Document ymbE9bzkyqBzyxv5Q8ogj3wqn

Title 40 - Protection of Environment DRAFT DO NOT QUOTE OR CITE CHAPTER I - ENVIRONMENTAL PROTECTION AGENCY .'jit - * SUBCHAPTER C - AIR PROGRAMS PART 61 - NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS STANDARD FOR VINYL CHLORIDE On December 24, 1975, under section 112 of the Clean Air Act, as amended (42 U.S.C. 1857), the Environmental Protection Agency (EPA) added vinyl chloride to the list of hazardous air pollutants (40 FR 59477) and proposed a national emission standard for it (40 FR 59532). The standard covers plants which manufacture ethylene dichloride, vinyl chloride, and/or polyvinyl chloride. EPA decided to regulate vinyl chloride because it has been implicated as the causal agent of angiosarcoma and other serious disorders, both carcinogenic and noncarcinogenic, in people with occupational exposure and in animals with experimental exposure to vinyl chloride. Reasonable extrapolations from these findings cause concern that vinyl chloride may cause or contribute to the same or similar disorders at present ambient air levels. The purpose of the standard is to minimize vinyl chloride emissions from all known process and fugitive emission sources in ethylene dichloride-vinyl chloride and polyvinyl chloride plants to the level attainable with best available contvol technology. This will have the effect of furthering the protection of public health by minimizing the health risks to the people living in the vicinity of these plants and to any additional people who are exposed as a result of new construction. DTH 000115054 Interested parties participated in the rulemaking by sending comments to EPA. The comments have been carefully considered, and where determined by the Administrator to be appropriate, changes have been made to the regulation as promulgated. Summary of the Standard In ethylene dichloride-vinyl chloride plants, the standard limits vinyl chloride emissions from the ethylene dichloride and vinyl chloride formation and purification processes to 10 p||R For the oxychlorination process, vinyl chloride emissions are limited to 0.2 g/kg of ethylene dichloride product. In polyvinyl chloride plants, the standard limits vinyl chloride emissionsfrom equipment preceding and including the stripper in the plant process flow to 10 ppm. Emissions from equipment following the stripper are to be controlled by stripping dispersion resins to 2000 ppm and other resins ^^406 ppm, or by using equivalent controls. :hloride emissions from reactor opening are to be reduced to 0.02 g/kg polyvinyl chloride product. In both ethylene dichloride-vinyl chloride and polyvinyl chloride plants, relief valve discharges ancNrrfanualventing of gases are prohibited except under emergency conditions .^gftive emissions are required to be captured and controlled. Health and Environmental Impacts EPA prepared a document entitled the Quantitative Risk Assessment for Community Exposure to Vinyl Chloride which estimates the risk from vinyl chloride exposure to populations living in the 2 DTH 000115055 vicinity of vinyl chloride-emitting plants before and after implementation of controls to meet the standard. There are no doseresponse data for the concentrations of vinyl chloride found in the ambient air. Therefore assessments of risk at ambient levels of exposure were extrapolated from dose-response data from higher levels of exposure using both a linear model and a log-probit model. Extrapolations made with each of these models entailed making assumptions. Because different assumptions can be made in extrapolating to low doses, the health risks are reported in ranges. It was estimated that 4.6 million people live within 5 miles of ethylene dichloride-vinyl chloride and polyvinyl chloride plants and that the average exposure around these plants before installation of controls to meet the standard is 17 parts per billion. The exposure levels for uncontrolled plants were calculated based on 1974 emission levels. Using the linear dose-response model, EPft 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 uncertainties in exrapolation to low doses. The cases initiated by exposure this year will not be diagnosed until 1991 or 1995. Vinyl chloride is also expected to produce an equal number of primary cancers at other sites, for a total of somewhere between less than one and twenty cases of cancer per year of exposure among residents around 2a DTH 000115056 plants. The number of these effects is expected to be reduced in proportion to the reduction in the ambient annual average vinyl chloride concentration, which is expected to be 5 percent of the uncontrolled levels after the standard is implemented. Changes in the standard since proposal do not affect the level of control required. Thus, the environmental impact of the promulgated standard is, with one exception, the same as that described in Chapter 6 of Volume I of the Standard Support and Environmental Impact Statement. Based on data submitted by the Society of Plastics Industry, Inc. (SPI), the impact on water consumption in the draft environmental impact statement was overstated. In estimating the impact on water consumption, F.PA based its estimates on worst case conditions. That is, EPA assumed that those control systems with the greatest water usage would be employed and that there would be no recycling of water. There is no regulation which would require water recycling.. . According to SPI, the control system utilizing the most water will not be used generally by the industry and economics will cause plants to recycle much of the water. Therefore, the impact of the standard on water consumption will be negligible. A summary of the environmental impact of the promulgated standard is as follows: The primary environmental impacts of the 2b DTH 000115057 standard aro beneficial and will consist of vinyl chloride emission reductions of approximately 94 percent at ethylene dichloride-vinyl chloride olants and 95 percent at polyvinyl chloride plants. Percentage numbers for both source categories are based on an estimated 90 percent reduction in fugitive emissions and 1974 emission levels. The potential secondary environmental impacts of the standard are either insignificant or will be minimized without additional action, except for one adverse impact. Hydrogen chloride is already emitted by Drocess equipment at ethylene dichloride-vinyl chloride plants and by other petrochemical plants in the complexes where ethylene dichloride-vinyl chloride olants are typically located. An incinerator used to attain the standard at an ethylene dichloridevinyl chloride plant could increase hydrogen chloride emissions by several fold. Typically, however, due to the corrosion problems which would otherwise occur both on plant prooerty and in the community, plants use scrubbers to control already existing hydrogen chloride emissions. Hydrogen chloride emissions resulting from control of vinyl chloride emissions are expected to also be controlled for the same reason. If even a moderately efficient scrubber (98 percent control) were used to control the hydrogen chloride emissions resulting from incineration of vinyl chloride emissions, the increase in hydrogen chloride emissions from a typical ethylene dichloride-vinyl chloride plant due to the standard would be reduced to 35 percent. However, EPA plans to further evaluate the need to control hydrogen chloride emissions, since diffusion model results indicate that under "worst-case" meteorological conditions, the DTH 000115058 3 hydrogen chloride emissions from the process equipment and the incinerator combined would cause maximum ambient concentrations of hydrogen chloride in the vicinity of ethylene dichloride-vinyl chloride plants to be in the same range of somewhat higher than existing foreign standards and National Academy of Sciences (NAS) guidelines for public exposure. Economic Impact In accordance with Executive Order 11821 and 0MB circular A-107, EPA carefully evaluated the economic and inflationary impact of the proposed standard and alternative control levels and certified this in the preamble to the proposed standard. These impacts are discussed in Chapter 7 of Volume I of the Standard Support and Environmental Impact Statement. Comments on the proposed standard have resulted in only one major change in the economic impact analysis. EPA estimated that there would be four plant closures as a result of the promulgated standard. Of the four plants identified as possible closure candidates, one has given notice that it no longer produces polyvinyl chloride and the other three have indicated that they do not intend to close as a result of the standard. A summary of the economic impact of the promulgated standard is as follows: The total capital cost for existing plants to meet the standard is estimated to be $198 million, of which $15 million is for ethylene dichloride-vinyl chloride plants and $183 million is for polyvinyl chloride plants. EPA estimates that these plants will have to spend $70 million per year to maintain the required emission levels. In addition, total capital cost for existing plants to meet the EPA's 1973 water effluent guideline limitations is $83 million and the total annualized operation cost is $17 million. The costs to the industry of meeting the OSHA standard cannot be quantified 4 DTH 000115059 at this time, but they are expected to overlap to some degree with the costs to meet EPA's fugitive emission regulations. The costs of meeting the fugitive emission regulations are included in the total costs cited above for meeting the promulgated regulation. Broken out separately, the capital cost of meeting the fugitive emission regulations is $37 million and the annualized cost is $25 million. The standard is not expected to deter construction of new ethylene dichloride-vinyl chloride plants or most types of new polyvinyl chloride plants. For one type of polyvinyl chloride plant (dispersion process) that represents 13 percent of the industry production, the standard would significantly deter the construction of smaller plants. It is estimated that the price of polyvinyl chloride resins will rise by approximately 7.3 percent in order to maintain orecontrol profitability and also to recover the total annualized control costs necessitated by the standard at ethylene dichloridevinyl chloride plants and polyvinyl chloride plants. This increase is estimated to translate into a maximum consumer price increase in goods fabricated from polyvinyl chloride resins of approximately 3.5 percent. Recovery of effluent annualized costs plus maintenance of precontrol profitability is estimated to add approximately 2 percent to oolyvinyl chloride resin prices and result in an additional maximum consumer price increase of 1 percent. 5 DTH 000115060 I'tihl ic i'.ii I ii. ip.i' ion During t.ho public comment per iod, L>() comment lette-s on the proposed standard were received. There were 24 from industry; 3 from environmental groups, 15 from Federal, State, and local agencies; and 8 from individual citizens. As required by section 112(b)(1)(B) of the Act, a public hearing was held on the proposed standard on February 3, 1976, in Washington, D. C. Presentations were made by the Environmental Defense Fund, the Society of the Plastics Industry, Inc., Dow Chemical Company, Diamond Shamrock Corporation, and Air Products and Chemicals, Inc. Copies of the comment letters received, the public hearing record, and a summary of the comments with EPA's responses are available for public inspection and copying at the EPA Public Information Reference Unit, Room 2922 (EPA Library), 401 M Street, S. W., Washington, D. C. In addition, copies of the comment summary and Agency responses may be obtained upon written request from the Public Information Center (PM-215), Environmental Protection Agency, 401 M Street, S.W., Washington, D. C. 20460 (specify Standard Support and Environmental Impact Statement, Emission Standard for Vinyl Chloride, Volume II). Significant Comments and Changes to the Proposed Regulation (1) Decision to List Vinyl Chloride as a Hazardous Air Pollutant Only three commenters (two companies and one Federal agency) argued that available data are not sufficient to justify regulating vinyl chloride under section 112. The Act specifies that EPA could remove TH 000115061 vinyl chloride from the list of hazardous air pollutants only if information were presented to EPA that shows that it is clearly not a hazardous air pollutant. The commenters did not provide conclusive evidence that vinyl chloride does not cause or contribute to death or serious illness. Several other commenters agreed with EPA's decision to list vinyl chloride as a hazardous air pollutant, but argued that EPA had overstated the health problem, the emission levels, and the projected ambient air concentrations around uncontrolled plants. With regard to the alleged overstated health problem, the commenters stated, for example, that the U. S. worker EPA discussed as having been exposed to vinyl chloride levels lower than those usually encountered in polyvinyl chloride production has been dropped from the National Institute of Occupational Safety and Health's listing of workers with angiosarcoma. EPA agrees that there are questions concerning the level of exposure of those cases not involved directly in polyvinyl chloride and vinyl chloride production, and in some cases the pathology. These uncertainties are stated in the appropriate footnotes of the Scientific and Technical Assessment Report on Vinyl Chloride and Polyvinyl Chloride (STAR) where the angiosarcoma cases are listed. However, in spite of these uncertainties, in view of the possible exposure patterns, these cases cannot be ignored in the evaluation of the potential public health problems. With regard to the alleged overstated emission levels, the uncon trolled emission levels reported by EPA were based on 1974 data. 7 DTH 000115062 This qualification was stated wherever emission data were presented.\ EPA recognizes that emissions have been reduced since that time, and stated this in the preamble to the proposed standard. EPA decided not. * to gather more recent data on emission levels, because these emission levels are expected to change, and gathering the data would take consid erable time both on the part of EPA and on the part of industry. Since the purpose of the standard is to minimize emissions, these more current data would not affect the standard itself. The 1974 emission levels were also used in diffusion modeling to project maximum ambient air concentrations around uncontrolled plants. These maximum air concen trations would probably be lower if 1976 emission levels were used. This would reduce the relative impact of the standard below that described in the Standard Support and Environmental Impact Statement, but should not affect the basis of the standard itself. (2) Approach for Regulating Vinyl Chloride Under Section 112. Two approaches other than using best available 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 polyvinyl chloride products as substitutes are developed. In the preamble to the proposed standard EPA named its reasons for not setting a zero emission limit for vinyl chloride, as follows: (1) There are beneficial uses of vinyl chloride products for which desirable substitutes are not readily available; (2) there are potentially adverse health and environmental impacts from 8 ** 0lisoe3 substitutes which have not been thoroughly studied; (3) there are a number of employees, particularly in the fabrication industries, who would become at least temporarily unemployed; and (4) control technology is available which is capable of substantially reducing emissions of vinyl chloride into the atmosphere. EPA agrees that substitutes do exist or could be manufactured for most polyvinyl chloride uses. However, in general, these substitutes do not have some of the more desirable characteristics of polyvinyl chloride, such as nonflammability. If vinyl chloride and polyvinyl chloride were banned, other substitutes with these more desirable characteristics would likely be developed. EPA presently has no direct control over which substitutes are developed or used. There is a risk that these substitutes would also have adverse health or environmental effects. Since control measures are available which can reduce vinyl chloride emissions by 90 percent or more, it does not seem prudent to reduce emissions by the remaining percentage and take the risk of introducing new untested chemicals into the environment. Another approach suggested by the commenters was to base the standard for each individual emission point on cost versus benefit. Several of the fugitive emission sources were named specifically as ones for which the costs of control were substantially higher than the benefits. Although EPA did determine a cost-effectiveness ratio for the controls required for a number of emission points, EPA does not favor using cost-effectiveness ratio as the basis of the standard. Section 111 of the Clean Air Act provides for the 9 DTH 000115064 i\ development of standards based on best control technology (considering costs). In developing standards under section 111, standards are not based on a fine balancing of costs versus benefits. Instead a study is conducted to determine the affordability of the control technology required to achieve a given emission level and to determine the impact of a control level on the viability of the industry. Section 112 does not even provide for consideration of costs, so it does not seem appropriate to consider costs to a greater extent under section 112 than would be done under section 111. In developing standards under section 112 based on the best control technology, EPA felt that it was necessary to place some type of limit on the technology required. Otherwise, there are all types of theoretical controls which could be required. One limit placed on best control technology was that the costs of the technology not be 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 commentators are relatively small compared with the amount of emission reduction achieved. (3) Selection of Source Categories. In the preamble to the proposed standard EPA recognized that some small research and develop ment 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 the standard, and encouraged interested parties to submit 10 DTH 000115065 such information during the comment period. Based on the information * submitted, EPA decided to exempt polyvinyl chloride reactors and associated equipment from applicability of the standard if the reactors are used in research and development and have a capacity of no more than 0.19 m (50 gal). Reactors in this size range can generally be found in a laboratory, whereas the larger reactors are typically pilot scale facilities. Emissions from laboratory scale equipment are relatively small, and application of the controls required by the standard would be expensive and impractical. EPA also decided to require research and development facilities containing reactors greater than 0.19 m3 (50 gal) and no more than 4.07 m3 (1100 gal) in capacity to meet the 10 ppm limit for reactors, strippers, monomer recovery systems, and mixing, weighing and holding containers. EPA decided not to require these facilities to meet other parts of the standard because of the technical problems involved in doing so. For example, the standard for reactor opening is based in part on reducing the frequency of opening the reactor. Research and development reactors have to be opened after every batch for thorough cleaning. Also, stripping technology is developed individually for each resin in research and development equipment. Therefore, attainment of the stripping limitations in the research and development equipment would not always be possible. The 4.07 m (1100 gal) figure was selected as an upper cut-off point because there are no commercial reactors smaller than this. 11 DTH 000115066 (4) Emission Limits. The only major change in the emission limits between proposal and promulgation is the addition of a provision for emergency manual venting of vinyl chloride from reactors to the atmosphere. The proposed standard prohibited all manual venting to the atmosphere. In the preamble to the proposed standard, EPA invited interested persons to comment on whether permitting manual venting to the atmosphere could result in overall lower emissions. There are several methods available for preventing relief discharges from reactors one of which is manual venting of part of the reactor contents for purposes of cooling and reduction in pressure within the reactor. The higher the temperature and pressure within the reactor, 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 relief valve. For this reason manual venting can result in lower emissions than would occur by allowing the reactor to discharge through the relief valve. Furthermore, a manual vent valve is under the control of an operator and can be closed. A relief valve may become clogged with resin and not close so that all the reactor contents are lost. 11a DTH 000115067 The contents of a reactor can be manually vented to a gasholder or other holding vessel. However, in some cases, such as during severe weather conditions, several 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 reactors to a gasholder. Therefore, when all other measures to prevent relief valve discharges have been exhausted, manual venting will be permitted as a last resort before the relief valve opens. The'same notification procedures are required for manual venting to the atmosphere as are required for relief discharges. There are several changes in the numerical emission limits in the promulgated standard. Except for the standard for reactor opening loss, these changes simply involve conversion to the International System of Units (SI). There was an error involved in the original calculation used to derive the standard for reactor opening. Correcting this error doubles the allowable emissions. It is emphasized that the change in this standard is a correction, and not a change fn the Intent for the degree of control required. The proposed standard required the installation of a rupture disc beneath each relief valve to prevent leakage from the relief valve. A provision has been added to the promutgal^tf Staftdeftl so that a rupture disc is not required if the relief valve:,fs #fed into a process line or recovery system. In this case, any 1eakage from the relief valve would be contained. 12 DTH 000115068 The regulation for obtaining vinyl chloride samples has been changed to an operating procedure. The proposed standard stated that there were to be no emissions from taking the samples. Several commenters pointed out that the use of the word "no" would make this regulation impractical to enforce. Therefore, the promulgated standard specifies the operating procedure which EPS originally intended to be used to control this source. This revision is only a change in wording and does not represent a change in the level of the standard. The regulation for taking samples has also been revised to apply only to samples containing at least 10 percent by weight vinyl chloride. This is consistent with the other parts of the standard which apply to equipment "in vinyl chloride service." "In vinyl chloride service" distinguishes between situations where vinyl chloride is clearly involved and situations where vinyl chloride is a minor component -or contaminant, and as defined in promulgated 61.61(1) means that a piece of equipment contains or contacts either a liquid that is at least 10 percent by weight vinyl chloride or a gas that is at least 10 percent by volume vinyl chloride. The proposed standard required a vinyl chloride monitoring system for continuously measuring vinyl chloride levels both within the plant (for leak detection) and within stacks. The proposed standard did not outline required specifications for the monitoring system, except it was to analyze the samples with gas chromatography. It required that each plant submit a description of its monitoring system to EPA, so that EPA could determine whether it was acceptable or not. Comments 13 dTH 000115069 were received indicating a need for CPA to specify some criteria for judging the acceptability of monitoring systems. The accuracy of the monitoring system would be related to the frequency of calibration. EPA is currently developing criteria for judging the adequacy of each plant's calibration and maintenance schedule for the instrument. TlMie are included in an enforcement guidelines document prepared by EPA. The portable hydrocarbon detector required by the proposed standard was required to have a sensitivity of 5 ppm. Comments were received indicating that instruments in this sensitivity range are I delicate and require continuing maintenance. The portable hydrocarbon detector is required for leak detection and for measuring vinyl chloride concentrations inside the equipment before opening it. A 5 ppm sirifftivlty is not needed in either case, and has been changed to 10 ppm in the promulgated standard. The proposed standard contained a single regulation for compressors. The promulgated standard has separate regulations for rotating and reciprocating compressors. This is consistent with having separate regulations for rotating and reciprocating pumps in both the proposed and promulgated standards. Section 61.66 of the proposed standard provided for the use of equivalent methods of control which have been approved by EPA. The promulgated standard requires that the plant owner or operator who submits a request for determination of equivalency within 60 days of the promulgation date. This is intended to provide time for EPA to evaluate the method before the plant has to be in compliance. EPA also suggests that this request for determination of equivalency be accompanied by a 14 DTH 000115070 request for waiver of compliance until EPA does determine whether the ^ method is equivalent. The request for a waiver of compliance should provide for the case where EPA determines that a method is not equivalent and the plant needs to purchase other equipment. In no case will the waiver of compliance be extended beyond two years from the date of promulgation. There are several wording clarifications which have been made in the promulgated standard. The definition for "in vinyl chloride service" [60.61(1)] has been clarified by stating that it means equipment that contacts vinyl chloride as well as equipment that contains vinyl chloride. This would include such equipment as agitators. Words have been added in 561.62, 61.63, and 61.64 to clarify that the 10 ppm emission limits do not have to be met when equipment has already been opened in compliance with the regulation for opening of ^ equipment. Equipment that has met the opening of equipment regulation can contain more than 10 ppm vinyl chloride and would be in violation of the standard if this statement were not included. The requirements for stripping polyvinyl chloride resins to i specified levels have been revised in 61.64(e), 61.67(a)(2)(ii), and 61.70(c)(2) so that measurement of the vinyl chToridelevels in the resins is to be made lyadfate^ after stripping is completed rather ~> i than as the resin is befng transferred out of the stripper. This allows a plant to carry out operations in a stripper after stripping has been completed but before it is transferred out of the stripper. This is consistent with the original intent of the standard. 15 DTH 000115071 / proposed standard takes into consideration that some resins are more difficult to strip than others by providing for averaging amonq different resins. (5) Testing, Reporting, and Recordkeeping. There are several relatively minor changes in the testing, reoorting, and recordkeeping requirements. A provision has been added to 61.67 which requires that stack gas samples taken with Test Method 106 are to be analyzed within 24 hours. This is consistent with the requirements in the proposed Test Method 106. The promulgated standard also specifies that in averaging the results 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 specified for the 10 ppm concentration standards. The ^ r- proposed standard specified that the vinyl chloride concentration is to be corrected to 10 percent oxygen (wet basis) if combustion is used as the control measure. In the promulgated standard, this requirement has been expanded to all control measures. A provision has been added to the promulgated standard which states that if a reactor is also used as a stripper, the reactor opening emissions may be determined immediately following the stripping operation. If a reactor is also used as a stripper, the resin is in the reactor when it is opened. This means that vinvl chloride in the resin which has already been stripped to acceptable levels can escaoe from the resin and become part of the reactor opening loss. It is FPA's intent that once a resin has been stripped to the 18 DTH 000115072 required levels, that additional controls are not required. Ureter the new provision, vinyl chloride escaping from the resin afteirf it has been strippedto acceptabllevels is not counted as part of the reactor opening loss. . A section requiring continuous monitoring of stack emissions has been added to the promulgated standard. The continuous monitoring of stack emissions 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 emissions. Several commenters pointed out that a detailed description would contain proprietary information. EPA agrees that a detailed description in the initial report is unnecessary. If additional information is needed, EPA can obtain it under section 114 of the Act and the plant can request that the information be handled confidentially. The proposed standard required that a semiannual report be sub mitted every 180 days. The promulgated standard specifies dates for the submittal of the reports. It also specifies that the first semiannual report does not have to be submitted until at least six months after the initial report is submitted. The standard has been revised to eliminate the requirement to record the cause of any leak detected by the vinyl chloride detector, the action taken to repair the leak, and the amount of time required 19 DTH 000115073 to repair the leak. EPA is concerned only that leaks are detected and repaired. That this has been done can be established by looking at the strip chart record of measurements made by the vinyl / chloride detector. These records are still required for theportafcle hydrocarbon detector, however. Several commenters recommended that the companies be allowed an extra two weeks to submit to EPA data from the initial performance test. They also recommended that they submit the data by regular mail rather than certified mail. EPA has not adopted either of these recommendations. A source is supposed to be in compliance with the standard within 90 days of the promulgation of the standard. The standard requires that the emission tests be done within the 90 day period, and permits an extra 30 days for determination of results. The purpose of using registered mail is to document the fact that emission data have been sent and received. This way if the results are lost in the mail, there will be no question that they were sent. (6) Test Method. Test Method 106 has been changed to recognize that the acetaldehyde peak on a gas chromatograph interferes with the vinyl chloride peak. When a sample is expected to contain acetaldehyde, mass spectroscopy or another absolute analytical technique is required to be used to confirm the vinyl chloride peak obtained with the gas chromatograph. In section 5.1.3 of Test Method 106 the requirement to use "oxygen gas" has been replaced with "oxygen gas or air, as required by the detector." Several commenters stated that most gas chromatographs are designed to use hydrogen and air for their 20 DTH 000115074 flame detectors. When used in this way, they are capable of detecting 0.5 ppm vinyl chloride in air. This is sensitive enough for monitoring the 10 ppm emission limits stipulated in the standard. In section 6.4 of Test Method 106 the requirement for an automatic integrator has been replaced with a requirement for a disc integrator for measuring peak area. This change is in response to a comment which states that automatic integrators are unnecessarily elaborate and expensive when peak height, triangulation and disc integrators are sufficiently accurate for this use. A new section 6.5 has been added to Test Method 106 which requires determination of the water vapor content of the sampling bag by measuring the ambient temperature and pressure near the bag. A provision for checking the rigid container for leaks has been added to section 7.4 of Test Method 106. The only change in Test Method 107 is the provision in Section 5.3.2 for use of Carbopak C as well as Carbopak A. AUTHORITY: Section 112 of the Clean Air Act as amended by sec. 4(a) of Pub. L. 91-604, 84 Stat. 1685 (42 U.S.C. 1857c-7; Section 114 of the Clean Air Act, as amended by sec. 4(a) of Pub. L. 91-604, 84 Stat. 1687, and by Pub. L. 93-319, sec. 6(a)(4), 88 Stat. 259 (42 U.S.C. 1857c-9); Section 30T(a 1 of the Clean Air Act, as amended by sec. 15(c)(2) of Pub. L. 91-604, 84 Stat. 1713 (42 U.S.C. 1857g(a)). Date ' ~',ministrator DTH 000115075 21 Subpart F--National Emission Standard for Vinyl CMeride 61.60 Applicability. ''This tubpart applies to plants which (a) produce: (fi'ethrimTin^ig^'bryfeSftqon'm-- -- (1) oxvgen and hydrogen chloride with eUivlene. fp> vinyl chloride by any process, (2) and/or __________ ____ (ff~ one or more polymers containing '(3) any fraction of polymerized vinyl chlo ride. (b) This subpart does not apply to equipment used in research and development if the reactor used to polymerize the vinyl chloride processed in the equipment has a capacity of no more than 0.19 m3 (50 gal) and the product is not sold. (c) Sections of this suboart other than 61.64(a)(1), (b), (c) and (d) do not apply to equipment used in research and development if the reactor used to polymerize the vinyl chloride processed in the equipment has a capacity of greater than 0.19 m3 (50 gal) and no more than 4.07 m3 (1100 gal), and the product is not sold. 61.61 Definitions. Terms used In this subpart are defined in the Act. In subpart A of this part, or In this section as follows: (a) "Ethvlene dichloride plant" In cludes any plant which produces ethylene dichloride bv reaction of oxygen and hydrogen chloride with ethvlene. <b> "Vlnvl chloride plant" Includes any plant which produces vinyl chloride by any process. (cl "Polvvlnvl chloride plant" Includes any plant where vinyl chloride alone or In combination with other materials Is polvmerlzed. <d> "Slip gauge" means a gauge which has a probe that moves through the gas/ liquid interface in a storage or transfer vessel and Indicates the level of vinyl chloride In the vessel bv the physical state of the material the gauge dis charges. (e> "Tvpe of resin" means the broad classification of resin referring to the basic manufacturing process for produc ing that resin. Including, but not limited to. the suspension, dispersion, latex, bulk, and solution processes. <f> "Grade of resin" means the sub division of resin classification which de scribes it as a unique resin, l.e., the most exact description of a resin with no fur ther subdivision.. (g) "Dispersion resin" means a resin manufactured In such a way as to form fluid dispersions when dispersed In a plasticizer or plastlclzer/dlluent mix tures. (h> "Latex resin" means a resin which is produced by a polymerization process which Initiates from free radical catalyst sites and Is sold undrled. (11 "Bulk resin" means a resin which Is produced by a polymerization process In which no water Is used. (.)) "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 treatment process or discharged untreated as wastewater. _ DTH 000115076 23 (k> "Wastewater treatment process" Includes anr process which modifies characteristics such as BOD. COD. IBS. and pH. usually tar the purpose ot meet ing effluent guidelines and standards: It does not Include any process the purpose ot which Is to remove vinyl chloride from water to meet requirements at this subpart. (l) "In vinyl chloride service" rny that a piece of equipment contaln^JEuEer a liquid that Is at least 10 percent by weight vinyl chloride or a gas that is at least 10 percent by volume vinyl chloride. -- . (m) "Vinyl chloride dstesterfmeans a device which obtains air samples from one or more points on a continuous se quential basis and analyses the samples with gas chromatography or. If the owner or operator assumes that all hy drocarbons measured ore vinyl chloride, with infrared spectrophotometry, flame Ion detection, or an equivalent or alter native method. (n) "Portable hydrocarbon detector" means a device which measures hydro-, carbons with s sensitivity ef sl luMt't' ppuruid Is of such design and size that it con be used to measure emissions from localized points. (o) "Standard operating procedure" means a formal written procedure offi cially adopted by the plant owner or operator and available on a routine basis to those persons responsible for carrying out the procedure. (p) "Bun" means the net period of time during which an emission sample is collected. (q) "Ethylene dichloride purification" Includes any part of the process of ethyl ene dichlorlde production which follows ethylene dichlorlde formation and In which finished ethylene dichlorlde is produced. (r) "Vinyl chloride purification" in cludes any part of the process of vinyl chloride production which follows vinyl chloride formation and in which finished vinyl chloride Is produced. (s) "Reactor" includes any vessel In which vinyl chloride is partially or totally polymerized into polyvinyl, chloride. (t) "Reactor opening loss" means the emissions of vinyl chloride occurring when a reactor is vented to the atmos phere for any purpose other than an emergency relief discharge as defined In | 01.65(a). (u) "Stripper" Includes any vessel In which residual vinyl chloride Is removed from polyvinyl chloride resin, except bulk resin. In the slurry form by the use of heat and/or vacuum. In the case of bulk resin, stripper includes any vessel which Is used to remove residual vinyl chloride from polyvinyl chloride resin immediately following the polymeriza tion step In the plant process flow. | 61.62 Emission standard for clhvleno dichloride plants. An owner or operator of an ethylene dichlorlde plant shall comply with the requirements of this section and 161.65. (a) Ethylene dichlorlde purification: The concentration of vinyl chloride in or contacts monitorino system" del etf 24 DTH 000115077 all cxhauat gose* discharged to the at mosphere from any equipment used In ethylene dlchlorlde purification la not to exceed 10 ppm. except aa provided in | 61.65(a). This requirement doea not apply to equipment timu the requirement In i 61.85(b) (6) (i) #--i----------^--------------------- tb) Oxychlorination reactor: Except aa provided In 161.65(a), emissions of vinyl chloride to the atmosphere from each oxychlorination reactor are not to exceed *jM kgj'l68li!to5#roii tot <ttf the 100 percent ethylene dlchlorlde prod uct from the oxyehlorinatlon process. 61.63 Emiuioa 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 I 61.05. (a) Vinyl chloride formation and puri fication: The concentration of vinyl chloride In all exhaust gases discharged to the atmosphere from any equipment used In vinyl chloride formation and/or purification Is not to exceed 10 ppm. ex cept as provided In ( 61.65(a). This re quirement does not apply to equipment thntifiiTfc-- anfl"tmrrm rrf i--im-mr-it In | 41.65(b) (6) (1).----------------------------- - 61.64 Emission standard for polyvinyl rliloride plants. An owner or operator of a polyvinyl chloride plant shall comply with the re quirements of this section and } 61.65. (a) Reactor: The following require ments apply to reactors: (1) The concentration of vinyl chlor ide In all exhaust gases discharged to the atmosphere from each reactor Is not to exceed 10 ppm. except as provided tn paragraph (a) (2) of this section and 161.85(a). (3) Hie reactor opening loss from each reactor to not to exi asHKHommaa Mftsdfc) of polyvinyl chloride product, with the product determined on a dry solids basis. This requirement applies to any vessel which is used as a reactor or as both a reactor and a stripper. In the bulk process, the product means the gross product of prepolymerization and poetpolyroerlzatJon. has been opened, is out of operation, and met before being opened. 0.2 g/kg (0.002 lb/100 lb) has been opened, is out of operation, and met before being opened. r r. > 2 ' --yi chloride/kc ('1.1000 2 1 h vinyl chloride/lb) (3) Manual vent valve discharge: Except for an emergency manual vent valve discharge, there is to be no discharge to the atmosphere from any manual vent valve or any reactor in vinyl chloride service. An emergency manual vent valve discharge means a discharge to the atmosphere which could not have been avoided by taking measures to prevent the discharge. Within 10 days of any discharge to the atmosphere from any manual vent valve, the owner or ODerator of the source from which the discharge occurs shall submit to the Administrator a report in writing containing information on the source, nature and cause of the discharge, the date and time of the discharge, the approximate total vinyl chloride loss during the discharge, the method used for determining the vinyl chloride loss, the action thatlJwas taken to prevent the discharge, and measures adopted to nrevent future discharges. DTH 000115078 * t> > JMHMp The concentration of vinyl cfflaHBeln all exhaust gases dis charged to the atmosphere from each stripper Is not to exceed 10 ppm, except as provided In f 61.65(a). This requiremeat does not apply to equipment that tI53i8BaBBSHRI^erequlrement in 161.65(b) (6)0),- (c) has been opened, is out of operation, and met before being opened. exhaust gases discharged to the atmosphere from each mixing, weighing, or holding container in vinyl chloride service which,precedes the strip per (or tbs reactor If the plant has no stripper) In the plant process flow is not to exceed 10 ppm. except as provided in 1 91.66(a). This requirement does not apply to equipment that/flMEpaa tma the requirement In } 61.63(b) <S) has been opened, is out of operation, and met before being opened. ..........The ylchloride InaUjexhaust gases discharged to tha attnospbere from each monomer recovery sys tem Is not to exceed 10 ppm. except as provided In 161.85(a). This requirement does not apply to equipment that=SP3&~ will meets the requirement In { 61.65(b) (6) (0___________ ________________________________ Th'ee) following requirements apply to: emissions of vinyl chloride to the at mosphere from the combination of all sources following the stripper(s) [or the reactor(s) if the plant has no strip per (a) 1 In the plant process flow. In cluding but not limited to. centrifuges, concentrators, blend tanks, filters, dry ers. conveyor air discharges, baggers, storage containers, and Inprocess waste- water: (l) in polyvinyl chloride plants using stripping technology to control vinyl chloride emissions, the 6f##rige residual vinyl chloride concentration In all grades of polyvinyl chloride resin processed through the stripping opera tion on each calendar_ftay. measure the-reslflWTtwvm the mrippac, may not exceed: (1) 2000 ppm for polyvinyltillspersion resins, excluding latex resins; ' (U> 400 ppm for all other polyvinyl chloride reams, including latex resins, averaged separately for each type of res in; or (2) In polyvinyl chloride plants con trolling vinyl chloride emissions with technology other than stripping or In addition to stripping, emissions of vinyl chloride to the atmosphere may not exceed: (i) irg tn ?n ib/ioo-w" product from the stripper(s) lor reae- tor(s' if the plant has no strlpper(s)) for dispersion polyvinyl chloride resins, excluding latex resins, with the product determined on a dry solids basis: .has been opened, is out of operation, and met .before being opened. -immediately after the stripping operation is completed, chloride 2 f/kn (0.002 lb/lb) DTH 000115079 26 I (tn-ib* mw--'-nr' iiT^iiiu ieT nr product from the strippers (or reac tors) If the plant has no atripper(s)1 for all other polyvinyl chloride resin*. Including latex resins, with the product determined on a dry solids basis. 61.65 Emission standard fur ethylena diehloride, vinyl chloride and poly vinyl chloride plants. An owner or operator of an ethylene . dtchloride, vinyl chloride, and/or poly vinyl chloride plant shall comply with the requirements of this section. <*. Bettet valve dtechape: 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 hare been avoided by taking riMBBHi.,measures to prevent the discharge. Within ft fays of any relief valve discharge, the owner or operator of the source from which the relief valve 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 time of the discharge, the approximate total vinyl chloride loss during the dis charge. the method used for datoimlaln*' the vinyl chlqij^to.loe^rjiiy actlmi th%i was taken to prevent the discharge, and measures adopted to prevent future dis charges. <b> Fugitive emission sources: (l > Loading and unloading lines: Vinyl chloride emissions from loading and un loading linesAare to be minimized as follows: u> After each loading or unloading operation and before opening a loading or unloading line to the atmosphere, the quantity of vinyl chloride in ail parts of each loading or unloading line that are to be opened to the atmosphere is to be reduced so that the narts combined contain no greater thar.SBftjftftflttl of vinvi chloride, standard temperature and pressure; and tiii Any vinyl chloride removed from a loading or unloading line in accord ance with paragraph ibMDU) of this section is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed l&ppm, or equivalent as pro vided in { 61.66. <2> Slip gauges: During loading or un loading operations, the vinyl chloride emissions from each slip gauge In vinyl chloride service are to be minimized b7 ducting any vinyl chloride discharged from the slip gauge through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as pro vided in 61.66. t3) Leakage from pump, compressor, and agitator seals: (1) 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 61.66. If double mechanical seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pres- 0.4 g/kg (0.0004 lb/lb) '.vitch are opened to the atmosphere after, each loading or unloading operation 0.0038 m3 (0.13;.ft*) at DTH 000115080 27 . sure between the two seals so that any leak that occurs 1* Into the pump; bg dusting atur vinyl chloride between the tmaeole ttunngh a ooutral aumtxu tank wMch the coeeprtytton ofyfayi ehtf _ rtwem OM gaiMlUB gaae* does not *ccMH IftMa; cr equivalent as provided in S 61.66. (11' Reciprocating pumps; Vinyl cldorlde emissions from seals on all recipro cating pumps in vinyl chloride service are to be minimised by installing double outboard seals, or equivalent as provtded in i 61.66. If double outboard seals are used, vinyl chloride emissions from the' seals are to bemlnimlsed by maintaining' the pressure between the two Beals so that any leak that occurs Is Into the pump; bjr ducting any vinyl chloride be tween tho two sods through a control sjglnn (mm which tha concentration of viagi chloride In the exhaust gases does not exceed 10 ppm; or equivalent as provided tni 61.66. . -Rotating (lttli--gprefad: Vinyl chloride emta- ' slons from seals on all compressors In vinyl chloride service are to be mini mised by Installing compressors with double mechanical seals, or equivalent as provided In i 61.66. Tt double mechan ical aealg arc used, vinyl chloride emis sions from the seals are to be minimized . by maintaining the pressure between the two seals so that any leak that occurs Is Into theAdUfi? tiyaturfitog iny " vinyl chloride between the two seals through a control system from which, tiie concentration of vinyl chloride in' the exhaust gases does not exceed 10 ppm; or equivalent as provided in 5 61.CO. compressor (iv) Reciprocating Compressors: Vinyl chloride emissions from seals on all reciprocating compressors in vinyl chloride service are to be minimized by installing double outboard seals, or equivalent as provided in 61.66. I' 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 tha^ 'ccu-s is into the compressor; by ducting any vinyl chloride between the two sea^ through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as provided in 61.66. itw> ^ggaggr: Vinyl chloride emissions (v) from seals on all agitators in vinyl chlo ride service are to be minimized by in stalling agitators with double mechani cal seals, cr equivalent as provided in i 61.CC. If double mechanical seals are used, vinyl chloride emissions from the re.'!: ?re to be minimized by maintaining the pressure between the two seals so mat any leak that occurs is into the -- agitated vessel ; jmmm by ducting any vinyl chloride be tween th'-1 two seals through a control syr::m from which the concentration of vinyl chloride in the exhaust gases does net exceed 10 ppm; or equivalent as pro- . idea to i 61.66. e bfoh<^?^nr?ions^due^c> fcf^fcage from each relief valve on equipment in vinyl chloride service are to be minimized by installing a rupture disk between the _.,by connecting the relief valve discharge to a e .ui.irmcnt and the relief valv<y>r equiva lent as provided to 61.56. _ _ process line or recovery system, 5 Manual venting of ease ./All gases ~~Except as provided in 61.64(a)(3), all which are manually vented from equip ment in vinyl chloride service are to be ducted through a control system from DTH 000115081 which the concentration of vinyl chloride the exhaust gases does not exceed 10 ppm. or equivalent as provided in 1.66.  G> Opening of equipment: Vinyl chloride emissions equipment /(are "to follows: from opening be minimized of as"'' .(including opened to loading or unloading the atmosphere after lines that each loading are or not <i> Before opening any equipment for any reason, the quantity of vinyl chlo unloading operation) ride is to be reduced so that the equip ment contains no more than 2.0 percent by volume vinyl chloride orQft BWt'TZo 0.0950 ni3 gal) of vinyl chloride, whichever Is larger, at standard temperature and pressure; and <ii> Any vinyl chloride removed from the equipment In accordance with para graph (b)(0) (1) of this section Is to-be ducted through a control system from which the concentration of vinyl chlo ride In the exhaust gases does not exceed 10 ppm, or equivalent as provided in $ 61.66. (7) __ ____ Unused portions of samples containing at least 10 ptreent by weight vinyl chloride are to be returned to the process, and sampling techniques are to be such that sample containers in vinyl chloride (6) bwfc detottton *! - Vinyl chloride emissions due to leaks from equipment In vinyl chloride service are to be minimised by instituting and Implementing a formal leak detection and elimination program. The owner or operator shall submit a description of service are purged into a closed process system. the program to the Administrator for approval. The program Is to be sub mitted within 45 days of the effective date of these regulations, unless a waiver of compliance is granted under ! 61.11. If a waiver of compliance Is granted, the program is to be submitted on a date scheduled by the Administrator. Ap.proval of a program will be granted by the Administrator provided he finds: ti' It includes a reliable and accurate vinyl chloride doteoteijnor detection of r.i.vor leaks and identification of the general area of the plant where a leak i.< located* - monitoring system I: includes a reliable and accurate permble hydrocarbon detector to be used r:u:rr.?!y to find small leaks and to pin- ?cd'.: the major leaks indicated by the ionde detector* - I: provides for an acceptable cali- *-r:.r.:r. ar.d malntenanc* schedule for The vicryl chloride daiaatariand portable c ircr.'.rbcn detector* -- :The location and number of points " :: monitored and the frequency of tr.rtutrring provided for to the program are r.rceptable when they are compared -. ;he number of pieces of equipment -. " i chloride sendee and the size and layoutof theplant,, I: contains an acceptable plan of arir.T. to be taken when a leak Is de- --r-c.swd It contains a deflriltlon of leak -- -. acceptable when compared with round" concentrations of vinj. .-..--r? in the areas of the plant to be r.:r.:t-:red by the vinyl chloride dotaotetyf" -- ?I?- =v.remer.ts of background concen- :r; :: cns :: vinvl chloride In the areas of The portable hydrocarbon detector is to measure hydrocarbons with a sensitivity of at least 10 pom. monitoring system monitoring system DTH 000115082 monitoring system 29 the plant to be monMagsd by the vinyl___ monitoring system chloride dotertw^are to be Included wltli the description of the program. The defi nition of leak for a given plant may vary among the different arena within `the plant and Is also to change over time ns background concentrations In the plant are reduced. (0) Inprocess wastewater: Vinyl chlo ride emissions to the atmosphere fmn inprocess wastewater are to be reduced ns follows: (I) The concentration of vinyl chlo ride In each Inprocess wastewater stream/' containing greater than 10 ppm vinyl chloride measured immediately as It leaves a piece of equip- ` ment and before befog mixed with any other lnprocceessss_ wjraasstteewater stream is to be reduced1 *1 yUI jJpink ttf^^hOjefore to no more than being exposed to the atmosphere? Wt 03fore being discharged to a wastewater treatment process; or discharged un before being mixed with any other inprocess wastewater stream which contains less than lOppm vinyl chloride; treated as a wastewater. This paragraph does apply to water which is used to dis place vinyl chloride from equipment be fore It is opened to the atmosphere In accordance with 161.64(a)(2) or para graph (b)(6) of this section, but does not apply to water which is used to wash out equipment after the equipment has already been opened to the atmosphere In accordance with 8 61.944a) (2) or para graph (b) (6) of this section. (II) Any vinyl chloride removed from the inprocess wastewater in accordance with paragraph (b) (9) (1) of this seetion is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided In 8 61.66. (c) The requirements in paragraphs (b)(1). (b)(2), (b)(5), (b)(6), (b)(7) and (b) (S) of this section are to be in corporated into a standard operating procedure, and made available upon re quest for inspection by the Administra tor. The standard operating procedure is to include provisions for measuring - 4.75 I7W vinyl chloride In equipment 1 (1230 gal) in volume for which amemis sion limit is prescribed in S 61.65(b) (6) (1) prior to opening the equipment and using Test Method 106, a portable hydro carbon detector, or an equivalent or al ternative method. The method of meas urement is to meet the requirements in { 61.67(g) (5) (1) (A) or (g) (5) (1) (B). 61.66 Equivalent equipment end pro cedure*. Upon written application from an own er or operator, the Administrator may approve use of equipment or procedures which have been demonstrated to his satisfaction to be equivalent in terms of reducing vinyl chloride emissions to the atmosphere to those prescribed for com pliance with a specific paragraph of this subpart.------------------------------------------- . 61.67 Emission tests. (a) Unless a waiver of emission teetlrig is obtained under $61.13, the-owner'or operator of a source to which this subpart applies shall test emissions from the source. Requests for using equivalent methods as the initial measure of control are to be submitted to the Administrator within 60 days of the effective date. DTH 000115083 30 Ui in thtfetoe bf ah learatii' sottfeibr' a sew source which has an initial startup date preceding the effective date, or ajraoarflm&'s. 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 teat 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. The average is to be computed on a time (d) Bach emission test is to consist weighted basis. of three runs. Bor the purpose of deter mining emissions, the average of results of all runs is to aoolv.-------- ------------------ .,, . .. . <e) All samples are to be analyzed*--Within 24 hours, and vinyl chloride emissions are to be, determined within 30 days after the etnlssion test. The owner or operator shall report the determinations to the Ad ministrator by a registered letter dis patched before the close of the next busi ness day following the determination. (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 emissions. (g) Unless otherwise specified the owner or operator shall use test Test Methods In Appendix B to this part for each test as reaulred bv naraar&ohs (g)(1), (g)(2), (g)(3), (g)(4), and (g) (5) of this section, unless an equiva lent method or an alternative method has been approved by the Administrator. If the Administrator finds reasonable grounds to dispute the results obtained by an equivalent or alternative method, he may require the use of a reference method. If the results of the reference and equivalent or alternative methods do not agree, the results obtained by the 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. U> Test Method 106 is to be used to determine the vinyl chloride emissions from any source for which an emission limit is prescribed in { 61.62(a) or (b) { 61.63(a), or 5? 61.64(a) (1), (b), (c),or (d), or from any control system to which reactor emissions are required to be ducted in S 61.64(a) (2) or to which fugitive emissions are required to be ducted in {} 61.65(b) (1)01), (b)(2), (b)(5), <b' (6) (ii), or (b) (9) (ti). . (i) For each run, one sample Is to be collected. The sampling site is to be at least two stack or duct diameters down- /*m\ MW 000116084 stream and one half diameter upstream from any flow dtotarbance such as a bend, expansion, contraction, or visible flame. For a rectangular cross section an equivalent diameter Is to be determined from the following equation: crp:i\nlfnl dinmoliT-^2 (length) (width) length-I- width The sampling point in the duct is to be at the centroid of the cross section. The sample Is to be extracted at a rate proportional to the gas velocity at the sampling point. Yfet sample to to be corrected to standard conditions. <10 Mstodhaae^mlasIsxaaiLuefllinuu - delete craatoi<||MBlwgpgb>wPBipssHitol'ililii sMewMMMMto.ne concentration of vinyl chloride ae detoiimlued by Teat Method .delete oxygen SA58m8n&. emissions by using the following equa tion: <*I (MrwraS --Cl 20.9 -- 10.9 percent Oj winn. C'tcwrwM) -Th* ooDeantnUon of Tlnyl obkaidt la ^ OwwbMMtsMw.eomctMltolOaw- C-Tl Mamtnttoo ol Tlnyl chlorite m a--ni by Teat Method ICS, aO-t-T'irmtipoqdtirotwryofiBtifsoMth.o omManX air at 19.#--Ptmat oxytai la the omblaat air at Maadoid eoadlttooa, ml tom tha 10 ponxat oiyr*o to which tha carna tion la beint made. rerernt Ot-FemroweaitnodrybteyaRlaWtmbaeoaxMhseathriocdott lMa till) For those emission sources where the emission limit to prescribed in terms M mass rather than concentration, mass emissions in kg/100 kg product axe to be determined fay using the following equation: ,, ic, 12.001 q in MiW] C tt\ ` y vbvs: Ctt Tli.y) <*V,\ruW.on ke i t*- The a:t'v.ilnufo.t of v.i y! chlorwi-* os iii'-i-im ! hy Test MvUoO loft. 5.60 - Density of Tiny! eWorld# M on* atmoapHwt and JiTC In kg'm*. Q-\ oiumtrte (low rat# In m'/hr na determined lf ilfr r*ne Method 2 of Appendix A Ur I'url *i0 of ibis chapter. Con version lartor for ppm* 7* Production raU <2> Twt Method Iff is to be used to determine the concentration of vinyl chloride in each inprocess wastewater stream for which an emission limit is prescribed in } 61.65(b) (9) (1). (3) Where a stripping operation is used to attain the emission limit in 161.64(e), emissions are to be determined using Test Method 107 as follows: (1) The number of strippers and sam ples and the types and grades of resin to be sampled are to be determined by the Administrator for each individual plant at the time of the test based on the plant's operation. Oi) Each sample is to be taken Imme diately following the stripping operation. rlplptp ub" the rehssiwt*aMadiwdwi> f tlx "*" Oil) The corresponding quantity ct material processed by each stripper is to be determined on a dry solids basis and by a method submitted to and approved by the Administrator. . 32 DTH 000115085 Uv) At the prior request of the Ad ministrator, the owner or operator shall provide duplicates of the samples re quired in paragraph (gK3)i) of this section. lit Where control technology other than or tn addition to a stripping opera tion is used to attain the emission limit In i 61.64(e), emissions are to be deter mined as follows: <1> Test Method 106 1s to be used to determine atmospheric emissions from all of the proceiw equipment simultane ously. The requirement* or paragraph (g) (I > of this section are to be met. < in Test Method 103 is to be used to determine the concentration of vinyl chloHde In each Inproeess wastewater stream summit to the amission limit pre scribed let UJMte) Themass 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: [c, n io-*i [looi ------ z..... " vbltfd Ci vtnyl chkMldVIOO kg product. t'd--th* conoectrafcWm of Tiny! chloride as measured by Teat Method 107. R -orator flow nl la 1/hr, determined In Accordant with a method which has been submitted ta and approved by the Administrator. \<T* -Cooverafoa factor tor ppm. Z-ProductiOQ rate (kg/ar). datortotaod in accord' anee with a method which baa beensubmitted and approvedby the Administrator. (5) The reactor opening loss for which an emission limit is prescribed In f 61.64 (a) (3) Is to be determined. The number of reactors for which the determination Is to be made is to be specified by the Administrator for each individual plant at the time of the determination based on the plant's operation^------- (D Except as provided In paragraph (g> (5) (11) of this section, the reactor opening loss is to be determined using the following equation: _ W (2.60) (IQ-*) (Cb) For a reactor that is also used as a stripper, the determination may be made immediately following the stripping operation. wti re: C-k? viay1 chloride omiariona/kg product. JP-- Capacityoi thereactor in m*. 2.60- Density oi vinyl chloride at one atmosphere sad 20 C in kg/m*. 10~** Conversion factor tor ppm. Cb--ppm by votame vinyl chloride as determined by Tca Method 106 or a portable hydrocarbon detecto^a........... .. ........ "si"iw y-Ketn&ber of batches 4uee the reactor was last 2 opened to theatmoepbere. -Awue kg of polyvinyl chloride produced per batch in the number of batches since the reactor was last opened to the atmosphere. (A) If Method 106 is used to deter mine the concentration of vinyl chloride (Cb). the sample Is to be withdrawn at a constant rate with a probe of sufficient length to reach the vessel bottom from the manhole. Samples are to be taken for 5 minutes within 6 Inches of the ves sel bottom, 8 minutes near the vessel center, and Sminutes near the vend top. <B> If a portable hydrocarbon detec tor is used to determine the concentra tion of vinyl chloride (Cb), a probe of sufficient length to reach the vessel bot tom from the manhole is to be used to make the measurements. One measure ment will be made with*n 6 Inches of the vessel bottom, one near the vessel center and one near the vessel top. Measure ments are to be made at each location until the reading Is stabilized. All hydro carbons measured are to be assumed to be vinyl chloride. which measures hydrocarbons with a sensitivity of at least 10 pom. MH 000115086 33 <C> The production rate of polyvinyl chloride (Z) is to be determined by a method submitted to and approved by the Administrator. ^ (ii> A calculation based cm the number ' evacuations, the vacuum Involved, and .ie volume of gas In the reactor Is hereby approved by the Administrator as an al ternative method for determining reac tor opening loss for postpolymerization reactors In the manufacture of bulk resins. itjl.68 Emission monitoring. (a) The vinyl chloride, monitoring system required in 61.65(b)(8)(i)s or equiv alent as to be used to monitor on a continuous basis the emissions from these sources for which emission limits are prescribed in 61.62(a) and (b), 61.63(a), and 61.64(a) (1) (b), (c), and (d), and for any control system to whfc^h reactor emissions are required to be ducted in 61.64(a)(2) or to which fugitive emissions are required to be ducted in 61.65(b)(1)(ii), and (b)(2), (b)(5), (b)(6)(ii), and (b)(9)(ii). 8 6h*i '` (a) An owner or operator of any source to which this subpart applies shall submit a statement in writing notifying the Administrator that the equipment and procedural specifications in fi 61.05 (b)(1), (b)(2), (b)(3), (b)(4), (b)(6). (b)(6), (b)(7), and (b)(6) are being Implemented. (b)(1) la the ease of an existing source or a new source baailo initial startup1 date preceding the effec ted wlthlxHM dMPM^i^Jff^iVe^date! 9 unless a:waiiigr,fiirMtolliiPi|i is starred tnder | gl.tl, iMti' wtth the lnforma- don required under 8 U& If a waiver of compliance Is granted, the statement Is to be submitted on a date scheduled by the Administrator. (2) In the case of a new source which did not have an initial startup date pre ceding the effective date, the statement is to be submitted within 90 days of the initial startup date. (c) The statement Is to contain the following Information: (1) A list of the equipment Installed for compliance, ^--------- --- delete (2) A defiled mglncu Ing^descrlp- tlon of the physical and functional char acteristics of each piece of equipment, (3) A description of the methods which have been Incorporated Into the standard operating procedures for meas uring or calculating the emissions for which emission limits are prescribed in 55 61.65 (b) UHl) and (b)(8)(i), (4) A statement that each piece of equipment Is Installed and that each piece of equipment and each procedure is being used. 61.69 Semlonmudreport. (a) The owner or operator of any source to which this subpart applies shall submit to the Administrator on MMMtRW basLi tael* M<Nhqu a report in writ ing containing the Information required by this section. ---- ........ - (b) (1) In the case of an existing source ir a new source which has an Initial startup date preceding the effective date, the first report is to be submitted within 180 days of the effective date, unless a waiver of compliance Is granted under 5 61.11. If a waiver of compliance Is granted, the first report Is to be sub mitted on a date scheduled by the Ad- in lr-itator. September 15 and March 15 of each year The first semi-annual report is to be submitted follow ing the first full 6 month reporting period after the initial report is submitted. DTH 000115087 34 (2) in the ewe of a new source which d not have an Initial startup date Drerting the effective date, the first report to be submitted within 180 days of the itial startup date. (c) Unless otherwise specified, the nier or operator shall use the Test (etliods in Appendix B to this part to induct emission tests as required by aragr&phs (c)(2) and (c)(3) of this jctlon, unless an equivalent or an alter ative method has been approved by the jdministrator. If the Administrator nds reasonable grounds to dispute the esults obtained by an equivalent or alernative method, be may require the use f a reference method. If the results of he reference and equivalent or alterna te methods do not agree, the results ibtalned by the reference method preail, and the Administrator may notify he owner or operator that approval of he method previously considered to be qulvalent or alternative is_ withdrawn. (1) The owner or operator shall In dude in the report a reoord of any emis sions In excess of the emission limits pre scribed in 55 61.63(a) or (b), 5 61.63(a), or 55 61.64(a) (1), <b>, (c), or (d), or for any control system to which reactor emissions are required to be ducted In 5 61.64(a) (2) or to which fugitive emis sions are required to be ducted In 161.65c(b)(1)(11), (b)(2), (b)(5), (b>(6)(11),or (b) (9) (11). The emissions are to be meas-. ured with-a Whirl nhlrrlilo detectbw-- (2H'Uie owner or operator shall in* elude In the report a record of the garni tHy of omtoMonc at f vinyl chloride peaa tho oousooa fallowing Ihestrippoi'C.r-tei1 ) the vonctwrU.) if the plant hoc no strip p*(o) 11 hi1 polyr1mjI shlarWe plaatwdos whlotra stripping eperaHen le unod to stiwht the cmteoioB limit prescribed 4b . Test Method 107 la to be used to determine umiuuhftm as toliows: (1> If lUjtkdl 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 operationl&i 4ha.iesln.lt tramfarred-aus of the stripper, and identified by resin type and grade and the date and time the batch is completed. The corresponding quantity of material processed in each stripper batch Is to be recorded and Iden tified by resin type and grade and the date and time the batch Is completed. (11) If continuous stripping Is used, one representative sample of polyvinyl chloride resin Is to be taken for each grade of resin processed or at Intervals of 8 hours for each grade of resin which Is being processed, whichever Is more fre quent. The sample Is to be taken as the resin flows out of the stripper and Iden tified by resin type and grade and the date and time the sample was taken. The corresponding quantity of material processed by each stripper over the time period represented by the sample during the eight hour period. Is to be recorded and Identified by resin type and grade and the date and time it represents. (ili) The quantity of material proc essed by the stripper Is to be determined on a dry solids basis and by a method submitted to and approved by the Ad ministrator. (iv> At the prior request of the Ad ministrator, the owner or operator shall provide duplicates of the samples re quired In paragraphs (c>(2)(l) and (c) (2) <U) of this section. in accordance with 61.68. In polyvinyl chloride plants for which a stripping operation is used to attain the emission level prescribed in 61.64(e), content in the polyvinyl chloride resin. vinyl chloride content 9 DTH 001150B8 35 film fntenantawi iut&tn.d fa <) > <lr<g ttila attUan tlw vlnyf nhlarHt done tration a& any paint nrrnltr thafiTwUn- tjaluji-of'ednfl altljfaria iaalgnisteey aa.a iwrfc. *-statemennt;fxj of-kha-kak ibk minfttn itf'the ajaountfUf time (2) A record of tbe leaks detected during routine monitoring with the portable hydrocarbon detector and the action taken to repair the leaks, as re quired by t 51.65(b) (8), Including a brief statement 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 emisslo measured in accordance with 61.68. "U> For the relief discharges'--from reactors subject to the provlaiona of *S 61.651/), a daitjr dperitmg record for' each reactor. Including pressures and temperatures. 4* Appendix 5 is amended by adding Test Methods 106 and 107 as follows: Mxthoo MHMmaiianox or Vmn. Cium non SnuoMuT Sonnets Performance of this method should cot be attempted by persona unfamiliar with the operation of a gaa chromatograph, nor by those vho are unfamiliar with source sam pling, aa there are many details that are beyond the scope of this presentation. Care must be exercised to prevent exposure of sampling personnel to rlnyl chloride, a car cinogen. 1. Principle and Applicability. 11 An Integrated bag sample of stack gas containing vinyl chloride (chloroethylene) is subjected to chromatographic analysis, using a flame Ionization detector. 12 The method U applicable to the meas urement of vinyl chloride In stack gases from both vinyl chloride and polyvinyl chloride manufacturing processes, except where the vinyl chloride ts contained In particulate matter. 2 Range and Sensitivity The lower limit of defection will vary ac cording to the chromurocrapb used. Values reported include t v no and 4 y 10 ' mg. 3. Interferences HFeSe The only compound which is known to co-elute with vinyl chloride is acetaldehyde. inrt ta pTsuaarV of the wfayl enrorra?- peak wfa -tse x,iuuiuumi1i'>ms 1 doi+trim lie meea JD resolution of the vinyl chloride peak Is not satisfactory fo- a par ticular sample, then chromatograph param- ,. acetal dehydeeti-rs may be altered v..t.tt prior approval of the -VtmirUtra-.-r If -..V.ere la reason to be-. lieve tliatysonie c1. swaacnnelnaH with an "compoundidentical reteu: ca rmr-e : present In the ,,.'.!vplc. then supplerrvr:-:*.". confirmation of the vlr.yl chloride pea\ rhro-.igh an absoHui* ar.alyti'al techrm;-. j .ch as mass .vp- - roat-epy. j> aid be cerf.vmed .. __ --must Mention of trade urate on specific prod ucts doee not constitute endorsement by the Environmental Frocecrson Agency. 37 or DTH 000115089 6 Reagents It Is necessary that all reatfa'i be of chromatographic grade. .s t Analysts. . i t Helium gas or nitrogen g3- Zero g-icje. for chromatographic carrier gns. ' : 2 Hydrogen icas-Zcro grade._______ __ . t :i Oxygen gas^Zero grade. ~~ ,or Ai r. as required by the detector. r 2 Calibration. f. 2.1 Vinyl chloride. 99.9) rl--For prep aration of standard gas mixtures. 5 2 2 Calibration cylinders fat optional-- One each of 00. 10 and 5 ppm vinyl chloride in nitrogen with certified analysis. 5.3.3 Nitrogen gas--Zero grade, for prep aration of standard gas mixtures. 6. Procedure. 3.1 Sampling. Assemble the sample train as In Figure 105-1. Perform a bag leak check according to Section 7.4. Observe that all connections between the bag and the probe are tight. Place the end of the probe at the centroid of the stack and start the pump with the needle valve adjusted to yield a flow of 0.5 1pm. After a period of time 'suffi cient to purge the Une several times has elapsed, connect the vacuum line to the bag and evacuate the bag until the rotam eter indicates no flow. Then reposition t&Q sample and vacuum lines and begin the ac tual sampling, keeping the rate proportional. exi ti HQ to the at isle velocity. Direct the gas eUthigjj' - the rotameter away mm samplingpMSaSORSN. stack At the end of the sample period, shut off the' pump, disconnect the sample Une from the bag. and disconnect the vacuum Une from the bag container. Protect the bag container from sunlight. it \ 3.2 Sample storage. Sample bags must be kept out of direct sunlight. When at all pos sible. analysts la to be performed wHhtn2^ hours of sample collection ' S3 sample recovery. With a piece of Tef lon tubing identified for that bag. connect a bag inlet valve to the gaa chromatograph sample valve. Switch the valve to withdraw gas from the bag through the sample loop. Plumb the equipment so the sample gaa passes from the sample valve to the leak-free pump, and then to a cjsggjQ&l-tUilp. followed by a 0-100 ml/min rotameter with flow con trol valve. 3.4 Analysis. Set the column temperature to 155' C. the detector temperature to 225* C. and the sample loop temperature to 70* C. When optimum hydrogen and oxygen, flow determined rates have been determine, verify and main tain these flow rates during all chromato graph operations. Using zero helium or nitrogen as the carrier gas, establish a flow rate In the range consistent with the manu facturer's requirements for satisfactory Se lector operation. A flow rate of approxi mately 15 ml/mln should produce adequate separations. Observe the base line periodi cally and determine that the noise level has stabilized and that base Une drift has ceased. Purge the sample loop for thirty seconds at the rate of 100 ml/mln, then activate th< sample valve. Record the injection time (tbJ position of the pen on the chart at the tlmel of sample Injection). the sample number, the] sample loop temperature, the column tem perature. carrier gas flow rate, chart speed and the attenuator setting. Record the lab oratory pressure. From the chart, select the peak having the retention time correspond-' tag to vinyl chloride, as determined In Bee. tlon 72. Measure the peak area. Am. by use of *1 gtuuJaUrfTntegrator. Record Am and a disc the retention time. Repeat the Injection a! least two times or until two consecutive vinyl | & chloride peaks do not vary In area more than 5%. The average value for these two areas will be used to compute the bag concentra if tion DTH 000115090 39 4 Apparatus. 4 1 Sampling (Figure 1. 4 11 Probe--Stainless steel. Pyres glaaa. or Teflon tubing according to stuck temper ature, each equipped with a glass wool plug to remove particulate matter. 4.1.3 Sample line---Teflon, 8 4 mm outMde diameter, of sufficient length to connect probe to bag. A new unused piece is employed lor each series of bag samples that constitutes an emtsston teat. 4.1.3 Mala (3) and female (2) stainless steel quick-connects, with ball checks (one pair without) located as shown In Figure l. 4.1.4 Tedlar bags, 100 liter capacity--To contain sample. 4.1.5 Bifid leakproof containers for 4.1.4, with covering to protect contents from sun- .light. 4.1.6 Needle valve--To adjust sample flow rate. 4.1.7 Pump--Leak-free. Minimum capac ity 3 liters pee minute. 4.1.8 OM*pH& tab#---To prevent admto- ,l,,> to atmosphere in vlcin.- 4.1 H floor meter--For observing sample flow rate; capable of measuring a flow range from 0.10 to 1.00 liter per minute. 4.1.10 Connecting tubing--Teflon. 6.4 mm outside diameter, to assemble sample train (Figure 1). _____________ 4.1.11 Pitot tube--Type * (or equivalent), attached to the probe ao that the t ampllng flow rate can be regulated proportional to thp stack gas velocity. 4.3 Sample recovery. 4.2.1 Tubing--Teflon, 8.4 min outside diameter, to connect bag to gaa chromato graph sample loop. A new unused piece is employed for each series of bag samples that constitutes an emission test, and Is to be dis carded upon conclusion of analysis of those bags. 4 3 Analysis. 4.3 1 Gas chromatograph--With flams' ionization detector, potentlometrtc strip I chart recorder and l.o to 6.0 ml heated sam pling loop in automatic sample valve. 4.3-2 Chromatographic column--Stainless sieel, 3.5 m x 3.2 mm, containing 80/100 mesh Chromosorb 102. > 43 3 Flow meters (2)--Rotameter type. 0 to 100 ml min capacity, with flow control valves 434 Gas regulators--For required gas cylinder . 4 3 5 Thermometer--Accurate to one de gree centigrade, to measure temperature of heated -ample loop at time of sample Injec- ~s 4.3 5 Barometer--Accurate to 5 mm Hg, to measure atmospheric pressure around gas coromstograph during sample analysis. 4.3.7 Pump--Leak-free. Minimum capac ity loo ml/mln. 4 4 Calibration. 4.4.1 Tubing--Teflon, 64 mm outside diameter, separate pieces marked for each calibration concentration. 4 4.2 Tedlar bags--Sixteen-inch square sire, separate bag marked for each calibra tion concentration. 4.4 3 Syringe--0 5 ml. gas tight. 4.4.4 Syringe--50A gas tight. 4.4.5 Flow meter--Rotameter type, 0 to !V>0 ml rola range accurate to 1%, to meter nitrogen in preparation of standard gas mixtures. 4.4.6 Stop watch--Of known accuracy, to time gas flow in preparation of standard gas mix'.'ires. 38 a f dth (Nuts: An alternatiwa teak chaok method Is to prsssurtas the ini *o A"10 cm H.O or 3-4 in. H.O and allow to stand overnight. A deflated bag Indicates a leak.)------------------ - 8. Calculations. 8.1 Determine the sample peak area as follows; w4c= A/ Equation 106-1 After placing a bag in its rigid container, place a rotameter in-line between the bag and the pump inlet. Evacuate the bag. Failure of the rotameter to register zero flow when the bag appears to be empty indicates a leak. There A .-The amp!* peak ana: A.-Tbemeasured peak ana; Ar--Tbs sMaaoatton factor. 8.2 Vinyl chlortd* oonoantratlooa. From tba calibration curra described m Section 7A. above, select the value of O, that ecrreeponda to A,, the sample peak area. Cal culate Ck as follow*: Cs- * C.PrTj PiTr where Equation 106-2 C.- The oodeentraHon of vinyl chloride In tire beg eemple la ppm. C.- The eoaeentradoo of vinyl chloride Indicated fay />,- the gas fhrnmsiugrspli. in The reference pressure, the ppm. laboratory pressure Ti records*! daring calibration, mm He. Tbs sample loop temperature oo the sbaolute Pi scale at tbs Urns of soslyds, *K. Tbs laboratory pressure at time of analysis, mm Hg. TV The reference temperature, the sample loop temperature recorded daring celibraUon, VE. P. Reference. 1. Brown, D. W,, Loy, B. W. and Stephen' son. M. H. -Vinyl Chloride Monitoring Near the B. F. Goodrich Chemical Company In Louisville, Kentucky." Region IV, UB. Envi ronmental Protection Agency, Surveillance' and Analysis Division, Athens, Georgia, June 24, 1974. ; 2. "Evaluation of A Collection and Analy- * tlcal Procedure for Vinyl Chloride In Air," by G. D. Clayton and Aasoclatee, Decembe. . 13, 1974. KPA Contract No. 68-02-1408, Task Order No. 2. ZPA Report ON. 75-VCL-l. (1-Bilb ) = The water vapor content of the bag sample, as analyzed. Jlj.ri ICi-X, W| wa^lit| trihi MrmfiUfityi(itmfryi(UmImwAmf--i kiwfl fryiwwlituiw J!piifMet CMMiiktt 41 6.5 Measure the ambient temperature and barometric pressure near the bag. From a water saturation vapor pressure table, determine and record the water vapor content of the bag. 7.1 Preparation of vinyl chloride standard gas mixtures. Evacuate a slxteen-lnch square Tedlar beg that has passed s leak check . (described In Section 7.4) and meter kT8.fi liters of nitrogen. While the bag la filling, use the 0.6 ml syringe to Inject 320*1 of 09.9+ % vinyl chloride through the wall of the hag. Upon withdrawing the syringe needle. Im mediately cover the resulting hole with a piece of adhesive taps. This gives a concen tration of GO ppm of vinyl chloride. In a like manner use the other syringe to prepare dilu tions having 10 and fi ppm vinyl chloride concentrations, place each bag on a smooth surface and alternately depress opposite aides of the bag SO times to further mix the 71) Determination of vinyl chloride re tention turn This section can be performed simultaneously with Section 7.3. Establish chromatograph conditions Identical with those in Section 0d, above. Set attenuator to X 1 position. Plush the sampling loop with aero helium or nitrogen and activate tbs sample valve. Raoacd the injection time, the sample loop temperature, the column temperature, the canter gas flow rate, the chart speed and the attenuator setting. Record peaks and detector responses that occur In the absence of vinyl chloride. Main tain conditions. With the equipment plumb ing arranged Identically to Section 03, flush the sample loop for 30 aeoonds at the rate of 100 ml/min with one of the vinyl chloride calibration mixtures and activate the sample valve. Record the Injection time. Select the peak that corresponds to vinyl chloride. Measure the distance on the chart from the Injection tlmeto the time at which the peak maximum occurs. This quantity, divided by the chart speed. Is defined as the retention time. Record. 7.3 Preparation of chromatograph cali bration curve. Make a gas chromatographic measurement of each standard gas mixture (described In Section 7.1) using conditions identical with those listed In Section S3 above. Flush the sampling loop for 30 seconds at the rate of 100 ml/mln with each standard gas mixture and activate the sample valve. Record C,, the concentrations of vinyl chlo ride Injected, the attenuator setting, chart speed, peak area, sample loop temperature, column temperature, carrier gaa flow rate, and retention time. Record the laboratory pressure. Calculate Ac, the peak area multi plied by the attenuator setting. Repeat until two injection areas are within S%, then plot those points vs Ct. When the other concen trations have been plotted, draw a smooth ctirve through the points. Perform calibra tion dally, or before and after each set of bag samples, whichever Is more frequent. 7.4 Tedlar bag leak checks. Before each use, make sure a bag Is leak-free by checking It for leaks. To leak check, connect a water . manometer and pressurize the bag to 6-10 cm H.O (2-4 in. R.O). Allow to stand for 1.,t!!'* toa_water in Check the rigid container for leaks in this manner. 40 dth 00011509Q JNTIOUUmul* Performance of Ibis method should not be attempted by persons unfamiliar with the operation of a gas chromatograph, nor by those who are unfamiliar with sampling, as there are many detail* that are beyond the cope of this preeeatatlon. Cara must be exercised to prevent exposure of sampling personnel to vinyl chloride, a carcinogen. 1. Principle and Applicability. 1.1 The basis for this method relates to the vapor equilibrium which Is established between RVCM, PTC. resin, water, and air In a cloeed system. It has been demonstrated that the BVCM In a FTC mein win equili brate In a cloeed vessel quite rapidly, pro vided that the temperature of the FTC resin Is maintained above the glass transition temperature of that specific resin. 12 This procedure la suitable for deter mining the vinyl chloride monomer (VCM) content of lnprocese wastewater samples, and the residual vinyl chloride monomer (RVCM) content of polyvinyl chlorto* (FTC) resins, wet cake, slurry, and latex samples. It cannot be used for polyassc in foesd form, such as sheet or cubes. If a reeoluflffiTbf the vinyl chloride peak Is not ssHtfactory far a particular sample, then chromatograph parameters may be altered with prior ap pro val of the Administrator. If there Is rea son to believe that some other hydrocarbon with an Identical retention time Is present In the sample, then supplemental confirma tion of the vinyl chloride peak through an .absolute analytical technique, such as mass prctroscopy, should be performed. 2. Range and Sensitivity. The lower limit of detection of vinyl chlo ride will vary according to the chromato graph used. Values reported Include IX10'T mg and 4 X10-* mg. With proper calibration, the upper limit may be extended as needed. 3. Precision and Reproducibility. An Interlaboratory comparison between seven laboratories of three resin samples, each split Into three parts. yteM-1 sl&naara deviation of 2.63% for a sample with a mean of 2.09 ppm. 4.16% for a sample with a mean of 1.66 ppm. and 3129% for a sample with a mean of 62.66 ppm. 4. Safety. Do not release vinyl chloride to the labora tory atmosphere during preparation of stand ards. Venting or purging with VCM/air mix tures must be held to e minimum. When they are required, the vapor must be routed to outside air. Vinyl chloride, even at low ppm levels, must never be vented inside the laboratory. After vials have been analyzed, the pressure within the vial must be vented prior to removal from the instrument turn table. Vials must 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. 5.1 Sampling. 5.1.1 Bottles--60 ml (2 oz), with waxed lined screw on tops, for PVC samples. 6.1.2 Vials--50 ml Hypo-vlals.1 sealed with Teflon faced Tuf-Bond discs for water sam ples. yielded 1 Mention of trade names on specific prodact* does not constitute endorsement by the Snvlronmental Protection Agency. 42 DTH 000115094 #4.3 Electrical tape--or equivalent, to prevent looeenlaf of bottle topt. BJ Bample recovery. 8,3.1 Vtale--Wltb eeele and cap*, PerkinE:a*T CorporaUoc No. 10&-0118. or eqnlva- 5 33 Analytical balance--Capable of welching to *0.001 gram. #3.3. Syringe, 100 *1--Precision Serlee "A" No. 010035. or equivalent. 5.9.4 Vial Sealer. Perkln-Elmer No. 1050108 or equivalent. 5-3 Analysis. 83.1 Oaa chromatograph--Perkln-Elmer Corporation Model F-40 head-space ana lyzer, No. 104-0001. or equivalent. 6.3.3 Chromatographic column--Stain less steel. 3 mXS.3 mm, containing 0.4% *1 ?ff.frC,Miirata No. 1M-010# or Carbopak C can be used in place of Carbopak matlc dosing, 13 mm, Perkln-Elmer No. 1051008, or equivalent. 5.3.8 Integrator - recorder-- Hewlett Packard Model 3380A. or equivalent. 5.3.7 niter drier assembly (8)--Perkinminer No. 3398117, or equivalent. 5.3.8 Soap film flowmeter--Hewlett Pack ard No. 0101-0113,^cr equivalent. 5.4 CaUbratlaB. 6.4.1 Regulators for required gae cjrin- dere. 8. Heagents. 8.1 Analysis. 8.1.1 Hydrogen gas--sera grade, 6-4.3 Nitrogen gaa--sero grade. 6.18 Air--sero grade. 0.2 Calibration. 6.3.1 Standard cylinders (4)--one each of 50. 500, 3000, and 4000 ppm vinyl chloride In nitrogen, with certified analysis. 7. Procedure. 7.1 Sampling. 7.1.1 PVC sampling--Allow the resin or slurry to flow from a tap on the tank or silo until the tap line has been well purged. Ex tend a 60 ml sample bottle under the tap, fill, aud Immediately tightly cap the bottle. Wrap electrical tape around the cap and bottle to prevent the top from loosening. Place an identifying label on each bottle, and record the date, time, and sample location both on the bottles and In a log book. 7.1.3 Water sampling--Prior to use, the in) ml vials (without the discs) must be rapped with aluminum foil and muffled at 100'C for at least one hour to destroy or remove any organic matter that could In terfere with analysis. At the sampling loca tion fill the vials bubble-free, to overflowing so that a oonvex meniscus forms' at the top. The excess water Is displaced as the sealing disc is carefully placed. Teflon side down, on the opening of the vial. Place the aluminum seal over the disc and the neck of the vial and crimp Into place. Afflx an Identifying label on the bottle, and record the date, time, and sample location both on the vials and In a log book. All samples must be kept re frigerated until analyzed. 7.2 Sample recovery. Samples must be run within 24 hours. 7.2.1 Resin samples--The weight of the resin used must be between 0.1 and 4.6 grams. An exact weight must be obtained (0.001 gram; for each sample. In the case of sus pension resins a volumetric cup can be pre pared which will hold the required amount of sample. The sample bottle Is opened, and the cup volume of resin Is added to the tarej sample vial (including septum and alumi num cap). The vial la Immediately sealed and the exact sample weight Is then obtained. Report this value on the data sheet aa It Is 43 DTH 000115095 required for calculation of RVCM. In the case of relatively dry reals sample* (water content <0.3 weight 4), 100 ^1 of distilled -jvater must be injected Into the vial, after ding and weighing, using a 100 u\ syringe. . the case of dispersion resins, the cup cannot be used. The sample la instead weighed approximately In an aluminum dish, transferred to the fared vial and weighed accurately In the vtal. The sample Is then placed in the Perfcin-Elmer head space ana lyzer (or equivalent) and conditioned tor one hour at 90*C. Non: Some aluminum vial caps have a center section which must be removed prior to placing Into Bample tray. If not removed, serious damage to the Injection needle will occur. 72.2 Suspension resin slurry and wet cake samples--Slurry must be filtered using a small Buchner funnel with vacuum to yield wet cake. The filtering process must be con tinued only ae long as a steady stream of water Is exiting from the funnel. Excessive filtration time could result In some loas of VCM. Tht wet cake sample (0.10 to 4-5 grams) is added to a taxed visa (Including septum and aluminum cap) and immediately sealed. Sample weight Is then determined to 3 deci mal place*. The sample la then placed in the Perkin-ELmer bead space analyzer (or equiva lent) and conditioned for one hour at B0*O. A sample of wet cake Is used to determine TS (total solids). This Is required for calcu lating tho RVCM. 12.3 Dispersion resin Blurry samples.-- This materiel should not be filtered. Eample must bo thoroughly mixed. Using a tared vial (Including septum and aluminum cap) add approximately fl drops (026 to 0.3S grams) of slurry or latex using a medicine dropper. This should be done immediately after mixing. Seal the vial as soon ss possible. Determine sample weight accurate to 0.001 grama. Total sample weight must not exceed 0.60' grams. Condition the vial for one hour at 90C In the analyser. Determine the TS on the slurry sample (Section 722). 7.2.4 InproceBS wastewater samples-- Using a tared vial (Including aeptum and aluminum cap) quickly add approximately 1 cc of water using a medicine dropper. Seal the vial as soon as possible. Determine sample weight accurate to 0.001 gram. Con dition the vial for two hours at 60*C In the . analyzer. 7.3 Analysis. 7.3.1 Preparation of gas chromatograph-- Install the chromatographic column and con dition overnight at I60*C. Do not connect the exit end of the column to the detector while conditioning. 7.3.1.1 Flow rate adjustments--Adjust flow rates as follows: a. Nitrogen canter gas--Set regulator on cylinder to read 60 pslg. Set regulator on chromatograph to 1.3 kg/cm*. Normal Bows at this pressure should he 26 to 40 cc/mlnute.' Check with bubble flow meter. ` b. Burner air supply--Set regulator on cyl inder to read 60 pslg. Set regulator on chromatograph to supply air to burner at a (ate between 260 and 300 cc/mlnute. Check with bubble flowmeter. 3. Hydrogen supply--Set regulator on cyl inder to read 30 pslg. Set regulator on chromatograph to supply approximately - 366 cc/mlnute. Optimize hydrogen flow to yield the most sensitive detectc response without extinguishing the flame. Check flow with bubble meter and record this flow 7.3.12 Temperature adjustments--Set temperatures os follows: a. Oven (chromatographic column), 60* C b. Dosing line. 140* C. c. Injection block, 140* C. d. Sample chamber, water temperature. 00* C1.0* C. 7.3.1.3 Ignition of flame Ionization detec tor--Ignite the detector according to the manufacturer's Instructions. 7.3.1.4 Amplifier balance--Balanoe the amplifier according to the manufacturer's Instructions. 7.3.2 Programming the chromatograph-- Program the chromatograph as follows: a. I--Dosing time--The normal setting 13 2 seconds. b. A--Analysis time--The normal setting Is 8 minutes. Certain types of samples con tain high boiling materials which can cause Interference wtlh 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--The normal setting is 0.2 minutes. d. VV--Stabilization time--The nomal set ting is 0.2 minutes. e. X--Number of analyses per sample--The normal setting Is 1. 7.3.3 Preparation of sample turntable--Be fore placing any sample Into turntable, be certain that the center section of the alu minum cap has been removed. The numbered sample bottles should be placed Is the corlespondlng numbered positions In the turn table. Insert samples In the following order: 44 DTH 000115096 ' ' / A Positions l ft 3--Old 3000 ppm standards for rerun; lcmiug. These are uerwsry only afirr tbo nimlywr lias not been used far 24 hours or longer. l',v.|u.ui 3--50 ppm standard, freshly pre pared fVMUon 4--500 ppm standard, freshly pre pared pui.i.U'ii 5--2000 ppm standard, freshly pieparoc: Position 6--4000 ppm standard. freshly pre pared. Position 7--Sample No. 7 (This le the first sample of the dsy. but Is given as 7 to be con sistent with the turntable and tbe Integrator printout!) After all samples hare been positioned, In sert the second set of 60, 500, 3000, and 4000 ppm standards. Samples, Including stand ards must be conditioned In the bath of 00* C for 1 hour (not to exceed 6 hours). 7.3.4 Start chromatograph program-- When all samples. Including standards, have been conditioned at 90' C for 1 hour, start the analysis program according to the manu facturers' Instructions. These Instructions most be carefully followed when starting and stoppizw program te prevent damage to the dosing assembly. 7.3A Determination of total solids (TS). For wet cake, slurry, resin solution, and PVC latex samples, determine TS for each sample by accurately weighing approxim ately 3 to 4 grama of sample In an aluminum pan before and after placing In a draft over (105 to 110* C). Samples must be dried to constant weight. After Hist weighing re turn the pan to the oven for a short pe riod of time and then reweigh to verify com plete dryness. TS is theu calculated as the Alls' sample weight divided by Initial sam 8ple weight. Calibration. Calibration is to be performed each elghthoui period when the instrument Is used. JEach day. prior to running samples, the col umn should be conditioned by running two of the previous days 3000 ppm standards. 8.1Preparation of Standards. Calibration standards are prepared by fill ing the vials with the vinyl chloride,'nitro gen standards, rapidly seating the septum and sealing with the aluminum cap. Use a sta'nleas steel line from the cylinder to the dal. Do not use rubber or tygon tubing. The sample line from the cylinder must be purged (into hood) for several minutes prior to filling vials. After purging, reduce the flow rate to approximately 600-1000 cc/mln. Place end of tpbtni; into vial (near bottom) and after one mbn.i.- slowly remove tubing. Pisco septum In visl as aoou as possible to ml litml7.o mixing air with aiimple. After the stand ard vials are wulcd, Inject I00pl of distilled water. 8.3 Preparation of chromatograph calibra tion curve. Prepsro two 50 ppm, two 500 ppm, two 2000 ppm, and two 4000 ppm standard samples. Run llto calibration samples In exactly the same manner as regular samples. Plot A., the Integrator area counts for each standard sample vs Cr. the concentration of vinyl chloride In each standard sample. Draw a line of best fit through the points. 9. Calculations. 9.1 Response factor. From the calibration curve described In Section 8ft, above, select the value of Ce that corresponds to A, for each sample. Com pute the response factor, Rr, for each sample, as follows: /?/=-- Equation 107-1 c* 4. v,-r, tn, -23 5 m i.4 wham V.-Vlfc) volume, oc (23JS). ft. Htujtpfo eottluSii* feat than 0.1ft wafer. C,.r~(4.HI7X 10-+--- i*f \ Wl| / Equation 107-3 Tin* folUiwlHir jM'iicmt ruuntlon cun f* usH fur any wUU-.h ctinuuiiM V OVt, l`VC atul/of water. r _ A-i'- X[*~f+ A*. (TS) Tz ~ A". (I -- TS) ra] Equation 107-4 where: if.--Total solids. J4ote: 2f. most be determined. ror a 1 ec (approximate) wastewater eample, Beputicn '19714 caa be slmpliiisd to the following: ff/l mi 1-- --1 Equation 107-5 (^ote) AUTHORITY: Section 112 of the Clean Air Act as amended bv sec. 4(a) of Pub. L. 91-604, 84 Stat. 1685 (42 U.S.C. 1857c-7); section 114 of the Clean Air Act, as amended bv sec. 4(a) of Pub. L. 91-604, 84 Stat. 1687, and by Pub. L. 93-319, sec. 6(a)(4), 88 Stat. 259 (42 U.S.C. 1857c-9); Section 301(a) of the Clean Air Act, as amended by sec. 15(c)(2) of Pub. L. 91-604, 84 Stat. 1713 (42 U.S.C. 1857g(a). DTM 00011S097