Document npdqeM5BzJn9qgo1KwEQwa41z

r v^aca^s'. INOUJTtlAl CHUMCUS DIVISION SHELL CHEMICAL COMPANY A DIVISION Of SHUl Oil COMPANY ONE 5HEU PLAZA HOUSTON. TEXAS 77002 August 15, 1973 Gentlemen: The necessity for limiting end controlling human exposure to high concentrations of vinyl chloride has been long recognized by Industry, A 500 ppm celling value Is specified by the Department of Labor, under the Occupational Safety and Health Act, as the permitted employee exposure level to vinyl chloride. The most recent Manufacturing Chemists Association safety data sheet for vinyl chloride reports this value. A copy of this data sheet Is enclosed for your Information. . :. ",-1' ' " r-t-**in.-.- . In dune of 1972, the American Conference of Governmental Industrial Hygienists (AC6IH) adopted an eight hour time weighted average Lli.1t Value (HV) of 200 ppa (Vbl/vbl) for ri*1&Ior1de; Wiu5iSt1oivf^t covering the considerations leading to the adoption of this value mayf6eViff?'5' obtained by request to the Chairman/ TLV Conolttee, American Conference f ; Goverrmental Industrial Hygienists, P. 0. Box .1937, Cincinnati, Otilo.,,45201. While the ACG1H adopted a 200 ppm level for vinyl chlorl^, Jthe _ ,, . TLV Documentation cites studies which reconmend levels from 50 ppm to 500 ppm. As you may be aware, the Manufacturing Chemists Association has contracted with Independent consultants, on behalf of a group of vinyl chi ride producers and consumers to conduct animal exposure studies and a comprehensive epidemiology study of vinyl chloride workers. It Is hoped that results from these studies will aid In clarifying what exposure limitation would be most appropriate. However, until these results are available and In view of the range In recommendations, we considered It prudent In aur operations to establish a vinyl chloride TLV of 50 ppm; further, measurements Indicate that this Is a feasible level for us. We urge you to give consideration to the vinyl chloride exposure levels which may be appropriate for your operations. -- ao, 9004 4 We would be pleased to make available our techniques for __ measuring low concentrations of vinyl chloride If you would consider them helpful. Very, truly yours, SHELL CHEMICAL COMPANY Attachment: . R. 0..Reynolds Manager, Vinyl Chloride Business Center fa / ; MCA Safety Data Sheet SD-56 (1972 Version) .Shell Method Series 5$SV>y -..'V*:-.. 854/73 SCOPE determination of VINYL CHLORIDE MONOMER IN AIR Gas Chromatographic-Flame Detector Method 1. This method is intended for the determination of traces of vinyl chloride monomer (VCM) in air in the range from 5 to 1000 ppm v/v. METHOD SUMMARY 2. A one-ml sample of air is analyzed by gas chromatography on either of two columns, having quite different selectivity, using a flame ionization detector. If a significant concentration is observed the identification of VCM is confirmed on another type of column. Results are calculated by comparison with a known standard. Note j. CAUTION. VCM is toxic and flammable and should be handled in a hood away from sources of ignition. The liquid should be kept cool to avoid polymerization. No copper or copper alloy should be used in contact with VCM. APPARATUS 3. (a) Chromatographs with flame detector, sensitive enough to detect 10 ppm of VCM in one ml of air with at least 10% scale deflection on the recorder, under the conditions of the method. : - '. ,, (b) Columns, five feet long by 1/8-inch O.D., 0,012* wall, stainless steal tubing, one packed with 80-100 mesh Durapek Carbowax 400/Porasti C and the other with Dur|^,iH^^rasil (c) Accessories, one-ml gas-tight syringe,:60-microliter gas-tight syringe,' f/fe 100-ml glass sample cylinders, vacuum pump for evacuating these; or a bottle V .^ can be used which can be flushed with the air to be analyzed and then serum capped. If glass sample cylinders with stopcocks are used, the syringe needle must reach through the stopcodt into the storage chamber. V' Note 2. A coulometric detector in the chloride mode would provide specific response for organic chlorides, eliminating the risk of interference from non-chloride atmospheric contaminants. An electron capture detector would probably also be satisfactory but has not been tested for this ,, _ 1 Avit*bte from WaWrs Associates, Framingham, Mass. ~ ~ Publish**! In 1973 Shall Oanropmwit Company Printed In USA 854/73 Shell Method Series application. Sinca the non-specific flame detector Is used in this method two different types of column ere employed to reduce materially the probability of an erroneous finding of VCM. REAGENT 4. VCM, Matheson Company3 or equivalent.. A lecture bottle is convenient. PROCEDURE 5. Set up the chromatograph as described in Table 1. Prepare a 100 ppm v/v VCM in air sample by adding 10 microliters of VCM vapor per 100 ml of air to a glass sampling vessel or to a serum capped bottle of known volume. The vapor can be obtained from the gas cap over the VCM liquid in the supply cylinder by venting the material at a moderate rate through a short length of tubing and sampling the exit end of the tubing with the SO microliter syringe. Mix the blend by rotating the vessel in a random manner or by shaking with previously enclosed glass beads. Analyze one ml of this blend using either column and note the retention time and the peak height. Repetitive analyses should agree within about 6 ppm. Obtain samples of the e:r to be analyzed and analyze them in the same way. If VCM is found in significant concentrations repeat the calibration and analyses on the other column to confirm or refute the identification of VCM. Table 1. Conditions for Gas Chromatography Helium Carrier Gas: flowing 3040 ml/minute. Hydrogen: 30 ml/minute, adjusted for optimum response. Air: 3S0 ml/minute. Injector end detector temperatures: 50-160C. Column temperature: Isothermal in the range 20-26C, 6. ' Calculate the VCM content ot heights corrected for the attenuation, as friHows: VCMppm v/v-100x Pe*heiflht of unknom Rede height of standard PRECISION ^ t ~ ; J: ---rr-y-jir 7. Limited data indicate that the precision is about 5 ppm at 100 ppm and about 2 ppm at the 10 ppm level. * Matheson Company. LaPorte, Texes 77S71 * ADAPTED FROM UIOL V FOAM MO-L-00-*-MAY IMS SHELL OIL COMPANY SHELL CHEMICAL COMPANY SHELL DEVELOPMENT COMPANY SHELL PIPE LINE CORPORATION HAZARD^/ RATING MATERIAL SAFETY DATA SHEET information on thi* form It furnlthotf tololy for tN purpot* of comptianc* with tho Occupational Safaty and Na#Hh Act of 1970 ontf tholl not M for Any othor pyrpoto. Uit or dintminition of tit or ony port of thia Information for any othor pgrpow may ratutt in I violation of low arcao titvu Qroundt for la^al action. SECTION 1 MANUfACfuKtK'S NAME ... Shell Chemical Company EMtAGCMCV TELEPHONE MO. (713) A73-9461 mwhimeSm City, s,ot.,,d ZIP c~h> p Q Box 2463> Houston, Texas 77001 CHEMICAL name Amo synonyms Vlnvl Chloride. Chloroerhvlene. Chloroethane CHEMICAL FAMILY formula Vinyl Halide __ Vlnvl Chloride Monomer fVCMT COMPOSITION Vinyl Chloride SECTION II HAZARDOUS INGREDIENTS* X SPECIES LOso oral DERMAL 100 LCjb CDNCCNTRATION hours Vinyl chloride ha s anaesrheti c properties at high co ncentrati ns (80,000-120,000 ppm). Card iac arrhythm las have been found In dogs at these levels. Liver changes have been report ad in rabbits at 200 ppa, hut not In rats, guinea pigs or dogs.-, Stuidies on exposed workers over .a 17 year period at a mean air concentration of 160 ppm failed to reveal"any overt condition attributable to VCM. One I tali an repor tinl?70 indicated-turn - "TiffTatner^OOO1?!*.;' nu fy'f ' jif* V/: v. > 'u;> i - , ^ Jtk, ------ ' -- 1 ... t -H. * , SECTION III PHYSICAL DATA .- *, - BOILING POINT |f) f(v SPECIPIC GRAVITY (HjO=t> 20* 7 0.91 VAPOR PRESSURE (mmhf) 9 68* F. VAPOR DENSITY ,AIR = I) 2580 2.15 PERCENT VOLATILE BV VOLUME (-.) EVAPORATION RATE 1 sail - ' * 100 solubility in pater Slight APPEARANCE AND ODOR Colorless, sweet smelling gas SECTION IV FIRE AND EXPLOSION HAZARD DATA fl*JH MINT {Method utedl -108* F., T.O.C. CiTINGuIShInG media C02> dry chemicals FLAMMARLC limits at ordinary temperatdre Ll 3.6 sptci*i. rmt neT(NS PRoctoMNi* 0O not use water except as a spray or fog. u*i 33.0 Wear self contained breathing apparatus. UNUSUAL TINC ANO EXPLOSION MAZANOS Handle as ao extremely flammable liquid and gas. Maferinl l SECTION V .HEALTH HAZARO DATA threshold limit value OSHA - 500 ppm (celling) ; ACGIH - 200 ppm (TWA); Shell - 50 ppm (-IWA; EFFECTS OF OVEREXPOSURE See over. Also prolonged contact with skin results to freezing. * CMCRtCHCr AMO FIRST AID PROCEDURES Remove victim to area free of vinyl chloride vapors. Give artificial respiration If necessary. Rgnove contaminated clothing to prevent freezing Remove from eyes with large amounts of water. stability UNftTASLC SECTION VI REACTIVITY DATA X CONDITIONS TO AVJI0 . Avoid sunlleht and/nr and exrlitrf* e11 axveen stake iNCQMFATlBlLItt to OVOfdJ air, oxygen HAZARDOUS DtCOMAO* T ON P*O0UCT* __ H Cl, CO and phosgene on combustion HAZAROOUS POLYMERl ZATION MAY OCCUK WILL MOT OCCUR CONDITIONS TO AVOID X air, sunlight and/or heat SECTION VII SPILL OR LEAK PROCEDURES steps to be taken in case MATCBiAL is released or spilled _ Remove all sources of Ignition. Remove all personnel not wearing protection eauimnent shown in Sect. VIII. Use forced ventilation from explosion-proof equipment. Allow to evaporate. WASTE DISPOSAL METHOD _ . .. ., ^ Do not permit material to enter sewers. Use controlled evaporation. Guard against fire and explosion hazards. SECTION VIII SPECIAL PROTECTION INFORMATION RESPIRATOR* FAcTECTIOM (Sp.Clfv Fypp) ... , Air pack or organic canister mask as required. VENTILATION local eahaust hlghly recommended SPECIAL - * ; ,t. mechahical (Gwwiwf; OTHER Highly recommende-'. -- use exnloslon--nroof < Quipment_______ . .- - PROTECTIVE CLOVES Rubbfer EVE PROTECTION _ , Chemical goggles ar. /or face shields "TTmER P.TOTECTIVE EOUIPMOT -- To prevent all contact with body as required. SECTION IX SPECIAL PRECAUTIONS precautiom. TO .E tare. ,m hamdl.m. amd stdr,M. Prevent any leakage. Provide sufficient ventilation to prevent high concentrations. Keep away from all sources of ImlHnn. Handle as an extremely flammable material which is stored under pressure. D. M. Sheets, Supervisor Regulatory affairs - Chemical Products Shell Cheg>lcl Company TMC INFORMATION CONTAINED HEREIN IN OAOfO ON DATA COMRIOENER AO* CURATE* HOWEVER. NO WAKRMTV IR EEFRCRBEE OR IMPLltO OCCARDIMO URhEe ATCHCEURREAOCFY* of There data OR THE 0ES7LTR TO OC OBTAINED FROM ?N VCNOOR AHVMtl NO RCSAONRlOltllT FOR INJURY TO VCNREE- OR TNlflO FERAOnR FRRtlMATELV C^URtO IT The MATERIAL IF REARONARLC RAFfTV FROCEDNRER ARE NOT ADHERER TO AR RtlPUtATED Id THE OATA RNEEY* AODlTfONALLV* VENDOR ABBUmER BO AERFONRIRiLITV FOR INJURY TO VENOEE