Document N28MRLNwemDjDazjewqZwgGdg

Distribution January 10, 1977 Corrected Copy of the EPA Vinvl Chloride Standard Attached is a corrected copy of the EPA Vinyl Chloride Standard. I suggest that you discard your previous file copy. a. n. R. N. Wheeler, Jr; /J n RNWJr. /pm Attachment UCC 102771 THURSDAY, OCTOBER 21,1976 G 0 O PART II: corrected as per FEDERAL REGISTER VOLUME 41-234, DECEMBER 3, 1976 ENVIRONMENTAL PROTECTION AGENCY NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS Standard For Vinyl Chloride UCC 102772 46560 RULES AND REGULATIONS Title 40--Protection of Environment CHAPTER I--ENVIRONMENTAL PROTECTION AGENCY SOBCHAPTEN C--AIN PROMAMS inti, eia-i] PART 61--NATIONAL EMISSION STAND ARDS FOR HAZARDOUS AIR POLLUTANTS Standard for Vinyl Chloride On December 24, 1975, under section 112 of the Clean Air Act, as amended (42 U.8.C. 1857). the Environmental Protec tion Agency (EPA) added vinyl chloride to the list of hazardous air pollutants (40 PR 59477) and proposed a national emission standard for It (40 FR 59532). The standard covers plants which manu facture ethylene dlchlorlde, 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 noncarclnogenlc, In people with occupa tional exposure and in animals with ex perimental exposure to vinyl chloride. Reasonable extrapolations from these findings cause concern that vinyl chlo ride 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 irom all known process and fugitive emission sources in ethylene dichlorideviny] chloride and polyvinyl chloride plants to the level attainable with best available control technology. This will have the effect of furthering the protec tion ol public health by minimizing the health risks to the people living In the vicinity of these plants and to any addi tional people who are exposed as a result of new construction. Interested parties participated In the rulemaking by sending comments to EPA. The comments have been carefully con sidered, and where determined by the Administrator to be appropriate, changes have been made to the regulation as pro mulgated. Summary or the Standard In ethylene dlchloride-vtnyl chloride plants, the standard limits vinyl chloride emissions from the ethylene dlchlorlde and vinyl chloride formation and puri fication processes to 10 ppm. For the oxyehlorinatlon process, vinyl chloride emissions are limited to 0.2 g/kg of ethyl ene dlchlorlde product. In polyvinyl chloride plants, the stand ard limits vinyl chloride emissions from equipment preceding and Including the stripper In the plant process flow to 10 ppm. Emissions from equipment follow ing the stripper are to be controlled by stripping dispersion resins to 2000 ppm and other resins to 400 ppm. or by using equivalent controls. Vinyl chloride emis sions from reactor opening are to be re duced to 0.02 g/kg polyvinyl chloride product. In both ethylene dlchlorlde-vlnyl chloride and polyvinyl chloride plants, relief valve discharges and manual vent- ot gases are prohibited except under cy conditions. Fugitive emissions are required to bo captured and con trolled. Health and Environmental Impacts EPA prepared a document entitled the Quantitative Risk Assessment toe Com munity Exposure to Vinyl Chloride which estimates the risk from vinyl chlorine exposure to populations living In the vi cinity of vinyl chloride-emitting plants before and after implementation of con trols to meet the standard. There are no dose-response data for the concentra tions of vinyl chloride found In the am bient air. Therefore, assessments of risk at ambient levels of exposure were ex trapolated from dose-response data from higher levels of exposure using both a linear model and a log-probtt model. Extrapolations made with each of these models entailed using different sets of assumptions. Because different assump tions can be made In extrapolating to low doses, the health risks are reported In ranges. It was estimated that 4.6 million peo ple live within 5 miles of ethylene dichoride-vinyl chloride and polyvinyl chlo ride plants and that the average ex posure around these plants before instal lation of controls to meet the standard is 17 parts per billion. The exposure levels for uncontrolled plants were cal culated based on estimated 1974 emis sion levels. Using the linear dose-re sponse model, 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-problt model gave predictions that are 0.1 to 0.01 times this rate. This wide range Is an indication of the un certainties In extrapolation to low doses. Due to the long latency time observed In cancer cases resulting from vinyl chloride exposure. Increases initiated by exposure this year will not be diagnosed until the 1990's or later. Vinyl chloride Is also es timated to produce an 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 ex posure among residents around plants. The number of these effects is expected to be reduced at least In proportion to the reduction In the ambient annual average vinyl chloride concentration, which 1* expected to be 5 percent of the uncon trolled levels after the standard ts im plemented. Changes In the standard since pro posal do not affect the level of control required. Thus, the environmental im pact of the promulgated standard Is, with one exception, the same as that described In Chapter 6 of Volume I of the Standard Support and Environmen tal Impact Statement. According to data submitted by the Society of Plastics In dustry, Inc. (SPI), the Impact on water consumption In the draft environmental Impact statement was overstated. In es timating the impact on water consump tion, EPA 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. Accord ing to SPI. the control system utilizing the mo6t water will not be used gener ally by the Industry and economic fac tors will cause plants to recycle much of the water. Therefore, according to SPI the Impact of the standard on water consumption will be negligible. The environmental Impacts ol the promulgated standard may be summar ized as follows: The primary' environ mental Impacts ol the standard are ben eficial and will consist of vinyl chloride emission reductions of approximately 94 percent at ethylene dlchlorlde-vlnyl chloride plants and 96 percent at poly vinyl chloride plants. Percentage num bers for both source categories are based on an estimated 90 percent reduction in fugitive emissions and 1974 emission levels. The potential secondary environmen tal impacts of the standard are either Insignificant or will be minimized with out additional action, except for one ad verse impact. Hydrogen chloride Is al ready emitted by process equipment at ethylene dlchlorlde-vlny! chloride plants and by other petrochemical plants in the complexes where ethylene dlchlorlde vinyl chloride plants are typically lo cated. An Incinerator used to attain the standard at an ethylene dlchlorlde-vlnyl chloride plant could Increase hydrogen chloride emissions by several fold. Typi cally, however, due to the corrosion prob lems which would otherwise occur both on plant property and In the community, plants use scrubbers to control already existing hydrogen chloride emissions Hydrogen chloride emissions resulting from control of vinyl chloride emissions are expected to be controlled for the same reason. If even a moderately effi cient scrubber (98 percent control) were used to control the hydrogen chloride emissions resulting from Incineration or vinyl chloride emissions, the Increase In hydrogen chloride emissions from a typ ical ethylene dlchlorlde-vlnyl chloride plant due to the standard would be re duced to 35 percent. However. EPA plans to further evaluate the need to control hydrogen chloride emissions, since dif fusion model results Indicate that under "worst-case" meteorological conditions, the hydrogen chloride emissions from the process equipment and the incinera tor combined would cause maximum am bient concentrations of hydrogen chlo ride in the vicinity of ethylene dichlo ride-vinyl chloride plants to be In the same range or somewhat higher than existing foreign standards and National Academy of Sciences <NAK) guidelines for public exposure. Economic Impact In accordance with Executive Order 11821 and OMB 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 FEDERAL REGISTER, VOL. 41. NO 20S_rHURS0AT, OCTOSER 21. 1976 UCC 102773 RULES AND REGULATIONS 46561 discussed In Chapter 1 of Volume I of the Standard Support and Zneironmental Impact Statement. Comments on the proposed standard have resulted to only one major change to the economic Im pact analysis. EPA estimated that there would be four plant closures as a result of the promulgated standard.-Of the four plants Identified as possible closure can didates, 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. The economic Impacts of the promul gated standard may be summarized as follows: The total capital cost for exist ing plants to meet the standard Is esti mated to be $198 million, of which $15 million Is for ethylene dichlorlde-vlnyl 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, the total capital cost for existing plants to meet the EPA's 1983 water effluent guideline limitations Is expected to be $83 million and the total annualized operation cost Is $17 million. The costs to the industry of meeting the OSHA standard cannot be quantified at this time, but they are ex pected to overlap to some degree with the costs to meet EPA's fugitive emission regulations. The costs of meeting the fugitive emission regulations are Included to the total costs cited above for meeting the promulgated regulation. Broken out separately, the capital cost of meeting the fugitive emission regulations Is $37 million and the annualized cost Is $25 million. The standard Is not expected to deter construction of new ethylene dlchlorldevinyl chloride plants or most types of new polyvinyl chloride plants. For one type of polyvinyl chloride plant (disper sion process) that represents 13 percent of the Industry production, the standard would significantly deter the construc tion of smaller plants. It Is estimated that the price of poly vinyl chloride resins will rise by approxi mately 7.3 percent to order to maintain precontrol profitability and also to re cover the total annualized control costs necessitated by the standard at ethylene dichlorlde-vlnyl chloride plants and poly vinyl chloride plants. This increase Is estimated to translate Into a maximum consumer price Increase to goods fabri cated from polyvinyl chloride resins of approximately 3.5 percent. Recovery of effluent annualized costs plus mainte nance of precontrol profitability is esti mated to add approximately 2 percent to polyvinyl chloride resin prices and result In an additional maximum consumer price Increase of 1 percent. Public Participation During the public comment period, 50 comment letters on the proposed stand ard were received. There were 24 from Industry; 3 from environmental groups; 15 from Federal, State, and local agen cies; 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, 1975, In Washington, D.C. Presentations were wivl by the Environmental Defense Fund, the Society of the Plastics Indus try, Inc- Dow Chemical Company, Dia mond 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 copytog at the EPA Public Information Ref erence Unit, Room 2922 (EPATJbrary), 401 M Street. 8W- Washington, D C. In addition, copies of the comment sum mary and Agency responses may be ob tained upon written request from the Public Information Center (PM-215), Environmental Protection Agency, 401 M Street, BW, Washington, D.C. 20460 (specify Standard Support and Environ mental Impact Statement, Emission Standard for Vtnyl Chloride, Volume II). SicNmcANT Comments and' Chances to thx Proposed Regulation (1) Decision to list vinyl chloride as a hazardous air pollutant. In general, the commenters did not contest EPA'b deci sion to list vinyl chloride as a hazardous air pollutant. However, three commentera (two companies and one Federal agency) argued that EPA placed undue emphasis on factors suggesting that vinyl chloride presented a health risk and Ignored factors suggesting that no sig nificant risk was Involved. Under section 112, however. EPA could remove vinyl chloride from the list of hazardous air pollutants only If information were pre sented to EPA that shows that vinyl chloride is clearly not a hazardous air pollutant. As discussed more fully to the comment summary, the commenters, did not provide conclusive evidence that vinyl chloride Is not a hazardous air pollutant which causes or contributes to death or serious illness, nor did they conclusively prove that the health risk lactors em phasized by EPA were Insignificant. Several other commenters agreed with EPA's decision to list vinyl chloride as a hazardous air pollutant, but argued that EPA had overstated the health problem, the emission levels, and the projected ambient air concentrations around un controlled plants. With regard to the al leged overstated health problem, the commenters stated, for example, that the U.8. worker EPA discussed as having been exposed to vinyl chloride levels low er than those usually encountered to polyvinyl chloride production has been dropped from the National Institute of Occupational Safety and Health's listing of workers with angiosarcoma. EPA agrees that there are questions concern ing the level of exposure and to some cases the pathology of these cases not involved directly to polyvinyl chloride and vinyl chloride production. These un certainties are stated to the appropriate footnotes of the Scientific and Technical Assessment Report on Vtnyl 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 to the evaluation of the potential public health problems. With regard to the alleged overstated emission levels, the uncontrolled emis sion levels reported by EPA were based on 1974 data. This qualification was stated wherever emission data were pre sented. EPA recognizes that emissions have been reduced since that time, and stated thto In the preamble to the pro posed 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 considerable time both on the part of EPA and on the part of Industry. Since the purpose of the stand ard Is to minimize emissions, these more current data would not affect the stand ard Itself. The 1974 emission levels were also used In diffusion modelln;; v> rroject maximum ambient air concentrations around uncontrolled plant.' These maxi mum air concentrations 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 Environmen tal Impact Statement, but would not affect the basis of the standard Itself. (2) Approach for Regulating Vinyl Chloride Under Section 112. Two ap proaches other than using best avail able control technology were suggested by the commenters for regulating vinyl Chloride under section 112. The first was to ban polyvinyl chloride products for which substitutes are currently available and to gradually phase out other poly vinyl chloride products as substitutes are developed. In the preamble to the proposed stand ard EPA specified its reasons for not set ting a zero emission limit for vinyl chloride, as follows; (11 There are bene ficial uses of vinyl chloride products for which desirable substitutes are not read ily available; (2) there are potentially adverse health and environmental im pacts from substitutes which have not been thoroughly studied; (3) there are a number of employees, particularly in the fabrication Industries, who would be come at least temporarily unemployed: and (4) control technology is available which Is capable of substantially reduc ing emissions of vtnyl chloride into the atmosphere. EPA agrees that substitutes do exist or could be manufactured for most poly vinyl chloride uses. However, to general, these substitutes do not have some of the more desirable characteristics of poly vinyl chloride, such as nonflammability. If vinyl chloride and polyvinyl chloride were banned, other substitutes with these more desirable characteristics would likely be developed. There Is a risk that these substitutes would also have adverse health or environmental effects. Since control measures are available which can reduce vinyl chloride emis sions by 90 percent or more, it does not seem prudent to reduce emissions by the remaining percentage and take the risk of Introducing new untested chemicals Into the environment FEDERAL REGISTER. VOl 41, NO 205--THURSDAY, OCTOBER 21. 197* CORRECTED DECEMBER 3. 1976 UCC 102774 46502 BUIES AND REGULATIONS Another approach suggested by the capacity of no more than 0.19 m* (50 venting will be permitted as a last teort commenters was to base the standard for gal). Reactors In this size range can gen before the relief valve opens. The same each Individual emission point on cost erally be found In a laboratory, whereas notification procedures are required for versus benefit Several of the fugitive the larger reactors are typically pilot manual venting to the atmosphere as uro emission sources were named specifically scale facilities. Emissions from laboratory required for relief discharges as ones for which the costs of control scale equipment are relatively smaD. and There are several changes In the mi were substantially higher than the bene- application of the controls required by merlcal emission limits in the promul fits. Although EPA did determine a cost- the standard would be expensive and im gated standard. Except for the standard benefit ratio for the controls required practical. EPA also decided to exempt re for reactor opening loss, these change;, Tor a number of emission points, EPA search and development facilities con simply Involve conversion to the Intern;-. - does not believe such a ratio Is an appro taining reactors greater than 0.19 m* (50 tlonal System of Units (SI*. There v... priate basis on which to set a standard. gal) and no more than 4.07 m* (1100 gal) an error Involved in the original calc illa Section 111 of the Clean Air Act provides in capacity from all parts of the standard tion used to derive the standard foi i im. for the development of standards based except the 10 ppm limit for reactors, tor opening. Correcting this error d... on best control technology (considering strippers, monome- recovery systems, and bles the allowable emissions. It Is em costs!. Even under section ill, however, mixing, weighing and holding containers. phasized that the change in this stand standards are not based on a fine bal EPA decided not to require these facili ard Is a correction, and not a change in ancing of costs versus benefits. Instead, ties to meet other parts of the standard the intent for the degree of control re costs are considered In terms of the af because of the technical problems In quired. fordability of the control technology re volved In doing so. For example, the The proposed standard reauireu the quired to achieve a given emission level standard for reactor opening is based In Installation of a rupture disc beneath and the economic impact of possible part on reducing the frequency of open each relief valve to prevent leakage iron, standards on the Industry in ques ing the reactor. Research and develop the relief valve. A provision has be* n tion. Unlike section ill. section 112 does not explicitly provide for consideration of costs, so It would clearly be Inappro priate to consider costs to a greater ex tent under section 112 than would be done under section ill. As discussed In the preamble to the proposed standard for vinyl chloride, EPA believes costs may be considered under section 112, but only to a very limited extent; l.e.. to assure that the costs of control technol ogy are not grossly disproportionate to the amount of emission reduction achieved. In comparison with other emission points, the costs of controlling the fugitive emission sources mentioned by the commenters are relatively small compared with the amount of emission reduction achieved. Several commenters recommended adding to the regulation a provision for excess emissions during startup, shut down. and malfunction. EPA considered this comment, and decided that this addition Is not necessary for the vinyl chloride standard. Startup and shutdown of the process has essentially no effect on emissions to the atmosphere for poly vinyl chloride production, and technology exists to avoid excess emissions during startup and shutdown at ethylene dichlorldevlnyl chloride plants. We do not believe plants should be allowed to emit excess emissions during malfunctions, and therefore are requiring them to shut down immediately. (3) Selection of source categories. In the preamble to the proposed standard EPA recognized that some small research ment reactors have to be opened after every batch for thorough cleaning. Also, stripping technology is developed indi vidually for each resin In research and development equipment. Therefore, at tainment of the stripping limitations in the research and development equipment would not always be possible. The 4.07 m* (1100 gal) figure was selected as an upper cut-off point because there are no commercial reactors smaller than this. (4) Emission limits. The only major change In the emission limits between proposal and promulgation Is the addi tion of a provision for emergency manual venting of vinyl chloride from reactors to the atmosphere. The proposed stand ard prohibited all manual venting to the atmosphere. In the preamble to the pro posed standard. EPA invited interested persons to comment on whether permit ting manual venting to the atmosphere could result In overall lower emissions. There are several methods available for preventing relief discharges from reac tors. 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 tem perature and pressure within the reac tor, the greater the amount of vinyl chloride which has to be removed to bring the reactor under control. Manual venting can be done at a lower pressure than the pressure required to open the relief valve. For this reason manual vent ing can result in lower emissions than would occur by allowing the reactor to discharge through the relief valve. Fur 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 bi contained. The regulation for obtaining vinvi chloride samples has been changed to an operating procedure. The proposed standard stated that there were to be no emissions from taking the sample Several commenters pointed out that the use of the word "no" would make this regulation Impractical to enforce. There fore, the promulgated standard specifies the operating procedure which EPA orig inally Intended to be used to control this source. This revision Is only a change in wording and does not represent a change in the level of the standard. The regulation for taking samples has also-been revised to apply only to sam*pies containing at least 10 percent by weight vinyl chloride. This Is consistent with the other parts of the standard which appiv to equipment "in vinyl chloride service." "In vinyl chloride serv ice" 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 J 61.61(1) means that a piece of equipment con tains or contacts either a liquid that Is at least 10 percent by weight vinyl chlo ride or a gas that Is at least 10 percent by volume vinyl chloride The proposed standard required a vinyl chlorldo monitoring system for continu and development facilities may exist thermore, a manual vent vaive Is under ously measuring vinyl chloride levels both where the emissions of vinyl chloride are the control of an operator and can be within the plant (for leak detection) and insignificant and covering these facilities closed. A relief valve may become clogged within stacks. The proposed standard did under the standard would be unnecessary with resin and not close. The result not outline required specifications for the and Inappropriate. However, EPA did not would be loss of all the reactor contents. monitoring system, except that it was to have sufficient Information available to The contents of a reactor car be man analyze the samples with gas chromatog clearly define which facilities should be ually vented to a gasholder or other hold raphy, or if all hydrocarbons were as excluded from the standard, and ing vessel. However, in some cases, such sumed to be vinyl chloride, with infrared encouraged Interested parties to submit as during severe weather conditions, sev spectrophotometry, flame Ion detection, such information during the comment eral reactors may be out of control at or equivalent It required that each plant Period. Based on the Information sub one time. There would be Insufficient submit a description of Its monitoring mitted, EPA decided to exempt poly holding capacity under these conditions system to EPA, so that EPA could deter vinyl chloride reactors and associated equipment from applicability of all parts of the standard If the reactors are used In research and development and have a to manually vent the contents of all the reactors to a gasholder. Therefore, when all other measures to prevent relief valve discharges have been exhausted, manual mine whether it was acceptable or not Comments were received Indicating a need for EPA to specify some criteria for judging the acceptability of monitoring systems. The accuracy of the monltor- FEOERAL REGISTER, VOL 41, NO, 105--TMURSDAT OCTOBER 21, 1V76 UCC 102775 RULES AND REGULATIONS 46563 In* system would be related to the fre (g)(3) (11), and 61.70(c) (2) (1) so that made the same as for other resins and quency of calibration. Therefore, EPA measurement of the vinyl chloride levels others requested that they be mode less has Included In the promulgated stand in the resins Is to be made Immediately stringent. EPA decided not to make the ard requirement lor the frequency ox after stripping Is completed rather than standard for stripping dispersion resins culthmUon and procedures to be carried as the reetn Is being transferred out of the same as for other resins because i lido mil in Uir oallbmUoii of (lie iiiunlterlng the strlwwr, This allowti a j4t in carry U sufficient evidence u. indicate licit umlnimeme. out upefbUous h) a ulilin'ei after strip ItiMb feqiiis art moitt dinO'dl in oiiq. Tlie portable hydrocarbon detector re ping has been completed but before It Is that) oilier resins With rsontd t" u>S quired by the proponed standard was re transferred out of the stripper This Is lng the stripping levels for dlspei quired to have a sensitivity of 5 ppm. consistent with the original intent of the resins less stringent, only one of the eight Comments were received Indicating that standard. manufacturers of dispersion resins spe instruments In this sensitivity range are The regulation for loading and unload cifically commented that the dispersion delicate and require continuing mainte ing lines In (61.65(b)(1) has been re resin standard should be made less nance. The portable hydrocarbon detec vised to clarify that it applies only to stringent. Only two of several grades of tor ls-requlred for leak detection and far lines that are disconnected after each dispersion resins made by this company measuring vinyl chloride concentrations loading or unloading operation. Perma cannot meet the 2.000 ppm limit The inside the equipment before opening It. nently installed pipelines that are opened proposed standard takes Into considera A 5 ppm sensitivity Is not needed In Infrequently for Inspection or mainte tion that some resins are more difficult either case, and the required sensitivity nance. for example, are covered by the -to strip than others by providing for has been changed to 10 ppm In the pro opening of equipment regulation rather averaging among different resins mulgated standard. than the loading and unloading line (5) Testing, reporting, and record The proposed standard contained a regulation. keeping. There are several relatively single regulation for compressors. The The regulation for toprocess waste- minor changes in the testing, reporting, promulgated standard has separate regu water In the proposed standard could and recordkeeping requirements. A pre lations for rotating and reciprocating have been misinterpreted to require In vision has been added to ! 61.87 which compressors. This is consistent with hav dividual treatment of wastewater requires that stack gas samples taken ing separate regulations for rotating and streams. Section 61.65(b) (9) (1) of the with Test Method 106 are to be analyzed reciprocating pumps In both the pro promulgated standard clarifies that within 24 hours. This is consistent with posed and promulgated standards. wastewater streams that are required to the requirements In the proposed Test Section 81.66 of the proposed standard be treated (Le, those containing greater Method 106. The promulgated standard provided for the use of equivalent meth than 10 ppm vinyl chloride) can be com also specifies that to averaging the re ods of control which have been approved bined to be treated. However, waste- sults of the three runs required by Test by EPA. The promulgated standard re water streams that contain greater than Method 106, a time-weighted average is quires that the plant owner or operator 10 ppm vinyl chloride cannot be com to be used. submit a request for determination of bined with wastewater streams that con One commenter requested that the equivalency within 30 days of the pro tain less than 10 ppm vinyl chloride be oxygen content and moisture content be mulgation date if the alternative control fore treatment; l_e., dilution cannot be specified for the 10 ppm concentration method Is Intended aa the initial means used to meet the standard. standards. The proposed standard speci of control. The purpose of this is to pro The commenters recommended several fied that the vinyl chloride concentration vide time for EPA to evaluate the method changes In the emission limits which is to be corrected to 10 percent oxygen before the plant has to be In compliance have not been Incorporated Into the (wet basis) if combustion Is used as the (for existing sources. 90 days after the promulgated standard. These are dis control measure In the promulgated promulgation date). EPA also suggests cussed In the following paragraphs. standard, this requirement has been ex that this request lor determination of It was recommended that the require panded to all control measures. equivalency be accompanied by a re ment for double mechanical seals on A provision has been added to the quest for waiver at compliance pursuant pumps, compressors, and agitators be re promulgated standard which states that to section 112(0 (1) (B) (11) of the Act. moved because the single seals currently if a reactor is also used as a stripper; the The request for a waiver for compliance used on this equipment have small emis reactor opening emissions may be deter should provide for the case where EPA sions and are more reliable than double mined Immediately following the strip determines that a method Is not equiv mechanical seals. EPA Is aware that each ping operation.' If a reactor is also used alent and the plant needs to purchase fugitive emission source, such as one as a stripper, the resin is to the reactor other equipment. In no case will the pump, taken by itself causes relatively when It Is opened. This means that vinyl waiver of compliance be extended beyond small emissions. Fugitive emissions con chloride to the resin which has already two years from the date of promulga sidered as a whole are a significant been stripped to acceptable levels can tion. source of emissions, however, and the In escape from the resin and become part There are several wording clarifica tions which have been made In the pro mulgated standard. The definition for "in vinyl chloride service" ((60.61(1)) has been clarified by stating that It means equipment that contacts vinyl chloride as weQ as equipment that con tains vinyl chloride. This would Include such equipment as agitators. tent of the standard is to reduce these Double mechanical seal pumps are com monly used In the Industry for emission reduction. Sealless pumps or equivalent systems are available as options to double mechanical seals. The commenters recommended In creasing the averaging time for the 10 ppm limits and the emission limits for of the reactor opening loss. It is EPA's Intent that once a resin has been stripped to the 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 moni 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 regula tion lor opening of equipment. Equip ment that has met the opening of equipment regulation can contain more than 10 ppm vinyl chloride and would bfe in violation of the standard If this statement were not Included. The requirements for stripping poly vinyl chloride resins to specified levels have been revised in (161.64(e), 61.67 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 determin ing compliance consists of three runs for a minimum of an hour each, the aver aging time for the 10 ppm limit is at least three hours. Increasing the averaging time to 30 days for any of the emission limits would permit higher peak emis sion levels. EPA has determined that this Is neither desirable nor necessary. Some commenters requested that the stripping levels for dispersion resins be toring of stack emissions has been added to the promulgated standard. The con tinuous monitoring of stack emissions was required to 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 tofonnatkm. EPA agrees that a detailed description to the FEDERAL REGISTER, VOl. 41. NO. 205--THURSDAY, OCTOBER 21, 1976 UCC 102776 / 46564 RULES AND REGULATIONS aitUl report Is unnecessary, H addl- In section 6.4 of Test Method 106 the ooal information is needed, EPA esn requirement for an automatic integrator obtain It under section 114 at the Act and has been rsplaoed with a requirement for the that eon request confidential treat a dtac integrator or planimetar tor meas ment in accordance with 40 CFR Part I uring peak area. This change to in re for information it believes to be sponse to a comment which slatm that proprietory. automatic integrators are unnecessarily Hie proposed standard required that elaborate and expensive. a semiannual report be submitted every 180 days. Hie 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. Hie standard has been revised to elim inate the requirement to record the cause of any leak detected by the vinyl chlo A new section 6.6 has been added to Test Method 106 which requires deter mination of the water vapor content of the sampling bag by measuring the am bient temperature and pressure near the tog. The vinyl chloride concentration of the bag can then to reported on a dry basis. A provision for checking the rigid container for leaks has been added to section 7.4 of Teel Method 106. ride detector, the action taken to repair the leak, and the amount of time re quired to repair the leak. EPA Is con cerned only that leaks are detected and repaired. That this has been done can be established by looking at the strip chart record of measurements made by the 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 113 of the Cleon Air Act as added by see. 4(0) of Pub. L. 81-804, 84 Stot. less (43 UJS.C. 18670-7; Section 114 of the Clean Air Act, as added by aec. 4(a) vinyl chloride detector. These records are of Pub. L. 01-004. 84 Stot. 1887, and amended still required for the portable hydrocar bon detector however. Several commentators recommended that the companies be allowed an extra two weeks to submit to EPA data from the Initial performance test. They also by Pub. L, 03-310. aec. 8(a) (4). 88 Stot. 360 (43 UB.C. 1807C-0); Section 301(a) of the Clean Air Act. ae amended by eec. 16(e) (3) Of Pub. L. 01-804, 34 Stot 1713 (43 U.S.C 1867g(a)). Dated: October 12, 1976. recommended that they submit the data by regular mall rather than registered John Quarles, Acting Administrator. mall. EPA has not adopted either of these recommendations. A source Is supposed Port 61 of Chapter I, Title 40 of the Code to be in compliance with the standard of Federal Regulations is amended as thln 90 days of the promulgation of follows; The table of sections for Pan e standard. The standard requires that 61 is amended by adding a list of sections e emission tests be done within the for now Subpart F and Part 6 1 is amend- ' 90 day period, and permits an extra 30 ed by revising the authority and adding a days for determination of results. Thenew Subpart F reading as follows; purpose of using registered mall Is toSubpart F--National Emission standard for Vinyl h11advtheoecburemeesenunltstsetnhatreeanflaodscttreItncheativhteede.mmTaishisl,iisotnhweadreyatas001e1.c.6610 Chloride AppUOabUlty. Definition*. will be no question that they were sent. 61.03 Emission standard for ethylene di (6) Test method. Test Method 106 has chloride plants, been changed to recognize that on a gas chromatograph equipped with a Chromosorb 103 column, acetaldehyde may Interfere with the vinyl chloride peak. When a sample Is expected to contain acetaldehyde, a secondary column as de scribed In section 4.3.2 must be employed. 01.03 01.64 01.66 01.06 Emission standard for vinyl chloride plants. Emission standard for polyvinyl chlo ride plants. Emission standard for ethylene dl- chlorlde, vinyl chloride and poly vinyl chloride plants. Equivalent equipment and procedures. Mass spectroscopy or another absolute 61.67 Emission tests. analytical technique Is required to con firm the vinyl chloride peak obtained with the gas chromatograph, only if peak resolution with the secondary column is 61.68 Emission monitoring 61.69 Initial report. 61.70 Semiannual report. 61.71 Recordkeeping. not successful. In section 4.1.4, aluminized Mylar bags can be substituted for Tedlar togs. EPA now has data to allow this substitution, provided that the samples are analyzed within 24 hours of collection. In section 5.1.3 of Test Method 106 the requirement to use "oxygen gas" has Authority : Section 113 of the Clean Air Act aa added by aec. 4(a) of Pub. L. 01-604, 64 Stat. 1686 (43 VS.C. 18670-7); section 114 of the Clean Air Act, as added by sec. 4(a) of Pub. L. 01-004, 64 Stat. 1687, and amended by Pub. L. 03-810. sec 0(a) (4). 88 Stat. 360 (42 U.S.C. 18670-0); section 301(a) of the Clean Air Act, as amended by sec 15(o) (3) of Pub. L. 91-604, 84 Stat. 1713 (43 UB.C. been replaced with "oxygen gas or air, as 1857g(a)). required by the detector." Several commentors stated that most gas chromato graphs are designed to use hydrogen and air for their flame detectors. When used Subpart F--National Emission Standard for Vinyl Chloride S 61.60 Applicability, in this way. they are capable Of detect ing 0.6 ppm vinyl chloride In air. This Is msltlve enough for monitoring the h >m emission limits stipulated In tb< standard. (a) This subpart applies to plants which produce: (1) Ethylene dlchlorlde by reaction of oxygen and hydrogen chloride with ethylene, <2> Vinyl chloride by any proooea. and/or (3) One or more polymer* containing any fraction of polymerised vinyl oldo* ride ii) Tills atlbpari dues not *pti tot equipment used in research and develop ment If the reactor used to polymerize the vinyl chloride processed in the equip ment has a capacity of no more than 0.19m* (50gal). (c) Sections of this subpart 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 po lymerize the vinyl chloride processed in the equipment has a capacity of greater than 0.19 m* (60 gai> and no more than 4.07 m* (1100 gal). 61.61 Definitions. Terms used in this subpart are defines in the Act, in subpart A of this part, or In this section as follows: (a) "Ethylene dichloride plant" in cludes any plant which produces ethyl ene dlchlorlde by reaction of oxygen and hydrogen chloride with ethylene. <b) "Vinyl chloride plant" includes any plant which produces vinyl chloride by any process. (c) "Polyvinyl chloride plant" includes any plant where vinyl chloride alone or in combination with other materials is polymerized. (d> "Slip gauge" means a gauge which has a probe that moves through the gas/ liquid Interface in a storage or transfer vessel and indicates the level of vinyl chloride in the vessel by the physical 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 ol resin" means the sub division of resin classification which de scribee it as a unique resin, l.e., the most exact description of a resin with no fur ther subdivision. (g) "Dispersion resin" means a resin manufactured in such away as to form fluid dispersions when dispersed in a plasticizer or plasticizer /diluent mix tures. (h) "Latex resin" means a resin which is produced by a polymerization process which initiates from free radical catalyst sites and is sold undried. (i) "Bulk resin' 'means a resin which is produced by a polymerization process in which no water is used. <1> "Inprocess wastewater" means any water which, during manufacturing or processing, comes into direct contact with vinyl chloride or polyvinyl chloride or results from the production or use of any raw material, intermediate product, finished product, by-product, or waste product containing vinyl chloride or polyvinyl chloride but which has not been discharged to a wastewater treat ment process or discharged untreated aa wastewater. (k) "Wastewater treatment process" Includes any process which modifies FEDERAL REGISTER, VOL. 4). NO 105--THURSDAY. OCTOBER 31. <036 CORRECTED DECFMRER 3. 1976 UCC 102777 RULES AND REGULATIONS 46565 characteristics such as BOD, COD, TSS, and pH, usually lor 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. tl) "In vinyl chloride service" means that a piece of equipment contains or contacts either a liquid that Is at least 10 percent by weight vinyl chloride or a gas that Is at least 10 percent by volume vinyl chloride. (m) "Standard operating procedure" means a formal written procedure offi cially adopted by the plant owner or operator and available on a routine basis to those persons responsible for carrying out the procedure. (n) "Run" means the net period of time during which an emission sample Is collected. (o) "Ethylene diehloride purification" Includes any part of the process of ethyl ene diehloride production which follows ethylene diehloride formation and In which finished ethylene diehloride Is produced. <p) "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. (q) "Reactor" Includes any vessel In which vinyl chloride Is partially or totally polymerized Into polyvinyl chloride. (r) "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 5 61.65(a). <s) "Stripper" Includes any vessel In which residual vinyl chloride Is removed from polyvinyl chloride resin, except built 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 flliyli'iir diehloride plants. An owner or operator of an ethylene diehloride plant shall comply with the requirements of this section and I 61.65. (a) Ethylene diehloride purification; The concentration of vinyl chloride in all exhaust gases discharged to the at mosphere from any equipment used In ethylene diehloride purification is not to exceed 10 ppm, except as provided in 5 61.65(a). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in 5 61.65(b) before being opened. (b) Oxychlorination reactor: Except as provided in 5 61.65(a), emissions of Vinyl chloride to the atmosphere from each oxychlorination reactor are not to exceed 0,2 g/kg the 100 percent ethylene diehloride product from the oxychlorlnatlon process. 5 61.63 Emission slandord for vinyl chloride plants. An owner or operator of a vinyl chlo ride plant shall comply with the require ments of this section and 5 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 5 61.65(a). Tills re quirement does not apply to equipment that has been opened. Is out of operation, and met the requirement In 5 61.65(b) (6) (1) before being opened. 61.64 Emission standurd for polyvinyl chloride plants. An owner or operator of a polyvinyl chloride plant shall comply with the re quirements of this section and 5 61.65. (a) Reactor: The following require ments apply to reactors; (1) The concentration of vinyl chlo ride in all exhaust gases discharged to the atmosphere from each reactor Is not to exceed 10 ppm, except as provided in paragraph (a)(2) of this section and S 61.65(a), (2) The reactor opening loss from each reactor Is not to exceed 0.02 g vinyl chloride/Kg (0.00002 lb vinyl chloride/ lb) of polyvinyl chloride product, with the product determined on a dry solids basis. This requirement applies to any vessel which is used as a reactor or as both a reactor and a stripper. In the bulk process, the product means the gross product of prepolymertzation and postpolymerization. (3> Manual vent valve discharge; Ex cept for an emergency manual vent valve discharge, there is to be no discharge to the atmosphere from any manual vent valve on a polyvinyl chloride 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 meas ures to prevent the discharge. Within 10 days of any discharge to the atmosphere from any manual vent valve, the owner or operator of the source from which the discharge occurs shall submit to the 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 determining the vinyl chloride loss, the action that was taken to prevent the discharge, and measures adopted to prevent future dis charges. (b) Stripper: The concentration of vinyl chloride in all exhaust gases dis charged to the atmosphere from each stripper Is not to exceed 10 ppm, except as provided In 5 61.85(a). This require ment does not apply to equipment that has been opened, is out of operation, and met the requirement In 5 61.65(b) (6) (1) before being opened. (c) Mixing, weighing, and holding containers: The concentration of vinyl chloride In all exhaust gases discharged to the atmosphere from each mixing, weighing, or holding container in vinyl chloride service which precedes the stripper (or the reactor if the plant has no stripper) In the plant process flow Is not to exceed 10 ppm, except as provided in 5 6165(a). Tills requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in | 61.65(b) (6) (1) before being openod. (d) Monomer recovery system The concentration of vinvl chlmtuc in clt ex haust gases di'Mdnrgcd in the piiere from each monomer recovery sys tem Is not to exceed in ppm, except ns provided In 5 61.65(a). This requirement does not apply to equipment that has been opened, Is out of operation, and met the requirement in 5 61.65(b) (6) (1) be fore being opened. <0 Sources following the stripper(s> : The following requirements applv (' emissions of vinyl chloride to the at mosphere from the combination of nil sources following the strippr.-is) lor the reactor(s) if the plant has no strip per (s'] In the plant process flow (ncluding but not limited to, centrifuges concentrators, blend tanks, filters, dry ers, conveyor air discharges, bearers, 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 opera tion on each calendar day, measured immediately after the stripping opera tion Is completed, may not exceed: (1) 2000 ppm for polyvinyl chloride dispersion resins, excluding latex resins; (ii) 400 ppm for all other polyvinyl chloride resins, including latex resins, averaged separately for each type of res in; or (2) In polyvinyl chloride plants con trolling vinyl chloride emissions with technology other than stripping or in addition to stripping, emissions of vinyl chloride to the atmosphere may not exceed: (I) 2 g/kg (0.002 lb/lb) product from the stripper (s) ior reactor<s) If the plant has no strlpper(s)] for dispersion polyvinyl chloride resins, excluding latex resins, with the product determined on a dry solids basis; (II) 0.4 g/kg (0.0004 lb,1b) product from the strippers Tor reactor(s) If the Plant has no stripper(s) 1 for all other polyvinyl chloride resins, Including latex resins, with the product determined on a dry solids basis. 61,65 Emission xtundurd for rlhrirne dirlilorhlc, vind chloride iitid poly vinyl chloride phmtti. An owner or operator of an ethylene diehloride, vinyl chloride, and/or poly vinyl chloride plant shall comply with the requirements of this section. (a) Relief valve discharge; Except for an emergency relief discharge, there Is to be no discharge to the atmosphere from any relief valve on any equipment In vinyl chloride service. An emergency relief discharge means a discharge which could not have been avoided by taking measures to prevent the discharge. With in 10 days of any relief valve discharge. FEDERAL REGISTER, VOL 41, NO. 205--THURSDAY, OCTOBER 21, 1976 UCC 102778 46566 RULES AND REGULATIONS the owner or operator of the source from system from which the concentration of which the relief valve discharge occurs vinyl chloride In the exhaust gases does ahull submit to the Administrator a re not exceed 10 ppm; or equivalent as port in writing containing Information provided in; 61.66. on the source, nature and cause of the (Ill) Rotating compressor: Vinyl discharge, the date and time of the dis chloride emissions from seals on all ro charge, the approximate total vinyl chlo tating compressors la vinyl chloride ride loss during U>o discharge, the meth service arc to be tittnimiw'd by installlnz od used for determining the vinyl chlo compressor* with double meclmnlml ride loss, the action that was taken to seals, or equivalent as provided in | 01.60. prevent the discharge, and measures If double mechanical seals are used, vinyl adopted to prevent future discharges. chloride emissions from the seals are to <b> Fugitive emission sources: be minimized by maintaining the pres (1) Loading and unloading lines: Vinyl sure between the two seals so that any chloride emissions from loading and un leak that occurs Is Into the compressor; loading lines which are opened to the by ducting any vinyl chloride between atmosphere after each loading or un the two seals through a control system loading operation are to be minimized from which the concentration of vinyl as follows: chloride In the exhaust gases does not (1) After each loading or unloading exceed 10 ppm; or equivalent as provided operation and before opening a loading In { 61.66. or unloading line to the atmosphere, the (lv) Reciprocating compressors: Vinyl quantity of vinyl chloride In all parts of chloride emissions from seals on all re each loading or unloading line that are ciprocating compressors in vinyl chloride to be opened to the atmosphere Is to be service are to be minimized by Installing reduced so that the parts combined con double outboard seals, or equivalent as tain no greater than 0.0038 m' (0.13 ft*) provided in $ 61.66. If double outboard of vinyl chloride, at standard tempera seals are used, vinyl chloride emissions ture and pressure: and .from the seals are to be minimized by (11) Aliy vinyl chloride removed from maintaining the pressure between the a loading or unloading line in accord two seals so that any leak that occurs Is ance with paragraph (b) (1) (i) of this Into the compressor; by ducting any section Is to be ducted through a control vinyl chloride between the two seals system from which the concentration of through a control system from which the vinyl chloride In the exhaust gases does concentration of vinyl chloride in the not exceed 10 ppm, or equivalent as pro exhaust gases does not exceed 10 ppm; vided In 161.66. or equivalent as provided in 5 61.66. (2) Blip gauges: During loading or un (v) Agitator: Vinyl chloride emissions loading operations, the vinyl chloride from seals on all agitators in vinyl chlo Emissions from each slip gauge in vinyl ride service are to be minimized by in jbhlorlde service are to be minimized by stalling agitators with double mechani ducting any vinyl chloride discharged cal seals, or equivalent as provided In from the slip gauge through a control 5 61,66. If double mechanical seals are system from which the concentration of used, vinyl chloride emissions from the vinyl chloride m the exhaust gases does seals are to be minimized by maintaining not exceed 10 ppm, or equivalent as pro the pressure between the two seals so vided In f 61.66. that any leak that occurs is Into the agi (3) Leakage from pump, compressor, tated vessel; by ducting any vinyl chlo and agitator seals: ride between the two seals through a (I) Rotating pumps: Vinyl chloride control system from which the concen emissions from seals on all rotating tration of vinyl chloride in the exhaust pumps in vinyl chloride service are to be gases does not exceed 10 ppm: or equiva minimized by installing sealless pumps, lent as provided In ! 61.66. pumps with double mechanical seals, or (4) Leakage from relief valves: Vinyl equivalent as provided In $ 61.66. if chloride emissions due to leakage from double mechanical seals are used, vinyl each relief valve on equipment in vinyl chloride emission from the seals are to chloride service are to be minimized by be minimized by maintaining the pres Installing a rupture disk between the sure between the two seals so that any equipment and the relief valve, by con leak that occurs Is Into the pump; by necting the relief valve discharge to a ducting any vinyl chloride between the process line or recovery system, or equiv two seals through a control system from alent as provided in 5 61.66. which the concentration of vinyl chlo (5> Manual venting of gases. Except ride in the exhaust gases does not ex as provided In 5 61.64<a i <3', all gases ceed 10 ppm; or equivalent as provided which are manually vented from equip in | 61.66. ment In vinyl chloride service are to be (II) Reciprocating pumps: Vinyl chlo ducted through a control system from ride emissions from seals on all recipro which the concentration of vinvl chloride cating pumpe in vinyl chloride service In the exhaust gases does not exceed 10 are to be minimized by installing double ppm: or equivalent as provided in } 61.66. outboard seals, or equivalent as provided (6) Opening of equipment: Vinyl In | 61.66. If double outboard seals are chloride emissions from opening of used, vinyl chloride emissions from the equipment (including loading or unload seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs Is Into the ,pump; by dusting any vinyl chloride beItween the two seals through a control ing lines that are not opened to the at mosphere after each loading or unload ing operation) are to be minimized as follows: (i) Before opening any equipment for any reason, the quantity of vinyl chlo ride is to be reduced so that the equip ment contains no more than 2.0 percent by volume vinyl chloride or 0.0950 m* (25 gal) of vinyl chloride, whichever is larger, at standard temperature and pressure; and (lii Any vinyl chloride ieinnve.ii from the equipment Ip nrciitilnnee ullli pan, Vrm'Ii (III Ml' (li Of title rpi Him to lit lv ihirtpd through a control vslmii from which the concentration of vlnvi chin ride In the exhaust gases does not exceed 10 ppm. or equivalent as provided In g 61.66. (7) Samples: Unused portions of sam ples containing at least 10 percent by weight vinyl chloride are to be returned to the process, and sampling techniques are to be such that sample containers in vinyl chloride service arc purged into a closed process system. i8> Leak detection and eliminationVinyl chloride emissions due to leaks from equipment In vinyl chloride service are to be minimized by instituting and implementing a formal leak detection and elimination program. The owner or operator shall submit a description of the program to the Administrator for approval. The program is to be sub mitted within 45 days of the effective date of these regulations, unless a waiver of compliance Is granted under 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 reliable and accurate vinyl chloride monitoring system for de tection of major leaks and identification of the general area of the plant where a leak is located A vinyl chloride monitor ing system means a device which obtains air samples from one or more points on a continuous sequential basis and ana lyzes the samples with gas chromatog raphy or. if the owner or operator as sumes that all hydrocarbons measured are vinyl chloride, with infrared spectro photometry flame Ion detection, or an equivalent or alternative method. fii i It Includes a reliable and accurate portable hydrocarbon detector to be used routinely to find small leaks and to pin point the major leaks indicated by the vinyl chloride monitoring system. A portable hydrocarbon detector means a device which measures hydrocarbons with a sensitivity of at least 10 ppm and Is of such design and size that It can be used to measure emissions from local ized points (ill1 It provides for an acceptable cali bration and maintenance schedule for the vinyl chloride monitoring system and portable hydrocarbon detector. For the vinyl clvlorlde monitoring system, a dally span check is to be conducted with a concentration of vinyl chloride equal to the concentration defined as a leak ac cording to paragraph (b) (8) (vl) of this section. The calibration Is to be done with either: (At A calibration gas mixture pre pared from the gases specified in seettom 5.2.1 and 5.2.3 of Test Method 106, or FEDERAl REGISTER, VOL. 41. NO. 205--THURSDAY, OCTOBER 21, iz* UCC 102779 rules and regulations 46567 (Bi A calibration gas cylinder contain vinyl chloride in equipment 75 of emission test results and other data ing the appropriate concentration of vinyl chloride. If a calibration gaa cylin der is used, the analysis must be trace* nblf to the National Bureau of Stand ards or to a gravlmetrloally calibrated i mvl'chloride permeation tube t iv > The loi'utbm and number ni ixiUiU (1,250 gel. ) in volume for which an iiinifl, aiuit limit ia prescribed m SOI,65 (b)(6) (i) prior to opening tb, equipment mid uatng Tetl Method in,,, > portable hydro carbon delei t,,l , 1,1 all equivalent lit el let native iiiU,,,,l ihu o,elb,,d ,d loeaa needed to determine emissions. (g) Unless otherwise specified, the owner or operator shall use lest Tc-i Methods In Appendix B to this purl in; each test as required by punu;i iipli (gi 111, (g I (Hi , - g C . 11 in 1 . 4 ...1 Igl Itll ill this Silk.Il',l ,iI,)l.ss ,,1i i,i tic monlloml and Mm ftetiuency f uietoonl 1* l>, iiin*l II,e (jnlmtiMil, n, ipflt lliplllll.1 III Oil pltni ,,o( Ivo ,,,,->1 monitoring provided for in the proa ram RM.I.I Igl (M |U (A I Ip) !r-t !)' 1"' Iirs hasp aiipinvs*' in (be .Atippqisi,,,i,`, are acceptable when they are compared If tile Admlntstintm finds reasonab1' with the number of pieces of equipment 61.66 Lqiiivnlciil etjtitimicnt mid pro grounds to dispute tin1 results obtniu-'fi in vinyl chloride service and the size and cedures. by an equivalent or alternative metho. physical layout of the plant. Upon written application from an own he mav require the use of a referent e (v) It contains an acceptable plan of action to be taken when a leak is de tected. (vl) It contains a definition of leak er or operator, the Administrator may approve use of equipment or procedures which have been demonstrated to his method. If the results of the reierence and equivalent or alternative metpoiu, do not agree, the results obtained by the reference method prevail, and the Ad which Is acceptable when compared with satisfaction to be equivalent in terms of ministrator may notify the owner or the background concentrations of vinyl reducing vinyl chloride emissions to the operator that approval of the method chloride In the areas of the plant to be monitored by the vinyl chloride monitor ing system. Measurements of background concentrations of vinyl chloride in the areas of the plant to be monitored by the vinyl chloride monitoring system are to be included with the description of the program. The definition of leak for a given plant may vary among the differ ent areas within the plant and is also to change over time as background con centrations in the plant are reduced. (9) Inprocess wastewater: Vinyl chlo atmosphere to those prescribed for com pliance with a specific paragraph of this subpart. For an existing source, any re quest for using an equivalent method as the Initial measure of control is to be submitted to the Administrator within 30 days of the ellective date. For a new source, any request for using an equiva lent method Is to be submitted to the Administrator with the application for approval of construction or modification required by 5 61.07. previously considered to be eauivalent or alternative is withdrawn (1) Test Method 106 is to be used to determine the vinyl chloride emission * from any source for which an emission limit is prescribed in 8$61.62ia> or (b' 5 61.63(a), or SS 61.64(a) (1), (b>, <c >. o: (d), or from any control system to which reactor emissions are required to be ducted in $ 61.64(a) (2) or to which fugi tive emissions are required to be ducted In ss 61.65(b) (1) (ii i, ib>(2, (b)(5', <b) (6) (ID ,or (b) (91 (in . ride emissions to the atmosphere from 61.67 Emission Itsls. <1* For each run, one sample is to be inprocess wastewater are to be reduced as follows: (I) The concentration of vinyl chlo ride In each lnprocess wastewater stream containing greater than 10 ppm vinyl chloride measured Immediately as It leaves a piece of equipment and before being mixed with any other lnprocess wastewater stream Is to be reduced to no more than 10 ppm by weight before being mixed with any other lnprocess wastewa ter stream which contains less than 10 ppm vinyl chloride: before being exposed to the atmosphere, before being dis charged to a wastewater treatment proc ess; or before being discharged untreated as a wastewater. This paragraph does apply to water which Is used to displace vinyl chloride from equipment before It is opened to the atmosphere In accord ance with 5 6164'a ' 2 i or paragraph (b) (6) of this :>(>r ti, but does not apply to water which i.-. used to wash out equip ment after the equipment has already been opened to the atmosphere In ac cordance with 161.64(a)(2) or para graph (b) (6) of this section. (a) Unless a waiver of emission testing Is obtained under { 61.13. the owner or operator of a source to which this sub part applies shall test emissions from the source. (1) Within SO days of the effective date In the case of an existing source or a new source which has an Initial startup date preceding the effective date, or (2) Within 90 days of startup In the case of a new source, initial startup of which occurs after the effective date. (b) The owner or operator shall pro vide the Administrator at least 30 days prior notice of an emission test to afford the Administrator the opportunity to have an observer present during the test. (c) Any emission test Is to be con ducted while the equipment being tested Is operating at the maximum production rate at which the equipment will be op erated and under other relevant condi tions as may be .specified by the Admlnlhtl liter based on icpri-cliUiUve jitTfunn- ance of the source.' (d> Each emission test is to consist of three runs. For the purpose of deter collected. The sampling site is to be at least two stack or duct diameters down stream and one half diameter upstream from any flow disturbance such ns a bend, expansion, contraction, or visible flame. For a rectangular cross section an equivalent diameter is to be determined from the following equation: 'fiiiivali'iit diaiiiHri , (length) (width) length-f width The sampling point m 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. (11) For gas streams containing more than 10 percent oxygen, the concentmtion of vinyle chloride .is dcLcnumrd bv Test Mellmd 106 in Lo be collected to 10 percent oxygen tor deterliUlHiUoii ot emission* by using the following equu lion (II) Any vinyl chloride removed from mining emissions, the average of results file lnprocess wastewater In accordance with paragraph (b) (9) (1) of this section of all runs Is to apply. The average is to be computed on a time weighted basis. where 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. (ei All samples are to be analyzed within 24 hours, and vinyl chloride emis sions are to be determined within 30 days after the emission test. The owner or operator shall, report the determinations ^ `icornv fed; ib* > < <*nlrution of vinyl I'hlund'1 in Iho exhaust gasofl, correulod to hi in porcent oxygen. Cv--The cwuteatT&Uon t>i T}ny\ chtownie measured by Test Method Mtit 20.{>=*Porooiit oxygen in the ambient atr ,t standard conditions. (c) The requirements In paragraphs to the Administrator by a registered (b)(1), (b)(2), (b)(5), (b)(6), (b)(7) letter dispatched before the close of the 10 9 = Percent oxygen in the ambient uir at standard conditions, minus the it) percent oxygen to which the correc and (b) (8) of this section are to be In next business day following the deter corporated into a standard operating mination. tion is being made. Tore* ni Oj-Percent oxygen in the exhaust gas ok measured by Reference Method 3 in procedure, anr made available upon re (f) The owner or operator shall retain Appendix A of Part do of this chapter. quest for Inspection by the Administra tor. The standard operating prooedure Is to Include provisions for measuring the at the plant and make available, upon request, for inspection by the Adminis trator, for a minimum of 2 years records (Ill) For those emission sources where the emission limit Is prescribed In terms of mass rather than concentration, mass FfOftAl REGISTER, VOL. 41, NO. 20S--THURSDAY, OCTOSER 21, 1976 CORRECTED DECEMBER 3. 1976 UCC 102780 46568 MILES AND REGULATIONS -rmlsslions In kg/100 kg product are to that Is also used as a stripper, the deter detection, or an equivalent or alterna deltermined by using the foOowtog ^Jtuiuaattlkm: Cu 1C> (3.00) 0 10~*11100] Z c'ar*ki vinyl blorldWlOO ki iiroduoL lAt'>--TDDobaatyiir*ttTft*tivnMtofnMvifimnUyiioaldatblaatta.vrlmdty*iiGwiikvfttdiw* moipulMmrmouarondd sroltiu/wV 0--VGlnnwlricnow rUt In mVhf ** dDUrmliMMl by mination may be made Immediately fol lowing the stripping operation. (I) Except as provided In paragraph (g) (t)Ul) at this section, the reactor opening loas Is to be determined using the following equation: ,, W (2.60) (10-*) (Cb) t---------- -- yX- vliw; tive method. The vinyl chloride monitor ing system used to meet the requirements m | Cl.C5(b) (8) (1) may be used to nvK the reaulramenta of this section (c) A daily *pan chock i to bi conduct ~ tod for iarh vinyl chloridt muMioniii; yitem ubuJ, tor All uf tile rnxvsiim DoufcNfa liilr.l |n |>a r d y r to pi i (n) .it this ('tli'ii, l)i' unr f"i v/niil tin nil I on ) i m 11 f I s ptfiBi r ib^d In b ( l, (. Bifcroiu^ Mtihod I of AppmmUx A id Port to f (fate obopiv. f'-kl vinyl nhtnrMp emMotWk* prodmtW- Capacity o! lb* reactor In ni*. (b)> th* daily upati check i In be > ondig'l- IO-*Oonyorat<Ni motor ter ppm- 1.00--DuuHt of riuyl ohloride at one atmosphere and ed with a concentration of vinyl chloride Z-Production rote (kt/hr). (2) Test Method 107 Is to be used to V Clnks/m*. W-* Convenlon factor for ppm. Cfc-ppra by vohnne vinyl eblorlde as determined by equal to 10 ppm. For the emission source for which an emission limit ip prescribed determine the concentration of vinyl chloride In each lnprocess wastewater stream for which an emission limit Is prescribed In f 61.65(b) (9) (1). (3) Where a stripping operation Is used to attain the emission limit In 161.64(e), emissions are to be determined using Test Method 107 as follows: (I) 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 6w of the test based on the plant's operation. (II) Each sample Is to be taken Imme Teat Matbod 106 or a portable hydrocarbon detector which measures hydrocarbon* wttb a aenaltlvity of at leaat 10 ppmI'-Nuuber of batebee alnoe the reactor wae last opened to the atmosphere. 7-Averina tg of polyvinyl eblorlde produced per baton in the number of batches since the reactor was last opened to the atmosphere. (A) If Method 106 Is used to deter mine the concentration of vinyl chloride (Cb>, the sample is to be withdrawn at a constant rate with a probe of sufficient length to reach the vessel bottom from the manhole. Samples are to be taken for 5 minutes within 6 Inches of the ves sel bottom, 5 minutes near the vessel in 161. 62 (b), the daily span check is to be conducted with a concentration of vinyl chloride which is determined to be equi valent to the emission limit for that source -- based on the__emission test required bv467.67 The calibration is to be done with either: fl> A calibration' gas mixture pre pared from the gases specified In sections 5.2.1 and 5.2.3 of Test Method 10P. or (2) A calibration gas cylinder con taining the appropriate concentration of vinyl chloride. If a calibration gas cylinder is used, the analysis must be traceable to the National Bureau of diately following the stripping operation. center, and 5 minutes near the vessel top. Standards or to a gravimetrlcally cali (III) The corresponding quantity of (fi) If a portable hydrocarbon detec brated vinyl chloride permeation tube. material processed by each stripper is to tor Is used to determine the concentra 61,69 Initial report. be determined on a dry solids basis and by a method submitted to and approved by the Administrator. (lv) At the prior request of the Ad minisiMtrator, the owner or operator shall ^TOroQvvidldeo duplicates of the samples re ^Hblred in paragraph (g)(3)(i) of this ^^eScetclotionn.. (4) Where control technology other than or In addition to a stripping opera tion Is used to attain the emission limit In | 61.64(e), emissions are to be deter mined as follows: (I) Test Method 106 Is to be used to determine atmospheric emissions from all of the process equipment simultane ously. The requirements of paragraph (g) (1) of this section, are to be met. (II) Test Method 107 Is to be used to determine the concentration of vinyl chloride in each lnprocess wastewater stream subject to the emission limit pre scribed In | 61.64(e). The mass of vinyl 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 within 6 inches of the vessel bottom, one near the vessel center and one near the vessel top. Measure ments are to be made at each location until the reading Is stabilised. All hydro carbons measured are to be assumed to be vinyl chloride. (C) The production rate of polyvinyl chloride (Z) to to be determined by a method submitted to and approved by the Administrator. (II) A calculation based on the number of evacuations, the vacuum Involved, and 'the volume of gas In the reactor Is hereby approved by the Administrator as an al ternative method for determining reac tor opening loss for postpolymerlzatlon reactors In the manufacture of bulk resins. (a) An owner or operator of any source to which this subpart applies shall submit a statement to writing notifying the Administrator that the equipment and procedural specifications in }S 61.65 (b)(1), (b)(2), (b)(3), (b)(4), (b)(5), (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 90 days of the effective date, unless a waiver of compliance is granted under f6l.ll, along with the informa tion required under f 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 to to be submitted within 90 days of the chloride In kg/100 kg product In each 6 61^68 Eantotoon nmailorjpa,. initial startup date. In process wastewater stream Is to be de (a) A vinyl chloride monitoring *y' (c) The statement to to contain the termined by using the following equa tem lb to be lined to monitor on a ronMn- following Information: tion: iimiii basin the emission* 11 om Lh hiktirtm il) A list of the equipment Installed .,h v - \r*lt intJ *| |iooi fit)' wllii.li e/|Mntu)i limits fail |iSfH i I thrift for compliance, 111 1, ft/ ( } n it'l (It |, lb | , /, I ) rtii! 21 A ut.i riiiUon of the physical and tbliorn t vinyl rhlortiWlOn kg prmln> I t'd-=th* oon^entraUmi of vinyl oblorMp on itiPiv>uiPd by Teft Mothorf 107. J? -water flow m* jn 1/br, (tetenrHnedln ftttnrdarx* with a method which hA been tubmltted to 16 1.61 (a) M). dO, (< ). end fd) id fnr any control system to who ) j r-v tot emissions are required to bf duclrd in |61, 64 (a) (?-} or to which fugitive emis functional chara<`teristiiT. of each piece of equipment. (3) A description of the methods which have been Incorporated Into the standard operating procedures for meas And approved by the Administrator. J(H -- Conversion factor tor ppm. Z--Production ram (kg/hr), determined In accord sions are required to be ducted vn 6 1. 65 (b) <1) (ii), and (b) (Zb (b) (5), (b) (6) (n), uring or calculating the emissions for which emission limits are prescribed In ance with a method which has been submitted and approved by the Administrator, (6) The reactor opening loss for which an emission limit Is prescribed in J 61.64 and (bi (9) (ii). <b) The vinyl chloride monitoring sys tem^) used to meet the requirement In paragraph (a) of this section la to be a Sf 61.65 (b) (1X1) and (b)(6Xl), (4) A statement that each piece of equipment to Installed and that each piece of equipment and each procedure (a) (2) Is to be determined. The number device which obtains air sampels from to being used. of reactors for which the determination t la to be made Is to be specified by Ui administrator for each Individual plan Jkt the time of the determination base one or more points on a continuous sequential basis and analyzes the samples with gas chromotography or, if the owner 61,70 Semiannual report. (A) The owner or operator of any source to which this subpart applies shall sub on the plant's operation. For a reactc ,or operator assumes' that all hydrocar mit to the Administrator on Septem- bons measured are vinyl chloride, with infrared spectrophotometry, flame ion CORRECTED DECEMBER 3, 1976 VJCC 102781 RULES AND REGULATIONS 46569 ber 15 and March 15 of each year a report Of 8 hours for each grade of resin which may be made immediately following the In writing containing the Information Is being processed, whichever la more fre stripping operation. required by this section. The first semi annual report Is to be submitted follow ing the first full 6 month reporting period after the initial report Is submitted. (b) (1) In me case of an existing source quent. The sample Is to be taken as me resin flows out of me stripper and Iden tified tv resin type and grade and the date and time me sample was taken. The corresponding quantity of material 61.71 Rerordkeeping. (a) The owner or operator of any source to which mis subpart applies shall retain me following information at the or a new source which has an Initial startup date preceding me effective date, the first report Is to be submitted within 180 days of me effective date, unless a waiver of compliance Is granted under 5 61.11. If a waiver of compliance Is granted, me first report is to be sub mitted on a date scheduled by me Ad ministrator. (2) In me case of a new source which did not have an Initial startup date pre ceding me effective date, me first report is to be submitted within 180 days of me initial startup date. (c) Unless otherwise specified, me owner or operator shall use me Test Methods In Appendix B to this part to conduct emission tests as required by paragraphs (c) (2) and (c) (3) of this section, unless an equivalent or an alter native method has been approved by me Administrator. If me Administrator finds reasonable grounds to dispute me results obtained by an equivalent or al ternative method, he may require me use of a reference method. If me results of the reference and equivalent or alterna tive methods do not agree, me results obtained by me reference method pre processed by each stripper over the time period represented by me sample during the eight hour period, Is to be recorded and Identified by resin type and grade and the date and time It represents. (ill) The quantity of material proc essed by me stripper is to be determined on a dry solids basis and by a method submitted to and approved by me Ad ministrator. (lv) At me prior request of me Ad ministrator, me owner or operator shall provide duplicates of me samples re quired in paragraphs (c)(2) (1> and (c) (2) (11) of this section. (v) The report to me Administrator by me owner or operator Is to Include me vinyl chloride content found In all me samples required In paragraphs (c) (2) (1) and (c) (2) (11) of mis section, aver aged separately for each type of resin, over each calendar day and weighted ac cording to me quantity of each grade of resin processed by me strlpper(s) mat calendar day, according to me following equation: A `"I source and make it available for inspec tion by me Administrator for a mini mum of two years; (1) A record of the leak.-, detected by the vinyl chloride monitoring system, as required by S61.65(bM8>, including the concentrations oi vinyl chloride a-, measured, analyzed, and recorded by tin* vinyl chloride detector, the location oi each measurement and the date and ap proximate time of each measiu-emem (2) A record of the leaks detected during routine monitoring with the portable hydrocarbon detector and the action taken to repair the leaks, as re quired by {61.65(b)(8), including a brief statement explaining me location and cause of each leak detected with me portable hydrocarbon detector, the date and time of me leak and any action taken to eliminate that leak measured in accordance with 5 61.68. (3) For the relief discharge*; fr.mi reactors subject to tire provisions oi {61.65(a), a daily operating record lor each reactor, including pressures and temperatures. 2, Appendix B is amended by adding Test Methods 106 and 107 s follows, vail, and the Administrator may notify MCTBOD 106--Determination of Vint, the owner or operator mat approval of CSLORIDS FROM STATIONARY SOURCES the method previously considered to be equivalent or alternative is withdrawn. (1) The owner or operator shall in clude In me report a record of any emis sions which averaged over any hour Pa, Ms, f Pa, Mo, 4 . . . Qrt Afo# /1--24-hour average concentration of type T, resin In Q-To&Yprodootion of type T, reatn over the 24-hour INTRODUCTION Performance of this method should no( on attempted by person-, unfamiliar with thn operation of a gas chromatograph, nor bv those who are unfamiliar with source sam period (commencing on the hour) are period. In kg. pling, as there are many details that arc in excess of me emission limits pre scribed In {{ 61.62(a) or (b), } 61.63(a), or 61.64(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 { 61.65 TV-Type of reein; /-l,2, . : . m where * It total number of resin types produced during the 24hour period. A/t Concentration of vinyl chloride In one sample of grade 0. resin, in ppm. Pt Production of grade Gi r4n represented by the ample, in kg. G:-Grade of resin, e.g., Gu Gt.andGv n-Total number ofgrades of reein produced during the 24-hour period. beyond the scope of this presentation. Canmust be exercised to prevent exposure of sampling personnel to vinyl chloride, a car cinogen. 1. Principle and Applicability. 1.1 An Integrated bag sample of stack gas containing vinyl chloride (chloroethylenei 1* subjected to chromatographic analyst-, (bHIHll), (b)(2), (b)(5), (b)(6) (U),or (b> (B) (ii). The emissions are to be meas ured in accordance with S 61.68. (2) In polyvinyl chloride plants for which a stripping operation is used to attain me emisison level prescribed in S 61.64(e), the owner or operator shall include in the report a record of the vinyl chloride content In the polyvinyl chloride resin. Test Method 107 is to be used to determine vinyl chloride content as follows: (i) If batch stripping Is used, one rep (vl) The owner or operator shall re tain at me source and make available for inspection by me Administrator for a minimum of 2 years records of all data needed to furnish me Information re quired by paragraph (c> (2) (v) of mis section: The records are to contain me following information: (A) The vinyl chloride content found in all me samples required in paragraphs (c) (2) (i) and (c) (2) (il) of this section, identified by me resin type and grade and the time and date of me sample, and using a flame Ionization detector. 1.3 The method is applicable to the men-- urement of vinyl chloride in stack gases from ethylene dichlorlde, vlnvl chloride and poly vinyl chloride manufacturing processes, ex cept where the vinyl chloride Is contained in particulate matter. 3. Range and Sensitivity The lower limit of detection will vary ac cording to the chromatograph uBed. Value-, reported Include 1 > 10 7 mg and 4 mg. 3. Interferences io ' Acetaldehyde, which can occur In some vinyl chloride source,;, will Interfere with iho resentative sample of polyvinyl chloride (B) The corresponding quantity of vinyl chloride peak from the Ohromoaorb 103 resin Is to be taken from each batch of each grade of resin immediately follow ing me completion of me stripping, and grade and me date and time me 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 me date and time me batch Is completed. (11) If continuous stripping is used, one representative sample of polyvinyl chloride resin Is to be taken for each grade of resin processed or at intervals polyvinyl chloride resin processed by the stripper(s), identified by the resin type and grade and the time and date it represents. (3) The owner or operator shall in clude In me report a record of me emis sions from each reactor opening for which an emission limit Is prescribed in f 61.64(a) (2). Emissions are to be deter mined in accordance with { 61.67(g) (5), except mat emissions for each reactor are to be determined. For a reactor mat la also used as a stripper, the determination column. See sections 4.8.2 and 6.4. If resolu tion of the vinyl chloride peak Is still not satisfactory for a particular sample, then chromatograph parameters can be further altered with prior approval of the Admin istrator. If alteration of the chromatograph parameters falls to resolve the vinyl chloride peak, then supplemental confirmation of the vinyl chloride peak through an abeolute analytical technique, such as mass spectro scopy, must be performed. 4. Apparatus. 4.1 Sampling (Figure 1) 4.1.1 Probe--Stainless steel, Pyrex glass, or Teflon tubing according to stack temper- FEDERAL REGISTER, VOL. 41, NO 205--THURSDAY, OCTOBER 21. 1976 UCC 102782 46570 RULES AND REGULATIONS ature, each aqulpped with a glftfti wool plug 4.4.6 Plow meter--Rotameter type, 0 to to remove particulate matter. 1000 ml/mln range accurate to 1%, to 4.1 A Bftmple line--Teflon, 6.4 mm outride meter niwogen In preparation of standard diameter, of sufficient length to connect gas mixtures. probe to bag. A new unused piece la employed 4.4.6 stop watch--or known accuracy, to for each eerlee of bag sunifies that oonstltutaa tune gaa flow In preparation of standard gas an emission test. mixtures. 4.1.3 Male (3) and female (3) stainless 6. Reagents It le necessary that all Ma steel quick-connects, with ball checks (one genta be of chromatographic grade. pair without) located as Shown In Figure 1. 6.1 Analysis. 4.1.4 Tedlar bags. 100 liter oapaclty--TO fi.l.l Bellum gas or nitrogen gas--Zero contain sample. Teflon bags are not aooept- grade, for chromatographic oarrler gas. able. Aluminized Mylar bags may be used, 6.1.3 Hydrogen gas--Zero grade. provided that the samples are analysed 6.1 A Oxygen gas, or Air, as required by Within 34 hours of collection. the detector--Zero grade. 4.1 A Rigid leakproof containers for 4.1.4, 6.3 Calibration. with covering to protect contents from sun 6.2.1 Vinyl chloride. 99,9+%--For prep light. aration of standard gas mixtures. 4.1.6 Needle valve--To adjust sample flow 6A.3 Calibration cylinders (3), optional-- rate. One each of 60, 10 and 6 ppm vinyl chloride 4.1.7 Pump--Leak-free. Minimum capac In nitrogen with certified analysis. Analysis ity 3 liters per minute. must be traceable to KBS (National Bureau 4.1.6 Charooal tube--To prevent admis of Standards) or to a gTavlmetrlcally cali sion of vinyl chloride to atmosphere In vicin brated vinyl chloride permeation tube. ity of samplers. 6.2.3 Nitrogen gas--Zero grade, for prep 4,1.9 Flow meter--For observing sample aration of standard gas mixtures-. flow rate; capable of measuring a flow range 6. Procedure. from 0.10 to 1.00 liter per minute. 6.1 Sampling. Assemble the sample train 4.1JO Connecting tubing--Teflon, 6.4 mm as In Figure 106-1. Perform a bag leak check outside diameter, to assemble sample train according to Section 7.4. Observe that all (Figure 1). connections between the bag and the probe 4.1.11 Pitot tube--Type S (or equivalent), are tight. Place the end of the probe at the attached to the probe so that the sampling centroid of the stack and start the pump flow rate can be regulated proportional to with the needle valve adjusted to yield a the stack gas velocity. flow of 0A 1pm. After a period of time suffi 4.3Sample recovery. cient to purge the line several times has 4.3.1 Tubing--Teflon, 6.4 mm outside elapsed, connect the vacuum line to the diameter, to connect bag to gaa chromato bag and evacuate the bag until the rotam graph sample loop. A new unused piece la eter indicates no flow. Thsn reposition the employed for each aeries of bag samples that sample and vacuum lines and begin the ac constitutes an emission test, and Is to be dis tual sampling, keeping the rate proportional carded upon conclusion of analysis of those to the stack velocity. Direct the gas exiting bags. the rotameter away from sampling personnel. 4.3 Analysis. At the end of the sample period, shut oil the 4.3.1 Gas chromatograph--With flame pump, disconnect the sample line from the Ionization detector, potentiametric strip bag. and disconnect the vacuum line from chart recorder and ID to 6.0 ml heated sam the bag container. Protect the bag container pling loop in automatic sample valve. from sunlight. 4.3 A Chromatographic column--Stainless 6.3 Sample storage. Sample bags must be steel, amx 3.3 mm, containing 80/100 merit kept out of direct sunlight. When at all pos Chromosorb 103- A secondary colum of GE sible, analysts Is to be performed within 24 SF-06, 30% on 60/80 mesh AW Ghramosorb hours of sample collection. P, stainless steel, 3.0 m X 8.3 mm, will be 6A Sample recovery. With a piece of Tef required if acetaldehyde is present. If used, lon tubing-identified for that bag, connect a the SF-96 oolumn Is placed after the Chromo- sorb 103 column. The combined columns should then be operated at 110*C. 4AA Flow meters (3)--Rotameter type, 0 to 100 ml/mln capacity, with flow control valvea. bag Inlet valve to the gas chromatograph sample valve. Switch the valve to withdraw gas from the bag through the eample'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 4.3.4 Gas regulators--For required gas by a 0-100 ml/mm rotameter with flow con cylinders. trol valve. 4A 6 Thermometer--Accurate to one de 6.4 Analysis. Set the column temperature gree centigrade, to measure temperature of to 100* c the detector temperature to 160* heated sample loop at time of sample Injec C, and the sample loop temperature to 70* C. tion. When optimum hydrogen and oxygen flow 4.3.6 Barometer--Accurate to & mm Rg, to rates have been determined verify and main measure atmospheric pressure around gas tain these flow rates during all chromato chromatograph during sample analysis. graph operations. Using zero helium or 4.3.7 Pump--Leak-free. Minimum capac nitrogen as the carrier gas. establish a flow ity 100 ml/mln. rate In the range consistent with the manu 4.4 Calibration. facturer's requirements for satisfactory de 4.4-1 Tubing--Teflon, 6.4 mm outside tector operation. A flow rate of approxi diameter, separate pieces marked for each mately 40 ml/mln should produce adequate calibration concentration. separations. Observe the base line periodi 4.4A Tedlar bags--Sixteen-Inch square cally and determine that the noise level has size, separate bag marked for each calibra stabilized and that base line drift has ceased. tion concentration. Purge the sample loop for thirty eeconds at 4.4A Syringe--0.6 ml, gas tight. the rate of 100 ml/mln, then activate the 4.4.4 Syringe--60gl, gas tight.1 sample valve. Record the Injection time (the position of the pen on the chart at the time 1 Mention of trade names on specific prod ucts doss not constitute endorsement by the Environmental Protection Agency. 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 laboratory pressure. From the chart, . select the peak having the retention time corresponding to vinyl chloride, as deter, mined in Section 7. 2, Measure the peak area, Am, by use of a disc integrator or a planimeter. Measure the peak height, Hm, Record Am, 11m, 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 foi these two areas will be used to compute the bag concentration. Compare the ratio of Hu to A. for the vinyl chloride sample with the same ratio for the standard peak which la closest in height As a guideline. If these ratios differ by more than 10%. the vinyl chloride peak may not be pure (possibly acetaldehyde Is present) and the secondary column should be em ployed (see section 4AA). 6, 5 Measure the ambient temperature and barometric pressure near the bag. (Assume the relative humiditv to be 100 percent. 1 From a water saturation vapor pressure table, determine and record the water vapor content of the bag. 7. Calibration and Standards. 7.1 Preparation of vinyl chloride standard gas mixtures. Evacuate a sixteen-inch square Tedlar bag that has passed a leak check (described In Bectlon 7.4) and meter in 6 0 liters of nitrogen. While the bag Is filling, use the 0 5 ml syringe to inject 360x1 of 99.9-1- % vinyl chloride through the wall of the bag. Upon withdrawing the syringe needle. Im mediately cover the rseitltlng hols with a piece of adhesive tape. This gives a concen tration of 60 ppm of vinyl chloride. In a like manner use the other syringe to prepare dilu tions having 10 and 6 ppm vinyl chloride concentrations. Place each bag on a smooth surface and alternately depress opposite sides of the bag 60 times to further mix the gases. 7.2 Determination of vinyl chloride re tention time. This section can be performed simultaneously with Bectlon 7 3. Establish chromatograph conditions Identical with those In Bectlon 6A. above Bet attenuator to X 1 position. Flush the sampling loop with zero helium or nitrogen and activate the sample valve. Record the Injection time, the sample loop temperature the column temperature, the carrier gas flow rate, the chart speed and the attenuator setting. Record peaks and detector responses that occur In the absence of vinyl chloride. Main tain conditions With the equipment plumb ing arranged Identically to Bectlon 8.3. flush the sample loop for 30 seconds at the rate of loo ml/mln with one of the vinyl chloride calibration mixtures and activate the sample valve. Record the Injection time Select the peak that corresponds to vinyl chloride. Measure the distance on the chart from the Injection time to the time at which the peak maximum occurs. This quantity, divided by the chart speed, Is dellned as the retention time Record. 7 3 Preparation of chromatograph cali bration curve. Make a gas chromatographic measurement of each standard gas mixture (described in Section 7.1) using conditions Identical with thoee listed In Section 6A above. Flush the sampling loop for 30 seconds 'at the rate of 100 ml/mln with each standard gas mixture and activate the sampls valve 'Record C,. the concentrations of vinyl chlo'rlds Injected, the attenuator setting, chart 'speed, peak area, sample loop temperature, column temperature, oarrtsr gas flow rate, land retention rime. Beoosd the laboratory pressure. Calculate A,, the peak area multl- FEDEkAl REGISTER. VOl 41,. NO. 205--THURSDAY, OCTQ6E* 21, 1976 CORRECTED DECEMBER 3. 1976 UCC 102783 RULES AND REGULATIONS 46571 piled by tbe attenuator Betting. Repeat until two Injection area* are within 6%, then plot thoee points r C,. When the other concen tration* have been plotted, draw a smooth curve through the points. Perform calibra tion dally, or before and after each eet of bug samples, whichever Is more frequent. 7 4 Bag leak checks. While performance of this section Is required subsequent to bag use, it Is also advised that It be performed prior to bag use. After each use, make sure a bag did not develop leaks ss follows. To lsak check, connect a water manometer and pres surise the bag to 6-10 cm H,0 (2-4 In H,0). Allow to stand for 10 minutea. Any displace ment in the water manometer indicates a leak. Also obeck the rigid container for leaks In this manner. (Not*: An alternative leak check method la to pressurize the bag to 6-10 cm H.O or 2-4 in. H.O and allow to stand overnight. A deflated bag Indicates a leak.) For each sample bag In Its rigid oontalner, place a rotameter in-line between the bag and the pump inlet. Evacuate the bag. Failure of the rotameter to register ano flow when the bag appears to be empty Indicates a leak. 8. Calculations. 8.1 Determine the sample peak area aa follows: WA At -- Am A r where1 A.-The lample peak ana. A_Tbe measured peak ana. A/-Tbe sttecusttoo (actor. Equation 106-1 8.3 Vinyl chloride concentratlona. rrom the calibration curve described In Section U, above, select the value of O, that cor responds to A,, the sample peak area, cal culate Ct as follows: r CtP,Tt PiTtU-Uw*) Equation 106-3 Where: B.t-Tbe water vapor content of the beg aambte, M analysed. C>-Tbe scnntretloo of vinyl chloride in the bag ample In ppm. C.-Tbe oonoenUaUon ol vinyl chloride Indicated by the gas chromatograph, in ppm. P<-The relerenoe pressure, the laboratory ptomuie reoorded dtuiag calibration, mm He. 7\-Th* sample loop temperature on the ebeolute scale at the ttme ot analysis, *K. Ft--The laboratory pressure et time of analyels, r"~ Hg. T.aTbe relerenoe temperature, the aample Imp temperature recorded during calibration, 'K 9. References. 1. Brown, Dr-W.. Loy, E. W. and Stephen son, M. H. "Vinyl Chloride Monitoring Near the B. y, Goodrich Chemical Company In Louisville, Kentucky." Region IV. UJB. Envi ronmental Protection Agency, Surveillance and Analysis Division, Athens, Georgia^ June 24, 1274. 2. "Evaluation of A Collection and Analy tical Procedure for Vinyl Chloride In Air," by G. D. Clayton and Associates, December 18. 1974. EPA Contract No. 88-03-1408, Task Order No. 2, EPA Report oN. 75-VCL-l. 3. "Standardization of Stationary Bouroe mission Method for Vinyl Chloride," by Mid west Research Institute, 1976. EPA Contract No. 88-02-1098, Teak Order No. 7. MzTHOn 107--DwraisENirfON or Vustx. Ohlozon OorvrmvT or Iktsoczss Wisnwms Samples, am Vnrn. CKLOamz oontemt or PoLTvxrfTt Cmoami Rzsns, Blcxbt, wm C*Kl, and Lara Salmas xntxoduction performance of this method should not be attempted by persons unfamiliar with tbs operation of a gaa chromatograph, nor by those who are unfamiliar with sampling, ss there are many details that are beyond the eoope of this presentation. Cars must he exercised to prevent exposure of sampling personnel to vinyl chloride, a carcinogen. 1. Principle and Applicability. l.l Hie basis for this method1 relates to the vapor equilibrium which Is established between RVOM, FVO. rosin, water, and air in a closed system. It has been demonstrated that the RVOM in a FVO main will equili brate In a closed vessel quite rapidly, pro vided that the temperature of the PVO resin Is maintained above the glass transition temperature of that specific resin. 13 This procedure is suitable for deter mining the vinyl chloride monomer (VCM) content of lnprocees wastewater samples, and the residual vinyl chloride monomer (RVCM) content of polyvinyl chloride (PVO) resins, wet cake, slurry, and latex samples. It cannot be used for polymer In fused form, eucb as sheet or cubes. If a resolution of the vinyl chloride peak Is not satisfactory for a particular sample, then chromatograph parameters may be altered with prior ap proval of the Administrator. If there Is rea son to believe that some other hydrocarbon with an Identical retention time is present In the sample, then supplemental confirma tion of the vinyl chloride peak through an absolute analytical technique, such as mam spectroscopy, should be performed. 2. Range and Sensitivity. The lower limit of detection of vinyl chlo ride will vary acoordlng to the **- xgraph used. Values reported include 1 10-* mg and 4 X10-' mg. With proper calibration, the upper limit may be extended as needed 3. Precision and Reproducibility. An interlaboratory comparison between seven laboratories of three resin samples, each spilt Into three parts, yielded a standard deviation of 2.63% for a sample with a mean of 2.09 ppm, 4.16% for a sample with a mean of 1.66 ppm, and 6.29% for a sample wltb a mean of 62.66 ppm. 4. safety. Do not release vinyl chloride to the labora tory atmoaphere during preparation of stand ards. Venting or purging with VCM/alr mix tures must be held to a minimum. When they are required, the vapor must be routed to outside air. Vinyl chloride, even at low ppm levels, must never be vented Inside the laboratory. After vials have been analyzed, the pressure within the vial must be vented prior to removal from the Instrument turn table. Vials must be vented Into an activated charcoal tube using a hypodermic needle to prevent release of vinyl chloride Into the laboratory atmosphere. The charcoal musf be replaced prior to vinyl cblorlde break through. 6. Apparatus. 6.1 Sampling. 6.1.1 Bottlas--60 ml (2 ce), with waxed lined acrew on tops, for FVO samples. 6.12 Vials--60 ml Hypo-rials,1 sealed with Teflon faced Tuf-Bobd discs for water sam ples. 6.13 Electrical tape--or equivalent, to prevent loosening of bottle tope. 62 Sample recovery. 62.1 Vials--With seals and cape. PerklnKlmer Corporation No. 106-0118, or equiva lent. 63.3 Analytical balanoe--Capable of weighing to 0301 gram. 822. Syringe, 100 *1--Precision Barlm "A" No. 010036, or equivalent.1 1 Mention of trade names on specific prod ucts does not constitute endonesaent by As Environmental protection Agsooy, KDERAt REGISTER, VOL 41, NO. 105--THURSDAY, OCT >11 21, 197* UCC 102784 46572 tULES AND IEGUIAYIONS 83.4 Vial Sealer, Perkln-Elmer Mo. 106- ^0108 or equivalent. ^^63 Analysls- 63.1 Om chromatograph--Perkln-Elmer ^^Vovpcratlon MOM F-40 bO^OpOM MU' lyzer. Mo. 104-0001, or equivalent. 63.3 Chromatographic oolumn--Btaln- 1ms stool, 3 mxll sun. containing &4% Carbowax 1800 on Oarbopak A, Perkln-Elmer Corporation Mo. 106-0138, or equivalent. Carbopak o cos bo used In plooo at Oarbopak 6.3.3 Thermometer--0 to 100* C, oocuroto to 0.1' C. Perkln-Elmer Mo. 106-0100 or equivalent. 63.4. Sample troy thermostat system-- Perkln-Elmer No. 106-0103, or equivalent. 8.3.6 Septa--Sandwich type, tor auto matic aoslsg. 13 mm, Perkls-Elmer No. 106- 1008, or equivalent. 83.6 Integrator - recorder -- Hewlett - Packard Model 3380A, or equivalent. 63.7 Filter drier assembly (3)--PerkinZlmer No. 3330117, or equivalent- 63.8 Soap film flowmeter--Hewlett Pack ard No. 0101-0113, or equivalent. 6.4 Calibration. 5.4.1 Regulators--tor required gae eytn- derx. 8. Reagents. 8.1 Analysis. 8.1.1 Hydrogen gze--zero grade. 6.13 Nitrogen gas--oero grade. 6.13 Air--oero grade. 63 Calibration. 6.3.1 Standard cylinders (4)--one each of 60, 600. 3000, and 4000 ppm vinyl chloride In nitrogen, with certified analysis. 7. Procedure. 7.1 Sampling. 7.1.1 PVC sampling--Allow the rosin or slurry to flow from a tap on the tank or alio until the tap line baa been well purged. Ex pand a 60 ml sample bottle under the tap, fill, ad Immediately tightly cap the bottle. Wrap Metrical tape around the cap and bottle eo prevent the top ftom loosening. Plaoe an Identifying label on each bottle, and reoord the date, time, and sample location both on the bottles and In a log book. 7.13 Water sampling--Prior to use, the 80 ml vials (without the discs) must bo capped with aluminum foil and muffled at 400'C for at least one hour to destroy or remove any organic matter that could In terfere with analysis. At the mtripling loca tion flu the vials bubble-free, to overflowing so that a convex meniscus forms at tha top. The excess water la displaced as the sealing disc Is carefully placed, Teflon side down, on the opening of the vial. Plaoe the aluminum seal over the disc and tha neck of the vial and crimp into place. Affix an Identifying label on the bottle, and record the date, time, and sample location both on the vials and In a log book. All samples must be kept re frigerated until analysed. 73 Sample recovery. Samples must be run within 34 hours. 73.1 Resin samples--The weight of the resin used must be between 0.1 and 4,5 grama. An exact weight must be obtained (0.001 gram) for each sample, in the case of sus pension resins a volumetric cup can he pre pared which will hold the required amount of sample. The sample bottle la opened, and the cup volume of main Is added to the taxed sample vial (including septum alumi num cap). The vial la Immediately sealed and the exact sample weight Is then obtained. Deport this value on the data sheet aa It la required for calculation of RVCM. In the oaae of relatively dry mein aamplee (water content <03 weight %). 100 -l of distilled water must be Injected Into the vial, after sealing and weighing, using a 100 *1 syringe. In the oase of dispersion resins, the cup cannot he used. The sample ts instead weighed approximately in an aluminum dish, transferred to the tared vial and wulglisil accurately in the vlaL The sample is than placed in the Perkln-Elmer heed space ana lyzer (or equivalent) and conditioned for one hour at 0O*C. Non: Some aluminum vial cape have a center section which must be removed prior to placing Into sample tray. If not removed, serious damage to the Injection needle will occur. 733 Suspension resin slurry and wet cake samples--Slurry must be filtered using a small Buchner funnel with vacuum to yield wet caXe. The filtering process must be con tinued only as long as a steady stream of water Is exiting from the funnel. Excessive filtration time could result In some loss of VCM. The wet cake sample (0.10 to 43 grains) Is added to a tared vial (Including septum and aluminum cap) and Immediately sealed. Sample weight la then determined to 3 deci mal places. The sample Is then placed In the Perkln-Elmer head space analyzer (or equiva lent) and conditioned for one hour at 90*C. A sample of wet cake is used to determine TS (total solids). This la required for calcu lating the RVCM. 733 Dispersion resin slurry samples.-- This material Should not be filtered. Sample must be thoroughly mixed. Using s tared vial (including septum and aluminum cap) add approximately 8 drops (036 to 036 grams) of slurry or latex using a medicine dropper. This should be done immediately after mixing. Seal the vial aa soon as possible. Determine sample weight accurate to 0.001 grams. Total sample weight must not exceed 0.60 grams. Condition the vial for one hour at 60*C In the analyzer. Determine the TS on the slurry sample (Section 733). 73.4 Inprocess wastewater samples-- Using a tared vial (Including septum and aluminum cap) quickly add approximately 1 co of water using a medicine dropper. Seal the vial as (soon ss possible. Determine sample weight accurate to 0.001 gram. Con dition the vial for two hours at 60*C In the analyzer. 73 Analysis. 73.1 Preparation at gas chromatograph-- Install the chromatographic column and con dition overnight at 160*C. Do not connect the exit end of the oolumn to the detector while conditioning. 73.13 Plow rate adjustments--Adjust flow rates ss follows: a. Nitrogen carrier gas--Set regulator on cylinder to read 60 pslg. Set regulator on chromatograph to 13 kg/cm'. Normal flows at this pressure should be 36 to 40 cc/mlnuteCheck with bubble flow meter. b. Burner air supply--Set regulator on cyl inder to read 60 pslg. Set regulator on chromatograph to supply sir to burner at a rate between 380 and 300 cc/mlnute. Check with bubble flowmeter. 3. Hydrogen supply--Set regulator on cyl inder to read 80 pslg. Set regulator on chromatograph to supply approximately 856 cc/mlnute. Optimize hydrogen flow to yield the most sensitive detector response without extinguishing the flame. Check flow with bubble meter and record this flow 73.13 Temperature adjustments--Set temperatures as follows: a. Oven (chromatographic C. b. Dosing line, 140* C. c. Injection block, 140* C. column), 60* <L Sample chamber, water temperature, 00" C1J0* C. 73.13 Ignition of flame Ionization detec tor--Ignite the detector according to the manufacturer's Instructions. 73.1.4 Amplifier balance Welsnce me amplifier according to the manufacturer's tnetruetioos. 733 Programming the chromatograph-- Program the chromatograph as follows: a- I--Dosing time--The normal setting Is 3 seconds. b. A--Analysis time--The normal setting W 8 minutes. Certain type# of sample* 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 hackflush system can also be used to solve this prob lem. c. B--Flushing--The normal setting Is 0.3 minute*. d. W--Stabilization time--The nomal rot ting le 03 minutes. e. X--Number of analyses per sample--The normal setting Is 1. 733 Preparation of sample turntable--Be fore placing any sample Into turntable, be certain that the oehter section of the alu minum cap has been removed. The numbered sample bottles should be placed in the cor responding numbered position* In the turn table. Insert samnles In the followlns order: Positions 1 A 3--Old 3000 ppm standards for conditioning. These are necessary only after the analyzer has not been used for 34 hours or longer. Position 3--60 ppm standard, freshly pre pared. Position 4--500 ppm standard, freshly pre pared. Position 6--2000 ppm standard, freshly prepared. Position 6--4000 ppm standard, freBhly pre pared. Position 7--Sample No. 7 (This Is ths first sample of the day. butts given as 7 to he con sistent with the turntable and the integrator printout.) After all samples have been positioned. In sert the second set of 60. 600, 3000, and 4000 ppm standards. Samples. Including stand ards must be conditioned in the bath of to* O for 1 hour (not to exceed 6 hours). 73.4 Start chromatograph program-- When all samples. Including standards, have been conditioned at 00* C for 1 hour, start the analysis program according to the manu facturers' Instructions. These Instructions must be carefully followed when starting and stopping program to prevent damage to the dosing assembly. 73.6 Determination of total solids (TS). For wet cake, slurry, resin solution, and PVC latex samples, determine TS for each sample by accurately weighing approxim ately 3 to 4 grams of sample in an aluminum pan before and after placing In a draft oven (105 to 110* c). Samples must be dried to constant weight. After first weighing re turn the pan to the oven for a short pe riod of time and then reweigh to verify com plete dryness. TS Is then calculated as the final sample weight divided by Initial sam ple weight. 8. Calibration. Calibration Is to be performed each eighthour period when the Instrument is used. Each day, prior to running samples, the col umn should be conditioned by running two of the previous days 3000 ppm standards. 8.1 Preparation of Standards. Calibration standards are prepared by fill ing the vials with the vinyl chlorlde/nitro- gen standards, rapidly seating the septum and sealing with the aluminum cap. Use a stainless steel line from the cylinder to the vial. Do not use rubber or tygon tubing. The ample line from the cylinder must be t FEDERAL REGISTER, VOL 41, NO. 305--THURSDAY, OCTOBER 21, 1976 UCC 102785 RULES AND REGULATIONS purged (Into bood) for Hrenl minute* prior to filling tlik. Altar purging, raduoa the flow rota to approximately 600-1000 ee/mln. Place and of tubing into rial (near bottom) and altar one minute (lowly remove tubing. Plao* aeptum In rial a* aoon aa poeelble to mlnlmlae mixing air with sample. Alter tbo stand ard title are reeled. Inject 100^1 of distilled water. 8.2 Preparation at chromatograph calibra tion curve. Prepare two 60 ppm. two BOO ppm. two 2000 ppm, and two 4000 ppm standard samples. Bun the calibration sample* In exactly the same manner as regular samplea. Plot A., the Integrator area counts for each standard sample vs Cr. the concentration of vinyl chloride In each standard sample. Draw a Una of best fit through the points. 9. Calculations. 9.1 Response lector. Prom the calibration curve described in Section 8-2. above, select the value of C. that corresponds to A, for each sample. Com pute the response lector, R>, lor each sample, as follows: R/--7W7-' Equation 107-1 9-2 Residual vinyl ohlorldft monomer oon* contrition, or vinyl chloride monomer eonoentntlon. Calculate Cr aa follows: RfTt \mtR+KT*J WtMT Equation 107-2 Cii"( oiwntmUon of vinyl chloride In the mmpfc, in ppm. 7\-Laboratory Atmosphere pressure, mm Bf. Tj-Room tompetmture, *K. M.-Molecular weight of VCM (*2,5). V',--Volume of vapor phase (vial volume lssi sample volume). f-Wght of sample, trams. A-Oaseonstaot (62,980). K"-Henry's Law eoustant tor VCM In PVO at 00*Cf 1T-6.52X10-*-*; far VOM to 1 m (Approximate) wastewater sample at flO*C, K-IJOX Tj-Equilibratlon temperature, *. If the fallowing eondttlons are met, Equation 107-2 sw be MapUftod as Mtowt: L Ti -23* O (206* K), 1 Ti-W* C (6S*). L P,*-7 rmn. Hg. 4. Vg = Vv -^=23.5 -t wbws K.-TW nfemx *e aui A B--npl* mnlBa* law than &*% water.: C"'ac% Equation 107-3 The toUowtni lotwral equation oen be used tor aey sample which eontains VCM. PYC end/or water. rt _ ^8Pm R?Ti x^^'+E.trs)r,: R.(i-rs)r,J where: T,Total solids. Not*: Km must be determined. Equation 107-4 Results calculated using Equation 107-4 represent oonoentrstlon based mi tbs total sample. To obtain results baaed on dry PVC content, divide by TO. For s 1 a* (approximate) wsrtswstsr *smple, Equation 10T-4 osd be simplified to the foliowing: C,,t"T, ^--+ (2.066X10-')] Equation 107-5 10. References 1. Residual Vinyl Chloride Monomer Con tent of Polyvinyl Chloride Reelns and Wet Cake Samples, B p. Goodrich Chemical Co. Standard Test Procedure No. 1005-T, B. p. Goodrich Technical Center, Avon lake, Ohio. January 30, 1975. 2. Borens, A. R., "The Solubility of Vinyl Chloride In Polyvinyl Chloride," AOS-Dlvlslon of Polymer Chemistry, Polymer Pre prints 15 (2): 197, 1974. 3. Bsrens, A. R., "The Diffusion of Vinyl Chloride in Polyvinyl Chloride," AOS-Dlvllon of Polymer Chemistry, polymer Pre prints IS (3): 203, 1974. 4. Berens, A. R,, L. B. Crider, C. J. Tomanek and J. M. Whitney. Analysis for Vinyl Chloride In PVC Powders by Bead-Space Gas Chromatography." to be published. [PR Doc.78-30849 Plied 10-20-76:8:46 am) 46573 CORRECTED DECEMBER 3, 1976 ffDEIAl RMISTER, WOt 41, NO 205---THURSDAY, OCTOBER 21, 1*7* UCC 102786