Document 2yE21kV2BZBMoYDoyLy0DB6L

-ns.r-i ft) . fit-&-(<*) THE DOW CHEMICAL COMPANY .y iMuU.MnSfft i uirnuum. M.r~ MIDLAND. M 1 C H 1 GAN T..C0- RESTRICTED V NBH3.5-6-6 (2), AC/7/ POt use OF DOW EMPLOVICt ONLY ACCT: 6MAITm(WT------------------------------- ------------------- ' __ Chemical Biology/Research October 3, 1972 TTOtlflu hlMCIR CiL -ut AMl <N VD ETHYLENE DIBROMTDE EXPOSURES TO OPERATORS IN MANUFACTURING I FACILITIES AND TO GASOLENE STATION OPERATORS IN PUBLIC GAS STATIONS VO inI INFORMATIVE SUMMARY WITH CONCLUSIONS m PC The ethylene dibromide exposures to the operators in 247 Building, the reaction facility, in 440 Building, the distil a lation and packaging facility, and in Bay Gasolene Stations 1 are well within acceptable criteria on a time-weighted average basis. However, a two-minute/eight-hour peak exposure to the operator in 440 Building exceeds permissible criteria. -> z SS 8t -e REVIEWED BY /D-H-7Z _____________ V IT SUED TO jir.d J?. DeMott, Halogens Lab, 768 Building D. A. Bugg7Bromine Products, 440 Building J. A. Kelly, inorganic Chemicals, 2020 Building J. L. Nichols, Inorganic Chemicals, 2020 Building J. J. Stauffacher, Bromine/iodine, 247 Building A. C. Wilcox, ICPD, 47 Building H. C. Scharnweber, M.D., Medical Department, 607 Building R. Cook, M.D., Medical Department, 607 Building R. R. Langner, Industrial Hygiene Services, 607 Building J. M. Norris, Chemical Biology Research, 1803 Building F. D. Axe, industrial Hygiene, WESTERN DIVISION, PITTSBURG R. A. DeGesero, Environmental Health, TERNEUZEN B. S. Horvath/O. N. Freemen, Industrial Hygiene, FREEPORT, B-101 N. Murray, industrial Hygiene, SARNIA M. Kelyman, Safety Department, 400 Building CRI, 566 Building VO .130589 CONF T DFNT T Al 2 PROBLEM Supervision in the Halogen Research Laboratory# respond ing to Research Personnel Product Stewardship obligations# requested the Industrial Hygiene Section of Chemical Biology Research evaluate the degree of exposure of manufacturing p rsonnel and gasolene station operators to ethylene dibromide. CONCLUSIONS 1. The Bay Gasolene Station operators are exposed well within permissible levels to ethylene dibromide, tetraethyl lead and total hydrocarbons. 2. The ethylene dibromide operator in 247 Building is exposed within permissible levels to ethylene dibromide. 3. The ethylene dibromide operator in 440 Building is exposed within permissible levels on a time-weighted average basis to ethylene dibromide. However# there is a two-minute per eight-hour shift period that the operator is exposed in excess of the allowable peak concentration for EDB. no i3onq0 TDFNT T At CONF1 3 DISCUSSION The acceptable level of ethylene dibromide exposure as defined by the American National Standards institute. Com mittee 2-37.31-1970, and adopted by the Occupational Safety and Health Act (OSHA) of the Labor Department, is 20 ppm time-weighted average concentration, with acceptable ceiling concentrations of 30 ppm and an acceptable maximum peak of 50 ppm of no longer than five-minute duration. The permissible occupational exposure to tetraethyl lead as defined by The American Conference of Governmental Industrial Hygienists and adopted under OSHA is 0.0076 ppm on a time-weighted average basis. There is no permissible exposure value for gasolene vapors, as it depends on the specific quantity of each hydro carbon component. However, a value often times used for gaso line mixtures is 500 ppm. Ethylene dibromide is manufactured at 247 Building by the reaction of ethylene and bromine to yield crude EDB. This is essentially a closed operation with the following exceptions. When leaks around pipe joint seals, or pump packings occur, the EDB is allowed to remain on the floor within a diked area, and eventually washed with water into the sewer system, in addition, samples of the crude EDB are taken, visually checked and spilled into an open bucket. 00 1305*91 CONF 1 OFNT TAt 4 The crude EDB from 247 Building is then pumped to 440 Building for distillation and packaging. The packaged material is then stored in a tank farm shed prior to shipment. The EDB is sold as an additive to gasolene, where it is added as a scavenger for the tetraethyl lead anti-knock com pound . The tetraethyl lead (TEL) is added to gasolene at an approximate concentration of 2.5-3 ml TEL per gallon of gasolene. The EDB is added at approximately 1.5 equivalents based on TEL. The Halogens Lab supervision were concerned about the industrial exposure to EDB at Dow and about occupational expo sure to EDB of gasolene station operators. In addition, super vision requested that the exposure of the gasolene station operators to TEL and total hydrocarbons also be evaluated for comparison to EDB exposures. The EDB exposures at 247 Building and the gasolene stations were sampled by use of breath tubes half filled with silica gel, and the sampled air drawn through the tube by means of a vacuum pump. The EDB in the air was adsorbed on the silica gel as the air was drawn through the tube. The EDB was eluted from the silica gel by hexane and analyzed by electron capture chromatography. The system was calibrated as to air flow, per cent EDB adsorbed on silica gel, percent desorbed, and amount of EDB detected by EC. The air flow was 1.0 1/m with 100% adsorp tion onto and desorption from the silica gel, with a detection limit by EC of 390 nanograms. The effect of other contaminants DO 13059? CONF TDFNTT M 5 on the system were investigated and found not to be significant. The EDB exposures at 440 Building were previously determined by filling 10-liter saran bags with the air by infrared spectroscopy. The limit of that means was 2 ppm. The total hydrocarbons were analyzed by means of a J&W Explosimeter, sensitive to all combustible hydrocarbons. The calibration of the J&W meter was based on gasolene vapor concen trations equivalent to that of n-hexane. The TEL methods tried were unsuccessful/ so the values reported are literature values reported in 1962 and related to the time distribution work pattern of the Bay Gasolene station I operators. These values should be considered as maximum order of magnitude exposures. The survey was conducted during the weeks of September 18 and 25. The data are reported in Tables I to III. Table I lists the data for the Bay Gasolene Station operators. The time-weighted average (TWA) exposures of the drive (pump) attendant are 0.005 ppm EDB, 0.0014 ppm TEL, and 49 ppm total hydrocarbons. The TWA exposures of the garage mechanic are 0.003 ppm EDB, 0.0011 ppm TEL, and 30 ppm total hydrocarbons. The exposures listed are maximum TWA concentrations. The work at different gas stations varies considerably depending on volume of business (number of cars serviced). 00 130593 00NFTDFN1 T At. 6 Table II lists the exposure values for the EDB operator at 247 Building. The TWA concentration to the operator is 2.9 ppm with a range from 0.4 ppm to 38.4 ppm. Although the author and one other person present during the survey experienced moderate eye irritation and moderately objectionable odor response to concentrations around 17 ppm and strong odor irritation to 38 ppm, the operator did not complain of the same symptoms. However, the presence of bromine vapors was not determined. For the time duration of work involved in each area (four minutes at 38.4 ppm, the remainder of the time under 20 ppm), the exposure profile is within permissible criteria from a systemic toxicity standpoint. Table III lists the exposure values for the EDB operator at 440 Building. The TWA concentration of EDB exposure to the operator is 4 ppm with a range of (0) to 110 ppm. Although the TWA concentration is within permissible criteria, the ceiling value of 50 ppm is exceeded for the two minute 110 ppm exposure in the EDB Tank Farm Shed. The sampling in 440 Building was accomplished between 10/7/70 and 6/8/71 and has been reported in Report No. NBH2.41-2-2(3) dated 10/6/71. DO 130594 OONFTDFNTT Al Table I. Exposure of Gasoline Station Operators to Ethylene Dibromide, Tetraethyl Lead and Total Hydrocarbons Job Location Drive Attendant 1) By gas pumps 2) Office, garage Time (min) Concentration EDB (ppm) Ranqe Averaqe 360 <0.0007- 0.007 0.010 120 <0.0007 Tim -Weighted Average Exposure o ^ (Time) (Cone) 480 - 480 Garaqe Mechanic 1) Garage, office 2) By gas pumps 330 160 Time-Weighted Average Exposure = S (T^rn,eM^onc) ** 499 0.005 <0.0007 0.007 0.003 Concentration TEL* Cone. Total HC (ppm) (ppm) Ranqe Averaqe Ranqe Averaqe 0.0009- 0.0015 0.0085 0.0009 10-1000 10-60 60 15 0.0014 0.0009 0.0015 0.0011 49 15 60 30 *Based on data reported in December, 1962 (Archives of Environmental Health, Vol. 5, pp. 527-531, 1962) o oTl wD X-_f4 '-*'JP0! \ Table II. Exposure of the Ethylene Dibromide Operator to EDB Vapors, 247 Building Work Location (A) Time 1) EDB reactor area 2) Sample taking, EDB reactor area 3) Laboratory 4) Control room and iodine area 60 8 52 360 Time-Weighted Average = 480 Exposure (B) Concentration EDB ppm Range Average 7.3-13.9 10.7 13.9-38.4 26.2 7.3 0.4 (A)x (B) 480 1.34 0.44 0.79 0.30 2.9 D0 1 30 F,9f> OONFTDFNT TAI Table III. Exposure of the Ethylene Dibromide Operator to EDB Vapors, 440 Building Work Location 1) EDB still and panel board 2) Drier room 3) Drier room (high concentration) 4) Tank car unloading 5) EDB tank farm 6) EDB tank farm shed 7) Venturi room 8) EDB wet tanks 9) Waste water area 10) Lunchroom (A) Time 95 100 20 60 73 2 40 15 15 60 (B) Cone. EDB ppm 6 5.2 23 (0) (0) 110 2 2 2 (0) (A)x(B) 480-- 1.19 1.08 0.96 (0) (0) 0.46 0.17 0.06 0.06 (0) Time-Weighted Average Exposure = 480 3.98 ~4 ppm DO OONF tOFN1"1 Al