Document baaKpvyKLK5q9d1jY1MVrGggo

Title 40 - Protection of Environment DRAFT DO NOT QUOTE OR CITE CHAPTER I - ENVIRONMENTAL PROTECTION AGENCY r : ' T97f SUBCHAPTER C - AIR PROGRAMS PART 61 - NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS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 dichioride-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. SPI-16651 Interested parties part ie ipat^d in the rul etnaki t. : by sending comments to EPA. The comments have been carefully considered, and .-.here 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/kg 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 opm, or by using equivalent controls. Vinyl chloride emissions from reactor opening are to be reduced to 2.C2 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 Chi pride which estimates the risk from vinyl chloride exposure to populations living in the 2 SPI-16652 vicinity of vinyl chloride-en i tting plants before arid 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 usinq 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 1951 or 1995. Vinyl chloride is also expected to produce an equal number of primary cancers at other sites, for a total of somewhere between less than one and twenty cases of cancer per year of exposure among residents around 2a SPI-16653 plants. The number of tile .e ' forte v. expet.fed to be reduced in proportion to the reduction in the an'hient annual averaqe 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, CPA 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-16654 \ fdnrJdt d ri>-c I if no Hci.il -md will consist of vinyl chloride emission r f In't- ions o i nnpt'os ism to 1 v '/! percent at ethylene di ch 1 or i de-vi ny 1 chlc'ido iilapt. .m,| ot p.-ricnt at onlwinyl chloride plants. r'errentflfir numbe>m f-" 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 olants and bv other petrochemical plants in the complexes where ethylene dichioride-viny1 chloride olants are typically located. An incinerator used to attain the standard at an ethylene dichloridevinyl chloride plant could increase hydrogen chloride emissions by several fold. Typically, however, due to the corrosion problems which would otherwise occur both on plant orooerty and in the community, plants use scrubbers to control already existing hydrogen chloride emissions. Hydrogen chloride emissions resultinq from control of vinyl chloride emissions are exoected to also be controlled for the same reason. If even a moderately evident scrubber (QF! nercent control) were used tc control the hvdroqen chloride emissions resulting from incineration of vi nyl chloride emissions, the increase in hvdroqen chloride emissions dom a typical ethylene dichioride-viny1 chloride plant due to the standard would be reduced to 35 percent. However, EPA olars to rurther e/a1 >ate the need to control hydrogen chloride emif signs, since dif fuc. ion mode: results indicate that under "worst-case1, meteorol oci ca ; conditions, the 3 SPI-16655 hydrogen chloride emissic ' " ^he process equipment and the incinerator combined woo'd cause niaxin.ui: anbien* onrentra ti ons of hydrogen ch 1 ori d< in the vicinity of ethylene dich1 nr ule-vlnyl chloride plants to be in the same rannp nf 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 EP/A1 s 1 973 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-16656 at this time, but the'. a,-o ex '-h ted to overlap some ur-m ee vvi lh the .posts to mt'!'' FF'A'r I'm; i t i v t >.-. i inn r. Mil lain .re '1 ' f meeti 1 lie t m) i 11 vr ('in I o', i on i a .u ! .1 I I n .i! 1 - C I wdod io ! !v ' ! . : i > <s t , i i t r above lor meet i on th i-t imui-iuti-il n > s i; 1 a I i mi. ,i o'.iti , y , ho ccT'i tal cost of meet i no, the fu-'i ti pc mission regula t ions is S37 -i 11 ion and the annualized cos* is 323 >ri 11 ion. The standard is not e-seiV1 "c deter construction of new ethvlene dichloride-viri/i chloride plant? or most types of new polyvinyl chloride plants. For r>ne tire c* poly/iny! chloride nlant (dispersion process) that represents 13 percent of the industry production, the standard would siorificantly deter the construction of sma1ler olants. ! is estimated tha* the sorice of oolvvinyl chloride resins will rise bv approximate!'' '.3 :;erc.enr in order to maintain n rpc o n t m 1 n>'of i t a hi 1 i tv and alsn to recover the total annualized control costs necessitated by tne standard at ethylene dichloride- vinvl cnloride olancs an-1 nol-/vinyl chloride plants, this increase is estimated to translate into a ma vimur consumer nr'ce increase in goods fabricated from od /vinyl chloride resins of approximately 3.5 percent. Recover/ cr ef fl uent en-i-ja - i zed costs plus maintenance of precontrol profitability is estimated to add approximately 2 npreent to oolwinyl chloride resin prices and result in an additional -'m/imum consume-- -rice increase of ' percent. I' i;! m 11. i, i " i i,'ur i ri<i I !i` pub1 11 omiin n : ; t i-!, '.0 < uii.iii<,nl I I t on the proposed standard wen > ui i- iv.i, lh--r<> were 24 f>i;m industry; 3 from environmental groups, lb I rom federal, ' Ij+r, 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 vir.j 1 chloride under section 112. The Act specifies that EPA could remove 6 SPI-16658 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 i llness. Several other commenters agreed with EPA1s 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-16659 This qualification was state:! \'it.-;v.er 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-16660 substitutes which have not been thoroughly studied; (3) there are a number of employees, particularly in the fabrication industries, who would become at least temporarily unemployed; and (4) control technology is available which is capable of substantially reducing emissions of vinyl chloride into the atmosphere. EPA agrees that substitutes do exist or could be manufactured for most polyvinyl chloride uses. However, in general, these substitutes do not have some of the more desirable characteristics of polyvinyl chloride, such as nonflammability. If vinyl chloride and polyvinyl chloride were banned, other substitutes with these more desirable characteristics would likely be developed. EPA presently has no direct control over which substitutes are developed or used. There is a risk that these substitutes would also have adverse health or environmental effects. Since control measures are available which can reduce vinyl chloride emissions by 90 percent or more, it does not seem prudent to reduce emissions by the remaining percentage and take the risk of introducing new untested chemicals into the environment. Another approach suggested by the commenters was to base the standard for each individual emission point on cost versus benefit. Several of the fugitive emission sources were named specifically as ones for which the costs of control were substantially higher than the benefits. Although EPA did determine a cost-effectiveness ratio for the controls required for a number of emission points, EPA does not favor using cost-effectiveness ratio as the basis of the standard. Section 111 of the Clean Air Act provides for the 9 SPI-16661 development of standards based on best control technology (considering costs). In developing standards under section 111, standards are not based on a fine balancing of costs versus benefits. Instead a study is conducted to determine the affordability of the control technology required to achieve a given emission level and to determine the impact of a control level on the viability of the industry. Section 112 does not even provide for consideration of costs, so it does not seem appropriate to consider costs to a greater extent under section 112 than would be done under section 111. In developing standards under section 112 based on the best control technology, EPA felt that it was necessary to place some type of limit on the technology required. Otherwise, there are all types of theoretical controls which could be required. One limit placed on best control technology was that the costs of the technology not be grossly disproportionate to the amount of emission reduction achieved. In comparison with other emission points, the costs of controlling the fugitive emission sources mentioned by the commentators are relatively small compared with the amount of emission reduction achieved. (3) Selection of Source Categories. In the preamble to the proposed standard EPA recognized that some small research and develop ment facilities may exist where the emissions of vinyl chloride are insignificant and covering these facilities under the standard would be unnecessary and inappropriate. However, EPA did not have sufficient information available to clearly define which facilities should be excluded from the standard, and encouraged interested parties to submit 10 SPI-16662 such information durinp the comment period. Based on the information omitted, 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'5 (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 m 3 (50 gal) and no more than 4.07 m 3 (1100 gal) in capacity to meet the in 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 doinq 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 commercia1 reactors srral ler than this . 11 SPI-16663 (4) Emission Limits. T^e only major change in the emission limits between proposal and promulgation is the addition of a provision for emergency manual venting of vinyl chloride from reactors to the atmosphere. The proposed standard prohibited all manual venting to the atmosphere. In the preamble to the proposed standard, 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 ODerator and can be closed. A relief valve may become clogged with resin and not close so that all the reactor contents are lost. 11a SPI-16664 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 SPI-16665 The regulation for obtaininn 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 cornmenters 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 notrepresent 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-16666 were received indicating a need ,r>r Lit. 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-16667 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" [560.61(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), 61.67(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 stripDing has been completed but before it is transferred out of the stripper. This is consistent with the original intent of the standard. 15 SPI-16668 The regulation for loading ..nd un loading lines in .61.65(b) ( : ) has been revised to clarify that it applies only tc lines that are disconnected after each loading or unloading operation. Permanently installed pipelines that are opened infrequently for inspection or maintenance, for example, are covered by the opening of equioment regulation rather than the loading and unloading line regulation. The regulation for inprocess wastewater in the proposed standard could have been misinterpreted to require individual treatment of wastewater streams. Section 61.65(b) (9) (i) of the promulgated standard clarifies that wastewater streams that are required to be treated (i.e., those containing greater than 10 ppm vinyl chloride) can be combined to be treated. However, wastewater streams that contain greater than 10 ppm vinyl chloride cannot be combined with wastewater streams that contain less than 10 ppm vinyl chloride before treatment; i.e., dilution cannot be used to meet the standard. The commenters recommended several changes in the emission limits which have not been incorporated into the promulgated standard. These are discussed in the following paragraphs. It was recommended that the requirement for double mechanical seals on pumps, compressors, and agitators be removed because the single seals currently used on this equipment have small emissions and are more reliable than double mechanical seals. EPA is aware that each fugitive emission source, such as one pump, taken by itself causes relatively small emissions. Fugitive emissions considered as a whole are a significant source of emissions, and the goal 16 SPI-16669 of the standard is to reduce these. Double mechanical seal pumps are commonly used in the industry for emission reduction. Sealless pumps or equivalent systems are available as options to double mechanical seals. The commenters recommended increasing the averaging time for the 10 ppm limits and the emission limits for reactor opening and stripping to 30 days. Some of the commenters apparently thought that the 10 ppm limits had to be met on an instantaneous basis. However, since the performance test for determining compliance consists of three runs for a minimum of an hour each, the averaging time for the 10 ppm limit is at least three hours. Increasing the averaging time to 30 days for any of the emission limits would permit higher peak emission levels. EPA has determined that this is neither desirable nor necessary. Some commenters requested that the stripping levels for dispersion resins be made the same as for other resins and others requested that they be made less stringent. EPA decided not to make the standard for stripping dispersion resins the same as for other resins because there is sufficient evidence to indicate that these resins are more difficult to strip than other resins. With regard to making the stripping levels for dispersion resins less stringent, only one of the eight manufacturers of dispersion resins specifically commented that the dispersion resin standard should be made less stringent. Only two of several grades of dispersion resins made by this company cannot meet the 2,000 ppm limit. The 17 SPI-16670 proposed standard takes into consideration that some resins are '-ore difficult to strip than others by providing for averaging amono different resins. (5) Testing, Reporting, and Recordkeeping. There are several relatively minor chanqes in the testing, reoorting, and recordkeeDing 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 time- weighted average is to be used. One commenter requested that the oxygen content and moisture content be specified for the 10 opm concentration standards. The / prooosed standard specified that the vinyl chloride concentration is to be corrected to 10 percent oxygen (wet basis) if combustion is used as the control measure. In the promulgated standard, this requirement has been expanded to all control measures. A provision has been added to the promulgated standard which states that if a reactor is also used as a stripper, the reactor opening emissions may be determined immediately following the stripping operation. If a reactor is also used as a stripper, the resin is in the reactor when it is opened. This means that vinvl chloride in the resin which has already been stripped to acceptable levels can escape 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 U SPl-16671 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-16672 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-16673 flame detectors. When used in this way, they are capable of detectinn 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 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 'mi nistrator 21 SPI-16674 Part 61 of Chapter I. Title 40 n* tK "ode of Federal Regulations is amended as follows: 1. The table of sections for Part 61 it 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 forethylene dichloride, vinyl chloride and polyvinyl chloride plants. 61.66 Equivalent equipment and procedures. 61.67 Emission tests. 61.68 Emission monitoring. 61.65 Initial report. 61.70 Semiannual report. 61.71 Recordkeepina. 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 Subpart F--National Emission Standard lor Vinyl Chmride 6 61.60 Applicability- *" This subpart applies to plants whfcTi" produce: rf" ethylene dlchlftHfle by MftHWT 51 oxvgen and hydrogen chloride with ethylene. (f) vinyl cnionde by any process. and/or ( ff" one or more polvmers containing any fraction of polymerized vinyl chlo ride. (a) (1) (2) '(2) (b) This subpart does not aoDly to equioment used in research and development if the reactor used to polymerize the vinyl cnloride processed in the equioment has a capacity of no more than 0.19 m3 (50 gal) and the nroduct is not sold. (c) Sections of this suboart other than 61.64(a) (1), (b), (c), and (d) do not apply to equipment used in research and development if the reactor used to polymerize the vinyl chloride processed in the equipment has a capacity of greater than 0.19 m3 (50 gal) and no more than 4.07 m3 (1100 gal), and the product is not sold. $ 61.61 Defivwtsons. Terms used In this subpart are defined in the Act. tn subpart A of this part, or In this section as follows: (a) "Ethvlene dlchlortde plant" In cludes any Riant which produces ethylene dlchlortde by reaction of oxygen and hydrogen chloride with ethvlene. (bi "Vtnvl chloride plant" includes any plant which produces vinyl chloride by any process. (cl "Polwlnvl chloride plant" Includes any plant where vinyl chloride alone or In combination with other materials is polymerized. (di "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. (e> "Type of resin" means the broad classification of resin referring to the basic manufacturing process for produc ing that resin, including, but not limited to. the suspension, dispersion, latex, bulk, and solution processes. (f> "Grade of resin" means the sub division of resin classification which de scribes It as a unique resin, l.e.. the most exact description of a resin with no fur ther subdivision. (g) "Dispersion resin" means a win manufactured In such a way as to form fluid dispersions when dispersed In a plasticizer or plastlclzer/dlluent mix tures. (hi "Latex resin" means a resin which Is produced by a polymerization process which Initiates from free radical catalyst sites and Is sold undried. (11 "Bulk resin" means a resin which Is produced by a polymerization process In which no water Is used. ( fi "Inprocess wastewater" means any water which, during manufacturing or processing, comes Into direct contact with vinyl chloride or polyvinyl chloride or results from the production or use of any raw materia), Intermediate product, finished product, by-product, or waste product containing vinyl chloride or polyvinyl chloride but wMeh his not been discharged to s wastewater treatment process or discharged untreated as wastewater. 23 SPI-16676 k' 'Wastewater treatment process" Includes any process which tuodlfiee characteristics such as BOD. COD, TBS, and pH. usually for the purpose of meet ing effluent guidelines and standards; It does not Include any process the purpose of which Is to remove vinyl chloride from water to meet requirements of this subpart. il> "In vinyl chloride service" means that a plea? of equipment contalnsJJ&lther 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. ------ on) "Vinyl chloride detesteyt means a device which obtains air samples from one or more points on a continuous se quential basis and analyzes 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 measures hydrnenrbevw with a aswrltlvltg of Ertlensl 0 pyursnd Is of such design and size 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) `Run" means the net period of time during which an emission sample Is collected. iq) "Ethylene dlchlortde purification" Includes any part of the process of ethyl ene dichloride production which follows ethylene dlchlortde formation and tn which finished ethylene dlchlortde Is produced. (r) "Vinyl chloride purification" In cludes any part of the process of vinyl chloride production which follows vinyl chloride formation and in which finished vinyl chloride Is produced. (s) "Reactor" Includes any vessel In which vinyl chloride Is partially or totally polymerized Into polyvinyl chloride. (t) "Reactor opening loss" means the emissions of vinyl chloride occurring when a reactor is vented to the atmos phere for any purpose other than an emergency relief discharge as defined In | 61.65(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 rth.vlrne dicliloride plants. An owner or operator of an ethylene dlchlortde plant shall comply with the requirements of this section and | 61.65. (a) Ethylene dlchlortde purification: The concentration of vinyl chloride tn or contacts _ tnoni torinc svsteo" deletf 24 SPI-16677 aU exhaust gases discharged to ttoe at mosphere from any equipment used In ethylene dlchkuide purification Is not to exceed 10 ppm. except as provided In ta>^---t-- been opened, is out of operation, and met mti.n,--lf-f--th--e--r-e--q-u-i-r-em--e--n-t--l-n---l-6--1-.-6-5-(-b-)--(8--)-----before being opened., ib) Orychlorination reactor: Except as provided In J 61.65(a), emissions of vinyl chloride to the atmosphere from e^oxycm^on^a^notm , , ^ {r} ^ lb/10Q ]b) the 100 percent ethylare dlchlortde prod uct from the oxyehlortnation process. $61.63 Rmiuim standard for vinyl chloride plants. An owner or operator of s vinyl chlo ride plant shall comply with the require ments of this section and I 61.65. (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 quirement does not apply to equipment thnt.i<g~ifrf mid r*in tk~ --* in I 61.65(b) (6) (1).------------- ----------------- j 61.64 Emission standard for polyvinyl cldoride plants. An owner or operator of a polyvinyl chloride plant shall comply with the re quirements of thta section and f 61.65. (a) Reactor: The following require ments apply to reactors: 11) The concentration of vinyl chlor ide in all exhaust gases discharged to the atmosphere from each reactor Is opt to exceed 10 ppm, except as provided In paragraph (a)(3) of this section antf | 61.65(a). (3) The reactor opening loss from ( reactor Is not to bias been opened, is out of operation, and met before being opened. 2 -. ' rblori de -V- ItMti of polyvinyl chloride product, with the product determined on a dry solids basis. This requirement applies to any vessel which Is used as a reactor or as both a reactor and a stripper. In the bulk process, the product means the trow product of prepolymerization and poetpolymerlsatton .'.ng/'2lb 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 nanual vent valve, the owner or operator oc the source from which the discharge occurs shall submit to the Administrator c report in writing containing information on the source, nature and cause of the ciscrarge, 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 adoDted tc prevent future discharges. 25 SPI-16678 oi Stripper: The concentration of vinyi chloride In all exhaust gases dis charged to the atmosphere from each tripper Is not to exceed 10 ppm, except as provided In J 61.65(a) This require ment does not apply to equipment that _has been opened, is out of operation, and met /'S^^HESEfiF^Setts tlje requirement In i 61.65(b) (6) (1),---------------------------------------------- -- before being opened. 'c> Mixing, weighing, and holding containers: The concentration ol vinyl chloride In all exhaust gases discharged to the atmosphere from each mixing, weighing, or holding container In vinyl chloride service which, precedes the strip per (or the reactor If the plant has no stripper) in the plant process flow Is not to exceed 10 ppm, accept as provided in {61.65(a). This requirement does not apply to equipment that/s<M>h to? has been opened, is out of operation, and met . the requirement In { 61.65(b) (8) before being opened. (d) Monomer recovery system. The concentration of vinyl chloride In aU ex haust gases discharged to ths aljnosphere from each monomer recovery sys tem Is not to exceed 10 ppm. except as provided in S 61.65(a). This requirement does not apply to equipment that?3F38~ .has been opened, is out of operation, and met mid mwts the requirement in J 61.65(b) (61 (1).------------------------------------- ei Sources following the strlpper(s) : The following requirements apply to emissions of vinyl chloride to the at mosphere from the combination of all -before being opened. sources following the stripper(s) (or the reactor(s) If the plant has no strip per (s)l In the plant process flow, in cluding but not limited to, centrifuges, concentrators, blend tanks, filters, dry ers, conveyor air discharges, baggers, storage containers, and inprocess 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 processed through the stripping operation on each calendar day. measured^ . ,. , , immedldtely dfter tie Stripping operation IS completed, the regie leaves the tfrtppac. may not exceed: * 1 > 2000 ppm for polyvlnylbdtypersion resins, excluding latex resins> chloride <il) 400 ppm for all other polyvinyl chloride resins, including latex resins, averaged separately fof each type of res in; or (2) In polyvinyl chloride plants con trolling vinyl chloride emissions with technology other than stripping or In addition to stripping, emissions of vinyl chloride to the atmosphere may not exceed: (1) ikSfr-ltgklOa_lsg._UL20 Ib/lQb- Ib) -- 2 r/!:r (q. 012 lb/lb) product from the stripper (s' lor reac tor's' If the plant has no strlpper(s) 1 for dispersion polyvinyl chloride resins, excluding latex resins, with the product de'r-mlned on a dry solids basis; 26 SPI-16679 -- 1.4 product Irom ttoe stripper# for rea/'tor<s> If the plant has no *txlpper<B>l for all other polyvinyl chloride rasing. Including latex resins, with the product determined or. a dry solids basis. f/ kn (0.0004 lb/lb) 61 .('5 F.mUftion ktandunl for rtlirlcnr dirhlorolr, rinrl rhloridf and polf,inyl chloride plant*. An owner or operator of an ethylene dichloride, vinyl chloride, and/or poly vinyl chloride plant shall comply with the requirements of this section. (a) Relief valve discharge: Except for an emergency relief discharge, there is to be no discharge to the atmosphere from any relief valve on any equipment In vinyl chloride service. An emergency relief discharge means a discharge which could not have been avoided by taking IHMBMe., 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 delefBtlnlnw the viayi ehioi^^e. loss, |h* aetton th^t was taken to prevent the discharge, and measures adopted to prevent future dis charges. 1 bFugitive emission sources: ' 1 > Loading and unloading lines: Vinyl riiionde emissions from loading and un loading UnesAare to be minimized as follows: ui After each loading or unloading operation and before opening a loading or unloading hne to the atmosphere, the quantity of vinyl chloride in all parts of each loading or unloading line that arc to be opened to the atmosphere is to be reduced so that thp nans combined contatn no greater thanE^Q^^C of vinyl chloride, a* standard temperature and pressure, and ui1 Any vmyl cldonde removed from a loading or unloading line m accord ance with paragraph ib'dWii of this section is to be ducted through a control system from which the concentration of vinyl chlonde in the exhaust cases does not exceed 10 ppm, or equivalent as pro vided In 5 61.66. (0 1 Slip gauges: During load.nc or un loading operations, the vinyl chloride emissions from each slip gaug in vinyl chloride service are to be minimized by ducting any vmyl chloride discharges from the slip gauge through a control system from which the concentration of vmyl chloride in the exhaust gases does not exceed 10 ppm or equivalent as pro vided m 5 61.66 '3' Leakage from pump, compressor. and agitator seals: (i1 Rotating pumps Vmyl chloride emissions from seals on al! rotating pumps in v.nyl chloride service arc to be minimized by installing sealless pumps, pumps with double mechanical seals, or equivalent as provided in 5 61 66 If double mechanic-1 seals are used, vinvl chloride emissions from the seals are to be minimized by maintaining the pres- rich ere opened to t ie atmosohere loading or unloading operation _0.0038 m3 (0.13 ft3) - at 27 S PI kure between the tun ,<. so that any leak that occurs 1> Into '.he pump; by ducting any vinyl chloride between the two seals tlirough a control system from which the conemtcatlon of vinyl chlo ride In the exhaust gases does not ex ceed 10 ppm; or equivalent as provided In 5 61.66. Hi' Reciprocating pumps: Vinyl rlilo- ricie emission? from seuls on nil recipro cating pumps in vinyl chloride service are to be minimized by installing double outboard seals, or equivalent as provided in I 81.66. If double outboard seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining" the pressure between the two seals so that any leak that occurs Is Into the pump; by ducting any vinyl chloride be tween the two seals through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as provided In 8 61.88. ________________ Rotatl ng (UMKBbm'preswr: Vinyl chloride emls- * slons from seals on all compressors In vinyl chloride eervlce are to be mini mised by installing compressors with double nwHnaleal seals, or equivalent as provided tn I 61.66. If double mechan ical seal$_are 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- compressor curs is Into the/^tttMU by Hueting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chloride In the exhaust gases does not exceed 16 rprr.: or equivalent as provided tn S 61X3 viv) 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. If double outboard seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak thapr.u-'s 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. .**' Agitator: Vinyl chloride emissions (v) from seals on all agitators in vinyl chlo ride service are to be minimized by in- suah.ag agitators with double mechani cal seals, or equivalent as provided in : 61 33 If double mechanical seals are us;-1, vinyl chloride emissions from the ' ue to be minimized by maintaining he pressure between the two seals so '...a: any leak that occurs is into the -- agitated Vessel ; h; ducting any vinyl chloride be- d tween the two seal? through a control s1":" m from which the concentration of vu7vl chionde in the exhaust gases doe:. hy er.-,'^ri 10 ppm; or equivalent as pro w-led in S 61 66. 1 11 Leakage from relief valves: Vinyl r_: inde emission? due to leakage from each relief valve or. equipment in vinyl cnionde service are to be minimized by a rupture disk between the __,uy connecting the relief valve discharge tc a : - apd the relief vah>pr equiva- orocess line or recovery system, . a? provided in 16166. ______ ___ JJ ' r Manual venting of past ^Aii pa?.- Except as provided in 561.64(a)(3), all ~ are mar.uallv vented from equin- -T :.t nr.;-1 chloride service are to be :-tec through a control system from l.nh the concent: a'lon of vinyl chloride . exhaust cases docs not exceed 10 p? p: ?r equivalent a? provided tn 5 51^6. _r SPI-16681 'G' Opening of equjpment: Viny chloride emissions from opening of equipment^are to be minimized as follows: *1' Before opening any equipment for nnv 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 orTOpBTTJ'T gal' of vinyl chloride, whichever is larger, at standard temperature and pressure: and ill Any vinyl chloride removed from the equipment In accordance with para graph (b>(6'(t) of this section is to-be ducted through a control system from which the concentration of vinyl chlo ride In the exhaust Rases does not exceed 10 ppm. or equivalent as provided in 5 61 86. 8' Leak detection and elimination: Vinyl chloride emissions due to leaks f rom 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 cf compliance Is granted under 5 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: -i' It includes a rellahle and accurate vinyl chloride doteetomor detection of rt.vor leaks nnd identification of the general area of the plant where a leak '.orated* (including loading or unloading lines tnat are not opened to the atmosphere after each loading or unloading operation) 0.0950 :13 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. - mon j t Or j n Q SyS^em I- include-; a reliable and accurate ble hydrocarbon detector to be used to find small leaks and to pin 'd-.? ma;or leaks indicated by the ride dates tor, ---------- provides for an acceptable cuhr. tir.d maintenance schedule for 1 chloride datofltaryand portable - rben detector, T.-.e location arid number of point-- n-.cr.itored nnd the frequency of t-rjig provided for in the program '.'eatable when they are compared the number of pieces of equipment : chloride service and the size nnd layout of the plant, ft contains an acceptable plan of - to be taker, when a leak is de- r. tains a definition of Ic^. stable v.hcn compared v.rh :r.cT concentrations of v;n\. he iren.c of the plarrt. to be the vinyl chloride t s of barkL'rcnmd concer- 1 * blonde In the ftreas ol Tne portable hydrocarbon detector is to measure hydrocarbons with a sensitivity o-f at least 10 0Dr\ npr,itoring system monitoring system monitorir\r sys ten 29 SPI-16682 t/c plant to be monltaffd by the vinyl non itorihc r'llorif'p oUw> airfare to be Included with the clcvcriiiticn of the prorrnm. The defl- i.iticm o: le ak far n Riven plant may vary nmniirr the different area.1! within `ihr plant and is also to chance over time a< background concentrations in tiie [ilant are reduced. ill) Inproeess wastewater: Vinyl chlo ride emissions to the atmosphere f**m inproeess wastewater are to be reduced ns follows: (i) The concentration of vinyl chlo ride In each inproeess wastewater stream/ containing greater than 10 ppm vinyl chloride measured immediately as it leaves a piece of equip- ` ment and before being mixed with any other lnprocs wastewater stream Is to no more than to be reduced ppm by, weignfrberore ~~ being exposed to ttoe atmosphere* < Mfore being discharged to a wastewater treatment process] or discharged un before being mixed with any other inprocess wastewater stream which contains less than lOppm vinyl chloride; treated as a wastewater. This paragraph does apply to warter 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) (8) of this section, but does not apply to water which is used to wash out equipment after the equipment has already been opened to the atmosphere In accordance with t 81.64(a) (2) or para graph (b)(6) of this section. (il) Any vinyl chloride removed from the inprocess wastewater In accordance with paragraph (b) (9) (1) 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 ! 61.66. (c) The requirements In paragraphs (b)(1). (b)(2), <b><5>. (b)(8). (b)(7) and (hi (8) of this section are to be In corporated into a standard operating procedure, and made available upon re quest for Inspection by the Administra tor. The standard operating procedure Is to Include provisions for measurlnsOto^ A.75 vinyl c icrlde in equipment '-CBM l (I2j0 gal) in volume for which an'emls- sion limit Is prescribed In i 61.65(b) (6) (1) prior to opening the equipment and using Test Method 106, a portable hydro carbon detector, or an equivalent or al ternative method. The method of meas urement Is to meet the requirements In ! 61.87(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, 61.67 Emission tesU. (a) Unless a waiver of emission tetir\g H obtained under {61.13, the owner or operator of a source to which this sub part applies shall test emission! 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-16683 (1) Wlthift 90 days of the effective ante in the case of an existing source or a' new source which has an Initial startup date preceding the effective date, or 12> Within 90 days of startup in the rase of a new source, Initial startup of. which occurs after the effective date ib) 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 ot the source. (d) Bach emission test Is to consist of three runs. For the purpose of deter T'ie averaae is to be computed on a tine weiqhted basis. mining emissions, the average of results of all runs Is to apply. (e) All samples are -------------to be analyzed/-- within 24 hours, 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 i 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 required bv paragraphs igill), (g)(2). (g)(3), (g)(4), and (g)(5) of this section, unless an equiva lent method or an alternative method has been approved by the Administrator If the Administrator finds reasonable grounds to dispute the results obtained by an equivalent or alternative method, he may require the use of a reference method. If the results of the reference and equivalent or alternative methods do not agree, the results obtained by the reference method prevail, and the Ad ministrator may notify the owner or operator thRt approval of the method previously considered to be equivalent or alternative is withdrawn. (11 Test Method 106 is to be used to determine the vinyl chloride emissions from any source lor which an emission limit is prescribed in S 61.62(a) or (b) 5 61.63la>. or $1 61.64(&' (1). (b), (c). or (d), or from any control system to which reactor emissions are required to be ducted In i 61.64(a) (2) or to which fugi tive emissions are required to be ducted in 5 61.65(b) (1 > (11), (b)(2), (b)(5), ' b' 16) (ID , or (b) (9) (11). . i i > For each run, one sample is to be collected. The sampling site is to be at leRst two stack or duct diameters down- SP1-16684 stream and one half diameter upstream irom any flow disturbance such as a bT.d expansion, contraction, or visible (lame. For a rectangular cross section an equivalent diameter Is to be determined i : the following equation : 't flianichT k'Jlgttl) ( WldUl length t width The sampling point In the duct Is to be at the centroid of the cross section. The sample Is to be extracted at a rate proportional to the gas velocity at the sampling point. The sample Is to be taken over a minimum of one hour, and Is to contain a minimum volume of 50 liters corrected to standard conditions, till H thn i-IiHib nuill8wIilhj MM --telo- i.'Bte concentration of vinyl chlorida as determined by Teat Method 108 Is to be oorTected to lfl aereart oxygen UMMIt rer determination of emissions by using the following equa tion : J -- C* ;; 10.9 20.9 -- percent Oj delete ^ delete C>,correif<l) cooo*ntnuioti of vinyl chlortd* to tPhetNaCb*OftiTia7gtgCuLMs, corrected to lc p*r- C-Tb axmotnaoc of vinyl cbkrid* w meoaorod by Test Method 106. 20- PsfftoanndtaordsyaotmodJiOnontAt. ">>* aiz a* 10.9--PaiTMnt ory|8o In the unblrat air at standard oooditiODS, mian U 10 pareact oiyfw to which tbs uam- Uoq Ls befog mads. pf:c<Oj-Peroect oiyreo to tbs sibnat faa aa msMoraa by Reference Method I la Appaodii A oi Fan 90 of thieoheptsr. till) For those emission sources where the emission limit Is prescribed In terms of mass rather than concentration, mass emissions m kgylOO kg product are to be determined by using the following equation: L' r.o (j i f> ' moi /. whv* Cg i - >n :iorif kr v. )u, lx i1 ? *8 !>ir->iq'|Iiycv-ot i Mrvt'>ttvvni JrbIu"6rt>r on* au-os|;hvc iv t Ai` in ze 111*. V * ^ a um^iric ilow rat# In rrVhr as iV'Th-rr,!i'i l,v KpfiTr.icp Mot'iud v Aj'privl t .'. Ur T iri >AI !<v-i >mf tviell?rsoohnviniviwto.'-for pprr. 7 =- l to Ui-'tmr r.ile ;K?. hr . < 2 ' Test Method 107 Is to be used lo determine the concentration of vinyl chloride in each inprocess wastewater stream for which an emission limit is prescribed In S 61.65(bi (9* U). (3) Where a stripping operation ls used to attain the emission limit In J 61.84'e), emissions are to be determined using Test Method 107 as follows: 11 j 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. ilii Each sample Is to be taken Imme diately following the stripping operation. Will* Lit tfl! delete ulli 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 SPI-16685 iv At the prior request of the Acintr.istralor, the owner or operator shall provide duplicates of the samples re quired in paragraph < g > <3 1' i> of this section i i' Where control technology other than or in addition to a stripping opera tion is used to attaLn the emission limit in 5 61.64` e>. emissions are to be deter mined as follows: it> Test Method 106 is to be used to determine atmospheric emissions from all of the process equipment simultane ously The requirements of paragraph t g' 11. of this section are to be met. 'll1 Test Method 107 Is to be used to determine the concentration of vinyl chloride In each Inprocess wastewater stream subject to the emission limit pre scribed In J 61.64(e). The mass of vinyl chloride In kg/100 kg product In each in process wastewater stream Is to be de termined by using the following equa tion : r r, n Hi :rnv WbftTd Cf i tit vinyl chlofldu/100 kjz product t '* '.he <'<?noaotrhnj! of vinyl chloride h.-- n.i.wured by Twt Method 107. K wwaiat Sow nOe In i/hr. determined in arvordai /w with e method which has been submitted m and approved by the Administrator. icr4 -Convtrafoo (actor tor ppm. / -1 *roducUon rate (kg/hr). determined In acrcwdance with method which has been submitted and appro red 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 Is to be specified by the Administrator for each Individual plant nt the time of the determination based on the plant's operation^- -------------------- ili Except as provided In paragraph (g1 (5) (11) of this section, the reactor opening loss Is to be determined uslns the following equation: ,, W (2.60) flO-) (Cb) C ~ YZ ( -kg vinyl cblorideemiaslons/kg product. W-Capacity of t-b reactor in tn. 2.60-Density of vinyl chloride at one atmosphere and 20 CJnkg/m*. Conversion factor tor pptn. C6 --ppm by volume vinyl chloride as determined by Test Method 106 or a portable hydrocarbon detactoyw -- -- l'-Namber o! batches dace the reactor was tost opened to the atmosphere. Z-Average kg of poiyvinyl chloride produced per batch in the Dumber of batches since tbe reactor was last opened to the atmosphere. (A) If Method 106 Is used to deter mine the concentration of vinyl chloride (Cb), the sample Is to be withdrawn at a constant rate with a probe of sufficient length to reach the vessel bottom from the manhole. Samples are to be taken for 5 minutes within 6 Inches of the ves sel bottom, 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 withm 6 inches of the vessel bottom, one near tiie vessel center and one near the vessd 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 stripper, the determination may be made immediately followin g the stripping operation. which measures hydrocarbons with a sensitivity of at least n pd'-. 33 SPM6686 iC' The production rate of polyvinyl -deride (Z> Is to be determined by a ettioc! submitted to and approved by the Adm Inisfcro tor. ill1 A calculation based on the number of evacuations, the vacuum Involved, and tne 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. d:.c8 emission nc"-'i tori ng. (a) The vinyl chloride. mom tori nc 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 ror which emission limits are prescribed in 61.62(a) and (b), 61.63(a), and 61.64(a) 'l)(b), (c), and (d), and for any control system to whe^'h reactor emissions are required to be ducted in 61.64(a)(2) or to which fugitive emissions are required to de ducted in 61.65(b)(1)(ii), and (b)(2), (b)(5), (b)(6)(ii), and (b)(9)(ii). % 61.64 Initial report. V9 (a) An owner or operator of any source to which this subpart applies shall submit statement In writing notifying the Administrator that the equipment and procedural specifications In 61.65 (b)(1). (b)(2), (b)(3), (b)(4), (b)(6). <b>(6>, (b)(7), and (b)(8) are being Implemented. (b) (1) In the case of an existing source or a new source which has an initial startup date preceding the effec tive date, the statement Is to be submit ted within 80 days of the effective date, unless a waiver of compliance Is granted under 5 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 engincertBg-*/aescrlp- tlon of the physical and functional char acteristics of each piece of equipment, <3) A description of the methods which have been Incorporated Into the standard operating procedures for meas uring or calculating the emissions for which emission limits are prescribed In i! 61.65 (b) (1)(D and (b)(6) (1), (4) A statement that each piece of equipment Is Installed and that each piece of equipment and each procedure is being used. delete o 61.gd Scmiumuial report. (a) The owner or operator of any source to which this subpart applies shall submit to the Administrator on Mmw baalveaiih lOfrdine a report In writ ing containing the information required by this section. ------ ---- -- < b' (1) In the c ase of an existing source or a new source which has an Initial startup date preceding the effective date, the first report Is to be submitted within 180 days of the effective date, unless a waiver of compliance Is granted under 5 61.11. If a waiver of compliance Is granted, the first report Is to be sub mitted on a date scheduled by the Adu.tr -rato:. Teotenber 15 and March 15 of each year The first seni-annual report is to be submi ted foi 1ow1nq the first full 6 month reporting oeriod p ft c. < initial report is submitted. 34 SPI-16687 (1'1 the case of a new source which d not have an Initial startup date preding liie eflcctlve date, the first report to be submitted within 180 days of the ltlal startuu date. tc i Unlose otherwise specified, the vner or operator shall use the Test 'ctliods In Appendix B to this part to induct emission tests as required by aragraplis <c 1 111 > and tc> (3) of this iction, unless an equivalent or an alter ative method has been approved by the dmlnistrator. If the Administrator nds reasonable grounds to dispute the esults obtained by an equivalent or aiernatlve method, be may require the use f a reference method. If the results of he reference and equivalent or altemalve methods do not agree, the results btalhed by the reference method preail, and the Administrator may notify he owner or operator that approval of he method previously considered to be equivalent or alternative Is withdrawn (1) The owner or operator shall ta;lude In the report a record at any emis sions In excess of the emission limits pre scribed In f! 61.63(a) or (b>, (61.63(a), or (9 81.64(a) (1), <b), <c), or (d), or for any control system to which reactor emissions are required to be ducted In ! 61.64(a) (2) or to which fugitive emis sions are required to be ducted In I 61.65*(bHlXUl. (b)(2). (b)(5), (b)(6) (11). or (b)(9)(H). The emissions are to be meaa-' ured with-a wlmrl ahhirtds-deteeUwe **' (2) owner or operator shall In* elude In the report a record of the-auaa- tity ef emleeioiM ot i vinyl chloride eeaa- tho pouioee fellowinp tho trippci'(rr-[ui - Hit roaeloixt) If the plont hoe no ttrlp ]M**e*^>lTr?epsriBpfcMerlde-plaatp4o* wHull a otrippteg operation Is unad to astubfthe emlerlow limit prescribed la ) . Test Method 107 la to be used to determine emtseWte as follows: (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 ogeratlonlba the tesla. Is trnrfarrad-wut at 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. (ti) 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 resm flows out of the stripper and Iden tified by resin type and grade and the date and time the sample was taken. The corresponding quantity of material processed by each stripper over the time period represented by the sample during the eight hour period. Is to be recorded and identified by resin type and grade and the date and time It represents. i liii The quantity of material proc essed by the stripper Is to be determined on a dry solids basis and by a method submitted to and approved by the Ad ministrator uv At the prior request of the Ad ministrator. the owner or operator shall provide duplicates of the samples re quired In paragraphs tc'<2wli and <c' (.2 (u i 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 561.64(e), content in the polyvinyl chloride resin. vinyl chloride content SPI-16688 tv The report to the Administrator by tiie coner or operator Is to Include the v:r>l chloride content found In all the samples required In paragraphs (c) (2) (i) and (c> (2) (111 of this section, aver aged separately tor each type of resin, over each calendar day and weighted ac cording to the quantity of each grade of resin processed by the strlpper(s) that calendar day. according to the following equation: 2 Pa, -Wo, , il P&i A/<7, -f-Po, . -+* Pon Mom "` u'i A = 34-hour iim raarataIMtauf type T, rata in ppm. Q* Total predocfcp rftype T/tata o^er tbe 24-boar pa4o6, la kf. * T. * T7pe at ratzr, 1A ...m * to total uumber of rata type* pn&tueed daring tbe 34- boor period. M = Casoeotratten at Ttnyl ehloeKe ta cot eemple of grade <7, resin, tn ppm. * * reproduction of pait Q\ reon rtptMsted by tbe sample, is kg. r Ci- Grade of ream, e.g., Ci, 0i,lAd 0%. n - Total somber of gzadas rf ram prodooed dortac tbe 24-boor period. (vi) The owner or operator shall re tain at the source and make available for inspection by the Administrator for a minimum of 2 years records of all data Deeded to furnish the Information re- red by paragraph (c) (2) (v> of this tlon: "T\e records are to contain the .ollowlnt information: iA> The vinyl chloride content found in all the samples required In paragraphs ci (2) (1> and (c> <2> (11) of this section, identified by the resin type and grade and the time and date of the sample, and (B * The corresponding quantity of polyvinyl chloride resin processed by the stripper(s), Identified by the resin type and grade and the time and date it represents. (3) Hie owner or operator shall in clude In the report a record of the emis sions from each reactor opening for which an emission limit is prescribed in 5 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.r*fcordkeeping. 1 ` ^ (a) The owner or operator of any 'N For a reactor determination that may is be also made imusmededaiastealysftoripl1 poweirn,g the the stripping operation. source to which this subpart applies shall retain the following information at the I 1 source and make it available for Inspec tion by the Administrator for a mini mum of two years; d' A record of the leaks detected by monitorirc system the vinyl chloride datoetop wid tlW ur--- twn takon to repair the leaks, as re quired by 5 61.65(b)(8). including Wee lellaewwginlarmallun delete The concentrations of vinyl chlo ride as measured, analy, d. and recorded by the vinyl chloride del ctor. imirnttme the location of each measurement and the date and approximate time of ea:h 'asureinent 36 SPM6689 Inin Ill-l^lllri t pM'ggr;' .:ih nation friimTTTtrtnt gTrrrr^ >hf -^n trau>>nof wfaiyl ahtat* !*. m- statement4m df teftjrtfffP!?--IP matte Wiartteakniiiil Die nMteHaMWMffir <2' A record of the leaks detected during routine monitoring with the portable hydrocarbon detector and the action taken to repair the leaks, as re quired by 5 61.8S(b) <8>, Including a brief statement explaining the location and cause of each leak detected with the portable hydrocarbon detector, the date and time of the leak and any action taken to eliminate that leak. (3) A record of emisslo measured in accordance with 61.68. '(4) For the relief discharged from reactors subject to the provisions of "S 61.65(^1, a flUIy'fiberaang record for each reactor, including pressures and temperatures. 4* Appendix E is amended by adding Test Methods 106 and 107 as follows: Method 106-~Dm:RjfiiNATioN or Vintl Chlorid* from Stationart Sources mOOOCTBOM Performance of this method should not be attempted by persona unfamiliar with the operation of a gas chromatograph, nor by those who are unfamiliar with source sam pling, as there are many details that are beyond the scope of this presentation. Care must he exercised to prevent exposure of sampling personnel to vinyl chloride, a car cinogen. J Principle and Applicability. 1 l An Integrated hag sample of stack gas containing vinyl chloride ichloroethylenej is subjected to chroauttographlc analysis, Using a flame lonUatJor; detector. 1 2 The method ; applicable to the meas urement of vinyl chloride in stack gases from both vinyl chloride and polyvinyl chloride manufacturing process^*, except where the vinyl rhloride Is contained In particulate matter. 2 Ranee and ^'nsitiT.t;- The lov.er Im..: of detection will vary ac cording to the rhJvmnTocrauh used Values reported mclv.de ' . n ^.nd 4 ' 10 mg. 3 In terlcrer.cc _____ -The only compound which is known to co-elute win ipumwi'~l` j klsiillfj the mterferame putyriia.1 vp- seeetrf -hy chloride is acetaldehyde. 'iooM awaoouia# wliU >*uyfr f^turi\WT v. exy'tQtm/l f proved* lEsuldViim-wf the wtayi cdharlourffCr.TnP 'lpltg'iseftt wwi *Jfsr s''v.:.ior of the vtny 1 thloride peak not a: :Martc.ry fo" a pai - \i-\ihvr sample, th-" .maiopraph param- *.t m;\y Pe a 1: i r .-*>4 prior approval of ?h<- tJn-r L-l.-a- -* ..ere l* reason acetaldehyde or thntVsom? :de'..'l'al retei aefrow with an present In th'- compound f ' nflrn.atlon of u h mi absol r u*' h'- onr.'-' * ~ - vi n A --must Mention of triwie :aae on epecJflc prod ucts does not c-.'tvstuew endorsement by the fcfirironmental Prvtev-taoa Apency 3/ SPI-16690 i Apparatus 4 ; sampling i Vlyure H i : \ Vrr>bo -Stainless steel. Pvtv. gi*w. r Teflon tubing nccordlns to stack temperirv. onoh equtpped with a glass wool plug : r- :no\ e particulate matter 4 1 2 Sample line--Teflon. 8 4 mm out^lUe diameter. of sufficient length lo connect .nrobe to bag. A new unused piece Is employed lor each series of bag samples that constitutes g;i emission test. 4 I S Male (2) and female (2) stainless steel quick-connects, -with ball checks (one pair without) located as shown In Figure l. 4 1.4 Tedlar bags, 100 liter capacity--To contain sample 4.1.6 Rigid leakproof containers for 4 1.4, with covering to protect contents from sun light 4.1.6 Needle valve--To adjust sample flow rate 4.1.7 Pump--Leak-free. Minimum capac ity 2 liters per minute. 4.1.8 Charcoal tube--To prevent admis sion of vinyl chloride to atmosphere In vicln- 1; ? of samplers. 4.1.9 now meter--For obeerving sample flow rata; capable of measuring a flow range from 0.10 to 100 liter per minute. 4.1.10 Connecting tubing--Teflon. 0 4 mm outside diameter, to aesemble sample train I Figure 1) - ---------------- - S 4 111 Pitot tube--'Type f (or equivalent), attached to the probe so that the i ampling flow rate can be regulated proportional to the stack gas velocity. 4 2 Sample recovery. 4J2.1 Tubing--Teflon, 8.4 rrm outside diameter, to connect bag to gas chromato graph sample loop A new unused piece is employed for each series of bag samples that constitutes an emission test, and Is to be dis.. rr.eq upon conclusion of analysis of those D;l_ - 4 3 Anahsis < 7 ; Gas chromatograph--With flame .Mu/mion detector, potemiometrlc strip nart recorder and 1.0 to 5.0 ml heated sam pling loop in automatic sample valve. 4 3.2 Chromatographic column--Stainless steel, 2.5 m ;< 3.2 mm. containing 80/100 mesh Chromostorb 102. 43 J Flow meters (2i--Rotameter type, 0 to iho ml min capacity, with flow control 434 Grvp regulator*--For required gaa cylinder . 4 3 5 Thermometer--Accurate to one de gree centigrade, to measure temperature of heated ample loop at time of sample Injec: i .i 11 4 3 C Barometer--Accurate to 5 mm Hg, to me a? atmospheric pressure around gas lnromaioeraph during sample analysis. 437 Pump--Leak-free Minimum capac.;. l oo ml min. 4 4 Calibration. 4 4 i Tubing--Teflon, 6.4 mm outside dtameter separate pieces marked for each calibration concentration. 4 42 Tedlar bags--Sixteen-Inch square *. p -eparate bag marked for each calibra tion concentration. 4 4 3 Syringe--0.5 ml. gas tight. SyTinge--50#J, gas tight. 4 4 5 Flow meter--Rotameter type, 0 to m: min range accurate to 1%, to nirrogen la preparation of standard aa* mixture: 4 4 6 Stop > atch--Of known accuracy, to t.rne pas fioj sn preparation of standard gas 38 SPI-16691 F-?cage!:,s It if necessary that all rea- i r:= rye of chromaiographlc grade Analysis ' Helium or nitreven for chromntocraphic eurrter j Hydrogen ^u>--^tTQ griulr____________ ' i Oxygen ga^2ero_:ru!e calibration ,:i vinyl chloride f>9 P i r; --For prrj>arailo:i of standard gas mixtures. 5 2 2 Calibration cylinders (3), optional-- One each of 60. 10 and 6 ppm vinyl chloride in nitrogen with certified analysis 5.2 3 Nitrogen gas--Zero grade, for prep aration of standard gas mixtures. q jr l\\ V ^ " R Procedure. C l Sampling Assemble the sample train a= in Figure U)6-l Perform a bag leak check according to Section 7.4. Observe that all connections between the bag and the probe are tight Place the end of the probe at the centroid of the stack and start the pump with the needle valve adjusted to yield a flow of 0.5 1pm. After a period of time suffi cient to purge the line several times has elapsed, connect the vacuum line to the bag and evacuate the bag until the rotam eter Indicates no flow. Then reposition th$ sample and vacuum lines and begin the ac tual sampling, keeping the rate proportional. e X i t i fl Q to the g--efc Telocity. Direct the gee eetettn^r------- the rotameter ewmy from eampllug pMWAIBR ^ At the end of the sample period, shut off the pump, disconnect the sample line from the bag. and disconnect the Tscuum line from Stack the bag container Protect the bag container from sunlight (V. require 6.2 Sample storage. Sample bags must be kept out of direct sunlight. When at all pos sible. analysis is to be performed within 24 hours of sample collection. 6 3 Sample recovery With a piece of Tef lon tubing Identified for that bag. connect a bag Inlet valve to the gas chromatograph sample valve. Switch the valve to withdraw gas from the bag through the sample loop. Plumb the equipment so the sample gas passes from the sample valve to the leak-free pump, and then to a charcoal tube, followed by a 0-100 ml/min rotameter with flow con trol valve. 6.4 Analysis. Set the column temperature to 155* C. the detector temperature to 225* C. and the sample loop temperature to 70* C. When optimum hydrogen and oxygen flow rates have been determine, verify and maintain these flow rates during all chromato graph operations. Using zero helium or nitrogen as the carrier gas, establish a flow rate in the range consistent with the manufacturer s requirements for satisfactory tletector operation. A flow rate of approxi mately 16 ml/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 the rate of 100 ml/mln, then activate the sample valve. Record the Injection time (the position of the pen on the chart at the time of sample injection). the sample number, the sample loop temperature, the column tem perature. carrier gas flow rate, chart speed and the attenuator setting. Record the lab oratory pressure. From the chart. 6elect the peak having the retention time correspond ing to vinyl chloride, as determined In Sec* tlon 12. Measure the peak arear A. by use of febe vutuuiAlk^ integrator Record Aa and 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 determined a disc bv the detector. 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 baq. 7. Calibration and Standards. 7.1 Preparation of vinyl chloride standard g&B mixtures. Evacuate a slxteen-lnch square Tedlax bag that has passed a leak check (described In Section 7.4) and meter kTSI) liters of nitrogen. While the bag la filling, use the 0.5 ml syringe to Inject 250*1 of 09.0+ % vinyl chloride through the wall of the hag. Upon withdrawing the syringe needle. Im mediately cover the resulting hole with a piece of adhesive tape. This gives s concen tration of 50 ppm of vinyl chloride. In a Uke 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 deprws opposite sides of the bag 00 times to turther mix the gases. 72 Determination of vinyl chloride re tention time. This section oan he performed simultaneously with Section 7.3. Establish chromatograph conditions Identical with those la Section 52, above. Set attenuator to X 1 position. Flush the sampling loop with esro helium or nitrogen and activate the sample valve. Beoord the Injection time, the sample loop temperature, the column temperature, the carrier gas flew rats, ths chart *>eed and the attenuator setting. Beoord peaks snd detector responses that occur in the absence of vinyl chloride. Main tain conditions. With the equipment plumb ing arranged Identically to Section 62. flush the sample loop for 30 seconds at the rate of 100 ml/min with one of the vinyl chloride calibration mixtures and activate the sample valve. Record the injection time. Select the peak that corresponds to vinyl chloride. Measure the distance on the chan from the injection ttmejbo the time at which the peak maximum occurs. This quantity, divided by the chart speed, Is defined as the retention time. Record. 7.3 Preparation of chromatograph cali bration curve. Make a gae chromatographic measurement of each standard gas mixture (described in Section 7.1) using conditions Identical with those listed In Section 63 above. Flush the sampling loop for 30 seconds at the rate of 100 xnl/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 Ar, the peak area multi plied by the attenuator setting. Repeat until two Injection areas are within 5%. then plot those points vs Ct. When the other concen trations have been plotted, draw a smooth curve through the point*. Perform calibra tion dally, or before and after each set of bag samples, whichever is more frequent. 7 4 Tedlar bag leak checks. Before each use, make sure a bag Is leak-free by checking It for leaks. To leak check, connect a water manometer and pressurize the bag to 6-10 cm H.O (2^4 In. R.O). Allow to stand for 10 minutes. Any displacement In the water manometer indicates a leak. . in Check the rigid container for leaks in this manner. 40 SPI-16693 (Note. An alternative leak chaok method la to prasaurIre Um jag to 5-i0 cm HtO or 2-4 in. R,0 and allow to stand overnight A deflated bag Indicate a leak.) 1 ---- 8. Calculations. 8 1 Determine the sample peak &rx as follows. At = Am A* Equation 10G-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. Where A ,-Tbe sample peak ana. A.-Tbe measured peak ana. Ar--Tbe atUDuaOoo taelor. 8.2 Vinyl chloride oonoentrattan. Tram the calibration curve described in Section 7.3. above, select the value oi C, that cor responds to Ar. the sample peak area. Qalculate Ck as follows: C.PrT. c. P.T, where:_________ Equation 106-2 C*Th oodceotrettoQ of vinyl chloride In the bng mm pie in ppm. C.-The conomtrattoo of vinyl chloride Indicated by the gas chromatograph, la ppm. r, - The reference pressure, the laboratory pressure recorded daring calibration, mm Hi. T,-Tbe sample loop temperature on the absolute scale el the time of analysis, *K. r,-Tbe laboratory preasure at time of analysis, mm Hg. T. = The reference temperature, the sample loop tempcratuiY reccraed 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, UjS. Envi ronmental Protection Agency, Surveillance and Analysis Division. Athens, Georgia. June 24. 1974. 2. "Evaluation of A Collection and Analy- ' Ucal Procedure for Vinyl Chloride In Air," by G. D. Clayton and Assoclatea, December V 13, 1974. SPA Contract No. 68-03-1406, Task Order No 2, EPA Report oN. 76-VCL-l. (1 "Bijb ) sWb = The water vapor content of the bag sample, as analyzed. NntlM f mil mmi m mhcu 4m rt ctwdnti toMint ky tk amrMMni&l rrcactia* i 41 SPI-16694 MrTiit'i' 107--DimviNAnoa or Vintl CVLonirtK C'onthvt or Iwnuc--u Wuiiitiu Bampleo. and Vlntx Ckuokzde Contoit or Pt'AoICtTXT, tANMTDLIiACTmTX-ouSAiDM**PLREbS zn, Sutmt, Wrr INTROCf<TJ;N Performance of this method should not be attempted by persons unfamiliar with the operation of a gas chromatograph, nor by those who are unfamiliar with sampling, as there are many details that are 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. M The basis for this method relates to the vapor equilibrium which Is established between RVCM, PTC. resin, water, and air in a cloeed system. It has been demonstrated that the BVCM In % FVC ream will equili brate In a closed vessel quits rapidly, pro vided that the temperature of the FVC ream is maintained above the glass transition temperature of that specific ream. ] j This prooedure Is suitable for deter mining the vinyl chloride monomer (VCM) content of lnprocess wastewater samples, and the residual vinyl chloride monomer (RVCM) content of polyvinyl chloride (FVC) resins, wet cake, alurry. and latex samples. It cannot be jsed for jinlj--i In fused form, such as sheet or cubes. If a rteohH0n~`of the vinyl chloride peak Is not sMtofactory for a particular sample, then chromatograph parameters may be altered with prior ap proval of the Administrator. If there la rea son to believe that some other hydrocarbon with an Identical retention time la present in the sample, then supplemental confirma tion of the vlny] chloride peak through an absolute analytical technique, such as mass spectroscopy, should be performed. 2. Range and Sensitivity. The lower limit of detection of vinyl chlo ride will vary according to the chromato graph used. Values reported include 1X 10~T mg and 4xlO-T mg With proper calibration, the upper Limit may be extended as needed. 3. Precision and Reproduclbtltty. An Interlaboratory comparison between seven laboratories of three resin samples, each spilt into three parts. y4eML*a~sl&BUrd ` 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 6.29 % for a sample with a mean of 62.66 ppm. 4. Safety. Do not release vinyl chloride to the labora tory atmosphere during preparation of stand ards. Venting or purging with VCM/atr mix tures must be held to a minimum. When they are required, the vapor must be routed to outside air. Vinyl chloride, even at low ppm levels, must never be vented inside the laboratory. After vials have been analysed, the pressure within the vial must be v< ~<ted prior to removal from the Instrument turn table. Vials must be vented into an activated charcoal tube using a hypodermic needle to prevent release of vinyl chloride Into the laboratory atmosphere. The charcoal must be replaced prior to vinyl chloride break through. 5 Apparatus 5.1 Sampling. 5.1.1 Bottles--60 ml (2 oz), with waxed lined screw on tops, for FVC sampler 5 1.2 Vials--50 ml Hypo-rials.1 sealed with Teflon faced Tuf-Bond discs for water sam ples. yielded 1 Mention of trade names on specific prod acta does not constitute endorsement by the Environmental Protection Agency. 42 SPI-16695 51.1 Electrical tape--or equivalent, t-o pre\ eat loosening of bottle topf. 5 2 Sample reoovery. 5 2.1 Vtsls--With seals and cape, Perkin- tTmer Corporation No. 106-0118, or equlva- 5 2 2 Analytical balance-- Capable of wishing to 0 001 gram 5.2 3. Syringe. 100 -Precision Series A" No. 010025. or equivalent. 5 2 4 Vial SeaJer, Perkln-Elmer No 106- 0106 or equivalent. 53 Analysis. 5.3.1 Oas chromatograph--Perkln-Elmer Corporation Model P--40 head-space ana- lyiser. No. 104-0001. or equivalent. 53.2 Chromatographic column--Stain less steel. 2 mx3.2 mm. containing 0.4% Carbowax 1600 on Carbopak A, Perkln-Elmer Corporation No 105-0133. or equivalent.-------------- 5 3 3 Thermometer--0 to 100* C. accurate to 0 1* C, Perkln-Elmer No. 106-0109 or equivalent. 6 3 4. Sample tray thermostat system-- Perkln-Elmer No 105-0103. or equivalent. 5.3.5 Septa--Sandwich type, for auto matic dosing. 13 mm. Perkln-Elmer No. 105- 1008, or equivalent. 5.3.0 Integrator - recorder -- Hewlett - Packard Model 3S80A. or equivalent. 5.3.7 Pllter drier assembly (8)--PerklnElmer No. 2330117. or equivalent. 5 3.8 8o*p film flowmeter--Hewlett Pack ard No. 0101-0113. or equivalent. 5 4 CallbratlonT 6.4 1 Regulators--for required gas cylti lers. 0. Reagents. 0.1 Analysis. 6 1.1 Hydrogen gas--zero grade. & 1 3 Nitrogen gas--zero grade. 0 i 3 Air--zero grade. C <. Calibration. 6 2.1 Standard cylinders (4)--one each of 50 . 500. 2000. *nd 4000 ppm vinyl chloride In nitrogen, with certified analysis. 7. Procedure. 7.1 Sampling. 7.1.1 PVC sampling--Allow the resin or slurry to flow from a tap on the tank or silo until the tap line has been well purged. Ex: end a 60 ml sample bottle under the tap, fill. Hud Immediately tightly cap the bottle. Wrap VetrlcaJ tape around the cap and bottle to nrevent the top from loosening. Place an Ivientlfylng label on each bottle, and record me date, time, and sample location both on the bottles and in a log book. 7 1.2 Water sampling--Prior to use. the :'v> ml vials (without the discs) must be capped with aluminum foil and muffled at *0Q`C for at least one hour to destroy or remove any organic matter that could In terfere with analysis. At the sampling loca tion fill the rials bubble-free, to overflowing so that a convex meniscus forms at the top. The excess water is displaced as the sealing disc is carefully placed, Teflon side down, on the opening of the vial. Place the aluminum seal over the disc and the neck of the vial end crimp Into place. Affix an identifying !abe: on the bottle, and record the date, time, a.;d sample location both on the vials and m a log book. All samples must be kept re frigerated untU analyzed. 7 2 Sample recovery Samples must be run vu'hin 24 hours. 7.2 1 Resin samples--The weight of the resm used must be between 0.1 and 4.6 grams. An exact weight must be obtained (^0.001 pram; for each sample. In the case of sus pension resins a volumetric cup can be pre pared which will hold the required amount of s&mpie The sample bottle is opened, and the cup volume of resin Is added to the tareJ sample vial (including septum and alumi num cap). The vial la Immediately sealed and the exact sample weivht is then obtained. Report this value on the data sheet as it Is Carbopak C can be used in place of Carbopa A. 43 SPI-16696 retiutrnd for calculation of RVCM. la Ue eft** of relatively dry resin samples (water content <0 3 weight %), 100 ^1 of distilled water must be Injected Into the vial, after sealing and weighing, using a 100 syringe. In the case of dispersion resins. the cup cannot be used. The sample is Instead weighed approximately m an aluminum dish, transferred to the t&red vial and weighed accurately in the vial. The sample is then placed in the PerKUi-Elmer bead space ana* lyzer (or equivalent) and conditioned for one hour at 90*C. notx: 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 7.2.2 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 % steady stream of water is exiting from the funnel. Excessive filtration time could result in some loss of VCM. The wet cake sample (0.10 to 4.5 grama) is added to a tared vlai (including septum and aluminum cap) and immediately sealed. Sample weight Is then determined to 3 deci mal places. The aample is then placed in the Perkln-EUner head space analyser (or equiva lent) and conditioned for one hour at 00*0. A sample of wet cake la used to determine TS (total solid*). Tills Is required for calcu lating the RVCM. 7.2.3 Dispersion resin slurry samples.-- This material should not be filtered. Sample must be thoroughly mixed. Using a tared vial (including septum and aluminum cap) add approximately 8 clropa (046 to 0.35 grams) of slurry or latex using a medicine dropper. This should be done Immediately after mixing. Seal the vial as soon as possible. Determine aample weight accurate to 0.001 grams. Total sample weight must not exceed 0 60 grams. Condition the vial for one hour at 00C Is the analyzer. Determine the TS on the slurry sample (Section 7.3.6). 7.2.4 Inproceas wastewater samples-- Using a tared vial (including septum and aluminum cap) quickly add approximately 1 cc of water using a medicine dropper. Beal the vial as soon as possible. Determine sample weight accurate to 0.001 gram. Con dition the vial for two hours at 90*C in the analyzer. 7.3 Analysis. 7.3.1 Preparation of gas chromatograph- install the chromatographic ooluxnn and con dition overnight at 160*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--Bet regulator on cylinder to read 60 pslg. Bet regulator on chromatograph to 14 kg/cm*. Normal flows at this pressure should be 35 to 40 cc/mlnute. Check with bubble flow meter. ` b. Burner air supply--Set regulator on cyl inder to read 60 pslg. Set regulator on chromatograph to supply air to burner at a rate between 350 and 300 cc/mlnute. Check with bubble flowmeter. 3. Hydrogen supply--Set regulator on cyl inder to read 30 pslg. Set regulator on chromatograph to supply approximately 366 cc/mlnute. Optimize hydrogen flow to yield the most sensitive detect* response without extinguishing the flame. Check flow with bubble meter and record tht* flow 7.3.14 Temperature adjustments--Set temperatures as follows: a. Oven (chromatographic column), 60* C b. Dosing line. 140* C c. Injection block, 140* C. d. Sample chamber, water temperature. 00 c1.0* c. 7 3.1.3 Ignition of flame Ionization detec tor--Ignite the detector according to the manufacturer's Instruction*. 73.1.4 Amplifier balance--Balance the amplifier according to the manufacturer'a instructions. 7.3.2 Programming the chromatograph-- program the chromatograph as follows: a. I--Dosing time--The normal setting 13 2 seconds. t>. A--Analysis time--The normal setting Is 8 minutes. Certain types of samples con tain high boiling materials which can cause Interference wtlh the vinyl chloride peak on subsequent analyses. In these cases the analysis time must be adjusted to eliminate the interference. An automated backflush system can also be used to solve this prob lem c. B--Flushing--The normal setting is 0.2 minutes. d. W--Stabilization time---The nomal set ting la 0.2 minutes. e. X--Number of analyses per sample--The normal setting is l. 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- lesponding numbered positions In the turn table insert samples in the following order: 44 SPI-16697 Pol,:IK"' 1 a 2 Old 2000 ppm alaodarda f,,r roitu: iii'.w' These arc nrwiry only nftrr the :.;m vmt ha* not uMd for 24 I'.p-irv i - linger 3--i'O pp-;i .s: indHrJ, Xrexhiy pre pared r.".n . n 4 r-itHi S'..'.third, freshly pre pared Fhvshu;-. o--2`il>0 ppm ia:\dHr<i, freshly prepare;' Poaltii-Li ( - 4v>h0 ppm *.uiidurd, G e.-.hly pre pared. Position 7--Sample No 7 (This Is the first sample of the day. but is given as 7 to be eon- si* tent with the turn table and the integrator printout, i After all samples hair 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 90 C for 1 hour (not to exceed 6 hours). 7.3.4 Start chromatograph program-- When all samples. Including standards, have been conditioned at 90' C for 1 hour, start t_K> analysts program according to the manu- Jactusam' Instructions. These Instructions muat be carefully followed when starting aad Sopping program te peevont damage to the dosing assembly. 7.3.5 Determination of total solids (TS). 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 ar.d after placing In a draft ore*- <105 to 110* C). Samples must be dried to constant weight. After first weighing retur the pan to the oven for a short perioc uf time and then reweigh to verify com plete drynaM. TS is then calculated as the an*' sample weight divided by initial sam ple w*hgf t. 8 Calibration _ Jibrx'lon u> be performed each eight- uoui period wheu the instrument Is used. ,^ccU day. priu,r to running samples, the col umn should be conditioned by running two cl the previous days 2000 ppm standards. p.l Prepara non of Standards. Calibration standards are prepared by fill ing the vials wuh the vinyl chlcride/nltrogen standards rapidly seating the septum uud sealing with the aluminum cap. Use a sra'nlen steel line tram the cylinder to the ini Do not use rubber or tygon tubing The ^rru'e line from the cylinder must be purged (into hr*.di (or several minutes pi mr to filling via* After purging, reduce the flow rato to approximately 500- 1000 cc min Place end of tublny `nu> vial (near bottom) and after one nilr.m. sioviU remove tubing Flare 4. v, . i wlier*' 6. M' - 23 -- 1.4 volume, oc Cil.'h con tub ip lew limn 0.fi% woter. neptun. Itt viul as anou a^ possible to mini mise inlxiii;: Hir with Miniplc After the stand ard vials arc scaled, inject 100^1 of distilled i.ORRy 104. M>7 > lO'M wat or. 8.2 Prcpanvl ion uf rlnonnitograph calibra Equation 107-Tf tion rum*. ) `repr )'c t w ' f*0 ppm, I \' o .`>00 ppm. two 2000 ppm, ii-ui tv. 4oo ppm standard sample*. Run flic CfiMorntlon .'.amplcs in exactly the same manner as regular samples. Plot A., the lnteyrur r area count-, for each standard aample vs cr, the concentration of vinyl chloride in each standard aample Draw a line of best fit through the points. 'll.. f>i I 111 J i h Vvtll .u`>ni\l Ii '.VjiiIu, illM`\nCcuumn ll'ie.r uwa`tder.(or an A.l\ n,r. rw.r, L /o, A', l r.S ; T. A. I TilTiJ 9. Calculations P.l Response factor. From the calibration curve described in Section 82, above, select the value of C that corresponds to A, for each sample. Com pute the response factor, Rt, for each sample, Equation 107--4 where: 7\Toial solids. Jiote: K* must be determined. "^rora 1 cc (appmrtmate) wastewater sample. Equal.on jor-4 can be simplified to the lollowin^. as follow-: .-1 t\ Equation J07-1 Cr..= A.f>,fiS8X 10- + '2.066X 10- 'C m, Equation 107-5 9.2 Residual vinyl chloride monomer con esults calculated using Equation 107-4 e- centration, or vinyl chloride monomer con centration. Calculate C . as follows; M.V,A.P. r ( ) Sit, t, m, It -r KT, 4 represent concentration baaed on the d sample. To obtain results based on dry : content, divide by TS. 19. References. 1. Residual Vinyl Chloride Monomer Con tent of Polyvinyl Chloride Resins and Wet wlicn C-, Equation 107 2 Cake Samples, B. F Goodrich Chemical Co. Standard Test Procedure Mo. 1006-T. B. F. ('oiHviiir.iimr, of vinyl chloride lu the sumpic, in ppm. , Goodrich Technical Center, Avon Lake. Ohio January 30, 1975. Laboratory atmosphere pressure, mm Ilg. 1 2. Berens, A. R., "The Solubility of Vinyl i'i-- Room temperature, K. , A/..Mofeniar weight of VCM (fl2_5). V,Volumeof vapor phase (vial volume loss sample volume). , Chloride In Polyvinyl Chloride," ACS-DlviBion of Polymer ChemLstrv polymer Pre prints 15 (2): 197, 1974. vi i* Weight of sample. prams. ; 3. Berens, A. R., "The Diffusion of Vinyl RGas constant (62,360). Kllrnrv'a Law constant for VCM In PVC aif f/C. for VCM In 1 od Chloride in Polyvinyl Chloride," ACS-Dmalon of Polymer Chemistry. Polymer Pre .approximate) wastewater sample at 90C,1 prints 15 (2): 203. 1974. A'*5,0Xl0-*-5f.. T.~ Equilibration temperature, aE. 4. Berens, A. R,, L. B. Crider, C. J Toma- If tbe following conditions arc met, Equation 107-2 nek and J. M. Whitney, Analysis for Vinyl n be Bunphhed as loQows: Chloride in PVC Powders by Head Space Oae 21.. TTji--9202*CC (!92965?6 KKb. 3. P,*750 jrrn Hr Chromatography," to be pubEfeed. [FR Doc 75-34513 Filed 12-23-75:8 45 an.) v`!ote) AlTHORITY: Section 112 of the Clean Air Act as amended bv sec. 4(a) of cub. L. 91-604, 84 Stat. 1685 (42 U.S.C. 1857c-7); section 114 of the Clean Air Act, as amended bv sec. 4(a) of Pub. L. 91-604, 84 Stat. 1687, and by Pub. L. 93-319, sec. 6(a)(4), 88 Stat. 259 (42 U.S.C. 1857c-9); Section 301(a) of the Clean Air Act, as amended by sec. 15(c)(2) of Pub. L. 91-604, 84 Stat. 1713 (42 U.S.C. 1857a(a) 4b SPI-16698