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HYGIENIC GUIDE SERIES American INDUSTRIAL HYGIENE ASSOCIATION Chlorodiphenyls (Containing 42% and 54% Chlorine) Significant Physical Properties' The chlorodiphenyls arc light straw-colored mobile (42% chlorinated) and viscous (51% chlorinated) liquids with typical chlorinated aromatic odors. These compounds are chlorinated to specific weights of chlorine. Chlorodiphenyl (42%) contains 42.0 -- 0.5 chlorine, an amount corresponding to three chlorine atoms in unassigned positions. Chlorodiphenyl (54%) contains 54.3% chlorine corresponding to five chlorine atoms in unassigned positions. Both compounds are insoluble in water, but soluble in benzene, kerosene, acetone, amyl alcohol, ether and chloroform. Chlorodiphenyl (42c.'c) Chlorodiphen; Molecular weight: 247.53 326.45 o p Flash point (Cleveland 1 76-180oC (349-356'-F\ None Distillation range: 325-366C . 365,'-390'C Specific gravity: 1.381-1.392 (25"/15.5C) 1.495-1.505 (65/15.5c C) Vapor pressure: oc 25C I50C 200C 0.001 mm 0.006 mm (cst) 4.3 mm 29.0 mm 0.00006 mm 0.00054 mm (cst) 1.4 mm 9.0 mm At 25C and 760 mm Hg: Saturated air contains 0.080 mg/litcr 0.009 mg/litcr 1 mg/litcr ~ 1 ppm = 98.8 ppin 0.010 mg/litcr 74.9 ppm 0.013 mg/liter I. Hygienic Standards A. Recommended maximal atmospheric concentrations (8 hours) : One milli gram chlorodiphenyl (42%) per cubic meter of air and 0.5 milligram chloro diphenyl (54%) per cubic meter of air.2 This is based on the results of The Committee wishes to acknowledge the preparation of the medical information section of this Guide by the Industrial Hygiene and Clinical Toxicology Committee of I. M. A., and to acknowledge also the assistance of Elmer P. Wheeler and Jack T. Garrett in the writing of this Guide. chronic animal inhalation studies.3 B. Short exposure tolerance: Ten mg of a diphenyl of unspecified chlorine content per cubic meter of air has been reported as unbearably irritating.4 C. Atmospheric concentration immedi ately hazardous to life: Not known for man. Irritation of the eyes, nose and throat at levels which have not caused acute illness preclude the likeli hood of voluntary exposure to immedi ately hazardous concentrations. . HARTOLDMONOOQ9898 January-Fttbruary, 1965 . Toxic Properties A, Inhalation: Experiments with chlorodiphcnyl (42% chlorine) were run at concentrations of 8.6 /<g/]itcr and at 6.83 /ig/litcr of air. Cats, mice, rabbits and rats were unaffected by the higher level while guinea pigs showed poor growth after seventeen 7-hour/day ex posures over 24 days. Eighty-four 7hour/dav exposures at the lower con centration had essentially no effect on similar species of animals.1 In the case of chlorodiphenyl (54% chlorinc) eighty-three 7-hour/day ex posures over 121 days to a concentra tion of 5.4 /ig/liter resulted in injury to liver cells and increased liver weights in rats. At a concentration of 1.5 /ig/liter for one hundred and fifty 7-hour/day exposures over 213 days, the rats showed distinct microscopic changes in the liver.-1 The literature contains many refer ences to the potential toxic effects of chlorinated diphenyls in man and ani mals. The early work included investi gations of chlorinated naphthalenes, chlorinated diphenyls, chlorinated diphenyl oxide and various mixtures of these. An early report indicated serious toxic effects from chlorodiphenyl chlori nated to the extent of 6554/' A later report by the principal author properly identified the earlier sample as a mix ture of chlorinated diphenyl and chlori nated diphenyl benzene.11 However, only a few authors of subsequent papers, bul letins or textbooks have noted this cor rection and the original data are cited repeatedly as relating to chlorinated diphenyl alone. B. Skin contact: Both compounds are readily absorbed through the clipped, intact skin of rabbits. The minimum lethal dose when the undiluted mate rials were applied to the covered clipped, intact skin of rabbits for 24 hours was approximately 1.0 gm/kg for the 42% chlorinated and 1.5 gm/kg for the 54% chlorinated.7 Local action on the skin is similar to that of common organic solvents where contact leads to removal of natural fats and oils with subsequent drying and cracking of the skin. Human cases of chloracne have not been reported from the use of these two specific chlorodiphenyls. The potential undoubtedly exists because of cases which were reported from the use of chlorodiphenyls with a higher chlorine content and from mixtures with other chlorinated aromatic compounds.5'*'8 C. Eyf. contact: The liquid products and their vapors are moderately irritating to eye tissues. D. Ingestion: The acute oral toxicides of the undiluted compounds are not great as evidenced by oral LD-,,`s in rats of approximately 8.65 gm (7.61 to 9.78 gm) per kilogram for the 42% chlori nated and 11.9gm (10.48 to 13.45 gm I per kilogram for the 54% chlorinated.7 Central atrophy of the liver appears to be the chief toxic effect. III. Industrial Hygiene Practice A. Industrial uses: The chlorodiphenyls are used as dielectrics for condensers, capacitors and transformers, plasticizers in synthetic resins, in emulsion adhes ives, as nonflammable hydraulic fluids and as transfer media. B. Evaluation of exposures: 1. zlir sampling and analysis: a. Direct field methods: None b. Laboratory methods: * (1) Collect in secondary butyl alcohol in fritted bubbler or two large itnpingers in series; concentrate sample and complete analysis by one of various methods for chlo rinated hydrocarbons.1 (2) Sample air through com bustion furnace, collect chloride ion from decom posed chlorodiphenyl in suitable alkaline solution and determine chloride ion con centration.3 C. Hazards and their recommended control: 1. Inhalation: Absorption is chiefly by inhalation, Concentrations in the workroom atmosphere should be maintained below the recommended levels. Where the chlorinated diphenyls are used at room tempera- l HARTOLDMONOOQ9899 January-February, 1965 tures, the hazard of inhalation is considered slight or absent. When these materials are subjected to elevated temperatures, the process either should he. completely enclosed or other adequate mechanical ex haust ventilation must he provided to reduce concentrations to safe levels. In heat transfer media appli cations, die system must be designed and constructed so that it is leak proof. Special gasket materials and pump seals are available to prevent leakage. The reservoir tank should be airtight except for a sent to the outdoors. In the event of spills or leaks of hot fluids, use chemical cartridge respirators or gas masks approved by the U. S. Bureau of Mines for protection against organic vapors. These will proside good protection up to the concentrations shown on the approval labels and the odor will give ample warning if it comes through the device. 2. Skin contact: Operations and handl ing procedures should be such as to avoid the possibility of prolonged or repeated skin contact. Contaminated clothing must be laundered before reuse. 3. Eye contact: Eye protection should be used where there is a possibility of liquid splashes. 4. Ingestion: Ingestion of these mate rials is not a problem in industry. 5. Fire and explosion: The chlorodiphenyls arc fire-resistant or essenti ally nonflammable liquids. When exposed to flame or hot surfaces they may decompose to form CO, CO;, HC1, phenolics and aldehydes depending on the temperature, avail ability of oxygen, area of the heated surface, rate of application of the liquid to the surface and other variables. IV. Medical Information A. Emergency treatment: Skin surfaces exposed to chlorodiphenyls should be thoroughly washed with soap and water at once. If clothing has been contami nated it should be removed promptly. If exposure to a high vapor concen tration occurs, as in the case of spills at elevated temperatures, the patient should be moved from exposure and kept at rest until seen by a physician. Oxygen should be administered if breathing is difficult. Eyes contaminated with chlorodiphcnyl should be irrigated with water for at least 15 minutes and the patient should be seen by a physician. Depend ing on the amount of inflammation and pain present, drugs like Cortisporin ointment and topical Pontocaine may be indicated. B. Special procedures: Persons who are regularly or repeatedly exposed to chlo rodiphenyls should be examined periodi cally to detect early evidence of skin irritation and/or liver damage. Persons with known liver disease should not be exposed to repeated contact with the chlorodiphenyls. y References 1. Monsanto Company, Organic Chemi cals Division: Tech. Bulletin #PL-306, Aroclor Plasticizers (Dec. 1960). 2. American Conference of Governmental Industrial Hygienists: Threshold Limit Values for 1964. AMA Arch. Environ. Health 9: 545 (1964). 3. Treon, J. F., F. P. Cleveland, J. Cappel, and R. W. Atchley: The Toxicity of the Vapors of Aroclor 1242 and'Aroclor 1254. Amcr. Ind. Hyg. Assoc. Quart. 17: 204(1956). ' 4. Elkins, H. B.: The Chemistry of Indus trial Toxicology. John Wiley and Sons, Inc., New York (1959). 5. Drinker, C. K., M. F. Warren, and G. A. Bennet: The Problem of Possible Systemic Effects from Certain Chlori nated Hydrocarbons. ]. Ind. Hyg. Tox icol. 19: 283 (1937). 6. Drinker, C. K.: Further Observations on the Possible Systemic Toxicity of Certain of the Chlorinated Hydrocar bons. }. Ind. Hyg. Toxicol. 21: 155 (1939). 7. Wheeler, E. P.: Personal Communica tion, Monsanto Company, St. Louis, Missouri 63166. 8. Greenburg, L., M. R. Mayers, and A. R. Smith: The Systemic Effects Result ing from Exposure to Certain Chlori nated Hydrocarbons. J. Ind. Hyg. Toxicol. 21: 29 (1939). HARTOLDMON0009900