Document Z4zawxEjeDKM26L3rQ4BgaNZZ

/tf> UNITED STATES ENVIRONMENTAL PROTECTION AOENCV ASMINGTOM, D.C. 204(0 OFFICIAL lUMNCll FCMALTV FOR FOlVAtC UVC $10# AM KCUAL OPPORTUNITY 8MPLOVCM U.L tNWinUOMMBMTKA^LAP4AMOTCCTIOM AOtNCV fib RECEIVED MAY 22 1974 * ' B. N. WHEELER, JR. O'Neill (202) 755-0344 . Farkas (202) 755-0.720 FOR IMMEDIATE RELEASE-THURSDAY, APRIL 4, 1974 EPA FORMS VINYL CHLORIDE TASK FORCE * The Environmental Protection Agency has formed an internal task force to assess the overall environmental impact of vinyl chloride, a gaseous chemical, and the plastic, polyvinyl chloride. Vinyl chloride has been implicated in the recently reported .deaths of ten. workers at plants where the gas is used to produce the polyvinyl chloride. All died from a reure form of cancer, called angiosarcoma of the liver. The task force, chaired by Glenn E. Schweitzer, Director of EPA*s Office of Toxio Substances, is charged with assessing possibl environmental and health risks associated with the manufacture, distribution, and disposal of vinyl chloride and polyvinyl chloride. At present, the task force is reviewing, collecting and assessing data on 1) the ambient emission and effluent levels of vinyl chloride in air and water from vinyl chloride and polyvinyl Chloride manufacturing plants 2) the'environmental' impact of all disposal methods for vinyl chloride and polyvinyl chloride wastes, including landfill, incineration, deep-well injection, and ocean dumping 3) ecological effects of vinyl chloride in the environment. The task force plans to meet with environmental and consumer groups to discuss its mission and exchange information. A similar meeting has taken place between the task force and the chemical industry. The task force is also working with other Federal (more) IMM W4 pMt ( grwi N NOT wW> la wdlvi tM* maMflal Q. a. If epa porn iii*i (rev. > f, M nuA.4 (MpMaM ctnn MMu4ln lip coM. .-.'t'.-."-xr ucc 011591 agencies concerned with vinyl chloride, including th D pertinent of Labor; the Department of Health, Education and Welfare; the Consumer Product Safety Commission, and the Department of Commerce. Vinyl chloride' is used as a propellant in 23 pesticid aerosols currently registered by EPA. The gas helps expel th contents from the pesticide containers. In a March 28 letter to the Health Research Group, a Washing D.C. based public interest organization, EPA said that it will shortly notify the manufacturers, formulators and distributors of these products of the need to substitute another substance for vinyl chloride. A copy of the letter is attached. The Agency said that, "Even though the health data for vinyl chloride are limited, we believe that it is prudent public policy for usjto request the manufacturers of these pesticides to make a voluntary change..." If a currently ongoing EPA evaluation of these pesticides indicates a substantial risk or imminent hazard to the user, and if voluntary compliance has not been obtained, the Agency will, invoke suspension of the products or other enforceable remedi s. On March 27, EPA mailed letters to the manufacturers giving them ten days in which to state any objections t the Agency's making public the brand names of the 23 products. This period for comment is required since the existence of vinyl chloride in the pesticides may be considered part of th products' confidential formulations. *# r *. "* 'V '1,1 ' ' ` " ucc 011592 THE NEW YORK ACADEMY OF SCIENCES WORKING GROUP ON toxicity of vinyl chloride-polyvinyl chloride nWIBOHHEBTAI, CONCEPTS BEYOND TBS WORKPLACE* Glenn E. Schweitzer Director, Office of Toxic Substances Environmental Protection Agency 401 M Street, S. W. uec 011593 Presentation to the Working Group on Toxicity of Vinyl Chloride-Polyvinyl Chloride The New York Academy of Sciences New York City, New York May 11, 1974 "ENVIRONMENTAL CONCERNS BEYOND THE WORKPLACE" Glenn E. Schweitzer Director, Office of Toxic Substances Environmental Protection Agency Washington, D. C. During the past several months vinyl chloride has awakened all elements of the environmental community to the presence of the plastics . Industry. In some respects it Is fortunate that we have been alerted in a rather dramatic fashion to the need for greater attention to this important segment of our Industrial base which will surely continue to expand in the years ahead. While this symposium is directed to the existing and potential risks Involved In the manufacture, distribution, and use of vinyl chloride monomer (VCM) and polyvinyl chloride (PVC), many of the types of considerations and uncertainties that punctuate these deliberations undoubtedly characterize a far broader swathe of concerns over chemicals in general. Hopefully, we can extrapolate from our current experiences with VCM and PVC In Identifying problems with other potentially important conrierclal chemicals early In their embry onic stage and thus minimize the economic dislocations attendant to corrective actions. Unfortunately, the proposed Toxic Substances Control Act has been lodged in a Joint Committee of the Congress for ten months. Thus, a very powerful tool for addressing the vinyl chloride problem, and similar problems with other chemicals. In an adequate manner Is not available to the Federal Government. We must rely on other statutory authorities and on the power of persuasion In our efforts to Insure that our population Is not being unnecessarily exposed to concentrations of VCM and other chemicals used In connection with VCM. It Is particu larly distressing that until this statutory authority Is on the books, the Federal Government will not be equipped -- In terms of experienced personnel and supporting resources -- to grapple with the Intricacies of this type of toxic substance problem In a manner which will Insure full attention to the balancing of risks and benefits. Today I will report to you on the preliminary Investigations under taken by the Environmental Protection Agency during the past three months. We are still several weeks away from reaching even tentative conclusions as to what additional steps. If any, should be taken by the Agency concerning VCM/PVC activities. Our monitoring data are not yet UCC 011594 In hand. Similarly, our analytical studies are not yet completed. Nevertheless, we are pleased to share with you some of our Initial thoughts. We will welcome your comments on the efforts to date and on further steps which are necessary. In this regard, the prioritization of our efforts is particularly important in view of the speed with which this problem is evolving and the limitations on our resources. At the outset it is important to underscore that the progress made to date would not have beerr possible without the extensive cooperation, of other federal agencies, industry, and environmental groups. We have profitted greatly from our discussions with these organizations, through our on-site industrial visits, and through constructive suggestions that we have received. EPA Regulatory Authorities To date EPA has exercised its authority in the pesticides area to suspend the use of vinyl chloride as a propellant in all pesticide pro ducts registered for indoor use in homes, food handling establishments, hospitals, and other enclosed areas, with a mandatory recall of stocks in the channels of trade. In addition, in response to the Agency's request, all registrants of pesticides which are used outdoors have agreed either to withdraw their registrations or to amend them to provide for the substitution of another propellant In their products. We are currently investigating what regulatory actions, if any, are needed with regard to air emissions, water effluents, and solid waste disposal at facilities involved In VCM and PVC activities. In addi tion the Agency has responsibility In the areas of drinking water standards, ocean disposal, and municipal waste disposal -- all areas of some relevance to the VCM/PVC concerns. As previously mentioned a principal authority which Is currently missing is the Toxic Substances Control Act. The requirements for reporting of Industrial production data envisaged In the Act would enhance our knowl edge of the types and extent of different uses of VCM. The testing pro vision would enable us to obtain much needed data -- and particularly data on toxicity and persistence -- for assessing the risks associated with low concentration levels of VCM, including those levels that are likely to persist beyond the workplace. The proposed regulatory provisions would provide a mechanism for addressing those products using VCM not now subject to regulation under other laws. Also, If considered appropriate, steps might be taken to limit the amount of unreacted VCM In certain PVC products which may eventually migrate out of these products to pose an unnecessary risk. 2 ucc 011595 The Materials Balance EPA's initial concern In this area centered on reports in February of a materials loss of six percent in the PVC production process. Our detailed Investigations indicate that these Initial reports were In the correct range. Clearly, the percentage of losses will vary with the type of process, the age of the plant, the level of technology that is employed, and manufacturing practices. However, there Is no doubt that In the United States substantial amounts of VCM --> probably exceeding 200 million pounds annually^-- and large quantities of PVC -- probably exceeding 50 million pounds^- are being discharged into the environment during the PVC production process. Most of the VCM escapes directly into the atmosphere as air emissions, with lesser amounts dissolved In water effluent streams and entrapped In sludge and solid wastes. PVC losses occur as particulate In air emissions, suspended solids In water effluents and components of solid wastes. Clearly, a principal area of VCM leakage Is associated with the operation of the polymerization kettles. Including losses when they are opened for recharging, cleaning, or sampling. Other losses occur during the transfer of VCM from tank cars to storage, during the drying process, and from leaks at a variety of valves, flanges, and pump seals throughout the process. Polymer losses are similarly distributed among a variety of activities Including dust collector losses, disposal of oversize particles and sampling losses. The enclosed flow diagram for a typical suspension process reflects such losses which according to our estimates usually range from four to eight percent. In this regard two aspects are particularly significant: there are a variety of PVC processes with differing problems and control possibilities, and In every case the num ber of potential leakage points Is very large. For economic reasons and in view of the fire hazard from VCM, Industry has always been concerned with reducing Its losses down to a point. Now some plants are taking steps to reduce these losses further In view of worker and environmental concerns. We understand that the tightening up on maintenance and housekeeping activities can Indeed have a significant Impact, and several PVC plants reportedly are now operating close to the four percent level for total losses. The data needed for conducting material balance analyses during VCM production and PVC compounding and fabrication processes are less readily available. However, we do not believe that these activities pose as serious an environmental concern beyond the fence line of the plant, at least at the present time, as the polymerization process. At the same time In the absence of constant vigilance VCM losses to the atmosphere during the latter phases of the VCM production process and during trans fer to and from storage can be significant. Also, throughout the process there are many seals and valves which Inevitably lead to leaks. With regard to compounding and fabrication, unreacted monomer Is Inevitably 3 ucc 011596 associated with the polymer following the polymerization process. In some cases this monomer concentration reaches 7000 ppm although a more representative level probably Is In the range of 500 to 1000 ppm. Dur ing the mixing and heating processes In the compounding and fabrication plants, some of this VCM undoubtedly escapes Into the environment. Now, In efforts to reduce further the level of unreacted VCM In the final product many companies are Introducing new techniques which Increase the migration rates during this phase of production. The Need for Epidemiological and Toxicological Studies Since some elements of our population in addition to the plant worker are being exposed to some level of VCM, we must address the question: What is the risk of such exposure? In considering non-worker populations, we are confronted with a host pf new unanswered questions. How relevant to this concern are the data generated for estimating worker exposure risks? Can meaningful extra polations be made from toxicological tests at relatively high dose levels to the lower levels of the dose-response relationship? Can realistic extrapolations be made from intermittent exposure, which characterizes the past and present toxicological and epidemiological investigations (e.g. eight hours per day, five days per week) to sustained exposure at the same dose levels or at lower levels? Are synergistic effects that result from exposure to other chemicals as well as VCM Influencing the worker's response to VCM, and are there similar opportunities for such synergism within a non-worker population? There are not sharp answers to these questions, and Indeed they go to the heart of many of the fundamental uncertainties of the biological sciences. To date the epidemiological and toxicological data that have been generated have been directed almost exluslvely to concerns over workers. This is the data base that we in EPA presently have available. I doubt that anyone Is more aware of Its Inadequacy than are those of us responsible for regulatory actions based on this data. Unfortunately, we often have no choice but to make judgemental decisions using whatever scientific Information Is available. Other reports presented at this symposium review past, current, and future studies directed to VCM. While they will undoubtedly be helpful to our assessment of the environmental problem, from our point of view they are clearly not adequate in Improving the basis for estimating non worker risks. Let me cite three examples of the types of studies v^hich appear to be needed: -- Epidemiological Investigations of populations near chemical plants that are likely to have been exposed to low ambient levels of VCM over a prolonged period of time. It Is the 4 uec 011597 M responsibility of Industry to support such efforts which will help clarify whether manufacturing activities pose a risk to neighborhood residents. At the same time we recognize the com plexities involved in designing and carrying out such studies, the advantages of drawing on governmental experience in this area, and the prototypic nature of such an undertaking. There fore, it seems likely that EPA will be prepared to participate in such efforts along with Industry and other interested parties. -- Toxicological tests at appropriate dose levels, with a suffi ciently large number of animals, and with appropriate exposures to provide the basis for meaningful conclusions concerning the likely health effects of VCM In ambient air near chemical plants. Such tests are clearly the responsibility of industry. Indeed, industrial responsibility for the testing of the safety of Its products is a basic tenet of the Toxic Substances Control Act. At the same time, we are aware that some Industrial firms are concerned about the possible Inadequacy of commercial test facilities to accoumodate the needed tests. Therefore, if necessary, the National Center for Toxicological Research, which is supported by FDA and EPA, is prepared to work with Industry toward suitable arrangements for utilizing available buildings in Jefferson, Arkansas. -- Research on animals and In vitro experiments to help clarify the toxicological significance of" impurities in VCM, synergistic effects due to exposure to other chemicals In addition to VCM such as vinylIdIne chloride, and metabolic reactions induced by VCM. Government, Industry, and academia all have responsibilities in this area, and EPA Is currently considering specific steps that might be taken to contribute to advancing the frontiers of our knowledge. Monitoring, Persistence, and Migration Studies We are obviously concerned about current and future background levels of VCM In the air and In the water throughout the country. Our more Immediate efforts, however, are being directed to determining ambient and peak levels near chemical plants. Recently, we Initiated a nationwide sampling and analysis program to determine, at least in a preliminary fashion, the VCM levels in ambient air and In water and semi-solid effluents at about ten PVC plants. These activities are currently underway, and we hope to have the results within several weeks. S ucc 011598 As a precursor to this nationwide effort, several weeks age we conducted a preliminary monitoring program at the B. F. Goodrich plant In Louisville using Inadequately tested sampling and analysis methods. At that time VCM levels were detected of 1 to 2 ppm In the ambient air outside the plant, 2 to 3 ppm in the primary water effluent, and 100 to 200 ppm in the sludge at the plant site. However, these numbers could be In error by as much as an order of magnitude due to the pioneering nature of the effort, and no conclusions should be drawn at this time. During the past several- weeks we have made a major effort to develop credible and standardized sampling and analysis procedures, building on this initial experience. Our current monitoring efforts are based on this recently improved methodology. The limit of detection for our current technique is approximately .06 mg/liter in water and .06 ppm {volume/volume) in air. However, when vacuum cans are used, the detection limit is .2 ppm because the gas sample must be diluted. The technique we are using is now publicly available with the hope that our efforts toward standardization will lessen the chaos characterizing current monitoring efforts of several federal agencies and industry. While the near-term objective of these monitoring efforts is to gain a limited perspective of the levels of VCM near PVC plants, we should also learn more about the persistence of VCM In air and water from our measurements. Samples are to be taken during daytime and at night, and there undoubtedly will be a range of temperature and humidity conditions. However, we have not structured the measurements with research as a prin cipal objective, and we will not be able to quantify persistence char acteristics with any degree of precision. Limited laboratory experiments are also being attempted to clarify persistence characteristics of VCM. Related to our decision to suspend pesticide sprays containing VCM, one laboratory test showed that in an unventilated and unlighted chamber, less than one percent of the VCM initially present was dissipated after four days. Current efforts are directed to clarifying the rate of retention of VCM entrapped In water effluent streams, as well as further work to understand the effect of light, heat, and moisture on VCM In air. There has been considerable discussion of the amount of unreacted VCM monomer remaining in PVC and the rates of migration out of the PVC. Many companies are now seized with this problem, and I suspect the number of samples being taken to determine VCM concentrations and migration rates has Increased considerably In recent weeks. We do not know whether such migration from finished products contributes significantly to back ground levels of VCM, but as you are aware FDA is seized with several aspects of this problem directly related to food. Should there be high levels of VCM background in the environment, then.our concern over all sources of VCM -- Including migration from many products -- should Intensify. 6 ucc 011599 In all of these areas Industry has a major responsibility for determining and alerting the public about the behaviour of Its products. I would hope that in the months and years ahead industrial monitoring efforts at the fence line will increase dramatically; persistence will become a key concern; and the ultimate fate of chemicals will be less uncertain. Already some chemical establishments have rather broad sampling and analysis programs, and as a direct result of VCM concerns, others are also making new efforts in this regard. At the same time EPA has-a responsibility to help insure the adequacy of the national effort In keeping abreast of the chemical crosssection of our environment. Concerns over Disposal of PVC While we tend to lump all types of PVC Into one category, I am sure you are aware of the variances In the chemical and physical properties of different grades of PVC. Also, end products made from PVC include a variety of other chemicals which are added throughout the production cycle. To date EPA's principal concerns relating to PVC have been directed to possible problems attendant to its disposal -- either in incinerators or landfills. We have not investigated in depth any of the special problems associated with inhalation or Ingestion of low concentrations of PVC particulate. With regard to incineration, HC1 Is a primary product of concern. Also, toxic metals may be present as additives and thus cause Inhalation problems, either as metal or oxide vapors. Landfill disposal operations have traditionally assumed that PVC Is stable with little likelihood of biological degradation or undesirable leachates. Taking a long-term perspective these assumptions seem clearly overly simplistic, and we should address In greater depth problems attend ant to the disposal of plastics. Experiences In the tropics, for example, have demonstrated the effect of bacteria on PVC which has not been specially treated for use In humid areas. The Risks, the Benefits, and the Costs The current problems with VCM have brought Into sharp focus the practical aspects of balancing the risks and benefits associated with conmerclal chemicals. The costs Involved to reduce these risks substan tially may be formidable -- or Indeed may be prohibitive. The aspect which Is perhaps the most troublesome goes to the heart of this meeting -- What Is the risk now and under alternative regulatory approaches? 7 ucc 011600 In the years ahead more chemicals wll' be in conmerce, the pr* perties of many chemicals will be better understood, ano consequently the list of chemicals considered to be hazardous to man and the environment will undoubtedly be much longer. Also, improved researr*. and analytical capabilities will show that the effect* of thes* chemicals -- acting individually and synerqisiicali.y a,e mucn farther reaching than currently susoected effects. As these realities of.the chemical age unfold, there must h* Vr greater sophistication in approaches to responsible regulation fully, we will develop the necessary precautionary measures tha- ..Vn limit exposure to chemicals when necessary, out not unnecessarily cur tail commercial activities. a ucc 011601 OUTDOORS '.A.irl iMui UtifUMt PRELIMINARY ESTIMATE OF LOSSES HI PVC SUSPENSION PCtTL'EElZATiOH (TYPICAL PROCESS awiwmtawu MATERIALS BALANCE PVC MANUFACTURE tutl -- !i 't- \\ ucc 011602 luifctnu. uoistno wc rnitnm bay textAW oiiwa rm IHtUUTU WtC I' -- x- - * ****-'* ^ii'i - - - ::#fc b^iV v: Interim Method for Monitoring Vinyl Chloride In Water Effluents and Air Emissions Being Used by the Environmental Protection Agency The sampling and analysis method described in the enclosure reflects current state-of-the-art and undoubtedly will be .improved In the months and years ahead. Indeed, It-sbould be recognized that these interim pro cedures have not been adequately tested. Several additional caveats should.be recognized. It Is exceedingly difficult to prepare stable aqueous calibration solutions of VCM. For this reason carbon tetrachloride solutions of vinyl chloride are used to calibrate the gas chromatograph for aqueous samples of vinyl chloride. Even these are difficult calibration solutions with which to work. The calibration procedure developed by the Southeast Environmental Research Laboratory is described in the enclosure. Another weakness Is that the stock'solution of VCM In carbon tetrachloride must be determined against mixtures of VCM in zero nitrogen. The FFAP on Gas Chrom Q packed columns which is used for aqueous sample analysis is not well suited to analysis of gas samples of VCM. _- - - At present, there Is no adequately tested method for continuously monitoring vinyl chloride. Based upon the experiences of the National 'Institute of Occupational Safety arid Health and EPA Region IV, the carbon adsorption column Is being used. Time constraints have made it necessary to specify Fischer Scientific activated coconut shell charcoal for standardization of interim EPA procedures although other charcoals or adsorbents may^prove to be more efficient. . Vinyl chloride to be used for calibration purposes (50 ppm In zero air) is being obtained from Scott Laboratories and tedlar bags from Fluorodynamics, Inc. However, the use of these sources of supply in no way reflects endorsement of their products as preferable to comparable products of other organizations. - Should there be questions concerning these procedures. Dr. Robert B. Medz (Area Code 202, 426-2382) may be able to clarify further the methodology that has been developed. Environmental Protection Agency 5/2/74 UCO 011603 METHOD FOR VINYL CHLORIDE (VC) IN INDUSTRIAL WASTE WATER EFFLUENTS AND ATMOSPHERIC SESSIONS 1. Scope and Application 1.1. This method is applicable to VC monomer determinations in industrial effluents, sludges and scuas, and atmospheric emissions. The limit of detection is approximately 0.06 mg/l in water (0.06 ppm v/v in air samples). When vacuum cans are used, the detection limit is 0.2 ppm because the gas sample must be diluted from 100 ml to about 350 ml. 2. Simmayrr without cleanup by gas chromatography (GC). Separations are . effected by selection of one of two types of columns dependim upon the nature of the sample. Detection is by means of the flame ionization detector (FID). Tetrahydrofuran extracts of 7l 7.7.. sludges and scums are used for injection into the G.C. Air continuous samples on activated carbon are extracted with * carbon disulfide and analyzed by G.C. . .v; 2.2. VC confirmation may be made by mass spectrometrlc analysis. of the GC eluent.' Independent confirmation may also be made - '7 in the event of extraordinarily high VC concentration samples ..'....7" ''by submitting" the samples to NERC-RTP for long-path Fourier transform I.R. spectrophotometry (requires 20 cu. ft. air samples but for high levels 2-3 cu. ft. of sample can be diluted) . . V. to VC.` None of these have bean shown to be present in discharge or air samples which have been analyzed In the limited field, experience so far.- compatible with the detector system. ucc 011604 2 4-4.. -GC Column Materials. > 4.4-1. For waste .water, sludge or scum samples. 4.4.I.I. Borosilicate glass tube - 6* x 2.5 mn X.D. -preferred. When G.C. oven configuration requires shorter columns, these ghcnid h$ used. >. 4*4.1-2- Solid Support - 60/80 mesh Gas Chrom Q. 4.4.1.3. Liquid Phase -- U% HPAP on solid sucport (weight percent). . .. , 4*4*2. For air samples. - v . 4-4.2.1. Borosilicate glass tube - 8* * 2.'5 mm I.D. preferred. When G.C. oven configuration - requires shorter columns, these should be . used. . 4*4*2.2. Solid Support - Carhopak A. '.".'""-'`.V...'.".j :,4.4*2.3. Liquid Phase.r 0J& Carbowai 1500 on solid y- - support (weight percent). ...... 4*6. Continuous Mr Monitoring Materials. . ;'4*'6*1- Tubing^ pyrexglass, 18" x 3/8* 0.1). * :` 4*6.2. Activated coconut charcoal, 8-16 mesh, Fischer Scientific Campapy*. . 4*6.3. Becton-Dickson 27 gage 3/8" hypodermic needle flow '-I. - control. - . V;' 4.6.4* Vacuum pump. -4*6.5* Air flow meter.. 4*10. Pressure Gas Regulator (0-5 PSIG) . . 4.12. Microsyringes - 10, 25, 50, and 100 mil. ' , 4*13* Gas-tight sample syringes - 1 nl, 50 ml graduated, 4.14* Vacuum Sampling Cans - 370 ml steel Vacu-Sanplers. UCC T*1 011605 4.15. Tedlar Bags - 12" x 12", 36" x 36", equipped with agtyTtyff system. . 4.16. Automatic sandier - compositor (manual samoling optional) equipped with sample refrigeration capabilities, a means to prevent loss *of vinyl chloride from open bottles. 4.17. Glass sampling bottles with teflon lined screw type caps 50 ml capacity (op otbap depending upon. sainpXcp xoculps-- ments). 4.18. Septum-sealed vials - 1 to 10 ml capacity. . 4*19. Dedicated G.C.^f.S. for confirmatory test. . 4.20. Barometer. : rr. " *' . \ * 4*21.. Thermitpeter. ... 5. Reagents. Solvents, and Standard ' .y:i ; */ ' - .... :: ' ; 5.1. Carrier gas - zero nitrogen, and helium,. . 5.2. fTD gas - zero hydrogen, otygen. ; _ 5.3. TetrahTdrofuran. ''' - . 5.4., ..Carbon tetrachloride (G.C. grade). . ,,5*5. . Carbon.disulfide (G.C. grade). 1 vJ... . . 5.6. Standards. - . v^.: ' . \. ,, :. 56.1. VCM in zero air, 50 ppm (+.2$) v/v. 6. Samoliwtf ^ 6.1. Water.Sample . 6.1.1. AH waste water discharge points identified in NPDES permits should he sampled for VCM. Three successive 24-hour composite samples of each site should be taken. Compositing interval should be 1 hour (manual or automatic sampling is optional). Compositing interval of 20 minutes cay be used if automatic^ sampler has this capability. Samples should also be taken at waste water treatnent units such as clarifiers. UCC 011606 4 and scum and sludge separators. 'Two 8-hour composites should be taken from the effluents from each of these points, and one 8-hour composite should be taken of scum and sludge from each separator unit. Compositing interval should be 1 hour. Three grab samples of clean process.water (city or well) should be taken as blanks. 6.1.2. Sandies should be taken in SO ml bottles uith gas tight, teflon sealed, screw-cap closures, or in - equivalent containers required by the characterists of automatic samplers. All water, sludge, and scum . samples should he refrigerated during collection and ' storage. Compositing volumes should be selected to ' assure head space above tha samples are minimized to avoid losses of VCM by its partitioning into the gas phase. Provisions should he made to avoid such losses when using continuous monitors. . 6.1.3. Estimates'of discharge flow should be made using any . appropriate measuring device (venturi, weir, magnetic meter,_,,eto.).".. 6.1.4. Samples should he preserved by refrigeration until are ready for analysis. They should also he ... protected from sunlight. / Air Samples . . .6 2 1 'Sanpling' sites should be selected which are downwind and in the plume of the atmospheric emissions from the . . plant. Samples should he collected only in areas where - local residents or neighboring industries, would be exposed. Sampling should he conducted over a period . of five days. Sampling sites should he selected in ' the.following array:" one site immediately upwind (A) and one immediately downwind (B) of the plant site; 4 sites about 0.4 miles from the plant site, one laterally left (C) and one laterally right (D) of the plant site on a line roughly perpendicular to the prevailing direction and two (E,F) downwind from the plant site; two sampling sites (Q,H) approxi mately 0.5 miles downwind; one sampling site each at distances approximately 0.6 (I), 0.8 (J), 1.0 (}> and 3.0 (L) miles downwind from the plant site. If wind is fish-tailing severely, locats sampling sites G end H approximately 0.5 mile upwind (prevailing wind direction orientation) from the plant. uco 011607 5 The sites specified are a mininun. Additional sites may be selected contingent upon overriding micro- meteorological considerations that must be determined by the sampler in consultation with the Regional meteorologist. These may be at ground or some elevated level. 6.2.2 Sam]alina Sites Prevailing Wind . ^ 'Direction ' Minimum Sampling Schedule Miles A ` Time ' Hon. - Wed. Fri. D 0800 A,A,B A,B,B - A,A,S - B 1000 C,D,F C,D C,D,D. 0.4 E F 0.5 G H 0.6 '' i 0.8 J 1200 A,E - A,G,G A,E . 1400 . B,B,F B,H B,B,G 1600 C,Q - E,K . . I,J 1800 .D,I V - . L,1 1.0 E 2000 H,L,L 3,0 - L All times are dt 30 minutes 6.2.3. Grab samples are to he taken in 50 ml gas tight syringe's ' 370 ml ,rVacu-Sanpler" metal cans, or 12" x 12" capacity Tedlar bags. The ,r7acur-Sanpler" is evacuated and back- ' filled to pressure of 10" Hg with zero nitrogen (equivalent to 246.6 ml at 760 mm Hg if can is filled V at 21C) . A nozzle on top of the can allows a sample to be taken nT*d sealed analyzed* Assume perfect gas laws to estimate volumes. Hypodermic syringes are flushed several times, then the sample is taken and ' the syringe is locked and sealed until it is ready to- be, analyzed. The Tedlar bag samplers are filled by pulling the vna of the bag apart to suck in the air sample, and then the bag is sealed until the sample is reedy to be analyzed. All samples should be protected from the sunlight. 6.2.4. Continuous samples are to be taken in pyrex tubes (approximately, 3/8" O.D. x 18" long) packed with activated coconut shall charcoal (fisher Scientific Co., S-16 mesh). The charcoal is added to the tube ucc 011608 6 in three 3-inch segments, each separated by a glass wool plug. The two ends of the packed tube are also plugged with glass wool. Both ends of the adsorp tion tube are plugged with serum caps for transit and storage. Flow rate through the tube should be controlled by inserting a Becton-Dicksoa 27 gage, 3/8" hypodermic needle through one of the serum caps, and into the end glass wool plug. . Air is sucked through the tube by connecting it to. a conventional vacuum pimp (the arrangement is similar to that used in the National . Air Surveillance Network). Flow rate should be about 200 ml/min. For each adsorption tube, the flow rate should be calibrated in the laboratory using a standard flow meter before a sample is taken and should be verified again in the laboratory after the sample is taken.; : X-.. The adsorption efficiency of the carbon afrirnH be ` verified In the laboratory by preparing a 3 ppm .v/v tVCM mixture in air in the 36w x 36" Tedlar bag and drawing this through the adsorption tube. Flow .. .. rates-through the tube should he verified before. '- ' "" and after t^ experiment.;_-.A ,.r s-, ... X' All collections should be made with the adsorption tubes protected from light - either by wrapping with foil or enclosure in a box. ' ..... Each segment of the adsorption sample is worked /- ~ up separately by etching the tube in the middle of . each 3W section with a file, successively breaking each segment and spilling the contents into measured " volumes of.carbon disulfide in glass stoppered test tubes. The additions should be effected cautiously and with cooling in an ice bath since the interaction of activated charcoal with carbon disulfide is exothermic. A 2 micro liter aliquot of the super- ' natant solution should he injected on the Gas Chrcm. supported FFAP column for estimation of .the adsorbed VCM. Successive analyses of the three adsorption tube segments will indicate the amount of break-through of VQd through the adsorbent The procedure should re uo>.-d for taking samples in the field. ucc 011609 7 6.2.5. Record the temperature and atmospheric pressure at which the samples are taken. 6.2.6 (See page 1a). 7. Calibration 7.1. Calibration for .Analysis of Gas samples. . 7.1.1* Record ambient temperature and afeaospherlc pressure. 7.1.2. Prepare dilutions of 50, 1.0, 0.2 ppm (v/v) of vinyl chloride in zero nitrogen by diluting standard VC gas mixture (50 ppm. in zero air) with appropriate volumes of nitrogen. Dilutions may be made using Tedlar bags :.V..stdd gas tight syringes. . - .- , .. . 7.1.3. Inject 1 ml aliquots of the calibration samples into , , a G.C. equipped with a Carbowax - 1500 (on Carbopak A) packed column and an FID detector. Use zero nitrogen ' as the carrier gas at a flaw rate of 60 ml/mLa, Operate the inlet and the column at room temperature. 7.1.4*. Prepare a calibration curve. Repeat dilutions and G.C. - V r.- injections until calibration curves are reproducible. . ` * 7.1.5. Assume the perfect gas laws to he applicable. 7.2. - Calibration for Analysis of Water Samples. . 7.2.1. Prepare a stock solution of 10 ppm vinyl chloride by' bubbling a slow stream of standard vinyl chloride gas - mixture (50 ppm) into a septum-sealed vial which has been ' . .. . completely filled with carbon tetrachloride. During this . psriod, the vial system should provide for free exhaust . ., . .;.^.1V.... .M ' . . of the nitrogen dilution gas. If a supply of reagent VC is available it may be used In place of the standard VC gas mixture. . 7.2.2. Determine the concentration of the stock solution by G.C. analysis using a FFAP on Gas Chrom Q packed column and FID detector. Operate the G.C. with zero nitrogen carrier gas at a flow rate of 60 ml/ain. inlet tempera ture of 150C, and a column temperature of 6CC,, The stock solution concentration should be cctemii;.'.", >7 c "CO fi at n di css of T.C zero gas. 7.2.3. Prepare dilutions of V.C. in carbon tetrachloride solu tion at concentrations of 2, 1*0, and 0.2 ppm using UCC 011610 septum sealed vials which, are completely filled with, known amounts of carbon tetrachloride* 7.2.4. Inject 2 microliter aliquots of carbon tetrachloride calibration samples into G.C. equipped as described in 7.2*2, 7.2.5. Prepare a calibration curve. Repeat dilutions and G.C. injections until calibration curves are " . reproducible. Procedure 8.1. ' Water Sample Analysis . V .. . - - 8.1,1. Untreated water samples (1-5 microliter aliquots) ,r. are injected directly into the G.C. . - 8.1.2. A 456 FFAP on "Gas Chrcm <}" packed column is used. Nitrogen aero gas is used as the carrier gas at a . ' flow rate of 60 ml/ain. Inlet temperature is set - -.. . at 150C. The column is operated isothermally at ' . 62C. Detection is by FID. . : 8.1.3. Report concentration of VC in ssoplaln mg/l. 8.2. ' Sludge and Scum Samples ... . .. . ,8*2.1. Extract 5 grams of sludge or scum sample with. 100 ml . of tetrahydrofuran (THF). Analyze THP extract in the same TM*rmav used for water samples in 8.1. If VC con centrations are too high, make appropriate dilutions ,. of .the THP extracts. . ' = - 8.2.2. Report concentration of V.C. in.sample in mg V.C./g of sample. 8.3. ' Air Sample Analysis 8.3.1. Grab samples. 8.3.1.1. Use a O.U% Carbowax 1500 on Carbo-Pak A packed column. Use nitrogen aero gas as the carrier gas with a flow rate of 60 nl/min. Operate the colum and inlet at room temperature. Use- a Xlane ionization detector. UCC 011612 ^1 / * & SUBJECT $ v: ''5; j * k , " * ., ' UNITED STATES ENVIRCMi'.'.sNTAL PROTECTION AUftMUY . Southeast Environmental Research Laboratory Athens, Georgia 30601 .- Determination of Vinyl Chloride Monomer in Aquatic Effluents DATE: April 24/ 197 FROM: -I-, * i Alfred D. Thruston,'Jr. /?CO Analytical Chemistry Branch _ .,;.v\ TO: Arthur W. Garrison "7- v'": ' " ' -"r : ; Analytical Chemistry Branch. . ` : * ' J-.A-i... H5Troduction_ , v;.. This technical assistance'project was undertaken at the request-of. Dr..-Henry-Enos .-in his memo of Mar.ch_ 15 * 1974. on ' "'V" "The Availability of an Analytical Method for Vinyl Chloride :in Water." - Vr . -- -iA,.. _ .. .v,.SUMMARY - ---- 'i -r-v'-r*-- . ' / ; - , . w.-4*..-' ' ** V ' . .* , " j"' < A method for preparation of quantitative standard . V-V solutions, of vinyl chloride monomer (VCM) incarbon tetra-. . i.cchloride was developed. Two gas chromatographic techniques - ; \ . to quantitatively determine VCM. in. aquatic samples were - ... tested. They are based on: (1) direct aqueous injection, and (2) carbon tetrachloride extraction.Both methods were - - ; tested on effluent samples from a vinyl chloride plant and shown to be reproducible and*quantitative at the mg/1 levels. V.': :r ,V Tily ar adequate for screening atthe yg/1 level.* The pre- eanna nF wiavI .rVhlwas ennir7n&d hv oas ehiroraafcoaranhv**"* - Water, samples containing vinyl chloride, should be : . collected by completely-: filling-a-glass bottle and sealed . ; ; with a teflon-lined cap. Samples'should be immediately -'V ; .refrigerated and keptLcold during shipping and storage. Quan' .>|.r titative' staihdards should be prepared gravimetrically.. _ . '7.- Direct aqueous injection GC is the. best method for screening samples for mg/1 levels, of vinyl chloride. Extraction methods should be used to analyze samples containing'yg/1 amounts of . ; ; vinyl "chloride. Gas chromatography-mass spectrometry is valuable for confirmation of the presence of vinyl chloride.' Equipment i*. ,, * *, f 1. Vinyl chloride - lecture bottle size (Matheson or -- .".'equivalent) >: . ' : - 2. Carbon tetrachloride (CCl^) - GC grade '. y r 3. 2 ml and 25 ml serum vials with teflon-coated rubber `j \septa . .. y -:\;t .V;. EPA e>n 1323-t (%'* *^2) ... ... ; * *' ****-. `` , t` : > " * , '*,*, * ; s* * ,, , . . -.,f5 Ji * r , * i A* 1 ^ * - % m *, 1 : * *' <* ' * , **. - . >*..--i.5 -. .. \ ^ *-./ * ' ,* .i'' * ^ ucc 011614 y i. 5. 1 ml gas syringe 6. . Gas chromatograph v; 1 th flame ionization detector/ tempera ture' programmed column ovenj, and a one millivolt recorder* Analytical Parameters '. Column s Packing - 1/8" OD x S1 long SS or glass filled with 10% FFAP on 80/1Q0. chremosorb I*?-AW Column. Temperature -- /TV/ >VVV;~- -. ; \; V- Vi-Vf/V--- . V'p- . Isothermal at 60" C. until VCM . !- elutes (50 seconds) , then, raise temperature-to 160" C. at 30/ min. .until water- or solvsnt-is - .VV eluted. V;v v/; Injection Port Temperature -7 . .200? C; ' VvjV " Detector Temperature Helium Plow Hate ' i - \m. m Chart Speed - , '.W *>*' *. . * 230" "C*. ........ . ** f , / ` , 40 cc/min. ' ''" ' *-r s s. - /.>- ;, 1/2"' per minute ; -1; /V,V Sample Preservation t ' V v.-*'v-.TV- . Store water sauries in the refrigerator in glass bottles * with teflon-lined screw tops. Particulate matter should be './ J ; allowed to settle. - Por convenient replicate sampling, several. 2 ml septum.vials can be filled with samples and capped before analysis...-./V^-- y.--VViV:/.: jaVV :V Standard Solution Preparation . ' .... r'' ; . '.i/V V `: VV';V:.' Pipet'25.0 mi CCI4 in a" 25 ml serum vial, cap, and accurately weigh to 0.1 mg. .-Attach..a. two-foct length, of tygon tubing to the cut-off valve~an the vinyl chloride lecture bottle and place the tubing end in a beaker of water. Adjust the lecture bottle valve to give a steady flow of gas as indicated by the bubbles. Pierce the tubing 1 inch frSm the valve with a 1 ml gas syringe. Flush the syringe twice and then withdraw 800 yl of VCM. (approximately 2 mg) . Inject the VCM slowly into the CCI4 in the serum vial. unpierced septum or transfer to a bottle closed with a teflon- lined screw cap. (The CCI4 attacks the septum rubber once tha teflon liner is pierced.) Dilute this stock solution to give working standards.' Two ml serum vials, which hold- about 1.8 ml.- . ' * ; . *7'-V,-iVl?**>Hl*?$* w\ i*: V' **-1.. ' * i r t *'! 4 i- -.--fi- .^ ^ '* u 1*' " )' y r ^ ^ * v W ... v ^ ^ J *"T*~/\r 4' *"*T *" .. -- . ucc 011615 to the neck (calibrate) , make good containers for the diluted 'standards. For example: aliquots of 90, 45, and 23 ul (ICO yl syring.e) diluted to 1.8 ml make 4, 2, and 1 ng/yl solutior.3. These solutions must be prepared fresh daily if the septa are pierced, - Analysis ' - '. A. ... V Direct Aqueous Injection - Inject,the sample (2 to 3 ul) directly into the GC. The sensitivity of this technique depends on the condition of the GC. For example, on three different GCs, 50% full scale chart deflection(FSCD) at the most sensitive attenuation corresponded to: (1) 20 ng, (2) 4 ng, and (3) 0.3 ng of VCM. On instru ment (1) with a 2 jil direct aqueous injection, the lower limit of detection (10% FSCD) va3 2 mg/1, while on instrument (3) the limit was 0.05 mg/1. B. Extraction with CCI4 - Carbon tetrachloride quantitatively . extracts VCM from water. If a sample contains too little" ! '.VCM for-direct aqueous-injection,. CCI4 concentration I"'1 ' / techniques may be used; - ...' \ -: - Add 5, 10, or 500 ml of settled sample-- depending on the' concentration of VCM - to ~a 15 ml stoppered centrifuge : tube, .or a 500 ml separatory funnel containing 1.0 ml - CCI4. - Stopper, shake for_l minute, allow the layers to separate, and inject 2 ul of the CCI4 layer into the GC. ' Recovery at the mg/l Level' Aliquots of 1, 2, and 3 ml of an effluent sample containing 7.1 mg/1 VCM (as measured by direct aqueous injection) were each extracted'with .1. ml CCI4. The aqueous and CCI4 layers from each. extraction were'analyzed by GC. As shown, in Table. 1,. .the concentrations, of VCM in the CCI4 layers indicates essen- . tially complete recovery.""vf-: -k `.rr ; ..'I .'/Table 1/-CCI4 Recovery- at 7.1 mg/1 VCM Level > Ratio ; - CCI4 Layer - - Sample:CCl4' ng VCM* . mg/l-in Sampla ; Aqueous' Layer ...; ng VCM i:i 3:1 --.v. *. ^ y * v 35.. . . -.55 ; ......, i :-; 5.8 .. *;.j "--i-V;-.'. <1: ,, 7.0 i. . vj-1 - - <1 >' .V- . 7#.3-' ' -X-i* ,, -- , ............ Recovery at the yg/1 level ' . A" sample, which analyzed 3.7 ng/1 VCM by direct aqueous injection, was diluted from 1 nl to 500 ml with tap water (7.4 vg/1 VCl-l), The 500 ml was extracted with 1 ml CCI4 74% of the VCM was recovered (5.5 yg/1). Another sample that analyzed 0.19 mg/1 VCM by direct aqueous injection was diluted 1 mi to 100 with tap water (1.9 ug/1) . The 100 ml was extracted with 1 ml CC14 and 345 of the VCM was recovered (1.6 ug/1)- Analysis of Industrial Effluent Samples . -. Four aqueous samples from three stations at a plastics manufacturing plant were analyzed by both techniques: 0468 - ' ` ' clarifier scum removal system discharge 0465 and 0472 - primary clarifier discharge (two different . days) .' 0463 '-- plant storm sewer \ Results are shown in Table 2. h ^...-v:. \ J -v/"': ' ' Tabie 2. VCM in Aqueous Industrial Effluent Samples. " --- \ Direct Sample .''.-Injection Sample ' mg/1 , Extraction with CC14 Ratio . Sample:CC14 ;'mg/l 0468* :9.3'; -. ' 1:1;;''". 6.8. ..... ,, 0465 V. ' -3*1' ..*3.0 \J-YJ "0472 . - r ,# .**- , ---, - -0463 /'*'*2-'3: ` ,1 * * .ViV ..`.Jw*.* *. * *V _ ;; *%' - 3:1. ; /' '^-2.9 . . v': sosii;;-. .""'f/KoJi -* Va v . . * .`v: *, * . *,*t*t Sample was- high in particulate matter. s .* * -r*/'T*w**?'^**>*>**>w! . ;Vv$!.'.|>- ' 1< . ' =.'.'V*. ` *. r i ' ~1' .s'jSr***. -. * - i *: - a^T*IP3,r7 t V' 5 \. 1. Ucc" -  Alternative Analytical Techniques for VCM A. Other .Columns for Direct Aqueous Injection - Columns 1/8" ID x 2* long packed with Chromasorb 102 or 1/8" . ID x 8' long packed with 0.4% Carbowax 1500 on Carbopack A have also been shown to give good results for VCM by Don Brown of the Chemical Service 3ranch, Surveillance and Analysis Division, Region IV, E?A. B. " Headspace Screening - This technique (also developed by Don Brown) is a sensitive and fast screening procedure, and is semi-quantitative if standardized. Fill a 2 ml . . serum vial to half capacity with the aqueous sample, cap, and place in a 400 c oven or water bath.. The VCM will equilibrate between the liquid and headspace gas. Withdraw 500 pi of the headspace gas with a 1 ml gas syringe and inject into the GC. After about 10 injec- - tions at 60 C, raise the column temperature to 160 . to remove water , vapor from the column.-. ... . . v` Confirmation by Gas Chromatography - Mas3 Spectrometry . /.. The presence of vinyl chloride is indicated by three' .x:. ' prominent ions in the mass spectrum: the vinyl ion at m/e 27, . the molecular ion at m/e 62,and.the chlorine isotope molecular - ion at m/e 64. The ion abundance at m/e 62 and m/e 64 must be approximately 3:1, corresponding to the natural abundance of the chlorine isotopes.' / ' - . -isr---;- ' : , *- --- v The presence of 0.2 mg/1 VCM in sample 0463 was easily . confirmed on a Finnigan 1015 GC/MS System. Good spectra were obtained using either a 2 yl direct aqueous injection or 2 ul of CCI4 extract. To test the sensitivity of GC/MS to VCM,. the CCI4 extract of this sample was diluted to successively lower concentrations and analyzed. Acceptable spectra were obtained with 0.14 ng of VCM injected into the GC -- this would, correspond to 0.07.vg/1 in,the original solution.', 2 f; .` - , . . ''V.ri*3fft?. ' * -``'rr---- 4:-' ^ ' * i ..1 * V* ' .,*< `A' KM' . '. >*.' -i--. / .i-i- -..Il; 1 *. v I'. : - 7. A:. f*ir 'u * . . . Mrvvf- ucec-- 011619 LA- * : yy\A^ \y EPA QUESTIONS FOR SPI (SOCIETY OF PLASTICS INDUSTRY) 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, 0 employees, polymer used, products line, quantities produced 5. list of PVC fabrication plants by name, location, 0 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 burled to data 11* toxicity of PVC resin and products 12. epidemiology studies of workers 13. population within square mile of plants 1/. C*. Xtf* 16. Additives used in PVC products UCC 011619 iieting Rs0sr 7^ CHEMICAL -V PVCPROFILE .............. - M* IM< -' *v n. Hntyo tt j SUPPLY j71 by William 0. Alhson ; by Harry J. Schnell mg Company, Inc. New 'fork. N. V 10007 dress Reporter. New Yore II Publisbmg Company. Inc. n MWIWMf ESK :aJ Company, and Sartomcr Industries, nulacture anaynarket ipecialtyjacrylat* ipany wilt be rated at Manchester and cd terntories."\ ] day ammonia p(anl hat been put into jie trcnnd such M|W Krllodt-designed the CSS It. Trcbma^himport, the compa nies in the Soviet Ibion, contracted (or puraticn, through it* m efrrrd to tupply T t u*e4 to purity ethytem ture com- Iplet Repubby selective CdK rhimie hat tlartrdldp a net* plant nrtnr too* a year nl "NoiUolene" SP hyet came up to oomiiul rapacity quick-. (tram cracker at Car:/ ' hasp *G ef |j0i<i.ytek i building neeswntit slycot uur.c it* olo teehnolo*ot. tuth m due ao itrem to igfS, will ..* * A Kiahtvr Company ha* told tt> 40 peri.'!.-iii.dU!**i^ Mceiieftjber now ret the wet h.e r*/oro Irom a>urrent - I--* * r-.itwr* vlneg Orel Sblriy edithjghldcn* 1 The move folio** a *" * ' **"'.* lncorporated\oo a>r* *te > * th density poly. .. Iw it* V4-*H^V.!*;,,|li#dtaI2, I f Pete* fku-ww-* tv wilt ex aa.fi i eciWm ta , ,, ,,Jrt lfJ --* *v -4 f.WlHtW .*** ii, W|f(- ` * 1 ................... . ! (.i ite iwcwi ireUcc<Hi|)n. **r PRODUCER . CAPACITY* Air Products, Calvert City, Ky............. ........................ISO Air Products, Pensacola, Fla......................................... 50 American Chem., Long Beach, Calif.......,,......... ........ ISO Berdtn, llllopeda. Id. ...............................'................... 140 Borden, Leominster, i.'aia..............................................ISO Conece, Aoerdeen, Mist...................................................285 Conoco, Oklahoma City, OMn.............................. 240 Diamond Shamrock, Deer Park, Tex ...........................270 Diamond Shamrock, Delaware City, Del......................100. Ethyl, Baton Rouge, La .................................................180 Firestone, Perryride. Md........................... ....v............ 230 . , Firestone, Pottatown, Pa....................... ....................... 270 General Tire, Ashtabula, OMe....................................... 125 General Tire, Pit. Pleasant, W. Va............... ................. 50 ' Goodrich, Avon Lake, Ohio ........................ . . Goodrich, Henry, Id................. Goodrich, Long Bench, CaHf ........... 140 ....140 J40 Goodrich, Louisville, Ky......................................... ..--,340 Goodrich, Pedricktown, N.J............................................ 170 Goodyear, Niagra Falla. N.Y.......................................... 100 Goodyear, Plaqnemine, La ........__.............................100 Great American Chem., Fitchburg, Maaa _____.............40 Honker, Burlington, NJ................................ Hooker, Hlckirtlle. N.Y.............*___________ 15 igo Keyaor-Century, Saugus, CaUf ............ 35 ' _ Menaaato, Springfield, Masa............... 70 National Starch, Moredosia, Id ................. Olia, Auonot, Maw 10 ..150 Pantaaotc, Passaic, N-J.............................. ,, .,..60 Pantasotc, Pt. Pleasant, W. Vn. ............................... 90 Roblntcch, Patncsridc, Ohio 250 Staaffor, Dolaware City, Del 175 Tenaeen, Burlington, N.J---------------------------------------..165 Tenaeen, Flemiagtoa, N 70 - Union Carbide, S. Charleston, W. Va........... .................160 * Union Carbide, Texas City, Tea................--........,.....240 Uniroyal, PainesriBe, Ohio ____ .....140' Total------------------------ 5,415 . d peunda aawaally d polyvinyl ehlarld* aad eopetya*era. ClMcUtl vuy with product mix. Apprexlmately 70 percent el talai aamafteta capacity la dtvaled to h*a*eetyn suspaautan retina, ppnilniMy 11 parcaal la davaled ta eepalymart. and apprexlmataly u parcant ia deratad ta taihln praeesa (diaperslaa) mkt Certain-Teed plana to hare a graa* reeta facility la Lahe Chariot; La., with a capacity d tdnMw paunde aaaaally, ia operaitan by tha taartk quarter at tbit year. Output win ha ICO paieeat capttre. Geergta Paeihc plant to earn# aawtfaam lata thil yaar with a ttO-mUnan paaml facility at Plaqaamlne. La,, a*U *4 the cutpul ef which will be ter captive use. Itahlntcch. la cm aperattoe with Shlnatou ef Japan, la kepiBX to hare a mllff-n ytand nalt eperatlag by tha fauth eaartcr, meat at the aatpul ef which win be captive ter the twe warm. Teaaeea It eempleting a new MO-nriltlato peaad plans to Paisade**, Tea., alto eapeeted la be etoetreaai by the teurth qaarter. Beeden ewae all the eutput at Menaaato'* Springfield, Mate., pleat, aad Baedao la ptoaniat to add 100 mllllea panada at aaw capacity to It* Illtopalt*. IB., facility by the ead at tha yaar. Diamoad Caattouad an Pag* 10 hivi d bi><*|i r**>try w ih* n -.1.1 to .f *>--* m/1 J.<* bee, ,M ^ liiitiii |um 4M 14 have Chemical Marketing Reporter ^ n* on tht problem sine# 111 r t9t mifkFtM mpKmi. - ucc 011620 im prance :$ ettcvrtvr emessi 410 E. Mn* ST, I mew remit eirv, n.y. lop OXOHE. ILLIMOIt WOW I (AM KUNCUCO *m I OfTlCES IM ALL MINC10AL CITIES. f I A0CNTS IM AU MlNCIOAL COUHTHIII IU CHEMICAL PROFILE ........ PVC CMMri (row I'M* Sbawrvck te pleasing I* It* Dear Park. Toe.. plan! ky IM aUn*a PmW. dartag Ik. fmrtk aaartar. Gaadyaaf will rul it* Pliaatwiaa, La., plan! hy IM wUU*a paesd* dartM Ik* third ttirlif aI ibl* rear. Suaffar kapaa I* add ! mtlUaa paaad* M di<praiM raaia capacity hr mid-IPT*. aad aaathar V- odllht pnada d lb* *** hr atid-ini. Fir*- taw in 4 4 piaaaiag a "slgnlOcaat axpaaaiM" aI lit diopariia. ca pacity hr aid-UTS, Air pradacu I* faid U baa* a 1M4M wliU** .aad capacity aspaaalaa plaanad "* Ik* haako" far III Cahrart City. Ky., plan. Oat * caactractiM haa hafaa. TaUI naw capacity by lb* aad at 1*74 aha.Id b* akMt I.S billlo. paaada. laeraaalag aamaplata capacity Im th. ladsatty la ahaat * hllUaa panada aaually. DEMAND 1*73:4.732 billion pound!; 1*74: 4.9 billion pounds; 1979: 9.3 hil- lion pound*. IADS mmi !vet end Aromatic* wly. N.Y. 11737, (211) / Williamson CARAMEL COLORING *w*s )Mti tawMAla, KaatacSp GROWTH Historical (1*93-1*72): 14 percent a year; 1*73: 9 percent; Fatare: 2-3 percent a year through 1979. PRICE USES Historical (1993-1973): High homopolymer suspension resin, hulk, ft. atld., 19 cents a pound; low, same basis, 10 cent* a pound. Current: homopolymer suspension, ssme basis, 17-20 cents a pound. Prelected: homopolymer suspension, same basis, 24-29 cent* a pound by year-end. .. : *> tx" * Pipe, conduit and fitting*, 27 percent; flooring, 10 percent; siding and other construction, 9 percent; wire and cable, 0 per cent; furniture, 9 percent; auto and transportation, 5 percent; film end sheet, 4 percent; textile, paper, and adhesives, S per cent; sound records, 3 percent; export, $ percent; miscellane ous, 20 percent. STRENGTH Cheapest material for most uses, often with no adequate sub stitute. Increasing prices have substantially improved profita bly with virtually no erosion of relative cost-effectiveness. Con struction end-uses should continue to grow rapidly and become increasingly dominant (pipe and fittings). Siding is considered a potentially rich market. Coated floorings, wire and cable, and ante use expected to grow strongly. 1 I -- l-*~ ' O *o IX WEAKNESS Toxicity is a serious threat, perhaps e preemptive market condition currently as monomer and polymer producer* sus pend capital investment pending research and regulatory devel opments. Some end-use markets, particularly packaging, have especial liability. Otherwise, there is insufficient feedstock (monomer and pre-` curlers) to food current PVC capacity, and a lack of new and an nounced feedstock capacity to support expanding PVC facilities. OUTLOOK Market* for PVC, especially in rigid and construction applica tions, continue to expand, while meny minor end-use* will be shaked-out (especially disposable products). The effect of gov-, emment toxicity investigations could esuso production disrup, tions. and heavy expenses, if substantial engineering and work; practice changes are demanded. Inadequate feedstock supply. lU-^yid, projected sanely. is expected to cripple growth in strong. -liiSiieoj and to inhibit the development of promisee. / ucc 011621 jdh***dP-^. ( ^aw Upheld / COATING & PLASTIC MATERIALS Ml Burner added that laws aimed at .<a(i'E\ardinc trade seeretj "encouage the dVcfopment and exploitatiof of those ifcms at leaser or different inven tion tha\ might be accorded protwrtion under (A patent laws, but whichltcms still havAam, important part to My In the techndlpgteal and scientific stance* ment of th\ nation." In the iiroiel district court Jil, Kew- anre asked namages and an mjunction acatnst its farmer employees alleging trjde secretnsueh as chemical com* pound formula, manufacttpng proce dures and evtm customer itsta of the company were tied in orgamting Bicron m iwi for the purpose of competing with llarshaw in the pfoductlonJbf the syntho- tie crystals. I / The Ohio appeal coua reaaoned that the state could not fexntf*monopoly pro- lection'' to processeianA manufacturing techniques that wen ntentable at ana lime, but were no lokgjpr patentable be cause they had beenvl commercial uaa Ior one year. 1 oal Schi my's Schfering emical producerif West Germany, has ent a scheme tqmeet thloU shortage and alcohols fAm coal. Vie Sobering Toxicity Debate Escalates; PVC Men See OSHA Threat The Occupational Safety and Health gnateot. But PVC It also the heart of VC Administration's proposed permanent use. consuming virtually all thet is pro standard for levels of vinyl chloride gas in work environments, and its as sociated medical and supervisory pro duced and in turn supplying one of the broadest, strongest, and most economics! end-use markets in the entire plastics in dustry. Thus the impect there will be felt cedures, has made the issue of VC tox icity the first concern of the PVC in dustry, according to some sources in that industry. The proposal, and its potential impact if formally adopted, with virtually equal fores both up and downstream. The kay sentence in the proposed rules is this: "The proposed standard for em ployee exposure is set at no detectable level as determined by a sampling and an has, these sources say, superceded alytical method capable of detecting vinyl feedstock shortages as the most worri some challenge faced by the industry. OSHA'i action reflects only one aspect of tbo current government Inquiry into the heeltn threat posed by VC, other research chloride at concentrations of 1 ppm with an. accuracy of Ippm plus SO percent'* This su percedes a level of 500 ppm, in effect up until April of this year when an emergency temporary standard of SO ppm waa put into offset: is being conducted by FDA and EPA, but The Society of the Plastics Industry the proposed standard represents the first promptly responded by calling the standard significant move toward regulation of tbo "excessively end unrealistically restric chemical intarmediate and' baa thereby tive." in a statement issued within hours of magnified and focused the toxicity issue. the proposal n May 10. SPI said thet adop. Although the proposed regulations apply tion of the standard "would make it virtual- to "any area or operation in which vinyl ty impossible for plants to operate." chloride is manufactured, reacted, re Spokesman for a Dumber of PVC producers leased. repackaged, stored, or used," it la backad-up SPI'i assessment. in polymerization facilitiee where environ One said "nobody cin operate at that mental levels of the gas are highest and where the impact of the standard would be Continued on 6*9< i coal prices, it would be uiwconomic to n did during the war), it midpt be feash blc to produce chemicals. The government has been a; to put up some of thunoney for a pilot. mt, cost- me 110 miUidk German marks,' lined at converting bwween 30,000 tons 30.000 tons of coal I yoar. L'S l/cREASE WEIGHED The GerJhan company is also lpniid- erini: huostmg its Investmanta in the IB duo t<> jIiiUs fi tho value of the DU. Wiich caused ulosi of oarnlnga from ovsAaaa participrfion. T Fchanges have reportedly made . f US pharmacologists more . *0 Schenng, and this, with the hi ' ot *U - sufficiency in raw mail otppting the board to look mo Continued on Pago 43 / -0 Setstfie Date 1 ^ Feedstock Hearing \ t ' l-rat Energy Office will hold s>a> 2S and 29 in Washing- Petals Facilities Am^nn Smelting & Refining Company bracts to proceed with plane for a lS&tflM - ton electrolytic zinc facility to beSited in Kentucky. The project, involvingNqvestment of about 9150 million, hat bSu compli cated by the energy shortagemtcoostraints placed on .new power struction due to the government'g air pollution regulations, as well at by the US duty on zinc concentrate*. The plant requires a dvperdable, petitiva soures of power before itjA sited. Also, it would depend on imports tor a little more than SO parent oUB raw moferial requirements. A US duly of 0.67 cents ir pound of contained zMe would bo sue-, inded by e bill nowidXongross. A company spoMfmaa says new domestil cspacity ij^dfgently needed and esti mates the USgms lost SO percent of its sine SsSund os Page 24 T-' , *. :] VED M/fr 22 1974 ^ J n/wheeler, m / m( 'Me*.. to#- ... ,, BECMTIL OFFICIAL: Robert X. Go has boon elected a vlea-ptastdent cMel Ine. Ho wia continue e* ntanegor i Boehtoi'o Refinery a Chomleal Division. ... of Petroleum s>nthctic natural, gas txasgulf Halt?Project At Kidd Creek lilf twit W.O ,h.t,, ucc 011622 Toxicity Debate Continued from '`ret level," another said, "the disruptions would be enormous," others said "we'd have to design new plants," "it would shut us down,'"`you could close the industry down because nobody &r pound. RON reds went up by 40c. toj Snge of. generally, $3 00-33 45 per poun. \piarylide yellows increased 70-T5e. J 33.k043.75 per pound. Hsnsa yellow went/ 20cl to 33.10 per pound. Benzidine orq nil* by 40c. to 34.80 per pound. could operate," "the economic impact iNkphthol reds went up 00041.40) would be enormous," and "no expo rang! of 34.90-3* 50. And qulnaeridod sure would mean no industry." Some others were more reserved. "I don't say it can't be done," one informed source at a large producer said, "but it would be very difficult and expensive. We're quite concerned, but it's part of the cost of doing business." Goodrich, the major producer of PVC in the world, said in a formal statement that "the `no detectable level' clause is Imprac tical and not justified," but added that "it' inteiids to continue to operate its plants and meet any reasonable standard." Many pro ducers expressed confidence that the final standard adopted would be above that pro posed. Maurice Johnson, M.D., chief medi cal officer at Goodrich, said last week that Goodrich la currently operatlnf with a work-place environmental level of about IS ppm at moat of ita plants. increased by 31.00 to 317.00 per pouf Tertis and conditions of change! ANTfcfONY OXIDE- Harshaw/Cherni es! incrAaed prices on antimony acids last week, effective May 17. but not t/tho level set by other manufacturers edrller this month. Stlndard grade was increased by 19'.ic. per wound to fl.44 per pound. MAT and N'L Industries had earlier r/iaed prices by 30`Ac. to VI.01 per pound. A spokesnfcn for Harohaw Aid the com- BW&KKRICEX'iANGES^ End > 17, #74 However, other amaller manufacturer! claim they hare spent "hundreds of thou sands of dollars" just to get beneath the SO ppm emergency standard, and added that 25-30 ppm would be as low as they could go in the near future. Summing up the indus try concern, one informed source said "the question now is `How do you stay aliveT' enL"The next two er throe months will be criti- "TOO HIGH*' Sidney Wolff, M.D., Director at Health pwavneyi. hospuavd --to --ho--ld. said. "We hope in sti want a repeat s< 1070/ e- It. We don't added, when a Research Group which hat been instrumen number at customers driven away by tal in pushing government recognition of rapidly rising prices- VC toxicity, has complained that the pro posed standard is "too nigh." lie argues that while it "goes in ihe right direction" and that the non-detectobte performance level is proper, the wording of the proposal in cffecl establishes a threshhold level of I ppm. He. adds that there is "no evidence that any carcinogen is safe at any level." OSHA. ho believes, should insist that nondetectabte means on instruments of any sensitivity, available now or available in the future. This he says was the Intent of NtOSH's recommendations, as well as those of OSHA's own Carcinogen Advisory CADMIUM PIGMEI r Effective May IS, Hercules mcreei rice of its end mium and "Mcrcsdiui owments. Cadmi- urn yellow iithopone 1blessed 3tc. to 33.50 per pound. Cad turn wallow cancan- trates rote by 53c. to, ,04 (|r pound. Cad- mium orange Ul increased 30C.44C. to 33.3543.! per pottMh Cadmium orange concentroti rose I75e.-S7e. to 38.1040.03 per poui Cadmii r38c.-58c. mium tore3d4.184c5i ,kceintrates And cadIncreased 31.0241-30 to 30.71 113.33 per Committee when It suggested 0 level of no BED LEAD- L Industrii increased exposure in January with regard to 14 other Utharge end red bad prices lai week, ef- suspect-carcinogens that It was convened to fective May 15. >31.50-31.00 Stendnrd study. litharge it now Ficed at 337.23 c J. 0150 red Bert Cottine, a staff legal associate at lead is now pried at 328.50 am [SOW rod lead is now prJed at 320.00 cwt. are HRG. says that industry always complains It will be put out of business when faced for truckload iuantities. with safety regulations. He suggests that HTANlUlif DIOXIDE-Efiecti they provide evidence to backup their IS, DuPont increased the price of I claim, that the emphasis be on technical grade anatefe and rutile tltaniuml feasibility rather than Just economic feasi by 3c. per Jaund. Both snatate an| bility, and that each company case be ha an now pmtd at the general indu ndled individually- with individual evidenti ure of Xcoer pound. Paper grads i ary hearings on hardship, and individual was increased 2c. to 32c. per pound.) rulings on performance and deadline doferrments. The Organization of Plastic Processors, a Washington group representing plastics . fabricators and end-users, had no immedi LOW-DENSITY POLYETHYL Effect!m June I. Dow win Incroesl Its L-DPEarleea at about 3C. per pound gi ally. Iwm liner will then be priced at fnd, clarity at 22c. per pound, ex! ate comment on the OSHA proposal but act ing director Michael Lang said that the ex ecutive committee had been convened to sting at 20c. per pound, and g.p. molding will' also be at 30c. study the development and establish formal policy toward it. A source close to the group, however, said the OSHA move "is not going to be helpful. It is going to disrupt supplies even further," Then he yielded to the fact: "There is certainly a health prob lem." PlGB-DENSlTY POLYETHYLENE MAsanto and Dow have both announced that effective June 1 their prices for H-DPB 111 go up. Monsanto will increase prices by 3c. per pound; blow molding. Injection molding, and extrusion grades win be priced at 22c. per pound. Dow will also raise prices bv 3e.: and both blow --u*-- W "'mm , nDw^UnCCnUl COMPANY^ po. Box 3. Houston, T. from MATHE'S Now " If you hgvon't triad it. MATHE DIVISION oI fho r Or- too, N. 4 h a scrub. myt/'-njlicsa Yew ucc 011623