MANGANESE GENERAL INFORMATION INDUSTRIAL HEALTH ASPECTS INDUSTRIES AID OCCUPATIONS SELECTED ABSTRACTS SELECTED REFERENCES OHIO. DEPARTMENT OF HEALTH. R. H. MARKWITH, M.D. Director of Health Columbus, 1940 This material compiled by the Adult Hygiene Division of the Ohio Department of Health, assisted by the personnel of Work Projects Administration in Ohio, Official Project No. 665-42-3-413. 1940 MANGANESE Manganese dioxide (pyrolusite) was confused with iron ore until 1740 when Pott showed that it contained no iron. Scheele proved that pyrolusite contained a new element in 1774 and Gahn was the first to isolate the netal itself. Manganese is valuable in the metallurgy of iron to increase its hardness and heat resistance. It has been very valuable in the manufac- ture of helmets. Manganese compounds are used for oil dryers, dyes, and in the manufacture of chlorine and oxygen. In 1837, Couper reported the first case of chronic poisoning by manganese dioxide of a worker who was engaged in crushing the mineral. In the early part of the twentieth century Von Jaksch, Embden and Friedel in separate investigations described the symptoms of poisoning due to manganese containing dusts. Since that time, industry has instituted measures to eliminate the danger of maganeso poisoning among its workers. GENERAL INFORMATION CHEMICAL FORMULA AM) SYNOIRfMS s (Manganese) Mn. (Pyrolusito) MnO? > manganese dioxide, black. PROPERTIES: (Manganese) A reddish-gray or silvery, brittle metallic clement. Sp. gr. 7*2 at 20°C.; m. p» 1,260°C.; b. p. 1,900°C. Decomposes water. (Pyrolusite) Iron black to dark steel-gray or bluish mineral; streak, black or bluish-black; luster, metallic or dull. Sufficient- ly soft to soil the fingers. Contains 63.2/o manganese. Sp* gr. 4.73 to 4*86; hardness 2 to 2.6. Soluble in hydrochloric acid. OCCURRENCE: (Manganese) Never found native. Important manganese ores are pyrolusite, braunite, manganite, psilomelane, rhodonite, wad. Manganiferous iron, silver and zinc ores also important. Princi- pal sources of ores: United States, Russia, India, Brazil, West Africa. (Pyrolusite) United States (Virginia, Georgia, Arkansas, Lake Superior Region, Massachusetts, Vermont, New Mexico), Germany, Bohemia, Transylvania, Austria, India, and Canada. PREPARATION: (Manganese) By reduction of the oxide with aluminum or carbon IMPORTANT COMPOUNDS; (Manganese) Manganese acetate, manganese borate, manganese carbon- ate, manganese chloride, manganese citrate, manganese dioxide, man- ganese glycerophosphate, manganese hypophosphito, manganese iodide, manganese lactate, manganese-load resinate, manganese linoleate, manganese monoxide, manganese olcate, manganese oxalate, manganese oxide, manganese peptonate, manganese resinate, manganic hydroxide, manganin, manganito, manganous fluoride, manganous ortho-phosphate, manganous oxide, manganous silicate, manganous sulfate, potassium permanganate. USES : (Manganese) Manufacturer of steel (deoxidizer); iron, copper and aluminum alloys; chemicals. (Pyrolusite) Preparation of manganese. INDUSTRIAL HEALTH ASPECTS MODES OF ENTRANCE: Inhalation. SYMPTOMS OF INDUSTRIAL POISONING: The symptoms of manganese poisoning are generally associated with the inhalation of its oxides and primarily concerned with affections of the central nervous system. The effect of manganese is said to be cumulative and the symptoms usually appear only after several months of exposure. They are evidenced by a peculiar slapping gait, weakness in legs and tremors of the whole body or extremities. Other symptoms frequently observ- ed are mask-like face, impulsive and uncontrollable laughter, disturbances of speech, languor and sleepiness, cramps and stiffness of the muscles, propulsion and retropulsion, and exaggeration of the reflexes. It is said that manganese, unlike lead, produces no life shortening degenerations. Seriously poisoned victims are life long cripples and often unfit for any gainful employment. The metal apparently makes a very definite attack upon some non-vital portion of the neuro-muscular system, destroys it thoroughly if there has boon sufficient exposure, and leaves the victims relatively well in every other respect. INDUSTRIES AND OCCUPATIONS INDUSTRIES; Ohio Industries using manganese as indicated in the Ohio Industrial Hygiene Survey are listed as follows: Glass factories Other chemicals Paint and varnish factories Patent medicine, drugs Potteries Storage batteries Tin and enameled ware Automobile factories Blast furnaces Brass factories Brick, tile, and terra cotta Dyestuffs, ink, etc. Electric fixtures Foundries 0 CClT PAT I PITS ; Occupations in Ohio where contact with manganese was indicat- ed are listed as follows: Annealers (foundries) Headers (tin and enameled ware) Bin room attendants (storage batteries) Blenders (paint & varnish factories) Bluers (automobile factories) Bottom makers (blast furnaces) Centrifugal operators (paint & varnish factories) Chemical engineers (paint & varnish factories) Chemists (brick, tilo and terra cotta; paint & varnish factories) Closers (paint & varnish factories) Cupola tenders (foundries) Decorators (potteries) Die and tool makers (foundries) Dippers (potteries; tin and enamel- ed ware) Dry cell paste mixers (storage batteries) Dry pan feeders (potteries) Enamel and paint makers (paint and varnish factories; tin and enamel- ed ware) Fettlers (potteries) Fillers (paint & varnish factories; glass factories; patent medicine, drugs) Filter pressmen (paint & varnish factories) Firemen (brick, tile and terra cotta) Foremen (paint & varnish factories) Foundry laborers (brass factories) Furnace room laborers (glass factories) Furnace tenders (brass factories; foundries) Glazors (potteries) Glaze preparers (potteries) Grinders (other chemicals; paint & varnish; electric fixtures; storage batteries) Handy men (paint A varnish fac- tories) Heaters (foundries) Heat treaters (foundries) Labelers (patent medicine, drugs) Labelers (blast furnaces; potteries; glass factories; tin and enamel- ed ware; patent medicine, drugs) Laboratory assistants (paint and varnish factories) Ladders (glass factories) Loaders (brick, tilo, terra cotta) Machine operators (electric fix- tures; foundries) Meltcrs (brass factories; found- ries; glass factories) Mill hands (dyestuffs, ink, etc.) Mixers (foundries; other chemicals; storage batteries; paint & varnish factories; tin & enameled ware) Holders (brass factories) Open hearth men (blast furnaces) Packers (glass factories) Painters (foundries; brick,tile, terra cotta; glass factories) Paint mixers (foundries; paints & varnishes) Porcelain mixers (tin and enameled ware) Porcelain sprayers (tin and enamel- ed ware) Sealers (storage batteries) Shaders (paint and varnish factories) Shake-out men (brass factories) Shipping clerks (glass factories) Smelters (tin and enameled ware) Sprayers (potteries; brick, tile and terra cotta) Tampers (storage batteries) Testers (paint and varnish fac- tories ) Thinnors (paint and varnish factories) Tinters (paint and varnish fac- tories) Transfer men (brick, tile & terra cotta) Truckers (dyestuffs, ink, etc.) Varnish makers (paint and varnish factories) Washers (automobile factories) Weighers (foundries; paint and varnish factories; dyestuffs, ink, etc.) Wrappers (storage batteries) Occupations which offer contact with manganese but not listed in the Ohio Survey are:* Battery makers Bleaching powder makers Calico printers Chlorine makers Dye makers Dyers Enamelers Fertilizer makers Fireworks makers Glass mixers Linoleum makers Manganese dioxide workers Match factory workers Soap makers Varnishers Zinc miners *Dublin, L.I., and Vane, R.J.; Occupation Hazards and Diagnostic Signs. U.S. Department of Labor, Bureau of Labor Statistics, Bulletin No. 582:40, 1933. SELECTED ABSTRACTS INDUSTRIAL MANGANESE POISONING-WITH A REVIEW OF THE LITERATURE. Wm. D. McNally. Indust. Med., vol. 4, p. 581, (1935). Abstracted in J. of Ind. Hygiene, vol. 18, no. 4, p. 49 (abstract section) April 1936. The author gives a detailed chronological review of 131 cases of chronic manganese poisoning, and in addition, the detailed history of 1 case of manganese poisoning, observed by himself. Eis patient was expos- ed to dust of manganese ores as used in the manufacture of batteries. The first symptoms were slight motor disturbances, and subsequently, fatigue, excitement, and tremors of the right leg developed. In the course of half a year the neurological symptoms became decidedly more marked and at this time the degenerative changes were seen not only in the lower extremities but also in the upper extremities and the ocularmotor apparatus. A short discussion of the prophylactic measures for the prevention of such poison- ings and the pathology of manganese poisoning are given. Directions for the detection of manganese in urine and blood and a discuaaion of the treat- ment of the conditions conclude this report.—W.F. von Oettingen. MANGANESE: ITS DISTRIBUTION, PHARMACOLOGY AND HEALTH HAZARDS. W.F. von Oettingen. Physiol. Rev., Apr. 1935, vol. 15, pp. 175-201. Abstracted in J. of Ind. Hygiene, vol. 17, no. 6, p. 124 (abstract section) Nov. 1935. This is an excellent review with a very complete bibliography and pertinent tables summarizing experimental work on manganese poisoning, the distribution of manganese in biological matter, and an analysis of reports on cases of manganese poisoning in man.—Philip Drinker. A NEW METHOD FOR THE MICRODETERMINATION OF MANGANESE IN BIOLOGICAL MATERIALS. A.C. Wiese and B. Connor Johnson. J. Biol. Choin. 127, 205-9 (1939). Abstracted in J. of Ind. Hygiene, vol. 22, no. 1, p. 22 (abstract section) Jan. 1940. The microdctn. of Mn is based upon the oxidation of benzidine by per- manganate in the presence of HNO^• The yellow-green color is read with the photoclec. colorimeter with a 4200 A. filter. It is possible to per- form 6-8 filtrations through the same filter and then read the colors developed, in this way reading 30-40 detns, in an hr. From 0.1 to 100 gamma of Mn can be estd. and rocovcries range from 92 to 106%> EXPERIMENTAL MANGANESE POISONING. A.M. Grunstein and N. Popowa. Abstr. as follows from Arch. f. Psychiat., July, 1929, vol. 87, p. 742, in Arch. Neurol, and Psychiat., June, 1930, vol. 23, p. 1275. Abstracted in J. of Ind. Hygiene, vol. 12, no. 10, p. 221 (abstract section) Dec. 1930. The authors report the results of clinical and anatomic observations of rabbits subjected to the effects of powdered manganese. They begin with a discussion of the literature, which they sum up as follows: In the reported cases of manganese poisoning in man, the clinical picture consistod of muscular rigidity, mask-like facies, compulsive laughing and crying, increased salivation, tremors, and disturbances of gait. These symptoms altogether usually presented a parkinson-liko picture, so that it could be assumed that the pathologic process would be mainly localized in the globus pallidus. So far, however, no anatomic observations in such cases have been reported. Experimentally, observations of this type have been studied in animals of different typos (Mella in this country studied the effects of manganese poisoning in monkeys). The observations of the authors are essentially similar to those of other observers, and the results are summed up as follows: Clinically, the symptoms varied from episodic paralyses of the hind legs to general weakness of the musculature without any definite neurologic changes. Anatomically, marked changes of the central nervous system were found in the form of advanced degenerative phenomena of the nerve colls. These were particularly intense in the small colls of the caudate nucleus and putamen, but were observed also in the pallidum and in some parts of the cortex. In some cases there were, in addition to these changes, prolifera- tions of the neroglia and lesions in the walls of blood vessels, as well as degeneration in the cells of the choroid plexus. There were marked degenerative lesions in the liver, spleen, heart, kidneys, and suprarenal glands. ANIMAL EXPERIMENTS ON LUNG CHANGES AFTER MANGANESE DUST INHALATION. H. Reploh. Arbeitsschutz, pp. 144-146 (1939). Abstracted in J. of Ind. Hygiene, vol. 21, no. 6, p. 146 (abstract section) Juno 1939, The author had rabbits and mice inhale dust containing 90%, MnOg• Of 32 animals employed, 9 died in the first 19 days, all of which showed more or less pronounced bronchopneumonia. Of the surviving animals 16 were infected intranasally with pneumococci and half of them were then exposed 15 minutes a day to drafts and cold. Throe of the animals only dusted survived, but only one that was infected with pneumococci and 2 infected and exposed to cold. Those last two had the most marked lung changes. Among the mice the ones only dusted had no changes. Since Thomas slag induces pneumonia in man also, the author experimented with dust containing 10% MnOg to simulate Thomas slag. Of 23 rabbits exposed, 7 died during inhalation, three of which showed clear lung changes. Later 13 animals were infected with pneumococci and the three that died showed very severe changes. Mn dust injected into the abdomen evoked a fibrinous suppurative hemorrhagic peritonitis. The author believes the pneumonia caused by Thomas slag dust may bo traced to the Mn02«--L. Teleky. PROGRESSIVE BULBAR PARALYSIS AUD AMIOTROPHIC LATERAL SCLEROSIS AFTER CHRONIC MANGANESE POISONING. H. Voss. Arch. f. Gewerbepath., vol. 9, pp. 454-476 (1939). Abstracted in J. of Ind. Hygiene, vol. 21, no. 9, p. 214 (abstract section) Nov. 1939. A careful clinical, anatomical and histological description of a case of progressive bulbar paralysis and omiotrophic lateral sclerosis, which developed in a man who worked 15 yrs. with lAriOg • The author thinks (correctly) that the manganese intoxication was partly responsible for this disease. The poisoning befell a man disposed to lateral sclerosis and produced a lateral sclerosis modified by certain symptoms of manganese poisoning.--!. Toleky. THE DIAGNOSIS OF INDUSTRIAL POISONING DUE TO MANGANESE. J. Leclorcq. Arch. Gcwerbepath. u. Gowerbohyg., Sept. 1934, vol. 5, pp. 537-344. Abstracted in J• of Ind. Hygiene, vol. 17, no. 2, p. 23 (abstract section) March 1935. A picture is given of poisoning by manganese resulting from occupation- al exposure to its dust and fumes. Manganese is used mctallurgically in making stool and such metals as copper, zinc, bronze, nickel and aluminium. It is also used in making glass, colors and varnish, pottery, and electric batteries. The portal of entry is said to bo the digestive tract rather than the lungs, while the skin can be disregarded. The poisonous dose has not been determined, but years of exposure seem required before any symptoms appear, slowly and insidiously. The nervous system is peculiarly affectedj and a clinical condition similar to Parkinson’s disease is established. Once established no improvement can be obtained, although the progress of the disease may be suspended by cessation of exposure to risk. While this article is based upon personal experience (the exact extent of which is not stated), no new points arise. The author stresses the probability of cases passing unrecognized to their graves, owing to their insidious onset and rarity, should the medical attendant be unaware of the occupational exposure of the patient.—E.L. Collis. MANGANESE POISONING. E.W. Baader. Arch. Mai. Profos., vol. 1, pp. 104-108 (1938). Abstracted in J. of Ind. Hygiene, vol. 21, no. 4, p. 98 (abstract section) April 1939. Cases of manganese poisoning from inhaling its dust are comparatively rare, only about 130 having boon reported in the literature, with a possi- bility that some have passed unrecognized. Some predisposition to the poi- soning seems to be necessary and the symptoms appear generally during the first 2 years of exposure. The illness begins rapidly and progresses in a few months to a typical and incurable condition. Symptoms usually are: the patient is easily tired and falls to sleep easily; unsteady gait; difficulty' in ascending a slope; little control over facial muscles or expression; both speech and writing are protracted and slurred; swallowing may be difficult; and there are sometimes violent pains and muscular cramps.—W.H. Buck. MANGANESE POISONING. D. Owen and E. Cowen. Lancet Nov. 3, 1934, pp. 989-990, and Annotation, Ibid., Nov. 10, 1934. Abstracted in J. of Ind. Hygiene, vol. 17, no. 2, p. 23 (abstract sec- tion) March 1935. References are made to 4 cases of chronic poisoning in men working in the same manganese works. Symptoms appeared in one case after only 8 months* exposure, and in the other three after 2-|, and 8 years. The clinical picture was indistinguishable from chronic post-encephalitic parkinsonism. No improvement occurred even though contact with manganese ceased for 1 to 2 years. General health is hardly impaired; but the patients survive for years in a more or less wretched and crippled state. The whole condition is well summarized in the second reference wherein full apprecia- tion is given to the work done in the United States and announced in this Journal (1919, vol. 1, p. 183).—E.L. Collis. MANGANESE POISONING CASE. W.D. McNally. Indust. Med., July 1935, vol. 4, pp. 349-350. Abstracted in J. of Ind. Hygiene, vol. 17, no. 6, p. 124 (abstract section) Nov. 1935. The case presented is that of a 29 year old man who worked as a laborer in the oro department of a battery company, transporting, loading, and handling manganese in powdered form. After 14 months' work, he noticed that after dumping a wheelbarrow, he had difficulty in stopping himself when he stopped back. In a week’s time this became progressively worse and the man stopped work. There was no change after 6 months by which time he had difficulty in walking, as his gait increased and ho would fall unless caught. More recently he has developed a tremor which involves the entire right leg, although there is no tremor in the hands, head, or loft log. Further clinical findings are given, with suggested treatment and points to be especially noted in making a diagnosis of manganese poisoning.— H.N. Lawson. SERIOUS MANGANESE POISONING AMONG EGYPTIAN MANGANESE MINERS. E.W. Baader, Arch. f. Geworbepath., vol. 9, pp. 477-486 (1939). Abstracted in J. of Ind. Hygiene, vol. 21, no. 9, p. 214 (abstract section) Nov. 1939. From 1921-1931 and since 1935, manganese oro mines were worked on the Sinai peninsula. Jackhammer drills were introduced in 1931. Egyptian physicians described 26 cases of poisoning and on a recent trip, the author saw some of the cases, which ho described here. It is remarkable that some cases show mental disorder at the beginning; furthermore, that at the time of hand drilling, the disease develops only after some years, but with the introduction of mechanical drilling (with terrible amounts of dust), it comes on after 3 weeks to 5 months (average, 3 mos.). Many deaths from pneumonia are noted.--!. Toleky. SELECTED REFERENCES Bickert, F.W.; The Health of Yforkers in Manganese Ore Mills. Arch, f. Goworbepathol• u. Goworbehyg., vol. 4, pp. 674-688, 1933. Bryan, A.W.: Chronic Manganese Poisonings Report of a Case. (Society Transactions), Arch. Neurol. & Psychiat., vol. 37, pp. 1448-1449, Juno 1937. Euttner, E.E., and Lentz, E.: Possibility of Manganese Poisoning in Pyrolusite Mines. Arch. Geworbepath. Gcv/erbohyg., vol. 7, pp. 672-684, 1937. Charles, J.R.; Throe Cases of Manganese Poisoning. Jour. Neurol, and Psychopath., vol. 3, pp. 262-268, Nov. 1922. Crouzon, 0., and Desoillc, H.: Nerve Damage in Industrial Manganese Poisoning. Paris Mod., vol. 26, pp. 361-365, 1936. Dairs, George G., M.D., and Huey, Walter B., M.D.s Chronic Manganese Poisoning; Two Cases. Jour. Ind. Hyg*, vol. 3, no. 8, pp. 231-238, 1921. Dragonetti, Hichelo; Chronic Intoxication with Manganese. Rass. med. applicata lavoro indust., vol. 9, pp. 94-106, 1938. Dragonetti, M. : Chronic Manganese Poisoning, a Study of One Case. Rass. di ned. appl. lavoro indust., vol. 9, pp. 94-106, April 1938. Edsall, Daird L., H.D., Wilbur, F.P., M.D., and Drinker, Cecil L., M.D.: The Occurrence, Course and Prevention of Chronic Manganese Poison- ing. Jour. Ind. Hyg., vol. 1, no. 4, pp. 183-193, Aug. 1919. Ehrismann, O.s Studies on tho Absorption of Dust in the Respiratory Passages. II. Absorption of Manganese Dioxide Dust. Ztschr. f. Hyg. u. Infectionskrank., vol. 117, p. 662, 1935. Factory and Workshop Ordor: Notification of Manganese Poisoning. (Great Britain), July 1936. Foil, Andros Manganese Poisoning in Industry. Prosse mod., vol. 45, pp. 1593-1594, 1937. Gaylo, R.F., Jr.; Manganese Poisoning and its Effect on tho Central Nervous System. Report of Six Cases. Jour. Am. Mod. Assn., vol. 85, pp. 2008-2011, Dec. 26, 1925. Hamilton, A.; Indust. Toxicology. Harper and Brothers, New York, 1934, pp. 92-96. Jotten, K.W.; Pulmonary Injury from Manganese and Thomas Slag Dust. Deutsch. med. Wchnschr., vol. 65, pp. 409-410, 1939. Jotten, K.W., and Roploh, H.; Experimental Study of Pulmonitis Pro- duced by tho Inhalation of Dust Containing Manganese. Rass. mod. applicata lavoro indust., vol. 9, pp. 395-398, 1938. Jotton, K.W., Roploh, H., anf Hagemann, G.: Experimental Investi- gation of Pneumonia Caused by Manganese and its Relation to Pneumonia from Thomas Slag. Arch. f. Gcwerbopath., vol. 9, pp. 314-336, 1939. Kobor, G., and Hayhurst, E.: Industrial Health. P. Blakiston’s Son and Co., 1924, pp. 589-592. Loobo, C.V.: Manganese Poisoning. Jour. f. Psychol, u. Neurol., vol. 47, pp. 220-221, 1936. McNally, W.: Toxicology. Industrial Medicine, Publishers, Chicago, 1937, pp. 134-139. Occupation and Health. International Labour Office, Geneva, 1934, pp. 158-161. Polonovski, K., and Briskas, S.B.: Hemopoietic Action of Zinc, Manganese and Nickel. Conpt. rend. Soc. Biol., vol. 129, pp. 493-496, 1938. Rastelli, G.: Complement Formation Ability in Manganese Poisoning. Mod. del lavoro, vol. 29, pp. 353-363, 1939. Scandcr, A., and Sallam, H.A.: A Report on Eleven Cases of Chronic Manganese Poisoning. Jour. Egyptian Med. Assoc., vol. 19, pp. 57-62, 1936. Schwartz, L., and Pagcls, J.s Experiments on the Early Diagnosis of Industrial Manganese Poisoning. Arch. f. Hyg., vol. 92, pp. 77-84, June 1923. Schwarz, L.: Industrial Manganese Poisoning. Santa, v. Vorgiftungsf., vol. 7, p. 5, 1936. Sharpe, N.C.: Some Clinical Aspects of Industrial Poisoning. Manga- nese Poisoning in Storage Battery workers. Pub. Health Jour., vol. 14, pp. 110-118, March 1923; pp. 172-174, April 1923. Surat, A.; Parkinson Syndrome in Chronic Manganese Poisoning. Sovietskaia neurologia u. psichiatria, no. 5, 1935. Trendtel, F.: Manganese Poisoning. Monatsschr. f. Unfallheil., vol. 42, pp. 69-84, 1936. Voss, H.; The Occurrence of Occupational Manganese Poisoning in the Stool Industry (Apropos of Manganese Poisoning in a Grinder of Forro-Manga- nese). Arch. f. Gewerbepath., vol. 9, pp. 453-463, 1939. Factory and Workshop Order: Notification of Manganese Poisoning. (Great Britain), July 1936.