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P7P6uC;,-/3Xu&_ x$&7XX .4wC;,HXw*0 xM7X2hL GMRQCG Times (Scalable)CG Times Bold (Scalable)CG Times Italic (Scalable)CG Times Bold Italic (Scalable)"Sh5^;LhddCCCdCCCCddddddddddCCȰdxLdxxoxxxCCCddCddYdYFdo88d8odddLL8oYdYLddddCdddddCddddddddd8dddddYYYYYL8L8L8L8oddddoooozYddddxYdxdddddddddddddddddood8ddddLdkdddxdxdxDx8ooddהddpLododxdxdxdoooooxdxLCddCCCWxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxNdddLdYYddddddCddddCCCkkd88ddzzdddsssCkdC"Ȑd~d尰dCCȐzȲxCddodȐȅdCdYdsȐ`ȐȐȮzȐUvŐdȐddCCCCŅzozoYNzYYYN8YooYdYzzdzddzYzYzozzzNdzzzYzzzzCCdddddddzzzzCzdYC   X Lp `F#` PjQ{P#Date of Release: 10/20/95; 15day changes Board Hearing: 9/28/95Њ California Environmental Protection Agency ]%AIR RESOURCES BOARD  Y -E PROPOSED ă  c < CALIFORNIA NON-METHANE ORGANIC GAS  c<YTEST PROCEDURES ă /Adopted: July 12, 1991 Amended: September 22, 1993 6Amended: _______________ 1 Monitoring and Laboratory Division, Southern Laboratory Branch -Mobile Source Division 59528 Telstar Avenue n&El Monte, California 91731  Y"-NOTE:` ` Mention of any trade name or commercial product does not constitute endorsement or recommendation of this product by the Air Resources Board. (#` XX` ` The regulatory amendments proposed in this rulemaking are shown in  Y&-underline to indicate additions and strikeout to indicate deletions from the version of the test procedures adopted on September 22, 1993. Modifications  Y](<to the originally noticed text are designated by bold italics and  bold strikeout  to represent additions and deletions, respectively.(#` "J),t*t*("     Y-! TABLE OF CONTENTS ă  Yw-A.General Applicability and Requirements`!(#nA1  YI-B.Determination of NonMethane Hydrocarbon Mass Emissions by Flame XIonization Detection(#`"(#pB1  Y -C.XMethod 1001: Determination of Alcohols in Automotive Source Samples by Gas (# XChromatography(#`!(#pC1  Y iD.Method 1002: Determination of C2 to C5  Hydrocarbons in Automotive XSource Samples by Gas Chromatography(#`!(#oD1  YziE.Method 1003: Determination of C6 to C12 Hydrocarbons in Automotive XSource Samples by Gas Chromatography(#`"(#qE1  Y5-F.XMethod 1004: Determination of Aldehyde and Ketone Compounds in(# XAutomotive Source Samples by High Performance Liquid Chromatography(#` "(#qF1  Y-G.Determination of NonMethane Organic Gas Mass Emissions`!(#pG1  Y-q@ APPENDICES ă  Y~-Appendix 1` `  List of LightEnd and MidRange Hydrocarbons`"(#r11  YP-Appendix 2` `  Definitions and Commonly Used Abbreviations`"(#r21  Y"-Appendix 3` `  References`"(#r31ă"",t*t*"   @A-@  Y-W Part A ă  X- v GENERAL APPLICABILITY AND REQUIREMENTS ă  Yw-1.XThese test procedures shall apply to all 1993 and subsequent model-year transitional low-emission vehicles (TLEV), low-emission vehicles (LEV), and ultra low-emission vehicles (ULEV) certifying to non-methane organic gas (NMOG) emission standards.(#  Y -2.XThis document sets forth the analysis and calculation procedures that shall be performed to determine NMOG mass emissions. The document consists of the following parts: (#  Y -XA.` ` General Applicability and Requirements(#  Y -XB.X` ` Determination of Non-Methane Hydrocarbon Mass Emissions by Flame Ionization Detection (#`  Yz-XC.X` ` Determination of Alcohols in Automotive Source Samples by Gas Chromatography (Method No. 1001) (#`  YLiXD.X` ` Determination of C2 to C5 Hydrocarbons in Automotive Source Samples by Gas Chromatography (Method No. 1002) (#`  YiXE.X` ` Determination of C6 to C12 Hydrocarbons in Automotive Source Samples by Gas Chromatography (Method No. 1003) (#`  Y-XF.X` ` Determination of Aldehyde and Ketone Compounds in Automotive Source Samples by High Performance Liquid Chromatography (Method No. 1004).(#`  Y-XG.X` ` Determination of NMOG Mass Emissions(#`  Y-Appendix 1 List of LightEnd and MidRange Hydrocarbons  Y}-Appendix 2 Definitions and Commonly Used Abbreviations  Yf-Appendix 3 References Alternative procedures may be used if shown to yield equivalent results and if approved in advance by the Executive Officer of the Air Resources Board.  Y-3.XThe analyses specified in the table below shall be performed to determine mass emission rates of NMOG in grams per mile (g/mi) or milligrams per mile (mg/mi) for vehicles operated on the listed fuel:(# "!,t*t* " ^ ddx !ddx """"^       Y- Fuel{"H NMHC by FID{"CuNMHC by GC{"Alcohols{" X-)PCarbonyls      Alcohol " X "m "X "EX q { h  CNG}h" }h"hX}h" }h"EXq q   hh  Dieselh" Xh"mh" h"EXq q } hh  Gasoline_h" X_h"m_h" _h"EXq    h  LPG " X "m "  "EX  _  Y - where "LPG" means "liquified petroleum gas", "CNG" means "compressed natural gas", "NMHC" means "non-methane hydrocarbon", "FID" means "flame ionization detector", and  Y -"GC" means "gas chromatograph." The specified analyses shall be performed in accordance with the following parts of this document:  Yv- NMHC by FID  --` Part B.VDetermination of Non-Methane Hydrocarbon Mass Emissions by Flame Ionization Detection(#  YIi NMHC by GC  --Part D. VDetermination of C2 to C5 Hydrocarbons in Automotive Source Samples by Gas Chromatography (Method No. 1002); and (#  YiXX` ` X XPart E.VDetermination of C6 to C12 Hydrocarbons in Automotive Source Samples by Gas Chromatography (Method No. 1003) (#  Y- CARBONYLS  --XPart F.VDetermination of Aldehyde and Ketone Compounds in Automotive Source Samples by High Performance Liquid Chromatography (Method No. 1004) (#  Ye- ALCOHOLS  --XPart C.VDetermination of Alcohols in Automotive Source Samples by Gas Chromatography (Method No. 1001)(#  Y -4XFor those manufacturers which choose to develop reactivity adjustment factors unique to a specific engine family, exhaust NMOG emissions shall be fully speciated. NMHC emissions shall be analyzed in accordance with parts D and E (Method Nos. 1002 and 1003). In addition, aldehydes and ketones, alcohols, and ethers shall be analyzed according to parts F, C, and E (Method Nos. 1004, 1001, and 1003). Analysis for alcohols shall be required only for vehicles which are operated on fuels containing alcohols.(#  YR%-5.XFor natural gas-fueled vehicles, the methane concentration in the exhaust sample shall be measured with a methane analyzer. A GC combined with a FID is used for direct measurement of methane concentrations. SAE Recommended Practice J1151 is a reference on generally accepted GC principles and analytical techniques for this  Y(-application. A density of 18.89 g/ft3 shall be used to determine the methane mass"(,t*t*(%" emissions. The methane mass emissions shall be multiplied by the appropriate methane reactivity adjustment factor and then added to the reactivity-adjusted NMOG emissions as specified in "California Exhaust Emission Standards and Test Procedures for 1988 and Subsequent Model Passenger Cars, Light-Duty Trucks,and Medium-Duty Vehicles."(#  Yv-6.XThe mass of NMOG emissions shall be calculated in accordance with part G, "Determination of NMOG Mass Emissions". The mass of NMOG emissions in g/mile or mg/mile shall be calculated by summing the mass of NMHC determined by the FID, the mass of aldehydes and ketones, and the mass of alcohols.(# " ,t*t* %"   @A-B-@  Y-zR PART B ă  X- &DETERMINATION OF  NON-METHANE HYDROCARBON MASS EMISSIONS  X- BY FLAME IONIZATION DETECTION ă  XI- 1.XINTRODUCTION (#  Y -1.1XThis procedure describes a method for determining non-methane hydrocarbon  Y - ( NMHC ) exhaust mass emissions from motor vehicles. Other applicable forms of instrumentation and analytical techniques which prove to yield equivalent results to those specified in this procedure may be used subject to the approval of the Executive Officer of the Air Resources Board.(#  Y-1.2All definitions and abbreviations are contained in Appendix 2 of these test procedures.  Xc- 2.XTOTAL HYDROCARBON MEASUREMENT (#  Y5-2.1XA flame ionization detector (FID ) is used to measure total hydrocarbon concentration  Y-in vehicle exhaust in accordance with the Code of Federal Regulations.[Ref 1] SAE  Y-Recommended Practices J254[Ref. 2] and J1094a[Ref. 3] are references on generally accepted gas analysis and constant volume sampling techniques. For Beckman 400  Y-FIDs only, implementation of the recommendations outlined in SAE paper 770141 , "Optimization of Flame Ionization Detector for Determination of Hydrocarbons in  Y-Diluted Automobile Exhaust;" author, Glenn D. Reschke [Ref. 4] shall be required. Other FID analyzer models shall be checked and adjusted, if necessary, to minimize any non-uniformity of relative response to different hydrocarbons.(#  XO- 3.XMETHANE MEASUREMENT (#  Y!-3.1XA gas chromatograph (GC ) combined with a FID constitute a methane analyzer and shall be used for direct measurement of methane concentrations. The SAE  Y-Recommended Practice J1151[Ref. 5] is a reference on generally accepted GC principles and analytical techniques for this specific application.(#  X!- 4.XTOTAL HC FID RESPONSE TO METHANE (#  Y#-4.1XThe FID is calibrated to propane and therefore tends to over respond to the methane portion of the vehicle exhaust sample during hydrocarbon analysis. In order to calculate the NMHC concentration, a methane response factor must be applied to the methane concentration (as measured by the methane analyzer) before it can be deducted from the total hydrocarbon concentration. To determine the total hydrocarbon FID response to methane, known methane in air concentrations traceable  Y(-to National Institute of Standards and Technology ( NIST ) shall be analyzed by the"(,t*t*'%" FID. Several methane concentrations shall be analyzed by the FID in the range of the exhaust sample concentration. The total hydrocarbon FID response to methane is calculated as follows:(#  Yi<XX` ` rCH T< 4   =hh,FIDppm/SAMppm(# Xwhere:(#  Y_i` ` rCH  $ 4 3  =hh,FID methane response factor.(#`  YHi` ` FIDppm= hh,FID reading in ppmC. (#`  Y1i` ` SAMppm = hh,the known methane concentration in ppmC.(#` XThe FID response to methane shall be checked at each calibration interval.(#  X - 5.XNMHC MASS EMISSION PER TEST PHASE (#  Y -5.1XThe following calculations shall be used to determine the NMHC mass emissions for  Y-each phase of the Federal Test Procedure. [Ref. 1].(#  Yb-5.2X Non-Alcohol Fueled Vehicles (#  Y5i<5.2.1` ` NMHCe = FID THCe - (rCH < 4  !  * CH4e )  YiX` ` NOTE: If NMHCe is calculated to be less than zero, then NMHCe = 0.(#  Yi<X5.2.2` ` NMHCd = FID THCd - (rCH < 4    * CH4d )(#  YiX` ` NOTE: If NMHCd is calculated to be less than zero, then NMHCd = 0.(#  YiX5.2.3X` ` COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem(#` XX` ` NOTE: If a CO instrument which meets the criteria specified in CFR 40,  Y}i86.111 is used and the conditioning column has been deleted, COem must be  Yfisubstituted directly for COe.(#`  Y8i` ` a) For gasoline, CH1.85 , where HCR = 1.85:  Y!iXX` ` X COe = (1 - 0.01925 * CO2e - 0.000323 * Ra ) * COem(#  Y i` ` b) For Phase 2 gasoline, CH1.94 , where HCR = 1.94:  Yi` `  COe = (1 - 0.01970 * CO2e - 0.000323 * Ra ) * COem  Yi` ` b c) For LPG, CH 2.66 2.64, where HCR = 2.66 2.64:  Y iXX` ` X COe = (1 - 0.02330 0.02320 * CO2e - 0.000323 * Ra) * COem(#  Y!i` ` d) For CNG, CH3.78, where HCR = 3.78:  Y"iXX` ` X COe = (1 - 0.02890 * CO2e - 0.000323 * Ra) * COem(#  Yi$- ` `  100 *  x  ` `  hh,x + y/2 + 3.76 * (x + y/4 - z/2)  Y;&-5.2.4` ` DF =    Y$'i` `  CO2e + (NMHCe + CH4e + COe ) * 10é4   Y(iXX` ` (where fuel composition is CxHyOz as measured for the fuel used.)(#` "(,t*t*--%"Ԍ YiԙXX` ` a) For gasoline, CH1.85 , where x = 1, y = 1.85, and z = 0:(#`  YiXX` ` X DF = 13.47 / [CO2e + (NMHCe + CH4e + COe ) * 10é4 ](#  Yi` ` b) For Phase 2 gasoline, CH1.94 , x = 1, y = 1.94 and z = 0.017:  Yi` `  DF = 13.29 / [CO2e + (NMHCe + CH4e + COe ) * 10é4 ]  Y-  YviXX` ` c)X For LPG, CH 2.66  2.64 , where x = 1, y = 2.66 2.64, and z = 0:(#  Y_iXX` ` X DF = 11.64 11.68 / [CO2e + (NMHCe + CH4e + COe) * 10é4 ](#  Y1i` ` d) For CNG, CH3.78, where x = 1, y = 3.78, and z = 0.016:  Y iXX` ` X DF = 9.83 / [CO2e + (NMHCe + CH4e + COe) * 10é4 ](#  Y -5.3X Vehicles Operating on Fuels Containing Methanol (#  Y ixX5.3.1` ` NMHCe = FID THCe - (rCH o< 4   * CH4e) - (rCH o< 3  OH * CH3OHe )(#  Y iXX` ` NOTE: If NMHCe is calculated to be less than zero, then NMHCe = 0.(#`  YzixX5.3.2` ` NMHCd = FID THCd - (rCH *< 4 f  * CH4d ) - (rCH *< 3 f OH * CH3OHd )(#  YciXX` ` NOTE: If NMHCd is calculated to be less than zero, then NMHCd = 0.(#`  Y5iX5.3.3X` ` COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem(#` XX` ` NOTE: If a CO instrument which meets the criteria specified in CFR 40  Yi86.111 is used and the conditioning column has been deleted, COem must be  Yisubstituted directly for COe .(#`  YiXX` ` a) For M100 (100% methanol), CH3OH, where HCR = 4:(#`  Yi` `  COe = (1 - 0.03000 * CO2e - 0.000323 * Ra ) * COem  Y}i` ` b) For M85 (85% methanol, 15% indolene), CH3.41 O0.72 , where ` `  HCR = 3.41:  Y8i` `  COe = (1 - 0.02705 * CO2e - 0.000323 * Ra ) * COem  Y -v` `  100 *  x  ` `  x + y/2 + 3.76 * (x + y/4 - z/2)  Y-5.3.4` ` DF =   Y -  Y!i` `  CO2e + (NMHCe + CH4e + COe + CH3 OHe + HCHOe ) * 10é4  Y"iv` ` (where fuel composition is CxHyOz as measured for the fuel used.)  X   Yi$i` ` a) For M100 (100% methanol), CH3OH, where x = 1, y = 4, and z = 1:  YR%i XX` ` DF = 11.57 / [CO2e + (NMHCe+ CH4e + COe + CH3OHe + HCHOe ) * 10é4 ]ƀ%`  Y$'i` ` b) For M85 (85% methanol, 15% Indolene), CH3.41 O0.72 , where x = 1, ` `  y = 3.41, and z = 0.72:  Y(i` ` DF = 12.02 / [CO2e + (NMHCe + CH4e + COe + CH3OHe + HCHOe) * 10é4 ] "(,t*t*.;%"Ԍ Y-ԙ5.4 Vehicles Operating on Fuels Containing Ethanol  Yi5.4.1` ` NMHCe = FID THCe - (rCH < 4    * CH4e ) - (rC < 2  H < 5  OH * C2H5OHe )  Yi` ` NOTE: If NMHCe is calculated to be less than zero, then NMHCe = 0.  Yi5.4.2` ` NMHCd = FID THCd - (rCH > < 4  z  * CH4d ) - (rC > < 2 z H > < 5 z OH * C2H5OHd)ƀ%`  Ywi` ` NOTE: If NMHCd is calculated to be less than zero, then NMHCd = 0.  YIi5.4.3` ` COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COemƀ%` XX` ` NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is  Y iused and the conditioning column has been deleted, COem must be substituted directly  Y ifor COe .ƀ%`  Y iX` ` a) For E100 (100% ethanol), C2H5OH, where HCR = 3:ƀ%  Y iX` `  COe = (1 - 0.02500 * CO2e - 0.000323 * Ra ) * COemƀ%  Y -` `  100 *  x   Y- ` `  hh,x + y/2 + 3.76 * (x + y/4 - z/2)  Yz-5.4.4` ` DF =   Yci` `  CO2e + (NMHCe + CH4e + COe + C2 H5 OHe + HCHOe ) * 10é4  YLi` ` (where fuel composition is CxHyOz as measured for the fuel used.)  YiXX` ` a) For E100 (100% ethanol), C2H5OH, where x = 1, y = 3, and z = 0.5:ƀ%`  Yi` ` DF = 12.29 / [CO2e + (NMHCe + CH4e + COe + C2 H5 OHe + HCHOe ) * 10é4 ]  Y-5.5X All Vehicles ƀ%  Yi5.5.1` ` NMHCconc = NMHCe - NMHCd * [1 - (1 / DF)]  Yi` ` NOTE: If NMHCconc is calculated to be less than zero, then NMHCconc = 0.  Ygi<X5.5.2` ` NMHCmass < n  S  = NMHCconc * NMHCdens * VMIX * 10é6ƀ%  X"- 6.XTOTAL WEIGHTED NMHC MASS EMISSIONS ƀ%  Y-6.1XAll Vehiclesƀ%   Y i` `   NMHCmass 1 + NMHCmass 2 NMHCmass 3 + NMHCmass 2%% Y!i6.1.1NMHCwm = 0.43 * ______________________ pp+ 0.57 * ___________________  Y"i` `  hh,Dphase 1 + Dphase 2   Dphase 3 + Dphase 2 "j$ ,t*t*)%"Ԍ X- E7.XSAMPLE CALCULATIONS ƀ%  Y-7.1XGiven the following data for a gasoline vehicle, calculate the weighted NMHC mass emission.ƀ%  XXX   !ddx """" AXddx  "   c _" 2 2  Test Phaseg FID  YiTHCe (ppmC) FID  YiTHCd (ppmC)  Y5iCH4e (ppmC)  Y5iCH4d (ppmC)  Y5iCOem (ppm)  Y5iCO2e (%) VMIX  Y-(ft3)  Y5iDphase n (mile)   Y5iRa (%)c q  2h 2  1a h 41.8a h 8.6a h 7.53a h 5.27a h 147.2a h 1.19a h 2846a h 3.583 a h 38q q  2hh 2  2 h 13.0 h 8.4 h 5.68 h 5.10 h 20.8 h 0.80 h 4856 h 3.848  h 38q   a  2h 2  3s  15.4s  8.9s  6.16s  5.20s  36.7s  1.04s  2839s  3.586 s  38     XXX EFor Phase 1:  Y.i<NMHCe = FID THCe - (rCH < 4   * CH4e ) ` `  = 41.8 ppmC - (1.04 * 7.53 ppmC) ` `  = 33.97 ppmC  Yi<NMHCd = FID THCd - (rCH < 4   * CH4d ) ` `  = 8.6 ppmC - (1.04 * 5.27 ppmC) ` `  = 3.12 ppmC  YviCOe ` ` = (1 - 0.01925 * CO2e - 0.000323 * Ra ) * COem XX` ` NOTE: If a CO instrument which meets the criteria specified in CFR 40,  YHi86.111 is used and the conditioning column has been deleted, COem must be  Y1isubstituted directly for COe .(#` ` ` = (1 - 0.01925 * 1.19% - 0.000323 * 38%) * 147.18 ppm XX` ` = 142.0 ppmƀ%`  YiDF ` ` = 13.47 / [CO2e + (NMHCe + CH4e + COe ) * 10é4  Y-` ` =  13.47   Yy - ` ` 1.19% + (33.97 ppmC + 7.53 ppmC + 142.0 ppmC) * 10é4 ` ` = 11.15  Y$i NMHCconc  = NMHCe - NMHCd * [1 - (1 / DF)] ` `  = 33.97 ppmC - 3.12 ppmC * [1-(1/11.15)] ` `  = 31.13 ppmC  Y'iNMHCmass n  = NMHCconc * NMHCdens * VMIX * 10é6  Y(-` `  = 31.13 ppmC * 16.33 g/ft3 * 2846 ft3 * 10é6"( ,t*t*?* "Ԍ YiԙNMHCmass 1  = 1.45 g  YiSimilarly, for Phase 2: hh,NMHCmass 2 = 0.33 g  Yiand for Phase 3:hh,NMHCmass 3 = 0.27 g Therefore,  Y_i` `   NMHCmass 1 + NMHCmass 2 NMHCmass 3 + NMHCmass 2  YHiNMHCwm` ` = 0.43 * ______________________ pp+ 0.57 * ________________  Y1i` `  Dphase 1 + Dphase 2pp Dphase 3 + Dphase 2  Y -` ` = 0.43 *  1.45 g + 0.33 g  + pp0.57 *  0.27 g + 0.33 g   Y -` `  3.583 mile + 3.848 milepp3.586 mile + 3.848 mile  Y iNMHCwm ` ` = 0.15 g/mile  Y-7.2XGiven the following data for a vehicle operating on 85% methanol and 15% gasoline (M85), calculate the weighted NMHC mass emission.ƀ%  XXX #c P7P# AXddx  aXddx4  "     " :9 :  Test PhaselI FID  xPKTHCe (ppmC)49 FID  xPKTHCd (ppmC)49  xPKCH4e (ppmC)49  xPKCH4d  xP-(ppmc)49  `F<CH3OHe (ppm)49  xPKCOem (ppm)49  xPKCO2e (%)49 VMIX  xP-(ft3) 49  xPKDphase n (mile) 49  xPKRa (%) 49  `F<HCHOe (ppm) P 4 :9Y :  1Y 88.5Y 5.5Y 17.76Y 2.82Y 72.9Y 303.2Y 1.28Y 2832 Y 3.570 Y 32 Y 0.96P P 4 :YY :  2Y 14.5Y 7.0Y 8.01Y 2.82Y 5.1Y 9.7Y 0.83Y 4827 Y 3.850 Y 32 Y 0.10P    :Y :  3T 21.8T 7.7T 10.13T 2.93T 7.4T 18.2T 1.13T 2825 T 3.586 T 32 T 0.12    YT-#Xw P7[hXP#  Y=i XXX [For this example, CH3OHd was assumed to be 0.0 ppmC for all three background bag samples.] vFor Phase 1:  YixNMHCe = FID THCe - (rCH "< 4 "  * CH4e ) - (rCH "< 3 " OH * CH3OHe )  Y-` `  = 88.5 ppmC - (1.04*17.76 ppmC) - (0.66*72.9 ppmC)  Y-` `  = 21.92 ppmC v  Y!ixNMHCd =FID THCd - (rCH 5&< 4 q&  * CH4d ) - (rCH 5&< 3 q& OH * CH3OHd )  Yn"-` `  =5.5 ppmC - (1.04*2.82 ppmC) - (0.66*0.0 ppmC)  YW#- ` `  = 2.57 ppmC "@$ ,t*t*&#"Ԍ YivCOe` ` = (1 - 0.02705 * CO2e - 0.000323 * Ra ) * COem XNOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and  Yithe conditioning column has been deleted, COem must be substituted directly for COe .ƀ% ` ` = (1 - 0.02705 * 1.28% - 0.000323 * 32%) * 303.2 ppm ` ` = 289.6 ppmv  Y_iDF` ` = 12.02 / [CO2e + (NMHCe + CH4e + COe + CH3OHe + HCHOe ) * 10é4]  Y1-=` `  12.02   Y - 1.28% + (21.92ppmC + 17.76ppmC + 289.6 ppmC + 72.9ppmC + 0.96ppm) * 10é4 ` ` = 9.10  Y iNMHCconc = NMHCe - NMHCd * [1 - (1 / DF)]  Y -` `  = 21.92 ppmC - 2.57 ppmC * [1 - (1 / 9.10)]  Y - ` `  = 19.63 ppmC  YyiNMHCmass n =NMHCconc * NMHCdens * VMIX * 10é6   YKiNMHCmass 1 = 0.91 g  YiSimilarly, Phase 2:NMHCmass 2 = 0.0 g  Yiand for Phase 3:NMHCmass 3 = 0.10 g Therefore,  Yi` `   NMHCmass 1 + NMHCmass 2 NMHCmass 3 + NMHCmass 2  YiNMHCwm` ` = 0.43 * ______________________ pp+ 0.57 * ________________  Y|i` `  Dphase 1 + Dphase 2pp Dphase 3 + Dphase 2  YN-` ` = 0.43 *  0.91 g + 0.00 g  + pp0.57 *  0.10 g + 0.0 g   Y7-` `  3.570 mile + 3.850 milepp3.586 mile + 3.850 mile  Y iNMHCwm ` ` = 0.06 g/mile  Y - 8.X DEFINITIONS ƀ%  Y"iCH3OHd = ` ` the methanol concentration in the dilution air as determined from the dilution air methanol sample using the procedure specified in Method No. 1001, ppmC.ƀ%`  YR%iCH3OHe =` ` the methanol concentration in the dilute exhaust as determined from the dilute exhaust methanol sample using the procedure specified in Method No. 1001, ppmC.ƀ%`  Y (iCH4d =` ` the methane concentration in the dilution air, ppmC.ƀ%` "( ,t*t*k+#"Ԍ YiCH4e =` ` the methane concentration in the dilute exhaust, ppmC.ƀ%`  YiC2H5OHd =` ` the ethanol concentration in the dilution air as determined from the dilution air ethanol sample using the procedure specified in Method No. 1001, ppmC.ƀ%`  YiC2H5OHe =` ` the ethanol concentration in the dilute exhaust as determined from the dilute exhaust ethanol sample using the procedure specified in Method No. 1001, ppmC.ƀ%`  YHiCOe =` ` the carbon monoxide concentration in the dilute exhaust corrected for carbon dioxide and water removal, ppm.ƀ%`  Y iCOem =` ` the carbon monoxide concentration in the dilute exhaust uncorrected for carbon dioxide and water removal, ppm.ƀ%`  Y iCO2e =` ` the carbon dioxide concentration in the dilute exhaust, %.ƀ%`  YiDphase n =` ` the distance driven by the test vehicle on a chassis dynamometer during test phase n (where n is either 1, 2, or 3), mile.ƀ%`  YK-DF =XX` ` dilution factor.ƀ%`  YiFID THCd =` ` the total hydrocarbon concentration including methane and methanol (for methanol-fueled engines) or ethanol (for ethanol-fueled engines) in the dilution air as measured by the FID, ppmC.ƀ%`  YiFID THCd =` ` the total hydrocarbon concentration including methane and methanol (for methanol-fueled engines) or ethanol (for ethanol-fueled engines) in the dilute exhaust as measured by the FID, ppmC.ƀ%`  YeiHCHOe =` ` the formaldehyde concentration in the dilute exhaust as determined from the dilute exhaust carbonyl sample using the procedure specified in Method No. 1004, ppm.ƀ%`  Y -HCR =` ` the hydrogen-to-carbon ratio for the fuel used.ƀ%`  YiNMHCconc =` ` the non-methane hydrocarbon concentration in the dilute exhaust corrected for background, ppmC.ƀ%`  Y!iNMHCd =` ` the non-methane hydrocarbon concentration in the dilution air corrected for methane and alcohol removal, ppmC.ƀ%`  Yh$iNMHCdens =` ` the mass per unit volume of non-methane hydrocarbon corrected to standard  YQ%-conditions (16.33 g/ft3 at 293.16o K and 760 mm Hg assuming a C:H ratio of 1:1.85  Y:&-and 17.28 g/ft3 for LPG at 293.16o K and 760 mm Hg), g/ft3 .ƀ%`  Y (iNMHCe =` ` the non-methane hydrocarbon concentration in the dilute exhaust corrected for methane and alcohol removal, ppmC.ƀ%` "( ,t*t*+#"Ԍ YiԙNMHCmass n=` ` the mass emission of non-methane hydrocarbon per test phase n (where n is either 1, 2, or 3), g.ƀ%`  YiNMHCwm =` ` the total weighted mass of non-methane hydrocarbon per mile for all three phases of the FTP, g/mile.ƀ%`  YviRa =XX` ` the relative humidity of the ambient air, percent.ƀ%`  YHi<rCH < 3 4 OH =` ` the FID response factor to methanol (see CFR 40, 86.121-90(c)).ƀ%`  Y i<rCH < 4   =` ` the FID response factor to methane (see section 4).ƀ%`  Y ixrC < 2  H < 5  OH =` ` the FID response factor to ethanol (same procedure for methanol response factor, see CFR 40, 86.121-90(c)).ƀ%`  Y -VMIX =` ` the total dilute exhaust volume measured per test phase and corrected to standard  Y-conditions (293.16o K and 760 mm Hg), ft3 .ƀ%`  YK-9.X REFERENCES ƀ%  Y-X(1)X` ` Code of Federal Regulations, Title 40, Part 86, Subpart Bƀ%`  Y-X(2)X` ` SAE J254, "Instrumentation and Techniques for Exhaust Gas Emissions Measurement"ƀ%`  Y-X(3)X` ` SAE J1094a, "Constant Volume Sampler System for Exhaust Emissions Measurement"ƀ%`  Yf-X(4)X` ` SAE 770141, "Optimization of a Flame Ionization Detector for Determination of Hydrocarbon in Diluted Automotive Exhausts". G.D. Reschke, Vehicle Emissions Laboratory, General Motors Proving Groundƀ%`  Y -X(5)X` ` SAE J1154, "Methane Measurement Using Gas Chromatography", (revised  Y-December 1991) ƀ%` ",t*t*9!#"   @B-C-@ XX     X- lPart C DETERMINATION OF ALCOHOLS IN AUTOMOTIVE SOURCE SAMPLES jBY GAS CHROMATOGRAPHY BMETHOD NO. 1001  Y1-   Y -1.X INTRODUCTION ƀ%  Y -1.1XThis document describes a method of sampling and analyzing automotive exhaust for alcohols  Y -in the range of 8 to 1200 micrograms g per 15 milliliters ( mL ) of solution. The "target"  Y -alcohols which shall be analyzed and reported by this method are methanol and ethanol.  Y-These alcohols, when present in concentrations above the LOD, shall be reported. ƀ%  Yc-1.2XThis procedure is based on a method developed by the U. S. Environmental Protection  YL-Agency, (U.S. EPA) [Ref 9.1 6] which involves flowing diluted engine exhaust through  Y5-deionized or purified water contained in glass impingers and analyzing this solution by gas  Y-chromatography (GC) .ƀ%  Y-1.3All definitions and abbreviations are contained in Appendix 2 of these test procedures.  Y-2.X METHOD SUMMARY ƀ%  Y-2.1XThe samples are received by the laboratory in impingers. Compound separation and analysis are performed using a GC. The sample is injected into the GC by means of a liquid  Yg-autosampler. Separation of the sample mixture into its components constituents is performed  YP-by using a temperatureprogrammed capillary column operated with a temperature  gradient .  Y9-A flame ionization detector ( FID ) is used for alcohol detection and quantification.ƀ%  Y -2.2XThe computerized GC data system identifies the alcohol associated with each of the peak s . The alcohol concentrations are determined by integrating the peak areas and using response  Y-factors determined with from external standards.ƀ%  Y!-3.X INTERFERENCES AND LIMITATIONS ƀ%  Y#-3.1XAn interference interferent is any component present in the sample with a retention time  Yk$-similar to that of any the target alcohol s described in this method. To reduce interference  YT%-error, proof of chemical identity may require performance of periodic confirmations using an  Y=&-alternate method and/or instrumentation, e.g., gas chromatograph/mass spectrometer  Y&'-( GC/MS ) .ƀ% "(,t*t*&#"Ԍ Y-3.2XThe concentration of the alcohols in the range of interest is stable for up to six days as long  Y-as the samples are sealed and refrigerated at a temperature below 40o F.ƀ%  Y-4.X INSTRUMENTATION AND APPARATUS ƀ%  Y-4.1XFor each mode of the CVS test, two sampling impingers, each containing a known amount of  Yw-deionized or purified water (e.g. 15 mL for this procedure), are used to contain the sample.ƀ%  Y`-X4.1.1X` ` A temperature-programmable GC, equipped with a DB-Wax Megabore column (30  YI- meter ( m ) , 0.53 millimeter ( mm ) ID, 1.0 micron (  ) film thickness) and FID is used.  Y2-Other columns may be used, provided the alternate(s) can be demonstrated to be equivalent or better with respect to precision, accuracy and resolution of all the target  Y -alcohols. ƀ%`  Y -X4.1.2X` ` A liquid autosampler is required.ƀ%`  Y -X4.1.3X` ` A PC-controlled data acquisition system for quantitation quantifying of peak areas is required.ƀ%`  Y-5.X REAGENTS AND MATERIALS ƀ%  Yd-5.1XMethanol shall have a purity of 99.9 percent, or be high performance liquid chromatography grade, EM Science or equivalent.ƀ%  Y-5.2XEthanol shall be absolute, ACS reagent grade.ƀ%  Y-5.3X American Standards for Testing Materials ASTM Type I purified or Type II deionized water  Y-shall be used.ƀ%  Y<5.4XA stock solution is prepared gravimetrically or volumetrically  by diluting methanol and  Y-ethanol with deionized or purified water, e.g., for this method the stock solution contains is  Y-approximately 1 g/mL percent by volume of each target alcohol.ƀ%  Yk-5.4.1` ` A calibration standard within at the expected concentration range of the samples is  YU-prepared by successive dilutions of the stock solution with deionized or purified  Y>-water, e.g., 50 parts per million (ppm) g/mL volume to volume (v/v) is typical.ƀ%`  Y'-5.4.2` ` A control standard containing all target alcohols is prepared by successive dilutions of a stock solution different from that of Section 5.4.1. This standard, at an  Y-approximate concentration of the samples, is used to monitor the precision of the  Y-analysis of update control charts for each target alcohol.ƀ%`  Y -5.4.3` ` All standards should be refrigerated at less than a temperature below 40o F during storage.ƀ%`  Y#-5.5XGas requirements.ƀ%  Yp$-5.5.1` ` Air shall be "Zero" grade. "Ultrazero" grade may be required to achieve the LOD  YY%-required by Section 8.8.ƀ%`  YB&-5.5.2` ` Nitrogen shall have a minimum purity of 99.998 percent.  Y+'-5.5.3` ` Helium shall have a minimum purity of 99.995 percent.  Y(-5.5.4` ` Hydrogen shall have a minimum purity of 99.995 percent. "(,t*t*'#"Ԍ Y-w6. PROCEDURE  Y-6.1XEach of the graduated fritted sampling impingers is filled with 15 mL of deionized or  Y-purified water.ƀ%  Y-w6.2XThe impingers are placed in an ice bath during the sample collection.ƀ%  Y`-6.3XAfter sampling, the impingers are allowed to warm to room temperature and the solution contained in each impinger is transferred to a vial and sealed.ƀ%  Y2-6.3.1` ` Samples should shall be refrigerated ( at a temperature below 40o F or lower) if immediate analysis is not feasible, or if reanalysis at a later date may be required.ƀ%`  Y -6.4XOne microliter aliquots of unmodified samples are injected via autosampler into a GC.  Y -Suggested standard operating conditions for the GC are:, configured as follows: ƀ%  Y -XColumn: DB- w Wax, 30 m, 0.53 mm ID, 1.0 film thickness ƀ%  Y -Carrier gas flow: Helium at 5 milliliters per minute ( mL/min )  Y-Make-up gas flow:Nitrogen at 25 mL/min  Yz-Detector: ` FID, Hydrogen at 30 mL/min and Air at 300 mL/min ƀ%  Yc-Injector: XPacked column injector with Megabore adapter insert; on-column injection ƀ%  Y5-Column t T emperature: hh,50o C (1 min), 50o C to 70o C (5o C/min), 70o C to 110oĠC (15o  Y-C/min), 110o C (4 min) ƀ%h  Y-XData system: PC-based data acquisition systemƀ%  Y-X6.4.1X` ` One calibration standard, one control standard, and one deionized or purified water blank are analyzed daily at the beginning of each set of samples.ƀ%`  Y-X6.4.2X` ` A replicate analysis is performed at least once per 24 hour period.ƀ%`  Y-X6.4.3X` ` The control standard is analyzed performed at least once per 24 hour period.ƀ%`  Y}-X6.4.4X` ` For Samples containing compounds having concentrations above the documented  Yf-range of instrument linearity , the sample must be diluted and reanalyzed.ƀ%`  YO-X6.4.5X` ` The peak integrations are corrected as necessary in the data system. Any misplaced baseline segments are corrected in the reconstructed chromatogram.ƀ%`  Y!-X6.4.6X` ` The peak identifications provided by the computer are checked and corrected if necessary.ƀ%`  Y-X6.4.7X` ` The target alcohol peaks at or above the maximum allowable limit of detection ( LOD )  Y-are reported (Section 8.8).  At the laboratory's discretion, peaks at or above the LOD calculated in section 8.8 may be reported. The calculated LOD must be lower than  Y!-the maximum allowable LOD .ƀ%`  Y#-7.X CALCULATIONS ƀ%  YS%-7.1XThe concentration of each target alcohol, in g/mL, is determined by the following calculation that compares the sample peak area with that of an external standard:ƀ%   Y(id Concentration (g/mL)sample = Peak Areasample x Response Factor "(,t*t*#(#"ԌXwhere the response factor (RF) is calculated during the calibration by:ƀ%  Yi` `  Concentrationstandard (g\mL)  Y-` ` RF =    Yi` `  Peak Areastandard  Yv-7.2XThis concentration is then used to calculate the total amount of alcohol in each impinger:ƀ% Mass (g) = Concentration (g/mL) x Impinger volume (mL)  Y1-7.3An internal standard method may also be used.  Y -8.X QUALITY CONTROL ƀ%  Y -8.1XCalibration and control standards are prepared at least every six months and analyzed daily.ƀ%  Y -8.2XBlank Run. A deionized or purified water blank run is performed before running the calibration standard. All target alcohol concentrations from the blank analysis must be below the LOD before the analysis may proceed.ƀ%  YL-8.3XCalibration Run. One run of the calibration standard is performed daily to generate the  Y5-response calibration factor needed for quantitating quantifying sample analyses.ƀ%  Y-8.4XControl Standard Run. One run of the quality control standard is performed after the calibration run. Measurements of all target alcohols in the control standard must fall within the control limits before sample analysis may proceed. To meet this requirement, it may be necessary to inspect and repair the GC, and rerun the calibration and/or control standards.ƀ%  Y-8.5XControl Charts. A q Q uality control chart (s) is are maintained for each analyte in of the  Y}-control standard sample . The control charts, used on a daily basis, establish es that the  Yf-method is "in "statistical é control". The following describes how to construct a typical control chart:ƀ%  Y!-X1.X` ` Obtain at least 20 daily control standard sample results;ƀ%`  Y -X2.X` ` Calculate the average control standard sample mean concentration and standard  Y-deviation (s) for the target analyte (s) ; andƀ%`  Y- X3.X` ` Create a control chart for the target analyte (s) by placing the concentration on the  Y -Y-axis and the date on the X-axis. Establish Draw an upper warning limit and a lower warning limit at two standard deviations (2s) above and below the average  Y"-concentration. Establish Draw an upper control limit and a lower control limit at three standard deviations (3s) above and below the average concentration.ƀ%`  YR%-X The control sample must be "in-control" for The measured concentrations of all target  Y;&-analytes contained in the control standard must be within the control limits ("incontrol") for  Y$'-the sample results to be considered acceptable. A control standard sample measurement is considered to be "out-of-control" when the analyzed value exceeds the 3s limit, or two  Y(-successive control standard sample measurements of the same analyte exceed the 2s limit.ƀ%"(,t*t*(#"Ԍ Y-ԙ8.6XDuplicates. A duplicate analysis of one sample is performed at least once a day. The relative percent difference (RPD) is calculated for each duplicate run:ƀ%  Y-RPD(%) = Difference between duplicate and original measurements x 100  X(#(#%%` ` Average of duplicate and original measurements XFor each compound, the allowable RPD depends on the average concentration level for the duplicate runs, as shown in the following table:ƀ%  Y1-XAverage Measurement for Duplicate RunsppAllowable RPD (%)ƀ%  Y -` ` 1 to 10hh,times LODpp  100  Y -` ` 10 to 20hh, " "pp  30  Y -` ` 20 to 50hh, " "pp  20  Y -` ` Greater than 50hh, " "pp  15 XIf the results of the duplicate analyses do not meet these criteria for all target alcohols, the sample must be reanalyzed. If the criteria are still not met, all sample results for the day  Yy-from this instrument must be deleted and the samples reanalyzed. ƀ%  YK-8.7XLinearity. A multipoint calibration to confirm check for instrument linearity is performed for  Y4-all target alcohols for new instruments, after making instrument modifications which can  Y-affect linearity, and at least once every year six months . The multipoint calibration consists  Y-of at least five concentration or mass loading levels, each above the LOD, evenly distributed  Y-over the range of expected sample concentration linearity of the instrument . Each concentration level is measured at least twice. A linear regression analysis is performed using concentration and area counts to determine the regression correlation coefficient (r). The r must be greater than 0.995 to be considered sufficiently linear for one point calibrations.ƀ%  Ye-8.8XLimit of Detection. The LOD limit of detection for the target alcohols must be determined  YN-for new instruments, after making instrument modifications which can affect the LOD and at  Y7-least once every year. every six months . To make the calculations, it is necessary to  Y -perform a multipoint calibration consisting of at least four "low" concentration levels, each  Y -above the expected LOD. A linear regression is performed on the data. The LOD must be  Y-calculated using the following equation [Ref. 7] (Ref 9.2) :ƀ%  Y-` `  hh,LOD =  b  + (t x s)  Y -` `  hh, m   Y"-X LOD = |A| + 3.3(S) ƀ%  Yh$-Xwhere each term in the equation is expressed in concentration units, and |A| is the absolute  YQ%-value of the least squares X-intercept calculated from the multipoint data. S  b  is the  Y:&-absolute value of the yintercept, m is the slope of the linear regression, s  is the standard  Y#'-deviation of at least five replicate determinations of the lowest concentration standard, and t is the tfactor for 99 percent confidence for a onesided normal (Gaussian) distribution. The" (,t*t*&#" number of degrees of freedom is equal to the number of replicates, minus one. An  Y-abbreviated ttable is:ƀ%  Y-` ` Degrees of Freedomhh,Vtvalue  Y-` `  4hh,V3.7  Y-` `  5hh,V3.4  Yv-` `  6hh,V3.1  Y_-` `  7hh,V3.0  Y1-X At least three replicates are required . The lowest standard must be of a concentration of at  Y -one to five times the estimated LOD detection limit . If data is not available in the  Y -concentration range near the detection limit, S may be estimated by:ƀ%  Y -d^S = RSD x |A|  Y -  Y -X RSD is the relative standard deviation of the lowest standard analyzed. ƀ% XAn example of typical LODs is given in the table below: ƀ%  Yy-XCAS Nos. COMPOUNDVLOD (ug/ml) ƀ%  Yb-X00067-56-1 methanolV0.24 ƀ%  YK-X00064-17-5 ethanolhh,V0.17 ƀ%  Y-8.8.1` ` The maximum allowable LOD for each alcohol is 0.50 g/mL. The calculated laboratory LOD must be equal to or lower than the maximum allowable LOD. All peaks identified as target compounds that are equal to or exceed the maximum allowable LOD must be reported. If the calculated laboratory LOD is less than the maximum allowable LOD, the laboratory may choose to set its reporting limit at  Y-either the maximum allowable LOD or the calculated laboratory LOD. ƀ%`  Y|-8.8.2.` ` For the purpose of calculating the total mass of all species, the concentrations of the  Ye-compounds below the LOD are considered to be zero.ƀ%`  Y7- 9.X REFERENCES ƀ%  Y!-9.1XU.S. Environmental Protection Agency, Characterization of Exhaust Emissions from  Y -Methanol and Gasoline Fueled Automobiles, EPA 460/3-82-004.ƀ%  Y-9.2XU.S. Environmental Protection Agency, Compendium of Methods for the Determination of  Y-Toxic Organic Compounds in Ambient Air, (Method T03-15) EPA-600/4-89-017 Research Triangle Park, North Carolina, June, 1989. ƀ%" ,t*t*#"  Y-   @C-D-@  Y-l Part D  Xx DETERMINATION OF C2 TO C5 HYDROCARBONS >IN AUTOMOTIVE SOURCE SAMPLES BY GAS CHROMATOGRAPHY  X`-BMETHOD NO. 1002 ă  Y -1.X INTRODUCTION ƀ%  Y i1.1XThis document describes a method of analyzing, by gas chromatography, C2 to C5  Y -hydrocarbons (light-end hydrocarbons) in the range of parts per billion carbon ( ppbC ) from  Y -automotive source samples. This method does not include sample collection procedures [Ref.  Y -8] (Ref 9.1) . The "target" hydrocarbons which shall be analyzed and reported by this  Y-method and M m ethod 1003 are listed in Attachment Appendix 1. All compounds on this list, when present in concentrations above the LOD, shall be measured and reported ("targeted")  Yd-by either Method 1002 or Method 1003. Each laboratory should divide the list into light-end  YM-(Method 1002) and mid-range (Method 1003) hydrocarbons in the manner which best suits  Y6-the laboratory instrumentation. All compounds on the list not targeted by M m ethod 1002  Y-must be targeted by M m ethod 1003. More compounds may be measured than those on the  Y-target list. ƀ%  Y-1.2All definitions and abbreviations are contained in Appendix 2 of these test procedures.  Y-2.X METHOD SUMMARY ƀ%  Y-2.1XThis is a rapid method intended for routine analysis.ƀ%  YQ-2.2XThe samples are received by the laboratory in Tedlar bags, which are sub-sampled into a gas  Y:-chromatograph ( GC ) for separation and analyses analysis.ƀ%  Y -2.3XThe gas chromatographic analysis is performed on a packed column operated isothermally at  Yi35oC, or an Alumina (Al203) Porous Layer Open Tubular (PLOT ) column temperature  Y-programmed from OoC to 200oC. An flame ionization detector ( FID ) is used for detection  Y -and quantification.ƀ%  Y"-2.4XThe sample is injected into the GC by means of gas sampling valves. Separation of the  Y#-sample hydrocarbon mixture into its components constituents takes place in the chromatographic column. The chromatographic column and the corresponding operating parameters described in this method normally provide complete resolution of most target compounds.ƀ% "&',t*t*&#"Ԍ Y-2.5XThe computerized GC data acquisition system identifies the hydrocarbons associated with  Y-each of the peak s . The hydrocarbon concentrations are determined by integrating the peak  Y-areas and using response calibration factors determined from with NIST-traceable standards.ƀ%  Y-3.X INTERFERENCES AND LIMITATIONS ƀ%  Yw-3.1XAn interference interferent is any component present in the sample with a retention time very  Y`-similar to that of any the target hydrocarbon s described in this method. To reduce  YI-interference error, proof of chemical identity may require performance of periodic  Y2-confirmations using an alternate method and/or instrumentation, e.g., gas  Y -chromatograph/mass spectrometer ( GC/MS ) , photoionization detector ( PID ) , different column, etc.ƀ%  Y -3.2XTo maximize sample integrity, sample bags should not leak or be exposed to bright light or excessive heat. Sampling bags must be shielded from direct sunlight to avoid reactions occurring due to reactive hydrocarbons. The compound 1,3-butadiene, most of which is in  Y-CVS bag no. 1, is unstable. Therefore all CVS bag no. 1 samples must be analyzed within 8  Yz- 4 hours; CVS bag no. 2, CVS bag no. 3, and background samples must be analyzed within 24 hours, although analysis within 8 hours is recommended.ƀ%  Y5-4.X INSTRUMENTS AND APPARATUS ƀ%  Y-4.1XTedlar bags, 2 mil in thickness, nominally 5 to 10 liters in capacity and equipped with  Y-quick-connect fittings, are used to contain the samples.ƀ%  Y-4.2XFor manual subésampling into a GC, a ground glass syringe is used to transfer gaseous samples from Tedlar bags to the GC sample inlet. For automated systems, a sample loop is used to transfer gaseous samples from the Tedlar bag to the sample inlet of the GC. Sample  Y~-aliquot size is chosen based on considerations of instrument sensitivity and/or linearity.ƀ%  YP-4.3XA temperatureéprogrammable GC equipped with a gas sampling valve system, a FID, and accessories is required.ƀ%  Y -4.4XA stainless steel column [6 feet ( ft ) x 1/8 inch ( in ) ] packed with phenylisocyanate Durapak  Y-80/100 mesh is used. An Al Alumina PLOT column ( 50 60 m x 0.32 mm) may also be  Y-used. has been shown to be equivalent A wax precolumn is recommended to prevent water damage to the PLOT column. Other columns may be used, provided the alternate(s) can be demonstrated to be equivalent or better with respect to precision, accuracy and resolution of  Y"-all the target hydrocarbons.ƀ%  Yj$-4.5A sample trap capable of being cryogenically cooled may be used.  YS%-4. 5 6XAn electronic integrator for quantitation of peak areas is required. If the data acquisition system cannot record the chromatogram, an analog recorder is also required.ƀ% "%',t*t*%#"Ԍ Y-5.X REAGENTS AND MATERIALS ƀ%  Y-5.1XHelium shall have a minimum purity of 99.995 percent. Higher purity helium may be  Y-required to achieve the LOD required by Section 8.7.1.ƀ%   Y-5.2XHydrogen shall have a minimum purity of 99.995 percent.ƀ%  Y`-5.3XAir shall be "Zero" grade. "Ultrazero" grade may be required to achieve the LOD required  YI-by Section 8.7.1.ƀ%  Y -5.4XNitrogen shall have a minimum purity of 99.998 percent.ƀ%  Y -5.5X Calibration Standard - The quantitative calibration standard for all target hydrocarbons shall be propane at a concentration level between 0.25 and 1 ppm-mole and within the calculated  Y -linearity of the method (see section 8.6). This propane standard must be traceable to a  Y -NISTcertified SRM to a Standard Reference Material (SRM) certified for propane by the National Institute of Standards and Technology (NIST). NIST traceable means that the  Y{-standard has been compared with not more than one intermediate standard to a NISTcertified  Yd-SRM . A comparison between a SRM and a candidate standard will yield a secondary NIST traceable standard, while a comparison between a secondary NIST traceable standard and a candidate standard will yield a tertiary NIST traceable standard. A NIST SRM propane standard, secondary NIST traceable propane standard, or tertiary NIST traceable propane  Y-standard is required for calibration of M m ethod 1002 or 1003.ƀ%  Y-X The minimum requirements for the manufacture and use of a secondary or tertiary NIST traceable propane standard shall be the following: 1) the standard must be packaged in aluminum cylinders which have been precleaned and passivated, 2) a gas chromatograph shall be used to compare the candidate cylinders with the NIST traceable standard using either direct or interpolation comparison. (In the direct comparison, the analyte concentration for the candidate standard may not differ more than 10 percent from the analyte concentration of the NIST traceable standard; while in the interpolation comparison, the analyte concentration of a candidate standard is bracketed between the analyte concentrations of the NIST SRM standards.), 3) analytes and balance gases in secondary candidate cylinders must be the same composition as the NIST SRM propane standards used in an interpolation comparison procedure, 4) hydrocarbon analytes (except propane) and balance gases may differ in secondary candidate cylinders from the NIST SRM propane standard used in a direct comparison procedure if there are no interferences with the propane measurement or stability, 5) comparison between a secondary and tertiary standard must be direct, 6) all candidate cylinders must be analyzed a minimum of 4 times and stated uncertainties must be determined for all secondary and tertiary standard analytes, and 7) gas in the cylinder cannot be used when the pressure of the cylinder falls below 300 pounds per square inch.ƀ% XIt is recommended that either the laboratory or standard supplier(s) for the laboratory certify the secondary standards through the NIST Traceable Reference Material program or obtain Research Gas Material/Mixtures of propane standards from NIST for use as secondary  Y(-standards. ƀ%"(,t*t*'#"Ԍ Y-ԙ5.6X Control Standard - A quality control standard, containing at least ethene, propane,  Y-n-butane, and 2-methylpropene with a concentration between 0.2 and 1 parts per million  Y-carbon ( ppmC ) based on a propane standard, is used for the following quality control purposes:ƀ%  Y-` ` 1. Daily update of control charts, and  Yw-` ` 2. Daily determination of marker retention time windows.  YI-X The control standard(s) must have concentrations verified against a NIST-traceable propane standard (See Section 5.5 for definition of NIST-traceable) when used for either LOD determinations or linearity checks. This verification can be performed at the laboratory  Y -conducting the sample analysis. ƀ%  Y -5.7XA high concentration standard (higher than the calibration standard), containing the target  Y -hydrocarbons listed in Section 5.6 is used semi-annually for linearity determinations. The  Y -high concentration calibration standard must have concentrations verified against a NIST-traceable propane standard (see Section 5.5 for the definition of NIST-traceable). This verification can be performed at the laboratory performing the analysis.ƀ%  YL-5.8XLiquid nitrogen may be required is used to cool the cryogenic sample trap and column oven where applicable.ƀ%  Y-6.X PROCEDURE ƀ%  Yi6.1XThe gaseous sample is analyzed for the target hydrocarbons C2 through C5.ƀ%  Y-6.2XSuggested standard operating conditions for the gas chromatograph are:ƀ%  Y~-6.2.1` ` Packed Column:  Yg-XHelium carrier gas flow:` hh,V50 milliliter/minute ( m l L/min) (packed column) ƀ%h  YP-Hydrogen gas flow:hh,V32 mL/min  Y9-Air flow: hh,V300 mL/min  Y"-Sample valve temperature: hh,Vambient  Y -Heating bath temperature: hh,V60o - 80oC  Y-Injector temperature:hh,V35oC (packed column)  Y-Column temperature:hh,V35oC (isothermal) (packed column)  Y -XX` ` X XXhh,XV 0oC to 200oC (temperature program) (Al PLOT Column) ƀ%  Y!-XDetector temperature:hh,V200 to 250 oCƀ%  Y#-X6.2.2X` ` PLOT Column:ƀ%`  Yj$-Helium carrier gas velocity:hh,V30 cm/sec at 200oC  YS%-Nitrogen makeup gas flow: hh,XVsufficient such that the total flow of helium plus nitrogen is 30 mL/minƀ%  Y%'-Hydrogen gas flow:hh,V30 mL/minƀ%  Y(-Air flow: hh,V300 mL/min  Y(-Sample valve temperature:hh,V150oC (PLOT column)"(,t*t*}(#"Ԍ Y-Column temperature:hh,V0oC (hold 7 min), 10oC/min to 200oC (hold 15 min)ƀ%  Y-XDetector temperature: hh, V250oCƀ%  Y-6.3XFor automated systems, connect the samples to the GC and begin the analytical process. ƀ%  Y-6.4Introduce the sample into the carrier gas stream through the injection valve.  Y_- 6.4XFor automated systems, connect the samples to the GC and begin the analytical process. ƀ%  Y1-6.5XEach separated component exits from the column into the FID where a response is generated.ƀ%  Y -6.6XConcentrations of hydrocarbons are calculated by an electronic integrator device, which has been calibrated using a NIST-traceable propane calibration standard.ƀ%  Y -6.7XFor compounds having concentrations above the documented range of instrument linearity, a smaller aliquot must be taken (for manual systems, a smaller syringe or smaller loop; for automated systems, a smaller loop).ƀ%  Yb-6.8XThe peak integrations are corrected as necessary in the data system. Any misplaced baseline segments are corrected in the reconstructed chromatogram.ƀ%  Y-6.9XThe peak identifications provided by the computer are checked and corrected if necessary.ƀ%  Y-6.10XAll The peaks areas of identified as target compounds (Appendix 1) at or above the  Y- maximum allowable LOD are reported (Section 8.7).  At the laboratory's discretion, peaks at or above the LOD calculated in section 8.7 may be reported. The calculated LOD must be  Y-lower than the maximum allowable LOD. ƀ%  Y|-6.11XTarget compounds which coelute are reported as the major component, as determined by the analysis of several samples by GC/MS or other methods. An exception to this is m and pxylene, where GC/MS data and fuel profiles are used to determine the relative contribution of each component to the peak. This method was used to determine the m and pxylene  Y -MIR value given in Appendix 1. ƀ%  Y- 6.11XThe maximum retention time in this analysis is typically about 15 30 mins. ƀ%  Y -6.12XAfter each run, the packed column is backéflushed with helium while the oven temperature is  Y!-raised and maintained at 60oC for 15 mins, or as required to flush the column. ƀ%  Y#-6.13XThe Al Alumina PLOT column is programmed to 200o C to assure all compounds are eluted before the next run.ƀ%  Y:&-6.1 3 4XBefore the next run, sufficient time (typically 15 mins) is allowed after backéflush of the packed column to re-establish the required temperature of the column.ƀ%  Y(- 6.14The total run time is typically about 45-60 mins. "(,t*t*(#"Ԍ Y-ԙ7.X CALCULATIONS ƀ%  Y-7.1XThe target hydrocarbon concentrations, in ppbC, are calculated by the data system using propane as an external standard.ƀ%  Yi Concentrationsample (ppbC) = Peak Areasample x Response Factor Xwhere the response factor (RF) is calculated during daily calibration by:ƀ%  Y2-RF = Concentration of NIST-traceable propane standard, ppbC ` `  Area of propane peak  Y -8.X QUALITY CONTROL ƀ%  Y -8.1XBlank Run. A blank (pure nitrogen or helium) is run once daily before running the calibration standard, control standard, and samples. All target hydrocarbon concentrations from the blank analysis must be below the LOD before the analysis may proceed. As an alternative to a daily blank run, a daily partial blank check in tandem with a weekly blank run may be used. A partial blank check is where the calibration standard, consisting of only propane and make-up gas (all organic compounds except methane and propane are below 2 percent of the propane standard concentration), is run daily and is checked for contamination except in the propane region of the chromatograph. The weekly blank run will provide a check on contamination in the propane region of the chromatograph.ƀ%  Y-8.2XCalibration Run. One run of the calibration standard is performed per day to generate the  Y-response calibration factor needed for quantitating quantifying sample analyses.ƀ%  Y-8.3XControl Standard Run. One run of the quality control standard is performed daily. Measurements of all compounds in the control standard must fall within the control limits before sample analysis may proceed. To meet this requirement, it may be necessary to inspect and repair the GC, and rerun the calibration and/or control standards.ƀ%  Y"-8.4XControl Charts. A Q quality control chart (s) are is maintained for each component of the  Y -control standard sample . The control charts, used on a daily basis, establish es that the  Y-method is "iné "statistical control." The following describes how to construct a typical control chart:ƀ%  Y!-` ` 1. Obtain at least 20 daily control standard sample results;  Y"-` ` 2. Calculate the average control standard sample mean concentration and standard  Y#-deviation (s) for the each target hydrocarbon; andƀ%  Yj$-` ` 3. Create a control chart for the each target hydrocarbon by placing the concentration on the Y-axis and the date on the X-axis. Establish an upper warning limit and a lower warning limit at two standard deviations (2s) above and below the average concentration. Establish an upper control limit and a lower control limit at three standard deviations (3s) above and below the average concentration.ƀ% "(,t*t*'#"Ԍ Y-ԙX The control sample must be "in-control" for The measured concentrations of all target  Y-hydrocarbons contained listed in the control standard sample must be within the control limits  Y-("incontrol") for the sample results to be considered acceptable. A control standard sample  Y-measurement is considered to be "out-of-control" when the analyzed value of the sample  Y-measurement exceeds the 3s limit, or two successive control standard sample measurements of the same analyte exceed the 2s limit.ƀ%  Y_-8.5XDuplicates. A duplicate analysis of one sample is performed at least once a day. The relative percent difference (RPD) is calculated for each duplicate run:ƀ%  Y -XRPD (%) =  Difference between duplicate and original measurements x 100 ` `  Average of duplicate and original measurementsƀ% XFor each compound in the control standard, the allowable RPD depends on the average concentration level for the duplicate runs, as shown in the following table:ƀ%  Y-_XAverage Measurement for the Duplicate RunsppAllowable RPD (%)  ƀ%  Yb-` ` 1 to 10 hh,timesVLOD pp  100  YK-` ` 10 to 20hh," V"pp  30  Y4-` ` 20 to 50hh,"V"pp  20  Y-` ` Greater than 50hh,"V"pp  15 _ XIf the results of the duplicate analyses do not meet these criteria for all target hydrocarbons in the control standard, the sample must be reanalyzed. If the criteria are still not met, all  Y-sample results for the day from this instrument must be deleted and the samples reanalyzed.ƀ%  Y-8.6XLinearity. A multipoint calibration to confirm check for instrument linearity is performed  Y|-for the target hydrocarbons in the control standard for new instruments, after making  Ye-instrument modifications which can affect linearity, and at least once every year six months  YN-unless a daily check of the instrument response indicates that the linearity has not changed. To monitor the instrument response, a quality control chart is constructed, as specified in section 8.4, except using calibration standard area counts rather than control standard concentrations. When the standard area counts are outofcontrol, corrective action(s) must  Y-be taken before analysis may proceed. The multipoint calibration consists of at least five concentration or mass loading levels (using smaller or larger volume sample sizes of existing  Y -standards is acceptable), each above the LOD, evenly distributed over the range of expected  Y!-sample concentration linearity of the instrument . Each concentration level is measured at least twice. A linear regression analysis is performed using concentration and average area counts to determine the regression correlation coefficient (r). The r must be greater than 0.995 to be considered sufficiently linear for one-point calibrations.ƀ%  Y:&-8.7XLimit of Detection. The limit of detection LOD for the target hydrocarbons in the control  Y#'-standard must be determined must be determined at least once every year six months . unless a daily check of the instrument response indicates that the LOD has not changed. To monitor the instrument response, a quality control chart is constructed, as specified in section"(,t*t*'#" 8.4, except using calibration standard area counts rather than control standard concentrations. When the standard area counts are outofcontrol, corrective action(s) must be taken before  Y-analysis may proceed. To make the necessary calculations, it is necessary to perform a  Y-multipoint calibration consisting of at least four "low" concentration levels, each above the  Y-LOD. The LOD must be calculated using the following equation [Ref. 9] (Ref 9.2) :ƀ%  Yv-` `  hh,LOD =  b  + (t x s)  Y_-` `  hh, m   Y1-X LOD = |A| + 3.3(S) ƀ%  Y -Xwhere each term in the equation is expressed in concentration units, and |A| is the absolute  Y -value of the least squares X-intercept calculated from the multipoint data. S  b  is the  Y -absolute value of the yintercept, m is the slope of the linear regression, s  is the standard  Y -deviation of at least five replicate determinations of the lowest concentration standard, and t is the tfactor for 99 percent confidence for a onesided normal (Gaussian) distribution. The number of degrees of freedom is equal to the number of replicates, minus one. An  Yy-abbreviated ttable is:ƀ%  YK-` ` Degrees of Freedomhh,Vtvalue  Y4-` `  4hh,V3.7  Y-` `  5hh,V3.4  Y-` `  6hh,V3.1  Y-` `  7hh,V3.0  Y-X At least three replicates are required . The lowest standard must be of a concentration of at  Y-one to five times the estimated LOD detection limit . If data is not available in the  Y-concentration range near the detection limit, S may be estimated by:ƀ%  Y|-d^S = RSD x |A|  Ye-  YN-X RSD is the relative standard deviation of the lowest standard analyzed. ƀ%  Y - X8.7.1.` ` The maximum allowable LOD for each compound is 20 ppbC propane . The calculated laboratory LOD must be equal to or lower than the maximum allowable LOD. All peaks identified as target compounds that are equal to or exceed the maximum allowable LOD must be reported. If the calculated laboratory LOD is less than the maximum allowable LOD, the laboratory may choose to set its reporting limit at either the maximum  Y!-allowable LOD or the calculated laboratory LOD.ƀ%  Y#-X8.7.2.` ` For the purpose s of calculating the total mass (ppbC) of all species, the concentrations of all compounds below the LOD are considered to be zero.ƀ%  Y:&-8.8XMethod No. 1002/Method No. 1003 Crossover Check For each sample, a compound shall be measured by both Method No. 1002 and Method No. 1003. The crossover compound shall be a compound that can reasonably be expected to be found and measured by both" (,t*t*&#"  Y-methods in the laboratory performing the analysis. The results obtained by the two methods  Y-should be compared and an acceptance criteria set for the relative percent difference. ƀ%  Y- 9.X REFERENCES ƀ%  Yi9.1XStandard Test Method for C1 through C6 Hydrocarbons in the Atmosphere by Gas Chromatography, American Standards for Testing Materials (ASTM) Standards on Chromatography (1981).ƀ%  Y2-9.2XU.S. Environmental Protection Agency, Compendium of Methods for the Determination of  Y -Toxic Organic Compounds in Ambient Air (Method T03-15),EPA-600/4-84-041. Research Triangle Park, North Carolina, April 1989.ƀ%  Y - " ,t*t* #"   @D-E-@  X- mPart E  Xx DETERMINATION OF C6 TO C12 HYDROCARBONS >IN AUTOMOTIVE SOURCE SAMPLES BY GAS CHROMATOGRAPHY  X_-BMETHOD NO. 1003 ă X` hp x (#%'0*,.8135@8:+c"ԌSimilarly, for Phase 2:  YiROHmass 2 = 0.08 g and for Phase 3:  YiROHmass 3 = 0.07 0.08 g  Therefore,  Y_i` `  (ROHmass 1 + ROHmass 2 )pp(ROHmass 3 + ROHmass 2 )  YHiROHwm` ` =  0.43 * ___________________ +pp0.57 * __________________  Y1i` `  (Dphase 1 + Dphase 2 )pp(Dphase 3 + Dphase 2 )  Y i` `  ( 0.55 0.56 mg  + 0.08 mg )( 0.07 0.08 mg + 0.08 mg )  Y iROHwm` ` =  0.43 * ___________________ +pp0.57 * __________________  Y -` `  (3.581 mile + 3.845 mile)pp(3.583 mile + 3.845 mile )  Y iROHwm` ` = 0.05 g (methanol weighted mass emissions) "9,t*t*c"  Y-}  5. CARBONYL MASS EMISSIONS CALCULATIONS ă  Y-1.X INTRODUCTION ƀ%  Yx-1.1XVehicular emissions are measured according to the Federal Test Procedure (FTP ) [Ref. 1]  Ya- (1) . For each of the three phases of the FTP, a set of two impingers (or cartridges) is used  YJ-to collect carbonyl emissions in the dilute exhaust. A fourth set of two impingers (or  Y3-cartridges) is used to collect a composite dilution air (background) carbonyl sample from all  Y -three phases of the FTP. All impingers (or cartridges) are analyzed according to Method  Y -No. 1004 to determine the mass of individual carbonyl compounds in each impinger (or  Y -cartridge). The measured carbonyl masses are used in the following equations to calculate the weighted mass emissions of each carbonyl compound.ƀ%  Y -2.X CARBONYL MASS EMISSIONS CALCULATION PER TEST PHASE ƀ%  Y|i2.1XRHOmass n = (RHOconc * RHOdens * VMIX * 10é6 )ƀ%  YNi2.2XRHOconc = RHOe - (RHOd * (1 - (1 / DF)))ƀ%  Y7iNOTE: If RHOconc is calculated to be less than zero, then RHOconc = 0.  Y i2.3XRHOe` ` = (Imasse / Ivole ) * (Mol. Vol. / Mol. Wt.)ƀ%  Yi2.4XIvole` ` = Ivolem * (Itempe / 293.16o K) * (760 mm Hg / PB ) ƀ%  YiXX` ` X (293.16oK / Itempe ) * (PB / 760 mm Hg)ƀ%  Yi2.5XRHOd` ` = (Imassd / Ivold ) * (Mol. Vol. / Mol. Wt.) ƀ%  Yhi2.6XIvold` ` = Ivoldm * (Itempd / 293.16o K) * (760 mm Hg / PB ) ƀ%  YQiXX` ` X (293.16oK / Itempd ) * (PB / 760 mm Hg)ƀ%  Y#-3.X WEIGHTED CARBONYL MASS EMISSIONS CALCULATION ƀ%  Yi` `  (RHOmass 1 + RHOmass 2 )pp(RHOmass 3 + RHOmass 2 )  Y iRHOwm` ` =  0.43 * ___________________ +pp0.57 * __________________  Y!i` `  (Dphase 1 + Dphase 2 )pp(Dphase 3 + Dphase 2 )  Y#-4.X SAMPLE CALCULATION ƀ%  YV%-4.1XCarbonyl emissions from a compressed natural gas ( CNG ) vehicle are collected in three sets  Y?&-of dilute exhaust impingers and one set of dilution air impingers during the FTP. High  Y('-performance liquid chromatography HPLC is used to determine the formaldehyde mass in each impinger. Calculate the weighted formaldehyde mass emissions based on the following data:ƀ%"(:,t*t**c"Ԍ ddx/7          ddx; X  H  H  z t **  Test Phasecg  YiIvolr  Yz-(mL)c  YiImasse  sNz-(g)c  YiIvolem (liter)c  YiImassd  Yz-(g)c  YiIvoldm (liter)c  YiItempe  Yz-(oK)c  YiItempd  Yz-(oK)z q  *h*  1h 15h 2.45h  8.49h 0.17h 31.57h 295h 292q q c *hh*  2Eh 15Eh 0.76Eh 14.55Eh 0.17Eh 31.57Eh 298Eh 292q    *h*  3 15 0.64  4.00 0.17 31.57 298 292  E   ddx; X  H  H  ddx ;            c E  . .  Test Phase2 g FID  YI iTHCe  Y2 -(ppmC)   Y` iCH4e  YI -(ppmC)   Y` iCO2e (%)   Y` iCOem (ppm)   Y` iRa (%)  VMIX  YI -(ft3)   Y` iDphase n (mile)   Y` iPB  sNI -(mmHg sN -)c q   .h .  1h 132h 108h 0.9h 8h 68h 2866h 3.581h 760q q   2h  4h  3h 0.1h 4h 67h 4841h 3.845h 760q    .h .  3  22  9 0.5 5 65 2837 3.583 760    For Phase 1: Mol. Wt. of HCHO = (1 * 12.01115) + (2 * 1.00797) + (1 * 15.9994)  Y+-` ` = 30.0268 g/mole  YiXIvole` ` = Ivolem * (Itempe / 293.16o K) * (760 mm Hg / PB ) ƀ%  Yi` `  (293/16o K / Itempe ) * (PB / 760 mm Hg)  Y-` ` = 8.49 liter * (295o K / 293.16o K) (293.16o K / 295o K) * ` `  (760 mm Hg / 760 mm Hg)  Y-` ` = 8.54 8.44 liter  Y\iRHOe` ` = (Imasse / Ivole ) * (Mol. Vol. / Mol. Wt.)  YE-` ` =  (2.45*10é6 g / 8.54 8.44 liter)*(24.055 liter/mole / 30.0268 g/mole)  Y. -` ` =  230 233 ppb  Y"iIvold` ` = Ivoldm * (Itempd / 293.16o K) * (760 mm Hg / PB )  Y"iXX` ` X (293.16oK / Itempd ) * (PB / 760 mm Hg)ƀ%  Y#-` ` =  31.57 liter * (292o K / 293.16o K) 293.16o K / 292o K) * ` `  (760 mm Hg / 760 mm Hg)  Y%-` ` = 31.45 31.70 liter  Yv'iRHOd` ` = (Imassd / Ivold ) * (Mol. Vol. / Mol. Wt.)  Y_(-` ` = (0.17*10é6 g / 31.45 31.70 liter)*(24.055 liter/mole / 30.0268 g/mole)  YH)-` ` = 4 ppb"H);,t*t**"Ԍ YiDF` ` = 9.77 / [CO2e + (NMHCe + CH4e + COe ) * 10é4 ] (see section 6, DF Calc.)  Yi<NMHCe = FID THCe - (rCH < 4   * CH4e )  Y-` ` = 132 ppmC - (1.04 * 108 ppmC)  Y-` ` = 20 ppmC  YviCOe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem XNOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and  YHithe conditioning column has been deleted, COem must be substituted directly for COe .ƀ%  Y1-` ` = (1 - 0.02900 0.02890 * 0.9% - 0.000323 * 68%) * 8 ppm  Y -` ` = 7.6 ppm  Y -DF` ` =  9.77 / [0.9% + ( 20 ppmC + 108 ppmC + 7.6 ppm) * 10é4 ]  Y -` ` = 10.69  Y iRHOconc = RHOe - (RHOd * (1 - (1 / DF)))  Y-` ` = 230 233 ppb - ( 4.33 4 ppb * (1 - (1 / 10.69 )))  Yy-` ` = 226 229 ppb  YKiXRHOdens = (Mol. Wt. * conversion of liter to ft3 ) / (Mol. Vol.)ƀ%  Y4-` ` = (30.0268 g/mole * 28.316 liter/ft3 ) / 24.055 liter/mole  Y- ` ` = 35.35 g/ft3  YiRHOmass n = (RHOconc * RHOdens * VMIX * 10é6 )  YiRHOmass 1 = ( 226 229 ppb * 35.35 g/ft3 * 2866 ft3 * 10é6 )  Y-` ` = 22.9 23.2 mg Similarly, for Phase 2:  Y|iRHOmass 2 =  6.3 6.6 mg and for Phase 3:  YNiRHOmass 3= 12.2 12.7 mg  Therefore,  Y i` `  (RHOmass 1 + RHOmass 2 )pp(RHOmass 3 + RHOmass 2 )  YiRHOwm=  0.43 * ___________________ +pp0.57 * __________________  Yi` `  (Dphase 1 + Dphase 2 )pp(Dphase 3 + Dphase 2 )  Y!-` `  ( 22.9 23.2 mg + 6.3 6.6 mg )( 12.2 12.7 mg + 6.3 6.6 mg )  Y"iRHOwm` ` =  0.43 * ___________________ +pp0.57 * __________________  Y#-` `  (3.581 mile + 3.845 mile)pp(3.583 mile + 3.845 mile )  YQ%iRHOwm = 3.1 3.2 g (formaldehyde weighted mass emissions) "Q%<,t*t*_("  Y-  6. DILUTION FACTOR CALCULATION ă  Y-1.X DILUTION FACTORS ƀ%  Yx-1.1X For Non-Alcohol Fueled Vehicles :ƀ%  YK-` `  100 *  x  ` `  x + y/2 + 3.76 * (x + y/4 - z/2)  Y -1.1.1DF` ` =    Y i` `  CO2e + (NMHCe + CH4e + COe ) * 10é4  Y i(where fuel composition is CxHyOz as measured for the fuel used.)  Y i1.1.2COe` ` = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem XNOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and  Yithe conditioning column has been deleted, COem must be substituted directly for COe .ƀ%  Yeia)` ` For gasoline, CH1.85 , where x = 1, y = 1.85, and z = 0:  YNi` ` DF = 13.47 / [CO2e + (NMHCe + CH4e + COe ) * 10é4  Y7iXX` ` COe = (1 - 0.01925 * CO2e - 0.000323 * Ra ) * COemƀ%`  Y ib)` ` For Phase 2 gasoline, CH1.94, where x = 1, y = 1.94 and z = 0.017,  Yi` ` DF = 13.29 / [CO2e + (NMHCe + CH4e + COe ) * 10é4  Yi` ` COe = ( 1 0.01970 * CO2e 0.000323 * Ra) * COem  Yi b c)` ` For LPG, CH 2.66 2.64, where x = 1, y = 2.66 2.64, z = 0:  Yi` ` DF = 11.64 11.68 / [CO2e + (NMHCe + CH4e + COe ) * 10é4  YiXX` ` COe = (1 - 0.02330 0.02320 * CO2e - 0.000323 * Ra) * COemƀ%`  YQiX c d)X` ` For CNG, CH 3.80 3.78 , where x = 1, y = 3.80 3.78, and z = 0.016:ƀ%`  Y:iXX` ` DF = 9.77 9.83 / [[CO2e + (NMHCe + CH4e + COe ) * 10é4 ]ƀ%`  Y#iXX` ` COe = (1 - 0.02900 0.02890 * CO2e - 0.000323 * Ra ) * COemƀ%`  Y-1.2X For Alcohol Fueled Vehicles :ƀ%  Y -` `  100 *  x  ` `  x + y/2 + 3.76 * (x + y/4 - z/2)  Y"-1.2.1DF` ` =    Y#i` `  CO2e + (NMHCe + CH4e + COe + ROHe + HCHOe ) * 10é4  Yl$i(where fuel composition is CxHyOz as measured for the fuel used.) "U%=,t*t*("Ԍ Yi1.2.2COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem XNOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and  Yithe conditioning column has been deleted, COem must be substituted directly for COe.ƀ%  YiXa)` ` For M100 (100% methanol), CH3OH, where x = 1, y = 4, and z = 1:ƀ%  Yi` ` DF = 11.57 / [CO2e + (NMHCe + CH4e + COe + ROHe + HCHOe ) * 10é4]  YviXX` ` COe = (1 - 0.03000 * CO2e - 0.000323 * Ra ) * COemƀ%`  Y_iXb)X` ` For M85 (85% methanol, 15% indolene), CH3.41O0.72 , where x = 1, y = 3.41, ƀ%` XX` ` and z = 0.72:ƀ%`  Y1iXX` ` DF = 12.02 / [CO2e + (NMHCe + CH4e + COe + ROHe + HCHOe ) * 10é4]ƀ%`  Y iXX` ` COe = (1 - 0.02705 * CO2e - 0.000323 * Ra ) * COemƀ%`  Y iXc)X` ` For E100 (100% ethanol), C2H5OH, where x = 1, y = 3, and z = 0.5:ƀ%`  Y iXX` ` DF = 12.29 / [CO2e + (NMHCe + CH4e + COe + ROHe + HCHOe ) * 10é4] ƀ%`  Y i` ` COe = (1 - 0.02500 * CO2e - 0.000323 * Ra ) * COem " >,t*t*<"  Y-@G-1-@ XX   4 Attachment APPENDIX  1 ă  Y-6 LIST OF COMPOUNDS ă  X- X X` hp x (#%'0*,.8135@8:&-00075-83-2 2,2-dimethylbutane  Bx'0.82  Y''-00142-29-0 cyclopentene  Bx'7.66  Y(-00691-37-2 4-methyl-1-pentene  Bx'4.42  Y(-00760-20-3 3-methyl-1-pentene  Bx'4.42"(?,t*t*'"Ԍ Y-00287-92-3 cyclopentane  Bx'2.38  Y-00079-29-8 2,3-dimethylbutane  Bx'1.07  Y-01634-04-4 1-methyl-tert-butyl-ether  Bx'0.62  Y-00691-38-3 4-methyl-cis-2-pentene  Bx'6.69  Y-00107-83-5 2-methylpentane  Bx'1.53  Y-00674-76-0 4-methyl-trans-2-pentene  Bx'6.69  Yv-00096-14-0 3-methylpentane  Bx'1.52  Y_-00763-29-1 2-methyl-1-pentene  Bx'4.42  YH-00592-41-6 1-hexene  Bx'4.42  Y1-00110-54-3 n-hexane  Bx'0.98  Y -13269-52-8 trans-3-hexene  Bx'6.69  Y -07642-09-3 cis-3-hexene  Bx'6.69  Y -04050-45-7 trans-2-hexene  Bx'6.69  Y -00616-12-6 3-methyl-trans-2-pentene  Bx'6.69  Y -00625-27-4 2-methyl-2-pentene  Bx'6.69  Y -01120-62-3 3-methylcyclopentene  Bx'5.65  Y-07688-21-3 cis-2-hexene  Bx'6.69  Yy-00637-92-3 1-ethyl-tert-butyl-ether  Bx'1.98  Yb- 00922-62-3 3-methyl-cis-2-pentene  Bx'6.69  YK-00590-35-2 2,2-dimethyl hexane pentane  Bx'1.40  Y4-00096-37-7 methylcyclopentane  Bx'2.82  Y-00108-08-7 2,4-dimethylpentane  Bx'1.78  Y-00464-06-2 2,2,3-trimethylbutane  Bx'1.32  Y-07385-78-6 3,4-dimethyl-1-pentene  Bx'3.48  Y-00693-89-0 1-methylcyclopentene  Bx'7.66  Y-00071-43-2 benzene  Bx'0.42  Y-03404-61-3 3-methyl-1-hexene  Bx'3.48  Y-00562é 0 49-2 3,3-dimethylpentane  Bx'0.71  Y|-00110-82-7 cyclohexane  Bx'1.28  Ye-00591-76-4 2-methylhexane  Bx'1.08  YN-00565-59-3 2,3-dimethylpentane  Bx'1.51  Y7-00110-83-8 cyclohexene  Bx'5.67  Y -00589-34-4 3-methylhexane  Bx'1.40  Y -02532-58-3 cis-1,3-dimethylcyclopentane  Bx'2.55  Y-00617-78-7 3-ethylpentane  Bx'1.40  Y-00822-50-4 trans-1,2-dimethylcyclopentane  Bx'1.85  Y -00592-76-7 1-heptene  Bx'3.48  Y!-00540-84-1 2,2,4-trimethylpentane  Bx'0.93  Y"-14686-14-7 trans-3-heptene  Bx'5.53  Y#-00142-82-5 n-heptane  Bx'0.81  Yh$-02738-19-4 2-methyl-2-hexene  Bx'5.53  YQ%-03899-36-3 3-methyl-trans-3-hexene  Bx'5.53"Q%@,&&33 $"Ԍ Y-14686-13-6 trans-2-heptene  Bx'5.53  Y-00816-79-5 3-ethyl- cis -2-pentene  Bx'5.53  Y-00107-39-1 2,4,4-trimethyl-1-pentene  Bx'2.69  Y-10574-37-5 2,3-dimethyl-2-pentene  Bx'5.53  Y-06443-92-1 cis-2-heptene  Bx'5.53  Y-00108-87-2 methylcyclohexane  Bx'1.85  Yv-00590-73-8 2,2-dimethylhexane  Bx'1.20  Y_-00107-40-4 2,4,4-trimethyl-2-pentene  Bx'5.29  YH-01640897 ethylcyclopentane  Bx'2.31  Y1-00592-13-2 2,5-dimethylhexane  Bx'1.63  Y -00589-43-5 2,4-dimethylhexane  Bx'1.50  Y -00563-16-6 3,3-dimethylhexane  Bx'1.20  Y -00565-75-3 2,3,4-trimethylpentane  Bx'1.60  Y -00560-21-4 2,3,3-trimethylpentane  Bx'1.20  Y -00108-88-3 toluene  Bx'2.73  Y -00584-94-1 2,3-dimethylhexane  Bx'1.32  Y-00592-27-8 2-methylheptane  Bx'0.96  Yy-00589-53-7 4-methylheptane  Bx'1.20  Yb-00589-81-1 3-methylheptane  Bx'0.99  YK-15890-40-1  1cis2trans (1a,2a,3b)-1,2,3trimethylcyclopentane1.94  Y4-00638-04-0 cis-1,3-dimethylcyclohexane  Bx'1.94  Y-02207-04-7 trans-1,4-dimethylcyclohexane  Bx'1.94  Y-03522-94-9 2,2,5-trimethylhexane  Bx'0.97  Y-16747505 cis1methyl3ethylcyclopentane  Bx'1.94  Y-00111-66-0 1-octene  Bx'2.69  Y-14850-23-8 trans-4-octene  Bx'5.29  Y-00111-65-9 n-octane  Bx'0.61  Y-13389-42-9 trans-2-octene  Bx'5.29  Y|-02207-03-6 trans-1,3-dimethylcyclohexane  Bx'1.94  Ye-07642-04-8 cis-2-octene  Bx'5.29  YN-01069-53-0 2,3,5-trimethylhexane  Bx'1.14  Y7-02213-23-2 2,4-dimethylheptane  Bx'1.34  Y -02207-01-4 cis-1,2-dimethylcyclohexane  Bx'1.94  Y -01678-91-7 ethylcyclohexane  Bx'1.94  Y-00926-82-9 3,5-dimethylheptane  Bx'1.14  Y-00100-41-4 ethylbenzene  Bx'2.70  Y -03074-71-3 2  2,3-dimethylheptane  Bx'1.14  Y!-00108-38-3 m-&p-xylene  Bx'7.64  Y"-02216344 4methyloctane  Bx'1.14  Y#-03221612 2-methyloctane  Bx'1.14  Yh$-02216-33-3 3-methyloctane  Bx'1.14  YQ%-00100-42-5 styrene(ethenylbenzene)  Bx'2.22"Q%A,&&33 $"Ԍ Y-00095-47-6 o-xylene  Bx'6.46  Y-00124-11-8 1-nonene  Bx'2.23  Y-00111-84-2 n-nonane  Bx'0.54  Y-00098-82-8 (1-methylethyl)benzene  Bx'2.24  Y-15869-87-1 2,2-dimethyloctane  Bx'1.01  Y-04032-94-4 2,4-dimethyloctane  Bx'1.01  Yv-00103-65-1 n-propylbenzene  Bx'2.12  Y_-00620-14-4 1-methyl-3-ethylbenzene  Bx'7.20  YH-00622 0 é96-8 1-methyl-4-ethylbenzene  Bx'7.20  Y1-00108-67-8 1,3,5-trimethylbenzene  Bx!10.12  Y -00611-14-3 1-methyl-2-ethylbenzene  Bx'7.20  Y -00095-63-6 1,2,4-trimethylbenzene  Bx'8.83  Y -00124-18-5 n-decane  Bx'0.47  Y -00538-93-2 (2-methylpropyl)benzene  Bx'1.87  Y -00135-98-8 (1-methylpropyl)benzene  Bx'1.89  Y -00535-77-3 1-methyl-3-(1-methylethyl)benzene  Bx'6.45  Y-005 7 26-73-8 1,2,3-trimethylbenzene  Bx'8.85  Yy-00099-87-6 1-methyl-4-(1-methylethyl)benzene  Bx'6.45  Yb-00496-11-7 2,3-dihydroindene(indan)  Bx'1.06  YK-00527-84-4 1-methyl-2-(1-methylethyl)benzene  Bx'6.45  Y4-00141-93-5 1,3-diethylbenzene  Bx'6.45  Y-00105-05-5 1,4-diethylbenzene  Bx'6.45  Y-01074-43-7 1-methyl-3-n-propylbenzene  Bx'6.45  Y-01074551 1methyl4npropylbenzene  Bx'6.45  Y-00135-01-3 1,2-diethylbenzene  Bx'6.45  Y-01074-17-5 1-methyl-2-n-propylbenzene  Bx'6.45  Y-01758-88-9 1,4-dimethyl-2-ethylbenzene  Bx'9.07  Y-00874-41-9 1,3-dimethyl-4-ethylbenzene  Bx'9.07  Y|-00934-80-5 1,2-dimethyl-4-ethylbenzene  Bx'9.07  Ye-02870-04 0 é4 1,3-dimethyl-2-ethylbenzene  Bx'9.07  YN-01120-21-4 n-undecane(hendecane)  Bx'0.42  Y7-00933-98-2 1,2-dimethyl-3-ethylbenzene  Bx'9.07  Y -00095-93-2 1,2,4,5-tetramethylbenzene  Bx'9.07  Y -03968852 (2methylbutyl)benzene  Bx'1.70  Y-00527-53-7 1,2,3,5-tetramethylbenzene  Bx'9.07  Y- 27138212 01074926 1(1,1dimethylethyl)2methylbenzene  Bx'5.84  Y -00488-23-3 1,2,3,4-tetramethylbenzene  Bx'9.07  Y!-00538-68-1 n-pentylbenzene  Bx'1.70  Y"-00098-19-1 1-(1,1-dimethylethyl)-3,5-DMbenzene  Bx'7.50  Y#-00091-20-3 naphthalene  Bx'1.18  Yh$-00112-40-3 n-dodecane  Bx'0.38 "Q%B,&&33 $"Ԍ X- ^>Carbonyl Compounds  Y-  Y-00050000 formaldehyde  Bx'7.15  Y-00075070 acetaldehyde  Bx'5.52  Y-00107028 acrolein  Bx'6.77  Y-00067641 acetone  Bx'0.56  Yv-00123386 propionaldehyde  Bx'6.53  Y_-00123728 butyraldehyde  Bx'5.26  YH-00066251 hexanaldehyde  Bx'3.79  Y1-00100527 benzaldehyde  Bx#0.55  Y -00078933 methyl ethyl ketone (2butanone)  Bx'1.18  Y -00078853 methacrolein  Bx'6.77  Y -04170303 crotonaldehyde  Bx'5.42  Y -00110623 valeraldehyde  Bx'4.41  Y -00620235  mtolualdehyde  Bx#0.55" C,&&33N " (  X- List of Light End and MidRange Hydrocarbons Compounds  X-4(Listed by CAS number) ă X`  x (#%'0*,.8135@8: