Document 85rwQErp40byJ7pNN2Lgxn6pB

Title 40 - Protection of Environment DRAFT DO NOT QUOTE OR CITL CHAPTER I - ENVIRONMENTAL PROTECTION AGENCY V< . ' 1976 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 control 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. SP1-16454 Interested parties participated in the rulemaki 1.0 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 ppm. For the oxychlorination process, vinyl chloride emissions are limited to 0.2 g/ka of ethylene dichloride product. In polyvinyl chloride plants, the standard limits vinyl chloride emissions from 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 to 400 ppm, or by using equivalent controls. Vinyl chloride emissions from reactor opening are to be reduced to C.02 g/kg polyvinyl chloride product. In both ethylene dichloride-vinyl chloride and polyvinyl chloride plants, relief valve discharges and manual venting of gases are prohibited except under emergency conditions. Fugitive 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 SPI-16455 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-resDonse model, EPA found that the rate of initiation of liver angiosarcoma among people living around uncontrolled plants is expected to range from less than one to ten cases of liver angiosarcoma per year of exposure to vinyl chloride. The 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 cancen per year of exposure among residents around 2a SPI-16456 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, FPA 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 SPI-16457 standard ,irc beneficial and will consist of vinyl chloride emission reductions of approximatedv 94 percent at ethylene dichloride-vinyl chloride plants and QS percent at oolyvinyl 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 equiDment at ethylene dichloride-vinyl chloride plants and by other petrochemical plants in the complexes where ethylene dichloride-vinyl chloride plants 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 exnected to also be controlled for the same reason. If even a moderately efficient scrubber (9P 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 olars to further evaluate the need to control hydroaen chloride emissions, since diffusion model results indicate that under "worst-case" meteorological conditions, the 3 SP1-16458 hydrogen chloride emissio n l rom 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 SPI-16459 at this time, but they are expected to overlap to some degree with the costs to meet EPA1s fugitive emission regulations. The msi' of mooting the fugitive emission regulations are included m I lie total costs cited above tor meetinq the promulgated regulation, broken out separat'd y, the capital cost of meeting the fugitive emission regulations is S37 million and the annualized cost is 325 million. the standard is not expected to deter construction of new ethylene dichloride-vinyl chloride plants or most types of new Dolyvinyl 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 hv approximately 7.3 percent in order to maintain nrecontrol orofitabi1itv 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 nrice 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 nercent to polyvinyl chloride resin prices and result in an additional maximum consumer price increase of 1 percent. 5 SPM6460 Pub I it .i1 1 i' 11m i.iii IJurinq 1 hr* public < onuiit-nt pi'tiud, !() coiiiiiiriit lotlc \ 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 vi nyl chloride under section 112. The Act specifies that EPA could remove 6 SPI-16461 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 SPI-16462 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 SPI-16463 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 reguired 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 SPl-16464 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 ill. 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 SPI-16465 such information during the comment period. Based on the information -ubmitted, EPA decided to exempt polyvinyl chloride reactors and associated equipment from applicabi1ity of the standard if the reactors are used in research and development and have a capacity of no more than 0.19 m'3 (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 3 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 SPM6466 (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 proDosed standard, FPA 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 SPl-16467 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 in 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 promulgated standard so that a rupture disc is not required if the relief valve is tied into a process line or recovery system. In this case, any leakage from the relief valve would be contained. 12 SPl-16468 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 EPA 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 SPI-16469 were received indicating a need ir>r EFA 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. These 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 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 sensitivity 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 SPI-16470 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 61.62, 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 specified levels have been revised in 61.64(e), 61.6 7(a)(2)(ii), and 61.70(c)(2) so that measurement of the vinyl chloride levels in the resins is to be made immediately after stripping is completed rather than as the resin is being 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 SPI-16471 proposed standard takes into consideration that some resins are nore difficult to strip than others by providing for averaging amono different resins. (5) Testing, Reporting, and Recordkeeping. There are several relatively minor changes in the testing, reporting, and recordkeeping requirements. A Drovision 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 timeweighted average is to be used. One commenter requested that the oxygen content and moisture content be specified for the 10 opm concentration standards. The proposed standard specified that the vinyl chloride concentration is to be corrected to 10 Dercent 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 SPI-16472 required levels, that additional controls are not required. Under the new provision, vinyl chloride escaping from the resin after it has been stripped to acceptable levels 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 SPI-16473 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 the portable 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 SPI-16474 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 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)). Date ' 'ministrator 21 SPI-16475 Part 61 of Chapter I. Title 40 nf the rode of Federal Regulations is amended as follows: 1. The table of sections for Part 61 is amended by adding a list of sections for Subpart F as follows: Subpart F - National Emission Standard for Vinyl Chloride Sec. 61.60 Applicability. 61.61 Definitions. 61.62 Emission standard for ethylene dichloride plants. 61.63 Emission standard for vinyl chloride plants. 61.64 Emission standard for polyvinyl chlorideplants. 61.65 Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants. 61.66 Equivalent equipment and procedures. 61.67 Emission tests. 61.68 Emission monitoring. 61.69 Initial report. 61.70 Semiannual report. 61.71 Recordkeeping. 2. The authority for Part 61 is revised as follows: 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 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). 3. Part 61 is amended by adding Subpart F as follows: 22 SPI-16476 Suhpart F--National Emission Standard lor Vinyl CMvtde S 61.60 Applicability. This sUbpart applies to plants which produce: fT"ethylene dkhlKWby FfcMnHTm----- oxvgen and hydrogen chloride with ethylene. .. vinyl chloride by any process. and/or (gT one or more polymers containing any fraction of polymerized vinyl chlo- ride. la; ~ (D U) '(3) (b) This subpart does not aDply to equipment used in research and development if the reactor used to polymerize the vinyl cnloride 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 subDart other than 1561.64(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 DeliiiWorn. Terms used In this subpart are defined In the Act. In subpart A of this part, or In this section as follows: (a) "Ethvlene dlchlorlde plant" In cludes any plant which produces ethylene dlchlorlde bv reaction of oxygen and hydrogen chloride with ethvlene. (b) "Vlnvl chloride plant" Includes any plant which produces vinyl chloride by any process. <c> "Polwinvl chloride plant" Includes any plant where vinyl chloride alone or In combination with other materials la 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 physleal state of the material the gauge dis charges. (el "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 far ther subdivision. <g) "Dispersion resin" means a realn manufactured In such a way as to form fluid dispersions when dispersed In s plasticizer or plastldzer/dlluent mix tures. fh) "Latex resin" means a resin which is produced bv a polymerization process which Initiates from free radical catalyst sites and Is sold undried. in "Bulk resin" means a min which is produced by a polymerization process In which no water is used. i.l) "Inproces* 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 vWeh hoe not been discharged to a wastewater treatment process or discharged untreated as wastewater. 23 SPI-16477 ik> 'WOustewoter treatment process" Includes any process which modifies characteristics such as BOD. COD. TSS, and pH. usually for the purpose of meetmg effluent guidelines and standards; It does not include any process the purpose of which is to remove vinyl chloride from water to meet requirements of this subpart. (1) "In vinyl chloride service''means__ that a piece of equipment cont&ln^jfelther 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. (ml "Vinyl chloride device which obtains 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 are vinyl chloride, with Infrared spectrophotometry, flame Ion detection, or an equivalent or alter native method. (n) "Portable hydrocarbon detector" means a device which meesnsss hydro- , earbeae with s hmUIuIIii at il least Ippiinaiil is of such design and sise that It can 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 dlchlorlde purification" Includes any part of the process of ethyl ene dlchlorlde production which follows ethylene dlchlorlde formation and In which finished ethylene dlchlorlde 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 relied discharge as defined In i 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 ethylene diehloride plants. An owner or operator of an ethylene dlchlorlde plant shall comply with the requirements of this section and | 61.65. (a) Ethylene dlchlorlde purification: The concentration of vinyl chloride In or contacts monitorinp system" deletf 24 n cxhauat gases discharged to the at mosphere from any equipment used In ethylene dlcbknide purification la not to exceed 10 ppm. except as provided In {61.05(a). Thle requlrimyt does not apply to equipment ;thatjp*SiM^^Sr i the requirement In s 61.65(b) (6) li)------------------ ib) Oxychlorlnation reactor: Except as provided In | 61.65(a). emissions of vinyl chloride to the atmosphere from each oxychlorlnation reactor are not to exceed lej'Wt tat W the 100 percent ethylene dlchlorlde prod uct from the oxychlorlnation process. has been opened, is out of operation, and met before being opened. 0.2 q/kg (0.002 lb/100 lb) $ 61.63 EffliuioD standard fear vinyl chloride plants. An owner or operator of a vinyl chlo ride plant shall comply with the require ments of this section and | 61.C5. (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 161.65(a). This re- auirement does not apply to equipment has been oDened. is out of operation, and met ttnilflfnim nxf --*1- 11-- --t **'--- i in *-------------------------------------before being opened. | 61.64 Emission standard for polyvinyl chloride plant*. An owner or operator of a polyvinyl chloride plant shall comply with the re quirements of Hti section and I 61.65. (a) Reactor: The following require ments apply to reacton: t L) The concentration of vinyl chlor ide in all exhaust gases discharged to the atmosphere from each reactor Is npt to exceed 10 ppm. except as provided In paragraph (a)(2) of this section and | 61.65(a). (2) The reactor opening loss from each reactor la not to i J n^~TS_Igni tkWMMUe (MMmvQWK Mt*4t) of polyvinyl chloride product, with the product determined on s dry solids basis. This requirement applies to any vessel which Is used as s reactor or as both a reactor and a stripper. In the bulk process, the product means the gross product of prepolymerization and postpolymerlsattan. 2 r- chloride.-V' "<0%2lh 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 operator of the source from which the discharge occurs shall submit to the Administrator e 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 that was taken to prevent the discharge, and measures adopted tc oreverit future discharges. 25 SPl-16479 - ' b > Stripper: The concentration of vinyl chloride In all exhaust gases dis charged to the atmosphere from each .^tripper is not to exceed 10 ppm. except as provided In | 61.65(a). This requiremeat does not apply to equipment that ^'SP9BS9BRHaS5S^j~requirement In | 61.65(b) (6) (1) c------ ------------------------- (c> Mixing, weighing, and holding containers: The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from each mixing, weighing, or bolding container in vinyl chloride service which,precedes the strip per (or the reactor If the plant bss no stripper) In the plant process flow Is not to exceed 10 ppm. accept es provided In J 61.65(a). This requirement does not apply to equipment that^MSpsa wna insate the requirement In i 61.65(h) (6) has been opened, is out of operation, and met before being opened. has been opened, is out of operation, and met before being opened. (d> Monomer recovery system. The concentration of vinyl chloride in all ex- haust gases discharged to th asnos- phere from each monomer recovery *ys- tem Is not to exceed 10 ppm. except as provided In i 61.65(a). This requirement .has been opened, is out of operation, and met does not apply to equipment thatsp-e^as Mid meets the requirement In S 61.65(b) (6) (l).-- ---------.----------------------- .before being opened. ve) Sources following the strlpper(s): The 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 (s) 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 lnprocess wastewater: (1) In polyvinyl chloride plants using stripping technology to control vinyl chloride emissions, the weighted average residual vinyl chloride concentration In all grades of polyvinyl chloride resin ptiroonceosnseedacthhrocuaglehndtahre dsatyri,pmpienagsuorep<eVraff-f------ imme,d. ia. te.ly after t. ,ie st. rip. pin g operation is completed, the tesla- Icnvw the rtrtppar. may not exceed: (I) 2000 ppm for polyvinyl(dispersion chloride resins, excluding latex resins (II) 400 ppm for all other polyvinyl chloride resins. Including latex resins, averaged separately for each type of res in; or r2) 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> icgiaw) kg m?n lwioo-ibi' 2 r/!'.n (0.002 lb/lb) product from the stripper(s> lor reac- tor(s ff the plant has no stripper(s)j for dispersion polyvinyl chloride resins, excluding latex resins, with the product determined on a dry solids basis; 26 SPI-16480 .... rfteA.M.r n - -- 0.4 product from the 6tripper lor reartor(a> U the plant has no atrtpper(s)? for all other polyvinyl chloride resin*. Including latex resins, with the product determined on a dry solids basis. fj/kn (0.0004 lb/1 b) 61.65 Emu*ion Htindanl for ethylene dichloride, vinyl chloride *nd polyt inyl chloride plant*. An owner or operator of an ethylene dlchloride, vinyl chloride, and/or poly vinyl chloride plant shall comply with the requirements of this section. (a) Relief valve discharge: Except for an emergency relief discharge, there is to be no discharge to the atmosphere from any relief valve on any equipment In vinyl chloride service. An emergency relief discharge means a discharge which could not have been avoided by talcing dMUit , measures lo prevent the discharge, within 10 days 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 deltnstelar the vinyl chlqrjfte. iote,jh# ,*etUm was taken to prevent the discharge, and measures adopted to prevent future dis charges. (b > Fugitive emission sources: 11 > Loading and unloading lines: Vinyl 'hlorlde emissions from loading and un loading lines/^are 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 all parts of each loading or unloading line that are to be opened to the atmosphere Is to be reduced so that the narts combined con- taln no greater of vinyl chloride. *4- standard temperature and pressure, and up Any vinyl ciiloride removed from a loading or unloading line in accord ance with paragraph ib'il'li) of this section is to be ducted through a control system from which the concentration of vinyl chloride m the exhaust gases does not exceed 10 ppm, or equivalent as pro vided In 5 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 by ducting any vinyl chloride discharge*.! 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 m 5 61.66 13' Leakage from pump, compressor, and agitator seals: <1> Rotating pumps: Vinyl chloride emissions from seals on all rotating pumps m vinyl chloride service are to be minimized by installing -sealless pumps, pumps with double mechanical seals, or equivalent as provided In 5 61.66. If double mechanical seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pres- '.. iich are opened to tOe atmosphe loading or unloading operation . 0.0038 m3 (0.13 ft3) - at 27 sure between the two seals so that any leak that occurs Is Into the pump; bp ducting any vinyl chloride between the two seals through a control system Crom which the concentration of vinyl chlo ride in the exhaust gases does not ex ceed 10 ppm; or equivalent as provided in 5 61.86. (if' Reciprocating pumps; Vinyl chlo ride emissions from seals on all recipro cating pumps in vinyl chloride service are to be minimized by installing double outboard seals, or equivalent as provided In I 61.66. If double outboard seals are used, vinyl chloride emissions from the seals are to brmlnlmlzed by maintaining' the pressure between the two seals so that any leak that occurs is into the pump; by ducting any vinyl chloride be tween the two seels 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 161.06. _________ ____ Rotating (13iWJOCH'wager: Vinyl chloride emia- sions from seals on all compressors in vinyl Chloride service are to be mini mised by compressors with double mechanical seals, or equivalent s provided in 161.66. If double mechan ical sealftjure 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 oc- _ curs Is into the/^Htib! By 'ducting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chloride to the exhaust gases does Dot exceed 10 rpm; or equivalent as provided in 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. 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^ is into the compressor; by ducting any vinyl chloride between the two seal's 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. iw Agitator: Vmyl chloride emissions (v) from seals on all agitators in vinyl chlo rine service are to be minimized by in- siah.iig agitators with double mechani cs! seals, cr equivalent as provided in 61 6; ir double mechanical seals are us;-: -.Inti chloride emissions from the 1 ' s: e to be minimized by maintaining he pressure between the two seals so any leak that occurs is into the -- anifafpd vessel : by ducting any vinyl chloride be tween the two seals through a control s'\" t. from which the concentration ol tnvl chioride in the exhaust gases does r.r"i.'xerr'r-Hfi 61!06r6p. m; or equivalent as pro- L Leakage from relief valves: Vinyl - r.: -.nde emissions due to leakage from each relief valve on equipment in vinyl cr.ionde service are to be minimized by f. :-!lire a rupture disk between the nc and the relief vah1 ^nr equiva- 3' provided In 5 61.66. : _ _ Manual venting of past ^M1 gasur ^ are manually vented from cquip- ,by connecting the relief valve discharge to a orocess line or recovery system, Except as provided in 61.64(a)(3), all rr : t vinyl ehlorjdc service are to be - ."L-c through a control system from hrr, the concent! afion of vinyl chloride tt.* exhaii'-t cases does not exceed 10 P'.x. or equivalent as provided In { QlJiS. 2ft SPI-16482 16> Opening of equipment: Vtnj'i chloride emissions from opening of equipment 4 are to W minimized as ' follows: (including loading or unloading lines that are nc opened to the atmosphere after each loading or Mi Before opening any equipment for any reason, the quantity of vinyl chlo ride is to be reduced so that the equip ment contains no more than 2.0 percent by volume vinyl chloride or"JMM 725 gal) of vinyl chloride, whichever is larger. at standard temperature and pressure; and (11 > Any vinyl chloride removed from the equipment in accordance with para graph CbHBMl) 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 5 61.66 unloading operation) 0.0950 r.i3 Samples: Unused portions of samples containing at least 10 percent by weight vinyl chloride are to be returned to the process, and sampling techniques are to be such that sample containers in vinyl chloride service are purged into a closed process system. (81 Leak detection and elimination; 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 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 j 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; (T It Includes a reliable and accilrnV vinyl chloride dotoetoqnor detection of n.vor leaks and identification of the tor oral area of the plant where a leak ;? '.cooled* -- monitoring system I" includes a reliable and accurate '--able hvdrocarbon detector to be used : y to find small leaks and to pin- ru ' the major leaks indicated by the j. : riae detector, ---------- I; provides for an acceptable cal.- nr.d maintenance schedule for ;e I chloride 4ateator\and portable : .rben detector, . Ta? location and number of point-- monitored and the frequency of provided for In the program t : - rentable when they are compared the number of pieces of equipment - 1 chloride service and the size and layout of the plant- I; contains an acceptable plan of - :o be taker, when a leak is de- *- contains a definition of leak ..c.epiable when compared with mcour.d concentrations of vin;.. I;-.-? ;r. the areas of the plant to be - - -re by the vinyl chloride i -trr.er.ts of background concen- vnv] <-hloride In the areas of The portable hydrocarbon detector is to measure hydrocarbons with a sensitivity of at least 19 DDr. -mpnitoring system monitoring system monitoring system 29 SPl-16483 ti)f plane to be monjtogyd by the vinyl monitoring system rliloririe d*4*et(are to be Included wlili the description of the program. The defi nition of leak for a given plant may vary Mitontr the different areas within `tlic plant and Is also to change over time ns background concentrations tn Wie Plant are reduced. <!>) Inproccss 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/- -cc.itaining greater than 10 ppm vinyl chloride measured immediately as It leaves a piece of equip- ' ment and before being mixed with any other inprocess wastewater stream is to be redueed tmo ppm by weigh^beidre to no more than being exposed to the atmosphere? De- fore being discharged to a wastewater treatment 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 wader 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 arith f 61.64(a) (2) or para graph <b) (6) of this section. (11) Any vinyl chloride removed tram the Inprocess wastewater in accordance with paragraph <b) (9) (i) of this section Is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm. or equivalent as provided in 5 61.66. (c) The requirements In paragraphs (b)(1), (b)(2), (b)(5), (b)(6), (b)(7) . and (t (Si af this section are to be tn- 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 measgenrtng the vinyl 11213 c) leride In equipment gal) in volume for which --afremia-1 4.75 rr3 sion limit is prescribed in 5 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 5 61.67(g) (5) (1) (A) or (g) (5) (1) (B). 61.66 Equivalent equipment and 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. S 61.67 Emission tests. (a) Unless a waiver of emission testiiig is obtained under 5 61.13, the owner or operator of a source to which this etibpart 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. 30 SPI-16484 (1) Within 90 days at the effective oat* In the case ol as existing source or a' new source which has an Initial startup date preceding the effective date, or (2) Within 90 dayB of startup In the case of a new source, Initial startup of, which occurs after the effective date. (b) The owner or operator shall pro vide the Administrator at least 30 days prior notice of an emission test to afford the Administrator the opportunity to have an observer present during the test. (c) Any emission test is to be con ducted while the equipment being tested Is operating at the maximum production rate at which the equipment will be op erated and under other relevant condi tions as may be specified by the Adminis trator based on representative perform ance of the source. The average is to be computed on a tine (d> Each emission test is to consist weighted basis. of three runs. For the purpose of deter mining emissions, the average of results of all runs Is to apply.-------------------- (e) All samples sire to be analysed/--wiunn nours , and vinyl chloride emissions are to be determined within 30 days after the emis sion 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 record* 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 reoulred bv narasranhs (g)(1). (g)(2). (g)(S), (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. 111 Test Method 106 Is to be used to determine the vinyl chloride emissions from any source for which an emission limit is prescribed in 55 61.62(a) or (b) 61.63(a), or 55 61.64<a) (I), (b). (c), or (d), or from any control system to which reactor emissions are required to be ducted In 5 61.64(a) (2) or to which fugi tive emissions are requited to be ducted in 58 61.65(b) (1) (11), (b)(2), (b)(5), ib' (6) di), or (b) (9) (11). (i) For each run, one sample Is to be collected. The sampling site Is to be at least two stack or duct diameters down 31 SPI-16485 stream and one hall diameter upstream iron) an; flow disturbance such as a bend, expansion, contraction, or visible flame. For a rectangular cross section an equivalent diameter is to be determined from the following equation: 'n n :ii. nt duimHrr -- 2 (length)_(width) length q width The sampling point in the duct Is to be at the centroid of the cross section. The sample is to be extracted at a rate proportional to the gas velocity at the sampling point. The sample Is to be taken over a minimum of one hour, and Is to contain a minimum volume of SO liters corrected to standard conditions. (11) na thieee-eastsst-- voiin.U^Wcw asitidta**afMwawtaaa^byteiilb- vtte-eaitrteaa.'n*! concentration of vinyl chloride as determined by Teat Method 10S is to be corrected to lfl Percent oxygen (flBMmMgr fbr determination of emissions by using the following equa tion: (- * l--T ... 10.9 j = C* 20.9 --percent Oj delete delete ^V.correct "Tb* oooeentrsUoo of Tinyl oblorlde la tba tftttail (mm, corrected to 10 pa C*-Th coMSotreaon of rtnyl ehlartda m HMMorod by Tsi Method lot. 20A-Pmtit orygon in tba & at toadord condition*. I0 9-Prai orygao to the ambient air s cUadard ecuuUtioDB, miaoa tba 10 pareaat otygac to which aareo- Uob U being mart*. PMOer.t Cm - pro*ct oxygen in tbe Mbs* gM m mscareo by Rtlweooe Method I la Appendix A of Part 60 of UtfaebepUr. it11) For those emission sources where the emission limit is prescribed In terms of mass rather than concentration, mass emissions in kg/100 kg product are to be determined by using the following equation: r z\rt r.n. (j in ' ! 100) Ca t * C4 1`n.vi Xr i'ritdui". ( , _ Th" (\)i >. arnUo.i of i v; i-hl.>r.,i` it'. :i..- < J ? <9D l)rMinTfV.ol lMwoltl'VlitixrlhlWuftr.td* Ht on* aimospiime utvI AfCin tt'ifi* V - \ o:iinirir tlo rot* tn m'/hr its (Vtorniinad t.? iiB/f'rBiic* Method i: of Afpei;)! Ur I'jrl <AJ c.t thi* eMptw jf> isi -iitIftritr Sot ppm. 7--l,foJu<'tir.r rat* (fcs, h: . '21 Test Method 107 is to be used to determine the concentration of vinyl chloride in each inprocess wastewater stream for which an emission limit is prescribed in { 61.65<b> i9> <i>. (3j Where a stripping operation is used to attain the emission limit in I 6184<e). emissions are to be determined using Test Method 107 as follows: < 11 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, liii Each sample Is to be.taken imme diately following the stripping operation. ay the rilwte tn,ifere*goMa-uf tta. ' delete Dili The corresponding quantity cf 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 SPI-16486 iiv' At the prior request of the Ad ministrator, the owner or operator shall provide duplicates of the samples re quired in paragraph <g)'3><i) of this section, t i i Where control technology other than or in addition to a stripping opera tion Is used to attain the emission limit in { 61.64(e). emissions are to be deter mined as follows. (l> Test Method 106 Is to be used to determine atmospheric emissions from all of the process equipment simultane ously The requirements of paragraph ig> n > of this section are to be met. ill' Test Method 107 Is to be used to determine the concentration of vinyl chloride In each lnprocess wastewater stream subject to the emission limit pre scribed In 161.64(e). The mass of vinyl chloride In kg/100 kg product In each in process wastewater stream Is to be de termined by using the following equa tion: n in-*; ;ioo) fz whar* Ox ~U rinyl chlorldWlOO kg product cone*otr**ir>n of vinyl chloride a* ;n' .urd by Tost Method 107. ft sVAter flov rmL* La I/hr. determined in ocrordunn* with * method which hM been submitted te and approved by the Administrator. KM >Convenrtoofactorfcrppm. /-Production rate (kg/hr) determined in accord ance with a method which has been submitted and approved by the Administrator. (5) The reactor opening loss for which an emission limit Is prescribed In | 61.64 (a) (3) Is to be determined. The number of reactors for which the determination is to be made la to be specified by the Administrator for each Individual plant at the time of the determination based on the plant's operation^ -- - 1 -- 11 > Except as provided In paragraph (g1 (51 til) of this section, the reactor opening loss Is to be determined usIns the following equation: W (2 60) (1IH) (Cl) YZ r*kg vinyl chloride omisslona/kg product. Capacity of ibe reactor to m*. 2.6b-- Density of vinyl chloride at erne atmosphere and 20 Clokg/zs'. K-*-Conversion factor tor ppm. O--ppm by volume vinyl chloride as determined by Teal Method 106 or a portable hydrocarbon detectote ...... ---- Y=Ncmber of batebea tfnee the reactor was last opened to the atmosphere. Z-Average kg of polyvinyl chloride produced per batch in the number of batches slnoethe 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 6 minutes within 6 Inches of the ves sel bottom, 5 minutes near the vessel center, and 5 minutes near the vessel 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 For a reactor that is also used as a striDper, the determination may be made immediately following the stripping operation. which measures hydrocarbons with a sensitivity of at least n nor. 33 SPl-16487 (C) The production rate of polyvinyl chloride (Z) Is to be determined by a method submitted to and approved by the Administrator. til) A calculation based an the number of evacuations, the vacuum Involved, and the 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. ib 1.68 Emission monitoring. (a) The vinyl chloride, monitoring system required in 61.65(b)(8)(i), 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 161.64(a) (1) (b), (c), and (d), and for any control system to wbctyh reactor emissions are required to be ducted in 561.64(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). 61.64 Initial report. (a) An owner or operator of any source to which this subpert applies shall submit statement In writing notifying the Administrator that the equipment and procedural specifications In {{ S1.6S (b)(1), (b)(2), (b)(3), (b)(4), lb)(6), (b)(6), (b)(7), and (b)(6) are being Implemented. (b) (1) In the case of an existing source or a new source which has an initial startup date preceding the effec tive date, the statement Is to be submit ted within to days of the effective date, unless a waiver of compliance is granted under 61.11, along with the informa tion required under ! 61.10. If a waiver 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, (2) A detailed eagtetertag^escrlptlon 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 SI 61.65 (b) (1X1) and (bX6Xl>, (4) A statement that each piece of equipment is Installed and that each piece of equipment and each procedure Is being used. 61.67 ^einiiinnual report. 9 delete 70 (a) The owner or operator of any source to which this subpart applies shall submit to the Administrator on wgmRw mims buulji taili lOOefu.ia a report In writ ing containing the Information required by this section. - ... - <b x 1) In the case of an existing source or a new source which h 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 S6l.il. u a waiver of compliance Is granted, the first report Is to be sub mitted on a date scheduled by the Ad- uilr -rator Seotenber 15 and March 15 of each year The first semi-annual report is to be submitted follow ing the *irst full 6 month reporting Period after the initial report is submitted. SPl-16488 (2i In the case of a new source which d not have an Initial startup date pre- ding the effective date, the first report to be submitted within 180 days of the itial startup date. (c> Unless otherwise specified, the mer or operator shall use the Test (etliods In Appendix B to this part to induct emission tests as required by aragraphs (c)(2) and (c) (3) of this ictlon. unless an equivalent or an alter ative method has been approved by the jdministrator. If the Administrator wit reasonable grounds to dispute the esults obtained by an equivalent or alernative method, be may require the use I a reference method. If the results of he reference and equivalent or alternaive methods do not agree, the results >btattled by the reference method pre vail, and the Administrator may notify he owner or operator that approval of he method previously considered to be jqulvalent or alternative is withdrawn. (1) The owner or operator shall m;lude in the report a record of any emis sions in excess of the emtwdon limits pre scribed in 85 61.63(a) or (b). 8 61.63(a), or 85 61.64(a) (1), (b), (c).or (d). or for any control system to which reactor emissions are required to be ducted in 8 61.64(a) (2) or to which fugitive emis sions are required to be ducted in 5 61.B&(b) (1) <li). (b> (2), (b)(5), (b)(6) (11), or (b)(9) (ID. The emissions are to be meaa- (2) Jnne'owner"or^cjinrator^BhaEl to? elude in the report a record of the gun tity ef wniseione at f vinyl chlorMe rem thooourocs fallowing tho stripsevCt) [oi | Hu voaetov(c) If the plant hoc bo strip pei uj1; Inr*pa8gu4uffi shlwirit plants 4ar wiitidra otripptng operation Is usad to attate-the emlsnlee limit psesertbed >b > <>t<a4e). Test Method 107 is to be used to determine eaHasMts as roilows! (1) If batch stripping is used, one rep resentative sample of polyvinyl chloride resin is to be taken from each batch of each grade of resin immediately follow ing the completion of the stripping oper ation's the main Is frsntfsrrad wut al 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. (iij 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 ol 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. iiii) The quantity of material proc essed by the stripper Is to be determined on a dry solids basis and by a method submitted Vo and approved by the Ad ministrator. (ivi At the prior request of the Ad ministrator. the owner or operator shall provide duplicates of the samples re quired in paragraphs (c>(2>iit and (c> (2> oi> 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 35 SPI-16489 iv > The report to the Administrator by the owner or operator Is to Include the vinyl chloride content found In all the samples required In paragraphs (c) (2) (i) and (c) (2) (11) at this section, aver aged separately lor each type of resin, over each calendar day and weighted ac cording to the quantity of each grade of resin processed by the stripper(s) that calendar day, according to the following equation: fl S **.*<>, P&! Af<7, -tfPoi - . . + PonMom A-2\-ht*n itv wnteMJk* typv T, rota In ppm. Q-Total pradncSoc r^Mi over Itw M-hoor pntoS.latg. T,-Typ* d ivtor, J--IX -m ebon a Mai Dumber of ram type* pnftaoed dailiic tbe 24- boarpffM. M - CaDornBMMn of vtnyl iMrahja one (ample of grade 0. ran, to ppm. . , r-ProduoHoo of pad* 0> ran iqpmntod by tbe sample, Ib kg. r Oi - Grade ofran, Ot, ft, aAd ft. n-Total somber <s greilee el ran prodooed dono( tbe 24-boui parted. (vi) The owner or operator shall re* tain at the source and make available for Inspection by the Administrator for a minimum of 2 years records of all data needed to furnish the Information re- wed by paragraph (c) (2) () of this tlon: ,rhe records are to contain the .oilowln* Information: (A) The vinyl chloride content found In all the samples required in paragraphs 'ci (2) (1) and (c) (2) (U) of this section, identified by the resin type and grade and the time and date of toe sample, and (B> The corresponding quantity of polyvinyl chloride resin processed by the strlpper(s). Identified by the resin type and grade and the time and date it represents. (3) The owner or operator shall in clude In toe report a record of the emis sions from each reactor opening for which an emission limit Is prescribed In 5 61.64(a) (2). Emissions are to be deter mined in accordance with 5 61.67(g) (5), .except that emissions for each reactor are to be determined. .... 61.7fl Recordkeeping. (a) The owner or operator of any source to which this subpart applies shall retain the following Information at the source and make It available for inspec tion by the Administrator for a mini mum of two years; (l)A record of toe leaks detected by the vinyl chloride datbetbv mill llg'W-- bien tnkiOB to repair tor leaks, as re quired by 5 61.65(b)(8). Including the' r-n tten. le concentrations of vinyl chlo- ride as measured, analy, d, and recorded by the vinyl chloride del ctor, metwdtwe the location of each measurement and the date and approximate time of each lsurement For a reactor determination that may is be also made used as a stripper, the immediately following the stripping operation. 1 monitoring svsten delete 36 5P\-'\6490 tlli- whop. tVl. I.lri'n. icqAliid ly pnragrjfrh W (1> <0' uf Hill jCHAan 1d4k-pAha wlnyf MiWe wmu uation mti niiT rnlwt mrrr4- tr&Ucn.-of glG'irtinj leak, r-jUHumUim1Wi.A^!AAtUJUluiUijiiiiiiiiH*'ltminil,/.Lamuui,tee of 4h9 itak IBMfyy aeMuu/ntompv tli nmaatafla*teMiattraiMllntMeriOct-Bttir; aJHOunMuf time (2> A record of the leaks detected during routine monitoring with the portable hydrocarbon detector and the action taken to repair the leaks, as re quired by } 61.95(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 fee wtatah nn ssnls measured in accordance with 61.68. i utIg1rJffBaWh O) ito) (V. -f4) For the relief discharged from reactors subject to the provisions of '5 61.65(^1, k dkltr bperaung record for each reactor, including pressures and temperatures. Appendix E is amended by adding Test Methods 106 and 107 as follows: Method 10$--Determination or Vinyl Chloride riou Stationary Sources Performance of this method should cot be Attempted bj persons unfamiliar with the operation of a gas chromatograph, nor by those who are unfamiliar with source sam pling. as there are man; details that are beyond the scope of this presentation. Care must be exercised to prevent exposure of Rampling personnel to rinyl cblortde, a car cinogen 1 Principle and Applicability. 1 1 An integrated bag sample of stack gas containing vinyl chloride (cbloroethylenei n subjected to chromatographic analysis, using a flame lonizatior. detector. 1 2 The method is applicable to the meas urement of vinyl chloride in stack gases from both vinyl chloride and polyvinyl chloride manufacturing processes, except where the vinyl chJorlde is contained lu particulate matter. 2 Range and Sensitivity The lower lirrn*. of detection will vary ac cording to the chrom.'.'.ocraph used. Values reported include ' : " :r and 4 >' 10 ' 3. In terfcrence.lrtin sum r,i tnterfereffoe ptrfq UwoenrspTsomuncdoi1a>taj>rr -The only compound which is known to co-elute with vinyl - vwvowrift--tstruyertfrf^yeathee- chloride is acetaldehyde. nbfortffe ywt -w T*lii umiwm l r- M2 ' doiiffnrt wewJf Tsr'v.LiOti Of the vinyi c hloride peak is not :s,fartory lo* a pai- Uvular sample, the:', .. v-mAVograph parain - pu r*' may be alic:^ Is. prior approval of acetaldehyde Uir Adir.ir.Lf.tra* T U . ..ere ic reason tp be - . hove identical retei. -a with ad present in th* ~compound -Ample. f;:tn (.'.nflrmatlon of the vi/n ! chVriUr .Trough an absohu*' :vr*alyt~V. tech.z.s ? > rh ns mrss ro*('c pv. r-e *- :*.icj --must or Mention of trade l.xjws on specific prod ucts does not .-onstitEW endorsement by the Lurtronment*: prvc*a.-Ortn Apency. 37 SPI-16491 4 Ai'jsarntu*. * ! sampling Figure !* i i 1 Probe -Stainless aleci. Pvtv*. gl*w. or Teflon tubing according to stark temperuwre. each equipped with ft gifts* wool pfetg \> remove particulate mutter 4.3 2 Sample line--Teflon. 64 mm outskie diameter. of sufficient length to connect probe to bag. A new unused piece is employed for each series of bag samples that constitutes a: i emission test. 4 1.3 Male (3) and female (2) stainless steel quick-connects, with ball checks (one pair without) located as shown in Figure 1. 4.1.4 Tedlar bags. 200 liter capacity--To contain sample 4 1.6 Bifid tearproof 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--Ljeak-fre. Minimum capac ity 2 liters per minute. 4.1.8 Charcoal tube--To prevent admis sion of vinyl chloride to atmosphere In victn- itv of samplers. 4.1 p plow meter--For observing sample flow rate; capable of measuring a flow range from 0.10 to 1 AO Uter per minute. 4.1.10 Connecting tubing--Teflon. 6.4 mm < Figure 1).outside diameter, to aesemble sample train 4.Ml Pitot tube--Type t (or equivalent), attached to the probe so that the tampUng flow rate can be regulated proportional to the stack gas velocity. 4.2 Sample recovery. 4.2.1 Tubing--Teflon. 8.4 xrm outside diameter, to connect bag to gas chromato graph sample loop. A new unused piece is employed for each series of bag samples tha* roiutinnes an emission test, and is to be diar.i.-rted upon conclusion of analysis of those je; ' Mi Analysis 4 3 : Gas chromatograph--With flame .onuruion detector, potentlometrlc strip . hart recorder and 1.0 to 5.0 ml heated sam pling loop \ii automatic sample valve. 4 3j2 Chromatographic column--Stainless steel. 2.5 m x 3.2 mm, containing 80/100 mesh Chromosorb 102. 4 3 3 Flow meters {31--Rotameter type, fl to too ml min capacity, with flow control * jive* 434 Gof regulator* -- For required gas cylinder . 4 3 5 Thermometer---Accurate to one de cree centigrade, to measure temperature of heated ample loop at time of sample Injecl Inn 4.3 rj Barometer--Accurate to 5 mm Hg, to mea* ::e atmospheric pressure around gas c.)roroKto?raph during sample analysis. 437 Pump--Leak-free Minimum capacr.. lho ml min. 4 4 Calibration. 441 Tubing--Teflon, 6 4 ram outside diameter, separate pieces marked for each calibration concentration. 4 4 2 Tedlar bags--Sixteen-inch square * -ep^rate bag marked for each calibra tion concentration. 4 4 1 Syringe--4).5 ml, gas tight 4 4 4 Syringe--50*J, gas tight, 4 4 5 Flow meter--Rotameter type, 0 to iooo m! min range accurate to 1%, to av.ter mrrogen in preparation of standard gas mixtures 4 4 5 Stop 'latch--Of known accuracy, to t.me co* flow m preparation of standard gas ^ 38 SP1-16492 ii Rcagrnts It If necessary that all reatpti'f he of chromatographic grade 5 > Analysis ' ! Helium gaa or nitrogen pa - Zr-n g um* for chromatographic carrier gns U Hydrogen gas*--Zero crude_________ __ .. ' :t Oxygen gaa^ Zero griutc :*.' t'allbralkon 1. J 1 Vinyl chloride. 00.0 1 T.--For preparallon of standard gas mixtures. 6 2 2 Calibration cylinders (3), optional-- One each of BO, 10 and B ppm vinyl chloride In nitrogen with certified snalysls. 5.2 S Nitrogen gae--Zero grade, for prep aration of standard gas mixtures. 6. Procrdure. 6.1 Sampling Assemble the sample train as In Figure 106-1. 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 tbs pump with the needle valve adjusted to yield now of 0.5 1pm. After a period of time suffi cient to purge the line several times has elapsed, connect the vacuum line to the bag and evacuate tbe bag until the rotam eter indicates no Bow. Then reposition th; sample and vacuum lines and begin the ac tual sampling, keeping the rate proportional to tbe *--a velocity. Direct the gaa eedettnd tbe rotameter awsy from sampling pBHBnnRu At the end of the sample period, shut off the' pump, disconnect the (ample line from the bag, and disconnect tbe vacuum line from tbe bag oontalner. Protect the bag container from sunlight ,or Air, as exiting ^stack required bv the detector. 6.2 Sample storage. Sample bags must be kept out of direct sunlight. When at all pos sible. analysis is to be performed within 24 hours of sample collection. 6.3 Sample recovery. With a piece of Tef lon tubing identified for that bag. connect a bag Inlet valve to the gas chromatograph sample valve. Switch the valve to withdraw gas from the bag through the sample loop. Plumb tbe equipment so the sample gaa passes from the sample valve to the leak-free pump, and then to a charcoal tube, followed by a 0-200 ml/min rotameter with flow con trol valve. 6 4 Analysis. Set the column temperature to 165* C. the detector temperature to 225* C. and the sample loop temperature to 70* C. When optimum hydrogen and oxygen flow__ rate* have been dslimiJfc*e7verlfy and main-" tain these flow rates during all chromato graph operations. Using aero helium or nitrogen as the carrier gas, establish a flow rate in tbe range consistent with the manu facturer's requirements for satisfactory cletector operation A flow rate of approxi mately 16 mJ/mLn should produce adequate separations Observe the base line periodi cally and determine that the noise level has stabilised and that base line drift has ceased. Purge the sample loop for thirty seconds at tbe rate of 100 ml/min. then activate tbe sample valve. Record the injection time (the position of the pen od the chart at the time of sample injection). the sample number, the sample loop temperature, tbe column tem perature. carrier gas flow* rate, chart speed and the attenuator setting. Record the lab oratory pressure. Prom the chart, select the peak having the retention time correspond ing to vinyl chloride, as determined in Sec* tlon 7.2. Measure the peak area. A. by use of tbe woujiuatte' integrator. Record A a53" the retention time/Repeat the Injection at 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 tion ,, u6t6rnVin6Q _j* _ " U 1 SC 39 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. Calibration and Standards. 7.1 Preparation of vinyl chloride standard gas mixtures. Evacuate a sixteen-inch square Tcellar bag that has passed a leak check (described In Section 7.4) and meter Id J.6 liters of nitrogen. While the bag la Oiling, use the 0.6 ml syringe to inject 360*1 of 88.0+ % vinyl chloride through the wall of the bag. Upon withdrawing the syringe needle. Im mediately cover the resulting hols with a place of adhesive tape. This gives a concen tration of SO ppm of vinyl chloride. In a like manner use the other syringe to prepare dilu tions having 10 and 5 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 73 Determination of vinyl chloride re tention time. This section can be performed simultaneously with Section 7.3. Establish chromatograph conditions Identical with inw In Section 63. above. Set attenuator to X 1 position. Flush the sampling loop with sero helium or nitrogen and activate the sample valve. Beooad the Injection time, the sample loop temperature, the column temperature, the carrier gas flow rate, the chart (gieed and the attenuator setting. Becord peaks and detector responses that occur In the absence of vinyl chloride. Main tain conditions. With the equipment plumb ing arranged Identically to Section 63, flush the sample loop for SO seconds at the rate of 100 ml/min with one of the vinyl chloride calibration mixtures and activate the sample valve. Becord the Injection time. Select the peak that corresponds to vinyl chloride. Measure the distance on the chart from the Injection tlme_to the time st which the peak maximum occurs. This quantity, divided by the chart speed. Is defined as the retention time. Becord. 7 3 Preparation of chromatograph cali bration curve. Make s gas chromatographic measurement of each standard gss mixture (described In Section 7.1) using conditions Identical with those listed In Bectlon S3 shove. Plush the sampling loop for 30 seconds st the rate of 100 ml min with each standard gas mixture and activate the sample valve. Record C,, the concentrations of vinyl chlo ride injected, the attenuator setting, chart speed, peak area, sample loop temperature, column temperature, carrier gaa flow rate, and retention time. Record the laboratory pressure Calculate A,, the peak area multi plied by the attenuator setting. Repeat until two injection areas are within 6%, then plot those points vs C. When the other concen trations have been plotted, draw a smooth curve through the points. Perform calibra tion dally, or before and after each set of bag samples, whichever Is mors 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 -10 cm H.o (2-4 in. R.O). Allow to stand for 10 minutes. Any displacement in the water manometer Indicates a leak. --------------------------- Check the rigid container for leaks in this manner. 40 SPi-16494 (Not*: Ad alternative teak cheok method la to praaaurm Um sag to HO em H,0 or 2-4 in. H,0 nod allow to stand overxitgbt. A deOatad bag Indicates a leak.) -- - 8. Calculations. 8 1 Determine the sample peak area as follows: A,= A,,Ar Equation 100-1 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. Vhrrr A,-Tbs aapi* peak ana. A.-Tbs measured peak ana. A/T) sttamstinn larinr SJ vinyl chloride ooncentrsttoou. From the calibration cum described In Section 7.3, aoerre, select U>e value of 0, that cor responds to A,, the sample peak eras Cal culate C, as follows: C*~ PiTr ---------------------------- There:_______ Equation 106-2 - c7-Tb eoricontratloB oi Tlnji ahloilda In the bag mmpic Id ppm. C.-Th ooacrntraaoo of nnyl chloride indicated by the fs obramoioKTOpb, la ppm. r,Tbe raternet prvura, the laboratory proasur* manM daring calibration, mm Hi. TV-The mmple loop leaperatort oo u DbcoluU r, - acak at the time of analysis. *K. Tb kbontory pwun ml ime of analysis, mm Hg. T. = The retoranoc lamparatore, tbc cample loop temperature recorded during calibration, *. 9 References 1. Brown, D. W,, Loy, S. W. And Stephen son, M. H. "Vinyl Chloride Monitoring Near the B. F. Goodrich Chemical Company In Louisville, Kentucky." Region IV, U.B. Envi ronmental Protection Agency, Surveillance and Analysis Division, Athens, Georgia, Juno 34, 1974. - 2. "Evaluation of A Collection and Analy- ` tlcal Procedure for Vinyl Chloride In Air/' by Q. D. Clayton and Associates, December ^. 13, 1974. XPA Contract No. 0&-O2-1406, Task Order No. 2. EPA Report oN. 76-VCL-l. (1 -Bi-lb ) Byb = The water vapor content of the bag sample, as analyzed. Vn\ Sp\-A6495 41 Mrruon 107--DiixmmAiiaa orViKn Cnoaipi Contiht or Imoao W151TWMSX Samples, and Vintx Cbandde Content or PoLTrom. Cm/iuDC tan, Bluest, Wet Cake, and I^atez Samples INTRODUCTION Performance or tills method should not be attempted by persons unfamiliar with the operation of a gas chromatograph, nor by those who are unlamlUar with sampling, as there are many details that ore beyond the scope of this presentation. Care must be exercised to prevent exposure of sampling personnel to vinyl chloride, a carcinogen. 1. Principle and Applicability. 1.1 The basis for this method relates to the vapor equilibrium which Is established between RVCM, FVC, resin, water, and air In a closed system. It has been demolishated that the STCU in a PVC resin will equili brate In a closed vessel quite rapidly, pro vided that the temperature of the FVC resin Is maintained above the glees transition temperature of that specific resin. 1.2 This prooeduie Is suitable lor deter mining the vinyl chloride monomer (VCM) content of Inprocess wastewater samples, and the residual vinyl chloride monomer (RVCM) content of polyvinyl chloride (FVC) resins, wet oaks, slurry, and latex samples It cannot be used for polysssr In fused form, such as sheet or cubes. If a reeolt?Qffn of the vinyl chloride peak Is not asMdactory far e particular sample, tbea chromatograph parameters may be altered with prior ap proval 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 spectroscopy, should be performed. 2. Range and Sensitivity. Tbe lower limit of detection of vinyl chlo ride will vary according to the chromato graph used. Values reported Include 1X10-' mg and 4X10-' mg. With proper calibration, tbe upper limit may be extended as needed. 3. Precision and Reproducibility. An interlaboratory comparison between seven laboratories of three resin samples, eacb split Into three parts. ytaWi, slUUra deviation of 2.63% for a sample with a mean of 2.00 ppm, 4.16% for a sample with a mean of 1.66 ppm, and 6120% for a sample wltb a mean of 62.66 ppm. 4. Safety. Do not release vinyl chloride to tbe labora tory atmosphere during preparation of stand ards. Venting or purging wltb VCM/alr mix tures must be held to s minimum. When they are required, tbe vapor must be routed to outside air. Vinyl chloride, even at low ppm levela, must never be vented Inside tbe laboratory. After vials have been analyzed, the pressure within tbe vial must be vtuted prior to removal from tbe 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 Tbe 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 12 Vials--50 ml Hypc-vlals.' sealed with Tenon faced Tuf-Bond discs for water sam ples.* vipldpd J 1 Mention of trade names on specific prod nets does not constitute endorsement by the Rnvlronmental Protection Agency. 42 SPI-16496 6.13 Electrical tape--or equivalent, to prevent loosening at bottle tope. 5.2 Sample recovery. 6.2.1 VUle--With seels and cape, Ferkin- fT.mer Cotpcratlon No. 106-0110, or equiva lent. . 5.2.2 Analytical balance--Capable of welshing to io.001 gram 5.2.3. Syringe. 100 Ml'-Prectslou Seriee mAT No. 010026, or equivalent. 5.2 4 Vial Sealer, Perkln-Elmer No. 106- 0106 or equivalent 5 3 Analyala. 6,8.1 Qaa chromatograph--Perkin -Elmer Corporation Model P-40 head-space ana lyzer. No. 104-0001. or equivalent. 5 3 2 Chromatographic column--Stain less steel. 2 nX32 mm. containing 0.4% Carbowax 1600 on Carbopak A, Perkln-Elmer Corporation No. 106-0133. or equivalent. -- 5.3.3 Thermometer--0 to 100* C, accurate to o.i* C. Perkin-Emer No. 106-0100 or equivalent. 6.3.4. Sample tray thermostat system-- Perkln-Elmer No. 105-0103, or equivalent. 6.3.6 Septa--Sandwich type, for auto matic dosing. IS mm Perkln-Elmer No. 105- 1008. or equivalent 6.3 6 Integrator - recorder -- Hewlett - Packard Model 3300A, or equivalent. 5.3.7 Filter drier assembly (8)--Perkin- Elmer No. 2230117, or equlvaJent. 6.3.6 Soap film flowmeter--Hewlett Pack ard No. 0101-0113, or equivalent. 5 4 CaUbrattonT 6.4.1 Regulators--for required gas cyin- deie. 6. Reagents. 6.1 Analyala. 61.1 Hydrogen gas--aero grade. 6>. 1.2 Nitrogen gas--aero grade. 6 1.3 Air--aero grade- Ci Calibration. 6 2 1 Standard cylinders (4)--one each or 50. 500. 2000, and 4000 ppm vinyl chloride in nitrogen, with certified analysis. 7. Procedure. 7.1 Sampling. 7.1 l 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. Hud immediately tightly cap the bottle. Wrap 'cctrical tape around the cap and bottle to nrevent the tof> irom loosening. Plane an identifying label on each bottle. record ri date. time, and sample location both on the bottles and In a log book. 7.1.2 Water sampling--Prior to use, the m' ml vials (without the discs) must be rapped with aluminum foil and muffled at "OO'C for at least one hour to destroy or remove any organic matter that could in terfere with analysis. At the sampling loca tion flu the vials bubble-free, to overflowing so that a convex meniscus forma 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. Affix an Identifying label on the bottle, and Tecord the date, time, ar.d sample location both on the vials and n a log book. All samples must be kept re frigerated until analyzed. 7 2 Sample recovery. Samples must be run wrhin 24 hours. 7.2 l Resin samples---The weight of the ream used must be between 0.1 and 4.6 grams. An exact weight must be obtained (-^0.001 gram i 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 ts 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 as it Is Carbopak C can be used in place of Carbopak A. 43 SPI-16497 required for calculation of RVCM. In the case of relatively dry resin samples (water content <0 3 weight *k). 100 A1 of distilled water must be injected into the vial, after sealing and weighing, using 100 tfl syringe, in the case ot dispersion rains, the cup cannot be used. The sample is Instead weighed approximately in an aluminum dish, transferred to the tared vial and weighed accurately In the vial. The sample is then placed in the Perkio-Elmcr head space analyaar (or equivalent) and conditioned for one hour at 00*C. Non: Some aluminum vial caps have a center section which must be removed prior to placing into sample tray. If not removed, serious damage to the injection needle will occur. ?12.2 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 as long as a steady stream of water is exiting from the funnel. Excessive filtration time could result in some toes of VCM. The wet cake sample (O.io to 4.5 grams) is added to a tared vial (including septum and aluminum cap) and immediately sealed. Sample weight la them determined to S deci mal places. The sample la then placed tn the Perkin-Slmer heed space analyzer (or equiva lent) and conditioned for one hour at 90*0. A sample of wet cake la used to determine T5 <total solids). This is required for calcu lating the BVCM. 7A.8 Dispersion resin slurry samples.--' This material should not be filtered, tample must be thoroughly mixed. Using a tared vial (including septum and aluminum cap) add approximately 8 drops (0415 to 0.35 grains) of slurry or latex using a medicine dropper. This should be done Immediately after mixing. Seal the via) as soon ae possible. Determine sample weight accurate to 0.001 grams. Total sample weight must not exceed 0.50 grams. Condition the vial for one hour at &0C in the analyzer. Determine the T9 on the slurry (Section 7.3.5). 7.2.4 Inproceea 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 bourn at OO'C in the analyzer. 7.3 Analysis. 7.3.1 Preparation of gas chromatograph-- Install the chromatographic oolumn and con dition overnight at 150*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 carrier gas--Set regulator on cylinder to read 60 psig. Bet regulator on chromatograph to 141 kg/cm*. Normal flows at this pressure Should be 35 to 40 cc/minute. Check with bubble flow meter. b. Burner air supply--Set regulator on cyl inder to read 50 pdg. Set regulator on chromatograph to supply air to burner at a rate between 350 and 300 ec/zcl&ute. Check with bubble flowmeter. 3. Hydrogen supply--Set regulator on cyl inder to read 30 psig. Set regulator on chromatograph to supply approximately cc/minute. Optimise hydrogen flow to yield the most sensitive detect* response without extinguishing the flame. Cheek flow v/itfa bubble meter and record thu flow 7.3.1.2 Temperature adjustments--Set temperatures as follows : a. Oven (chromatographic column), 50* C b Dosing line. 1*0* C. c. Injection block, 140* C. d. Sample chamber, water temperature. 90* C 1.0* 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--Balance the amplifier according to the manufacturer's Instructions. 7.3.2 Programming the chromatograph-- Program the chromatograph as follows: a. 1--Dosing time--The normal setting la 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 wtib the vinyl chloride peak on subsequent analyses. In these esses the analysis time must be adjusted to eliminate the Interference. An automated baekflush system can also be used to solve this prob lem. c. B--Flushing--The normal setting is 0.2 minutes. d. W--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 in the cor responding numbered positions In the turn table. Insert samples in the following order: 44 SPI-16498 Posltirtv. l (. 2-Old 2000 ppm standards for Conui loniu^. These we nraatr; only slier tlie nualyarr ha* not l>teu used for 24 hours or lon^r iwin.'ii 3--M> |i|im stundurd. fnobly pre pared. posit vn 4- 5tK) ppm 6iandnifl, freshly pn- pnrrii roM:u*n 5--2000 ppm RtaudHrcl, freshly prepare Posltlou t>- 4tX>0 ppm standard, freshly pre pared. Position 7--Sample No. 7 (This is the flr*t sample of the day. but is given as 7 to be con sistent with the turntable and the integrator printout, i After all samples have been positioned. In sert the second set of 60. 600. 2000. and 4000 ppm standards. Samples, including stand ards must be conditioned In the bath of &0 C for l hour (not to exceed 6 hours). 7.3.4 Start chromatograph program-- When all samples. Including standards, have been conditioned at 90' C Tor 1 hour, start the analysis program according to the manu facturers' instructions. These instructions TnT* be cwefully followed when starting and stopping program to present damage to the dosing sseembly. 7.3.6 Determination of total solids (T8). For wet cake, slurry, resin solution, and PVC Latex samples, determine T8 for each sample by accurately weighing approxim ately 3 to 4 grams of sample in an aluminum pan before and after placing in a draft ore'- (105 to 110* C) . Samples must be dried to constant weight. Alter first weighing re cur t the pan to the oven for a short pe rl nc at time and then reweigh to verify com plete drynees TS is then calculated as the fins' sample weight divided by Initial sam ple w*i^ t. 8 Ccld,ration '..Jibrn'ion k to be performed each elghtucu: period when the Instrument Is used. Each day. prior to running samples, the col umn should be conditioned by running two cf the previous days 2000 ppm standards. 8.2 Preparation cf Standards. Calibration standards are prepared by fill ing the vials with the vinyl chlorlde/nltropen standards, rapidly seating the septum and eealtug with the aluminum cap. Use a M-a'nleas steel line Cram the cylinder to the 'l*l. Do not use rubber or tygon tubing. The s-,tn;le line from the cylinder must be purged (into hnodt lor several minutes prior to filling vlalB After purging, reduce the flow rate to approximately 500-1000 ce/mm. Place end of tublm* nu> vial (near bottom) and after one mtm.i,- slowly remove tubing. Place septtin; lu vial as anou an possible to mintmi7.o mixing air with sample. After the stand ard vials are sealed, inject 100^1 of distilled water. 6.2 Preparation of :liv<mmU>graph calibra tion curve. Prepare two 50 ppm. two n(K) ppm, two 2000 ppm, in.i > 4000 ppm .standard samples. Run the calibration i.uinples In exactly the same manner as regular samples. Plot A, the lnte^rutor area counts for each standard ample 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. Prom the calibration curve described in Section 8.2, above, select the value of Cc that corresponds to A* for each sample. Com pute the response factor, Rr, for each sample, as follows: Kf~jr Equation 107-1 t 4. v,-r whom r,_ 1.4 V,-Vta) volume, oc (123.5). 6. Hdi|U- eoiituliiK lam lIiiui 0.6% water. Equation 107-3 TIi. lolltmlne (rt'iuTtil i'i|uiilinn cun I* uwrl for Buy Bumplr which ctincims \ <'M, l'VC aitihur water. A.I . K/T, rm,v L ttm, + K,(. T,S) T; K.n- rsiTjJ Equation 107-4 where: Tg--Total solids. _^iOte: Km must be determined. "ror a 1 cc (approximate) wastewater sample, Equation 107-4 can be itmplilied to the following: I- -A&.l088X1O-S VI t -H2.066X10 9.2 Residual vinyl chloride monomer centration, or vinyi chloride monomer centration. Calculate Cm. as follows: con con * If Results calculi,ted using Equation 107-4 vrepresent conoentratlon baaed on the I total sample. To obtain results baaed on dry \VC content. divide by T8. r.." -k,Pt`, 1*. Referem*. { l. Residual Vinyl Chloride Monomer Con\ tent of Polyvinyl Chloride Resin, and Wet when > cake Bamplee. B. P. Ooodrlch ChcmInal Co. Equation 107 2 I Standard Test Procedure No. 10Q6-T. B. P. I Ooodrlch Technical Center, Avon Lake, Ohio. C. *- <'<meemiuiti of vinyl chloride iu the sum pic, in ppm. Laboratory atmosphere pressure, mm Hg. I January 30, if 2. Berens, 1076. A. R,, "The Solubility of Vinyl /'i--Room temperature, K. \ Chloride In Polyvinyl Chloride," ACS-Dlvi- A/*--Moleeaiar weight of VCM (62.5). ! Bion of Polymer Chemistry, Polymer Pre V ,--V olume of vapor phase (vial volume loss sample volume). i Weight of sample, grams. / prints 15 (2) : 197, 1974. 3. Berens, A. R,, "The Diffusion of Vinyl if--Gas constant (62,360). Chloride In Polyvinyl Chloride," ACS-Divl- if--Henry's Law oonstant lor VCM In PVC at slon of Polymer Chemistry. Polymer Pre if-6A2XlO-*-Af, lor VCM la I oa approximate) wastewater sample at 90C, prints 15 ( 2): 203, 1974. jr-S.OXiO-s-AT.. 4. Berens, A. R,, L. B. Crider, C. J. Toma- T.-Eguilibratioo temperature, "K. nek and J. M. Whitney, Analysis for Vinyl If the following conditions arc met, Equation 107-2 saa be amplified as follows; j Chloride In PVC Powders by Bead-Space Gee 1. Ti-22 C <295* K\ i Chromatography," to be pablMied. Z T: -90* C (363* K . t. P#--750 irre. H?. (PR Doc 75-34513 Filed 12-23-75:8:45 am) (Uote) 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, 8A stat. 1687, and by Pub. L. 93-319, sec. 6(a)(4), 88 Stat. 259 (42 U.S.C. 1057c-9); Section 301(a) of the Clean Air Act, as amended by sec. 15(c)(2) of Pub. L. 91-604, 84 Stat. 1713 (42 U.S.C. 1857p(a). 4b SPl-16499