Document v6K4B6qYNevpKZv5R4pNzDb6R

Environmental Health Program A-2400, A-7000 2" '' November 24, 1981 _h'j- R&S 037059 PURPOSE -''r* The intent of thin protocol is to document priorities established for the on-going indr '.trial hygiene program in the Chlorinated Ethane Products plan s. This document will also serve as a reference source for plant supervision and personnel responsible for the industrial hygiene programs. It is recognized that by definition an "on-going" program is one that is. responsive and can easily b& adjusted to changes m priorities. These may result from changes in process design, job procedures, the chemicals being handled as well as new toxicology data, exposure guidelines, or monitoring techniques. GOALS There are"two ba sic goals"the industrial, hygiene program is designed to meet. Theyiare; ... (1) To annually educate plant personnel on how overexposures to chemicals may occur, methods of reducing overexposure, potential adverse health effects of overexposure, primary information sources on health effects, and on the way in which the work done by various health related groups, wiLhin The Dow Chemical Company, help protect the health ot employees. (2) To annually monitor and communicate the results to employees who have a potential fo*- being overexposed to ct 'cals or physical agents in then work environment. Meeting the Goals 1. Dow has established the coal of educating the employees on health related questions as a part of the corporate policy. It is recognized that an. effective employee education program is one of the best methods 'or controlling workplace? exposures to hazardous materials. Three video tapes have been prepared for use by the plants to cover the basic asr-*?et of the educational goals. The Environmental health Tear. is a tape which summarizes the work of Toxicology, Industrial Hyg.tcne, and Industrial Medicine functions. The second tape. How Overexposures Mav Occur and Methods of Controlling Overexposures reviews now various types o: workplace stresses may occur and familiarizes the employee with various methods of exposure control. The last tape, Sources of Information, deals with how information on the toxicity ol chemica1s anu physical agents is obtained. Employees are educated in the potential adverse health effects of chemicals lay a fourth aspect of the program where they are asked to read a uencral discussion of potential adverse health effects and iwiew specific selected Environmental Health Program A-2400, A-700C , " ' Produced PuiTA;~s:t , . ' - .'7 November 24, 1981 Meeting the Goals (continued) Consequences of Overexposure To Toxic Amounts sheets and Toxicology Data Sheets incorporated into booklets. These booklets are distributed throughout the plant in easily accessible areas such as offices and control rooms. The viewing of the video tapes and review of the booklets is documented and summarized each quarter to monitor the progress of the educational program. This documentation and summary of the progress is reported via the Index I form shown in Appendix I. While use of the video tapes and hazard booklets will suffice for meeting the minimum Dow.crjjteria,,._a,,.s,uccefi.wfu 1, "?Twraployc- ^ ed'-tSafcyail levels jof stipet-- Vision be :activiisi'^|?ilSTOved in the .presentation of.,.bel ; program. 2. The vehicle for establishing both educational and monitoring priorities is the Chemical and Physical Agent Inventory sheet. An inventory sheet for each 30b classification is prepared. The completed inventories for the CEP areas are contained in the following sections of this report. The inventory contains a complete list of the chemicals and physical agents that persons in a given 30b class have a recognized potential for exposure to while performing their normal job. An estimate of the degree of exposure is mace based on job procedures, plant process design, and the quantity and physical properties of the material. Definitions for the ratings (1-4: Dow-High) are given in Table 1. Based on these estimates of exposure potential and the toxicity of the compound, hazard ratings are assigned. The hazard rating defines the necessary industrial hygiene action to be taken with respect to the two industrial hygiene goals. Definitions of the five hazard ratings are given in Table 2. The exposure and i.azard ratinqs were assigned during and following discussions with various CEP supervisory personnel. Considerations concerning 30b procedures, how the chemicals are encountered or handled, the likoiyhood of being overexposed, previous monitoring results, toxicology data, ar.d exposure criteria assistcu in assigning hazard ratines. For those auents where tho hazard rating indicate?'. he' r.ionitouinq is warranted, ,1 raonitorir.q urogram ' r> u? ; e<-r e,: and the results ot tins monitor 1no is communicatee to the employees throuuh super vision. The communication ji the monitor wic results is R&S 037060 R&S 037061 Environmental Health Program A-2400, A-7000 4 Meeting the Goals (continued) November 24, 1981 documented and summarized each quarter to monitor the progress of the exposure communication effort. The documentation and summary of the progress is reported via the Index II form shown in Appendix I. PROCESS DESCRIPTIONS, JOB DESCRIPTIONS. AND INVENTORIES The CEP complex is located ir the A-2400, A-1600 and A-7000 blocks. The major products of the unit are ethylene dichloride, vinylidene chloride, beta-trichloroethane, alpha-trichloroethane, alpha-dichloroethane, ethyl chloride, tetrachloroothane, and hydrochloric acid. Administratively the unit is broken down into the following areas: vinylidene chloride/ethyl chloride/betatrichloroethane production, ethylene dichloride production, alphadichloroethane/alpha-trichloroethane production, CEP unit services, A total-, o- approximately 145 full' (these areas. i For each of the above areas a description of the process (where applicable), the associated job descriptions, and industrial hygiene inventories are given in the following appendicies: Appendix 13 vinylidene Chlv i 'o/Ethyl Chlorlde/BetaTrichloroethane "reduction Appendix III Alpha-Dichloroot hane/Alpha-Trichioroathane Production/THROX Appendix I',' ethylene Dichloride Production Appendix V CEP Maintenance Appendix VI CEP Unit Services Appendix '.'II CEP Lab INDUSTRIAL HYGIENE MONITORING METHODS `* 1 A list of the compounds and physical agents which will require some degree of monitorinc is given in Table 3. The methods used for performing the monitoring are referenced in the table and described beiow. The momtorinq and analysis will be per formed by CEP Lab personnel with the support and assistance of the plant industrial hygienist. 1 , Charcoal Tube Mt'nitvr 1 ng This method n to be used for determining both short term and fi-iiout t l me-wt-ich ted nvesnue potential exposures. The metlioc involves collect :on cl t.ho compounds on activated charcoal adsorption media and analysis by gas >1 '.vcd io-.ll I nil Wal < ion-t R&S 037062 'Miff! Environmental iWlth Program A-2400, A-70U0 November 24, 1981 INDUSTRIAL HYGIENE MONITORING METHODS (continued) chromatography via solvent desorption. Commercially available charcoal tubes containing one gram of PCB 20 X 40 mesh activated charcoal are used to collect organics from the sampled air. Personnel sampling pumps pull air through the tubes at known constant flow rates. The maximum flow rate and total sample volume criteria are established to ensure that no loss is occurring due to breakthrough. Recommended values for those compounds collected on activated charcoal are listed in Table w . Where more than one of these compounds is to be collected on the same sample, the lowest recommended flow rate and total sample volume among the compounds to be monitored should be used. The recommended sample voxumes and flow rates allow quantative collection of the compounds. Flow rates may be increased for short term monitoring or periods less than 8 hours so that adequate..sensitivity may be obtained. , The "total sample volumes,;'Wbweve#,, should riot be' exceeded,. y ' fy". TM Analysis of the samples should follow standard desorption with 10 ml of dry ice chilled carbon disulfide (or othersolvents as necessary) and gas chromatographic analysis of the extract. Desorption efficiencies are reported in various references, however the values to be used in the calculations shall be determined by the CEP Lab by analysis of spiked samples. Reevaluation of desorption efficiencies should be done at least annually. .2 Peak Mom tor mo This method is to be used o determine peak exposure tc organics for personnel dun rig very specific jobs such u sampling, brcakir.o into ecu lpmer.t, entering vessels, or otherwise working on procos s equipment. A clean alass air tight syrinqo is taken to the job site and a sample of air is taken in the brea thing zone of the worker by pumping the piston in and o it several times and then slowly drawing the air into the cylinder. The syringe is closed securely to preve nt air leaks ar.d taken to ti laboratory for analysis by injection into a gas chroma! graph as soon as possible, A gas chromatograph dedicat for this type of analytical work should be used. The i. chromatograph should be sta ndardized with inown air samples at tegular interval 3 . Colorimetric Indicator Exposures co chlorine, be evaluatec os me indicating tube1- . m iCii ior ic acid, and ammonia w'b) f-r- 'irr.ucr.t 1; i cot readme coL-gti.ritf rih....... -vd.-r ;.rr R&S 037063 Environmental Hath program A-2400, A-7000 November 24, 1981 INDUSTRIAL HYGIENE MONITORING METHODS (continued) 4. Membrane Filters Silica dust exposures will be determined by collection on PVC membrane filters (MilliporeG1, 0.6 micron, 47 mm) at calibrated flow rates of 1.5-2.0 liters per minute and analyzed by X-ray diffraction. Validation of the analytical procedure is reported in Analytical Services report TC-566. . . ! Welding fume exposures will be evaluated by collection on Millipore membrane filters (GSHP, 0.2 microns, 47 mm) using a calibrated 10-15 liters per minute) high volume sampling pump. Analysis of the samples will be done by atomic absorption analysis, 1 "........ T'"1"1'' POtPnti^^jasbea.tos exposures Will 'be^evaluated using ^BtajWard il^OSfe.'pil.Ocedures ^Method 239). Sandies are' ^collected on 0.8 micron", 37 mm Millipore cellulose acetate filters at calibrated flow rates of 2.0-2.5 liters per minute. Asbestos fibers are counted using phase contract microscopy. 5 . Continuous Air Monitor The continuous air monitor in place in the A-2400 block will be used for the out pose of identifying problems in the process area which could lead to potential exposures to chemicals. When the continuous air monitor data indicates a high level of airborne chemical concentration, consideration of this data will be used to determine necessary rAsts to reduce potentia) exposures. The continuous air monitor data will net, however, be used to calculate individual doses. EVALUATION CRITERIA Personnel monitoring is performed to determim potential exposur, levels both, as a daily t ime-weighted uverauo ami short term exposure. The results the monitoring are compared with the recommenced exposure guidelines aiven m Table 7. Also listed in the table is tn<* source of the recommended, standard. These values are nas.-e or. re 1,able toxicology data and inoustr.al experience. I; , s i jf 1 i. : t! at nearlv all worker:; w-iii toierafexposure to tries,, level;, without adverse health effects. The exposure eu ide 11 ih.-s represent the acceptable time-weighted average exposures. ;c,, norma; ii-auuj .work cay, 40 hours her week. Short Term Exposure bimts (STr:N' s) represent the maxi-mu-nv" r.sriv fviWj) i rrt-3narrwt.it R&S 037064 & Environmental Health Program A-2400, A-7000 November 24, 1981 EVALUATION CRITERIA (continued) concentration for a IS minute exposure. The STEL should be considered a maximum or ceiling concentration that should not be exceeded unless other criteria state otherwise. Further, no more than four excursions per day are acceptable. At least 60" minutes must elapse between exposure periods, and the timeweighted average (TWA) should not be exceeded. As a group, the chlorinated hydrocarbons exhibit similar consequences of overexposure. Among these are systemic effects to the liver and kidney from chronic overexposure and central nervous system depression from acute overexposure. Due to this similarity and the likelyhood that potential exposures will -...e occur to mpre^than. one. of,,the |Chlorin^t-ed Thy;dfcocarbons. during the work 'day`it;"is -^neceWaryf j,to: givd fpirimairy' consideration to the combined, ra^^r'5thSn individual'^ feffedt of the compounds when evaluating the "monitorincj results: The; additive effect of different compounds is accounted for by calculating the sum of the ratios of observed exposure concentration to the exposure guide for each compounc. If this sum exceeds unity then the combined exposure is m excess of acceptable limits. An example calculation is uivon m Table 6. In addition to personnel sampling, grab sampling with gas tiqht syringes should be performed to evaluate potential pear, exposures This sampling snould be ]ob task oriented involving those routine tasks that result in a high potential for exposure. These include process sampling, connecting and disconnectino loading lines, breaking into process equipment, tank qauumg, and any open transfers of materials. The results of this monitoring will be evaluated relative to the STEL1s given in Table 6. Employees shall De informed of the the significance of * tie data. All exposure data is to be documented. results of all monitoring informing of employees on and RECOMMENDED MINIMUM MONITORING REQIJ IREMENTS As stated earlier, monitoring to warranted for those agents indicate' ; :jy the hazard rating on the industrial hygiene inventor u-.ei't;, as described m Table 2. The induutr'ai hygiene nvnj'.t'" r ies have been reviewed and the recommenced monitor: : e ti reme r.ts are outlined below. Given ip t r.e outli:; r noni'or, hi classification; unci chemical: for wu i' cone. The outline is broken .sown into Spec:f: ; Class;!, r.n service an-js although some job -ver ! ,-e. I * Indicate C ;L<t 4 Environmental Health Program A-2400, A-7000 November 24, 19l VINYLIDEtJE CHLORIDE PRODUCTION Chemicals Job Classifications Vinyl Chloride Vinylidene Chloride 1,1,2-Trichloroethane Syn-Tetrachloroethane Unsym-Tetrachloroethane EngineerP ". C;. r:!zc: rv .* Shift Foreman Control A Operator Control C Operator ETHYL CHLORIDE PRODUCTION Vinyl Chloride Ethyl Chloride 1,1-Dichloroethane Ethylene Dichloride Engineer Shift Foreman Control A Operator '1 BETA-TRICHLOROETHANE PRODUCTION Ethylene Dichloride Vinyl Chloride ' 1` 1,1,2-Trichloroeth|uie Sym-Tetrachloroetha'ne Unsym-Tetrachloroethane Pentachloroethane Hexachloroethane Engineer Shift Foreman Control A operator Control C Operator ALPHA-DICHLOROETHANE PRODUCTION Vinyl Chloride Ethylene Dichlonde Sym-Tetrachloroethane Unsyrr.-Tetrachloroe thane Pentachloroethane Hexachloroethane Engineer Shift Foreman Control A Operator Control B Operator ALPHA-TRICHLOROETHANE PRODUCTION 1.1-Dichloroethane 1.1.1-Trichloroethane Sytn-Tetrachloroetnane Unsym-Tetrachloroethane Pentachloroethane Hexachloroethane Production Foreman Control A Operator Control C Operator Vinyl Chloride THROX Shift Foreman Control C Operator Pufi R&S 037065 Environmental Health Program A-2400r A-7000 November 24, 1981 ETHYLENE DICHLORIDE TDDUCTION Chemicals Ethylene Dichloride 1,1,2-Trichloroethane Sym-Tetrachloroethane Unsym-Tetrachloroethane ui. Classifications Shift Foreman Control A Operator Control C Operator CEP MAINTENANCE Ethylene Dichloride 1.1-Dichloroethane 1.1.1-Trichloroe thane 1.1.2-Trichloroethane Vinyl Chloride Vinylidene Chloride Ethyl Chloride Sym-Tetrachloroethane Onsym-Te'trachloroe thane Pentachloroethane Hexachloroethane Electricians Machinists Pipefitters CEP UNIT SERVICES Vinyl Chloride Vinylidene Chloride 1,1,2-Trichloroethane Ethylene Dichlondo Sym-Tetrach leroe th a no Unsym-Tetrachloroo thane Ethyl Chloride Perchloroe thy 1en e Asst, Production Supt. Loading Supervisor Control E Operator CEP LAB Vinyl Chloride Vinylide: a Chloride 1.1-Dichloroe thane 1.1.1-TrichLoroetha: 1.1.2- Tnchloroetha; Ethylene Dichloride Sym-Tetrachloroetha: Unsym-Tetrach Loroo t; Eth>l Chloride Production Chemist Chemical Technologist Chemical Technicians Sr, Asst. Chemist Class II ru/Jj ..n R&S 037066 PLR/bbj : v >i.; 1 !-i I ( !i II,).' n il Il.lt l Rli.i'l, (l\) n.-v: Par.-ul I nil ii'.ifr i iv c.'.i Mitl.ii l''it 'fl.tt t)tw . Xl.ti*K iii-t yi-i R&S 037067 * Environmental Health Program a-2400, a-7000 10 November 24, 1981 TABLE 1 DEGREE OF EXPOSURE No contact- Sources of exposure are isolated from the work area. Minor contact- Work performed in areas where the material is handled or processed io closed systems. Exposures are passive in nature, not direct result of work activities. 3- Occasional.T<Saily contact-- Some work tasks result in direct contact with the material. Examples are: process sampling, breaking into process equipment, manually gauging tanks, loadinu and unloading tank trucks. Gross contact likely-------- Prolonged amount of time spent m an area of high concentration or performing tasks resulting in large exposures. ). c-i.anr :;;7 R&S 037068 6^ Environmental Health Program A-2400, A-70C0 . * November 24, 1981 TABLE 2 INDUSTRIAL HYGIENE HAZARD RATING The rating indicates the necessary industrial hygiene actionr to be taken for each chemical HAZARD RATING ACTION REQUIRED More frequent than annual monitoring (usually defined law, e.g. vinyl chloride). Include in annual education program. by Annual monitoring is required as ^a.minimum. . Include in. annual^ ^education' program. Some monitoring may be required. Include m annual education program. No monitoring necessary, but should be inciudec : r. annual education program. No action requircc. ''Pursued - ;'Jw -in-rf Environmental Health Program A-24O0, A-7000 November 24, 1981 TABLE 1 compounds AND fhycials agents requiring monitoring COMPOUND OR PHYSICAX, AGENT MONITORING METHOD Vinyl Chloride Ethyl Chloride Methylene Chloride Vialyidene Chloride 1.1- Dich.loroethane (Alyhj-di) 1.2- Dichlo-nethane (EDO 1.1.1- Tnchloroethanc (Alpha-tri) . 71.1.2- TrichIoroean&"CB.ta-tri); ' "V Perobloroothylene (Pcrchlor) 1.1.1.2- Tetravhloroethar.c- (Unsym-tet) 1.1.2.2- Tetrachloroethane ^Sym-tet; Pentacnloro-i thane flexachloroothanc 1,2,5. 1,2,5 1,2 1,2,5 1,2,5 1,2,5 A, 2,5 1,2,5 1,2 1,2 1,2 1,2 1.2 ">rv( Chlorine R&S 037069 1. Charcoal tube 2. Gas tiyht syringe 3. Color imo tr i r indicating tube 4. Membrane til ter 5. Continuous urea monitor monitcr:no : o i t- dont us r i ream:; cancer dictate