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Hazardous Air Pollutants-VC EXHIBIT IV November 1976 ____ Air Reg 151" Hazardous Air Pollutants Vinyl Chloride, 40 CFR 61, FR October 21, 1976 On December 24. 1975, under section Summary or the Standard at ambient levels of exposure were ex 112 of the Clean Air Act, as amended (42 TT.S.C. 1857), the Environmental Protec tion Agency (EFA) added vinyl chloride to the list of hazardous air pollutants (40 PR 59477) and proposed a national emission standard for It (40 FR 59532). The standard covers plants which manu facture ethylene dichloride, vinyl chloride, and/or polyvinyl chloride. In ethylene dlchloride-vlnyl chloride plants, the standard limits vinyl chloride emissions from the ethylene dichloride and vinyl chloride formation and puri fication processes to 10 ppm. Ftor the^oiychlorination process, vinyl chloride emissions are limited to 0.2 g/kg of ethyl ene dlchloride product In polyvinyl chloride plants, the stand trapolated from dose-response data from higher levels of exposure both a linear model and a log-probit model. Extrapolations made with each of these models entailed using different sets of assumptions. Because different assump tions can be made in extrapolating to low doses, the health risks are reported in ranges. EPA decided to regulate vinyl chloride because it has been implicated as the causal agent of angiosarcoma and other ard limits vinyl chloride emissions from equipment preceding and including the stripper in the plant process flow to 10 serious disorders, both carcinogenic and ppm. Emissions from equipment follow noncarcinogenic, in people with occupa tional exposure and in animals with ex ing the stripper are to be controlled by stripping dispersion resins to 2000 ppm perimental exposure to vinyl chloride. and other resins to 400 ppm, or by using Reasonable extrapolations freon these Onrfinps cause concern that vinyl chlo ride may cause or contribute to the same or imilm- disorders at present ambient equivalent controls. Vinyl chloride emis sions from reactor opening are to be re duced to 0.02 g/kg polyvinyl dhloride product. air levels. The purpose of the standard Is to minim vinyl chloride emissions from all known process and fugitive emission sources in ethylene dlchlorldevtnyl chloride and polyvinyl chloride plants to the level attainable with best available control technology. This will have the effect of furthering the protec In both ethylene dlchloride-vlnyl chloride and polyvinyl chloride plants, relief valve discharges and manual vent ing of gases are prohibited except under emergency conditions. Fugitive emissions are required to be captured and con trolled. tion at public health by minimizing the Health and Environmental Impacts 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. EPA prepared a document entitled Ore Quantitative Risk Assessment tor Com munity Exposure to Vinyl Chloride which estimates the risk from vinyl chloride It was estimated that 4.8 million peo ple live within 5 miles of ethylene dichorlde-vinyl chloride and polyvinyl chlo ride plants and that the average ex posure around these plants before instal lation of controls to meet the standard Is 17 parts per billion. The exposure levels for uncontrolled plants were cal culated based on estimated 1974 emis sion levels. Using the linear dose-re sponse model, efa 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 log-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. >ue to the long latency time observed in cancer cases resulting from vtnyl chloride exposure, increases Initiated by exposure this year will not be diagnosed until toe Interested parties participated in the exposure to populations living in the vi 1990's or later. Vinyl chloride is also es rulemaking by sending comments to EPA. cinity of vinyl chloride-emitting plants timated to produce an equal number of The comments have been carefully con before and after Implementation of con primary cancers at other sites, for a total sidered, and where determined by the trols to meet the standard. There are no of somewhere between less than one and Administrator to be appropriate, changes dose-response data for the concentra twenty eases of cancer per year of ex have been made to the regulation as pro tions of vinyl chloride found in the am posure among residents around plants. mulgated. bient air. Therefore, assessments of risk The number of these effects is expected Copyright 1976 by Environment Information Center, Inc. COLORITE 019482 Air Reg 152 November 1976 Air Regulations to be reduced at least In proportion to the the process equipment and the incinera nance of precontrol profitability is esti reduction to the ambient annual average tor combined would cause maximum am mated to add approximately 2 percent to vinyl chloride concentration, which Is bient concentrations of hydrogen chlo polyvinyl chloride resin prices and result expected to be 5 percent of the uncon ride to the vicinity of ethylene dlchlo- to an additional maximum consumer trolled levels after the standard Is Im rlde-vinyl chloride plants to be to the price increase of 1 percent. plemented. Changes to 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 to Chapter 6 of Volume 1 of the Standard Support and Environmen same range or somewhat higher than existing loreign standards and National Academy of Sciences (NAS) guidelines for public exposure. Economic Impact In accordance with Executive Order 11621 and OMB circular A-107, EPA Public Paxuofation During the public comment period. 50 comment letters fm the proposed stand ard were received. There were 24 from industry; 3 from environmental groups; 15 from Federal, State, and local agen cies; and 8 from Individual citizens. As tal Impact Statement. According to data carefully evaluated the economic and required by section 112(b) (1) (B) of the submitted by the Society of Plastics In Inflationary Impact of the proposed Act, a public hearing was held on the dustry, Inc. (SPI). the impact on water standard and alternative control levels proposed standard on February 3, 1975, consumption'In the draft environmental and certified thin to the preamble to the in Washington. D.C. Presentations were hnpact statement was overstated. In es proposed standard. These impacts are made by the Environmental Defense timating the Impact on water consump discussed to Chapter 7 of Volume I of Fund, the Society of the Plastics Indus tion. EPA based its estimates on worst the Standard Support and Environmen try. Inc., Dow Chemical Company, Dia case conditions. That Is, EPA assumed tal Impact Statement. Comments on the mond Shamrock Corporation, and Air that those control systems with the proposed standard have resulted to only Products and Chemicals.'Inc. Copies of greatest water usage would be employed one major change to the economic Im the comment letters received, the public and that there would be no recycling pact analysis. EPA estimated that there bearing record, and a summary of the of water. There Is no regulation which would be four plant closures as a result comments with EPA's responses are would require water recycling. Accord of the promulgated standard. Of the four available for public Inspection and copy- ing to SPL the control system utilizing plants identified as possible closure can tog at the EPA Public Information Ref the most water will not be used gener didates, one has given notice that it no erence Unit, Room 2922 (EPA Library). ally by the industry and economic fac longer produces polyvinyl chloride and 401 M Street. 8W, Washington, D.C. In tors will cause plants to recycle much the other three have Indicated that they addition, copies of the comment sum of the water. Therefore, according to do not intend to close as a result of the mary and Agency responses may be ob SPI the impact of the standard on water standard. tained upon written request from the consumption will be negligible. The economic impacts of the promul Public Information Center (PM-215), . The environmental impacts of the gated standard may be summarized as Environmental Protection Agency, 401 promulgated standard may be summar follows; The total capital cost for exist M Street, SW,, Washington, D.C. 20460 ised as follows: The primary environ ing plants to meet the standard is esti (specify Standard Support and Environ mental Impacts of the standard are ben mated to be $198 million, of which $15 mental Impact Statement. Emission eficial and will consist of vinyl chloride million is for ethylene dichloride-vtoyl Standard for Vinyl Chloride, Volume II). emission reductions of approximately 94 chloride plants and $183 million is for percent at ethylene dichloride-vtoyl polyvinyl chloride plants. EPA estimates Significant Comments and Changes to chloride plants and 95 percent at poly that these plants win have to spend $70 irs Proposed Rxculahoh vinyl chloride plants. Percentage num million per year to maintain the required (1) Decision to list vinyl chloride as a bers for both source categories are based emission levels. In addition, the total hazardous air pollutant. In general, the on an estimated 60 percent reduction to capital cost for existing plants to meet commenters did not contest EPA's deci fugitive emissions and 1974 emission the EPA's 1983 water effluent guideline sion to list vinyl chloride as a hazardous levels. The potential secondary environmen tal impacts of the standard are either limitations is expected to be $83 million and the total annualized operation cost Is $17 million. The costs to the industry air pollutant. However, three commenters (two companies and one Federal agency) argued that EPA placed undue Insignificant or will be. minimized with out additional action, except for one ad of meeting the OSHA standard cannot be quantified at this time, but they are ex emphasis on factors suggesting that vinyl chloride presented a health risk and vene impact. Hydrogen chloride is al pected to overlap to some degree with the Ignored factors suggesting that no sig ready emitted by process equipment at costs to meet EPA's fugitive emission nificant risk was involved. Under section ethylene dichloride-vtoyl chloride plants regulations. The costs of meeting the 112. however, EPA could remove vinyl and by other petrochemical plants to the cranplmMB where ethylene dichloride- fugitive emission regulations are included the total costs cited above for meeting chloride from the list of hazardous air pollutants only If information were pre vtoyl chloride plants are typically lo cated. An incinerator used to attain the e promulgated regulation. Broken out separately, the capital cost of meeting sented to EPA that shows that vinyl chloride is clearly not a hazardous air Standard at an ethylene dichloride-vtoyl the fugitive emission regulations Is $37 chloride plant could Increase hydrogen million and the annualized cost Is $25 pollutant. As discussed more fully to the comment summary, the commenters did chloride emissions by several fold. Typi million. not provide conclusive evidence that vinyl cally, however', due to the corrosion prob The standard is not expected to deter chloride is not a hazardous air pollutant lems which would otherwise occur both construction of new ethylen^ dichloride- which causes or contributes to death or on plant property and to the community, vtoyl chloride plants or most types of serious illness, nor did they conclusively plants use scrubbers to control already new polyvinyl chloride plants. For one prove that the health risk factors enp existing hydrogen chloride emissions. type of polyvinyl chloride plant (disper phasized by EPA were insignificant. Hydrogen chloride emissions resulting sion process) that represents 13 percent Several other commenters agreed with from control of vinyl chloride emissions of the industry production, the standard EPA's decision to list vinyl chloride as a are expected to be controlled for the would significantly deter the construc hazardous air pollutant, but argued that same reason. If even a moderately effi tion of smaller plants. EPA had overstated the h--1tn problem, cient scrubber (98 percent control) were It Is estimated that the price of poly the emission levels, and the projected used to control the hydrogen chloride vinyl chloride resins will rise by approxi ambient air concentrations around un emissions resulting from Incineration of mately 7.3 percent to order to maintain' controlled plants. With regard to the al vinyl chloride emissions, the increase to precontrol profitability and also to re leged overstated health problem, the hydrogen chloride emissions from a typ cover the total annualized control costs commenters stated, for example, that the ical ethylene dichloride-vtoyl chloride necessitated by the standard at ethylene U.S. worker EPA discussed as having plant due to the standard would be re dichloride-vtoyl chloride plants and poly been exposed to vinyl chloride'levels low duced to 35 percent. However, EPA plans vinyl chloride plants. This increase is er than those usually encountered to to further evaluate the need to control estimated to translate Into a maximum polyvinyl chloride production has been hydrogen chloride emissions, since dif consumer price increase to goods fabri dropped from the National Institute of fusion model results indicate that under cated from polyvinyl chloride resins of Occupational Safety and Health's fisting "worst-case" meteorological conditions, approximately 3.5 percent. Recovery of of workers with angiosarcoma. EPA the hydrogen chloride emissions from effluent annualized costs plus matate- agrees that there are questions concera- Environment Regulation Handbook COLORITE 019483 Hazardous Air PoTIutants-VC November 1976 Air Reg 153 ing the level of exposure ana in some WMch can reduce vinyl chloride emis equipment from applicability of all parts cases the pathology of these cases not sions by 90 percent or more, It does not of the standard if the reactors are used involved directly in polyvinyl chloride seem prudent to reduce emissions by the In research and development and have a and vinyl chloride production. These un certainties are stated in the appropriate footnotes of the Scientific and Technical remaining percentage and take the risk ot introducing new untested chemicals into the environment. capacity of no more than 0.19 m* (50 gal). Reactors In this size range can gen erally be found In a laboratory, whereas Assessment Report on Vinyl Chloride and Another approach suggested by the t.hc larger reactors are typically pilot Polyvinyl Chloride (STAR) where the angiosarcoma cases are listed. However, commenters was to base the .standard for each Individual emission point on cost scale facilities. Emissions from laboratory scale equipment are relatively small, anil in spite ot these uncertainties, in view of versus benefit. Several of the fugitive application of the controls required by the possible exposure patterns, these emission sources were named specifically the standard would be expensive and Un cases cannot be ignored in the evaluation as ones for which the costs of control practical. EPA also decided to exempt ic- of the potential public health problems. were substantially higher than the bene scarch and development facilities con With regard to the alleged overstated fits. Although EPA did determine a cost- taining reactors greater than 0.19 m' (50 emission levels, the uncontrolled emis benefit ratio for the controls required gal) and no more than 4.07 m1 (lioo gal) sion levels reported by EPA were based for a number of emission points. EPA in capacity from all parts of the standard on 1974 data. This qualification was does not believe such a ratio is an appro except the 10 ppm limit for reactors, stated wherever emission data were pre priate basis on which to set a standard. strippers, monomer recovery systems, and sented. EPA recognises that emissions Section 111 of the Clean Air Act provides mixing, weighing and holding containers, have been reduced since that time, and for the development of standards based EPA decided not to require these facili stated this in the preamble to the pro on best control technology (considering ties to meet other parts of the standard posed standard. EPA decided not to costs). Even under section 111, however, because of the technical problems In gather more recent data on emission standards are not based on a fine bal volved in doing so. For example, the levels, because these emission levels are ancing of costs versus benefits. Instead, standard for reactor opening Is based In expected to change, and gathering the costs are considered in terms of the af part on reducing the frequency of open data would take considerable time both fordability of the control technology re ing the reactor. Research and develop on the part of EPA and on the part of quired to achieve a given emission level ment reactors have to be opened aftci Industry. Since the purpose of the stand and the economic impact of possible every batch for thorough cleaning. Also, ard Is to minimize emissions, these more standards on tire industry in ques stripping technology is developed Indi current data would not affect the stand tion. Unlike section 111, section 112 does vidually for each resin In research and ard Itself. The 1974 emission levels were not explicitly provide for consideration development equipment. Therefore, at also used In diffusion modeling to project of costs, so it would clearly be inappro tainment of the stripping limitations hi maximum ambient air concentrations priate to consider costs to a greater ex the research and development equipment around uncontrolled plants. These maxi tent under section 112 than would be would not always be passible. The 4.07 mum air concentrations would probably done under section 111. As discussed in m' (1100 gal) figure was selected as an be lower if 1976 emission levels were used. the preamble to the proposed standard upper cut-off point because there are no This would reduce the relative impact for vinyl chloride. EPA believes costs commercial reactors smaller than this. of the standard below that described in the Standard Support and Environment tat Impact Statement, but would not affect the basis of the standard itself. (2) Approach for Regulating Vinyl Chloride Under Section 112. Two ap proaches other than using best avail able control technology were suggested by the commenters for regulating vinyl chloride under section 112. The first was to ban polyvinyl chloride products for which substitutes are currently available and to gradually phase out other poly vinyl chloride products as substitutes may be considered under section 112, but only to a very limited extent; i.e,, to assure that the costs of control technol ogy are not grossly disproportionate to the amount of emission reduction achieved. In comparison with other emission points, the costs of controlling the fugitive emission sources mentioned by the commenters are relatively small compared with the amount of emission reduction achieved. Several commenters recommended adding to the regulation a provision for (4) Emission limits. The only rnajoi change In the emission limits between proposal and promulgation Is the addi tion of a provision for emergency manual venting of vinyl chloride from reactors to the atmosphere. The proposed stand ard prohibited ail manual venting to the atmosphere. In the preamble to the pro posed standard. EPA invited Interested persons to comment on whether permit ting manual venting to the atmosphere could result in overall lower emissions. There are several methods available for are developed. excess emissions during startup, shut preventing relief discharges from reac In the preamble to the proposed stand ard EPA specified Its reasons for not set down, and malfunction. EPA considered tors, one of which Is manual venting of this comment, and decided that this part of the reactor contents for purposes ting a zero emission limit for vinyl addition is not necessary for the vinyl of cooling and reduction In pressure chloride, as follows: (1) There are bene ficial uses of vinyl chloride products for chloride standard. Startup and of the process has essentially shutdown no effect w-lthln the reactor. The higher the tem perature and pressure within the reac which desirable substitutes are not read ily available; (2) there are potentially adverse health and environmental Im pacts from substitutes which have not been thoroughly studied; (3) there are a on emissions to the atmosphere for poly vinyl chloride production, and technology exists to avoid excess emissions during startup and shutdown at ethylene dlchloridevinyl chloride plants. We do not tor, the greater the amount of vinyl chloride which has to be removed to bring the reactor under control. Manual venting can be done at a lower pressure than the pressure required to open the number of employees, particularly in the fabrication Industries, who would be believe excess plants should be allowed to emit emissions during malfunctions, relief valve. For this reason manual vent ing can result In lower emissions than come at least temporarily unemployed: and therefore are requiring them to shut would occur by allowing the reactor to and (4> control technology Is available down Immediately. discharge through the relief valve. Fur which Is capable of substantially reduc (3) Selection of source categories. In thermore, a manual vent valve Is under ing emissions of vinyl chloride into the the preamble to the proposed standard the control of an operator and can be atmosphere.' EPA agrees that substitutes do exist or could be manufactured for most poly vinyl chloride uses. However, In general, these substitutes do not have some of the more desirable characteristics of poly vinyl chloride, such as nonflammability. If vinyl chloride and polyvinyl chloride were banned, other substitutes with these more desirable characteristics would likely be developed. There Is a risk that these substitutes would also have EPA recognized that some small research and development facilities may exist where the emissions of vinyl chloride are Insignificant and covering these facilities under the standard would be unnecessary and inappropriate. However, EPA did not have sufficient information available to clearly define which facilities should be excluded from tile standard, and encouraged interested parties to submit such Information during the comment period. Based on the information sub closed. A relief valve may become clogged with resin and not close. The result would be loss of aH the reactor contents. The contents of a reactor can be man ually vented to a gasholder or other hold ing vessel. However. In some cases, such as during severe weather conditions, sev eral reactors may be out of control at one time. There would be Insufficient holding capacity under these conditions to manually vent the contents of all the adverse health or environmental effects. mitted, EPA decided to exempt poly reactors to a gasholder. Therefore, when Since control measures are available vinyl chloride reactors and associated all other measures to prevent relief valve Copyright 1976 by Environment Information Center, Inc. COLORITE 019484 Air Reg 154 November 1976 Air Regulations discharges have been exhausted, manual quency ol calibration. Therefore, EPA as the resin 1$ being transferred out of venting will be permitted as a last resort has included in the promulgated stand before the relief valve opens. The same ard requirements for the frequency of notification procedures arc required for calibration and procedures to be carried manual venting to the atmosphere as are out in the calibration of the monitoring required for relief discharges. instruments. There are several changes in the nu The portable hydrocarbon detector re merical emission limits in the promul quired by the proposed standard was re the stripper. This allows a plant to cany out operations in a stripper after strip ping has been completed but before It is transferred out of the stripper. This is consistent with the original Intent of the standard. The regulation for loading and unload gated standard. Except for the standard quired to have a sensitivity of 5 ppm. ing lines in {61.65(b)(1) has been re for reactor opening loss, these changes Comments were received indicating that vised to clarify that It applies only to simply involve conversion to the Interna instruments in this sensitivity range are lines that are disconnected after each tional System of Units (SI), There was delicate and require continuing mainte loading or unloading operation. Perma an error involved in the original calcula nance. The portable hydrocarbon detec nently Installed pipelines that are opened tion used to derive the standard for reac- tor is required for leak detection and for infrequently for inspection or mainte tor opening. Correcting this error dou- measuring vinyl chloride concentrations nance. for example, are covered by the hies the allowable emissions. It Is em- inside the equipment before opening it. opening of equipment regulation rather phasized that the change in this stand- A 5 ppm sensitivity is not needed in than the loading and unloading line ai d Is a correction, and not a change in either case, and the required sensitivity regulation. the intent for the degree of control re- i1^ been changed to 10 ppm in the pro- The regulation for lnprocess waste- Qulred. mulgated standard. water in the proposed standard could The proposed standard required the The proposed standard contained a installation of a rupture disc beneath single regulation for compressors. The each relief valve to prevent leakage from promulgated standard has separate regu the relief valve. A provision has been lations for rotating and reciprocating added to the promulgated standard so compressors. This is consistent with hav- have been misinterpreted to require in dividual treatment of wastewater streams. Section 61.65 (b> (8) (1) of the promulgated standard clarifies that wastewater streams that are required to that a rupture disc is not required if *"6 separate regulation* for rotating and be treated (Le, those containing greater the relief valve is tied into a process line reciprocating pumps is both the pro- than 10 ppm vinyl chloride) can be com or recovery system. In this case, any and promulgated standards, bined to be treated. However, waste leakage from the relief valve would be Section 61.66 of the proposed standard water streams that contain greater than contained. provided for the use of equivalent meth- 10 ppm vinyl chloride cannot be com The regulation for obtaining vinyl pdsol coaapl whiebbaxebeai approved bined with wastewater streams that con chloride samples has been changed to an "y TOe prommgated standard re- tain less than 10 ppm vinyl chloride be operating procedure. The proposed that the plant owner or operator fore treatment; Le, dilution cannot be standard stated that there were to be sublnt4 a re^t for determination of used to meet the standard. no emissions from taking the samples. 30 days of the Pro- The eommenters recommended several Several eommenters pointed out that the muJgatioti date If ttie alternative control changes in the emission limits which use of the word "no" would make this nJetho? H ^tended as the Initial means have not been incorporated into the regulation impractical to enforce. There- *2fHco2tn:>^ The purpose ! 40 ^0- fore, the promulgated standard specifies time fw EPA to evaluate the method promulgated standard. These are dis cussed in the following paragraphs. the operating procedure which EPA orig- ^ffore plan4 to be in compliance lnally intended to be used to control <for e?lst?e sources. 90 _days after the this source. This revision is only a change "**? s288'esH in wording and does not represent a re'^*6t determination of change in the level of the standard. .be afolnP`^led *W * 7 The regulation for taking sampies has also been revised to apply only to sam pies containing at least 10 percent to section 113(c) (1) CB) Ol) The request for a waive- fra- of the Act. compliance It was recommended that the require ment for double mechanical seals on pumps, compressors, and agitators be re moved because the single seals currently used on this equipment have email emis sions and are more reliable than double mechanical seals. EPA is aware that each fugitive emission source, such as one pump, taken by itself causes relatively with the other parts of the standard which apply to equipment "in vinyl *L Hi"* 'T* chloride service." "In vinyl chloride serv- ice" distinguishes between situations ^ . ^ be'?nd where vinyl chloride is clearly Involved yeM dat* of promula' and situations where vinyl chloride is a __ ___ , .. , minor component or contaminant, and ,, There are several wording clanflca- as defined in promulgated 5 61.61(1) tloPS which have been made in the pro- means that a piece of equipment contains or contacts either a liquid that is -Hi 5 80;11(.1),. at least 10 percent by weight vinyl chlo- has bee?L clarified by stating that It ride or a gas that is at least 10 percent equHTMelrt thaiJHiaSHiTtayl by volume vinyl. c,hloride, , tains vinyl chloride.e*T^hPismwenout ldIn*calumde~ small emissions. Fugitive emissions con sidered as a whole are a significant source of emissions, however, and the In tent of the standard is to reduce these. Double mechanical seal pumps are com monly used in the industry for emission reduction. Sealless pumps or equivalent systems are available as options to double mechanical seals. The eommenters recommended in creasing the averaging time for the 10 ppm limits and the emission limits for reactor opening and stripping to 30 days. Some of the eommenters apparently nvi7HfrfPr0l><>Sf? standard required a vinyl such equipment as agitators, thought that the 10 ppm limits had to be chloride monitoring system for continuously measuring vinyl chloride levels both within the plant (for leak detection) and within stacks. The proposed standard did HPif h ,/< ic/ll HTMlt6,d? not,ha'^e tPj met on an instantaneous basis. However, since the performance test for determin ing compliance consists of three runs for a mlnimnTn of an hour each. the aver not outline required specifications for the b^en monitoring system, except that It was to analyze the samples with gas chromatog- mTM/ HS8'1)*" "f,.eq^n"i ,Equlp' raphy, or if all hydrocarbons were as- SHLHj ,TMet **" ope4ln of sumed to be vinyl chlonde, with Infrared thiufinHJni^SJJv?1'^ spectrophotometry, flame ion detection, H? v/LtmTM co"tato or equivalent. It required that each plant tHe, u 41115 submit a description of its monitoring ^t^?-eP-Lwe^e not Included,-- system to EPA, so that EPA could deter- 'rhe requirements for stripping poly mine whether It was acceptable or not. chloride resins to specified levels Comments were received indicating a have been revised In St61.84(e), 61,67 aging time for the 10 ppm limit is at,least three hours. Increasing the averaging time to 30 days for any of the emission limits would permit higher peak emis sion levels. EPA has determined that this is neither desirable nor necessary. Some comments* requested that the stripping levels for dispersion resins be made the same as for other resins and others requested that they be made less stringent EPA decided not to make the need for EPA to specify some criteria for (g)(3) (if), and 61.70(c) (2) (i) so that standard for stripping dispersion resins judging the acceptability of monitoring measurement of the vinyl chloride levels systems. The accuracy of the monitor- in the resins Is to he made lrnmAHt&tJiy the same as for other resins because there is sufficient evidence to indicate that ing system would be related to the fre- after stripping is completed rather than these resins are more difficult to strip Environment flagulaiion Handbook COLORITE 019485 Hazardous Air Pollutants-VC July 1977 Air Rea 155 than other resins. With regard to mak specifies dates for the submittal of the bag. The vinyl chloride concentration of ing the stripping levels for dispersion reports. It nlso specifies that the first the bag can then be reported on a dry resins less stringent, only one of the eight semiannual report does not have to be basis. A provision for checking the rigid manufacturers of dispersion resins spe submitted until at least six months after container for leaks has been added to cifically commented that the dispersion the Initial report Is submitted. section 7.4 of Test Method 106. resin standard should be made less The standard has been revised to elim The only change ta Test Method 107 is stringent. Only two of several grades of inate the requirement to record the cause the provision ta Section 5.3.2 for use of dispersion resins made by this company of any leak detected by the vinyl chlo Carbopak C as well as Carbopak A. cannot meet the 2,000 ppm limit. The proposed standard takes Into considera ride detector, the action taken the leak, and the amount of to repair time re Authoritt: Section 112 of the Clean Air Act u added by ec. 4(a) of Pub. L. 91-SIM, tion that some resins are more difficult quired to repair the leak. EPA Is con 84 Stat. less (43 U.3.C. 1667C-7; section 114 to strip than others by providing for cerned only that leaks are detected and of the clean Air Act. as added by sec. 4(a) averaging among different resins. repaired. That this has been done can be of Pub. 1- 91-604. 84 Stat, 1687, and amended (S) Testing, reporting, and record- established by looking at the strip chart by Pub. L. 93-319, aec. 6(a)(4), 88 Stat. 359 keeping. There are several relatively record of measurements made by the (43 U.S.C. 18S7C-9): Section 301(a) of the minor changes In the testing, reporting, and,recordkeeplng requirements. A pro vision has been added to S 61.67 which vinyl chloride detector. These records are still required for the portable hydrocar bon detector however. Clean Air Act, ae amended by aec. 16(e) (3) of Pub. L, 91-604, 84 Stat, 1713 (43 C.S.C. lS67g(a)). requires that stack gas samples taken Several commentators recommended Dated: October 12, 1976. with Test Method 106 are to be analyzed that the companies be allowed an extra John Quarles, within 24 hours. This is consistent with two weeks to submit to EPA data from the requirements In the proposed Test the Initial performance test. They also Acting Administrator. Method 106. The promulgated standard recommended that they submit the data Part 61 of Chapter I, Title 40 of the also specifies that In averaging the re sults of the three runs required by Test Method 106, a time-weighted average Is to be used. One commenter requested that the oxygen content and moisture content be by regular mall rather than registered mall. 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 Code of Federal Regulations Is amended as follows: The table of sections for Fart 01 is amended by adding a list of sections for new Subpart F and Part 61 Is amended by adding a new Subpart F reading as follows: specified for the 10 ppm concentration the emission tests be done within the Subpart F--National Emillion standard for Vinyl standards. The proposed standard speci fied that the vinyl chloride concentration is to be corrected to 10 percent oxygen 90 day period, and permits an extra 30 days for determination of results. The purpose of using registered mall is to Sec, 61.60 61.61 (wet basis) If combustion Is used as the document the fact that emission data 81.63 control measure. In the promulgates have been sent and received. This way Cliloftda Applicability, Definitions. Emission standard for etbylene dl- chloride plants. standard, this requirement has been ex If the results are lost In the mall, there 61.63 Emission standard for vinyl chloride panded to all control measures. will be no question that they were sent, plants. A provision has been added to the (6) Test method. Test Method 106 has 61.64 promulgated standard which states that been changed to recognize that on a gas If a reactor is also used as a stripper, the chromatograph equipped with a Chrom- 61.65 reactor opening emissions may be deter osorb 102 column, acetaldehyde may mined Immediately following the strip Interfere with the vinyl chloride peak. 51.66 Emission standard for polyvinyl chlo ride plants. Emission standard for ethylene dlclilorlde, vinyl chloride and poly vinyl chloride plants. Equivalent equipment and procedures. ping operation. If a reactor Is also used When a sample Is expected to contain 61.67 Emission tests. as a stripper, the resin Is in the reactor acetaldehyde, a secondary column as de 61.68 Emission monitoring. when It Is opened. This means that vinyl scribed In section 4.3.2 must be employed. 61.69 Initial report, chloride in the Testa which has already Mass spectroscopy or another absolute been stripped to acceptable levels can analytical technique Is required to con 61.70 61.71 Semiannual report. Recordkeeping. escape from the resin and become part firm the vinyl ctiloride peak obtained Authoiutt: Section 113 of the Clean Air of the reactor opening loss. It Is CPA's with the gas chromatograph, only if peak Act as added by sec. 4(a) of Pub. L. 91-604. intent that once a resin has been stripped to the required levels, that additional controls are not required. Under the new resolution with the secondary column is not successful. In section 4.1.4, aluminized Mylar bags provision, yinyl chloride escaping from can be substituted for Tedlar bags. EPA the resin after It has been stripped to now has data to allow this substitution, B4 stat. 1685 (43 US.C. 1867o-7); section 114 of the Clean Air Act, as sdded by sec. 4(a) of Pub. L. 91-604, 84 Stat. 1687, and amended by Pub. L. 93-319. sec. 6(a) (4), 88 Stat. 363 (42 U-S.c. 1857C-9); section 301(s) of the Clean Air Act. aa amended by sec. 16(c) (2) acceptable levels Is not counted as part provided that the samples are analyzed of Pub. L. 91-604, 84 Stat. 1713 (43 US.C. of the reactor opening loss. within 24 hours of collection. 1857g(a)). A section requiring continuous moni In section 5.1.3 of Test Method 106 toring of stack emissions has been added the requirement to use "oxygen gas" has to the promulgated standard. The con been replaced with "oxygen gas or air. as Subpart f--National Emission Standard for Vinyl Chloride tinuous monitoring of stack emissions required by the detector." Several com- 61.60 Applicability. was required In the proposed standard. The addition of a specific paragraph for emission monitoring serves' only to clarify the requirement. The standard has been revised so that the Initial report requires a "description" rather than a "detailed description" of the equipment used to control fugitive mentors stated that most gas chromato graphs are designed to use hydrogen and air for their flame detectors. When used In tills way. they are capable of detect ing 0.5 ppm vinyl chloride In air. This Is sensitive enough lor monitoring the 10 ppm emission limits stipulated in the (a) This subpart applies to plants which produce: < 1) Ethylene dlchlorlde by reaction of oxygen and hydrogen chloride with ethylene, (2) Vinyl chloride by any process, and/or emissions. Several conunenters pointed standard. (3) One or more polymers containing out that a detailed description would In section 6.4 of Test Method 106 the any fraction of polymerized vinyl chlo contain proprietary information. EPA requirement for an automatic Integrator ride. agrees that a detailed description lit the has been replaced with a requirement for <b) This subpart does not apply to Initial rciiort Is unnecessary. If addi a disc Integrator or planlmctcr for meas equipment used In research and develop tional information Is needed, EPA con uring peak area. This change Is ta re ment If the reactor used to polymerize obtain It under section 114 of the Act and sponse to a comment which states that the vinyl chloride processed ta the equip the plant can request confidential treat automatic Integrators are unnecessarily ment has a capacity of no more than ment In accordance with 40 CFB Part 3 elaborate and expensive. 0.19 m* (50 gal). for Information It believes to be A new section 6.5 has been added to (c) Sections of this subpart other than proprietary. Test Method 100 which requires deter *5 61.81; 61.64 (a)(1), (b), (c). and (d)j The proposed standard required that mination of the water vapor content of 61.67; 61,68: 61.69; 61.70; and 61.71 a semiannual report be submitted every the sampling bag by measuring the am apply to equipment used ta research and 180 days. The promulgated standard bient temperature and pressure near the development If the reactor used to po- Copyrighl ' 1977 by Environment Information Center, Inc. COLORITE 019486 Air Reg 156 _____________ July 1977_______ Air Regulations lymerize the vinyl chloride processed In to those persons responsible for carrying 61.64 Emission standard for po!y\ii*\l the equipment has a capacity of greater out the procedure. chloride plants. than 0.19 m' <50 gal) and no more than 4.07 m1 <1100 gal). 01 -C 1 Definitions. Terms used to this subpart are defined to the Act, to subpart A of this part, or to this section as follows: <a) 'Ethylene dichloride plant" In cludes any plant which produces ethyl ene dichloride by reaction of oxygen and hydrogen chloride with ethylene. (b) "Vinyl chloride plant" Includes any plant which produces vinyl chloride by any process. <c) "Polyvinyl chloride plant" Includes any plant where vinyl chloride alone or to combination with other materials Is in' "Run" means the net period of tune 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 to which finished ethylene dlchlorlde is produced. (p> "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. <q) "Reactor" includes any vessel to which vinyl chloride is partially or totally 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: ' 1' The concentration of vinyl chlo ride in all exhaust gases discharged to the atmosphere from each reactor is not to exceed 10 ppm, except as provided lu paragraph ta>(2) of this section and 5 61.65ta'. (2' The reactor opening loss from each reactor is not to exceed 0.02 g vinyl chloride'Kg (0.00002 lb vinyl chloride/ lb i of polyvinyl chloride product, with the product determined on a dry solids polymerized. polymerized Into polyvinyl chloride. basis. This requirement applies to any (d) "Slip gauge" means a gauge which (r> "Reactor opening loss" means the vessel which is used as a reactor or as has a probe that moves through the gas/ emissions of vinyl chloride occurring both a reactor and a stripper. In the liquid Interface to a storage or transfer when a reactor is vented to the atmos bulk process, the product means the vessel and Indicates the level of vinyl phere for any purpose other than an gross product of prepolymerization and chloride to the vessel by the physical emergency relief discharge as defined to postpolymerization. state of the material the gauge dis f 61.65(a). (31 Manual vent valve discharge: Ex charges. <s) "Stripper" includes any vessel to cept for an emergency manual vent valve <e) "Type of resin" means the broad which residual vinyl chloride is removed discharge, there is to be no discharge to classification of resin referring to the from polyvinyl chloride resin, except 'the atmosphere from any manual vent basic manufacturing process for produc bulk resin, to the slurry form by the use valve on a polyvinyl chloride reactor In ing that resin. Including, but not limited of heat and/or vacuum. In the case of vinyl chloride service. An emergency to, the suspension, dispersion, latex, bulk, bulk resin, stripper Includes any vessel manual vent valve discharge means a and solution processes. which is used to remove residual vinyl discharge to the atmosphere which could <f) "Grade of resin" means the sub chloride from polyvinyl chloride resin not have been avoided by tHnf meas division of resin classification which de Immediately following the polymeriza ures to prevent the discharge. Within 10 scribes it as a unique resin, Le., the most tion step to the plant process Sow. days of any discharge to the atmosphere exact description of a resin with no fur ther subdivision. (g) "Dispersion resin" means a resin manufactured to such away as to form fluid dispersions when dispersed In a plasticizer or plasticizer/diluent mix <t> "Standard temperature" means a temperature of 20* C <69" P). (u) "Standard pressure" means a pressure of 760 mm of Hg (2992 in. of Hg). from any manual vent valve, the owner or operator of the source from which the discharge occurs shall submit to the Ad ministrator a report in writing contain ing information on the source, nature and cause of the discharge, the date and tures. time of the discharge, the approximate (h) "Latex resin" means a resin which 61-62 Emission standard lor ethylene total vinyl chloride loss during the dis is produced by a polymerization process dichloride plants. charge, the method used for determining which initiates from free radical catalyst sites and Is sold undried. (1) "Bulk resin' 'means a resin which is produced by a polymerization process In which no water Is used. (1) "Inprocess wastewater" means any water which, during manufacturing or processing, comes Into direct contact with vinyl chloride or polyvinyl chloride or results from the production or use of any raw material, intermediate product, finished product, by-product, or waste product containing vinyl chloride or polyvinyl chloride but which has not been discharged to a wastewater treat ment process or discharged untreated as wastewater. (k) "Wastewater treatment process" includes any process which modifies characteristics such as BOD, COD, TSS, and pH, usually lor the purpose of meettog 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. (a) Ethylene dlchlorlde purification: The concentration of vinyl chloride in all exhaust gases discharged to the at mosphere from any equipment used in ethylene dlchlorlde purification is not to exceed 10 ppm, except as provided to 5 61.65(a). This requirement does not apply to equipment that has been opened. Is out of operation, and met the require ment in 161.65(b) (6) H) before being opened. <b) Oxychlorination reactor: Except as provided in ! 61.65(a). emissions of vinyl chloride to the atmosphere from each oxychlorination reactor are not to exceed 0.2 g/kg (0.0002 Ib/lb) of the 100 percent ethylene dlchlorlde product from the oxychlortoatlon process. 61.63 Emission standard for vinyl chloride plants. An owner or operator of a vinyl chlo ride plant shall comply with the require ments of this section and { 61.65. (a) Vinyl chloride formation and puri the vinyl chloride loss, the action that was taken to prevent the discharge, and measures adopted to prevent future dis charges. (b) Stripper: The concentration of vinyl chloride in all exhaust gases dis charged to the atmosphere from each stnpper is not to exceed 16 ppm. except as provided to 61.85(a). This require ment does not apply to equipment that has been opened, is out of operation, and met the requirement in 161.65(b) (6) (1) before being opened. (c> Mixing, weighing, and holding containers: The concentration at vinyl chloride to all exhaust gases discharged 'to the atmosphere from each mixing, weighing, or holding container in vinyl chloride service which precedes the stripper (or the reactor if the plant has no stripper) to the plant process flow is not to exceed 10 ppm. except as provided to { 61.65(a). This requirement does not apply to equipment that has been opened. Is out of operation, and met the requirement to 5 61.65(b) (6) (1) before being opened. (l) "In vinyl chloride service" means fication: The concentration of vinyl (d) Monomer recovery system. The that a piece of equipment contains or chloride in all exhaust gases discharged concentration of vinyl chloride to all ex contacts either a liquid that Is at least to the atmosphere from any equipment haust gases discharged to the atmos 10 percent by. weight vinyl chloride or a used in vinyl chloride formation and/or phere from each monomer recovery sys gas that te at least 10 percent by volume purification Is not to exceed 10 ppm. ex tem is not to exceed 10 ppm, except as vinyl chloride. cept as provided to 5 61.65(a). This re provided to 5 61.65 (a). This requirement (mi "Standard operating procedure" quirement does not apply to equipment does not apply to equipment that has means a formal written procedure offi that has been opened. Is out of operation, been opened. Is out of operation. and met cially adopted by the plant owner or and met the requirement to {61.65(b) the requirement in 161.65(b) (6) (i> be operator and available on a routine basis 1611 i i before being opened. fore being opened. Environment Regulation Handbook COLORITE 019487 Hazardous Air Pollutants-VC July 1977 Air Reg 157 <e Sources following the stripper(s>: (i> After each loading or unloading nvi Reciprocating compressors: Vinyl The following requirements apply to operation and before opening a loading chloride emissions from seals on all re emissions of vinyl chloride to the at or unloading line to the atmosphere, the ciprocating compressors in vinyl chloride mosphere from the combination of all quantity of vinyl chloride in ail parts of service are to be minimized by installing sources following the stripper (s' [or the each loading or unloading line that are double outboard seals, or equivalent as reactor(s) if the plant has no strip- to be opened to the atmosphere is to be provided in 5 61.66. If double outboard peris) 1 in the Plant process flow in reduced so that the parts combined con seals are used, vinyl chloride emission,* cluding but not limited to, centrifuges, tain no greater than 0.0038 m' (0.13 ft1) from the seals are to be minimized by concentrators, blend tanks. Alters, dry of vinyl chloride, at standard tempera maintaining the pressure between tht ers, conveyor air discharges, baggers, ture and pressure: and two seals so that any leak that occurs is storage containers, and lnprocess waste- (il> Any vinyl chloride removed from into the compressor; by ducting any water: a loading or unloading line in accord vinyl chloride between the two seals (1) In polyvinyl chloride plants using ance with paragraph (b)(1) (ii of this through a control system from which the stripping technology to control vinyl section is to be ducted through a control concentration of vinyl chloride in the chloride emissions, the weighted average system from which the concentration of exhaust gases does not exceed 10 ppm; residual vinyl chloride concentration in vinyl chloride in the exhaust gases does or eqviivalent ns provided in 5 61.66. all giades of polyvinyl chloride resin not exceed 10 ppm. or equivalent as pro ivi Agitator- Vinyl chloride emissions processed through the stripping opera vided in ( 61.66. from seals on all agitators to vinyl chlo tion on each calendar day, measured (2) Slip gauges: During loading or un ride servire are to be minimized by in immediately after the stripping opera loading operations, the vinyl chloride stalling agitators with double mechani tion is completed, may not exceed: emissions from each slip gauge in vinyl cal seals, or equivalent as provided m (li 2000 ppm for polyvinyl chloride chloride service are to be minimized by f 61.66. If double mechanical seals are dispersion resins, excluding latex resins; ducting any vinyl chloride discharged used, vinyl chloride emissions from the (ii> 400 ppm for all other polyvinyl from the slip gauge through a control seals arc to be minimized by maintaining chloride resins, including latex resins, system from which the concentration of the pressure between the two seals so averaged separately for each type of res vinyl chloride m the exhaust gases does that any leak that occurs is into the agi in: or not exceed 10 ppm, or equivalent as pro tated vessel: by ducting any vinyl chlo (21 In polyvinyl chloride plants con vided in $ 61.66. ride between the two seals through a trolling vinyl chloride emissions with technology other than stripping or in addition to stripping, emissions of vinyl chloride to the atmosphere may not exceed: <112 g/kg (0.002 lb/lb) product from the stripper(si Cor reactor(s) if the plant has no stripper(s) 1 for dispersion polyvinyl chloride resins, excluding latex resins, with the product determined on a dry solids basis: (ill 0.4 g/kg (0.0004 lb/lb> product from the strippers for reactor(s) if the plant has no stripper(si ] for all other polyvinyl chloride resins, including latex resins, with the product determined on a dry solids basis. 61.65 Emission -latidwed for ,-ilt' Irnc dicfiloride, vinri chloride and pol*- \ittyl chloride plants. An owner or operator of an ethylene dichloride, vinyl chloride, and/or poly vinyl chloride plant shall comply with the requirements of this section. (a) Relief valve discharge: Except for an emergency relief discharge, there is to be no discharge to the atmosphere from any relief valve on any equipment 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 (3) Leakage from pump, compressor, and agitator seals: ti) Rotating pumps: Vinyl chloride emissions from seals on all rotating pumps in vinyl chloride service are to be minimized by installing sealless pumps, pumps with double mechanical seals, or equivalent as provided in S 61.66. If double mechanical seals are used, vinyl chloride emission from the seals are to be minimized by maintaining the pres sure between the two seals so that any leak that occurs is into the pump; by ducting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chlo ride in the exhaust gases does not ex ceed 10 ppm; or equivalent as provided in i 61.66. (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 outboard seals, or equivalent as provided in 5 61.66. If double outboard seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is Into the pump; by ducting any vinyl chloride be tween the two seals through a control control system from which the concen tration of vinyl chloride to the exhaust gases does not exceed 10 ppm; or equiva lent as provided in ! 61.66. i4) Leakage from relief valves: Vinyl chloride emissions due to leakage from each relief valve on equipment to vinyl chloride service are to be minimized by installing" a rupture disk between the equipment and the relief valve, by con necting the relief valve discharge to a process line or recovery system, or equiv alent. as pro: ided in S 61.66. >S> Manual venting of gases: Except as provided in f 61.64<a i (31. all gases which are manually vented from equip ment in vinyl chloride service are to be ducted through a control system from which the concentration of vinyl chloride in ihe exhaust gases docs not exceed 10 ppm: or equivalent os provided in 5 61.66. 161 Opening of equipment: Vinyl chloride emissions from opening of equipment 'including loading or unload ing lines that are not opened to the at mosphere after each loading or unload ing operation) are to be minimized as follows: (i) Before opening any equipment for any reason, the quantity of vinyl chlo in 10 days of any relief the owner or operator ol valve discharge, the source from s's;?m from v Inch the concentration of vinyl chloride in the exhaust gases does ride ts to be reduced so that the equip ment contains no more them 2.0 percent which the relief valve discharge occurs not exceed 10 ppm; or equivalent as by volume vinyl chloride or 0.0950 m1 (25 shall submit to the Administrator a re provided m ? 61.6G. gal) of vinyl chloride, whichever is port in writing containing information ui) Rotating compressor: Vinyl larger, at standard temperature and on the source, nature and cause of the chloride emissions from seals on all ro pressure: and discharge, the date and time of the dis tating compressors in vinyl chloride (li) Any vinyl chloride removed from charge, the approximate total vinyl clilo- son ice are to be minimized by installing the equipment in accordance with para ride loss during the discharge, the meth compressors with double mechanical graph (b) <6> (1) of this section is to be od used for determining the vinyl chlo seals, or equivalent as provided in S 61,66. ducted through a control system from ride loss, the action that was taken to If double mechanical seals are used, vinyl which the concentration of vinyl chlo prevent the discharge, and measures chloride emissions from the seals are to ride in tlie exhaust gases does not exceed adopted to prevent future discharges, be minimized by maintaining the pres- 10 ppm. or equivalent as provided to i b > Fugitive emission sources: eure between the two seals so that any 5 61.66. leak that occurs is Into the compressor; <7i Samples: Unused portions of sam (1) Loading and unloading lines: by dueling any vinyl chloride between ple', containing at least 10 percent by Vinyl chloride emissions from loading (he two seals through a control system weight vinyl chloride are to be returned and unloading lines In vinyl chloride from which the concentration of vinyl to the process, and sampling techniques service which are opened to the atmos chloride in the exhaust gases does not are to be such that sample containers in phere after each loading or unloading op exceed 10 ppm: or equivalent as provided vinyl chloride service are purged into a eration axe to be minimized as follows: in 5 61.66. dosed process system. Copyright 1977 by Environment Information Center, Inc. COLOR!TE 019488 Air Reg 1 58 July 1977 Air Regulations <8( Leak detection and elimination: Method 106. The requirements in sec- (i) prior to opening the equipment and Vinyl chloride emissions due to leaks tion 5.2.3.1 and 5.2.3.2 of Test Method using Test Method 106. a portable hydro from equipment In vinyl chloride service are to be minimized by instituting and implementing a formal leak detection 106 for certification of cylinder stand ards and for establishment and verifica and elimination program. The owner or tion of calibration standards are to be carbon detector, or an equivalent or al ternative method. The method of meas urement is to meet the requirements in operator shall submit a description ol followed. S 61.67(g) (5>(i) (A) or (g> ((5) (1) (B). the program to the Administrator for approval. Toe program is to be sub mitted within <5 days of the effective date of these regulations, unless a waiver (iv) The locatiotfand number of points to be monitored and the frequency of monitoring provided for in the program are acceptable when they are compared 61.66 equivalent equipment and proeedures. Upon written application from an own of compliance Is granted under S 61.ll. with the number of pieces of equipment er or operator, the Administrator may If a waiver of compliance is granted, the to vinyl chloride service and the size and approve use of equipment or procedures program is to be submitted on a date physical layout of the plant. which have been demonstrated to his scheduled by the Administrator. Ap proval of a program will be granted by the Administrator provided he finds: <i) It Includes a reliable and accurate (vi it contains an acceptable plan of action to be taken when a leak is de tected. (vii it contains a definition of leak satisfaction to be equivalent to terms of reducing vinyl chloride emissions to the atmosphere to those prescribed for com vinyl chloride monitoring system for de which is acceptable when compared with pliance with a specific paragraph of this tection of major leaks and identification the background concentrations of vinyl subpart. For an existing source, any re of tile general area of the plant where a chloride to the areas of the plant to be quest for using an equivalent method as leak is located. A vinyl chloride monitor monitored by the vinyl chloride monitor- the initial measure of control is to be ing system means a device which obtains tog system. Measurements of background submitted to the Administrator within air samples from one or more points on concentrations of vinyl chloride to the 30 days of the effective date. For a new a continuous sequential basis and ana areas of the plant to be monitored by the source, any request for using an equiva lyzes the samples with gas chromatog vinyl chloride monitoring system are to lent method is to be submitted to the raphy or, it the owner or operator as be included with the description of the Administrator with the application for sumes that all hydrocarbons measured program. The definition of leak for a approval of construction or modification are vinyl chloride, with infrared spectro given plant may vary among the differ required by 5 61,07. photometry flame ion detection, or an ent areas within the plant and Is also to equivalent or alternative method. change over time as background con 61.67 Emission tests. ii) It includes a reliable and accurate centrations to the plant are reduced. (a > Unless a waiver of emission testing portable hydrocarbon detector to be used routinely to find small leaks and to pin point the major leaks indicated by the vinyl chloride monitoring system A portable hydrocarbon detector means a device which measures hydrocarbons with a sensitivity of at least 10 ppm and is of such design and size that it can be used to measure emissions from local ized points. 1 ill i It provides for an acceptable cali bration and maintenance schedule for the vinyl chloride monitoring system and portable hydrocarbon detector. For the vinyl chloride monitoring system, a daily span click is to be conducted with a concentration of vinyl chloride equal to the concentration defined as a leak ac cording to paragraph ibKSXvii of this section. The calibration is to be done with either: (A) A calibration gas mixture pre pared from the gases specified In sections 5.2.1 and 5.2-2 of Test Method 106 and to accordance with section 7,1 of Test Method 106, or _____ (B) A calibration gas cylinder stands ard containing the appropriate concen tration of vinyl chloride. The gas com position of the calibration gas cylinder standard is to have been certified by the (9) Inprocess wastewater: Vinyl chlo ride emissions to the atmosphere from inprocess wastewater are to be reduced as follows: <i) The concentration of vinyl chlo ride to each toprocess wastewater stream containing greater than 10 ppm vinyl chloride measured Immediately as it leaves a piece of equipment and before being mixed with any other toprocess wastewater stream is to be reduced to no more than 10 ppm by weight before being mixed with any other toprocess wastewa ter stream which contains less than 10 ppm vinyl 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 to accord ance with { 61.64(a) (2) or paragraph (b) (6) of this section, but does not apply to water which Is used to wash out equip ment after the equipment has already , been opened to the atmosphere in ac cordance with t 61.64(a) (2) or para graph (b) (6) of this section. (11) Any vinyl chloride removed from the toprocess wastewater in accordance with paragraph (b) (9) (i) of this section is to be ducted through a control system is obtained under f 61.13. the owner or operator of a source to which this sub part applies shall test emissions from the source, (11 Within 90 days of the effective date in the case of an existing source or a new source which has an Initial startup date preceding the effective date, or (21 Within 90 days of startup to the case of a new source. Initial startup of which occurs after the effective date. (b) The owner or operator shall pro vide the Administrator at least 30 days prior notice of an emission test to afford the Administrator the opportunity to have an observer present during the test. (c> 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) [Reserved] te) When at all possible, each sample is to be analyzed within 24 hours, but In no case to excess of 72 hours of sample collection. Vinyl chloride emissions are to be determined within 30 days after the emission test The owner or operator shall report the determinations to the Administrator by a registered letter dis manufacturer. The manufacturer must from which the concentration of vinyl patched before the close of the next busi have recommended a maximum shelf life chloride to the exhaust gases does not ness day following the determination. for each cylinder so that the concentra exceed 10 ppm, or equivalent as provided tion does not change greater than 5 to { 61.66. percent from the certified value. The date of gas cylinder preparation, certified vinyl chloride concentration and recom mended maximum Shelf life must halve. (c) The requirements In paragraphs (b)(1). (b)(2), (b)(5), (b)(6), (b)(7) and (b) (8) of this section are to be In corporated Into a standard operating been affixed to the cylinder before ship procedure, anr made available upon re ment from the manufacturer to the i quest for Inspection by the Administra buyer. If a gas chromatograph Is used as! tor. The standard operating procedure is the vinyl chloride monitoring system, | to include provisions for measuring the these gas mixtures may be directly used j vinyl chloride to equipment --4.15 m* to prepare a chromatograph calibration , 01250 gal In volume for which an mis curve as described in section 7.3 of Test1 sion limit Is prescribed In i 6L65(b> (6) (f) The owner or operator shall retain at the plant and make available, upon request, for inspection by the Adminis trator, for a minimum of 2 years records of emission test results and other data needed to determine wntgin^; (g) Unless otherwise specified, the owner or operator ahull use test Test Methods to Appendix B to this part for each test as required by paragraphs (g)(1), (g)(2), (g)(3), <g><4), and (g) (5) of this section, unless an equiva lent method or an alternative method Environment Regulation Handbook COLORITE 019489 Hazardous Air Poliutants-VC July 1977 Air Reg 159 has been approved by the Administrator. If the Administrator finds reasonable grounds to dispute the results obtained [a (2.60) <310'*] [100) Cax: ' " Z Administrator for each individual plant at tlie time of the determination based on the plants operation. For a reactoi by an equivalent or alternative method, where: that, is also used as a stripper, the deter he may require the use of a reference C'ar=kg vinyl chloride/100 kg prod mination may be made immediately fol method. If the results of the reference uct. lowing the stripping operation. and equivalent or alternative methods do not agree, the results obtained by the reference method prevail, and the Ad ministrator may notify the owner or operator that approval of the method previously considered to be equivalent or alternative is withdrawn. Ci,=The concentration of vinyl chlo ride as measured by Test Method 106. 2.60= Density of vinyl chloride at one atmosphere and 20 C in kg/m1. Q=Volumetric flow rate in up/hr as determined by Reference (i) Except as provided in paragraph (g)(5)(Ji> of tins section, tlie reactor olKinng loss Is to bo determined using the following equation: irjfM.0) (Kb*) (Cb) ~YZ U> Test Method 106 is to be used to Method 2 of Appendix A to determine the vinyl chloride emissions from any source for which an emission limit is prescribed in |{ 61.62(a) or (b) Part 60 of this chapter. 10-* -- Conversion factor for ppm. Z = Production rate (kg/hr). > * i id'.i.<h 'minion.'leg|n-<hliKi H < '..pm tiy c/ihe n'urii'f in ni\ r J-h,,>'i.r'-Hcvinofk*gm/my*.l etilondc at oho aimi-phctv mui 5 61.63(a), or H 61.64(a) (1). (b), (c), or l,`* f -< factor (wppm. (d). or from any control system to which >2) Test Method 101 is to be used to * f ppm hv t ohtnio vinyl chktrliH* v d-` (rimM hy ) *-t Xl-lhnd Hoi or a porc.iWe bon reactor emissions ate required to be ducted in { 61.64(a) (2) or to which fugi tive emissions are required to be ducted in 15 61.65(b) (1) (U>, (b)(2), (b)(5), (b) (6) (ti) ,or (b) (9) (ii). determine the concentration of vinyl chloride in each inprocess wastewater stream for which an emission limit is prescribed in { 61.65(b) (9t 0). (3) Where a stripping operation is i/'i-it-f whi*-h wo.nurr* hyilrw .irbons 'Mils a `rnsltlrlty of at 10 ppm. } '..:,i !i. fd mii!i liPiFjM.(pinoOs rilHioro.tli* fiMtior w-45 lost / !,1.!n.`I*itffcitrho0/('piintHlyixT'Hr aiyUl tfahPlo'hrjodt*fupiwr*dih',-d i>cr i.W n|t-ed l0thonHinj*phoH(, (i) For each run, one sample Is to be used to attain tire emission lunit in ; 61- collected. The sampling site Is to be at 64(e), emissions are to be determined ' A1 If Method 106 is used to deter least two stack or duct diameters down using Test Method 107 as follows: mine tlie concentration of vinyl chloride stream and one half diameter upstream (i) The number of strippers and sam <Cbi. (lie sample is to be withdrawn at from any flow disturbance such as a ples and the types and grades of resin to a constant rate with a probe of sufficient bend, expansion, contraction, or visible be sampled are to be determined by the length 10 reach the vessel bottom from flame. For a rectangular cross section an Administrator for each individual plant the manhole. Samples are to be taken equivalent diameter is to be determined at the tunc of the test based on the for 5 minutes within 6 inches of the ves from the following equation: plant s operation. sel bottom, 5 minutes near tlie vessel equ.iva.lent, d..uiiiietrr = 2. (length) (width) length-r width (ii) Each sample is to be taken imme center, and 5 minutes near the vessel top. diately following tlie stripping operation. Ei If a portable hydrocarbon detec (iii) The corresponding quantity cf tor is men to determine the concentra The sampling point In the duct Is to material processed by each stripper is to tion of vinyl chloride (Cb), a probe of be at the centroid of the cross section. be determined on a dry solids basis and sufficient length to reach the vessel bot The sample is to be extracted at a rate by a method submitted to and approved tom from the manhole is to be used to proportional to the gas velocity at the by the Administrator. make the measurements. One measure- . sampling point. The sample Is to be (iv) At tlie prior request of the Ad ment will be made within 6 inches of the taken over a minimum of one hour, and ministrator, the owner or operator shall \ esscl bottom, one near tlie vessel center is to contain a minimum volume of 50 provide duplicates of the samples re and one near the vessel top. Measure liters corrected to standard conditions. quired In paragraph (g)(3)(t) of this ments are to be made at each location (U> Each emission test is to consist of section. until tiie reading is stabilized. All hydro three runs. For the purpose of determin (4) Where control technology other carbons measured are to be assumed to ing emissions, the average of results of than or in addition to a stripping opera be vinyl chloride. all runs is to apply. The average is to be tion is used to attain the emission limit <C> Tlie production rate of polyvinyl computed on a time weighted basis. in 5 61 64(e), emissions are to be deter chloride <Z) is to be determined by a (lib For gas streams containing more mined as follows: method submitted to and approved by the than 10 percent oxygen the concentra <i> Test Method 106 is to be used to Administrator. tion of vinyl chloride as determined by Test Method 106 is to be corrected to 10 determine atmospheric emissions fiom all of the process equipment simultane ' ii) A calculation based on the number of evacuations, the vacuum involved, and percent oxygen (dry basis) for determi ously. The requirements of paragraph the volume of gas in the reactor is hereby nation of emissions by using the follow <g) (1) of this section are to be met. approved by the Administrator as an al ing equation: iii) Test Method 107 Is to be used to ternative method for determining reac C'.;20.9--p10e.r9cent Ot where: CnTM,r.n.di = The concentration of vinyl chloride in the exhaust gases, corrected to 10-percent oxygen. C=The concentration of vinyl chloride as measured by Test Method 106. determine the concentration of vinyl chloride In each lnprocess wastewater stream subject to the emission limit pre scribed In J 61.64(e). The mass of vinyl chloride in kg/100 kg product in each in process wastewater stream is to be de termined by using the following equa tion: tor opening loss for postpolymerization reactors in the manufacture of bulk resins. fit.fiil i nM-i.,i nmniloriiip. 'ai A \injle chloride monitoring sys tem is to be used to monitor on a con tinuous basis the emissions fiom the 20.8=Percent oxygen in the ambient air at standard conditions. f'v = [C..j. !l - 10-] [ 1001 sources for which emission limits are pre scribed in 5 61.62(a) and (b), f 61.63(a), 10.9=Percent oxygen in the ambient *Ji ro and ! 6l.64<a) (l), (b). (c), and (d'. and air at standard conditions, minus the (f'kCMn\l( liWl'i*' Uk> ktf |il<w|u* * for any control system to which reactor 10.0-percent oxygen to which the correction is being made. Percent Os= Percent oxygen in the exhaust gas as measured by Refer ence Method 3 in Appendix A of Part 60 of this chapter, (Iv) For those emission sources where the emission limit Is prescribed in terms of mass rather than concentration, mass emissions in kg/100 kg product are to be ( 4 * I he CrtritTnlfiU urn f( l oliUwnlo tl emitnon are required to be ducted in hy Tr Method * alcr flow In determined in fHYprd.mct with n method which hu$ Ur*u submitted to E 61.65'b i (1) (ii), and (b'(2i, >b) <6' iii), and (b) (9) (U). ibi<5), nd approved hy the Administrator. Ki * = t 'oneomon ftn*tor rK ppm, < b' Tlie vmyl chloride monitoring sys- /. - J'rMwtiOn ratfl fkp/hr), drt.Timn. d in tcni'Si used to meet the requirement in .Tnce with a Hid hod which U.w ht'di ml approved hy ilte Admmhtinlor, paragraph (a) of this section is to be a device which obtains air sampels from (5) The reactor opening loss for which an emission limit is prescribed in $ 61.64 (a) (2) Is to be determined. The number one or more points on a continuous sequent ial basis and analyzes the samples determined by using the following equa of reactors for which the determination with ca rhromotography or, if the owner tion: is to be made is to be specified by the oi operator assumes that all hydrocar- - Copyright 1977 by Environment Information Center, tnc. COLORITE 019490 Air Reg 160 July 1977 Air Regulations bon-: 1'ipr-r.ierj are vinyl chloride. with ceding the effective date, the statement in excess of the emission limits pre infrared sreriioohotometry, flame ion is to be submitted within 90 days of the scribed in {{ 61.62(a) or (b), { 61.63(a) detection, or an equivalent or alterna initial startup date. or St 61.64(a) (1), (b), (c), or <d), or for tive method. The vinyl chloride monitor- (c) The statement is to contain the any control system to which reactor in" system used to meet the requirements following information: emissions are required to be ducted in in 61.65(b) (81 (i) may be used to meet (1) A list of the equipment installed S 61.64(a) (2) or to which fugitive emis tile requirements of this section. for compliance, sions are required to be ducted In { 61.65 <c> A daily span check is to be con (2) A description of the physical and (b)(1) (U), <b> (2), (b) (5), (b)(6) (11).or ducted for each vinyle chloride monitor functional characteristics of each piece (b) (9) (il). The emissions are to be meas ing system used. For all of the emission Of equipment. ured in accordance with { 61.68. sources listed in paragraph <a> of this (3) A description of the methods (2) In polyvinyl chloride plants for section, except the one for which an emis which have been incorporated into the which a stripping operation is used to sion limit is prescribed in | 61.62(b), the standard operating procedures for meas attain the emisison level prescribed in daily span check is to be conducted with uring or calculating the emissions for S 61.64(e), the owner or operator shall a concentration of vinyl chloride equal which emission limits are prescribed in Include in the report a record of the to 10 ppm. For the emission source for {{ 61.65 ib> U) (1) and <b)(6)(i). vinyl chloride content in the polyvinyl which an emission limit is prescribed in (4) A statement that each piece of chloride resin. Test Method 107 is to be t 61,62'bi. the daily span check is to be equipment is installed and that each used to determine vinyl chloride content conducted with a concentration of vinyl piece of equipment and each procedure as follows: 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 {67.67. The calibration is to be done with either: - Cl) A calibration gas mixture pre pared from the gases specified in sections 5.2J. and 5.2.2 of Test Method 106 and In accordance with section 7.1 of Test Method. 106, or 121 A calibration gas cylinder stand ard containing the appropriate concen tration of vinyl chloride. The gas com position of the calibration gas* cylinder standard Is to have been certified by the manufacturer. The manufacturer must bave recommended a maximum shelf life for each cylinder so that the concen tration does not change greater than 5 percent from the certified value. The date of gas cylinder preparation, certified vinyl chloride concentration and recom mended maximum shelf life must have been affixed to the cylinder before ship ment from the manufacturer to the buyer. If a gas chromatograph is used as the vinyl chloride monitoring system, these gas mixtures may be directly used to prepare a chromatograph calibration curve as described in section 7.3 of Test Method 106. The requirements in sec tions 5-2.3.1 and 52,3-2 of Test Method 106 for certification of cylinder Stand ards and for establishment, .and.verifica tion of calibration standards are to be followed.' 1 is being used. 61.70 v-mtHtnnial report. ia( (2) is to be determined. The number source to w hich this subpart applies shall submit to the Administrator on Septem ber 15 and March 15 of each year a report in writing containing the information 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 ISO days of the effective date, unless a waiver of compliance is granted undet {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 i"W) startup date pre ceding the effective date, the first report is to be submitted within 160 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 Administrate! finds reasonable grounds to dispute the results obtained by an equivalent or al (1) If batch stripping is used, one rep resentative sample of polyvinyl chloride resin is to be taken from each batch of each grade of resin Immediately follow ing the completion of the stripping op eration. and identified by resin type and grade and the date and time the batch is completed. The corresponding quan tity of material processed in each strip per batch is to be recorded and identi fied by resin type and grade and the date and time the batch is completed. (li> If continuous stripping is used, one representative sample of polyvinyl chloride resin Is to be taken lor each grade of resin processed or at intervals of 6 hours for each grade of resin which is being processed, whicheveris more fre quent. The sample Is to be taken as toe 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 quantify of material processed by each stripper ewer the time period represented by Ore sample during the eight hour period, is to be recorded and identified by resin type and grade and the date and time It represents. (Ill) The quantify 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 (Secs. 112. 114. and 301(a). Clean Air Act (42 ternative method, he may require the use quired in paragraphs (c) (2) (1) and (c) tJ-B.C. 1837c--7,18S7C-0. and 18Mg(a) > ) of a reference method. If the results of <2> (li) of this section. Al-0'1 IM II iwl rrpert. the reference and equivalent or alterna (v) The report to the Administrator tive methods do not agree, the results by the owner or operator is to include 'a) An owner or operator of any obtained by the reference method pre the vinyl chloride content found in each source to which this subpart applies shall vail. and the Administrator may notify sample required by paragraphs (c) (2) submit a statement in writing notifying the owner or operator that approval ol (i) and (c) (2) (ii) of this section, aver tire Administrator that the equipment the method previously considered to be aged separately for each type of resin, and procedural specifications in 61.65 equivalent or alternative is withdrawn over each calendar day and weighted (b)(1), (b)(2), (b)(3). (b)(4), (b)(5), (1) The owner or operator shall in according to the quantify of each grade (b)(6). <bi (7). and (b)(8) are being clude in the report a record of any emis of resin processed by the stripper(s) implemented. sions which averaged over any hour that calendar day, according to the fol (b)(1) In the case of an existing period (commencing on the hour) are lowing equation: source or a new source which has an initial startup date preceding the effec tive date, the statement is to be submit ted within 90 days of the effective date, Ar,=- Po.Afo, PoiMe}+ 4- Pc,Me. unless a waiver of compliance is granted under { 61.11. along with the informa tion required under { 61.10. If a waiver of compliance is granted, the statement is to be submitted on a date scheduled where : 4 =24-hour average concentration of type Tf resin in ppm (dry weight basis), by the Administrator. Q*= Total production of type Tx (2) In the case of a new source which resin over the 24-hour period, did not have an initial startup date pre in kg. 7\=Type of resin; =1,2 . . , m where m is total number of resin types produced during the 24-hour period. M = Concentration of vinyl chloride in one sample of grade <7, resin, in ppm. Environment Regulation Handbook COLORITE 019491 Hazardous Air Pollutants-VC July 1977 Air Req 161 />= Production of grade (T, refin represented by the sample, in kg. G,--Grade of rain; e.gM G\, Gj, and G>. n ^ Total number of grades of resin produced during the 24-hour period,________ _____ __ _ (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 ail data n sded to furnish the information re quired by paragraph (c) (2) (v) of this section: The records are to contain the following information: (A) The vinyl chloride content found in all the samples required in paragraphs (c) (2) (i) and (c) (2) 01) of this section* identified by the resin type and grade and the time and date of the sample, and (B> The corresponding quantity of polyvinyl chloride resin processed by the strtpper(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 S 61.64(a) (2>. Emissions are to be deter mined in accordance with $ 61.67(g) (6), except that emissions for each reactor are to be determined. For a reactor that Is also used as a stripper, the determination may be made immediately following the stripping operation. 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 for a mini mum of two years: (1) A record of the leaks detected by the vinyl chloride monitoring system, as required by $ 61.65(b)(8), including the concentrations of vinyl chloride 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 dur ing routine monitoring with the portable hydrocarbon detector and the action taken to repair the leaks, as required by 5 61.65(b) (8), Including a brief state ment explaining the location and cause of each leak detected with the portable hydrocarbon detector, the date and time of the leak, and any action taken to eliminate that leak.______ _________ (3) A record of emissions measured in accordance with S 61.68. (4) A dally operating record for each polyvinyl chloride reactor, lnrJufHng pressures and temperatures. _ 2. Appendix B is amended by adding Test Methods 106 and 107 as follows: MSTBOCl 106--D*TERAtINAT10N OP VtNTL CBLOusc Pfto&t Stationary Somers nmooucTioK Performance of this method should not oe attempted by persons unfamiliar with the operation of a gas chromatograph, nor hr those who are unfamiliar with source sam pling, as there are many details that are beyond the scope of this presentation. Care must be exercised to prevent exposure of ta-mpiing personnel to vinyl chloride, a car 4.3-3 Chromatographic column. Stainless cinogen. steel. 2 mm, containing 80/100 mesh 1. principle end Applicability. Chromasorb 102. A secondary column of GE 1.1 An Integrated hag sample of stack SF-96,20 percent on 60/80 mesh AW Chroma- gas containing vinyl chloride (chloroethene) sorb P, stainless steeU2 mxn mm or Fora* is subjected to chromatographic analysis, us pak T, 80/100 mesh, stainless steel. 1 mx3J3 ing a dame ionization detector. mm Is required if acetaldehyde is present, if ~1.2 The method Is applicable to the meas urement of vinyl chloride in stack gases from ethylene dlchlorlde, vinyl chloride and poly used, a secondary column is placed after the Chromasorb 102 column. Hie combined columns should then be operated at 120* C. vinyl chloride manufacturing processes, ex 4 33 Flow meters (2)--Rotameter type. cept where the vinyl chloride is contained In 0 to 100 ml, min capacity, with flow control particulate matter. valves 2. Range and Sensitivity. 4.3.4 Gas regulators--For required gas The lower limit of detection will vary ac cylinders. cording to the chromatograph used. Values 43 5 Thermometer---Accurate to one de reported include 1 x 10-T mg and 4 x 10- gree centigrade, to measure temperature of mg. heated sample loop at time of sample Injec tion. 3. Interferences, Acetaldehyqp, which can 4.3.6 Barometer--Accurate to 5 mm Hg. lo occur in some vinyl chloride sources, will in measure atmospheric pressure around gas terfere with the vinyl chloride peak from chromatograph during sample analysis. the Chromasorb 102 * column. See sections 4.3.7 Pump--Leak-free. Minimum capac 4.3-2 and 6.4. If resolution of the vinyl ity 100 ml/mln. chloride peak is still not satisfactory for a 4 4 Calibration, particular sample, then chromatograph pa 4.4.1 Tubing--Teflon. 6.4 mm outride rameters can be further altered with prior diameter, separate pieces marked for each approval of the Administrator. If alteration calibration concentration. of the chromatograph parameters falls to 4 4.2 Tedlar bags--Sixteen-Inch square resolve the vinyl chloride peak, then sup size, separate bag marked for each calibra plemental confirmation of the vinyl chloride tion concentration. peak through an absolute analytical tech 4 4 3 Syringe--0.5 ml. gas tight, nique, such as mass spectroscopy, must b* 4 4 4 Syringe--50*1, gas tight. performed. 4. Apparatus. 4.1 Sampling (Figure 106-1). -- 4.1.1 Probe---Stainless steel. Pyrex glass, 4 4 5 Flow Ji'.cUi--Rotameter type, 0 to 1000 ml/mln range accurate lo + \%* to meter nitrogen in preparation of standard gas or Teflon tubing according to stack temper 4.4 6 stop astch--Of known accuracy, to ature, each equipped with a glass wool plug time* c*%s flow in preparation of standard gas to remove paniculate matter. miv vrcfc. 4 1,2 Sample line--Teflon, G.4 mm outride diameter, of Riioiclent lencth to connect probe to bnp A now unused piece is employed ~ Pendent* It is necessary that ail reabe of chromatographic grade. 5 l AliH'.Ulii. for earn serie*; of bag samples that constitutes All Jl'J'im ga or nitrogen gas--Zero an ciute^ion. te%t,___________________________ ________ P' r.r r. f-r e* n.*na*oprapUiC carrier gas. 4.1.5 Male (2) and female (2) stainless T> l 1 I'ydrrpen gas--Zero grade steel quick-connects, with ball checks (one ^ 1 1 Cwpen par. or Air. as required bv pair without) located as shown In Figure tbf' (ifirivr--Zero grade 106-1. _______________________________________ 5J Calibration. Use one of the following 4 T.T Tcdlnf baps.' 17T0 liter capacity--To options: either &2.1 and 6,2.2. or 6.3.3. contain sample. Teflon bag* are not accept 5.2.1 Vinyl cfcjortde, 99S+ percent, pure able. Almninl7cd Mylar boos may be used, vinyl chloride gas certified by the manufac provided that the samples are analysed turer to contain n minimum of 99.fi percent within 21 hours of collection. vinyl chloride far use in the preparation of 4 1 5 Ri?id leakproof container.*; for 4 1 4, standard gas mixLore* In Section 7.1. If the with covering to protect contents from sun gas manufacturer maintains a bulk cylinder light supply of 90.94- percent vinyl chloride, the 4 1 G ,*`.'ecclle valve--To adjust sample flow certification analysis may have been per rate 417 Fump--Leak-free Minimum capac formed on this supply rather than on each gas cylinder prepared tram this bulk supply. ity 2 liter* per muvutc. The date of gee cylinder preparation and the 418 Charcoal tube--To prevent admis certified analysis most have been affixed to sion of vinyl chloride to atmosphere in \icln- the cylinder before shipment from the gm Ity of sampler* manufacturer to tbe buyer. 4.1.9 Flow meter--For observing sample 5JJ Nitrogen pat. Zero grade, for prepa flow rate: capable of measuring a flow range ration of standard gas mixtures. from 0.10 to 1.00 liter per minute. 4.1.10 Connecting tubing. Teflon. 8.4 mm outside diameter, to assemble sample train (Figure 106-1). 6.2.3 Cylinder standards <g). Gas mix ture standards (SO, 10, and 6 ppm vinyl chloride in nitrogen cylinders) for which the gas composition has been certified by tbe 4.1.11 Pitot tube--Tvpe S tor equivalent), manufacturer. Tbe manufacturer must have attached to the probe so that the sampling recommended a shelf life for each flow rate can be regulated proportional to cylinder so that tbe concentration does not the stack gas velocity change greater than ^6 percent from the 4.2 Sample recovery. certified value. The.date of gae cylinder prep 4 2.1 Tubing--Teflon, 6.4 mm outside aration, certified vinyl chloride concentra diameter, to connect bag to gas chromato tion and iiim<thm shelf life graph sample loop. A new unused piece Is must have been <**** to the cylinder before employed for each series of bag samples that shipment from tbe gas manufacturer to the constitutes an emission test, and Is to be dis buyer. These gas mixture standards may be carded upon conclusion of analysis of those directly used to prepare * chromatograph bat > 4 3 Analysis. calibration cures as described In section 7-3. 6-2.3.1 Cylinder standards certification* 4.3.1 Gas chromatograph--With flame The concentration of vinyl chloride in nitro Ionization detector, potentiometrlc strip gen In each cylinder must have been certified chart recorder and 1.0 to 5.0 ml heated sam by the manufacturer by a direct n*iyififf of pling loop In automatic sample valve. each cylinder uttng an analytical procedure 1 Mention of trade names on specific prod ucts does not constitute endorsement by the Environmental Protection Agency. that the manufacturer had calibrated on the day of cylinder analysis. The calibration of the analytical procedure shall, as a wn^tT^m have utilized a tfirns pmm calibration cures. Copyright 1977 by Environment Information Center, Inc. COLORITE 019492 Air Reg 162 July 1977 Air Regulations It is recommended that the manufacturer tion 7.2. Measure the peak area, A, by use vinyl chloride injected, the attenuator set* rvm_tntjin two calibration standards and use of Hm, and a disc Integrator or a planlmeter. ting, chart speed, peak area, sample loop these standards in the following way: (1) a Measure the peak height. H-. Record A* and temperature, column temperature, carrier high concentration standard (between 50 and the retention time. Repeat the injection at gas flow rate, and retention time. Record the 100 ppm) for preparation of a calibration least two times or uritTT two consecutive vinyl laboratory pressure. Calculate A, the peak curve by an appropriate dilution technique; chloride peaks do pot vary in area more than area multiplied by the attenuator setting. (2) a low concentration standard (between 5rt. The average value lor these two areas Repeat until two injection areas are within 5 and 10 ppm)-for verification of the dilution v.iJl be used to compute the bag concentra 5 percent, then plot these points v. C*. When technique used. tion. the other concentrations have been plotted, 52.3.2 Establishment and verification of Compare the ratio of Km to Am for the vinyl draw a smooth curve through the points, calibration standards. The concentration of rhjoridc mmph* with the same ratio for the perform calibration dally, or before and kner each calibration standard must have been standard pern which is closest in height. As each set of bag samples, whichever is more established by the manufacturer using a guideline if these ratios differ by more frequent. reliable procedures. Additionally, each than 10"r the vinyl chloride peak may not calibration standard must have been veri fied by the manufacturer by one of the following procedures, and the agreement be pure (|>ossibly acetaldehyde Is present) and the xecondary column should be <m* plovod i see Section 4.3.2). _____ 7.4 Bag leak checka. While performance of this section Is required subsequent to bag between the Initially determined concen use, It Is also advised that tt ba performed tration value and the verification concen t; 5 Mrimire the ambient temperature and prior to bag use. After each use, make sure tration value must be within 5 percent r b.iH`v>Mr>r procure near the bag. (Assume a bag did not develop leaks as follow*. To leak (1) vertlficatlon value determined by com llir rclaihe humidity to be 100 percent.) check, connect a water manometer and pres parison with a calibrated vinyl chloride- From a water saturation vapor pressure table, surise the bag to 6-10 cm H,0 (2--4 In H,0). permeation, tube, (2) verification value determine the record and water vapor con Allow to stand for 20 minutes. Any displace determined by comparison with a gas mix ture prepared In accordance with the pro cedure described in section 7.1 and using tent of the bag. 7 Calibration and Standards^ ment In the water manometer Indicates a leak, Alao check the rigid container for leeks In manner. 00-9-t- percent vlnyie chloride, or (3) verifi cation value obtained by having the calibration standard analyzed by the Na 7*1 Preparation ard gas mixtures. of vinyl chloride stand Evacuate a sixteen-Inch (Non: An Dltamstln lank check method t> to preuuilze the bee to MO cm H.O or M In- 8,0 end allow to stead overnight. tional Bureau of Standards. AH calibration square Tediar bag that has passed a leak A dedeted beg ladloet e leek.) For each standards must be renewed on a time, check (described in Section 7.4) and meter antriple bag In lta rigid container, place a Interval consistent with the shelf life of; In 6 liters of nitrogen. While the bat Is rotameter In-line between the bag and the the cylinder standards sold. | filling, use the Ofi ml syringe to inject pomp Inlet. Bracnaa# the bag. Felllire at tbe -250/u erf 09-0+ percent vinyl chloride rotameter to taglater who flow 1ud the bag t?. Fry*dU'? through the wall of the bag- Upon with appears to be empty Indicate* a leak. drawing the syringe needle, immediately C! Sampling Avemiile the sample tiam cover the resulting hole with a piece of 8. Calcnlettone. si in Figure JOC-l. Perform a bag leak check adhesive tape. The bag now contains a 8.1 Determine the sample peak area aa according t* Section 7.4 Observe that all vinyl chloride concentration of 60 ppm. In follows: coined ions between the bag and the probe a like manner use the other syringe to are light. Fine* the end of the probe at the prepare gas mixtures having 10 and 6 ppm A,-- AeA; centroid of the Mack and start the pump with the nredle valve adjusted to yield a flow of 0.5 lpm. After a period of time suffi cient to purge the line several limes has elapsed, connect the vacuum hue to the bag and e\senate the bag until the rotam eter Indicates no flow. Then reposition the sample and vacuum lines and begin the ac tual t.imphnp. keeping the rate ptoporlional i4 the **nck ^clocltv. Direct the gas exiting the rot ami ter away from sampling personnel. At the end of lhc sample period, shut off the pump, d`iconnect Ue sample line from the bng, and disconnect tire vacuum line from the hag container. Protect the bag container from (-un)ight. vinyl chloride .concentrations. Place each bag on a smooth surface and alternately depress opposite sides of the bag 50 times to further mix the gases. These gas mixture standards may be used for 10 days from the date of preparation, after which time prep aration of new gas mixtures is required. (CafTTioit.---Contamination may be a prob lem when a bag is reused if the new gas mixture standard contains a lower .con centration than the previous gas mixture standard did.) 7.2 Determination of vinyl chloride re tention inue. This section can be performed rbm: A,-Tbs ample peak ana, AA.r--TTtah.. amnawaamuamtllmpnfceman.a. Equation 106-1 If Vinyl chloride oonoentmtlona. m>m the calibration cure* daaolbod In Section 1Z. sbov. select the mine of O, that aarteeponda to A., the --]*, peak arm Cal culate C, as follows: CtP'Tj C.- PtTAl-Br>) Equation 106-2 MinuhnncouMy with Section 7.3. Establish 6,2 Sample storage. Sample bags must be leapt out of direct sunlight. When at all possible analysts Is to be performed within 24 hours, but in no case in excess of 72 hours of sample collection. f*4 Anaiyn: Set the column teiiv'eratnre to l*'Oi C the detector temperature to 150' C. and the 'ample loop temperature to 70* C- Whrn optimum hvdrogen and oxvgcn flow ime* nave keen determined verifv and main tain flow rates during all rliromato- chromatograph conditions identical with Whom: thoxc in Section 6-3. above. Set attenuator F*-Th# water vapor oouteuL ef the bag Kemble, m to X l pwinon Flush the sampling loop oslned. tmli 7fro helium or nitrogen and activate lhc sample valve. Record the injection time, the sample loop temperature, the column C-n>e cyrrartiafleei rf vtoyl dilorfA* in the beg peihpto in ppm. C-T) eoooentzaaoa ef vinyl chloride i&dfeMed bj the pa* ehromtoexapta, in ppm. temperature, the carrier gas flow rate, the Fr--Tb* rafortoov imwnii, the kbomfcvr [Hramri chart speed and the attenuator setting. Record peaks and detector responses that occur m the absence of vinyl chloride. Main tain conditions With the equipment plumb fcceeded taring cakbrattoa, mm Be. ft-Tbe sample loop temperatore on the ahmtnte oak *i the me of aoaiyrii, Ff^The laboratory prams at Use d analyria, mm Bf* ing arranged identically to Section 6.3, flush the sample loop ior 30 seconds at the rate of TV-Tkw whuam temparatma, the sample loop temperature recorded during calibratloa, *K` traph operations. IKiny zero helium or 100 ml'mm with one of the vinyl chloride nitrogen *' the carrier gas, establish a flow ra** in the range consistent with the manu facturer's requirements for satisfactory de tector opfixiion. A flow rate of approximaidlv 40 mi min should nroduce adequate frepatatmr.*. Observe the base line periodi cally and <lcermine that the noise level has stabilised and that base line drift has ceased. Turge the sample loop for thirty seconds at calibration mixtures and activate the sample valve, Record the injection time. Select the 9. Reference*. peak that corresponds to vinyl chloride. 1. Brown, D* W,, Loy, E. W. and Stephen- Measure the distance on the chart from the eon, M. H. "Vinyl Chloride Monitoring Near injection time to the time at which the peak the B. F. Goodrich Chemical Company in maximum occurs Thm quantity, divided by lntuevllle, Kentucky.** Region IV, UR, Envi the chart speed, is defined as the retention ronmental Protection Agency, Burvelilano* time Recfuo and Analysis Division, Athens. Georgia. June 34. 1674* the rate of 100 ml/ min. then activate the 3, "Evaluation of A Collection and Analy sample valte Record the injection time (the position of the pen on the chart at the time of sample Injec' ion) , the sample number, the sample loop temperature, the column tern* 7.3 Preparation of chromatograph cali bration curve. Make a gas chromatographic measurement of each gas mixture standard (described In section 5*2.2 or 7*1) using con tical Procedure for Vinyl Chloride in Alr," by G. D. Clayton and Associate*. December 13, 1074. ERA Contract No, 68-03-1406, Task Order No. 2, EPA Report ON. 7fi-7Ct-L p*rau:re. earner gas flow rate, chart speed ditions identical with those listed In sections and the attenuator setting. Record the lab' 6.3 and 6.4. Flush the sampling loop for 30 3. **Bta ndardiaation at Stationary Source oratory pressure. From the chart, select the seconds at the rate of 100 mi/min with each Emission Method for Vinyl Chloride.** by Mid peak, having the retention time correspond standard gas mixture and activate the sam west Research Institute. 2976. EPA Contract ing to vinyl chloride, as determined in. Sec ple valve. Record c*, the concentration of No. 68-02-1008, Task Order No. 7. Environment Regulation Handbook COLORITE 019493 Hazardous Air Pollutants-VC July 1977 Air Reg 163 6.3 3 Thermometer--0 to 100* C. accurate to 0.1* C, Perkln-ELmcr No. 105-0100 or equivalent. 5.3.4. Sample tray thermostat system-- Perkln-EUner No. 105-0103, or equivalent- 6.3 5 Septa--Sandwich type, for auto matic dosing, 13 mm, Perkln-Elmer No. 1061008, or equivalent. 5.3.6 Integrator - recorder -- Hewlett Packard Model 3330A, or equivalent. 54.7 Filter drier assembly (3)--PerklnElmer No. 2230117, or equivalent. 5.3.8 Soap film flowmeter--Hewlett Pack ard No. 0101-0113. or equivalent. 5.4 Calibration. 5.4.1 Regulators--for required ders. 6. Reagents. 6.1 Analysis. 6.1.1 Hydrogen gas-^ero grade. gas cyln* 6.14 Nitrogen gas--aero grade. 0.14 Air---zero grade._______ __________________ 64 Calibration. 64.1 Cylinder standards (4). Gas mixture standards (60, 600,2,000, and 4,000 ppm vinyl chloride in nitrogen cylinders) for which the gas composition has been certified by the manufacturer. Lower concentration stand ards should be obtained if lower concentre- * tlons of vinyl chloride samples an expected, MfttROS 107--<"Drxuczhatxok of Vwn Chlo- of 3.00 ppm, 4.10% for a sample with a mean as the Intent la to bracket the sample con am* CowncFT or Ikpsoczss Wasttwateb of 1,00 ppm, and 549% for a sample with a centrations with standards. The manufac Samples, Vam. Chlo*h>* Oomtxwt or mean of 02.66 ppm. turer must have recommended a maximum PoLTvnm, Cbloudi Rxsxn, Sldut, W Caxx, amo IiATn Samples rMTSODucnoir Performance of this method should not be Attempted by persons with the operation of s gas chromatograph. nor by thnpa who ere nnfawinuf with ***TipHT1g, ss there ere many details that sre beyond the cope of this presentation. Cere must be exercised to prevent exposure of sampling personnel to vinyl chloride, a carcinogen 1. Principle end Applicability. 1.1The basis for this method relates to the vapor equilibrium which Is established between R.VCM, 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 quit* rapidly, pro vided that the temperature of the PVC resin is maintained above the glass transition 4, Safety. Do not release vinyl chloride to the labora tory atmoephere during preparation of stand ards. Venting or purging with VCM/alr mix tures must be held to a minimum. When they are required, the vapor must be routed to outeide air. Vinyl chloride, even at low ppm levels, must never be vented Inside the laboratory. After rials have been analyzed, the pressure within the vial must be vented prior to removal from the instrument turn table. Vials must be 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. 6.1 Sampling. 5.1.1 Bottles--60 ml (3 oc), with waxed shelf life lor each cylinder so that the con centration does hot change greater than 5 percent from the certified value. The date of gas cylinder preparation, certified vinyl chloride concentration and recommended maximum shelf life must have been affixed to the cylinder before shipment from tbi manufacturer to the buyer, 64.1.1 Cylinder standards certification. The concentration of vinyl chloride in nitro gen In each cylinder must have, been certi fied by the manufacturer by a direct analysis of each cylinder using an analytical proce dure that the manufacturer had calibrated on the day of cylinder analysis. The calibra tion of the analytical procedure shall, as a minimum, have utilized a three-point cali bration curve. It Is recommended that the manufacturer maintain two calibration standards and use these standards In the following way: (I) a high concentration temperature of that specific resin. 14 This procedure Is suitable for deter* mining the vinyl cborlde monomer (VCM) content of inprocesa wastewater samples, and the residual vinyl chloride monomer (RVCM) content of polyvinyl chloride (PVC) resins, wet cake, slurry, and latex lined screw on tops, for FVC samples. 6.1.3 Vials--A0 ml Hypo-rials.1 sealed with Tenon faced Tuf-Bond discs for water sam ples. Electrical tape--or equivalent, to prevent loosening of bottle topi, 64 Sample recovery, 54.1 Vials--With seals and cape, Perkin- standard (between 4,000 and A000 ppm) for preparation of a calibration curve by an ap propriate dilution technique; (2) a low con centration standard (between 50 and 600 ppm) for verification of the dilution tech* nlque used. 64.14 Establishment and verification of calibration standards. The concentration Of samples. It cannot be used for polymer In Zlxner Corporation No. 106-0113, or equiva each calibration standard must have been fused forms, such as theet or cubes. If a resolution of the vlbyl chloride peak la not satisfactory for a particular sample, then chromatograph parameters may be altered provided that the precision and reproduct* bUtty of the analysts of vinyl chloride cylin der standards are not Impaired. If there is reason to believe that some other hydro carbon with an Identical retention time is present In the sample, then supplemental confirmation of the vinyl chloride jjeaJc through an absolute analytical technique, such as mass spectroscopy, should be per formed. 2. Range and Sensitivity. The lower limit of detection of vinyl chlo- Hd# will vary according to the chromate* graph used. Values reported Include 1X10-* mg and 4X 10~f mg. With proper calibration, the upper limit may be extended as needed. 3. Precision and Reproducibility. lent. established by the manufacturer using reli 544 Analytical balance--Capahia weighing to 0,001 gram. of able procedures. Additionally, each calibra tion standard must have been verified by the 644. Syringe. 100 --Precision Scries manufacturer by one of the following proce "A** No- 010025. or eauivalent. dures, and the agreement between the ini 6.2.4 Vial Senior, Perkin-Elmer No. 106- tially determined concentration value and 0106 or equivalent. the verification concentration value must be 5.3 Analysis. within 6 percent: (1) verification value de 6 3.1 Gas chromatograph--Pcrktn-Elmcr termined by comparison with a gas mixture Corporation Model F-40 hcad-spoco ana standard generated In a ewi<it> manner to lyzer, No, 104-0001, or equivalent, the procedure described In section 7.1 of 54.2 C?iromatoyrap?itc column. Stainless steel, 2 m X 34 mm, Containing 0.4 percent Carbowax 1500 on Carbopak A, Pcrkln-Elmer Corporation No. 105-0133, or equivalent. Carbopak C can be used In place of Carbopak A. If methenol and/or acetaldehyde Is pres ent In. the sample, a pair of Poropak Q col umns in series (1 m X 34 mm followed by 2 m x 34 mm) with provision for backflush of the first column has been shown to pro vide adequate separation of vinyl - chloride. Method 106 for preparing gas mixture stand ards using 904+ percent vinyl chloride, or (2) verification value obtained by haring tire calibration standard analysed by the Nation al Bureau of Standards. All calibration stand ards must be renewed on a time Interval consistent with the shelf life of`the cylinder standards sold. 7. Procedure. 7.1 Sampling. 7.1.1 PVC sampling--Allow the resin or An interlaboratory comparison between slurry to flow from a tap on the tank or silo seven laboratories of three reeln- samples, 1 Mention of trade names on specific prod until the tap line has been well purged. Ex each split into three parts, yielded a standard ucts does not constitute endorsement by the tend a 60 ml sample bottle under the tap, fill, deviation of 2 03% for a sample with a mean Environmental Protection Agency. and Immediately tightly cap the bottle. Wrap Copyright 1977 by Environment Information Center, Inc. COLORXTE 019494 Ai r Rea 164 July 1977 Air Regulations Xlcctrlcaj tap orouod tb cap and bottte to analyser. the analysis program according to the manu prevent the top from loosening. Place an, identifying label on each bottle, and record 7.3 Annlysl*. 7 3.) Preparation of ras chromatograph-- facturers' must be instructions. These instructions carefully followed when starting the date, time, and sample location both on Install the chromatographic column and con and stopping program to prevent damage to the bottle* and in a log book, dition overnight at 160*C. Do not connect the the dosing assembly. 7.1.2 WAter sampling--Prior to ugc, the 60 ml vials (without the discs) must be capped with aluminum foil and muffled at 4QQ*C for at least one hour to destroy or remove any organic matter that could in terfere with analysts At the sampling loca tion fill the vials bubble-free, to overflowing o that a convex meniscus forms at the top. The excess water Is displaced as the scaling disc is carefully placed. Teflon side down, on the opening of the viol. Tiace the aluminum seal over the disc and the neck of the viM and crimp into place. Affix an identifying label on the bottle, and record the date, tlm, and sample location both on the vials and In a log book.. All samples must be kept re frigerated until analyzed. 7.2 fiamplo recovery. Samples must be tun within 24 hours. 7,2,1 Resin samples--The weight of the resin used must be between 0.1 and 4.6 grnmn. An exact weight must be obtained (^o^Ol gram) for each sample. In the case of sus pension resins a volumetric cup can be pre pared which will hold the required amount of sample, The sample bottle is opened, and tbo cup volume of resin la added to the tared sample viol (including srpium and alumi exit end of the column to the detector while 7.3,6 Determination of total solids (TS). conditioning- For wet coke, slurry, resin solution, and 7.3 l-l Flow rate adjustments--Adjust PVC latex sample.*, determine TS for each flow Tate* as follow*: sample by accurately weighing approxim a, Nitrogen carrier gas--Set regulator on ately 3 to 4 grams of sample in an aluminum cylinder to read 60 psig. Set regulator on pan before and after placing in a draft chromatograph v> 13 kg/cm' Normal flows oven (105 to 110* C). Samples must be dried at this prcr-Mirc rhouid be 25 to 40 cc/minute. to constant weight. After first weighing re Check with bubble flow meter. turn the pan to the oven for a short pe b. Burner air supply--Set regulator on cyl riod of time and then rcweigh to verify com inder to read 60 psig. Set regulator on plete diyness. TS is then calculated as the chromatograph to supply air to burner at a final sample weight divided by Initial sam rate between 260 and 300 cc/nUnute. Check ple weight with bubble flowmeter. 8. Calibration. 3. Hydrogen supply--Set regulator on cyl Calibration Jr to be performed each eight- inder to rend 30 psig, Set regulator on hour period when the instrument is used. chromatograph to supply approximately Each day, prior to running samples, the col 35+3 cc/mlnute. Optimize hydrogen flow to umn should be conditioned by running two yl>Md the moat sensitive detector response of the previous days 2000 ppm standards. without extinguishing the flame. Check flow 8.1 Preparation of Standards. with bubble meter and record this flow Calibration standards are prepared by fill 72.1.2 Temperature adjustments--Set ing the vials with the vinyl chloride/nitro- temperatures as follows: gen standards, rapidly seating the septum a. Oven (chromatographic column), 60" and scaling with the aluminum cap. Use a C b. Dosing Hue. 140* C. stainless steel line from the cylinder to the vial. Do not use rubber or tygon tubing. The c. Injection block. 140* C. sample line from tbo cylinder must be purged (into hood) fdraovermX minutes prior d Sample chamber, water temperature. to filling vials. After purging, reduce the flow num cap). The vial Is immediately scaled 00 CrtlA* C. rate to approximately 600-1000 cc/mtq. Place and the exact sample weight is then obtained. 7.3.12 Ignition of flame Ionization detec end of tubing Into vial (near bottom) and Report this value on the data sheet as It Is required for calculation of RVCM. In the cas of relatively dry resin samples (water content <0.3 weight %). loo ,,) of distlUed water must be injected into the vial after renting and weighing, u*teg a lw #1 syringe. In tho case of dispornioo resins, the cup cannot be used. The sample la Instead weighed approximately In an aluminum dish, tram Icrrod to the tared vial And weighed accurately in the vial. The sample is then placed in the Pcrkia-Elmcr bend space ana lyzer (or equivalent) and conditioned, for one hour at 00"C. Notfi: Some aluminum vial caps have a center section which must be removed prior to placing into sample tray If not removed, serious damage to the Injection needle WIU occur. 7.2Suspension resin slurry and wet cake samples--Slurry must b filtered using a small Buchner funnel with vacuum to yield tor--Ignite tli detector according to tbo manufacturer's Instructions. 7.3.1.4 Amplifier balance--Balance the amplifier according to the manufacturer's instructions. 72.2 Programming the chromatograph-- Program the chromatograph as follows: a. I--Dosing time--The normal setting is 2 seconds. b. A--Analysis time--The normal setting Is 8 minute*. Certain types of samples con tain high bolting materials which can cause l niorference wtlb the vinyl chloride peak on subsequent analyses. In these cases the analysts time must be adjusted to eliminate the interference. An automated backflush system can also be used to solve this prob lem. c. B--Flushing--Tho normal setting is 0.2 minutes, ______ d. IV--Stabilization time. The normal set* after one minute slowly remove tubing. Place septum in vial as soon as possible to mini mize miring air with sample. After the stand ard vials are sealed,`Inject 100^1 of distilled water. 8.2 Preparation of cferomatogrwph calibra tion curve. Prepare two 60 ppm. two 600 ppm, two 2000 ppm, and two 4000 ppm standard samples. Run dhe calibration samples in exactly the same manner as regular samples. Plot A*, the integrator area counts for each standard sample vs C*. the concentration of vinyl chloride in each standard sample. Draw a line of best fit through the points. 9. Calculations. 92 Response factor. Prom the calibration curve described in Section 82. above, select the value of C that corresponds to A* for each sample. Com pute the response factor. fU, few each sample, as follows:' wet cake. The filtering process must be con- tag is 02 minutes. _ _________ Uuuod onl7 ns long as a steady stream of e. X--Number of'analyses per sample--The Equation 107-1 water Is exiting from the funnel. Excessive filtration time could result in some loss of VCM. The wet cake sample (0.10 to 4.6 grams) la added to a tared vial (including septum and aluminum cap) and immediately scaled. Sample weight is then determined to 3 deci mal places. The sample is then placed in the Ferkin-Elmer head space analyzer (or equiva lent) and conditioned for one hour at 90*C, A sample of wet cake Is used to determluo TS (total solids), This is required for calcu lating tho RVCM. 7.2.3 Dispersion resin slurry samples -- This material should not be filtered. Sample must bo thoroughly mtxcd. Using a tared vial (including septum and aluminum cap) add approximately 8 drops (0.25 to 0 36 grams) of slurry or latex using a medicine dropper. This should be doue Immediately after mixing. Seal the vial as soon as possible. Determine sample weight accurate to 0.001 gram*. Total sample weight must not exceed 0.80 grams Condition the vial for one hour at 00*C lu the analyzer. Determine the TS on the slurry sample (Section 7.3.6). 7.2-4 inproceas wastewater samples-- Using a Larrd vial (Including septum and o'uminnm 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 vloJ for two hours at 00*C in the normal setting is 1. 72.3 Preparation of sample turntable--Be fore placing anv 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 samules in the following order: Positions l it 2--Old 2000 ppm standards for conditioning. These are necessary only after the analyzer has not been used for 24 hour* or longer. Position 3--60 ppm standard, freshly pre pared. Position 4--500 ppm standard, freshly pre pared. Position 6--2000 ppm standard, freshly prepared. Position 6--4000 ppm standard, freshly pre pared. Position 7--Sample No, 7 (This is the first sample of the day, but is given as 7 to be con sistent with the turntable and the integrator printout.) After all samples have been positioned, in sert the second set of 60, 600, 2000, and 4000 ppm standards. Samples, Including stand ards must be conditioned in the bath of SO* C foT l hour (not to exceed 6 hours). 7.3.4 Start chromatograph program-- When all samples. Including standards, have been conditioned at So* C for l hour, start 8.2 Residual vinyl cblarlde monomer con centration, or vinyl chloride monomer con centration. Calculate Cr,, as follows: A.P./M.V. \ C... STTx vSjT+K7V where: Equation 107-2 C,,,= Concentration of vinyl chloride in the sample, in ppm. Laboratory atmosphere pres sure, ram Bg. rt=Room temperature, "K. Jlf,= Molecular weight of VCM _____ (62m),___ _ lr,'= Volume of vapor phase (vial volume less sample volume), m Weight of sample, grams. R -- tia- constant (62,360 (cc-mm* mole-degrees Kelvin)] K = Henry's Law constant. For VCM in PVC at 90 C, K=6.52X 10-4-K. For VCM in 1 cc (approximate) wastewater sample at 90 C, A' = 5.0X10-*=K.. Environment Regulation Handbook COLORITE 019495 Hazardous Air Pollutants-VC July 1977 ^4.l07y IC-3-1- -- ) Equation 107-3 The following general equation can be u->cd for air' sample which contains VCM, PVC and water. x c TM > r: - K.<! - TS' r,] Equation 107-4 where. TS = Total solids. Ncm : Kv must bo determined for sam ple with a vapor volume to liquid volume ratio other than 22.5 to ]. This ratio can be obtained by adjusting the sample weight through giving consideration to the total solids and density of the PVC. Results calculated using Equation 107-4 represent concentration based on the total sample. To obtain results based on dry PVC content, divide by TS, For a i-ce wastewater sample (that is, 22.5 to I vapor volume to liquid volume ratio), Kv is 5.0X1Q-4. Thus Equation 107-4 can be simplified to the following: ----r(2-066XIG"3)J Equation 107-5 (Secs. 112 and 301(a) of the Clean Air Act, 42 L'.b.C. lS57c-7 and 1857g(a).) T35= Equilibration temperature, K, If the following conditions are met, Equation 107-2 can be simplified ns follows: 1. Tt*=22* C (295 IQ 2. r? = 90 C (363 K) 3. E>* = 750 mm Hg. where V,=Vial volume, cc (23.5). 5. Sample contains less than 0,5 percent water. 10, Reference*. 1. Residual Vinyl Chloride Monomer Con tent of Polyvinyl Chloride Retina end Wet C*k# Semple*, B. 7. Goodrich Chemical Co. Standard Tm% Procedure No. 1005-T. B. P. Goodrich Technic*! Center, Avon Lake, Ohio. January 30, 1875. 3. Berent, A. B., ^The Solubility of Vinyl Chloride in Polyvinyl Chloride.' ACS-Divtslon of Polymer Chemistry, Polymer pre print* 15 (2): 18T. 1974. 3. Berena. A. R., **The Diffusion of Vinyl Chloride in Polyvinyl Chloride.** ACS-Divlslon of Polymer Cbemtttry, Polymer Pre print* 15 (3): 303, 1974. 4. Berens, A. R., L. B. Crider, C. J, Tomenek and J. M. Whitney, Analyst* for Vinyl Chloride in PVC Powder* by Heed-Space Ga* Chromatography,' to be publlehed. IFft Doc.77-15828 Fi'eU 6-6-77.6:45 *m| Air Req 165 Copyright 1977 by Environment Information Center, Inc. COLORITE 019496