Document M4X6E9oZY23kDgywEv3rQYwpz

^ it l{ 4 gHg/j INDUSTRIAL HYGIENE DIVISION OF INDUSTRIAL HYGIENE, NEW YORK STATI DEDEPARTMENT OF LABOR LEONARD GREENDURG, M. D,, EXECUTIVE DIRECTOR .Reprinted from The Industrial Bulletin issued each month at Albany by the Industrial Commissioner of the State of New York Vol. 22; No. 10; October, 1943 SAFETY VIEASURES FOR USE OF CHLORINATED NAfrfTHALrNES AND DIPHENYLS IN INDUSTRY I); LKOMAUl) GHFENBURO, M.D. The chlorinated naphthalenes comprise a group of chemical substances made by the addition of various amounts of chlorine to a naphthalene base. The amount of chlorine may vary from three to six or possibly more atoms providing compounds from tricnlomaphthalene to hexachlornaphthalene. In the same manner, the varying amounts of chlorine are added to a diphenyl base providing a group of compounds of varying chlorine content. As a rule, the final substances, as used in industry, are mixtures of differing chlorinated naphthalenes. Earlier, these were, as a rule, possessed of a lower degree of chlorination and later on the compounds were usually of a higher degree of chlorination with varying amounts of chlorinated diphenyls added thereto. These substances are not new. Perchlornaphthalenc was used in Germany during the last war. It is to be clearly understood that these groups of compounds are not manufactured by any one com* pany but rather by approximately five in the United States and they are sold under varying trade names by the manufacturers. The chlorinated naphthalenes and diphenyls are valuable industrial products. Because of certain properties which they possess, we may briefly state ihese valuable properties as follows: \--Resistance to water and alkali. 2--Hi|h insulating value. They possets high di electric constant. 3--Thermo plasticity. 4--Quite stable chemically. 9--Flame resistant For these reasons, these substances possess much value industrially in the making of electric con densers and in the insulation of wtre and cable, etc. Method of Use in Industry The chlorinated naphthalenes and diphenyls are used in industry by two methods. 1--A cold method in which the material ii dis solved in a solvent usually a mixture of petro leum naphtha and toluene and, 2--A hot method wherein the material is rendered pfMtic by heat. Toxic Effects The toxic effects of the chlorinated naphthalenes and diphenyls have been known for a long time. In tllc`interval 'between reports in uvul the French and German literature indicated an association between exposure to chlorine and acne and even though in some cases wax-like materials were a portion of the exposure, the general belief was that chlorine was more or less responsible for the acne. At the 1901 Congress of the German Derma tological Society, Herxheimer1 pointed out that chlorinated hydrocarbons might be the etiological cause for the acne and in the same year Bettmann* stressed the possible effect of chlorinated hydrocar bons. The first concise publication which definitely at tributed the acne to chlorinated naphthalenes was a publication by Wauer3 in 1910. This was followed on the continent by a number of confirmatory pub lications. In the United States, Sulzberger* and ins co workers in 1934 reported three cases of acne from contact with "hot oils and waxes." Sulzberger did not specifically identify the chemical substances res ponsible for the production of the acne. In 1935, Schwartz* in a paper read before the American Public Health Association, described the typical acne form eruptions and attributed them to exposure to the chlorinated naphthalenes and diphenyls. This contribution was published in the American Journal of Public Health in 1936. Fulton and Matthews* of the Pennsylvania Department of Labor reported 101 cases of dermatitis due to chlorinated naphtha lenes and diphenyls in a wire insulating plant. Jones and AldenT reported similar findings in the Archives of Dermatology and Syphilology in the same year. In 1938, Mayers and Silverberg described acneform skin eruptions in workers making electrical condensers.* Space does not permit a discussion of the histology of these dermatological changes produced by this substance. In general, it can be said with a fair measure of certainty that these changes are brought about in the skin, primarily by the contact of the skin with the vapors of these compounds or by actual contact with them in the form of solid or particulate matter. * We have found, for example, that workers exposed to fumes have more acne than those exposed to dust alone and we have also found that workers exposed to the solid material or its particulate form have developed dermatitis. In this connection, the report of Fulton and Matthews is very interesting. They picture and describe a case of an infant, two and one-half years of age, who developed the dermatitis as a result of contact with the soiled working ciothes of its father who was in the habit of playing with the child prior to changing his clothing. More recently, Schwartz* has described cases of dermatitis among cable strippers employed at ship building establishments and working with cables which had been impregnated with these compounds. Svstemic Effects In the United States, systBEE "> form of acute yellow atrophy of the liver were reporii*. by Flinn and Jarvik1* in 1936 among njen working with tetra and pentachlornaphthalene. These find ings were verified by animal experimentation. Tn 1937, Drinker, Warren and Bennett11 repotted such MGNS 096703 liver changes among animals exposed (0 the material by inhalation and similar findings were obtained with the chlorinated diphenyl compounds. These latter authors also mention four non-fatal cases among humans and the three fatal cas.cs previously cited by Ffinn and Jarvik. [ should like to cite two or three cases which we have encountered in our own experience12 and which may be of interest from the point of view of duration of exposure prior to this type of poisoning. A girl 17 years of age was engaged in soldering electrical condensers which were impregnated with tri- and tctruchlornaphthalene for a period of approximately seven month*. The autopsy for this case showed mild to severe degeneration of the liver and presented a clear picture of what is generally known as acute yellow atrophy. It was apparent in this case that the latter organ displayed areas of healing and new areas of pathology. In the second case, a man 24 yeais of age de veloped jaundice after five months of exposure in the coating of wires with wax containing the higher chlorinated naphthalenes, He was away from work for a period of time and four months later the jaundice became quite intense with general malaise and loss of appetite. After two months more of work he was sent to the hospital where he rather rapidly passed away. The autopsy in this case showed extensive areas of necrosis and fibrosis of the liver with regeneration. In a third case, published by Drs. Mayers and Smith1* of the staff of the New York State Depart ment of Labor, Division of Industrial Hygiene, an (8 year old girl became ill after five months of ex posure in the soldering of electrical condensers. The waxes in this case were composed principally of trichlomaphthalene. She was hospitalized and re covered after a long and slow period of convales cence. Recent Industrial Experience During the past year the Division of Industrial Hygiene of the New York State Department of Labor has conducted an investigation in two cable plants using chlorinated naphthalenes and diphenyls. In this investigation, many cases of dermatitis were found, and several deaths due to liver damage among workers in the industry. The examination of workers in the two factories showed relatively few cases of enlarged liver--five in all, on palpation. Comparison in these two plants showed a very much Higher incidence of acneform dermatitis in one of the plants as compared with the other; namely 21 per cent as compared with 60 per cent, the former being in the cold process establishment and the latter Luing in the establishment employing the hot process only. The dermatitis appeared to take place on the average in about seven and one-half months in the hot process plant as compared with 10 months in the cold process plant. "'rfs a result of our general re-study of this whole problem and our experience in two recent outbreaks, as well as several isolated experiences we desire to draw several basic conclusions: <- 1-- Chlorinated naphthalenes and dip'.envls .ire in general highly toxic compounds and must he tl.od with extreme care. Industrial hygienists should make every effort to see that such exposures aie controlled, insofar as humanly possible. In this effort, u<? do not believe it safe to rely on limiting atmo-pheric concentrations but rather to depend on a maximum of maintenance and engineering control. 2-- Toxic exposures may be more readily ontrolM . where the cold or solvent method of impregnating cable is employed than where the hot process is u ed. 3-- Of the known cases of liver disease in our experience, the available history and experience generally points to exposure to vapors or fumes from the hot process. There is no clear evidence in our experience although it is possible that <km ahorption may produce systemic poisoning. Physiologi cally we see no reason why this is not possible. However, most dermatitis cases do not develop liver damage. And finally, I should like to call your .mention to a group of recommendations which were finally agreed upon by all of the groups involved in the last outbreaks of poisoning as being of utmost importance in the control of this hazard. Recommendations 1-- Unless there is a very good reason for using the hot method of impregnation, all new installations should use the cold or solvent method of impregna tion with chlorinated naphthalenes and diphenyls. Where the hot method is now being used it should be changed over to cold, if possible, or surrounded with every known protective measure. 2-- General hygienic measures should be followed but in no case should these be allowed to supercede engineering control of the primary source of the exposure, the operations in the plant. The following hygienic measures may be con sidered good practice where these compounds are handled. a--Two locker* for each worker exposed io chlori nated wixu ton* for workini and one for street clothes). b--All work clothe* above the underwear should be rovided and laundered at leait twice a week y the management. c--The worker* should change to clean underwear at the end of each shift before getting into hi* street clothe*. d--Supervised cleaning. 1--At noon the worker* should remove outer clothing and scrub hands and face under supervision. 2--At the end of the shift they should be re quired to take a supervised shower bef ore changing back to street clothe*. e--Protective skin creams or protective clothing should be provided by the management at the discretion of the foreman, nune, medical, or plant superintendent. f--All department* handling chlorinated synthetic waxes should be thoroughly cleaned according to a prearranged schedule. ThU should in clude the removal of all depoeiu of waxy material from the Machine*. *hjj| am' IU| . okiftM. Wofkirtdoifif U>, clcui.n, 'mould be provided with protective clothing and supplied air or organic vapor eseaka where exhaust ventilation i* inadequate or not pos sible. 3--The foremen of all departments where this 403 MOWS 096704 material is handled should be apprised of the toxic- responding to the range of l to 10 per cent benzene nature of the material and instructed In safe hand with unit intervals was first used. The color was ling procedures. These men should make it their then reproduced simultaneously with several stand duty to check up on the workers in their departments ards of concentrations with increments corresponding and instruct them in safe practice. to 0.1 per cent of benzene varying from the standard 4-- Preemployment and periodic physical examina most closely matching the test solution. Whenever tions should be made of all exposed workers. These the concentration of (he test solution appeared to be should include the taking of a full clinical history greater than 10 per cent benzene, the test solution with spreial emphasis on gastrointestinal disturb waa diluted tenfold with alcohol, the color rede ances and dermatitis. In addition, the skin should veloped, and the comparison repeated. be carefully examined periodically and the more The determinations listed in Tables III and IV reliable liver function tests performed. Gastro were made with the aid of the graph in Figure 1 intestinal complaints developing in a worker at any The errors found when differences in readings be time should be a signal for an immediate medical tween the five- and 15-minute intervals were con check-up. A history of liver disease, jaundice, or siderable were greatly minimized by the use of antisyphilitic treatment should automatically ex empirically derived corrections. The correction ap clude a worker from jobs involving a possible toxic plied in Table IV as well as the final results was exposure. Pregnant women should not be rtnployed multiplied by 10, since the test solutions were diluted where there is a possible exposure to the synthetic tenfold. The formula used in computation for the chlorinated waxes. series in Table III was benzene #>=C-(B-A-25) 5-- Engineering control of plant operations cannot be over-emphasized but specific recommendations arc 0.005; the formula used for the aeries in Table was benzene % = I0(C - (B - A - 25) 0.005). IV C not applicable to all cases. It would be wise for a is benzene per cent corresponding to reading B on plant using this class of materials to check their galvanometers. B and A are as given under "Pro control measures with the State industrial hygiene cedure." agency, the insurance carrier and some competent consultant before occupational disease occurs. Accuracy and Sensitivity BIBLIOGRAPHY t H*rxh*lmw <V1I Contrm of tha German Dermatottcal Society, 1901) explained that ohloroxide or chlorinated hydrocarbons may ba the cause. ' Rettmnnn (Chloraene, Deutsche Med. Wochachr., 1001. No. 27 ami at the Conareaa mentioned above) atroaeed the effect of chlorinated nriyrocarbnna. Waoer: Oewerbltche erkrankunfen durch rechlorte Kohlenwaeeereloft* (PernakrankheUI. Zentratoiatt (. Oewerbehyfflane. Vol, VI. p. 100. 1918. Sulsberper. M.B., Rosenberg, A.I. and Sher, I I : Actteform eruptions. N. Y. State J. Med.. Vo). 54. 899, 1934. Schwarts. I..: Dermatltla from Kymhetle Realne and Waxes. Amer. Jour, of Public Health, Vol. 20, p. 5B6. 1910. a Pulton. W.. and Matthews, J.L.: A preliminary report of the dermatological and ayetemie efiecte of exposure to hexachlomaphthaiena and chlorodlphenyi. Penn. Dept, of Labor, Spec. Bull. No. 43. 1030. t Jon**, J.W. and Alden, H.S.: Acneform dermatergoale. Arch. Dermatol, and Syphll. Vol. 33. p. 1022, 1930. Mayers. M.R. and SUverbers. M.O.: Skin condition* re sulting from exposure to oertaln chlorinated hydrocarbon*. Jour, of Itid. Hjr*. A Toxicology. Vol. 20. p. "it. 1938. Schwarts. L: An outbreak of hainwax acne ("cable rash") among electricians. J.A.M.A.. Vol. 122. p. isi. 1943. i* Fltnn. K.D. and Jarvlk. NB.: Action of certain chlori nated naphthalene* on (he liver. Proe. Soc. Exper Blolog. aitd Med., Vol, St, lit. im. Fllnn, p. n. and Jarvlk, N.B.: Llnr lealona cnuaad bjr chlorinated naphthalene. Amer. Jour. Hygiene, Vol. 27, II. 1931. n Drinker, C.K., Warren. M.F. and Bennett. U.A : The problems of possible systemic effect* from certain chlori nated hydrocarbons. Jour, of Ind. Hyg. and Toxicology. Vol. If. p. Ml. 1*17. i Ureenburg, L.. Mayer*. M.R. and Smith, A.R.: The eye- lemla affect* resulting from exposure to certain chlorinated hydrocarbons. Jour, of Ind. Hyg. and Toxicology. Vol. 21, 6 29. ItM. ayera, M.R and Smtth. A.R.: Systemic effects from expoaure to certain chlorinated napnthalonee. Ind. Hy- Jlene, IndtMlrlal Bulletin, M. Y. State labor Dept., anuary, list. DETERMINATION OF BENZENE IN THE PRESENCE OF TOLUENE, XYLENE AND OTHER SUBSTANCES* By B. H. DOLIN, M.A. Table II illustrates the results obtained with test solutions compared by the alternative visual method of standards comparison. A series of standards cor * Continued 1mm page 378, September 1941 laaue if rfc Indttttrial Bmllrtin. The presence of petroleum naphtha, ethyl acetate, butyl acetate, isobutyl alcohol, acetone, toluene, and xylene did not interfere with the determinations of benzene in the experiments tabulated. Reasonable accuracy, with a mean error of 1.6 per cent, was attained when the intensity of color produced wag matched without the aid of a colorimeter. Greater accuracy was attained with the aid of a photoelectric colorimeter where a mean error 0.9 per cent lor a similar range of concentrations was in evidence. Con centrations less than 0.2 per cent benzene could not be determined with the naked eye, whereas concentra tions down to 0.01 per cent benzene could be determined by the use of a photoelectric colorimeter. The errors involved at concentrations less than 0.2 per cent benzene, however, were considerable and amounted to 10 per cent at 0.05 per cent ben^ne and more at lower concentrations. The 10-mi. aliquot of solution used for color de velopment represents 0.01 ml. of the sample of 0.30 ml. taken for analysis and diluted to 100 x 5. Since 0.01 per cent benzene can be detected, the method appears to be sensitive to lx 10-* ml. or 8.8x 10-r g. of benzene. By visual comparison, in the absence of a photoelectric colorimeter or when an error above 1 per cent is not permissable, the sensitivity is reduced to 2 x 10-* ml. or 1.8 x 10-* g. of benzene. The concentration of benzene vapor in air may be determined by the above method after the vr.por has been transformed from the gaseous to the liquid phase. This may be accomplished by absorbing or dissolving the vapor in petroleum naphtha or alcohol. The concentration of benzene in the resulting solution may then be determined as prescribed. Without diluting the ether extract, but using the total nitrated material in alcoholic solution, 8.8 x 10-f g. or 0.27 p.p.m. may be detected on a sample of one liter of air. Concentrations of 1.8 x 10-* g. per liter of air or 5.6 p.p.m. may be determined with an error less than 1 per cent. By sampling 10 ml. portions of air, 406 MONS 096705 concentrations down to as low as 8.8 x 10*' g. of benzene per liter of air or 27 p.p.m. should be possi ble of detection. The significance of this may be realized when it is perceived that numerous samples of air may be taken in a comparitively short time and that many small portable containers may be used. Sources of Error The products formed on treating benzene with nitrosulfuric acid depend not only on the volume of acid used and the temperature surrounding the solu tion hut also on the rate of adding the acid. The heat formed in the reaction must be allowed suffi cient time to dissipate. Too rapid addition of the nitrating acid- tends to form undesirable by-products with a Tower yield of m-dinitrobenzene. m-Dinitrobenzene is soluble in ether to the extent j l 5 7 grams per 100 ml. at 15 C. It is soluble in water to the extent of 0.047 gram per 100 ml. at 15 C. Although most of the nitrated compound enters the ether layer on extraction, some of it tends to re main in the aqueous layer. The favorable distribu tion of m-dinitrobenzene between ether and water ls probably adversely affected by the mutual misci bility of the two solvents. However, even with this effect, a single extraction might be sufficient were it possible to separate the two phases completely. To ensure reasonably complete extraction, four ether extractions are made, and only small volumes of water are used to wash the ether extract. Increase in temperature, as is often the case in chemical reactions, hastens the production of color in alkaline' media and the disappearance of color in the acid media in the case of the dinitrobenzene as well as the nitrated toluene and xylene. Light also has some effect on the rate of color develop ment and deterioration. The temperature should be within 0.4 C., and light conditions and the time elapsed should all be the same when the readings are taken with the photoelectric colorimeter as when the reference curve was prepared. When the color is compared by visual inspection, the unknown and standard are subjected to the same conditions and the effect is the same on all solutions. A series of permanent standards made from dyes or inorganic salts is not recommended because this would be applicable for only one given set of conditions. The sensitivity of the individual observer to line Sedations of color and color intensity will influence e magnitude of error resulting from visual color comparison. This personal error, which inevitably accompanies all colorimetric determinations, may be eliminated by the use of the photoelectric colori meter. The photoelectric colorimetric determinations lifted in Tables I and II show mean errors of 0.4 and 1.2 per cent respectively, for concentratins above 0.2 per cent of benzene. The lower apparent accuracy in Table II is not due so much to the added manipulation of additional dilution as to r'ie resultant decrease in benzene concentration of the test solutions. This dilution, necessitated by the fact that the solutions testrd developed too intense a color in the X 1000 dilution, may perhaps be obvi ated by the substitution of a more appropriate hit' r than that used in the above experiments. Since the galvanometer scale used can be read only to the nearest 0.25 division, the accuracy of the apparatus is limited in the presence of very high or very low concentrations of chromogen. The probability of an error of 2 per cent in 95 per cent benzene, for sample, is high, even if all precautions are carefully taken. In the case of high transmit tance or low concentrations of benzene, an experi mental error of the magnitude of 0.005 per cent may produce an error of 10 per cent in material con taining 0.05 per cent benzene. It would (bus jeera advisable to read the concentration of benzene at light transmittance between 20 and 80 per cent in order to avoid the upper and lower extremes of the reference curve. This may be attained by adjusting the dilution of the test solution after a preliminary determination. Summary A method developed for the estimation of benzene in the presence of toluene, xylene, and other sub stances requires-little material for analysis, is rapid, and is sensitive to 8.0 x 10-r g. of benzene. Concentrations varying from 0.25 to 75 per cent of benzene by volume nave been determined with a mean error of 0.9 per cent The method may be used for the determination of small air samples. * Means for the identification of toluene, xylene, and benzene have been given. The accuracy of the method, the sources of error, and the precautions to be taken in order to minimize the effect of the errors are discussed. BfBUOGKAPHY i Alekaeem If, V., Okhrona Truda, No. I. IS (19)9), 1 Ber-ftr, Zntr. G*w*rk*hrt. Unfatlverbul, N.F. J. ti7 i1 Cota, P. A., tad Aiimtroof, D.WJ.. J. Optical So*, Am., Jl. No. 13, 740-3 (1941). .......... ...... __ Bum < Greenburr, L., Miwa, M.X.. Heim , k., and Motfcoantt, S.. J. Am. Med. Aaaoe., IIS. S73-I (1443). r Heffmaa, It A.. and HHoebtien, F., Ber,. J6. 1144 (l40)t Lind, G., Area. GtwofbtpMtk. Gewbobr*., 4. ))-M (ISIS). National Ssfetr Council, Chemical and lubber Section*. "Com. mitleo oa Bentol, Final Resort,'' CtuacM, Nttionol Bui Caitialty and Surety Underwriter*. Mar. I?2a. 11 Pfeiffer. P., Chem.-Ztf., 31. SS4 (1904). I Sckrcnk, H.H., Pura, S.J.. and Yant, W.P., U. S. Bur. Miota. Kept intreetiniioai 3313 (Oat, 19JS). 14 Sotytk. (Iff., J. tnd. Hr*. U. .1)1 (1929). 14 Sank. H.F-. and Smrta. H.F., Jr., (bid.. 10. 16J (1928). HONS 096706 407