Document KEgvbD0q0yjMqoNmxNYKDDy2

Vo ^ V Ob U. tv iMjr <u/ O'-'. .I oL. /Q 3&1G0 Federal Register / Vol. 47, No. 173 / Tuesdnv. September 7. I'tflL' / Rules ;tin! Rev'iLi (ions MMU'l'U). liri.iuse the strategy is based on these ,issiuu|ilions. a change in either of them would inquire the sliutegv to be reexamined to assure that the NAAQS remain protected Subsequent to EPA's conditional approval of the hake County SOa plan. NII'SCO informed F.PA on April 26. 1982. that the stack height increase for NIPSCO's Mitchell Station could conflict with Federal Aviation Administration Regulations (14 CFR Part 77) and the City of Gary Zoning Ordinances. EPA has examined the potential for conflict and rescinds its approval of the stack height increase at .Mitchell Station. EPA's action on the stack height does not affect its approval of Mitchell Station's 1.2 lbs/MMBTU emission limitation. EPA's March 12.1982 conditional approval of the Lake County strategy is based on the requirement that the State submit additional data: including a determination that the 24-hour strategy is constraining, a justification of the background level, a revised emission inventory, and an adequate receptor network. Additionally, if in the State's analysis of these additional data the State determines that change in its regulations are necessary, the State has committed itself to revise its regulations and submit them to EPA as a revision to the SIP. Indiana has informed EPA that Lake County currently is being reanalyzed to meet the above conditions. Because the present Mitchell Station stack height may require changes in the Lake County strategy, EPA is adding a condition to its previous conditional approval of the Lake County strategy that the State must address the Mitchell Station stack height in its revised analysis of Lake County. EPA proposed on March 12.1982 that the Lake County reanalysis is due by November 1982. This proposal is still applicable, and EPA will take final action on the date by which the conditions must be fulfilled in a future Federal Register notice. For a discussion of conditional approvals and their practical effect, see 44 FR 38583 (July 2. 1979) and 43 FR 87182 (November 23. 1979). Because EPA considers today's action noncontroversial. we are approving it today without prior proposal. The action will become effective 60 days from the date of this notice. However, if we receive notice by 30 days from the date of this notice that someone wishes to submit critical comments, then EPA will publish a notice that (1) withdraws EPA's final action and (2) begins a new rulemaking by proposing the action and establishing a comment period. Under 5 U.S.C. 6051b). the Administrator has certified that SIP approvals do not have a significant economic impact on a substantial number of small entities (See 4b FR 8709). Under Executive Order 12291. todal s action is not "Ma)or". It has been submitted to the Office of Management and Budget (OMB) for review. Under Section 307(b)(1) of the Act. petitions for judicial review of thts action must be filed in the United States Court of Appeals for the appropriate circuit within 60 days of today. This action may not be challenged later in proceedings to enforce its requirements. (See sec. 307(b)(2).) List of Subjects in 40 CFR Part 52 Air pollution control. Ozone. Sulfur oxides. Nitrogen dioxide. Lead. Particulate matter. Carbon monoxide. Hydrocarbons. Intergovernmental relations. Note.--Incorporation by reference of the State Implementation Plan for the State of Indiana was approved by the Director of the Federal Register on |uly 1.1982. (Sec. 110 and 172 of the Clean Air Act. as amended (42 U.S.C. 7410 and 7502)) Dated: August 24.1982. John W. Hernandez, Jr., Acting Administrator. PART 52--APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS Indiana Title 40 of the Code of Federal Regulations. Chapter I. Part 52 is / amended as follows: \f 1. Section 52.770 is amended by ' revising paragraph (c)(19) as follows: $ 52.770 Identification of plan. ***** (c)* ` * (19) On June 28.1979. the Governor submitted a revised sulfur dioxide strategy, including regulation APC 13 with appendix, which was promulgated by the State on June 19,1979 for all areas of the State. This included the Part D sulfur dioxide regulations for Lake. LaPorte. and Marion Counties. On August 27. I960 and July 16.1981 the State committed itself to correct conditionally approved items within their strategy. On October 6.1980. the State submitted a recodified version of APC 13 which was promulgated by the State on August 27.1980. This included 325 IAC 7. 325 IAC 1.1-6. 325 JAC 1.1-72 and 4. 325 IAC 12-5-1 and 2(a). 325 IAC 12-9-1 and 4. and 325 IAC 12-18-1 and 2. EPA is not taking action on: (1) 325 IAC 7 as it applies to Floyd and Vigo Counties. |2|Jhe .'to-d.iv iser.n.'ine compliant.!' mi'lhod conl.mied in l.:_i IAC 7-1-3. ami (3) llic Mill.hell Slalinn stack height provision in the Lake County SO, strategy. 2. Section 52.795 is amended hv revising paragraph (e)(1) as follows 52.795 Control strategy: Sulfur dioxide. (c) * * * (1) Lake County--The plan must either contain an acceptable demonstration that the 24-hour standard is the constraining standard or 3-hour and annual attainment analyses must be provided. The plan must justify appropriate SOi background levels for all averaging periods. These must be used in all analyses. The plan must contain a complete emission inventory, including process sources. This inventory must be appropriately used in all analyses. Adequate receptor resolution must be used in the attainment analyses. The plan must be based on NIPSCO Mitchell Station's existing stack height. If revisions to the Lake County limitations are necessary, they must be submitted as revisions to the SIP. ** * (FR Doc I2-244S8 Filod O-O-Si .S am| BILUMO COOC (SM-SO-M 40 CFR Part 61 [AD-FHL-2070-81 Appendix B; Test Methods; R vised Methods 106 and 107; and App ndix C, Quality Assurance Pr cedures 1 and 2; Revision agency: Environmental Protection Agency (EPA). action: Final rule. summary: Revised Test Methods 106 and 107 for vinyl chloride were proposed in the Federal Register on November 18.1980 (45 FR 76346). This action promulgates the revised test methods. The intended effect of this action is to require all sources of vinv ! chloride specified to conduct emission tests under Subpurts A and F of 40 CFK Part 61 to hereafter (see effective date below) use these methods for determining compliance. Appendix C. Quality Assurance Procedures 1 and 2. was proposed in the Federal Register on April 18.198(1 (45 FR 26682). This action promulgates CTL030436 Federal Register / Vol. 47, No. 173 / Tuesday. September 7, 1002 / Rules and Retaliations 39167 the distrir.t court order is stayed, modified, or vacated, this rule may be revised or revoked, and actions taken on applications submitted pursuant thereto may be modified or reversed. List of Subjects in 32 CFR Part 724 Administrative practice and procedures, Military personnel. PART 724--NAVAL DISCHARGE REVIEW BOARD Accordingly. 32 CFR Part 724 is amended as follows: 1. The authority citation for Part 724 reads as follows: Authority: 10 U.S.C. 1553. unless otherwise noted. 2. A new $ 724.904 is added to Subpart I which reads as follows: f 724.904 Special standards. (a) Pursuant to the order of the United States District Court for the District of Columbia in Walters v. Secretary of Defense (Civil Action No. 81-0962), a former Navy or Marine Corps servicemember who presently possesses a less than honorable administrative discharge, which was characterized as less than honorable in an administrative proceeding in which evidence was introduced that was developed by, or as a result of. compelled urinalysis testing administered for the purpose of identifying drug abusers, is entitled to special processing. (b) Applicants who believe that they fall within the scope of paragraph (a) of this section should place the words "CATEGORY W" in block 8. DD Form 293, Application For Review of Discharge or Dismissal From the Armed Forces of the United States. Such applications shall be reviewed expeditiously by a designated official who will either cause the individual to be sent an honorable discharge certificate or will forward the application and the service personnel and medical records to the military service concerned to determine whether a new administrative proceeding should be convened to determine whether a less than honorable discharge can be justified. Applicants determined not to qualify for either of the foregoing forms of processing will have their applications forwarded to the Naval Discharge Review Board for appropriate review and action. The action of the designated official shall not constitute an action or decision by the Naval Discharge Review Board. Dated: September 1. 1982. F. N. Otlic. I.ieutenant Commander. /ACC. U.S. Navy. Alternate Federal Heyister Liaison Officer. |KF Hoc H2-244JI2 Kilrd 8 <5 m| BILLING COOt MIO-AE-U ENVIRONMENTAL PROTECTION AGENCY 40 CFR Part 52 [A-5-FRL 2182-8] Approval and Promulgation of Implementation Plans; Indiana AGENCY: Environmental Protection Agency (EPA). action: Final rulemaking. summary: On March 12.1982 (47 FR 10813), EPA conditionally approved the Lake County, Indiana State Implementation Plan (SIP) for sulfur dioxide (SO,). including a stack height increase for the Northern Indiana Public Service Company's (NIPSCO) Mitchell Power Plant. Subsequently, NIPSCO informed EPA that increasing the stack height would endanger airplanes landing at the nearby Gary Municipal Airport EPA reviewed the information and is rescinding its approval of the Mitchell stack height increase. Additionally, EPA is adding another condition to its previous conditional approval of the Lake County SIP. The condition is that Indiana must address the Mitchell stack height issue in Indiana's responses to EPA conditional approval for the Lake County SIP. DATE: This action is effective November 8,1982, unless notice is received within 30 days that someone wishes to submit adverse or critical comments. ADDRESSES: Copies of the materials relating to this rulemaking are available for inspection at the following addresses: (It is recommended that you telephone Robert B. Miller at (312) 8866031 before visiting the Region V Office). The Office of the Federal Register. 1100 L Street. N.W., Rm. 8401, Washington, D.C. 20408 Air Programs Branch (5AP-11). 230 South Dearborn Street. Chicago, Illinois 60604 Environmental Protection Agency. Public Information Reference Unit. 401 M Street. S.W., Washington. D.C. 20460 Indiana Air Pollution Control Division. Indiana State Board of Health. 1330 West Michigan Street. Indianapolis. Indiana 46206 Written comments should be sent to: Gary Gulezian, Chief. Regulatory Analysis Section. Air^Progriims Branch (5AP-11). Environmental Protection Agency. Region V. 230 South Dearborn Street. Chicago. Illinois 00004. FOR FURTHER INFORMATION CONTACT: Robert B. Miller. Air Programs Branch, Environmental Protection Agency. Region V, Chicago. Illinois 60604. (312) 886-6031. SUPPLEMENTARY INFORMATION: Under Section 107 of the Clean Air Act (CAA), EPA has designated certain areas in Indiana as not attaining National Ambient Air Quality Standards (NAAQS) for SO,. See 43 FR 8962 (March 3.1978) and 43 FR 45993 (October 5,1978). For these areas. Part D of the CAA requires that the State revise its SIP to provide for attaining the primary SO, NAAQS by December 31. 1982. These SIP revisions must also provide for attaining the secondary NAAQS as soon as practicable. The requirements for an approvable SIP are described in a "General Preamble" for Part D rulemakings published at 44 FR 20372 (April 4.1979). 44 FR 38583 (July 2, 1979), 44 FR 50371 (August 28.1979). 44 FR 53761 (September 17,1979), and 44 FR 67182 (November 23.1979). The Lake County SO, SIP strategy was developed by the Lake County Task Force using computer dispersion modeling. This strategy was adopted by the State of Indiana and, on |une 26. 1979, was submitted to EPA as a revision to Indiana's SIP. EPA reviewed these revisions and proposed them for conditional approval on March 27.1980 (45 FR 20432). In response to this proposal, on August 27,1980 and July 18, 1981, Indiana committed itself to submit additional data and regulations, if necessary, to fulfill EPA's conditions. At a later date Indiana agreed to meet its commitments by November 1982. EPA reviewed Indiana's commitments and the comments received in response to EPA's notice of proposed rulemaking, and on March 12.1982, EPA conditionally approved the Lake County SO, plan as meeting the requirements of Part D of the Clean Air Act (47 FR 10813). Additionally. EPA proposed on March 12.1982 to approve the November 1982 date by which Indiana committed itself to fulfill the conditions (47 FR 10860). EPA will take final rulemaking at a later time on the date by which Indiana committed itself to respond to the Part D SO, conditions. Indiana's strategy for Lake County includes an increase in the NIPSCO Mitchell Station's stacks from 71.9 meters to 104 meters and on a status quo emission limitation of 1.2 pounds of SO, per million British Thermal Units (lbs/ CTL030437 Fotlor.nl Register / Vnl. 47, Nn, 171 / Tnostl.ny, September 7, 1<1I!2 / Ruins rtntl itintis 3`iif.n Procedures 1 and 2 of Appendix C. The intended effect of Procedure 1 is to provide a method for determination of gas r.lirnmutogiuph ICC) column resolution, und the intended effect of Ptocedure 2 is to provide ;i method for auditing GC sample analysis. EFFECTIVE DATE: September 7,1982. Under Section 307(b)(1) of the Clean Air Act. judicial review of this rulemaking is available only by (he filing of a petition for review in the U.S. Court of Appeals for the District of Columbia Circuit within 60 days of today's publication of this rule. Under Section 307(b)(2) of the Clean Air Act. the requirements that are the subject of today's notice may not be challenged later in civil or criminal proceedings brought by EPA to enforce these requirements. ADDRESSES: Summary of Comments and Responses. The summary of comments and responses for the proposed test methods may be obtained from the U. S. EPA Library (MD-35), Research Triangle Park, North Carolina 27711. telephone number (919) 541-2777. Please refer to "Revised Test Methods 106 and 107-- Summary of Comments and Responses, EPA 450/3-82-002." The document contains (1) a summary of the changes made to the test methods since proposal and (2) a summary of all the public comments made on the proposed revised methods and the Administrator's responses to the comments. Docket. A docket, number A-80-50, containing information considered by EPA in the development of the test methods and docket number OAQPS 793 Part 2 that contains background information pertaining to Appendix C are available for public inspection between 8:00 a.m. and 4:00 p.m.. Monday through Friday, at EPA's Central Docket Section (A-130). West Tower Lobby. Gallery 1. 401 M Street. S.W.. Washington. D C. 20460. A reasonable fee may be charged for copying. F R FURTHER INFORMATION CONTACT: Roger T Shigchara, Emission Measurement Branch. Emission Standards and Engineering Division (MD-19), U. S. Environmental Protection Agency. Research Triangle Park. North Carolina 27711. telephone (919) 5412237. Public Participation The revised test methods were proposed and published in the Federal Register on November 18.1980 (45 KR 76346). Public comments were solicited at the time of proposal. The public comment period was from November 18. I960, to [antiurv 19. 15181. with an extension to February 19. 15181. Five r.iininient letters were received concerning issues relative to the proposed test methods. The comments have been carelully considered; und where determined to be appiopriate by the Administrator, changes have been made in the proposed revisions to the test methods. Procedures 1 and 2 of Appendix C were proposed and published in the Federal Register April 18.1980 (45 FR 2G6GQ). Public comments were solicited at the time of proposal. The public comment period was from April 18.1980. to August 21.1930. No comment letters were received. Significant Comments and Changes to tho Proposed Test Methods Comments on the proposed revisions to the test methods were received from industry, industry counsel, engineering firms, and equipment manufacturers. A detailed discussion of these comments and responses can be found in the summary of comments and responses which is referred to in the ADDRESSES section of this preamble. The summary of comments and responses serves as the basis for the revisions which have been made to the test methods between proposal and promulgation. The major comments and responses are summarized in thi3 preamble. Most of the comment letters contained multiple comments. The comments have been divided into the following areas: Proposal ofRevised Test Methods 106 and 107 One commenter felt that EPA should publish a notice in the Federal Register to clarify the November 18.1980. notice on Test Methods 106 and 107 (45 FR 76346) as to whether the changes in the methods were proposed or final amendments. The EPA considered the suggestion to be reasonable: and a notice was published in the Federal Register on January 6.1981 (46 FR 1318) to clarify that the changes in Methods 106 and 107 published on November 18. 1980. were proposed changes. Sample Analysis Procedure--Method 106 One commenter suggested that Section 7.2.2. Preparation of Chromatograph Calibration Curve, be changed to require calibration at least once every 8 hours of continuous operation of the chromatograph, whereas the method requires daily calibration. The EPA has decided it would be an unnecessary burden to arbitrarily set 8 hours as a cutoff point for valid calibration. However, the comment has identified the need for mxlriii lion in the method a* to the use of multiple calibration curves in d.il.i interpretation, und Section 7.2.2 has been revised to provide lh.it instruction One commenter questioned the use of Figure 106-2 because it appeared to illustrate a standards preparation procedure different from the one described tn the method. Figure 106-2 did illustrate a different sample preparation procedure and has been deleted from the method. Sample Collection end Analysis Procedure--Method 107 One commenter questioned the need for the sample prcprrssurization procedure that is included in the revised test method. The Agency believes the prepressurization procedure is valid as prepressurization of sample vials prior to analysis has been shown to produce k, values which agree with theoretical values. A paper describing a study of this technique has been added to the bibliography section of the method as an aid in the use of this procedure. Quality Assurance--Method 106 One commenter requested that Section 5.2.4, Audit Cylinder Standards, further describe commercial gas manufacturers as an alternative source of these standards. The Agency considered the request to be reasonable, and Section 5.2.4 has been revised to define the acceptability of audit cylinders obtained from commercial gas manufacturers. Docket The docket is an organized and complete file of all the information considered by EPA in the development of this rulemaking. The docket is a dynamic file, since material is added throughout the rulemaking development. The docketing system is intended to allow members of the public and industries involved to readily identify and locate documents so that they can intelligently and effectively participate in the rulemaking process. Along with the statement of basis and purpose of the proposed and promulgated test methods dnd EPA responses to significant comments, the contents of the docket will serve as the record in case of judicial review (Section 307(dl(7)(A)]. Miscellaneous This rulemaking docs not impose any additional emission measurement requirements on facilities affected by this rulemaking. Rather, this rulemaking revises the test methods to which the CTL030438 39170 Fedrr.il Re^isler / Vol. 47. No. 17.') / TurstLiv. September 7. 1*102 / Rules ;fut Resolutions nffecled f.iolities ;ire ulre.ulv so|i|ee.t. The revisions ilo mil .iflei I the pii",i-nl emission si.mil.inis If future si,mil.nils impose emission nie.isiuenienl re(|uiremenls, the imp,ids of the revised test methods promulgated tod.iy will lie evaluated during developmenl of those standards. Under Kxeeutivc Order 12291, EPA must judge whether h regulation is "major" and. therefore, subject to the requirement of a regulatory impact analysis. This regulation is not major because it will not have an annual effect on the economy of S100 million or more: it will not result in a major increase in costs or prices: and there will be no significant effects on competition, employment, investment, productivity, innovation, or on the ability of U.S.based enterprises to compete with foreign-based enterprises in domestic or export markets. The regulation was submitted to the Office of Management and Budget for review as required by Executive Order 12291. Pursuant to the provisions of 5 U.S.C. 605(b), I hereby certify that the attached rule will not have a significant economic impact on a substantial number of small entities. List of Subjects in 40 CFR Part 61 Air pollution control. Asbestos, Beryllium, Hazardous materials. Mercury, Vinyl chloride. (Secs. 112.114. 301(a) of the Clean Air Act. as amended (42 U.S.C. 7412. 7414. 7601(a)) Dated: August 24. 1982. John W. Hernandez, Acting Administrator. PART 61--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS 40 CFR Part 61 is amended by revising Test Methods 106 and 107 of Appendix B to read as follows: Appendix B--Test Methods *** Method 106--Determination of Vinyl Chloride From Stationary Sources Introduction _ Performance of this method should not be attempted by persons unfamiliar with the operation of a g.ts chromatograph (C.C) nor by those who are unfamiliar with source sampling, because knowledge hevond the scope of this present.ilmn is required. Care must be exercised to prevent exposure of sampling personnel In vinyl chloride, a carcinogen. I. Applicability and Principle 1.1 Applicability. The method is applicable to the measurement of vinvl chloride in stack gases from ethylene du blonde, vinvl chloride, and (xiivvinvl i Id on 11.* ni.muf.n I mmg pi oirsses I he lltelhoil does Mol measure vinvl I blonde colli.lined in p.irtu id.de ni.liter. 1.2 I'riin tple. Alt integrated hag sample of si.ii k gas i olllalliing Mini i blonde (chlorof thene) is subjected lo CC aualvsis using a flame lom/alion detector |FID). 2. /tailin' ami Sensitivity This method is designed for the 0.1 lo 50 ppm range, ltnwrver. common CC instruments arc capable of delecting 002 ppm vinvl chloride. With proper calibration. Ihe upper limit may be extended as needed. 3. Interferences The chromatographic columns and the corresponding operating parameters herein described normally provide an adequate resolution of vinyl chloride: however, resolution interferences may be encountered on some sources. Therefore, the chromatograph operator shall select the column and operating parameters best suited to his particular analysis requirements, subtcct to the approval of the Administrator. Approval is automatic, provided that the tester produces confirming data through an adequate supplemental analytical technique, such as analysis with a different column or CC/mass spectroscopy, and has the data available for review by the Administrator. 4. Apparatus ' 4.1 Sampling (see Figure 106-1). The sampling train consists of the following components: 4.1.1 Probe. Stainless steel Pyrex glass, or Teflon tubing (as stack temperature permits) equipped with a glass wool plug to remove particulate matter. 4.1.2 Sample Lines. Teflon. 8.4-mm outside diameter, of sufficient length to connect probe to bag. Use a new unused piece for each series of bag samples that constitutes an emission test, and discard upon completion of the test. 4.1.3 Quick Connects. Stainless steel, male (2) and female (2). with ball checks (one pair without), located as shown in Figure 1061. 4.1.4 Tedlar Bags. 50- to 100-liter capacity, to contain sample. Aluminized Mylar bags may be used if the samples are analyzed within 24 hours of collection. 4.1.5 Bag Containers. Rigid leak-proof containers for sample bags, with covering to protect contents from sunlight 4.1.6 Needle Valve. To adjust sample flow rates. 4.1.7 Pump. Leak-free, with minimum of 2liter/min capacity. 4.1.8 Charcoal Tube. To prevent admission of vinvl chloride and other organics to the atmosphere in the vicinity of samplers. 4.1.9 Flowmeter. For observing sampling flow rate: capable of measuring a flow range from 0.10 to 1.00 litrr/nun. 4.1.10 Connecting Tubing. Teflon. 6.4-mm outside diamt-lcr. lo assemble sampling train (Figure 106-1). 4.1.11 Tubing Fillings and Connectors. Tellon or stainless steel, to assemble sampling train. 4.2 Sample Kei n\er\ Teflon inhtug. I, 4 nun 4 ml side (h.iui.-ti-r In 1 i>mn-i I h.|.> 1,1 (.( sample Iii4i|i tin sample rei mu 1 I'se.im-w unused pin e for e.11 It si nes of li.ig s.iie|ilrs dial (unsliluti s .01 euiissuin lest, .mil ills, .ml upon i.imi lusmii of analssis of those hag-. 4..'I Analysis I he follow my eqm|iiiienl ,s required. 4:i.l C,as Chromatograph Willi FID. potenliometm. strip chart recorder .uni 1 (>. ni 5.0-ml healed sampling loop m aultmi..tu. sample valve. The chromatographic system shall he capable uf producing a response lo 0 1-ppm vinvl chloride dial is at least as greal as the average noise level. (Response is measured from the average vnlne of Ihe base line lo Ihe maximum of Ihe wave form, while standard operating conditions arc in use.) 4.3.2 Chromatographic Columns. Columns as listed below. The analyst may use other columns provided that the precision and accuracy of the analysis of vinyl chloride standards are nnt impaired and he has available for review information confirming that there is adequate resolution of the vinyl chloride peak. (Adequate resolution is defined as an area overlap of not more than 10 percent of the vinyl chloride peak by an interferent peak. Calculation of area overlap is explained in Appendix C. Procedure 1: ''Determination of Adequate Chromatographic Peak Resolution.") 4.3.2.1 Column A. Stainless steel. 2.0 m bv 3.2 mm. containing 80/100-mesh Chromasorb 102. 4.32^ Column B. Stainless steel. 2.0 ni by 32 mm. containing 20 percent GE SF-96 on 60/80-mesh Chromasorb P AW: or stainless steel. 1.0 m by 32 mm containing 80/100mesh Porapak T. Column B is required as a secondary column if acetaldehyde is present. If used, column B is placed after column A. The combined columns should be operated at 120* C. 4.3.3 Flowmeters (2). Rotameter type. 100ml/min capacity, with flow control valves. 4.3.4 Cas Regulators. For required gas cylinders. 4.3.5 Thermometer. Accurate to V C. to measure temperature of heated sample loop at time of sample injection. 4.3.8 Barometer. Accurate to 5 mm Hg. to measure atmospheric pressure around CC during sample analysis. 4.3.7 Pump. Leak-free, with minimum of 100-ml/min capacity. 4.3.8 Recorder. Strip chart type, optionally equipped with either disc or electronic integrator. 4.3.9 Planimetc-r. Optional, in place of disc or electronic integrator on recorder, to measure chromatograph peak areas. 4.4 Calibration. Sections 4.4 2 through 4.4.4 are for the optional procedure in Section 7.1. 4.4.1 Tubing Teflon. 6.4-mm outside dumeter. separate pieces marked for each calibration concentration. 4.4.2 Tedlar Bags Sixtecn-inch-squarc size, with valve: separate bag marked for each calibration concentration. 4.4.3 Svrings. 0.5-ml and 50-pl. gas tight, individually calibrated to dispense g.e-emis vinyl chloride. CTL030439 Fcrdcr.il Roister / Vol. 47. No. 173 / Tuesday. SoplcmlMir 7, 1`1I12 / Rules and Regulations 3H171 4 4.4 Drv ('.os Meter. wall Temperature and I'les-one (i.nines. Singer model DTM-115 with I>U2 uniev or i qmv.ilenl. lo nielop nitrogen m piep.ir.ilioit <>! sl.nul.iiil gas mixlmes. i.nlihr.i'ed <i I I her flow mil' used to prepare standards. 5. Hraxrnts Usi only reagents that arc of chromatograph grade. 5.1 Analysis. The following arc required for analysis. 5.1.1 Helium or Nitrogen. Zero grade, for chromatographic carrier gas. 5.12 l lydrogcn. Zero grade. 5.1.3 Oxygen or Air. Zero grade, as required by the detector. 5.2 Calibration. Use one of the following options: cither 5.2.1 and 5.2.2. or 5.2.3. 5.2.1 Vinyl Chloride. Pure vinyl chloride gas certified by the manufacturer to contain a minimum of 99.9 percent vinyl chloride, for use in the preparation of standard gas mixtures in Section 7.1. If the gas manufacturer maintains a bulk cylinder supply of 99.9+ percent vinyl chloride, the certification analysis may have been performed on this supply rather than on each gas cylinder prepared from this bulk supply. The date of gas cylinder preparation and the certified analysis must have been affixed to the cylinder before shipment from the gas manufacturer to the buyer. 5.2.2 Nitrogen. Zero grade, for preparation of standard gas mixtures as described in Section 7.1. 5.2.3 Cylinder Standards (3). Cas mixture standards [50-. 10-. and 5-ppm vinyl chloride in nitrogen cylinders). The tester may use cylinder standards to directly prepare a chromatograph calibration curve as described in Section 7.2.2, if the following conditions are met: (a) The manufacturer certifies the gas composition with an accuracy of 3 percent or better (see Section 5.2.3.1). (b) The manufacturer recommends a maximum shelf life over which the gas concentration does not change by greater than 5 percent from the certified value, (c) The manufacturer affixes the date of gas cylinder preparation, certified vinyl chloride concentration, and recommended maximum shelf life to the cylinder before shipment to the buyer. 5.2.3.1 Cylinder Standards Certification. The manufacturer shall certify the concentration of vinyl chloride in nitrogen in each cylinder by (a) directly analyzing each cylinder and (b) calibrating his analytical procedure on the day of cylinder analysis. To calibrate his analytical procedure, the manufacturer shall use. as a minimum, a three-point calibration curve. It is recommended that the manufacturer maintain (1) a high-concentration calibration standard (between 50 and 100 ppm) to prepare his calibration curve by an appropriate dilution technique and (2) a low-concenlr.ition calibration standard (between 5 and 10 ppm) to verify the dilution technique used. If the difference between the apparent concentration read from the calibration curve and the true concentration assigned to the law-concentration calibration standard exceeds 5 percent of the true concentration, the manufacturer shall determine the source of error and correct it. then repeat the threepoint calilir.ilion. 5 2 .1.2 Veilin'.ilion of Manufacturer's Calibration Standards. Itefore using a standard, the manufacturer shall verify each calibration standard (a) by comparing it to gas mixtures prepared (with 99 mob: percent vinyl chloridi'l in ai cnrdanre with the procedure described in Section 7.1 or (b) calibrating it against vinyl chloride cylinder Standard Reference Materials (SRM's) prepared by the Nutinnal bureau of Standards, if such SRM's are available. The agreement between the initially determined concentration value and the verification concentration value must be within 5 percent. The manufacturer must reverify all calibration standards on a time interval consistent with the shell life of the cylinder standards sold. 5.2.4 Audit Cylinder Standards (2). Cas mixture standards with concentrations known only to the person supervising the analysis of samples. The audit cylinder standards shall be identically prepared as those in Section 5.2.3 (vinyl chloride in nitrogen cylinders). The concentrations of the audit cylinder should be: one lowconcentration cylinder in the range of 5 to 20 ppm vinyl chloride and one highconcentration cylinder in the range of 20 to 50 ppm. When available, the tester may obtain audit cylinders by contacting: Environmental Protection Agency. Environmental Monitoring Systems Laboratory. Quality Assurance Division (MD-77). Research Triangle Park. / North Carolina 27711. Audit cylinders obtained from a commercial gas manufacturer may be used provided: (a) the gas manufacturer certifies the audit cylinder as described in Section 52.3.1, and (b) the gas manufacturer obtains an independent analysis of the audit cylinders to verify this analysis. Independent analysis is defined here to mean analysis performed by an individual different than the individual who performs the gas manufacturer's analysis, while using calibration standards and analysis equipment different from those used for the gas manufacturer's analysis. Verification is complete and acceptable when the independent analysis concentration is within 5 percent of the gas manufacturer's concentration. 6. Procedure 6.1 Sampling. Assemble the sample train as shown in Figure 100-1. A bag leak check should have been performed previously according to Section 7.3.2. Join the quick connects as illustrated, and determine that all connection between the bag and the probe are tighL Place the end of the probe at the centroid of the stack and start the pump with the needle valve adjusted to yield a flow that will fill over SO percent of bag volume in the specific sample period. After allowing sufficient time to purge the line several times, change the vacuum line from the container to the bag and evacuate the bag until the rotameter indicates no flow. Then reposition the sample and vacuum lines and begin the actual sampling, keeping the rate proportional to the stack velocity. At all times, direct the gus exiting the rotameter away from sampling personnel. At the end of the sample period, shut off the pump, disronnei I the s.imp'll' line Imm llie Im,>. .,n,l disconnect the \ .e in,ill line fmm the li.ig container. Prolei.l the bug container from sunlight. 6.2 Sample storage keep the sample hags out uf direct sunlight. When at all pos-alile analysis is to be perfumied within 24 hours but in no case in excess of 72 hours uf sample collection. Aluminized Mvlar bag samples must lie analyzed within 24 hours. 6.3 Sample Recovery. With a new piece of Teflon tubing identified for lhai bag. connect a bag inlet valve to the gas chromatograph sample valve. Switch the valxe to receive gas from the bag through the sample loop. Arrange the equipment so Ihe sample gas passes from the sample valve to 100-ml/mm rotameter with flow control valve followd by a charcoal tube and a 1-in. HiO pressure gauge. The tester may maintain the sample flow either by a vacuum pump or container pressurization if the collection bag remains in the rigid container. After sample loop purging is ceased, allow the pressure gauge to return to zero before activating the gas sampling valve. 6.4 Analysis. Set the column temperature to 100* C and the detector temperature to 150' C. When optimum hydrogen and oxygen flow rate* have been determined, verify and maintain these flow rates during all chromatography operations. Using zero helium or nitrogen as the carrier gas. establish a flow rate in the range consistent with the manufacturer's requirements for satisfactory detector operation. A flow rate of approximately 40 ml/min should produce adequate separations. Observe the base line periodically and determine that the noise level ha* stabilized and that base line drift has ceased. Purge the sample loop for 30 seconds at the rate of 100 ml/min. shut off flow, allow the sample loop pressure to reach atmospheric pressure as indicated by the HtO manometer, then activate the sample valve. Record the injection time (the position of the pen on the chart at the time of sample injection), sample number, sample loop temperature, column temperature, carrier gas flow rate, chart speed, and attenuator setting. Record the barometeric pressure. From the chart, note the peak having the retention time corresponding to vinyl chloride as determined in Section 72.1. Measure the vinyl chloride peak area. Aa. by use of a disc integrator, electronic integrator, or a. planimetcr. Measure and record the peak heights. H.. Record A,, and retention time. Repeat the injection at least two times or until two consecutive values for the total area of the vinyl chloride peak do not vary more than 5 percent Use the average value for these two total areas to compute the bug concentration. Compare the ratio of If,, to An for the vinyl chloride sample with the same ratio for the Standard peak that is closest in height. If these ratios differ by more than 10 percent, the vinyl chloride peak may not be pure (possibly acetaldehyde is present I and the secondary column should be employed (tee Section 422.2). 6.5 Determination of Bag Water Vapor Content. Meusurc the ambient temperature CTL030440 39172 Fndnrnl Koxislnr / Vol. 47. No. 173 / Tuc'sci.iv, September 7. 19H2 / Rules and JV'C'bitions and h.irnnirlrir pressure ni'.ir the hag From ii water h:iturntion vapor piessure lalile. detrrmii'e and rin ord the water vapor r.onlent of the bag .is .1 ilri 1n1.1l figure. lAssumr the rrl.llivr 11111111 <111v In lir 1(H) percent unless <1 lesser value is known.) ?. I'n'/tamfiitn nf Sltnnlnnl (ins .Mislurt's. Cu/ibralinn. anil (Juu/ity Assurance 7.1 Preparation of Vinvl Chloride Standard (.as Mixtures. (Optional Procedure--delete if cylinder standards are used.) Kvucuute a 16-inch square Tedlar baft that has passed a leak check (described in Section 7.3.2) and meter in 5.0 liters of nitropen. While the bap is filling, use the 0.5ml syringe to inject 250 pi of 99.9 + percent vinyl chloride gas through the wall of the bag. Upon withdrawing the syringe, immediately cover the resulting hole with a piece of adhesive tape. The bag now contains a vinyl chloride concentration of 50 ppm. In a like manner use the 50 pi syringe to prepare gas mixtures having 10- and 5-ppm vinyl chloride concentrations. Place each bag on a smooth surface and alternately depress opposite sides of the bag 50 times to further mix the gases. These gas mixture standards may be used for 10 days from the date of preparation, after which time new gas mixtures must be prepared. (Caution: Contamination may be a problem when a bag is reused if the new gas mixture standard is a lower concentration than the previous gas mixture standard.) 7.2 Calibration. 7.2.1 Determination of Vinyl Chloride Retention Time. (This section can be performed simultaneously with Section 7.2.2.) Establish chromatograph-conditions identical with those in Section 6.4 above. Determine proper attenuator position. Flush the sampling loop with zero helium or nitrogen and activate the sample valve. Record the injection time, sample loop temperature, column temperature, carrier gas flow rate, chart speed, and attenuator setting. Record peaks and detector responses that occur in the absence of vinyl chloride. Maintain conditions with the equipment plumbing arranged identically to Section 6.3. and flush the sample loop for 30 seconds at the rate of 100 ml/min with one of the vinyl chloride calibration mixtures. Then activate the sample valve. Record the injection time. Select the peak that corresponds to vinyl chloride. Measure the distance on the chart from the injection time to the time at which the peak maximum occurs. This quantity divided by the chart speed is defined as the retention time. Since other organics may be present in the sample, positive identification of the vinyl chloride peak must be made. 7.2.2 Preparation of Chromatograph Calibration Curve. Make a CC measurement nf e.n h g.is mixture standard (dnxr ribeil in Section 5 2 3 or 7 1) using i umlituns ulnnlirnl u till lluise listed III Set linns It .1 .Hid li 4 1 lush the s.inifilmg lon|i for 'tit sei ends .it the rule of 1(H) ml/nuii with one of the standard mixtures, .mil .11 tiv.ile the sample valve Record the eonrentr.ition of v on I chloride iniccted (0,|. .itteiui.ilor setting, chart speed, peak area, sample loop temperature, column temperature, carrier gas flow rate, and retention time. Record the barometric pressure. Calculate Ar. the peak area multiplied by the attenuator setting Repeat until two consecutive inaction areas are within 5 percent, then plot the average of those two values versus C,. When the other standard gas mixtures have been similarly analyzed and plotted, draw a straight line through the points derived by the least squares method. Perform calibration daily, or before and after the analysis of each emission test set of bag samples, whichever is more frequent. For each group of sample analyses, use the average of the two calibration curves which bracket that group to determine the respective sample concentrations. If the two calibration curves differ by more than 5 percent from their mean value, then report the final results by both calibration curves. 7.3 Quality Assurance. 7.3.1 Analysis Audit. Immediately after the preparation of the calibration curve and prior to the sample analyses, perform the analysis audit described in Appendix G Procedure 2: "Procedure for Field Auditing GC Analysis." 7.3.2 - Bag Leak Checks. Checking of bags for leaks is required after bag use and strongly recommended before bag use. After each use. connect a water manometer and pressurize the bag to 5 to 10 cm H>0 (2 to 4 in. H<0). Allow to stand for 10 min. Any displacement in the water manometer indicates a leak. Also, check the rigid container for leaks in this manner. (Note: An alternative leak check method is to pressurize the bag to 5 to 10 cm HiO and allow it to stand overnight. A deflated bag indicates a leak.) For each sample bag in its rigid container, place a rotameter in line between the bag and the pump inlet. Evacuate the bag. Failure of the rotameter to register zero flow when the bag appears to be empty indicates a leak. 8. Calculations. 6.1 Determine the sample peak area. A, as follows: Ac = \ Af Eq. 106-1 Where: A,, = Measured peak area. A(=Attenuation factor. 6 2 Vmy I Chloride ( nn< entratnms I mm thr calibration rurvrs ilrxi riberi mi Sri Him 7 2 2. ilrtrrniinr thr aveiage i uni 1-1111 . 11.n 1 value of vinyl 1 hloriilr. C, th.il urtespnnd-, to A,, thr sample pr.ik .irr.i t'.i|< ulalc the concentration of viny l chloride in thr h.ig. C,,. as follows Cb = P.V? - Bwb) Eq- 106-2 Where: P, = Reference pressure, the lalmratory pressure recorded during calibration, mm Hg. T, = Sample loop temperature on the absolute scale at the time of analysis. `K. P, = Laboratory pressure at time of analysis, mm Hg. Tr = Reference temperature, the sample loop temperature recorded during calibration. "K. Bw= Water vapor content of the bag sample, us analyzed. 9. bibliography. 1. Brown D.W.. E.W. Loy. and M.H. Stephenson. Vinyl Chloride Monitoring Near the B. F. Goodrich Chemical Company in Louisville. KY. Region IV. U.S. Environmental Protection Agency, Surveillance and Analysts Division. Athens. GA. june 24.1974. 2. G.D. Clayton and Associates. Evaluation of a Collection and Analytical Procedure for Vinyl Chloride in Air. U.S. Environmental Protection Agency, Research Triangle Park. N.C. EPA Contract No. 66-02-1408. Task Order No. 2, EPA Report No. 75-VCL-l. December 13.1974. 3. Midwest Research Institute. Standardization of Stationary Source Emission Method for Vinyl Chloride. U.S. Environmental Protection Agency. Research Triangle Park. N.C. Publication No. EPA-600/ 4-77-026. May 1977. 4. Scheil. G. and M.C. Sharp. Collaborative Testing of EPA Method 106 (Vinyl Chloride) that Will Provide for a Standardized Stationary Source Emission Measurement Method. U.S. Environmental Protection Agency. Research Triangle Park. N.C. Publication No. EPA 600/4-78-058. October 1978. MLUNO COOC SSSO-SO-M CTL030442 Fodnrnl Rngistnr / Vol. 47, No. 173 / Tuesday, Soplnmhor 7, 192 / Rules and Radiations oi9s^w;\?r6nrn,lin^9rilted`ba9 samp.lin9 train. (Mention of trade names mVni" Pro?*tim Aj.n"yT CnSmu'e encl0TMn'enI bV ** Environ- CTL030442 39174 Fedornl Rngistor / Vol. 47, No. 173 / Tuesday, September 7, 1?)H2 / Rules and Regulations Method 107--Determination of Vinyl Chloride Content of Inprncrss W.ntrw.ilrr Samples, and Vinyl Chloride Content of Polyvinyl Chloride Resin. Slurry, Wet Cake, and Latex Sample! Introduction Performance of this method should not be attempted by persons unfamiliar with the operation of a gas chromatograph (GC). nor by those who are unfamiliar with source sampling, because knowledge beyond the scope of this presentation is required. Care must be exercised to prevent exposure of sampling personnel to vinyl chloride, a carcinogen. 1. Applicability and Principle. 1.1 Applicability. This method applies to the measurement of the vinyl chloride monomer (VCM) content of inprocess wastewater samples, and the residual vinyl chloride monomer (RVCM) content of polyvinyl chloride (PVC) resins, wet cake, slurry, and latex samples. It cannot be used for polymer in fused forms, such as sheet or cubes. This method is not acceptable where methods from Section 304(h) of the Clean Water Act, 33 U.S.C. 1251 et seq. (the Federal Water Pollution Control Amendments of 1972 as amended by the Clean Water Act of 1977) are required. 1.2 Principle. The basis for this method relates to the vapor equilibrium that is established between RVCM. PVC resin, water, and air in a closed system. The RVCM in a PVC resin will equilibrate rapidly in a closed vessel, provided that the temperature of the PVC resin is maintained above the glass transition temperature of that specific resin. 2. Range and Sensitivity. The lower limit of detection of vinyl chloride will vary according to the chromatograph used. Values reported include 1 x 10'' mg and 4 x 10"7 mg. With proper calibration, the upper limit may be extended as needed. 3. Interferences. The chromatograph columns and the corresponding operating parameters herein described normally provide an adequate resolution of vinyl chloride; however, resolution interferences may be encountered on some sources. Therefore, the chromatograph operator shall select the column and operating parameters best suited to his particular analysis requirements, subject to the approval of the Administrator. Approval is automatic provided that the tester produces confirming data through an adequate supplemental analytical technique, such as analysis with a different column or GC/mass spectroscopy, and has the data available for review by the Administrator. 4. Precision and Reproducibility. An interlaboratory comparison between seven laboratories of three resin samples, each split into three parts, yielded a standard deviation of 2.63 perepnt for a sample with a mean of 2.09 ppm. 4.16 percent for a sample with a mean of 1.66 ppm. and 5.29 percent for a sample with a mean of 62.G6 ppm. 5. Safety. Do not release vinyl chloride to the laboratory atmosphere during preparation of standards. Venting or purging with VCM/ air mixtures must be held to a minimum. When they arc required, the vapor must be routed to oulsidc air. Vinyl chloride, even at low ppm levels, must never be vented inside the laboratory After vials have been analyzed, the gas must be vented prior to removal of the vihI from the instrument turntable. Vials must be vented through a hypodermic needle connected to an activated charcoal tube to prevent release of vinyl chloride into the laboratory atmosphere. The charcoal must be replaced prior lo vinyl chloride breakthrough. 6. Apparatus. 6.1 Sampling. The following equipment is required; 6.1.1 Class bottles. 60-ml (2-oz) capacity, with wax-lined screw-on tops, for PVC samples. 6.1.2 Glass Vials. 50-ml capacity Hypovial. scaled with Teflon faced Tuf-Bond discs, for water samples. 6.1.3 Adhesive Tape. To prevent loosening of bottle tops. 62 Sample Recovery. The following equipment is required: 6.2.1 Glass Vials. With butyl rubber septa. Perkin-Elmer Corporation Nos. 0105-0129 (glass vials), B001-0728 (gray butyl rubber septum, plug style), 0105-0131 (butyl rubber septa), or equivalents. The seals must be made from butyl rubber. Silicone rubber seals are not acceptable. 6.2.2 Analytical Balance. Capable of weighing to 0.0001 gram. 6.2.3 Vial Sealer. Perkin-Elmer No. 1050106. or equivalent. 6.2.4 Syringe. 100-pl capacity, precision series "A" No. 010025. or equivalent. 6.3 Analysis. The following equipment is required; 6.3.1 Gas Chromatograph. Perkin-Elmer Corporation Model F-40. F-42. or F-45 HeadSpace Analyzer, or equivalent. Equipped with backflush accessory. 622 Chromatographic Columns.'Stainless steel 1 m by 3.2 mm and 2 m by 3.2 mm. both containing 50/80-mesh Porapak Q. The analyst may use other columns provided that the precision and accuracy of the analysis of vinyl chloride standards are not impaired and he has available for review information confirming that there is adequate resolution of the vinyl chloride peak. (Adequate resolution is defined as an area overlap of not more than 10 percent of the vinyl chloride peak by an interferent peak. Calculation of area overlap is explained in Appendix C. Procedure 1: '`Determination of Adequate Chromatographic Peak Resolution.") Two 1.83 m columns, each containing 1 percent Carbowax 1500 on Carbopak B. have been suggested for samples containing acetaldehyde. 6.3.3 liiermometer. 0 to 100' G accurate to 0.1* C. Perkin-Elmer No. 105-0109. or equivalent. 6.3.4 Sample Tray Thermostat System. Perkin-Elmer No. 105-0103. or equivalent. 6.3.5 Septa. Sandwich type, for automatic dosing. 13 mm. Perkin-Elmer No. 105-1006. or equivalent. - 6.3.6 Integrator-Recorder. Hewlett- Packard Model 3380A. or equivalent. 6.3.7 Filter Drier Assembly |3|. Perkin- Elmer No. 2230117, or equivalent. 6.3.8 Soap Film Flowmeter. Hewlett Packard No. 0101-0113. or equivalent. 6.3.9 Regulators. For required gas cylinders. 6.3.10 Headspace Vial Pre-Pressunzer. Nitrogen pressurized hypodermic needle inside protective shield. (Blueprint available from Test Support Section, fjmssion Measurement Branch. Office of Air Quality Planning and Standards. Environmental Protection Agency. Mail Drop 19. Research Triangle Park, N.C. 27711.) 7. Reagents. Use only reagents that are of chromatographic grade. 7.1 Analysis. The following items are required for analysis: 7.1.1 Hydrogen. Zero grade. 7.1.2 Nitrogen. Zero grade. 7.1.3 Air. Zero grade. 7.2 Calibration. The following items are required for calibration: 7.2.1 Cylinder Standards (4). Gas mixture standards (SO-. 500-. 2000- and 4000-ppm vinyl chloride in nitrogen cylinders). The tester may use cylinder standards to directly prepare a chromatograph calibration curve as described in Section 9.2. if the following conditions are met: (a) The manufacturer certifies the gas composition with an accuracy of 3 percent or better (see Section 7.2.1.1). (b) The manufacturer recommends a maximum shelf life over which the gas concentration does not change by greater than 5 percent from the certified value, (c) The manufacturer affixes the date of gas cylinder preparation, certified vinyl chloride concentration, and recommended maximum shelf life to the cylinder before shipment to the buyer. 7.2.1.1 Cylinder Standards Certification. The manufacturer shall certify the concentration of vinyl chloride in nitrogen in each cylinder by (a) directly analyzing each cylinder and (b) calibrating his analytical procedure on the day of cylinder analysis. To calibrate his analytical procedure, the manufacturer shall use. as a minimum, a 3point calibration curve. It is recommended that the manufacturer maintain (1) a high- concentration calibration standard (between 4000 and 8000 ppm) to prepare his calibration curve by an appropriate dilution technique and (2) a low-concentration calibration standard (between 50 and 500 ppm) to verify the dilution technique used. If the difference between the apparent concentration read from the calibration curve and the true concentration assigned to the lowconcentration calibration standard exceeds 5 percent of the true concentration, the manufacturer shall determine the source of error and correct it. then repeat the 3-point calibration. 72.12 Verification of Manufacturer's Calibration Standards. Before using, the manufacturer shall verify each calibration standard by (a) comparing it to gas mixtures prepared (with 99 mole percent vinyl chloride) in accordance with the procedure described in Section 7.1 of Method 1U6 or by (b) calibrating it against vinyl chloride cylinder Standard Reference Materials (SRM's) prepared by the National Bureau of Standards, if such SRM's are available. The agreement between the initially determined concentration value and the verification concentration value must be within + 5 CTL030443 Federal Register / Vol. 47. No. 173 / Tuesday. September 7, 1<)H2 I Rules and Regulations pcrrrnl The ni.inuf.u liiriT must rrvrrify all r.alil>i.iltnn sl.intl.niU on .( linn* uitriv.il ronvistrnl with Ihr shelf life of the cylinder ttiinilarils sold 8. /'nitriJurr 81 Samnling. 8.1.1 l`VC Sampling. Allow the resin or slurry to flow from a tap on the tank or silo until the tap line has been well purged. Extend and fill a GO-ml sample bottle under the lap. and immediately tighten a cap on the bottle Wrap adhesive tape around the cap and bottle to prevent the cap 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. 8.1.2 Water Sampling. Prior to use. the 50ml vials (without the discs) must be capped with aluminum foil and heated in a muffle furnace at 400' C for at least 1 hour to destroy or remove any organic matter that could interfere with analysis. At the sampling location fill 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, with the Teflon side down, on the opening of the vial. Place the aluminum scat over the disc and the neck of the vial, and crimp into place. Affix an identifying label on the bottle, and record the date. time, and sample location both on the vials and in a log book. All samples must be kept refrigerated until analyzed. 8.2 Sample Recovery. Samples must be run within 24 hours. 8.2-1 Resin Samples. The weight of the resin used must be between 3.5 and 4.5 grams. An exact weight must be obtained (0.0001 g) for each sample. In the case of suspension resins, a volumetric cup can be prepared for holding the required amount of sample. When the cup is used, open the sample bottle, and add the cup volume of resin to the fared sample vial (fared, including septum and aluminum cap). Obtain the exact sample weight, add lOOjd or about two equal drops of distilled water, and immediately seal the vial. Report this value on the data sheet: it is required for calculation of RVCM. In the case of dispersion resins, the cup cannot be used. Weigh the sample in an aluminum dish, transfer the sample to the tared vial, and accurately weigh it in the vial. After prepressurization of the samples, condition them for a minimum of 1 hour in the 90* C bath. Do not exceed 5 hours. Note.--Some aluminum vial caps have a center section that must be removed prior to placing into sample tray. If the cap is not removed, the injection needle will be damaged. 8.2.2 Suspension Resin Slurry and Wet Cake Samples. Decant the water from a wet cake sample, and turn the sample bottle upside down onto a paper towel. Wait for the water to dram, place approximately 0.2 to 4.0 grams of the wet cake sample in a tared vial (tared. including septum and aluminum cap) and seal immediately. Then determine the sample weight ( rOOOOl pi. All samples must be prepressurized and then conditioned for 1 hour at 90* C. A sample of wet cake is used to determine total solids (TS| This is required for calculating the KVCM 8 2.3 IlispeiMon Resin Slurry anil Cron I-atex Samples The materials should not be filtered. Sample must be thoroughly mixed. Using a tared vial (tared. including septum and aluminum cap) add approximately eiRht drops (0.25 to 0.35 g) 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 (0.0001 g). After prcpressurization. condition the vial for 1 hour at 90* C in the analyzer bath. Determine the TS on the slurry sample (Section 8.3.5). 8.2.4 Inprocess Wastewater Samples. Using a tared vial (tared. including septum and aluminum cap) quickly add approximately 1 cc of water using a medicine dropper. Seal the vial as soon as possible. Determine sample weight (0.0001 g). Prepressurize the vial, and then condition for 1 to 2 hours as required at 90* C in the analyzer bath. 8.3 Analysis. 8.3.1 Preparation of Equipment. Install the chromatographic column and condition overnight at 100* C. In the first operation. Porapak columns must be purged for 1 hour at 230* C Do not connect the exit end of the column to the detector while conditioning. Hydrogen and air to the detector must be turned off while the column is disconnected. 8.3.1.1 Flow Rate Adjustments. Adjust flow rates as follows: a. Nitrogen Carrier Cas. Set regulator on cylinder to read 50 psig. Set regulator on chromatograph to produce a flow rate of 30.0 cc/min. Accurately measure the flow rate at the exit end of the column using the soap film flowmeter and a stopwatch, with the oven and column at the analysis temperature. After the instrument program advances to the "B*' (backflush) mode, adjust the nitrogen pressure regulator to exactly balance the nitrogen flow rate at the detector as was obtained in the "A" mode. b. Vial Prepressurizer Nitrogen. After the nitrogen carrier is set, solve the following equation and adjust the pressure on the vial prepressurizer accordingly. Where: T,Ambienl temperature. *K. T,Conditioning bath temperature. *K. PisCas chromatograph absolute dosing pressure (analysis mode), k Pa. P.i--Water vapor pressure @90* C (525.8 mm Hg). P,, Water vapor pressure @ 22* C (19.8 mm Hg). 7.50 m mm Hg per k Pa. 10 k Pas Factor to adjust the prepressurized pressure to slightly less than the dosing pressure. Because of gauge errors, the apparatus may over-pressunze the vial. If the vial pressure is at or higher than the dosing pressure, an audible double injection will occur. If the vial pressure is too low. errors will o< rnr on resin samples because of inaileqiiale tune for hr.nl space gas equilibrium This cimthluin can lie avoided by running several stand.ml gas samples at various pressures armiml the calculated pressure, and then seiec ting the highest pressure that does not produce a double injection. All samples and standards must be pressurized for tiO seconds using the vial prepressurizer. The vial is then placed into the 90* C conditioning bath and tested for leakage by placing a drop of water on the septum at the needle hole. A clean, burr-free needle is mandatory. c. Burner Air Supply. Set regulator on cylinder to read 50 psig. Set regulator on chromatograph to supply air to burner at a rale between 250 and 300 cc/min. Check with bubble flowmeter. d. Hydrogen Supply. Set regulator on cylinder to read 30 psig. Set regulator on chromatograph to supply approximately 35 5 cc/min. Optimize hydrogen flow to yield the most sensitive detector response without extinguishing the flame. Check flow with bubble meter and record this flow. 8.3.1.2 Temperature Adjustments. Set temperatures as follows: a. Oven (chromatograph column). 140* C. b. Dosing Line. 150* C. c. Injection Block. 170* G. d. Sample Chamber. Water Temperature. 90* C 1.0* C. 8.3.1.3 Ignition of Flame Ionization Detector. Ignite the detector according to the manufacturer's instructions. 8.3.1.4 Amplifier Balance. Balance the amplifier according to the manufacturer's instructions. 8.3.2 Programming the Chromatograph. Program the chromatograph as follows: a. I--Dosing or Injection Time. The normal setting is 2 seconds. b. A--"Analysis Time." The normal setting is approximately 70 percent nf the VCM retention time. When this timer terminates, the programmer initiates backflushing of the first column. c. B--Backflushing Time. The normal setting is double the "analysis tin. d. W--Stabilization Time. The normal setting it 05 min to 1.0 min. e. X--Number of Analyses Per Sample. The normal setting is one. 8.3.3 Preparation of Sample Turntable. Before placing any sample into turntable, be certain that the center section of the aluminum cap has been removed. All samples and standard# must be pressurized for 60 seconds by using the vial prepressurizer. The numbered sample vials should be placed in the corresponding numbered positions in the turntable. Insert samples in the following order Position 1 and 2--Old 2000-ppm standards for conditioning. These are necessary only after the analyzer has not been used for 24 hours or longer. Position 3--50-ppm standard, freshly prepared. Position 4--500-ppm standard, freshly prepared. CTL030444 39176 Fedoriil RojjisUtr / Vnl. 47. No. 17.'1 / Tucsd.iv. Soplcmlirr 7. 1!U! / Roli-s .itulf Kru'iil.itinns PosiImhi r,--2<xxi|>pni si.mil.ml. freshly prcp.iri'il. I'omIkiii l>--lixxippm sl.ind.ird, freshly prepared. Position 7--S.imple Nn. 7 (This is the first sample of the il.iv, lint is given .is 7 tu lie consistent with the lornt.ilile .mil the integrator printout ) After .ill samples hnvi> hern positioned, insert the second set of SO-. 500-. 20(X)-. and 4000-ppm standards. Snmples. including standards, must lie conditioned in the hath of 90` C for 1 hour (not to exceed 5 hours). 8.3.4 Start Chromatograph Program. When all samples, including standards, have been conditioned at 00' C for 1 hour, start the analysis program according to the manufacturer's instructions. These instructions must be carefully followed when starting and stopping a program to prevent damage to the dosing assembly. 8.3.5 Determination of TS. For wet cake, slurry, resin solution, and PVC latex samples, determine TS for each sample bv accurately weighing approximately 3 to 4 grams of sample in an aluminum pan before and after placing in a draft oven (105 to 110* C). Samples must be dried to constant weight. After First weighing, return the pan to the oven for a short period of time, and then reweigh to verify complete dryness. The TS are then calculated as the final sample weight divided by initial sample weight. 9. Calibration. Calibration is to be performed each 8-hour period when the instrument is used. Each day, prior to running samples, the column should be conditioned by running two 2000-ppm standards from the previous day. 9.1 Preparation of Standards. Calibration standards are prepared as follows: Place lOOpI or about two equal drops of distilled water in the sample vial, then Till the vial with the VCM/nitrogen standard, rapidly seat the septum, and seal with the aluminum cap. Use a Vin. stainless steel line from the cylinder to the vial. Do not use rubber or tygon tubing. The sample line from the cylinder must be purged (into a properly vented hood) for several minutes prior to filling the vials. After purging, reduce the flow rate to 500 to 1000 cc/min. Place end of tubing into vial (near bottom). Position a septum on top of the vial, pressing it against the K-in. filling tube to minimize the size of the vent opening. This is necessary to mimimize mixing air with the standard in the vial. Each vial is to be purged with standard for 90 seconds, during which time the filling tube is gradually slid to the top of the vial. After the 90 seconds, the tube is removed with the septum, simultaneously sealing the vial. Practice will be necessary to develop good technique. Rubber gloves should be worn during the above operations. The sealed vial must then be pressurized for 60 seconds using the vial prcprcssurizcr. Test the vial for leakage by placing a drop of water on the septum at the needle hole. 9.2 Preparation of Chromatograph Calibration Curve. Prepare two 50-. 500-. 21XXI . and 4IXXI ppm stand.iril samples Kan the r.ililir.itum samples ill exactly the same manner as regular samples. Pint A,, the integrator area counts for each standard sample, versus C,, the concentration of vinyl chloride in each slundard sample. Draw a straight line through the points derived by the least squares method. 10. Calculations. 10.1 Response Factor. If the calibration curve described in Section 9.2 passes through zero, a response factor. R,. may be used to compute vinyl chloride concentrations. To compute a response factor, divide any particular A. by the corresponding C^ As Rf * " c Eq. 107-1 Where: A, = Chromatograph area counts of vinyl chloride for flic sample P. Amhienl almosphein pressure, mm t le K, - Response l.u lor m aiea counts per ppm VCM T|- Ambient laboratory temperature. K M. - Molecular weight of VCM. ti2 5 g/ inolc. V. - Volume of the vapor phase, cm ' R = Cus constant. (fi23ti(l cm,) (mm I ig/ mole) ("K). m ~ Sample weight, g. K, = Henry's 1-iw Constant for VCM in PVC (oi 90* C. 6.52 x 10* g/g/mm I Ig. If the calibration curve does not pass through zero, the calibration curve must lie employed to calculate each sample concentration unless the error introduced by using a particular Rf is known. 10.2 Residual Vinyl Chloride Monomer Concentration. (C,,c) or Vinyl Chloride Monomer Concentration. Calculate C^, in ppm or mg/kg as follows: ArPa H.. V rvc -T51 * S (TS) T2 * S, <' T2 Eq. 107-2 Results calculated using these equations represent concentration based on the total sample. To obtain results based on dry PVC content, divide by TS. 11. References. 1. B.F. Goodrich. Residual Vinyl Chloride Monomer Content of Polyvinyl Chloride Resins. Latex. Wet Cake. Slurry and Water Samples. B.F. Goodrich Chemical Croup Standard Test Procedure No. 1005-E. B.F. Goodrich Technical Center. Avon Lake. Ohio. October 8.1979. 2. Berens. A.R. The Diffusion of Vinyl Chloride in Polyvinyl Chloride. ACS-- Division of Polymer Chemistry, Polymer Preprints 15 (2):197.1974. 3. Berens. A.R. The Diffusion of Vinyl Chloride in Polyvinyl Chloride. ACS-- Division of Polymer Chemistry. Polymer Preprints 75 (2):203.1974. 4. Berens. A.R.. L.B. Crider. C.J. Tomanek. and J.M. Whitney. Analysis for Vinyl Chloride in PVC Powders by Head--Space TS=Total solids expressed as a decimal fraction. T=Equilibrium temperature. *K. K = Henry's Law Constant for VCM in water @ 90* C. 7 x 10" ' g/g/mm Hg. Assuming the following conditions are met. these values can be substituted into Equation 107-2: P,=750 mm Hg. V,=Vial volume--sample volume (Fisher vials are 22.0 cm9 and Perkin-Elmer vials are 21.8 cm1). T, = 23* C or 296* K. T,=90* C or 363* K. a 750 r s (?1-8 Crvc * 5^T5S I-------- *--------nsars l>... 325 x 10'*(TS)(361) 7.0 x !0'7 (1-151(361) Gas Chromatography, journal of Applied Polymer Science. 79:3169-3172.1975. 5. Mansfield. R.A. The Evaluation of Henry's Law Constant (Kp) and Water Enhancement in the Pcrkin-Elmer Multifract F--10 Gas Chromatograph. B.F. Goodrich. Avon Lake. Ohio. February 10.1978. 40 CFR Part 61 is amended by adding Appendix C as follows: Appendix C--Quality Assurance Procedures Procedure 7--Determination of Adequate Chromatographic Peak Resolution In this method of dealing with resolution, the extent to which one chromatographic peak overlaps another is determined. For convenience, consider the range of the elution curve of each compound as running from -2<r to +2<r. This range is used in other resolution criteria, and it contains 95.45 percent of the area of a normul curve. If two CTL030445 Fedora! Register / Vnl. 47, No. 17.1 / Tuesrlay, September 7, I'MI / Rules and rfrqulnlinns 301 i peaks air separated by ,i known distance. b, one cun determine On* fraction of I lit* arr.i of onr curve fh.it hrs wilhm tlr rung** of the other. The extent to which the elution curve of a contaminant compound overlaps the curve of a compound that is tinder analysis is found by integrating the contaminant curve over the limits b- 2cr, to ba 2cr%, where <r, is the standard deviation of the sample curve. This calculation can be simplified in several ways. Overlap can be determined for curves of unit area; then actual areas can be introduced. Desired integration can be resolved into two integrals of the normal distribution function for which there are convenient calculation programs and tables. An example would be Program 15 in Texas Instruments Program Manual STl. 1975. Texas Instruments. Inc.. Dallas. Texas 75222. atujMQ cooe sko-so-m CTL030446 _3_`_M__7n JI Fctlor.-il Krjjistor / Vol. 47. No. 173 / Tiicsd.iv. Scplcmlicr 7, 1*1)12 / Rules ;m<f Rcuul.it inns b+2o < SLxf^L.^f.-V2Lria .Jf jmj r-y2 V2n J e' dx b-2o, b-2o b'- b+2o. The following calculation steps are required:* 1. 2o$ = tj/rTTiT? .2 oc = tc/2V21h2 3. x, = (b-2as)/oc 4. x2 = (b+2as)/oc f.(^ lx 5. Jx X1 f,(^ L6. Q(**) = -- V5ri *X2 7. I0 = Q(xj) - Q(x2) 8. Ao " !oAc/As 9. Percentage overlap = A0 x 100 , where: A = Area of the sample peak of Interest determined by electronic inte gration or by the formula As = hst$. Ac = Area of the contaminant peak, determined in the same manner as A$. b = Distance on the chromatographic chart that separates the maxima of the two peaks. H = Peak height of the sample compound of interest, measured from the average value of the baseline to the maximum of the curve. t$ = Width of samplepeak of interest at 1/2 peak height. t = Width of the contaminant peak at 1/2 of peak height. o s Standard deviation of the sample compound of interest elution curve. ac = Standard deviation of the contaminant elution curve. Q(x,) = Integral of the normal distribution function from xt to infinity. Q(x2) = Integral of the normal distribution function from x2 to infinity. IQ = Overlap integral. A, = Area overlap fraction. 0 *In most instances, Q(x2) is very small and may be neglected. BILLING COO 50>M>C CTL030447