Document 3NEjzJgvdK0OjyRwM5k94xx3O

// / Attachment for SPI Questionnaire Letter Dated May 21, 1974 The following table shows the breakdown of losses for the Oklahoma City PVC plant for our present operation. The figures are based on weight percent of the incoming VCM feed rate, and are only approximate. Most of the data is subject to fluctuations of i 50% and on some figures by as much as - 300%. Overall it is the best data available. The table shows that almost all the unaccountable losses are vapor and not solids losses. Location VCM RR Car Unloading VCM Storage to Reactor Reactor Cleaning Slurry Hold Tank Centrifuge Water Slurry Strainer Recovery Venting Slurry Hold Tk Vent Dust Collector PVC Dryer PVC Loss Sifter Oversize Dryer Exhaust Product Samples Slurry Strainer Vent Lump Sum Unaccountable Losses Solids or Vapor Okla. City w/ o V ap or Vap o r Solids) Solids) Solids Solids Vapor Vapor Solids Solids Solids Vapor Solids Vapor _ 0.10 - 0.00 0.22 0.16 - 0.01 0.17 0.81 0.01 0.06 0.71 2.25 SPI Ind u s t r y Typical w/ 0 VCM in V ent ppm #/100 # 0.40 0.50 0.10 0.10 0.20 0.10 3.75 0.30 0.20 0.20 0.40 0.30 0.20 - - - - - 12,000 - - 1,200 4,000 - - - - - 1.2 - - 0.12 0.4 - 6.75 Gary R. Johnson Research Engineer Chemicals Research Division Question *1 C3D0 SPI EPA QUESTIONNAIRE PVC PLANT 1 esa S3 <SS *s OJ r ** 100* VCM > 96.7 lbs Resin. Product .1 lbs Lost from Reactor (PVC) - 2.9 lbs Lost from Dryer Q 300 ppm as'VCM- 0.3 lbs Lost from Dryer as PVC Question 4 2 Yes 2 b) Rang G Average 0.0 - 1.3 1.0 3 a) (1) (c) (2) 24 H TWA (3) 30 D TWA (A) No Yes Yes Guess 3 (1) (2) (3) (A) No-- ___ No No Guess 4 (1) C No (2) 24 II TWA Yes (3) 30 0 TWA Yes (A) Fairly Sure 4 b) (1) (2) (3) (A) No No No Probably Not SPI EPA QUESTIONNAIRE PVC PLANT 2 50 O CeCsS r*> CS3 --J OJ cu Question ?/ 1 100?/ VCM - .. 98.15 lbs Resin Product and Accountable ResTh. 0.16 lbs Lost from Slurry Hold Tank 0 12000 ppm as VCM 0.01 lbs Lost from Dryer as PVC 0.81 lbs Lost from Dryer as VCM 0 1,200 ppm .06 lbs Lost from Slurry Strainer Vent .71 lbs Lost - Unaccountable .10 lbs Lost from Reactor (PVC) Question 4 2_JL> 2. bl Rang;eAverage Yes - Preliminary 0-3 <1 3 a) (1)(c) (2) 24 H TWA (3) 30 D TWA (4) No No,, Yes Guess 3 Jll (1) (2) (3) (4) No No No Guess 4 a) (1) C (2) 24 H TWA No Yes (3) 30 D TWA Yes (4) Fairly Sure 4 b) (1) (2) (3) (4) No No No Probably Not I 30 O.v THE SOCIETY OF THE PLASTICS INDUSTRY. INC. <53 250 PARK AVENUE NEW YORK. NEW YORK 10017 212/687 <S9 r*> ICA^ RESEARCH MAY 2 B19?4 May 21, 1974 TO: Members of EPA Committee and Other Committees of the VC Monomer and PVC Resin Group This communication is directed to those members who attended the May 20 EPA Committee meeting for response, and to the members of the other committees for their information. If your company was not represented at the May 20 meeting, please supply the requested information. Time is critical -- so please respond before June 4, 1974. Your cooperation in promptly supplying this in formation is greatly appreciated. Cordially, T. J. McGrath TJM/cl 0002007435 QUESTIONNAIRE ITEMS . 30; 1) Material balance - please fill in material balance flow sheet (enclosed) with your best estimate of losses to air, water and solid waste at each exit point. Show vent emissions both as #/100# and ppm concentration. Do not distribute unaccountable losses. List as a lump sum in lower left corner of sheet in place provided. 2) a) Have you made a perimeter survey of airborne VCM? _____ b) If so, what is the range and average of results on the downwind vector? 3) Ambient air standards a) Could you comply with 1 ppm (v/v) maximum concentra tion on your most critical downwind vector: 1) As a ceiling? 2) As a 24 hour TWA? 3) As a 30 day TWA? 4) Degree of certainty a) > b) dispersion calculations _ c) actual measurement __________ b) Repeat for 60 parts per billion (v/v) 4) As of December 31, 1977, assuming realistic investments, could you comply with 1 ppm on your most critical downwind vector? Questionnaire Items - Page #2 a) (1) (2) (3) (v/v) as a ceiling as a 24 hour TWA as a 30 day TWA Degree of confidence: certain _____ fairly sure b) Repeat for 60 ppb Degree of confidence: certain ____ fairly sure doubtful ___ probably not OUTDOORS ' 'ir>i i r t '*1 'liilib.mh,^m PRELIMINARY ESTIMATE OF LOSSES IN PVC SUSPENSION PCIYUERIZATIGN (TYPICAL PROCESS ENCLOSED IN BUILDINGS MATERIALS BALANCE IN PVC KANOFACTURE a y tISIl' loot*. WHW7E wrc intopukT I HAY CONTAIN 0-1030 PPM IMBEACTEO HVC pvc PtoeucT .i n u & B iU L aaa Friday June 7 - 8 am Olga Jordano, RWG secretary, phoned. She had received word from the Society of the Plastics Industry that they plan to reconvene their meeting of June 5 on Monday, June 10 - 9:30 am Mayflower Hotel, Washington She needs to inform Miss Jones of SPI, before 4 pm today, who from Conoco will attend this meeting. She gave this information to RWG when he phoned in this morning from Greenbrier. He told her to pass the information on to you. She has also informed KLS. The SPI have reserved a block of rooms at the Mayflower for Sunday night arrival. Please phone RWG secretary. 8:45 am Marsha Joseph, KLS secretary, phoned. She has made reservations for you and Dr. Whetstone at the Mayflower Hotel, Sunday night, June 9. ~ 303 ***. - ^ ENVIRC UNITED STATES ENTAL PROTECTION AGENCY WASHINGTON, O.C. 20450 O F FI C IM UUilNi:!5 PCNAUTV FOH PHIVATE USE! $300 AH EQUAL QPPOHTUNITY EMPLOYER f POSTAGE AND FEES PAID U.5. ENVIRONMENTAL PROTECTION AGLNC V tPA-330 -C l1 <w9 -H fl Arsht (202) 755-0496 O'Neill (202) 755-0344 FOR IMMEDIATE RELEASE FRIDAY, MAY 31, 1974 EPA REQUESTS VINYL CHLORIDE DATA FROM MANUFACTURERS 1 The Environmental Protection Agency has requested "process, Ji 1 emission and air quality data" from the 27 U.S. manufacturers of vinyl chloride, a gaseous chemical, and polyvinyl chloride, a plastic derived from the gas. The information is being sought from 14 vinyl chloride and 35 polyvinyl chloride plants operated by these 27 companies. EPA said in letters to the manufacturers dated May 30, 1974, that the Agency is "gathering information for possible use in the development of air pollution control standards for vinyl i chloride in accordance with the Clean Air Act of 1970." i EPA is now taking atmospheric samples near polyvinyl chloride and vinyl chloride plants to determine amounts of the gas present in the ambient air. The monitoring data will be available to the public as soon as it has been processed and verified. At present, no Federal air pollution control standards exist for vinyl chloride. < \ The EPA request for information from the manufacturers covers three areas: (1) Identification of emission points in the manufacturing process and the amounts lost from those points. The identification c emission control procedures that have been or could be instituted and an evaluation of their effectiveness i i (more) / A this EPA FOHM If : NOT v;ih lo jeeeive ihis nrstirial Q. cr if change gf JddrciS ii needed (indicate change, including im c</0* (REV. 02> R-471 <33 are also being sought. (2) Cost and economic data, including *the capital and operating costs for each emission control device^ or procedure. (3) Ambient air quality data v.'hich has been collected by the rr.anufacturcrs near their plants. EPA is requesting the information under the authority of Section 114 of the Clean Air Act, which enables the Agency to develop data needed for standard-setting pursuant to the Act. Vinyl chloride has been implicated in 19 world-wide cases of a rare but fatal form of cancer, angiosarcoma of the liver, among workers engaged in the conversion of the chemical to polyvinyl chloride. Similar cancers also have been produced in experiments exposing rats and mice to vinyl chloride. In both cases, exposure to vinyl chloride gas occurred repeatedly over extended periods of time. Today's action follows several steps already taken by EPA in an effort to protect the public from the potential adverse effects of vinyl chloride: --February 14, 1974, Administrator Russell E. Train formed an internal task force to assess the overall environmental impact of the chemical. --April 5, 1974, EPA notified the producers of all pesticides with aerosols containing vinyl chloride of the need to substitute another propellant. --April 10, 1974, EPA Regional Administrators were asked to assess the extent to which vinyl chloride is escaping beyond the confines of the polyvinyl chloride production facilities in their regions. --April 17, 1974, EPA released the brand names .of 20 pesti cides containing vinyl chloride. --April 24, 1974, EPA suspended from sale and requested a recall of all pesticide aerosols for indoor use containing vinyl chloride. Based on the April 5 noticeand a follow-up of April 30, all of the manufacturers of pesticide aerosols containing vinyl chloride either huive substituted or are now in the process of substituting an alternate propellant. ## P-4 71 9 M 1 B 0 Z 0 B B (MfA VI.WL CHLORIDE AMD POLYVINYL' HLORIDE MANUFACTURERS CONTACTED BY ERA AIR PRODUCTS AMD CHEMICALS, INC. PPG INDUSTRIES, INC. .AMERICAN CHEMICAL CORPORATION BORDEN CHEMICAL, INC. CONTINENTAL OIL COMPANY DIAMOND' SHAMROCK CHEMICAL COMPANY SHELL CHEMICAL COMPANY ETHYL CORPORATION FIRESTONE PLASTICS COMPANY GENERAL TIRE AND RUBBER'COMPANY B.F. GOODRICH CHEMICAL COMPANY GOODYEAR TIRE AND RUBBER COMPANY GREAT AMERICAN CHEMICAL COMPANY HOOKER CHEMICAL KEYSOR-CENTURY CORPORATION MONSANTO COMPANY NATIONAL STARCH AND CHEMICAL CORPORATION OLIN CORPORATION THE PANTASOTE CO. OF NEW YORK, INC. ROBIWTECH, INC. STAUFFER CHEMICAL COMPANY TENNECO CHEMICALS, INC. UNION CARBIDE CORPORATION UNIROYAL INCORPORATED ALLIED CHEMICAL CORPORATION DOW CHEMICAL COMPANY MONOCHEM, INC. jt' UNITED STATES ENVIRONMENTAL PROTECTION AGENCY ' 0`lico of Air C 11ty Planning and StandnrrisResearch Trianij.j Park, North Carolina 27711 Dear The Office of Air Quality Planning and Standards of EPA is in the process of gathering information for possible use in the development of national emission standards for vinyl chloride (VC) and polyvinyl chloride (PVC) plants in accordance with the Clean Air Act of 1970. This information will be obtained from a number of such plants for purposes of quantifying the emissions, ambient concentrations, and identifying control techniques presently being used to reduce emissions. We will need trie following information from your company regarding your PVC plant located Process and Emission Data Please provide a brief description of the process to include all transfer and storage points. Include information on the manufacture of PVC through the formation of PVC pellets* The following information should also be Included. A. Process flow sheet - Provide a simple process flow sheet shewing all major equipment and the amount of product produced. B. Emissions - On the process flow sheet indicate all continuous and intermittent sources of air emissions. Give the composition and amount of each emission expressed in terms of pounds per pound of product produced, concentration, and pounds per hour. If emission data are not available "best estimates'1 are to be prepared. The bases and assumptions used in preparing the emission estimates are to be discussed in detail. 2- - C. Control Device - Emiss n control devices presently in use should *= be indicateG on tne process flow sheet. Show the amount and composition of process streams into and out of each control device. Provide a S brief engineering description and significant operating and design ^ parameters for each device. Provide a discussion of the control devices3 or techniques that could be applied to each source of emissions am! ^ the approximate emission reductions that would result from application ^ of that technology. D. Fugitive Emissions - Estimate by material balance (or other method) the total amount of vinyl chloride lost from leaks through valve stems, safety valves, pump seals and other miscellaneous sources. In addition, emissions resulting from line or vessel blow down, reactor ventilation, storage or transfer operations within the plant are to be estimated and summarized. The individual locations and amount of each emission in pounds per hour is to be specified. E. Emission Control Procedures - If special maintenance procedures, process design features or pi ant operating procedures are used to control emissions describe the methods used and estimate their effectiveness. Discuss procedures that could be used or are planned to reduce emissions. Control and Economic Data For each of the control devices or emission control procedures currently in use or planned give the following information. A. Investment Cost - Provide separately the total investment cost and the cost of installation (where applicable). Include a list of the equipment, the year of purchase, and whether the system was part of the original plant or was retrofitted. B. Operating and Maintenance Cost - Provide estimates of the expected life of the control equipment ana the annual operating and maintenance costs required. Operating costs should distinguish labor costs, capital charges, cost of utilities used, fuel costs, and costs of chemicals and other materials. Give amount and value of any material recovered, both annually and per unit of production. Ambient Air Data A. Provide the results of any`ambient air sampling for vinyl chloride which you have done. Show layout of plant with location of major process areas, sampling points, and concentrations found. f'RD 0002 00 74 49 ^ Give the analytical and sampling method used and v:eathe'r data during the sampling period* B. Where possible for each source of emission provide the information that is necessary to estimate ambient air concentrations. This would include stack heights, configurations and diameters, the gas flew rates, temperature, and gas velocities to the atmosphere. The Environmental Protection Agency has broad authority to secure any information deemed necessary for development of standards under the Federal Clean Air Act (42 U.S.C. section 1857, et. sec;.). Section 114 of the Act (42 U.S.C. section 1657c-S) authorizes this agency to make Inspections, conduct tests and require owners or operators of any emission source to submit information for the purpose of developing emission standards. This letter and the requests for information contained herein are being sent pursuant to section 114. Any records or information obtained 'during an investigation shall be available to the public unless a satisfactory shoving has beer, made to the Administrator that the release of the information obtained would divulge a trade secret. Information requested pursuant to section 114 cannot be with held from EPA on the grounds that you consider it to be confidential. If you believe that any of the information we are requesting would revzeeaal a trade secret if divulged, you should clearly identify that infor- motion, and set forth reasons for your claim, including suoportivc* data or legal authority. Tour reasons ar.d supportive data should be esent! A separately for each item of information, U_ nsuppcrt' s...t.a..t.e...m....e..n..t..s..... r?-t you consider certain information confidential will not be accepted. Emission data, however, will alv:ays fce available to the public. Any information dICe^ tCej..rimv^ i--iinei d to constitute a copy ot a trade JU-UlC9 n. c* *u secret will i J Cl iv* I uiCu be covered by 18 U.S.C., or your convanicuCc. Please provide all of the information requested in writing before June 14, 1974. In addition, we may be requesting that representatives of your company meet with the EPA to discuss the information requested in this letter and other matters concerning the vinyl chloride emission problem. EPA may also request additional information. *r* -4- VRD 0002007450 Please contact"Mr. Leslie V. Evans at 919-638-8145, extension 295, if you have any questions regarding the specific information requested in this letter. Enclosure Sincerely yours, l oi'X^A. Goodwin Di rector Emission Standards and Engineering Division VRD 000200 T4 51 SPI -- VCM/PVC MAY 1973 through MAY 1974 VRD 0602007457 Study of Vinyl Chloride EPA Cancer Data Being Withheld Proift News Dl'patchw "represents the investigation team is testing for the chemi of technology," Anton Vittcne' HOUSTON, May 25--Data files of a law enforcement cal at IQ plants around the said, "And, if imposed, could from a study of the concentration here of a potentially can cer-causing chemical is being agency" and polluters releas country, including those in ing the gas could -be subject to Houston. Dr. Glenn E. prosecution. Schweitzer, head of the EPA display not nyl chloride only the 6,500 vi monomer and po withheld because of possible' At least 12 deaths in the team, said an estimated 200 lyvinyl chloride production criminal prosecution, accord United States and elsewhere million pounds of the gas es workers, but also hundreds of ing of federal officials. have been linked to vinyl, capes annually into the atmos thousands of other employees As part of an Environ chloride gas. It is suspected as phere in the United States. in the companies which use mental ` Protection Agency a causp of a form of liver can Meanwhile, in Akron, the PVC." study of vinyl chloride, air cer, angiosarcoma. president of B.F. Goodrich's Vittone said about 100 scien samples are being collected The EPA attorney, Jim Col Chemicals Division raised the tists and others are working near chemical plants along the lins, said the information was spectre of massive job losses six to seven days a week in a Houston Ship Channel to de being withheld at the instruc in a critique of the proposed multimillion-dollar effort to termine the concentration of tion of George Marcontbal of new Occupational Safety and reduce employee exposure to the chemical in the atmos EPA headquarters in Washing Health Administration stand vinyl chloride. phere. ton. ards for worker exposure to Five of the reported vinyl An EPA lawyer in the agen The information would be vinyl chloride. chloride deaths were among cy's Dallas regional office said released only after evaluation "The proposed standard of former employees of . Good Friday that the results of the and possible legal disposition, no detectable level of expo rich's plant in Louisville. Two Houston study would be with Collins said. sure does not appear to be cases were reported among held because the study The EPA vinyl chloride possible with the cunent state living employees there. VRD 8002007458 THE SOCIETY O. THE PLASTICS INDUSTRY. INC. 250 PARK AVENUE NEW YORK. NEW YORK 10017 2 1 2/687*2675 A . *4^ IMPORTANT MEETING IK)TICE May 28, 1974 TO: Members of the VCM and PVC Producers Group Dear Member: Confinning our phone call of May 28, a very important committee meeting will be held Wednesday, June 1974 at the Statler Hilton Hotel In Washington, D.C. (located at 16th and K Streets) starting at 8:30 a.m. in the Federal Room. The purpose of the meeting is to establish an industry position regarding the proposed O.S.H.A. standard for VCM. In addition, we will begin preparations for the Q.S.H.A. hearings which will start on June 25. In view of the nature of this meeting, your representative should be senior management so that he can commit your company to the actions that will be taken. You are also strongly urged to bring a technical representative and an attorney. Due to space llmlations, we must restrict attendance to three per company. Please call Laura Jones of SPI (212-687-2675) to advise who will represent your company. For hotel rooms Tuesday evening, you must make them directly with the Statler Hilton - call Mrs. Zyderfeld in reservations at (202) 393-1000. The hotel is holding a block of rooms in SPI*s name up until May 31* Please make your reservations as soon as possible. I look forward to seeing you on June 5 let me know. Should you have any questions, please RLH:lj Cordially, Thomas J. McGrath General Manager CHEMICALS RESEARCH JUN4 1974 o fc. m i0 0 Z 0 0 0 May 24, 1974 Air Mall - Certified Mall Hearing Clerk Food and Drug Administration Room 6-86 5600 Fishers Lane Rockville, Maryland 20852 Dear Sir: Mr, Jerome H. Heckman has Indicated that Information related to residual vinyl chloride monomer (VCM) In typical polyvinyl chloride (PVC) materials. Including potable water pipe, should be sent to your attention per the request in the April 22, 1974 Federal Register, p. 14215. You will find enclosed In qulntupllcate the following Information: Enclosure I. Analysis of Polyvinyl Chloride (PVC) Resin for Residual Vinyl Chloride Monomer (VCM) Enclosure II Extractablllty of Vinyl Chloride Monomer In Polyvinyl Chloride Pipe Enclosure III Gas Chromatogram of VCM In Water Enclosure IV Gas Chromatogram - Water Blank Table I Residual VCM in PVC Pipe Table II Residual VCM In Flexible PVC Compound Pellets Table III Residual VCM In Miscellaneous PVC Items Table IV Water Extraction of Residual VCM In PVC Pipe VRD 0002 0 07 +61 Hearing Clerk Food and Drug Administration Hay 24, 1974 Page 2 * Summary The samples of commercial PYC pipe analyzed by Enclosure I of the attached procedures generally contain zero to 90 parts per million (ppm) of residual VCM. When the pipe Is subjected to water extraction at 25C or 50C for 72 hours per Enclosure XI of the attached procedures, less than 50 parts per billion (ppb) of VCM Is normally found In the extract. The exceptions to the latter occurred when pipe was extracted for periods of 18 days and 3 years. These lengthy extractions under stagnant conditions are thought to be very unrealistic representations of normal piping system usage. We believe the data submitted clearly show that PVC pipe can be used for potable water and not cause any problem related to extraction of the residual VCM. The analysis of various other finished PVC Items, including compound pellets used In extrusion of finished Items, shows that In most cases there Is either no detectable VCM present or very low levels. However, a value of 150 ppm In one compound pellet sample was found and Is Indica tive of random scatter. Determination of Residual VCM in PVC Materials The intention was to examine a variety of fabricated products for residual VCM levels. A significant variable Is the time lapse following fabrica tion, on the assumption that VCM will diffuse from the structure with time. Therefore, an effort was made to sample materials with a variety of elapsed times since production; emphasis was on VCM content as soon after production as possible to better assess the highest VCM levels that could possibly be encountered In product use. Another variable Is the amount of residual VCM In the PVC resin from which the object Is made. Where possible, the resin was analyzed for VCM, although a certainty that a given resin sample corresponds to a subse quently produced section of product Is clearly not possible. The data presented In Table X Indicate that PVC pipe may contain up to 100 ppm of VCM, with a general trend to lower levels of VCM with Increasing time. The data do show some random scatter; it is believed that additional samples will show the scatter to be statistically expected. The data found In Table II show that very low quantities of VCM are present in compound pellets with the exception of one value of 150 ppm. We have no explanation for the high value other than of random scatter in data. VRD 0002007462 Hearing Clerk Food and Drug Adnlnlstratlon May 24, 1974 Page 3 * In Table III, various miscellaneous Items were analyzed for residual VCM. In all cases, less than one ppm of VCM was found. Extractablllty of Residual VCM In PVC Pipe Data are presented In Table IV related to extraction of residual VCM from PVC water pipe. The data, except for the last two samples, are derived from an extraction method (Enclosure II) essentially Identical to that used by the National Sanitation Foundation (NSF). The only difference Is that deionized water was used In the present test method; NSF uses water at pH 5 to facilitate the extraction of heavy metal Ions which are of concern to NSF. For the current purpose. It was judged that the use of neutral, deionized water would not affect the extraction of VCM. The last two samples (Ref. No. 26 and 27) represent analyses of water which was contained in a two-foot length of two-inch diameter soiled pipe for the period Indicated. Since the pipe had been set aside, neither the temperature nor the ratio of surface to water was controlled. The tempera ture probably varied from 5 to 35C. It Is believed that lengthy exposure of stagnant water In a piping system, as In these samples. Is an unrealistic representation of exposure under practical circumstances. We plan to do additional work on this point. Future Plans Additional data will be collected regarding residual VCM In PVC pipe, compound pellets, and miscellaneous Items, along with the continuing work related to extractablllty of residual VCM from PVC pipe. Since the method for determining residual VCM in PVC will probably be a required plant function. It Is advisable to adapt the methods (Enclosures I and II) of detection to flame Ionization. Flame Ionization detection (FID) Is potentially equally as sensitive as coulometry but requires more attention to chromatography since FID is not selective. Impurities which could come from the solvent and/or the resin must be separated chromatographies!ly from the VCM before entering the detector. We have made good progress In adapting the method for FID but much more work must be completed before the method becomes routine. Should you require additional information or believe a meeting would aid your evaluation of these data, please advise me. Yours very truly. lm enc Copy w/enc to: Mr. Jerome H. Heckman 1150 17th Street N.W. Washington, D.C. 20036 bcc w/enc: KLS WRS (EAS REL) 1/RD 0002007463 ENCLOSURE I ANALYSIS OF POLYVINYL CHLORIDE (PVC) RESIN FOR RESIDUAL VINYL CHLORIDE MONOMER (VCM) Various PVC resins have been analyzed for residual VCM by first dissolving the resin in tetrahydrofuran (THF) and then chromatographing the headspace gas for quantitative analysis of VCM present in the resin. Microcoulometry is used for detection because this detector is specific for the chlorinated species. Compounds other than halogenated materials will not be detected; consequently, separation of components via the chromato graphic column is not nearly so critical as with other types of detection. EXPERIMENTAL Samples. The samples of resin are dissolved using 5 grams of resin in 50 milliliters of THF. This mixture must be stirred or shaken to dissolve the resin. Using either a roller-mixer or magnetic stirring, it can take up to two hours to complete solution. The mixture is dissolved in a 4-oz bottle equipped with a Teflon-lined septum cap. Before sampling, shake the solution vigorously and withdraw 5 milliliters of the headspace gas. When sampling, inject the same volume of air equal to the volume of headspace gas to be taken for injection. This prevents depletion of the headspace volume. The sample is injected into a chromatograph equipped with a Dohrmann model C-2QQ coulometer as a detector. The sample is converted to HC1 in an oxidation furnace; the resultant HC1 is then titrated in an Ag-AgCl coulometric cell. Standards. Into a 4-oz bottle put 50 milliliters of THF. Close the bottle with a Teflon-backed septum cap. Inject one milliliter of VCM into the liquid and mix thoroughly. Let stand for 10 minutes and inject sample. Inject into the bottle a volume of air equal to the volume of headspace gas to be taken for the injection. This amount of VCM in 50 milliliters of THF is the equivalent of 280 ppm by weight of a 5-gram portion of PVC dissolved in 50 ml of THF, uncorrected for pressure and temperature. Standard temperature and pressure corrections should be made when actually running the standards. Various concentrations are prepared and a calibration graph plotted. This graph is then used when analyzing the samples to determine concentration. Chromatographic Conditions. The column used is a 5' x 1/4" 0.0. aluminum tube packed with 8 percent SE-30 (silicon oil from General Electric Company) on 80/100 mesh Chromosorb G (Johns-Manvilie). The column is not critical when using the coulometer for detection since the detector is specific for halogenated compounds. The sample is injected using a gas syringe. The oxidation furnace is maintained at 850C with a flow rate of %20 cc/min of oxygen. Load resistors are chosen dependent on sample concentration and sample size, varying from 50ft to 300ft. Carrier gas is helium at a flow rate of 35 cc/min. VRD 0002007464 LmoLOSURE I Page 2 DISCUSSION The method as set forth above giyes accurate, reproducible results. Linearity of response is maintained from one ppm to 18,000 ppm. Accuracy at the 100 ppm level or less is three percent at the 99% confidence, level. At higher concentrations the deviation approximates 10%. In theory the coulometer is straightforward and permits absolute determina tions of concentration. However, in practice the detector requires considerable technique and careful control of operating parameters. Its major advantage is the fact that it is selective for only halogenated species, thus eliminating numerous possible interferences. May 24, 1974 VRD 800200 T46 5 ENCLOSURE 11 EXTRACTABILITY OF VINYL CHLORIDE MONOMER IN POLYVINYL CHLORIDE PIPE Polyvinyl chloride (PVC) pipe can be safely used for potable water providing significant amounts of vinyl chloride monomer (VCM) are not extracted with water when treated at either room temperature (25 degrees Centigrade) or at elevated temperature (50 degrees Centigrade). Signifi cant amounts are those in excess of 50 ppb. The tests are made under static conditions using an appropriate ratio of one thousand square inches of pipe to four thousand milliliters of water. APPARATUS Glass Syringes. Fifty-milliliter, glass syringes are used for prepara tion of standards and as equilibration chambers for sample preparation. Sample Container. A 4-liter Mariotte bottle is used to hold the sample (PVC pipe) and the water. The bottle outlet is equipped with a short length of Latex tubing and a clamp. This provides a means for with drawing a sample. A stopper is affixed with a short length of Saran tubing to permit degassing of the water as well as allowing for filling of the bottle completely with water. Gas Chromatograph. The gas chromatograph (F&M Company Model 810 or equivalent) is equipped with a suitable column, a gas sampling valve and a specific detector, i.e., a microcoulometer. The specificity of the detector, in this case specific for halogenated materials, eliminates interference from other non-halogenated species which may be present. The instrument is operated using conditions adequate to separate VCM from the halogenated species with a sensitivity capable of detecting vinyl chloride when present in concentrations of 50 parts per billion or greater. Gases. Helium is used as the carrier gas for transport of the sample through the column and into the microcoulometric detector. High-puritygrade helium is used with the appropriate regulator. Extra-dry-grade oxygen, with the appropriate regulator, is used as a supply to the combustion furnace of the microcoulometer. PROCEDURE Standardization. Forty milliliters of deionized water is added to a fifty-milliliter syringe equipped with a syringe valve. All of the air is expelled from the syringe and ten microliters of VCM is discharged into the center portion of the water. This is accomplished using a ten-microliter syringe, inserting it through the syringe valve and discharging the contents into the water. The syringe containing the tnCLOSURE II Page 2 water is in an inverted position for tiiis operation. The tcn-microliter syringe is withdrawn after discharge of its contents, the valve closed and the water-VCM mixture shaken until the VCM bubble is dissolved. Ten milliliters of air is drawn into the syringe and the syringe is shaken vigorously for fifteen minutes. The air is injected into a one-milli liter, flow-through sample loop and injected into the chromatograph. The gas sampling loop is maintained at 50 degrees Centigrade. The peak area obtained is ratioed to the peak area obtained from the sample. A ten-microliter sample of VCM in 40 milliliters of water corresponds to 625 ppb VCM by weight using a calculated density for gaseous VCM of 2.49 mg/ml at 25C and 740 Torr. Sample Analysis. A sample of PVC pipe is cut so as to obtain approxi mately 1000 square inches of surface area. This material is placed in the 4-liter Mariotte bottle and the bottle filled with deionized water. Water is added one liter at a time. After each water addition the bottle is connected to house vacuum and agitated slightly until all visible air bubbles are removed. The second, one-liter portion of water is added and the same procedure followed. This is repeated after each water addition until the bottle is full to the lip of the bottle. A rubber stopper equipped with a short length of Saran tubing is forced into the neck of the bottle until water overflows through the tube. The tube is then stoppered with a microstopper. The volume of water is recorded as well as the surface area of the pipe. The bottle plus sample is immersed in a thermostated water bath and controlled at the temperature of choice. Samples can be taken at time intervals selected. A typical series of sampling times is zero, 24 hours, 48 hours, and'72 hours. When a sample is to be withdrawn, the bottle is removed from the water bath and a syringe equipped with a three-way valve is affixed to rubber tubing at the outlet. The microstopper is removed and 40 milliliters of water is drawn into the syringe. The syringe is withdrawn from the outlet and 10 milliliters of air is drawn into the syringe. The valve is closed and the syringe is shaken vigorously for 15 minutes. The syringe is then attached to the heated, one-milliliter, flow-through gas sampling valve and the air sample injected. The peak area obtained is ratioed to the peak area of the standard to determine the concentration of vinyl chloride. Operating Conditions. The gas chromatograph is equipped with a column consisting of a 6-foot by 1/4-inch O.D. aluminum tube packed with SE-30 (silicon oil from General Electric Company) on 80/100 mesh Chromosorb G (Johns-ManviHe). The helium carrier gas rate is 45 milliliters per minute. The transfer line from the chromatographic column is maintained at 200C and the column temperature is maintained at ambient. The furnace temperature of the combustion oven is 850C with a 20-milliliter-perminute flow of oxygen. The load resistor is maintained at 300 ohms for 99H B B U B d OH p* VRD 0002007467 b.wLOSURE ir Page 3 the sample and 50 ohms for the standard. Under these conditions, 50 parts per billion of VCM gives a peak height consistently ten times the average noise level, and substantially better (up to 40 times noise) when the instrument is prepped for maximum performance. May 24, 1974 11 i 11 11 1: ji J j |! i! t1 !I J i: l: 1 ; ENCL 'jUREjlll _ j iGAS i | CHROMATO^QAM i INSTRUMENT OF 1VCM ! IN ii 1i 1 ATER ii i in i Dohrpiann, mic ro coulomete r : i ?rl UeiT 4--: ^ ^oadj Resisto r 30pn i j --~j------- Oxidation ov -n_C.ernp.; .850 >c- H i......... )xygen flow '0 tnVmin I ! r-i i] ji i! m 1 -4 hhromatocrat mrtONDTTTO ! \1 ii --1----------- : i! Column 5' x L/4": SE30 on 80/100 tn Chrom; G i1 !! Harrier gas - Helium. 1 1 rj Harrier gas flow- rate 45 mi/min [ ^ Holumn temp - Ambient ii . 1t <5COl*derr^"H imeytaeTli 1.0 mv full! sea Le Hhart speed - one inch/m mute j j i i i I : : ; ( ji j i ! I | i r i i. i "1 " | ! 1' ' i 1 i--i H --i ; SAMPLE ! " r :1 i 55:----------- 1------------ parts-rper -billion, (pp a) w/w .i i vinyl:cbl dride monorae r (VCM) -- i ! i-t iti water. 1i l |1 ; r"1 ii ii WJ i lj i; !i !i 1: 1 K1 X i< -4-U 1 i iw ii i on || I"'" 1i ij ii i -------------!------------- i-------------1 i------------ :--Z3 - i- *- n "i" ii i | i -- j ; i1 -------------- :--tn i! j* -----------;------------: ;i Q3 1 ; jl i ; i 1 \! .! ;j ;i - j 1 i; -i f i ] \ i i ! ! |i -- ; an 1 j 1 -4 1 1 !1 !; t! i on LO U_l 1*1 ---------- o---------- ;----------- o1 1 : i" o j kA i! oUQJ a z | X 1 i1 ------------ -------------- -------- ixj I .1 -t t ; ;i i i j .i 1i i i --nr ii _1 ;j f j] | |! i| i* ~--f -------------i------------- ;---------- -j i ;J |i i i __ j______ t ;1 1 J i| i i tt i! i: J: 1 i i : t j I -- 1 | ! ! j' I ! |- i -i i : .1 h1 i j 1 i 1 I! 1! <1 i) i t 1 1 j : i : ! ! j ! ! i i i i1 ii VRD 0002007468 I DVR ,0002007469 VRD 0002 0 0 74 7^ TABLE I RESIDUAL VCM IN PVC PIPE Sample* Reference 1 2 3 4 5 6 7 8 9 10 Estimated Time from Production Unti1 Analysis Estimate of VCM (ppm) in Resin Used in Fabrication Residual VCM in Pipe (ppm 7 days 5" 5 11 4 months 5" 12 " 13 11 20 " 30 " 36 11 120 150 530 .- - 67 15 18 91 <1 7 4 3 23 <1 *See attached Bibliography i XL H b B W b B A M TABLE II RESIDUAL VCM IN FLEXIBLE PVC COMPOUND PELLETS Sample* Reference n n 12 13 14 15 Estimated Time from Production Until Analysis Estimate of VCM (ppm) in Resin Used in Fabrication Residual VCM in Article (ppm) 7 days 7" <3 months <3 " 3 days 7" 5,000 2,500 - - 7 230 54 150 <1 <1 <1 6 *See attached Bibliography VRD 0002007472 TABLE III RESIDUAL VCM IN MISCELLANEOUS PVC ITEMS * Sample* Reference Item and Estimated Time from Production Until Analysis Estimate of VCM (ppm) in Resin Residual VCM Used in Fabrication in Article (ppm) 16 Laboratory Tubing, 1/2-in. Unknown Production Date 17 Electrical Cable Coating, 7 days 18 Calendered Sheet, 0.010-in. Thickness, 3 days 19 Calendered Sheet, 0.015-in. Thickness, 3 days 20 Medical Tubing, 3 mm.. 2-4 weeks * - 1 ,400 1,800 - <1 <1 <1 <1 <1 *See attached Bibliography 0 IH 0 0 1 0 0 0 AHA TABLE IV WATER EXTRACTION OF RESIDUAL VCM IN PVC PIPE * Sample* Reference 21 22 23 24 25 26 27 Estimated Time from Production Until Extraction Extraction Temperature C/Time 9 months <2 weeks 6 weeks <4 weeks 6 weeks 10 weeks 10 weeks 25/72 hours 50/72 25/24 hours 25/48 " 25/72 11 50/72 hours 25/15% hours 25/72 hours 25/432 " -/10 weeks** -/108 weeks** Extracted VCM (ppb) <50 <50 <50 <50 <50 <50 <50 <50 370 730 1,560 *See attached Bibliography **Temperature ranged from 5 to 35C. BIBLIOGRAPHY Sample References 1. IOC, W. R. Sorenson to F. Kennedy, April 11, 1974, "VCM in Resin and Downstream Materials," item A-l. 2. Ref. 1, item A-2 3. Ref. 1, item A-3 4. Notebook No. 1, W. R. Sorenson, p. 141-1 5. Ref. 4, p. 141-6 6. Ref. 4, p. 141-5 7. Ref. 4, p. 141-4 8. Ref. 4, p. 141-3 .9. Ref. 4, p. 141-2 10. Ref. 4, p. 141-1 11. Ref. U item B-l ab, - led 12. Ref. 1, item B-2 13. Ref. 1, item B-3 14. IOC, W. R. Sorenson to F. Kennedy, April 17, 1974, "VCM in Resin and Downstream Materials II," items B-l, -2. 15. Ref. 14, items B-3, -4 16. Ref. 1, item B-3a 17. Ref. 4, p. 139-5 18. Ref. 14, items B-l, -2 19. Ref. 14, items B-3, -4 20. Ref. 1, item C-8 A VRD 000200 74 74 Bibliography Page 2 Sample References (Continued) 21. IOC, E. A. Setzkorn to F. Kennedy, "Analysis for VCM in PVC Pipe,11 June 29, 1973. 22. IOC, R. E. Laramy to F. Kennedy, "Analysis for VCM in PVC Pipe by Water Leaching," April 9, 1974, item 5. 23. Research Notebook L2923, pp. 126-130, Continental Oil Company. 24. Research Notebook L3190, pp. 164, 168, Continental Oil Company. 25. Research Notebook L2960, p. 152, Continental Oil Company. 26. Ref. 4, p. 141-6a 27. Ref. 4, p. 141-2a * VRD 80020B 74 7 5 VRD 80810014L7 associated wit1' increased volume, improved production U ques and the performance f repetitive * (the learning curve con cept) are reulu-.d. Recovery of deferred production Mid other eturt'Up costs l.s dependent on the number of aircraft ultimately sold nnd actual selling prices and production c t.s related to future transactions. Sules significantly under esti mate;; or costs significantly over estimate:; could t'-v.dt in the rcaU/ntion of su'.v.tantin', lo.v.e.-. on the program In future years. Ronllnition of approximately $721,000 of the m'or.s commercial aircraft Inventoried at Decem ber ul, 1074 Is dependent on receipt of future Arm orders. Baaed on studies made by and on behalf of the Company, management believe;, there extits for this aircraft a market for over 2.70 vmjtr, Inci'Jd;;-" dellteries to date, v.-itli pro duction n;i ! defiverles continuing at a nor ma! rate to at least JOHO, At December 31, 1D71, 117 aircraft had been delivered under the program, and the backlog Included C4 firm v.nfiiled orders and options for 43 units. During 1074, 5251.000 of general and ad ministrative expense and 5.33,000 of research aid development expense were incurred and charged to inventories. Comparable amounts In 1973 were 5239,000 ond $42,000. respec tively. Title to certain Inventories t ! contracts In progr,- . la vested m the g -r,States Govtnuni-at pursuant to cor ract ; .`Visions related to progress payments. Such amounts were $1,743,000 and $1,347,000 at December SI, 1074 and 1073, respectively, [FR Doc.74-11904 Filed 5-23-74;8:45 am] DEPARTMENT OF LABOR Occupational Safety and Health Administration [29 Crn Part 1910] [Docket osn-3C] VINYL CHLORIDE; OCCUPATIC' ' L EXPOSURE STANDARD Hearing On May 10. 1974, notice of proposed rulemaking with regard to a permanent standard for ocr atlonal exposure to vinyl chloride w;t .Wished in the FkpEiiAL Register (39 hi.t 1009GJ. Tlic notice provides an opportunity for public par ticipation in the proceeding, by means ol written submissions to be mailed to the given address, postmarked r.o later than June 10, 1974. The notice also per mits interested persons to file objections to the proposed standard set out in the notice and request a hearing thereon. The objections must specify the pro visions of the proposed standard to which objections arc made, state the Grounds for the objections, be accom panied by a summary of the evidence to be adduced at the requested hearing, and must be postmarked no later than June 10, 1974. Informal contacts with Occupational Safety and Health Administration staff have disclosed widespread interest In the proceed;! a probability of requests for a hearing, and an alleged need lor more time for the submission of written com ments and the formulation of objections In accordance with the requirements of the notice. Accordingly, It has been decided to waive the requirements for objections and request for a hearing thereon and instead to set for hearing the entire pro posed standard, set forth In. the May 10 notice. It Js hoped that this decision will: <1) Eliminate the possible difficulty of formulating appropriate objections with in the short period of time fixed in the notice; (2) permit full participation at the hearing, without limitation as to is sues; and (3) expedite the prceceding, in view of the six-month provision in sec tion 6(c) of the WiUiams-Steiger Occu pational Safety and Health Act of 1970, and the expectation that a hearing would be requested and scheduled anyway. Therefore, pursuant to sections 6(b), 6(c), and 8(c) of the Occupational Safe ty and Health Act of 1970 (81 Slat. 1503. 1596, 1500; 29 U.S.C. G55, C57>. Secretary of l abor's Older No. 12-71 C3C 1 ;7 0794) and 20 CFR Part 1911, the notice of the proposed rulemaking on vinyl chloride published on May 10, 1974 at 29 FR lCgf.'G, is hereby amended in the follow ing respects: (1) The part of the notice concerning the filing of objections and requests for hearing, in the third fu'.l paragraph of tin; middle column of page 3(1997 of the May 10 issue of the Federal Reoistkr, is withdrawn; and (2' m lieu thereof the following paragraphs are added: Data, views, and arguments concerning the proposed stnndrrcl win be received by an i.-'nifiilslrn.tlve law JiuVe, to be appointed by the Chief Administrative Law Judce of the Department ol Labor at an Informal hear ing to begin at 9:30 a.m. June 25, 1974 In the Departmental Auditorium or. Constitution Avenue, between 12th & 14th Sheets, NW,, Washington, D.C. T2ie hearing shall be conducted hi accord ance wi:h the rules of procedure m 22 CFR. Part lfn. Any Interested person desirinr to participate ftt the bearing must file a notice of intention to appear with Ms. Joanne Ooodeli, Attn: Docket OSH-3C. Occupational Bafety and HeaV-e Administration, 172G M Street. MW.. Room 200, U.S. Department of Labor, Washington. D.C. 20210 no later than June 17, 1974 A notice must state the name and address of the person to appear, the ca pacity In which he will appear, and the ap proximate amount of time required for Ills presentation. In addition, to the e"tent prac ticable. th> notice should contain a general statement of the position to be taken with respect to any provision of the propo.od standard, and cf the evidence to be adduced In support of the position. In all other respects, the May 10. 1974 notice of proposed rulemaking remains unchanged. Signed this 22d day of May 1974. John H. Stender. Assistant Secretary of Labor. [FR Doc. 74--12IBS Filed S-23-74;ll:15 am] * Mo. 102--Pt. I----5 FEDERAL REGISTER, VOL 39, NO, 102 FRIDAY, MAT 24, 1974 i i VRD 00020 0 7,4 8 1 * X 16 `Vonrfay,.V<7v:o, 7974 THE WASHINGTON POST '-a ]]| Jpi ISAJi.'w/ o By SIorten Mintz Was&ir.jton Post s;*:: waiter icrs of -rats "breathing vinyl: Malloni observed that tumors! May 10. Ho disclosed that in-.- chloride in a ratio of 25p parts i were continuing to occur inj rats he had found one liver an- ' For at least a year, chemical 'l-cr million (ppm). ' I rats at 250 ppm, firms in. the United States and1 That v;as in August, 1072. At j magazine says. Europe withheld significant I that time, the permissible j The first public the trade! j iosarcoma at only 50 disclosure i along with other types ppm, b of tu-: scientific findings linking;h:ycl for workers allowed by-j of his findings came on Feb.j mors. : liver cancer to 32s used toi*he Occupational Health ar.C| 15, 1974. This was 24-days of-l For some nine months, a ' make .one of the commonest: Safely Administration (OSHA); tor B.F. Goodrich Co. an-; House-Seriate conference com-: plastics, the An nican Chemi-jW5 o00 ppm, or twice as j nounced that since 1071 three; miucc has had a bill before 1*. cal Society's weekly newsimuch- A workers at its polyvinyl plant that would require manufac magazine reports today. In January. 1973, five: in Louisviile had died of .an turers to test new chemicals'! The gas is vinyl chloride, months after Malloni found'giosarcoma of the liver, under rules laid down by the \ used to make the plastic poly- the first rat angiosarcoma, ajj Since then, the total of con Environomental Protection : vinyl chloride. The trade association of team of three U.S. chemical!firmed victims of anciosarthe: industry scientists visited him;:coma at the Goodrich facility Agency (EPA). The stalled legislation is the 1 American chemical the .Manufacturing industry,1 in Bologna Chemists1 work. to learn about bis)jI arindde at other polyvinyl chloplants in the United Association, joined in holding; The visit was preceded by;' States has increased to 13 and proposed toxic substances''controll bill. Senate confen.es, have been waiting for P.op. the findings in confidence, ` months of negotiations with Chemical and Engineering the European firms in addi- News reports in its May 20is-;ticn to Molcdison that had sue. [joined in sponsoring his The Italian scientist who [studies: Imperial Chemical In- made the findings said that al-;distnes, Solvay and Rhonethough preliminary, they wevc|Proiiil. ` predictive'' of the fatal can-j But "U.S. chemical industry ters recently recognized in I sources say they were bound several workers employed in;by an agreement under which converting the gas into polyvi- i IMie? four European firms con- nyl chloride. | trolled any release of animal The scientist is Prof. Ccsare' lest data obtained by Prof. : in other countries to six. Two [of the American workers sur vive. All of the others have died. On April 5, OSHA an nounced an emergency rule drastically lowering the perjmissible concentration of vinyl [chloride from 503 ppm to 50 ippm. Workers engaged in j manufacturing vinyl chloride and polyvinyl chloride number Harley O. Staggers (D-W. Yu.),, chairman of the House confer- ` ces, to announce his readiness to meet. Senate sources say. The House bill would re- i quire pre-production testing of only those new chemicals that | are listed as potentially danIgerous^with results to be re-' j ported to the EPA 90 clays he-I fore production is to begin. ! j The stronger Senate version' Malloni, director of the Inst;-! Mniloni," Chemical and Engi- lG.500 in the United States and jwould require- in addition that- tuto di Oncologia in Bologna, i neering News says. In a study initiated in Scptem-1 name any of the It did not '26-000 elsewhere. American ! Even the 50 ppm level j companies notify the may j of all new chemicals agency' consul-' ber, 1971, by one of the Euro-.firms. ;bc hazardous, Maltoni told a ;cred for production, so that pcas> firms, discovered a Montedison, he' A key second experiment at rare form of can-1 levels of 200. 150, and 100 ppm meeting of Academy of the New York I the EPA could order tvsting of Sciences and the j chemicals that are not on the; cor, angiosarcoma, in the liv-' began about July 0, 1973, when American Cancer Society on 'list but that may be suspect wangaBartrer. irr? VRD 0002007483 Withholding of vinyl chloride data hinted Fosm is Mo Frobiem Fight foam with this Hodag combination-- a complete line ot antifoam products and the technical knowledge to apply them effectively. Superior Products FDA-approved and industrial antifoams developed over ma;,; years to meet the tougr.est foaming conditions. Technology Special knowledge of surface activity helps many industries abate unique processing foams. Technical Facilities Equipped and staffed to develop just the antifoam you need. Let us help solve your foaming problems. Use this coupon to get the Hodag combination of products and technical service. Please send me information on Hodag antifoam agents for Piease send sample for this purpose. Piease have representative contact me. Firm name Address City Name Stale Title Zip HODAG CHEMICAL CCr '"ORATION 7247 N. Central Park Avenue Skokie, Illinois 60076 c European and U.S. chemical firms, to wealth of new medical findings now gether with the Manufacturing Chem appearing on vinyl chloride exposure, ists Association. a U.S. trade group, partly through the May 1(M] meeting. held in confidence for at least a year MCA's epidemiological study on 712k preliminary, albeit significant, scientif vinyl chloride workers, for example, ic findings on vinyl chloride as an finds that cancers of the liver tprimari- agent causing liver cancer in rats, ly angiosarcoma), respiratory system, C&EN learned early last week. U.S. brain, and cancers of unknown primary chemical industry sources say they site, as well as lvm; sarcoma, "oc were bound by an agreement under curred more often t;.,.n expected in which four European firms controlled those members of the study population any release of animal test data ob with the greatest exposure." with the tained by Prof. Cesare Maltoni, direc caveat added that although these ex tor. Istituto Di Oncologia, Bologna, cesses "were not statistically' signifi Italy. cant, the findings warrant further The first public disclosure of Prof. study." And a major bias in the study Maltoni's findings came on Feb. 15, is the "discovery"--too late to include 1974, in the U.S. The disclosure came it--of 1500 to 2000 workers with the after B. F. Goodrich's announcement longest exposures, up to 35 years. on Jan. 22, 1974. of three deaths due to In August 1972 Dr. Maltoni found angiosarcoma of the liver since 1971. his first angiosarcoma in the fir*; of a among workers at its polyvinyl chloride series of studies that, according to data plant in Loui.-ville, Ky. Subsequently, available to C&EN, began about Sept. the number of confirmed cases of an 5, 1971. A key, second experiment at giosarcoma at the BFG plant, at other levels of 200, 150. and luO p.p.m. U.S. PVC plants, and at plants abroad began about July 8, 1973, when it was has risen steadily to a total of 19, in observed that the 250-p.p.m. level cluding 13 U.S. cases. 17 of the workers "was still showingoncogenic effects." have died of the liver cancer; two U.S. In January 1973 a team of three U.S. workers are still living. The U.S. chemical industry scientists visited deaths date back to 1961. Prof. Maltoni in Bologna to learn of hi Prof. Maltoni's animal data have results and to see his bdes. Some been a key to much of the regulatory months of negotiations with the Euro actions taken by the Occupational pean company group preceded this Safety and Health Administration. In visit. The group is made up of Monted February, the lowest dose level of vinyl ison, which first approached Prof. Mal chloride in the Italian scientist's study toni to do the study. Imperial Chemi at which liver angiosarcoma developed cal Industries, Solvay, and Rhonewas 250 p.p.m. Guided, in part, by Progil. All four were supporting the these findings, OSHA on April 5 set an emergency rule that lowered the per missible OSHA worker exposure level work at the time of the visit, U.S. sources say. Subsequently, the liver angiosarco to 50 p.p.m. from the previous ceiling ma in four U.S. deaths of workers of 500 p.p.m. have been judged by OSHA to be "hi- Since then, additional animal data tulogieaUy indistinguishable" from the have appeared. At a May 10-11 meet angiosarcoma tumors Pruf. Maltoni has ing of the Xew York Academy of Sci found. And he believes that hi experi ences and American Cancer Society, ments were "predictive" of what was Prof. Maltoni disclosed that he had subsequently recognized in man. found one liver angiosarcoma in his Much remains to be answered in the rats at 50 p.p.m., together with several way the release of the Maltoni data has other types of tumors. At higher levels been handled. There are allegations, of exposure there were more tumors of unfounded from all that CicEN can various types, including liver angiosar learn, that word of early re.-ult was comas. as he reported earlier (C&EN, passed to U.S. and Italian government Feb. 25, page 16). official. A major question mark con On April 16, MCA announced that cerns what was said by MCA to the preliminary findings on mice in its own National Institute for Occupational study under way at Industrial Biu-Test Safety and Health in July 1973 and Laboratories tended to confirm the earlier. As the trade association testi Maltoni data then available publicly. fied before OSHA on Feb. 15, 1971. Anri as presented by MCA before the "MCA's first direct contact with May 10-11 meeting, the data show that NIOSH specifically on vinyl chloride under conditions of exposure of seven led to a conference between an indus hours per d;iv, five days per week, for try delegation, including a European eight months, liver angiosarcomas de representative, and i)r. Marcus Key velop as follows: 2500 p.p.m.. 28 liver [NIOSH director| and staff on July 17. angiosarcomas; 200 p.p.m., 11; and 50 1973, at which time the MCA program p.p.m., two. MCA's study also showed was presented in some detail, and other types of tumors. 'Pests also have study protocols, industry statistic, and just begun at dose levels of 25, 10, and selected items from the scientific liter 5 p.p.m. ature were provided." MCA has hid Jh;> 0 / VRD 0002007484 EPA CVES7I0NS POP SPI (SOCIETY 0? PLASTICS imJSTRY) 1. lint of cop 50-100 ly'C products by sales vo Irene 2. list of cop 50-100 PVC products by volume of plastic in product 3. amounts of unreacted monomer in above products 4. list of PVC compounding plants by name, location,i- employees, polymer used, products line, quantities produced 5. list of PVC fabrication plants .by name, location, # empolyees, polymer used, fabrication methods utilized, quantities produced 6. ' levels ofVCM in plants in 4. and 5. by plant area and detection method utilized 7. levels of VCM beyond the plants and detection method(s) used 8. levels of VCM in water effluents 9. `decomposition products from various incineration conditions for PVC and quantities of PVC involved 10. amounts of VC leaching out of landfills and total amount PVC buried to date 11. toxicity of PVC resin and products 12. epidemiology studies of workers 13. population within square mile of plants 14. substitutes for VC and PVC 15. Future PVC markets New products New workers for old products 16. Additives used in PVC products VRD 00020 0 74 9 1 ' A 16 uTM^y.MOy20,w;4 THE VASniNGTON POST V . Vinyl Cl3?o-r:c5e ILhikotl to CtincQv -,,i mieal Hazard1 J< r illlT O'; U/ By Morton Mintz crs of -rats breathing vinyl] Malloni observed that tumorsjMay 10. Ho disclosed that in: Wtibianon Pom stsUIWrucr chloride in a ratio of 25J) parts were continuing to occur in rats he had found one liver an- For at-lcast a year, chemical per million (ppm). * (rats at 250 ppm, the trade liosarcoma at only 50 pp:n, firms in the United States and! T--h--a--t--was...i.n....A. -ug--ust*,.-1--9-7--2-.--A---t-!--m--a--g-a-z--i-n--e--says. nt Europe withheld significantIthat time.- the permissible! The first public' disclosure. "8 W1,n othcr l>pcs o tu'j; scientific findings linking!level for workers allowed "by;of his findings came on Feb.jmors- -v</-v*-'ij WP cal Society's weekly news mt,ch* . -*i workers at its polyvinyl plant that would require maninac-; magazine reports today. The gas is vinyl chloride, In January, 1973, months after Maltoni five; jn Louisville had died of anfound'siosarcoma 0f the liver, turers to test new chemicals" under rules laid down by the ' used to make the vinyl chloride. plastic poly the first teom of rat angiosarcoma, a SinCC thcn> ,,.e total of conthree U.S._ chemical | f. d vietims 0f angiosar- Environomer.tal Agency (EPA). Protection; ` i The trade association of the industry scientists visited him;coma 0t the Goodrich facimy T4MhIeS stalled 1leVgi>Jisa4la..ti,oa n..5.s. the1' American chcmicM industry, .m Ro.ogna to learn about-his. d flt other poiyVinyl chlo- proposed toxic substances'co:;- the .Manufacturing Chemists wort. L.iH. ,,iant. i,, the t'niirdU^n h?t >.0 ' i sue. j joined in sponsoring his The Italian- scientist who studies: Imperial Chemical In- made the findings said that al- dustrics, Solvay and Rhone- though preliminary, they were Progil. *'pr -tictive" of the fatal can But "U.S. chemical industry cers recently recognized in sources say they were bound several workers employed in^by an agreement under which died. to meet. Senate sources say. On April 5. OSHA an The House bill would re nounced an emergency rulee quire pre-production testing of drastically lowering the per-|only those r.ew chemicals that" m. is, sib.,le c,oncen.t.ra.tion of . vin.y.l are listed as potentially car.-:' chloride from 500 ppm to aO gerous^with results to be re- converting the gas into polyvi-Uthe] four European firms con- PPm- , Workers engaged m ported to the EI>A GO days no-; nyl chloride. ! trolled any release of animal manufacturing vinyl chloride foreproduction :s to begin. The scientist is Prof. Ccsare ' test data obtained bv Prof.;polyvinyl chlorine number The stronger Senate version Maltoni, director of ihe lnsii-1 Maltoni," Chemical and Engi-!6-500 the United States and: would require- m adnilion t.:ai tuto di Oncologia in Bologna. I nuering News says. It did noti^S'OOO elsewhere. (companies notify the agency In a study initiated in Scptcm- j name any of the American Even the 50 ppm level may of all new chemicals consul-: ber, 1971, by one of the Euro-[firms. " be hazardous, Maltoni told a'ered for production, so that1 pean firms, Montedison, hej A key second experiment at meeting of the New York the EPA could order testing of discovered a rare form of can-' levels of 200, 150, and 100 ppm Academy of Sciences and the chemicals that are not on Du* | ccr, angiosarcoma, in the liv-| began about July 8, 1973, when! American Cancer Society on list but that may be suspect ; Rrinawa-wri'* / ' VRD 0002007492 Withholding of vinyl chloride data hinted Foam Is Mo Problem Fight loam with this Hodag combination-- a complete line ol antifoam products and the technical knowledge to apply them effectively. Superior Products FDA-approved and industrial antifoams developed over many years to meet the toughest foaming conditions. Technology Special knowledge of surface activity helps many industries abate unique processing foams. Technical Facilities Equipped and staffed to develop just the antitoam you need. Let us help solve your foaming problems. Use this coupon to get the Hodag combination of products and technical service. Please send me information on Hodag anlifoam agents for ____________ O Please send sample tor this purpose. Please have representative contact me. Firm name Addicts Ciiy Nemo SUio Title Zip HODAG CHEMICAL CORPORATION 7247 N. Central Park Avenue Skokie, Illinois GCD7S c European and U.S. chemical firms, to wealth of new medical findings now gether with the Manufacturing Chem appearing on vinyl chloride exposure, ists Association, a U.S. trade group, partly through the May 10 11 meeting. held in confidence for at least a year MCA's epidemiological study on 712s preliminary, albeit significant, scientif vinyl chloride workers, for example, ic findings on vinyl chloride as an finds that cancers of the- liver tprimari- agent causing liver cancer in rats, ly angiosarcoma), respiratory system, C&EN learned early last week. U.S. brain, and canters of unknown primary chemical industry sources say they site, as well as lymphosarcoma, "oc were bound by an agreement under curred more often than expected in which four European firms controlled those members of the study population any release of animal test, data ob with the greatest exposure." with the tained by Prof. Cesare Maltoni, direc caveat added that although tht-s-e ex tor, lstituto Di Oncologi .. Bologna, cesses 4`were not statistically signifi Italy. cant, the findings warrant further The first public disclosure of Prof. study." And a major bias in the study Maltoni'& findings came on Feb. 15, is the "discovery"--too late to include 1974, in the U.S. The disclosure came it--of 1500 to 2000 workers with the after B. F. Goodrich's announcement longest exposures, up to 35 years. on Jan. 22, 1974, of three deaths due to In August 1972 Dr. Maltoni found angiosarcoma of the liver since 1971. his first angiosarcoma in the- first of a among workers at its polyvinyl chloride series of studies that, according to data plant in Louisville, Kv. Subsequently, available to C&EN, began about sept. the number of confirmed cases of an 5, 1971. A key, second experiment at giosarcoma at the BFG plant, at other levels of 200, 150. and 100 p.p.m. U.S. PVC plants, and at plants abroad began about July 8, 1973, when it was has risen steadily to a total of 19, in observed that the 250-p.p.m. level cluding 13 U.S. cases. 17 of the workers have died of the liver cancer; two U.S. workers are still living. The U.S. "was still showing oncogenic effects." In January 1973 a team of three 1 S, chemi: 1 industry scientists visaed deaths date back to 1961. Prof. ultoni in Bologna to learn of bis Prof. Maltoni's animal data have results and to see his slides. Some been a key to much of the regulatory months of negotiations with the Euro actions taken by the Occupational pean company group preceded this Safety and Health Administration. In visit. The group is made up of Monted February, the lowest dose level of vinyl ison, which first approached Prof. Mal chloride in the Itc'riian scientist's study toni to do the study, Imperial Chemi at which liver angiosarcoma developed cal Industries, Solvay, and Iihonc- was 250 p.p.m. Guided, in part, by Progil. All four were supporting the these findings, OSHA on April 5 set an emergency rule that lowered the per missible OSHA worker exposure level to 50 p.p.m. from the previous ceiling of 500 p.p.m. work at the time of the visit, U.S. sources say. Subsequently, the liver angiosarco mas in four U.S. deaths of workers have been judged by OSHA to be "his Since then, additional animal data tologically indistinguishable" from the have appeared. At a May 10-11 meet angiosarcoma tumors Prof. Maltoni has ing of the New York Academy of Sci found. And he believes that hi? experi ences and American Cancer Society, ments were "predictive" of what was Prof. Maltoni disclosed that he had subsequently recognized in man. found one liver angiosarcoma in his Much remains to be answered in the rats at 50 p.p.m., together with several way the release of the Maltoni data has other types of tumors. At higher levels been handled. There are allegations, of exposure there were more tumors of unfounded from all that CiiEN can various types, including liver angiosar learn, that word of early results was comas, as he reported earlier (C&KN, passed to U.S. and Italian government Feb. 25, page 16). On April 16, MCA announced that preliminary findings on mice in its own study under way at Industrial Bio-To.-t Laboratories tended to confirm the officials. A major question mark con cerns what was said by MC'A to the National Institute for Occupational Safety and Health in July 1973 and earlier. As the trade association testi Maltoni data then available publicly. Anri as presented by M('A before the May 10-11 meeting, the data show that fied before OSHA on Feb. 15, 1971, "NK'A's first direct contact with NIOSH specifically on vinyl chloride under conditions of exposure of seven led to a conference between an indus hours per clay, five clays per week, for try delegation, including a European eight month.., liver angiosarcomas de representative, and Dr. Marcus Key velop as follows: 2500 p.p.m,, 28 liver INIOSH director) and staff on July 17. angiosarcomas; 200 p.p.m., 11; and 50 1973, at which time the MCA program p.p.m., two. Mt'A's study also showed was presented in some detail, and other typc*s of tumors. Tests also have just begun at dose levels of 25, ]U, and 5 p.p.m. study protocols, industry statistics, and selected items from the scientific liter aturc ver provided." Mt'A has slu.il VRD 0002007493 ___ <J ' ' f& epa our.STio::s rop spi (society or puisnes industry) 1. line of too 50-100 PVC produces by sale* volu-.ee 2. list of top 50-100 PVC products by volume of plastic in product 3. amounts of unreacted monomer in above products 4. list of PYC compounding plants by name, location,# employees, polymer used, products line, quantities produced 5. list of PVC fabrication plants .by name, location, # empolyees, polymer used, fabrication methods utilized, quantities produced 6. levels of VO! in plants in 4. and 5. by plant area and detection method utilized \ 7. levels of VCM beyond the plants and detection method(s) used 8. -levels of VCM in water effluents 9. `decomposition products from various incineration conditions for PVC and quantities of PVC involved 10. amounts of VC leaching out of landfills and total amount PVC buried to date 11. toxicity of PVC resin and products 12. epidemiology studies of workers 13. population within square mile of plants 14. substitutes for VC and PVC 15. Future PVC markets Kew products New workers for old products 16. Additives used in PVC products K. L. Schurter F. Kennedy Hay 17* 1974 Questionnaire on Vinyl Chloride Exposure The attached questionnaires were sailed to Thomas 0. McGrath* The Society of the Plastics Industry* on May 17, 1974. Plant Identifica tion Is as follows: Vinyl Chloride Plant 1 -- Lake Charles VCM Plant PVC Plant 1 -- Aberdeen Plant PVC Plant 2 -- Oklahoma City Plant Flynt Kennedy Is enc cc w/enc: R. D. 6amblln - L.C. VCM E. M. Salth - Aberdeen Plant Manager Oklahoma City J. D. Burns sa *3 J 6 H 0 0 1 0 0 0 AHA May 17, 1974 Mr. Thomas 0. McGrath Director of Packaging Services The Society of the Plastics Industry, Inc. 250 Park Avenue New York, New York 10017 Dear Mr. McGrath: Please find enclosed three completed forms for Conoco Chemicals manu facturing facilities for PVC and vinyl chloride monomer. Yours very truly. 1m enc bcc: KLS 9 iM B B W It (HM THE SOCIETY O. I HE PLASTICS INDUSTRY. INC. 250 PARK AVENUE NEW YORK. NEW YORK IOOI7 2 12/607-2675 QUESTIONNAIRE ON VINYL CHLORIDE EXPOSURE VIHYL CHLORIDE PLANT 1 Exposure Levels: 1. Odor of vinyl chloride monomer present throughout much of the day. Not Applicable From yearsto . 2. Odor of VCM present occasionally during the work day. From years1968to 1974. 3. Odor of VCM a rare event in any work day. From years Not applicablsto _____ . 4. Have there been process or processing changes introduced which have resulted in an increased escape of VCM. List years when these occurred. 1969 5. Have there been process or processing changes introduced which have resulted in a reduction in the escape of VCM. List years when these occurred. 1970. 1972. 1973. 1974 6. Do you have environmental measurements prior to 1970? Yes No X Personnel Exposure Data: 1. When did the plant start to work with VCM? Give year 1 968. 2. How many employees are working with VCM? Give number81. 3. How many employees are still working for you who once worked with VCM but do not do so now? Give number0. 4. Of the persons identified in 2 and 3 above give the number who have been exposed for the following time intervals. > % . L b n j M l H t GHA 2- - More than 1 and up to 10 years 10 and up to 15 years 15 and up to 20 years 20 and up to 25 years 25 years and more 81 5. Of the persons identified in 2 and 3 above give the number falling within each latent period given below and considering only employees with more than one years service. A latent period is the time lapse from first exposure to the present date. More than 1 and up to 10 years 10 and up to 15 years 15 and up to 20 years 20 and up to 25 years 25 years and more ____8] ~ _ Data From Current Examination Programs 1, Give the number of persons who have been examined since January, 1974, 99, 2. Were liver profile studies made? Yes X__________ No. 3.. Did the studies include at least bilirubin, SGOT, LDH and alkaline phosphatase? Yes X No. 4. How many of those examined showed an abnormality in: one test 0 two tests 0 three or more tests u 5. Have you had any cases of angiosarcoma? Yes No X 6. Was this determination made by your own survey? Yes X No 86U0-0Z000 -3- 7. What per cent of the total exposed population was covered in the survey? 100% 8. Were retired personnel included? Yes X________ No 9. Were persons who had left your employ and gone to work elsewhere included? Yes X No. 10. Did you review causes of death of those who died while still employed by you? Yes X- No* 11. Did your plant participate in the Tabershaw-Cooper epidemiologic survey? Yes X No 30 > May 3, 1974 THE SOCIETY O 'HE PLASTICS INDUSTRY. INC. 250 PARK AVENUE N E V/ YORK. NEW YORK 10017 212/607-2675 QUESTIONNAIRE ON VINYL CHLORIDE EXPOSURE PVC PLANT 1 Exposure Levels: 1. Odor of vinyl chloride monomer present throughout much of the day. Not Applicable From yearsto. 2. Odor of VCM present occasionally during the work day. From years 1 963to1974. 3. Odor of VCM a rare event in any work day. From years April 1974 to present. 4. Have there been process or processing changes introduced which have resulted in an increased escape of VCM. List years when these occurred. None 5. Have there been process or processing changes introduced which have resulted in a reduction in the escape of VCM. List years when these occurred. See attachment _____ _____ ______ . 6. Do you have environmental measurements prior to 1970? Yes No X Personnel Exposure Data: 1. When did the plant start to work with VCM? Give year 1 963, 2. How many employees are working with VCM? Give number 84. 3. How many employees are still working for you who once worked with VCM but do not do so now? Give number 22. 4. Of the persons identified in 2 and 3 above give the number who have been exposed for the following time intervals. 66 TO o * VRD 0002007500 Page 1-A Exposure Levels: 5. Have there been process or processing changes introduced which have resulted in a reduction in the escape of VCM. (1} (2) (3) (4) (5) . (6) (7) (8) (9) Blowdown tanks, 1966 Distillation system, 1970 Recovery to a greater vacuum, 1970 Quit making co-polymer in 1971 Better filtering system for finish products, 1970 Quit making plastisol resin, 1972 Quit making high absorption resins, 1972 Lids on compound blenders kept closed Air mover to vent tanks in 1971 VRD 0002007501 ( 2- - Morc than 1 and up to 10 years 10 ancl up to 1 5 years 15 and up to 20 years 20 and up to 25 years 25 years and more 78 ~ - 5* Of the persons identified in 2 and 3 above give the number falling within each latent period given below and considering only employees with more than one years service. A latent period is the time lapse from first exposure to the present date. More than 1 and up to 10 years 10 and up to 15 years 15 and up to 20 years 20 and up to 25 years 25 years and more 78 ~ - Data From Current Examination Programs 1, Give the number of persons who have been examined since January, 1 974. _______339. 2. Were liver profile studies made? Yes X No . 3. Did the studies include at least bilirubin, SCOT, LDH and alkaline phosphatase? Yes X No . 4, How many of those examined showed an abnormality in: one test 36 two tests _5 three or more tests 2 5. Have you had any cases of angiosarcoma? Yes No X .6 Was this determination made by your own survey? Yes X No . VRD 0002007502 -3- 7. What per cent of the total exposed population was covered in the survey? est. 50%. 8. Were retired personnel included? Y.esX No. 9. Were persons who had left your employ and gone to work elsewhere included? YesX______ No. 10. Did you review causes of death of those who died while still employed by you? Yes X No. 11, Did your plant participate in the Tabershaw-Cooper epidemiologic survey? Yes X No May 3, 1974 c m a flZ flM qua THE SOCIETY O HE PLASTICS INDUSTRY, INC 250 PARK AVENUE NEW YORK. NEW YORK 10017 212/687-2675 e. % ^' QUESTIONNAIRE ON VINYL. CHLORIDE EXPOSURE PVC PLANT 2 Exposure Levels! 1. Odor of vinyl chloride monomer present throughout much of the day. From years__ to . Not applicable 2. Odor of VCM present occasionally during the work day. From years1971to present, 3. Odor of VCM a rare event in any work day. From years not applicable to _. 4. Have there been process or processing changes introduced which have resulted in an increased escape of VCM. List years when these occurred. No 5. Have there been process or processing changes introduced which have resulted in a reduction in the escape of VCM. List years when these occurred. 1973, 1974. 6. Do you have environmental measurements prior to 1970? Yes___________ No X Personnel Exposure Data: 1. When did the plant start to work with VCM? Give year _______1971 2 . How many employees are working with VCM? Give number47. 3. How many employees are still working for you who once worked with VCM but do not do so now? Give number___________1 4. Of the persons identified in 2 and 3 above give the number who have been exposed for the following time intervals. 2- - More than 1 and up to 10 years 10 and up to 15 years 15 and up to 20 years 20 and up to 25 years 25 years and more 46 1 5* Of the persons identified in 2 and 3 above give the number falling within each latent period given below and considering only employees with more than one years service. A latent period is the time lapse from first exposure to the present date. More than 1 and up to 10 years 10 and up to 15 years 15 and up to 20 years 20 and up to 25 years 25 years and more 46 _________ 1 -_____________ " ~ Data From Current Examination Programs 1. Give the number of persons who have been examined since January, 1974. ________4 (remainder scheduled) 2. Were liver profile studies made? Yes X No . 3. Did the studies include at least bilirubin, SGOT, LDH and alkaline phosphatase? Yes X_______________ No . 4. How many of those examined showed an abnormality in: one test __________________ ) two tests __________________ three or more tests ]_ ) n0 results yet 5. Have you had any cases of angiosarcoma? Yes No X. .6 Was this determination made by your own survey? Yes X No AHA 9 t VRD 6002 0*07505 % -3- 7. What per cent of the total exposed population was covered in the survey? 1 00%. 8. Were retired personnel included? not applicable Yes No 9. Were persons who had left your employ and gone to work elsewhere included? Yes No X. 10. Did you review causes of death of those who died while still employed by you? YeB No. not applicable 11, Did your plant participate in the Tabershaw-Cooper epidemiologic survey? Yes X_____________ No May 3, 1974 p