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JSJH 0 9 REC'D b Annals New York Academy of . Sciences Cht.T.ie. W.; 3. Vol. 14: 306. Urban & Schwarzenberg. Muncben, West . Germany. yioo. Ost&r, A H., fcuw <& J. C. Krantz. 1947. Anesthesia. XXVII. Narcosis wim vinyl c lyrlOl. OSTERMAYERj ie. Anesthesiology 8: 339. )67. Vinylchlorid. In Ullmanns Encyldopadie der technischen r` cht 'oerst, F.d-Vnl IS: S7--Urban & Schwarzenberg. Milnchen, West Gtraai i IAJi- Otto, "H.. Krause, H. 0. Jester, F. W. Schmidt & K. H. Glatzel. 1972. Idi 'sche portale Hypertension. Med. Klin. (Munich) 67: 447. 103- P Oani, L. & C. Sassi. 1955. Rischi e patologia professionale nella pro- ,__ie e nella lavorazione di alcune materie plastiche. Med. Lavoro 46: 14. F. A., W. P. Yant & C. P. Waite. 1930. Acute response of guinea pigs to pors of some new commercial organic compounds. V. Vinyl chloride. Public eaith Rep. 45: 1963. tooJ^T06. Patty, F. A., Ed. 1963. Industrial Hygiene and Toxicology. Vol. II. Toxicology. D. W. Fassett & D. D. Irish, Eds. 2nd edit Interscience Publishers, New York, N.Y. f oo ' ^UJ ^Polish, E., J. Christie, A. Cohen & B. Sullivan. 1962. Idiopathic presinusoidal portal hypertension (Band's syndrome). Ann. Internal Med. 56: 624. per, H., F. Paronetto, r. Schaffner & V. Perez. 1961. Studies on hepatic :rosis. Lab. Invest. 10: 265. i, H. 1968. Pathology of portal hypertension. In The Therapy of Portal pertension. N. G. Markoff, Ed. Georg Thieme Veriag. Stuttgart, West Ger- PoSHL H. & F. Hutteres. 1970. Hepatic fibrogenesis and disturbance of hepatic tion. Ann. N.Y. Acad. Sci. 170: 88. ^/ll2. Pop? &. S. Udenfriend. 1970. Hepatic fibrosis. Correlation of biochemical and I 1>3. P(JSH!N,' 7> 1 j'atyifc y \ 14. PVC pri hologic investigations. Am. J. Med. 49: 707. K. 1965. O porashenii pebeni i zelinyikh putei u raboiikh' zanroizwodstlve nekatoryikh widow plastmass. Sov. Med. 28: 132. see good business ahead. 1969. Chem. Eng. News August 4: 18. 115. Quooss, `9. Gesundheitsgefahren in der Kunststoffindustrie. Johann Ani- brosius__ ' tg. Leipzig, East Germany. 116. Ramalinoas' , K. L. Wio & S. K. Sama. 1962. Cirrhosis of the liver in ,}. S Northern In a ciinicopathoiogical study. Arch. Internal Med. 110: 350. .f- 0yt~\yr. Ramaungasw &. N. C. Nayak. 1970. Liver disease in India. In Progress in I'/,Liver Disease. opper & F. Schaffner, Eds. Vol. Ill: 222. Grune & Stratton. New York, N. y/\ 18. Rappaport, A. M.,' rosLAUCH, R. G. Black & S. Ohira. 1970. Hepatic micro- Y circulatory iding to portal hypertension. Ann. N.Y. Acad. Sci. 170: / 48. 1/M19. Ravenna, P. 1940. ^syndrome (fibrocongestive splenomegaly). Definition, classification and patfl nesis. Arch. Internal Med. 66: 879. VH20. Remmer, H. 1970. The i . W1 Dcvwnt nt T R Jit A t gf the liver in drug metabolism. Am. J. Med. 49: 617.' \tveo 1 W^natiri K^mAklvnamirt #nrl fWMrfal Kv. 602468 Thank you for choosing Ck-in Itle Advanced Information Consultants Vendor for your document delivery needs MI MaU Trane Typo -- GEO02 Verification $ Stop Ooco POQOO 1 ICoot H $ 5 $ M Charge $ I I | 1 H 6.S.8E------ ISH662 io mii mm, wcihe INI TOXICOLOGY Second Revised Edition FRANK Al^ATTY, Editor VOLUME II TOXICOLOGY David W. Fassett and Don D. Irish, Editors Index by Mrs. Kathleen Kumleb Authors W. B. Deichmann D. W. Fassett H. W. Gerarde C. L. Hake D. O. Hamblin L. W. Hazleton F. W. Hetroth C. H. Hine D. D. Irish R. A.Kehoe M. L. Keplinger F. A. Paitt V. K. Rowe H. E. Stokinger W. L. Sutton J.F.Treon R. J. Weir M. A. Wolf INTERSCIENCE PUBLISHERS o division of John Wiley & Sons, Neu> York/London 24934002 ALIPHATIC HALOGENATED HYDROCARBONS 1303 Skin Irritation. Propylene dichloride on the open skin causes only mild irritjtion. Single short contacts will probably be without any effects. The intensity of reaction is greatly increased when bandaged on the skin or when held close to lie skin by clothing. gsr Eye Irritation. Propylene dichloride causes some pain and irritation when ,plashed into the eye. It would not be expected to cause serious or permanent "feijtiry. It should be washed out immediately with water. fl'ffrgienie Standards of Permissible Exposure The threshold limit of propylene dichloride was established by the American Conference of Governmental Industrial Hygienists, in April, 1959, at 75 p.p.m. (350 mg-/cu. meter.) 5. flammability ^The flammable limits of propylene dichloride are 3.4 to 14.5 per cent in air. pie ignition temperature is 557 to 570C. , CHLORIDE, CH2=CHC1 (Monochloroethene) f Uses and Industrial Exposures Vinyl chloride is used as a chemical intermediate primarily as a monomer in fpastic manufacture. The fire and explosion hazard is by far the dominant prob- i in handling vinyl chloride. ; Physical and Chemical Properties ^ Physical state: gas Molecular weight: 62.5 X Specific gravity: 0.9121 (20/4C.) Melting point: --153.71C. /'Boiling point: --13.8C. 'Vapor density: 2.15 (air =1) / Vapor pressure: 2580 mm. Hg (20C.) Solubility: slightly soluble in water; soluble in ethanol and ethyl ether .. Flashpoint: --78C. (opencup) 1 mg./liter O 391 p.p.m. and 1 p.p.m. c= 2.56 mg./cu. meter at 25C., 760 a.Hg Physiological Response Vinyl chloride appears to be a material of relatively low toxicity. The principal "response seems to be one of central nervous system depression, which may result in symptoms of dizziness and disorientation that are somewhat similar to the re sponse from ethyl chloride exposure. There is the possibility of some lung irrita tion occurring from chronic exposure as some edema is observed in acute vapor 1304 DON D. IRISH ALIPHAT1 i; exposure. Most investigators did not observe kidney or liver damage. One group Skin. The boiling point 01 of authors indicated some hyperemia of the liver and kidneys from acute ex rere spilled on the skin, there posure. It is concluded that the material has essentially a narcotic effect, with some late. lung irritation and a possibility of organ injury. There has been quite extensive Absorption, Excretion, an< use of this material in the chemical industry but no clinical reports of injury. Jsm of this compound. It is ap Acute Vapor Exposure. Patty et al.100 reported the response of guinea pigs gcreted by the lungs. The litt to single exposures to varying concentrations. The maximum time-concentrations j large part is excreted by the 1 in air for a single exposure survived by guinea pigs were as follows: 5 to 7 per cent for 1 hour and 2V* per cent for 8 hours. The maximum time-concentration in air for a single exposure without serious disturbance was IV2 per cent for 1 hour and 0.5 per cent for 8 hours. It will be noted that it requires a high concentration cause death. The same authors report that a concentration of 2V2 per cent of vinyl chloride ^ Hygienic Standards of Permiss The threshold limit of vii [erence of Governmental Ind (1300 mg./cu. meter). Torkelson et al.10211 sugges in the air for a period of 3 minutes will cause dizziness and disorientation in ex j. Flammability** posed men. They also observed a faintly pleasant odor at this concentratio||j ~ The explosive limits of vii Animals that died from acute exposures showed edema of the lungs and hyperemia^ in air). The autoignition temp of the kidneys and liver. Men exposed to vinyl chloride detected a slight odor at 4100 p.p.m. Thi| L Odor and Warning Properties the lowest concentration at which an odor was detected. At 6600 p.p.m. for.| hour, they noticed dizziness, sleepiness, and distinct odor. Vinyl chloride has been investigated as a possible material for anesthi purposes by Peoples and Leake101 and by Oster et al.102 It was concluded th vinyl chloride was unsatisfactory for use as an anesthetic because of its circulate and cardiac effects. These studies were at 10 to 20 vol. % and are hardly signifii for industrial exposure. i Vinyl chloride has a mild Iproperty for excessive exposur I mHVYUDENE CHLORIDE, *v 11/ Uses and Industrial Exposure I ?- Vinylidene chloride is v. Chronic Vapor Exposure. Essentially no investigations have been publish on the response to chronic vapor exposure. Schaumann85 exposed mice and rats found that they tolerated a level sufficient for "light narcosis" for periods'^ hours daily for 5 to 8 consecutive days or for 1 hour daily for 4 weeks wita showing kidney or liver injury. Torkelson et al.102* (to be published) report repeated exposures of animals? 7 hours/day, 5 days/week. At 500 p.p.m., rats showed increased liver weight micropathology. At 200 and 100 p.p.m., rats showed increased liver weight, b changes could be observed in dogs or guinea pigs. All species tolerated 50 p for 6 months. Repeated exposures for 1 hour/day at 200 or 100 p.p.m. were to ated without observable effect. [fionomer in the production of | IlnPAysieai and Chemical Prope. Physical state: clear col Molecular weight: 96.9f Specific gravity: 1.218 ( Freezing point: --122.5 !Boiling point: 31.7C. Vapor density: 3.34 (ai: j-Vapor pressure: 591 mn Refractive index: 1.427 Per cent in "saturated" a " Chemical Safety Data Sheet SD-66. Manufacturing Chemists Assoc., Washington, 1954. 100 F. A. Patty, W. P. Yant, and C. P. Waite, Public Health Repts. U. S., Reprint^ 1405,45, No. 34 (Aug, 1930). MS. A. Peoples and C.D. Leake,/.Pharmacol. Exptl. Therap^48,284 (1933). 1 "*R. H. Oster, C. J. Carr, J. C. Krantz, and M. J. Sauerwald, Anegtheaiotb$[/f& Density of "saturated" a ^Solubility: insoluble in Flashpoint: --15C. (( tl mg./liter O 252 p.p.n |?g (1947). R*T. R. Torkelson, F. Oyei ALIPHATIC HALOGENATED HYDROCARBONS 1305 One grod Skin. The boiling point of vinyl chloride is so low that if the liquid material a acute a rere spilled on the skin, there is a possibility of severe cooling and possibly frost t, with son te. Absorption, Excretion, and Metabolism. Very little is known of the metabo- jsm of this compound. It is apparently readily absorbed by the lungs and rapidly guinea pi| xcreted by the lungs. The little information that is available would indicate that ncentratioi large part is excreted by the lungs unchanged. o 7 per cei Hygienic Standards of Permissible Exposure ation in ai 1 hour ail The threshold limit of vinyl chloride was established by the American Conentration [erence of Governmental Industrial Hygienists, in April, 1959, at 500 p.p.m. 1300 mg./cu. meter). nyl chloril Torkelson et ai-102* suggest 100 p.p.m. ation in 6^ Flammability** ncentratiop The explosive limits of vinyl chloride are: lower, 4% and upper, 22% (by vol. 1 hyperemj In air). The autoignition temperature is 472.22C. i.m. This Odor and Warning Properties n.m. for Vinyl chloride has a mild, sweetish odor. The odor is not an adequate warning Property for excessive exposure, r anesthefl cb ' thjiNYLIDENE CHLORIDE, CH2=CC12 (1,1-Dichloroetliylene) circulate / signifies}' Vses and Industrial Exposures Vinylidene chloride is used as a chemical intermediate, particularly as a n publishjionomer in the production of plastics. md rats aM >eriods o| Physical and Chemical Properties eks withol Physical state: clear colorless liquid Molecular weight: 96.95 animals, weight jp iAig?hhVtt,) bbr>uuntt-1i id 50 p.pwere tol Specific gravity: 1.218 (20/4C.) Freezing point: --122.5C. Boiling point: 31.7C. Vapor density: 3.34 (air = 1) Vapor pressure: 591 mm. Hg (25C.) Refractive index: 1.427 (20C.) mgton, JU Per cent in "saturated" air: 78 Density of "saturated" air: 2.8 (air =1) Solubility: insoluble in water; soluble in organic solvents Reprint : Flash point: --15C. (open cup) 1 mg./liter O 252 p.p.m. and 1 p.p.m. o 3.97 mg./cu. meter at 25C., 760 ology, feHg g? T. R. Torkelson, F. Oyen, and V. K. Rowe, Am. Ind. Hyg. Assoc. /, 22, 354 (1961). POTENTIAL EXPOSURES IN INDUSTRY 2251 cause characteristic, ^ Cement and Concrete t-producing machines l- Cement is made from cement rock or a mixture of finely ground limestone, or strong joinings with cases cause a cliarac- v . ler parts of the body other form of calcium carbonate, with clay, shale, slate, or blast furnace slags, rarely sandstone, and certain accelerators or retarders. The mixed powders are heated in a kiln, usually rotary, to about 1300 to 1400C. The kilns are heated by fuel jets of powdered coal, gas, or oil. The cement rock rarely contains more than 6 ontrol methods (see' or 8 per cent quartz; the finished product usually less than 1 per cent, though occasionally it may contain up to 6.5 per cent. The dusts are ordinarily classed as nuisance dusts but their concentration may exceed the most liberal ideas of permissible limits. There are several dust-producing operations and they are amenable to control and nitric acid, now *, measures. Some of these sources are: stone quarrying, crushing, grinding, the ning associated with ! rotary kiln, screens, bagging operations, and the loading and unloading of cars. the fur on processed! Dust clouds, if uncontrolled, not only are conducive to undesirable working condi ) improve the felting] -vW tions but also constitute an atmospheric pollution nuisance in the community. Electrostatic precipitation as well as centrifugal collectors have been used success ; carrot or at 160 tol fully to remove the dust from the effluent air from kilns and silos, and the amount several months, or4^ recovered is said sometimes to exceed 5 per cent of total raw materials. A method ; brushed to smooth! that has been successfully applied to the rotaiy kiln elsewhere (see Sand Refining) cleaned and sent tol is to exhaust the hot kiln gases through baffled water-spray chambers and conduct the water flowing from the sprays through a settling basin from which the sludge jsures varying from! may be recovered. The important factors in evaluating exposures are the degree of cu. meter of air fori dust control and the free silica content of dust particles less than 5 n in diameter. on kin-handling Lung injury from exposure to cement dust, however, has not been demonstrated ant* ..owing opera|| and the most frequent, harmful result of exposure is that of skinjiritation from res associated witfil oms as quickly the alkaline action of cement. In the mixing and use of concrete, the irritant, alka line action of the wet mixture is similar to that of the cement dust, and both :eeping and sanita^ warrant suitable control to prevent prolonged contact with the skin. of operation, with! * ?4j ot can be obtaine ridizing acids such Chlorinated Waxes and Oils Synthetic Chlorowctxes. The synthetic chlorowaxes comprise a number of with hydrolyzir chlorinated hydrocarbons that are derivatives of naphthalene or diphenyl. Halo- filed by Beal ana [ ^wax is the trade name of one manufacturer for the chlorowaxes. hloric and sulfurio The damage that may occur from inhalation, ingestion, and skin absorption med that the only | ;>.of the chlorowaxes will vary with the degree of chlorine saturation of the com- rrosion. Adequate | pounds. The amount of dermatitis and poisoning increases rapidly as the amount" tilation capable M ;|/bf chlorine in the waxes increases. The commonly accepted maximum permissible les evolved during I fj limit for atmospheric contamination with trichloronaphthalene is 5 mg. per cubic 3d. There are sail I fmeter of air. Pentachloronaphthalene, one of the chlorowaxes carrying a high .tions. 5 percentage of chlorine is restricted to 0.5 mg. per cubic meter of air. (1937). 19,1239 (1941).i t i| Systemic poisoning from the chlorowaxes is generally characterized by II damage to the liver. Serious exposure may produce acute yellow atrophy. The 4 I . 4* 2252 FRANK A. PATTY skin effects are commonly in the form of acne, which is more widely distributed on the body than common acne. ff Among the recommendations for the prevention of ehlorowax poisoning are: I (1) vapors and dust should be controlled by exhaust ventilation to prevent'! exposure to amounts of the compounds in excess of the safe limits mentioned above; (2) foremen and workers should be told of the toxicity of the materials that they are handling and instructed to keep skin contacts with the material to & minimum; (S) preemployment and periodical physical examinations should be given with special attention to the skin and to the liver, liver function tests being performed periodically; and (4) the best hygienic conditions should prevail^ including the provision of clean work clothing, protective gloves, and protective" creams. Those manufacturers who have had the most favorable results in pre venting ehlorowax poisoning have provided double locker rooms, one for street] clothes and one for work clothes, with a shower room in between. The worke: Cl hydro; corrosi to pon use of used.' recogi exposi T consic prope work) should be required to take a shower every day before leaving the factory; it is wel to provide supervision to make certain that this practice is complied with. Air analysis for the chlorowaxes is most commonly performed by passing thl !?; air over heated platinum in an electrically heated quartz tube; the waxes decom pose and the effluent gas is scrubbed in a column of glass beads moistened wit|| sodium carbonate; the chlorine is converted to sodium chloride which is recovere by washing the beads, and is usually determined nephelometrically. The impinge| using amyl acetate as the collecting medium, has also been employed for collectio of samples; afterward the samples are burned, products of combustion codec and chlorides determined. Chlorinated Oils. There are two general types of oils falling within this clasi the first contains additive substances such as carbon tetrachloride to impro|j cutting properties; the second has chlorine combined in complex organic struct! The chlorine additive agents may be recovered by distillation and are releasi from the oils in accordance with vapor pressure laws. The use of oil plus chli rinated hydrocarbon may be hazardous unless exhaust ventilation is providi steri Nausea and malaise are common complaints of workers handling the mixtm| The haphazard methods used in preparing the mixtures tend to increase the dahgi \ requ ."is 'A metl Commonly the chlorine compound is added in unknown proportion as an antid for cutting difficulties. In some instances the mixture has been found to contain] much as 40 per cent carbon tetrachloride. In time t the; The chlorine in the second type of oil is firmly bound at lower temperati upon heating, little decomposition occurs below 200C.; near and above 21 hydrogen chloride is evolved. It is known that temperatures in excess of 300 are produced locally from heavy cutting operations. This type of oil probaj can be used safely for light precision machining. x ibe a gr-supc | infe |t adv IA Animal experimentation has shown that chlorine compounds in oils majri absorbed through the intact skin to cause liver damage. Dermatitis fro: rinated oils also occurs. -t* x)d. During cooking, the digester or along s of "sulfate wood aldehydes, traces of iium sulfide, methyl e pulp and digestion [ling, and some subaporators, salt cake very furnaces, where aving the alkali and combustion gases are sulfurous gases and rbonate, and sodium ;reeable. Although in ntrations, there are flammable gases or ipe of odorous gases, hem through caustic, washing with water irecipitation has also; liq is an aqueous : bisulfites. The sulfur burning of sulfur or11 ntains high amounts ! .1 operation. This is? se of chlorine, whicluj m bleaching powder^ ie vat and be carried owever, the exposure^ neral ventilation, .chines and the mate|| dyes, plastics, gumsj rposures arising fror s resulting from thj from the coating arid dissolved in organic ir-conditioned roomij t. 54,35 (1939) POTENTIAL EXPOSURES IN INDUSTRY Photographic Industry Dermatitis and skin sensitization are the hazards of the photographic in dustry. Nasal and bronchial irritation and asthma are also reported from contact with developers and other photographic chemicals. The aminophenols are among the most common sources of skin disease from developers. Other irritating chemi cals include caustics, iron salts, mercuric chloride, strong acids, bromides, iodides, pyrogallic acid, and silver nitrate. The last substance is reported to have caused argyria, a condition in which silver is deposited beneath the skin. It is difficult, if not impossible, to remove the deposits completely. The prevention of dermatitis lies in reducing to a minimum the contact of the chemicals with the skin. Cleanliness, protective clothing, and protective creams are the triumvirate for controlling the hazard. Plastics and Synthetic Resins Synthetic resins that have undergone complete condensation cause little difficulty in the cold, but where heat is applied, or an imperfectly combined com ponent is present, skin irritation and sensitization may result. The phenolformaldehyde and urea--formaldehyde resins owe their irritant and sensitizing properties chiefly to formaldehyde,38 but phenol and furfural (phenol-furfural resins) may also have some irritant effect. It is advisable to provide process ventilation for any dust-producing or vapor-producing process involving the manufacture, fabrication, or use of plastics whereby formaldehyde is released into the workroom atmosphere. Hexamethylenetetramine, which has a bad repu tation as a sensitizer, is harmful because it releases formaldehyde.36 Cashew nutshell liquid-formaldehyde resin is particularly offensive if any uncombined cashew nutshell liquid remains in the resin. "Oil stop," a waterproof resin made by mixing cashew nutshell liquid to a paste with powdered paraform (a polymer of formaldehyde) and allowing it to "set" or condense, is popular with electricians. Both of the constituents are irritants and sensitizers and there is a high incidence of dermatitis among users who carelessly contaminate their hands and clothing with the mixture. Plastic glues for the manufacture of plywood, laminated asbestos, fiberboard, glass fabric, and similar products may be made of incompletely condensed resins containing formaldehyde along with acids, alkalies, peroxides, and other irritants and sensitizers. The screening, scaling, and mixing of such powdered glues are productive of dust and conducive to dermatitis. Many plastics such as vinyl chloride, vinyl acetate, polyethylene, poly styrene, and methyl methacrylate have proved to be more or less inert physio logically. Antioxidants and stabilizers added to some plastics, however, may occasionally cause adverse physiological effects. The majority of the dermatitis " A. G. Crunch, Ind. Med, 15,168 (1946). ** L. Schwartz, J. Invest. Dermatol, 6,239 (1945). AN nr i 2298 FRANK A. FATTY cases arising from prolonged contact with plastics of this nature are caused by plasticizers added to eliminate brittleness and to produce flexibility. Some of these plasticizers are susceptible to the effects of heat and moisture and may separate from plastics that are in prolonged contact with the skin and cause either primary irritation or, more likely, sensitization. This presents a use problem rather than a production problem. These plasticizers30 include derivatives of glycol, glycolic acid, phthalic acid, phosphoric acid, ricinoleic acid, and sebacic acid. In evaluating and controlling exposures arising from the manufacture, fabri cation, or use of plastics, dermatitis is the primary consideration, but eye irrita tion and even the possibility of lung irritation should be considered. Dusts, especially those involving incompletely reacted materials, and curing agents, especially organic amine vapors, should be controlled by engineering methods; excessively warm and humid atmospheres also should be controlled; and direct skin contact with suspected irritants or sensitizers should be avoided. A supervised program of personal cleanliness and frequent changes of clothing are the best personal control measures wherever dermatitis is involved. Occasionally persons do not respond to "hardening" and the standard pre ventive and protective measures. In such cases of unusual susceptibility it is necessary to transfer the workers to other work. Pottery Industry Silicosis and lead poisoning are the traditional occupational diseases tol potters. Free silica is present as flint in the pottery slip in amounts that make dustj control of a high order imperative. Respirable sizes of dust commonly show 40 toaS 50 per cent free silica in slip houses. The use of lead compounds in decorating ware| also necessitates a high degree of dust elimination. Most of the dangerous silica operations are concentrated in a few departments^ The slip house normally has more than half of the total significantly exposed! workers. Lead exposure is confined to sprays and dust from ware prior to itej being fired. Jiggering and batting out normally do not involve harmful exposures.! Stampers should be provided with exhaust ventilation, however, as should! finishers. Dish makers do not have significant dust exposures. This statement^ also applies to casting shops. Bisque and glost kiln placing and drawing are dust-free operations. Flatware brushing is one of the dustiest occupations outsidej of the slip house and it requires control. The transfer of raw materials froij boxcars to storage bins may involve excessive dust exposures. It is poor hygienic practice to draw hot air directly from the fire chamber of the kilns into the workrooms to heat them: a system of heat exchangers should be used. The perioi 1 been