Document 159eQzV0b4DoBDw3k6qVMYKyq

cm CHEMICAL MANUFACTURERS ASSOCIATION January 22, 1980 Dr. Leo W. Ziemlak American Hoechst Corporation Route 202-206 North Somerville, New Jersey 08876 Dear Leo: Thank you for your letter of January 14. A copy of the study conducted by the prestigious Institute of Occupational Medicine and entitled, "An Epidemiological study of Respiratory Disease in Workers Exposed to PVC Dust" is enclosed. Also enclosed is a copy of Dr. Stafford's letter to Dr. Anthony Robbins, NIOSH, Cincinnati. Dr. Stafford's letter presents a perceptive historical perspective as well as a thorough-going recapitulation of ICI's investigative work on PVC dusts to date. During one of your visits to CMA offices, please stop by and we'll have a moment or two of Mellon Institute Old Home Week. It was good to hear from you. Kindest personal regards. Sincerely, JTS:das Enclosures CMA 004119 Formerly Manufacturing Chemists Association--Serving the Chemical Industry Since 1872. 1825 Connecticut Avenue, NW Washington, DC 20009 Telephone 202/328-4200 Telex 89617 {CMA WSH) JHN 1 0 O&d AMERICAN HOECHST CORPORATION ROUTE 202-206 NORTH, SOMERVILLE, N J 08876 * TELEX 833-AA9 . CABLE' HOECHSTUS SOMERVILLE. N J . TELEPHONE (201 I 685-2000 MY DIRECT DIAL NUMBER IS 685- 2021 January 14, 1980 Mr. J. T. Seawell Chemical Manufacturers Association 1825 Connecticut Avenue, N.W. Washington, D.C. 20009 Re: VCM/PVC - Letter December 13, 1979 Dear Joe: In your referenced letter, you refer to a study conducted by the Institute of Occupational Medicine (I0M) on "An Epidemiological Study of Respiratory Disease in Workers Exposed to PVC Dust." Would it be possible for you to send me a copy of the report and Dr. Stafford's letter to Dr. A. Robbins of NIOSH? American Hoechst is a member of CMA and we have plants in Delaware and Illinois engaged in the manufacture of PVC products. Each time I visit CMA I intend to stop by to say hello, but somehow there never seems to be time. Best wishes for the New Year. Very truly yours, D emlak LWZ:ecl CMA 004120 State of California Air Resources Board March 27, 1978 Public Hearing to Consider a Limitation on Ambient Concentrations of Vinyl Chloride Research Division P. 0. Box 2815 Sacramento, Calif. 95812 CMA 004122 CONTENTS Page No. I. Introduction 1 II. Summary and Conclusions 4 III. Recommendations IV. Evaluation of the NESHAP Program 10 14 A. NESHAP as an Enforcement Program 15 B. Estimates of Community Concentrations of Vinyl Chloride with the NESHAP Program 25 C. Recent Ambient Vinyl Chloride Data 41 V. Measurement Methods 47 Appendix 1 - Basic VC Monomer and PVC Production Processes Appendix 2 - Environmental Protection Agency - National Emission Standards for Hazardous Air Pollutants, Standard for Vinyl Chloride, October 21, 1976 (41 FR 46560) Appendix 3 - South Coast Air Quality Management District (SCAQMD) Rule 1005 - Emission Standard for Vinyl Chloride, Adopted September 14, 1977 Appendix 4 - EPA Proposed Rule for Vinyl Chloride, June 2, 1977 (42 FR 28154) Appendix 5 - ARB Method - Vinyl Chloride in Air (March 13,1978) Appendix 6 - Glossary Appendix 7 - ARB Staff Report No. 78-1-1. Effects of Airborne Vinyl Chloride Appendix 8 - Public Hearing Notice CMA 004123 I. Introduction The adverse effects of vinyl chloride (VC) upon human health -- its role as a carcinogen, mutagen and suspected teratogen -- have been discussed in detail in Air Resources Board Staff Report 78-1-1 (available for revipw upon request) and by several medical experts at the January 25, 1978, meeting of the Board. After reviewing a substantial body of medical, epidemiological and scientific literature dealing with the toxicity and carcinogenicity of vinyl chloride, the staff was unable to specify any level of exposure other than zero that could be considered safe. However, the staff reasoned that a regulation requiring an ambient level of zero would be, in effect, unenforceable, since violations in the range between zero and the limit of detection inherent in the measurement method selected for monitorinq VC could not be detected. The lowest enforceable ambient standard that could be adopted will depend, then, on the monitorinq method soecified in the standard. The staff concluded that, if methodologies requiring elaborate, extremely expensive instrumentation are excluded from consideration, standard at the level of about 0.010 ppm with an averaging time of several hours could be enforced using instrumentation that is readily available at a reasonable cost and can be operated by paraprofessional staff. On the basis of these considerations, the staff recommended that the Board establish, on an interim basis, a maximum allowable level for ambient concentrations of vinyl chloride within the range of 0.01 to 0.05 parts per million, twenty-four hour average. CMA 004124 -2- The State Health Department and its Air Ouality Advisory Committee (AQAC) were generally in concurrence with the staff's position. The AQAC, following discussions at a meetina on January 18, 1978, advised the Board: "In light of the evidence of emissions of vinyl chloride, and the knowledge about the seriousness of its effects, it is desirable to establish an air quality standard, even though the basis would be substantially different than other standards recommended by the Department...." "The Committee concurs in the Staff Report's position that no exposure level above zero can be considered safe or acceptable. The level for an enforceable standard should reflect the lowest concentration measurable by available and practical methods, and in any event, is not a matter which needs to reflect medical judgement." Dr. John Goldsmith, in presenting the Health Department's recommendation to the Board, expressed the view that, while a standard within the ranqe recommended in the staff report was appropriate, a standard at the lower end of that range, namely, 0.01 ppm, twenty-four hour average, was preferable. He expressed the general view that, in the case of airborne carcinogens, the only acceptable exposure is the absolute minimum achievable through the application of the best possible controls, accompanied by care and good practice in the operation of facilities. CMA 004125 -3Other testimony given at the January meeting urged the Board to delay the setting of an ambient air quality standard until the federal NESHAP program is fully implemented in October 1978. Other concerns were expressed relating to the monitoring method proposed by the ARB staff. The Board requested the staff to evaluate the adequacy of the NESHAP program, to obtain additional air monitoring data in the South Coast Air Basin near facilities that emit vinyl chloride, and to notice a public hearing for March or April to consider the regulation of vinyl chloride. CMA 004126 11. Summary and Conclusions -d- In response to requests made by the Board at the January meetinq, the staff has carried out an analysis of the EPA`s NESHAP regulations and prepared estimates of the maximum ambient levels of VC that can be expected when the largest VC facilities in California come into full compliance with these regulations. This report presents the results of this analysis along with the results of additional air monitoring work requested by the Board. In addition, an updated discussion of the measurement method proposed for adoption by the Board is presented. The staff, following a careful review of the federal NESHAP Standard, has reached the following conclusions: o NESHAP does not, in all cases, require the application of best available control technology. Indeed, some California VC processors are currently installing equipment that provides far more effective control of VC emissions than is called for under NESHAP. o Enforcement of NESHAP, because of the complexity of its requirements, is extremely difficult and would appear to place inordinate demands upon the regulatory agency charqed with ensuring compliance. o Fugitive emissions from miscellaneous sources such as tank cars and associated unloading facilities, pipe and hose joints, flanges, seals and packing glands are not adequately controlled under NESHAP. CMA 004127 -5- o NESHAP places no upper limit on the total emissions from the stacks of a VC facility; only a concentration limit is specified. o Although the regulations were developed under a general policy calling for a goal of zero emissions (and, presumably, zero ambient concentration), NESHAP does not assure that community exposure to VC will be maintained below any specified level. o Finally, NESHAP does not deal adequately with the critical upset/breakdown question. There is no adequate mechanism to minimize such occurrences; there is no specification of measures to be taken to prevent community exposure to hiqh levels of VC when breakdowns occur. The staff has used air quality simulation modeling techniques to provide the Board with estimates of ambient levels of VC that may result from application of the federal NESHAP regulations. The following conclusions have come from this analysis: o Point source (stack) emissions from a facility just in compliance with the federal 10 ppm limitation (assuming mass flows scaled to plant throughput) Droduce maximum 1-hour levels of VC of about 0.01 ppm. Ground level maxima nenerallv occur within 100m of the plant, because of the low bouyancy of the plumes. Twenty-four hour average values at a single monitoring site would be expected to be somewhat lower because of variations in wind direction and mass flow. CVUk 004128 -6o Fugitive emissions of VC ol ay a dominant role in determininq ambient VC levels in the vicinity of the plants studied. Using current EFA estimates for fugitive emission rates, our calculations predict tnat worst case 24-hour average VC levels in excess of 1 ppm could occur immediately downwind of the combined Stauffer - B. F. Goodrich facilities. o Comparison of these estimates with the results of recent air measurements in the vicinity of VC facilities suggests that the EPA emission factor for fugitive emissions is too hiqh. A more refined inventory of fugitive emissions is clearly desirable. o Our calculations show that if total emissions (fugitive and stack) from the combined Stauffer - Goodrich facility, potentially California's most critical location, can be reduced to about 0.5 kg/hr, ambient levels of VC outside the facility are not likely to exceed 0.01 ppm, 24-hour average (absent accidental releases of VC under upset/breakdown conditions). In response to the Board's request in late January, the staff resumed air monitoring activities in the vicinity of VC facilities in the Los Angeles area. In addition, data from monitoring programs conducted by B. F, Goodrich Chemical Company and Stauffer Chemical Company in Long Beach and Keysor-Century Corporation in Saugus have been made available to the staff. These data are discussed in Section IV-C of this report. CMA 004X29 -7- Although the unusual weather conditions that occurred during this Deriod were not, on the average, conducive to the buildup of high concentrations of pollutants, a review of the monitoring data by the staff suggests several tentative conclusions: o Ambient levels of vinyl chloride in the Saugus community have dropped dramatically, relative to those observed in October and November 1977. Although meteorological factors may have accounted for some of the observed change, there appears to have been a substantial decrease in VC emissions from the Keysor-Century facility. o Air monitoring data from the Long Beach area continue to show VC levels comparable to those reported to the Board in January, with levels less than 0.10 ppm VC. o Ambient levels of VC in Saugus and Long Beach appear to be averaging well below the worst-case levels predicted by air quality models. This may indicate that fugitive emissions from VC facilities are lower than EPA estimates or, alternatively, that weather conditions have not been conducive to maximum buildup of VC emissions. OOAl30 -8- In Staff Report 78-1-1, we discussea several candidate methods that are available for sampling and analyzing ambient air to determine the concentration of VC. All of the acceptable methods rely ultimately on the use of a gas chromatograph to analyze the sample. They differed principally in the method of sample collection and in the amount of preparation required prior to analysis. The method developed by the staff of ARB's Atmospheric Studies Branch uses a bag sampler, followed by direct-injection gas chromatographic analysis. The method found to provide a minimum mp^urahlp vr. IpvpI of about 0.010 ppm with a standard deviation of about + 0.005 ppm over the range between zero and 1.0 ppm with good linearity. The staff has done further work on the development of an accurate, reliable and precise measurement method that can be adopted for general use. The results of this work are summarized in Section V of this report. The staff has concluded that: o The ARB method using direct injection is sufficiently sensitive to provide reliable measurements at the 0.010 ppm level with a precision of + 0.002 ppm. o The ARB method can be made less sensitive to hydrocarbon interference by using a different gas chromatographic column than originally proposed. This will increase the ability of CMA 004131 -9analysts to quantify low concentrations of VC in the presence of relatively high ambient concentrations of hydrocarbons. o The staff, following discussions with analysts employed by the VC industry, has concluded that other sampling and analysis techniques may also be suitable for monitoring ambient VC. The industry has not yet demonstrated equivalency of it's methods to the ARB method. CMA 004132 -10- III. RECOMMENDATION Following our original recommendation to adopt an interim air quality standard for vir.yl chloride, the staff has explored other options that might be proposed to the Board to achieve essentially the same objectives. All of those with whom the Board and the staff have discussed the issue -- the State Health Department, the Air Quality Advisory Committee, the Board's ad hoc Panel on Atmospheric Carcinogens and other medical and public health experts -- agree that no exposure to vinyl chloride for any period of time at any level, other than zero, can be said with certainty to be safe. There is no known threshold level for its proven carcinogenic and mutagenic (bacterial effects and so little is known about dose-response relationships for materials such as vinyl chloride that the magnitude of risks associated with low level exposures simply cannot be quantified. There is unanimous agreement, however, among those mentioned that ambient levels of vinyl chloride should be reduced to the absolute minimum -- ideally to zero -- as quickly as possible. Reliance on the federal NESHAP regulation for vinyl chloride, for which enforcement authority as now been delegated to the South Coast Air Quality Management District (SCAQMD), is one of the CMA 004133 -11- options available to the Beard. The staff cannot say with certainty how much full compliance with NESHAP will do to reduce community exposure, although it seems likely that some additional control of fugitive emissions will be required to meet an ambient standard in the range of 0.01 to 0.05 ppm, twenty-four hour average. Of more concern to the staff in making a recommendation on NESHAP are questions of enforceability, apparent loopholes that could permit total VC emissions to increase even while a facility remains in compliance, and inadequate incentive for facility operators to adopt operating and maintenance procedures that will prevent fugitive emissions. On balance, NESHAP's shortcomings and uncertainties about achieving any specified ambient level under its provisions cause us to recommend against California's relying solely on NESHAP to protect the public health from the adverse health effects of vinyl chloride. Adoption of an air quality standard for vinyl chloride or other known carcinogens presents other problems. An ambient air quality standard is generally taken to represent a safe or "no effect" level of exposure to the pollutant in question, at least for the vast majority of the population; this generalization CMA 004134 -12does not apply to vinyl chloride and most other chemical carcinogens. There is a risk, probably extra ordinarily small, but not precisely quantifiable, of grave consequences to ordinary individuals at any level the Beard might adopt for a standard. Moreover, since emission rates consistent with attaining an ambient standard vary substantially with prevailing meteorological conditions, a standard for a site-specific pollutant could represent, in industry's eyes, a "license" to pollute up to the level of the standard, absent carefully designed and vigorously enforced emission control regulations. On the other hand, adoption of a standard or other limits on maximum ambient concentrations of vinyl chloride will ensure that exposure to VC will not exceed a specified level at any location outside the facilities themselves, assuming the SCAQMD and/or the Board use a standard as a basis for developing, adopting and enforcing the appropriate emission regulations to augment, as necessary, the provisions of NESHAP. On balance, the staff's view is that an ambient standard provides a more effective way of ensuring that low levels of vinyl chloride will be maintained in the community. Therefore, the staff recommends that the Board adopt an ambient standard, to be designated as a significant harm level (a level never to be exceeded) in the range of 0.01 to 0.05 parts per million, twenty-four hour average. The staff further recommends that this standard be adopted pursuant to the Board's authority to establish ambient air quality standards for the protection of the public health Section 39606 (b) of CMA 004135 -13- the Health and Safety Code and to implement and interpret Section 41700, of the Health and Safety Code, which prohibits any person from discharging quantities of air contaminants which endanger the health of a considerable number of persons or the public. By including this latter authority, the Board will distinguish the significant harm level established in February, 1976 for sulfates, which are not associated with the more serious carcinogenic, mutagenic and possible teratogenic effects if vinyl chloride. By referencing 41700, the Board will be establishing a basis for immediate enforcement (e_.., through legal action in a court or abatement proceedings before a district hearing board) which, in the staff's view is appropriate for pollutants with carcinogenic or other special health consequences. The staff recommends further that the Board require that suitable vinyl chloride air monitoring instrumentation be installed on or near the property lines of facilities using and/or producing vinyl chloride monomer to ascertain whether or not the significant harm level is being violated at locations to which the general public has access. It would seem fair that such instrumentation be installed and maintained by the operators of those facilities , as a part of their existing emission control programs. The staff recommends further that the Board specify the measurement method developed by the ARB staff and described in detail in Appendix 5 of this report as the one to be used in determining violations of the significant harm level. Although other methods may also be acceptable, equivalency with the ARB method with respect to accuracy, precision and specificity will need to be demonstrated before such methods can be approved. CMA 004X36 -14- Final ly, the staff recommends tnat the Board urge the SCAQMD to act expeditiously to formulate and adopt rules and regulations that will ensure that ambient vinyl cnloride levels are reduced to and maintained at or, preferably, well below the level designated as a significant harm level. IV. Evaluation of the NESHAP Program At its January 25 meeting, the Board requested that the staff assess the adequacy of the NESHAP emission standard as a means of achieving acceptably low levels of vinyl chloride in the community. In addition, the staff was asked to resume its monitoring efforts in the Los Angeles area to gather additional data on current vinyl chloride levels. Section IV-A, below, provides a discussion of the NESHAP regu/ lation and its enforceability. Section IV-B summarizes the results of air quality modeling calculations of projected ambient levels of VC in the vicinity of facilities in compliance with the NESHAP regulation. Section IV-C provides updated information on ambient levels of VC now being observed in the Los Angeles area, along with a short discussion of the implications of these results with respect to the magnitude of the fugitive emissions problem. CMA. 004133 -15- A. NESHAP as an Enforcement Program The NESHAP Standard for control of VC emissions was adopted by the EPA and became effective on October 21, 1976. A copy of the Standard is attached as Appendix 2. Subseauently, on September 14, 1977, the South Coast Air Quality Management District (SCAQMD) adopted an equivalent regulation. Rule 1005 (Appendix 3 of this report). The authority to enforce NESHAP was delegated to the District on November 23, 1977. Prior to this delegation, in order to meet certain requirements of NESHAP, the EPA issued individual waivers of compliance to each of the four affected facilities in California. The scheduled date for full compliance with NESHAP is October 21, 1978. 1. Existing NESHAP Program The following is a brief summary of NESHAP for control of VC emissions from ethylene dichloride (EDC), VC monomer and PVC plants. For EDC-VC plants, VC concentrations in qaseous effluents from control devices are limited to 10 ppm. In addition, emissions from the oxychlorination process in EDC plants are limited to 0.2 q/kq of EDC produced. For PVC Plants, VC oas concentrations in the effluent from control devices are also limited to 10 ppm for sources preceding the stripper and for the stripper CMA 004138 -16- itself. PVC companies that choose not to strip the residual VC below 400 ppm are required to achieve an emission limitation cf 0.4 g/kg of PVC produced for the processes immediately following the strippinq operations, namely the blending, centrifuging, drying and packaging. All four facilities in California have chosen the option of reducing residual VC in the resin to 400 ppm. Another requirement for PVC plants is to control VC emissions from reactor openings to 0.02 q/kq of PVC produced. In EDC-VC and PVC plants, the regulations require that fugitive emissions be captured and controlled. Discharges from relief valves and manual venting of qases are prohibited, except under emergency conditions. As Dart of the requirement to control fugitive emissions, it is required that a leak detection and elimination program be implemented. In addition, the regulations require extensive monitoring, sampling, analyses, record keeping, and reporting. The orginal intent of NESHAP for VC was to compel industries to utilize best available control technology (BACT) on emission sources, because VC is a carcinogenic pollutant and is therefore to be controlled to the maximum extent possible. Our analysis of the regulation indicates that in many cases NESHAP does not require BACT and further CMA 004139 -17control measures could be used. This is supDorted by the fact that some companies have voluntarily achieved emission rates well below current limitations. For example, one of the PVC plants located in Long Beach has achieved greater than an order of magnitude reduction residual VC content below limitation levels for some of its resin formulations with the VC stripping process. Moreover, some of the waivers of compliance issued by EPA reguire installation of control equiDment above and beyond the basic requirements of NESHAP, which provides further indication that NESHAP does not represent BACT in all cases. Table IV-1 summarizes the emission sources in facilities that emit VC, their respective emission limitations and the potential for further emission reductions: CMA 004140 TABLE IV-1 COMPARISON OF EXISTING NESHAP REQUIREMENTS AND AVAILABLE ADDITIONAL CONTROL FOR VINYL CHLORIDE EMISSIONS Emission Source Current Limit Potential Limit Oxychlorination reactors .2 g/kg product By incineration, approach nondetectable (ND) level. Railroad tank cars No regulation No leaks. Opening of mixing, weighing and holding containers 10 ppm Vent to incinerator, approach ND. Polyvinyl chloride reactor opening .02 g/kg product By cleaning reactor while closed or ducting losses to incinerator, approach ND. Reactor exhaust gases 10 ppm By incineration, approach ND. Monomer recovery exhaust system 10 ppm By incineration, approach ND. Stripper Exhaust Gases 10 ppm By incineration, approach ND. Sources following stripper* 400 ppm residual in slurry Variable depending on type res being stripped (10-400 ppm). a) blend tanks Controlled by stripping re quirement Vent head space emissions to incinerator, approach ND. b) centrifuge Controlled by stripping re quirement Enclose system and vent to incinerator, approach ND. X^X^OO c) dryer Controlled by Stripping re quirement Enclose system and vent to incinerator, approach ND. TABLE IV-1 (continued) d) packager Controlled by stripping re quirement Enclose system and vent to incinerator, approach ND. Relief, and manual vent valve discharges 0 (except emergency) Hood and vent to incinerator, approach ND. Fugitive sources Capture and control Maintain to prevent leaks; on control systems approach ND. a) unloading line .13 cubic feet VC at std. temp, and pressure during opening Vent VC to incinerator, approach ND; or install valves to decrease volume of VC released. b) rotating pumps Double mechanical seals; or control to 10 ppm No leaks. c) reciprocating pumps Double outboard seals; or control to 10 ppm No leaks. d) rotating compressors Double mechanical seals; or control to 10 ppm No leaks. e) reciprocating compressors Double outboard No leaks. seals; or control n to 10 ppm f} agitators Double mechanical seals; or control to 10 ppm No leaks. 004142 g) equipment opening < 2D percent volume VC or 25 gallons at stand ard temperature and pressure (whichever is larger) Vent to incinerator, approach ND; strip waste water used to backfill and clean, approach ND. TABLE IV-1 (continued) h) inprocess waste water 10 ppm Strip, approach ND. i) leaks (i.e. all valves, flanges, fittings, etc.) Detect and eliminate Weld threaded fittings; no leaks. *If any residual VC remains in resin after stripping then steps a-d should be implemented. r01Io 004143 -21- The potential reductions shown in Table IV-1 are based on a limited amount of source test information and a limited number of plant inspections. Further enqineerinq evaluation must be performed to determine the precise method and extent of implementing these or further reductions. Another area of the regulation that needs to be considered concerns emergency or accidental releases of VC. Appropriate procedures should be adopted whereby during such a release of VC the air pollution control officer of the District is immediately notified in order to have an opportunity to take appropriate action. 2. Proposed Changes to NESHAP for VC As a result of a lawsuit filed by the Environmental Defense Fund, EPA proposed changes to the NESHAP regulation on June 2, 1977 (See Appendix 4). These proposed changes include: a. A reduction of VC in exhaust gases from control equipment from 10 ppm to 5 ppm for EDC-VC and PVC plants. The purpose of this requirement is to optimize existing control equipment; however, if a company were not able to meet the requirement without additional control equipment, an interim emission limit would be set and reviewed every three years. CMA 004144 -22- b. A reduction in residual VC from the slurry in PVC plants to one quarter of the current limitation. This would apoly only to those qrades of resin which had not been produced by the plant on or before June 2, 1977. c. A reduction of VC emissions from oxychlorination reactors to 5 ppm from the present limit of 0.2 g/kg of EDC produced. This would apply only to reactors which were constructed after June 2, 1977. d. Outright prohibition of increases in emissions within a 5 mile radius of an existing source due to new construction. This would include plant expansions and new facilities. The offset provision, d. above, of the proposed regulation will have the effect of allowing no plant expansion without emission trade-offs. Industry's opposition to this provision of the proDosed regulation and EPA's consideration of changes in its general carcinogen policy are apparently the major stumbling blocks delaying adoption of the proposed augmented regulation. The staff's view is that the trade-off provision is important and should be adopted immediately by the SCAQMD so that ambient levels of VC do not increase around present facilities. CMA 004145 -23- 3. Enforceability The NESHAP regulations for facilities using,or oroducing VC requires them to sample for, analyze, record, and report VC emissions and concentrations in the facility. In accomplishing this general objective, firms are required to do the followinq: a. Implement a VC leak detection and elimination program through means of stationary and portable in-plant monitoring. The levels are recorded and reported when levels of VC are found to be above the level defined as a leak. Programs for detection vary from plant to plant. b. Determine and report reactor opening losses from oxychlorination and PVC reactors. c. Determine residual VC levels in each batch of PVC slurry after it has been stripped. d. Monitor all exhaust gases that must meet ',.,e 10 ppm VC limit and report VC levels over the limit. e. Record emergency releases from manual vent valves on PVC reactors and from relief valves. This information is required to be reported within 10 days after the occurrence. CMA 004146 -24- The SCAQMD receives and reviews semi-annual reports with the above information included and has access to other records that are maintained for two years by the companies. The District can perform, when it deems necessary, plant inspections and/or source testing. The requirements of the regulation are very detailed and complex; they necessitate constant surveillance by a regulatory aqency to ensure they are beinq complied with. More importantly, the federal regulation places no upper limit on the total mass emissions of VC from these facilities or the total amount of VC exhausted through stacks. These two shortcomings, along with what many view as too heavy a reliance on self-monitoring of compliance, combine to provide little assurance that corrmunity levels of VC can be maintained at acceptably low levels under the federal regulations as they are now written. CMA 004147 -25- B. Estimates of Community Concentrations of Vinyl Chloride with the NE5HAP Program _ Introduction In resDonse to the Board's request, a preliminary study has been undertaken by the ARB Modeling Section to assess the air auality impacts from polyvinyl chloride (PVC) and vinyl chloride monomer (VC) plants in Los Angeles County on receDtor areas in their vicinity, and to determine the probable degree of compliance of these facilities with the proposed ARB air quality standard for vinyl chloride when they come into full compliance with NESHAP emission standards. At the present time, four PVC or VC facilities are operating in the Lcs Angeles area. These are the Keysor-Century PVC plant at Saugus, the B.F. Goodrich PVC and Stauffer Chemical Company PVC and VC plants at Long Beach, and the Union Carbide PVC plant in Torrance. The B.F. Goodrich and Stauffer Chemical facilities are located adjacent to one another on a north-south axis with the B.F. Goodrich plant to the south and Stauffer Chemical to the north. Emission estimates for these facilities were comoiled by the ARB Enforcement Branch based on data supplied by B.F. Goodrich, Keysor-Century and EPA, and the following analyses were performed o An evaluation of the effects of typical PVC and VC point sources on downwind receptors (point source releases are limited to 10 ppm in stack concentration by C0A NESHAP regulation). CMA 004148 -26- o An evaluation of the effects on adjacent receptors of the three of the four facilities described above using both point and area source emission estimates.^ 1. Study Methodology and Data Description Due to time constraints and the preliminary nature of the data gathered to date, it was decided that a Gaussian dispersion model was best suited for this study. Gaussian models incorporate the following assumptions: a. Steady state emission sources and wind fields b. Bimodal Gaussian distribution of pollutants vertically and horizontally c. No vertical wind shear d. Uniform vertical temperature stratification e. Flat or gently rolling terrain f. No aerodynamic downwash effects attributable to buildings g. Chemically inert pollutants h. Effective stack height based on Briggs' buoyant Dlume rise formula (1). The impacts from the PVC and VC facilities investigated here involve short range transport of a relatively inert pollutant from sources with little or no plume rise. Pollutant dispersion under these conditions should be well characterized by Gaussian type models. The only assumptions which might be questionable 1) No analysis was made of receptor sites near the Union Carbide facility. CMA 004149 -27- are numbers e> f, and h. Assumption e, that the terrain is relatively flat, is satisfied at the Long Beach sites, but not at Saugus. This will increase the uncertainty of the results obtained for the Keysor-Century plant. The assumption that no aerodynamic downwash or building effects occur may also be incorrect for these facilities since the pollutants are emitted close to qround level. Downwash and building effects can be important at high wind speeds, but it is expected that the increased dilution of the pollutants under these conditions will offset whatever increases the aerodynamic effects might cause. Assumption h was tested by comparing both momentum and buoyant plume rise formulas using the point source parameters provided for the B.F. Goodrich and Keysor-Century plants. The two different formulations were found to coincide for almost all conditions tested to within a meter or two. In those cases where the two calculations differed significantly, the buoyant plume rise formulation was found to be the correct method of describing the height of pollutant release (2). The data used in this study were compiled by the ARB Enforce ment Branch and consisted of a point source inventory for the B.F. Goodrich and Keysor-Century plants, and estimated fugitive emissions for all three facilities based on EPA factors for CMA 004150 -28- typical PVC and VC facilities (3). These values were scaled according to plant production capacity. The staff was unable to obtain point source emission estimates for the Stauffer Chemical plant. Since the estimated point source emissions from the B.F. Goodrich plant were found to comprise approximately 0,5 percent of the total plant emissions, it was decided that a reliable estimate of the Stauffer plant imoact could be made using only the value for the fugitive emissions. Point source emissions were also neglected for the B.F. Goodrich facility, except that one simulation using a point source having the maximum allowable vinyl chloride concentration of 10 ppm was run to assess the type of impacts expected from such controlled point sources. The data used in this study are listed in Tables IV-2 and IV-3. Preliminary runs to determine meteorology for cases corresponding to maximum one hour levels were made using the EPA Gaussian model PTMAX. This program computes the maximum downwind concentrations from point source emissions for a variety of wind speeds and atmospheric stabilities. The worst case meteorological conditions for each stability class were determined from these calculations and are shown in Table IV-4. The ARB program, HRSTAB, was then used to determine the typical stability distribution in the Los Angeles area for a winter (January) and a summer (July) day with clear skies and low wind speeds. The stability distributions are also listed in Table IV-4. CMA 004151 -29- Worst case meteorological scenarios were then' formulated by combining the worst case meteorological conditions for each stability class and weighting them by their exoected frequency of occurrence in each 24-hour scenario. These meteorological conditions, combined with the point and fugitive source emissions, were also run using the EPA orogram PTDIS. PTDIS computes downwind concentrations from point source emissions at distances specified by the user. The fugitive emissions for each facility were treated as a uniformly distributed area source with a release height of 3m. The area of the Keysor-Century plant was assumed to be 100m x 100m, while the B.F. Goodrich and Stauffer plants were each assumed to be 120m x 120m. Area sources are treated by the use of virtual point sources in PTDIS. A virtual source of release for the area source emissions upwind from the actual location of the area source is specified such that the horizontal spread of the virtual plume, characterized by the parameter a , obeys the ' .lation (Jy=L/4.3 where L is the length of one side of the area source at the center of the area source. As described by Turner (4), this value of a represents treatment of the area source as a crosswind line source with a normal distribution of pollutant about the center line of the plume. CMA 004152 -30- Values for the worst case meteorological conditions in Table IV-4 were run using PT3IS for each stability class represented in the 24-hour stability distributions for both winter and summer days. Seperate runs were made for the point and area source emissions. These results were combined, using each stability type, to produce worst case 24-hour averages. Twenty-four hour average values were also computed for meterological conditions typical of the Los Angeles area. These conditions represent sea breeze meteorology during the day and drainage flow conditions (toward the ocean) at night. All these results are given in Table IV-5. In the case of the Keysor-Century plant, maximum 24-hour values representing worst case meteorological conditions for both the point source and the area source (fugitive) emissions were calculated. (The values calculated for the vicinity of the B.F. Goodrich and Stauffer plants represent worst case conditions for fugitive sources alone, because point source contributions were assumed to be negligible, on the basis of the data currently available). 2. Results and Conclusions The results give in Tables IV-5 show that, under current conditions, the air quality impacts of controlled point sources (stack) are insignificant in relation to the impacts from fugitive sources, if EPA emission rates are assumed. The worst case 24-hour average vinyl chloride concentrations CMA 004153 -31predicted at the plant boundaries range from 0.316 ppm at Saugus to 1.18 ppm in the vicinity of the Stauffer and B.F. Goodrich facilities. For the more typical meteoroloqical scenarios, which include sea breeze and drainage flow conditions, these worst case values are reduced to 0.247 ppm at Sauqus and 0.709 ppm at the Long Beach facilities. These values represent the best estimate that can be made at the present time, considering the uncertainty involved in estimating fugitive emissions from PVC and VC plants. There are several reasons to believe that these results represent upper limits on the concentrations actually to be expected. These reasons are: a. The EPA fugitive emissions estimate is conservative, since it is based on a mass balance calculation which does not specify loss mechanisms for vinyl chloride other than emission into the atmosphere. b. Gaussian models tend to over-predict ground level concentrations. c. Wind directions were held constant over multi-hour averaging periods. CMA 004154 -32d. The release height assumed for the fugitive emissions is probably a lower limit for the actual release height. The following facts snould also oe considered when attempting to relate these predicted values to actual air quality measure ments. a. Downwind concentrations fall off substantially with distance from the plant. For example, at 0.5 km down wind, the worst case concentration values calculated for the Long Beach facilities are approximately 0.1 to 0.2 ppm. b. Atmospheric concentration values depend linearly on the emission source strength. c. Emission rates for fugitive emissions are probably of order of magnitude accuracy and are conservative,i.e., likely to be higher than actual, rather than lower. d. The assumed spatial and temporal uniformity of fugitive *' emissions is probably not correct. In addition, the release height of these emissions will vary from source to source. CMA 004155 -33- These results should, therefore, be considered order of magnitude estimates of the air quality impacts involved largely because of uncertainties in the emissions data available to the staff at the time the calculations were performed. Be fore any final results can be obtained, a more refined emissions inventory of these facilities should be conducted. The results of these preliminary calculations demonstrate that ambient levels of vinyl chloride in the vicinity of VC and PVC facilities are largely determined by fugitive emission rates. Stack emissions, even at the 10 ppm upper concentration limit allowed under NESHAIJ contribute very little to the totals. Additional calculations corresponding to fugitive emission rates of 50% and 10% of the EPA estimates were carried out. These results are summarized in Table IV-6. These results lead to the conclusion that concentrations of vinyl chloride in the . range suggested by the proposed significant harm level can be achieved at all of the facilities studied even under the most unfavorable meteorological conditions, if fugitive emission rates can he reduced .to about.0.5 kg/hr (1.1 Ib/hr) and the proposed 5 ppm upper limit on VC concentrations in stack effluent.is pro mulgated. (These estimates aDDlv to the combined plants at the Long Beach location.) CMA 004156 -34- Table IV-2 Keysor-Centur.y Source and Emission Data Point Source Height Temperature Source Strength Vol. Flow Rate 9.75m (32 ft.) 310 K (100F) 0 .289 g/sec (lOppm in stack) 11.81 m^/sec Area Source (fugitive)* Height 3m (9 ft.) Temperature ambient Source Strength 0.797 g/sec Dimensions PVC Production Capacity 100m x 100m 15 MM kg/year *These emission strengths are based on EPA fugitive emission estimates of 3.61 g/sec (29 Ib/hr) for a plant with produc tion capacity of 68MM kg/year (3). \ CMA 004157 -35Table IV-3 B. F. Goodrich and Stauffer Chemical Source and Emission Data Point Source (BFG typical source) Height Temperature Source Strength Vol. Flow Rate 24.4m (-80 ft.) ambient 0.16 g/sec 3 5.6m /sec Area Sources (fugitive)* Height Temperature Source Strength Dimensions PVC Production Capacity VCM Production Capacity 3m ambient 2.68 g/sec (BFG) 4.06 g/sec (Stauffer) 120m x 120m 50MM kg/year (BFG) 70MM kg/year (Stauffer) 75MM kg/year (Stauffer) These source strengths are based on EPA emission estimates of 3.6 g/sec for a PVC plant with 68MM kg/year capacity and 1.2 g/sec (9.7 Ib/hr) for a VC plant with 316MM kg/year capacity (3). CMA 004158 -36- Table IV-4 Worst Case Meteorology and Stability Distributions Worst-Case Conditions For Point Source (St*ckl Tmnact (summer) No. of Hours Stability Windspeed (m/sec) 5 A1 4 B4 2 C4 1 D4 12 F* 1 Worst-Case Conditions For Area Source (Fugitive) Impact winter No. of Hours 7 1 16 Stability C D F* Windspeed (m/sec) 2 2 1 summer 5 4 2 1 12 A1 B1 C2 D2 F* 1 *For Long Beach F stabilities have been increased to E to account for the urban heat island effect CMA 004159 Table IV-5 Maximum 24-Hour Ambient Concentrations of Vinyl Chloride Under Various Weather Conditions (ppm) Results for B.F. Goodrich and Stauffer Chemical -37004160 1 Hour Worst Cases for Area Source (Fugitive) Impact Stability A B C D E Wind Speed(m/sec) 1 1 2 2 1 ST Plant Boundary 1.24 1 .10 0.412 0.341 0.674 FFER . 1 km 0 .34 0.50 0.29 0.22 0 .62 0.5 km 0.050 0.070 0.060 0.090 0 .220 B. F. GOOD RICH P lant Boundary 0.1 km 0.5 km 0.817 0.724 0.271 0.225 0.444 0.224 0.329 0.191 0.145 0.408 0.033 0.046 0 .040 0.059 0.145 24 Hour Worst Case Conditions r Area Source (Fugitive) Imnact (at the boundaries of the combined BFG nd Stauffer facilities) 24 hour northerly flow typical meteorology* davtime recentors nightime receptors winter 0.917 n.lOfi ( ft hniircl 0.709 (16 hours) summer 1 .18 fl.fii? /I? hniirs) 0.532 (12 hours) Table IV-5 (Cont.) Results for Keysor-Century (all values for distance 4.1 km from source) Worst-Case Conditions For Point Source (Stack) Impact Summer: O.Bg/s source*(ppm) constant winds for 24 hours typical meteorology daytime receptor site (8 hours) nlghtlme receptor site (16 hours) 0.265 0.080 0.080 0.185 -B- Worst Case Conditions For Area Source (Fugitive) Impact Sunnier: O.Bg/s source*(ppm) constant winds for 24 hours typical meteorology daytime receptor site (12 hours)* nlghtlme receptor site (12 hours)* 0.316 0.131 0.185 Winter: constant winds for 24 hours typical meteorology daytime receptor site (8 hours)* nlghtlme receptor site (16 hours)* 0.295 0.049 0.247 +The O.Bg/s source results are for fugitive emission estimates scaled by plant production capacity (see Table IV-2) *These values are based on onshore flow during the day and drainage flow at night. The number of hours each receptor Is exposed under these conditions Is given in parenthesis. Daytime wind direction is from the south, and nightinie wind direction Is from the north. Table IV-6 Twenty - Four Hour Worst Case Concentrations (ppm) for Reduced Fugitive Emissions at Long Beach {results at the combined plant boundaries) Meteorological Conditions 24 hour northerly flow Season winter summer 50% emission** reduction 0.459 0.590 90% emission** reduction 0.092 0.118 Typical winter Meteorology (daytime receptors)* summer Typical winter Meteorology (riightime receptors) *summer 0.098 (8 hours) 0.32 {12 hours) 0.355 (16 hours) 0.266 (12 hours) 0.020 (8 hours) O.Go4 (12 hours) 0-071 (is hours) 0.053 (12 hours) 004162 o *These values are based on sea breeze meteorology during the day and drainage flow meteorology at night. The night of hours each receptor is exposed under these conditions is given in parenthesis. Daytime wind direction is from the south, and nighttime wind direction is from the north. **Percentage reductions are scaled down from the EPA estimate of fugitive emissions from the combined facilities. If actual fugitive emissiors are lower than the EPA estimate, maximum ambient levels of VC would decrease to correspondingly lower values. References -40- 1. G.A. Briggs, Plume Rise U.S. Atomic Energy Comission, 1969 2. R..i. Schultze, Notes on Diffusion Modeling Trinity Consultants, Dallas Texas, 1976, p.61 3. Point source emission estimates were supplied to ARB from B.F. Goodrich and Keysor-Century. Fugitive emission estimates were obtained from : EPA Supplement Document #28155, and plant production capacities were obtained from "Standard Support and Environmental Impact Statement: Emission Standard for Vinyl Chloride1,' EPA-450/2-75-009, October 1975, Table 3-3 4. D.B. Turner, Workbook of Atmospheric Dispersion Estimates EPA, Research Triangle"Park, 1970, p. 38. CMA 004163 -41- C. Recent Ambient Vinyl Chloride Data The ARB monitored the vinyl chloride concentration in the ambient air at the Saugus School, located near the Keysor-Century plant, on 38 days from January 30 through March 22, 1978. The sampling period was 24 hours on 35 days, and 12, 16 and 20 hours on 3 days. On the three partial days, none of the sampled concentrations exceeded the minimum measurable concentration of 0.01 ppm. Four of the 35 days had 24 hour average values that reached or exceeded 0.01 ppm. (On those days 24-hour averages were computed by substituting one-half the detectable limit for those samples whose concentration was below the detectable limit*). On those four days the 24-hour average concen trations were 0.01, 0.01, 0.012, and 0.064 ppm. The maximum concentration observed was 0.18 ppm in an 8-hour sample on February 6, 1978 (1600-2400). Other sample concentrations above 0.01 ppm include: 0.05 for four hours, two 5-hour samples of 0.02, and a 4-hour sample of 0.012. All other samples were 0.01 ppm or less. In addition to the continuous monitoring several instantaneous "grab" samples were obtained in the vicinity of the three other plants emitting vinyl chloride in southern California. On February 8, 1978, at approximately 1930 hours, two syringe .samples were taken on 223rd Street, Long Beach immediately adjacent to the northern boundary of the Stauffer Chemical facility *This procedure follows "Guidelines for the Evaluation of Air Quality Data", 0AQPS No. 1.2 - 015, EPA, February 1974. However, in these cases more than 25% of the observations are less than the minimum detectable, and the Guidelines advise that no statistics should be computed. CMA 004164 -42- and about 200 meters north of the 3.F. Goodrich plant. The concentration of vinyl chloride in the samples was 0.375 ppm and 0.058 ppm. Weather conditions included rain with a southeast wind estimated at 5 to 10 knots. Three samples were obtained at approximately 1030 hours on the same day in the vicinity of the Union Carbide Company in Torrance. The concen tration of vinyl chloride from a sample taken on Prairie Avenue, west of the plant was less than 0.001 ppm. A sample from 190th Street, north of the plant contained 0.004 ppm. A sample taken at the Torrance Children's Center, approximately one-half mile north of the plant had a concen tration of 0.002 ppm. The wind was southwest at 1 to 2 mph. B.F. Goodrich - Stauffer Monitoring Results B.F. Goodrich and Stauffer Chemical are conducting a cooperative air monitoring effort in the vicinity of their facilities, in the Long Beach - Carson community and at several remote locations. These data were made available to the staff and are presented as received in the accompanying table (Table IV -7), Compared with the staff's modeling estimates, these levels are somewhat lower than might have been expected. A single notable exception to this is the value of 0.098 ppm (24-hour average) reported for the Long Beach site 3 miles southeast of the plants. A simultaneous measurement at the southeast corner of the Stauffer facility shows a much lower reading, so this result is all the more surprising. The companies have not been able to account for this discrepancy. CMA 004165 TABLE IV-7 B F GOODRICH CHEMICAL DIVISION STAUFFER CHEMICAL DIVISION VINYL CHLORIDE COMMUNITY MONITORING PROJECT 3/13/7S -43- DATE 2/2/78 2/7/78 2/16/78 2/22/78 2/23/78 3/7/78 2/2/78 2/7/78 2/9/78 2/14/78 2/16/78 2/22/78 2/23/78 2/28/78 3/2/78 2/2/78 2/7/78 2/22/78 2/23/78 3/7/78 2/2/78 2/7/78 2/9/78 2/14/78 2/16/78 2/22/78 2/23/78 2/28/78 3/2/78 2/2/78 2/7/78 2/14/78 2/16/78 2/2/78 2/7/78 2/16/78 2/22/78 2/3/78 2/7/78 2/10/78 LOCATION 100 yds. NW of Source (Fire Station h It II II BFG II II Samples II M II tl SE Corner of Stauffer Property H >1 " " Stauffer " " Samples II It II II One Mile East in Carson Community II II II II BFG it Samples M II Three Miles SE in Long Beach Community II II II " Stauffer II " Samples II It II It II II It It II If Eighteen Miles SE in Huntington Beach Community "" '* " Stauffer " " Samples Thirty-eigIIht Milesii SE in Mission Veijo II l BFG_ " " Samples Colorado River Near Blyth, Calif. (BFG) Snowmass, Colorado (BFG) " " (3 hr. sample, BFG) vc(ppb) 6.2 13.0 8.9 10.3 10.4 8.9 28.1 N.D 10.5 1.0 94.0 52.4 2.0 O.7 0.2 2.8 N.D O.6 0.2 5.9 3.9 N.D. 5.9 < 1.0 < 1.0 1.0 < 1.0 98.0 1.0 7.9 N.D. 0.6 < 1.0 0.5 N.D 1.9 O.2 < 0.1 0.2 < 0.1 All samples collected continuously for 24 hours beginning at 6 A.M. on the date indicated. CMA 004166 -44- Keysor - Century Monitoring Results The Keysor - Century Company monitored vinyl chloride concentrations in the ambient air at three sites in the vicinity; the Saugus School, the Mohawk Gas Station and the railroad station (see Figure 1). Sampling was performed daily on three 8-hour shifts from January 27 through March 22, 1978 except for approximately a dozen samples lost at various sites on various shifts because of malfunctions. Concentrations at or below 0.05 ppm are not detectable with the measurement system employed. Concentration values above 0.05 ppm were observed on twelve days during this time period. On each of those twelve days the concentration exceeded 0.05 ppm only on one shift at one of the three sites. Each of the three shifts had four of the excesses. Three of the values were at the Saugus School, four at the railroad station and five at the Mohawk Gas Station. Comparison of ARB and Keysor - Century Measurements at Saugus School The Saugus School was the only sampling site used by both the ARB and keysor - Century. Keysor - Century reported values above the detectable limit of 0.05 ppm at the site on February 3 (0.09 ppm), February 19 (0.06 ppm) and March 5, 1978 (0.08 ppm). ARB reported no detectable values on February 3, or on March 5. The ARB did not monitor on February 19. CMA 004167 FIGURE 1 Keysor-Century and Air Resources Board Ambient Air Sampling Locations U-o Source: ARB Enforcement Branch CMA 004168 -46- On February 6, ARB recorded a concentration of 0.18 ppm for the time interval 1600 - 2400 hours, at the Saugus School, Keysor-Century reported a non-detectable level for that same time interval at Saugus School, but reported a simultaneous reading of 0.07 ppm at the Mohawk Gas Station. The staff has prepared a number of^standard samples for analysis in the ARB's Haagen-Smit Laboratory, the Keysor-Century Laboratory and an independent referee 1 aborairbry'i^lA^bmparfton of results obtained by the three laboratories shows good agreement. This suggests that the discrepancy may be traced to the calibration standard currently in use at Keysor-Century. The staff is continuing to explore the reasons for this apparent lack of agreement. These recent data suggest that, even prior to full compliance with NESHAP, ambient levels of VC in the vicinity of these facilities are averaging well below the calculated levels based on the EPA's emission factor for fugitive emissions. The staff finds this result encouraging, in that it suggests that fugitive emissions of VC may be reduced to a level that approaches that required under the proposed ambient standard when these facilities are in full compliance with NESHAP. Further reductions, if any, needed to meet the proposed ambient standard should be relatively easy to achieve. CMA 004169 -47- V. Measurement Method A. Background Another major factor for the Board to consider in setting an air quality standard or a significant harm level for VC is the selection of a measurement method that is precise, accurate, and specific to VC. In Staff Report 78-1-1 presented to the Board at the January 25, 1978 public meeting, the staff recornnended that the "ARB Method-Vinyl Chloride in Air" be adopted as the official method for quantifying ambient levels of VC. This method had been developed by the ARB Research staff specifically for purposes of detecting VC in the vicinity of facilities that emit VC. Several issues were raised with regard to the method, specifically: 1. The method's ability to measure VC accurately at 0.010 ppm, the lower level under consideration. 2. The specificity of the method because of possible interference from other organic compounds. 3. Other possible methods in use by some of the manufacturers, especially those utilizing charcoal sampling tubes. In response to these issues the staff included further refinements to the description of the method in response to the specificity and accuracy concerns. Additionally, the staff held a meeting, at the request of.B.F. Goodrich with representatives of B. F. Goodrich, Dow Chemical, KeysorCentury and Stauffer Chemical, to discuss the method. CMA 004170 -48- 2. Modifications to the AR3 Method In response to the several concerns raised about the method, the staff made several changes to the method. The revised method, attached hereto as Appendix 5 and dated March 13, 1978, includes the following changes: Page 1, Line 7 - Range is redefined in terms of ppm by volume in order to eliminate any ambiguity and to conform with the concentration units used for other standards and methods. Page 1, Paragraph 2 - The limits of analysis capability are expressed in terms of "minimum measurable" rather than "minimum detectable" concentrations in response to a man ufacturer's concern that the "minimum measurable" level can be accurately and precisely quantified whereas "the mimimum detectable"level cannot. This eliminates any possible ambiguity in the meaning of the terms "detection" and "quantification". Page 4, Paragraph 6.4 - A different gas chromatographic column is specified. This column is preferred over that originally specified because, under the prescribed operating conditions, there are no known interferences with the quantification of VC. The above modifications are based on new calibration data (Table V-1) that the staff has acquired, using the new column, for the two variations of the method (i.e., direct injection and preconcentration by freeze-out). CMA 004171 -49- Table X-l Loop (1 ml.) method bration# 1 2 1 1 2 2 2 # samples 8 3 6 10 3 3 4 nominal cone, (ppm) resp'J!''.se (PPm) 0.08 0.08 0.008 0.123 0.008 0.400 .024 0.0818 + 0.0047 0.0780 + 0.0004 0.0064 + 0.0016 0.1234 + 0.0070 0.0079 + 0.0027 0.4092 + 0.0023 0.0270 + 0.009 calibration# 1 2 1 2 3 1 2 2 (response) = 1 .0234 * (cone) -0.009 Sy = 2.23 (PPb) r = 0.999896 Table 2. Freeze-out (100ml.) Method # samples nonimal cone, (ppm) response 4 0.008 0.0078 + 0.00006 3 0.008 0.0077 + 0.0003 4 0.080 0.0768 + 0.0017 5 0.080 0.0750 + 0.0020 1 0.080 0.0826 3 0.123 0.1214 + 0.0042 3 0.0008 0.0Pn9 + 0.0001 3 0.024 0.0225 + 0.00006 (response) = 0.984616 * (cone) - 0.00036 Sy = 2.35 PPB r = 0.998836 Sy = standard error of estimate r = correlation coefficient CMA 004172 -50- This section of the report describes the originally proposed method, modifications to the proposed ARB method, the basis for these modifications and the resolution of tne issues and comments raised by the manufacturers at the January 25, 1978 Board meeting and the March 16, 1978 staff meeting. B. The ARB Measurement Method 1. Originally Proposed Method The ARB method involves constant-flow sample collection into a Tedlar bag. The sample is then injected directly into the sampling loop of a gas-liquid chromatograph which separates the VC from other compounds. Finally, the VC concentration is quantified using flame ionization detection. The sampling loop is adequate for samples down to approximately 0.010 ppm VC. For lower levels of VC, a freeze-out concentrating technique is used pripr to analysis. In the January 25, 1978 report, the detection limit was defined as 0.02 nanograms per cubic meter (approximately 0.010 ppm) for direct injection, and precision was defined as "Using ten calibration points between 0.025 and 1.0 ppm VC, the 95 percent confidence interval is + 0.010 ppm, which is essentially equivalent to a standard deviation of 0.005 ppm VC. With a freeze-out trap, a lower limit of detection of 0.001 ppm can be achieved, with a standard deviation of about 0.0005." CMA 004173 -51Each calibration sample was prepared independently in a Tedlar bag Repeated analyses of the samples demonstrate the accuracy and pre cision of the methods. The direct injection (loop) method is accurate and precise at 0.010 DDm, and the preconcentration freeze out method is accurate and precise to 0.001 Dpm, as noted in Table V-l. A simple linear regression illustrates the linearity of the instruments. CMA 004174 -52- C. Meeting of March 16, 1978 with the Manufacturers B.F. Goodrich requested a meeting with the staff in order to clarify and resolve concerns that it ,iad with the proposed ARB method. The staff met with representatives of B.F. Goodrich on March 16, 1978 in Berkeley. Representatives of Stauffer Chemical, Dow Chemical, and Keysor-Century also attended the meeting. The staff provided detailed analytical data demonstrating the specificity, precision, and accuracy of the proposed method. Based on the staff's data and our field experience, the representatives of B.F. Goodrich appeared to acknowledge that the quantitative measurement of VC could be accurately performed at the level of one part per billion by volume in air using the ARB method. The representatives of Stauffer Chemical and Dow Chemical did not object to the staff's conclusions. At the same meeting, representatives of B.F. Goodrich presented their own analytical method for review and acceptance by the ARB. The B.F. Goodrich method involves sample collection with charcoal tubes rather than the Tedlar bags as proposed by the ARB staff. The VC is then thermally desorbed from the charcoal and directly injected into the chromatograph for analysis. However, since Goodrich did not submit any analytical data to establish the specificity, precision, and accuracy of the proposed method, the staff was unable to determine whether it is equivalent to the ARB method. B.F. Goodrich agreed to exchange further information with the ARB analytical staff regarding experimental techniques employed in its analysis of VC. CMA OO4175 -53- D. Staff Response to Comments on Methodology The Air Resources Board staff has received a number of comments from B.F. Goodrich and Stauffer Chemical Company regarding the analytical method employed by the staff in measuring ambient levels of VC. This subsection summarizes the manufacturers' comments and the staff responses thereto. 1. January 25 comnents of B.F. Goodrich Company (8FG) a. BFG questions whether or not vinyl chloride can be measured accurately at concentrations of 0.G1 - 0.05 parts per million by direct injection (page 7, No. 1). The staff has included calibration data in Section V-B which demonstrates the accuracy of the ARB direct injection method at and below these concentrations. b. BFG suggests that the National Institute of Occupational Safety and Health method employing carbon adsorption coupled with thermal desorption and total injection may be as effective and easier to implement than the AFw s freeze-out method (page 8, No. 2). The staff will entertain acceptance of other analytical procedures by any other laboratory group, provided there is ample evidence as to the specificity, precision, and accuracy of these procedures. c. BFG seeks to clarify the distinction between detection and measurement. CMA 004176 -54- The ARB staff has modified its analytical method (see Section V-S) so that the minimum measurable amount is clearly defined. d. BFG recommends a minimum measurable concentration of 500 parts oer billion by volume of VC because the detection limit of many BFG analytical instruments is 100 parts per billion (Appendix E). The staff notes that this request was not discussed at the meeting of March 16 in Berkeley. During the meeting the BFG staff expressed confidence that VC can and should be quantified accurately at and below 10 parts per billion by volume. The ARB staff can detect VC at 2 parts per billion by direct injection and accurately quantify VC at 10 parts per billion. The use of a freeze-out preconcentration technique, routinely employed at the ARB laboratory, lowers the detection limit to less than 0.1 part per billion by volume. One part per billion can be accurately quantified by this technique (see Section V-B). 2. January 25 Comments of Stauffer Chemical Company. a. Stauffer requests experimental data from the ARB demonstrating that vinyl chloride can be accurately quantitated at 10 parts per billion. The ARB staff presents calibration data in Section V-B to demonstrate the accuracy and precision of the method at the 1 part per billion level. CMA 004177 -55- b. Stauffer suggests that the presence of VC in the samples be verified by mass spectrometry or other means because of the possibility of interferences. The ARB staff routinely verifies the presence of VC by mass spectrometry. Also, the staff has recently developed new analytical methods that eliminate possible interferences with the quantification of VC (see Section V-B). c. Stauffer requests information about the standard reference materials and calibration standards. The ARB staff purchased standards of vinyl chloride at approximately 0.8 parts per million in nitrogen. A 1-1 iter precision gas sampling syringe is used to prepare calibration standards at 0.4t 0.124. n.DR. 0.02a, 0.008, 0.0008. and 0.00008 ppm VC by volume in zero air. d. Stauffer requests detailed information regarding the use of nitric oxide as an ozone quencher. Ozone levels in the South Coast Air Basin no longer are expected to exceed 0.5 ppm. Therefore, the highest concentration of nitric oxide that is required is 0.5 ppm. A 10-liter air sample, therefore, requires 50 milliliters of 100, ppm nitric oxide in nitrogen. This small amount does not measurably affect the concentration of VC in the sample. None of the VC/PVC plants to be monitored is in a high ozone area. Therefore, the required quantity of nitric oxide could be substantially reduced. CMA 004178 -56- More importantly, the NIOSH, EPA, 3.F. Goodrich and Stauffer methods relying on VC adsorption on charcoal may be unaccept able because ozone in the sample stream may destroy some of the VC adsorbed on the charcoal. e. Stauffer points out the importance of obtaining a representative composite sample. The ARB staff utilizes a constant flow sampler to partially fill a Tedlar bag. Thus, a truly representative composite sample is obtained. f. Stauffer seeks a definition of parts per million. The ARB bases its standards on and reports measurements as parts per million volume/volume. g. Stauffer questions the use of a Rotameter to to measure sample air flow. The ARB method requires a Rotameter only at the beginning and end of the sampling period to assure constant flow. Therefore, contamination of the Rotameter is not a problem. Since the bags are not filled completely, back pressure is not a problem. h. Stauffer points out that the analyses should be performed within 24-hours of taking the samples. CMA 004179 -57This is standard practice at the ARB and is discussed in the proposed method. i. Stauffer questions the sensitivity and accuracy claimed for a 1 ml direct injection. The staff presents calibration data to substantiate its claims in Section V-B. j. Stauffer points out that sampling valves may adsorb and desorb VC leading to spurious results. The ARB staff has performed repeated experiments in which air zero is analyzed imnediately following a sample of 800 parts per billion VC in air. No outgasing was ever observed. k. Stauffer suggests that the column employed by the ARB may have a memory effect that could lead to errors in analysis. Repeated ARB experiments involvinq blanks following samples reveal no memory effects due to the column. CMA 004180 -58E. Conclusion In summary, some of the concerns of che manufacturers with regard to the proposed ARB method appear warranted, such as defining the minimum "measurable" level rather than the minimum "detectable" level for the direct injection and preconcentration freeze-out techniques, and the type of column used for separation. The staff has modified the method, thus, defining the lower measurable levels as 0.010 ppm VC for the direct injection and 0.001 ppm VC for the freeze-out techniques, and changing the column specifications, thereby improving the proposed method. Based on discussions between the staff and the manufacturers at a meeting of March 16, 1978 in Berkeley, there appears to be agreement that the proposed method can measure VC accurately and precisely at 0.001 ppm. The only remaining concern is that some manufacturers would prefer to use their own methods, which should pose no problem provided they demonstrate method equivalency. Oo APPENDICES Appendix 1 - Basic VC Monomer and PVC Production Processes Appendix 2 - Environmental Protection Agency - National Emission Standards for Hazardous Air Pollutants, Standard for Vinyl Chloride, October 21, 1976 (41 FR 46560) Appendix 3 - South Coast Air Quality Management District (SCAQMD) Rule 1005 - Emission Standard for Vinyl Chloride, Adopted September 14, 1977 Appendix 4 - EPA Proposed Rule for Vinyl Chloride, June 2, 1977 (42 FR 28154) Appendix 5 - ARB Method - Vinyl Chloride in Air (March 13,1978) Appendix 6 - Glossary Appendix 7 - ARB Staff Report No. 78-1-1. Effects of Airborne - Vinyl Chloride Appendix 8 - Public Hearing Notice CMA 004182 APPENDIX I Basic VC Monomer Production and Polymerization Processes Figures 1 and 2, taken from the reference below*, illustrate the basic elements and the flow of materials in the production of VC monomer and the production of VC polymers. Each step in the process may have associated with it pumps, compressors, agitators, columns, and similar apparatus common to the chemical industry, and these pieces of equipment must be considered as possible sources of VC emissions. The types, numbers and arrangement of such equipment will vary from plant to plant and are not shown on the simplified diagrams. Vinyl Chloride Monomer Production Nearly all vinyl chloride manufacture begins by either oxychlorination of ethylene or direct chlorination of ethylene to produce ethylene dichloride. In the oxychlorination process, ethylene dichloride is made by the reaction of air and hydrogen chloride (HC1) with ethylene in a catalytic process. Inthe direct chlorination process, ethylene dichloride is made by the reaction of ethylene and chlorine. The crude ethylene dichloride produced by these processes is then purified by scrubbing, drying and fractionating as indicated in Figure 1. The purified ethylene dichloride then enters a cracking furnace, where vinyl chloride and HC1 are produced. The HC1 is then removed/from the furnace and recycled to the oxychlorinator. *SRI International, Cancer Control Monograph: Vinyl Chloride, Prepared for National Cancer Institute (in press). CMA 004183 The fractionating column following the cracking furnace seoarates the residual ethylene dichloride frcm the vinyl c.nloride monomer. The ethylene dichloride is recycled into the purifying system and the monomer is transferred to storage. Polymerization Process As indicated in Figure 2, vinyl chloride monomer for the polymerization process is obtained from a storage tank. The storage tank is supplied from tank cars or from a monomer production facility at the same site. Although different types of polymerization processes are used, most PVC resin is produced by loading VCM, water, and other materials, such as emulsifying agents into polymerization vessels commonly called "reactors". The reaction proceeds under controlled conditions of temperature and pressure. After polymerization the mixture of resin and liquid, called "slurry", is transferred to the stripping device. (In some plants stripping is carried outin the reactor.) The stripping process, by the use of heat and reduced pressure, drives most of the unreacted monomer out of the slurry. The extracted monomer is introduced into the VCM recovery system where it is processed for recycling into the polymerization process. The stripped slurry is sent to a blending tank to be combined with slurry from other reactors, in ordei; to obtain the desired product composition. From the blend tank the slurry enters a centrifuge where most of the water is removed. From the centrifuge the polymer enters a flash dryer which removes the remaining water. The dry polymer resin is screened and shipped, either in bulk or packed in bags. CMA 004184 Recycle HCII FIGURE 1 SIMPLIFIED "TYPICAL" PROCESS FOR PRODUCTION OF VINYL CHLORIDE MONOMER (VCM| Source: SRI International, Cancer Control Monograph: Vinyl Chloride. Prepared for National Cancer Institute (in presY) 004185 CMA 0 0 4 1 8 6 FIGURE 2 SIMPLIFIED "TYPICAL" POLYMERIZATION PROCESS Source: SRI International, Cancer Control Monograph: Vinyi Chloride. Prepared for National Cancer Institute (in press). APPENDIX 2 NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS Standard For Vinyl Chloride CMa 4l87 IGGGO RULES AND REGULATIONS Till# 40--Protection of Environment are required to be cw.ituicd and ccr.- CHAFT.TR I--ENVIRONMENTAL trolied. PffOVECTiON AGENCY I It ALT!! AND E.V.TP.O:. Mi.'.TAt 111 CACTI 5U30tArr;.-t c--m* p*purams ;;t'U ct3-11 J'PA prej.-.red a ci'X..7.-n: entitl'd the Qu-intitalive Flick ,/r`^r.t lor Cum- PART Gi--NAT.'C : -.L FAUSSICN STANDASOS FOR hA-AfiCCUS AIS POLLUTANTS Stor.darJ for Vinyl Chloride nu;:v tzorwert to ,. Cl'.'.on.lt 7 '.dch estimates the rfn.-r. vinyl cnioride expenu.-e to popuiat,m tie \ clnity of vinyl ciilo.-ide-emitt.ng r.L.r.L'i On December 2 4, 1375, under section before and uft.r imp'.em.i'ntr.tion of con 113 or the CUr.n ALr Act. as amended (42 trols to meet the stai.cij.rt:. There are no V S C. IE571. the Environmental Protec doso-response data fur me concentra tion Agency iLPA) r.ddcd vc.;i ridor.de tions of vinyl chloride found In the am to t:.- lut or r--'.Miious n; pollutants bient air. Therefore, asses-rr,onto of risk (40 1-Ti 55477; and proposed a national at ambient leveis of exposure were ex cmis.'.on standard For It (43 FP. 50502). trapolated from cose-re>poase data from The standard covers plants which manu higher levels of exposure using both a facture ethylene dlchloride, vinyl IL'iear model and a log-probit model. chloride, and/or polyvinyl chloride. Extrapolations made with each of these EPA decided to regulate vinyl chloride models entailed using d.decent sets of because It has been implicated as the assumptions. Because different assump causal ageut of angiosarcoma and other tions can be made ln extrapolating to serious disorder, both carcinogenic and low dooes, the health risks are reported tmncirainoKcnlc. In people with, occupa ln ranges. tional exposure and Ln animals with ex- It was estimated that 4.6 million peo- penuiental exposure to vinyl chloride. plo live within 5 miles of ethylene dicho- Reasonable extrapolations from these ride-vmyl chloride and polyvinyl chlo findings cause concern that vinyl chlo ride plants and that the average ex ride may cause or contribute to the same posure around these plants before instal or similar disorders at present ambient lation of controls to meet the standard air levels. The purpose of the standard Is Is 17 parts per billion. The exposure to minimize vinyl chloride emissions levels for uncontrolled plants were cal from all known process and fugitive culated based on estimated 1974 emis emission sources In ethylene dichlorlde- sion levels. Using the Uneat dose-re vinyl chloride and polyvinyl chloride sponse model, EFA found that the plants to the level attainable with best rate of Initiation of Uver angiosarcoma available control technology. This will among people living around uncontrolled hue the effect of furthering the protec plants is expected to range from less than tion of public health by minimizing the one to ten cases of liver angiosarcoma health risks to the people living ln the per year of exposure to vinyl chloride. vicinity of these plants and to any addi The log-problt model gave predictions tional people who are exposed as a result that are 0.1 to 0,01 times this rate. This of new construction. wide range Is an Indication of the un Interested parties participated ln the certainties ln extrapolation to low doses. rulemaking by sending comments to EPA. Due to the long latency time observed in The comments have been carefully con cancer cases resulting from vinyl chloride sidered, and where determined by the exposure. Increases initiated by exposure Administrator to be appropriate, changes this year will not be diagnosed until the have been made to the regulation as pro 1990`s or later. Vinyl chloride Is also es mulgated. timated to produce an equal number of Summary or th* Standard primary cancers at other sites, for a total of somewhere between less than one and In ethylene dlchloride-vlnyl chloride twenty bases of cancer per year of ex plants, the standard limits vinyl chloride posure among residents around plants. emissions from the ethylene dlchloride The number of-these effects Is expected and vinyl chloride formation and puri to be reduced at least ln proportion to the fication processes to 10 ppm. For the ox- reduction ln the ambient annual average ychlorlnatlon process, vinyl chloride vinyl chloride concentration, which Is emissions are limited to 0.2 g/kg Of ethyl expected to be 5 percent of the uncon ene dlchloride product. trolled levels after the standard Is Im In polyvinyl chloride plants, the stand plemented. ard limits vinyl chloride emissions from Changes to the standard since pro equipment preceding and Including the posal do not affect the level of control stripper ln the plant process flow to 10 required. Thus, the environmental Im ppm. Emissions from equipment follow pact of the promulgated standard Is, ing the stripper are to be controlled by with one exception, the same as that stripping dispersion resins to 2000 ppm described ln Chapter 6 of Volume I of and other resins to 400 ppm, or by using the Standard Support and Environmen equivalent controls. Vinyl chloride emis tal Impact Statement. According to data sions from reactor opening are to be re submitted by the Society of Plastics In duced to 0.02 c/kg polyvinyl chloride dustry. Inc, (SPI>, the Impact on water product. consumption to the draft environmental In both cthyleno dlchloride-vlnyl Impact statement was overstated. In es chloride and polyvinyl chloride plants, timating the Impact on water consump relief valve discharges and manual vent tion. EPA based Its estimates on worst ing of Eases are prohibited except under case conditions. That Is. EPA assumed emergency conditions. Fugitive emissions that those control systems with the greatest wal'.r U. age would be employed ard th,,t 'rt'j-re would be no rcv/ciing of water. There 1.1 no regulation which would require water recycling. Accord ing to AIT, tile control syucera utilizing trie r:io>t water will not be Lied gener ally by the industry and economic fac tor-; will cause plants to recycle much of t.-.e v.Ltcr. Mnercfore, according to SPI the impact of the standard on water consumption will be negligible. The environmental impacts of the promulgated standard may be summar ized as foticTrs: The primary environ mental impacts of the standard are ben eficial and will consist of vinyl chloride - emission reductions of approximately 94 percent at ethylene dichloride-vinyl chloride plants and 9a 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 dlchloride-vlnyl chloride plants and by other petrochemical plants In the complexes where ethylene dlchlorldevtnyl chloride plants are typically lo cated. An incinerator used to attain the standard at an ethylene dlchloride-vlnyl chloride plant could Increase hydrogen chloride emissions by several fold. Typi cally. however, due to the corrosion proolems which would otherwise occur both on plant property and to 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 (S3 percent control) were used to control the hydrogen chloride emissions resulting from Incineration of vinyl chloride emissions, the Increase In hydrogen chloride emissions from a typ ical ethylene dlchloride-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 dtchlorlde-vtoyl chloride plants to be in the some range or somewhat higher than existing foreign standards and National Academy of Sciences (NAS> guideline* for public exposure. Economic Impact In accordance with Executive Order 11S21 and OMB circular A-107. EPA carefully evaluated the ccbnomlc and Inflationary Impact of the proposed standard and alternative control levels and certified tills to the preamble to the proposed standard. These Impacts are HOilAl tfCISTM, VOU 41. MO. >03--!HU*SO*T. OCTOStt II, I*/* CMA 004188 RULES AND REGULATIONS IGGfil discussed Li Chapter 7 of Volume I at the Standard S'.'.ppcrt Cr.d Ercironmery. tal Impact S'.clcmj-nt, Canments on the proposed r.'.'.r.'-'ird hive resulted in only or.e cu.1',: charge In th-; economic Im pact analysis. EPA estimated that there would to four plant cIo-.ujvn us a result or the prvut ligated standard. Of the lour plants idcr-tilied as possible closure can didates, or.e 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 ma7 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 515 million is for ethylene dichlorlde-vinyl chloride plants and $183 million Is for polyvinyl chloride plants. EPA estimates that these plants will have to spend $70 million per year to maintain the required emission levels. In addition, the total capital cost for existing plants to meet the EPA's 1903 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 in the total costs cited above for meeting the promulgated regulation. Broken out separately, the capital cost of meeting the fugitive emission regulations Is $37 million and the annualized cost Is $25 million. The standard is not expected to deter construction of new ethylene dichlorldevinyl 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 in order to maintain preeontrol profitability and also to re cover the total annualized control costs necessitated by the standard at ethylene dichlorlde-vinyl chloride plants and poly vinyl chloride plants. This Increase is estimated to translate into a maximum consumer price Increase In goods fabri cated from polyvinyl chloride resins of approximately 3.3 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. PunLie Participation During the public comment period, 50 comment letters on the proposed stand ard were received. There acre 24 from Industry; 3 from environmental groups; 15 from Federal. State, and local agen cies; and $ from individual citizens, Aa required by section 112(b) (1) (B) of the Act. a public hearing v.as held on 'he proposed sl.-u'idard on February 3. 1373. in V/ashing+ur*.. DC. Presentations iters mnde by the Environmental Defense Fund, the Society of the Plastics Indus try, Inc.. Dow Cl; '-'cal Company. Dia mond Shamrocl: Corporation, and Air Products and Chemicals. Inc. Cop.es of the comment letters received, the publ.c hearing record, and a summary of the comments with EPA's responses are available for public inspection and copy ing at the EPA Public Information Ref erence Unit, Room 2922 (EPA Library). 401 M Street. SV/- 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. SW, Washington. D.C. 20430 (specify Standard Support and Environ mental Impact Statement, Emission Standard for Vinyl Chloride, Volume II), Significant Costuznts and Changes 10 ihx Pxorospp Regulation (1) Decision to list vinyl chloride as a hazardous air pollutant. In general, tho commenters did not contest EPA's 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 in 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 factors 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.S. worker EPA discussed as having been exposed to vinyl chloride levels low er than those usually encountered In polyvinyl chloride production has been dropped from the National Institute of Occupational Safety and Health's listing of workers with angiosarcoma. EPA agrees that there are questions concern ing the level of exposure and in some cases the pathology of these cases not Involved directly In polyvinyl chloride and vinyl chloride production. These un certainties are stated In the appropriate footnotes of the Scientific and Technical Assessment Deport on Vinvl Chloride end Polyvinyl Chloride (STAR) where the angiosarcoma cases are listed. However. In spite of these uncertainties. In view of the po-uublc exposure patterns, there cases cannot be Ignored in `-be es aiuv.mn of the potential puollc health problems. With regard to the alleged overstated emission levels, the uncontrolled emis sion levels reported by EPA were bared Oh 1974 .(lita. This quaLficatton was stated wherever emission data were pre sented. FPA recognizes tna: err.iss cits have been reduced since that erne, and stated this In the preamble to the pro posed standard. EPA decided not to gather more rtvent data on emission levels, because these emission levels are expected to change, and gathering tr.e data would lake 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 modeling to pro.-oct maximum ambient air concentrations around uncontrolled plants. 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 Encironmenfal 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 rvs 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: (1) 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: t3> there are a number of employees, particularly In the fabrication Industries, who would be come ** least temporarily unemployed; and (4) control technology Is available which is capable of substantially reduc ing emissions of vinyl chloride Into the atmosphere. EPA agrees that substitutes do exist or could be manufactured for most poly vinyl chloride uses. However, in general, these substitutes do not have some of the more desirable characteristics of poly vinyl chloride, such as nonflammability. If vinyl chloride and polyvinyl diiorlde were banned, other substitutes with these more desirable characteristics would likely be developed. There Is a risk that these substitutes would also huvo adverse health or environmental effects. Since control measures are available which can reduce vinyl cliloride omis sions by 90 percent or more, It docs not teem prudent to reduce emissions by the remaining percentage and take Uie risk of Introducing new untested chemicals into the environment. HDiRAt tECISTft, VOt. 41. NO JOS--THURSDAY. OCTOBER 11. 1VJ4 CMA 004189 RULES AND REGULATIONS A:icr r(qvoxqh (1 by hie c parity of no more titan 0.19 m* (50 vcnt.ng ?,HI Go p.-nnlib.d hi a I;--! re.or*, co.':..t.c.'i::,-s v. v> Ui t-*_o i:.v n;.'.Gsrd for gi.l;. E-.zcfOm In 'ills rr.r.'jc err. before Lha r.'.G.f valve opens. T.-.c s.-.ms C.ich 1: G.\;:<:'G emlnor. no: 1 on co'l c ..'.iv be found In a laboralory. v, heror.s r.ocJlcx:.or. r:::rxercj ?.re required f-r t-tr.xs bi-.-v. of the fu ;Kivc i.l: trier reactor-. .-..a p.lot maiiuai u;.:..-' : ' j lie iimo.vhcre :: .im nr.L...'-r. r jj: r..i.v-Co'.-tr.Uy ..tale factiaic".. E;uG-./j:. .'fin .antra1,try re.V:iri_G for rc.-cf d, Mil urges. :.s o'-- v..-. ..*.e cf cou'-.'oi .'.ale equipment ;;ie Gv.ivcl/ - - There are i-:-,;rnl changes In the ,-_u- r.r.-e s..,, .Gy 1.u.ot'. Me L't'r.c- npplcat..on of u.o cof.t.ols .-c-q.,;r:-:i lj citrical caM-im Lmifs la foe pro.-r.ui- fi-:. A.i..ci. :I. G?A d;U Gel-. the a coc:- ii:c stand, zd wotilu i.c c/.p-tn, .re .r.G izn- f ;'.cu sh-nasra. Except for the standard brr.c.'.f r.v. o f-r '_-.e c.i t.roN rcqu'-id prscttcsl. EPA sho ut.idoc no exempt re- for reactor o.'.(.**--ig loss, these char.;TM for a m,...of emission pm-vj, G?A seercit nr.-1 con v.::,;ify ihv-jf. e conversion to the Ir terr..'.- dortt not ruoh a r-t.o aopro- taining rc.ctorf gre; itor chan CGj ,iP ,.r) t:oi;al Sy.F..-m of Units <S1;. There was prir.tc br:.-'o> on wr.:;h to ; : a standard. gal) and r.o more tsar. 4.07 m` (ECO gal) an error involved in the original exhala Section ill of tl.a Clear. A-r -V. t provides m capacity from ah pares of the standard tion used to tier.vo me standard for rec for tl.c d-.VLlo 'n-.ont of s *,..'.birds bmeil except the 13 ppm limit for reactors, tor opening. Correcting this error cox- on best control technology (considering strippers, monomer recovery systems. ar.d bios die iGGj-.'so'.c emli-Iom. It Is err.- costs), liven ur.der section 111. 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 facul ard is a correction, ar.d not a charge m ancing of costs versus benefits. Instead, ties to meet other parts of the standard the Intent for the degree of control re costs are cor.F.dered 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 required the quired to achieve a given emission level standard for reactor opening Is based In Installation of a rupture disc beneatn and the economic impact of possible part on reducing the frequency of open each relief valve to prevent leakage from standards on the Industry In ques ing the reactor. Research and develop the relief valve. A provision has been tion, Unlike section 111, section 112 does ment reactors have to be opened after added to the promulgated standard so not explicitly provide for consideration every batch for thorough cleaning. Also, that a rupture disc Is not re,uirid If of costs, so It would clearly be inappro priate to consider costs to a greater ex stripping technology Is developed Indi vidually for each resin In research and the relief valve is tied into a process Ime or recovery system. In this case, any tent under section 113 than would be done under section 111. 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; Le,, 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 development equipment Therefore, at tainment of the stripping limitations In the research and development equipment would not always be possible. The 4.07 m1' (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 leakage from the relief valve would be contained. The regulation for obtaining vinyl chloride samples has been changed to an operating procedure. The proposed standard stated that there were to be no emissions from taking the samples. Several commenters pointed out that the use of the word "no" would make this regulation Impractical to enforce. 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 chance 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 ples containing at least 10 percent by weight vinyl chloride. This is consistent 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 clilorlde production, and technology preventing relief discharges from reac tors, one of which Is manual venting of part of the reactor contents for purpose* of cooling and reduction In pressure within the reactor. The higher the tem with the other parts of the standard which apply to equipment "In vinyl chloride service." "In vinyl chloride serv ice" distinguishes between situations where vinyl chloride Is clearly involved exists to avoid excess emissions during startup and shutdown at ethylene dlehlortdcvliiyl chloride plants. We do not perature and pressure within the reac tor, the greater the amount of vinyl chloride which has to be removed to and situations where vinyl chloride is a minor component or contaminant, and as defined in promulgated J 61.61(1) believe plants should be allowed to emit bring the reactor under control. Manual means that a piece of equipment con excess emissions during malfunctions, venting can be done at a lower pressure tains or contacts either a liquid that Is and therefore are requiring them to shut than the pressure required to open the at least 10 percent by weight vinyl chlo down immediately. relief valve. For this reason manual vent ride or a gas that is at least 10 percent (3> Selection of source categories. In ing can result in lower emissions than by volume vinyl chloride. the preamble to the proposed standard would occur by allowing the reactor to The proposed standard required a vinyl EPA recognised that some small research discharge through the relief valve, Fur- chloride monitoring system for a or.qinu- and development facilities may exist thennorc. a manual vent valve Is under ourly 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 under the standard would be unnecessary and inappropriate. However, EPA did not have sufficient information available to closed. A relief valve may become clogged with resin and not close. The result would be loss of all the reactor content*. The contents of a reactor can be man within stacks. The proposed standard did not outline required specifications for the monitoring system, except that it was to analyze the samples with gas chromatog clearly denne which facilities should be excluded from the standard, and encouraged Interested parties to submit such Information during the comment period. Eased on the information sub mitted, EPA decided to exempt poly vinyl chloride reactors and associated ually vented to a gasholder or other hold ing vessel. However, In some cases, such ns during severe weather conditions, sev eral reactors may be out of control at one time. There would be Insufficient holding capacity under these conditions to manually vent the contents of nil the raphy, or If all hydrocarbons were as sumed to be vinyl chloride, with Infrared spectrophotometry, flams ion detection, or equivalent. It required that each plant submit a description of its monitoring system to EPA. so that EPA could deter mine whether It was acceptable or not. Comments were received indicating s equipment from applicability of all parts reactors to a gasholder. Therefore, when need for EPA to specify some criteria for of Uie standard if the reactors are used all other measures to prevent relief valve Judging the acceptability of monitoring in research and development and hnvc a discharges hove been exhausted, manual systems. Tile accuracy Of the monitor- noteai tecum, von s>. no. 70s--thuso*y. octosir n, tvrs CMA 004190 RULES AND REGULATION'S Inn system would be related to the fre (g)(3)(H). and 61.70'cl f2> (!) ro (hat made the same as for other resmr ;::rt quency of calibration. Therefore. El'A measurement or the vinyl chloride levels others requested that they be mode --; ],os included in the p.-.-.rm.Icntcd slund- In the rC'irj: la to be node- ircmcdi.VcI? stringent. EPA decided not to molig il-.e ;rd requirements for '--'.a frequency of after stripr-'-g b> completed rather than standard for stripping dispersion rev.-;.-, ca!ib;at:o.n and pcecaiiurps to be carried as the resin t- being tranr-Tcrreii out of the some as for other resins bec.vt-e tr.-'s e out in the collocation of the monitoring the stripper. This allows n plant to carry is sufficient evidence to indicate th it in .tiurnents. out operations in a stripper alter strip these re'irts arc rr.oic difficult ;o '.'.rip The portable hydrocarbon detector re ping has been completed but be lore It la than other resins. With regard to trail quired by the proposed ..tnndard war. re transferred out of the stripper. Tula Is ing the stripping levels for di-p.-r-ujii quired to have n sensitivity of 5 ppm. consistent with the original intent of the resins less stringent, only one of 'he eight Comments were received Indicating that standard. manufacturers of dispersion resins s'ie- instruments in thin scns.tivity range are The regulation for loading and unload eiflcally commented that the eiispers.on delicate and require continuing mainte ing lines In 5 61.05(b) (D 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 is required for leak detection and lor lines that are disconnected tiler each dirnorslon resins made by this company measuring vinyl chloride concentrations loading or unloading operation. Perma ca.tr.ot 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 S 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, end record The proposed standard contained a regulation. keeping. There are several relatively single regulation for compressors. The The regulation for lnprocess waste- minor changes in the testing, reporting, promulgated standard has separate regu water In the proposed standard could and recordkeeping requirements, a pro lations for rotating and reciprocating have been misinterpreted to require in vision has been added to } 61 S7 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 61.55(b) (9) (1) of the with Test Method 106 are to be analysed 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 61.66 of the proposed standard be treated (l,e, 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 in 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 100. 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 Oho eommenter 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; Le,, dilution cannot be specified for the 10 ppm concentration method is intended as 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 ihe (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 for 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 of compliance pursuant pumps, compressors, and agitators be re promulgated standard which stales that to section 112(c) UMB) (11) at the Act. moved because the single seals currently If a reactor is also used as a stripper, (lie The request for a waiver for compliance used on this equipment have small emis reactor opening emissions may be deter should provide for the ease where EPA sions and are more reliable than double mined Immediately following the strip determines that a method Is not equiv mechanical seals. EPA 1s 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 in 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 in the resin which has already two years from the date of promulga sidered as a whole ore a significant been stripped to acceptable levels can tion. source of emissions, however, and the in esc' -2 from the resin and become part There are several wording chrrtflca tions which have been made in the pro mulgated standard. The definition for "in vinyl chloride service'* (160.61(D) has been clarified by stating that It means equipment that contacts vinyl chloride as well as equipment that con tains vinyl chloride. This would include such equipment as agitators. Words have been added in H 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 for opening of equipment. Equip ment that has met the opening of equipment regulation can contain more Uiau 10 ppm vinyl chloride and would be in violation of the standard If this .'-tatemeut were not Included. The requirements for stripping poly vinyl chloride resins to specified levels 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 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 tills is neither desirable nor necessary. Some commenters requested that the of the reactor opening loss. It is EPA's Intent that once a resin has been stripped to the required levcLs. 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 ns part of the reactor opening loss. A section requiring continuous moni toring of stack emissions has been added to the promulgated standard. The con tinuous monitoring of stack emissions was required in the proposed standard. The addition of a specific paragraph for emission monitoring serves only to clarify the requirement. The standard has been revised so that the initial report requires a "description'' rather than a "detailed description" of the equipment used to control fugitive emissions. Sevcnd commenters point'd out that a detailed description neiiM cont.-m proprietary information. EI'A have been revised la f I 61.64(c), 61.67 stripping levels for dispersion resins be agrees that a detailed description in Uio FfOftAL tfCISTI*. VOt. SI. NO. 305--THUMOAT. QCTOeCI II. 1V76 CMA 004191 4-rSA RULES AND REGULATIONS lnl'.IJ report la unnecessary. IT oddlt;.informalijn La needed, J.VA c"-i o'jU'.'.n It tind;r see*-loa 114 of the Act and the p'. vnt con r<q.. hit confidential tre-ttuens In nccordar.ee with 40 ClT. Part 2 for irlomuiti'-.t It believes to bo pr. The pro.'iOsed standard require'.: t-sat a semiannual reps-- be submitted every ICO days. The promulgated t'ortir.-tl specifies dates for the subrmttsi of the reports. It cho saveLies that tne --mt semiannual report does not have to bo submitted until at iea^t six months after the Initial report Is submitted. The standard has been revised to e'.imlnato tlio requirement to record the cause of any leak detected by the vunyl chlo ride detector, the action taken to repair the leak, and the amount of turns re quired to repair the leak. EPA Is con cerned onl7 that leaks are detected and repaired. That this has been done can be established by locking at the strip chart record of measurements made b7 the lnyl chloride detector. These records are 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 recommended that they submit the data by regular mall rather than registered mall. EPA has not adopted either of these - recommendations. A source Is supposed to bs In compliance with the standard within 90 days of the promulgation of the standard. The standard requires that the emission tests be done within the 00 day period, and permits an extra 30 days for determination of results. The purpose of using registered mall Is to document the fact that emission data ha7e been sent and received. This way If the results are lost in the mail, there will be no question that they were sent (6) Test method. Test Method 106 has been changed to recognize that 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. XfriM spectroscopy or another absolute 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 not successful. In section 4.1.4, aluminized Mylar bags can be substituted for Tedlnr bags'. EPA now has data to allow this substitution, provided that the samples ue analyzed within 24 hours of collection. In section 5.1.3 of Test Method 106 the requirement to use "oxygen gas" has been replaced with "oxygen gas or air. as required by tile detector." Several commentors stated that most gas chromato graphs arc designed to use hydrogen and atr for their llame detectors. When used In tilth way, they ore capable of detect ing 0.5 ppm vinyl ehlorlde In air. This Is sensitive enough for monitoring the 10 ppm emission limits stipulated In the standard. In section e.4 of Test Method 10C the requirement for on automatic integrator has bean replaced with a requirement for a disc integrator or planlmoter fer meas uring ;Hr.r r.rem Tins change Is La re sponse to a comment which states that automatic -r' .:.J.*. ;..<_* unnecessarily elaborate and cape mi vs. A new section 6.5 has been added to Test Method 105 which requ.rjs co-ter mination. of the water vapor content of the sampling bag by measuring the am bient temperature and pressure near the bag. The vinyl chloride concentration of the bag can then be reported cn a cry basis. A provision for checking the rigid container for leaks has been added to section 7.4 of Test Method 106. The only change in Test Method 107 Is the provision In Section 5.3.2 for use of Carbopak C as well as Carbopak A. Authorttt: Section 112 of the Clean Air Act a* added by see. 4() of Pub. L. 91-604, 64 Stat. ISOS (42 U.S.C. 1S5To-7; Section 114 of too Clean Air Act, u added b7 sec. 4 (a) of Pub. I*. 61-604,04 Scad 1667. and amended by Pub. L. 90-319. mc. 6(a) (4). S3 Stat. 253 (42 U.S.C. ia57o-9) I Section 301(a) of the Clean Air Act, ae amended by eee. 15(c) (2) Of Pub. L. 91-604. 84 Stat. 1713 (43 U.S.C. 16S7g (a)). Dated: October 12, 1076. JOUK Qt7AM.ES, Acting Administrator, Part 61 of Chapter I, Title 40 of the Code of Federal Regulations is amended as follows: The table of sections for Part 61 Is amended by adding a list of sections for hew Subpart F and Part 61 Is amended by adding a new Subpart P reading as follows: Subpart F--National EmUslon Standard for Vinyl Chlorid, See, ei.SO Applicability. 61.61 Definitions. 61.63 Emission standard for etbyleo* dl- cbloride plants. 61.63 Emission standard for vinyl chloride plants. 61.64 Emission standard for polyvinyl chlo ride plant*. 61.65 Emission standard for ethylene dt- ebiocide, vinyl chloride and poly vinyl chloride plants. 61416 Equivalent equipment and procedures. 61.67 Emission toots. 61.68 Emission monitoring. 61.69 Initial report. 61.70 Semiannual report. -- 61.71 Recordkeeping. AumoaiTT: Section 113 of the Clean Air Act as added by see. 4(a) of Pub. L. 91-604. 64 Stat. 1635 (43 CS C. 18S7o-7): section 114 of the Clean Air Act, as added by sec, 4(a) of Pub. L. 91-604. 64 Slot. 1687. and amended by Pub. L. 93-310, sec. 6(a) (4). 66 Stat- 256 (43 SAC. 18570-9): section 301(a) of tho Clean Air Act, as amended by sec. 15(c) (3) of Pub. L. 61-604. 64 Stat. 1713 (43 tJ-S.C. 18376(a)). Subpart F--National Emission Standard (or Vinyl Chloride 5 61.60 Applirnbilily, (a) This subpart applies to plants which produce: (1) Ethylene dichlorlde by reaction of oxygen and hydrogen ehlorlde with ethylene, -- <2) Vinyl chloride by any proc-eos, ond/cr (3) One or mom polymers containing any fraction of polymerized vinyl chlo ride. (b) Thli subpart does net apply to equipment used In. research and devehnment If the reactor used to poiymer.se the vinyl chloride processed In the equip ment has a rapacity of no more than 0.19 m' (50 gal). (c) Sections of this subpart other than 5 6LClfa) (1), (b). (c), and (d) do net 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 o* (50 gal) and no more than 4.07 m'(1100 gal). 61.61 Definition-. Terms used In this subpart are defined In the Act. In subpart A of this part, or In this section as follows: (a) "Ethylene dichlorlde plant" In cludes any plant which produces ethyl ene dichlorlde 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. (O "Grade of resin" means, the sub division of resin classification which de scribes It as a unique resin, Le.. 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 plasticlzer/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. (1) "Bulk resin' 'means a resin which Is produced by a polymerization process in which no water is used. (j) "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 wnstewatcr. <ki "Wastewater treatment process" Includes any process which modifies FfOltAt KCISTEI, VOL 41. NO. 305--TMimOAT, OCTOSit 71, 147* CMA OO4192 RULES AND REGULATIONS IGjGj eharaclert5tlC3 such as BOD, COD. TSS, anil yi. dually for the purpose of meetjn- eluent guidelines and standards; it daes not Include any process the purpose of which Is to remove vinyl chloride from water to meet requirements of this subpart. (l) "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 Ylnyl chloride, (m) "Standard operating procedure" means a formal written procedure offlcially 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 dlchlorlde purification" Includes any part of the process of ethyl ene dlchlorlde production which follows ethylene dlchlorlde formation and In which finished ethylene dlchlorlde Is produced. - (pi "Vinyl chloride purification" In cludes any part of the process of ylnyl chloride production which follows vinyl chloride formation and In which finished ylnyl 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 Teactor Is vented to the atmos phere for any purpose other than an emergency relief discharge as defined In { 61.65(a). (s) "Stripper" Includes any vessel In which residual vinyl chloride Is removed from polyvinyl chloride resin, except bulk resin. In the slurry form by the use of heat and/or vacuum. In the case of bulk resin, stripper Includes any vessel which Is used to remove residual vinyl chloride from polyvinyl chloride resin immediately following the polymeriza tion step in the plant process flow. 61-62 Emwiwv standard for dltflrtit dichloride plants. An owner or operator of an ethylene dlchlorlde plant shall comply with the requirements of this section and l 61.65. (a) Ethylene dlchlorlde purification: The concentration of vinyl chloride In all exhaust gases discharged to the at mosphere from any equipment used In ethylene dlchlorlde purification 13 not to exceed 10 ppm, except as provided in i6l.GS(a). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement In I 61.65(b) before being opened. <b) Oxychlorlnntion reactor: Except as provided In J61.G5ta>, emissions of vinyl chloride to the atmosphere from each oxichlorination reactor are not to exceed 0.2 g/kg the 100 percent ethylene dlehlorldc product from the oxychlorlnatlon process. 61.63 Kiiii-'ion st.-inibird for vinvi stripper (or the reactor If the plant has chloride pi.nil-. no stripper) In the plap.t process slow b An owner or operator of a vinyl chlo not to exceed 10 ppm. except as pro\ u'.ed ride plant shall comply with the require in 5 61.Cola). This requirement cioe> pn: 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 docs not apply to equipment that has been opened. Is out of operation, and met the requirement la 5 61.65vb) (6) (1) before being opened. 61.6 1 Emission standard fur polss insl cliluride plants. An owner or operator of a polyvinyl chloride plant shall comply with the re quirements of this section and S 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 } 61.65(a). apply to equipment that has beer opened, is out of operation, and met the requirement in 5 61.65' b> (6) (1) befov. being opened. 'cl) Monomer recovery system. The concentration of vinyl chloride m all ex haust gases discharged to the atmos phere from each monomer recovery sys tem is not to exceed 10 ppm. except as provided in 1 61.65(a), This requirement Jjcs not apply to equipment that has been opened. Is out of operation, and met the requirement In 5 61.65(b) i6> (1) be fore being opened, (e) Sources following the stripper'5) The following requirements apply t" emissions of vinyl chloride to the at mosphere from the combination of all sources following the stripperis) lor the reactor(s) If the plant has no strinper(s)] in the plant process flo-.v in cluding but not limited to, centrtfuvcs concentrators, blend tacks, filters, dry ers. conveyor air discharges, ba-yers storage containers, and inprocess wastewater: (2) The reactor opening lose 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 prepolymerization and postpolymerization. (3) Manual vent valve discharge: Ex cept for an emergency manual vent valve (1)In polyvinyl chloride plants u<in; stripping technology to control vinyl chloride emissions, the weighted avrruve residual vinyl chloride concentration Ir all grades of polyvinyl chloride restr processed through the stripping opera tion on each calendar day. measured Immediately after the stripping opera tion is completed, may r.ct exceed: (1) 2000 ppm for polyvinyl chloride dispersion resins, excluding latex resins; (il) 400 ppm for all other polyvinyl chloride resins, including latex resins, discharge, there is to be no discharge to averaged separately for each type of res the atmosphere from any manual vent in: or 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 (2) In polyvinyl chloride plants con trolling vinyl chloride emissions with technology other than stripping or Ir. addition to stripping, emissions of vinyl chloride to the atmosphere may not exceed: 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 (1)2 g/kg (0.002 lb/lb) product from the strlpper(s) Cor reactor(s) If the pla"*'- has no stripper(s) 1 for dispersion polyvinyl chloride resins, excluding latex resins, with the product determined on a dry solids basis; (il) 0.4 g/kg (0.0004 !b/lb> product from the strippers (or reactor(s) If the plant has no stripper(s)) for all other polyvinyl chloride resins. Including latex resins, with the product determined on a dry solids basis. charges. 61.63 Emi--ion /ijinljnl (or cilis l.-m- (b) Stripper: The concentration of vinyl chloride in all exhaust gases dis divliloriilc, vind rliluriJr mid ji.tli. sins I rliloridv plmit*. charged to the atmosphere from each An owner or operator of an ethylene stripper Is not to exceed 10 ppm. except dichloride, vinyl chloride, and/or poly as provided in f 61.G5(a). Tills require vinyl chloride plant shall comply with ment does not apply to equipment that the requirements of this section. lias been opened. Is out of operation, and (a) Relief valve discharge: Except for met tile requirement in I 61.65(b) (6) (1) an emergency relief discharge, there ij before being opened. to be no discharge to the atmosphere (c> Mixing, weighing, and holding from any relief valve on any equipment containers: The concentration of vinyl In vinyl chloride service. An emergency chloride in all exhaust gases discharged relic, discharge means a discharge which to the atmosphere from each mixing, could not have been avoided by t_v-:inc weighing, or holding container in vinyl measures to prevent the dlschnrre. With cluortdc service which precedes the in 10 days o( any relief valve discharge. FIDEIM MCISTEK, VOL 41, NO. 205--THUKSQAY, OCTOSft 21, 1974 CMA 004193 -l'j.ZPP RULES AND REGULATIONS t;ic O'.wicr O' curator of '.he .-'..nee from system from winch the concentration of T-iilcfi the rci.'.f Vidvo dtscn: rye occurs v.nyi chionae In tno exhau .t does sL.t!! sub:; if to '.he AdmmbUator a re not exceed 10 pom; or e',ui\alcnt as port In t cor.!r.i:or.~ IrJornuilion pio'.nlcd in i Cl.C-j. on the r.ou.'ct', i-itura 0"-; cause of the (nil Kotnlin'T comnri-nor' Vimi cAch.ir.;-1, cv.o ana ;:n:o of the du- cklor.de emission* fr^m ser.Ls on ci! ro- c.iar'e, t o,-- ro'- `...w.e iotul v.nyl eiuo- co.T.;irc.'.o:.i :n v.r.yl c. ..rid: r.ce it-:: :.:e u..:;'.zr,-e. t-.e rr.c-th- serv.ee ere to be ming.-i/ci b7 In.-*-.!:.r? O-i urr.u for C'.'e."2tir.:he ins vut-I ch'o- c p: cr50rj> ii r.ce ip-.;. the action thr.t was u-ken to seals, or equivalent es provided in ' CLOT. prevent t'.-.c c.'c::z:;e. and rue'-iures If double mechanical seals are mca. vinyl adopted to pre.cr.t future r,:c'.::-.rga$. chloride cm.isij.v; from the sea;? are to (b) ruzihve en-.Louou source:-: be minimized by maintain;:::: the pres (1) Lo.'.r...".d and unlo.tctu'.p ht.e-. Vinyl sure between the two seals so that any chlorine ent.-i.otts front loaamg and un- leak that occurs is into t!:e compressor: IcucLn; Lnts which are opened to the by ducting any vutyl 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 sss provided operation and before opening a loading in 5 81.66. or unloading Lae to the atmosphere, the (iv) Reciprocating compressors: Vutyl quantity of vinyl chloride in all parts of chloride emissions from seals on all re eaeh loading cr unloading line that are ciprocating compressors in vutyl 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 J 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 (ID Any vinyl chloride removed from maintaining the pressure between the a loading or unloading line in accord two seals so that any leak that occurs Ls ance with paragraph (b)(1) (U 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 chlonde in the not exceed 10 ppm, or equivalent as pro exhaust gases does not exceed 10 ppm: vided In | 61.65. or equivalent as provided in 5 61.66. (2) Slip gauges: During loading or un (v) Aeltator: Vinyl chloride emissions loading operations, the vinyl chloride from seals on all agitators in vinyl chlo emissions from each slip gauge in vinyl chloride service are to be minimized by ducting any vinyl chloride discharged from the slip gauge through a control system from which the concentration of vinyl chloride in the exhaust gases does ride service are to be minimized by in stalling agitators wich double mechani cal seals, or equivalent as- provided in ] 61.66. If double mechanical seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining not exceed 10 ppm, or equivalent as pro the pressure between the two seals so vided in | 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 (1) 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 tn 5 61.60. 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 oil 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 vnlve 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 ! C1.66. which the concentration of vinyl chlo (5) Manual venting of gases: Except ride in the exhaust gases does not ex as provided in 3 61.G4(aii3<. 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 vinyl ciiloridc cating pumps tn vinyl chloride service in the exhaust gases docs not exceed 10 are to be.minimlzed by Installing double ppm; or equivalent as provided in ] 61.C6. outboard seals, or equivalent as provided <6> Opening of equipment: - Vinyl tn | 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 ing lines that arc not opened to the at the pressure between the two seals so mosphere after each loading or unload ing operation) are to be minimized as that any leak that occurs is Into the follows: pump; by ducting any vinyl ciiloridc be (1) Before opening any equipment for tween the two seals through a control any reason, the quantity af vinyl chlo ride is to bo reduced so that the cqu.;>mr-tit rout.'.;,-., r\rt more than 2 0 r'-n-cus by vr.LUr.e w. >1 ciiloridc or 0 C'.'jO rrh (35 gal) of wnvl ciiloridc, wiucue.cr i> larger. r.i standard temperature an.l pretsure: ar.d (hi Any vinyl chloride removed from the eq'iip'r.tut m accordance with para graph (b)(6i(|i of this section la to be cacicu through a control system ;rn:u which the concentration of vmyl chlo ride in the exhaust gases does not cxcpcd 10 ppm, or equivalent as provided in 5 C1.6C. <7> Samples: Unused portions of --a:'.'.ples containing at least 10 percent by weight vuiyl chloride are to be returned to the process, and sampling techniques are to be such that sample containers in vinyl chloride service are purged into a closed process system. "31 Leak detection and elimination: Vinyl chloride emissions due to leaks from equipment in vinyl cltlonde 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 w aiver of compliance ls granted under 3 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 tlie samples with gas chromatog raphy or, if the owner or operator'assumes that all hydrocarbons measured are vinyl chloride, with infrared spectro photometry flame ion detection, or an equivalent or alternative method. <ii> 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 pf at least 10 ppm and is of such design and size that it can be used to measure^missions from local ized points. (lii) It provides for an acceptable cali bration and maintenance schedule for the vinyl chloride monitoring system and portable hydrocarbon detector. For the vinyl chloride monitoring system, a daily span check Ls to be conducted with a concentration of vinyl chloride equal to the concentration defined as a leak ac cording to paragraph (b) (8) (vi) of this section. The calibration ls to be done with either: (A' A calibration gas mixture pre pared from the gases specified in sections 5.2.1 and 5.2.3 of Test Method 106. or FiOftAl MGIlIi*. VOl. 41. NO. JOJ--TMUKVOAY. OCtOSM *1. 17A CMA 004194 RULES and regulations (B) A cahbi atlon gas o 1 con tain- lr.TM to appro:.: rite C'1"' 'iP.: .it ion of vi:iyl ch!ov.:ie Ifa calibre.*..un etas cylin der is u.,cd, the analy:-. mu t Lie trace able to t'.tc National Iituc-m or Star.d- aic!>, or to a rruvimetrivii'-iy calibrated uml c'.'loi*:fI: peimearion tube, <n i 1 lie location and numbe-'oi poults to be mondored and l ho iicdutncy of mor.-.tom g provided for m tnc program are acceptable v. hen they ore compared with the number of pieces of equipment in vinyl chloride service end the size and physical layout of the plant. (vi It contains an acceptable Plan of action to be taken when a leak is de tected. Cvi) It contains a definition of leak xvhlch is acceptable when compared with the background concentrations of vinyl chloride in the areas of tire plant to LG 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 ride emissions to the atmosphere from inprocess wastewater are to be reduced as follows: (i) Hie concentration of vinyl chlo ride in each Inprocess wastewater stream containing greater than 10 ppm vinyl chloride measured immediately as It loaves a piece of equipment and before being mixed with any other inprocess wastewater stream Is to be reduced to no more than 10 ppm by weight before being mixed with any other inprocess wastewa ter stream which contains less than 10 ppm vinyl chloride: before being exposed to the atmosphere, before being dis charged to a wastewater treatment proc ess; or before being discharged untreated as a wastewater. The paragraph does apply to water which is used to displace vinyl chloride from equipment before it is opened to the atmosphere in accord ance with | 61.64(a) (2) or paragraph (b) (6) of tills section, but does not apply to water which is used to wash out equip ment alter the equipment has already been opened to the atmosphere in ac cordance with 5 61.64(a)(2) or para graph (b) (6) of this section. (ill Any vinyl chloride removed from the lnprocess wastewater hr accordance with paragraph (b) ($> (1) of tills section is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 npm, or equivalent as provided in 1 61.66. (c> The requirements In paragraplis Uil). tb)(2). (b)(5), (b)(6). (b)O) and it>> (8> of tills section are to be in corporated Into a standard operating procedure, nnr made available upon re quest for Inspection by the Administra tor. The standard operating procedure Is to include proitalons for measuring the \:n;.l chloride m equipment '.'175 m* 011:50 gal in voiamc for which an mis sion limit is pi- '.rrd.'d ia 5 Gl.OVb) (C) (i> prior to opening the cquipn'.'-n*. and using Test Metdiof IC'J, a portable hydro cs', bon detector, or , equivalent or al ternative method. The method c-i meas urement Ls to inert Hie requirements in 5 61.67(g) <5Mi) 'A) or {%, < 5) rii (B). (i 1 .C>(i r.quiMilmt t-qliipiiieiil atnl pit.* Upon written application from an own er or operator, the Administrator may approve use of equipment or procedures which hove been demonstrated to his satisfaction to be equivalent in terms of reducing vinyl chloride emissions to the atmosphere to those prescribed for com pliance with a specific paragraph of this subpart. 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 effective 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. Cl.67 Emission tests. (a) Unless a waiver of emission testing is obtained under 5 61.13. the owner or operator of a source to which this sub part applies shall test emissions from the source, (1) Within 90 days of the effective date hi 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, iidtial 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 os may be specified by the Adminis trator based on representative perform ance of the source. (d) Each emission teat is to consist of three runs. For the purpose of deter mining emissions, the average of results of all runs is to apply. The average is to be computed on a time weighted basis. (e) All samples are to be analyzed within 24 hours, and vinyl chloride emis sions arc to be determined within 30 days after the emission test. The owner or operator shall report the determinations to tlie Administrator by a registered letter dispatched before the close of the next business day following the deter mination. if) The owner or operator shall retain at the plant and make available, upon request, for lnsiiection by the Adminis trator. for a minimum of 2 years records of em:-.ion te-t c vj'.ii and other tidi needed to dcMrui.iio tur.i. .tons. <g> Uiilf..'. b'-.ri.o ;-,e 'pec:f:-d, p.e O'*.*.er or ope:'..'or *rv.i! i.-tr i f,r Me*.hods in App.."','!lx !' to this pi.-*, p,- cacli i.it .o.: returned by p.u .igr,,pu, (g) I I I . (ft) ' : tgl fjl . ' - I .'-l, . (g) f3> of this `..on. ur.ic-i an c q ,. - lent method or an altcrnni', e im'.l.' i lias bem approved by the Aumuuy.rr.v.: If the Admmistr.itor finds reasonable grounds to dispine `-he icsults obuir.en by an equivalent or alternative metr.od he may requite the u^e of a referem'" method. If the results of the rcityrpt... nr.a equivalent or alternative merino> do not agree, the results obtained by tit* reference method prevail, and the Acl- mmi.jtratur may notify the owner r.r operator that approval of the method previously considered to be equhaP-n* <. alternative is withdrawn. (1) Test Method IOC Is to be used to determine the vinyl chloride emission, from any source for which an cnils.-iot: limit is prescribed in >5 61.62(a) or 't>' 3 61.63' a). or 54 61.G4(a) (1), (b), (c. or (d). or from any control system to winch reactor emissions are required to h1* ducted In ! 61.G4(a' (2) or to which fugi tive emissions are required to be ducted in 55 61.05(b) (11 (il). <bn2>, <b/'5>. (b) (6> (11). or (b) (9) (li>. (I) For each run, one sample Is to be collected. The sampling site ts to be at least two stack or duct diameters down stream and one half diameter upstream from any flow disturbance such as a bend, expansion, contraction, or bio flame. For a rectangular cross section t.n equivalent diameter is to he determ i.ed from the following equation: equivalent dialing. r=! (length) (iii'lij lengths n .ill I> The sampling point In the duct is to be at tlie 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. (i'' For gas streams containing more than 10 percent oxygen, the concentra tion of vinyle chloride as determined bv Test Method 106 Is to be corrected to it) percent oxygen for determination o( emissions by using tlie following equa tion: C .T.r .. -J"1'. UtO it>t Ct'ff-vl.-l I j.. r- ti* 0*Tltn conO'*nif'irt*M of\! vJ r' vi 3).9JVSnrt^iaV'mtuiifvconi^JlytuthemytnlUIfi*' *U''-..c jniln.-t*.'>i . **r it JO.fl--nc$fI',tw'ntiii\rOiJvjc^tr>nntllint!ot*tiii* vfititf.uiw*,*.tti,i.*r 11 JVft** m Oj *IVlt*lrrrttrnftrtrit4iilMOo^ivi.i^*Ct'uuitn'Idrttoo.ih*tur*n1' i* r .i"t ri.riv. f ts * *y lo ft r> :v \l. I'.-M j >u tijil A Of I'jTI tAi /f Hit t * ti r (ill) For (hose emission soitrrrs where the emission limit is presenhed In tcrm3 of nin-s rather than concemiatlon, uu;^ tfotust MGtSTEK, VOL' 41. NO, 305----THURSDAY, OCTOIH 31. 1436 4 05GS GULES AND REGULATIONS rml'dO!'-*. lu kg/ICG product fl--<s to that L-. also tired as a stripper. the cltlc-r- detection, or an equivalent or alterna tv determined by using the foUowlhi cunation m,-y be mode Iv.mediuteiy fol tive method. The vinyl cliiorile m.cn.tor- cv,t.'iiUb.".: if. c: on) o io-i; :ico] If ru.v. >. i\`` r,-I-.'. >: prc-U^t. r' 4> oy r. ; <5 Q --*.DVo'}j/'.^Wh''*L.*`w*.->.o*.f'k*>,,r .`t or:it *; do atmosphere a.*4 r/v*2in0nAi1f^P?-'-w.J.t A U> i'.-Tl*Uy) of -3 cfii; ft r. J<3- ** C," Tr-*lor. I m' r !rr r- -t lowing tl:c stripping ct^c.-ahon. (I) copt a.-, provid'd in paragraph (g)(6)(H) of this teed on, the reactor opening lass is to be determined using the following equation: ,, IP (2.GO) (10-*) (Cl) C.. YZ wli-,-'-: C* Tif.vi, , lid '"i.vvorsAj producL k'= i'a---.'.y of i.id r*ic;of in ;nh 2.60*Ue.i57:t*y of vwyl ei.ijr.Jo it one airno^pnero ^r.d Su* C m kf'fr.h inq svstem u:i\! to meet the requirements L". { Cl.65(b) (fl) (U nay be used to meet the requirements of this section. (c) A duly span check .s to be con ducted for each vinyle chloride monitor ing system u,.cd. For all of the emission sources iisied m paragraph (a) of this section, except the one for which an emis sion limit is prescribed In 5 61.62(b). the daily span check is to be conducted with a concentration of vinyl chloride equal to 1C ppm. For the emission source for (2) Test Mcthc-i 107 w to be used to |0-*-ron>-fr. .on fc.r ppm. O "ppm \jy Vvlum* s1 cMori'l* v <1- f*frby determine the concentration of vinyl chloride In cash !r.process wastewater stream for which an emission limit Is prescribed in 5 Gl.CStb) (9) U). (3) Where a stripping operation Is Trot iftftbiy'i K*j or a detector wt'.co wej*' ,r+$ h}<iro< arboa* vvith a e^aaltlvity o! ac leant 10 yS'\unbe? of Mtcn*** trie riiktor wjo 1<^ opened lotlieatn (Viif.-T.}- kj of pol/vmyl chlnndo prq,du`e*h ;ser Lxtcbin thonamN-r offiit^neaffixeth* rihici'* used to attain the emission limit In 5 61.- was list opened to tbe GKe), emissions ore to be determined using Test Method 107 as follows: (A) If Method 106 is used to deter <i> The cumber of strippers and sam mine the concentration of vinyl chloride ples and the types and grades of resin to (Cb), the sample is to be withdrawn at be campled ore to be determined by the a constant rate with a probe of sufficient Administrator for each Individual plant length to reach the vessel bottom from at the time of the test based on the the manhole. Samples are to be taken plant's operation. for 5 minutes within 6 inches of the ves (ID Each sample Is to be taken Imme sel bottom. 5 minutes near the vessel diately following the stripping operation. center, and 5 minutes near the vessel top. (1U) The corresponding quantity of material processed by each stripper is to be determined oa a dry solids basis and by a method submitted to and approved by the Administrator. (tv) At the prior request of the Ad ministrator, the owner or operator shall provide duplicates of the samples re quired In paragraph (g)(3)tl) of this section. (4) Where control tecimology 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 U 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. (ID Test Method 107 Is to be used to determine the concentration of vinyl chloride in each Inprocess wastewater stream subject to the emission limit pre scribed In ; 61.64(e). The mass of vinyl (B) If a portable hydrocarbon detec tor is used to determine the concentra tion of Yinyi chloride <Cb). a probe of sufficient length to reach t{ie 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 stabilized. All hydro carbons measured are to be assumed to be vinyl chloride. i (C) The production Tate of polyvinyl chloride (Z) Is 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 postpolymerization reactors In the manufacture of bulk resins. chloride In kg/100 kg product In each g 61.68 Kmliiion monitoring. In process wastewater stream Is to be de termined by using the following equa tion: C,, .s-[-C--,--tl 1j0--*-1--(-1-0-0-] (a) A vinyle chloride monitoring sys tem is to be used to monitor on a con tinuous basis the emissions from the sources for which emission limits are pre scribed In 5 61.62(a) and (b). { 61.63(a), and 161.64(a)(1), (b), (c). and (d), and Cm*rlnyl rltWMt'lOftktt proturt. concvtii/uuon of ttuyl ChkxiU? aa U"M?uf*d by 7Vl MoCtuM W. How r:oin Vhr.i1ftcmtlf\*iinaccnrU;w for any control system to which reactor emission arc required to be ducted in I 61.66(b) (1) <il), and (b)(2), (b)(5), vltb a mrihQtl hjch b-i bwn $ubuutt4 ml Appro**! by ih Adndid*tf.Uor. 10 -Co<.*Tfton f - Ujr for ppm, 7*.[*roCut:iion rL (ke/lif). tlct^rmhi^d fa i*voM- nrt^llh omcU.oii whLb ixs-nsubmlttod nj op|in>vvU by tl* ALbuiuliir^Lyf. (b)(6) (11), and (b)(9) (in. (b) The vinyl chloride monitoring system(s) used to meet the requirement In paragraph (a) of this section Is to be a vhtch an emission, limit ts prescribed m 1 Cl.62<b), the daily span check is to be conducted with a concentration of vinyl chloride which is determined to be determined to be equivalent to the emis sion limit for that source based on the emission test required by { 67.67. The calibration is to be done with either; (1) A calibration gas mixture pre pared from the gases specified in sections 5.2.1 and 5.2.3 of Test Method 106, 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 Standards or to a gravimetrically cali brated vinyl chloride permeation tube. 61,69 Inltiul report. - (a) An owner or operator of any source to which this subpart applies shall submit a statement In writing notifying the Administrator that the equipment and procedural specifications In Sj 61.65 (b)(1). (b)(2), (b)(3), (b)(4), <bMS>, (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 3 61.11, along with the informa tion requued under 3 61.10. If a waiver of compliance is granted, the statement is to be submitted on a date scheduled by the Administrator. (2) In the case of a new source which did not have an Initial startup date pre ceding the effective date, the statement is to be submitted within 90 days of the initial startup date. (c) The statement Is to contain the following information: (1) A list of the equipment Installed for compliance. (2) A description at the physical and functional characteristics of each piece of equipment. (3) A description of the methods which have been incorporated into the standard operating procedures for meas uring or calculating the emissions for which emission limits are prescribed In 33 61.65 (b) (1)(1) and (b)(6)(l), (4) A statement that each piece of (5) The reactor opening loss for which an emission limit is prescribed in i 61.64 (a) (2) Is to be determined. The number device which obtains air sampcls from equipment is installed and that each one or more points on a continuous piece of equipment and each procedure sequential basis and analyzes the samples is being used. of reactors for which the determination Is to be nude Is to be specified by the Administrator for each individual plant at the time of the determination based on the plant's operation. For a reactor with gas chromotogrnphy or. 1( the owner or oi>crator assumes that ail hydrocar bons measured are vinyl chloride, .with infrared spectrophotometry, flame ion 61.70 SoiMinmiua! rr|Hr1. ra) (2) is to be determined. The number source to which this subpart applies shall submit to the Administrator on Septcm- HOflAl ItCISTH,' VCl, 41. NO. JOS--THueSOAY, OCTOtU 71, 147* CMA 004196 RULES AND REGULATIONS lb.V',0 her 25 and March 15 of each year a rciiovt ,u v, ritins contf-uiii'k; the inform.v.'.'vri joqiiiied by (his rgclior,. The finA semi annual report Is to be suomitteil folt-rvm; the fii'it full C mouth reportin'.; per.od after tile initial report :s subinistc-ti. (b)(1> IU the v.-;i->; of a:i existing source or a new source nhlrh lias an Initial startup date preceding the effective tloke. the first report is to L; submitted within ISO days of the elective date, unless a waiver of compliance is granted under 5 61.11. If a waiver of compliance Is granted, the first report Is to be sub mitted on a date scheduled by the Ad ministrator. (2) In the case of a new source which did not have an initial startup date pre ceding the effective date, the first repot t is to be submitted within 180 days of the initial startup date. (c) Unless otherwise specified, the owner or operator shall use the Test Methods in Appendix B to this part to conduct emission tests as required by paragraphs (c> (2) and (c) (3) of this section, unless an equivalent or an alter native method has been approved by the Administrator. If the Administrator finds reasonable grounds to dispute the results obtained by an equivalent or al ternative method, he may require the use of a reference method. If the results of the reference and equivalent or alterna tive methods do not agree, the results obtained by the reference method pre vail, and the Administrator may notify the owner or operator that approval of the method previously considered to be equivalent or alternative is withdrawn. <l) The owner or operator shall in clude in the report a record of any emis sions which averaged over any hour period (commencing on the hour) are in excess of the emission limits pre scribed in S3 61.62(a) or (b), 5 6E63(>, or 33 61.64(a)(1), (b), (c),or (d), or for any control system to which reactor emissions are required to be ducted In 3 61.64(a)(2) or to which fugitive emis sions are required to be ducted in | 61.65 (b) (1) (11), (b)(2), (b)(5), (b)(6) (11), or (b) (9) (U). The emissions are to be meas ured in accordance with 3 61,68. (2) In polyvinyl chloride plants for which a stripping operation is used to attain the emislson level prescribed In 3 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: (1) If batch stripping Is used, one rep resentative sample of polyvinyl chloride -resin la to be taken from each batch of each grade of resin immediately follow ing the completion of the stripping, and grade and the date and time the batch is completed. The corresponding quantity or material processed in each Mrlnjx-r batch is to be recorded and Iden tified by resin type and grade nnd the date and time the batch Is completed. Mil If continuous stripping Is used, one representative sample of polyvinyl chloride resin Ls to ha taken for each Bratio of resin processed or at Inten-Vs of 8 hours for each g.-at.7 of I'-Mn which is boln.": [ucce-sed. whichever is more fre quent. The .rmp'.e b to be ti-.u-.m os the rcun liov.s o of the stripper r.t-.d iden tified by rt-ia typo and c ratio and the date and t.-.T.e the sample was taken. The corresponding quar.t.ty of material processed by each stripper over the time period represented by the sample during the eight hour period, is to oe recorded and Identified by resin type and grade and the date and time it represents. (iil) The quantity of material proc essed by tiie stripper ls to be determined on a di7 solids basis and by a method submitted to and approved by the Ad ministrator. (lv) At the prior request of the Ad ministrator. the owner or operator shall provide duplicates of the samples re quired In paragraphs (c)(2)(l) and (c) (2) (U) of this section, (v) The report (o the Administrator by the owner or operator ls to Include the vinyl chloride content found In all the samples required in paragraphs (c) (2) (i) and (c) (2) (il) of this section, aver aged separately for each type of resin, over each calendar day and weighted ac cording to tiie quantity of each grade of resin processed by the stripper(s) that calendar day, according to the following equation; T~1 Pa Ma, A <-( P0[ 5/o, I- Po; .Vf<7. 4- . . . -t- Pam Afa, Qt, A-iUisur iiruaja cooceatrattoa V type T, twin U ppm. e--Total production of typo T, rosin over the ?t-hocr period, in kg. Ti-Typo ol resin; /-IP, . . ; * whir* to Is total number o( rtsla types produce! during tbs PVhour period. Ai-Cancentrotton of Ttnyl eb!ori!. In one sample of grado Qi rodto, ia ppm. P-Production f trade Q\ resin rcpft?at*d by tbo sampt*. In kg. <7i- ol rw:n, ., <7, Cu *nd ~Totat number ol frod oi nna produced during tbo 21-dour period. (vi> The owner or operator shall re tain at the source and make available for Inspection by the Administrator for a minimum of 2 years records of all data needed to furnish the Information re quired by paragraph (c) (I) (v) of this section: The records are to contain the following Information: (A) The vinyl chloride content found in all the samples required in paragraphs (c) (2) (1) and (c) (2) (11) of this section, identified by the resin type and grade and the time and date of tiie sample, nnd (B) The corresponding quantity of polyvinyl chloride resin processed by the strlpper(s), identified by the resin type and grade and the time and date it represents. (3) Tiie owner or operator shall in clude In the report a record of the emis sions from each reactor oi>cniiic for which an emission Unfit is prescribed In 3 61.64(a) (2), Emissions are to be deter mined in accordance with i Gl,G7(g) i5>, except that emissions for each reactor are to bo determined. Eor a reactor that ls also used as a stripper, the determination may be made Immediately follow .eg t; c stripping operation. (I I. i 1 Jtm.i'ukvt'j.ttiu. (a) llie owner or operator oi a;--, source to which tills subpar: ayphe.. -.bn: retain tfte following Information at Hu source and make It available for inspec tion by the Administrator for a m;;i: mum of two years: <U A record of the leaks detee'ed li the vinyl chloride monitoring system, a required by 5 Gl.Gjib) (8', Includ.ng tin concentrations of vinyl chion-e a mcasm ed. analyzed, and recorded i;.- lie vinyl chloride detector, the hit.y.tJn c each measurement and the date a:.d .u proximate time of each measurer..cut. (2) A record of the leak? de-.ccuu during routine monitoring with t': portable hydrocarbon detector and tu. action taken to repair th* leaks, as re quired by 5 61.65tb) (3 >, Including brief statement explaining tiie locatln and cause of each leak detected wtti the portable hydrocarbon detector, tldate and time of the leak and any actmi taken to eliminate that leak measured n accordance with J 61.68. (3) For the rellel discharges fir reactors subject to the provisions 3 61.65(a), a dally operating record lr each reactor. Including pressures m temperatures. 2. Appendix B Is amended by addin Test Methods 106 and 107 as follows- Method 10S--Determination or Vinyi. Chloride rsost Stationaet somri mTROUCPTlO.V Performance of this method should r.o; attempted by persons unismlltar ui'h i. operation of a gas chromatograph. cor those who are unfamiliar with sourer ? m phng, as there are many details i:..it ,<; beyond the scope of this preoental'cn. Ca must be exercised to prevent uy -ure sampling personnel to vinyl chloride, a cr. elnogcn. 1. Principle and Applicability. 1.1 An Integrated bag sample of stack g. containing Tlnyl chloride (chloroeihylcn; is subjected to chromatographic ar-ilyusing a flame lonlrattou detector. 1J2 The method is applicable to the men u--ment of Tlnyl chloride In stack goaes fro j-jyleno dlchiorlde. vinyl chloride and poi vinyl ehiorido manufacturing procc--e5. c eept where the vinyl chloride Is contained particulate matter. 2. Range and Sensitivity. The lower limit of detection will varj ^ cording to the chromatograph used v.uu reported! include l y. 10-: mg and 4 \ u mg, d. Interferences. Acetaldehyde, which can occur m vbtyl chloride sourcca. will interfere wl;h - vinyl chloride peak from the Chromo-orii 1 columu. See sections 4.J.2 and 6 4. If -1 tion of the vinyl chloride peak is *-.ut r anti-factory for a particular sample, tl. chromatograph parameters can be fur: r altered with prior approval of the Adin- istrator. If nltemtlon of th* ehrom V'-grw parameters falls to resolve the vinyl chiori peak, then supplemental confirmation of t vinyl chloride penk tiirougb an afv-oh analytical tcchnlquo. such as ma-a -pee-,senpy, must be performed. 4. Apparatus. ..1 Sampling ITtgure 1). 4.1.1 Probe--fsflnlcaj steel. Pyres gi. or Teilon tubing according to stack temp HOdAt etoism. vet ei, no. ios--immoA-r. octoseh i. 197* CMA 004197 40370 RULES AND REGULATIONS *turf, cr*ch <q.:`ppcd alth ft g!.v^3 vo^l plug < 4.5 Hot r.^/:--Rotameter lyp*. 0 tr> and the at*c::witor scVIrg. RecTd the to rci-'-'V* 1 " s,",`<-.i!a> n> V-^r. 4 12 f - `;/l- Ilr.e--TcHort. C 4 mm outsido <!!a.1*?l i\ cf C':.T.C',-nt J*`. Ttll tp COliGT'Tt p,"w.^` to / A r.r,w r.:rj *ti p'ccc Li employed tor cs-c2i cT b.ig constitutes an4c1m3:'. Vr ; J-AwC i?) k:'.2 fc1tuIo (2) 5lMn>ss atccl qult.^ornect"', vl*.!t t:.ll checks (cue pair vuM'.ili lo^ixt^d au slitjwn In Figure 1. 414 "ov/'vr bxgs. 100 1 icer capacity--To Yciloa are not accept able. Al-ijr,';,.. id Mylar Lru;* may be uood, 1000 ml/tnin r-.vnge accurate to r_l%. to ji.clcr nU-'-igea in preparation o' s;^r.d*rd zr.R nU?:ti:rcs. 4 ?>:op v^teh --o: kno.vn Accuracy, to tlt/v'1 Eft.5 In preparation of stand'--d mixtures. 5. P.tAgcntn. It is ne;i.V.a.*7 thv. gents cw of chroiuftlo^rfcphlc ^raue. 8 1 Analyst, 5 l.l Helium, z or nitrogen coa--Zero grade, for chromatvCraphlc enrri* r g-s. 5 1,2 Hydrogen g^s--Zero or-.'/vry pressure From cnart. sK'-c; tr* pc-.., tbe retention tlGxe correspond ed to v.r./l cs.oride, a* determined la b'.r.- lion 7.2. :'\^..r3 the arts. AM, by v.io of If-*, r.rut r. Cizc lntee--atcr or a pixmaietcr. Mi-.u>i:re :no fceich-.: H-. Record Ac cr.d thu rc.cntiou Rcpcr.t tbe Injf'.t.on at lc?-s: two tunes or until two cj--->outive einvl eh,or.-2c do not vxry in sj-ea more tr.^'n. 5%. average value for these two areas v.,;i bo uivJ to compute the bog ccucer.tra- tlon. p.-G'.Idtd that the CGGiplcj are a::a!y^e<i wltbla 21 tours o' collect.on. 4.15 TV. "id leakproof containers for 4 1.4, With co'.truvj to protect contents from sun light, 4.1.C NcetUo valve--To adjust sample flow rate. 4.1.7 Pun:p~~Leak*free. Minimum capac* Ily 2 liters per minute. 4.1.8 Cfcarcoul tube--To prevent tdmla< flloa of vinyl chloride to atmosphere in vicin ity of samplers. 4.15 How meter--For observing sample flow rate: capable of measuring a flow range from 0 10 to 1.00 liter per minute. 4.1.10 Connecting tubing--Teflon. 8.4 nun outside diameter, to assemble sample train (Figure 1), 4.151 Pitot tube--Type 3 (or equivalent) f attached to the probe so that the sampling flow rate can be regulated proportional to the stack gas velocity. 45 Sample recovery. 45.1 Tubing--Teflon, 0.4 mm outside diameter, to connect bog to gas chromato graph sample loop. A new unused piece is employed for each series of bag samples that constitutes an emission test, and is to be dis carded upon conclusion of analysis of those bags. 45 Analysis. 4.3.1 Gas chromatograph--With flame lonl7atlon detector, potenttometrlc strip chart recorder and 1.0 to 8.0 ml heated sam pling loop in automatic samplo valve. 4.35 Chromatographic column--Stainless steel. 2.0 x 35 mm, containing S0/100 mesh Chromosorb 102. A secondary cotum of GE SF-96. 20% on 80/80 mesh AW Chromosorb P, stainless steel, 2.0 m x 35 mm. will be required If acetaldehyde Is present. If used, 5.1 3 Oxygen gas, or Air, as required by the detector--Zero grade. 5.2 Calibration. 5 2.1 Vinyl chloride. 03 9--For prep aration of standard goo mixtures. 5.2.2 Calibration cylinders (3). Qptlor.il-- Ono each of 50, 10 and 8 ppm vlayl chloride la nitrogen with certified analysis. ArtniysU must be n-aceable to NU3 (National Bureau #of Standards) or to a gravlmetricAlly cali brated vinyl chloride permeation tube. 5.3.3 Nitrogen gas--Zero grade, for prep aration of standard gas mixtures, G. Procedure. 6.1 Sampling. Assemble the sample train as In Figure 106^1. Perform a bag leak check according to Section 7.4, Observe that ail connections between the bag and the probe aro tight. Place the end of the probe at the centroid of the stock and start the pump with the needle valve adjusted to yield a flow of 0.5 1pm. After a period of time sufli- cient to purge the line several times has elapsed, connect the vacuum line to the bag and evacuate the bag until the rotam eter indicates no flow. Then reposition the sample and vacuum lines and begin the ac tual sampling, keeping the rate proportional to the stack velocity. Direct the gas exiting the rotameter away from sampling personnel. At the end of the samplo period, shut ofl the pump, disconnect the sample line from the bag, and disconnect the vacuum line from the bag container. Protect the bag container from sunlight. 65 Sample storage. Sample bags must be kept out of direct sunlight. When at all pos sible. analysis is to bo performed within 24 hours of sample collection. - 65 Sample recovery. With a piece of Tef lon tubing Identified for that bag, connect a Compare the ratio of IT* to A for the vlr.vl chloride sample with the same ratio for the stnhd'xrd p^.xk which is close**, in height. As a ru:df*I:.*.e. if these rttlov differ by mo-e than 1011. tho vinyl chloride peak mar not bv pure (possibly oeetaidehyde is present) and the secondary column should be em ployed (see Section 4 3 2;. 6 5 Measure the ambient temperature and barometric pressure nexr the ha<. (Assume the relative humidity to bo 100 percent ) From a water saturation vapor pressure table, determine the record and water vapor Con tent of the bag. -- 7. Calibration and Standards. 7.1 Preparation of vinyl chloride standard fas mixtures. Evacuate a sixteen-inch square Tedlar bag that bos parsed a leak check (described in Section 7.4) and meter in 5 0 liters of nitrogen. While the bag is Ailing, use the 0.5 ml syringe to Inject 2501] of 99 9-}- % .vinyl chloride through the wall of the bag. Upon withdrawing the syringe needle, im mediately cover the resulting hole with a piece of adhesive tape. This gives a concen tration of 80 ppm of vinyl chloride. In a like manner use the other syringe to prepare dilu tions having 10 and 5 ppm vinyl chloride concentrations. Place each bag on smooth urface and alternately depress opposite ides of the bag 80 times to further mix the gases. 75 Determination of vinyl chloride re tention time. This section can be performed simultaneously with Section 75. Establish chromatograph conditions identical with those la Section 85^ above. Set 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 the SF-03 column Is placed after the Chromoeorb 102 column. The combined columns should then be operated at HQ'C, bag Inlet valve to the gas chromatograph sample valve. Switch the valve to withdraw gas from the bag through the sample loop. temperature, the carrier gas flow rate, the chart speed and the attenuator setting. Record peaks and detector responses that 455 Flow meters (2)---Rotameter type, Plumb the equipment so the sample gas occur In the absence of vinyl chloride. Main 0 to 100 ml/mia capacity, with flow control valves. passes from the sample valve to the leak-free pump, end then to a charcoal tube, followed tain conditions. With the equipment plumb ing arranged Identically to Section 8,3, flush * 4.3.4 Gas regulators--For required fu by a 0-100 ml/mln rotameter with flow con the sample loop for 30 seconds at the rate of cylinders, trol valve. 100 ml/mia with one of the vinyl chloride 4.3 8 Thermometer--Accurate to one de- 0.4 Analysis. Set the column temperature calibration mixtures and activate the sample gree centigrade, to measure temperature of to 100* G the detector temperature to ISO* valve. Record tbe Injection time. Select the heated sample loop at time of Sample Injec C. and the sample loop temperature to 70* C. peak that corresponds to vinyl chloride. tion. When optimum hydjogen and oxygen flow Measure the distance on the chart from the 45.0 Barometer--Accurate to 5 mm Hg, to measure atmospheric pressure around gas chromatograph during sample analysis. 45.7 pump--Leak-free. Minimum capac ity 100 ml/mln. rates have been determined verify and main* tain these flow rates during all chromato graph operations. Using zero helium or nitrogen as the carrier gas, establish a flow rate In the range consistent with the manu injection time to the time at which the peak maximum occurs. This quantity, divided by the chart speed. Is defined ^a the retention time. Record. 75 Preparation of chromatograph cali 4.4 Calibration. facturer's requirements for satisfactory de bration curve. Make a gas chromatographic 4.4.1 Tubing--Teflon, 0.4 aun outside tector operation. A flow rate of approxi measurement of each standard gas roLxiur* diameter, separate piece* marked for each calibration concentration. 4.45 Tedlar bags--Sixteen-Inch square mately ^0 ml/mln should produce adequate separations. Observe the base Uno periodi cally and determine that the noise level has (described in Section 7.1) using conditions identical with those listed In Section 65 above. Flush the sampling loop for 30 seconds size, separate beg marked for each calibra stabilized and that base line drift bos ceased. at the rate of 100 ml/mln with each standard tion concentration. Purge the sample loop for thirty seconds at (u mixture and activate the sample valve. 4.4.3 Syringe--0.5 ml. gas tight. tbe mte of 100 ml/mln. then activate the Record Ct, the concentrations of vinyl chlo * 4.4.4 Syringe---50^1, gas tight. sample valve. Record the injection time (tbe ride injected, the attenuator setting, chart position of tbe pen on the chart at the time peed, peak ares, sample loop temperature, 1 Mention of trade names on specific prod ucts docs 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 Column temperature, carrier gas flow rate, and retention time. Record tbe laboratory pressure. Calculate A^ the peak area multi- FI0I8AI *ClSIt*. VOL 41, NO. 200--TMUSS0AY, OClOttt 21, 1*74 CMA 004198 RULc> AND RSGULA7I0 >71 pl'.ort by the attenuator .`tung. Hopwi rnM t vo lajvc'l'vn areas t.UKu G'^, pl-ji *(*r)aCtCloonpsoihnatsvevsb*C*,a. Vprlnlimtlcdth. edroa>thvefrt csom'o.'.o?t:hi- curv? thro'!,:h the point-"#. i\r;wm e-^l. */*'- uoq cU.lly, or brfore 40cl nftor ecveh o' b,.e ^-.:npl^, whichever Is more fr.q :*nt. T * b.wc; h.ok While p-r.''V'i.?.h':e oT thr.s f.tcctofl 11 rcqu!:rd sub sequent to b?.j 'i: j?. U Li aLo ad`. It'd tii.i.t it t>o perforiOAd P'lir to> t>;v; uo.j. Alter cftcli ur>e, niu.he sura a br,~ diet not develop leak* os follow*. To leak chec*:. connect a water hu*non;tcr and pru- surVe the b?.g to 5-10 cm rip f2-i in H-O). a;:o** to stand for 10 minutes. An7 dUph-cv- m*-nt la the 'UiiU.-r manometer Indicates u M kk, Also check the rigid container for leaks la this manner. (Note: An alternative leal: cheek method Is to pre:5url4e the ba.j to 5-10 cm HO or 2-4 lo, H,0 and allow to stand overnight. A deflated beg Indicate & leak..) For each sample bog In Its rl^id container, place a rotameter in-line between the bat; and the pump Inlet, Evacuate the bag. Failure of the rotameter to register zero How when the hoc appears to be empty Indicated a leak. 8. Calculations. 8.1 Determine the sample peak area as follows: fMno*Mt t2Vt4tMMfMtTl*i*twucd rf'^u(UeaU AAo%muw*{ witiatl A,-AmA, whets: A.^Tb* sample peak area. j4--The measured peak area. A/"Tbe alteaastiOQ lector, Equation 105-1 84 Vinyl chloride concentrations. From the calibration curve described In Section T-3, above, select the value of C, that cor responds to A,, the cample peak area. Cal-* culate Ch as follows: r C.P,T, `-*'>.7\(1-Sr) Mkrsoo 107--DmatfUfATioK ot VmrL Chloimi CowtiNT or Jcrpaoccss Wistiwatu Samples, and VnfTL Chlokzdz Cdktent or POLTYCfTT, CltLOR&>B RCSC<, SLtTRltT, WfT Caxs, and Latex Samflxs IWTRODUCnON Performance of this method should not be attempted by persons unfamiliar with the operation of a gas chromatograph, nor by those who are unfamiliar with sampling, ns there are many details that are beyond the scope of this presentation. Care must be exercised to prevent exposure of sampling mg and 4xl0-f mg. With proper calibration, the upper limit may be extended as needed. 3. Precision and Reproducibility. An interlaboratory comparison between seven laboratories of three min aamnie-x each split into three part-v yielded a Ataad,ird deviation of 2.C39^* * f*o13r a aampte wl:h a mean of 2.09 ppm. 4.16*^ for a sample with a mean of 1.6G ppm, and 5.29% for a sample with a mean of G2.G6 ppm, 4. Safety. Do not release vinyl chloride to the labora tory atmosphere during preparation of ardj. Venting or purging with VCM/air tvl\- Equation 105-3 personnel to vinyl chloride, a carcinogen, X. Principle and Applicability. turcs must be held to a minimum- Wh>*n they are required, the vapor must be routed Where: 1.1 The basis for this method relates to to outside air. Vinyl chloride, even at low Xt.i-Theavnuaelyezemd,iw couidu ot :hfi tm* suable,'m the vapor equilibrium which is mtabllahed between RVCM, PVC, resin, water, and air ppm levels, must ncv*r be vented inslae the laboratory. After vials have teen anoly^d. / Ci*Th# eonaratretion o( vinyl chloride la the h*f cample la ppm. C.-Tbe concentration of vlcyl chloride indicated by the fas ebroftatepraph, la ppm. In a closed system. It has been demonstrated that the RVCM In a PVC resin will equili brate In a dosed vessel quite tHpidly, pro the pressure within the vial must be vented prior to removal from the lasmintent turn table. Vials must bo vented into an activated PT-Th* tvfervfioe prewuro. the laboratory presnn vided that the temperature of tho PVC resin charcoal tube using a hypodermic needle to recorded during calibration, mm lie* I\--The sample loop temperature oa the absolute scale at the time of analysis, *il P,--The laboratory prefeu.-e at Ucae of aoalyds, oa Uf. T,*The reference temperature, the sample loop Is maintained above the gloss transition temperature of thatepeclfic resin. 14 This procedure Is suitable for deter mining the vinyl chloride monomer (VCM) prevent release of vinyl chloride into ths laboratory atmosphere. The charcoal must be replaced prior to vinyl chloride break through. 5. Apparatus, temperature recorded dunne coUbraUou, content of ltxprocesa wastewater samples, and the residual vinyl chloride monomer 8.1 Sampling. 6,1.. Bottles--GO ml (3 oz), with waxed 9. Reference*. 1. Brown, D. W., Loy, fi. W. and Stephencon. M. H. *Vinyl Chloride Monitoring Near the B. P, Goodrich Chemical Company in l^uisvUle, Kentucky." Region IV, TJ.S. Envi ronmental Protection Agency, Surrelltanoe and Analysis Division, Athens, Georgia. June 24, 1974. 3. "Evaluation of A Collection and Analy tical Procedure far Vinyl Chloride in Air," by G. D. Clayton and Associates, December 13, 1974. EPA Contract No. 68-03-1408. Task Order No. 3, EPA Report r>N. 75-VCD-l. (RVCM) content of polyvinyl chloride (PVC) rcelna, wet cake, slurry, and latsi samples. It cannot be used for polymer in fused form, such as sheet or cubes. If a resolution of the vinyl chloride peak la not satisfactory lor 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 othor 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 ouws spectroscopy, should bo performed. lined screw on tops, for PVO samples. 5.14 Viola--50 ml Hfpo-vlals.1 sealed with Teflon faced Tuf-Borxl discs for water sam ples. 6.14 Electrical tape--^>r equivalent, to prevent loosening of bottle topi. 54 Smple/recovery, 64.1 VUis--With seals and capo Perkin- Elmer Corporation No. 106-0118, or equiva lent. 6,34 Analytical balance Capable weighing to 0.001 gram. of 644. Syringe, 100 si--Precision 3*na "A" No. 010026, or equivalent. 3. "standardization of Stationary Source 3. Range and Sensitivity. Emission Method for Vluyl Chloride," by Mid west Research Institute, 1976. EPA Contract No. 66-03-1098, Task Order No. 7. The lower limit of detection of vinyl chlo ride will vary according to the chromato graph used. Values reported tnclude 1X\<t* * Mention og trade name# on speclfle prrdnets does not constItste endorertnent by tho Environmental Protection Agency. ttOCtAl ftCl$TER, VOL 41, NO. 105--THURSOAr. OCTOOlt 21, 1976 CMA 004199 .1C572 RULES AND REGULATIONS 5 24 7>.l fPerVlD^Nlm^r No. 103- 0103 c*t 63 At 6-3 t O .\ rUmr^^'^rupli^- I'rrUn-r'.rzor Cory'-^vM'. v ??^>l F-4 0 LeM-*p*eo ar*v \yz6>0'rJ.1.So iC t - C` -t.jVl,, erririMe*i.c.ihalecu.n!ut-.HA-0--3U^c.~ 1^-j *;*'. 2 r i > - -2 r.-.m. ccatAtr.ii*? 0.4*i Cyl-,, * .', \l</} <- C A, lNjrki-a-J'Ts;-r Cvrpo*'.V No or equivalent. C:u-bop,%k C Ch\t. bo u^rd in, pine* of Carbopak A. 5 3 3 7* ?rrr.omcter---0 to 100* C. -^C urate to *0.1* C, Pcfkic-UJmer No. 105-0109 o- equivalent. 6 3 4. vTipto tray thr.-mbstat cyatem-- perkm;:r No. 105--0:03. or equivalent, $3 5 Sintlwlch typo, fer auto matic dosiiic. 13 mm, rerkln-Limer No. 105- 1608, cr equlvulsTit. 53 J-u.-mUjr - recorder -- Hewlett - Packard J'odcl 3330A, or equivalent. 53.7 Filter drier assembly (3)--Perkin- Elmer No, 2X30117, or equivalent, 5.3.3 Soap fllm flowmeter--Hewlett Pack- art! No. 0101-0113, or equivalent, 6.4 Calibration. 5 4.1 Regulators--for required gas cyln- Cera. t. Reagents. 6.1 Analysis. 66..11.1J HN;Oitrrooggeennggaaos----zzeerrooggrraaddee.. ,, 6.1.3 Air--zero grade. . 6.3 Calibration. 62.1 Ctand&rd cylinders (4)---one each of 50. 500, 2000, and 4000 ppm Ttnyl chloride In nitrogen, with certified analysis. 7. Procedure. 7.1 Sampling. 7J.1 PVC sampling--Allow the resin or lurry to flow from a tap on the tank or silo until the tap line has been well purged. Ex tend a 60 ml sample bottle under the tap, flu, and immediately tightly c^p the bottle. Wrao electrical tape around the cap and bottle to prevent the top from loosening. Place an Identifying label on each bottle, and record the date, time, and sample location both on the bottles and In a log book. 7.1,2 Water sampling--Prior to use, the 50 ml vials {without the discs) must be capped with aluminum foil and mufSed at 400*C for at least one hour to destroy or remove any organic matter that oould In terfere with analysis. At the sampling loca tion dll the vials bubble-free, to overflowing so that a convex meniscus forms at the top. The excess water is displaced as the sealing disc is carefully placed. Teflon side down, on the opening of the viol. Place the aluminum seal over tho disc and the neck of the vial and crimp Into place, Aidx an Identifying label on the bottle, and record the date, time, and sample location both on the vials and In a log book. All sampled must be kept re frigerated until analyzed. 7.3 Sample recovery. Samples must be run within 24 hours. 7.2.1 Resin samples--The weight of the resin used must be between 0.1 and 45 grama. An exact weight must be obtained (6,001 gram) for each sample. In the case of sus pension resins a volumetric cup can be pre pared which wui hold the required amount of sample. Ihe sample bottle u opened, and the cup Toluene of resin Is added U> the taxed sample vial (Including septum and alumi num cap). The viol Is Immediately sealed and the exact cample weight la then obtained. Report this value on the data sheet as It U required for calculation of RVCM- In the cat# of relatively dry resin samples (water content <0.3 weight z*)t 100 of distilled water must bo injected Into the vial, after r-caliog and welrhln*:. using a 100 ^1 frying. In the ca.i of di*>-r*lan r-sio-!, u.e cup c-j.r.oOt bo v-V'd. Vt,.* sample fa lrvivrvl wcl^ncd e.pprvxk'T-.a.t.c'y la an s-umtsum d-l^h. transferred to the U-rc<l vtai rvnd r^ourately la the vLaL The comp! U then place*.* lh the Fcrlla-inmcr herd space i\ca'.iXf (or equivalent) and condltloc-id for on hour s G0*C, Note: Some aluminum viol caps have a renter section w.-jch U'.uit be removed price to placing Into e.uuple tray. If not rfmoved, serious dama.' to the injection nte-.il wiu occur. 7-22 Suspension resin slurry and wet coke m.mptes--Slurry must b furred using a email Buchner funnel with vacuum to yield wet cake- Tho altering process must bo con tinued only as long as a steady stresun of water Is exiting from the funnel, Excessive titration Urn could result In some low of VCM. The wet cake sample (0.10 to 4-5 grams) Is added to a tared vial (including septum. and aluminum cap) and immediately sealed. Somplo weight is then determined to 3 deci mal ptaCes- The sample Is then placed in the Pcrkln-Emer 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 th RVCM- 722 Dispersion resin slurry samples.-- This material should not be filtered. Sample must be thoroughly mixed. Using a taxed vial (including septum and aluminum cap) add approximately 8 drops (025 to 025 grams) of slurry or latex using a medicine dropper. This should be done immediately after mixing. Seal the vial as soon as possible. Determine sample weight accurate to 0.001 grams. Total sample weight must not exceed 0.50 grams. Condition the vial for one hour at 90*C in the analyzer. Determine the TS on the slurry sample (Section 72.5). 72.4 Inprocess wastewater sample*-- Using a tared vial (Including upturn and aluminum cap) quickly add approximately 1 ec of water using a medicine dropper. Seal the vial as soon as possible. Determine sample weight accurate to 0.001 gram. Con dition the vial for two hours at 90*C in the analyzer. 72 Analysis. 72.1 Preparation of gas chromatograph-- Install the chromatographic column and con dition overnight at 150*C. Do not connect the exit end of the column to the detector while conditioning. 72.1.1 Flow rate adjustments--Adjust flow rate* as follows: u Nitrogen carrier gas--Set regulator on cylinder to read 56 psig. Set regulator on chromatograph to 12 kg/cmfl. Normal flows at this pressure should be 25 to 40 cc/minute. Check with bubble flow meter. b. Burner air supply--Set regulator on cyl inder to read 50 palg. Set regulator on chromatograph to eupply air to burner at a rate between 250 and 300 cc/mlnute. Check with bubble flowmeter. 3. Hydrogen *upply--Set regulator on cyl inder to read 30 pslg. Set regulator on chromatograph to supply approximately 355 ec/mlnute. Optimize hydrogen flow to yield the most sensitive detector response without extinguishing the flame. Check flow with bubble meter and record this flow 72.12 Temperature - adjustments--Set temperature* as follows: a. Oven (chromatographic column), 60* C. b. Dosing line. 140* C. c. Injection block, 140* C. d. Sample chamber, water temperature, 60* Cd;lJ0* C. 72.12 Ignition of flame Ionization detec- to.*--T^ni`e the detector according to the ma.n-.Lf vciurtr '* Instructions 72.1.4 Amplifier balance--Balance th amnl.Ztcr according to tho manufacturer' fr-j cru1ir-4. 723 I7^*rammlny th chromatograph-- a.Program the chHromma--toignrapnhoarms faolllsoewtsti:ng Is 2 seconds. b. a--Analysis time--The normal setting fa 8 minutes. Certain t.of eamplee co.:teln hl^h foiling mater Jda which can eau.* interference wiih the vinyl chloride peak on subsequent analyses. In these c&vn ?b analysis tise must be adjusted to eliminate the interference. An automated baeijiush system can also be used to solve this prob lem. c. B--Flushing--The normal setting is 02 minute*. i w--Stabilization time--The nomal set ting Is 02 minute*. e. X--Number of analyses per sample--The normal sotting Is 1. 722 Preparation of sample turntable--Be fore placing any sample into turntable, be certain that the center section of the alu minum cap ho* been removed. The numbered sample bottle* should be placed in the ccrresponding numbered position* la the turn table. Insert samnle* in the following order: Positions 1 ti 2--Old 2000 ppm standard* for conditioning. These are seceauary only after the analyzer has not been used for 24 hours or longer. Position 3--50 ppm standard, freshly pre pared. Position 4--500 ppm standard, freshly pre pared. Position 5--2000 ppm standard, freshly prepared. Position (5--4000 ppm standard, freshly pre pared. Position 7--Sample No, 7 (This la the first sample of the day, but fa 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 0. 600, 2000, and 4C-0Q ppm. standards. Sample*, including stand ard* tnuat b conditioned in the bath of 60* C for 1 hour (not to exceed 5 hours). 72.4 Start chromatograph program-- When all samples, including standards, have been conditioned at 90* C for \ 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. 722 Determination of total solids (TS). For wet coke, 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 la a draft oven (105 to HO* C), Samples must be dried to constant weight. After first weighing re turn tho pan to the oven far a short pe riod of time and then reweigh to verify com plete dryncs*. TS U then Calculated as the final sample weight divided by Initial sam ple weight. 8. Calibration. Calibration-fa to be performed each eighthour period when the Instrument U tued. Each day. prior to running samples, the coldata should be conditioned by running two of the previous days 3000 ppm standard*. 8.1 Preparation of Standards. Calibration atandarda are prepared by fill ing the vials with the vinyl chlorlde/nltrogen standards, rapidly seating the septum and sealing with the aluminum cap. Use a atalntarts steel line from the cylinder to the Vial, Do not use rubber or tygon tubing. The ample line from the cylinder must be fKOIftAl UCISTU, VOL 41, NO. 305--THUIS0AY, OCTOOf* 31, 1674 CMA 004200 RULES AND REGULATIONS purged (into h<v<t) for sever:C, nlmttc* prior to fiiMng y'.&'.s, A.fiw purging. rcduco tLio flow rata to approximate*/ IsjO-IQOq cc/rda. Place end of tubing into vlii (near buf,(.o:n) and after oaa minute slowly remove Tl'\c septum In vial cv* toon an popclble to mini mi re mUlr^ Mr with sample AJu-t viic itnnd- Tvfd Vtii3 M-fJ Sailed, 100^1 of distilled wwter. 8-2 Freparut'oa of chromatograph calibra tion curve. Prepare two CO ppm, two 500 ppin. Uvo 2000 ppm. and two 40C0 ppm standard samples. Kim the calibration samples in. exactly the same manner ax regular sample* Plot A., the Integrator area counts for pm-Ii standard sample vs cp, the concentration of -vinyl chloride la each giantlard cample. Dtr-w a Une Of best fit through the poluts. 9, Calculations. 9.1 Response factor. Prom the calibration curve described in Section 8.3, above, ael^ct the value of C* that cofTespOE-1* to A* for each sample. Com pute -the response factor, R*. for each sample, a* follow*: C Equation 107-- i i 9J2 Residual vinyl chloride monomer con centration. or vinyl chloride monomer con centration. Calculate C*** as follow*: C, '*Sf(SS-0 Equation 107-2 >Con*eMr*?loa of vinyl ehlortdv In the sompU, fV la pptn. 'Laboratory atmosphere pressure, tun 0c. M**. TV Room temperature, *K, `Molecular %ei*bt of VCM (.). V*M Volome of r&p&t pbw* (rial volume toe sample toluene). Weight of simple, rm Oaa constant Beery'* law coar'aM for VCM to PVC at arc, A'-UWO^-K, for VCM In 1 eo (approximate) wastewater sample at 90*0, r- K*-5.0Xl0-*-JT.. Equilibration temperature, *E. If the following condition* are met, Equation 107-1' an he MrapUded as fohoir*: L Ti-22" O TO5* JCT" % ri-r c oor kj. 1. f.-TV) mm. tic. * t trhrr* v-ti 2L&- V.^Viel volume, eo C^L5). S. S.%4iple contains U*ae ('j' WAlM. F)5 033X 10-' 107X10 '+ Equation 107-3 1`M /cDow- In ft E-jnfrel wjnMloo ran S tty*\ for euy Mini*!* which cotiLAlru VCM, i'VC **vtor *>r. c, AJ\ ~rn\ X[;^'^7 + K-(TS> T - A - (l -- TS) 7'iJ where; Equation 107-4 7", -Total solids. Sot*; jf* must bo determined. Reaults calculated using KquAllcm 107-A represent concentration baaed on the total sample. To obtain result* based on dry PVC content, divide by TS. For a 1 et (approximate) wastewater sample. fcquatioe 107-4 can be simplified to the foilowieg: Equation 107-5 10. References. 1. Realdual vinyl Chloride Monomer Con tent of Polyvinyl Chloride Resina and Wet Cake Sample*, B. F. Goodrich Chemical Co. Standard Teat Procedure No. 1005-T, B. p. Goodrich Technical Center, Avon I-Ake, Ohio. January 30, 1975. 2. Berena, A, R., "The Solubility of Vinyl Chloride la Polyvinyl Chloride," ACS-Divi* eion of Polymer Chemistry, polymer Pre prints IS (3) : 197. 1974. 3. Berens, A_ R., "The Diffusion of Vinyl Chloride la Polyvinyl Chloride.** ACS-Dlvl- lou of Polymer Chemistry, Polymer Pre prints IS (3); 203, 1974. 4. Berena, A. R_ L. B. Crider, C- 3. Totaonek and J. M. Whitney. Analysi* for Vinyl Chloride In PVC Powders by Head-Space Oaa Chromatography," to be published. IFRDO0.70-30S49 Filed 10-20-75-.8:45 am) ftOCtAl tCClSKI. VOL 41. *0 105--tMUtSOAY, OCTOftlt 21. 197* CMA 004201 APPENDIX 3 RESOLUTION NO. 77-10 A Resolution of the South Coast Air Quality Management District Board enacting Rule 1005, Emission Standard for Vinyl Chloride. BE IT RESOLVED that the South Coast Air Quality Management Board in regular session assembled on September 14, 1977, hereby adopts Rule 1005 as attached hereto. That rule to become effective upon the date that the United States Environmental Protection Agency delegates authority to implement and enforce this rule to the South Coast Air Quality Management District. DATED: SEPTEMBER 14, 1977 Ayes: Beam, Geoghegan, Hansberger, Harwood, Heii.sneimer, Raver, McCar Noes: None Absent: Braude, Haley, Meade 004202 CMA SOUTH COAST AIR QUALITY MAKAGEKEHT DISTRICT Proposed Sale 1005 Emission Standard for Vinyl Chloride Por Hearing on September 2, "1977 CMA 004203 adopted by th South Cant Air Quality Mjnagtmvft Oitrtct Eotrd Resolution No. 77-40 Rule 1005 Emission Standard for Vinyl Chloride (a) Applicability (1) This rule applies to plants which produce: (A) Ethylene dichloride by reaction of oxygen and hydrogen chloride with ethylene, (B) Vinyl chloride by any process, and/or (C) 'One or more polymers containing any fraction of polymerized vinyl chloride. (2) This rule does not apply to equipment used in research and development if the reactor used to polymerize the vinyl chloride processed in the equipment has a capacity of no more than 0.19 m^ (50 gal) . (3) Sections of this rule other than (e)(1)(A), (2), (3) and (4) do not apply to equipment used in research and development if the reactor used to polymerize the vinyl chloride processed in the equipment has a capacity of greater than 0.19 (50 gal) and no more than 4.07 (1100 gal). (b) Definitions (1) ETHYLENE BICHLORIDE PLANT includes any plant which produces ethylene dichloride by reaction of oxygen and hydrogen chloride with ethylene. (2) VINYL CHLORIDE PLANT includes any plant which produces vinyl chloride by any process. (3) POLYVINYL CHLORIDE PLANT includes any plant whsre vinyl chloride alone or in combination with other materials is polymerized. CMA 004204 (4-) SLIP GAUGE cleans a gauge which has a probe that roves through the gas/lieuid 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 dischar^gC_>e" s. (5) TYPE OF RESET means the broad classification of resin referring to the basic manufacturing process for producing that resin, including, but not limited to, the suspension, dispersion, latex, bulk and solution processes. (6) GRADE OF RESET neans the subdivision of resin class ification which, describes it as a unique resin, i.e., the most exact description of a resin with no further subdivision. (7) DISPERSION RESET means a resin manufactured in such a way as to form fluid dispersions when dispersed in a plasticizer or plasticizer/diluent mixtures. (8) DATES RESIN means a resin which is produced by a polymerization process which initiates from free radical catalyst sites and is sold undried. (9) BULK RESET means a resin which is produced by a polymerization process in which no water is used. (10) EIPROCESS WASTEWATER means any water which, during manu facturing 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 polyviny chloride but which has not been discharged to a wasiev;ater treatne process or discharged untreated as wastewater. as characseristics CMA 004205 the purpose of meeting 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. (12) IN VINYL CHLORIDE SERVICE means that a piece of equip ment 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. (13) STANDARD OPERATING PROCEDURE means a formal written procedure officially adopted by the plant owner or operator and available on a routine basis to those persons responsible for carrying out the procedure. (14) RUN means the net period of time during which an emission sample is collected. (15) ETHYLENE DICHLORIDE PURIFICATION includes any part of the process of ethylene dichloride production which follows ethylene dichloride formation and in which finished ethylene dichloride is produced. (16) VINYL CHLORIDE PURIFICATION includes any part of the process of vinyl chloride production which follows vinyl chloride formation and in which finished vinyl chloride is produced. (17) REACTOR includes any vessel in which vinyl chloride is oartially or totally polymerized into polyvinyl chloride. (13) REACTOR OPENING LOSS means the emissions of vinyl chloride occurring when a reactor is vented to the atmosphere for any purpose other than an emergency relief discharge as defined in (f)(1)- (19) 5TP.IPPER includes any vessel in which residual vinyl chloride is removed from polyvinyl chloride resin, except bulk rosin, in the slurry form by the use of heat and/or vacuum. In the case of CMA 004206 bulk resin, strioper includes any vessel v/hich is used to rcaove residual vinyl chloride from. polyvinyl chloride resin immediately follow't'^e -'olvrerization sten in the riant rrocess flow. (c) Emission standard for ethylene dichloride plants. An owner or operator of an ethylene dichloride plant shall comply with the requirements of this section and section (f). (1) Ethylene dichloride purification: The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from any equipment used in ethylene dichloride purification is not to exceed 10 ppm, except as provided in (f)(1). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in (f)(2) before being opened. (2) Oxychlorination reactor: Except as provided in (f)(1), emissions of vinyl chloride to the atmosphere from each oxychlorinatio reactor are not to exceed 0.2 'g/kg (0.0002 Ib/lb) of the 100 percent ethylene dichloride product from the oxychlorination process'. (d) Emission standard for vinyl chloride plants. An owner or operator of a vinyl chloride plant sh-11 comply with the requirements of this section and section (f). Vinyl chloride formation and purification: The concen tration' of vinyl chloride in all exhaust gases discharged to the atmosphere from any equipment used ir. vinyl chloride formation and/ or- purification is not to exceed 10 son, except as provided in (f)(1) This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in (^)(2)(E)(i) before :;'c i ng opened. CMA 004207 (e) nnission standard for polyvinyl chloride plants. An o'.cer or operator of a polyvinyl chloride plant shall comply v/ith the requirements of this section and section (f). (1) The following requirements apply to reactors: (A) X tle concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from each reactor is not to exceed 10 ppm, except as provided in paragraph (1)(3) of this section and section (f)(1). (3) 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 prepolymerization and postpolymerization. (C) Manual vent valve discharge: Except for an emergency manual vent valve discharge, there is to be no discharge to the atmosphere from any manual vent valve 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 measures to prevent the discharge. Within 10 days of any discharge to the atmosphere from any manual vent valve, the owner or operator of the source from which the discharge occurs shall submit to the Air Follution Control Officer a report in writing containing information on the source, nature and cause of the discharge, the date and time of the discharge, the approximate total vinyl chloride loss during the discharge, the * method used for determining the vinyl chloride loss, the action CMA 004208 that v;as talier. to prevert the discharge, and measures adopted to prevent future discharges. (2) Stripper: The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from each stripper is not to exceed 10 ppm, except as provided in (f)(1). This requirement does not apply to equipment that has been opened, is cut of operation, and met the requirement in (f)(2)(F)(i) before being opened. (5) Mixing, weighing, and holding containers: The concen tration 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 (f)(1). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in (f)(2)(F)(i) before being opened. (4) Monomer recovery system: The concentration of vinyl chloride in all exhaust gases discharged to the atmosphere from each monomer recovery system is not to exceed 10 ppm, except as provided in (f)(1). This requirement does not apply to equipment that has been opened, is out of operation, and met the requirement in (f)(2)(F)(i) before being opened. (5) Sources follov/ir.g the stripper: The following require ments apply to emissions of vinyl chloride to the atmosphere from the combination of ail sources following the stripper (or the "'j.ictor if the cl ant has no r,trirrer) in t'-e ol-nnh rvocerm flov: including but not limited to, centrifuges, concentrators, blend tanks, filters, dryers, conveyor air discharges, baggers, storage CMA 004209 containers, and inprocess wastewater: (A) In polyvinyl chloride plants using stripping techr.olo to control vinyl chloride scissions, the 'weighted average residual vinyl chloride concentration in all grades of polyvinyl chloride resin processed through the stripping operation on each calendar day, neasurec innedlately after the stripping operation is conpieted, nay not exceed: (i) 2000 ppn for polyvinyl chloride dispersion resins, excluding late:! resins; (ii) 400 ppn for all other polyvinyl chloride resins, including latex resins, averaged" separately for each, type of resin; or (B) In polyvinyl chloride plants controlling vinyl chloride enissions with technology other than stripping or in addition to stripping, enissions of vinyl chloride to the atmosphere may not exceed: (i) 2 g/Tcg (0.002 lb/lb) product from the stripper (or reactor if the plant has no stripper) for dispersion polyvinyl chloride resins, excluding latex resins, with the product determined on a dry solids basis; (ii) 0.4 g/kg (0.004 lb/lb) product from the stripper (or reactor if the plant has no stripper) for all other polj/inyl chloride resins, including latex resins, with the product determined on a dry solids basis. (f) Additional standards for ethylene dichloride, vinyl chloride and polyvinyl chloride plants. in addition to other requirements in this rule, an owner or operator of an .ethylene cichloride, vinyl chloride, and/or polyvinyl chloride plant shall comply with the requirements of this c^ction. CMA 004210 (1) Relief valve discharge: Except fox' an emergency relief discharge, there is to he no discharge to the atmosphere from any relief valve on any equipment in vinyl chloride service. An emergency relief discharge means a discharge which could not have been avoided by talcing measures to prevent the discharge. Within 10 days of any relief valve discharge, the owner or operator of the source from which the relief valve discharge occurs shall submit to the Air Pollution Control Officer a report in writing containing information. on the source, nature and cause of the discharge, the date and tine of the discharge, the approximate total vinyl chloride loss during the discharge, the method used for determining the vinyl chloride loss, the action that was taken to prevent the discharge, and measures adopted to prevent future discharges. (2) Fugitive emission sources: (A) Loading and unloading lines: Vinyl chloride emis sions from loading and unloading lines which are opened to the atmosphere after each loading or unloading operation are to be minimized as follows: (i) After each loading or unloading operation and before opening a loading or unloading line to the atmosphere, the quantity of vinyl chloride in all parts of each loading or unloading line that are to be opened to the atmosphere is to be reduced so V that the parts combined contain no greater than 0.0058 nr (0.15 ftO of vir.yl chloride, at standard temperature and pressure; and (ii) Any vinyl chloride removed from a loading or uni on-'.nr line in accordance v.'ith unrnr-'rn.nh (P)(R)(u) of thi'r s--'r1'ioo. is to be ducted through a control system from which the concentration CMA 0042H of vinyl chloride in the exhaust gases docs not exceed 10 non, or equivalent as provided in (g). (3) Slip gauges: During loading or unloading operations, the vinyl chloride emissions iron each slip gauge in vinyl chloride service are to be minimized by ducting any vinyl chloride discharged from the slip gauge through a c.ontrol system from which the concen tration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided in (g). (C) Leakage from pump, compressor, and agitator seals: (i) Rotating pumps: Vinyl chloride emissions from seals on all rotating pumps in vinyl chloride service are to be minimized by installing sealless pumps, pumps with double mechanical seals, or equivalent as provided in (g). If double mechanical seals are used, vinyl chloride emission from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the pump; by ducting any vinyl^^ chloride between the two seals through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed "10 ppm; or equivalent as provided in (g). (ii) Reciprocating pumps: Vinyl chloride emissions from seals on*all reciprocating pumps in vinyl chloride service are to be minimized by installing double outboard seals, or equivalent as provided in (g). . If double outboard seals are used, vinyl chloride emissions from the seals are to be minimized by main taining the pressure between the two seals so that any leak that occurs is into the pump; by ducting any vinyl chloride between the two seals through a control system from which the concentration vinyl chloride in the exhaust gases does not exceed *10 ppm; or equivalent as provided in (g). CMA 004212 (iii) Rotating compressor: Vinyl chloride emis sions from seals on all rotating compressors in vinyl chloride service are to be minimized by installing compressors with doable mechanical seals, or equivalent as provided in (g). If double mechanical seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the compressor; by ducting any vinyl chloride between the two seals through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as provided in (g). (iv) Reciprocating compressors: Vinyl chloride emissions from seals on all reciprocating compressors in vinyl chloride service are to be minimized by installing double out board seals, or equivalent as provided in (g). If double out board seals are used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between the two seals so that any leak that occurs is into the compressor; by ducting any vinyl chloride between the two'seals through a -ontrol system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm; or equivalent as provided in (g). (v) Agitator: Vinyl chloride emissions from seals on all agitators in vinyl chloride service are to be mir.imized by installing agitators with double mechanical seals, or eriivalenc as provided in (g). If double mechanical seals, arc used, vinyl chloride emissions from the seals are to be minimized by maintaining the pressure between, the two seals so that any look > r. ' : : k; by dudl.'g any vi.yi k.'.c-' between the tv:o seals through a control system from which the CMA 004213 concentration, of vinyl chloride m tie exhaust gases does not exceed 10 pen; or equivalent as provided in. (g). (D) Leakage iron relief valves: Vinyl chloride emis sions due to leal-cage fron each relief valve on equipment in vinyl chloride service acre to be minimized by installing a rupture dish between the equipment and the relief valve, by connecting the relief valve discharge to a process line or recovery system, or equivalent as provided in (g). (E) Manual venting of gases: Except as provided in (e)(1)(C), all gases which are manually vented from, equipment in vinyl chloride service are 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 (g). (E) Opening of equipment: Vinyl chloride emissions from opening of equipment (including loading or unloading lines that are not opened to the atmosphere after each loading or un loading operation) a!re to be minimized as follows: (i) Before opening any equipment for any reason, the quantity of vinyl chloride is to be reduced so that the equip ment contains no more than 2.0 percent by volume vinyl chloride or 0.0950 n? (25 E^l) of vinyl chloride, whichever is larger, at standard 4 temperature and pressure; and (ii) Any vinyl chloride removed from the equip ment in accordance with paragraph (2)(F)(i) of this section is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided in (5). (G) Samples: Unused portions of samples containing at least 10 percent by weight vinyl chloride are to be returned to CMA 004214 the process, and sampling techniques are to be such that sarnie containers in vinyl chloride service are purged into a close! process system. (K) Leah detection and elimination: Vinyl chloride emissions due to leaks fr*. a 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 Air Pollution Control Officer for approval. The program is to be submitted within 4-5 days of the effective date of these regulations. Approval of a program will be granted by the Air Pollution Control Officer provided he finds: (i) It includes a reliable and accurate vinyl chloride monitoring system for detection of major leaks and identification of the general area of the plant where a leak is located. A vinyl chloride monitoring system means a device which * obtains air samples from one or more points on a continuous sequential basis and analyzes the samples with gas chromatography 0 if the owner or operator assumes that all hydrocarDons measured are vinyl chloride, with infrared spectrophotometry flame ion detection, or an equivalent or alternative method. (ii) It includes a reliable and accurate portable hydrocarbon detector to be used routinely to find small leaks and to pinpoint 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 p;.r. and is of such design and size ^r?t it c-in bo used to no->sure emissions from localized seine... CMA 004215 (iii) It provides for an acceptable calibration and maintenance schedule ior the vinyl chloride monitoring O ' ^ - C- and nortabl; :'ocarbon detector. For the vinvl chloride monitoring system, a daily span check is to he conducted with a concentration of vinyl chloride equal to the concentration defined as a leak according to paragraph (2)(K)(vi) of this section. The calibration is to be dons with either a calibration gas mixture prepared from, the gases specified by the Air Pollutio Control Officer, or a calibration gas cylinder containing the appropriate concentration of vinyl chloride. If a calibration gas cylinder is used, the analysis must be traceable to the National Bureau of Standards or to a gravimetrically calibrated vinyl chloride permeation tube. (iv) The location and number of points to be monitored and the frequency of monitoring provided for in the program are acceptable when they are compared with the number of pieces of equipment in vinyl chloride service and the size and physical layout of the plant. (v) It contains an acceptable plan of action to be taken when a leak is detected. (vi) It contains a definition of leak which is acceptable when compared with the background concentrations of vinyl chloride in the areas of the plant to be monitored by the vinyl chloride monitoring 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 different areas within the plant and is also to change over time as background concentrations in tile plant are reduced- CMA 004216 (I) Inprocess V/nstevater: Vinyl chloride omissions to the atmosphere from ir.oroceor. wastewute r are to be reduced =3 follows: (i) The concentration of vinyl chloride in each inprocess wastewater stream containing greater than 10 ppm vinyl chloride measured immediately as it leaves a piece cf equipment and before being mixed with any other inprocess wastewater stream is to be reduced to no more than 10 ppm by weight before being nixed with any other inprocess wastewater stream which contains less than 10 ppm vinyl chloride, before being dis charged to a wastewater treatment process, or before being dis charged 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 accordance with (e)(1)(B) or paragrpah (2)(F) of this section, but does not apply to water which is used to wash out equipment after the equipment has already been opened to the atmosphere in accordance with (e)(1) B) or paragraph (2)(F) of this section. (ii) Any vinyl chloride removed J'rom the inprocess wastewater in accordance with paragrpah (2)(I)(i) of this section is to be ducted through a control system from which the concentration of vinyl chloride in the exhaust gases does not exceed 10 ppm, or equivalent as provided in (g), (?) The requirements in parngrg V.:s (2)(A), (2)(B), (2)(b), (-'')(!), (2)(G) and (2)(K) of this section are to bo incorporated into a standard operating procedure, and made available upon rec:-*." t for inspection Vv t''1'- ~ : : V ol \ " t i n p. Co" t -cd C ffi "c r. standard operating procedure is to include provi r ions fo;- measuring CMA 004217 the vinyl chloride in equipment which is A. 75 m2 (1250 gal) -in. volunj or greater for which an emission limit is prescribed in (f)(2)(E)(ip prior to opening the equipment and using a portable hydrocarbon doctor, or an equivalent or alternative method. The method of measure ment is to meet the requirements specified by the Air Pollution Control Officer* (g) Equivalent equipment and procedures. The Air Pollution Control Officer may approve use of equipment or procedures which have been demonstrated to his satisfaction to be equivalent in terms of reducing vinyl chloride emissions to the atmosphere to those prescribed for compliance with a specific paragraph of this rule. For a new or modified source, any request for using an equivalent method is to he submitted to the Air Pollution Control Officer with the application for authority to construct and permit to operate. (h) Testing" procedures (1) Unless a waiver of emission testing is obtained under Rule 1001 (b) each owner or operator of a source subject to the standard in Rule 1005 shall test emissions from that source. Such tests shall he conducted in accordance with the procedures set 4 forth 'below. (2) Emissions shall he tested according to methods specified by the Air Pollution Control Officer: (A) The test shall be performed within 90 days of the effective date of these regulations in the case of an existing source or a new source which has an initial startup date preceding the effective date. CMA. 004218 (E) The test shall be performed within 90 days of start up in the case of a new source which did not have an initial startup cate preceding the effective date. (3) The Air Pollution Control Officer shall he notified at least 30 days prior to an emission test, so that he nay, at his option, observe the test. (4-) All samples shall he analyzed within 24 hours, and vinyl chloride emissions shall he determined within 30 days after the stack test. Each determination shall he reported to the Air Pollution Control Officer hy a registered letter dispatched before the clcse of the next business day following such determination. (5) Records of emission test results and other data needed to determine total emissions shall be retained at the source and shall be made available for inspection by the Air Pollution Control Officer for at least two years. (1) Emission monitoring- (1) A vinyl chloride monitoring system is to bo used to monitor on a continuous basis the emissions from the sources for which emis sion limits are prescribed in (c)(1) and (2); (d)(1); (e)(1)(A), (2), (3) and (4) and for any control system to which reactor emission are required to be ducted in (f)(2)(A)(ii) and (2)(B), (2)(E), (2)(F)(ii) and (2)(I)(ii). (2) The vinyl chloride monitoring system(s) used to meet the recuironen* in pe-vagrarh (1) qc this section is to be a device which obtains air samples from one or more points on a continuous r.ccu-.nt j si basis and analyzes the samples v:\th gas chromotogl uphy, or, if she c-mwc we operator ;-!sr.:v. .-r- 'wm r._l p d-w i WO:in or-, cii.y.i. chloride, with infrared spectrophotometry, flame ion defection, CMA 004219 or an equivalent: or alternative method. The vinyl chloride monitoring system used to meet the requirements in (f)(2)(H)(i) may be used to meet the requirements of this section. (3) A daily spam check is to be conducted for each vinyl chloride monitoring system used. For all of the emission, sources listed in paragraph (T) of this section, except the one for which an emission limit is prescribed in (c)(2), the daily span check is to be conducted with a concentration of vinyl chloride equal to 10 ppm. For the emission source for which an emission limit is prescribed in (c)(2), the daily span check is to be conducted with a concentration of vinyl chloride which is determined to be equivalent to the emission limit for that,source based on the emission test required by (h). The calibration is to.be done with either: (A) A calibration gas mixture prepared from the gases specified by the Air Pollution Control Officer; or (B) A calibration gas cylinder containing the appropriate concentration of vinyl chloride. If a calibration gas cylinder is used, the analysis must be traceable to the National Bureau of Standards or to a gravimetrically calibrated vinyl chloride permeation tube. (j) Initial rep ort. (1) An owner or operator of any source to which this rule applies shall submit a statement in writing notifying the Air Pollution Control Officer that the equipment and procedural cp-ecifications in (f)(2)(A), (2)(B), (2)(C), (2)(C), (2)(E), (2)(F), (2)(G) and (2)(H) are being implemented. CMA 004220 (2) (A) In the case of ar. existing source or a new source which has an initial startup date preceding the effective date, the statement is to be submitted within 90 days of the effective date. (3) In the case of a r.ew source which did net have an initial startuo date preceding the effective date, the statement is to be submitted within 90 days of the initial startup date. (3) The statement is to contain the following information: (A) A list of the equipment installed for compliance. (B) A description of the physical and functional characteristics of each piece of equipment. (C) A description of the methods which have been incorporated into the standard operating procedures for meas uring or calculating the emissions for which emission limits are prescribed in (f)(2)(A)(i) and (2)(F)(i). (4) A statement that each piece of equipment is installed and that each piece of equipment and each procedure is being used. (k) Semiannual report. (1) The owner or operator of any source to which this rule applies shall submit to the Air Pollution Control Officer on Septem ber Ip and March 15 of each year a report in writing containing the information required by this section. The first semiannual report i to be submitted following the first full 6 month reporting peried after the initial report is submitted. (2) (a) In the case of an existing source or a new source which has an initial startup date preceding the effective date, the first rvnori. in to be CMA 004221 (B) In the case of a new source v/hich did not have ar, initial startup date preceding the effective date, the first report is to be submitted within 180 days of the initial startup date. (5) Unless otherwise specified, the owner or operator shall use the test methods specified by the Air Pollution. Control Officer to conduct emission tests as required by paragraphs 0)(B) and (3)(C) of this section, unless an equivalent or an alternative method has been approved by the Air Pollution Control Officer. If the Air Pollution Control Officer finds reasonable grounds to dispute the results obtained by an equivalent or alternative method, ha may require the use of a reference method. If the results of the reference and equivalent or alternative methods do not agree, the results obtained by the reference method prevail, and the Air Pollution Control Officer may notify the owner or operator that approval of the method previously considered to be equivalent or alternative is withdrawn. (A) The owner or operator shall include in the report a record of any emissions which averaged over any hour period (commencing on the hour) are in excess of the emission limits prescribed in (c)(1) or (2), (d)(1) or (e)(1)(A), (2), (3), or (4) -* or for any control system to v/hich reactor emissions are . required to be ducted in (e)(1)(B) or to which fugitive emissions are required to be ducted in (f)(2)(A)(ii), (2)(B), (2)(E), (2)(F)(ii) or (2)(l)(ii). The emissions are to be measured in accordance with (i). (B) In polyvinyl chloride plants for which a stripping operation is viced to attain the emi.5r.ion level prescribed in (e)(5) the owner or operator shall include in the report a record of the * vinyl chloride co:*.L-;-nt in ede polyvinyl chlo'-iric resin. Tost methods CMA 004222 scorified by the Air Pollution Control Officer are to be used to do t :-mir.e vinyl chloride content as follows: (i) If batch stripping is used, one representative sample of polyvinyl chloride resin is to be taken from each batch of each grade of resin immediately follov/ing the completion of the stripping, and grade and the date and tine the batch is completed. The corresponding qualtity of material processed in each stripper batch is to be recorded and identified by resin type and grade and the date and time the batch is completed. (ii) If continuous stripping is used, one represen tative sample of polyvinyl chloride resin is to be taken for each grade of resin processed or at intervals of 8 hours for each grade of resin which is being processed, whichever is more frequent. The sample is to be taken as the resin flows out of the stripper and identified by resin type and grade and the date and time the sample was taken. The corresponding quantity of material processed by- each stripper over the time period represented by the sample during the eight hour period, is to be recorded and identified by resin type and grade and the date and time it represents. (iii) The quantity of material processed by the strioper is to be determined on a dry solids basis and by a method submitted to and approved by the Air Pollution Control Officer. (iv) At the prior request of the Air Pollution Control Officer, the owner or operator shall provide duplicates of the samples required ir. paragraphs (3)(B)(i) and (3)(B)(ii) of thin section. (v) The rc.icrt to the Air Pollution Control Officer- by the owner or operator is to include the vinyl chloride content found in all the samples required in paragrpahs (3)(B)(i) CMA 004223 and (5)(3)(ii) of this section, averaged separately for each type of resin, ever each calendar cay and weighted according to the quantity of each grade of resin processed by the stripper(s) that calendar day, according to the following equation.; n a p'ug,- n-Gd.- Ap i = l %i PG, "0, + p02 G2 + - + PGn "Gn Qm i A = 24-hour average concentration of type T^ resin in. ppm. Q = Total production of type T^ resin over the 24--hour period, in kg. Th = Type of resin i=1,2,___m where m is total number of resin types produced during the 24-hour period. M = Concentration of vinyl chloride in one sample of grade Gg resin, in ppm ? = Production of grade resin represented by the sample, in' kg. = Grade of resin, e.g., G^, G2, and G^. n = Total number of grades of resin produced during the 24-hour period. (vi) The owner or operator shall retain at the source and make available for inspection by the Air Pollution Control Officer for a minimum of 2 years records of all data needed to furnish the information required by paragraph (5)(B)(v) of this rccMior.: The records ar-, to contain. " h-j following information: (I) The vinyl chloride content found in all ^ r- ^--.. i r.- ^q p nnd of this CMA 004224 section., identified by the resi e and grade and the and date of the sample, and (II) The corresponding quantity of poly vinyl chloride resin processed by the stripper(s), identified by the resin type and grade and the tine and date it represents. (C) The owner or operator shall include in the report a record of the emissions from each reactor opening for which an emission limit is prescribed in (e)(1)(B). Emissions are to be determined in accordance with (h), except that emissions for each reactor are to be determined. For a reactor that is also used as a stripper, the determination may be made immediately fol lowing the stripping operation. (1) Recordkeeping (1) The owner or operator of any source to which this rule applies shall retain the following information at the source and make it available for inspection by the Air Pollution Control Officer for a minimum of two years: (A) A record of the leaks detected by th' vinyl chloride monitoring system, as required by (f)(2)(H), including the concen trations of vinyl chloride as measured, analyzed, and recorded by the vinyl 'chloride detector, the location of each measurement and the date and approximate time of each measurement. (B) A record of the leaks detected during routine monitoring with the portable hydrocarbon detector and the action taken to repair the leaks, as required by (f)(?(K), including a brief statement explaining the location and cause of each leak i--u.v.c.-cd with the portable hycir ojarbon ctecfor, tun dote r.'l Lire of the leak and any action taken to eliminate that leak measured /i \ CMA 004225 (c) For the relief discharges iron reactors subject to the provisions of (f)(1), a daily operating record for each reactor, including pressures and temperatures(r) Effective Date `This rule is effective upon the date that the United States Environmental Protection Agency delegates authority to irplerert and enforce this rule to the South Coast Air Quality Management District. CMA 004226 append:- ^ 2313-1 PROPOSED RULES ENVIRONMENTAL PROTECTION AGENCY additional actions. These include a re be achievable only by banning vinyl chlo statement of EPA's policy for regulating ride emissions completely. That, in turn, [ 40 CFR Part 61 ] carcinogens under section 112 of the would require closing the entire industry. Clean Air Act: the proposal of amend As explained in the eaiiier rulemaking it (ERL 733--5] ments which would require increased is not clear that Congress would have VINYL CHLORIDE National Emission Standards for Hazardous Air Pollutants efficiency of existing control equipment, require more stringent control at new sources, and prohibit increases in emis sions within the vicinity of an existing intended this result, so instead EPA re quired the lowest level achievable using technological means. (See 40 FR 59534 and 41 FR 45562). AGENCY: Environmental Protection Agency. ACTION: Proposed rule. SUMMARY: The proposed amendments are being made to the vinyl chloride standard which has promulgated Octo ber 21. 1978, and would apply to new and existing ethylene dichloride, vinyl chloride, and polyvinyl chloride plants. The standard and the proposed amend- source due to new construction: and the initiation of a review of the vinyl chlo ride standard three years after the pro mulgation of the amendments. Zero Emission Goal The vinyl chloride standard has been critrizcd fir allegedly placing unwar ranted emphasis on technological rather than hca'th considerations. Although EPA disagrees with this criticism, it In order to insure that the standard continues to approach the only level of emissions which is known to be abso lutely protective of health, namely zero emissions. EPA is proposing amendments which require more efficient use of exist ing control technology at existing plants and more effective controls at new plants, and which encourage technology to reach this goal without banning vinyl chloride. - ments implement the Clean Air Act and are based on the Administrator's deter mination that vinyl chloride is a hazard ous air pollutant. The intended effect of the proposed amendments is to require improved effectiveness of control tech nology at existing plants, impose more stringent emission limits on new sources, and prohibit an emission increase within the vicinity of an existing source due to the construction of a new source. DATES: Comments must be received on or before August 1,1977. stems appropriate to restate EPA's ap proach to the regulation of carcinogens in eeneral and under Section 112 of the Clean Afr Ait. and to explain how the vinyl chloride standard and the pro posed amendments are consistent with this approach and with the protection of public health. On Mav 25, 1976. EPA published in terim procedures and guidelines for health rick and economic impact assess ments of susiected carcinogens (41 FR 21402). whicn define EPA's approach to regulatory action for suspect carcino More Strincevt Eta.vdards ro Existing Sources . EPA is proposing amendments which would require sources presently subject to a 10 ppm emission limit to reduce emissions to 5 ppm within three years of promulgation of the amendments. The affected sources include ethylene dlchloride purification; vinyl chloride forma tion and purification: reactors, strippers: mixing, weighing, and holding contain ers; monomer recovery systems; and fugitive emissions which have been cap ADDRESSES: Comments should be sub mitted (preferably in triplicate) to the Emission Standards and Engineering Division. Environmental Protection Agency. Research Triangle Park. North Carolina. Attention: Mr. Don R. Good win. All public comments received may be inspected and copied at the Public In formation Reference Unit <EPA Li brary), P.oom 2922, 401 M Street, SW., Washington, D.C, gens. As Indicated in that publication, there are two steps involved in the deci sion-making process with regard to the regulation of a potential carcinogen. Al though different EPA statutory author ities impose different requirements, in general two decisions must be made with regard to each potential carcinogen. The first decision is whether a particular sub stance constitutes a cancer risk. The second decision Is what regulatory ac tion, if any, should be taken to reduce that risk. tured in accordance with the existing regulation.* If the owner or operator of a source believed that a control system would not be capable of meeting the 5 ppm limit, he would be able to request that the Administrator approve an in terim emission limit for that source. Such requests would have to be made one year before the compliance date. In re questing an interim emission limit, the owner or operator would have to submit supportive data and meet with EPA to discuss his particular problems In attain FOR NURTHKM INFORMATION CON In deciding whether a cancer risk ing compliance. The meeting would be TACT: exists. EPA will consider a substance a announced in the Federal Register and Don R. Goodwin, Emission Standards presumptive cancer risk when it causes and Engineering Division, Environ a statistically significant excess incidence mental Protection Agency, Research of benign or malignant tumors in hu Triangle Park, North Carolina 27711, mans or animals. In the case of vinyl Telephone No. 919-038-8146. ext. 271. chloride. EPA evaluated all available data and concluded that a cancer risk SUPPLEMENTARY INFORMATION: exists. In deciding how and whether to Background On October 21, 1978, EPA promulgated a standard for vinyl chloride under the authority of section 112(b) (1) (B) of the Clean Air Act. as amended (41 FR 46561). The standard applies to ethyl regulate. EFA examined section 112 of the Clean Air Act. Section 112 of the Act requires that emission standards be set "at the level which In the judgment of the Administrator provides an ample margin of safety to protect the public health from such hazardous air pollut ene dichloride. vinvl chloride, and poly ants." This requirement appears to as vinyl chloride plants. sume that each pollutant regulated will On November 19. 1976, the Environ have a threshold level of effects below mental Defense Fund (EDF) petitioned which no health effects will occur. As the United States Court of Appeals for explained in the documentation for the the District of Columbia Circuit to review current standard <40 FR 59532. Decem the standard. Motions to intervene were ber 24, 1975; 41 FR 46560. October 21, subsequently filed on behalf of the So 1976). it has not been possible to deter ciety of the Plastics Industry. Inc., the mine if there is a threshold level of Goodyear Tire and Rubber Company and effects for vinyl chloride and it is not Aar Products and Chemicals, Inc., and certain that such a threshold may be were granted by order of the Court on determined In the near future. In the January 18. 1977. On March 24, 1977, absence of strong evidence to the con EDF and EPA moved to dismiss the trary, then, the only level of vinyl chlo proceedings in view of a settlement ride which would appear to be absolutely agreement requiring EPA to take certain protective of health is zero, which may any interested party would be allowed to attend and submit written or oral com ments. If an interim emission limit were granted to the source, the required emis sion level would be specified in a written notification from EPA and in the Fed eral Register, "ich source granted an interim emission limit would be reviewed every three years to determine whether emissions could be reduced to 5 ppm, or at least to a lower interim emission limit In proposing the reduction from 10 to 5 ppm. it is not EPA's intent that a con trol system which has been installed to As an explanatory note, paragraph (P) of ! 61.SS contains nine fugitive emission regu lations. For several of these, the fugitive emissions are required to he captured and ducted to a control device meeting 19 ppm. According to the proposed amendments, the emissions from this control device would have to he reduced to 5 ppm In the same way any other source currently required to meet 10 ppm would have to do. Rather than In corporating both the 5 and 10 ppm emisaion limits In each paragraph In i 61.65(b), a separata paragraph (e) containing these emission limits Is helog sdded to I 61,65. Ail the other paragraphs In (b) are crossreferenced In part --aph (c) FEDEIAl UGirrii, voi sj, no. loe--Thursday, jun* i, 1977 CMA 004227 PROPOSED RUIES 28155 mt the 10 ppm emission limit be re moved and replaced with another more efficient control system or that a second control system be added behind the first control system. The purpose of the pro posed amendment is to force owners and operators to maximize the effectiveness of existing confroi systems. Moi SrerBcairr St*kmus rot Niw Sodas The proposed amendments would also require more stringent controls for new sources; he- sources for which construc tion Is commenced after the date of pro posal of these amendments. According to 5 81.02 of the General Provisions, "commenced" mum* that an owner or operator hm undertaken a continuous program of construction or modification or that an owner or operator has entered into a contractual obligation to under take and complete, within a reasonable time, a continuous program of construc tion or modification. New sources of types which would be subject to the 10 ppm emission limit under the current standard would be required under the amendments to meet a 5 ppm emission limit at the time of startup. With new sources there would be no provision allowing requests for EPA approval of an Interim rml.vilnn limit. New sources would be required to meet the more stringent emission limit at the time of startup, because they have an opportunity to design their equipment to meet the 5 ppm emission limit at the time construction is commenced. Existing sources, on the other hand, require time to maximize the effectiveness of their control systems. The proposed amendment would also require ethylene dichloride-vinyl chlor ide plants to control emissions from new oxychlorlnation reactors to 5 ppm. This requirement is based on installation of a recycling and oxygen feed system with an Incinerator or equivalent control de vice. The current standard limits emis sions from the oxychlorlnation reactor to 0.2 g/kg (0.0003 lb/lb) of the 100 per cent ethylene dlchlorlde product from the oxychlorlnation reactor. This emis sion limit can be met by. changing proc ess parameters, rather than Installing a control device. During the development of the current standard EPA considered requiring *rtting sources, to control emissions with an incinerator or equiva lent technology, but rejected this ap proach because a large quantity of fuel would be required to reduce emissions from a relatively small source. An exist ing oxychlorlnation reactor typically has a large volume, low hydrocarbon effluent gas stream, and large quantities of sup plemental fuels would be required for combustion of its emissions. A new plant can reduce the volume of Its effluent gas stream and make It more concentrated by recycling the gas stream and using oxygen instead of air to feed Into the proces. (J, <1 the current standard waa not based on this technol ogy because It was not considered feasi ble to retrofit existing plants so that they could use oxygen instead of air. The je- cycltetg and oxygen feed methodolgy Is considered feasible for new oxychlortna- tlon reactors because it can be Incorpo rated at the time of construction. Since the use of this technology would elimin ate the supplemental fuel problem re ferred to above. It Is EPA's judgment that new oxychlorlnation reactors should be controlled to the same extent that is proposed for other emission sources. The proposed amendment also includes a more stringent emission limit for new polyvinyl chloride resins being processed In equipment following the stripping operation. That is. the amendment would apply to resins for which produc tion for the purpose of marketing was commenced alter the proposal of the amendment. The amendment would re quire all new resins except new disper sion resins to be stripped to loo ppm and new dispersion resins to be stripped to 500 ppm. These limits for new products would be one-fourth of the limits con tained. in the standard for existing prod ucts. Consistent with the current stand ard. the amendment would permit the use of control devices rather than strip ping technology to meet the emission limit. In tht* case equipment being used to process all new resins except new dis persion resins would have to be con trolled to 0.01 kg/kg product and the equipment used for new dispersion resins would have to be controlled to 0.05 kg/kg product. ____ A "new source* Is defined in 40 CFR 61.02 as a stationary source, the con struction or modification of which is commenced after proposal of a standard. There was some question based on this definition as to whether the amendment to the stripping standard for new sources should apply to new polyvinyl chloride resins or the Installation of new equip ment following the stripper. If the ap plicability of the amendment for new sources were based on the installation of new equipment following the stripper. It would be difficult to determine what con stitutes a new source at an existing plant. This Is based on the reasoning that the stripping standard requires that all equipment following the stripper in the process be controlled ss a unit The series of equipment following the stripper In cludes pumps and conveying equipment which might be expected to be replaced on a frequent and routine basis. Replac ing one of these pieces of equipment would in effect cause the whole series of equipment following the stripper to have to meet the standard for new sources. In other words, all resins processed In the series of the equipment would have to meet the lower standard even though only a minor part of the equipment had been replaced. EPA decided that a more reasonable and direct approach was to. make the proposed amendment apply to the pro duction of new polyvinyl chloride resins. This Is based on the reasoning that emis sions from the equipment following the stripper are a function of the amount of vinyl chloride left In the resin after the stripping operation Is completed; le, the resin Is the source of the emissions rather than the equipment. The same equipment can be used to process differ ent resm grades. Variations in the emis sions from tne equipment are a function of the resin being processed rather than the characteristics of the equipment. The control technology which Is used for the equipment following the stripper Is like wise more directly linked to the resin than the equipment. Stripping is used to control the emissions due to the vmyl chloride In the resin before the resin is processed in the equipment. Before the hazards of vinyl chloride became known, stripping technology was employed by polyvinyl chloride manu facturers to recover raw materials for economic purposes. As a result of a standard promulgated by the Oecuoatlonal Safety and Health Administration (39 PR 35890). some companies Investi gated improvements In stripping meth odology for emission control purposes. (f> Optimum stripping consists of a set of operating conditions which must be de veloped experimentally on an individual basis for the many resins. In developing the current standard. EPA recognized that stripping technology for dispersion resins had not been refined to the same extent as it had been for other resins and that there was more difficulty In strip ping dispersion resins than other resins. For this reason a less stringent emission limit was established for dispersion res ins. Dispersion resins are permitted a higher emission limit under the proposed amendment for the same reason. EPA believes that for some resins, companies have already developed strip ping technology which would meet the proposed amendments (2) For other resins, the proposed standard would re quire additional Improvement In strip ping technology. If stripping technology has not been developed to the extent necessary to meet the proposed amend ment for a particular resin, the manu facturer would have the option of de veloping the technology or not producing the resm. The current standard, unlike the proposed amendment, was not based on the premise that an owner or operator would have the option of not producing 1 a particular resin. It Is EPA's judgment that the owner or operator making a new product has more freedom of choice than the owner or operator already making a particular product in selecting those resins which are to be produced. EPA's standard would be Included In the variables under consideration when decisions are being made as to which resins are to be produced. The proposed amendment would apply to any new source, whether It constituted replacement of an existing source in an existing plant, the expansion of an exist ing plant, or part of an entirely new plant. That Is. if a new oxychlorlnation reactor or a new polyvinyl chloride re actor were installed at an existing plant. It would be subject to the emission limits for new sources. This means that as witting sources are gradually replaced with new sources In an existing plant. maul ttorjTw, vot. *j. no. iqs--tmuxsoay, juni z, tv77 ' ' .. , CMA 004228 23156 PROPOSED RULES the overall emission level from that existing plant would be reduced. Emission Orrsrr Because the present vinyl chloride standard focuses on reducing emissions rather than attaining a particular am bient air Quality concentration, there is no provision for limiting the size of plants or the clustering of plants in a geographical area. The doubling of the size of an existing plant or the construc tion of a new plant beside an existing plant would considerably increase the ambient air concentrations of vinyl chloride In the vicinity of the plantis) even if the vinyl chloride standard was met. EPA determined at the time of promulgation of the current standard that the costs of prohibiting the produc tion of vinyl chloride and polyvinyl chloride were too high and the continued operation of existing plants should be allowed. EPA believes, however, that the standard should include a mechanism for prohibiting an increase in ambient concentrations of vinyl chloride dne to new construction in areas where evicting sources are already located. Accordingly, EPA is proposing an amendment which would prohihit an in crease in *Tntinn within 8 kilometers (km) (approximately five miles) of an existing source due to the construction Of a new emission source. This means that If a new source were added to an existing plant, the Increase in emissions due to that new source would have to be offset by a reduction in emissions from other existing sources within that plant or at other plants within 8 km of the construction site of the new source. Simi larly, a new plant could not be con structed within 8 km of an existing planus) unless the emission Increase due to the new plant were offset by an emission reduction at the existing plant or plants. This provision may result in few existing plants being expanded and few new plants being constructed in the vicinity of existing plants. However, the proposed amendment does not preclude this possibility. The offset provision would apply only, to new construction which results in an increase in production rate. Replacing or adding equipment such as pumps, com pressors. agitators, sampling equipment and unloading hoses is a routine practice at existing plants. Additions of equip ment of th( nature would. In and of it self. be expected to result In little, if any, increase in emissions. In EPA'3 judg ment, a plant should not be required to prove this fact each time one of these pieces of equipment is added. The addi tion of this type of equipment in con junction with major process equipment, however, is likely to result in both an in crease in emissions as wen as an in crease in production rate, and is there fore covered by the offset provision. If the offset provision were adopted, the reduction in, emissions could be achieved in the production rate of an existing source or sources. The baseline emission rate would be determined based on the maximtm production rate which had been attained by each existing source. The allowable emission rate for each source would be based on the maxi mum production rate at which that source would be operated in the future. Also, if the emissions from an existing source were already below the emission limit applicable to it the proposed amendment would give the source credit for the difference between the emission limit and the actual emission level. That is the baseline emission rate would be based on the standard rather than on an emission test It is EPA'3 judgment that this is a more equitable approach than penalizing a source which has already taken measures to reduce emissions below the standard. Such a source would have less room for further reducing emissions. The mission limits applicable to both the existing and new sources Involved in the offset arrangement would be con tained In the approval of new construc tion granted by the Administrator under 40 CFR 81.08. EPA believes that a policy of no net Increase in missions due to new con struction Is justified because of the haz ardous nature of vinyl chloride. How ever. EPA recognises the potential diffi culties in implementing such a policy and interested persons are urged to sub mit oomments and factual Information relating to this policy. Rrvrxw or Stanhazd EPA plans to undertake a full-scale review of Subpart P of 40 CFR Part 81 beginning three years from the promul gation of any amendments. In the study EPA will review information concerning technological advances in the control of vinyl chloride emissions to determine what further.changes might then be ap propriate to move toward the goal of zero vinyl chloride emissions. EPA will also consider recent health data to de termine whether the approach for regu lating vinyl chloride should be altered. EmmoNumTAi. Impact The proposed amendment, in contrast to the current standard, would encourage the development of new technology andimprovements in existing technology and would have the following three positive environmental impacts: (1) further re duction of emissions at existing plants, (2) no increase in emissions within 8 km of an existing source, and (3) lower emissions from new sources than would be accomplished through the current standard regardless of the construction site. These environmental impacts would provide progress toward the ultimate goal of zero emissions without banning vinyl chloride, and in the process would provide additional protection of public health by further minimizing the health risks to the people living in the vicinity of existing plants and to any additional people who are exposed as a result of new construction. Specifically, for those existing sources which are currently subject to a 10 ppm emission limit, emissions would be re duced by half within three years after the promulgation date of these amend ments. At both an existing average-sized ethylene diehlortde-vlnyl chloride plant and an existing average-sized polyvinyl chloride plant, which contain other sources than the ones required to meet a 5 ppm emission limit it Is estimated this will have the effect of reducing total emissions by less than one percent. Emis sions at existing plants would be further reduced as existing oxychlorination re actors are replaced with new oxychlorinatlon reactors and as new polyvinyl chloride resins are produced to replace existing ones. Under the proposed amendment, emis sions from new plants would be consider ably lower th.n they would be under the current standard. For a typical new average-sized ethylene dlchloride-vinyl chloride plant (318x10* kg/yr or 700 XlQ* lb/yT produced), the hourly emis sions would be 5.1 kg (11.5 lb) instead Of 10.3 kg (23.1 lb). For a tyT'ical new average-sized dispersion polyvinyl chlo ride plant (46x10* kg/yr or 100x10* Ib/yr production), the emissions would be about 9 kg/hr (20 Ib/hr) instead of 17.5 kg/hr (39 lb/hr) and for a typical new average-sized suspension polyvinyl chloride (68x10* kg/yr or 150x10* lb/yr production) the emissions would be 13 5 kg/hr) (30 ib/hr) instead of 16 kg/hr (36 Ib/hr). These emissions are calcu lated based on the emission factors pub lished in the documentation for the ex isting standard. (f) Ambient air concen trations axe expected to be reduced proportionately. The only negative environmental im pact would be an inErease in hydrogen chloride emissions at ethylene dlchlo ride-vinyl chloride plants if incineration were used to control emissions from new oxychlorination reactors. However, due to the corrosion problems which would otherwise occur on plant property and in the community, plants are expected to use scrubbers to control the hydrogen chloride emissions. The proposed amend ment is not expected to have a signifi cant impact on energy consumption. Economic Impact The potential economic impacts of the proposed standard are: (1) Costs for research and develop ment of improved methodology for oper ation of exisL-t-e control technology so that it can be used to meet the 5 ppm emission limit. (2) Costs for research and develop ment of improved stripping techniques to meet the standard for new polyvmyl chloride resins. (3) Cost of research and development or licensing for converting over to the oxygen system for a new oxychlorination reactor. (4) Possibly increased transportation costs of raw materials in the case that the offset policy results in the construc tion of a new plant farther from an existing plant than it otherwise would havq been. (5) Costs of building a new plant more than g tan from an existing plant in the event that the offset requirement pre cluded the expansion of an existing plant. ftoeeat nciufl vdi 43, no. 10*--txussday. jun* 1, 1*77 CMA 004229 PROPOSED RULES 28157 (61 Delay in the production of a par ticular resin due to time spent develop ing stripping technology for that resin. v 71 No growth in the production of a particular resin due to the inability to strip that resin to required levels. (2) "Goodrich Heportx Impressive Progress in Solving Vinyl Chloride Problem." Ameri can Paint and Coarmyi Journal, Vol. 60, No. 31, January 12. 1976. p. 24. (3) . W. Wlmer and H. . Feathers. "Ox ygen Gives Low Cost VCM," Hydrocarbon Procsjnnp, March 1976, pp. 81-84. (a) Vinyl chloride formation and pu rification: Except as provided in 3 61.65(a), the concentration of vinyl chlonde in all exhaust gases discharged to the atmosphere from any equipment used m vinyl chloride formation and/or The types of costs which have been named would be difficult to quantify. The costs would be expected to vary consider (4) Peter Belch, "Air or Oxygen For VCM?," Hydrocarbon Processing, March, 1976. pp. 63-69. purification is not to exceed the appro priate emission limit as follows: (1) Each source, for which construc ably from one plant to another depend It is proposed that Subpart F of 40 tion had commenced on or before June 2. ing on the amount of research and de CFR. Part 61 be amended as follows: 1977, 10 ppm until (date three years af velopment than had already been done, 1. In 61.08, paragraph (b) is revised, ter promulgation of these amendments) the extent to which technology could be to read as follows: and 5 ppm after (date three years after transferred from other plants and proc esses. and the plans for new construction. One area in which cost estimates can be generated is the use of an oxygenrecycle oxychlorination process as op posed to an air-based system. The pro posed amendment does not require the use of the oxygen-recycle system, but many plants would be expected to em ploy this system to avoid the high costs of incinerating the high volume gas stream from a typical air-based system. The primary cost of using the oxygen- 61,08 Approval by the Administrator. V, 88 8 (6 (b) If the Administrator determines that a stationary source for which an application pursuant to 5 61.07 was sub mitted will not, If properly operated, cause emissions in violation of the standard or violation of J 61.73. he will approve the construction or modification of such source. ' * 2. Section 61.62 is revised to read as promulgation of these amendments). (2) Each source for which construc tion- commenced after June 2. 1977, 5 ppm. (b) The requirements of this section do 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. 4.Section 61.64 is amended by revis ing paragraphs (a)(1), (b), (c), (d) and (e) and by adding paragraph (f> as fol* lows: recycle system is the cost of the oxygen follows: , S 61.64 Emission standard for polyvinyl itself. The cost of the oxygen for a par chloride plants. ticular plant would depend on whether 61.62 Emission standard for ethylene diehloride plants. An owner or operator of a polyvinyl the plant was located where there is a considerable demand for both the oxygen and nitrogen products of air separation. According to one recent article, if it is An owner or operator of an ethylene diehloride plant shall comply with the requirements of this section and 5 61.65.' chloride plant shall comply with the re quirements of this section and 3 61.65. (a) Reactor: The following require ments apply to reactors: assumed that such a demand exists, the (a) Ethylene diehloride purification: . (1) Except as provided In paragraph, cost of the oxygen (214.34/ton) would be approximately equivalent to the cost of compressing air for use in the airbased system. (1) Another report in which this assumption was not made and the economics of the air and oxygen sys tems were being compared, it was con cluded that overall production economics "favor the oxygen process even if vent gas incineration would not be required Except as provided in-'J 61.65(a). the, concentration of vinyl chloride In all exhaust gases discharged to the atmos phere from any equipment used In ethylene dichioride purification is not to exceed the appropriate emission limit as follows: - (1) Each source for which construc tion had commenced on or before (date of proposal of these amendments), 10 (a) (2) .of this section and 3 61.65(a), the concentration of vinyl chloride in all ex haust gases discharged to the atmos phere from each reactor is not to exceed the appropriate emission limit as fol lows: (i) Each source for which construction had commenced on or before June 2,1977 10 ppm until (date three years after pro mulgation of these amendments) and 5 for an air-based plant since the sum of all remaining advantages offered by oxygen-based plant operation more than outweighs the incremental cost for the oxygen feed." (2) Miscellaneous: The Administrator in vites comments on all aspects of the pro posed amendments. ppm until (date three years after pro mulgation of these amendments) and 5 ppm after (date three years after the promulgation of these amendments). (2) Each source for which construc tion commenced after June 2, 1977. 5 ppm. (b> Oxychlorinatlon reactor: Except as provided in 3 61.65(a), emissions of ppm after (date three years after pro mulgation of these amendments). (11) Each source for which construc tion commenced after June 2, 1977, S ppm. ***** (b) Stripper: Except as provided in 3 61.65(a), the concentration of vinyl (Section 112 of the Clean Air Act, ho. 4(a) of vinyl chloride to the atmosphere are chloride in all exhaust gases discharged pub. L 81-604. 84 Stat. 1S8S (42 CS C. 1867071 and section 301(a) of the clean Air Act, sec. 2 of Pub. L. No. 80-148, 84 Stat. sot as amended by tec. (16) (c) (2) ot Pub. 1* *1-804. S4 stat. 1713 (42 U.S.C. 1867 g(a)). flees. 61.$7 and 61.68 alto proposed under the au thority of section 114 of the Clean Air Act, at added by aec. 4(a) of Pub. L. B1-S04, 84 Stat. 1687 and amended by Pub. L. 83-312. tec. 6(a)(4), 88 Stat, 290 (43 X7A.C. not to exceed the appropriate emission limit as follows: (1) Each source for which construc tion had commenced on or before (date of proposal of these amendments), 0-2 I/kg (0.0002 lb/lb of the 100 percent ethylene dichloride product from the oxychlortnation reactor. to the atmosphere from each stripper Is not to exceed the appropriate emission limit as follows: (1) Each source for which construc tion had commenced on or before June 2. 1977 10 ppm until (date three years after promulgation of these amend ments) and 5 ppm after (date three years after final promulgation of these 18S7C-B).) (2) Each source for which construc amendments). Note.--The Environmental Protection Agency hat determined that this document tion commenced after June 2. 1977, 5 ppm. (2) Each source for which construction commenced after June 2. 1977. 5 ppm. does not contain a major proposal requiring (c) The requirements of this section (c) Mixing, weighting, and holding preparation of an Economic Impact Analysis under Executive Order* 11831 and 11840 and OMB Circular A^107. do not apply to equipment that has been opened, is out of operation and met the requirement In f 61.65(b) (6) (1) before containers: Except as provided in 3 61.65(a), the concentration at vinyl chlo ride In all exhaust gases discharged to Dated: May 27, 1977. being opened. the atmosphere from each mixing, weigh Douglas M. Costlx, Administrator. Kboskm (1) Standard Support and Environmental Impact Statement: Emtteton Standard for 3. Section 61.63 is revised to read as follows: S 61.63 Emission standard for vinyl chloride plants. An owner or operator of a vinyl chlo ing, or holding container in vinyl chlo ride service which precedes the stripper (or the reactor If the plant has no strip per) In the plant process flow is not to exceed the appropriate emission limit ax follows: vinyl Chloride. EPA-4B0 12-78-608. October, ride plant shall comply with the require (1) Each source, for which construc 1973. ments of this section and 3 61.65. tion had commenced on or before (date XL F8H1AI MGISTfl. VOL 43, NO. 104--TMUXSOAT, JUNf 2, 1877 or CMA 004230 2S1S8 PROPOSED RULES oT proposal at thene amendments), -10 resin ah of which had been produced by od of measurement Is to meet the re ppm until (date three years alter pro the plant on or before June 2, 1977: quirements in 5 61.67(g) (3) (J) (A) or mulgation at these amendments) and 5 (A) 2 g/kg (0.003 lb/Xb> product from (g) (5) (1) CB). ppm alter (date three years alter pro the stripper(j) tor reactor(s) If the 6. m ; 61.67, paragraph (a) Is revised mulgation at these amendments). plant has no strlpper(s) ] for dispersion to read as follows: (2) Each source tor which construc tion commenced alter dune 2. 1077, 5 polyvinyl chloride resins, excluding latex reams, with the product determined on 61.67 Eumnita!i, ppm. a dry soLids basis; (a) Unless a waiver of emission test <d) Monomer recovery system. Except (B) 0.4 g/kg (0.004 lb/lb) product ing Is obtained under { 81.13. the owner as provided In 9 61-65<a), the concentra from the stripper CD (or reactor(s) if or operator of a source to which tion at vinyl chloride in all exhaust gases the plant has no stripper(s)) for all subpart applies shall test emissions discharged to the atmosphere Irom *anh other polyvinyl chloride resins, including from the source as follows: monomer recovery system Is not to ex latex resins, with the product deter (1) For an existing source or a new ceed the appropriate concentration as mined on a dry solids basis. source which has an Initial startup date follows: <H> For sources being used to process preceding October 21,1976: (1) Each source for which construc any grade of polyvinyl chloride resin not (1) Within 90 days following October tion had commenced on or before (date produced by the plant on or before June 21, 1976, and of proposal ol these amendments), 10 2. 1977: (ID For those sources subject to ppm until (date three years alter pro (A3 0.5 g/kg (0.0905 Ib/lb) product 1161.62(a); 61.63(a); 61.64 (a)(1), (b), mulgation ol these amendments) and & from the stripper<s) (or reactor(s) If the (c). and (d); and/or 8i-65<b)(i)! (b)' ppm alter (date three years alter pro plant 1ms no strlpper(s)) for dispersion (2), (b)(3), (b)(5), (b)(6), and/or (b> mulgation ol these amendments). polyvinyl chloride resins, excluding la (9), within 90 days following (date three (2) Each source lor which construc tex resins, with the product determined years after the promulgation date of tion commenced alter June 2, 1977, b on a dry solids basis; these amendments). ppnj. (B) 0.1 g/kg. (0.0001 Ib/lb) product (2) For a new source lor which initial (e) Sources following the stripper(a) : from the strippers (or reactor(s) if the startup occurs after October 21. 1976, The following requirements apply to plant has no stripper(s)) for all other within 90 days of startup. emissions ol vinyl chloride to the atmos phere from the combination of aQ sources following the stripper(s) for the reactor(s) If the plant has no stripper} polyvinyl chloride resins, Including latex rosins, with the product deter mined on a dry solids basis. (f) The requirements of paragraphs ** * 7. In S 61.68. paragraph (c) is revised to read as follows: In the plant process flow Including, bat <t>). (cl, and (d) of this section do not 61.68 Enuatn monitoring. not limited, to centrifuges, concentra apply to equipment that has been v* * -- tors. blend tanks. Alters, dryers, conveyor air discharges, baggers, storage con tainers. and lnproceas wastewater. in(1) polyvinyl chloride plants Using stripping technology to control vinyl chloride emissions: (0 For a grade or grades of polyvinyl chloride resin which have been produced by the plant on or before June 2, 1977, the weighted average residual vinyl chloride concentration In all the grades processed through the stripping opera tion on each calendar day, measured im mediately after the stripping operation fa completed, may not exceed the appro priate emission limit as follows: (A) 2,000 ppm for polyvinyl chloride dispersion resins, excluding latex resins; (B) 400 ppm for all other polyvinyl chloride resins. Including latex rmins. averaged separately few each type of resin; opened, is out of operation, and met the requirement In 9 61.65(b) (8) O) before being opmed. 5. Section 61.55 Is amended as follows: A. By replacing the phrase "10 ppm" with the phrase "the appropriate emis sion limit specified in 9 91.65(c)" In paragraphs (b)(1)(H), (b)(2), (b)(3) (D. (b)(3) (ID. (b)(3) (ill), (b) (3) (Iv), (b) (3) (v). (b)(5), (b> (6)Ui), and (b) (9) (ID; B. By revising paragraph (c) and add ing paragraph (d) as set forth below. $ 61.65 Emission standard for ethylate fKkbnde, vinyl chloride, snd poly vinyl chloride plants. ** (e) The emission limit which Is not to be exceeded Is as follows: (1) Each source, tor which construction had oomnuwtMi on or briore June 2, 1977. 10 (c) A dally span check Is to be con ducted for each vinyl chloride monitor ing system used. For all of the sources listed In paragraph (a) of this section, except for the one for which an emission Hmlt Is prescribed In 9 61.62(b) (1), the dally span check Is to be conducted with a concentration of vinyl chloride equal to the concentration emission limit appli cable to It. For a source subject to the emission limit prescribed In 161.62(b) (1), the dally span check is to be con ducted with a concentration of vinyl chloride which Is determined to be equivalent to the emission limit for that source based on the emission test re quired by 9 6L67. The calibration is to be done with either. * * i 8. A new 9 61.72 is added to read as follows: (U) For a grade or grades of polyvinyl ppm until (date three years after pro 61.72 RiqiH.il for Interim emimtoo chloride resin which have not been pro mulgation of these amendments) and limit. duced by the plant on or beftwe June 2, 1977. the weighted average residual vinyl chloride concentration in aQ the grades processed through the stripping operation on each calendar day, meas ured Immediately after the stripping op eration Is completed. may not exceed the appropriate emiwlon limit as follows: (A) 500 ppm for polyvinyl chloride dispersion resins, excluding latex resins; 5 ppm after (date three years after pro mulgation of these . (2) Bach stance for which construc tion emnmeneed after June 2, 1977, 5 ppm. (d> The requirements in paragraphs (b)(1), (b)(3), (b)(5), (b)(6), (b)(7) anti (b) (6) of this section are to be in corporated Into a standard operating procedure, and made available upon re , (a) If In the opinion of the owner or operator of an existing source, that source will be unable to comply with the 5 ppm emission limit in 99 61.62(a) (1); 61.63(a)(1); 61.64 (a) (1) (1), (b)(1), (c)(1), (d)(1); and/or 61.65(c)(1) on or before (date three years after pro mulgation at these amendments). the owner or operator of that source may re quest that the Adminstrator approve an CB) 100 ppm for all other polyvinyl quest for Inspection hy the Administra toterim limit for that source. chloride resins. Including latex resins, tor. The standard operating procedure The request is to be In writing and Is to averaged separately for each type of Is to wiehide provisions for measuring be submitted to the Administrator within resin; or the vinyl in equipment --4.75 six months prior to (date two years after (2) In polyvinyl chloride plants con m* (1290 gal) in volume for which an promulgation of these amendments). trolling vinyl chloride nHMinn with emission limit Is prescribed In 161.65 The request is to Include: t*,-htiningy other than stripping or In (b)(6) (1) prior to opening the equip (1) The reasons the source Is In addition to stripping: ment using Test Method 106, a port capable of being in compliance with the (1) For sources being used to process able hydrocarbon detector, or an equiv 5 ppm emission Hmlt and data to support a grade or fivdcs of polyvinyl chloride alent or alternative Mthn) The meth those reasons, and wmii USISTH, VOL. 42, MQ. 104--TWMSOAY, JtMI 2. 1477 PROPOSED RULES 28159 (21 A suggested Interim emission limit and description ol the methodology for attaining that limit.(b) Any owner or operator of a source uho has submitted to the Administrator a written request for an interim emis sion limit in accorcance with 5 61.72(a), (f) The emission limits applicable to both the new source(s) and the source(s) at which emissions are being reduced to balance the increase in emissions due to the new construction are to be estab lished by the Administrator In the ap proval for construction required by shall within 60 days of the date of the 5 61.08. written request meet with the Admin (Secs. 112 and 301(a) of the Clean Air Act. istrator concerning the information con sec. 4(a) of Pub. L. No. 91-604, 84 Stat. 16S3: tained in the request. The meeting is to *C. 2 of Pub. L. NO. 90-148. 81 stat. S04 (43 be open to interested persons, who are to be allowed to submit oral or written testimony relevant to compliance of the source. (c) The Administrator will within 120 Uh.C, 185SO-7, 1837g(a)), Seca. 81.67 and 61.68 also lwued under sec, 114 of the Clean Air Act, aec 4(a) of Pub. L, No. 91-604, 84 Stat. 1687 (42 Uh.C. 1867c-*).) (PH Doc.77-16672 FUed 6-1-77:8:46 am] days of receipt of the written request required by paragraph (a) of this sec DEPARTMENT OF HEALTH, tion, notify the owner or operator In writing of approval or denial of approval of an Interim emission limit. EDUCATION, AND WELFARE Office of Education (d) If an Interim emission limit Is ap [45 CFR Parts 163 and 163a ] proved the notification Is to Include the level of the Interim emission limit, which may be the level requested or a more stringent one. CAREER EDUCATION AND CAREER DEVELOPMENT Addition of Programs (e) A determination to deny approval AGENCY: Office of Education, HEW. Of an interim emission limit is to set forth the specific grounds on which such ACTION: Proposed rule. denial is based. SUMMARY: The Commissioner of Edu (f) Approval for any Interim emission cation. with "the approval of the Secre Timit granted for any source under tary of Health. Education, and Welfare, S 61.72(c) shall expire three years from proposes to add two new career educa the date of Issuance. The owner or op tion programs as enacted by the Educa erator may request an extension of ap tion Amendments of 1976. Part 163 con proval for an interim emission limit or a tains provisions for a new one-year pro lower Interim emission limit. The re gram at financial assistance to States and quest Is to be In writing, is to be sub other allottees for Fiscal Year 1978 to mitted within six months prior to a year plan for the improvement and develop before the expiration date and is to in ment at career education and career de clude the information listed in i 61.72 velopment programs and activities for (b), (c), (d). and (e) are to apply. individuals of all ages. Part 163a con 9. A new ] 61.73 Is added to read as tains provisions for the Commissioner of follows: Education to conduct a number of career 61.73 Offset of tmiMiona doe to new construction* . (a) No owner' or operator Is to con information activities during Fiscal Year 1978, including the collection, analysis, and dissemination of Information per taining to career trends and options in struct a new source which alone or In the United States as well as exemplary combination with other sources being materials from the career education constructed at the same time results in Add. Both these programs are new au an increased production rate unless he thorizations for which no funding has demonstrates to the Administrator's sat been requested by the Administration. isfaction that such construction will not cause an Increase in vinyl chloride emis sions within 8 Ion of any other source DATES: Comments must be received on or before July 5,1977. which is subject to this subpart. ADDRESSES: Comments should be ad (b) Reduction in production rate is dressed to Sidney High. US. Office of an allowable mechanism for attaining an Education. 7th and D Streets, S.W., offset in emissions. -- Room 3108-A. Washington, D.C. 20203. (c) The baseline emission rate is to be determined based on the level of emis sions allowable by the standard. (d) Reducing emissions from an in FOR FURTHER INFORMATION CON TACT: Sidney High. 202-248-3331. terim emission limit to the standard for a source is not an acceptable means Of achieving an emission offset. (e) In the application for approval of construction required by f 61.07, owners' SUPPLEMENTARY INFORMATION: (a) Organization. Part .183 (sections 331-334 of Pub. L. 94--482), as set forth in this proposed rule, contains those pro visions which are applicable to the pro or operators of sources subject to this gram of Federal assistance to States and subpart shall'include, in addition to the other allottees to enable them to plan for information required by t 61.07, the fol the development of career education and lowing Information: ...... career development programs. The as (1) The name, address, and location sistance provided under this Part is also of any plant subject to this subpart subject to the applicable provisions con which is located within 8 km of the pro tained in the Otnce ol Education General posed location of the source to be con Provisions Regulations published in 45 structed. CFR Farts 100 and 100b (38 FR 30664, November 6. 1973). Part 163a (section 335 of Pub. L. 94--482) contains those provisions applicable to the program of collection, analysis, and dissemination by the Commissioner of career informa tion and exemplary materials. To the ex tent the Commissioner proceeds by con tract, as authorized by section 335 of Pub. L. 94--482, the program will also be gov erned by the applicable provisions of the Federal Procurement Regulations. 41 CFR Chapters 1 and 3. To the extent the Commissioner proceeds by grant, the ap plicable provisions of 45 CFR Part 100a- (38 FR 30662. November 6, 1973) will apply. (b) Comments and responses. In the Notice of Intent to Issue Regulations (published in 41 FR 51550 on November 22, 1976) the Commissioner requested public comment on a number of specific issues in addition to Inviting expressions of public sentiment on any issue consid ered worthy of comment. In the thirty days afforded Interested persons in which to make their views known, 64 State and national organizations, associations, and agencies and 3 individuals submitted comments. The comments on the specific Issues listed In the Notice of Intent are summarized below: (1) Given the apparent overlap be tween the planning authorities contained In section 406(f) (2) of Pub. L. 93-380 and sections 331-34 of Pub. L. 94-482, how can the latter program be designed to avoid duplication of the former pro gram? (a) Should planning under sec tions 331-34 focus on career education for individuals beyond the secondary school level? (b) Should States be re quired to explain the relationship be tween activities carried out and proposed Under the two authorities? The commented were overwhelmingly supportive of the view that duplication of activities conducted under-both au thorities (Pub. L. 93-380 and Pub. I*. 94- 482) should be as limited as passible. They clearly thought the regulation should require a careful explanation of the relationship between these two plan ning efforts. It was suggested that plan ning activities conducted pursuant to Pub. L. 94--482 might properly extend and augment the planning already begun under Pub. L. 93-380. It was also noted by several commenters that State plan ning already being conducted under Title I and Title X of the Higher Education Act of 1965 (20 U.S.C. 1001 etseq.) should also be coordinated with planning efforts conducted pursuant to Pub. L. 94-482 be cause those titles deal with the continu ing education of adults and. therefore, are closely related to the concept of career education for individuals of all ages. The. proposed- ] 163.6(b) attempts to avoid duplication by requiring the allottee to explain the relationship be tween planning activities carried out un der Pub. L. 93-380 and proposed Under Pub. h. 94-482 in the event that the plan ning is addressed to the same age groups. - On the related question of priorities between K-12 and postsecondary plan ning, while the majority of commenters Identified the need for cooperation be- mm*L *kmstm, voc 42, no. ios--wuesoAr, juni 2, 1*77 i tt CMA 004232 APPENDIX 5 ARB Nfciiod VINYL CHLORIDE IN AIR Crcanics Evaluation Section Analytical Method1 2 3 Analyte: Matrix: Procedure: Vinyl Chloride (VCM, Chloroethe.no) Ai r Collection in Tedlar bag, Gas Chromatography Date: Range: 3/13/78 0.001 to ICO PPn by volume per injection 1. Principle of the Method 1.1 Air is sampled into a Tedlar bag at a constant rate during selected time intervals fcy means of an automatic sampler. 1.2 A portion of the air sample is transferred via syringe to the heated volumetric sample loop of the gas chrorru .ograph. 1.3 The sample is introduced into the chromatograph by means of a gas sampling valve. 1.4 The GC data system quantitates the VCM by integrating the peak area ar.d calculating concentration from a factor determined during calibration with a VCM standard. 2. Range and Sensitivity 2.1 The minimum measurable concentration of vinyl chloride mono: r was determined to be 0.010 ppm = 0.02 ng./cnr using the prescribed instrument conditions and a 1 cm3 sampling loop. 2.2 The minimum measurable concentration of vinyl chloride monomer was determined to be less than 0.001 ppm = 0.002 ng/cr.3 using the prescribed instrument conditions and pre-concentrating by freezing a 100 ml. sample. 2.3 The minimum detectable amount of VCM was determined to be less than one fifth the concentrations indicated in sections 2.1 and 2.2. 3. Interferences 3.1 Any organic comDound present in the sample having a retention time very similar to that of VCM under the operating conditions described in this method is an interference. Therefore, prof of chemical identity requires confirmation by other means. CMA 004233 3.2 If a particular interfering compound is thought likely to bo present, new chromatcgrspnic parameters must oa chosen so as co resolve the VCM peak from the interfering peak. 3.3 Water vapor in the sample does not interfere with the separation and and quantification of VCM. Calibration, precision and accuracy. 4.1 The calibration procedure employed follows closely the concepts and principles set forth in the "Quality Assurance Handbook for Air Pollution Measurement Systems" (U.S. Environmental Protection Agency, 1976). It includes periodic Pulticomponent calibrations, linearity checks, and frequent zero-span checks, it also includes a calculation of the confidence interval as a measure of precision for any given sample concentration. 4.2 Multicomponent Calibration: Several authors have described the linearity of flame ionization detectors (see Purnell, 1562, and references cited). This linearity extends over seven orders of magnitude at the milligram level. Therefore, we use standard reference materials and standard reference samples which bracket the anticipated range of pollutant concentrations. Four independent determ,inations of the instrument response are made at both a high and a low reference concentration. An additional two independent determinations are made at two midrange reference concen trations to check the linearity of the instrument. 4.3 Linearity Check: The calibration data are fitted to a straight line, Y = a + bX, by Lhc- method of least squares (see Bennett and Franklin, 1954). The response, Y, is expressed as a function of the concentration, X. An analysis of variance table is constructed from the regression data (see Draper and Smith, 1966). The mean-square error due to lack of fit about the regression line is compared to the total mean-square error of the independent replicates about their individual means. The calibration is accepted if the F-ratio is less than the 95% rejection limit. 4.4 Confidence Intervals: The variance of the concentration corresponding to a given instrument reponse (or average response of il repeated measures) is estimated by the method of Bennett and Franklin (1954). The 9551 confidence intervals are obtained by multiplying the square root of t.iis variance by the appropriate value of 1t` from the :t' table. 4.5 Sample Calibration: A sample multipoint calibration including linearity check and confidence intervals is given in the appendix. 4.6 Zero-Span Checks The laboratory data system monitors the detector zero continuously after the instrument baseline has been established. A span check is made each day at the high reference concentration to verify that the instrument is responding accurately. CMA 004234 4.7 References: Bennett, C. A. and Franklin, N. L. (1954), "Statistical Analysis in Chemistry and the Chemical Industry," John Wiley & Sons, Inc., Nev: York, up 222-232. Draper, N. R. and Smith, H. (1966), "Applied Regression Analysis," John Wiley & Sons, Inc., New York, p. 30. Purnell, H. (1962), "Gas Chromatography," John Wiley & Sons, Inc., flew York, pp. 301-302. U. S. Environmental Protection Agency (1976), "Quality Assurance Handbook for Air Pollution Measurement Systems, Volume I - Principles," EPA600/9-76-005 Environmental Monitoring and Support Laboratory, Research Triangle Park, North Carolina 27711. 5. Advantages and Disadvantage of the Method 5.1 The air sampling equipment is easily set-up and involves no liquids. The concentration of vinyl chloride monomer in the range of interest is stable for at least one v.eek in the Tedlar sampling bags, provided that no ozone is present. Ozone removal is assured by adding small amounts of nitric oxide to the bag prior to sampling. 5.2 The sample is easily and repeatably introduced into the instrument by means of a volumetric gas sampling valve. 5.3 A representative composite sample is readily obtained for any selected time interval, because the equipment samples at a constant rate. 5.4 The lower concentration limit of the analysis may be extended by concentrating the sample further by freezing out a larger volume. The precision of the analysis at low concentrations is considerably enahanced by this technique. 5.5 Chromatographic conditions can be readily selected so that interferences are eliminated and so that the analysis time is minimized. 6. Apparatus 6.1 A sampler consisting of a diaphragm pump, a flow metering valve, fittings and tubing to convey air samples to sample bags, timers, solenoid valves and associated electrical circuitry to control filling of the sample bags, all compactly mounted on a metal chassis operating on 110 VAC. 6.2 Tedlar bags, nominally of 30 to 100 liter capacity, equipped with quickconnect fittings. 423s 6.3 A QjS chromatograph equipped with a gas sampling valve or freeze-out inlet system and flame ionization detector. 6.4 A stainless steel colurn (2 meters \ 1/S in.) pacled with 0.19/ Picric Acid on SO/1 CO mash Carbooak C, or otner column caosble of resolving VCM from other organics with, simil t physical/retenticn properties. 6.5 An analog recorder and means to quantitate peak areas. 6.6 100 ml ground glass syringes or other suitable devices to transfer ai r samples from Tedlar bags to sample inlet of the G.C. 7. Reagents 7.1 Vinyl chloride reference standard, 0.70 ppm in N2 (Katheson, or equivalent) 7.2 Helium, 99.995/ 7.3 Hydrogen, 99.995% 7.4 Oxygen, 99.6% 8. Procedure 8.1 Preparation of bags: All bags are filled with nitrogen and inspected for leaks. Bags are pumped empty prior to use, refilled with pure N? and tested for absence of vinyl chloride. 8.2 Preparation of sampling device: Metering valves are adjusted to secur appropriate air sampling rates, as determined by rotometer. 'Timers ar set so that air will be sampled for desired time intervals. The sampler is set up in sampling location, and empty sample bags are labeled and connected to the sampler. 8.3 Transport of bags to laboratory: Filled bags are protected from exposure to direct sunlight while being transported to the laboratory. Care is exercised not to puncture the plastic. 8.4 Samples received at the laboratory are logged in and placed on storage racks. 8.5 Analysis of Samples (loop method). 8.5.1 Introduction of sample into gas chromatograph: Air is transferred from the air sample bag to the sample loop of the gas chromatograph by means of a clean 100 ml syringe fitted with Luer-lok to quick-connect adapter. 8.5.2 The gas samp! ing valve (rotary type) is equipped with 1 ml. loop. Other loop sizes may be used. CMA 004236 OJ <u 8.5.3 G. C. conditions: With the suggested n-cctane/Porasil C column typical operating conditions for the gas chromatograph arc: 1. 25 ml./min helium carrier gas flow. 2. 30 ml./min hydrogen gas flow to detector 3. 300 ml./min oxygen flow to detector 4. 83C sample valve temperature 5. 125C detector temperature 6. 60C isothermal column temperature 8.5.4 Measurement of concentration: Concentrations of VCM rry be calculated by a Varian CDS 111 chromatographic data system or by any other suitable integration device. 8.6 Analysis of Samples (Freeze-out method) 8.6.1 Freeze-out/Injection: 1. Immerse the sample loop in liquid nitrogen and allow the temperature to stabilize. 2. After discarding about 50 ml of the sample, withdraw exactly 100 cc from the sample bag with a 100 ml. syringe. 3. Add about 5-10 ml. Helium to the syringe and transfer the sample into the loop. 4. Back fill the syringe with another 20 cc of Helium and flush the 20 cc through the loop; then flush Helium through the loop for 3 minutes. 5. Isolate the trap by using an "isolation valve." 6. Replace the LN2 Dewar with a Dewar containing hot water at about 80C. 7. Allow all the ice to melt from the trap. CMA 004237 8. Inject the sample into the carrier gas stream. 8.6.2 Measurement of area: The area of the sample peal is measured by any suitable integration device. 8.6.3 The instrument operating conditions are similar to those describee in section 8.5.3 above. Calibration and Standards CAUTION: Laboratory operations ir.volvino carcinogens Because vinyl chloride has been identified as a human carcinogen, observe appropriate precautions when handling this gas. The OSHA regulations pertaining to the use and handling of vinyl chloride may be found in 29 CFR 1910.S3q fSection 1910.93q in Title 29 of the Code of Federal Regulations available in the Federal Regi ster, Vol. 39, No. 194, Friday, October 4, 1974, pp 9.1 A commercially prepared and certified reference standard containing approximately 1 ppm vinyl chloride in nitrogen is used to calibrate ti.e instrument. 9.2 The concentration of vinyl chloride in nitrogen referred to in 2.1 above is certified (or corrected) by the National Bureau of Standards, Washington, O.C. 9.3 Additional standards of lower concentrations of VCM in nitrogen are prepared at one half, one tenth, one hundredth and one thousandth the label value. At least two sets of standards with not less than three independent analyses are performed on each instrument to create multipoint calibrations and to perform zero-span checks. Calculations. 10.1 The Vinyl Chloride Monomer (VCM) concentration, in ppm, is calculated by the CDS 111 data system using the external standard method Concentration-j * Areai x Calibration Factor CMA 004238 10.2 The calibration factor (CF) is calculated during calibration by the equation CF = C0nc Area Replicate calibrations are averaged and the arithmetic mean is stored 10.3 as the CF to be used in subsequent analyses. Concentrations may be converted from ppm to mg/m3 by means of the folio ing formula P (62.5) (ppm) (103) mg/m3 = ng/cm3 (82.o7j * f where P = pressure in atmospheres 62,5 = molecular weight of vinyl chloride 82.07 = gas constant in cm3 atm./deg. mole T = absolute temperature (K) The concentration unit of mg/m3 is equivalent to ng/cm3. 11. Additional references Hill, R. H., C. S. McCaimor, A. T. Saalwaechter, A. W. Teass, and W. J. Woodfin, "Determination of Vinyl Chloride in Air," in preparation. White, L. D., D. G. Taylor, P. A. Mauer, and R. E. Kupel, "A Convenient Optimized Method for the Analysis of Selected Solvent Vapors in the Industrial Atmosphere," Am. Ind. Hyg. Assn. J., 31, 225 (1970). CMA 004239 APPENDIX 6 GLOSSARY Terms used in the NESHAP regulation for vinyl chloride are defind as follows.* (a) "Ethvlene dichloride plant" includes any plant which produces ethylene dichloride by reaction of oxygen and hydrogen chloride with ethylene. (b) "Vinyl chloride plant" includes any plant which produces vinyl chloride by any process. (c) "Polyvinyl chloride plant" includes any plant where vinyl chloride alone or 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 discharges. (e) "Type of resin" means the broad classification of resin referring to the basic manufacturing process for producing that resin, including, but not limited to, the suspension, dispersion, latex, bulk, and solution processes. (f) "Grade of resin" means the subdivision of resin classification which describes it as a unique resin, i.e., the most exact description of a resin with no further subdivision. (g) "Dispersion resin" means a resin manufactured in such a way as to form fluid dispersions when dispersed in a plasticizer or plasticizer/ diluent mixtures. (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. (j) "Inprocess wastewater" means any water which, during manufacturing or processing, comes into direct contact with vinyl chloride or polyvinyl chloride or results from the production or use of any raw material, intermediate,product finished product, by-product, or waste product containing vinyl chloride or polyvinyl chloride but which has not been discharged to a wastewater treatment process or discharged untreated as wastewater. *Federal Register, Volume 42, page 29006, and Volume 40, page 59544 and 59545. CMA 004240 GLOSSARY (continued) (k) "Wastewater treatment process" includes any process which modifies characteristics such as BOD, COD, TSS, and pH, usually for the purpose of meeting 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. (l) "In vinyl chloride service" means that a piece of equipment contains 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) "Vinyl chloride detector" means a device which obtains air samples from one or more points on a continuous sequential basis and analyzes the samples with gas chromatography or, if the owner or operator assumes that all hydrocarbons measured are vinyl chloride, with infrared spectro photometry, flame ion detection, or an equivalent Or alternative method. (n) "Portable hydrocarbon detector" means a device which measures hydrocarbons with a sensitivity of at least 5 ppm and is of such design and size that it can be used to measure emissions from localized points. (o) "Standard operating procedure" means a formal written procedure officially adopted by the plant owner or operator and available on a routine basis to those persons responsible for carrying out the procedure. (p) "Run" means the net period of time during which an emission sample is collected. (q) "Ethylene dichloride purification" includes any part of the process of ethylene dichloride production which follows ethylene dichloride formation and in which finished ethylene dichloride is produced. (r) "Vinyl chloride purification" includes any part of the process of vinyl chloride production which follows vinyl chloride formation and in which finished vinyl chloride is produced. (s) "Reactor" includes any vessel in which vinyl chloride is partially or totally polymerized into polyvinyl chloride. (t) "Reactor opening loss" means the emissions of vinyl chloride occurring when a reactor is vented to the atmosphere for any purpose other than an emergency relief discharge as defined in 61.65(a). (u) "Stripper" includes any vessel in which residual vinyl cloride is removed from polyvinyl chloride resin, except bulk resin, in the slurry form by the use of heat and/or vacuum. In the case of bulk resin, stripper includes any vessel which is used to remove residual vinyl chloride from polyvinyl chloride resin imnediately following the polymerization step in the plant process flow. CMA 004241 GLOSSARY (continued) (v) "Standard temperature" means a temperature of 20 C (69 F). (w) "Standard pressure" means a pressure of 760 mm of Hg (29.92 in. of Hg). (x) "Oxychlorination" is a process for the production of ethylene dichloride which is made by the reaction of air and hydrogen chloride with ethylene in a catalytic process.** ** Defined by ARB staff. CMA 004242 APPENDIX 7 EFFECTS OF AIRBORNE VINYL CHLORIDE Air Resources Board Staff Report 78-1-1 Available upon request from the Air Resources Board CMA 004243 APPENDIX 8 State of California AIR RESOURCES BOARD NOTICE OF PUBLIC HEARING TO CONSIDER ESTABLISHMENT OF STATE AMBIENT AIR QUALITY STANDARDS AND/OR SIGNIFICANT HARM LEVELS FOR VINYL CHLORIDE NOTICE IS HEREBY GIVEN that the Air Resources Board, pursuant to the authority vested by Section 39601 of the Health and Safety Code, and to implement, interpret or make specific Sections 39606(b) and 41700 of the Health and Safety Code, will conduct a public hearing, at the time and place specified below, to consider the establishment of one or more state ambient air quality standards or significant harm levels (levels never to be exceeded) for vinyl chloride. On January 25, 1978, the Board received a status report from its staff and comments from interested persons on this item. As a result of information received on January 25 and subsequent thereto, the Board is proposing to take one or more of the following actions with respect to vinyl chloride air pollution: -- Pursue enforcement of the emission regulations for vinly chloride monomer and related substances promulgated by the Environmental Protection Agency (EPA) on October 21, 1976 pursuant to Section 112 of the Clean Air Act [National Emission Standards for Hazardous Air Pollutants (NESHAPS)], and defer further state regulatory action until the NESHAPS emission regulations are fully implemented in October 197-8. -- Pursue enforcement of the NESHAPS emission regulations for vinyl chloride and related substances and adopt a state ambient air quality standard or standards for vinyl chloride or designate a Significant Harm Level or Levels for vinyl chloride on the basis of existing scientific evidence. The ambient air quality standard would be attained or exceedances of the Significant Harm level(s) would be prevented by means of rules to be adopted subsequently by the South Coast Air Quality Management District (SCAQMD). These rules could be enforced, for example, by an air measurement program that includes con tinuous or frequent intermittent monitoring of vinyl chloride levels at the boundary line of vinyl chloride facilities to be conducted by the operators of such facilities, and/or by specific emission limitations. If the action taken is to set a Significant Harm Level, enforcement under Health and Safety Code Section 41700 could also be taken, through district permit requirements and/or legal action before a court of competent juris diction. The Board requests evidence and testimony relating to the effects of vinyl chloride exposures on health, illness, and irritation to the senses. The Board also seeks information relating to the appropriateness of a 24-hour or other averaging period, and appropriate test methods. Staff analysis of comments received during and subsequent to the January 25, 1978 Board meeting will be presented. CMA 004244 2- - If one or more new state ambient air quality standards and/or Significant Harm Levels for vinyl chloride are established, the Board will make appropriate amendments to its regulations in Section 70200, Title 17, California Administra tive Code, relating to ambient air quality standards. The time and place for public hearing on this matter are as follows: DATE: April 27, 1978 TIME 10:00 a.m. PLACE: Crystal Ballroom Hotel San Franciscan 1231 Market Street San Francisco, CA Copies of the staff report on this matter will be available for inspection at, or may be obtained from, the headquarters office of the Air Resources Board, 1102 Q Street (P.0. Box 2815), Sacramento, California 95812, Attention: Public Information Office, at least 30 days prior to the scheduled hearing date. All documents reviewed by the staff in connection with its consideration of the issues in the staff report, together with written comnents received from interested persons, if any, will also be available for inspection and copying. NOTICE IS FURTHER GIVEN that any interested person may present oral or written statements at the public hearing referred to above. The Board requests that interested persons who have written statements on this matter submit 10 copies of the same at least seven days prior to the scheduled hearing date in order to provide adequate time for staff analysis and comnent, and to allow early review by the Board. Interested persons are further advised that the Chairman may require oral testimony to be limited in scope or duration; however, all persons will be allowed at least five minutes for presentation of oral testimony. Following com pletion of the public hearing, the Air Resources Board, on its own motion or at the instance of any interested person, may establish one or more ambient air quality standards and/or Significant Harm Levels for vinyl chloride. The Air Resources Board has determined that this action creates no additional cost to local government pursuant to Section 2231 of the Revenue and Taxation Code. March 22, 1978 William H. Lewis, J Executive Officer CMA 004245