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INDUSTRIAL HYGIENE SURVEY OF THE Polychlorinated Biphenyl Production Operation Monsanto Industrial Chemicals Company Sauget, Illinois SURVEY DATE July 21-22, 1976 SURVEY CONDUCTED BY Mark Jones Janson Becker REPORT WRITTEN BY Mark Jones DATE OF REPORT May 6, 1977 Industrial Hygiene Section Industrywide Studies Branch Division of Surveillance, Hazard Evaluations and Field Studies National Institute for Occupational Safety and Health Cincinnati, Ohio MCNS 000191 PLACE VISITED: DATE OF VISIT: PEOPLE CONTACTED: PERSONS MAKING VISIT: PURPOSE: Monsanto Company W.G. Krummrich Sauget, Illinois July 21-22, 1976 Mr. Art Leisy Manufacturing Superintendent Mr. Paul Heisler Director, Safety and Environmental Control Mr. Bruce Eley Corporate Industrial Hygienist Mr. Virgil Brawley Supervisor - PCB Production __ Mr. John Ped.U2.si ... .......... Supervisor ~ Incineration Mr. Julio Munoz Senior Technician, Environmental Control Mr. Nell Sullivan Technician, Environmental Control Mr. Frank Baalle Senior Engineer, Environmental Control Mr. Ed Neumann Technician, Environmental Control Mr. Dale Rachel - Foreman, PCBs Production Mr. Tom Carrico - Foreman, PCBs Production Mark Jones Janson Becker To conduct an Industrial hygiene survey to determine the workers' level of exposure to chemicals present in the polychlorinated biphenyls production area at the Sauget, Illinois facility. HONS 000191 INTRODUCTION Recent literature has linked polychlorinated biphenyls with possible carcinogenic effects. Because this literature is incomplete* the Division of Surveillance, Hazard Evaluations and Field Studies of the National Institute for Occupational Safety and Health has underway an "industrywide" study of industries using polychlorinated biphenyls. Since Monsanto is the sole producer of polychlorinated biphenyls in the United States, an industrial hygiene survey was conducted st their PCBs production area in Sauget, Illinois, on July 21-22, 1976. This survey was conducted by Janson Becker and Mark Jones. During the visit, 18 air samples were collected for evaluation of poly chlorinated biphenyls exposure. In addition, samples were collected for exposure to iron silica and chlorine. DESCRIPTION OF THE FACILITY The polychlorinated biphenyls production operation is one of many operations preeent at the Monsanto facility in Sauget, Illinois* Sulfuric acid, benzene derivatives, rubber chemicals (antioxidants, etc.), chlorine and phosphorous products are other products produced at the facility. The facility began production of polychlorinated biphenyls around 1936. Production continued to grow until 1970 when Monsanto began restricting the sale of PCBs to use In closed systems. The entire work force at the facility is approximately 1300 persons, with approximately 835 of these persons being hourly employees. Approxl mately 25 employees are Involved with the production of PCBs. The union representing this group is the International Chemical Workers, Local #12 . MEDICAL, INDUSTRIAL-HYGIENE AND SAFETY PROGRAMS.......... A dispensary Is located at the plant. Nurses are present at the dis pensary 24 hours a day and a physician is present during the day. All employees are required to take a pre-employment physical examination and annual physical examinations. Certain employees are required to 'take additional examinations and/or special tests. Industrial hygiene matters at the facility are handled by the Environ mental Control Group. The six people who are assigned to this group work In conjunction with the safety department. The only sampling that has been done for polychlorinated biphenyls is the waste water discharged from the area is sampled continuously and analyzed twice a week and the collection of a few air samples (Appendix B). HONS 000193 Four people work In the safety department. Safety meetings are held every month and safety Information Is provided to the different work areas through safety committees. Personal protection programs used at the plant include safety shoes, safety glasses, hard hats, pro tective clothing and respirators (where needed). Corporate industrial hygienists also give support to the industrial hygiene and safety programs. DESCRIPTION OF PROCESS Three products are made in the PCBs production area: Aroclor 1016, Aroclor 1262, and Aroclor 1254. Aroclor 1016 is used in capacitors and Aroclor 1242 and 1254 are used in transformers. The operation is outdoor and consists mainly of pipeline, reaction vessels, distillation columns and storage tanks. Even though the system is theoretically a closed system, samples are drawn off and leaks occur which give a potential for employee exposure. Biphenyl Is brought to the facility by tank car and pumped to storage tanks. The chlorine used for the operation comes by pipeline from another pert of the plant. The chlorine and biphenyl are piped into a chlorinator In the presence of a catalyst and allowed to react. There are two separate groups of chlorinators, one group for producing Aroclor 1254 and the other for Aroclor 1242. The product from the Aroclor 1254 chlorinators goes through a purifying operation which includes a still, receiving tank and filtering system. From this operation the polychlorinated biphenyls go to the appropriate storage tank. The product from the Aroclor 1242 chlorinators goes to an intermediate storage tank and then either through a similar operation as the Aroclor 1254 or to a distillation column for producing Aroclor 1016. From here it goes to the storage tanks. The mixing tanks are used to formulate the final product by the Intro duction of the appropriate additives needed to give the polychlorinated biphenyls the properties desired by the customer. Diatomaceoua earth is used as an aid to filtration. INSPECTION OF PLANT Potential Health Hazards Potential health hazards observed during this survey were as follows: 1. Polychlorinated biphenyls exposure 2. Chlorine exposure 3. Free silica exposure MONS 000194 -2- Ventilation The polychlorinated biphenyls production operation is located outdoors. Local exhaust ventilation is used in two operations. The drumming operation is equipped with a hose which is placed near the opening of the 55 gallon drum while it is filled. Near the chlorinators is a work station where employees perform specific tests on samples drawn from the chlorinators. This work station has an-exhaust fan and a hood over the area whare the teats are performed. Housekeeping Housekeeping In the polychlorinated biphenyls production area was taken care of fairly well. The alslevays were kept clean and clear. SURVEY PROCEDURES General Air samples were collected in the polychlorinated biphenyls production area for evaluating exposure to polychlorinated biphenyls, iron chloride, and chlorine. A bulk sample of the dlatomaceous earth used waa analyzed for free silica content. The following paragraphs describe the methods used to collect and analyze the air samples. Polychlorinated Biphenyls Both personal and area air samples were collected in the polychlorinated biphenyls production area. Sipin Spl pumps were used to collect the air samples on floroell tubes. The tubes contain a magnesium silicate absorbent called florosil and have a 100 mg primary section and a 50 mg backup section. Samples were collected for six to eight hours at a flow rate of approximately 200 cc/min. The polychlorinated biphenyls were desorbed from the florosil with hexane and analyzed by using a gas chromatograph with an electron capture detector. Iron Chloride Area air samples were collected for iron chloride while the employees poured the Iron chloride (powder) into a vessel. MSA Model G pumps were used to collect the sir samples on a 0.8 micrometer pore size mixed cellulose ester filter (37 mm in diameter). Samples were collected for the duration of the task which was approximately three minutes at a fl^tw rate of 1.7 liters per minute. The samples were analyzed for iron by at^oc.4c absorption and are reported as such. -3MGNS 000195 Free Silica One bulk sample of the dlatoroaceous earth used was collected for analysis of free silica content. The per cent free silica was determined by x-ray diffraction. Chlorine Detector tubes were used to evaluate concentrations of chlorine in the PCBs production area. Chlorine measurements were made using "Bendlx Gastec Analyzer Tubes - Low Range (1-8 ppm)". RESULTS AND DISCUSSION Polychlorinated Biphenyls The results of the area and personal air samples arc given in Table 1 and the job descriptions corresponding to the Job titles are in Appendix A. Eleven personal and seven area air samples were collected for analysis for polychlorinated biphenyls. The polychlorinated biphenyls being produced at the time of the survey were for ArocJor 1016 (42% chlorine). The personal air samples ranged from a concentration of 20 pg/m^ to 86 pg/m* while the area air samples ranged from 16 Mg/nr* to 53 pg/m . These are all well below the current Federal Standard for chlorodiphenyl (42% of chlorine) of 1 mg/m3. The dermatological effect and systemic effect on the liver resulting from. polychlorinated^ biphgnyls. ip well documented in the literature; however, recent literature has linked possible carcinogenic effects to polychlorinated biphenyls.*>2,3 There fore this standard may not adequately protect the workers health. Iron Chloride The results of the air samples are given in Table II. Two samples were collected for determining worker exposure to iron chloride. No iron could be detected on one of the samples, but the other sample had an iron concentration of 8.1 mg/m^. Since this procedure of adding the iron chloride only takes an average of 3 minutes per shift, the workers time weighted average is well below the current recommended ACG11I TLV for Iron salts of 1 mg/m3 based upon soluble iron. The big difference In sample results was probably due to the differences in operating pro cedures observed each time the task was performed. MONS 000196 -4- Free Silica The bulk sample of dlatomaceous earth was analyzed and determined to have a free silica content of 9.8%. Since the material is usually handled only once a week, the survey team was unable to observe this procedure. Chlorine ' No concentrations of chlorine ware detected. CONCLUSIONS AND RECOMMENDATIONS Based on the observetions made during this survey and the results of the air samples, the following conclusions are drawn and recommendations for Improvements made: 1) Even though the concentration of iron chloride found while handling the material is below the ACG1B recommended TLV it would be good industrial hygiene practice to wear an approved respirator when this task is performed. 2) Since the dlatomaceous earth contains 9.8% free silica, an approved dust respirator should be worn whan the worker performs this task if this practice is not presently employed. Because of the recent concern of the possible carcinogenic effect of polychlorinated biphenyls, engineering methods should be used to prevent employee exposure to polychlorinated Table X CONCENTRATIONS OF POLYCHLORINATED BIPHENYL (detected as Aroclor 1016) TN A FACILITY MANUFACTURING POLYCHLORINATED BIPHENYLS Personal Air Samples Job Title Premium Operator II .Second Operator It Column Operator t Still Operator II Standard Operator Distribution Operator H Date Sampled Total Sampling Time (min.) 7/21 7/22 436 451 Volume (liters) 91.0 97.8 7/21 7/22 432 448 80.0 95.3 7/21 7/22 446 74.9 85.7 7/21 7/22 432 444 94.6 67.6 7/22 445 96.1 7/21 413 88.3 7/22 419 91.3 Concentration (Mg/ra3) 47 20 46 43 64 51 . 40 86 61 54 36 (pIP 33 44 57* 63 61 45 Area Air Samples Location Drumming ti Date Sampled 7/21 7/22 Total f Sampling Time (min.) 418 418 Volume (liters) 89.1 87.6 Temperature Testing it 7/21 7/22 417 455 201.6 105.4 Clilorlnators M 7/21 7/22 419 459 89.0 70.3 Incinerator Burner 7/21 409 81.6 Concentration. Average (pg/m3) (up./m ) 45 48 51 25 52 39 55 46 36 16 16 Arithme*Average HONS 000198 Table II CONCENTRATIONS OF IRON CHLORIDE FOUND WHILE OPERATOR ADDED IT AS A CATALYST Location Date . Total Sampling Time (rain.) Volume (liters) Near Reactor Lid it i 7/21 7/22 3 3 5.1 5.1 Concentration of Iron (mg/m3) N.D. 8.1 Concentration of Iron Chloride (mg/m1) -- 18.4 HONS 000199 Appendix A JOB DESCRIPTIONS Premium Operator - Operates both the continuous and batch chlorinators. This Includes keeping the chlorinators running, adding Iron chloride and drawing samples. Second Operator - Loads the tank cars for shipment and takes care of the tank farm and blend tanks. Standard Operator - In charge of making sure area is clean and does all the filling of the 55 gallon drums. Column Operator - Operates the distillation column used to produce Aroclor 1016. Still Operator - Operates both stills used in producing Arolcor 1256 and 1262. Distribution Operator - Works in a different area of the plant and is in charge of operating the incinerator. HONS 000200 Appendix B CONCENTRATION IN THE ATMOSPHERE IN THE MANUFACTURING DEPARTMENT BATTERY LIMITS AS MEASURE IN OCTOBER, 1975 Pate 10/9/75 10/9/75 10/13/75 10/13/75 10/19/75 10/16/75 Location 12 ft. operating level at batch chlorinator 12 ft. operating level at continuous chlorinator 12 ft. operating level at batch chlorinator 12 ft. operating level at continuous chlorinator Ground floor operating level Ground floor, scrubber discharge area mg//in 3 0.022 0.012 0.057 0.058 0.006 0.338 SOURCE: Monsanto MONS 000201 REFERENCES 1. Urabe Hi (Foreward the fourth reports of study of "Yasho" and PCB) Fukuoka Acta Med 65:1-4, 1974 (Jap.). 2. Kimbrough, R.D., Squire, R.A,, bonder, R.E., Strandberg, J.D., Montalll, R.J., Durao, V.W.: Induction of Liver Tumors in Sherman Strain Female Rats by Polychlorniated Biphenyl Aroclor 1260. J. National Cancer Institute 55:1453-59, 1975. 3. Kimbrough, R.D., Linder, R.E.: Industion of Adenofibrosis and hepatomas of the liver in BALV/J mice by polychlorinated biphenyls (Aroclor 1254) J. National Cancer Institute 53:547-52: 1974. HONS 000202