Document Ne1bN9MXONMdR4a6dnvmqppOV

r"L--, PART II: J ENVIRONMENTAL PROTECTION AGENCY NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS Standard For Vinyj Chloride BOR 004916 COPIED BY MCA FOR DISTRIBUTION TO THE VINYL CHLORIDE TECHNICAL PANEL, NOVEMBER 11, 1976, MR, MILTON FREIFELD { 46500 RULES AND REGULATIONS Title 40--Protection of Environment CHAPTER I--ENVIRONMENTAL, PROTECTION AGENCY ore required to be captured and con trolled. Health and Environmental Impacts greatest wnter usere would be emplovr and that there would be no recycling of water. There is no regulation which would require water recycling. Accord SUBCHAPTER C--AIR PROGRAMS Epa prepared a document entitled the ing to SPL the control system utilizing Ino. bib-11 Quantitative Jlisk Assessment for Com the most water will not be used gener PART 61--NATIONAL EMISSION STANDARDSvFOR HAZARDOUS AIR POLLUTANTS Standard for Vinyl Chloride munity Exposure to Vinyl Chloride which estimates the risk from vinyl chloride exposure to populations living in the vi cinity of vinyl chloride-emitting plants ally by the industry and economic fac tors will pause plants to recycle much of the water. Therefore, according to SPI the impact of the standard on water On December 24. 1075, under section before and after implementation of con consumption will be negligible. 112 of the Clean Air Act. as amended <42 trols to meet the standard. There are no The environmental impacts of the U.S.C. 1857), the Environmental Protec dose-response data for the concentra promulgated standard may be summar tion Agency (EPA) added vinyl chloride tions of vinyl chloride found in the am ized as follows: The primary environ to tile list of hazardous air pollutants bient air. Therefore, assessments of risk mental impacts of the standard are ben (40 FR 59477) and proposed a national at ambient levels of Exposure were ex eficial and will consist of vinyl chloride emission standard for it (40 FR 595321. trapolated from dose-response data from emission reductions of approximately 94 The standard covers plants which manu higher levels of exposure using both a percent at ethylene dichloride-vinyl facture ethylene dichloride, vinyl linear model and a log-probit model. chloride plants and 95 percent at polv- chloride, and/or polyvinyl chloride. Extrapolations made with each of these vinyl chloride plants. Percentage num EPA decided to regulate vinyl chloride models entailed using different sets of bers for both source categories are based because it has been implicated as the assumptions. Because different assump on an estimated 90 percent reduction in causal agent of angiosarcoma and other tions can be made in extrapolating to fugitive emissions- and 1974 emission serious disorders, both carcinogenic and low doses, the health risks are reported levels. noncarcinogenlc, in people with occupa in ranges. The potential secondary environmen tional exposure and in animals with ex It was estimated that 4.6 million peo tal impacts of the standard are either perimental exposure to vinyl chloride. ple live within 5 miles of ethylene dicho- insignificant or will be minimized with Reasonable extrapolations from these ride-vinyl chloride and polyvinyl chlo out additional action, except for one ad findings cause concern that vinyl chlo ride plants and that the average ex verse impact. Hydrogen chloride Is al ride may cause or contribute to the same posure around these plants before instal ready emitted by process equipment at or similar disorders at present ambient lation of controls to meet the standard ethylene dichloride-vinyl chloride plants air levels. The purpose of the standard is is 17 parts per billion. The exposure and by other petrochemical plants in the to minimize vinyl chloride emissions levels for uncontrolled plants were cal complexes where ethylene dlchloridefrom all known process and fugitive culated based on estimated 1974 emis vinyl chloride plants are typically lo emission sources in ethylene oichloridevinyl chloride and polyvinyl chloride plants to the level attainable with best available control technology. This will have the effect of furthering the protec tion of public health by minimizing the health risks to the people living in the vicinity of these plants and to any addi tional people who are exposed as a result of new construction. Interested parties participated in the rulemaking by sending comments to EPA. The comments have been careiuily con sidered, and where determined by the Administrator to be appropriate, changes have been made to the regulation as pro mulgated. sion levels. Using the linear dose-re sponse model, EPA found that the rate of initiation of liver angiosarcoma among people living around uncontrolled plants is expected to range from less than one to ten cases of liver angiosarcoma per year of exposure to vinyl chloride. The iog-probit model gave predictions that are 0.1 to 0.01 times this rate. This wide range is an indication of the un certainties in extrapolation to low doses. Due to the long latency time observed in cancer cases resulting from vinyl chloride exposure, increases initiated by exposure this year will not be diagnosed until the 1990's or later. Vinyl chloride is also es timated to produce an eo.ual number of cated. An Incinerator used to attain the standard at an ethylene dichloride-vinyl chloride plant could increase hydrogen chloride emissions by several fold. Typi cally. however, due to the corrosion prob lems which would otherwise occur both on plant property and in the community, plants use scrubbers to control already existing hydrogen chloride emissions. Hydrogen chloride emissions resulting from control of vinyl chloride emissions are expected to be controlled for the same reason. If even a moderately effi cient scrubber (98 percent control) were used to control the hydrogen chloride emissions resulting from incineration of vinyl chloride emissions, the increase in Summary or the Standard In ethylene dichloride-vtnyl chloride plants, the standard limits vinyl chloride emissions from the ethylene dichloride and vinyl chloride formation and puri fication processes to 10 ppm. For the oxychlorination process, vinyl chloride emissions are limited to 0.2 g/kg of ethyl ene dichloride product. In polyvinyl chloride plants, the stand ard limits vinyl chloride emissions from equipment preceding and including the stripper in the plant process flow to 10 ppm. Emissions from equipment follow ing the stripper are to be controlled by stripping dispersion resins to 2000 ppm and other resins to 400 ppm. or by using ' equivalent controls. Vinyl cnloride emis sions from reactor opening are to be re duced to 0.02 g/kg polyvinyl chloride product. primary cancers at other sites, for a total of somewhere between less than one and twenty cases of cancer per year of ex posure among residents around plants. The number of these effects is expected to be reduced at least in proportion to the reduction in the ambient annual average vinyl chloride concentration, which is expected to be 5 percent of the uncon trolled levels after the standard is im plemented. Changes In the standard since pro posal do not affect the level of control required. Thus, the environmental im pact of the promulgated standard is, with one exception, the same as that described ui Chapter 6 of Volume I of the Standard Support and Environmen tal Impact statement. According to data submitted by the Society of Plastics In dustry. me. (SPI), the impact on water consumption in the draft environmental hydrogen chloride emissions from a typ ical ethylene dichloride-vinyl chloride plant due to the standard would be re duced to 35 percent. However, EPA plans to further eraluate the need to control hydrogen chloride emissions, since dif- > fusion model results indicate that under "worst-case" meteorological conditions, the hydrogen chloride emissions from the process equipment and the incinera tor combined would cause maximum am bient concentrations of hydrogen chlo ride In the vicinity of ethylene diehloride-vinyl chloride plants to be in the same range or somewhat higher than existing foreign standards and National Academy of Sciences (NAS) guidelines for public exposure. Economic Impact In accordance with Executive Order 11821 and OIVfB circular A-107, EPA In both ethylene dichloride-vtnyl impact statement was overstated. In es carefully evaluated the economic and chloride and polyvinyl chloride plants, timating the impact on water consump inflationary impact or the proposed relief valve discharges and manual vent tion. EPA based its estimates on worst standard and alternative control levels ing of gases are prohibited except under case conditions. That ts. EPA assumed and certified this in the preamble to the emergency conditions. Fugitive emissions that those control systems with the proposed standard. These Impacts are FEDERAL REGISTER, VOL. 41, NO. 205--THURSDAY, OCTOBER 21, 1976 BOR 004917 RULES AND REGULATION'S 4&5G1 ' discussed In. .Chapter 7 of Volume I of the Standard Support and Environmen tal Impact Statement. Comments on the proposed standard have resulted In only one major change In the economic im pact analysis. EPA estimated that there would be four plant closures as a result of the promulgated standard. Of the four plants Identified os possible closure can didates. one has given notice that it no ldnger produces polyvinyl chloride and the other three have indicated that they do not Intend to close as a result of the standard. The economic Impacts of the promul gated standard may be summarized as follows: The total capital cost for exist Act. a public hearing was hold on the the possible exposure patterns, these proposed standard on February 3. 1976. eases cannot be ignored ta the evaluation in Washington. D.C. Presentations were made by the Environmental Defense of the potential public health problems. With regard to the alleged overstated Fund, the Society of the plastics Indus emission levels, the uncontrolled emis try, Inc.. Dow Chemical Company. Dia sion levels reported by EPA were based mond Shamrock Corporation, and Air on 1974 data. This qualification was Products and Chemicals, Inc. Copies of stated wherever emission data were pre the comment letters received, the public sented. EPA recognizes that emissions hearing record, and a summary of the have been reduced since that time, Rnd comments with EPA's responses^, are stated this in the preamble to the pro available for public Inspection and copy posed standard. EPA decided not to ing at the EPA Public Information Ref gather more recent data on emission erence Unit, Room 2922 (EPA Library), levels, because these emission levels are 401 M Street, SW,, Washington. D.C. in expected to change, and gathering the addition, copies of the comment sum -data would take considerable time both mary, and Agency responses may be ob on the part of EPA and on the part of ing plants to meet the standard is esti tained upon written request from the mated to be $198 million, of which $15 .Public Information Center (FM-2I5). industry. Since the purpose of the stand ard is to minimize emissions, tnese more million is for ethylene dichloride-vinyl Environmental Protection Agency, 401 current data would not affect the stand chloride plants and $183 million Is for M Street, SW,, Washington, D.C. 20460 ard itself. The 1974 emission levels were polyvinyl chloride plants. EPA estimates (specify Standard Support and Environ also used in diffusion modeling to project that these plants will have to spend $70 mental Impact Statement, Emission maximum ambient air concentrations million per year to maintain the required Standard tor Vinyl Chloride, Volume II). around uncontrolled plants. These maxi emission levels. In addition, the total capital cost for existing plants to meet the EPA's 1983 water effluent guideline Significant cowmotts and Changes to the Proposed Regulation mum air concentrations would probably be lower If 1976 emission levels were used. This would reduce the relative impact limitations is expected to be $83 million, (1) Decision to list vinyl chloride as a of the standard below that described in and the total annualized operation cost hazardous air pollutant. In general, the the Standard Support and Environmen is $17 million. The costs to the industry commenters did not contest EPA's deci tal Impact Statement, but would not of meeting the OSHA standard cannot be sion to list vinyl chloride as a hazardous a&ect the basis of the standard Itself. quantified at this time, but they are ex air pollutant. However, three comment (2) Approach for Regulating Vinyl pected to overlap to some degree with the ers (two companies and one Federal Chloride Under Section 112. Two ap costs to meet EPA's fugitive, emission agency) argued that EPA placed undue proaches other than using best avail regulations. The costs of meeting the emphasis on factors suggesting that vinyl able control technology were suggested fugitive emission regulations are included chloride presented a health risk and by the commenters for regulating vinyl in the total costs cited above for meeting ignored factors suggesting that no sig chloride under section 112. The first was the promulgated regulation. Broken out nificant risk, was involved. Under section to ban polyvinyl chloride products for separately, the capital cost of meeting 112, however, PPA could remove vinyl which substitutes are currently available the fugitive emission regulations is $37 chloride from ihe list of hazardous air and to gradually phase out other poly million and the annualized cost is $25 pollutants only if Information were pre vinyl chloride products as substitutes million. sented to EPA that shows that vinyl are developed. The standard Is not expected to deter chloride is clearly not a hazardous air in the preamble to the proposed stand construction of new ethylene dlchloride- pollutant- As discussed more fully in the ard EPA specified Its reasons for not set vinyl chloride plants or most types of comment summary, the commenters did ting a zero emission limit for vinyl new polyvinyl chloride plants. For one not provide conclusive evidence that vinyl chloride, as follows: (1) There are bene type of polyvinyl chloride plant (disper chloride is not a hazardous air pollutant ficial uses of vinyl chloride products for sion process) that represents 13 percent which causes or contributes to death or which desirable substitutes are not read of the industry production, the standard seriohs illness, nor did they conclusively ily available: (2) there are potentially would significantly deter the construc prove that the health risk factors em adverse health and environmental Im tion of smaller plants. phasized by EPA were insignificant. pacts from substitutes which have not It Is estimated that the price of poly Several other commenters agreed with been thoroughly studied; (3) there are a vinyl chloride resins will rise by approxi EPA's decision to list vinyl chloride as a number of employees, particularly in the mately 7.3 percent in order to maintain hazardous air pollutant, but argued that fabrication industries, who would be precontrol profitability and also to re EPA had overstated the health problem, come at least temporarily unemployed: cover the total annualized control costs the emission levels, and the projected and (4) control technology is available necessitated by the standard at ethylene ambient air concentrations around un which Is capable of substantially reduc dichloride-vlnyl chloride plants and poly controlled plants. With regard to the al ing emissions of vinyl chloride into the vinyl chloride plants. This increase is leged overstated health problem, the atmosphere. estimated to translate into a maximum commenters stated, for example, that the EPA agrees that substitutes do exist or consumer price increase in goods fabri U.S. worker EPA discussed as having could be manufactured for most poly cated from polyvinyl chloride resins of been exposed to vinyl chloride levels low vinyl chloride uses. However, in general, approximately 3.5 percent. Recovery of er than those usually encountered In these substitutes do not have some of the effluent annualized costs plus mainte nance of precontrol profitability Is esti mated to add approximately 2 percent to polyvinyl chloride resin prices and result In an additional maximum consumer price Increase of 1 percent. polyvinyl chloride production has been dropped from the National Institute of Occupational Safety and Health's listing of workers with angiosarcoma. EPA agrees that there are questions concern ing the level of exposure and in some more desirable characteristics of poly vinyl chloride, such as nonflammability. If vinyl chloride and pOJyvinyl chloride were banned, other substitutes with these more desirable characteristics would likely bedeveloped. There Is a risk Public Participation During the public comment period. 50 comment letters on the proposed stand ard were received. There were 24 from Industry; 3 from environmental grouus; 15 from Federal, State, and local agen cies; and 6 from Individual citizens. As required, by, section 112(b) (1) (B> of the cases the pathology of these cases not involved directly in polyvinyl chloride and vinyl chloride production. These un certainties are stated in the appropriate footnotes of the Scientific and Technical Assessment Report on Vinvt Chloride and Polyvinyl Chloride (STAR) where the angiosarcoma coses are listed. However, in 6pite of these uncertainties, in view of that these substitutes would also have adverse health or environmental effects. Since control measures are available which can reduce vinyl chloride emis sions by 90 percent or more. It does not seem prudent to reduce emissions by the remaining percentage and take the risk of introducing new untested chemicals Into the environment. FEDERAL REGISTER, VOL 41, NO. 205--THURSDAY, OCTOBER Jl, 1976 BOR 004918 4G5G2 RULES AND REGULATIONS Another approach suggested by the commenters was to base the standard for each Individual emission point on cost versus benefit. Several of the fugitive emission sources were named specifically as ones for which the costs of control were substantially higher than the bene fits. Although EPA did determine a costbenefit ratio for the controls required for a number of emission points, EPA does not believe such a ratio is an appro priate basis on which to set a standard. Section 111 of the Clean Air Act provides for the development of standards based on best control technology (considering costs). Even under section 111, however, capacity of no more than 0,19 m* (50 gal). Reactors in this size range can gen erally be found in a laboratory, whereas the larger reactors are typically pilot scale facilities. Emissions from laboratory scale equipment arc relatively small, and application of the controls required by the standard would be expensive and Im practical. EPA also decided to exempt re search and development facilities con taining reactors greater than 0.19 m' (50 gal) and no more than 4.07 m3 (1100 gal) in capacity from all parts of the standard except the 10 ppm limit for reactors, strippers, monomer recovery systems, and mixing, weighing and holding containers. venting will be permitted as r. last resort before the relief valve opens. The same notification procedures are required for manual venting to the atmosphere as are required for relief discharges. There arc several changes in the nu merical emission limits in the promul gated standard. Except for the standard for reactor opening loss, these changes simply involve conversion to the Interna tional System of Units (SI). There was an error involved in the original calcula tion used to derive the standard for reac tor opening. Correcting this error dou bles the allowable emissions. It is em phasized that the change m this stand standards are not based on a fine bal EPA decided not to require these facili ard is a correction, and not a change in ancing of costs versus benefits. Instead, ties to meet other parts of the standard the intent for the degree of control re costs are considered in terms of the af because of the technical problems in quired. fordability of the control technology re volved in doing so. For example, the The proposed standard required the quired to achieve a given emission level standard for reactor opening is based in installation of a rupture disc beneath and the economic impact of possible part on reducing the frequency of open each relief valve to prevent leakage from standards on the industry in ques ing the reactor. Research and develop the relief valve. A provision has been tion. Unlike section 111. section 112 does ment reactors have to be opened after added to -the promulgated standard fio not explicitly provide for consideration every batch for thorough cleaning. Also, that a rupture disc is not required if of costs, so it would clearly be inappro stripping technology is developed Indi the relief valve Is tied into a process line priate to consider costs to a greater ex vidually for each resin in research and or recovery system. In this case, any tent under section 112 than would be development equipment. Therefore, at leakage from the relief valve would be done under section 111. As discussed in tainment cf the stripping limitations in contained. the preamble to the proposed standard the research and development equipment The regulation for obtaining vinyl for vinyl chloride, EPA believes costs would not always be possible. The 4.07 chloride samples has been changed to an may be considered under section 112, but m' (1100 gal) figure was selected as an operating procedure. The proposed only to a very limited extent; i.e., to upper cut-oS point because there are no standard stated that therE were to be assure that the costs of control technol ogy are not grossly disproportionate to commercial reactors smaller than this. (4) Emission limits. The only major no emissions from taking the samples. Several commenters pointed out that the the amount of emission reduction change in the emission limits between use of the word "no" would make this achieved. In comparison with other proposal and promulgation is the addi regulation impractical to enforce. There emission points, the costs of controlling tion of a provision for emergency manual fore, the promulgated standard specifies the fugitive emission sources mentioned venting of vinyl chloride from reactors the operating procedure which EPA orig by the commenters are relatively small compared with the amount of emission reduction achieved. to the atmosphere. The proposed stand ard prohibited all manual venting to the atmosphere. In the preamble to the pro inally Intended to be used to control this source. This revision is only a change in wording and does not represent a Several commenters recommended posed standard, EPA invited interested change in the level of the standard. adding to the regulation a provision for persons to comment on whether permit The regulation for taking samples has excess emissions during startup, shut ting manual venting to the atmosphere also been revised to apply only to sam down, and malfunction. EPA considered could result in overall lower emissions. ples containing at least 10 percent by this comment, and decided that this There are several methods available for weight vinyl chloride. This is consistent addition is not necessary for the vinyl preventing relief discharges from reac with the other parts of the standard chloride standard. Startup and shutdown tors, one of which is manual venting of which apply to equipment "in vinyl of the process has essentially no effect part of the reactor contents for purposes chloride service." "In vinyl chloride serv on emissions to the atmosphere for poly of cooling and reduction in pressure ice" distinguishes between situations vinyl chloride production, and technology within the reactor. The hlgher'the tem where vinyl chloride is clearly Involved exists to avoid excess emissions during perature and pressure within the reac and situations where vinyl chloride is a startup and shutdown at ethylene di- tor, the greater the amount of vinyl minor component or contaminant, and ehloridevinyl chloride plants. We do not chloride which has to be removed to as defined In promulgated 5 Cl.Old) believe plants should be allowed to emit bring the reactor under control. Manual means that a piece of equipment con excess emissions during malfunctions, venting can be done at a lower pressure tains or contacts either a liquid that is and therefore are requiring them to shut than the pressure required to open the at least 10 percent by weight vinyl chlo down immediately. relief valve. For this reason manual vent ride or a gas that is at least 10 percent (3) Selection of source categories. In ing can result in lower emissions than by volume vinyl chloride. the preamble to the proposed standard would occur by allowing the reactor to The proposed standard required a vinyl EPA recognized that some small research discharge through the relief valve. Fur chloride monitoring system for continu and development facilities may exist thermore, a manual vent valve is under ously measuring vinyl chloride levels both where the emissions of vinyl chloride are the control of an operator and can be within the plant (for leak detection) and Insignificant and covering these facilities closed. A relief valve may become clogged within stacks. The proposed standard did under the standard would be unnecessary with resin and not close. The result not outline required specifications for the and inappropriate. However. EPA did not would be loss of all the reactor contents. monitoring system, except that it was to have sufficient Information available to Tiie contents of a reactor can be man analyze the samples, with gas chromatog clearly define which facilities should be ually vented to a gasholder or other hold raphy, or if all liydrocarbons were as excluded from the standard, and ing vessel. However, In some cases, such sumed to be vinyl chloride, with infrared encouraged Interested parties to submit as during severe weather conditions, sev spectrophotometry', flame ion detection, such Information during the comment eral reactors may be out of control at or equivalent. It required that each plant period. Based on the information sub one tunc. There would be insufficient submit a dcscriptioh of its monitoring mitted, EPA decided to exempt poly holding capacity under these conditions system to EPA, so that EPA could deter vinyl chloride reactors and associated equipment from applicability of all parts of the standard If the reactors are used In research and development and have a to manually vent the contents of all the reactors to a gasholder. Therefore, when all other measures to prevent relief valve discharges have been exhausted, manual mine whether it was acceptable or not. Comments were received indicating a need for EPA to specify some criteria for judging the acceptability of monitoring systems. The accuracy of the monltor- FEDERAL REGISTER, VOL 41, NO, 205--THURSDAY, OCTOBER 21, 1976 BOB 004919 RULES AND REGULATIONS 4G5G3 ' inn system would bo related to the fre (g) (3) (ii>, and 61.70(c) (2) (i) so that quency of calibration. Therefore. EPA measurement of the vinyl chloride levels has Included in the promulgated stsmd- in the resins is to be made immediately ard requirements for the frequency of after stripping is completed rather than calibration and procedures to be carried as the resin is being transferred out of out in the calibration of the monitoring the stripper. This allows a plant to carry instruments. out operations in a stripper after strip The portable hydrocarbon detector re ping has been completed but before it is quired by the proposed standard was re transferred out of the stripper. This Is quired to have a sensitivity of 5 ppm. consistent with the original intent of the Comments were received indicating that standard. Instruments in this sensitivity range arc The regulation for loading and unload delicate and require continuing mainte ing lines in 5 61.65(b)(1) has been re nance. The portable hydrocarbon detec vised to clarify that it applies only to tor Is required for leak detection and for lines that are disconnected after each uuidc the same as for other resins andothers requested that they be made less stringent. EPA decided not to make the standard for stripping dispersion resins the same as for other resins because there is sufficient evidence to Indicate that these resins are more difilcult to strip than other resms. With regard to mak ing the stripping levels for dispersion resins less stringent, only one of the eight manufacturers of dispersion resins spe cifically commented that the dispersion resin standard should be made less stringent. Only two of several grades of dispersion resins made by this company measuring vinyl chloride concentrations loading or unloading operation. Perma cannot meet the 2.000 ppm limit. The inside the equipment before opening it. nently installed pipelines that are opened proposed standard takes into considera A 5 ppm sensitivity is not needed in infrequently for inspection or mainte tion that some resins are more dittiru't either case, and the required sensitivity nance, for example, are covered by the to strip than others by providing for has been changed to 10 ppm in the pro opening of equipment regulation rather averaging among different resins. mulgated standard. than the loading and unloading line (5) 'Testing, reporting, and record The proposed standard contained a regulation. keeping. There are several relatively single regulation for compressors. The The regulation lor Inprocess waste- minor changes in the testing, reporting, promulgated standard has separate regu water in the proposed standard could and recordkeeping requirements. A pro lations for rotating and reciprocating have been misinterpreted to require In vision has been added to 5 61.67 which compressors. This is consistent noth hav dividual treatment of wastewater requires that stack gas samples taken ing separate regulations for rotating and streams. Section 61.65(b) (S) (1) of the with Test Method 10$ are to be analyzed reciprocating pumps in both the pro promulgated standard clarifies that within 24 hours. This is consistent with posed and promulgated standards. wastewater streams that are required to the requirements in the proposed Test Section 61.66 of the proposed standard be treated (i.e., those containing greater Method 106. Hie promulgated standard provided for the use of equivalent meth than 10 ppm vinyl chloride) can be com also specifies that in averaging the re ods of control which have been approved bined to be treated. However, waste- sults of the three runs required by Test by EPA. The promulgated standard re ' water streams that contain greater than Method 106, a time-weighted average is quires that the plant owner or operator 10 ppm vinyl chloride cannot be com to be used. submit a request for determination of bined with wastewater streams that con One commenter requested that the equivalency within 30 days, of the pro tain less than 10 ppm vinyl chloride be oxygen content and moisture content be mulgation date If the alternative control fore treatment; i.e., dilution cannot be specified for the 10 ppm concentration method Is intended as the initial means used to meet the standard. standards. The proposed standard speci of control. The purpose of this is to pro Hie commenters recommended several fied that the vinyl chloride concentration vide time for EPA to evaluate the method changes in the emission limits which Is to be corrected to 10 percent oxygen before the plant has to be in compliance have not been incorporated into the (wet basis) If combustion Is used as the. (for existing sources. 90 days after the promulgated standard. These are dis control measure. In the promulgated promulgation date). EPA also suggests cussed in the following paragraphs. standard, this requirement has been ex that this request for determination of It was recommended that the require panded to all control measures. equivalency be accompanied by a re ment for double mechanical seals on A provision has been added to the quest for waiver of compliance pursuant pumps, compressors, and agitators be re promulgated standard which states that to section 112(c) (1) (B> (ill of the Act. moved because the single seals currently If a reactor Is also used as a stripper, the The request for a waiver for compliance used on this equipment have small emis reactor opening emissions may be deter should provide lor the case where EPA sions and are more reliable than double mined immediately following the strip determines that a method is not equiv mechanical seals. EPA is aware that each ping operation. If a reactor is also used alent and the plant needs to purchase fugitive emission source, such as one as a stripper, the resin is in the reactor other equipment. In no case will the pump, taken by itself causes relatively when it is opened. This means that vinyl waiver of compliance be extended beyond small emissions. Fugitive emissions con chloride in the resin which has already two years from the date of promulga tion. . sidered as a whole are a significant source of emissions, however, and the in been stripped to acceptable levels can escape from the resin and become part There are several wording clarifica tent of the standard is to reduce these. of the reactor opening loss. It Is EPA's tions which have been made in the pro Double mechanical seal pumps are com intent that once a resin has been stripped mulgated standard. The definition for monly used in the industry for emission to the required levels, that additional "in vinyl chloride, service" ($60.61(1)) reduction. Sealless pumps or equivalent controls are not required. Under the new has been clarified by stating that it systems are available as options to double provision, vinyl chloride escaping from means equipment that contacts vinyl mechanical seals. the resin after it has been stripped to chloride as well as equipment that con The commenters recommended In acceptable levels is not counted as part tains vinyl chloride. This would include creasing the averaging time for the 10 of the reactor opening loss. such equipment as agitators. ppm limits and the emission limits for A section requiring continuous moni Words have been added in 55 61.62, 61.63, and 61.64 to clarify that the 10 reactor opening and stripping to 30 days. Some of tlie commented apparently toring of stack emissions has been added to the promulgated standard. The con ppm emission limits do not have to bo thought that the 10 ppm limits had to be tinuous monitoring of stack emissions met when equipment has already been met on an instantaneous basis. However, was required in the proposed standard. opened In compliance with the regula since the performance test for determin Hie addition oka specific paragraph for tion for opening of equipment. Equip ing compliance consists of three runs for emission monitoring serves only to ment that has met the opening of a minimum of an hour each, the aver clarify the requirement. equipment regulation can contain more aging time for the 10 ppm limit is at least Hie standard has been revised so that than 10 ppm vinyl chloride and would be three hours. Increasing the averaging the initial report requires a "description" In violation of the standard ff tills time to 30 days for any of the emission rather than a "detailed description" of statement were not Included. limits would permit higher peak emis the equipment used to control fugitive The requirements for stripping poly vinyl chloride resins to specified levels have been revised In 55 61.64(e), 61.67 sion levels. EPA has determined that this is neither desirable nor necessary'. Some commenters requested that the stripping levels for dispersion resins be emissions. Several commenters pointed out that a detailed description would contain proprietary information. EPA agrees that a detailed description in the FEDERAL REGISTER, V L. 41, NO. JOS--THURSDAY, OCTOBER 21, 1976 SOJR 4920 4G5GI RULES AND REGULATIONS Initial report Is unnecessary. If addi In section 6.4 of Tost Method 103 the (2) Vinyl chloride by any process, tional infor:n."i;:on la nceactl, LPA can requirement for n.n automatic integrator and/or obtain It under section 114 of the Act and has been replaced with a requirement for (3) One or more polymers.containing the plant can request confidential treat a disc integrator or planimcter for meas any fraction of polymerized vinyl chlo ment In accordance with 40 CPU Part 2 uring peak area. This change is in re ride. for Information It believes to bo sponse to a comment which states that . <b> This subpart does not apply to proprietary. automatic integrators are unnecessarily equipment used in research and develop The proposed standard required that elaborate and expensive. ment if the reactor used to polymerize a semiannual report be submitted every A new section 6.5 has been added to the vinyl chloride processed In the equip 180 days. The promulgated standard Test Method 106 which requires deter ment has n capacity of no more than specifies dates for the submittal of the mination of the water vapor content of 0.19 m* (50 gal). reports. It also specifics, that the first tlie sampling bag by measuring the am (c> Sections of this subpart other than semiannual report does not have to be bient temperature and pressure near the 5 G1.64(a) (1). <b>, (c.>, and (d) do not submitted until at least six months after bag. The vinyl chloride concentration of apply to equipment used in research and the Initial report is submitted. the bag can then be reported on a dry development if the reactor used to po The standard has been revised to elim basis. A provision for checking the rigid lymerize the vinyl chloride processed in inate the requirement to record the cause container for leaks has been added to the equipment has a capacity of greater of any leak detected by the vinyl chlo section 7.4 of Test Method 106. than 0.19 m" (50 gal) and no more than ride detector, the action taken to repair The only change in Test Method 107 is 4.07 m* (1100 gal). the leak, and the amount of time re the provision in Section 5.3.2 for use of 61.61 Definitions. quired to repair the leak. EPA is con cerned only that leaks are detected and repaired. That this has been done can be established by looking at the strip chart record of measurements made by the vinyl chloride detector. These records are still required for the portable hydrocar bon detector however. Several commentators recommended that the companies be allowed an extra two weeks to submit to EPA data from the initial performance test. They also recommended that they submit the data by regular mall rather than registered mail. EPA has not adopted either of these recommendations. A source Is supposed to be In compliance with the standard within 90 days of the promulgation of the standard. The standard requires that the emission tests be done within the 90 day period, and permits an extra SO days for determination of results. The purpose of using registered mail is to document the fact that emission data have been sent and received. This way If the results nre lost In the mail, there will be no question that they were sent. (6) Test method. Test Method 106 has been changed to recognize that on a gas chromatograph equipped with a Chrom- osorb 102 column, acetaldehyde may Interfere with the vinyl chloride peak. When a sample is expected to contain acetaldehyde, a secondary column as de scribed in section 4.3.2 must be employed. Mass spectroscopy or another absolute analytical technique Is required to con firm the vinyl chloride peak obtained with the gas chromatograph, only if peak resolution with the secondary column is not successful. In section 4.1.4, aluminized Mylar bags can be substituted for Tedlar bags. EPA now has data to allow this substitution, provided that the samples are analyzed within 24 hours of collection. In section 6.1.3 of Test Method 106 the requirement to use "oxygen gas" has been replaced with "oxygen gas or air, as Carbopak C as well as Carbopak A. Terms used in this subpart are defined Authority : Section 112 of the Clean Air in the Act, in subpart A of this part, or Act as added bv eee. 4(a) of Pub. L. 91-604, 84 Stat. ices (42 C.S.C. 1857C-7; Section 114 of the Clean Air Act, ns added by sec. 4(a) of Pub. h. 81-C04, 84 Stat. 1687, and amended by Pub. L. 83-319. sec. 6(a) (4). 88 Stat. 259 (42 D.S.C. 1857C-9); Section 301(a) of the Clean Air Act, as amended by sec. 16(c) (2) in this section as follows: (a) "Ethylene dichloride plant" in cludes any plant which produces ethyl ene dichioride by reaction of oxygen and hydrogen chloride with ethylene. (b) "Vinyl chloride plant" Includes of Pub. L. 61-604. 84 Btat. 1713 (42 O.S.C. any plant which produces vinyl chloride 1857g(a)). by any process. Hated: October 12,1976. (c) "Polyvinyl chloride plant" includes any plant where vinyl chloride alone or John Quarles, Acting Administrator. in combination with other materials Is polymerized. Part 61 of Chapter I. Title 40 of the (d) "Slip4gauge" means a gauge which Code of Federal Regulations is amended has a probe that moves through the gas/ as follows: The table of sections for Part liquid Interface in a storage or transfer 61 is amended by adding a list of sections vessel and indicates the level of vinyl for new Subpart P and Part 61 is chloride in the vessel by the physical amended by adding a new Subpart F state of the material the gauge dis reading as follows: charges. Subpart F--National Emission Standard for Vinyl ^ Chloride <e) "Type of resin" means the broad classification of resin referring to the - basic manufacturing process for produc 61.GO Applicability. ing that resin, including, but not limited 61.61 Definitions. 61.63 Emission standard for ethylene di- chlorlde plants. 61.63 Emission standard for vinyl chloride plants. 61.64 Emission standard for polyvinyl chlo ride plants. to, the suspension, dispersion, latex, bulk, and solution processes. <f) "Grade of resin" means the sub division of resin classification which de scribes it as a unique resin, i.e,, the most exact description of a resin with no fur 61.65 Emission standard for ethylene (11- ther subdivision. chloride, vinyl chloride and poly (g) "Dispersion resin" means a resin 61.66 61.67 61.68 6169 61.70 vinyl chloride plants. Equivalent equipment and procedures. Emission tests. Emission monitoring. Initial report. Semiannual report. manufactured in such away as to form fluid dispersions when dispersed In a plasticizer or plasticizer/diluent mix tures. <h) "Latex resin" means a resin which 61.71 Recordkeeping. is produced by a polymerization process Authority; Section 112 of the- Clean Air Act as added by sec. 4(a) of Pub. L, 81-604. which initiates from free radical catalyst sites and is sold undried. 84 Stat. 1685 (42 UJS.C. 1057C-7); section 114 (i) "Bulk resin' 'means a resin which of the Clean Air Act. os added by sec. 4(a) is produced by a polymerization process of Pub. L. 91-604. 84 Stat. 1687. and amended in which no water is used. by Pub. b. 93-310, sec. 6(a) (4), 88 Stat. 259 (42 U.S.C. 1057C-9); section 301(a) of the Clean Air Act. as amended by sec. 15(c) (2) of Pub. L. 01-604, 84 Stat. 1713 (42 U.S.C. 1857g(a)). (j) "Inprocess wastewater" means any water which, during manufacturing or processing, comes into direct contact with vinyl chloride or polyvinyl chloride required by the detector." Several commentors stated that most gas enromato- graphs are designed to use hydrogen and air for their flame detectors. When used Subpart F--National Emission Standard for Vinyl Chlorido g 61.60 Applicability. or results from the production or use of any raw material, intermediate product, finished product, i hv.-^rnduct, or waste product containing vinyl chloride or in this way, they nre capable of detect ing 0.5 ppm vinyl chloride in air. This Is sensitive enough for monitoring the 10 (a) This subpart applies to plants which produce: <1) Ethylene dichloride by reaction of polyvinyl chloride but which has not been discharged to * wastewater treat ment process or discharged untreated as wastewater. ppm emission limits stipulated In the oxygen and hydrogen chlorido with (k) "Wastewater treatment process" standard. ethylene. includes any process which modifies FEDERAL REGISTER, VOL 41, NO. 205--THURSDAY, OCTOBER 21, 1976 BOR 004921 RULES AND REGULATIONS 4G,'G.~ characteristic.1; such as BOD. COD. TSS. and pH, usually for the purpose of meet ing effluent guidelines and standards; it does not include any process the purpose of which is to remove vinyl chloride from water to meet requirements of this subpart. (1) "In vinyl chloride service" means that a piece of equipment contains or contacts either a liquid that is at least 10 percent by weight vinyl chloride or a gas that is at least 10 percent by volume vinyl chloride. <m> "Standard operating procedure" means a formal written procedure offi cially adopted by the plant owner or operator and available on a routine basis to those persons responsible for carrying out the procedure. (n) "Run" means the net period of time during which an emission sample is collected. (o) "Ethylene dichloride purification" includes any part of the process of ethyl ene dichloride production which follows ethylene dichloride formation and in which finished ethylene dichloride is produced. (pi "Vinyl chloride purification" in cludes any part of the process of vinyl chloride production which follows vinyl chloride formation and to which finished vinyl chloride is produced. (ql "Reactor" includes any vessel in which vinyl chloride is partially or totally polymerized into polyvinyl chloride. 5 (tl.fi.) I'mi--*m wlamlnrd for siiisl rlilorulr lil.niK. An owner or operator of a vinyl chlo ride plant shall comply with the require ments of this section and 5 61.65. ia) Vinyl chloride formation and puri fication: The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from any equipment used in vinyl chloride formation and/or purification is not to exceed 10 ppm, ex cept as provided in f 61.65(a). This re quirement does not apply to equipment that has been opened, is out of operation, and met the requirement to 5 61.65(b) < 61 < 11 before being opened. 61.61 Kiiii-mimi .inndard for polliujI rllliiritli* pk'illr- An owner or operator of a polyvinyl chloride plant shall comply with the re quirements of this section and 5 61.65. (a> Reactor: The following require ments apply to reactors: (11 The concentration of vinyl chlo ride in all exhaust gases discharged to the atmosphere from each reactor is not to exceed 10 pom. except as provided in paragraph <z> <2> of this section and 5 61.65(a>. i ?1 The reactor opening loss from each reactor is not to exceed 0.02 g vinyl chloride'Kg `0.00002 lb vinyl chloride/ lb' of polyvinyl chloride product, with the prouuct determined on a dry solids basis. This requirement applies to any vessel whicii is used as a reactor or as stripper *or the reactor if the plant has no stripper) in the plant process How is not to exceed 10 ppm, except as provided to i 61.65(a). nils requirement does not apply to equipment that has been opened, is out of operation, and met the requirement to 61.65(b) (6> (i) before being opened. (d' Monomer recovery system. The concentration of vinyl chloride in all ex haust gases discharged to the atmos phere from each monomer recovery sys tem is not to exceed 10 ppm. except as provided to S 61.65(a). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in S 61.65ibH6> <i> be fore being opened. (e Sources following the stripper(s1: The following requirements apolv to emissions of vinyl chloride to the at mosphere from the combination of all sources following the stnppens) I nr the reactor(s) if the plant has no strioper(s)] to the plant process flow in cluding but not limited to, centrifuges, concentrators, blend tanks, filters, dry ers. conveyor air discharges, baggers, storage containers, and inprocess wastewater: (1) In polyvinyl chloride plants using stripping technology to control vinyl chloride emissions, the weighted average residual vinyl chloride concentration m all grades of polyvinyl chloride resin processed through the stripping opera tion on each calendar day. measured (r) "Reactor opening loss" means the both a reactor and a stnpper. In the immediately after the stripping opera emissions of vinyl chloride occurring hulk process, the product means the tion is completed, may not exceed: when a reactor is vented to the atmos gross product of prepolymerization and (1) 2000 ppm for polyvinyl chloride phere for any purpose other than an postpolymeriza tion. dispersion resins, excluding latex resins: emergency relief discharge as defined in <31 Manual vent valve discharge: Ex (iii 400 ppm for all other polyvinyl f 61.65(a). cept for an emergency manual vent valve chloride resins, including latex resins, (s) "Stripper" includes any vessel in. discharge, there is to be no discharge to averaged separately for each type of res which residual vinyl chloride is removed tlie atmosphere from any manual vent in: or from polyvinyl chloride resin, except valve on a polyvinyl chloride reactor in (2) In polyvinyl chloride plants con bulk resin, in the slurry form by the use vinyl cnloride service. An emergency trolling vinyl chloride emissions with of heat and/or vacuum. In the case of manual vent valve discharge means a technology other than stripping or in bulk resin, stripper includes any vessel discharge to the atmosphere which could addition to stripping, emissions of vinyl which is used to remove residual vinyl not have been avoided by taking meas chloride to the atmosphere may not chloride from polyvinyl chloride resin ures to prevent the discharge. Within 10 exceed: immediately following the polymeriza days of any discharge to the atmosphere (i)2 g/kg (0.002 lb/lb) product from tion step in the plant process flow. from any manual vent valve, the owner the stripper (s) lor reactor (s' if the 61.62 Emission standard for ethylene dirliloridf plants. An owner or operator of an ethylene or operator of the source from which the discharge occurs shall submit to the Ad ministrator a report to writing contain ing information on the source, -nature plant has no stripper(s)] for dispersion polyvinyl chloride resins, excluding latex resins, with the product determined on a dry solids basis: dicliloride plant shall comply with tlie requirements of this section and 5 61.65. (a) Ethylene dichloride purification: The concentration of vinyl chloride in all exhaust gases discharged to the at mosphere from any equipment used in and cause of the discharge, the date and time of the discharge, the approximate totai vinyl chloride loss during the dis charge, the method used for determining tlie vinyl chloride Joss, the action that was taken to prevent the discharge, and measures adopted to prevent future-dis (ii> 0.4 g/kg (0.0004 lb lb) product from the strippers lor reactor(s) if the plant has no stripper(s) ] for all other polyvinyl chloride resins, including latex resins, with the product determined on a dry solids basis. ethylene dichloride purification is not charges. 61.65 Fiiii*ion Mitiultml for vtiii Ii-iii- to exceed 10 ppm, except as provided in $ 61.65(a). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement to 61.65(b) before being ib) Stripper: The concentration of vinyl chloride in all exhaust gases dis charged to the atmosphere from each stripper is not to exceed 10 ppm, except as provided m 5 61.C5ta). This require ment docs not apply to equipment that dicliloriilc. viny 1 rliWiilr am) poly vinyl i-ltloriiic plant!.. An owner or operator of an ethylene dichloride, vinyl chloride, and/or poly vinyl chloride plant shall comply with the requirements of this section. opened. has been opened, is out of operation, and (a) Relief valve discharge: Except for (b) Oxychlorination reactor: Except as provided in S 61.65(a), emissions of met the requirement to 61.65(b) (6) (1) before being opened. an emergency belief discharge, there is to be no discharge to the atmosphere vinyl chloride to the atmosphere from (ci Mixing, weighing, and holding from any relief valve on any equipment each oxychlorination reactor are not to exceed 0.2 E/kg the 100 percent ethylene dichloride product from the oxychlori nation process. containers: The concentration of vinyl chloride in all exhaust gases discharged to the ` atmosphere from each mixing, weighing, or holding container in vinyl chloride service which precedes the in vinyl chloride service. An emergency relief discharge means a discharge which could not have been avoided by taking measures to prevent the discharge. With in 10 days of any relief valve discharge. FEDERAL REGISTER, VOL. 41, NO. 205--THURSDAY, CTOBER 21, 1*76 BOR 004922 4G566 RULES AND REGULATIONS the owner or operator of tlic source from which the relief valve discharge occurs shall submit to the Administrator a re port in wriLing-containing information sv.stcm from which the concentration of vinyl chloride ill the exhaust gases does not exceed 10 ppm; or equivalent as provided in f 61.G6. ride is to bo reduced so that the equip ment contains no more then 2 0 pci-'cnt by volume vinyl chloride or 0 C.Oi) m `-5 gal) of vinyl chloride, wi vhevor is ou the source, nature and cause of the discharge, the date and time of the dis charge. the approximate total vinyl chlo ride loss during the discharge, the meth od used for determining the vinyl chlo ride loss, the action that was taken to prevent the discharge, and measures adopted to prevent future discharges. tin' Rotating compressor; Vinyl cliioncle emissions from seals on all ro tating compressors in vinyl chloride service are to be minimized by installing, compressors with double mechanical seals, or equivalent as provided in 5 61.66. If double mechanical seals are used, vinyl chloride emissions from the seals are to larger, at standard temperature anu pressure; and ii Any vinyl chloride removed from the equipment in accordance with para graph (b)(6) (i) of this section is to be ducted through a control system from winch tiie concentration of vmyl chlo ride in the exhaust gases does not exceed <b) Fugitive emission sources: be minimized by maintaining the pres 10 ppin, or equivalent ns provided in (1) Loading and unloading lines: Vinyl chloride emissions from loading and un leading lines which are opened to the atmosphere after each loading or un loading operation are to be minimized sure between the two seals so that any leak that occurs is into the compressor; by ducting any vinyl chloride between the tv;o seals through a control system from winch the concentration of vinyl 61.66. (71 Samples: Unused portions of sam ples containing at least 10 percent by weight vinyl chloride are to be returned to the process, and sampling techniques as follows : chloride in the exhaust gases1 does not arc to be such that sample containers in (i) After each loading or unloading exceed 10 ppm; or equivalent as provided vinyl chloride service arc purged into a operation and before opening a loading mf 61.66. closed process system. or unloading line to the atmosphere, the (ivi Reciprocating compressors: Vinyl <81 Leak detection and elimination; quantity of vinyl chloride in all parts of chloride emissions from seals on all re Vinyl chloride emissions due to leaks each loading or unloading line that are ciprocating compressors in vinyl chloride from equipment in vinyl chloride service to be opened to the atmosphere is to be service arc to be minimized by installing are to be minimized by instituting and reduced so that the parts combined con double outboard seals, or equivalent as implementing a formal leak detection tain no greater than 0.0036 m! (0.13 ft5) provided in 61.66. If double outboard and elimmation program. The owner or of vinyl chloride, at standard tempera seals are used, vinyl chloride emissions operator shall submit a description of ture and pressure; and from the seals are to be minimized by the program to the Administrator for (ii) Any vinyl chloride removed from maintaining the pressure between the approval. The program is to be sub a loading or unloading line in accord two seals so that any leak that occurs is mitted within 43 days of the effective ance with paragraph tb)(l)(i> of this into the compressor: by ducting any date cf these regulations, unless a waiver section is to be ducted through a control vinyl chloride between the two seals of compliance is granted under S 61.11. system from which the concentration of through a control system from which the If a waiver of compliance is granted, the vinyl chloride in the exhaust gases does concentration of vinyl chloride in the Program is to be submitted on a date not exceed 10 ppm, or equivalent as pro exhaust gases does not exceed 10 ppm; scheduled by the Administrator. Ap vided in $ 61.66. or equivalent as provided in 61.66. proval of a program will be granted by <2) Slip gauges: During loading or un <v) Agitator: Vinyl chloride emissions the Administrator provided he finds: loading operations, the vinyl chloride from seals on all agitators in vinyl chlo (i) It includes a reliable and accurate emissions from each slip gauge m vinyl ride service are to be minimized bv in vinyl chloride monitoring system for de chloride service are to be minimized by stalling agitators with double mechani tection of major leaks and identification ducting any vinyl chloride . .'Charged cal seals, or equivalent as provided in of the general area of the plant where a from the slip gauge through control 61.66. If double mechanical seals ore leak is located. A vinyl chloride monitor system from which the concentration of used, vinyl chloride emissions from the ing system means a device which obtains vinyl chloride in the exhaust gases does seals are to be minimized by maintaining air samples from one or more points on not exceed 10 ppm, or equivalent as pro the pressure between the two seals so a continuous sequential basis and ana vided in S 61.66. that any leak that occurs is into the agi lyzes the samples with ess chromatog (3) Leakage from pump, compressor, tated vessel; by ducting any vinyl chlo raphy or, if the owner or operator as and agitator seals: ride between the two seals through a sumes that all hydrocarbons measured (i) Rotating pumps: Vinyl chloride control system from which the concen are vinyl chloride, with infrared spectro emissions from seals on all rotating tration of vinyl chloride in the exhaust photometry dame ion detection, or an pumps in vinyl chloride service are to be gases does not exceed 10 ppm: or equiva equivalent or alternative method. minimized by installing sealless pumps, lent as provided in 5 61.66. i ii) It includes a reliable and accurate pumps with double mechanical seals, or (4) Leakage from relief valves: Vinyl portable hydrocarbon detector to be used equivalent as provided in 61.66. If chloride emissions due to leakage from routinely to find small leaks and to pin double mechanical seals are used, vinyl each relief valve on equipment in vinyl point the major leaks indicated by the chloride emission from the seals are to chloride service are to be minimized by vinyl chloride monitoring system. A be minimized by maintaining the pres installing a rupture disk between the portable hydrocarbon detector means a sure between the two seals so that any eauipment and the relief valve, by con device which measures hydrocarbons leak that occurs is into the pump; by necting the relief valve discharge to a with a sensitivity of at least 10 ppm ducting any vinyl chloride between the process line or recovery system, or equiv and is cf such design and size that it can two seals through a control system from alent. as provided in 61.66. be used to measure emissions from local which the concentration of vinyl chlo i5> Manual venting of gases: Fxcept ized points. ride in the exhaust gases does not ex as provided in 61.64(a) (3). all gases i iii) It provides for an acceptable cali ceed 10 ppm; or equivalent as provided which are manually vented from equip bration and maintenance schedule for in 61.66. ment in vinyl chloride service are to be the vinyl chloride monitoring system and (ii) Reciprocating pumps: Vinyl chlo ride emissions from seals on all recipro cating pumps in vinyl chloride service are to be minimized by installing double ducted through a control system from winch the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm: or equivalent as provided in $ 61.66. portable hydrocarbon detector. For the vinyl chloride monitoring system, a daily span check is to be conducted with a outboard seals, or equivalent as provided (G> Opening of equipment: Vinyl concentration of vinyl chloride equal to in 61.66. If double outboard seals are chloride emissions from opening of the concentration defined as a leak ac used, vinyl chloride emissions from the equipment (including loading or unload cording to paragraph (b) (8) (vi) of this seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the ing lines that arc not opened to the at mosphere after each loading or unload ing operation) are to be minimized as follows: section. The calibration is to be done with either: ' (A) A calibration gas mixture pre pump; by ducting any vinyl chloride be (i) Before opening any equipment for pared from the gases specified in sections tween the two seals. through a control any reason, the Quantity of vinyl chlo 5.2.1 and 5.2.3 of Test Method 106, or TEDERAL REGISTER, VOL 41, NO. 305--THURSDAY, OCTODER 21, l7ft Bor 004923 RULES AND REGULATIONS 40367 <B' A calibration gas cylinder contain ing the appropriate concentration of vinyl chloride. II o calibration gas cylin der is used, the analysis must be trace able to the National Bureau of Stand ards or to a gravimetncally calibrated vinyl chloride permeation tube. <fv> The location and number of points to be monitored and the frequency of monitoring provided for in the program are acceptable when they are compared with the number of pieces of equipment in vinyl chloride service and the size and physical layout of the plant. (v) It contains an acceptable plan of action to be taken when a leak is de tected. (vi) It contains a definition of leak which is acceptable when compared with the background concentrations of vinyl vinyl chloride in equipment s4,75 m" 01250 gal In volume for which an mis sion limit is prescribed In $ 61.65(b) (6) (i) prior to opening the equipment and of emission test results and other data needed to determine emissions. (g) Unless otherwise specified, the owner or operator shall use test Test Methods In Appendix B to this part for using Test Method 106, a portable hydro each test as required by paragraphs carbon detector, or an equivalent or al (g)(1), (g)(2), (g)(3). (g)(4), and ternative method. The method of meas (g)(5) of this section, unless an equiva urement is to meet the requirements in 5 61.67(g) (5) (i> (A) or (g)((5)(i)(B). lent method or an alternative method has been approved by the Administrator. If the Administrator finds reasonable (il.fiA Equivalent ff|iti|>niciit mid pro grounds to dispute the results obtained cedure?. , by an equivalent or alternative method, Upon written application from an own er or operator, the Administrator may approve use of equipment or procedures he may require the use of a reference method. If the results of the reference and equivalent or alternative methods do not agree, the results obtained by the which have been demonstrated to his reference method prevail, and the Ad satisfaction to be equivalent in terms of ministrator may notify the owner or reducing vinyl chloride emissions to the operator that approval of the method chloride in the areas of the plant to be monitored by the vinyl chloride monitor ing system. Measurements of background concentrations of vinyl chloride in the areas of the plant to be monitored by the vinyl chloride monitoring system are to be included with the description of the program. The definition of leak for a given plant may vary among the differ ent areas within the plant and is also to change over time as background con centrations In the plant are reduced. <9> Inprocess wastewater: Vinyl chlo atmosphere to those prescribed for com pliance with a specific paragraph of this subpart. For an existing source, any re quest for using an equivalent method as the initial measure of control is to be submitted to the Administrator within S3 days of the effective date. For a new source, any request for using an equiva lent method is to be submitted to the Administrator with the application for approval of construction or modification required by 5 61.07. previously considered to. be equivalent or alternative is withdrawn. (1) Test Method 106 is to be used to determine the vinyl chloride emissions from any source for which an emission limit is prescribed m in 61.62(a) or (b) I 61.63(a), or II 61.64(a) (1), (b). (c), or (d), or from any control system to which reactor emissions are required to be ducted in | 61.64(a) (2) or to which fugi tive emissions are required to be ducted in IS 61.65(b) (1) (ii), (b)(2), (b)(5), (b) (6)(ti),or (b)(9)(ii). ride emissions to the atmosphere from 61.67 Emission tcsls. (i) For each run, one sample is to be lnprocess wastewater are to be reduced as follows: (i) The concentration of vinyl chlo ride in each inprocess wastewater stream co'ntaining greater than 10 ppm vinyl chloride measured immediately as it leaves a piece of equipment and before being mixed with any other inprocess wastewater stream is to be reduced to no more than 10 ppm by weight before being mixed with any other inprocess wastewa ter stream which contains less than 10 ppm viijy] chloride: before being exposed to the atmosphere, before being dis charged to a wastewater treatment proc ess : or before being discharged untreated as a wastewater. The paragraph does apply to water which is used to displace vinyl chloride from equipment before it is opened to the atmosphere in accord ance with 5 61.64(a)(2) or paragraph (b) <G) of this section, but does not apply to water which is used to wash out eouipment after the equipment has alreaay been opened to the atmosphere in ac cordance with 5 61.64(a) (2) or para graph (b) (6) of this section. (ii) Any vinyl chloride removed from the inprocess wastewater in accordance with paragraph (b) (9) (i) of this section is to be ducted through a control system from which the concentration of vinj'l chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided In I 61.66. (c> The requirements in paragraphs (b)(1), (b)(2). (b)(5), (b)(6), (b)(7) la) Unless a waiver of emission testing is obtained under 61.13, the owner or operator of a source to which this sub part applies shall test emissions from the source, (1) Within 90 days of the effective da te in the case of an existing source or a new source which has an initial startup date preceding the effective date, or (2> Within 90 days of startup in the case of a new source, initial startup of which occurs after the effective date. (b) The or,Tver or operator shall pro vide the Administrator at least 30 days pnor notice of an emission test to afford tile Administrator the opportunity to have an observer present during the test. tc> Any emission test is to be con ducted while the equipment being tested is operating at the maximum production rate at which the equipment will be op erated and under other relevant condi tions as may be specified by the Adminis trator based on representative perform ance of the source. (d> Each emission test is to consist of three runs. For the purpose of deter mining emissions, the average of results of all runs is to apply. The average is to be computed on a time weighted basis. <e> All samples are to be analyzed witlnn 24 hours, and vinyl chloride emis sions are to be determined within 30 days after the emission test. Hie owner or operator shall report the determinations to the Administrator by a registered letter dispatched before the close of the collected. The sampling site is to be at least two stack or duct diameters down stream and one half diameter upstream from any flow, disturbance such as a bend, expansion, contraction, or visible flame. For a rectangular cross section an equivalent diameter is to be determined from the following equation: equivalent diameter 2 length) (width) length + width ; The sampling point in the duct is to be at the centroid of the cross section. The sample Is to be extracted at a rate proportional to the gas velocity at the sampling point. The sample is to be taken over a minimum of one hour, and is to contain a minimum volume of 50 libers corrected to standard conditions. (ii) For gas streams containing more than 10 percent oxygen, the concentra tion of vinyle chloride as determined bv Test Method 106 is to be corrected to 10 percent oxygen for determination of emissions by using the following equa tion : C,, (correilct!) 10,1) CtK2?0i .0--ixrc^nt O* whore; ttnifMitisUion of vinyl chlnridr in the exhaust cases, corrected to lo j i . porfrnt oiypen. C*The concentration of vinyl chloride ns measured by Ten Method lot#. 20.9pcrccut otyfft'ii in tbo ambient nir at standard conditions. fO.ftspcrrcm oxycen in the ambient air at standard conditions, minus the 10 percent otypen to which tho foinv and (b) (8) of this section are to be in next business day following the deter corporated into a standard operating mination. ... U<m Is being mode, Pcrccnl O:--Percent otveon in the exhaust pu* ns sncfttttffd Ivy Ueft'Tonce Method 3 in Procedure, nnr made available upon re (f) The owner or operator shall retain Appendix A of Part Co of Due clniptor. quest for inspection by the Administra tor. The standard operating procedure is to include provisions for measuring the at the plant and make available, upon request, for inspection by the Adminis trator, for a minimum of 2 years records (ill) For those emission sources where the emission limit Is prescribed In terms of mass rattier than concentration, mass FEDERAL REGISTER, VOL. 41, NO. JOS--THURSDAY, OCTOBER 21, 1476 BOR 004924 4G56S RULES AND REGULATIONS emissions in kg'100 kq product are to be dclcnnincd by using the following equation: ,, IC (2.60) 0 10-*] 1100] C.x--------------- z-------------- where; O j m kR vinyl clUoridc/iofl kt product. that is also used as a stripiier. the deter mination may be made immediately fol lowing the stripping operation. <i) Except as provided in paragraph (g) (5) (ii) of this section, the reactor opening loss Is to be determined using the following equation: detection, or an equivalent or alterna tive method. The vinyl chloride monitor ing system used to meet the requirements in s 6l.G5(b> (8) <i) may be used to meet the requirements of this section. (c) A daily span check is to be con ducted for eacli vinyle chloride monitor ing system used. For all of the emission C*-Tlic eoucAntraiiou of vinyl chloride te measured by Twt Method 10U. 2.60^DrnsiLy of vinyl chloride at one atmosphere and c,,~ TT (2.G0) Y(1y0-*) (Cl.) sources listed m paragraph 'a> of this section, except the one lor which an emis 1 *J0C in QYt)lnmrtnc how rate In tns/hf iw determined lw Vvh* TM sion limit is prescribed m 5 61.621b', the Hefi*reo Method 2 of Appendix A Co Purl W> of this chanter. SO-*Coim'rsiotinM-tor for ppm. #Bi>roduruon rate (kg/ht). M -skf'af vpi^ncyiilyfMnnoiirrtndMf c<m'UKihrImoiTisuAc\J! product 2.ttO~ 1/CiiMt v af vmj, I chloride nt one AlUHKpln'r** 3>V1 20* Cin kp'Tii*. dally span check is to be conducted with a concentration of vinyl chloride equal to 10 ppm. For tlic emission source lor (2) Test Method 107 is to be used to determine the concentration of vinyl chloride in each inprocess wastewater stream for which an emission limit is prescribed in 5 6l.65<b) (9> (i). (3) Where a stripping operation Is used to attain the emission limit in S 61.- jo-r Com version Liclor tor ppm. C0|pin by volume vinyl chloride a* determined by Ten Method IOC or o portable Jivdiocnrhoii detector which measures hydrocarbon* with a *<*u>dlmi,v of At bsiht jo ppm. J*--Nmol-er ef Intehe* since the rcielor wti$ opened to the at mospbero, 'Average k(L of poiyvmyl chloride pindiiicd per lurch to t he nmobiT of batches iucf tn* n^ctor was l;vi opvncd to Lite aUUQphcic. which an emission limit is prescribed in S 61.02'b). the daily span check is to be conducted with a concentration of vinyl chloride which is determined to be determined to be equivalent to the emis sion limit for that source based on the emission test required by S 67.67. The 64(e), emissions are to be determined using Test Method 107 as follows: calibration is to be done witli cither: tA) If MeUiod 106 is used to deter tl) A calibration gas mixture pre (i) The number of strippers and sam mine the concentration of vinyl chloride pared from the gases specified in sections ples and the types and grades of resin to iCb>, the sample is to be withdrawn at 5.2.1 and 5.2.3 of Test Method 106, or be sampled are to be determined by the a constant rate with a probe of sufficient 121 A calibration gas cylinder con Administrator for each individual plant length to reach the vessel bottom from taining the appropriate concentration of at the time of the test based on the the manhole. Samples are to be taken vinyl chloride. If a calibration gas plant's operation. for 5 minutes within 6 inches of the ves cylinder is used, the analysis must be (ii) Each sample is to be taken imme sel bottom, 5 minutes near the vessel traceable to the National Bureau of diately following the stripping operation. center, and 5 minutes near the vessel top. Standards or to a gravimetncally cali- (iii) The corresponding quantity ef <B> If a portable hydrocarbon detec braioti vinyl chloride permeation tube. material processed by each stripper is to tor is used to determine the concentra 61,60 lm'li.il report. be determined on a dry solids basis and by a method submitted to and approved by the Administrator. (iv) At the prior request of the Ad ministrator, the owner or operator shall provide duplicates of the samples re quired in paragraph (g)(3)(i) of this section. (4) Where control technology other than or in addition to a stripping opera tion is used to attain the emission limit In Gl.C4(e), emissions are to be deter mined as follows: (i) Test Method 106 is to be used to determine atmospheric emissions from all of the process equipment simultane tion of vinyl chloride (Cb), a probe of sufficient length to reach the vessel bot tom from the manhole is to be used to make the measurements. One measure ment wj)] be made within 6 inches of the vessel bottom, one near the vessel center and one near the vessel top. Measure ments are to be made at each location until the reading is stabilized. All hydro carbons measured are to be assumed to be vinyl chloride. (C> The production rate of polyvinyl chloride (Z) is to be determined by a method submitted to and approved by the Administrator. (ii) A calculation based on the number (a) An owner or operator of any source to which this subpart applies shall submit a statement in writing notifying the Administrator that the equipment and procedural specifications in j 61.65 (b)(1), >*<2), (b)(3), (b)(4). (b)(5), (b)(6>, (b)(7i, and (b)(8) are being implemented. (b) (1) In the case of an existing source or a new source which has an initial startup date preceding the effec tive date, tire statement is to be submit ted within SO days of the effective date, unless a waiver of compliance is granted under 61.11, along with the informa tion required under 61.10. If a waiver ously. The requirements of paragraph (g) <1) of this section are to be met. (ii) Test Method 107 is to be used to determine the concentration of vinyl chloride in each inprocess wastewater stream subject to the emission limit pre scribed in 61.64(e). The mass of vinyl of evacuations, the vacuum involved, and the volume of gas in the reactor is herebyapproved by the Administrator as an al ternative method for determining reac tor opening loss for postpolymerization reactors m the manufacture of bulk resins. of compliance is granted, the statement is to be submitted on a date scheduled by the Administrator. (2) In the case of a new source which did not have an initial startup date pre ceding the effective date, the statement is to be submitted within 90 days of the chloride in kg/100 kg product in each 61.68 Emit.Nun monitoring. initial startup date. in process wastewater stream is to be de termined by using the following equa tion; r JC,, R 10-1 [100| t'BY-t'fi vinyl chlorldc/100 L'p product. C'j~fl>< concentration o1 rinjl ciiloudc its liir.MUcl bv Test Method 107. M jtcr How r.ilr m I hr. determined in nrronl.tnro with tv method which hits lirrn svilnnitted to tntd ttPproscU by the Adminjstr.itor. lO-t^Convereton factor for ppm. Zt Production rate (kc'hrj, determined m accord* auio wnli a method wIulU \\wr Uvn M\UiriU>-tl And approved Ijy (he Administrator. a) A vinyle chloride monitoring sys tem is to be used to monitor on a con tinuous basis the emissions from the sources for which emission limits are pre scribed in 5 61.62(a) and (b), 5 61.63(a). and 5 61.64(a) (1), (b), <c). and 'd>. and for any control system to which reactor emission are required to be ducted in 5 6i.65tb> tl> <ii), and fb)(2>. <bM5>, (b. (6) (ii), and (b) (0) (ii). <b) The vinyl chloride monitoring sys tem <$) used to meet the requirement in paragraph (a) of this section is to be a (c) The statement is to contain the following information: (1) A list of. the equipment installed for compliance, (2> A description of the physical and functional characteristics of each piece of equipment. (3) A description of the methods which have been incorporated into the standard operating procedures for meas uring or calculating the emissions for which emission limits are prescribed in S 61.65 (b> (1) (i) and (b)(6)(i), (4) A statement that each piece of (5) The reactor opening loss for which dciiee which obtains air sampels from equipment is installed and that eacli an emission limit is prescribed in 5 61.G4 one or more points on a continuous piece of equipment and each procedure (a) (2) is to be determined. Tlic number sequential basis and analyzes the samples is being used. of reactors for which the determination Is to be made is to be specified by the with cas rhromotography or. if the owner 61.70 S-niisnm:'.l r. port. Administrator for eacli individual plant or operator assumes that all hydrocar (a> (21 is to be determined. The number at the time of the determination based bons measured are vinyl chloride, with source to which this subpart applies shall on the plant's operation. For a reactor infrarea spectrophotometry, flame ion submit to the Administrator on Septcm - FEDERAL nHClSTEW, VOL. 41, NO. JOS--THURSDAY, OCTOBER S1, TV70 BOR 004925 RULES AMD REGULATIONS 4G5G9 bcr 15 find March 15 of each year a report In writing containing the information of 3 hours for each grade of resin which is being processed, whichever is more fre may be made immediately following the stripping operation, required by this section. The first semi annual report is to be submitted follow ing the first full 6 month reporting period after the initial report is submitted. (b) (1) In the case of an existing source or a new source which has an initial startup date preceding the effective date, the first report is to be submitted within 180 days of the effective date, unless a waiver of compliance is granted under {61.11. If a waiver of compliance is granted, the first report is to be sub mitted on a date scheduled by the Ad ministrator, (2)In the case of a new source which did not have an initial startup date pre ceding the effective date, the first report is to be submitted within 180 days of the initial startup date. (c) Unless otherwise specified, the owner or operator shall use the Test Methods in Appendix B to this part to conduct emission tests as required by paragraphs (c> (2) and (c) (3) of this section, unless an equivalent or an alter native method has been approved by the Administrator. If the Administrator finds reasonable grounds to dispute the results obtained by an equivalent or al ternative method, he may require the use of a reference method. If the results of the reference and equivalent or alterna tive methods do not agree, the results obtained by the reference method pre quent, The sample is to be taken as the resin flows out of the stripper and iden tified by resin type and grade and the date and time the sample was taken. The corresponding quantity of material processed by each stripper over the time period represented by the sample during the eight hour period, is to be recorded and identified by resin type and grade and the date and time it represents. (iii) The quantity of material proc essed by the stripper is to be determined on a dry solids basis and by a method submitted to and approved by the Ad ministrator. (iv) At the prior request of the Ad ministrator, the owner or operator shall provide duplicates of the samples re* ciuired in paragraphs (c) (2) (i) and (c) fif'Ui) of this section. ) v> The report to the Administrator by the owner or operator is to include the vinyl chloride content found in all the samples required in paragraphs (c) (2) (i) and (c) (2) (ii) of this section, aver aged separately for each type of resin, over each calendar day and weighted ac cording to the quantity of each grade of resin processed by the stripper(s) that calendar day, according to the following equation: n S Po.Afo, 61,71 Recordkeeping. (a) The owner or operator of any source to which this subpart applies shall retain the following information at the source and make It available for inspec tion by the Administrator ior a mini mum of two years: (I) A record of the leaks detected by the vinyl chloride monitoring system, as required by 5 61.65(b)(8), including the concentrations of vinyl cliionde as measured, analysed, and recorded by the vinyl chloride detector, the location of each measurement and the date and ap proximate time of each measurement, <2) A record of the leaks detected during routine monitoring with the portable hydrocarbon detector and the action taken to repair the leaks, as re quired by 5 61.65(b)(8), including a brief statement explaining the location and cause of each leak detected <witn the portable hydrocarbon detector, the date and time of the leak and any action taken to eliminate that leak measured m accordance with 6 61.68. (3) For the relief discharges from reactors subject to the provisions of 5 61.65(a), a daily operating record for each reactor, including pressures and temperatures. 2. Appendix B Is amended by adding Test Methods 106 and 107 as follows: vail, and the Administrator may notify Mtthod 108--Determination or Vinyl the owner or operator that approval of Chloride root* Stationary Sources the method previously considered to be equivalent or alternative is withdrawn, (1) The owner or operator shall in clude in the report a record of any emis sions which averaged over any hour period (commencing on the hour) are AfC| + Pg, A/tfj + ... + P<7w Qti A "24-Ikjui average concentration of type T, rosin in ppm, production of tyi>c T, resin over the 24-hour portod.m kg. introduction Performance of this method should not oe attempted by persons unfsmillar with the operation of a gas chromatograph, nor bv those who are unfamiliar with source sam pling. as there are man; details that are in excess of the emission limits pre scribed in 61.62(a) or (b), 5 61.63(a), or 55 61.64(a) (1), (b), (c), or (d), or for any control system to which reactor emissions are required to be ducted in 5 61.64(a) (2) or to which fugitive emis sions are required to be ducted in 5 61.65 Typo of re?ir; , m where m is total number of ri-riu types produced durine the 24- hour period, .V^Concj'iitration of vinyl chloride in one sample of crado U% re?ln, in ppm. /'-Production of grade <n resin represented by the f7i = SA/npIo, in kg. (Jrodt*of resm.e.c., G\, ft;, And 0j. n--Tottd number ol trades of rosin produced during the <tf'hour period. beyond the scope of this presentation. Care must be exercised to prevent exposure of sampling personnel to vinyl chloride, a car cinogen. 1. Principle and Applicability. 1.1 An integrated bag sample of stack gas Containing vinyl chloride (chloroethylene) is subjected to chromatographic analysts, (b) (1) (ii), (b)(2), (b)(5), (b) (6) (ii), or (b) (9) fli). Hie emissions are to be meas ured in accordance with 61.68. (2) In polyvinyl chloride plants for which a stripping operation is used to attain the emisison level prescribed in 5 61.64(e), the owner or operator shall include in the report a record of the vinyl chloride content in the polyvinyl chloride resin. Test Method 107 is to be used to determine vinyl chloride content as follows: <i) If batch stripping is used, one rep resentative sample of polyvinyl chloride (vi) The owner or operator shall re tain at the source and make available for inspection by the Administrator for a minimum of 2 years records of all data needed to furnish the information re quired by paragraph (c) (2) (v) of this section: The records are to contain the following information: (A) Tlie vinyl chloride content found in all the samples required in paragraphs (c) (2) (U and (c> (2) (ii) of this section, identified by the resin type and grade and the time and date of the sample, and (B) The corresponding quantity of using a flame Ionization detector. 1.2 The method Is applicable to the meas urement of vinyl chloride in stack gases from ethylene dlchloride, vinyl chloride and poly vinyl chloride manufacturing processes, ex cept where tlie vinyl chloride is contained In particulate matter. 2. Range and Sensitivity. The lower limit of detection will vary ac cording to the chromatograph used. Values reported Include 1 x 10-T mg and 4 x 10-T mg. 3. Interferences. Acetaldehyde, which can occur m some vinyl chloride sources, will Interfere with the vinyl chloride peat from the phromosorb 102 resin is to be taken from each batch of each grade of resin immediately follow ing the completion of the stripping, and grade and the date and time the batch is completed. The corresponding quantity of material processed in each stripper batch is to be recorded and iden tified by resin type and grade and the date and time the batch is completed. (ii) If continuous stripping is used, one representative sample of polyvinyl chloride resin is to be taken for each grade of resin processed or at intervals polyvinyl chloride resin processed by the stripper's), identified by the resin type and grade and the time and date it represents, (3> The owner or operator shall in clude in the report a record of the emis sions from each reactor opening for which an emission limit is prescribed in 5 Cl.64(a) (2), Emissions are to be deter mined in accordance with 61.67(g) (5). except that emissions for each reactor are to be determined. For a reactor that is also used as a stripper, the determination column. See sections 4.3.2 end 6.4. if resolu tion of the vinyl chloride peak is still not satisfactory for a particular sample, then chromatograph parameters can be further altered with prior approval of the Admin istrator. If alteration of the chromatograph parameters fails to resolve the vinyl chloride peak, then supplemental confirmation of the vinyl chloride peak through an absolute analytical technique, such os moss spectro scopy, must be performed. 4. Apparatus. 4.1 Sampling (Figure 1). 4.1.1 Probe--Stainless steel, Pyrcx glass, or Teflon tubing according to stack temper- FEDERAL REGISTER, VOL. 41, NO. 20S--THURSDAY, OCTOBER 21, 1974 BOR 004926 46570 RUIES AND REGULATIONS attire, each equipped with a glass wool plus to remove pailiculnts r ci. 4.12 tamiilc line--Teflon, 6.4 mm out.-,Ido diameter, of sufficient lenitth to connect probe to bag. A new unused piece Is employed tor each eerie* of bog samples that constitutes an emission test. 4.1.3 Mole (2) and female (2) stainless Steel qulck-eonnects. with ball checks lone pair without) located os shown in Figure 1. 4.1.4 Tedlar bags. 100 liter capacity--To contain sample. Teflon bogs ore not accept able. Aluminized Mylar bags may be used, provided that the samples are analyzed within 24 hours ot collection. 4.1.6 Rigid leokproor containers for 4.1.4. with covering to protect contents from sun light. 4.1.6 Needle valve--To adjust sample flow rate. 4.1.7 Pump--Leak-free. Minimum capac ity 2 liters per minute. 4.1.8 Charcoal tube--To prevent admis sion of vinyl chloride to atmosphere In vicin ity of samplers. 4.1.6 Flow meter--For observing sample flow rate; capable of measuring a flow range from 0.10 to 1.00 liter per minute. 4-1.10 Connecting tubing--Teflon. 6.4 mm outside diameter, to assemble sample train (Figure 1). 4.1-11 Pitot tube--Type S (or equivalent), attached to the probe so that the sampling flow rate can be regulated proportional to the stack gar velocity. 4.2 Sample recovery. 4.2.1 Tubing--Teflon, 6.4 mm outside diameter, to connect bag to gaa chromato graph sample loop. A new unused piece is employed for each series of bag samples that constitutes an emission test, and Is to be dis carded upon conclusion of analysis of those bags. 4.3 Analysis. 4.3.1 Gas chromatograph--With flame Ionization detector, potentlometric strip chart recorder and 1.0 to 5.0 ml heated sam pling loop in automatic sample valve. 4.3.2 Chromatographic column--Stainless steel, 2.0 X 3.2 mm, containing 80/100 mebtx Chromosorb 102. A secondary colum of GE SF-9G, 20% on 60/80 mesh AW Chromoeorb P, stainless steel, 2.0 m x 32 mm, will be required If acetaldehyde Is present. If used, the SF-96 column la placed after the Chromo- Borb 102 column. The combined columns should then be operated at 110'C. 4.3.3 Flow meters (2)--itotameter type. 0 to 100 ml/min capacity, with now control ' valves. 4.3.4 Gas regulators--For required gas cylinders. 4.4 5 Flow meter--Rotameter tvpe. 0 to 1000 ml/min range accurate to 1%. to meter nitrogen In preparation of standard gas mixtures. 4.4.6 Stop watch--Of known accuracy, to time gas flow in preparation of standard gas mixtures. 5. Reagents. It is necesuury that all rea gents be of chromatographic grade. 5.1 Analysis. 5.1.1 Helium gas or nitrogen gas--Zero grade, for chromatographic carrier gas. 5.1.2 Hydrogen gas--Zero grade. 5.1.3 Oxygen gas, or Air. as required by the detector--Zero grade. 5.2 Calibration. 5.2.1 Vinyl chloride, 99.9+%--For prep aration of standard gas mixtures. 5.2.2 Calibration cylinders (3), optional-- One each of 50. io and 5 ppm vinyl chloride in nitrogen with certified analysis. Analysis must be traceable to NBS (National Bureau of Standnrds) or to a gTavlmetrically cali brated vinyl chloride permeation tube. 5.2.3 Nitrogen gas--Zero grade. 4or prep aration of standard gas mixtures. 6. Procedure. 6.1 sampling. Assemble the sample train as In Figure loc-1. Perform a bag leak check according to Section 7.4. Observe that all connections between the bag and the probe are tight. Flnce the end of the probe at the centroid of the stack and start the pump with the needle valve* adjusted to yield a flow of 0.5 ]pm. After a period of time suffi cient to purge the line several times has elapsed, connect the vacuum line to the bag and evacuate the bag until the rotam eter Indicates no flow. Then reposition the sample and vacuum lines and begin the ac tual sampling, keeping the rate proportional to the stack velocity. Direct the gns exiting the rotameter away from sampling personnel. At the end of the sample period, shut off the pump, disconnect the sample line from the hag. and disconnect the vacuum line from the bag container. Protect the bag container from sunlight. 6.2 Sample storage. Sample bags must be kept out of direct sunlight. When at all pos sible, analysis is to be performed within 24 hours of sample collection. 6.3 sample recovery. With a piece of Tef lon tubing identified for that bag, connect a bag inlet valve to the gas chromatograph sample valve. Switch the valve to withdraw gas from the bag through the sample loop. Plumb the equipment so the sample gas passes from the sample valve to tho lealt-free pump, and then to a charcoal tube, followed by a 0-100 ml/mln rotameter with flow con trol valve. and the attenuator celling. Record the lab oratory protfiuxe. Fiona the court, select the peak having the retention time corresuond- teg to vinyl chloride, as determined in Sec tion 7.2. Measure the peak area. An. by use of 1I>, and a disc Integrator or a pianlmetcr. Measure the peak height, H. Record An and the retention time. Repent the Injection at least two times or until two consecutive vlnvl chloride peaks do not vary in area more than 5%. The average value lor these two areas will be used to compute the bag concentra tion. Compare the ratio of H.,, to An for the vinyl chloride sample with the same ratio lor the standard peak which is closest in height. As a guideline, if these ratios differ by more than 10%. tbe vinyl chloride peak may not be pure (possibly acetaldehyde is present) and the secondary column should be em ployed (see Section 422). 6.5 Measure tho ambient temperature and barometric pressure near the bag. (Assume the relative humidity to be 100 percent.) From a water saturation vapor pressure table, determine the recced and water vapor con tent of the bag. 7. Calibration and Standards. 7.1 Preparation of vinyl chloride standard gas mixtures. Evacuate a sixteen-inch square Tedlnr bag that has passed a leak check (described in Section 7.4) and meter in 5.0 liters of nitrogen. While tbe beg Is filling, use tho 0.5 ml syringe to inject 250sl of 99.9+ % vinyl chloride through the wall of the bag. Upon withdrawing the syringe needle, im mediately cover the resulting hole with a piece of adhesive tape. This gives a concen tration of SO ppm of vinyl chloride. In a like manner use the other syringe to prepare dilu tions having 10 and 5 ppnr vinyl chloride concentrations. Place each bag on a smooth surface and alternately depress opposite sides of the bag 60 times to further mix the gases. 72 Determination of vinyl chloride re tention time. This section can be performed simultaneously with Section 7.3, Establish chromatograph conditions Identical with those In Section 62, above. Bet attenuator to X l position. Flush the sampling loop with zero helium or nitrogen and activate the sample valve. Record the injection time, the sample loop temperature, the column temperature, the earner gas flow rate, tho chart speed and the attenuator setting. Record peaks and detector responses that occur in tho absence of vinyl chloride. Main tain conditions. With the equipment plumb ing arranged identically to Section 6.3. flush the sample loop for 30 seconds at the rate-of 100 ml/min with one of the vinyl chloride 4.3 5 Thermometer--Accurate to one de 6.4 Analysis. Set the column temperature calibration mixtures and activate the sample gree centigrade, to measure temperature of to 100* C the detector temperature to 160* valve. Record the Injection time. Select the heated sample loop at time of sample injec C, and the sample loop temperature to 70* C. peak that corresponds to vinyl chloride. tion. , When optimum hydrogen and oxygen flow Measure tho distance on tbe chart from tho 4.3.6 Barometer--Accurate to 5 mm Hg. to rates have been determined verify and main injection time to the time at which the peak measure atmospheric pressure around gas tain these flow rates during all chromato maximum occurs. This quantity, divided bv chromatograph during sample analysis. 4.3.7 Pump--Leak-free. Minimum capac ity 100 ml/min. graph operations. Using zero helium or nitrogen as the carrier gas, establish a flow rate In the range consistent with the manu the chart speed, is defined as the retention time. Record, 7.3 Preparation of chromatograph cali 4.4 Calibration. facturer's requirements for satisfactory de bration curve. Make a gas chromatographic 4.4.1 Tubing--Teflon, 6.4 mm outside diameter, separate pieces marked lor each calibration concentration. ' 4.42 Tedlar bags--Sixteen-Inch square size, separate bag marked for each calibra tion concentration. 4.4.3 Syringe--0.5 ml, gaa tight. 4.4.4 Syringe--S0A, gas tight. tector operation. A flow rate of approxi mately 40 ml 'min should produce adequate separations. Observe the base line periodi cally and determine that the noise level has stabilized and that base line drift has ceased. Purge the sample loop for thirty seconds ut the rate of 100 ml/mln, then activate the sample valve. Record the Injection time (the measurement of each standard gas mixture (described in Section 7.1) using conditions identical with those listed In Section G.3 above. Flush the sampling loop for 30 seconds at the rate of 100 ml/min with each standard gas mixture and activate the sample valve. Record C,, the concentrations of vinyl chlo ride injected, the attenuator setting, chart position of the pen on the chart at the time speed, peak area, nample loop temperature, 5 Mention of trade names on specific prod of sample injection), the sample number, the column temperature, carrier gaa flow rate, ucts docs not constitute endorsement by the sample loop temperature, the column tem and retention time. Record the laboratory Environmental Protection Agency. perature, carrier gaa flow rate, chart speed pressure. Calculate At, the peak area multl- FEDERAl REGISTER, VOL 41, NO. 205--THURSDAY, OCTOBER 21, 1776 BOR 004927 RU1.ES AMD T.E-GU1AT10N3 C371 piled by the attenuator sotting. Repeat until two Injection areas are within 5%, then plot those points vs Cr. When the other conccntratlous bevo been plotted, draw a smooth curve through tho points. Perform calibra tion daily, or before and after each set of bag wimples, whichever is more frequent. 7.4 Bag leak checks. While performance of this section is required subsequent to bag use, it Is also advised that It bo performed prior to bag use. After each use, moke sure a bog did not develop leaks as follows. To leal; check, connect a water manometer and pres surize the bag to 5--10 cm li,0 (2-4 In H.Ol. Allow to stand for 10 minutes. Any displace ment in the water manometer indicates a leak. Also check the rigid container for leaks In this manner. (Note: An altemattvo leak check method Is to pressurize tho bag to 5-10 cm K.O or 2-4 In. H.O and allow to stand overnight. A deflated bag Indicates a leak.) For each sample bag in its rigid container, place a rotameter in-line between the bag'and the pump Inlet. Evacuate the bag. Failure of the rotameter to register zero flow when the bag appears to be empty indicates a leak. 8. calculations. 8.1 Determine the sample peak area as follows: ttia ^ Hent't*n at inti Nf -n ,pectric. paOcu not uulluu U Xnvireaaaneal Acftey* A,e=AmAr whore: A ,*>The sample peak area. A.*Tlw measured peak area. A/=Tbo attenuation lanor. Equation 100-1 8.2 Vinyl chloride concentrations, rrom the calibration curve described in Section 78. above, select the value of Cc that cor responds to A,. tho sample peak area. Cal culate Cb as follows: Cv C'P.Tj PiTril-Bwt) Equation 106-2 Where: Bmi--The water vapor content of the hag ssiuhto, at snalyred. Ci=The concentration ol Tinyl chloride in the hag sample in ppm. C."The concentration ot vinyl chloride Indicated by tlte gas chromnlorrapri, in ppm. J\r'The reference presaiue, the laboratory pressnre recorded during cauoratron, mm lie. 2VThe sample loop teiop-tiitute ott tne absolute scale at the Line ol auatvsis,1 k. F,-The laboratory pressure at time of analysis, nun Hg. T,"The reference temperature, the sample loop temperature recorded during cilrbrolicm, K' t). References. 1. Brown, D. W,, Loy, E. W. and Stephen son, M. H. "Vinyl Chloride Monitoring Near the B. F. Goodrich Chemical Company m Louisville, Kentucky." Region IV, U.S. Envi ronmental Protection Agency, Surveillance and Analysis Division, Athens, Georgia, June 24, 1974. 2. "Evaluation of A Collection and Analy tical Procedure for Vinyl Chloride in Air," by G. D. Clayton and Associates, December 13. 1974. EPA Contract No. 68-02-1408. Task Order No. 2. EPA Report oN. 75-VCL-l, 3. "Standardisation of Stationary Source Emission Method for Vinyl Chloride," by Mid west Research Institute. 1076. EPA Contract No. 66-02-1098, Task Order No. 7. Method 107--Determination or Vinyl Chlosrer Content or Inpeocess Wastewater Samples, and Vinyl Chloride Content or Polyvinyl Chloride Resin, Slurry, Wet Cake, and Latex Samples INTRODUCTION Performance of this method should not be attempted by persons unfamiliar with the operation of a gas chromatograph, nor by those who are unfamiliar with sampling, as there are many details that arc beyond the scope of this presentation. Care must be exercised to prevent exposure of sampling personnel to vinyl chloride, a carcinogen. 1. Principle and Applicability. 1.1 The basis for this method relates to the vapor equilibrium which is established between RVCM, PVC, resin, water, and air In a closed system, it has been demonstrated that the RVCM in a PVC resin will equili brate In a closed vessel quite rapidly, pro vided that the temperature of the PVC resin is maintained above the glass transition temperature of that specific resin. 18 This probedure is suitable for deter mining the vinyl chloride monomer (VCM) content of Inprocess wastewater samples, and the residual vinyl chloride monomer (RVCM) content of polyvinyl chloride (PVC) resins, wet cake, slurry, and latex samples. It cannot be used for polymer m fused form, such as sheet, or cubes. If a resolution of the vinyl chloride peak is not satisfactory for a particular sample, then chromatograph parameters may b- altered with prior ap proval ot the Administrator. If there is rea son to believe that some other hydrocarbon with an ldcntlr.aJ retention time Is present in the sample, then supplemental continua tion of the vinyl chloride peak through an absolute analytical technique, such as mass spectroscopy, should be performed. 2. Range and Sensitivity, The lower limit of detection of vinyl Chlo ride will vary according to the chromato graph used. Values reported include lxlO-r mg and 4 x 10-T mg. With proper calibration, the upper limit may be extended as needed. 3. Precision and Reproducibility. An interlflboratory comparison between seven laboratories of three resin samples, each split Into three parts, yielded a standard deviation of 2.63% for a sample with a mean of 2.09 ppm, 4.16% for a sample with a mean of 1.C6 ppm. and 5.29 % for a sample with a mean of 62.66 ppm. 4. Safety. Do not release vinyl chloride to the labora tory atmosphere during preparation of stand ards. Venting or purging with VCM/alr mix tures must be held to a mtnlmum. When they arc required, the vapor must be routed to outside air. Vinyl chloride, even at low ppm levels, must never be vented inside the laboratory. After vials have been analyzed, the pressure within the vial must be vented prior to removal from the instrument turn table. Vials must bo vented into an activated charcoal tube using a hypodermic needle to prevent release of vinyl chloride into the laboratory atmosphere. The charcoal must be replaced prior to vinyl chloride break through. 5. Apparatus. 5.1 Sampling. 5.1.1 Bottles--60 ml (2 oz), with waxed lined screw on tops, for PVC samples. 6.1.2 Vials--50 ml Hypo-vtals,1 sealed with Teflon faced Tuf-Bond discs for water sam ples. 5.1.3 Electrical tape--or equivalent, to prevent loosening of bottle tops. 68 Sample recovery. 5.2.1 Vials--With seals and caps. PcrkinElmer Corporation No. 105-0118. or equiva lent, 5.28 Analytical balance--Capable of weighing to 0.001 gram. 58.3. Syringe, 100 si--Precision Series "A" No. 010025, or equivalent. 1Mention of trade names on specific prod ucts docs not constitute endorsement by the Environmental Protection Agency. FEDERAL REGISTER, VOL 41, NO. 305--THURSDAY, OCTOBER 21, 1978 > BOR 004928 46572 RULES AND REGULATIONS 6.2.4 Vial Sealer, Perkln-Elmer No, 105- sealing and weighing, using n 100 a1 vyrlnge. 0108 or equivalent. Ir; Iho case of dinner: Ion resins, the cup 53 Analysis. cannot be used. The sample Is lusteod 6.3.1 Oas chromatograph--Perkln-Elmer weighed approximately In an aluminum dish, Corporation Model F-40 head-space ana transferred to the tared vial and weighed lyzer. No. 104-0001, or equivalent, uccuratcly In the vial. The sample is then 6.3.2 ChromatogTaphle column--Stain* placed in the Perkln-Elmer head space ana lew steel, 2 mx3D mm, containing 0.4% lyzer (or equivalent) and conditioned for one Carbowax 1600 on Carbopalc A, Perkln-Elmer hour at 90*C. Corporation No. 105-0133, or equivalent. Note: Some aluminum vial caps have a Carhopak c can be used in place Of Carbopalc center section which must be removed prior A. to placing into sample tray. If not removed, 6.3.3 Thermometer--0 to 100* C. accurate serious damage to the Injection needle will to 0.1* C, Perkln-Elmer No. 105-0109 or occur, equivalent. 733 Suspension resin slurry and wet cake 6.3.4. Sample tray thermostat system-- samples--Slurry must be filtered using a Perkln-Elmer No. 105-0103, or'equivalent. small Buchner funnel with vacuum to yield 5.3.5 Septa--Sandwich type, lor auto wet cake. The filtering process must be con matic dosing. 13 mm, Perkln-Elmer No. 105- tinued only as long as a steady stream of 1008, or equivalent. water Is exiting from the funnel. Excessive 6-3.6 Integrator - recorder -- Hewlett - filtration time could result In Some loss of Packard Model 33S0A, or equivalent. VCM. The wet cake sample (0.10 to 43 grams) 6.3.7 Filter drier assembly (3)--Perkln- is added to a tared vial (Including septum Elmer No. 2230117, or equivalent. and aluminum cap) and immediately sealed. 6.3.8 Soap film flowmeter--Hewlett Pack Sample weight is then determined to 3 deci ard No. 0101-0113, or equivalent. mal places. The Bample is then placed In the 6.4 Calibration. Perkln-Elmer head space analyzer (or equiva 6.4.1 Regulators--for required gas cyln- lent) and conditioned for one hour at 90C. ders. A sample of wet cake is used to determine 6. Reagents. TS (total solids). This is required for calcu 6.1 Analysis. lating the RVCM. 6.1.1 Hydrogen gas--zero grade. 7.2.3 Dispersion Wsln -slurry samples.-- 6.1.3 Nitrogen gas--zero grade. This material should not be filtered. Sample 6.13 Air--zero grade. must be thoroughly mixed. Using a tared 6.2 Calibration. vial (including septum and aluminum cap) 63.1 Standard cylinders (4)--one each Of 50. 500, 2000, and 4000 ppm vinyl chloride In nitrogen, with certified analysis. add approximately 8 drops (0.25 to 0.35 grams) of slurry or latex using a medicine dropper. This should be done immediately 7. Procedure. 7.1 Sampling. 7.1.1 PVC sampling--Allow the resin or elurry to flow from a tap on the tank or silo until the tap line has been well purged. Ex tend a 60 ml sample bottle under the tap. fill, and Immediately tightly cap the bottle. Wrap electrical tape around the cap and bottle to prevent the top from loosening. Place an Identifying label on each bottle, and record the date, time, and sample location both on the bottles and in a log book. after mixing. Seal the vial as soon as possible. Determine sample weight accurate to 0.001 grams. Total sample weight must not exceed 0.50 grams. Condition the vial for one hour at 90c in the analyzer. Determine the TS on the slurry sample (Section 7.3.5). 7.2.4 Inprocess wastewater samples-- Using a tared vial (Including septum and aluminum cap) quickly add approximately 1 cc of water using a medicine dropper. Seal the vial as soon as possible. Determine sample weight accurate to 0.001 gram. Con dition the vial for two hours at 90 *C In the 7.13 Water sampling--Prior to use, the analyzer. 60 ml vials (without the discs) must be 7.3 Analysis. capped with aluminum foil and muffled at 7.3.1 Preparation of gas chromatograph- 400 *C for at least one hour to destroy or install the chromatographic column and con remove any organic matter that could In dition overnight at 150"C. Do not connect tho terfere with analysis. At the sampling loca exit end of the column to the detector while tion All the vials bubble-free, to overflowing conditioning. eo that a convex meniscus forms at the top. 7.3.1.1 Flow rate adjustments--Adjust The excess water Is displaced as the sealing flow rates as follows: disc is carefully placed, Teflon side down, on a. Nitrogen carrier gas--Set regulator on the Opening of the Vial. Place the aluminum cylinder to read 60 psig. Set regulator on seal over the disc and the neck of the vial chromatograph to 1.3 kg/cm:. Normal flows and crimp into place. Affix an identifying at this pressure should be 25 to 40 cc/mlnute. label on the bottle, and record the date, time, Check with bubble flow meter. and sample location both on the vials and b. Burner air supply--Set regulator on cyl In a log book. All samples must be kept re inder to read 60 psig. Set regulator on frigerated until analyzed. chromatograph to supply air to burner at a 7.2 Sample recovery. Samples must be run rate between 250 and 300 ce/mmute. Check within 24 hours. with bubble flowmeter. 73 l Resin samples--The weight of the resin used must be between 0.1 and 4.6 grams. An exact weight must be obtained (^0.001 gram) for each sample. In the case of sus pension reams a volumetric cup can be pre pared which will hold the required amouut of sample. The sample bottle Is opened, and the cup volume of resin Is added to the tared sample vial (Including Eeptum and alumi num cap). The vial Is Immediately scaled and the exact sample weight Is then obtained. Report this value on the data sheet as It is required for calculation of RvcM. In the 3. Hydrogen supply--Set regulator on cyl inder to read 30 psig. Set regulator on chromatograph to supply approximately 35^5 cc/mlnute.-Optlmizo hydrogen flow to yield the most sensitive detector response without extinguishing the flame. Check flow with bubble meter and record this flow 7.3.13 Temperature adjustments--Set temperatures as follows: a. Oven (chromatographic column), 60" C, b. Dosing line. 140" C. . c. Injection block, 140* C. case of relatively dry resin samples (water d. Sample chamber, water temperature, content <0.3 weight %), loo ,,l of distilled 90" C1.0 C. water must be injected into the vial, after 7.3.1.3 Ignition of flame Ionization detec tor__Ignite tho detector according to the manufacturer's instructions. 7.3.1.4 Amplifier balance--Balance the amplifier according to the manufacturer's Instructions. 733 Programming the chromatograph-- Program the chromatograph ns follows: a. I__ Dosing time--The normal setting Is 2 seconds. b. A--Analysis time--The normal setting Is 8 minutes. Certain types of samples con tain hlgb boiling materials which can cause Interference wtlh the vinyl chloride peak on subsequent analyses. In these cases the analysis tune must be adjusted to eliminate the interference. An automated backflusn Eystem Can also be used to solve this prob lem. c. B--Flushing--The normal setting is 03 minutes. d. w--Stabilization time--The nomal set ting Is 03 minutes. e. X--Number of analyses per sample--The normal setting Is 1. 73.3 preparation of sample turntable--Be fore placing any sample Into turntable, be certain that the center section of the alu minum cap has been removed. The numbered sample bottles should be placed in the cor responding numbered positions In the turn table. Insert samnles in the following order: Positions 1 &. 2--Old 2000 ppm standards for conditioning. These are necessary only after the analyzer has not been used for 24 hours or longer. Position 3--50 ppm standard, freshly pre pared. Position 4--500 ppm standard, freshly pre pared. Position 5--2000 ppm standard, freshly prepared. Position 6--4000 ppm standard, freshly pre pared. Position 7--Sample No. 7 (This ts the first sample of the day, but la given os 7 to he con sistent with the turntable and the integrator printout.) After all samples have been positioned, in sert the second set of 60, 500, 2000, and 4000 ppm standards. Samples, Including stand ards must be conditioned In the bath of 90* c for 1 hour (not to exceed.5 hours). 73.4 Start chromatograph program-- When all samples. Including standards, have been conditioned at 90* c for 1 hour, start the analysis program according to the manu facturers' instructions. These Instructions must be carefully followed when starting and stopping program to prevent damage to the dosing assembly. 7.3.5 Determination of total solids (TS). For wet cake, slurry, resin solution, and FVC latex samples, determtno TS for each sample by accurately weighing approxim ately 3 to 4 grams of sample In an aluminum pan before and after placing in a draft oven (105 to 110* C). Samples must be dried to constant weight. After first weighing re turn the pan to the oven for a short pe riod of time and then reweigh to verify com plete dryness. TS Is then calculated as the final sample weight divided by Initial sam ple weight. 8. Calibration. Calibration Is to be performed each eighthour period when the Instrument Is used. Each day. prior to running samples, the col umn should bo conditioned by running two of the previous dnys'EOOO ppm standards. 8.1 Preparation pf Standards. Calibration standards are prepared by fill ing the vials with the vljjyl chlorlde/nltrogen standards, rapidly seating the septum and sealing with the'aluminum cap. Use a stainless steel line from the cylinder to the vial. Do not use rubber or tygon tubing. The sample line from the cylinder must be ROEKAL REGISTER, VOL 41, NO. 305--THURSDAY, OCTOBER 21, 1*76 BOR 004929 RULES AND REGULATIONS purged (Into hood) (or several minutes prior to filling viols. Alter purging, reduce ths flow rate to approximately 600-1000 cc/mln. Place end o( tuning Into vial (near bottom) and after one minute slowly remove tubing. Place septum in vlnl as soon as possible to mini mize mixing air with sample. After the stand ard vials are scaled, Inject 100M1 of distilled water. 8.2 Preparation of chromatograph calibra tion curve. Prepare two 50 ppm. two 500 ppm, two 3000 ppm. and two 4000 ppm standard samples. Pun the calibration samples In exactly the same manner as regular samples. Plot A*. the integrator area counts Ior each standard sample vs C,,, the concentration of vinyl chloride In each standard sample. Draw a line of best fit through the points. 0. Calculations. S.1 Response factor. Prom the calibration curve described In Section 8.3, above, select the value of C that corresponds to A. for each sample. Com pute the response factor. Pi, for each sample, as follows: ii/=^ Equation 107-1 0.2 Residual vinyl chloride monomer con centration, or vinyl chloride monomer con centration. Calculate Cr as follows: c--w, (S'+*r*) wbaie: Equation 107-2 C...--Concentration of vinyl chloride la tbs sample, to ppm. P,--Laboratory atmosphere pressure, mm Hf. Pi--Room temperature, K, M,-Molecular weight of VCM (62.5). Pi-Volume of vapor phase (vial volume lees sample volume). w,--Wpighi of somplo, vrnms. R--Gaa constant (62,360). i if--Henry's Law constant lor VCM In PVC at tore, A'"6.52X10-*-K, tor VCM In 1 00 (approximate) wastewater sample at 00*C, Ar=5.oxio--fir,. 2"EQUllibmUon temperature, K. If the foUcwfw; conditions are met, Equation 107-2 can be simplified as follows; I. T, -22" C (2W K). *. Ti --00 C (363 K). S. P,--760 mm. Hg. r 4. V,mV In whero V\Vl4l volume cc <235). 3* Sample contnin* less than 045% vatar. c..-(r.mx,.-.+5lie) Equation 107*3 The following joncrM equation can bo udwJ (or pay gatuple which contains VCM, 1`VC and/or waters ft d tP RfT% X [;^~ + KATS)Ti+Km(l-TS) T,J where: T.-Total tollde. Note: K* must bo determined. Equation 107-4 Results calculated using Equation 107-4 represent concentration based on the total sample. To obtsln results based on dry PVO content, divide by TS. For a 1 cc (approximate) wastewater sample. Equation I07-f can be simplified to the following: C,.,=4-* f5--88 ttf L rn, + (2.066X 10-) ] J Equation 107-5 to. References. J. Residual Vinyl Chloride Monomer Con tent of Polyvinyl Chloride Resins and Wet Cake Samples, B. F. Goodrich Chemical Co. Standard Tost Procedure No. 1005-T. B. P. Goodrich Technical Center, Avon Lake, Ohio. January 30, 1975. 2. Berens, A. R., "Hie Solubility of Vinyl Chloride In Polyvinyl Chloride," ACS-Dlvlslon of Polymer Chemistry. Polymer Pre prints iS (2): 197,1974. 3- Berens, A. K., "The Diffusion of Vinyl Chloride in Polyvinyl Chloride," ACS-Dlvlsion of Polymer Chemistry, Polymer Pre prints 15 (2) ; 203, 1974. 4- Berens, A, R., L. 13. Crider, C. J. Tomanek and J. M. Whitney, Analysis for Vinyl Chloride in PVC Powders by Head-Space Qaa Chromatography," to be published. |FR Doc.76-30849 Filed t0-20-76;8:46 am) / / 46573 \ \ f0RAL REGISTER, VOL 41, NO. 205--THURSDAY1, OCTOBER 21, 1070 BOR 004930 ITEM 3 COPIED BY MCA FOR DISTRIBUTION TO THE VINYL CHLORIDE TECHNICAL PANEL, NOVEMBER ll, 1976, MR. MILTON FREIFELD 'ZfiT. r Capillary Abnormalities in Polyvinyl Chloride Production Workers Examination by In Vivo Microscopy Hildegard R. Maricq, MD; Maurice N. Johnson, MD; Charles L. Whetstone, MD; E. Carwile LeRoy, MD Examination by wlde-lield capillary microscopy of Ihe hands of 1S2 workers In vinyl chloride (VC) polymerization plants demonstrated scat-" tered, scleroderma-like mlcrovascular abnormalities In 21 workers and iso lated capillary abnormalities in 27, as compared with only three isolated ab normalities In 50 manual workers not exposed to vinyl chloride. Thirteen of 17 VC workers with objective evidence of VC-associated abnormalities (an giosarcoma or fibrosis of liver, acroosteolysis, or scleroderma-like skin le sions) were observed to have mlcrovascular abnormalities. If prospective studies confirm the Implications of this study, capillary mi croscopy may become a useful mass-screening procedure In the early de tection and prevention of VC-associated disease. (JAMA 236:1368-1371, 1976) INITIAL reports of human disease in which vinyl chloride (VC) has been implicated as pathogenetic were lim ited to descriptions of such peripheral changes as distal phalangeal resorp tion, ie, acroosteolysis (A0L)., J Re cently, a systemic effect of VC has been suggested by an unusual pat tern of hepatic portal, intralobular, and capsular fibrosis; angiosarcoma of the liver, and pulmonary functional abnormalities suggesting early pul monary fibrosis, all of which occur more frequently among workers em ployed in polyvinyl chloride produc tion plants than among the general population.'"' Furthermore, animal From the Division of Rheumatology and Im munology. Department of Medicine. Medical University ol South Carolina, Charleston (Drs Maricq and LeRoy). The B F Goodrich Com pany, Akron, Ohio (Dr Johnson), and Continen tal Oil Company. Ponca City. Okla (Dr Whet stone) Reprint requests to Division ot Rheumatology and Immunology, Department ol Medicine, Med ical University ot Soutn Carolina. BO Barre St. Charleston, SC 29401 (Dr Maricq), experiments have demonstrated that VC can produce a variety of tumors in rodents." 1: There are several similarities be tween VC disease and scleroderma (systemic sclerosis): Raynaud phe nomenon is prominent among the symptoms associated with AOL' localized scleroderma-like lesions have been reported in some patients with A0L, u; and, in both VC-associ ated disease and scleroderma, smallblood-vessel lesions and interstitial fibrosis are thought to be important in pathogenesis."'-15-" In scleroderma, changes in small blood vessels of the skin have been observed in vivo by capillary micros copy."-" Using the technique of widefield capillary microscopy, distinctive abnormal capillary patterns in the fingers of patients with Raynaud syn drome and scleroderma have been demonstrated." Furthermore, a posi tive correlation is noted between the severity of capillary pattern abnor malities and multisystem involve ment in these connective-tissue dis orders.'5 The possibility that VCassociated disease might be charac terized by microvascular abnormal ities similar to those observed in scleroderma led to the present study of VC workers, using techniques of wide-field capillary microscopy. The specific questions of this study were the following: (1) Do symptomatic VC workers have finger-skin-eapillary abnormalities? (2) Are the abnormal ities similar to or different from those seen in patients with idiopathic scleroderma and Raynaud syndrome? (3) Are microvascular abnormalities related to the type of VC-associated abnormality (peripheral vs systemic), especially liver abnormalities? (4) Are microvascular abnormalities related to the nature and duration of VC-exposure? (5) Are microvascular abnor malities found in a control group of manual workers not exposed to VC? SUBJECTS VC Workers Selected by Symptoms (n * 44).--The 44 subjects in this group gave a history of symptoms and signs possibly related to VC exposure. They were 31- to 57-year-old men (mean age, 42 years) wHb had worked in the polyvinyl chloride industry for 5 to 25 years (mean, 15 years), A history of-- past reactor-cleaning experience (ranging from 0.2 to 8 years; mean, 2.5 years) was present in 35 of 44 workers. Table 1 shows the com plaints and the pathologic findings in group 1. VC Workers Selected by Question- 1368 JAMA, Sept 20, 1976-Vol 236. No. 12 Capillary Abnormalities--Maricq et al BOR 004931 nalrc (n= IOS).--Those subjects wore selected on the basis of their answers 10 a questionnaire used in the poly vinyl chloride production plant to de tect early* AOL. All available subjects who had given one or more affirma tive answers to the questionnaire ,,(Q + ) were examined, a total of G6 subjects. Seventy-one subjects were examined from a random selection of those who had given negative an swers to all questions (Q--). Data on 29 of the 137 subjects examined were excluded because of unreliable obser vations caused by skin injuries or deep pigmentation, leaving 1GS em ployees (50 Q+ and 5S Q-) in this group. Control Manual Workers (n = 5fl).-- The possibility that repeated minor injuries associated with manual labor might contribute to the abnormal findings seen in VC workers led to the examination of workers from compa nies making neither VC nor polyvinyl chloride and hospital employees work ing as carpenters, truck drivers, and maintenance men, a total of 50 work ers. All were men and ranged in age from 19 to 62 years (mean age, 43 years). METHODS Wide-field Cspillary Microscopy.--The technique of wide-ficld capillary micros copy as previously reported'* consists of the observation of selected skin sites under immersion oil, using a stereo wide-field mi croscope at magnification xll Wide-field microscopy permits the detection of microvascular patterns, such as the presence and distribution of dilated or deformed mi crovessels and the absence of capillary loops, without attempting to measure ab solute vessel dimensions. The technique is rapid and suitable for mass screening. Twelve standard sites were examined in each subject: four nailfolds and two each of the following sites: dorsum of the distal phalanx other than the nailfold, dorsum of the middle phalanx, dorsum of the proxi mal interphalangeal joint, and the finger pad. Photography of Microessels.--The widefield photographic technique as previously described" was used to photograph at least one finger of each subject. All photographs were coded for blind comparison of capil lary findings in VC workers and control subjects. Clinical and Occupational Djta.-All sub jects were interviewed.as to length of em ployment, job assignment, general state of health, presence or absence of Ravnaud phenomenon, and smoking and drinking Table 1.--Clinical Findings and Complaints of Group 1 Vinyl Chloride Workers' Severe AOL with Raynaud phenomenon No. at Suhicc'.s No. of Sub With Capillary jects Examined Chanqesr e4 Sclfcroderma-hkc kn lesions wm Raynaud phenomenon Liver abnormalities; Subtotal Healed AOL with Raynaud phenomenon Healed AOL without Raynaud phenomenon 54 G5 17 13 60 \0 Raynaud phenomenon alone Nonspecific skin rashes without Raynaud phenomenon 9 7 3 1 Miscellaneous compiainls Subtotal Total 40 27 4 44 17 *AOL indicates acroosteolysis. tOf 17 subjects with abnormal capillaries, ten had scattered changes (8/13 and 2/4 of the two groups above) and seven had isolated changes. Two patients with anoiosarcoma of the liver and one each with (1) portal tibrcsrs and en larged spleen. (?) portal fibrosis with early cirrhosis and fatty metamorphosis. (3) thrombosis of the splenic verb, mild liver damage, and reticuloendothelial cell hyperplasia, (4) fatty metamorphosis with focal capsular and subcapsular fibrosis and splenomegaly with vascular congestion. Table 2.--Comparison of Capillary Observations Between VC Workers and Controls' Scattered capillary abnormalities Abnormal capillaries present, but tew in number No capillary abnormalities seen Tola) Employees of VC Industry 11 27 70 108 Manual Workers Not Exposed to VC 0 3 47 so *VC indicates vinyl chloride. Difference in the prevalence of capillary abnormalities be tween VC workers and controls ts statistically signilicant (x1 = 15.50, P<.001). habits. A limited physical examination was performed. All data were coded for later analysis and were unknown to the capil lary observer and photographer. RESULTS Group 1 (VC Workers Selected by Symptoms).-Examination of group 1 subjects showed scattered capillary abnormalities similar to those found in scleroderma (Fig 1 and 2). Defi nitely dilated capillar}' loops were seen in the nailfold and in other fin ger sites, contrasting with the sur rounding normal vasculature. Pale avascular areas were frequently ob served. The capillary abnormalities were usually more discrete and less numerous than those seen in most pa tients with scleroderma. They were seen more frequently in subjects with severe AOL, liver abnormalities (as defined in Table 1) and sclerodermalike lesions (13/17) than in those with healed AOL, nonspecific skin rashes, or Ilayn;\ud phenomenon alone (4/27; Xs --14.21, p< .001). Moreover, 5 of 6 subjects with liver abnormalities ver ified by biopsy specimens had microvascular abnormalities (Table 1). In a few subjects, lesions resem bling mini versions of clinically vis ible papular skin lesions were ob served microscopically (Fig 3, left). In two subjects with active AOL, capil lary hemorrhages were observed un der the proximal nail plate in addi tion to the common type of "splinter hemorrhages" under the distal nail plate (Fig 3, center). Group 2 (VC Workers Selected by Questionnaire).--Dilated capillaries were observed in 3S of 10S group 2 workers; both the number and distri bution of dilated capillaries differed from those observed in most sclero derma patients? Many group 2 work ers had isolated, extremely dilated capillaries (Fig 3, right and Table 2). No correlation was found between the length of time employed as a reactorcleancr (or the length of time with the company) and the capillary abnor malities. Office and supervisory per sonnel who had never been produc- JAMA, Sep! 20. 1976-Vol 236, No. 12 Capillary Abnormalities--Maricq ct al 1369 BOR 004932 Fig 1.--Top left, Wide-held view of nailfold area in normal sub ject. Bottom left. Nailfold capillaries of patient with sclero derma. Bottom right, Naiifold capillary pattern in worker of polyvinyl chloride production plant. Note similarity with pat tern seen in scleroderma patients. - ---r-' , 4 . V*.ji .1 11- "-r--- v-j .`_I. Fig 2.--Left. Dorsum of middle phalanx in normal subject Center, Cluster of dilated capillaries in same anatomical site in patient-with scleroderma. Right, Vinyl chloride worker with pattern similar to that seen in scleroderma. Fig 3.--Left, Miniplaque on dorsum of distal phalanx in VC worker with acroosteoiys's (AOL) Cen ter, Capillary hemorrhages under both distal and proximal nail plate in a vinyl chloride (VC) worker with AOL. Right, Single extremely dilated capillary in nailfolcd of VC worker with liver abnormalities. 1370 JAMA. Sept 20, 1976-Vol 236. No 12 Capillary Abnormalities--Mancq ct al BOR 004933 lion workers hml fewer nicnivascul'" abnormalities (3/3") tlmn prinlucti workers (.`O/Jjfl, = -I.T1,2 3/'4<5 6 7 however, production wiukc.-* showed no diirerences in Capillary abr.urmnlitics accurding to job category. 1 here was no significant difference (x = 1.32, P>.5) between employees who had been classified as Q+ or Q- on the basis of the questionnaire. It was noted, however, that there was little or. no correlation between the re sponses regarding Raynaud phenom enon obtained from the questionnaire and those obtained from the inter view at the time of examination. Physical examination disclosed two workers with AOL (one "active" and one "healing" by roentgenographie examination) and papular skin le sions, and ten workers with hepato megaly (4 cm or more below the right costal margin). The subject with ac tive AOL showed scattered capillary changes, the subject with healing AOL had a "normal" capillary exami nation. There was no correlation be tween hepatomegaly and capillary findings. Comparison of VC Workers With Control Subjccts.-Capillary abnor malities in group 2 VC workers were significantly more frequent than in the control manual workers examined (x-= 15.50, p< .001) (Table 2). Analysis of Photographic Data.-- Three hundred seventeen uniden- tilied photographs of VC workers wen: tnixi-d with 13d photograph.. of control subji-els am! 1U0 photographs of patients with scLroib ima and rclaled diseasi-s; all photographs were rated for the presence of capillary abnormalities. The results demon strated that significantly more VC workers (;w/l.">2) than control sulri jects (3/30) had capillary abnormal ities (x: = VG9, P < .01). Although ob jective, for technical reasons, photographs are slightly less sensi tive than direct observations in de tecting capillary abnormalities. COMMENT The results of this study demon strate that capillary abnormalities seen in the finger skin by in vivo mi croscopy are present in VC workers more frequently than in control sub jects. These capillary abnormalities are not exclusively related to pe ripheral pathological conditions such as AOL, scleroderma-like lesions of hands, and Raynaud phenomenon, but are also found in subjects with liver abnormalities (as defined in Table 1) and in subjects who have papular lesions elsewhere on the body. Microscopic papular or fibrutic lesions can also be observed in VC workers. In 33fe of the subjects who show any capillary' changes, the pat tern appears similar to the microvascular changes seen in scleroderma; : <Jip remaining majority, changes -ist of a few dilated capillaries unlv; very few control swim , is -j.i.u* even these minimal capillary I.n'-rmalities. Since microvaseuh.r ch.tng-i occur mure frequently than overt VCassociutcd pathologic conditions in VC workers, they may represent an early manifestation of the VC elfect. More work is needed to determine the nature and evolution of such microvascular abnormalities, their rela tionship to VC-associatcd disease (as opposed to a transient reaction to VC exposure), and their relationship to the subject's susceptibility to VC dis ease, Further studies are also needed to compare the capillary changes re ported here with those seen ;n small blood vessels and endothclia of ani mals exposed to VC." Capillary mi croscopy might then he used as a re producible, noninvasive technique to monitor VC workers and to identify VC-assoeiated peripheral and visceral disease in susceptible individuals at an early and possibly preventable stage. This investigation was supported in pan by the Charlotte and Sidney Lif.-chultz Foundation, National Institutes of Health grant AM 1x994, the South Carolina State appropriation for re search, and the RGK foundation, Irving J. SelikofT, MR, supplied 24 control industrial workers for capillary exanvr.iilion. Karen Month. Eleanor Galtoni. ami Villa Maria) provided technical assistance. 1. Harris DK, Adams WGF: Acro-osteolysis occurring in men engaged in the polymerization of vinyl chloride. Br M'd J 3.712-714, 1907. 2. Wilson RH, McCormick WE, Tatum CF, et al: Occupational acroosteolysis: Report of 31 cases. JAMA 201377.Oil, 'e07 3. Dinman BR, Cook WA, Whitt house WJ|, et at Occupational acroostcotysis: 1. An epidemio logical Study. Arch Environ Health 22.01-73, 1571. 4. Falk H, Creech JL, Heath CW. et al: He patic disease among- workers at a vinyl chloride polymerization plant. JAMA 230:59-63, 1974. 5. Lange CE, Juhe S. Stein G, et al: Die sogenannte \ iml-dilond-Krankhoit-einC berufshedir.gtc Sv'temsklerose? Int Arch Atbeitsmed 32.1-32, 1974. 6. Lilis K, Anderson H, Nicholson WJ, et al: Prevalence of disease among vinyl chlondc and polwinvl chlondc workers, Ann AT Acod Sci 24522-41, 1975. 7. Mameller H J, Lolbach WK, Muller P,, et al: Unusual splenomegalic liver disease as evi- References deneed bv peritoneoscopy and guided liver biopsy among polyvinyl chlondc production workem. Aim AT Acad Sci 246 9.5*134. 1975. S Miller A, Toir^.ein AS, Cbuarg M, et al: Changes in pulmonary function in workers ex posed to vinyl chloride and polyvinyl chloride. Ann \Y Acad Sci 240 45-52. 1975. 9. Suciu I, Prorian L, Ilea E, et al. Clinical manifestations in vmvl chloride poisoning. Aim AT Acad Sci 246.53-09. 1973. 10. Thomas LB, Popper H. Berk PR, et al: Vinyl-chloride-induced liver disease: From idio pathic portal hypertension (Banti's syndrome) to angiosarcomas .V W J M'd 292.17-22. 1975, 11. Viola PL, Bigotii A, Cr.puto A: Oncogenic response of rat skin, lungs, and bones to vinyl chloride. Cancer />,s 31:310-322, 1971. 12. Maltoni C, Lcfviome G. Carcinogenicity bioa&savs of vim I chloride: Current results. Ann NY Acad Sci 245 193-219, ly75. 13. Markowitz SS, McDonald CJ, Fetbiero W, et al: Ocrupalionai acroosteoiysis. Arch Derm. 106.219-223, 1972. 14. Rodnan CP: Progressive systemic sclerosis (scleroderma) and calcinosis, in Hollander .JL, McCarty RJ Jr (eds): Arthritis aid Al't-d Can- diiiuns, ed S. Philadelphia, Lea i: Febiger. 1972, pp 962-1095. 15. David E, Landau J: Clinical Capillary Mi- criiicipij, Springfield, 111, Charles C Thomas Pub lisher, 1966. 1G Muricq HP., LeRoy EC: Patterns of finger capillar.- abnormalities ;r ronnieuve tissue dis ease by widcfield microscope. Arthritis flhenm 16,619-629, 1973. 17. Maricq HP., Spencer-Groon G, LeRoy F.C: P.elation entre la distribution des cap:!!a:res anormsUT et le dr-gro d'envahisscmenl system- ique d3n$ la sclerodermic (progressive general- isee). J Sci Mfd Lille 93.253-2-3. 1975. 13. Maricq HR: "Wide-field" photography of nailfold capillary bed and a scale of plexus visu alization scores (PVS), Microcase lies 2.335-340, 1970. n JAMA, Sepl 20. 197G--Vol 236, No. 12 t '. i Capillary Abnormalities--Maricq et al 1371 BOR 004934 COPIED BY MC "OR DISTRIBUTION TO THE V: X CHLORIDE TECHNICAL PANEL, NOVEMBER 11, 1976, MR. MILTON FREIFELD ! HEPATIC ANGIOSARCOMA IN A VINYL CHLORIDE WORKER f P. M. Smith, M.D., M.R.C.R D. M. J. Williams, M.B., B.Ch. \ AND D. M. D. Evans, AI.D, M.R.C.P., F.R.C. Path. , . llejtrinted from IIULLKTIN OF TlIK Xl'.W vokk acadk.mv of mkimcink Second Scries, vul. .r>i\ im. I, pj>. 4.17052, May lfi'fi Cojtyrifcht 1V/6, liy tUr Ntw Yotl. At^dviiiy of Medicine .......... BOR 004935 'V ,u 4* - !. A ' \ HEPATIC ANGIOSARCOMA IN A VINYL CHLORIDE WORKER P. M. Smith, M.D., M.R.C.P.; D. M. J. Williams, M.B., B.Ch.; and D. M. D. Evans, M.D., M.R.C.P., F.R.C. Path. Llandeugh Hospital B.P. Chemicals International limited Sully Frnarth, Glamorgan, Wales England ore than 38 cases of angiosarcoma so far have been confirmed M among workers exposed to vinyl chloride monomer gas (VCM) during the manufacture of polyvinyl chloride (PVC). The median in terval from first exposure to diagnosis was 17 years; the average time of exposure was 16 years,1 We are reporting on a patient whose exposure to VCM lasted only y-/ years. A 36-ycar-old white male was admitted to the hospital for treatment of peptic ulcer pain that had recurred intermittently for 15 years. His health otherwise had been good; lie did not smoke and he drank very litilc alcohol. For 3 /2 years lie had worked as a "polyclcaner," a cleaner of polymerization vessels in a factory where VCM is processed to PVC. After this he hacl worked for three years prior to admission as a store man of raw materials, handling resins only. On examination the patient looked well; the only abnormal physical sign was a liver palpable to 6 cm. Barium meal revealed the presence of Bor 004936 f o' 448 r. M, KM ml AND OllMRs Fig. 1. Focal severe sinusoidal dilatation on liver biopsy (X 500) a deformed duodenal cap. At operation a large duodenal ulcer was found, for which a Polya partial gastrectomy was performed. The liver appeared cirrhotic, with grossly distended veins forming a collateral circulation in the anterior abdominal wall and the falciform ligament. Tests of liver function gave normal results, but an operative liver biopsy showed noncirrhotic fibrosis; there were several foci of severe dilata tion of the sinusoids (Figure i). Recovery from operation was uneventful. The serum alltaline phos phatase level rose to 87 l.U./L (normal range: 15 to 40) after six weeks, but all other liver-function tests and the erythrocyte sedimentation rate were normal, apart from a bromstilphalein retention of 17% (45 min.). Tests for smooth-muscle and mitochondrial antibodies and for Australia antigen Averc negative. One year after operation the patient was working full rime as a dock laborer. There were no abnormal physical signs apart from the enlarged liver. Liver-function tests now showed a further rise in the serum alka line phosphatase level to 115 I.U./L, with an elevated bilirubin value of 32 /unole/L (normal range: 5 to 17). s Bull. N.Y. Acad. Med. BOR 004937 -'<V / J i* >a 3 41 <s iver cral ent. .psy ita- '.0S- :ks, "ate x). alia oclc ged ilea- tluc Med. nj-nit m ^><*' "*'*** .n S-m. htpatic anuiosakguma 449 Fig. 2. G ross appearance of liver at postmortem Four months later he was admitted to the hospital as an emergency patient. He now had dyspnea, ascites, ankle edema, and jaundice. He looked ill and wasted. Liver palms and numerous spider nevi were pres ent, The liver extended io cm. below the costal margin. Diuretics caused an appreciable loss of edema, with great relief of the dyspnea. Results of the liver-function tests were grossly abnormal: serum biliru bin 103 /unolc/L, alkaline phosphatase 120 I.LT./L, scrum glutamic oxalacctic transaminase 35 I.U./L, albumin 17 gm./L, globulin 40 gm./L. During the next month the bilirubin rose steadily to 390 /unole/L. A scan showed the liver to be massive, with numerous areas of decreased uptake. A hepatic arteriogram revealed a widespread pathological cir culation, with multiple areas of tumor blush, suggestive of a highly vas cular multicentric hepatic neoplasm. Tests for -fetoprotein and car- cinoembryonic antigen were negative. A barium-swallow test demon strated varices. Dilated veins appeared on the anterior abdominal wall, but at no time was a hepatic bruit heard. Soon afterward the patient lapsed into hepatic coma and died. N At necropsy there was edema of both lungs. The right lower lobe Vol. 52, No. 4, May 1976 BOR 004938 Tt 4 5 J\ A!. nmijii /ivi) (mints * j j I J Fig. 3. Postmortem hcji.ilic \eiu>gr;tm ..-.J showed patchy collapse and consolidation and evidence of several hem orrhages. The pericardium contained clear yellow fluid but there was no significant ascites. Apart from rhe old partial gastrectomy, the ali mentary tract was normal. The liver weighed 3,240 gm. and was greatly enlarged by a vascu lar rumor which had almost completely replaced normal hepatic tissue (Figure 2). Large blood lakes and cavernous vascular spaces were shown well by injection of barium suspension into the hepatic vein after death (Figure 3), The spleen was congested and very firm, bur weighed only 200 gm. Microscopy showed replacement of much hepatic parenchyma by hemorrhagic and necrotic tumor tissue. 1 he tumor consisted of vascular channels, varying greatly in size and shape, lined by plump endothelial cells and also by large multinudcaic tumor cells (Figure 4"), belieyed Bull. ty. Y. Aud. Med. BOR 004939 iir.r.vi k: an'ciosaucoma 45 1 Fig. i, Microscopy of tumor (X 600) to be malignant KupfTcr cells. In some parts of the tumor these cells were sparse and the dilated sinusoidal structure resembled that seen in. the biopsy specimen, bur in other parts these giant tumor cells were very numerous. A few had desquamated into the vascular channels and there was evidence of tumor-ccll embolism in the pulmonary hemorrhages, although no cohesive metastatic tumor tissue was found in the lungs or other orgOans. Discussio.v This patient was remarkable in several respects. The duration of ex posure to VCM of 3 \\ years, compared with the mean of i<5 years for the previously repurred 38 eases of angiosarcoma, was unusually short. Only one younger ease has been described. The latent period from the first exposure to VCM ro diagnosis was eight years, whereas for the other reported cases the mean interval was 17 years (ranges 11 to 30 years).1 We. have no evidence that the exposure ro VCM was in any way unusual; in particular, the patient had not been a gas "sniffer" and Vol. 52, No. 4, May 1976 BOR 004940 45 2 P. M. SMITH ANT) OTIII.ks his subsequent periods of employment had consisted of laboring and handling bananas, lie had, however, been a polvclcnner, and 84% of eases of VCM-treatcd angiosarcomas s<> far described have occurred in persons similarly employed.' 1 le is only the second patient with angio sarcoma to be reported in Britain. This patient also was unusual in that the liver biopsy performed 15 months prior to his death revealed striking focal dilatation of the sinus oids. This change has been described recently in the early stages of some other angiosarcomas linked ro vinyl chloride.* We have performed liver biopsies on a number of other YCM workers with appreciable periods of exposure, but have seen only a nonrirrhuric fibrosis* and arc unable to confirm that the sinusoidal dilatation can be considered a precursor to the formation of rumor. It is to he hoped that stricter environmental controls will prevent further angiosarcomas arising dc novo, but work ers who have already developed portal hypertension and those who have been exposed ro high concentrations of the chemical in the past must be monitored carefully in the future. Summary A man aged 36 years who had been a YCM process worker for only 3 Vi years was unexpectedly found at laparotomy for a peptic ulcer to have an enlarged liver and portal hypertension, Biopsy showed striking focal dilatation of the sinusoids. Fifteen months later the patient died of a hepatic angiosarcoma. Acknowledgment We thank Dr. G. dc B. 1 lindc for the radiological studies and Mr. D. A. Aubrey for referring the patient. n /; F1; it h' ,v C1: N 1. l.loyd, W.; Aii;rii"v.ircoi<f.i nf 11 to liver in vinyl <hIoiide/]iolyvinyl chlo ride workers. J. Orrup. Mnl. 17.7I.TI, 1073. 2. Thmn.is, I,, 11., l'ii|i|ier, II., Itrrk, 1*. 1)., SelikofT, 1,, jind V'.dk, 11.: Vinyl chin- ride induced liver disease- AVie Flip. J. Mnl. ..'I'.'.-n, 1073. a. Smith, I', M. ,.,,,fl Willi-nns, n. M. J.: Vinyl chhiriflc niid cirrhn,j.,. Itiijrfhnu M.a.'I, 1071. Pint ol Chjrlei C. Morclum) Co.. Inc., N.Y.C. BOR 004941 ITEM 5 UNIROYAL, Inc. Oxford Management & Research Center Middlebury, Connecticut 06749 August 12, 1976 Dr. T. R. Torkelson Building 2030 Dow Chemical Co. Midland, MI 48640 Dear Ted: On page 10 of the August 11 issue of Chemical Week is a notice that NIOSH is asking for information on toxicity of 10 chemicals including vinyl chloride. Recently I compiled the attached data taken from November 12, 1975 list of NIOSH known Angiosarcoma cases. I listed only actual deaths by year of death. It seems to me that the last column is the most meaningful. If we assume roughly a 20 year induction period 1975 relates to 1955 when the industry was expanding rapidly. However, plants were larger and as time went on for various reasons fewer people were exposed at high levels. This indicates to me that the iceberg just isn't there, I would expect that at worst the average would rise a bit and then ease down until it blends with the background about 1990 or 2000. It is too much to hope that a government agency would ease off on its regulations but it might be wise to publicize these results so that they don't further tighten them. The information should be updated. Sincerely WDH/df Attachment cc: M. Freifeld D. E. Dudrow W. D, Harris Corporate Industrial Toxicologist S \ BOR 004942 i'OMMII UFtZRGVAL, Inn. i OXFORD (UCIIIM) August 5, 1976 TO: R. J, Dowling FROM: W. D. Harris SUBJECT: U.S. Cases of Confirmed Deaths Due to Vinyl Chloride Enpoaure The attached table from NIOSH lists the cases of angiosarcoma acccr-ed by the pathologists as typical vinyl chloride induced angiosarcoma. The Bridgeport G.E. worker and the accountant in a fabricating plant have been eliminated. The two cases who ere still alive were not included in my calculations which follow the table. WDH/df Attachments CCj B, R. Leach D. E. Dudrow R. E. Lowell J. D. Forbes* M.D. L. F. Dlcringer '. i ; I* * BOR 004943 REPORTED CASES OF ANGIOSARCOMA OF THE LIVER AMONG VINYL CHLORIDE POLYMERIZATION WORKERS ;-- COUNTRY United States United States United States United States United States United States United States United States United States United States Uni ted States United States United States United States United States United States United States Yugoslavia Yugoslavia CASE 01* 02* 03* * 04* 05* 06* 07* 03* 09* 10* 11* 12* 13* 16* 17* 18* 19 01* C2* BIRTH LATE 10-17-23 03-19-33 05-25-.15 01-15-24 01-25-12 00-00-29 05-03-22 05-06-20 11-03-31 08-16-13 05-27-09 11-17-13 12-01-21 11-04-27 05-06-31 04-22-23 00-00-15 04-05-14 11-15-31 1st VC or PVC EXPOSURE 12-09-43 11-15-55 11-23-45 07-06-52 06-19-44 01-17-62 03-00-44 10-07-46 09-09-54 06-12-51 10-14-46 09-13-49 08-19-44 05-03-50 06-23-55 03-00-54 C0-00-43 00-00-53 00-00-50 DX ANGIO SARCOMA AGE AX LX 03-03-73 05-00-70 12-19-73 03-19-67 04-09-64 02-00-74 GO-OO-68 00-00-61 03-01-74 05-00-68 03-00-70 05-02-69 05-00-74 00-00-69 10-11-74 CO-OQ-75 06-19-75 04-08-73 07-12-73 1 49 ` 37 58 43 52 45 45 41 43 55 61 50 52 41 43 46 60 59 42 YRS 1st EXP TO LX ` 22 14 28 15 . 20 12 24 15 17 17 23 20 . 30 17 19 21 32 20 23 Total Reported Cases = 45 Median Values: 17 U.S. Cases 17 Non-U.S. Cases , 34 Total Cases 46.0 43.0 45.0 20.0 17.0 18.0 mosa - Npv, 12 TOT YRS EXP ..LATE OF. DEATH 16 03-03-73 13 09-22-71 28 12-19-73 15 01-07-63 18 04-03-64 12 07-24-75 13 03-23-53 15 08-29-61 17 03-00-75 17 - 05-10-63 23 03-16-70 15 05-07.-69 30 07-C4-74 4 03-27-69 19 ALIVE 13 11-C2-7J 32 ALIVE 20 0*i-08--73 18 07-12-73 17.0 15.0 16.0 * Indicates microscopically confirmed angiosarcoma of the liver* nQ0" Indicates unknown data COPIED BY MCA 11/26/75 BOR OO4 9 4 4 t Year of Death 1961 1962 1963 1964 1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 Code No's. of workers who died during year 08 05 04 07, 10 12, 16 02, 11 01, 03 06, 09, 13 18 Rolling Ave. Starting 1961 Starting 1968' . 1.0 0.50 ' r :`:r 1 \r 0.33 0.50 ,0.40 0.33 0.43 if \l i , '/" * '1 0.63 2.0 0.78 2.0 0.9 2.0 0.82 1.5 0.75 1.2 0.84 1.3 1.0 1.7 1.0 i.8 ; Recognizing that the big build-up of the industry came in the `50 and ^O's and with a 20 year median period between first exposure and diagnosis, there has been no rapid build-up as was feared. It is likely that improvements in new plants offset volume. I would anticipate that there might be a slight increase in incidence over the next few years followed by a decline throughout the remainder of the century. i t .- BOR 004945 COPIED BY MCA FOR DISTRIBUTION TO THE VINYL CHLORIDE TECHNICAL PANEL, NOVEMBER 11, 1976, MR. MILTON FREIFELD Effect of Occupational and Journal of Occupational Medicine October 1976 Vol 18 No 10 Nonoccupational Factors on Respiratory System of Vinyl Chloride and Other Workers John Gamble, Ph.D.; Shuguey Liu, M.S.; A. J. McMichael, M.D., Ph.D.; and Richard ). Waxweiler, M.S.I.E. There are suggestions in the literature that vinyl chloride (VC) acts as a lung irritant. Respiratory questionnaires and lung function tests were administered to 174 chemical (VC) workers, 81 polyvinyl chloride (PVC) workers, 72 former VC workers, and 136 rubber workers, and 68 maintenance workers with exposure to VC, PVC, and rubber. Except for small air ways obstruction associated with rubber, increased respiratory symptoms and decreased pulmonary function were not associated with working in chemicals, plastics, or rubber. Some increases in baseline pulmonary function were associated with VC exposure. Acute reductions in pulmonary function were observed in smokers working in chemicals, plastics, and rubber. Heavier cigarette smokers over 40 years of age had the most adversely affected respiratory system. Work was not associated with chronic respiratory effects, but all exposure groups experienced some acute respiratory insult. At high exposures, vinyl chloride (VC) is a nervous system depressant, and in fact was investigated as a possible anesthetic, but was not used because of circulatory and cardiac eftects at concentrations of 10-20 vol, %,' In the late 1960's, acroosteolysis was associated with the polymerization of VC to form polyvinyl chloride IPVC) J`4 Early in 1974, four fatal cases of angiosarcoma of the liver wore reported in reactor operators working in a VCpolymcrization plant.' Subsequently the d'sease has been discovered among VC workers all over the world. Experimental and epidemiologic studies suggest that exposure to VC may carry an increased risk of respiratory impairment.''As a result, the Occupational Health Studies Croup (OHSC) at the University of from Oicup.nmjl Hi-.ilth Siudun C/u|i Sthixil uf Publn Health. University <>l North Cdrohnj Ch.ipel Hill NC 2T"i 14 Krprint wquetts to NCNB PU/a, 5uitr 12, Chapel Hill. NC 27514 (Df Gimhle) Journal of Occupational Medicine/Vol. 18, No. 10/0ctober 1976 North Carolina and the National Institute of Occupational Safety and Health (NIOSH) and CDC jointly earned out an epidemiologic study of VC-PVC workers. A part of this study was the investiga tion of lespiratory function and symptoms in currently employed VC and PVC workers, former VC workers, and a sample of control rubber workers employed in the same plant. Methods and Materials The plant under study has three major divisions The chemical plant produces primarily polyvinyl chloride IPVC) resin, although some copolymers such as vinylidene chloride and styrenebutadiene are also produced. The polvmers are either shipped or used in the Film and Sheeting division of this same plant in the production of plastic products. Film and Sheeting division (plastics) is in a building adjacent to the Chemical Plant, which also contains the Rubber Products division manufacturing primarily tires and tubes. All workers currently employed in the VC-PVC plants were invited for examination. A sample of 136 rubber workers from cleaner areas of the rubber division (i.e., tire building, final inspection, shipping and receiving) and without prior exposure to either VC or PVC, were selected and groupmatched with the VC workers on age and sex. A total of 71 former VC workers and 68 maintenance workers were also examinedThe response rate varied from a low of 62% in rubber workers to 77% in chemical workers. Clinical, smoking and occupational histories, complete physical examinations, chest roentgenograms, sputum cytology, symptoms, blood and urine chemistries were obtained on all 531 workers, and will be reported elsewhere. The British Medical Research Council respiratory questionnaire was administered by trained medical interviewers. Each worker performed a minimum of five forced .exhalations, seated and with a noseclip. The three best performances were selected on the basis of forced expiratory volume in 1 second (FEV) and forced vital capacity (FVC) within 10% of each other, and acceptable re producibility of the flow-volume curve. In addition to FEV and 659 BOR 004946 FVC. expired flow at 25% fFEF.'s). SO"'.. irrFtn). and 75% FEF-s) of exhaled FVC were obtained Al ItM't t sinitlu-hroatn nitrogen testi were .ilsn pertormed Hoi timmi-nded priK ednres and selei tion criteria were followed U r nht.iinint; dosing volume k-v pressed as ratio of closing volume to vital capacity CV VC) In addition, a random sample ol iittv-si\ VC. PVC and rubber workers were administered lung tunc tion tests hetore work and again after work. The difference m flow rates is calculated as after - before/mean with afterwork flow rates measured using the maxi mum pre-exposure FVC. The following questions were of interest in this study: 1. What are the effects of work on respiratory symptoms and function? Symptoms and baseline lung function were analyzed ac cording to three work exposure categories' la) current |ob (hourly VC salary VC. PVC. rubber, marntenance. former chemical): (b) all jobs, past and present (only in VC. only in PVC, only in rubber, or in a combination of the three). In this mixed exposure group an analysis of covariance was used to sort out the contributions of the VC, PVC. and rubber work experience to baseline pulmonary function: (c) man-months of exposure to VC: All VC jobs were given a high (10). medium (3) or low (1) exposure rating. Time 'in months) spent in each pb multiplied bv the exposure index provided a cumulative exposure to VC. This cumulative exposure score (CES) was then compared to baseline pulmonary function. The association of dose (years worked in the exposure categories or CESI and baseline lung function were assessed by calculating lung function regression equations for each smoking category of the total population. Then, within each exposure group, actual values of each smoking category were expressed as a percentage of expected values for all workers in that same smoking category In this way, the effect of work exposure on lung function was adpsted for differences in age. height and smoking between exposure categories. 2. What are the potential hazards of work exposure as measured by changes in pulmonary function over a work shift (APF)? A reduction in lung function suggests the likelihood ot some harmful exposure in the working environment. 3. Are symptoms rates and lung function parameters com parable to other occupation groups? Because the PVC and rubber control groups were themselves exposed to varied levels o! dust and fumes, comparisons with other studies are made. Results The age-smoking distribution of the population is shown in Table 1. Slightly over half of the population were smokers, 20% nonsmokers, and 16% exsmokers. The exsmrikers were older than the other smoking "guru's, with proportional.* tewur * x- smokers in the . 3*) s gr group vyiuktrs and nnn.m.isi'i' Had approximately the same tiivliihutuin m all age groups alttrough a higher proportion ot noO'-mukiMs were older, ami a h.gtier pmour- tion ot smok'.rs were in the middle age groups S.me ot die light smokers '<1 paik.dav' smoked more than 23 paik-sears, and they were equally distributed in the < 35 pack-years category .Most 161%) ol tlic heavy smokers ' 21 PJl k d*iV w,'r<',n ^ pack-year category-. 25% smoked 10-25 pack-veary. and 14".. < 10 pack-years. Table 2 shows the distribution of symptoms related to smoking and age. Prevalence of tough, phlegm, and persistent cough and phlegm did not increase with age. Breathlessness increased slightly but steadily with age. with the oldest age group repotting a rate ot breathlessness 2 5 times greater thin the youngest age group Smoking had a strong effect that was dose-related tor all respiratory symptoms. Light smokers ' < 1 pack day) had the same symptom rate for cough, phlegm, and persistent i ough and phlegm as exsmokers and pipe or cigar smokers Exsmokers, pipe Cigar, and <C 1 pack/day smokers had similar rates ot breathlessness. Because of the potential confounding effects of age and smoking, comparison of symptoms in each exposure category were adjusted for smoking and age differences Table 3 shows the prevalence of respiratory symptoms according to current |ob. The salaried chemical workers consistently had the lowest prevalence for all symptoms. Plastics, former chemical, and maintenanre workers reported the highest rates for cough, phlegm, and per sistent cough and phlegm: rubber and hourly chemical worker* were intermediate for these symptoms. All workers except the salary chemical workers observed similar rates of breathlessness Table 4 reports the age and smoking adjusted prevalence ot respiratory symptoms in workers working only in the rubber division, only in plastics, and only m the chemical plant Main tenance workers move back and forth among chemical, plastics and tubber. with no epidemiologicallv appropriate records kept ot time spent in any of these areas. The mixed group comprised those who had worked in two or more exposure categories The plastics only and chemical plant only workers had marked reduc tions in reported symptoms when compared to all currently em ployed workers in these same categories. Symptom rates for the mixed group were slightly higher than observed in the total population, and similar to the former chemical group Those working only in chemical, plastics, or rubber appear to be a select group of healthier workers, A high proportion ot those with symp toms in current job categories had a mixed exposure of rubber, chemicals and'br plastics. 660 Tabid 1. -- Age-Smoking Composition ol Study Population. Smoking Stilus Noosmokft* Eivrcwt Smofcsf J Pipe a<-<J CifiatS Alt Age < 29 N () 26 (24 3: $ < 7S1 62 162 61 6 t 3 bi 107 (20.2) 30-39 N (%> 19 Cl 31 8 ( SO' 5? <55 41 K* ill 2) 69 (16 8) 4049 N (%) V 116 J) 2^ >W9> 5? (56 Si 14 1 Bril 162 (30.5) 50-59 N (%) 21 (179) 75 \7U) 25 .44?) i4 t : \ 151 (28 4) >60 H <%> 9 140 51 ns 2) 6 12? j) 3 11361 22 ( 4.1) Totil N f% of Total) 106 120 3) 94 05 9: 155 0) 4? ( f9) 531 'Nonsmokei - hes smaeeo less llien 100 cgereMes in e lifetime . ftismoker - fus slopped smoking for more then 1 .ee' end does not now smoke j pipe of tiger tSmoker = lies smoked more then 100 cigarettes in e lifetime end hes smmed within the lest yeer Pipe Of tiger smokers who elso smoke cigarettes ere vciudrd m this cetegay IPipe end C.ger = ell those who smoke e pipe pr tiger now Out do not smoke t.geiettes or fiete not smoked tigerettes lor e ye* or more Fcfcenuges m the margins!; eie V of totals, percentages in tells e column percentages Occupational and Nonoccupational Factors on the Respiratory System of VC Workers/Gamble et al BOR 004947 Teble 2. -- Rtspiiatory Symptoms* by Age *nd Smt SmcK-'j Ctttjory Nonsmoto Eismoker All smokers 1 pxk/dey 1 ptdi/Oiy > 1 pKA/dey Pipe end Cigar All It) Cetegery < 29 30 39 4049 5059 a 60 H IDS 120 3*t.) 14 (156%) 292 (550%) 61 111 SA) 143 (269%) '88 (166%) 47 ( 69%) 531 107 (20 2%) 89 (168%) 162 1305%) 151 (28 4%) 22 ( 4 IV Ceegh 1 l2 % 66 71 216 96 189 341 S6 149 140 15 7 15.4 146 136 Phkgm 1l2 % S3 131 264 131 23 S 396 10.6 192 206 15.7 204 18.5 227 Pn*st*nt Cough 1 FMofm % 26 60 137 16 112 261 2.1 92 93 90 10.5 7.9 91 = Scared ttf criteria from British Medical Research Council Respiratory questionnaire t = t musing t= 3 missing Ireilhl \ 11 1 19 3t 26 it 23 3t 189 409 15 2t 2121 12 51 191 216 265 318 Figures 1-6 display the regressions of pulmonary function tests for the different smoking categories. Age and height significantly affected FEV and FVC values: age. but not height, was a statistically significant predictor of flow rates and closing volume (CV/VC). Heavy smokers (.1 pack/dav) had markedly reduced ventilatory capacity compared to other smoking groups (except for FVC where smoking did not signiticantlv affect lung volume'. Lung function values of exsmokers decreased at a rate in termediate between the heavy smoker and nonsmoker groups. Pipe or cigar smokers resembled nonsmokers tor FEV, FEFso, and FEF?s, but resembled exsmokers for FEFas--; and closing volume (CV/VC). Except for CV/VC, the least reduction of ventilatory capacity was observed in the light smoker (< 1 pack/dav' group All Smokers had similar functional reductions of CV VC with in creasing age. Current smoking behavior showed a better correlation with pulmonary function than did pack-years of smoking, and for this reason regressions based on current smoking categories were used in calculating predicted lung lunction values Table 5 summarizes the prevalence of impaired lung function as related to age and smoking. Except for fVC and CVVC pulmonary function impairment (see Table 5 for definitions) con sistently increased with age: and for all parameters consistently in creased with increased smoking Impairment rates for FEEis'v FEFso/FVC and CV/VC were significantly higher for smokers than nonsmoking categories: the smaller number of pipe or cigar smokers precluded them from achieving statistically significant de ferences. Age and smoking were then analyzed simultaneously. Regressions of pulmonary function with age (Figs 1-6) suggested that after about age 40, smokers of .1 pack/dav clearlv had lower lung function values than the other categories of smokers. As there was little difference in prevalence of impairment among ex smokers. nonsmokers and pipe or cigar smoker categories, thev were combined into a nonsmoker category, divided into age groups above and below 40 years of age, and compared with cigarette smokers Smokers and nonsmokers in the younger age group had similar rates of lung function impairment. Smokers oxer Symptom Cough 1 and 2 Phlegm 1 and 2 Persistent Cough and Phlegm Breathlessnesst (Gudf 2. 3. 4) H Age (years) Height (in) We.gbl libs) Table 3. -- Age and Smoking Adjusted Prevalence Rates of Respiratory Symptoms by Current Job. Rubber % 103 151 59 20 6' 136 40 4 (12 8) 695 1 2 - 1749 123 3)' Plot!let % 209 261 138 221 B1 44 1 113 8) 692 1 26) 180 8 (27 3) Howrty \ 14.8 15 5 Chemical Safety 4b 87 84 83 3.5 216 124 41.9 (12 8) 1550 365 I 89) 695 ( 22) 696 ( 296) 184 5 (30 7) 1774 (25 71' Fenner Chemtc?1 V 15 5 259 114 26 9* 22 43 1 (10 7) 697 [ 28) 1839 127 5) Malnlenence \ 16 5 22.3 137 194 68 N 46 7 11021 694 I 28) 166 1 (24 6) * -- I missing t - 3 missing Journal of Occupational Medicine/Vol. 18. No. 10/0ctober 1976 All b 15 6 192 9.2 71 24 931 421 (12 3) *69 5 (2 5) 1810 (26 91 661 BOR 004948 'A*. V V\n\ \Ov>, \ V, \VX \ xx\ *\ %* X \ \\ \ * \\ \\ \ % % Fig 1. -- Prediction Equations for FVC in Total Population by Smoking. PhMiHHtlfUrt i<l1lpw*tlk/4i*lyl I ptek/day tlM**r*kr/4ctytar -ol ,4:47i -i.m -1.27} *1.404 -1.401 -2.774 lilt-oInot?mf i) --0o.0o2n2 0.022 -0.0*0 -0.070 -0.027 (MUM **00c 00o4444 *c.ioo 0.042 0.12* l ict/4F S(I 0.201 0.274 0.242 0.101 0 174 0.1*2 .0Ail 78 1 ' JJ 1 ' 10 is 1 1 .3 'so if 1 40 years of age had significantly increased impairment compared to their nonsmoking counterparts. A synergistic effect of age and smoking was not observed for FVC (impairment was not affected by age or smoking) and CV/VC (both young and old smokers had rates of impairment higher than nonsmokers at any age). To preclude confounding effects of age, height, and smoking in assessing the importance of occupational exposure, mean percent pulmonary function for each |ob group was calculated by dividing individual pulmonary function values by predicted values derived from the appropriate smoking category, and calculating the mean. Smoking-adjusted impairment rates were directly adjusted Fig 2. -- Prediction Equations for FEVi in Total Population by Smoking. using the smoking distribution of the standard (total) population Baseline lung function as measured by mean percent predicted was the same in all current job groups. Table 6 summarizes the prevalence of impaired pulmonary function by current |ob. Former chemical workers tended to have the highest impairment, salary chemical workers the lowest. The other job categories generally had impairment rates betweeh these extremes. The effect of duration of exposure on lung function was then analyzed. Age, height, and smoking variables were adjusted in the manner previously described. Predictive equations were Symptom Cough 1 and 2 Phlegm 1 sis) 2 Persistent Cough and Phlegm Breathlessness! (Crept Z. 3 41 H Age (years) Height (m ) Weight (IM) * = 1 missing t = 3 missing 662 Table 4. *-- Age end Smoking Adjusted Prevalence Rites of Respiratory Symptoms by Exposure Categories. Muod * 202 23 0 112 27 4* 217 44 7 (110) 693 (Z 61 184.9 (294) Rubbor Only % 103 15.4 64 213132 40] (128) 695 (2 1) 1752 (23 Or Espcmi Cesspit Pitltics On hr Hourly ** 84 28 12.9 95 Chmfcal Only Slltry * 82 7.9 2.5 20 2.0 121 28 416 11521 66 44 34 7 (14 3) 1.9- 42 36.1 (90) 700 (24) 698 (19) 69 7 (2 7) 1804 (2591 175 3 (266) 1762 (25.81* All * 156 192 97 212 531 421 (123) 69 5' (25) 1810 (26 9) Occupational and Nonoccupationa! Factors on the Respiratory System of VC Workers/Gamble et al BOR 004949 linear Kill HlMI i*m i 1p***e<l'/**ate rRiH**(f*'*>**? > (l r* -*9 0>)1* *-o;) l tis J4IOO'U* 0j r\ I*i_ 0 4>4 0o0 lm4i/tt MI a. m N V; \\ \ \>x \\ \ n\> v N\V VN =' ^ N i Mtfc/*#r \ 1 **<-4/4j *lo 1 Js' 40 jo ys o /* / /: //' // // / //' / // // // // // /'// . // / // X V/ '/'f ///* IhWwlrkt'iW All wun 1<1 ^i(k/llT H1***<iWd<4iar r u llk**ooU.si**:***> *1 11 *0, II *0.42 *0.fet *l.4 *0.41 *1,M *0.4) *1.14 *0.1* ot000oon.,1JTmVijM*4\TI* 0,202 Flf j. -- Prediction Equation lor FEFrs in Total Population by Smoking. Fig 6. -- Prediction Equation for Cloting Voluroe/Vite! Capacity (CV/VC) in Total Population by Smoking. calculated using length of work in years as the independent vari able, i.e., predicted pulmonary iunction = % predicted + % change in pulmonary functionryear spent in exposure category. Table 7 summarizes regression for which a significant change oc curred. For exposure category 1 (rubber only, chemical only, plastics only), rubber workers observed a significant decrease of -0.8%/year in FEF75, plastics workers a decrease of -1%/vear. All other significant changes were increases in lung function. Health-related selective migration of workers is a potential source of bias in a cross-sectional study. In an attempt to take ac count of this, the effects of working in rubber and chemical, rub ber and plastics, chemical and plastics, rubber, chemical, and plastics, or any one alone, were examined by analysis of covariance (Table 7). By backwards elimination method, exposure variables not statistically significant <p >0.05' were sequentially re moved until onlv the most significant exposure variables remained in the model. The analysis was done first on the total population (No. 2), then on the mixed exposure group (No 3) and finally on the combination of categories within the mixed exposure group (Nos. 4-6). For the total population, working in chemicals was as sociated with increased FEV, FEFM.75. FEFzs. and FEF50. The onlv re ductions in ventilatory capacity were observed in FEFrs. a highly significant reduction associated with rubber, and increased CV/VC, a functional decrease associated with plastics. The analysis of the mixed exposure groups (exposure categories 3-6! tended to support the results observed in the total population Table 6. -- Age and Smoking Adjusted Prevalence of Impaired Pulmonary Function* by Current Job. Pulmoufy Function N FLV/FVC rvc f[fJS 7S FFFW/FVC FEFlS/FVC CVVP Rubber 136 41 36o 74 IS 9 1? 6 4G4 62' Plastics 81 32 SS 13 2 ni 11 7 4:4 121- Current Job Chemical Hourly Sibry 124 31 4S 64 133 6? 46 7 138 so 29 76, 0 141 0 336 36 former Chemical 72 4 :o\ 85 26 2 144 64 4 126* Maintenance 68 31 *% 101 129s- 79 45 6 7 0' . Alt 531 38 2S 81 14 9 10 2 47 5 10 6 'Ottmittcm cf impaired Pf in Table 5 1 = 1 taming 2=2 missing 8=6 missing 9--9 imsimg 664 Occupational and Nonoccupational Factors on the Respiratory System of VC Workers/fiamhle of al BOR 004951 lipeture Category* ) i 3 1 6 i ; 4 1 2 3 4 6 1 2 1 1 2 3 4 5 .2 3 5 6 Title 7. -- Selected Weiieticn Rcffessrcns lor Pulmonary function Related to Exposure A*-*, Height ini Smoking Ad|uJt| Predicted Puknanary function FtV = FVC FCF2S-7S FEF25 FEFS0 FEF7S CV/VC % Predicted SMS 992 100 8 93 3 98 3 93.8 980 I07J 94 4 91 0 980 968 1060 94 8 94 0 982 109 2 1118 100.5 948 109 9 955 983 97 6 107.9 92 7 + % Change For loch Voar Sp+m In iioosurt Cettgoey +0 47A +01S 0 25 +0 38 +0 57 +0 66 +0 33 094 +0 86 +0 89 +036 +0,35 OB5 +0 90 +099 +0 30 0.77 10 0.67 097 2 30 -10 +043 +0 46 0.75 + 116 ' Saar* Chemical Only Chemical Rubber PVC Only PVC Hourly Chemical Only Chemical Rubber Chemical Hourly Chemical Only Ctem>cal Chemical Rutter Chemical Hourly Chemical Only Chemical Rubber Only PVC Only Rubber Rubber Rubber RutOer PVC PVC Chemical I've Exposure Category Is Rubber Only. PVC Onfy. Chemical (H S) Only 2=H^a! Population (Rubber. Chemical. PVC) 3=Mixed Exposure (Rutter Chemical Plastics Chemical. Rubber Plastics. Rubber Chemical 8 Piastres! 4=Ruiber Plastics (N = 52) 5-- Rubber Chemical (N=fi6J 6-Rubber, Chemical & Plastics IN=3) p Value for % Change 0 02 005 . 010 004 008 0002 0009 004 003 0 003 0005 010 007 002 003 008 001 007 0.0001 QQOft 0 004 004 0 04 009 008 005 # Work in the chemical plant was associated primarily with in creased flow measured over mid vital capacity. Work in plastics was associated with functional reductions of from 0A to 1.2%/year in CV/VC. The most consistent and greatest changes were reductions of from -0.7 to 2 3%/vear in expired flow rates at low lung volumes (FEFrs), associated with work in rubber. Table 8 summarizes the relation of pulmonary function and cumulative exposure to vinvl chloride (see Table 8 for definition of CES-cumulative exposure score). Increasing exposure to VC in all workers ever exposed to VC was not associated with any sigmticant reduction in pulmonary function. The general tendency was for pulmonary function to improve with increasing exposure. Only reductions in FVC approached statistical significance Dividing the group into those with current VC exposure, and those that worked in chemical or plastics in the past liormer chemical) and repeating the analysis produced the same results The relation between respiratory symptoms and baseline pulmonary function is summarized in Fig 7. All respiratory symp toms were significantly associated with reduction in expiratory flow (TEF2S.7S. FEFzs). Cough, phlegm, and persistent cough and phlegm were significantly associated with reductions in FEFsii. Those with cough 2. phlegm 2 and persistent cough and phlegm had reduced percent predicted CV/VC. Reduced FEFzs was asso ciated with symptoms of cough and persistent cough and phlegm. In addition to baseline pulmonary function, 56 workers vs'ere Journal of Occupational Medicine/Vol. 18. No. 10/0ctober 1976 tested before work and again after work. Since the workers were also takmg physical exams, actual working time averaged about 4hours. As there were about twice as many smokers <82%! among chemical workers as plastics (36%) and rubber (41%) workers, acute etfocts were compared in cigarette smokers and all others combined (nonsmokers). Current smokers observed significant Ttbl* 8. -- Ag*. Height nnd Smoking Adjusted Regressions of Portent Predicted TJulmonery Function in Chemlcel end Former Chemicel Workers IN = 196) by Cumulitive Weighted Exposure* to Vinyl Chloride. PufeTlQftlfy function FEV FVC fcfm n Ft F FEF50 FEFls CV/VC lnt*reapt 1% predicted) 989% 1008 964 960 95 9 97.5 102 4 Slope (% chengs/CES*) +0 10% 016 ^+044 +053 +0 35 0 43 `034 p value of Slop* 0 47 013 004 002 019 017 024 "CES = airman** unsure sure All icos in in* chemical punt Ken rued la DC eipiswe as high (TWA = aporotimateJy 250 ppm), medum (TWA appwitfnattly 75 ppm) and tow (TWA approximated 25 ppm) CES was calculated by mutttplying months worked tunes a relative exposure rating Hugh = 10. medum = 3. low =; 1) lor that job, aid summing over an jobs flange a 0 2877 exposure-months. Bor 49 Si 66S II* BREATHLESSNESS no 5 0 V\ vA \o a J oL 1234 1234 1234 1234 5 PERSISTANT COUGH and PHLEGM 1234 1234 1234 X \u D I 90 nor Ot 0i Oi 01 01 01 01 PHLEGM ** 0 AAA*9 90 - 0(2 0(2 012 012 0 I 2 0(2 0(2 3 COUGH 100 95 90 83 -a i i FVC oil FEV oi; oi2 FEFm.tsFEF,, 0 12 FEFa0 FEFT5 0 12 CV/VC Fig 7, -- Pbrcent Predicted Pulmonary Function in Workers With end Without Respiratory Symptom* Adjusted by Age, Height end Smoking. HfiiKtionN in txil'i inn\ s ,in(l ''"u""'' uimii. .m-i i>-. l. , > CflMxrv )n FVC .tni1 ik ilmv iiut nthr-r lung turn !">n p.-.r im.-t.-i- dr'< fiMsi'd, \ignttu ,i. , unK Inf FtFm> 'l.iblr M: Xmnknrx m .ill |i.|> get sup* li.ul uxlut (infix in i1(<ii!il.it,,fv t .tp.n itv tfw I'/i .tli-'t fi' ' ii" men l ik tuning in Him - ,it low king \ online' 1 hr red m Imii' w e*r ot tin' Some order oi magnitude Ini .ill three expovure group' hut worn significant only tor vinyl i hloridi' <tnd rubber workers (\i epl for reductions over the shift of FEFso and Ftf rx in nonsmoking rub ber workers, ventilatory capacity ot nonsmokers did nut change significantly from zero Discussion This study was stimulated bv the finding of an increased inci dence of liver angiosarcoma in vinyl chloride IVCi workers Experi mental studies, case histories, and epidemiologic studies all suggest VC acts as a lung irritant. This literature is brietlv sum marized. Patty, Yant and Waite* exposed guinea pigs for 30 minute-, to 10-40% VC The principle gross pathological etlect was congestion and edema of the lungs, and hv|teremia of the kidnevs and lungs. Exposure to 10% VC resulted in slight signs ol lung hyperemia while hemorrhages, edema, and severe damage to the tracheal epithelium were observed at the higher concentrations in animals dying from the initial exposure. Pulmonary congestion was present after two weeks in surviving animals lower exposures lor longer time periods 150-500 ppm tor six monthsi resulted in no change in lung weight in rats, guinea pigs, rabbits and dogs Expo sures at concentrations greater than 100 ppm produced reversible liver injury in the more sensitive species ' Lester, et al * exposed rats to 20.000 ppm '.2% VO for three months, and 50,000 ppm (5% VC) for 19 days They observed increases in liver weight and decreases in white blood cells, but concluded that the observed Teble 9. -- Acuta Effects (Mean K Chance*) in Chemical. Plastics and Rubber Workers by Smoking Cetecories. The hypothesis was that PF should not differ significantly from zero (H:APF = 0). The one-sided I test was used to test i.gnificance. Standard deviation is in parenthesis. Currant Job n A FEV A FVC %% NSt 3 1 53 *020 12 55) Chemical S5 14 -! 61" Vinton 12 54) (2.191 0336 12 45) Pintles NS s 8 +041 1315) 4 3,57 (5 6?) + 109 12 61) -203* (1 54) Rubber NS s 17 +0 50 (4 821 10 3 33" (4 311 +0 72 (2 641 7 75" (3 021 MS 28 +028 +0 73 14 15) (2.531 All s 28 -2.50*** 1 44"* (389) (274) APEF % -0 97 (8 40) -4,2!' (8 70) 2 39 (9 59) 4 05 (8 73) +3 82' (8 731 *5 70 (11 73) + 1.53 (9 10) 4 72" (9 56) A FEFJS 7S % +040 (8 87) *1006"** (5 11) 193 (9 85) 4 53 (9 48) +0 25 (10 08) 9 72" (116*1 +036 (9 55) 915"" (8 47) A FEFH % + 163 (6 83) 943"" (4 87) 185 (8 60) -100 (14 99) +0 62 (7 56) 8 30" (11 \2) +0 03 (7 62) 7 82"" (9 27) A FEFSO % 093 (1243) 8 28" " (6 35) -053 (6 78) 11.73 (13 01) a 53 113 99) 8 75 (15 161 144 (11 831 887"" (1076) *p = < 005 "p = < 0025 *"p = < 0005 *"p= < 0005 fRS -- nonsmrKer, eismoker. pipe or cigar smoker IS -- smoker t = A positive Sign indiaios t Otaease in perloinunct as Me attei k CV/VC late is Oiger than tie More work CV/VC ratio *Mean Sk change = after work PF . before work Pf . nean Pf = jflrf + pefae mean PF 2 A FEF7S \ -2,77 (1542) 14 75*" (13 46) 4 24 (25 85) 72 76 (26 83) 5 76 (23 93) 1976" (27 14) -5 04 (2305) 1751"" 08 43) x. * A cv/vct S + 14 70 (32 95) +851 145 19) -12 35 (25 261 + 15 10' (12 3?) 055 (29 51) + J89 133 40) 2 34 128 71) +709 (37 33) 666 Occupational and Nonoccupational Factors on the Respiratory System of VC Workers/Gamble et al BOR 004953 lung edema and cong'-Mion cnuld nut be attributed to the irritating effects of VC. and the pneumonia observed was prohahlv dun to secondary infection Kcuhler''1 exposed rats mice and guinea pigs to 5.000.15.000 and 25.000 ppm VC tor 2*hours a day for 100 days without observing any histological damage In a report of a case of VC gassing in a plant in Croat Britain, a worker washing out a polymerisation vessel with water collapsed and was given artifi cial respiratory. Subsequent svmptoms included chest tightness."1 Boytsov' reports (without giving the number of species or . animals, length or amount of exposure! that inhalation and intra tracheal administration of PVC resin produced a "development of peribronchitis in the lungs" and local thickening of interalveolar septa. Two studies of PVC workers in Russia and Germany con clude that the respiratory system was afiected." " A "consider able number" of % PVC workers in Russia had a "changed bronchovaseular pattern and increased pulmonary ventilation at test"." Eight of thirteen German PVC workers employed for 1.75 to 18 years showed partial pulmonary insufficiency with signs of predominantly restrictive changes of the lungs '- This latter finding is in agreement with the case described by Szende. et al." A 31 year old male had shoveled PVC dust in a draftv place tor 1-year prior to being examined for severe dyspnea. The possibility of pneumoconiosis elicited by inhalation of PVC resin was suggested. There are a number of problems with the experimental studies of animals. Only at very high VC concentrations are effects ob served, and these are anatomical changes from gross pathology or histology. More sensitive functional measurements at lower, more realistic, VC exposure concentrations have not been reported. The foreign studies are only suggestive, and do not provide enough information to evaluate. There is onlv one reported epidemir)lr>gic study of VO and PVC workers m the U S.'4 Cough and sputum production tor must nt 1year or mine clinical signs of emphysema were reported in 11 . ot the 148 currently and previously emplovr-d VC and PVC workers Smokers and nonsmokers over 40 years ol aite liad similar rates ot flow impairment. In the age group under 40 however, smokers Kid about tsvice the prevalence of tlow impairment as nnnsmokers The higher prevalence of flow impairment rn smokers t ompared to nonsmokers converged slightly with increasing duration of exposure, nonsmokers and smokers with more than 20 vears exposure had the same prevalence or tlosv impairment The authors conclude that the etiologic agents producing the reduced air flow in workers over 40 vears of age or with > 20 vears expo sure is unclear but is not due to smoking. Exposure was to VC monomer. PVC resin dust, and pollution in a heavily industrialized city. The effect of smoking on respiratory svmptoms has become common knowledge following the report ot the Surgeon General on the Health Consequences of Smoking <1%4> and its sub sequent supplements K The results of this studv confirm these re ports, with the possible exception that light smokers (<1pack.day) in this study resembled exsmokers more than heavier smokers (2.1 pack dav). Pipe or cigar smokers have been less studied, although it has been suggested that pipe smokers are to be distinguished from cigar smokers Because of small num bers this has not alwavs been done, and in this studv these smokers were combined. They generally resembled light smokers and exsmokets in both svmptoms and lung function. The effects of smoking on symptoms have generally shown cough and phlegm to be higher in smokers, with prevalence relat- Pepuktloft Thti Study (All) Nonsmokerj Smokers Mining Community West Virginia0 Nonsmokers Smokers .Random Sample. Mates Berlin. N H * Notwmokers Smokers Stratified Sample. Industrial town m England5 Nonsmoker* Smokers White, male nonsmokers 35*4-" Maryland NYC Postmen Nonsmokers Smokers NYC Transit Vipers* Nonsmokers Smokers * Grade 2, 3. 4 breathWisness IGrede 3 nd 4 6itith*ivi I Cruft 2 m13 bftjlhleiiiwi Teble 10. --- Companion of Respiratory Symptom Prevalence. N Cough Phlegm PentftMt % % Cough & Phlegm % 531 14 9 192 108 56 83 292 216 264 9.2 28 13 7 163 154 311 513 47 2 462 140 38 3 75 107 172 401 165 162 73 170 96 553 -- -- 169 55 4.1 903 70 >31 3687 27 0 289 1012 64 95 3745 235 237 90 <34 15 40 190 26 152 Journal of Occupational Medicine/Vol 18. No 10/0ctober 1976 BOR 004954 BrottMefinan * 212* nr 26 5' 50t 107- 361 18 07 51 89 2261 2161 34 0 1241 233 667 ed to the amount of xnn >kmg, a re' whip supported by this Study. Breathlessness, while generally .uglier in smokers, is oticn not related to the amount of smoking This is hypothesized as due to selective reduc lion of smoking m those developing symptoms of breathlessness, a more severe and disabling condition than "smokers cough"." Although movement ot less fit heavy smokers into lighter smoking or nonsmoking categories seems a plausible explanation, selection docs not appear to be a strong factor in this population as there was a high prevalence of breathlessness cn the heavy smoker category. A trend for breathlessness to increase with increasing age is commonly observed,"* and was apparent in this study. The associ ation of cough and phlegm with increasing age has not been as consistent. Some studies report an increase with age;" others (including this study' find little tendency for cough and phlegm to increase with age." *' Two studies in West Virginia have observed an association be tween educational level and prevalence of respiratory symptoms and ventilatory lung function capacity, with the lower prevalence of symptoms partly attributed to fewer smokers in the higher educational categories 22 2 1 Stebbings2' in 469 white male nonsmokers found no effect of social class (based on occupation, education, and income) on most respiratory symptoms; only dyspnea was significantly less common in the upper social class, lower pulmonary function was also associated with lower socio economic status in these nonsmoking males.2' Salaried chemical workers in this study resemble the upper social class in that they smoke less than hourly workers, and are probably more educated. Exposure to VC and PVC resin is generally less than rhat of the hourly workers. It is not known from this studv whether social class, exposure, smoking, or some combination of these factors can explain the lower symptom rates of salaried chemical workers when compared to hourly workers. The same argument applies to the slightly better pulmonary function of salaried chemical workers compared to hourly workers. Among hourly workers, no consistent or convincing differences in respiratory symptoms or function were observed. When workers were divided into exposure categories of work ing only in plastics or chemicals, the respiratory symptom rate was reduced considerably. Workers with more |ob mobility were loss healthy in the sense that thev reported more symptoms. This could be due to a greater susceptibility, to having a more unfavor able job experience in terms of exposure, to self-propelled move ment to less symptom producing jobs, or some combination of these factors. Although the reasons are unknown, the fact remains that the less mobile "pure'' exposure groups had lower symptom rates than control rubber workers, maintenance, and the mixed exposure workers. Are the symptom rates observed in this population comparable to those in other populations2 Table 10 compares the prevalence of respiratory symptoms in this study with other studies. There is considerable variation between reported svmptoms in the various populations. The workers in this study compare favorably except for perhaps breathlessness The effects of age and smoking on pulmonary function ob served in this population are comparable to other reported studies. There were no significant statistical differences in the in tercepts of the smoking regression equations. Heavier smokers m this cross-sectional analysis had sigmticantlv greater reductions of FEV. FtFjs rs, FEFso. and FEFxs with increasing age. Two points are of interest with regard to the effect of smoking Before the age of 40, smoking had no apparent effect on pulmonary function. Secondly, light smok vere'obvouslv less affected than moder ate and heavy smokery, in tlte analysis of smoking one should ex amine this dose response relation, and not aibitranix lump to gether all smokers. Careful consideration of possible smoking-exposure intera< turns is also required For example, in a group of workers exposed to asbestos dust, smokers reported worse lung function than nonsmokers when a single regression was used for height and age ad justment.-"' The inference was that smoking increased the e'tec t ot dust exposure. Using only a Single regression equation for `i.indardoation is misleading however, as smokers pulmonary rum hon decreases more fapidly than exsmokers and nonsmokers Rossiter and Weil" point out that an apparent synergism between dust and age may instead be a smoking-age interaction Wtien separate regression equations were used for standardization, i.e., one car h for nonsmokers, exsmokers, and smokers, thev observed no de ference in pulmonary function related to dust exposure In fact, the asbestos dust exposure had a more detrimental etiect on nonsmokers titan smokers. We know there was a smoking-age inter action in this study. Since we are primarily interested in the Htect of VC exposure on pulmonary function, age and smoking ad justments were made using the regression equations of the various smoking categories (Figs 1-6). As there xvas no deference m pulmonary function between current job categories, and no nonex posed group of workers was available, the regression equations used for standardization were derived from the smoking cate gories of the total population. After standardization, increasing duration of exposure in chemi cals, plastics, and rubber was not associated with large changes m pulmonary function. Reductions in FEFr;, the most sensitive mea sure of small airways obstruction, was consistently and significant ly associated with working in rubber; less significant reductions m FEFjs were associated with hourly chemical and plastics workers, and FVC in hourly chemical workers. Other pulmonary function parameters generally remained the same or improved with in creasing duration m chemicals or plastics, and with increasing cumulative VC exposure. The reported case of pneumoconiosis on exposure to PVC resin'J is suggestive that high exposure to PVC resin may result in a restrictive type of respiratory disease. Baggers in the chemical plant are exposed to from 1-5 mgm' of particulate (measured bv area Hi-volume samplers); respiratory paniculate is 1/10 to 1/20 these levels. Exposure to the PVC resin in plastics appears higher for Banbury operators but lower tor workers in milling, and negligible for other plastics workers. The low prevalence of FVC impairment in both chemical and plastic s workers does not support the hypothesis of PVC resin exposure producing volume restriction. What difference is there between the workers in this study and those reported on bv Miller, et all Pulmonary function impairment tor FEVTVC, FVC. and FEFrs/FVC in this studv employed the same definition as Miller, et al.14 in their study of VC-PVC xvurkers The prevalence of impairment for FEFzs-75, using the same criteria, was essentially zero, and thus far below the 53% they observed. The cutoffs for impaired flow as measured by FEFso/FVC and FEF-s/FVC have been shown to be reasonably effective in distinguishing nor mal subjects from those with obstructive lung disease '- The high est prevalence (almost 50%) of impairment was for FEF's TVC and supports the observed association of reduced FEF--, with increas ing duration ot work. All VC-PVC nonsmokers less than 40 years of age, and all workers in this study less than 40 years of age, had about a 20% prevalence of impairment for FEV'FVC and FEF.VFVC. The prevalence of impairment increased for non 668 Occupational and Nonoccupational Factors on the Respiratory System of VC Workers/Gamble et al BOR 004955 smokers ovtt 40 in both population-, but morn so in tho Miller Study. The rates of flow impairment in both studios are the same for smokers over 40 In both studies the prevalence ot impaired FVC (<10%) is considerably lower tor llow impairment (18-75%' and much lower than expected from exposure to asbestos " The association of increased pulmonary function performance with increasing exposure and work duration, particularly in chemi cals, suggests that selection is occurring in this population. The reason for the lack of association between VC exposure and respiratory effects may be due to differential migration of more susceptible workers out of chemicals. Note that the mixed exposure group reported a higher symptom rate than chemical and rub ber workers who had never moved. Tho current plastics worker had symptom rates comparable to or higher than this mixed expo sure group, suggesting that net migration of "susceptibles" may have been into plastics. The association ot small airwavs ob struction with exposure mav he more informative than symptoms because (1) small airwavs may be more sensitive to the effects of environmental agents; and (2) small airways obstruction is probably not noticed by the individual to the same extent as symptoms and FEV reductions, and would therefore not be af fected as much by selective migration. Several conclusions emerge concerning factors that affect base line pulmonary function in this population: ID age and smoking were the two most important factors reducing pulmonary func tion; smoking was associated with obstruction only 'no significant effect on FVC). (2>-small auwavs function as measured bv FEF?s was affected by both smoking and work exposure, primarily rub ber worker exposure. (3> work, whether measured by duration or estimated cumulative exposure to VC and after adjustment for smoking effects, was not associated with reduced baseline pulmonary function (except for FEFrs). (4) although prevalence rates of impairment are not often reported, the air flow im pairment (FFV/FVC, FEFrs), rates appeared elevated only in the older smoker. Respiratory symptoms and measurement of pulmonarv function are two somewhat independent and yet overlapping methods for investigating the risk ot environmental exposures to the respira tory system. Symptomatology suffers from the disadvantage of be ing subjective, can show interobserver variation, and requires adequate recall on the part ot the person being interviewed: symptomatology is useful m diagnosis, particularly chronic bron chitis. Independent validation ot symptoms in practice turns out to be pulmonary function measures, despite the fact that different, albeit overlapping, parameters are being measured. The observed association of reduced pulmonary function with increasing severity of symptoms increased the validity of respiratory symp tom information. The conclusion that VC exposure did not consti tute a significant respiratory hazard in this population was strengthened by similar results for both symptoms and pulmonary function. While one methodologic strength of this present study is the ability to make internal comparisons between work groups, it must be stressed that none of the groups can be regarded as hav ing worked in hazard-free conditions Both rubber and plastics workers are exposed to varied levels of dust and fume, and it could bo that reduction in lung funclion among chemicals workers (whether due to vinvl chloride exposure, or to some other agent' are being obscured because of similar reductions in the other |ob groups. The results oi FFF-vFVC impairment (pertaining to that part of Ihe respiratory tract thought to be first aftectod by harmful exposure -- the small bronchioles) suggest increased abnormality rates in ill workers ..ideed. lot xcx'ora! of the pulmonarv function tests the chemical workers had belter results thin rubber and plastics workers. To assess the potential respiratory hazard of each exposure category before-and-after shift tests were carried out on some workers. Any reduction m respiratory tunc turn over the shitt suggests the likelihood of some harmful exposure in the working environment.,J Smokers overall had statistically significant reductions for all ventilatorv tests, nonsmokers showed little reduction The most obvious reductions were flow rates at low lung volumes, i e . mea sures of small airways performance. Chemical workers who were smokers had significant reductions for five of the seven tests, pre dominantly reflecting small airwavs obstructive change; both plastics and rubber workers who smoked showed reductions of similar magnitude No clear picture emerges -suggesting one |ob group faced greater daily respiratory insult than the others Re duction in small airways performance among nonsmokrrs in each job group suggests that all workers were exposed to agents with adverse respiratory effects. In a clean environment the average re sult for these nonsmokers would have been a slight increase m test performance. Whether these acute reversible changes have anv permanent effect is not known. The significance of these findings is unclear. The small airways obstruction associated with work in the rubber division, i e. the control group, could be related to a number of environmental agents. The complexity of the industry and the heterogeneity of the control group does not allow for determining the etiologic agents. The rubber worker group was selected on the basis ot lower particulate exposure and never hav ing worked in chemical or plastics. But they could have, and probably did. work m other jobs with higher exposures within the rubber division. A complete work history for each rubber worker would be required to investigate further the association of re duced small airways function with work in rubber. Fundamental and more difficult questions remain. What is the biological significance of acute reversible reductions in small air wavs function over a shift? What is the biological significance of statistically significant reductions in baseline pulmonary function over a longer time period? For FEFrs, the reduction is on the order of -1 %/year. Over a 40 year period, this would amount to a 40% decrease. However, some individuals have a reversible change of 40% in the course of a day. The association of working in rubber with a downward slope of the percent predicted FEFrs is a finding that requires further investigation of workers in other areas of the rubber plant, an investigation currently underway. The* authors thank Mike Svmons for advise on statrstrcal matters NIO^H industrial hvtfiemvts tor assurance m derive the VC exposure source Marv lane Thomas tot manuscript preparation, and union and company officials for their assistance in the project References 1 Patty FA Industrial Hygiene and Toxicology, Vol 2. Inhn Wiley and Sons. New Yoik. 1963 2. Wilson RH. McCormitk WE, Tatum CF. and Creech 11 Oi rupaliunal aeroosteolvsis. report ot 31 cases IAMA 201:577-581, 1967 3 Dinm.m BD et at Occupational aeroosteolvsis I. An e|ndeiniological study Arch Fmrrori tilth 22.61-73 1971. 4 Ctxik WA el al Oi t ufMtionaf aeroosteolvsis II An indu-lrul Hsgieno study Arch fnvimn llhh 22 74-82, 1971 5 Creech IL and lohnson MN Angiosarcoma of the liver m the manufac ture or polvvmsl chloride. /OW 16,150-151, 1974. Joutnal of Occupational Medicme/Vol. 18, No. 10/Octobet 1976 BOR 004956 -69 6. Patty FA. Yant WP .1nd Waite CP Aiutu n ~.piimo- nt emnea pigs to vapors of some nrw tnmmivi latlirranic compixmilx V vinvl ihlixidi* L/ 5 Pub Hlrh Report- 4S 1963-W71 1'10 7. lorkclson TR, Oven F, and Rowe VK The toxicity of vinvl chloride as determined by repeated exposure of laboratory animals. Amer Indus H)R Assoc I 22:354*361, 1961. 8. tester D. Greenberg IA. and Adams WR- Effects of single and repeated exposures ol humans and rats to vinyl chloride Amer Indus Hyp Anne / 24:265-275. 1963. 9. Boystov AN Problems of industrial hygiene in new plants far the manufacture of synthetic resins and plastics. Ogyena Truda 11.20-27. 1963 10. Ruebler H. The physiological projxrties of aerosol propellants Aerosol Age 9.44, 47-48. 50, 90*91. Ahstract only, 1964 11. Vertkm Yl and Mamontov YR: Condition or the bronchopulmonary system in workers manufacturing articles of polyvinylchloride Gig Tr Prof Zabol 14:29-32. 1970 12. tangc CE. |uhe 5. Stein C. and Veltman G. Die Sogcnante Vmylchloride-Rrankheit*ein berufsbedingte Svstcms Klerose' Ini Arch Arbeits med 32 1-32, 1974 13. Saende B, lapis K, Nemes A. and Pinter A. Pneumoconiosis caused by the inhalation of polyvinylchloride dust Med lav 61 433-436, 1970 14. Miller A ct al. Changes in pulmonary tunclion in workers exposed to vinyl chloride and polyvinyl chloride Ann .% Y Acad Sa 246 42-52. 1975 15. Suggested Standardised Procedures for Closing Volume Determina tions (Nitrogen Method), distributed bv Division of lung Diseases, National Heart and Lung Institute, lulv ;1973) 16. Annual Report of the Chief Inspector ol Factories for the Year 1951 london: HMSO Cond 8772. March. 1953 17. Smoking and Health. Report of the Advisory Committee to the Surgeon General of the PHS. USGPO, Washington. DC., 1964 and sub sequent reports 18. Seltzer CC. Morphologic constitution and smoking /AMA 183 639645. 1963. 19. Higgins ITT The epidemiology of chronic respiratory disease, Prev Med 2:14-33, 1973 20. Higgins ITT., et al Chronic respiratory disease in an industrial town' A nine-year follow-up study. (Preliminary report) Am I Pub Hlth S8:1667, 1968, 21 Ferns BC Ir and Anile, -on DO The prevalence nf chrome rrxpirjtnrv disease in a New Hampshire town Am Rev Resp fin 86 lfii-1" 1`"j2 22 Higgins IIT. Higgins MW. Lixkshin MD anil t.unolo N Chronn respnatory disease tn mining enmmunmes m Marion County. West Virginia. Bril / Ind Med 25 165, 1968 23. Enterline PE and lainhart WS: The relationship between coal mining and chronic nonspecific respitatory disease. Am f Publ tilth 57 484 1967 24. Ferris BG |r et al: Chronic nonspecific respiratory disease m Berlin. New Hampshire, 1961 to 1967. ARRD 107:110-122. 1973, 25 Higgins ITT Oi < ujiatumal Factors in Chronic Bronchitis and Em physema. in Bronchitis III. Proc of 3rd Int Cont on Rmm hitts at Groningen, The Netherlands. 23-26 Sept. 19f>0 26 Stebbins |H: Chronic respiratory disease among nonsmokers in Hagerstown. Maryland -- III. Social class and chronic respiratory disease tnv Res 4 213-232, 1971. 27 Stehbings |H. Chronic rcspiratorv disease among nonsmokers in Hagerstown, Maryland -- I Design ot the study and prevalence ol symp toms frrv Res 4.146*162, 1971, 28. Denson PM et al A survey of respiratory disease among New York City postal and transit workers. I. Prevalence of symptoms fnv do 1 265286. 1967 29 Rossiter CE and Weill H Synergism between dust exposure and smoking An artefact tn the statistical analysis of lung tunclion' Bull PhvsioPath Resp 10 717, 1974. 30 Morns IF. Koski A, and lohnson 1C: SpirometrtC standards tor healthy nonsmoking adults Amer Rev Resp Dis 103 57-67. 1971 31 Lapp Nl and Hvatt RE Some factors affecting the relationship of maximal expiratory flow to lung volume in health and disease. Do Chest 51475. 1967 32, Bader ME et al Pulmonary function and radiographic change in 590 workers with varying duration of exposure to asbestos / 5ft smai Hmp 37.492. 1970 33, Buist SA and Ross BB Predicted values lor closing volumes using a modified single breath nitrogen test Amer Rev Resp Dis 107 "44-752 1973 34, Camble IF, McMichael A|, Williams T, and Battigelli MC Respiranw function and Symptoms' An environmental-epidemiologic study of ruliher workers exposed to a phenol-formaldehyde type resin. Amer Ind Hyg Assoc I 37:1976 Correction In "UV Keratoconjunctivitis Vs. Established Dose Effect Relationships," JOM, Aug 1976, p, 573, the term "Amp" was erroneously used with reference to emission characteristics of lamp Wherever `'Amp" appears, it was intended to read "Angstrom Units." N BOR 004957 670 Occupational and Nonoccupational Factors on the Respiratory System of VC Workers/Gamble et al