Document XODEeXrem68ny0Xdap3mOK3nG

\i":",,KS': J'W V* :Tp; .T-r..' --" -_.^t--.V.---' * - Vvi^s;, ..;,>*\l~*V ... . A ' ' . '.' * ' ^ vi* .- *.,* *. f: . PRELIMINARY ASSESSMENT OF THE ENVIRONMENTAL PROBLEMS i - ASSOCIATED WITH VINYL CHLORIDE AND POLYVINYL CHLORIDE / (Appendices) r Report on the Activities and Findings of the Vinyl Chloride Task Force Environmental Protection Agency Washington, DC September 1974 SCC 3-0462 APPENDICES I. II. III. IV. V. Selected Economic Considerations '1 ' Production Levels- .. Competitive Substitution...... International Aspects . Control Technology,. . : ' 1. . _._1 . 4-- . 4 .Producers of Vinyl Chloride and Polyvinyl Chloride 6 VC "Producers. PVC Producers PVC Copolymer Producers '.6. 6. . .. .8 The Materials Balance at Vinyl Chloride and Polyvinyl Chloride Facilities 10 Vinyl Chloride Production Facilities Polyvinyl Chloride Polymerization Facilities 10 11 Interim Method for Sampling and Analysis of Vinyl Chloride in Waste Water Effluents and Air Emissions 17 Scope and Application Summary of Analytical Procedures Interferences Apparatus and Materials Reagents, Solvents, and Standards Sampling Calibration Procedure Quality Control 17 17 17 18 19 20 23 25 25 Summary of Regional Activities 26 Region I: Region II: Region III: Region IV: Region V: Region VI: Region IX: Leominster, Massachusetts Flemington, New Jersey Delaware City, Delaware S. Charleston, W. Virginia Louisville, Kentucky Painesville, Ohio Plaquemine, Louisiana Long Beach, California 26 27 27 28 .28 29 29 \ see 3-0463 VI. VII. VIH. x IX. Persistence of Vinyl Chloride . ' 31 . Behavior of Vinyl Chloride in Air;r': Behavior of Vinyl Chloride inWater -~r Behavior of Vinyl Chloride in Closed Rooms - . 31 31 Health Effects of Vinyl Chloride 32 Occupational Cases of Liver Angiosarcoma -V Cases of Hepatic Angiosarcoma,- Connecticut; .- - 1935-1973 : - r..--- . , - ' -.C Observed Deaths/Expected Deaths in VC y Workers - .' . Summary of Toxicological and Epidemiological Studies on Vinyl Chloride 34 38 .40 44 Disposal of Products ContainingPolyvinylChloride 63 Incineration Landfilling Resource Recovery _ 63 64 65 Activities of Task Force 67 see 3-0464 ii .-. -r..-. ,-v~" ^T-TWi'".'; -- 'l I , .7;:*;?^ : r.:~`.: -- < '. i-rz-rix-zT.-y.rrrfr-;.c:.--i ' - _.- .. ---- ' ' .-AA'PD`PD7E?TN\TDT\ITX'V,-:Tl SELECTED ECONOMIC CONSIDERATIONS l-*r 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 apd components-fabricated from, this plastic. In Table 1, major PVC products manufactured during 1973 are iden tified. . The U. S. VC/PVC. industry.- has been operating^ for more than forty years, andoverthe 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 woi'kers 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 by 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.- sec 1 3-0465 L Market Category I. Apparel . i II. Building and' " Construction - ' .............. - III. Electrical IV. ' Home V. Packaging 1# VI. VII. Recreation ' Transportation VIII. Miscellaneous products' Products 1973 1000 metric tons - Baby pants Footwear 'Outerwear-- ' \ * y_ . ' 12 ; y : ' Extruded foam moldingsr _ --Flooring .. .. ;211--.--y;;;-:-:- y Lighting .'- .5 , Panels and siding.. ^V;- 39 . >:., .. Pipe and'conduit' ........... ............. -'525 ` Pipe fittings ,.44' Rainwater systems, 'soffits, -''facias - - ;;i6 v. . .Swimming pbol liners.!i-. ' vV^18 Weatherstripping - -- 16 Windows v- 26 Wire and cable . 194 Appliances Furniture Garden hose - Housewares Wall coverings and wood surfacing films 20 145 18 51 54 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 36 9 9 59 35 66. 25 - 88 18 15 83 66 8 23 23 7 18 8 45 Total 2158 2 see 3~0466 >i!:; -'V. ;; Table 2 SUBSTITUTE MATERIALS FOR PVC PRODUCTS PYC PRODUCT SUBSTITUTES SAME PRICE RANGE' .HIGHER PRICE Pipe & Tubing .* Polyethylene . Polypropylene . Metals . ABS resins Flooring ` * Electrical Insulation - Asphalt Wood ... ABS resins . * Polyethylene Polypropylene EPDM rubbers SBR rubbers TFE plastics X X .. . X . X X :-x X v.X .: X **..,,,* I' X X X Records Film & Sheet Products ABS resins Acrylics Polyvinylidene chloride Polyethylene Polypropylene ' Cellulosics X X X X X X Coatings Acrylics Polyurethanes Cellulosics X X X Household Goods Styrene Polyethylene Polypropylene Wood Metals Acrylics X X X ^r A. X X Packaging Polyethylene Polypropylene Polyvinylidene chloride Cellulosics Acrylics 'Polyurethanes Glass .X X X X X X X SCC 3-0467 3 U. S. based manufacturers currently produce about one-third of the . western world5 s supply of resins, with the U. S. market also consuming about one-third of the total. In 197^/3.7 percent of FVC and 7.3 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:ichange in:.the":7 7 U. S. share of production or market during the-next few years. Recent, r-.. 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. , . 7 :-V There is presently an import duty on. PVCuresin from - countries - with; _ status as. Most Favored Nations ofll/4 centsper pound plus six'percent""..' ad valorem and from other nations of four cents per`pound plus 30 per-V^:cent ad valorem. .Given the current U. S.-market price of 18 to 24 cents--*1*2 3 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 tlie discharge 01 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 seme 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 minimise this problem. 3. Venting unintentional leaks and spills into a system which is flared and, preferably, scrubbed. see 3-0468 4 **! > FOR PVC RESIN PLANTS: . 1. Collection and destruction of purgases 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!. '.. . .C. . ' ' 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. . 5 Laboratory data have shown that VC can be adsorbed; on-activated carbon. Concentrated VC vapor streams have .produced a recovery .work-'^-' -; .v ing capacity on carbon equivalent to about ten percentpf the carbon weight. . .. Ambient air contaminated with low levels-of VC iprodubes significantly. lower adsorbent working capacities. Control of dilute VC is ^therefore V - ; 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. Modem Plastics, Jan 1974, p. 432 3 2. The 1972 Census of Manufacturers shows 7, 574 plants manufacturing miscellaneous plastics products (SIC 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. see 5 3-0469 APPENDIX'* II PRODUCERS OF VINYL CHLOR*I**DE 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 - C;' ^Annual Capacity' ; Location (Millions of Pound's)- 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 "-viY - 175 -650 200 700 390 300 150 1000 300 400 ... 500 340 700 / 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 50 150 140 130 235 240 see 3-0470 6 The Firestone Tire & Rubber Company Perryville, Md.' Pottstown, :Pa- ,y. The General Tire & Rubber. Company Ashtabula,; Ohio y Pleasants County, W.-Va. B. F. Goodrich Chemical Company Avon Lake,"'Ohio Henry, 111. Long Beach, -Calif. --- - Louisville, Ky. ' : Pedricktown, N. v The Goodyear Tire & Rubber Company Niagara Falls; N.Y.Plaquemine, La. Great American'Chemical Corporation Fitchburg, Mass. Hooker Chemical Corporation Burlington, N. J. Hicksville, N.Y. Keysor-Century Corporation Saugus, Calif. Delaware City, Del. Monsanto Company Springfield, Mass. National Starch &. Chemical Corporation Meredosia, ILl. Olxn Corporation Assonet, Mass. The Pantasote Co. of New York, Inc. Passiac, N. J. Point Pleasant, W.Va. Robintech, Inc. Paine sville, Ohio Stauffer Chemical Company Delaware City, Del. Tenneco Chemicals, Inc. Burlington, N. J. Flemington, N.J. Union Carbide Corporation South Charleston, W.Va. Texas City, Tex. Uniroyal, Inc. Paine sville, Ohio - 230 ; 270.. _ 125 y 50 ... - - 14 0 . - 140. -140 . 340 -:~:-170 " 100 100 40 ISO 15 35 35 70 10 ... 150 60 : 90 250 175 165 70 160 240 140 7 see 3-0471 PVC Copolymer' Company > A. Polyvinyl Air. Products and ( B. Polyvinyl C: Air Products and C American Chemical Atlantic Tubing & K' .. Borden, Inc. ' The Firestone Tiro B.F\ Goodrich Che* Hooker Chemical C Keysor-Century C>.National Starch anc Olin Corporation The Pantasote Conr C. Polyvinyl C-l* BASF Wyandotte C Borden, Inc. jgpssw-? SgLocat. Tier n polymei svCaive fe tffci .. ..on* ;any ' fSjjJLong Beach,.: Calif. * Scranston, R. I.- ' ;i- ^Bainbridge, M. Y. . .. ^Compton, Calif. yy yu.:. u-i ^rbemopolis, Ala.' C: - - . ft|Bii-opolis,'`Ill.-C At- "S-Leominst^r; Mass fe jfepoitstown, Pa. i/jj - j|Avon Lake, Ohio ^`Louisville, Ky. L Hicksville, N.Y.C J*.>ri)o ration v York, Inc. ylidene Chloride Cope J;; Saugus, Calif. i' i 'C.leredosia, 111. JrSAssonet, Mass. gr .* is;- Passaic, N. J. B^Point Pleasant, W. Va. V*;u * b Resins v-l South Kearny, N. J. Bainbridgc, N. Y. Compton, Calif. Demopolis, Ala. pi- aiiopolis,* 111. Leominster, Mass. rY ( rL " yK t a see 3-0472  * - .-** 4* Dow Chemical, U.S.A. B.F. Goodrich Chemical'Company W. R. Grace Company . Morton-Norwich Products, Inc. National Starch and Chemical-Corporation SCM Corporation -" Tenneco, Inc. Union Carbide Corporation ' Midland, Mich. Louisville, Ky..; ... . i : Owensboro/ Ky, . t. ' South Acton,* -Mass. ' Ringwood, HI. * m ' T1 Meredosia,-111. . ... Huron, Ohio Burlington, N. -1:" Flemingtdh,: N.-J. .. institute and South Charleston, W.Va. Texas City, Texas REFERENCES 1. 1974 Directory of Chemical Producers, USA;- Chemical Information .Ser-. vices, Stanford Research Institute, Menlo Park, California, 1974. 2. Chemical Marketing Reporter, May 20, 1974. SCC 3-0473 9 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. V A simplified block diagram for production of VC from ethylene "and ^- chlorine is shown inFigurel. . Some VC complexes' utilize oxychlorination - ; 'Y . units; others produce ethyl chloride from the by-product, hydrogen chloride:' ;;V^: (HC1) and ethylene. However, the production of di'chloroethane (EDC) allows for many approaches to recycling of light and heavy materials such"-. *;;,v that the losses of VC -are reduced. ....Even vent streams of inerts can be scrubbed with EDC ; for { maximum removal of VC before venting. Light ends such as methane are usually flared'and VC is converted to water.':~v and small amounts of HC1. ' '*' ` ' VC losses have come primarily from vent streams, .the storage and i. transportation loading systems, and seepages from pumps. If vent 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 the 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. 1 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 present a 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. see 10 3-0474 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 .'op erating .the PVC plant, types of products produced,, frequency of product_change,;: - - * ; method of PVC shipment, and emergency situations,.-^-EstimatesLoflosses have varied widely in the industry, indicating the: complexity of establishV. ing precise losses for a given facility and overall losses on a nationwide basis. v In general, older PVC plants are smailer,,,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 forloss of both VCand PVC. Further, a small plant has the disadvan tage of havingto make frequent resin changes to meet customer demands. During these changeovers a certain amount of off-grade resin is produced. V.,: ^ ^ J 7. :7 In addition, older plants have the added burde# of higher maintenance than new plants, but this tends to stabilize after a few years. The handl ing of VCand 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 wornout 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. see 3-0475 11 The traditional fetethod of stating yield of VC in FVC plants been based upon pounds of prime resin in the bag as compared . to 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 the weight, of tank cars accurately, some of the losses are in the form of PVC scrap, ` and 'some'-losses escape as PVC -particles. . \ ;' - . * ''-v A properly run and maintained suspension plant using technology, that is ten years old should be capable of obtaining a 95% ..or., highsr. 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 .r will probably be 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,C. v drier/ product collector vent air, the veiiting of the reactor, and th.e.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 ventecT After recovery and emptying the PVC resin, the reactor is full of a mixture of air, moisture, and VC at ambient conditions. see 3-0476 .12 'T* V* L 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 essen-. tially 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;-..'' den'sed 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. cvi .-p ~ 8v ~ Product'Collector -'Most plants use bag collectors so that the loss of resin is less than one pound per hour, but there are. losses due..to-.r . : J -_ v product changes which raise the total. ,- . .'r.'.JJj .'...i 9. Screening - Oversize resin is removed from the final products^ : 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. b. . Samples - Probably about 0.05% or 5 pounds per hour and is usualiy de stroyed 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. See 3-0477 13 * J ' V 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%. . .V~ see 14 '0^7s PRODUCTION OF VC FROM ETHVLENE AND CHLORINE- 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 mohi-V-- './L.* toring program .carried' out by ^EPA Region IVi in March. and . L 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 " v " : the original Region TV approach. ' -.r . "V This method is applicable.to -VC ' determinations iii 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. . .. \ ___- .'LL L p . vV '. T:f' i..: Summary of Analytical Procedures '-..p . .. ` . . PP'.- V''.pp' Water composite samples, air continuous composite bag 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). Tetrahyclrofuran 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 presentedproblems of resolution of the VC peak. When column substrates other than those specified have been used, impurities from solvents and carbon adsorbents have been see 3-0481 17 Cfi? found to interfet%-with the VC elution'peak. Under certain condi tions a peak is associated with the injection and subsequent with- * ' drav/al of the microsyringe into and from the GC septum. These' peaks can also give interferences wrffi*the VC peak. Withdrawal , should be timed to avoid overlap of this peak with the VC peak. . ... . . Apparatus and Materials ;, _- y - ' .. Gas Chromatograph . _; . ;;'" y : Flame Ionization Detector . ,; .: ; r ;: Recorder A any .potentiometric strip _cha'rt recorder whieh/is - compatible with the. detector system. An integrator is also desirable to estimate peak areas. / 'V. '*Y Column Materials for. Waste Water,. Sludge, or Scum-Samples / >. Borosilicate glass tube' or'stainless steel tube - 6.1 x 2. 5 ' mm ID preferred. When GC configuration requires columns of other dimensions, these should be used. *" . Solid support - 60 to 80 mesli 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 glass tubing or stainless steel tubing 81 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 rneter SCC 18 3-0482 _i- "-ru.-.-- .rJr?.'-T* . -.-L- .7-'- ' Continuous Air Monitoring Materials and Equipment - Bag. Sampling Option . iw : ^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 clear.:-; air-or nitrogen and evacuated prior, to use: .--Evacuated.containers should be protected fromrough-handling to prevent-implosion'or ;collapse. Sampling Bags (Tedlar or equivalent) - 12n 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 mi 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 See 3~0483 19 Carbon Wtrachlo ride (reagent grade) Carbon disulfide (reagent grade) Standards VC in zero air, 50 ppm (+ 2%) v/v VC, analyzed reagent grade (lecture bottle) Sampling d. / ... ,v '5 . A, Water Samples All waste water discharge points identified in NPDES permits should be sampled for VC,,. `A minimum of three successive r.- 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 inihutes may-; be used if the automatic sampler lias this capability. Samples ' .- should be taken at waste treatment units such as clarifiers and scum and sludge separators. Ty/o 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 be taken as blanks. Samples should betaken in50 ml bottles with gas-tight, teflon- sealed, 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 minimised 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 Sample's 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 e:cposed. At a minimum. see 20 3-0484 sampling should be conducted over 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 fKe 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)^.;;;v.; approximately 0. 5miles downwind; single sampling sites,; each7?'V, . - ; at distances approximately 0. 6 (I), 0. 8 (J), 1,0. (K),. and 3. 0 miles downwind from the plant site. ... If wind is fish-tailing . >. .severely, move sampling sites Gand H approximately 0.5.mileV;-.. upwind of the fish-tailing wind direction from :the plant.':'.The, V sites specified are minimum. Additional sites may be selected contingent on overriding micrometeorological. considerations. >-v :_2v, 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 - ' . V- ' "-" of meteorological balloons, anemometer,- and wind direction - 'indicators, etc. SAMPLING SITES Prevailing Wind Direction Minimum Sampling Schedule Miles from plant site 0.0 0.4 - 0.0 0.4 0.5 0.6 0.8 1.0 3.0 Site Symbol AC Plant- . EF GH I J K L D Time Mon Wed Fri 0800 A, A, B A, B, B A, A, B 1000 C, D, F C,D C,D,D 1200 A, E A, G, G A.E 1400 B, B, F B,H B, B, G 1600 C.G E,K I, J 1800 D,I - L,L 2000 - H,L,L - (Note: All times are + 30 minutes for manual grab samples, or + 3"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 vaon-Sampler'1 metal cans, or 12n 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-rtight 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. see 3-0485 21 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 vapuum 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 Adsprption Option: .. ,/ Continuous samples are taken .inipyrex 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 Becton- Dickson 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 v;iii indicate the amount of break-through of VC through the adsorb ent. SCC 22 3-048 t-.A. The sami procedure should be used for taking samples in the field/^ Continuous Sampling - Programmable^Jlag 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.-atT^ ground level, unless otherwise indicated .by micrometeorological..r conditions. -- . ............. ............. Calibration A. Gas Analysis - Gas Dilution Option: :T- - 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 withaflow meter or v/itha gas-tight syringe. Dilute with nine liters of zero nitrogen or helium carrier gas. Tiiis gives a concentration of 5. Oppm <vv) of VC. (13 ng/ml at 25C and one atmosphere.) Evacuate a 12" x 12" 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 1211 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 or helium carrier gas. This gives a concentra. tionof 0.G6 pprn (v/v) VC (about 0.16 ng/ml at 25 C 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 xlov/ r?ite of 60 ml/min. Operate the inlet and tne column isothermally at room temperature. SCC 3-0487 23 Prepare a cafo^atton curve. Repeat until the calibration curve is reproducible. B. Gas or Water Analysis - Gravimetrip^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 . : V..-, ... Attach a tygon'delivery tube to the VClecture bottle. valve. v. ;..f. :: Attach the end of the delivery tube to a piece of glass tubing.. - `vYry:v?;;. 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 15CPC and the column at 60 C. After the VC- peak has been eluted, program the column temperature to 150 C to elute solvent. Cool column back to 60C for follow-on concentrations. Repeat procedure using a GC equipped with a 4% FFAP on Gas Chrcm Q packed column and FID detector. Operate under the same conditions. Prepare a calibration curve to be used be used with water samples.- . 24 sec 4se Procedure Water Sample Analysis Untreated water samples (1-5 microliter aliquots) are injected directly into the GC. A 4% FFAP on "Gas Clirom 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 FIDJ 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 TKF 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 Ig 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 the column and inlet at room temperature.. Use a flame ionization detector. Untreatedair samples (1 ml) 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. ' - see 25 3-0489 .. 'v.* SUMMARY OF REGIONAL ACTIVITIES This Appendix briefly summarizes the results of the preliminary. VC monitoring activities conducted by EFA Regional. Offices.during .the L. Spring of 19 74 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 .short1period of time using new methods, based on the Agency!.s'best scientific' judge,?* T; 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.' - V r;.- . " Prior to and during the sampling and measurement only. limited quality control and standardization of procedures could be applied in the 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 v/ere 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 from less 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. Co ppm level on a wet basis. see 26 3-0490 perty. 6. Shifting meteorological conditions and rain hampered the sam: pling program. Region II: Flemington,. New Jersey: Tenneco Chemicals, Inc. (PVC); - Ma*y* 29-31. *.** '* * . '. y s. >-+*.-**.** "... ,Kv''.**** **9''' 1. Forty-three discrete ambient -air samples were colleetedion W plant property and within a 2. 0 mile radius of the plant.' - The \rG:. c6n-.;- ,: v, .v. centrations;outside the plant property ranged from less-:than*'detec.$ayr. ble (0.01' ppm) to 0. 05 ppm. ' On plant property, a single ,.s^iple '^.;^?..v- 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. / ...................... ` v 'V- - 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 maximum level of 20 ppm was detected in three 24-hour composite samples taken from the water ' effluent discharge into the Bushkiil Brook, which Immediately flows into the Raritan River. This amounts to approximately 400 Ibs/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 III: 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 SCC 3-0491 r.-v.;>.V ;h\Hn\:drsbY:e'ioimbioh:raiiY'jrdnqMyi^ pllaanntt'-' ranggeedd' from ( :aV lio'o7'O0..'T7 ppppniu'VO."v The ' highest level `\vus VtVhrtlrd 0.5 niilot! from th&>plant and tin lower levels a! 0. 25 miles from It plant. 4. The aroa immediately adjacent to I hv^lolawa re City roniplox'iH light ly populated residential areas for several miles. 5. Water, samples collected at the lhiion Ca rbido plant. L^avr VC'...-values of 1.1 and -.0. 8 ppm for. 'grab samples at' several outfalls;`and: 0. 85- for a v.. 24-hour composite. . Samples obtained from the Kanawha KiverMidMoi have a detectable level of VC. .. V;,. - 6. ; Sampling was attempted but was not feasible due to .limited tijoe 'anil ;;^'.;-. ^ equipment difficulties at the PVC plants of the Firestone Plasties Company ; in Porrvyillo, Maryland, and PoUslown/ Pennsylvania.-. . . Region IV: Louisville, Kentucky: H. F. Goodrich Chemical Company (PYC);-Mareh IQ-21 and May 8-1G. ..'-jvi;' ' 1. The initial air monitoring 'program conducted-in March was .pre liminary to the more extensive program in May which showed significant-, lv higher levels. 2. In May there were 89 discrete ambient air samples collected in the area designated industrial (within 0.8 miles from the plant center). The YC concentrations ranged from Jess than 0.05 to 5.6 pom, 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 front less than 0.05 to 88 ppm. The average concentra tions at the site registering 88 ppm were between 0.5 and l 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 1C2 ppm of VC, respectively. Region V: " Painesville, Ohio: Vniroyal, Irio. (PVC) and Bobintech, 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. see 28 3-0492 !'2'*v ;Nin'e^24-hoS?Vint'egrated^inbient'Vair;^Ba,mpjLesr'taken at Varlous'Mis-' ;T "r' tances from the plj^rt 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: Plaquemine, 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 thar. 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 Morrisonvilie and Eliza are located less than 1 mile north and northwest respectively of the Goodyear plant. A few homes from Morrisonvilie 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 :\vithin 3.1 miles of the complex. About 11 percent of the 29 SCC 3-0493 r readings ^exceeded 5 ^ppm r:^hil^'5 ^per.cent ^excT'.?e:t^eerd. ed^rO^pmt^T:^^^^^ maximum value me&sured was 3.'4 ppm in a sample taken 3; 1 miles `f^oi-ri^ the plant; however,'*6cthe average level measured at this point was about 0. 5 ppm. 2. Samples of wastewater effluente"\vere 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"mibro- 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 see 3-0494 J^RSiSTENCE:IN V iJ-.'C HLORIDE > The. available ^-reformation on .the stability and persistence of VC*`in the environment is currently very limited. Some literature and laboratopv studies have recently been initiated by industry and by EPA. This discus sion summarizes the findings of EPA tb^dale and particularly the rcsulis 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. seeip. jo. be consistent with the discussion. ; ' ,r` 7V -- v - Behavior of Vinyl Chloride in Air ... ..... . , - ' - - . T * 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 'reaction1 of about 8 to 10% per hour for VC, recognizing that reaction rates may Z . 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 ot 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 22^C 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 fi'om 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 ioss mechanism. 31 3^0495 Hydrolysispyer aipHange:bW4^3fib73h'^d6esm portajit pathwayVor loss'of VC from water. 'Chemical reaction o T VC in i:" the clarifier effluent from a VC plant was followed at 50C for 57 hours at pH 4.3, 8.0, aft* 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 los.s^of VC occurred by-volatilization rather than hydrolysis, or at least there is a very slov/ hydrolysis rate. This experiment should be repeated in leak-proof reaction vials. Very preliminary `experiments do not show photolysis!`as-an:-'impor - L:.. ` <.'-J tant pathway for loss of VC in water. However, there are many uncertain-, ties in the experimental techniques, and additional studies are needed in r ' this area. ~\v. Earlier theoretical-studies'are corisistentwith'these experimental -re- . " suits. One study on the transfer of small non-reactive molecules across ; the air-water interface (as in stream a.eration) 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, mixings 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 lon? enough to accumulate biologically, via d*rrect 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 No. 1 Collected at breathing zone during spray No. 2 15 minutes VC COLUMN I FREON-12 41.64 ppm 8.15 ppm 16.91 3. 13 COLUMN II VC FREON-12 41. 9 ppm 7.94 ppm 17.1 3.30 No. 3 No. 4 Mo. 5 30 minutes' 60 minutes 120 minutes 1.33 0.03 0.012 0.27 0. 018 - 1.32 0.061 0. 010 0.25 0.018 - see 3-0496 32 > TABLE II Thirty Secid Release of Insect Spray in 21,400 Liter Room SAMPLE TIME . COLUMN 1 TVTC/*1 *w FRE"mONT -1 2A *J. COLUMN II . VC FRE^O-N-12- No. 1 , Collected one . . . 380. 1 ppm /. 84. 8 ppm ;:'_w/'383;..6j)pm ... 83. 2 ppm minute after ; spray 1'. ^ ' No, 2 . 30 minutes later No. 3 60 minutes - No. 4 ' 150 minutes No. 5 Collected in *1 2 3' 4 adjacent hall 151 minutes _ 52. 1 - V \ v- 24: 6 ` 4.8 ^ v. 1^'r22^~-;r 10.3 2. 1 9. 3^P : ' ' 2.2 \ ' 0.83 b.17;?"' !7V J; - ;^ i5-^: ^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 wEPAR3-72-012 (October, 1972). 4. MacKay, Donald and Aax'on W. Wolkoff, "Rate of Evaporation of LowSolubility Contaminants from Water Bodies to Atmosphere, " Environ mental Science & Technology, 7 (7):6ll-614 (July,' 1973). see 33 3-0497 ^ HEALTH EFFECTS OF VC This Appendix presents much 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 body of the/ report. / However, the. Appendix does not 'present.`an.-exhaustive"--'reviewor - evaluation of available information. ` ; V- Table 1 summarizes the data, collected by .CDC/.NIOSH, : "on the . ; confirmed cases .of angiosarcoma of the liver in VC/-PyC-workers in--:/ . the United States and abroad. .. A total of 15 occupational ' cases have --*' been discovered in the United States and confirmed as angiosarcoma oftheliver. Of the 15 cases, 2 are still alive and undergoing treat- . .-.V ment. Fourteen of the 15 were employed in PVC production plants andV .... . the remaining one"in a PVC fabrication plant. .The! average, age at death for the U.S. PVC production workers was 43. 5 years (with a ; . V ';. 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 tv/o 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 hud lived for 35 years within one-half mile of the vinyl products plant at which the accountant had been employed. see 3-049B 34 ---- "I*-** ... ' . While the findings establish" no causal connection between exposure to i- Ti-liU wl. i i ot tna n they cto r-use t-1; possibility of such a relationship. Tfime wiiT be needed to deiiru the possi1ble TrisZk factors in persons who have worked with PVC sfince 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--; V additional cases of'hepatic angiosarcoma that may be, -found to - have had possible community exposure to VC'will be necessary, to clarify, ii-1. the significance of these cases. -' v -H ' Tables'3A - 3D present the findings of the MCA-funded mortality. . . study of VC/PVC workers, conducted by Tabershaw/Cooper Asso ciates. ' ;'r ' -- In calculating the riskof death, the usual method is'toexpress 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 mo;taility 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 expected value o 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 industi'ial 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. Taole 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. see 35 3-0499 ' --y. V 'i.'Vvs's-V *,4* Is- lam< long) using the ferae dichotomization 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.. v. In the high exposure . group with 5 years or more exposure (Table 3D) there are~.36,pbserved. ' cases and 26. 11 expected; For cardiovascular.; .7 renal .diseases .as.a, group, there are also increases .in..the ' SMR'with increasing exposure, : -but the -nuinber 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 as a whole. However, in those workers with Els of 1.5 or higher, there are 12observedcases 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 SB). The relationship with exposure is more pronounced, since those with exposures of less than 5 years have fewer cases than expected. The tymphosarcomas, although occurring al 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 Study 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 see 3-0500 36 standard, (b) absence of 15% of the study population (untraceable), and <c) discovery, as Lhc study ended, of a group of 1500 workers whose exposures occurred up to 3'6*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. - .y- y vy /r y - 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. ; yyyyk y -y: ' . v'v; W'w 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. , . see 3-0501 37 ' t fyT: Occupation 1, . VC Uonocier Production 2. ?VC Polysiaricntian 3. PVC Con:poundra, Fabricators; life. * 4. Other VC Exposure TcMe 1 OCCUPATIONAL CAS*:S OK LIVER ASGLOSARCOKA Country Swadan Case ff 01 BIRTH DATE oo-oo-u lat VC/PVc Diagnosis Age Uork of Angloanr - at cotta Diagnosis 00-00-45 00-00-72 61 Yr,s. 1st' Total Trs. V0/PVC Work VC/PVC To Dlacnoslti Exposure ' Data of Death 27 23 00-00-72 United States United States United States United States United States Uni tod States United States United States United States United States United States United States United States \>, Germany y. Oeroany Great Britain Norway Sweden Czechoslovakia Caeehoslovflkla United States United Stotea Great Britain 01 00-00-22 02 00-00-34 03 00-00-15 04 00-00-24 05 00-00-12 0G 00-00-29 07 05-03-22 0& 05-06-20 09 00-00-31 10 08-16-13 a 05-27-0? 12 11-17-18 13 12-01.-21 01 07-26-51 02- 06-04-30 01 00-00-01 01 12-23-15 02 00-00-27 01 02 14 11-04-27 ...15 - - 00-00-25 02 0O-0P-14 12-09-48 03-00-71 11-15-55 .05-00-70 11-2C-4S 12-00-73 07-06-52 06-19-44 OC-OO-67 04-00-64 01-17-62 02-00-74 08-00-44 00-00-68 10-07-45 08-00-61 05-23-43 03-01-74 06-00-51 05-00-58 10-14-46 03-00-70 09-13-49 05-00-69 OB-19-44 05-00-74 10-14-57 00-00-71 10-01-57 00-00-69 C9-00-46 12-00-72 03-00-50 12-20-71 00-00- ill- 00-00-70 * 11-11-51 00-00-00 nn-<yi-A>$ 00-00-69 - 07-00-72 <`2-0')-70 . 49 36 58 43 52 45 45 41 43 55 61 50 53 40 39 71 55 43 41 4? : 55 22 . 16 14 ' 13 *: 23 , . 28 IS 15 20 " ia 12 M2 24 18 . 15 ' 29 1'7 15 . . . 17- - 17 . 23 - 20 30 23 ? . 15 . > 30 ` 14 14 11 *.\-v . . 11 ' 26 ` (V: 20 V 22 ' 21 .' 19 ' . , .18 .1 03-03-73 09-23-7J. 12-19-73 01-07-AB 04-09-64 A1 ive 03-23-C'v 08-29-61 'Alive 05-10-CU .03-16-;'.: 05-O2-6V 07-04-74 12-14-71 01-^5-CJ ' 12-00-7: . 01-04-72 00-00-70 17 - ' 4` * ... , . ' 00 ! 00 : -aV 24 : ' ' 11 i . 03-27-6-7 02-15-73 12-00-70 V. Gcnaany ?,,y ' $3 \ Vj-f' A" *4 \ ;v.\ 1 * ;A !',s) ti' DKf: li: yr-: i) tA, \ . 'A; i< .'I'll' i : .' V; 'M r :`k : ' U'f f iW ir )* . ih . V A' - n- ii'ij'i |r >.r Notes 'CO* Indicate* unknown date W SOURCE: NIOSH fii: ' * * fc'l, r r . III \M-:. i` }' \ see -0 5 0 2 'M . ( m Table 2 CASES OF HEPATIC ATCCI0SARC0M5, CONNECTICUT, 1935-1973 Case NCI Ho.____Ar.o Sex Diagnosis Dace of Original Diagnosis Date of Death Mrdlc.nl H<st o r y 73 M Hepatic 11-25-67 Angiosarcoma 12-3-67 2 months history of diarrhea, , anorexia, and 20 11> weight loss. Intermittent abdominal pain. Non-tender, five: epigastric mass. Died after 9 days with spontaneous ruptured liver leading to shock. Pest history of alcohol in take. Occupation Place of Residence Fireman 1917-42 . Aluminum worker 1942-44 Corset cutter 1945-61 Retired 1961-67 Bridgeport entire life i '''Vi /' * l 1 ' r "V-V: ''Vi'j; W-: 47 >1 Alcoholic Cirrhosis Portal Fibrosis 1-15-73 2-15-73 Initial symptoms K1IQ abdominal pain with vomiting. Cecal volvulus found, Rx cecopexy, over next 6 weeks pain continued with weak ness. RUQ tenderness with 2 FB liver. Diagnosed by needle biopsy on 1-15-73. Deteriorated slowly until death 31 days later. Accountant - Vinyl Co. 1 ' 1963-73 Accountant - Plastic '. .'. Belt Co., 1956-63; Previously accountantother states Bridgeport 1956-73 . Previously many locations ' -4/ .J . 5a U: S3 Hepatic 12-19473 1-22-74 Admitted 12-2-73 with short history of RUQ Housewife . Stratford Angiosarcoma abdominal pain radiating tc R shoulder. Had Restaurant cook 35. yrs 35 years -. RUQ tenderness. Open .liver biopsy 12-19-73 showed large tumor. No resection. Deteriorated until death 34 days later. 'i->i I . ".;V ; .'0$. 76 Hvp.itlc 3-12-50 3-19-50 1 month history of anorexia vtth ahdominal pain Housewife Angiouiircnma and back pain. Firm epigastric mass. Died 6 days after admission with corciuomatosis and pulmonary(- emboli. Windsor bocks Mr* m 50 Hepatic - 5-4-73 Admitted for abdomin-.l pain and jaundice Fisherman'and carpen 'Puerto Rico I ^ .1 Angiosarcoma 3-27-73. 4 FB liver. Dluvhnrgvd. lU-ndnitted ter before 1959 Plas 1923-59- 4-29-73 with nbd distension, general edema, terer 1959-60. Unem `New York City icterus, fever, shaking chills. Hnpld down ployed 1960-73.- - ; 1959-73 hill course with death due to renal and hepa Bridgeport' '! W tic failure. Pant history of alcohol intake. 1973 ;;;'. f*1; ' - > - m t i. s' M j ' \ty. ! 3S&, see -0 5 0 3 OBSERVED DEATHS/EXP2CfED DSaTHS AND STANOARP/IRKi) fS '& m iT Y RATIOS IN VINYL CHLORIDE WORKERS BY ESTIMATED LEVEL 0? EXPOSURE ' ' ; *X-v3-* f-; ' * <> r.`7Z*C> \/: .r<frf?3Sf*r"t Mc{ td CJ '-\sf SI Si Si wi r--I <j Si Hi SI w t> CJ c CO K< c3 o <<<c5y m- -ri 1! CJ 4t3J M CM -H a<j oy o c to jii; -iOrjt <to 3 <S V- M yo-i cP- <3 .-i % 41 > -a c ^Q K1 KH -*o fj .C _ ^2 "b si fw-| -*c< r- y *5mH o Cs^J: A. to r *>$ M W ~ * *S +. see 3-0504 <arit 2 > tOrt oCm', .O!W a q aw au fc K S VCM0O3-)i **. ' -*0.. '7 Si, 41 Xu01 *-i O-< fV3l i> r>4-) M O f-i rt w --tno --5,<6i s/j ;: see -0505 Table 3C OBSERVED DEATHS/EXPECTE9 DEATHS AHD STANDARDIZED MORTALITY RATIOS IN VINYL CHLORIDE WORKERS WITH EXPOSURE INDICES RSLCW 1.5, BY DURATION OF EXPOSED EMPLOYMENT Cause of death with I.C.D. number All causes Tuberculosis (001-019) Tuberculosis of respiratory system (001-003) Mili^r.unt ncoplaacts (140-205) Malignant neoplasms, buccal cavity end pharynx (140-148) Malignant neoplasms, digestive organs end peritoneum (150-159) Malignant neoplasms, respiratory system (100-104) Malignant neoplasms, genital organs (170-179) Malignant neoplcstss, urinary organs (180-161) Malignant neoplasms, other and unspecified sitc3 (ISO-199) Lei'l.2.uia and elcukcuia (204) Lyu-phosarcona, lymphatic and hematopoietic tissues (200-203,205) Diabetes mollitus (260) Major cardiovascular and renal diseases (330-334, 400-46$, 592-594) Vascular lesions affecting CMS (330-334) Rhc-v;r.icic fever c, chronic rheumatic heart <513. (400-402, 410-410) Arteriosclerotic heart disease (420) IJonrhou-.-tatlc endocarditis (421, 422) Hyparter.aive heart dicease (440-443) Oth.-.v hypertensive tliseaoe (444-447) Qirr.nic U unspecified nephritis & renal sclerosis (592-594) Inflate .i.:c and pncu.rc\\La (4S0-493) Ulcer of ;'.(:oa>ach uni duodenum (540, 541) j- Appendicitis (350-533) hernia and intestinal obstruction (560, 561, 570) Cn3trici3, duodenitis, enteritis and colitis (543, 571, 572) CJ.rrhc;ifi of liver (5QI) lryperplxsis of prostate (610) Sytaptc:./;, senility and ill-defined conditions (780-795) All other diseases (residual) Kotor vehicle accidents .(810-Q35) Other accidents (800-302, 040-962) Suicide (963, 970-979) . l-fcwlcidc (964, 900-905) Number of -workers Fsrson-ycrirs ^SMR'c adjusted for deaths with cause unknown. ^Significant at 5X level. *rfSictufleant at 17 level. ! <60 months exposure 260 months exposure obs/exp ! SI'S*1 obs/exp .SMU*- 56/89.23 63** 132/181.28 73** 0/1.41 0/1.31 8/12.06 4/0.45 1/3.43 2/3.58 0/0.68 0/0.55 ,1/0.97 0/0.79 0/1.26 2/1.15 : .21/33.38 2/3.93 2/1.50 16/21.14 0/1.18 1/1.58 0/0.50 0/0.97 3/1.86 0/0.68 0/0.15 0/0.27 . 0/0.26 . 1/2.80 0/0.05 ' 0/1.43 4/7.45 3/9.87 3/7.98 3/4,08. 0/3.55 0 0 73 1036 : , 34 65 0 0 120 0. 0: 203 73 ** 59 L55 88 o.; 74 0 0 180 0 0 ` :0 0 42 .0 .0 63 35 44 ftfi 0 0/1.97 0/i;85 29/31.46 1/1.17 6/9.08 9/10.00 2/1.62 1/1.53 8/4.43 . 1/1.40 1/2.23 3/2.50 63/86.02 5/10.51 1/2.49 52/57.8 7 0/3102 0/3.90 1/1.02 0/1.53 2/3.95 1/1.53 . 0/0.24 . 0/0.61 0/0.51 1/6.09 ; 0/0.20 . 0/2.79 10/12.92 5/9.22 8/9.85 VA//^edtvcv ' 0/3.43. 0 0 95 88 63 93 127 67 187 73 46 124 75** 49* 41 93 TO <0 101 0 53 67 O' 0 0 16 0 0 7956 83 10? 0 1715 21418 ..82317 ;23920 see 0506 Table 3D OBSERVED D?.AT;iS/EXPECTEO DEATHS l HD STANDARDIZED MORTALITY RATIOS IN VINYL C1D.OP.IDE WORKERS WITH EXPOSUrx INDICES OF 1.5 OR GREATER, BY DURATION OF EXPOSED EMPLOYMENT Csusc of death with I.C.D. nmbsr All cruses Tui'^svculosio (001-019) Tuberculosis of resporatory 3ystca (001-002) Vi-Hgnant neoplasms (140-205) IN-Lignant neoplasms, buccal cavity and pharynx. (160-148) Kallgnonc n^cplassis, digestive organs end peritoneum (150-159) Malignant neoplasms, respiratory syotcrc (160-164) Jlalignanc necplasos, genital organs (170-179) H.-.lignant neoplasms, urinary organs (LSO-lUt) M'liSftant neoplasms, other and unspecified sites (190-199) L-:uhcula and clcukct:la (2C4) Ly^phosarcoca, lymphatic and hematopoietic tissues (200-203, 205) Dlab.iCCS r.ellitu3 (260) rlijor cardiovascular and renal dioeases (330-334, 400-468, 592-594) V.'-L-cular lesions affecting CWS (330-334) r.iii'tuJaatlc lever & chronic-rheumatic heart dis. (400-402, 410-416) .-.(.arioselaroitc heart disease (420) r,,-.:'.rhcu:n:itlc endocarditis (421, 4Z2) 'Hpurtenaive heart disease (440-443) hypertensive disease (444-447) Ciror.ic & unspecified nephritis & renal sclerosis (592-594) Influenza end pneumonia (480-493) Ulcer of stomach and duodenum (540, 541) | Appendicitis (550-553) K'-.-aiu and intestinal obstruction (560, 561, 570) ttjstrlcls, duodenitis, enteritis and colitis (543, 571, 572) Cirrhosis of liver (581) Hyperplasia of prostate (610) S) .i.ptcma . senl 1 tty and ill-defined conditions (7S0-795) Ail other diseases (roslducl) Motor vehicle accidents (810-835) Other accidents (800-002, 040-962) Suicide (963, 970-979) :v....unie (964, 930-935) N-u.bur of'workers F-nc.n-ycars 1 *ii adjusted for deaths with cause unknown. vi!i -jni (leant At SZ Level, r ficant ut'17. level'; <60 months exposure 260 months exposure obs/exp SHR1 ob3/exp t: t - 38/47.93 79 119/147.SI Cl* 0/0.76 0 0/1.57 0 0/0.71 0 0/.1.46 0 . 5/6.57 96 36/26.11 14 i 0/0.23 1/1.67 1/1.79 ' 0 76 71 0/0.99 11/7.47 12/8.50 0*, 1 144 . . 0/0.29 ,0 t/1.41 73 " 0/0.26 0 0/1.26 0 1/1. u- 107 7/3.51 204 1/0.44 283 1/1.13 90 1/0.71 178 4/1.04 222 0/0.61 7/16.54 0 54*-* 2/2.04 1.00 '62/70.46 : 90 2/1.87 ' 135 ; 4/8.19 50' 0/0.82 : 0 12/2.04 100 5/10.41 . 61* ,46/47.65 ' 98 0/0.57 `i o. 1/2.32.- 44; - 0/0.76 ' .0 2/3.10, 66 0/0.27 0 ' 2/0/81 253 0/0.54 0 0/1.23 0 0/0.99 0 ; 0/3.13 0 1/0.35 362 0/1.25 0 0/0.08 0 ' 0/0.19 - 0 0/0.14 0 1/0.49 ! 209 1/0.14 904 0/0.41 . 0 0/1.56 .0 . . 1/5.03 20 0/0.01 0 . 0/0.13 ! 0 1/0.80 156 P 0/2.30 0 * 0/4.02 0 ` ;6/11.68: 51* 7/6.05 , 146 - - 2/7.43 28 4/4.73' 107 / i. 2/7.96 26 3/2.40 158. h 4/4.62 00 1/2.18 ' v58 ' .'0/2.76 : 0 1240, . 12828 . "1.817 19305 ,, TAbie 4 SUMMARY OF TOXICOLOGICAL AND EPIDEMIOLOGICAL STUDIES ON VINYL CHLORIDE Author a Species Sex__ Uo. EXPOSURE Krs. per HUMAN DATA Cone. Total Done Observations Pathology Von Oettingen (1955) Hunan 12,000 10,000 25,000 Dangerous Narcosis Produced symptoms of dizziness, disorientation, hcvdac'ie and burning sensation on soles of feet. Cnbor Mcoca-Radu Kanta (1962) Chen. Abstract Human 82 Workers exposed to DDT, Benzene, Hexachlorocyclo- hexr.ne, VC, ?VC. Blood: Decrease In catalase Increase in peroxidase, (ndonhenoloxldase nr.d gluthathione Changes occurred during second year of work. None reported Lsscer Greenberg AcfiOS (1963) Human Cr.bor F.adu Predi /ibrviSran Jujr.cf Ar.cn V.ilcxUav (1964) Cher.. Abstract Huncn U3 Twice per day 0 0 1/5 slightly dizzy F 3 for 3 days, 4,000 83.3 0/6 had uny effects 5 min. sessions 8,000 166.7 1/6 slightly dlszy at 6 hours in- 12,000 250.0 2/6 definitely dizzy ' tervala . 16,000 333.2 5/6 dizzy, nausea, blurred vision and heaving symptoms stopped after exposure 20,000 416.7 6/6 Intoxicated, one with persistent headaches 50% level of no effect is 1.3% Ho statement about repeated exposures - 78 PVC Workers Decrease plaumu albumin Increased B and 8 globulin Decrease In B/R for serum lipoproteins Decrease in fseruu cholinesterase Deereace In puvudo cholincr.teranc Hi); a?.1 bli'Od catalase hot ;..il cec-is pyruvic acid 1 r. ` None reported None reported Crigor-iscu To Da <i*66) Chen. Abstract Human U Experimental: PVC Workers Control: Other clinically healthy people llypothnf.r.s: VC-ttljOehloral + chloracctic acid. (1). Results; {1) van found in 603 of exjirl. people, but !n none of controls. ' Must of + findings were in people exposed 2-3 years. In these canes,.{-globulin is higher,^-globulin is'; lcw.ir than people with no (1) iti urine' rapacity to i.iutabalisc 0) d'.'i.-roascct after 2 voars.,,1" None reported see -0 5 0 8 i . r:!?ipS*j'. v:' . <${ i- , - :p|; Author: Karri?. Adaas (1967) Species Sex No. EXPOSURE Krs. Total pee Cone. Dose Day Oayg ppa pptt-Days Huaan HUMAN RATA Observations Pathology -- One worker had knee cap and 'tons involved In the aero-ostteeoollyyssisis.', Other worker only hands j-rjr Wilcon McCormick Tatum Creech (1967) Human SI No cases of ocro-ostcolysis diagnosed in 1000 . individuals who handled finished resin or used for plastic product production Age range of affected workers 26-47. Incubation period greater than 12 months of polycleaning experience. 31/3000 (32) workmen acsoristpd 'V-T ., polymerization founds to have:'' osteolysis, . '. .'^KV 22/31 Acro-osteoly3is associated * ' pilffmf ^ '' with Reynoud's Symptoms', Baresta Stuart .Mutch lor (196?) Human 13 7.5 1 50 250 500 15.6 78.1 156.2 Breach decay curves. 0 to 20 hrs. after exposure were measured. Level in breath at 4 hrs. is 2? IX. No adverse effects noted. About the same set of breath decay curves following occupational exposure. None Reported Xudrvaucscv.-i (1970) Abstract Hunan 50 63 1. Changes in ECC: (rhythm, conductance; polarisation. None Reported. 2. Increacc In syr.tolic index. Viola (1970) Unpublished Hunan w 1.8. 1095 58 1825 15 ` - 500* *Xn several ocher factories A;ro-osteolvsis symptoms, Reynaud's syndrome, aversion to fats, enlarged liver Raynaud's uyndrouio t Enlarged liver, minor liver insufficiency'.'., J3/500 h; ><t ;u:ro-os, vol y h I h . 0 l ul ariory' lluva- ; }uld (k O.m to li'.. .Vi.lu ttorvoti.v Ky&'f'ldms become evident wl> n it is easily perceptible. Aerometry: ';^NaWHFr' (VC) on factory filters at air discharge time: -2'000 ppn (VC) at point `o'.'vj'worhe.r .e.ntry: _ 2,000 ppm inplialannttss where ,-icro- . osteol''i(s occurred-150 ppm. (nt.ix) In ` |i w l t h nil il I i r; i*i ni* . .4 ` | Vt;l on .'`.iiiti'wny ;ni.!. otluT par'l l of. plant: 10 to.15 ppm. i r : p-i;. ill mr M: 1 ;mmi see 0509 -t human data A.V?!>.:>i.Vj_____grades' Sex No. Hrs. per Day Total Cone. Dose Days pen ppm-Davs Observations Pathology u i r.r.'r. n Coo'/ U'aterhcuE !'.i;>r.son Di cchnck <1971) Human Dodunn Dinxjn Whltcivoo: Nnsr >!;.f,::unon <1973.) Hunan Kir finer H'jcooJei (1?71) Hunan 5011 4 98 21,510 Has-yer.ro .Experience 1-23 Months -Up to 25 years Experience Conditions associated with hand cleaning of polymerize?.*. There appeared Co be correlation between reactor degassing tine and acro-osteolysis. 25 cases .of aero-osteolysis. YtKrEi; 16 ocher individuals quest lonab'fb1 Acro-osceolysls appears tc hesgSiJ' systemic rather chan local disease.. Raynaud1a phenomenon was statii'-?^ tlcally. related to acro-osteoi&jj> \ All pntients had worked as PVC reactor-vessel cleaners. *is- .)-/ Raynaud's phenomenon anccc.cde^Wj} I','.1, osteolytic lesions in all foij-` Ncg. Cn and P balance in one subject. Plothysnopmphlc Abnormalities were present In subjects. ' 18p sclntiscuns correlated 3 subjects. Esophageal motility within normal limits. radiographic lesion*. ' .No liver. enlargement or hypothy^Jw .<! Cfitficholcnir.fi. -Hydroxyindole Acetic Acid roidism.. excretion rsorrt.il. Addi tJonal '.srnal 1 er' abnorina litie;*j? All other numerous clinical laboratory investigations found In.ulnor styloid, oscalc negative. and patella... r Performed stacistie.il correlation between several 'None reported. clinical mersurowonts and total dose and time- weighted Average VC concentration* ! 2 liver function indices show a positive correlation" with total done (:.'bnornuilly high)., . a) Icterus Index . b) Smsulphaleln . 3 other indices are dose-related but are not'outside norrnril limits: o) systolic and diastolic blood f. W pressure. b) h*?!:n';jloh 1 o negative correlation. c) bel':<-protolri. see " 0510 dlLL.'i'A`>_ y,t'nT (I772) c r.'u:t Spftciefl Kumar* Sex No. -1 MasV-.iiviix McHon;.)<J fi: t li; nfo- r znt*r (1 * 7 2) \bl t filf C Human St iU V- I : -i i:: < i (.i; i > Human - 1J Hl^L',N_U,\TA Hrs/Uav flays EXPOSURE Cone. Total Hose ppm.____ ppei-dav < . . ' .____________ OBSERVATIONS___ PATHOLOGY _ Arroosteolysls ; . Had unique papular skin lesions'which have been.. described only in PVC workers , i" Oeser/bes acroosteolysis-- symptoms. Incidence Is <3X j amorig workers . .! ' Ay.es 29-32 Reactor cleaners Latent period:..-lS"3$i years ' 2-tH yrs. employment -t.In 11 patients; 7. and 11. _ S' years In other'2 patients. . ; Aero-ost *<>] ywis symptoms; Peripheral vt'Hpel stenosis. Thrombopeny (low ccunt) is ` , ,- j- ` ` the f J rm t object ive', symptom H (!.<'r f heel fn ail patients; I imp. Hhroiilx orglnnt.lng in l>..rt.il svstem. la rgv i spleen, :. impaired lung functions. |tl-' non ,i 1 i t y. fhl s Is the i' I r *41 ! 1i i vo ivmptom'' , t les.- r i !'-d . w see '0 5 1 1 i. ai._ ,J_ ' e xc o * -<-r*33o-- -0v n-*r-.nc- ci--e w_ -^' c r_ BB*^/ oii c > c;:.. uw*:, Sin ^ s 0" V - 5 "-3 - - <= - u a *-- **-: O C4i..oC4 C* O wo* -c ^.. S. v**;:; rp*--c-<>1--<5sti >oos*"-* ^ w ^ on --Cfl h --3ea !c_>^--j>vswc2.fo =-.-- -H <0 xi c a o 2 s. ".; OR"1a3>.X*J 6O. "Q3"--*. OWI '-- . a V J -- ? *xr *- r6-ia>wQno..Aou o^* ` B -->v`--C. M-- --O---ro X. - t-~% ", _. ^ __ _s - <-c* --* o-c. 0>..3 o 5i4>1 wo 3--*_1 il rt S? pg - --<3> Ol eI *O-> O 6C. f-> a a - "1 -- .c >-1 HOC. u -.3 -N XT-j ^*fl-49l Mi fiuC ir'> s| n *, ~ 3 j "i % -- <1 ~ ~j ~ -- >4 a. > ->- 44 see 3-0512 Table 4 SUMMARY OF TOXICOLOGICAL AND EPIDEMIOLOGICAL STUDIES OK VINYL CHLORIDE * ANIMAL DATA Au t1iOT3 ANIMALS Sncclcs Sax No,. Hrs/dav Davs EXPOSURE Cone. Total Doss ppn Pi}ti"U:vn Observations Von Gottingen (1935) (Review Article) Cnts Cats Cato i;o HD HD KB ND <4 '.D HD <4 ND 1 1 Cats Cuts KD UD Caca HD Rabbits HD Dogs ND <4 HD 4 ND ND KD 1 u.tn. 1 1 ND 1 ND ND VC in promptly excreted by lungs, 82% Is eliminated after Inhalation stops 100,000 to <1,200 130,000 180.000 <30,000 200,000 <33,000 250,000 to<40,000 to 300,000 50,000 ND ND 170,000 118 Blood VC concentration reaches 15-17 tag! This concentration causes sane intra-auricular preapuro reduction as 13,000 ppm dichloroethylene, 30,000 ppr. ether Caruiac insufficiency . Even tills does not produce complete cardiac failure Blood levels arc 40 mg% at time of cardiac arrest, 27-30 agl at time of respiratory orrest This As the narcotic concentration Mice fogs fill ND 1 min. :;i> HO <4 1 1 86,000 to 60 to 85 123,000 100,000 <12,00i) This i.f the. narcotic concentration Cardiac irregularities, ECG abnormalities Dogs ND Dogs NO Klee KD C. Pigs NO NO 3 7 for Several wks HD 3 7 for several wks ND 10 min. 1 ND chore time 2 10,000 200,000 245.000 to 295.000 200.000 to 400.000 475 9,500 1,700 to 2,040 HD No major change in liver.or;kidney Marked salivation, vomiting, respiratory arrest Thin Is che lethal range for 10'minutes exposure All killed ' ; Patholoev /( C' -< ; 4! r -',-j ;; . see -0 5 1 3 Ah'tKAL DATA Mir.hara Men O^r.u Li,'.n (W55) P.iivJ cm Article Cor.c iivj'-J ANIMALS Spectra $<ex No. Hm/day C. Pigs no HC 0.5-1 C. Pigs "m HD O.S-l G. Pis* OT rn> 0.5-1 Pays 1 1 EWOSORS Cone* ^Total Ooso ppm ppm-dav.'.- Observations 100,000 5,000 NO 2.000 to 4.000 100 to 200 Dangerous to life. Hfftivec concentrations than this cause' severe lung cc.tiai and hyperemia of liver and kidney Order of cojcicity is: carbon tetrachloride chloroform <VCm-ethyl chloride PatbolonY . , '; v'-..' Mastroau: ceo Mice HD 3 0.5 1 100,000 .2,060 Sequential effects were: 1. irritation, Mice: Light lung ^ Fisher 2. increased motor activity,'- 3. twitching,-. engorgmant, kidney - Chris!:i Dunyigc.r 4. tremor, Incoordination,-5. unconscious.;' swelling; Rate and 6. deep narcosis. All animals recovered in. C. Pigs: ssae. lung :. am) 5 minutes. picture. < Fir.iivr Rats ND 5 0.5 U Chrisrt.; Dar.y.li'cr <mo) C. rip,9 ND 5 0.5 1 Humber of animals and duration 200,000 4,160 1/5 mice died after 30 minutes,.same Lung engorgement, no of exposure same' as above flynptnas as above but appeared sooner. . edema in all speclcu. Guinea pigs unsteady for 20 min. after ' One rat had'fatty liver orpociufu. * Number of anlmale and duration 300,000 6,250 5/5 mice and 5/5 rnts died; 1/5 guinea' Liver and kidney .was of exposure same as above pigs died; 4/5 guinea pigs recovered in congested, traehaal 25 minutes. epithelium damaged w Number of animals and duration 400,000 6,330 2/5 guinea pigu died . Seme symptoms, more I of exposure same os above severe TotIu t5ov. (1) Rac.-t M 10 7 <5d/uk> 500 14,000 Growth #.d gross appearance were normal. Central lobular.llvor P 10 7 (4.5Ko) Li.wr/body weight ratio and absolute liver degeneration. weight larger than control in males. Kidney tubular.damage. <w.i; J. fvc r/tv.ly weight and absolute liver: wuigkt not larger than control In Females' Dicee SCOT, SC?T, SUM, alkaline phosphatase >. r " " ;;- were normal, . _ ' see 0514