. Gew.-Hyg._ 1908, S. -574, und S. 181. - - -HYDROGEN SULPHIDE - -Lehmann, ‘Exp. Studien über Schwefelw.,’ _Arch f. Hyg._, Bd. 14, -S. 142; ‘Gewöhnung an Schwefelw.,’ _ibidem_, Bd. 34, S. 303; -‘Absorption von Schwefelw.,’ _ibidem_, Bd. 17, S. 332; Blumenstock, -‘Lehre von der Verg. mit Kloakengasen,’ _Vierteljahrsschr. f. ger. -Med._ 1873, Bd. 18, S. 295; Kasper, ‘Massenverg. mit Kloakengas,’ -_Vierteljahrsschr. f. ger. Med._, Bd. 2, S. 593; Römer, ‘Akute tödl. -Schwefelwasserstoffverg.,’ _Münchn. med. Wochenschr._ 1897, S. 851; -Oliver, dieselbe, _Lancet_, 1903, S. 225; ‘Schwefelwasserstoffverg. -bei der Saturation v. Schwefelbarium,’ _Ber. d. Berufsgen. f. Chem. -Ind._ 1907, _Chem. Ind._ 1908, S. 323; ‘Schwefelwasserstoffverg. in -einer Fabrik auf Ammoniaksalze’; Egli, _Unf. b. chem. Arb._, II, S. 46; -‘Schwefelwasserstoffverg. in England, Ber. d. engl. Gew.-Insp.,’ siehe -_Concordia_, 1909, S. 105; ‘Schwefelwasserstoffverg. in d. chem. Ind.,’ -_Techn. gewerbl. Ratgeber_ 1906, S. 108; ‘Schwefelwasserstoffverg. und -Sauerstoffinhalation,’ _Zeitschr. f. Gew.-Hyg._ 1906, S. 587; ‘Erste -Hilfe bei Schwefelwasserstoffverg.,’ _Zeitschr. f. Gew.-Hyg._ 1908, S. -455, auch _Chem Ind._ 1908, S. 327. - - -CARBON BISULPHIDE - -Delpech, ‘Accidents qui développent chez les ouvriers en caoutchouc et -du sulfure de carbone etc.,’ _L’Union méd._ 1876, No. 66; ‘Nouvelles -recherches sur l’intox. du _CS_₂ etc.,’ _Ann. d’Hyg. publ._ Nr. 37; -Sapelier, ‘Étude sur le sulfure de carbone,’ Thèse, Paris 1885; -Rosenblatt, _Ueber die Wirkung v. CS₂-Dämpfen auf den Menschen_, Diss. -Würzburg 1890; Pichler, _Ein Beitrag z. Kenntn. d. akuten CS₂-Verg._, -Berlin 1897 (Fischer); Lehmann, ‘Exp. Stud. über Schwefelk.,’ _Arch. -f. Hyg._ 1894, Bd. 20, S. 56 ff.; _Zeitschr. f. Gew.-Hyg._ 1899, -‘Schutzmassregeln der Kautschukindustrie in England’; Laudenheimer, -_Schwefelk.-Verg. d. Gummiarb._ 899, Leipzig, Veit & Comp.; Harmsen, ‘Die -Schwefelk. im Fabr. Betrieb,’ _Vierteljahrsschr. f. ger. Med._ 1905, -S. 149; Riegler, ‘Die nervösen Störungen bei CS₂-Verg.,’ _Zeitschr. f. -Nervenh._ 1907, Bd. 33; Roth, ‘Gewerbl. CS₂-Verg. usw.,’ _Berl. klin. -Wochenschr._ 1901, S. 570; Reiner, ‘Schwefelk.-Amblyopie,’ _Wiener klin -Wochenschr._ 1895, S. 919; Quensel, ‘Geistesstörungen nach CS₂-Verg.,’ -_Monatsh. f. Psych._ 1905, Bd. 16. - - -CYANOGEN AND CYANOGEN COMPOUNDS (PRUSSIC ACID, &C.) - -Merzbach, ‘Chron. Zyanverg. bei einem Galvaniseur,’ _Hyg. Rundsch._ -1899, Nr. 1; Pfeiffer, ‘Zyanverg. d. Kanalgase (Abgänge v. d. -Zyangewinnung),’ _Vierteljahrsschr. f. öffentl. Ges.-Pfl._ 1904; -Stritt, ‘Verg. d. Zyanverb. im Düngemittel,’ _Zeitschr. f. Hyg._ 1909, -Bd. 62, S. 169; Tatham, ‘Zyanverg. beim Reinigen v. Goldspitzen,’ -_Brit. Med. Journ._ 1884, S. 409; Kockel, ‘Blausäureverg. bei einem -Zelluloidbrand,’ _Vierteljahrsschr. f. ger. Med._ 1903, S. 1; ‘Zyanverg. -u. Sauerstoffinhal.’ (Brat), _Zeitschr. f. Gew.-Hyg._ 1906, S. 588; -Lehmann, ‘Ueber die Gift. d. gasförm. Blausäure (Giftigkeitsgrenzen),’ -_Berl. klin. Wochenschr._ 1903, S. 918; Blaschko, ‘Berufsdermatosen d. -Arb. (Hautleiden b. Verwendung v. Zyaniden),’ _D. med. Wochenschr_, 1889, -S. 915; MacKelway s. (Hautleiden), _Amer. Journ. of Medic. Science_, -1905, S. 684; Wilkes (ditto), _Lancet_, 1904, S. 1058. - - -ARSENIURETTED HYDROGEN GAS - -‘Arsenwasserstoffverg. (Verfertigen v. Kinderballons),’ _Zeitschr. -f. Gew.-Hyg._ 1902, S. 441; ‘Arsenwasserstoffverg. (Ausleeren eines -Schwefelsäuretanks),’ _Gewerbl. techn. Ratgeber_ 1906, S. 109; -‘Arsenwasserstoffverg. im Hüttenbetriebe (_O_-Inhalation),’ _Zeitschr. f. -Gew.-Hyg._ 1906, S. 589 u. S. 617; ‘Arsenwasserstoffverg.,’ _Zeitschr. -f. Gew.-Hyg._ 1908, S. 263, u. 1910, S. 179; ‘Arsenwasserstoffverg. in -England, nach den Ber. d. engl. Gew.-Insp.,’ _Concordia 1909_, S. 105; -Egli, ‘Arsenwasserstoffverg.,’ _Unf. b. chem. Arb._, II, S. 42; Lunge, -‘Arsenwasserstoffverg. beim Löten,’ _Chem.-Ztg._ 1904, S. 1169; Barié, -‘Arsenwasserstoffverg. durch Ballongas,’ _Arch. f. krim. Anthrop._ 1906, -S. 147. - - -CARBONIC OXIDE - -_General Literature on CO-Poisoning._—Becker, ‘Die _CO_-Verg. u. ihre -Verhütung,’ _Vierteljahrsschr. f. ger. Med._ 1893, S. 349; Greiff, -‘_CO_-Verg. bei d. Teerdestill., _Vierteljahrsschr. f. ger._ Med. 1890, -S. 359; Brouardel, ‘_CO_-Verg. d. Kalkofengase,’ _Ann. d’Hyg. publ._ -1840; Becker, ‘Nachkrankheiten d. _CO_-Verg.,’ _D. med. Wochenschr._ -1893, S. 571; Reinhold, ‘Chron. _CO_-Verg.,’ _Münchn. med. Wochenschr._ -1904, S. 793; ‘_CO_-Verg. beim Sengen des Garnes,’ _Zeitschr. f. -Gew.-Hyg._ 1909, S. 267. - -_Literature on CO-Poisoning in Gas Works._—Jehle, ‘Hyg. d. Gasarbeiter,’ -_Zeitschr. f. Gew.-Hyg._ 1901, Heft 14 u. 15, S. 245 ff.; Schütte, -‘Krankh. d. Gasarb.,’ Weyls _Arbeiterkrankh._ 1908, S. 239 ff.; -Rambousek, _Concordia 1910_, Nr. 6. - - -CARBON OXYCHLORIDE (PHOSGENE GAS) - -‘Tödl. Verg. d. Phosgen in einer Farbenfabrik,’ _Jahresber. d. Berufsgen. -f. d. Chem. Ind._ 1905, vgl. _Gewerbl. techn. Ratgeber_, 1906, S. 108; -Klocke, ‘Mehrere gewerbl. Phosgenverg.,’ _Zeitschr. f. Gew.-Hyg._ 1906; -Sury-Bienz, ‘B. z. Kasuistik d. Intox.,’ _Vierteljahrsschr. f. ger. Med._ -1907, S. 251; Müller, _Zeitschr. f. angew Chemie_, Bd. 13 (Heft v. 12. -Aug. 1910). - - -CARBON DIOXIDE - -‘Kohlensäureverg. b. d. Kesselreinigung,’ _Zeitschr. f. Gew.-Hyg._ -1906, S. 129; Kohlensäureverg. und _O_-Inhalation,’ ebenda 1906, -S. 589; Lehmann, ‘Unters. über die langdauernde Wirkung mittlerer -Kohlensäuremengen auf den Menschen,’ _Arch. f. Hyg._ 1900, S. 335. - - -PETROLEUM, BENZINE, &C. - -_Petroleumvergiftung._—Borthenson, ‘Die Naphthaind. in sanit. Beziehung,’ -Vortrag auf dem XII. Intern. Aerztekongr. in Moskau 1897 u. _D. -Vierteljahrsschr. f. öffentl. Ges.-Pfl._ 1898, Bd. 30, S. 315; Burenin, -‘Die Naphtha u. i. Verarb. in sanit. Beziehung, Petersburg 1888; Lewin, -‘Ueber allg. und Hautverg. d. Petrol.,’ _Virchows Arch._ 1888, Bd. 112, -S. 35; Sharp, ‘The Poison Effects of Petrol.,’ _Med. News_, 1888; Samuel, -‘Verg. in Petroleumtanks,’ _Berl. klin. Wochenschr._, 1904, Bd. 41, S. -1047; Foulerton, ditto, _Lancet_ 1886, S. 149; Mabille, ditto, _Revue -d’Hyg._ Bd. 18, 1896, Nr. 3; _Ber. d. engl. Gew.-Insp._; vgl. _Concordia_ -1909, S. 105. - -_Skin diseases in Petroleum und Paraffinarbeiter._—Chevallier, _Ann. -d’Hyg._ 1864; Lewin, _Virchows Arch._ 1888 (siehe oben); Mitchell, _Med. -News_, Bd. 53, S. 152; Derville u. Guermonprez (Papillome), _Annal. -derm._ 1890, S. 369; Brémont, _Revue d’Hyg._ 1895, S. 166; Rambousek, -_Concordia_ 1910, Nr. 6. - -_Benzinvergiftung._—Dorendorf (b. Kautschukarb.), _Zeitschr. f. klin. -Med._ 1901, S. 42; Finlayson, _Brit. Med. Journ._ 1903, S. 546; Bürgi -(Verg. d. Autobenzin), _Korr. f. Schweiz. Aerzte_, 1906, Bd. 36, S. 350; -Box, _Brit. Med. Journ._ 1908, S. 807; _Zeitschr. f. Gew.-Hyg._ 1908, -S. 333, 1907, S. 157, und 1906, S. 515; Schäfer, ‘Verwendung u. schädl. -Wirkung einiger Kohlenwasserstoffe u. anderer Kohlenstoffverbindungen,’ -_Hamb. Gew.-Insp.-Arb. u. Sonderberichte_, 1909, S. 7. - - -BENZENE - -Benzolverg. b. d. Benzoldestill: _Zeitschr. f. angew. Chemie_, 1896, S. -675; _Chem. Ind._ 1906, S. 398; _Chem. Ztg._ 1910, S. 177. Benzolverg. -(Benzolextrakt.-Appar.): Egli, _Unf. b. chem. Arb._ 1903, S. 58; _Chem. -Ind._ 1907, S. 347; vgl. Lewin, _Münchn. med. Wochenschr._ 1907 und -_Zeitschr. f. Gew.-Hyg._ 1907, S. 581. Benzolverg. b. Reinigen von -Benzollagerkesseln: _Chem. Ind._ 1905, S. 444; 1907, S. 347; ferner 1909, -Nr. 14, Beil. S. 25. Benzolverg. in einer Gummifabrik: _Chem. Ind._ 1905, -S. 442. Benzolverg. bei d. Fabr. v. Antipyrin: Egli, _Unf. b. chem. -Arb._, I, 1903, S. 58. Benzolverg. d. Asphaltanstrichmasse: _Zeitschr. f. -Gew.-Hyg._ 1904, S. 292. Santesson, ‘Bensolverg. in einer Gummiw.-Fabrik. -(und exper. Untersuchungen),’ _Arch. f. Hyg._ 1897, Bd. 31, S. 336. -Rambousek, _Die gewerbl. Benzolverg. Bericht am II. Int. Kongr. f. -Gewerbekrankh. in Brüssel_ 1910. Wojciechowski, _Ueber die Giftigkeit -versch. Handelssorten des Benzols in Gasform_, Inaug.-Diss. Würzburg, -1910; Lehmann, ‘Aufnahme von Benzol aus der Luft durch Tier und Mensch,’ -_Arch. f. Hyg._ 1910, Heft 4; Sury Bienz, ‘Tödliche Benzolverg.,’ -_Vierteljahrsschr. f. ger. Med._ 1888, S. 138; Schaefer, ‘Verwendung u. -schädl. Wirkung einiger Kohlenw. u. anderer Kohlenstoffverbindungen,’ -_Hamb. Gew.-Insp., Arb. und Sonderberichte_, 1909. - - -HALOGEN SUBSTITUTION PRODUCTS OF THE ALIPHATIC HYDROCARBONS (NARCOTICS) - -Lehmann, ‘Aufnahme chlorierter Kohlenwasserstoffe aus der Luft durch -Mensch und Tier (Chloroform, Tetrachlorkohlenstoff, Tetrachloräthan),’ -_Arch. f. Hyg._ 1910, Bd. 72, Heft 4; Grandhomme, _Die Fabr. d. A.-G. -Farbwerke in Höchst a. M. in sanit. und soz. Beziehung_, 1893, 3 Aufl., -S. 88 (Jodmethylverg. b. d. Antipyrinbereitung); Jacquet, ‘Gewerbl. -Brom- und Jodmethylverg.,’ _D. Arch. f. klin. Med._ 1901, Bd. 71, S. -370; Schuler, ‘Gewerbl. Brommethylverg.,’ _D. Vierteljahrsschr. f. -öffentl. Ges.-Pfl._ 1899, Bd. 31, S. 696; Schaefer, ‘Verwendungsart u. -schädl. Wirkung einiger Kohlenwasserst. u. anderer Kohlenstoffverg.’ -(Tetrachlorkohlenstoff),’ _Ber. d. Hamburger Gewerbe-Inspektion_, 1909, -S. 11. - - -HALOGEN SUBSTITUTION PRODUCTS OF THE BENZENE SERIES (CHLORBENZENE, &C.). - -Leymann, ‘Erkr.-Verh. in einigen chem. Betr.,’ _Concordia_ 1906, Heft 7 -(Chlorbenzol, Benzoylchlorid); ‘Verg. mit Chlorbenzol, Nitrochlorbenzol -usw.,’ _Vierteljahrsschr. f. öffentl. Ges.-Pfl._ 1902, Suppl. S. 371, und -_Concordia_ 1902, Nr. 5; Mohr, ‘Chlorbenzolverg.,’ _D. med. Wochenschr._ -1902, S. 73. - - -HYDROXYL SUBSTITUTION PRODUCTS OF THE ALIPHATIC SERIES (ALCOHOLS) - -Pohl, ‘Wirkungen von Methylalkohol,’ _Arch. f. exp. Path._ 1893, S. 281; -Patillo u. Colbourn, ‘Gewerbl. Methylalkoholverg.,’ _Ophthalm. Rec._ -1899. - - -NITRO AND AMIDO DERIVATIVES OF BENZENE (NITROBENZENE, ANILINE, &C.) - -Leymann, ‘Erkr.-Verh. in einer Anilinfarbenfabrik,’ _Concordia_ 1910, -Heft 17, S. 355; Grandhomme, _Die Fabr. d. A.-G. Farbw. in Höchst. a. -M. in sanit. u. soz. Beziehung_, 1896 (und _Vierteljahrsschr. f. ger. -Med._ 1880); ‘Nitrobenzol- und Anilinverg., Vorschr. f. d. Verhalten,’ -_Zeitschr. f. Gew.-Hyg._ 1906, Nr. 22, S. 619; ‘Nitrobenzol (in -Mineralöl),’ _Zeitschr. f. Gew.-Hyg._ 1910, S. 159; Röhl, ‘Akute u. -chron. Verg. m. Nitrokörpern d. Benzolreihe,’ _Vierteljahrsschr. f. -ger. Med._ 1890, S. 202; Letheby, ditto, _Proceed. of the Roy. Soc. -London_, 1863, S. 550; Thompson, ditto, _British Med. Journ._ 1891, -S. 801; Friedländer, ‘Intox. m. Benzol- u. Toluolderivaten,’ _Neurol. -Zentralbl._ 1900; S. 294; ‘Nitrotoluolverg. in einer Sprengstoffabrik,’ -_Zeitschr. f. Gew.-Hyg._ 1908, S. 383; ‘Nitroxylolverg.,’ _Chem. -Ind._ 1905, S. 444; ‘Intox. m. Nitrokörpern. u. deren Behandl. m. -Sauerstoffinhal.,’ _Zeitschr. f. Gew.-Hyg._ 1906, S. 617; Brat, -‘Gew. Methämoglobinverg. u. deren Behandl. m. Sauerstoff,’ _D. med. -Wochenschr._ 1901, S. 296; Leymann, ‘Verg. m. Nitrobenzol, Nitrophenol, -Dinitrophenol, Nitrochlorbenzol, usw.,’ _Concordia_ 1902, Nr. 5; Schröder -und Strassmann (Verg. in Roburitfabriken), _Vierteljahrsschr. f. ger. -Med._, Suppl. 1891, S. 138; Brat, ‘Erkr. in einer Roburitfabrik,’ _D. -med. Wochenschr._ 1901, Nr. 19 und Nr. 20; ‘Verg. m. Dinitrobenzol -in England,’ _Concordia_ 1909, S. 105; Mohr, ‘Verg. m. Chlorbenzol, -_D. med. Wochenschr._ 1902, S. 73; Silex, ‘Augenschädigungen d. -Nitronaphthalin,’ _Zeitschr. f. Augenheilk._ 1902, S. 178; Häusermann -und Schmidt, ‘Gewerbl. Nitrobenzol- u. Anilinverg.,’ _Vierteljahrsschr. -f. ger. Med._ 1877, S. 307; ‘Gewerbl. Anilinverg.,’ _Zeitschr. f. -Gew.-Hyg._ 1909, S. 350 u. S. 602, 1908, S. 384, 1906, S. 455, S. 599, -S. 617 u. 619 (Behandlung), 1903, S. 133, 1902, S. 63; ‘Anilinverg. -in England,’ _Concordia_ 1909, S. 105; Hildebrandt, ‘Anilinderivate, -Giftwirkung (Intern. med. Kongr. Budapest 1909),’ _Chem. Ztg._ -1909, S. 997; Seyberth, ‘Blasengeschwülste d. Anilinarb.,’ _Münchn. -med. Wochenschr._ 1907, S. 1573; ‘Erhebungen über das Vorkommen von -Blasengeschwülsten bei Anilinarb.,’ _Zeitschr. für Gew.-Hyg._ 1910, S. -156; Rehn, ‘Blasengeschwülste bei Anilinarb.,’ _Arch. f. klin. Chir._ -1895, S. 588; Lewin, ‘Paranitranilinverg., Obergutachten,’ _Zeitschr. f. -Gew.-Hyg._ 1909, S. 597; Criegern, ‘Gewerbl. Paraphenylendiaminverg.,’ -XX. Kongr. f. inn. Medizin, Wiesbaden, 1902; Erdmann, Vahlen, ‘Wirkung -des Paraphenylendiamins,’ _Arch. f. exp. Path._ 1905, S. 401; Georgievics -(Wirkung d. Teerfarbstoffe), _Farbenchemie_, 1907, S. 13; Prosser White, -Researches into the Aromatic Compounds, _Lancet_, 1901, Case of Aniline -Poisoning, Intern. Cong. Brussels, 1910. - - -TURPENTINE - -Lehmann, ‘Beiträge z. Kenntn. d. Terpentinölwirkung,’ _Arch. f. Hyg._ -1899, S. 321; Reinhard, ‘Gewerbl. Terpentinintox.,’ _D. med. Wochenschr._ -1887, S. 256; Drescher, ‘Terpentindampfinh. tödl. Verg. eines Arb. beim -Innenanstrich eines Kessels,’ _Zeitschr. f. med. Beamte_ 1906, S. 131; -Schaefer, ‘Verwendungsart u. schädl. Wirkung einiger Kohlenwasserstoffe -u. and. Kohlenstoffverbind.,’ _Hamburger Gew.-Insp., Arbeiten und -Sonderabdrücke_, 1909, S. 9. - - -PYRIDENE - -Blaschko, ‘Möbelpoliererekzem,’ _D. med. Wochenschr._ 1890, S. 475. - - -TOBACCO, NICOTINE - -Jehle, ‘Gesundh. Verhältn. d. Tabakarb.,’ _Arch. f. Unf.-Heilk._ 1901, -ref. _Zeitschr. f. Gew.-Hyg._ 1901, S. 236; Rochs, ‘Einfluss d. Tabaks -auf die Gesundheitsverhältnisse d. Tabakarb.,’ _Vierteljahrsschr. f. ger. -Med._ 1889, S. 104. - - - - -PART III - -PREVENTIVE MEASURES - - -GENERAL MEASURES (NOTIFICATION, LISTS OF POISONOUS SUBSTANCES, &C.) - -Fischer, _Liste der gewerbl. Gifte_ (_Entwurf_), Frankfurt a. M. (als -Manuskript gedruckt), 1910; Sommerfeld, _Liste der gewerbl. Gifte_ -(_Entwurf_) Verlag Fischer, Jena, 1908; Carozzi, _Avvelenamenti ed -infezioni professionali_ (_gewerbl. Gifte und Infektionen_), Verlag -Fossati, Mailand, 1909; Rambousek, _IIᵉ Congrès int. des maladies prof. -Bruxelles_ 1910, S. 14; ‘Anzeigepflicht bei gewerbl. Erkrankungen,’ -Ber. über die Verh. d. Abt. f. Gewerbekrankh. auf der 36. Jahresvers. -der British med. Assoc. in Sheffield 1908, _Brit. Med. Journ._ 1908, S. -401-408 und 480-496; Rambousek, ‘Arbeiterschutz und Versicherung bei -gewerbl. Erkrankungen,’ _Sozialtechnik_ 1909, Heft 4, S. 65; Lewin, -_Grundlagen für die med. und rechtl. Beurteilung des Zustandekommens und -des Verlaufes von Vergiftungs- u. Infektions-Krankheiten im Betriebe_ -(Monogr.) Berlin, Heymanns Verlag, 1907. - - -SULPHURIC ACID INDUSTRY - -‘Schwefelsäureerzeugung, Schutz gegen Nitroseverg.,’ _Gewerbl. techn. -Ratgeber_, 1906, Heft 6, S. 109; ‘Schwefelsäureerzeugung, Reinigung -von Tankwaggons,’ _Gewerbl. techn. Ratgeber_, 1906, Heft 6, S. 109; -‘Schwefelsäuretransport,’ _Zeitschr. f. Gew.-Hyg._ 1902, Nr. 4, S. 63; -‘Schwefelsäureverg., Verhütung,’ _Chem. Ind._ 1909, Beilage, _Ber. -d. Berufsgen. f. d. chem. Ind. f. d. J._ 1908, S. 26; ‘Ausräumen des -Gay-Lussac, Verhütung von Verg., _Chem. Ind._ 1907, S. 351; ‘Sauerstoff -gegen Schwefelsäureverg., Atemapparate,’ _Zeitschr. f. Gew.-Hyg._ 1906, -Nr. 20, S. 562, und 1906, Nr. 22, S. 617. - - -PETROLEUM, BENZINE - -Berthenson, ‘Die Naphthaindustrie in sanit. Beziehung,’ -_Vierteljahrsschr. f. öffentl. Ges.-Pfl._ 1898, Bd. 30, S. 315; -Korschenewski, _Wratsch_, 1887, Nr. 17; Burenin, ‘Die Naphtha und ihre -Verarbeitung in sanit Beziehung,’ Petersburg 1888; Mabille, ‘Revue -d’Hygiène,’ Bd. 18, Nr. 3; _Bericht der Berufsgen. f. chem. Ind._ 1905; -_Bericht der preuss. Gew.-Insp._ 1904; Klocke, _Zeitschr. f. Gew.-Hyg._ -1908, S. 379; ‘Benzinersatz (in chem. Wäschereien),’ _Zeitschr. f. -Gew.-Hyg._ 1906, S. 248, und 1908, S. 384; ‘Schutz des Arbeiters vor -Benzindämpfen,’ _Zeitschr. f. Gew.-Hyg._ 1906, S. 236. - - -CARBON BISULPHIDE - -‘Nachweisung von Schwefelkohlenstoffdämpfen in Fabrikräumen,’ -_Zeitschr. f. Gew.-Hyg._ 1908, Nr. 5, S. 107; ‘Hygienische -Einrichtung beim Vulkanisieren (Glibert),’ _Zeitschr. f. Gew.-Hyg._ -1902, Nr. 1, S. 1; ‘Absaugung der Dämpfe an Vulkanisiertischen,’ -_Zeitschr. f. Gew.-Hyg._ 1903, Nr. 14, S. 305; Laudenheimer, ‘Die -Schwefelkohlenstoffverg. bei Gummiarbeitern,’ Leipzig, Veit & Comp., -1899; Roeseler,’Schwefelkohlenstofferkrankungen und deren Verhütung,’ -_Vierteljahrsschr. f. Med. u. öffentl. Sanitätswesen_ 1900, 3. Folge, Bd. -20, S. 293 (ref. _Zeitschr. f. Gew.-Hyg._ 1901, S. 164); ‘Einrichtungen -von Gummifabriken,’ _Zeitschr. f. Gew.-Hyg._ 1903, S. 260 u. 484. - - -ILLUMINATING GAS - -‘Leuchtgasverg.-Verhütung,’ _Zeitschr. f. Gew.-Hyg._ 1909, Heft 22, S. -604; ‘Kokslöscheinrichtung,’ _Zeitschr. f. Gew.-Hyg._ 1908, Heft 10, S. -231; ‘Bedeutung der Sauerstoffinhalationen in der Leuchtgasindustrie,’ -_Zeitschr. f. Gew.-Hyg._ 1906, Heft 21, S. 590; ‘Entleerung der -Reinigungskästen in der Leuchtgasfabrik, _Zeitschr. f. Gew.-Hyg._ -1903, Nr. 13, S. 283; Jehle, ‘Hygiene der Gasarbeiter,’ _Zeitschr. f. -Gew.-Hyg._ 1901, Nr. 14, S. 245. - - -COAL TAR COLOURS (ANILINE FACTORIES) - -Grandhomme, _Die Fabriken der A.-G. Farbwerke vorm. Meister, Lucius & -Brüning zu Höchst a. M._, Frankfurt a. M. 1896; Leymann, ‘Ueber die -Erkrankungsverhältnisse in einer Anilinfabrik,’ _Concordia_ 1910, -Heft 17, S. 355 ff.; Leymann, _Die Verunreinigung der Luft durch -gewerbliche Betriebe_ (Fischer, Jena, 1903); ‘Sauerstoffinhalationen in -Anilinfabriken,’ _Zeitschr. f. Gew.-Hyg._ 1906, Nr. 22, S. 617, und 1908, -S. 327. - - -LEAD (GENERAL) - -Legge & Goadby, ‘Lead Poisoning and Lead Absorption,’ 1912; _Bleiverg. -in gewerbl. u. hüttenmänn. Betrieben Oesterreichs_, herausgeg. vom. k. -k. Arbeitsstatist. Amte, I-VI, Verlag Hölder, 1905-1909; Leymann, _Die -Bekämpfung der Bleigefahr in der Ind._, Verlag Fischer, Jena, 1908; -Wächter, _Die gewerbl. Bleiverg. im Deutschen Reiche_, Verlag Braun, -Karlsruhe 1908; Blum, ‘Untersuch, über Bleiverg., Frankfurt a. M. 1900,’ -_Wiener klin. Wochenschr._ 1904, S. 1935; Rambousek, _Ueber die Verhütung -der Bleigefahr, Wien_, Hartleben, 1908; Teleky, ‘Die gewerbl. Bleiverg. -in Oesterr.,’ _Sozialtechnik_ 1909, S. 333, _Wiener klin. Wochenschr._ -1907, S. 1500. - - -LEAD SMELTING - -_Bleiverg. in gewerbl. u. hüttenmänn. Betrieben Oesterr._, I und -III, Verlag Hölder, Wien; Müller, _Die Bekämpfung der Bleigefahr in -Bleihütten_, Verlag Fischer, Jena, 1908; Wutzdorff, _Bleiverg. in -Zinkhütten_, Arb. a. d. Kaiserl. Ges.-Amte, Bd. 17, S. 441; Elsässer, -‘Schädl. in Blei- und Silberhütten,’ _Vierteljahrsschr. f. ger. Med._ -1903, Bd. 25, S. 136. - - -PAINTS AND COLOUR FACTORIES - -Über Hygiene der Erzeugung und Verwendung von Bleifarben: _Bleiverg. -in gewerbl. u. hüttenm. Betrieben Oesterreichs_, IV., V. und VI. Teil, -_Hölder Wien_; Stüler, ‘Bleiverg. bei Malern’; _Vierteljahrsschr. f. -öffentl. Ges.-Pfl._ 1895, S. 661; ‘Bleiweissfabriken (Staubabsaugung),’ -_Zeitschr. f. Gew.-Hyg._ 1909, Nr. 22, S. 601; ‘Kampf gegen die -Bleifarben in Frankreich,’ _Zeitschr. f. Gew.-Hyg._ 1909, Nr. 23, S. 543; -‘Gefahren in Bleiweissfabriken,’ _Zeitschr. f. Gew.-Hyg._ 1907, Nr. 9, -S. 205; ‘Bleiweissersatz (Ausstellung),’ _Zeitschr. f. Gew.-Hyg._ 1907, -Nr. 11, S. 254; ’ Bleifarbenverbot,’ _Zeitschr. f. Gew.-Hyg._ 1904, Nr. -10, S. 221; ‘Bleigefahr im Gewerbe der Anstreicher, Maler usw.,’ _Soz. -Technik._ 1909, Nr. 17, S. 333; ‘Bleiweissfrage,’ _Sozialtechn._ 1908, -Nr. 16, S. 310. - - -ELECTRIC ACCUMULATOR FACTORIES - -Wutzdorff, _Bleiverg. in Akkumul.-Fabr._, Arb. a. d. Kaiserl. Ges.-Amt -1908, Bd. 15, S. 154; ‘Hygiene der Akkumulatorräume,’ _Zeitschr. f. -Gew.-Hyg._ 1909, Heft 3, S. 79, und Heft 21, S. 494; Chyzer, ‘Hygiene -der Akkumulatorräume,’ _Zeitschr. f. Gew.-Hyg._ 1907, Nr. 20, S. 476; -‘Bekämpfung von Verg. in Akkumulatorräumen,’ _Concordia_ 1908, Heft 13, -S. 273. - - -LETTERPRESS PRINTING - -_Bleiverg. in gewerbl. u. hüttenm. Betrieb. Oesterr._, k. k. -Arbeitsstat. Amt, VII. Teil, Wien, Hölder 1909; Panwitz, _Bleiverg. in -Buchdruckereien_, Veröff. d. Kais. Ges.-Amtes, Bd. 17, S. 503; ‘Bleiverg. -in der Buchdruckerei (Enquete),’ _Zeitschr. f. Gew.-Hyg._ 1909, Heft 6, -S. 152 ff.; ‘Bleifreie Druckfarben und Bronzen (Preisausschriebung),’ -_Zeitschr. f. Gew.-Hyg._ 1909, Heft 23, S. 630 ff.; ‘Setzkasten mit -doppeltem Boden,’ _Zeitschr. f. Gew.-Hyg._ 1908, Nr. 10, S. 237; -‘Bleinachweis in den Dämpfen der Typengiesserei,’ _Zeitschr. f. -Gew.-Hyg._ 1906, Nr. 24, S. 677; ‘Schriftsetzerei (Typenbläserei),’ -_Zeitschr. f. Gew.-Hyg._ 1904, Nr. 8, S. 176; ‘Bleigefahr in -Druckereien,’ _Concordia_ 1908, Heft 18, S. 384. - - -FILECUTTING - -‘Bleiverg. bei Feilenhauern in England,’ _Zeitschr. d. Zentralst. f. -Arb.-Wohlf.-Einr._ 1901, S. 232; ‘Bleierkr. b. Feilenhauern,’ _Gewerbl. -techn. Ratgeber_ 1905, Heft 3, S. 50; ‘Hygiene d. Feilenhauerei -(Chyzer),’ _Zeitschr. f. Gew.-Hyg._ 1908, N. 13, S. 303. - - -ZINC SMELTING - -Frey, _Die Zinkgewinnung im oberschles. Industriebezirk und ihre -Hygiene_, Berlin 1907, Verlag Hirschwald; Sigel, ‘Das Giesserfieber und -seine Bekämpfung,’ _Vierteljahrsschr. f. ger. Med._ 1906, Bd. 32, S. -173; ‘Lehmann, Beiträge zur hyg. Bedeutung des Zinks,’ _Arch. f. Hyg._ -1897, Bd. 28, S. 300; ‘Giess- oder Zinkfieber,’ _Arch. f. Hyg._ 1910, -Bd. 72, S. 328; ‘Hyg. der Zinkerei,’ _Zeitschr. f. Gew.-Hyg._ 1907, Nr. -2, S. 39; ‘Zinkhütten, hyg. Einricht.,’ _Zeitschr. f. Gew.-Hyg._ 1901, -Nr. 18, S. 321, und 1910, Heft 11, S. 250; ‘Giesserfieber, Bekämpfung,’ -_Soz. Techn._ 1907, Heft 3, S. 51; ‘Giesserei, Hyg.,’ _Zeitschr. f. -Gew.-Hyg._ 1903, Heft 16, S. 351, Heft 21, S. 479, und 1904, Heft 13, S. -344, ‘Schutz gegen Säuredämpfe bei der Metallbearbeitung,’ _Zeitschr. f. -Gew.-Hyg._ 1904, Heft 1, S. 5 u. 11, ferner Heft 14, S. 317, u. 1905, -Heft 10, S. 287, Heft 22, S. 643. - - -MERCURY - -Quecksilberhütten in Idria: Laureck in Weyls _Handb. d. Arb.-Krankh._ -1909, S. 62; ‘Quecksilberhütten in Amiata’: Giglioli, _Ramazzini_ 1909, -Bd. 3, S. 230. - -Quecksilberbelegerei, Hyg: Schönlanck, _Fürther Spiegelbelegen_ (Monogr.) -1888; Wollner, ‘Fürther Spiegelbelegen,’ _Vierteljahrsschr. f. öffentl. -Ges.-Pfl._ XXIX 3, S. 421, und _München. med. Wochenschr._ 1892, Bd. 39, -S. 533; Charpentier, ‘Fürther Spiegelbelegen,’ _Ann. d’Hyg. publ._ 1885, -S. 323. - -Quecksilber in Hutfabriken, Quecksilberbeize: Stickler, _Revue d’Hygiène_ -1886, S. 632; Henke (Monogr.), Frankfurt a. M. 1899; Hasenfellbeize -(Ersatz), _Jahresber. d. Fabr.-Insp._ 1884, S. 489, _Zeitschr. f. -Gew.-Hyg._ 1902, S. 360, 1909, S. 281, _Soz. Techn._ 1910, S. 39; -Hutfabriken in Italien (Hyg.), _Ramazzini_ 1909, S. 230. - -Sonstige Gewerbe: Glühlampenind. (Hyg.): Donath, _Wiener med. -Wochenschr._ 1894, S. 888, _A. Mitt. a. d. Ber. d. Gew.-Insp._ 1899, -_Zeitschr. f. Gew.-Hyg._ 1902, Heft 20, S. 356, und 1908, Heft 20, S. -469, Thermometererzeug. (Hyg.), _Zeitschr. f. Gew.-Hyg._ 1901, S. 32. - - -ARSENIC - -‘Arsenikbestimmung im Hüttenrauch’ (Harkins & Swein), _Journ. Amer. -Chem. Soz._ 1907, Bd. 29, S. 970; _Chem. Ztg._, Rep. 1907, S. 447; -‘Arsenikverg. in der Ind.’ (Heim, Herbert), _Zeitschr. f. Gew.-Hyg._ -1907, Bd. 14, S. 354; ‘Arsenverg. in der Delainage,’ _Zeitschr. -f. Gew.-Hyg._ 1906, Nr. 3, S. 71; ‘Gewerbl. Arsenverg.’ (Legge), -_Zeitschr. f. Gew.-Hyg._ 1903, Heft 21, S. 476; ‘Arsenwasserstoffverg. -im Gewerbe (Prophyl.),’ _Zeitschr. f. Gew.-Hyg._ 1908, Nr. 10, S. -229; ‘Arsenwasserstoff im Ballongas (Beseitigung),’ _Zeitschr. f. -Gew.-Hyg._ 1908, Nr. 11, S. 263; ‘Arsenwasserstoff beim Ausleeren von -Schwefelsäuretanks (Verhütung),’ _Gewerbl. techn. Ratgeber_ 1906, Heft 6, -S. 109; ‘Arsenfreier Wasserstoff zum Löten,’ _Gewerbl. techn. Ratgeber_ -1906, Heft 10, S. 173; und _Zeitschr. f. Gew.-Hyg._ 1905, Heft 9, S. 252; -‘Befreiung der Salzsäure vom Arsengehalt,’ _Zeitschr. f. Gew.-Hyg._ 1903, -Heft 21, S. 477. - - - - -INDEX - - -Heavy type (Transcriber’s Note: =like this=) refers to the main treatment -of the subject and the Roman figures in brackets following to the Part of -the book: (i) Occurrence of Poisoning; (ii) Pathology; (iii) Preventive -Measures. - - - Absorption towers, 256, 258, 289 - - Accumulator manufacture, =135= (i), 145, 295, =305-9= (iii) - - Acetic acid, 9, 46, 333 - - Acetylene, 52, =85-87= (i), =278= (iii), 279 - - Acrolein vapour, 326 - - Aerograph, 138 - - Akremnin soap, 294 - - Alcohol, 99, 100, 210, 216, 333 - - Alcoholism, 241 - - Aliphatic series. See Hydrocarbons - - Alizarin, 111, 113 - colours, 3, 10, 57, 96, 111, 112, 114 - - Alkaline bromides, 36 - hydroxides, 176 - - Alkaloids, 216 - - Alternation of employment, =227= (iii), 293, 299 - - Amalgam. See Mercury amalgam - - Amido compounds, 110, 112, 201, 211, =212= (ii), 287 - - Amines, 33, 107, 111 - - Ammonia, 44, 68, 71, 72, 76-79, 82, =90-93= (i), 94, =175= (ii), =279= - (iii), 280 - - Ammonia soda process, 14, =20= (i), 92, 258 - - Ammonium carbonate, 44, 91, 92 - compounds, 67, =90= (i), 92, =174= (ii), =279= (iii) - nitrate, 44, 115 - oxalate, 115 - phosphate, 50, 92 - superphosphate, 55 - - Amyl alcohol, 45, 210 - nitrite, 45, 46, 212 - - Aniline, 3, 57, 69, 70, 96, 105, 109, 111, 112, 114, =116-119= (i), 145, - 156, =212-214= (ii), =286-288= (iii) - - Aniline black, 117, 156 - colours, 3, 4, 57, 112, 115, 117, 118, 156, 214, =285-288= (iii) - oil, 117, 214 - poisoning, 3, 69, 113, =116-119= (i), =212-214= (ii), =256-288= (iii) - - Animal products, 154 - - Anthracene, 3, 60, 96-97, 101, 107, 108, 111, 113, 285 - - Anthraquinone, 55, 111 - - Antimony, 122, 124, =146= (i) - chloride and oxide, 37 - - Antipyrin, 3, 4, 36, 102, 104, 114 - - Argyria, =45=, 152, 188, 329. See also Silver - - Aromatic series. See Hydrocarbons - - Arsenic, 12, 65, 119, 122, =143-146= (i), 154, 189, =159= (ii), 257, - 323, =328-329= (iii) - - Arseniuretted hydrogen gas, 12-14, 32, 113, 114, =145-146= (i), 148, - 149, 188, 189, =197= (ii), 257, 279, 286, 316, =328-329= (iii) - - Artificial manure, 38, =53= (i), 54, 55, 92, =176= (ii), =261-265= (iii) - - Artificial respiration, 164, =284= (iii) - - Asphalt, =98= (i), 285 - - Aspirin, 102 - - Azo-colours, 96, 110, 214 - - - Balloon filling, 145, 329 - - Barium chloride, 16, 66 - nitrate, 44 - - Barometers, manufacture of, 141, 142, 328 - - Baryta, 66, 67, 135 - - Basic slag, 49, 53, =54= (i), 148, =261-264= (iii) - - Basophil granules, 178 - - Baths, 237, 292 - - Beer brewing, 65, 154, 333 - - Benzalchloride, 35, 110, 287 - - Benzaldehyde, 35, 109 - - Benzene (Benzene poisoning), 3, 4, 69, 77-79, 85, 96, =99-100= (i), 101, - 102-106, 112-114, =204-208= (ii), =285-286= (iii), 288, 330 - - Benzidine, 118 - - Benzine, 34, 53, 54, =59= (i), =61=, 62, 63, 64, 68, 69, 85, 96, 156, - 203, =204= (ii), =267= (iii), 268, 330 - - Benzol. See Benzene - - Benzo-trichloride, 35, 109, 287 - - Benzoyl chloride, 35, 209 - - Benzyl chloride, 35 - - Bessemer process, 148 - - Beth filter, 254 - - Bichromate, 50, 54, 55. See Chromates - - Bladder, cancer of, 114, 117, 214 - - Blast furnace, =146= (i), =289= (iii) - gas, 65, 82, 88, =89= (i), 146, =289-290= (iii) - - Blasting gelatine, 47 - - Bleaching, 156, 337 - powder, =26= (i), =259= (iii) - - Blood poisons, 158, 164, 199-201, 211-214 - - Bone extraction, 68, 69, 267 - - Boracic acid, 138 - - Bottle capsules, 323 - - Brass (brass-casters’ ague), =152= (i), =182= (ii), 188, =325= (iii) - - Breathing apparatus, =231-237= (iii), 267, 286, 288, 290, 310 - - Briquettes, 96, 101 - - Bromine, =29= (i), 36, 52, =173= (ii) - - Bronze, 45, 139, 316 - - Brunswick green, 144 - - Butyl alcohol, 210 - - Butyric acid, 75 - - - Calamine, 125 - - Calcium carbide, 52, =85= (i), 87, 90, 278 - sulphide (soda waste), 18 - - Calomel, =143= - - Camphor, 49 - - Cancer, 64, 102, 114, 118, 203, 214 - - Carbon bisulphide, poisoning by, 30, 31, 34, 50, 65, =68= (i), 68-71, - 74, 80, 93, 96, 104, 156, 192, =193-195= (ii), =271-275= (iii) - oxychloride, =32= (i), 33, =294= (iii) - tetrachloride, =34= (i), 69, 208, 268, 275 - - Carbonic acid gas (carbon dioxide), =17=, 50, 53, 54, 68, 74, 82, 131, - 149, 153, =201-202= (ii), 330, 332 - oxide, 17, 21, 31, 32, 50, 74-76, 80, 82, =87-90= (i), 102, 107, 119, - 148, 149, 153, 154, 156, 188, =199-200= (ii), 288, 289, 323, 330, - 332 - - Carbonising, 156, 336 - - Carborundum. See Silicon carbide - - Carburetted gas, 61, 83, 87 - - Caustic alkali, 25 - potash, 3, 25, 34, 176 - soda, 18, 19, 25, 36, 157, 176 - - Celluloid, 48, 49 - - Cellulose, 156, 336 - - Chamber acid, 5, 8, 53, 258 - - Chance-Claus process, 19 - - Chemical cleaning. See Benzine industry, =1= (i), 134, 145, =256= (iii) - - Chili saltpetre, 35, 39, 41, 45, 54 - - Chloral, 34 - - Chlorates, =23= (i), 25, 26, 29, 30, 52 - - Chloride of lime. See Bleaching powder - sulphur, 31, 32, 68, 70, 174, 272-274 - - Chlorides, =30= (i), =174= (ii) - - Chlorine, =23= (i), 25, 26, 27, 30-32, 34, 35, 39, 44, 52, 58, 156, - =173= (ii), 209, =259= (iii), 285 - rash, 28, 35, 173, 174, 209, 259 - - Chlorine compounds, organic, 27, 69, 209, 285 - - Chloroform, 26, 33, 34, 208 - - Chrome colours, 55, 56, 265 - poisoning, 52, =56= (i), 57, 58, 114, 153, =185= (ii), =265= (iii) - tanning, =55= (i), 57, 58, =266= (iii) - yellow, 44, 55, 57 - - Chromium (chromates), 3, 52, =55= (i)-58, 114, 134, 153, =185= (ii), - =265= (iii), 271 - - Coal tar. See Tar - - Cobalt, =144= - - Coke ovens, =77= (i), 78, 79, 92, 102, 104, =276= (iii) - - Compositors. See Printing - - Condensation, =255= (iii), 323, 327 - of mercury, 141 - zinc, 125 - - Copper, =151= (i), =188= (ii) - - Cresols, 96, 101, 109 - - Cumene, 207 - - Cyanogen, 77, =93= (i), 152, =195= (ii), 261, 279, =280= (iii) - compounds, 71, 79, 92, =93= (i), 94, 95, 103, 152, 154, =195= (ii), - 196, 262, 279, =280= (iii), 289 - - - Deacon process, 23, 28 - - Denitration, 6, 43, 47, 48, 287 - - Desilverising, 124, 126, 128 - - Diaphragm method (chlorine), 24 - - Diazo-compounds, 110, 286 - - Diethyl sulphate, 23 - - Digestive tract, diseases of, 76, 129, 130, 133, 179, 182, 186 - - Dimethyl aniline, 109 - - Dinitrobenzene, 35, 108, 112, 115, 116, 212 - - Dinitrochlorobenzene, 115, 209, 212 - - Dinitrophenol, 115, 212, 213 - - Dinitrotoluol, 108, 212 - - Distillation, 253, 255 - of alcohol, 333 - petroleum. See Petroleum distillation - tar. See Tar distillation - - Dowson gas, 82, 83, 87, 276 - - Dräger’s oxygen apparatus, 165-167 - - Dry cleaning. See Benzine - - Dust removal, =243-256= (iii). See also Ventilation - - Dye stuffs, =107-119= (i), =214= (ii), =285-288= (iii), 337 - - Dyeing and colouring, 44, 45, 55, 57, 92, 134, 144, 156, 265, 310-316, - 337 - - Dynamite, 43, 47 - - - Earthenware. See Pottery - - Eczema, 64, 186 - - Electric furnace, 85 - - Electroplating, 196, 327, 329 - - Enamel, 135, 322 - - Encephalopathy, 181 - - Etching on glass and metal, 37, 40, 45, 57 - - Ether, 68, 69 - - Ethyl alcohol, 34, 210 - chloride, 34 - - Explosives, =45= (i), 49, 115, =260= (iii) - - Extraction, 54, 61, =68= (i), 68-69, 71, 100, 103, 117, 186, =253= - (iii), 267, 272-274 - - Eye affections, 21, 23, 38, 55, 57, 65, 68, 70, 75, 93, 115, 116, 119, - 171, 174, 175, 210 - - - Fans, =244-247= (iii). See also Ventilation - - Fat extraction, 34, 61, 68, 70, 71, 272-274 - - Fermentation, 154, 333 - - Ferrosilicon, 53, 85, 146, =149-151= (i), 199, =291= (iii) - - File cutting, =140= (i), 294, =322-323= (iii) - - Fluorine. See Hydrofluoric acid - - Fluorine compounds, 37, 54, 153, 171, 265 - - Flux, 135, 149 - - Frit, 135, 136, 137, 138, 320 - - Fuchsin, 111, 113, 119, 144, 287 - - Fulminate of mercury, =46= (i), 143, 261 - - - Galvanising, 94, 95, 152, 326, 329 - - Gas engines, 82, 88, 89, 100, =276-278= (iii) - lighting, =71-89= (i), 92, 93, 175, =275= (iii) - lime, 65, 94, 153, 275 - purifying material, 5, 65, 68, 74, 75, =93= (i), =275= (iii), 276 - - Gay-Lussac tower, 5, 6, 10, 11, 256, 257, 287 - - Generator gas. See Producer gas - - Glass etching, 37, 38, 153, 330 - industry, 19, 37, 39, 55, 58, 82, 88, 138, 143, =153= (i), 322 - pearl silvering, 152 - - Glazing, =135-138= (i), =319-322= (iii) - - Glover acid, 6, 8 - tower, 5, 6, 257, 287 - - Gold, 44, 94, 125, 152 - - Gun-cotton, 47-49 - - Guttapercha, 69 - - - Hæmolysis, 158 - - Halogens, =31= (i), =173-174= (ii) - - Hargreaves process, 19, 28 - - Hatters’ furriers’ processes, 45, 141, 142, 154, 327 - - Hausmannite, 58 - - Health register, 227, 264, 274, 298, 304, 307 - - Hides and skins, preparation of, 142, 143, 144, 184, 327 - - Hops, sulphuring of, 154, 333 - - House painting, 121, 122, =132-133= (i), 294, =314-316= (iii) - - Hydrocarbons, 96, 106, 158, 286, 287, 330, 331 - (aliphatic), 96, 202 - (aromatic), 96, 108, 109, 202, 204, 330 - - Hydrochloric acid, =14= (i), 15, 20, 21, 23, 30-35, 39, 44, 50, 54, 59, - 113, 145, 131, =170= (ii), =257-258= (iii), 286, 326 - - Hydrofluoric acid, =29= (i), 37, 38, 50, 54, 96, 153, =171= (ii), - =265= (iii) - - Hypochlorite, 25, 30 - - - Incandescent lamps, 141, 327 - - Indiarubber, 31, 61, 63, =68-71= (i), 100, 103, 134, 194, 267, - =271-274= (iii) - - Indigo, 34, 92, 111 - - Injectors, 245 - - Insurance, Workmen’s, 224 - - International Labour Bureau, 219 - - Iodine, =30= (i), 36, =173= (ii) - compounds and poisoning, 36 - - Iron, 44, 124, 144, =146-149= (i), =289-291= (iii) - - - Kidney disease, 57, 130, 181, 185, 215 - - - Lampblack, 97 - - Lead, 8, 13, 29, 44, 55, 68, 69, =120-140= (i), 144, 149, 152, 156, - =177-182= (ii), 329 - acetate, 55, 131, 134 - burning, 140, 323 - carbonate. See White lead - chloride, 55, 181 - chromate, 55, 57, 132, 134, 138, 310 - colic, 179. See Lead poisoning - colours, =131-134= (i), 293, 294, 295, =310-316= (iii) - nitrate, 50, 55 - oxide, 44, 45, 122, 131, 134, 135, 136, 137, 181 - piping, 140, 323 - poisoning, 3, 13, 44, 69, 93, 114, =120-122= (i), 146, 149-152, - =177-182= (ii), =292-323= (iii) - silicate, 135 - smelting, =122-131= (i), =299-305= (iii) - sulphate, 55, 122, 181 - sulphide, 122, 131, 136, =293= (iii) - - Leblanc soda process, =14= (i), 18, 19 - - Light oils, 98 - - Ligroine, 61 - - Lime kilns, 55, 153, 330 - - Litharge, 124, 126, 129, 131, 132, 134, 135, 138, 300-305 - - Lithopone. See Zinc white - - Lungs, diseases of, 9, 40, 54, 68, 75, 76, 106, 118, 169-177, 189, 201, - 204, 213-216 - - - Mahogany, 156 - - Malt drying, 333 - - Manganese (manganese poisoning), 23, 29, =58= (i), 59, 153, =179-180= - (ii) - - Meal rooms, 236 - - Mercaptan, 22, 96 - - Mercury and mercury poisoning, 40, 44, =141= (i), 152, 154, =184= (ii), - =326-327= (iii), 329 - amalgam, 141, 142, 327 - - Metals, recovery of, =120= (i), =176= (ii) =288= (iii) - - Metaphenylene diamine, 118 - - Methyl alcohol, 33, 34, 36, 37, 107, 156, 209, =210= (ii), 336 - bromide and iodide, 36, 209 - chloride, 33, 209 - violet, 112, 119 - - Methylamine, 96 - - Methylene chloride, 34, 208 - - Mineral acids, =169-172= (ii) - - Mineral oil, =59= (i), 60-63, 64, 65, 85 - - Mirbane, oil of. See Nitrobenzene - - Mond gas, 82, 87 - - Mordants, 32, 55, 337 - - Muffle furnace, 15, 20, 22, 125, 137, 138, 143, 258, 325 - - - Naphtha. See Petroleum - vapour, 42, 63, 267 - wells, 61, 62, 267 - - Naphthalene, 74, 96, 100, 101, 113, =208= (ii) - - Naphthol, 9, 96, 101, 109, 110 - yellow, 110 - - Naphthylamine, 103, 110, 118, 287 - - Narcotic poisons, 208, 209 - - Nephritis. See Kidney disease - - Nerve poisons, 158, 192, 205 - - Nervous diseases, 70, 107, 163, 181, 184, 189, 190, 193, 194, 196, 197, - 199, 202, 204, 205, 215 - - Nickel, 144, =186= (ii) - carbonyl, =186-188= (ii) - eczema, 186 - - Nicotine, 216 - - Nitrating, 41-43, 47, 49, =108= (i), =261= (iii), 286 - - Nitric acid, 2, 6, 9, 10, =39= (i), 43-49, 107, 116, 182, =172= (ii), - =260= (iii), 261, 285-287, 326 - - Nitrobenzene, 3, 9, 35, 40, 41, 45, =108-115= (i), =212= (ii), - =285-288= (iii) - - Nitro-cellulose, 40, 42, 47, 48, 336 - - Nitrochlorobenzene, 116, 209 - - Nitro-compounds, 40, =108= (i), 109-112, 114, 115, =211-214= (ii), - =286-288= (iii) - - Nitro-glycerin, 9, 40, 41, 43, =46= (i), 47, 48, =212= (ii), =261= (iii) - - Nitronaphthalin, 115, 116, 214 - - Nitrophenol, 3, 46, 115, 212, 288 - - Nitrous fumes, 10, 12, =40-44= (i), 48, 116, 171, =261= (iii), 286, 326 - - Notification of poisoning, =220-225= (iii) - - - Oil, extraction, 61, 68, 69, 267 - - Organ pipe making, 140 - - Oxalic acid, 55, 259 - - Oxygen inhalation, 43, 63, 64, =164-168= (ii), 188, 192, 196, 200-202, - 204, 208, 227, =231-237= (iii) - - - Painting. See House painting - - Paints (quick-drying), =330-332= - - Paper, manufacture of, 336 - - Paraffin, 50, 59, 60, 96, 98, 101, 107, 203 - eczema, 27, 64, 65, 102, 203 - - Paranitraniline, 114, 118, 214 - - Paraphenylene diamine, 118, 214 - - Parkes’ process, 125, 127 - - Pattinson process, 125, 127 - - Petrol ether, 60, 331 - - Petroleum (petroleum poisoning), =59-65= (i), =202-204= (ii), =267= (iii) - - Phenanthrene, 96 - - Phenol, 75, 90, 96-100, 108, 109 - - Phenylhydrazine, 36 - - Phosgene. See Carbon oxychloride - - Phosphor bronze, 52 - - Phosphoretted hydrogen gas, 50, =52= (i), 86, 90, 149, =191-192= (i) - - Phosphorus, 31, 36, =49= (i), 50, 52, 148, 149, =190-191= (ii), - =268-271= (iii) - necrosis, =51= (i) 52, =190-191= (ii), =268-271= (iii) - prohibition of, 51, 220, =268-271= (iii) - - Photography, 36, 45, 58, 94, 152 - - Picric acid, 40, 96, 100, 108, 115, 116, =213= (ii) - - Pitch, 96, 97, 107, 281, 282 - - Plate towers, 7, 16, 39 - - Poisons, classification of, =157-163=, =169= (ii) - - Porcelain, =138= (i), 322 - - Potassium bichromate. See Chromium chlorate, 26, 29, 37, 50, 52 - - Pottery, =135-138= (i), 153, 294, =319-321= - - Power gas, =80-90= (i), =277= (iii) - - Printing, =138-139= (i), 146, =317-319= (iii) - - Producer gas, 80-82, 87-89, 153, 276-278 - - Propyl alcohol, 248, 249 - - Prussic acid. See Hydrocyanic acid - - Pulmotor, 167, 168 - - Pyridine, 59, 90, 96, 101, 152, =216= (ii), 285 - - Pyrites burner, 5, 6, 65, 256 - - Pyroxyline, 48, 261 - - - Quick-drying paints, =330-332= - - Quicklime, 54, 73 - - Quinoline bases, 110 - - - Realgar. See Arsenic - - Refrigeration, 92, 93, 154 - - Regenerator firing, 81, 148, 153 - - Rescue appliances, =164-168= (ii), =230-235= (iii) - - Respirators, =229= (iii) - - Roasting (calcining furnaces, &c.), 5, 11, 65, 119, 120, 125-127, 129, - 130, 131, 141, 143, 253, =288-289= (iii), 299, 323, 327 - - Roburite, 115, 116 - - Roofing felt, 96, 101, 281 - - Rubber. See Indiarubber - - - Salt, 32, 33 - - Saltcake. See Sodium sulphide - - Saltpetre, 35, 42, 50, 257 - - Satinwood, 154, 155 - - Sewer gas, 66, 67, 93, 95 - - Shot, 121, 140, 143 - - Silicon carbide, 85, 140, 323 - - Silicofluoric acid, 38, 50, 54, 171 - - Silk, artificial, 49 - - Silver (argyria), 45, 92, =120= (i), 122-125, 144, 152 - nitrate, 40, 45, 142, 188, 227 - smelting, =122=, =131= (i) - - Skin diseases, 27, 38, 47, 52, 55, 56, 58, 62, 64, 65, 71, 96, 102, 107, - 118, 143, 144, 154-156, 171, 173, 185-189, 203, 208, 209, 265 - - Smelting processes, 89, 94, =119= (i), 143, 144, 182, =288-290= (iii), - 299, 323-325, 326 - - Smokeless powder, 49, 211 - - Soda, 2, =14= (i), 17-20, 55, 65, 92, 95, =258= (iii) - electrolytic, 20 - waste, 18, 65, 258 - - Sodium bichromate. See Chromate sulphate and sulphide, =14= (i), 17, - 19-22, 22, 112, =258= (iii), 286 - - Soldering, 145, 316, 329 - - Solvay method. See Ammonia soda - - Solvent naphtha, 99-102, 106, =207= (ii), 330 - - Spirit, denaturing of, 99, 100, 210, 216 - - Substitutes for poisonous materials, =243= (iii) - - Suction gas, =82= (i), 83, 87-89, =276-278= (iii) - - Sulpho-cyanide compounds, 75, 90, 93 - - Sulphonal, 22, =259= (iii) - - Sulphur, 31, 52, =65= (i), 65, 68, 74, 93, 122, 288 - - Sulphur dioxide, =5= (i), 9, 13, 14, 19, 21, 23, 31, 54, 63, 65, 119, - 120, 122-125, 148, 154, =171= (ii), =257= (iii), 259, 267, 279, - 288, 323, 326, 327, 333 - dyes, 112 - soap, 294 - - Sulphuretted hydrogen, 8, 12, 13, 16, 18, 21, 50, 52-54, =65= (i), 66, - 67, 74, 79, 90-93, 95, 96, 101, 102, 103, 106, 107, 112, 114, 175, - =192= (ii), 193, 258, 271, 279, 280, 285, 286, 290 - - Sulphuric acid, =5= (i), 9, 14, 18-20, 23, 33, 37-41, 46, 47, 49, 50, - 53, 54, 60, 64, 65, 67, 92, 93, 108, 112, 119, 145, 151, 154, 156, - =171= (ii), =256-257= (iii), 261, 279, 286 - arsenic free, 9 - - Superphosphate industry, 38, =53= (i), 54, 55, 92, =176= (ii), - =261-265= (iii) - - Swedish matches, 50, 52, 55, 58, 265 - - - Tanning, 55, 56, 58, 66, 67, 94, 143, 144, 153, 265, 329 - - Tar, 71, 77-80, =96-107= (i), 156, 275, =280-285= (iii) - colours. See Aniline colours - derivatives, 40, 46, =96-107= (i), =204-208= (ii), 210, =213-215= (iii) - - Teak wood, 154 - - Textile industry, 134, =156= (i), =336= (iii) - - Thermometers, manufacture of, 141, 328 - - Tiles, =137-138= (i). See also Pottery - - Tin, 44, 138 - - Tobacco industry, =154= (i), =335= (iii) - - Toluene, 32, 35, 96, 108, 112, 204, =206= (ii), 285 - - Toluidine, 109, 111, 118, 214, 285, 287 - - Treatment of poisoning, =163-127= (ii) - - Turpentine, 69, 104, =215= (ii), 331 - - Type casting, 138, 139 - - - Ultramarine, 19, 22, 259 - - Ursol, 118 - - - Varnish, 58, 61, 101, 215, 330-332, 337 - - Vaseline, 60 - - Vegetable food stuffs, preparation of, =154= (i), =332-336= (iii) - - Ventilation, =243-255= (iii) - artificial, 244-247 - localised, 248-250 - natural, 243 - - Vermilion, 57 - - Vulcanising, 31, =68= (i), 68-70, =272-274= (iii) - - - Washing accommodation, =237= (iii) - - Waste sulphuric acid, 43, 53 - water, 66 - - Water gas, 82, 84, 87, 88 - gilding, 141, 142, 327 - - Weldon process, 23, 29, 58, 59 - - White lead, 55, =131-134= (i), =310-313= (iii) - - Wood (poisonous), =154-156= (i), =216= (ii), =335= (iii) - - Workmen’s baths, 237, 292 - clothing, 229 - insurance, 219 - welfare, 237-242 - - - Xylene, 32, 99, 100, 107, 204, 206 - - - Zinc, =120= (i), 121, =122-131= (i), 139, 144, 151, =182-183= (ii), - =294=, 299-305, =323-325= (iii) - ashes, 125 - oxide, 32, 38, 125, 145, 182 - poisoning, =182-183= (i), =325= (iii) - smelting, 122-125, =125-131= (i), =323-325= (iii) - white, 68, 293 - -THE END - - PRINTED BY - SPOTTISWOODE AND CO. 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