Document vB0dB7j7YZo58qnzV4Vn92Q68

PRELIMINARY ASSESSMENT OF THE ENVIRONMENTAL PROBLEMS ASSOCIATED WITH VINYL CHLORIDE AND POLYVINYL CHLORIDE (Appendices) Report on the Activities and Findings of the Vinyl Chloride Task Force ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. SEPTEMBER 1974 RSV 0019102 PRELIMINARY ASSESSMENT OF THE ENVIRONMENTAL PROBLEMS ASSOCIATED WITH VINYL CHLORIDE AND-POLYVINYL CHLORIDE (Appendices) Report on the Activities and Findings of the Vinyl Chloride Task Force Environmental Protection Agency Washington, DC September 1974 RSV 0019103 1 *j-_ TABLE OF CONTENTS APPENDICES I. II. in. IV. V. Selected Economic Considerations Production Levels Competitive Substitution International Aspects Control Technology Producers of Vinyl Chloride and PolyvinylChloride VC Producers PVC Producers PVC Copolymer Producers The Materials Balance at Vinyl Chloride and Polyvinyl Chloride Facilities Vinyl Chloride Production Facilities Polyvinyl Chloride Polymerization Facilities Interim Method for Sampling and Analysis of Vinyl Chloride in Waste Water Effluents and Air Emissions Scope and Application Summary of Analytical Procedures Interferences Apparatus and Materials Reagents, Solvents, and Standards Sampling Calibration Procedure Quality Control Summary of Regional Activities Region I: Region II: Region HI: Region IV: Region V: Region VI: Region DC: Leominster, Massachusetts Flemington, New Jersey Delaware City, Delaware S. Charleston, W. Virginia Louisville, Kentucky Painesville, Ohio Plaquemine, Louisiana Long Beach, California 1 1 1 4 4 6 6 6 8 10 10 11 17 17 17 17 18 19 20 23 25 25 26 26 27 27 28 28 29 29 1 RSV 0019104 VI. VII. VIII. IX. Persistence of Vinyl Chloride Behavior of Vinyl Chloride in Air Behavior of Vinyl Chloride in Water Behavior of Vinyl Chloride in Closed Rooms Health Effects of Vinyl Chloride Occupational Cases of Liver Angiosarcoma Cases of Hepatic Angiosarcoma* Connecticut. 1935-1973 Observed Deaths/Expected Deaths in VC Workers Summary of Toxicological and Epidemiological Studies on Vinyl Chloride Disposal of Products Containing Polyvinyl Chloride Incineration Landfilling Resource Recovery Activities of Task Force 31 31 31 32 34 38 40 44 63 63 64 65 67 i1 RSV 0019105 APPENDIX I SELECTED ECONOMIC CONSIDERATIONS Production Levels During 1973. VC production was at the 5.3 billion pound level with PVC and its copolymers at the 4.6 billion pound level. PVC has become a very important polymer as evidenced by the broad dependence of nearly every branch of industrial and commercial activity upon products and components fabricated from this plastic. In Table 1, major PVC products manufactured during 1973 are iden tified. TheU.S. VC/PVC industry has been operating for more than forty years, and over the past five years has shown an average annual growth rate of 14 percent - - a rate of growth that had been expected to taper off only moderately in the next few years. The size of this industry can be appreciated by considering that the synthesis of the monomer is conducted in fifteenU. S. plants, and forty-three facilities are engaged in polymerization of PVC (including its use as a copolymer) with almost all of these plants currently operating at or near capacity. At least 7,500 plants are engaged in fabricating products from PVC. About 1,500 workers are employed in monomer synthesis and an additional 5,000 in polymerization operations. Estimates have suggested that up to 350,000 workers may be associated with the fabrication plants. The wholesale value of the annual output of fabricated products based on PVC is at least several billion dollars. Competitive Substitution Should requirements for worker safety or environmental controls drive the price of PVC resin upward, it seems likely that some PVC products would be displaced tty products using other plastics or other materials. Other products dependent on PVC might disappear alto gether from the marketplace. Probably one-fourth to one-third of current PVC products by value are marginally competitive with other plastic products. At significantly higher prices a lesser number probably would find substitutes in other materials at higher costs. Identified in Table 2 are a few of the substitute materials that might be considered. For some uses, there are no apparent substitutes. RSV 0019106 1 Market Category I. Apparel n. Building and Construction m. Electrical IV. Home v. Packaging VI. Recreation VII. Transportation VIII. Miscellaneous Table 1 MAJOR PVC PRODUCTS Products Baby pants Footwear Outerwear Extruded foam moldings Flooring Lighting Panels and siding Pipe and conduit Pipe fittings Rainwater systems, soffits. facias Swimming pool liners Weatherstripping Windows Wire and cable Appliances Furniture Garden hose Housewares Wall coverings and wood surfacing films Blow molded bottles Closure liners and gaskets Coatings Film Sheet Phonograph records Sporting goods Toys Auto mats Auto tops Upholstery and seat covers Agriculture (incl. pipe) Credit cards Laminates Medical tubing Novelties Stationery supplies Tools and hardware Other Total 1973 1000 metric tons 12 66 31 26 211 5 39 525 44 16 18 16 26 194 20 145 18 51 54 36 9 9 59 35 66 25 88 18 15 83 66 8 23 23 7 18 8 45 2158 RSV 0019107 Table 2 SUBSTITUTE MATERIALS FOR PVC PRODUCTS PVC PRODUCT Pipe A Tubing Flooring Electrical Insulation Records Film A Sheet Products Coatings Household Goods Packaging SUBSTITUTES SAME PRICE RANGE HIGHER PRICE Polyethylene Polypropylene Metals ABS resins X X XX XX Asphalt Wood ABS resins X X X X >1 X X X X X X Polyethylene Polypropylene EPDM rubbers SBR rubbers TFE plastics X X ABS resins Acrylics Polyvinylidene chloride Polyethylene Polypropylene Cellulosics X X Acrylics Polyurethanes Cellulosics Styrene Polyethylene Polypropylene Wood Metals Acrylics X X X XXXXX XXX Polyethylene Polypropylene Polyvinylidene chloride Cellulosics Acrylics Polyurethanes Glass X X RSV 0019100 3 International Aspects U. S. based manufacturers currently produce about one-third of the western world's supply of resins, with the U. S. market also consuming about one-third of die total. In 1973. 3.7 percent of PVC and 7.8 percent of VC manufactured in the United States were exported. Prior to the recent U. S. concern over worker and environmental controls at VC and PVC facilities, there was no reason to anticipate a major change in the U. S. share of production or market during the next few years. Recent increases in demand for PVC resins -- and concurrently for VC --at attractive prices have been of worldwide dimensions with expansion plans for PVC manufacturing being considered by a number of companies at home and abroad. There is presently an import duty on PVC resin from countries with status as Most Favored Nations of 1 1/4 cents per pound plus six percent ad valorem and from other nations of four cents per pound plus 30 per cent ad valorem. Given the current U. S. market price of 18 to 24 cents per pound for the general purpose uncompounded resin, there has been little incentive to import PVC resin. Also, there currently is little export incentive because of short U. S. supply and unattractive foreign prices. However, higher prices as a result of more stringent worker or environmental controls in PVC resin plants in the United States than abroad might well stimulate significantly increased imports. Control Technology While there appear to be a number of general approaches for reducing the discharge of VC into the environment at VC and PVC resin plants and the discharge of PVC at resin plants, in many respects the approaches must be tailored to the individual plants. All VC plants and some PVC resin plants are outdoors while other PVC plants are at least partially enclosed. A variety of production processes are used, and different kinds of technology are employed. However, there are some common measures that would reduce VC emissions. FOR VC PLANTS: 1. Reducing the escape into the atmosphere of VC when venting the tank car gauge tube, disconnecting the feeding line, and closing the valves during rail tank car loading. Mechanical disconnect de vices and double block and bleed piping are available to ease this problem. 2. Improving the quality of pumps to reduce the possibility of leakage due to failure of seals. Pumps are available today which could minimize this problem. 3. Venting unintentional leaks and spills into a system which is flared and, preferably, scrubbed. 4 RSV 0019109 FOR PVC RESIN PLANTS: 1. Collection and destruction of purge gases from the reaction kettles prior to opening for cleaning* sampling, or recharging. 2. Centralized collection and filtering of VC vapor discharges from dryers and centrifuges. With regard to PVC particulate in air and water discharges, improved housekeeping and relatively simple ventilation filtering systems are usu ally technically feasible and effective. Laboratory data have shown that VC can be adsorbed on activated carbon. Concentrated VC vapor streams have produced a recovery work ing capacity on carbon equivalent to about ten percent of the carbon weight. Ambient air contaminated with low levels of VC produces significantly lower adsorbent working capacities. Control of dilute VC is therefore possible but may not be practical using activated carbon. Carbon regene ration using steam or pressure swing appears possible, with recovery of desorbed VC for recycle. Clearly, these approaches will not eliminate losses but should mate rially reduce them. In the longer run, the development of continuous flow processes, the use of larger kettles, better housekeeping, and/or reductions in the number of feed lines might result in more dramatic reductions of VC leakage. REFERENCES 1. Modern Plastics, Jan 1974, p. 43 2. The 1972 Census of Manufacturers shows 7,574 plants manufacturing Tnigr:gllflngQUfl piagticta pmdurta (Me 3079), a substantial number of which use PVC. SIC 3079 probably covers most, but not all, PVC fabricators. 3. Discussions with representatives of the Department of Commerce, Manufacturing Chemists Association, and Society of Plastics Industry. 5 RSV 0019110 APPENDIX II PRODUCERS OF VINYL CHLORIDE AND POLYVINYL CHLORIDE The major producers of VC, PVC, and PVC copolymers are listed in this section with the plant location and available capacity data. VC Producers ~~ Location Annual Capacity (Millions of Pounds) Allied Chemical Corporation American Chemical Corporation Continental Oil Company Dow Chemical, U.S.A. Ethyl Corporation B. F. Goodrich Chemical Company Monochem, Inc. PPG Industries, Inc. Shell Chemical Company Tenneco, Inc. Baton Rouge, La. Long Beach, Calif. Westlake, La. Freeport, Tex. Oyster Creek, Tex. Plaquemine, La. Baton Rouge, La. Pasadena, Tex. Calvert City, Ky. Geismar, La. Lake Charles, La. Guayanilla, P.R. Deer Park, Tex. Norco, Tex. Houston, Tex. 300 175 650 200 700 390 300 150 1000 300 400 500 840 700 225 PVC Producers Air Products and Chemicals, Inc. American Chemical Corporation Borden, Inc. Continental Oil Company Calvert City, Ky. Pensacola, Fla. Long Beach, Calif. Illiopolis, 111. Leominster, Mass. Aberdeen, Miss. Oklahoma City, Okla. 150 50 150 140 180 285 240 RSV 0019111 6 Company Locations Annual Capacity (Mirons of Pounds) Diamond Shamrock Chemical Company Deer Park, Tex. Delaware City, Del. 270 100 Ethyl Corporation Baton Rouge, La. 180 The Firestone Tire fit Rubber Company Perryville. Md. Pottstown, Pa. The General Tire fit Rubber Company Ashtabula, Ohio Pleasants County, W.Va. 230 270 125 50 B. F. Goodrich Chemical Company Avon Lake, Ohio Henry, HI. Long Beach, Calif. Louisville, Ky. Pedricktown, N.J. 140 140 140 340 170 The Goodyear Tire fit Rubber Company Niagara Falls, N. Y. Plaquemine, La. 100 100 Great American Chemical Corporation Fitchburg, Mass. 40 Hooker Chemical Corporation Burlington, N.J. Hicksville, N. Y. 180 15 Keysor-Century Corporation Saugus, Calif. Delaware City, Del. 35 35 Monsanto Company Springfield, Mass. 70 National Starch fit Chemical Corporation Meredosia, 111. 10 Olin Corporation Assonet, Mass. 150 The Pantasote Co. of New York, Inc. Passiac, N.J. Point Pleasant. W.Va. 60 90 Robintech, Inc. Painesville, Ohio 250 Stauffer Chemical Company Delaware City, Del. 175 Tenneco Chemicals, Inc. Burlington, N.J. Flemington, N.J. 165 70 Union Carbide Corporation South Charleston, W.Va. Texas City, Tex. 160 240 Uniroyal, Inc. Painesville, Ohio 140 RSV 0019112 7 PVC Copolymer Producers Company Locations A, Polyvinyl Chloride-Propylene Copolymer Resins Air Products and Chemicals, Inc. Calvert City, Ky. B. Polyvinyl Chloride-Vinyl Acetate Copolymer Resins Air Products and Chemicals, Inc. American Chemical Corporation Calvert City, Ky. Long Beach, Calif. Atlantic Tubing & Rubber Company Cranston, R.I. Borden, Inc. Bainbridge, N.Y. Compton, Calif. Demopolis, Ala. Illiopolis, El. Leominster, Mass. The Firestone Tire fit Rubber Comany Pottstown, Pa. B. F. Goodrich Chemical Company Avon Lake, Ohio Louisville, Ky. Hooker Chemical Corporation Hicksville. N.Y. Keysor-Century Corporation National Starch and Chemical Corporation Saugus, Calif. Meredosia, El. Olin Corporation Assonet, Mass. The Pantasote Company of New York, Inc. Passaic, N. J. Point Pleasant, W. Va. C. Polyvinyl Chloride-Vinylidene Chloride Copolymer Resins BASF Wyandotte Corporation South Kearny, N.J, Borden, Inc. Bainbridge, N.Y. Compton, Calif. Demopolis, Ala. Illiopolis, El. Leominster, Mass. 8 RSV 0019113 >s*L \ Dow Chemical, U. S.A. B. F. Goodrich Chemical Comparer W. R. Grace & Company Morton-Norwich Products, Inc. National Starch and Chemical Corporation SCM Corporation Texmeco, Inc. Union Carbide Corporation Midland, Mich. Louisville. Ky. Owensboro, Ky. South Acton, Mass. Ringwood, HI. Meredosia, HI. Huron, Ohio Burlington, N.J. Flemington, N.J. Institute and South Charleston, W. Va. Texas City, Texas REFERENCES 1. 1974 Directory of Chemical Producers, USA* Chemical Information Services, Stanford Research Instituted Menlo Park, California, 1974. 2. Chemical Marketing Reporter, May 20, 1974. 9 RSV 0019114 i ' <. , ,..'. -- - APPENDIX m THE MATERIALS BALANCE AT VINYL CHLORIDE AND POLYVINYL CHLORIDE FACILITIES Vinyl Chloride Production Facilities Detailed, reliable data for estimating material losses at VC facilities with precision are not readily available. Therefore, only generalized estimates have been attempted. A simplified block diagram for production of VC from ethylene and chlorine is shown in Figure 1. Some VC complexes utilize oxychlorination units; others produce ethyl chloride from the by-product hydrogen chloride (HC1) and ethylene. However, the production of dichloroethane (EDC) allows for many approaches to recycling of light and heavy materials such that the losses of VC are reduced. Even vent streams of inerts can be scrubbed with EDC for ma-yin-mm removal of VC before venting. Light ends such as methane are usually flared and VC is converted to water and small amounts of HC1. VC losses have come primarily from vent streams, the storage and transportation loading systems, and seepages from pumps. Ifvent streams are not scrubbed or flared, the amount of VC reaching the atmosphere increases considerably. This in turn is influenced by the purity of the ethylene and the chlorine being fed into the units. Usually, these inerts come out in the EDC unit but may be carried on depending upon the pro ducer1 s philosophy regarding the purity of the EDC to be fed to toe cracker. Experience has been that the higher the purity of EDC both with regard to light and heavy material, the greater the efficiency of the cracking. It is frequently difficult to pinpoint the areas and quantities of VC losses. However, some generalizations can be made for, as an example, a plant producing 500 million pounds per year of VC. (The industry is heading toward plants of this size and larger.) Tank car loading losses may be several hundred pounds per day. Vent stream losses could reach another 100 pounds per day while losses of VC entrapped in the water effluent might be a few pounds per day. In addition to these very small operating losses, there are undoubtedly unintentional losses from leaking pumps, flanges, and containment vessels, with total plant losses probably less than 0.1% or less than 500,000 pounds per year. From an environmental standpoint, the disposal of the heavy chlori nated hydrocarbons may also presenta problem. Some are sold to solvent scrap dealers for salvage. In the past much of the material has been dumped at sea or put into landfills or deep wells. More recently, incin eration has been used, which is known to produce HC1 emissions. RSV 0019115 10 r;-. Polyvinyl Chloride Polymerization Facilities Reasonably reliable data are available for estimating material losses at PVC facilities. However* generalizations applicable to the entire industry must be surrounded with many caveats. It must be emphasized that there are a number of PVC processes* and each plant has its own idiosyncrasies. VC losses will fluctuate depending on the care exercised in operating the PVC plant* types of products produced* frequency of product change* method of PVC shipment* and emergency situations. Estimates of losses have varied widely in the industry* indicating the complexity of establish ing precise losses for a given facility and overall losses on a nationwide basis. In general, older PVC plants are smaller than those being built today and are equipped with smaller sized reactors. With small reactors, the number of batches required to produce a given amount of PVC is greater* and thus the number of process steps are increased with a greater poten tial for loss of both VC and PVC. Further, a small plant has the disadvan tage of having to make frequent resin changes to meet customer demands. During these changeovers a certain amount of off-grade resin is produced. In addition, older plants have the added burden of higher maintenance than new plants* but this tends to stabilize after a few years. The handl ing of VC and the production of the high quality resins which are demanded by the marketplace require a reasonable maintenance program. Mainte nance consists primarily of the care of agitator seals, pump seals, and valves and the removal of polymer which slowly builds up in VC lines primarily in the recovery system. Although many older facilities have been in operation for years, they are usually not the same as when first installed. Some of the operators have continually updated the plants for many reasons including labor savings systems, new product require ments, replacement of woraout equipment* addition of new product lines, and safety. When VC was cheap and there was little concern about its toxicity* the emphasis was almost exclusively on productivity. Often this resulted in high losses of VC to the environment as recovery cycles were reduced. Today* the picture is changing. Not only are the producers trying to reduce the direct VC losses* but they are also trying to minimize PVC losses by scheduling longer production runs between product changes. As an example* the newer large plants are setup with multiple production lines. This allows the dedication of one line to a given product which results in very low resin loss due to product change. 11. RSV 0019116 The traditional method of stating yield of VC in PVC plants has been based upon pounds of prime resin in the bag as compared to VC Invoiced. This often has led to a misunderstanding about VC losses with the interpretation that a 94% yield means 6% VC loss to the envi ronment. In fact some VC may never actually be received because of the inability to measure 'die weight of tank cars accurately, some of the losses are in the form of PVC scrap, and some losses escape as PVC particles. A properly run and maintained suspension plant using technology that is ten years old should be capable of obtaining a 95% or higher yield unless some especially esoteric resin is being produced along with large amounts of scrap or off-grade resin. For the older plants, the losses will probablybe significantly higher. Other than overall sloppy operation, the recovery system is the single most important part of the plant govern ing VC losses. If insufficient time is allowed or vacuum is not applied, then the VC content in the PVC/water slurry will be greater than neces sary. As a result, VC losses will occur in the centrifuge effluent water, drier/ product collector vent air, the venting of the reactor, and the slurry tank. The magnitude of VC and PVC losses in a typical PVC plant is described in Figure 2. These losses are expressed as a range of losses depending on the feed rate, reactor size, reactor cleaning procedures, batch sizes, level of technology, and general housekeeping and operating procedures. The following comments on manufacturing practices may help put these losses into perspective: 1. VC Feed - This is shipped, as virtually 100% VC and does not - normally contain an inhibitor. - 2. VC Unloading - Considering normal losses in disconnecting the piping, sampling, tank gauging, pump and compressor seals to the tank cars, losses to the atmosphere should not be greater than 100 pounds per car. 3. VC Charging - A 0.05% loss between storage and polymerization should cover losses from flanges and seals throughout all VC handling equipment. 4. Polymerization - The loss from build-up of PVC on the walls of the reactor is split between reactor wash-out and the slurry strainer. 5. Reactor Venting - Before the reactor can be cleaned, residual VC is vented. After recovery and emptying the PVC resin, the reactor is full of a mixture of air, moisture, and VC at ambient conditions. RSV 0019117 12 6. Recovery - Processing schemes will vary, but one of the most widely used is the direct recovery of unreacted VC from the reactor. While the reaction can be carried out further, economically it is essentially complete at 90% conversion or even less depending on the type of resin. At this point the residual VC is recovered by means of compres sors which evacuate VC from the reactor. The recovered VC is con densed and distilled before recycling to the reactor. 7. Drying - Unreacted VC is collected in the recovery system but there are losses of polymer in the drier due to coalescence of the resin and periodic clean-out. This is almost entirely scrap. 8. Product Collector - Most plantsruse bag collectors so that the loss of resin is less than one pound per hour, but there are losses due to product changes which raise the total. 9. Screening - Oversize resin is removed from the final product. This material consists of scrap and off-grade resin. With the current PVC shortage much of this off-grade resin is used as prime resin by special customers. 10. Miscellaneous - In addition to the above losses, others occur as scrap or off-grade polymer and as quality control samples. a. Bad Batches - Most plants experience batches which are off specification. These range from "just slightly off" to solid batches, with losses at 2 to 3 batches per month or about 0.4% or 40 pounds per hour average. Salvage value depends upon the degree of "off-grade" and market conditions. d. Samples - Probably about 0.05% or 5 pounds per hour and is usually "destroyed in testing. c. Polymer Build-up - VC slowly polymerizes in the pipe lines, particularly the recovery system, and must be removed peri odically. No quantitative value is available for this loss. d. Spillage - Some of the product is shipped in bulk and some is bagged. While some spillage occurs in bulk handling, more occurs in bag filling and in bag breakage, e. Centrifuge Effluent - Some PVC enters the effluent water. 11. Product Change-Over - As indicated previously there are losses in the drier and collector due to cleaning for changes from one product to another. In addition one must segregate the first product that comes through this system. The amount can vary widely depending upon the number of changes and the sensitivity of the product to contamination from the previous product. 13 RSV 0019118 The foregoing analysis, together with estimates provided by industry, suggests that the losses of VC at PVC polymerization facilities' currently range from about 3.0 to 6.3% while PVC losses are on the order of 1.3%. 14 RSV 0019119 PRODUCTION OF VC FROM ETHYLENE AND CHLORINE S IM P L IF IE D BLOCK DIAGRAM W ater Figure 1 u>1 41 \ i>ri* -r i <Oi-u --uo>> t.--uc <>aa> u u1*9- u>* a> OC e k_ --kOO C<aO+kj -C -C u -TU-- *tt>j U3 T3 i- c C ufl 15 RSV 0019120 PRELIMINARY ESTIM V*'E OF LOSSES IN PVC SUSPENSION POLYMEmlATIGN (TYPICAL PR(CESS) RSV 0019121 l MVC LOSSES E PVC LOSSES l"LOSSES 3.0 - 6.3% 1.35% 4.35 - PVC lew 01 PVC ion >0.1 Otot111. PVC 0.1 PVC Ion 01 rlM Ion 04 MVC 0.1 T~ PVC * .1.0 *n s H A K> l 1 APPENDIX IV INTERIM METHOD FOR SAMPLING AND ANALYSIS OF VINYL CHLORIDE IN WASTE WATER EFFLUENTS AND AIR EMISSIONS Scope and Application The initial basis for this method was developed during the moni toring program carried out by EPA Region IV in March and April. The techniques used by Region IV provided guidance for the monitoring activities of other Regions, and the experiences of all Regions were then incorporated into this refined version of the original Region IV approach."- This method is applicable to VC determinations in water effluents, sludges and scums, and atmospheric emissions. The limit of detection is approximately 0.06 mg/1 inwater and 0.06 ppm (v/v) in air samples. Summary of Analytical Procedures Water composite samples, air continuous compositebag samples, and air and water grab samples are analyzed without cleanup by gas chromatography (GC). Separations are effected by selection of one of two types of columns depending upon the nature of the sample. Detection is by means of the flame ionization detector (FID). Tetrahydrofuran extracts of sludges and scums are used for injection into the GC. Air continuous samples on activated carbon are extracted with carbon disulfide, and the extract is analyzed by direct injection into the GC. Calibration curves are developed using gravimetrically prepared calibration solutions, or by using known dilutions of VC in carrier gas. VC confirmation should be made by mass spectrometric analysis of the GC eluent if possible. Independent confirmation may also be made in the event of extraordinarily high VC concentration sam ples by using long path Fourier transform IR spectrophotometry. This IR technique requires special equipment and about 20 cubic feet of air samples. Interferences Certain volatile hydrocarbons such as neopentane, butadiene, and freon 12 have elution characteristics similar to VC. However, on the GC column substrates specified in these procedures, these have not usually presented problems of resolution of the VC peak. When column substrates other than those specified have been used, impurities from solvents and carbon adsorbents have been RSV 0019122 17 found to interfere with the VC elution peak. Under certain condi tions a peak is associated with the injection and subsequent with drawal of the microsyringe into and from the GC septum. These peaks can also give interferences with the VC peak. Withdrawal should be timed to avoid overlap of this peak with the VC peak. Apparatus and Materials Gas Chromatograph Flame Ionization Detector Recorder - any potentiometric strip chart recorder which is compatible with the detector system. An integrator is also desirable to estimate peak areas. Column Materials for Waste Water* Sludge* or Scum Samples Borosilicate glass tube or stainless steel tube - 6* x 2. 5 mm ID preferred. When GC configuration requires columns of other dimensions* these should be used. Solid support - 60 to 80 mesh Gas Chrom Q Liquid Phase - 4% FFAP on specified solid support (weight percent). Liquid phase on solid support can be purchased directly from commercial distributors. Column Materials for Air Samples Borosilicate glasB tubing or stainless steel tubing - 8' x 2.5 mm ID preferred. When GC .configuration requires columns of other dimensions* these should be used. Solid support - Carbopak A Liquid phase - 0.4% Carbowax 1500 on solid support (weight percent). Liquid support on solid phase can be purchased directly from commercial distributors. Continuous Air Monitoring Materials - Carbon Adsorption Option Adsorption Tube * pyrex glass* 18" x 3/8" OD Activated coconut charcoal, 8-16 mesh. Any good commer cial grade* e.g. Fischer Scientific Company can be used. Becton-Dickson 27 gage 3/8" hypodermic needle flow control Vacuum pump Air flow meter 18 RSV 0019123 Continuous Air Monitoring Materials and Equipment * Bag Sampling Option Environmental Measurements. Inc.. Programmable Bag Sampler Tedlar bags (or equivalent) Gas Pressure Regulator (0-5 PSIG) Microsyringes - 10. 25. 50. and 100 microliter (graduated) Gas-tight sample syringes - 1 and 50 ml (graduated) Vacuum Sampling Cans - 370 ml steel Vacu-Samplers. or glass sampling bottles. Cans and bottles should be flushed with clean air or nitrogen and evacuated prior to use. Evacuated containers should be protected from rough handling to prevent implosion or collapse. Sampling Bags (Tedlar or equivalent) - 12" x 12". 36" x 36". equipped with sampling valves and speta for GC sample withdrawal Automatic water sampler - compositor (manual sampling is optional) equipped with sample refrigeration capabilities, and a a means to prevent loss of vinyl chloride from open bottles Glass sampling bottles with teflon lined screw type caps - 50 ml capacity or other sizes depending upon sampler requirements Septum-sealed vials - 1 to 10 ml capacity Volumetric Flask. Glass stoppered. 25 ml Medicine droppers Dedicated GC/M. S. for confirmatory tests (preferable) Barometer Thermometer Anemometer Reagents, Solvents, and Standards Carrier gases - zero nitrogen or helium FID gases - zero hydrogen, oxygen Tetrahydrofuran. reagent grade, peroxide-free 19 RSV 0019124 Carbon tetrachloride (reagent grade) Carbon disulfide (reagent grade) Standards VC in zero air, 50 ppm (+ 2%) v/v VC, analyzed reagent grade (lecture bottle) Sampling A. Water Samples All waste water discharge points identified in NPDES permits should be sampled for -VC. A mini-mum of three successive 24'hour composite samples of each site should betaken. Com positing interval should be one hour (manual or automatic sampling is optional). Compositing interval of 20 minutes may be used if the automatic sampler has this capability. Samples should be taken at waste treatment units such as clarifiers 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 betaken of scum and sludge from each separator unit. Compositing interval should be one hour. Three grab samples of clean process water (city or private well) should he taken as blanks. Samples should betaken in50 ml bottles with gas-tight, teflonsealed, screw cap closures, or in equivalent containers re quired by the characteristics of automatic samplers. All water, sludge, and scum samples should be refrigerated dur ing collection and storage. Compositing volumes should be selected to assure head space above the sample is absent or minimized to avoid loss of VC by its partitioning into the gas phase when samples are sealed. Provisions should be made to avoid such losses during continuous monitoring operations. Estimates of discharge flows should be made using any appro priate measuring device (venturi, weir, magnetic meter, etc.). Samples should be preserved by refrigeration and protected from sunlight until they are ready for analysis. B. Air Samples Sampling sites should be selected which are downwind and in the plume of the atmospheric emissions from the plant. Samples should be collected only in areas where local residents or neighboring industries would be* exposed. At a minimum. 20 RSV 0019125 sampling should be conductedover a period of five days. Sites should be selected in the following array: one site immediately upwind (A) and one immediately downwind (B) of the plant site: four 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 wind direction and two <E, F) downwind from the plant site: two sampling sites (G, H) approximately 0.5 miles downwind: single sampling sites, each at distances approximately 0.6 (1), 0.6 (J), 1.0 (K), and 3.0 (L) miles downwind from the plant site. If wind is fish-tailing severely, move sampling sites G and H approximately 0.5 mile upwind of the fish-tailing wind direction from the plant. The sites specified are minimum. Additional sites may be selected contingent on overriding microsxeteorological considerations. These should be determined in consultation with the Regional meteorologist. These may be at ground or some elevated level, as determined by the plume survey or as estimated by release of meteorological balloons, anemometer, and wind direction indicators, etc. SAMPLING SITES Prevailing Wind Direction Minimum Sampling Schedule Miles from plant site Site Symbol Time Mon Wed Fri 0.0 A 0.4 C ""Plant D 0800 A,A,B A.B.B A.A.B 0.0 --B------ 1000 C.D.F C.D C, D,D 0.4 E F 1200 A, E A.G.G A, E 0.5 G H 1400 B.B.F B,H B, B, G 0.6 I 1600 C.G E,K I.J 0.8 J 1.0 1800 D.I - L.L K. 2ooe - H.L.L - 3.0 L (Note: All times are + 30 minutes for manual grab samples, or + 2"minutes for automatic, programmable bag~samplers). Grab samples should be taken in 50 ml gas-tight syringes, 50 to 100 ml glass sampling bottles. 370 ml "Vacu-Sampler" metal cans, or 12" x 12" capacity Tedlar-type bags. Both the Vacu-Samplers and the glass sampling bottles should be evacuated prior to use. (Caution: These may implode or collapse when under vacuum. Use due care in their handling). The perfect gas laws should be assumed to estimate gas vol umes. Gas-tight syringes are flushed several times with am bient air before a sample is taken. After the sample is taken, the gas-tight syringe is locked and sealed until it is ready for analysis. 21 RSV 0019126 The Tedlar-type bag samplers may be filled by pulling the walls of the bag apart manually, or better, by placing the bag in an enclosure and pulling a vacuum on the outside sur faces of the bag. The bag is sealed until it is ready to be analyzed. Tedlar-type bags are preferred for grab sampling. All samples should be protected from sunlight. Continuous Sampling - Carbon Adsorption Option: Continuous samples are taken in pyreac tubes (approximately 3/8" O.D. x 18" long) packed with a good grade of activated coconut shell charcoal. ~ The charcoal is added to the tube in three segments, each 3-inches long, and each separated by a glass wool plug. The two ends of the tube are also plugged with glass wool. Both ends of the pack adsorption tube are plugged with serum caps during transport and for storage pur poses. Flow rate through the tube is controlled by inserting a BectonDickson 27 gage, 3/8" hypodermic needle through one of the serum caps into the end glass wool plug. Air is sucked through the tube by connecting it to a conventional vacuum pump. The arrangement is similar to that used in the National Air Surveillance Network. Flow rate should be about 200 ml per minute. For each adsorption tube, the flow rate should be calibrated in the laboratory before the sample is taken and should be verified again in the laboratory after the sample is taken. Clean needles frequently to prevent plugging. The adsorption efficiency of the carbon in the adsorption tube should be verified in the laboratory by preparing a 5 ppm v/v VC mixture in the 36" x 36" Tedlar-type bag and drawing this through the adsorption tube. Flow rates should be verified before and after the experiment. It is important to note that all collections should be made with the adsorption tubes held in an upright position to minimize channeling. Adsorption tubes should be protected from sunlight either by wrapping with foil or by enclosing them in a box. Each segment of the adsorption tube is worked up separately by etching the tube in the middle of a 3" section with a file, successively breaking each segment and spilling its 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 carbon with carbon disulfide is quite exothermic. ' A 2 microliter aliquot of the supernatant solution should be injected on the carbowax 1500 column for estimation of the adsorped VC. Suc cessive analysis of the three adsorption tube segments will indicate the amount of break-through of VC through the adsorb ent. 22 RSV 0019127 I t *fc<"s.l'l. I " 'ft The same procedure should be used for taking samples in the field. Continuous Sampling - Programmable Bag Sampler Option: The sampler is programmed to take twenty-four consecutive one-hour composite samples. Each one-hour sample is analyzed separately for VC content. Sampling rate of the individual pumps should be verified before and after use of the sampling device. Record the temperature and atmospheric pressure at which the samples are taken. All gas volumes and concentrations should be corrected to 25C and one atmosphere (760 mm Hg). At a minimum, con tinuous samples should be taken at sites A, B, C, and D at ground level, unless otherwise indicated by micrometeorological conditions. Calibration A. Gas Analysis - Gas Dilution Option: Record ambient temperature and atmospheric pressure. Evaluate the 36" x 36" Tedlar-type bag. Add 1 liter of the standard VC gas mixture (50 ppm, v/v) to the bag. This addi tion maybe made with a flow meter or with a gas-tight syringe. Dilute with nine liters of zero nitrogen or helium carrier gas. This gives a concentration of 5. Oppm (v/v) of VC. (13 ng/ml at 25C and one atmosphere.) Evacuate a 12" x 12n Tedlar-type bag and add 0.5 1 of the 5.0 ppm (v/v) concentration mixture. Dilute with 2 liters of zero nitrogen or helium carrier gas. This gives a concentration of 1. 0 ppm (v/v) VC, (2.6 ng/ml at 25C and one atmosphere). Evaucate a 12" x 12" Tedlar-type bag and add 0. 5 1 of the 1.0 ppm (v/v) VC calibration mixture. Dilute with 2 liters of zero nitrogen or helium carrier gas. This gives a concentration of 0.2 ppm (v/v) VC (about 0.52 ng/ml at 25C and one atmosphere). Evacuate a 12"x 12" Tedlar-type bag and add 0.75 1 of the 0.2 ppm (v/v) VC calibration mixture. Dilute with 1. 75 liters of zero nitrogen orhelium carrier gas. This gives a concentra tion of 0.06 ppm (v/v) VC (about 0.16 ng/ml at 25C and one atmosphere). This is about the limit of detection for direct injection into the GC. With a gas-tight syringe, inject 1 ml aliquots of the 5.0, 1.0, 0.20 and 0.06 ppm (v/v) VC calibration mixtures into a GC equipped with a Carbowax 1500 or Carbopak column and an FID detector. Use zero nitrogen or helium as carrier gas at a flow rate of 60 ml/min. Operate the inlet and the column isothermally at room temperature. RSV 0019128 23 Prepare a calibration curve. Repeat until the calibration curve is reproducible. Gas or Water Analysis - Gravimetric option: Stock solution of VC. Pipet 40.0 ml of carbon tetrachloride into a tared 50 ml glass stoppered volumetric flask and accurately weigh to 0.1 mg. i Attach a tygon delivery tube to the VC lecture bottle valve. Attach the end of the delivery tube to a piece of glass tubing which has been constricted at one end, flush out the tube with VC, and slowly bubble VC into the CCI4 containing volumetric flask until about 5.0 mg of VC has been added. Precautions should be exercised to prevent loss of carbon tetrachloride during this operation. Reweigh the volumetric flask to determine the weight of added VC. Fill the volume tric flask to the 50 ml mark (approximately 100 ppm wt/vol). (These operations should be carried out in a hood). Transfer 1 ml of the stock solution of VC to a 25 ml volume tric flask and dilute to the 25 ml mark with carbon tetrachlo ride (approximately 4 ppm w/v). Transfer 5 ml of the 4 ppm VC solution to a 10 ml volume tric flask and dilute to the 10 ml mark (approximately 2 ppm, w/v). Repeat dilution for a solution approximately 1 ppm, and 0.2 ppm. Transfer the stock solution to a teflon-lined screw capped bottle. This solution can be kept for extended periods of time Transfer the diluted solutions to serum vials and cap them with teflon-lined serum cap septa. Inject 1 ml aliquots of the calibration solutions in the GC equipped with Carbowax 1500 on Carbopak.A packed columns and an FID detector. Use Zero nitrogen or helium carrier gas at a flow rate of 60 ml/min. Operate the inlet at 150C and the column at 60C. After the VC peak has been eluted, program the column temperature to 150 C to elute solvent. Cool column back to 60 C for follow-on concentrations. Repeat procedure using a GC equipped with a 4% FFAP on Gas ChromQ packed column and FID detector. Operate under the same conditions. Prepare a calibration curve to be used be used with water samples. 24 RSV 0019129 Procedure Water Sample Analysis Untreated water samples (1-5 microliter aliquots) are injected directly into the GC. A 4% FFAP on "Gas Chrom Q" packed column is used. Nitro gen zero gas or helium is used as the carrier gas at a flow rate of 60 ml/min. Inlet temperature is set at 150C. The column is operated isothermally at 62C. Detection is by FID. Report concentration of VC in sample in mg/1. Sludge and Scum Samples Extract 5 grams of sludge or scum sample with 100 ml of tetrahydrofuran (THF). Analyze THF extract in the same manner used for water samples. If VC concentrations are too high, make appropriate dilutions of the THF extracts. Report concentration of VC in sample in mg /g of sample. Air Sample Analysis Grab samples. Use a 0.4% Carbowaxl500 on Carbopak A packed column. Use nitrogen zero gas or helium as the carrier gas with a flow rate of 60 ml/min. Operate die column and inlet at room temperature. Use a flame ionization detector. Untreated air samples (lml) are injected directly into the GC. VC contamination of syringes requires attention. Report concentration of VC in gas samples in ppm (v/v). Continuous Samples Use same procedure as previously discussed for calibration of adsorption tube efficiency. Quality Control Duplicate sample analyses are recommended as a quality con trol check. 25 RSV 0019130 APPENDIX V SUMMARY OF REGIONAL ACTIVITIES This Appendix briefly summarizes the results of the preliminary VC monitoring activities conducted by EPA Regional Offices during the Spring of 1974 at the request of the Task Force. More detailed reports are available from the Regional Offices. The sampling and analyses were carried out in a very short period of time using new methods, based on the Agency's best scientific judge ment. They represent, in the Agency's opinion, the best methods then available. In large measure, the sampling and analysis methods were based on previous analytical studies in which similar chemicals were evaluated. However, they had not been thoroughly tested for accuracy and precision under field conditions. Prior to and during the sampling and measurement only limited quality control and standardization of procedures could be applied in die time available. The methods utilized were interim procedures which have already been subjected to further modification. The nature of the PVC manufacturing process results in the escape of VC pulses which could lead to widely fluctuating levels of VC in the ambient air. So, too, changes in air movement may influence concen trations at a given station at any one time. Therefore, the VC data reported are preliminary in nature and are subject to change as addi tional monitoring is performed. Individual measurements probably underestimate the VC levels due to the possibility of VC leakages and other inaccuracies in the monitoring system. Region I; Leominster, Massachusetts: Borden Chemical Company (PVC); May 9, 10, 13. 1. One hundred and fifty-seven discrete (grab) ambient air sam ples were collected on plant property and within a 3. 0 mile radius of the plant. The VC concentrations ranged from less than the detectable limit of 0.06 ppm to 6.0 ppm. The samples exceeding 1 ppm were obtained on plant property near the fenceline. 2. Twelve 24-hour integrated ambient air samples were collected at the fenceline on plant property. The VC values ranged fromless than the detectable limit of 0.06 ppm to 1 ppm. 3. VC concentrations in three 24-hour composite waste water samples taken from the lagoon effluent ranged from 0.15 to 0. 29 ppm. 4. VC concentrations in two sludge samples taken from the lagoon near the outlet measured at the 0.05 - 0.06 ppm level on a wet basis. 26 RSV 0019131 5. The plant is located in a residential/industrial area on the edge of Leominster with residential developments adjacent to plant pro perty. 6. Shifting meteorological conditions and rain hampered the sam pling program. Region II: Flemington, New Jersey: Tenneco Chemicals, Inc. (PVC); May 29*31. 1. Forty-three discrete ambient air samples were collected on plant property and within a 2. 0 mile radius of the plant. The VC con centrations outside the plant property ranged from less than detecta ble (0.01 ppm) to 0.05 ppm. On plant property a single sample collected on the dryer building roof contained 5.6 ppm. At ground elevation, the VC concentrations on plant property ranged up to 0. 30 ppm. 2. Twenty-three integrated ambient air samples were collected for 24-hour periods on plant property and within 2. 0 miles of the plant. The VC values ranged from 0.005 to 0.038 ppm on plant property and from less than detectable to 0.031 ppm outside the plant area. 3. Two integrated one-hour ambient air samples collected within 0.1 mile of the plant showed VC at levels of 0.32 ppm and 0.18 ppm. 4. A Tnarfrmmi level of 20 ppm was detected in three 24-hour composite samples taken from the water effluent discharge into the BushkiU Brook, which immediately flows into the Raritan River. This amounts to approximately 400 lbs/day. 5. VC concentrations in sludge samples taken from the lagoon areas on plant property ranged from less than detectable to 1,000 ppm in wet weight concentrations; however, the concentration at the sludge disposal area was 54 ppm. 6. The plant is located in an area in which manufacturing facili ties are interspersed with farmland and relatively large acreage residential properties. There are a number of small communities within a few miles of the plant. Region HI: Delaware City, Delaware: Stauffer Chemical Company (PVC) and Diamond Shamrock Chemical Company (PVC); May 20-22. S. Charleston, West Virginia: Union Car bide Corporation (PVC); May 24. 1. The air sampling and analysis activity was organized around a mobile laboratory equipped with a gas chromatograph using a flame ionization detector. VC levels were later confirmed by mass spectro meter. 2. A single discrete ambient air sample at the fenceline of the Diamond Shamrock plant showed 0. 2 ppm VC. 27 RSV 0019132 3. Four discrete ambient air samples taken near the Stauffer Chemical plant ranged from 0.3 to 0.7 ppm VC. The highest level was recorded 0.5 miles from the plant and the lower levels at 0.25 miles from the plant. 4. The area immediately adjacent to the Delaware City complex is light ly populated residential areas for several miles. 5. Water samples collected at the Union Carbide plant gave VC values of 1.1 and 0.8 ppm for grab samples at several outfalls and 0.35 for a 24-hour composite. Samples obtained from the Kanawha River did not have a detectable level of VC. 6. Sampling was attempted but was not feasible due to limited time and equipment difficulties at the PVC plants of the Firestone Plastics Company in Perryville, Maryland* and Pottstown* Pennsylvania. Region IV: Louisville, Kentucky: B.F. Goodrich Chemical Company (PVC); March 19-21 and May 8-16. 1. The initial air monitoring program conducted in March was pre liminary to the more extensive program in May which showed significant ly higher levels. 2. In May there were 39 discrete ambient air samples collected in the area designated industrial (within 0.8 miles from the plant center). The VC concentrations ranged from less than 0.05 to 5.6 ppm* with 10 samples exceeding 1 ppm. In the area designated residential/ industrial* 149 samples were collected within 0.8 miles of the plant with VC concen trations ranging from less than 0.05 to 33 ppm. The average concentra tions at the site registering 33 ppm were between 0.5 and 1 ppm, but 18 samples had concentrations greater than 5.0 ppm. Four samples were obtained in strictly residential areas with VC values of 0.05 to 1.6 being observed. The 1.6 value was 0. 8 miles from the plant. 3. Five sampling sites were established within 0.6 miles of the plant for integrated air sampling over 24 hours. VC values ranged from less than 0.001 to 0.53 ppm. The highest value was obtained from a sampling site 0.2 miles from the plant center. 4. Wastewater from the clarifier discharge was measured in March at 2 to 3 mg/1 in 24-hour composite samples. 5. Dewatered clarifier sludge and clarifier scum contained 193 and 162 ppm of VC, respectively. Region V: Painesville, Ohio: Uniroyal, Inc. (PVC) and Robintech, Inc. Inc. (PVC); May 9-14. 1. Four of 137 ambient air samples taken at distances up -to 3.0 miles from the plant showed levels exceeding 1 ppm of VC with the highest level being 2.26 ppm. Many of the samples were less than 0.1 ppm. RSV 0019133 28 Il ;: 2. Nine 24-hour integrated ambient air samples taken at various dis tances from the plant showed levels up to 0. 2 ppm of VC. 3. VC levels In 11 of 17 water effluent samples were less than 0.2 ppm, with three samples exceeding 1 ppm, including a high of 3.7 ppm. 4. VC levels in nine sludge samples, as the sludge would leave the plant property, ranged from 9 to 3520 ppm. 5. The complex is surrounded by residential areas. Region VI: Flaquemine, Louisiana; The Goodyear Tire and Rubber Company (PVC) and Dow Chemical Company (VC); April 7-9. 1. There were 31 discrete ambient air samples collected within 3.0 miles of the complex with VC concentrations ranging from less than detec table (.001 ppm) to 7.81 ppm. Most of the readings were less than 1 ppm, with the highest value at the property line. 2. VC concentrations in wastewater effluent measured by 24-hour com posites were all below . 05 ppm. 3. VC concentrations in residual reactor scrapings at the Goodyear plant ranged from 23 to 31 ppm. 4. The small communities of Morrisonville and Eliza are located less than 1 mile north and northwest respectively of the Goodyear plant. A few homes from Morrisonville extend almost to the north property line of the Goodyear plant. 5. Very limited air sampling was conducted in the Houston area in the vicinity of the plants listed below. However, in view of the inadequacy of this activity, the sampling effort in this area is being continued. Deer Park, Tex., PVC Plant - Diamond Shamrock Corp., Diamond Sham rock Chemical Co. Deer Park, Tex., VC Plant - Shell Chemical Co., Industrial Chemicals Division Houston, Tex., VC Plant - Tenneco, Inc., Tenneco Chemicals, Inc. Pasadena, Tex.* VC Plant - Ethyl Corporation Region IX: Long Beach, California: B.F. Goodrich Chemical Company (PVC); American Chemical Corporation (VC); American Chem ical Corporation (PVC); May 7-10. 1. One hundred and eighty 10-minute integrated ambient air samples were collected within 3.1 miles of the complex. About 11 percent of the 29 RSV 0019134 readings exceeded 0.5 ppm. while 5 percent exceeded 1.0 ppm. The maximum value measured was 3.4 ppm in a sample taken 3.1 miles from the plant; however, the average level measured at this point was about 0.5 ppm. 2. Samples of wastewater effluents were composited for 8 to 24 hours and yielded values from 3.5 to 8.9 ppm. with individual samples reading up to 22 ppm. 3. Sludge samples showed values ranging from 290 to 4200 micro grams of VC per gram of dry sludge. 4. The complex is surrounded by residential areas. Within the three mile radius of the plants there are eleven schools. 30 RSV 0019135 APPENDIX VI PERSISTENCE OF VINYL CHLORIDE The available information on the stability and persistence of VC in the environment is currently very limited. Some literature and laboratory studies have recently been initiated by industry and by EPA. This discus sion summarizes the findings of EPA to date and particularly the results of research efforts at EPA research facilities undertaken in response to the needs of the Task Force for at least preliminary data on environmental fate. Results of related experiments reported by industry seem to be consistent with the discussion. Behavior of Vinyl Chloride in Air The peak absorption of VC in the ultraviolet region is very far below the solar cutoff of about 2900 A, indicating that VC would not undergo reaction in sunlight in the absence of other reactive chemicals. 'When irradiated with simulated solar radiation in the presence of nitrogen oxides (nitric oxide and nitrogen dioxide)* VC reacts to form a variety of products. The available laboratory results indicate a rate of reaction of about 8 to 10% per hour for VC* recognizing that reaction rates may vary with concentrations. The direct and indirect reaction products identified included ozone* nitrogen dioxide* carbon monoxide, formalde hyde, formic acid, and formyl chloride. High eye irritation levels were found with human exposure panels which is consistent with the products identified. The low reaction rate of VC, including reactions in the presence of nitrogen oxides, indicates that within a few miles downwind of VC emission sources VC will persist and can be considered a stable pollutant. The usual meteorological dispersion equations for gases could be applied to approximate concentrations. Because of temperature inversions and the absence of sunlight at night during the fall and winter, buildup of VC might be of particular concern during such periods. Clearly at greater distances from emission sources, VC will have greater opportunity to disperse and degrade. The noxious gases which are products of VC reactions should not be ignored. In air quality regions with large industrial activities involving large volume production of these chemicals, such products may contribute appreciably on particularly sunny days to eye, nose, throat, and lung irri tation. Behavior of Vinyl Chloride in Water The loss of VC from water at constant temperature and pressure de pends on the rate of agitation or aeration. Distilled water in a beaker spiked with 16 ppm VC, when rapidly stirred at 22C with a magnetic stirrer, lost 96% of VC in two hours, while quiescent water at the same concentration lost only 25% VC. There was no-significant difference in the rate of VC losses from distilled water* river water, or effluent from a VC plant stirred at the same rate* indicating negligible adsorption effects with particulate matter. Plots of log water concentration versus time give straight lines, indicating volatility to be the only important loss mechanism. 31 RSV 0019136 Hydrolysis over a pH range of 4.3 to 9.4 does not appear to be an im portant pathway for loss of VC from water. Chemical reaction of VC in the clarifier effluent from a VC plant was followed at 5CPC for 57 hours at pH 4.3, 8.0, and 9.4 in sealed septum vials. Concentrations indicated that VC at these three pH values decreased at the same rate. This lack of pH dependence suggests that the loss of VC occurred by volatilization rather than hydrolysis, or at least there is a very slow hydrolysis rate. This experiment should be repeated in leak-proof reaction vials. Very preliminary experiments do not show photolysis as an impor tant pathway for loss of VC in water. However, there are many uncertain ties in the experimental techniques, and additional studies are needed in this area. Earlier theoretical studies are consistentwith these experimental re sults. One study on the transfer of small non-reactive molecules across the air-water interface (as in stream aeration) used a kinetic approach to predict that VC will be rapidly lost from an aqueous solution, with the rate of loss being a function of water turbulence, mixing efficiency, and molecular diameter. Another study, using a thermodynamic approach, predicted a rapid rate of evaporation of low solubility chlorinated hydro carbons. including compounds of low vapor pressure. Despite the foregoing efforts there is a general absence of data con cerning VC in aquatic systems. It is conceivable that as the result of poor or erratic mixing in lakes or ponds, together with slow but con tinuous release of VC from sediments and sludges. VC could persist long enough to accumulate biologically, via direct absorption or via the food chain, or to cause other ecological effects. Behavior of Vinyl Chloride in Closed Rooms Tables 1 and 2 present data concerning concentrations of VC in a typical room following release of a pesticidal spray containing VC. TABLE 1 One Hundred and Twenty Second Release of Insect Spray in 133, 000 Liter Room SAMPLE TIME COLUMN I VC FREON-12 COLUMN H VC FREON-12 No. 1 Collected at breathing zone during spray 41.64 ppm 8.15 ppm 41.9 ppm 7.94 ppm No. 2 15 minutes 16.91 3.13 17.1 3.30 No. 3 No. 4 No. 5 30 minutes 60 minutes 120 minutes 1.38 0.08 0.012 0.27 0.018 _ 1.32 0.061 0.010 0.25 0.018 - RSV 0019137 32 TABLE n Thirty Second Release of Insect Spray in 21,400 Liter Room SAMPLE TIME COLUMN I VC FREON-12* COLUMN H VC FREON-12* No. 1 Collected one minute after spray 380.1 ppm 84.8 ppm 383. 6 ppm 83. 2 ppm No. 2 No. 3 No. 4 No. 5 30 minutes later 60 minutes 150 minutes Collected in adjacent hall 151 minutes 52.1 24.6 10.3 0.83 9.9 4.8 2.1 0.17 48.7 22.5 9.3 0.17 10.3 4.7 2.2 0.15 *Freon-12 concentrations were determined using hydrocarbon response factors to compare dilution effects; the actual concentration is higher by a factor of 5. 3. REFERENCES 1. Unpublished results of experiments and analyses conducted at EPA laboratories in Research Triangle Park, N. C., and Athens, Georgia, during April and May 1974. 2. Unpublished results of experiments on persistence of VC in water conducted by Dow Chemical Company. 3. Tsiroglou, E. C. and J. R. Wallace, "Characterization of Stream Reaeration Capacity," EPA Ecological Research Series Report #EPAR3-72-012 (October, 1972). 4. MacKay, Donald and Aaron W. Wolkoff, "Rate of Evaporation of Low- Solubility Contaminants from Water Bodies to Atmosphere, " Environ mental Science & Technology. 7 (7):611-614 (July, 1973). ---------- 33 RSV 0019138 APPENDIX Vn HEALTH EFFECTS OF VC This Appendix presents much of the epidemiological and toxi cological data available as of August 1974, on the health effects associated with exposure to VC, together with a few interpretive com ments supplementing information presented in the bocfy of the report. However, the Appendix does not present an exhaustive review or evaluation of available information. Table 1 summarizes the data, collected by CDC/NIOSH, on the confirmed cases of angiosarcoma of the liver in VC/PVC workers in the United States and abroad. A total of 15 occupational cases have been discovered ih the United States and confirmed as angiosarcoma of theliver. Of the 15 cases, 2 are still alive and undergoing treat ment. Fourteen of the 15 were employed in PVC production plants and the remaining one in a PVC fabrication plant. The average age at death for the U.S. PVC production workers was 48.5 years (with a range from 36 to 61 years) which is about seven years younger than the average age of death from liver cancer in the U. S. male population. Based on the data available for the workers, the latent period for this disease appears to be on the order of twenty years, a period consistent with latencies observed for other occupational, chemically induced cancers. In the U.S. PVC production worker cases, all of the men were at one time "pot cleaners", required to enter the reactors in order to chip the residue of the chemical reaction from the sides of the "pots." Since the residue often contained pockets of trapped gases that were literally released in the cleaner's face when they were ruptured by his chipping operation, the potential for exposure to high levels of VC while cleaning these tanks was particularly great during the early years of this operation. Ten cases of worker-related angiosarcoma of the liver have been reported from five foreign countries to date. Table 2 summarizes the epidemiological data, collected by CDC from the Connecticut Tumor Registry, on five confirmed cases of angiosarcoma of the liver, including one accountant in a PVC fabrication plant and two residents near PVC fabrication plants. The case of occupational exposure occurred in a man who had been employed for 10 years as an accountant in a factory which pro duces vinyl sheets and processes PVC resins; it is reported that he frequently visited the production area of the plant. Of the two cases who had no occupational exposure to VC or PVC, one was a 73 year-old man who lived his entire life within two miles of a PVC wire insulation plant. The other was an 83 year-old woman, a housewife and retired cook, who had lived for 35 years within one-half mile of the vinyl products plant at which the accountant had been employed. RSV 0019139 34 i* While these findings establish no causal connection between exposure to pVc and angiosarcoma of the liver, they do raise the possibility ot such a relationship. Time will be needed to define the possible risk iactors m persons who have worked with PVC since the latency period appears to be so long. Because of the rarity of this tumor, the additional finding in this study of angiosarcoma of the liver in persons who had no occupational exposure to VC, but who may have had community exposure, is also worrisome but again establishes no causal connection* Epidemiologic investigation of additional cases of hepatic angiosarcoma that may be found to have had possible community exposure to VC will be necessary to clarity the significance of these cases. Tables 3A - 3D present the findings of the MCA-funded mortality study of VC/PVC workers, conducted by Tabershaw/Cooper Asso ciates. In calculating the risk of death, the usual method is to express the number of deaths which actually occurred as a percentage of the number which would have been expected in a comparable population observed over the same age and time intervals. This statistic is called the Standardized Mortality Ratio (SMR). Using the U. S. male population as the standard population of comparison, the SMRs were calculated for each of the 35 cases of death for which detailed mor tality rates are published on a national basis. In the standard population each SMR would be equal to 100. The statistical signifi cance of the deviation of each SMR in the study population from the exacted value of 100 was tested. A single asterisk indicates those SMRs which differed significantly from 100 at the 5 percent level, that is, which had a probability of . 05 or less of occurring by chance. A double asterisk indicates those which were significant at the 1 percent level. SMRs based on fewer than 5 observed cases were not tested for significance. The overall mortality of the study population is statistically significantly lower than that of the U.S. male population. There were 352 observed deaths compared with 467 expected, for an SMR of 75. For each job, an exposure score was estimated by industrial hy giene and safety personnel in each plant. A score of 1 was given for low exposure, 2 for medium, and 3 for high. The number of months each worker spent on a given job was multiplied by the appro priate exposure score. The total for each worker was then divided by the total number of months of exposure to give an Exposure Index (El) for that worker. Table 3A shows the SMRs for workers with an El below 1. 5 versus those at 1.5 or above. The dividing point of 1.5 represents a level halfway between low and medium exposure. Table 3B shows similar results for workers with less than 5 years exposure versus those with 5 years or more. In order to examine the possible interaction between duration and level of exposure, the study population was divided into 4 groups on the basis of both El (low vs. high) and duration of exposure (short vs. 35 RSV 0019140 long) using the same dichotomy zation as Tables 3A and 3B. Table 3C shows the results for short versus long exposure in the low El group* and Table 3A shows the same comparison in the high El group. When the study population is divided according to length and duration of exposure (Tables 3A and 3B) and combinations of these measurements (Tables 3C and 3D)* three major patterns emerge. For malignant neoplasms as a whole* the SMR increases with increasing exposure* whether measured by level* duration, or both. In the high exposure group with 5 years or more exposure (Table 3D) there are 36 observed cases and 26.11 expected. For cardiovascular - renal diseases as a group* there are also increases in the SMR with increasing exposure, but the number of observed cases remain less than expected* the differences being statistically significant in all groups except the high exposure* long duration group. For all other causes* there are no con* sistent relationships with exposure. Within the malignant neoplasms, the largest (although not statisti cally significant) SMR is in cancers of the buccal cavity and pharynx* with 5 observed, 2.84 expected* and an SMR of 189. However* Tables 3A and 3D show that all these cases have an El below 1.5, and 4 out of 5 have less than 5 years exposure. Cancer of the digestive system shows no excess in the study popu lation asa whole. However* in those workers with Els of 1.5or higher* there are 12 observed cases where9.14 are expected (Table 3A). In the subgroup of the above workers with 5 years or more exposure* there are 11 observed cases and 7.47 expected. Respiratory cancer shows a slight excess in the total group* and a similar pattern for different exposure categories* with 13 observed versus 10.28 expected when the El is 1.5 or higher, .and 12 observed versus 8.50 expected when* in addition* the duration of exposure is 5 years or more. Malignant neoplasms of other and unspecified sites show an excess in the total group, and an increase with both level and duration of exposure (Tables 3A and 3B). The relationship with exposure is more pronounced, since those with exposures of less than 5 years have fewer cases than expected. The lymphosarcomas, although occurring at about the expected rate when the whole group is considered, are concentrated almost entirely in the high exposure long duration group. In that category there are 4 cases observed and 1.84 expected. The Tabershaw/Cooper Stuffy is based on an examination of 328 death certificates. The authors acknowledge three areas where bias might have entered: (a) choice of the U. S. male population as the 36 RSV 0019141 standard, (b) absence of 15% of the study population (untrac eable), and (c) discovery, as the study ended, of a group of 1500 workers whose exposures occurred up to 35 years ago and who are not included in the study group. Since the latency period fo r angiosarcoma of the liver is averaging 18 years at least, it would appear desirable to examine the data for these 1500 workers. In addition to the Tabershaw/Cooper study several other epidemio logical studies presented during the recent OSHA hearings suggest the possibility' of a multiple cancer risk. Table 4 summarizes many of the published and unpublished toxi cological and epidemiological studies of human and animal exposures to VC. A list of the references cited in Table 4 completes this Appendix. 37 RSV 0019142 VJtS'V''- Occupation 1. VC Honour Production 2. PVC Polymerisation -- 3. PVC Compounder*, Fabricators, Etc. Country Sweden United State* United States United States United States United States United States United States United States United States United States United States United States United States W. Germany W. Germany Crest Britain Norway Sweden Csechoslovakla Csechoalovakla United Stataa United State* Crest Britain Table 1 OCCUPATIONAL CASES OF LIVER AHCIOSAKCOHA Caaa 1 BIRTH DATE 1st VC/PVC Diagnosis Age Work of Angloear- at coma Dlacnoele 01 00-00*11 00-00-45 00-00-72 61 01 00-00-22 12-09-48 03-00-71 49 02 00-00-34 11-15-55 05-00-70 36 03 00-00-15 11-28-45 12-00-73 59 04 00-00-24 07-06-52 08-00-67 43 05 00-00-12 06-19-44 04-00-64 52 06 00-00-29 01-17-62 02-00-74 45 07 03-03-22 08-00-44 00-00-68 45 08 05-06-20 10-07-46 08-00-61 41 09 00-00-31 05-28-45 03-01-74 43 10 09-16-13 06-00-51 05-00-68 55 11 05-27-09 10-14-46 03-00-70 61 12 11-17-18 09-13-49 05-00-69 50 13 12-01-21 08-19-44 05-00-74 S3 01 07-26-31 10-14-57 00-00-71 40 02 06-04-30 10-01-57 00-00-69 39 01 00-00-01 00-00-46 12-00-72 71 01 12-23-15 03-00-50 12-20-71 56 02 00-00-27 00-00-51 00-00-70 43 01 02 14 11-04-27 11-11-51 00-00.64 41 IS 00-00-25 00-00-00 07-00-72 47 02 n<)-09-14 Aft-rtn-Afi 02-00-70 55 Yre. let Total Tra. VO/PVC Work VC/PVC To Dlagnoala Exposure Data Death 27 23 00-00-72 22 14 28 IS 20 > 12 24 15 29 17 23 20 30 14 11 26 22 19 16 13 29 15 18 12 18 15 17 17 1 23 15 30 14 11 20 21 18 03-03-71 09-28-71 12-19-73 01-07-68 04-09-64 Alive 03-23-69 08-29-81 Alive 05-10-61 03-18-70 05-02-69 07-04-74 12-14-71 01-23-69 12-00-72 01-04-72 00-00-70 17 4 00 00 24 11 03-27-69 02-15-73 12-00-70 A. Other VC Exposure U. Germany Notai '00' Indicate! unknown data UJ 43 SOURCEl NIOSH 14 ' , t i * 1 t i i RSV 0019143 RSV 0019144 Table 2 CASES OF HEPATIC AHC1DSARCOHA, COHNRCTICUT, 1935-1973 Caaa NCI No. Aee Sex Dlagnoale Data of Original Data of Dlaenoala Death Kadlcal Hlatorv Occupation Pleca of Kaaldanca 1 73 H Hepatic 11-25-67 12-3-67 2 month# hlatory of diarrhea, , anorexia, and Angiosarcoma 20 lb tl|ht loaa. Intermittent abdoaloal pain. Non-tender, firm eplgaatrle mi*. Died after 9 day* with epontaneoua ruptured liver leading to ehock. Paat hlatory of alcohol In take. Fireman 1917-62 Aluminum worker 1942-66 Corset cutter 1965-61 Retired 1961-67 Bridgeport entire life 2 47 H Alcoholic 1-15-73 2-15-73 Initial aymptoma RUQ abdominal pain with Accountant - Vinyl Co. Bridgeport - Clrthoala vomiting. Cecal volvulua found,' Rx cacopaxy, 1963-73 1956-73 over next 6 weak# pain continued with week- Accountant - Plietlc Prevloualy many Portal neae. RUQ tendarnaaa with 2 FB liver. Dlagnoaed Belt Co., 1956-63 locatlona Plbroala by needla blopay on 1-15-73. Daterlorated elowly Prevloualy accountant- until death 31 'daya later. other atataa 3 Hepatic 12-19-73 1-22-74 Admitted 12-2-73 with ahort hlatoty of RUQ Houeewife 9fratford Angtoaarcoma abdominal pain radiating to 11 (boulder. Had Reeteurant cook 3$ yra 35 yeere RUQ tendernese. Open liver blopay 12-19-73 ahowed latga tumor. Mo teaectlon. Daterlorated until death 34 deye later. 4 Hepatic 3-12-50 3-19-50 1 month hlatory of anorexia with abdominal pain Houaawifa Angloaarcoma and back pain. Firm eplgaatrle maaa. Died 6 daye altar adulation with carclnomatoal* and pulmonary emboli. Windsor lock# 5 Hepatic 5-4-73 Admitted for abdominal pain end jaundice Fisherman and carpen Puerto Rico Angloaarcoma 3-27-73. 4 PB liver, Dlecharged. Readmitted ter before 1959 Flat 1923-59 4-29-73 with abd dlatenalon. general edema. terer 1959-60. Unem New Totk City Icterus, fevar, shaking chllla. Rapid down ployed 1960-73. 1959-73 hill ceuraa with death due to ranal and hepa Bridgeport tic failure. Paat hlatoty of alcohol Intake. 1973 f . < ~ rI - i i i RSV 0019145 S- Table 3A OtSUVtD MATKS/KXROtD Dt.VIHS AMO STANOAAD1ZID WtTALITY RATIOS IM VDITL CICOtIH WOU&IS, BT BST1HATBD LBVIL OF KZFOSVU CawAa of daatb with I.C.D.+ amber Cl <1. 3 oba/eap SMt1 1*1. 3 obe/eip SM' All eaaaaa 166/270.33 70** 137/193.66 60** Tuberculoele (001-019) Tubarculaala of reaplratery ayila (001-006) Malignant neoptoene (1A0-2O3) Maltanant nooploene, buccal cavity and pharynx (140-146) Malignant oeoplaene, dlgeetlve ergaoa and perltoneun (130-139) Malignant oeoplaene, reaplratery ayeten (140-164) Malignant anoplaana, genital organa (170-179) Malignant aeoptaena, urinary organa (160*161) Malignant meoplaeea, other and unepeclfled altaa (190-199) Louhaala and alauhmla (204) tynphoaarcoM, lynphatlc and hoMtopoletlc tlaiuao (200-203, >03) Blabatoa nollltna (260) Major cardlovaacnlar and ranal dlaoaaoo (330-334, 400-466, 392-394) Vaacnlor laalona affactlng <11 (330-334) hematic favor 6 chronic rhomatlc heart dta. (400-402, 410-416) Roarhematlc endocardttlo (421, 422) Myperconalve heart dlaeaae (440-443) Other hypertanalva dleaaan (444-447) Chronic 6 unepeclfled nephrltla 6 ranal acleroale (392-394) Influansa and pnemoole (460-493) Ulcer of atonach end duodanun (340, 341) Appandlcltla (330-333) Bernta end lnteatinal obatrwctlon (360, 361, 370) Caecrltle, dundenltla, entarltla and collcte (343, 371, 372) Clrrhoele of liver (361) Eyperplaala of proatate (610) Synpteou, aenlllty and lll-deflaed coodlctona (760-793) All other dlaoaaae (realdual) Niter vehicle accident# (610-633) Other accldeata (600-602, 640-962) Suicide (963, 970-979) onlclde (964. 960-963) 0/3.36 0/3.16 37/44.26 3/1.62 7/12.30 11/13.36 2/2.30 1/2.07 9/6.37 1/2.16 1/3.46 3/3.63 64/120.11 7/14.42 3/3.96 46/76.94 0/4.20 1/3.46 1/1.32 0/2.30 3/3.60 1/3.21 0/0.39 0/0.66 0/0.76 2/6.90 0/0.23 0/4.22 14/21.90 6/19.06 11/17.63 9/9.73 0/6.96 0 0 90 330 60* 66 93 31 146 49 31 146 73** 32** 60 92 0 19 70 0 92 46 0 0 0 23 0 oA 66* 43** 64* 96 0 0/2.33 0/2.10 41/32.67 0/1.21 12/9.14 13/10.26 1/1.43 0/1.32 6/4.32 2/1.37 3/2.34 2/2.63 69/66.99 6/10,.06 2/2.63 31/36.03 1/2.69 2/3.66 2/1.07 0/1.77 0/4.13 1/1.60 0/0.27 1/0.63 1/0.33 1/6.64 0/0.14 1/3.09 7-/13.69 9/13.46 6/12.67 7/7.02 1/4.96 0 0 134 0 141 133 73 0 190 136 212 61 63* 64 73 93 36 36 201 0 0 66 0 171 196 16 0 34 41** 72 50** 107 21 Umber of vorhore pereoa-yeara 4032 43334 3037 32106 idjvatd for doethe with cmm unknown. t 31 lml. **SlBiflcaat At It level. +Ioten>aelonal Clarification of Dloeaaea SOURCE! Tabnrohav Cboper Aaaoclataa, Inc., Bpldealolcmlcal Study of Vinyl Chlorlda Workers. final Raport 1. :i 1 ! S'! i * ti f i i i RSV 0019146 Table 38 oinmD WATHS/Kxneite nun and staxd.*dubd mutamty iatios w vihtl cklqoik wokkbks IT BUIATIOM Of ONSKD IKFLOYMHT Cause of 4tb wick l.C.D. ttabir AU eeueee Tuberculosis (001-019) tuberculosis of mflmoi; ijna (001-008) Hallfoaec neoplasms (140-205) Malignant nsoplasns, buccal cavity and pharynx (140-148) MallgnaaC neoptasaa, digestive organa and perltooeun (150-1S9) Ha 11(mbC Mylini, respiratory syttaa (160-164) Hallgaeot Meylaiai, genital organa (DO-179) Malignant aeoplesas, urinary organa (180-111) Malignant oeeplaene, other and unspecified altea (190-199) Laukauta and alaukenla (104) IgraffenircMit lynphatlc and hematopoietic tlaauea (100-203, 203) Olabotoa uellltwe (240) Major cardlovaacular and renal dlaaeaoa (330-334, 400-448, 392-394) Vaaewlar laaleoa affecting Oil (330-334) Ihmatlc fever A cbroele rbeoMtlc heart dia. (400-402, 410-414) ArtetlMclerotlc heart dlaaaae (420) gonrbewnatlc endocarditis (421, 422) Qrpcrunaive heart dlaeaaa (440-443) Other hypertensive disease (444-447) Chronic A unspecified nephritis A renal sclerosis (392-394) Influents and pnawonla (400-493) Qlcer of stonach and duodonuss (340,341) Appendicitis (530-333) Betels and intestinal obstruction (340, 341, 370) Gastritis, duodenitis, enteritis and colitis (343, 371, 372) Cirrhosis of liver (Sll) Hyperplasia of proatete (410) ' Synptona, senility end lll-deflned condtctone (790-793) All ether diseases (residual) Motor vehicle Occidents (810-833) Other accidents (800-802, 840-942) Suicide (943, 9)0-979) unlclda (944, 980-983) Bunker of workers fntsoo-ysara l8' adjusted Ter deaths with caul* unknown. *91gnlflesnt at 51 level. **SignLflcant at 11 level. <40 uonths obs/exp SMI1 94/140.33 4?** 0/2.23 0/2.07 13/19.94 4/0.70 2/3.24 3/3.32 0/0.99 0/0.93 2/3.40 1/1.23 1/2.01 2/1.80 28/31.43 4/5.97 2/2.39 21/32.34 0/1.74 1/2.42 0/0.79 0/1.33 3/2.93 1/1.07 0/0.24 0/0.42 I/O.40 1/4.49 0/0.07 1/2.28 4/11.97 10/14.14 7/12.94 4/4.34 1/3.80 0 0 79 498 44 43 0 0 71 96 60 134 63** 81 101 78* 0 49 0 0 123 112 0 0 301 24 O 31 40 73 AS* 114 20 2935 34201 k(0 Booths obs/eap sm1 231/129.30 76** 0/3.53 0/1.33 43/37.61 1/2.16 17/16.34 21/19.31 3/2.74 1/2.79 13/8.23 2/2.33 S/4.07 5/4.34 123/157.39 9/18.71 3/4.33 . 98/105.39' 1/3.33 2/7.01 3/1.82 0/2.76 2/7.09 1/2.78 0/0.43 1/1.10 0/0.41 2/11.18 0/0.33 0/3.09 16/26.34 7/16.43 10/17.82 10/10.28 0/4.20 0 0 114 47 106 116 111 37 187 1 126 113 81** 49** 61 96 20 30 170 0 29 37 0 93 0 19 0 0 43* 43** 58* too 0 4134 43240 ...... / ;t *, V4 ri I 1 \ i i i \f r\\ ' i1 i. |, i i i i i tti i `\ otsnviD K A ru /e x n c m deaths ;md STAUftutDizeo n a t a l it y iatios m yuotl c k lo iik w a n ts WITH EXPOsuit INDK33 SILOW 1 .5 , IT BUtATIOM OF KXFOSCD CNPUrYMUrr # *V xnoe-^o'*^eeeee*><n'i m m S'*!;98SSnO"Ben5*^n^**^ ><i^aM-MwoeeMnAnniMnAaineaN>aK*^*NNan##.i ti oo-- n n, wMOo^OffaOCCMOOOni t tVft >5a n 1 ek aoaoeeeween<0Mn^#e li S* s; 58 il S c; * * "E. r ---RS1 S"S B. B SOM -- a * 8SSS &MQ "4 > 9 V t> Mla la b i X Q| U M 8S e 4* nvr#t -ae a* AeauCN>Nw* 44nn4i>4. 4A SI 1 .-*sjj4 'w81W S ^3**5b5^S s ?,,#.: m i b o i t t v A- - . ii M9'S < J srsI2!2illi:-: a* i i3 I * * * s* 1 -i Sj 4Ui1 5^b> :^ Sr# aSO *^Ma**leOi AX*I J A <* *1 Q 9 9 40 ^ > ^m 9K 8 ISiS -""I 42 RSV 0019147 RSV 0019148 60C61 nil 0 91*1/0 M 19*9/9 91 96*1/1 I C9*l/l ,11 99*11/9 0 oc*i/o 0 Cl*0/0 01 IO'C/1 0 19*0/0 toe 69*0/1 0 61*0/0 0 M`I/0 0 crc/o 0 CC't/O CM 10*0/1 99 orc/i 9* ic*i/i 96 69'19/99i 001 90*1/1 Of 61*9/9 06 9*01/19 OOI 90'1/t CIC 99*1/9 06 CI*I/1 901 IfC/1 0 91*1/0 Cl 19*1/1 991 Of*9/11 161 19*4/11 0 66*0/0 191 ll*9I/9C 0 99*1/0 0 1C1/0 1* 19*191/611 |MS dt/qt Of 9fl 101 991 0 9f 1 0 0 906 0 0 19C 0 0 .0 0 0 *19 0 SCI M 0 11 991 101 0 0 11 91 0 96 0 0 61 91911 0911 iri/i 09'1/C Cl `9/9 fO'9/1 10*9/0 09*0/1 10*0/0 96*1/0 91*0/1 91*0/0 90*0/0 fC'0/1 66*0/0 9f *0/0 11*0/0 91*0/0 16*0/0 19*01/6 19*0/0 19*1/1 9f*91/1 19*0/0 11*0/1 99*0/1 91*1/1 91*0/0 61*0/0 61*1/1 19'1/t CI'O/O 16*9/6 11*0/0 91*0/0 C6'19/9C OLn aq)HM g|> *1***1 \\ ) ju.aijjuljs,, *l*A*l IC 1* JU*3|Jlulls, hmu|m ttfita tm jj p*)n(pt ^wSj JO 4qmM (696-096 *996) |>!ai4| (616-016 *C96) Plt"S (196-099 *109-009) aimpiaaa imo (sea-019) *impiaat (linillii) 00M IJV (661-091) p*0|j#p.|11 pur 63111* 'mojdals (019) *1*9*049 JO *|**|9j*91h (196) 1*M1 J *|*ot|i413 <116 `116 *696) *IJIo pm map **Ut*pop ,*|j|Jio (016 `196 `096) m|iaiJi*q* |*uu**)ai put |iuH (C66-06S) W*lpmdd (196 *096) mpmp put Hatmj* J* J*lft ((69-099) *1m*u9 pm *su*n|ju| (966-166) *|*04i* i*o*J * *lm|4*u p|jiadt<ui 9 aioojio (199*999) IP *lil4*9ii| a*|io (C99*099) Ip lM *1*J4*41h (119 *119) n!p43p jnwimi (019) IP UHM aTi4*ia*|4ii9 (919-019 *109-009) **1P ia*H fitmti|j ia*iq> 9 *! afimotn (9CC-0CC) SO |ia*jj0 1*I 4*n* (966-166 '099-009 *9CC-0CC> ip ! pm J*in**o|pj aaf| (091) "mi" 1M?a (fOl *01-001) 11 a||tdoj*mq pm atl*Hd*l| * Noaitmqdali (901) I9"l P* I"*1**1 (661-061) >!* pMjta*don pm i|i< 'niitton inulnui (611-011) >4 |ii|Ml 'mt|dota iaut||H (991*091) 1wiij|1ij 'iMtfdma )uu9||n (661-Ofl) M>w)|d pat niln (MimOlP '|4om amuSi|*M (091-091) Mla<|d pm 1)|M> |ijm| `tt|doan juaulijiw (601*091) midmu jnmlnM (OOO-IDO) laoitjodatj jo tjtoinajtqni (610-100) loinajqn* ttanta U9 4qana *0*9*! Ill* qimp jo nnQ iraucruMi oisojxi so hoiiron a `oitvno *o s*i .10 sskmi nnsun inn union miaows -uni* mi soixn xinvum aiziaiYaKvu an' shiv*j oiuun/aixvm tuusn ac iq*x y RSV 0019149 Table 4 SUMMARY OR TOXICOLOGICAL AMD EP1DEHIOLOCICAL STUDIES ON VIWTL CHLORIDE Authors Von Oettlngen (1955) Gabor Hacca-Radu Manta (1962) Chen. Abstract Lester Greenberg Adana (1963) Cabor Radu Prada Abmdaan J uano f Anca Valcskey (1964) Chen. Abacracc Crlgorescu Toba (1966) Chan. Abatraet Snaclaa Hunan Hunan Hunan Hunan Human Sex No. EXPOSURE Hta. P Dav. Dave Cone. ppn HUMAN DATA Total Does ppn-Pava Observations 12,000 10,000 25,000 Dengerou* Narcosis Produced eynptona of dlsslnaaa, dlaorlantatlon. haadacha and burning aanaatlon on aolao of fast. 82 Workers exposed to DDT, Bensana, Hexschlorocyclo- hexane, VC, PVC. Blood: Oecraasa In Catalans Increase In peroxidase, Indopitenoloxldase and gluthathlone Changes occurred during second year of work. M 3 Twice par day 0 0 1/5 slightly ditty P 3 for 3 days. 6,000 83.3 0/6 had any affaeta 5 nln. aeselooa 8,000 166.7 1/6 slightly dlasy > at 6 hours In- 12,000 250.0 2/6 definitely dlasy tervala 16.000 333.2 5/6 dlsty, nausea, blurred vision and heaving eynptona stopped after exposure 20,000 416.7 6/6 intoxicated, one with persistent headaches SOX laval of no affect la 1.3X 78 PVC Uorkera Decrease plasna albunle Increased l and B globulin Dectcaae In 1/8 foe sttin lipoproteins Daeraaaa In aerun cholinesterase Daeraaaa In pseudo eholinoataraaa Normal blood cataleee Normal serum pyruvic ecld Experimental: PVC Workers Control: Other clinically healthy people Hypothesis: VC+B20>chlorat + chloracetlc acid (1). Result*I (1) vaa Covad la SOX of expel. people, but In none of controle. Moat of flndinge vara tn people exposed 2-5 years, Xn thaae cases,((-globulin la hlgher,>lglobulio la lover then people with ao (1) In urine* tenacity to metabolize (1) decreased after 2 years. PethalotT Rone reported Rone reported Rone reported Hone reported RSV 0019150 Author* Harris Mm (107) Wilson McCormick Tatum Craach 0967) Species Human Human Bareeta Stewart Tfuechler (1909) Human Kudrysutseva Human (1970) Abstract Viola (1970) Unpublished Human i exposure Hr*. Total f*r Cone. Doae Sex No. py. Dav* Pf ppm-Devs 2- - HUMAM DATA Observations Pathology One worker had knee cep end toe* involved is the acro-oatoolyala. Ocher worker only hand*. H 31 _ _ Ho caaas of acro-ostaolyaia diagnosed in 1000 Individuals who handled finished resin or used for plastic product production 31/3000 (31) workmen associated 1C polywerlsetlon founds to have aerooeteolyals. Aga rang* of affected workora 26-47. Incubetion period greater than 12 months of polycloaning experience. 22/31 Acro-oateolyala aaoocletod with teyneud'e luapteaa. H 13 7.S 1 SO IS.6 2S0 78.1 500 150.2 Breath decay curves, 0 to 20 bra. after exposure were measured. Level in breath at 4 hr*, leaf It. Ho advereo effecte noted. About the same eat of breath deeay corvee following occupational exposure. Hone Reported H SO _ _ P *3 __ 1. Changes In ECO* rhythm, conductance, polarisation. Mom Reported. 2. Increase in ayetollc index. 1 S IS soo* 8 e 1095 1825 - *In several other faetori** Acro-oateolyeie ayaptome, Raynaud's syndrome, aversion to fata, enlarged liver Raynaud's syndroms Enlarged liver, minor liver Insufficiency, 13/500 had acro-oateolyala. Olefactory threehold 1* 0.0 to IX. Acute nervous eymptoma become evident when It 1* easily perceptible. Aerometryi (VC) on factory filter* at air discharge tine: 2.000 ppa (VC) at point of worker entry* 2,000 ppm In plants where aero6*t*oW*<a occurred-150 ppa (wax) in plant with no dlaaaae (VC) on p.engwey and ether petto of plant* 10 to IS ppa. HUMAN DATA Aurhora Snaciea 8 No, Hr*. per Par Total Cone. Doae Dave ppm ppn-Pava Obaervatlona Patholoav Dioman Oook Waterhouae Kagnueen Dltchack (1971) Hul m Dodaon Dloaan Uhltehouae Naar Magnueon (1971) Buau M 5011 21,510 Nii-jura Experience 1-23 Hontha Condltlone enunciated with hand cleaning of 25 caaaa of acro-ooteolyale. polynerltera. 16 other lndlvlduala gueetlonabla There appeared to be correlation batwaan reactor degaeelng tine and acro-ooteolyale. Acro-oateolyaia appeera to be ayatealc rather then local dlaeaaa. Raynaud'a phenomenon wea atatlo- tlcally related to acro-eateoly- aie. All patlente had worked ea PTC reactor-veeeel Raynaud'a phenomenon antaceded cleenere. ooteolytlc leelona In all four Hag. Ca and t balance In one aubjaet. aubjacta. Pletbpanographlc abnornalltiea ware preaent In 19p acfnClacana correlated with 3 aubjacta. radlogrbphlc lealona. Eaophageal motility within normal linlta. Catachblanlne, -Rydronylodole Aeetle Acid No liver enlargement or hypothyroldien. excretion normal. Additional aneller abnornalltiea All other nuneroua clinical laboratory lnveatlgatlono found la ulnar atyloid, oacalela negative. and patella. Kramer Mutchler (1971) Hunan K 96 -Up to 25 yearn Experience Performed atatlatlcal correlation between eevaral clinical neaeuramante and total doae and timeweighted average TC concentration. None reported, 2 liver function indlcea ehov a poeltlve correlation with total doae (abnormally high). a) Icterue index b) brooeulphalein 3 other indlcea are doae-releted but era not outalde normal llnltet a) nyatolic and dlaetollc blood JJ preaaure. b) hemoglobin negative correlation. <CO c) beta-protein. O O CO Ol RSV 0019152 Authora _ Snarias Meyarson Halar (1971) Abstract Hunan Sax No. -1 Karkowltx McDonald Pethlere Kersoar (1972) Abstract Hunan Langs Juba Spain Veltnan (1973) Hunan - 13 W1IHAH DATA EXPOSURE Cone. Total Dosa Hra/Dav Pavs non. pgn-dsrs ORSERVATIOMS PATHOLOGY Acrooataolyala Rad unlqua papular skin laalons which bars bsan described only lo PVC workers DascTlban acrooataolyala symptoms. Insldanca Is <31 anong workara Agea 29-32 Raactor claanara HI yra. anploynant Latent period! 1>-JJ| yaa^a In 11 patients; 7 and 11 years lo other 2 patients. Acro-oataolyals symptoms. Peripheral vassal stenosis. Thronbopeny (low count) ta the first objectlvs synpton described In all pstlanta; lung fibrosis orgloat log In portal ijritm, large ipltu, lnpalrad lung functloa| 101 nortallty. This la the first objective ajnaptoa described. Il 1 i I i i t ft ri i i s Mai m*r HUMAN DATA Author* Marotallar Laibach Millar Juh* Longa Pohaar Valtaan (1*73) Soactaa Hunan Sea No. 120 Bra. parDay CXF0SURB Cone. Dava oon Total Dot* ppn-Davr Obaarvatlona IS to 21 yaara. 20 PVC workara wara atudtad out of 65 with auapactad akin problca*. 30 to 56 yaara old. Fatholoav Llvar enlarged In 13/20. Palo to It. upper abdomen to 2/20. Hyperlipidemia boo boon diagnooad to 1967 oftor 6 yoara to 1/20. Jaundice hlitair to 1955 Mart tapoouro to 1966. Hoar dpafiaaettoo woo dlagaooed, oo alcobollpm. Spleanomagaly is 7/20. Total bilirubin aroo 1 mg/100 (which ta upper normal llott) In 9/20. Brombulphalaln toot woo abaoraal in 19/20 (>5I ratootlon attar 65 nloutaa). flCOT waa >12 nU/ol In 17/20. SOFT woo alaratad (15-30) in 16/20. Alkaline pboophataao woo >60 uU/nl tn 2/20 Ryporhrombocytanla ((150s 103 /a*3) woo found 19/20eC100X103/*3) lnl2/2> Acro~o*tyeolyela van aaao tn 6/20. Verlcoae valna of ooophagua tn 3/20 Liver hlatologyi Collagen tranaforatlon of walla of alouaolda to 3/20. Focal activation of Kupfer calla In 19/20. focal fatty Infiltration tn 14/20. Ftbroal* of oapta and eapaula intralobular and portal apocao'lo 17/20. IS additional blood paranoiac* war* oornal. 9 lMunologlcol taota war* dona once, not repeated* I RSV 0019153 1 Table 4 SUMMARY OP TOX1COLOCICAL AHO EPIDEMIOLOCICAL STUDIES ON VINYL CHLORIDE AM1MAL DATA Author! ANIMALS Sttclti Sax No Hn/liv Dava EXPOSURE Cone. Total Dose on on-dare Observations Von Oettingen (1955) (Review Article) Cat* Cata Cat* KD KD ND ND ND <4 ND ND <4 ND 1 1 Cata Cata ND ND Cata ND Rabbits ND Doga Mica Doga ND ND ND <4 ND 4 ND ND HD l min. ND 1 alii. ND <4 1 1 NO 1 1 1 ND ND VC la praptlp excreted bp lungs; 622 la eliminated after Inhalation stops 100,000 to <1,200 130,000 160,000 <30,000 200,000 <33,000 250,000 to<40,000 to 300,000 50,000 ND ND 170,000 116 Blood VC concentration reaches 15-17 a|t This coneeatretlon ceueea list lotra-aurlcular pressure reduction as 13,000 ppn dlchlotoethplene. 30,000 ppn ether Cardiac inauffldsnep Evan this doas not product conplats cardiac failure Blood levels are 40 ngX at tlaa of cardiac arrest, 27-30 agl at tine of raapiratorp arraat Thlo la tha narcotic concentration *1 86,000 to 60 to 85 This la the narcotic concentration 123,000 100,000 <12,000 Cardiac irregularities, ECC abnormalities Doga ND Doga KD Mica ND C. Pig# ND ND 3 7 10,000 475 No najor change in liver or kidnap for several vka ND 3 7 200,000 9,S00 Harked aellvatlon, vomiting, raapiratorp arraat for avaral vka ND 10 Bln. 1 245,000 to 1,700 to This la the lethal ranga for 10 nlnutaa axpoaura 295,000 2,040 ND short tlaa 1 200.000 eo ND 400,000 All ktllad Patholocv .1 ;l , . . ;, \ l > I 1 ' l ' I RSV 0019154 k \ t Von Oittln|tn (1955) Review Article Continued ANIMALS Specie# See No. Hre/dav G. PlR# m> ND 0.5-1 C. PlR# ND ND 0.5-1 C, Pile HD ND 0.5-1 Dnve 1 1 AHIHAL DATA EXPOSURE Cone. Total Doee on ppm-daye Observation# 100.000 5.000 ND 2.000 to 4.000 100 to 200 Dangerous to life Higher concentration# than thl# cauae never# lung edema and hyperemia of liver end kidney Order of tonicity lot carbon tetrachloride a chloroforn <VCethyl chloride Petholoev Haetromatteo Flaher Chrlatle Dentiger (1969) Pleher Chrlatle Deoslgar (1960) Nice ND 5 0.5 1 Rata C. Plga ND 5 ND 5 0.5 0.5 1 1 Nunber of anlaala and duration of azpoaura nan# aa above 100.000 2.0B0 200,000 4,160 Nunber of enlnal# and duration 300,000 6,250 Torkaleon (1) Open Rowe (1961) Nunber of anlnals and duration of azpoaura aene aa above Rata H 10 7 (5d/wk) P 10 7 (4.SKo) 400,000 8,330 500 14,000 Sequential affecta verat 1. irritation, 2. lncraaaed notor activity, 3. twitching, 4. tramor, Incoordination, 5. vnconecioua, 6. deep narcoala. All eninala recovered In 5 nlnutea. (flees Light lung engorgnent, kidney swelling! Rote end Q. Ptgas aane lung picture, 1/3 nice died after 30 nlnutea, aane aynptona aa above but appeared aooner. Guinea plga uneteedy ter 20 nln. after azpoaura. 5/5 nice and 5/5 rata died! 1/5 guinea piga died; 4/5 guinea plga recovered In 25 nlmitaa. Growth and groan appearance ware norual. Livar/bddy weight ratio and abaoluta liver weight larger than control In naleo. Llver/body weight and abaoluta liver weight not larger than control in female# Blood 8GOT, SCPT, SUN, alkallnn phoaphetnen ware normal. Lung engorgement, no edema In ell npeciee. One rat had fatty liver Liver end kidney waa eoogeeted, tracheal epithelium damaged Same aymptome, more aavara Central lobular liver degeneration. Eldnay tubular damage. RSV 0019155 RSV 0019156 AH1HAL DATA Author* ANIMALS Soeclee______ Sex EXPOSURE Cone. Total Doaa Ho. Hr*/day Day*_________ ppm ppm-dve Observations Torkeleon Oyeo Howe (1961) continued K57 FS7 (Sd/wk) (4.Sno) 0 0 Control anlnal* (2a) Rate H 12 7 200 All iroupa vara normal In appearance, r 12 7 13S mortality and growth. C. Figs M 10 7 expoaurao 200 Hematology (heaoglobln, hematocrit, F 87 In 204 call*) waa oormal. Rabbits M 37 days 200 Liver function teata (SUB, SCOT, SCPT, F 37 (6H alkaline phoaphateae) vera normal. u Doga H 17 month*) 200 8,030 All organ/body weight ratio normal F 17 to except M and F rata, where llver/body Hatched controls. 8,400 weight ratio waa Ineraeead. both exposed and nouexposed Sd/vk roup* Patholotv Croaa pathology waa normal. Microscopic pa thology waa nor mal In all epeelaa except liver of H and F rabbltet Central lobular granular degenera tion and necroale. (2b) Sana protocol* 100 4,000 to 4,200 All anlmela were normal In appearance, nortallty and growth. Crose end micro Hematology (henoglobln, hematocrit, cell*) scopic appaocaneo wee normal. nf disuse were Liver function teete (SUN, SCOT, SCPT, elka- normel. line phoepheteee) were normel. Llver/body weight redo of M end F rate ware larger then controls. t: i *I tl ' f IV 1 i: . . I: I it i :' 'I *i i ' Ii ANIMALS ANIMAL DATA exposure Authors Torkalaon Oyan Row# <1961) eontlnutd (2c) O) * Sotclu Sex Ho. Hre/day Rata H54 MS2 H51 M 5 0.4 M54 HS2 MS 1 M 5 0.5 Rata M 24 7 F 24 7 0. Plge M 12 7 r 12 J Rabblta H 1 7 r37 Doga M17 F17 Matched control#. axpoaad and wttipeiid groups. Cone. Total Does days ___ EBB___ BBS-lUYf__________________ Obeervationa Sd/wk for 6.5 months aa above 200 4,600 200 2,300 200 1,150 200 S75 100 2,300 100 1,150 100 575 100 265 Liver/body/ weight ratio largar than control#, not atatlatlcally algnlfl- cant. " " " " " " " ' " Llver/body weight ratio aaae aa controla " MM H Llver/body weight ratio higher than eontrola, not atatlatlcally algnlfl- cant. " Normal in all reapecta All paraaatara normal In all apedae. 130 expoaure In 199 daya Leater Sherman ND 2 0-2 1 Craanbarg rata ND 2 0-2 1 Adana (1) ND 2 0-3 1 (1963) ND 2 0-2 1 ND 1 5 min. 1 42 mil. 1 ND 1 2 1 50,000 60,000 70,000 100,000 150,000 150,000 0-4,160 0-5,000 0-5.930 0-9,330 552 4,380 12,500 Moderate Intoxication, righting reflex loot. Mara tntenee intoxication, righting reflex preaent. Mora latenee intoxication, righting reflex loat. Cornaal reflex disappear^ no greee pathology. Deep aneathaala. Raaplratory failure of aaae animal. Deep aoaathaala, complete recovery after expoeure. No pitholotf obaarved. RSV 0019157 EXPOSURE Hr* Per Cone. Sax No. Dav Total Does AH1HAL DATA Obeervatlone Lceter (2) Craanbarg Mama (1963) Coat'd Sherman rata M T 98 98 2 than 13 100,000 Variable 80,000 Same exposure* aa above. Aftar animal deaths, replacements wars made In chambers. Two sale* survived all 15 expo sures. Remaining animals and raplaeamenta survived an average of eight exposures On* died after two exposure* at 100,000 and twelve at 60,000. One died aftar two exposures at 100,000 and tvelva at 80,000. SlxMln# survived all fiftaan exposures. Fatholoav N 9 0 Control anlmala t 98 0 Control animal* Growth itorftd 4ut1i| apoiurtt end ruiacd at normal rata aftar apoiuru. External appaarane* normal. Livar color, appearance, consistency, degree of congestion Lungs had focal pnsumosia which healed after two weeks of rseof sry froa exposure. One-third of enlmals'ihad parasitic cysta in waa aana aa control*. liver. Livar pathology same aa controls, hut more variation In amount of fatty infiltration. Spleen had advanced lymphocy tic hyperplasia. Rldoay pathology aana as con (!) Sherman M rata F IS 8 Waya/20,000 IS 8 weak 20,000 434,000 434,000 1/30 dlsd. trols. All organa had aornal gross ap for 3 months External appaaranea of all animals normal. pearance . Liver larger, spleen smaller than controls, Whit# blood call* lower* lymphocytes higher, Liver parasitic cysts In all animals. Liver fat normal Ro neutrophils lower chan control*. abnormal histology, Congaatloa Body weight sod hemoglobin war* earn* e* control*. and availing greater la livar M 13 8 Sam* F 15 * Same 0 0 0 0 Control animals. 4/30 died. than controls. Congestion and swelling leas In kidney chan controls. Conges 3 tion and availing same In 3 spleen a* controls. Lester Mu (196)) (4) thinu H Tltl t H r EXPOSURE Br*. par Mo. Dav Cone. Dava AH 1 HAL DATA Total Doaa non-Dave Observation s6 s s1 56 19 50,000 317,000 Ho aortallty. On days 1-4, animals loat weight, shoved 19 50,000 317,000 neoorologlcel symptoms. On days 4-19, weight gain vaa nonal. Sara transaminase, hematocrit, and prothrombin tlaaa wara normal. Wilts and rad call counts vara lower than controls. lain all 5 nalaa had thin hair and scaly tellst famalaa and controls wars normal. Ljlver/body weight ratio waa higher than controls. Control animals. 19 0 0 Control animals. 19 0 0 Patholoav Cross organ appearance waa aana as controls. Liver pathology showed congested calls. Liver pareslcle cysts assn In all animals. 'l RSV 0019159 tr Kuebler (1964) Abatract ANIMAL DATA |tn Nfli Hr*. per Cone. Dave Total Doae Observations Rata Klee C. Plga Klca NO ND ND ND HD 2 100 9,000 41,600 Mo effect at 5,000 and 150,000 ppn. ND 2 100 19,000 125,000 At 50,000, anlaale were hyperactive, but ND 2 100 50,000 416,000 returned to normal after expoaure. HD 0.9 Minutes Distance ND Anlaale sprayed with ahellac-hased 20-25ca. heir spray No hlatologlcal damage Mo change In lung htstelogy Vasin Flokhova (1966a) Abetraet Vasin Flokhova (1961b) Abstract Vaaln Flokhova (1969a) Abatract Rabbits ND ND "chronic" 3,500 3,900 ND Rabblta ND ND 4 Chinchills rabblta * ND 04 167 3,900 (5.5 to oe.; 3,900 ND ISO 0 to 12 200 ' ta 300 Brain electrical activity changaat Appearance of beta wavea (80 Marts) in anterior and peaterlor hypothalamus along with circulatory changes. Decreased heart rate, srrhythnla Altered fwdves In BBC fro* posterior hypothele Decreased BCG voltage sue. Potentials (ros Decreased duration of ayetole 'i anterior end posterior Reduced blood flow, increased arterial pressure. hypothalamusincreased by 16-301 and 70-851 respectively. After 20 days, blood edreaallna roee froa 3.5 A4*l to 6.1S>tqo2; at 40 and More daya, It waa 6.6 Aqml. Foaterlor hypothal anus alsctrlcal activity also changed, Thle is tha direct cauaa of hypertension. Vasin Flokhova Rats (1969b) Abstract ND ND ISO (5 months) Disrupted cardiac work rhytha. Bradycardia end inhjtlaU> Mueid relative duration of 1-11 and T-II Intervale. Kalatlva duration ol QRS complex did not change. After 19 day* recovery! cardiac activity rhythm returned to normal, but tha duration of the aound Interval remained below initial levele for another 19 days. Therefore, mx. permissible VC concentration la algnlflcantly lean than .03mg/l (12ppm). ' j& v I ;V.- iil. \ ! h. fb / i 5' e t , RSV 0019160 p j EXPOSURE Hra. par Sts nt Dov Dan Cone. ooa AMIHAL DATA Total Doaa oa-nava Obaarvatlana Clapp Rata Uya Young ((69) Abatract ND ND " 1 Sub- ND Urlna contalna allylaarcapturlc acid Cutaneoua aod 3-hydroxypropylaareapturle acid. Thaaa coapounda arlaa by tha raaetlona of allyl coapounda with glutathlonaa. Viola Viator M (1970a) Kata M 2S 6 23 260 30,000 (Sdaya 0 par wk lor 12 aontha) 1.300xl03 Anlaala allghtly alaapy during axpoaura. Croaa bahavior datarloratad after 10 nontha. 13/50 dlad el eardlo-raaplratory coapllcaelooa. 2/50 dlad ol blaadlag In tha parltonaal cavity. No anation of akin tuaora. viola Rato (1970b) Viator 300 gn 90 1 1 Viola Blgottl Caputo (1971) Rata * K Viator M 26 6 260 5day/wfc 2S 1 260 Sday/vk 10,000 30,000 0 417 lSOOmlO3 0 Olatributlen el VC In tlaaua] Rad calla had auch aora VC than aarunhlgh variation VC la In urlna, but m)ot quantity la loot via lunge.'(VC) falla rapidly la llrat hour expired air, blood, urlna, and brain, llvar kidney. After 3 hra. no VC la nenourablo. rathoioav Hoat 1m1i had pathological lnvolvaant of bralo, llvar, kidnap thjroU, govern prollleratlon of cartilage aad booa abnormalltiea la mall netataraal koMi. Savara tlaaua daganaratloa la brain and llvar and thyroid. Connective tlaaua lnvadad mall attarlaa In faat. Salaried, prelifaratlng Kupftr (ilia in llvar. Moon obaervod. Controla abowed m turnra. Alnoot all taptl. anlmla developed akin aod lung tuaora. Vary law booa tuooia( whan aaan thay warn In all 1 axtranltlaa. (Sl-701 ol tuaora wara akin tuaora naar parotid and oubmalllary glanda. Frequeaeitet SKIN LUNGS BOMS 26/26 16/26 16/26 Lung tuaora warn glandular. Nov eartllaga and eubaequont oaolllcetlon la 6 entrmetlae. Bard aaaa Clrat aaan altar 10 aontha axpoaura. RSV 0019162 Author* Basel** Sex Wo, Basalaev Rabbits NO ND Vasin Rata Kochetkov HD HD (1972) Abstract EXPOSURE Hra. par Da? Data HD 6 noa. MO <110 to ISO days) AH1HA1 DATA Cone. Total Doac ppm_______ ppa-Dava 12-lb HD Obaarvationa ChanRaa io alactrlcal activity of hypothalaaus Byp*xadr*o*llaala< Cardio-vaacular function Inpslrad. Boo* raaorptlon and osteoporosis. Theory* All aynptons ar* caused by hypothalaws diafivctlan and aubssfusat hornons Inbalanc*. Patholoav ANIMAL DATA Author*AnlaalaEapoauraaObaervatlon*Patholony Ipteln Sar No. .lr*/Day Day* cone. PP Total dost ppa-day# Survivor* Total Llvar Angloaarcoaaa Zyabal Sarcoaaa HaphroBlaatoaai Maltoni 1974 Kata M 309 4 Spii|u* P 368 Sda/wk Dawlay 633 10,000 U060X10* 6,000 <633X10* 2,300 <265X10* 300 <52.9X10* 230 (26.5X10* 30 < 3.3X10* 00 0/69 0/72 0/74 0/67 1/67 3/64 1/68 27 21 21 16 11 0 0 6 11 9 7 2 0 0 Rata H 263 4 Spri|ji- r 280 Sda/wk Dawlay 280 10,000 6,000 2,300 500 250 50 0 466X10* 200X10* 167X10* 23X103 11.7X10* 2.3X10* 0 36/60 43/60 54/60 56/60 44/60 30/60 101/190 3 1 0 0 0 0 0 0 0 0 0 0 0 0 Hit* 5pr*guaDawlay H t 30 4 30 Sda/wk 135 30,000 775X10* 60/60 2 0 Data H 36 r 110 4 1 10,000 6,000 (day 12-18 of prog.) 11667 7000 20/30 28/30 0 0 offaprlni 10,000 6,000 11667 7000 30/34 (?> 1 (aubcutanaou* ansloaareoa*) 30/32 l (aubcutanaou* antloaareoaa) 13 5 2 3 0 0 0 3 1 0 0 0 0 0 2 3 3 6 3 5 0 0 0 0 0 0 0 0 0 0 ). ' 1 I' I I Ir ' RSV 0019163 t i i i /t 1 V.. *;, . fTSTJs ea I ^o ? I V JolmaZ S A> SSS ggS N MN Ot O mSO 6 O O sss * Oo n iI a 9 i u- wa * ib ol :j 59 ji SS RSV 0019164 REFERENCES Baretta, E.D., R. D. Stewart, and J.E. Mutchler. Monitoring Expo sures to Vinyl Chloride Vapor: Breath Analysis and Continuous Air Sampling. American Industrial Hygiene Association Journal. Volume 30. pp. 537-544. Basalaev. A.V., A.N. Vazin and A.G. Kochetkov. Pathogenesis of Changes Developing Due to Long-term Exposure to the Effect of Vinyl Chloride. GIG TR Prof Zabol 16 (2) : 24-27. 1972. Clapp. J.J.. C.M. Kaye, and L. Young. Metabolism of Alkyl Com pounds in the Rat. Biochem. Journal 114 (1). pp. 6-7. 1969. Dinman. B.D., W.A.. Cook. W.M. Whitehouse. H. J. Magnuson, and T. Ditcheck. Occupational Acroosteolysis: I. An Epidemiological Study. Archives of Environmental Health, Volume 22, pp. 61-73, January, 1971. Dodson, V. N., B.D. Dinman, W.M. Whitehouse, A.N.M. Nier, and H. J. Magnuson. Occupational Acroosteolysis: III. A Clinical Study. Archives of Environmental Health, Volume 22, pp. 83-91, January 1971. Gabor, S., M. Lecca-Radu. and I. Manta. Certain Biochemical Indexes of the Blood in Workers Exposed to Toxic Substances (Benzene, Chloroben zene, Vinyl Chloride). Prom. Toksikol. i Klinika Prof. Zabolevanii Khim. Etiol. Sb. 221-223. 1962. Gabor, S., M. Radu, N. Preda, S. Abrudean. L. Ivanof, Z. Anea, and C. Valaezkay. Inst. Hyg. Cluj., Romania. Bucharest 13 (5). 409-418. 1964. Grigorescu, I. and G. Tova. Vinyl Chloride; Industrial Toxicological As pects. Rev. Chim. 17(8): 499-501. 1966. Harris, D.K. and W.G. F. Adams. Acroosteolysis Occurring in Men En gaged in the Polymerization of Vinyl Chloride. Brit. Med. Journal, 5567, pp. 712-714. Ulus. 1967. Kramer, C.G., and J.E. Mutchler. The Correlation of Clinical and En vironmental Measurements for Workers Exposed to Vinyl Chloride. American Industrial Hygiene Association Journal, Volume 33(1): 19-30. 1971. Kudryavtseva, O.F. Characteristics of Electrocardiographic Changes in Patients with Vinyl Chloride Poisoning. GIG TR Prof Zabol I4(8):54-56. Kuebler, H. The Physiological Properties of Aerosol Propellants. Aero sol Age 9(4), 44,47-48, 50, 90-91. 1964. Lange, C.E., S. Juhe, G. Stein, and G. Veltm&n. Uber die Sogenannte Vinylchlorid-Krankheit. Dtsch. med. Wschr. 98, pp. 2034-2037. (Ger man) 1973. RSV 0019165 60 1* ... Lester, D., L.A. Greenberg* and W. R. Adams. Effects of Single and Repeated Exposures of Humans and Rats to Vinyl Chloride. Amer ican Industrial Hygiene Association Journal* pp. 265-275* May-June* 1963. Maltoni* C. Preliminary Report on the Carcinogenicity Bio-assays of Vinyl Chloride. Presented at OSHA Vinyl Chloride Pact Finding Hearing* February 15* 1974. Markowitz, S.S. * C.J. McDonald, W. Fethiere and M.S. Kerzner. Occupational Acroosteolysis. Arch Dermatol 106 (2):219-223. 1972. Marsteller, H. J. Chronic Toxic Liver Damage in Workers Engaged in PVC Production. Deutsche Medizinische Wochenschift 98 2311-2314. 1973. Mastromatteo, E., M. D. * A. M. Fisher, H. Christie, and H. Danziger. Acute Inhalation Toxicity of Vinyl Chloride to Laboratory Ani mals. American Industrial Hygiene Association Journal* Volume 21, No. 5, October* 1960. Meyerson, L. B. and G.C. Meier. Cutaneous Lesions in Acroosteoly sis. Arch Dermatol 106(2):224-227. 1972. Torkelson, T. R. * F. Oyen, and V.K. Rowe. The Toxicity of Vinyl Chloride as Determined by Repeated Exposure of Laboratory Animals. American Industrial Hygiene Association Journal, Volume 22, No. 5, pp. 354-361. 1961. Vazin, A. N. and E. I. Plokhova. Creation of an Experimental Model of "toxic angioneurosis" Developing from the Chronic Action of Vinyl Chloride Vapors on an Organism. GIGTRProf Zabol 12(7):47-49. 1968a. Vazin, A.N., E.I. Plokhova. Pathogenic Effect of Chronic Exposure to Vinyl Chloride on Rabbits. Farmakol Toksikol, 31(3):369-372. 1968b. Vazin, A.N., and E.I. Plokhova. Dynamic Changes in Epinephrine like Substances in Rabbit Blood Following Chronic Exposures to Vinyl Chloride fumes. GIG TR Prof Zabol 13(6>:46-47. 1969a. Vazin, A. N., E.I. Plokhova. Changes in the Cardiac Activity of Rats Chronically Exposed to Vinyl Chloride Vapors. Farmakol Toksikol, 32(2): 220-222. 1969b. Viola, P.L. Pathology of Vinyl Chloride. Medicina del Lavoro, Vol ume 61, No. 3 March, 1970. Translated from the Italian. 1970a. Viola, P.L. The Vinyl Chloride Disease, {unpublished translation) Sum mer, 1970. Viola, P. L., A. Bigotti, and A. Caputo. Oncogenic Response of Rat Skin, Lungs, and Bones to Vinyl Chloride. Cancer Research, Volume 31, pp. 516-522. RSV 0019166 61 Von Oettingen, W. F., M. D. The Halogenated Aliphatic, Olefinic, Cyclic, Aromatic, and Aliphatic-aromatic Hydrocarbons including the Halogenated Insecticides .Their Toxicity and Potential Dangers, Public Health Service Publication No. 414, U. S. Department of Health, Edu cation, and Welfare, Washington, D. C. 1955. Wilson, R.H., W. E. McCormick, C.F. Tatum, andJ.L. Creech. Occupational Acroosteolysis, Report of 31 Cases. The Journal of the American Medical Association, Volume 201. No. 8, pp. 577-581. 1967. r$V 0019167 62 APPENDIX VIII DISPOSAL OF PRODUCTS CONTAINING POLYVINYL CHLORIDE This discussion on disposal of PVC emphasizes incineration and landfilling, the only presently used large-scale methods for the disposal of solid wastes. There is also a limited discussion of resource recovery possibilities. Incineration The two areas of concern related to FVC incineration are incinerator air pollution and incinerator and gas scrubber corrosion. Hydrogen chloride is the major toxic material released when PVC is burned. It has been shown that virtually all of the chlorine is released from PVC on combustion, resulting in HC1. It is estimated that 0. 2 per cent of solid waste is PVC, and 16 x l(r tons per year of solid waste are incinerated in the United States. Thus, on the order of 32,000 tons of PVC are burned annually, releasing approximately 18,500 tons per year of HC1 as air emissions. Other solid waste sources which can produce HC1 are chlorides in food waste, plants, grass clippings, and inorganic salts. The formation of compounds requires volatilization and reaction with incinerator flue gases. Achinger and Baker compiled data indicating an emission factor of six pounds of HC1 per ton of solid waste burned. Recent data on HC1 emissions obtained by Battelle show a factor of 5.1 pounds per ton. A value of five to six pounds per ton would be a reasonable emission factor to use for HC1 emissions from municipal incinerators. Using an emission factor of 5.5 pounds per ton gives 44,000 tons per year of HC1 produced by incineration of municipal solid waste. The amount or HC1 produced from PVC using the above calculation is 42 percent of the total. Much more HC1 is probably now emitted to the atmosphere from the nation's coal-burning power plants than from our municipal incinerators. However, there still could be a hazard in the immediate vicinity of an incinerator as a direct result of its HC1 emissions. Of particular concern is the possible dispersal of the stack gases to cause the ambient concen trations of HC1 at ground level to exceed harmful concentrations. How ever, HC1 is not at the present time regulated by EPA. Other air pollutants could be formed from the additives in PVC dur ing incineration. Several additives are usually incorporated into the poly mer to emphasize particular properties not inherent in the base polymer. The types of additives are antioxidants, antistatics, colorants, fillers, plasticizers, and stabilizers. Some of the additive agents used are: anti oxidants--phenols, amines, phosphates, and sulfur compounds; antistatics --amine derivatives, quaternary ammonium salts, phosphate esters. RSV 0019168 polyethylene glycolesters; colorants - -salts or oxides of metals, aluminum, copper and inorganic pigments; fillers--silica, glass, calcium carbonate, metallic oxides, carbon, cellulose fillers, asbestos; plasticizers - -phthal ates, organic phosphates; stabilizers--lead salts of acids, barium, cad mium, calcium, zinc, alkyl tin compounds. It is highly unlikely that large quantities of VC will be emitted during incineration of PVC. There is no evidence that PVC will chemically revert to VC. Some small amounts of entrapped monomer might conceivably survive incineration, but these quantities would be very low. The second area of concern with incineration of PVC is firebox corro sion and corrosion of pollution control equipment. HC1 can be a major factor related to corrosion of this equipment during incineration at certain temperatures. In the case of plastics, PVC is the major source of chlorine leading to HC1, but other plastics may also contain some chlorine. Incinerators with heat exchangers will have corrosion problems on the fire side of the exchange equipment when the combustion gases contact the outer metal surface. Other surfaces of concern are in the cooling area and in the gas scrubbers. Estimates indicate that in incinerators with heat-recovery systems PVC in the refuse will increase tube maintenance costs by 15 to 20 perpercent over that to be expected if PVC-free refuse was used as fuel. About 95 percent of -the incinerators in this country have some type of air pollution control equipment that is exposed to the high chloride envi ronment resulting from refuse combustion. Because of the high chlorine content of the combustion products, the cooling and precipitating water from the scrubbers that contacts the flue gas contains large quantities of chloride and is extremely corrosive to the structure. In summary, technology exists for controlling the HC1 emissions that result from incineration of solid waste; however, the application of this technology will resultin increased costs. If technology is not applied, then the contribution of PVC to the nation's air pollution problem will increase because of the projected increases in the usage and disposal. HC1 scrubbing technology is available, but its application results in corro sion problems. Depending on construction materials, design, and opera tion, these problems can be either large or small. PVC does not decompose significantly within the normal time frame of most other municipal solid wastes. It comprises only about 0.2 percent of the total municipal solid waste being landfilled today, and the effect of PVC on the reuse of the landfill site, at least in the short run, should be negligi ble. 64 RSV 0019169 Since PVC degrades very slowly, in the landfill environment it should not add significantly to the production of leachate or decomposition gases as do other parts or the refuse. The additives of greatest concern are probably the plasticizers. However, if a sanitary landfill is designed and operated with today's technology, disposal of PVC products in a sanitary landfill should pose no special problems to the operation or to the ultimate use of the site. Resource Recovery Recycling of solid waste is a growing industry. Technology has been developed to recover some resources from many of the items in the municipal waste stream. However, the technology to separate plastics or PVC from the waste stream has not yet been commercially demonstrated. The solution to the separation of plastic waste from other components of the municipal waste stream is one deterrent to direct recycling and reuse of plastics, including PVC. However, gathering and centralizing the waste products are also major problems. Some types of scrap PVC from the fabrication process are presently being recycled back into the manufacturing process. This reduces the solid waste from plastic fabrication plants and reduces the need for new raw materials. There is work underway to develop means for utilizing the benefits of recycling the total municipal waste stream. Examples of these recycling techniques are listed below: -- To recover heat given off during the incineration of solid waste containing PVC and other combustible materials as electricity or steam for heating. An example is EPA's research contract with the Combustion Power Company of Menlo Park, California, in which combustion gases are expanded through a turbine to produce power. -- To recover the products of a refuse pyrolysis operation either as a pipeline gas or as feed material for a nearby refinery. An example is EPA's research grant with West Virginia University in which refuse pyrolysis is being studied on a bench-scale. A second example is the Bureau of Mine's research effort to convert refuse to pipeline gas. Also, US and Japanese industrial firms are actively exploring this area. The recent change in the world's supply of crude oil should speed up research and development on new and existing ways to utilize more fully the resource of waste PVC. 65 RSV 0019170 \ ' V- ..\*s REFERENCES 1. E.A. Boettner, G. L. Bell, B. Weiss, "Combustion Products from the Incineration of Plastics, "Report No, EPA-670/2-73-049, July 1973. 2. "Compilation of Air Pollution Emission Factors," 2nd Edition, Publication No. AP-42, EPA, April 1973. 3. W.C. Achingerand R.L. Balter, "Environmental Assessment of Muni cipal-Scale Incinerators," Report No. SW-111, EPA, 1973. 4. G.L. Huffman, "Hie Environmental Aspects of Plastics Waste Treat ment, " Symposium on the Disposal and Utilization of Mastics, New Paltz, New York, June 25, 1973/ 5. "Threshold Limit Values," American Conference of Governmental and Industrial Hygienists, 1972. 6. Fessler, R., H. Leib, H. Spahn, "Corrosion in Refuse Incineration Plants," Mitt. Ver. Grosekesaelbets, 48_ 126 - 140, April 1973. 7. Vaughan, D.A., and P. D. Miller, "A Study of Corrosion in Municipal Incinerators," Cincinnati, Research Grant, April 1973. 8. Miller, P.D. et al, "Corrosion Studies in Municipal Incinerators," SHWRL - NERC, Report SW - 72-3-3. $ 9. Baum, B. and C. H. Parker, "Incinerator Corrosion in the Presence of Polyvinyl Chloride and Other Acid-Releasing Constituents," report by DeBell and Richardson, Inc. Qk> date) 10. George L. Huffman and Daniel J. Keller, "The Plastics Issue, " SHWRL NERC, Cincinnati, Ohio* August 28, 1972. 11. "Incinerator. Gas Sampling at Harrisburg, Pennsylvania," EPA Con tract No. 68-02-0230, Office of Air Programs, September 1973. 66 RSV 0019171 * APPENDIX IX ACTIVITIES OF TASK FORCE The principal activities undertaken or stimulated by the Task Force are set forth below: MARCH - Recognition of problem of pesticidal sprays containing VC-- Responsibility assigned to Office of Pesticide Programs MARCH - Analysis of material losses during PVC polymerization pro cess MARCH 19-21 Pilot monitoring effort at B. F. Goodrich Plant in Louisville MARCH Preliminary evaluation of health effects data APRIL 2 Meeting with representatives of PVC manufacturers organ ized by Manufacturing Chemists Association APRIL 4 Meeting with representatives of interested environmental groups APRIL Development of interim methodology for VC sampling and analysis APRIL/MAY Visits to VC manufacturing facilities and to PVC polymeri zation, compounding, and fabrication facilities APRIL 12 First of series of interagency meetings convened by EPA APRIL/MAY Monitoring at seven complexes involving 10 PVC and 2 VC plants APRIL/MAY Review of health effects data APRIL 30 Review of Industrial Biotest toxicological experiments MAY 27-31 Preliminary VC water persistence studies MAY Preliminary VC air persistence studies MAY/JUNE Recognition of air emissions problem -- Responsibility assigned to Office of Air Quality Planning and Standards JUNE 3 Technical review of monitoring activities JUNE 11 Administrator's meeting with senior executives of 29 com panies producing PVC and VC JULY Development of improved methodology for VC sampling and analysis RSV 0019172 67