1 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 California Environmental Protection Agency AIR RESOURCES BOARD



### CALIFORNIA NON-METH ANE ORGANIC GAS TEST PROCEDURES

Adopted: July 12, 1991 Amended: September 22, 1993 Amended: June 24, 1996 Amended: August 5, 1999 Amended: July 30, 2002 Amended: March 22, 2012 Amended: December 6, 2012

Monitoring and Laboratory Division , Southern Laboratory Branch Mobile Source Division

9528 Telstar Avenue El Monte, California 91731

NOTE: Mention of any trade na me or commercial product does not constitute endorsement or recommendation of this product by the Air Resources Board. Note: The proposed amendments to this document are shown in unde rline to indicate addi tions and strikeout to indicate deletions compared to the test procedures as last amended March 22, 2012. [No change] indicates proposed federal provisions that are also proposed for incorporation herein without change. Existing intervening te xt that is not amended in this rulemaking is indicated by “* * * *”.2 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 * * * *

PART B

DETERMINATION OF NON-METHANE HYDROCARBON MASS EMISSIONS BY FLAME IONIZATION DETECTION

* * * *

5. NMHC MASS EMISSION PER TEST PHASE

* * * *

5.2 All Vehicles

* * * *

5.2.5 The density of the NMHC is determined using the carbon:hydroge n ratio of the fuel,
C x H y O z , according to the following equation:

         liter/mole 055

. 24 liter/ft3 316847

. 28 * mole) / g )( 00797

. 1 * y 01115

. 12 (x NMHC dens where: 12.01115 = atomic weight of carbon 1.00797 = atomic weight of hydrogen

except when using any gasoline-based fuel, includ ing Phase 2 gasoline and E85 fuel, for which the NMHC dens is defined as 16.33.

* * * *

7. SAMPLE CALCULATIONS

7.1 Given the following data for a gasoline vehi cle operated on phase 2 certification fuel, CH 1.964 O 0.0182 , calculate the weighted NMHC mass emission.3 As Amended: December 6, 2012 Date of Hearing: November 15, 2012

Test Phase FID THC e (ppmC) FID THC d (ppmC) CH 4e (ppmC) CH 4d (ppmC) CO em (ppm) CO 2e (%) VMIX (ft 3 ) D phase n (mile) 1 21.928 3.557 3.667 2.545 94.758 0.9581 2745 3.610

2 3.826 3.533 2.694 2.490 16.516 0.5925 4700 3.876

3 4.242 3.386 2.769 2.414 11.524 0.8225 2738 3.611

For Phase 1: NMHC e = FID THC e - (r CH 4 * CH 4e ) = 21.928 ppmC - (1.15 * 3.667 ppmC) = 17.711 ppmC

NMHC d = FID THC d - (r CH 4 * CH 4d ) = 3.557 ppmC - (1.15 * 2.545 ppmC) = 0.630 ppmC

The numerator of the DF = 100 * ( x / ( x + y/2 + 3.76 * ( x + y/4 – z/2) ) = 100 * ( 1 / 1 + 1.964 / 2 + 3.76 * ( 1 + 1.964 / 4 – 0.0182 / 2) = 13.2381

DF = 13.2381 ÷ [CO 2e + (NMHC e + CH 4e + CO e ) * 10 -4 ]

DF = 

##   4 10 ppmC 758

. 94 ppmC 667

. 3 ppmC 711

. 17 9581

. 0 13.2381

     

= 13.653

NMHC conc = NMHC e - NMHC d * [1 - (1 ÷ DF)] = 17.711 ppmC – 0.630 ppmC * [1 - (1 ÷ 13.653)] = 17.127 ppmC

         liter/mole 0547

. 24 liter/ft3 316847

. 28 * ) / )( 00797

. 1 * y 01115

. 12 (x NMHC dens mole g

NMHC dens = 16.33 g/ft 3 (1 * 12.01115 + 1.964 *1.00797 )* (28.316847/24.055) = 16.470 g/ft 3

NMHC mass n = NMHC conc * NMHC dens * VMIX * 10 -6 = 17.127 ppmC * 16.3347 g/ft 3 * 2745 ft 3 * 10 -64 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 NMHC mass 1 = 0.77043 g

Similarly, for Phase 2: NMHC mass 2 = 0.0068 g and for Phase 3: NMHC mass 3 = 0.02179 g

Therefore,



###        

           

   
phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm 

### D D NMHC NMHC 0.57 D D NMHC NMHC 0.43 NMHC

       

           

    miles 3.876 miles 3.611 g 0.0068 g 0.0217 0.57 miles 3.876 miles 3.610 g 0.0068 g 0.768 0.43 NMHC

wm



###        

           

    miles 3.876 miles 3.611 g 0.0068 g 0.0217 0.57 miles 3.876 miles 3.610 g 0.0068 g 0.770 0.43 NMHC

wm

NMHC wm = 0.047 g/mile

7.2 Given the following data for a vehicle ope rating on 10% ethanol a nd 90% gasoline (E10) CH 1.87842.7841 O 0.03380.3835 , calculate the weighted NMHC mass emission.

Test Phase FID THC e (ppmC) FID THC d (ppmC) CH 4e (ppmC) CH 4d (ppmC) CO em (ppm) CO 2e (%) VMIX (ft 3 ) D phase n (mile)

1 14.398 2.971 3.639 2.125 97.83 0.9203 3508 3.590

2 2.882 2.830 2.176 2.010 12.25 0.5935 6010 3.858

3 3.976 2.642 2.621 2.058 19.86 0.7624 3502 3.581

For Phase 1:

NMHC e = FID THC e - (r CH 4 * CH 4e ) = 14.398 ppmC - (1.15 * 2.215 ppmC) = 10.213 ppmC

NMHC d = FID THC d - (r CH 4 * CH 4d ) = 2.971 ppmC - (1.15 * 2.125 ppmC) = 0.527 ppmC

The numerator of the DF = 100 * ( x / ( x + y/2 + 3.76 * ( x + y/4 – z/2))) = 100 * ( 1 / (1 + 1.8784 / 2 + 3.76 * ( 1 + 1.8784 / 4 – 0.0338 / 2))) = 13.5115 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 DF = 13.511 ÷ [CO 2e + (NMHC e + CH 4e + CO e ) * 10 -4 ]



##   4 10 ppmC 83

. 97 ppmC 639

. 3 ppmC 213

. 0 1 9203

. 0 13.511

     

= 14.505

NMHC conc = NMHC e - NMHC d * [1 - (1 / DF)] = 10.213 ppmC – 0.527 ppmC * [1 - (1 / 14.505)] = 9.722 ppmC

NMHC mass n = NMHC conc * NMHC dens * VMIX * 10 -6

NMHC mass 1 = 0.5578 g

Similarly, Phase 2: NMHC mass 2 = 0.0 g and for Phase 3: NMHC mass 3 = 0.040 g

Therefore,



###        

           

   
phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm 

### D D NMHC NMHC 0.57 D D NMHC NMHC 0.43 NMHC

       

           

    miles 3.858 miles 3.581 g 0.00 g 0.040 0.57 miles 3.858 miles 3.590 g 0.00 g 0.558 0.43 NMHC

wm



###        

           

    miles 3.858 miles 3.581 g 0.00 g 0.040 0.57 miles 3.858 miles 3.590 g 0.00 g 0.557 0.43 NMHC

wm

NMHC wm = 0.035 g/mile

* * * *6 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 Part D

DETERMINATION OF C 2 TO C 5 HYDROCARBONS IN AUTOMOTIVE SOURCE SAMPLES BY GAS CHROMATOGRAPHY

METHOD NO. 1002

* * * *

2. METHOD SUMMARY

* * * *

2.2 The samples are received by the laboratory in Tedlar ® , Kynar ® , or Solef ® bags, which are sub-sampled into a GC for separation and analysis.

* * * *

4. INSTRUMENTS AND APPARATUS

4.1 Kynar® (polyvinylidene fluoride) Sample collection bags, 4 mil in thickness, nominally 5 to 10 liters in capacity and equipped with quick-connect fittings, are typically used to contain the samples. Sample collection bags may be made of Tedlar ® (polyvinylfloride, or PVF), 2 mil in thickness, or of Kynar ® or Solef ® (polyvinylidenefloride, or PVDF), each 4 mil in thickness. Other sample bag material or sample collection containe rs, such as bags made of Tedlar® (polyvinyl fluoride) film or nickel-coate d stainless steel canisters, may be used, provided they are made of non-reactive ma terial and do not cause sample loss or contamination.

* * * *7 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 Part E

DETERMINATION OF C 6 TO C 12 HYDROCARBONS IN AUTOMOTIVE SOURCE SAMPLES BY GAS CHROMATOGRAPHY

METHOD NO. 1003

* * * *

2. METHOD SUMMARY

* * * *

2.2 The samples are received by the laboratory in Tedlar ® , Kynar ® , or Solef ® bags, which are sub-sampled into a GC for separation and analysis.

* * * *

4. INSTRUMENTATION AND APPARATUS

4.1 Kynar® (polyvinylidene fluoride) Sample collection bags, 4 mil in thickness, nominally 5 to 10 liters in capacity and equipped with quick-connect fittings, are typically used to contain the samples. Sample collection bags may be made of Tedlar ® (polyvinylfloride, or PVF), 2 mil in thickness, or of Kynar ® or Solef ® (polyvinylidenefloride, or PVDF), each 4 mil in thickness. Other sample bag material or sample collection containe rs, such as bags made of Tedlar® (polyvinyl fluoride) film or nickel-coate d stainless steel canisters, may be used, provided they are made of non-reactive ma terial and do not cause sample loss or contamination.

* * * *8 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 Part F

DETERMINATION OF ALDEHYDE AND KETONE COMPOUNDS IN AUTOMOTIVE SOURCE SAMPLES BY HIGH PERFORMANCE LI QUID CHROMATOGRAPHY

METHOD NO. 1004

* * * *

7. CALCULATIONS

* * * *

7.3 For tolualdehyde, the sum of all isomers pr esent is reported as m-tolualdehyde.

Under the conditions of the system descri bed in Section 6.6, the isomers coelute. The m-tolualdehyde response factor is appl ied to the single tolualdehyde peak. This concentration is reported as m-tolualdehyde.

* * * *9 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 Part G DETERMINATION OF NMOG MASS EMISSIONS

* * * *

3. DILUTION FACTOR AND NMHC MASS EMISSION CALCULATION

* * * *

3.2 The density of the NMHC is determ ined using the carbon :hydrogen ratio of the fuel, C x H y O z , according to the following equation:

         liter/mole 0547

. 24 liter/ft3 316847

. 28 * mole) / g )( 00797

. 1 * y 01115

. 12 (x NMHC dens

where: 12.01115 = atomic weight of carbon 1.00797 = atomic weight of hydrogen

except when using any gasoline-based fuel, including Phase 2 gasoline and E85 fuel, for which the NMHC dens is defined as 16.33.

* * * *

b) For Phase 2 gasoline, CH 1.94 O 0.017 , where x = 1, y = 1.94 and z = 0.017, DF = 13.295 / [CO 2e + (NMHC e + CH 4e + CO e ) * 10 -4 ]

NMHC dens = 16.33 16.44

* * * *

e) For E85, CH 2.7841 O 0.3835 , Wwhere x = 1, y = 2.7841, and z = 0.3835: DF = 12.4253 / [CO 2e + (NMHC e + CH 4e + CO e ) * 10 -4 ]

NMHC dens = 16.33 17.44

3.3 Sample Calculation

A flex-fuel vehicle using E85 fuel CH 2.7841 O 0.3835 , where x = 1, y = 2.7841, and z = 0.3835:

Test Phase FID THC e (ppmC) CH 4e (ppmC) CO 2e (%) CO e (ppm) FID THC d (ppmC) CH 4d (ppmC) CO 2d (%) CO d (ppm) VMIX (ft 3 ) D phase n (mile)

1 27.230 6.918 0.8564 117.801 3.532 2.261 0.0438 0.5224 3495 3.591

2 3.5459 2.357 0.5595 10.8229 3.476 2.247 0.4446 0.3322 5799 3.846

3 3.8510 2.590 0.7163 5.1538 3.396 2.188 0.4507 0.6752 3484 3.59110 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 FID response factor of methane is experiment ally determined for each individual FID. The value of 1.15 used here is for example only.

For phase 1:

NMHC e = FID THC e – r CH 4 * CH 4e = 27.230 – 1.15 * 6.918 = 19.274 ppmC

DF = 12.4253 / [CO 2e + (NMHC e + CH 4e + CO e ) * 10 -4 ] = 12.4253 / [0.8564 + (19.274 + 6.918 + 117.801) * 10 -4 ] = 14.2688 ppmC

NMHC d = FID THC d – r CH 4 * CH 4d = 3.532 – 1.15 * 2.261 = 0.9319 ppmC

NMHC conc = NMHC e –NMHC d* (1 – 1/DF) = 19.274 – 0.9319*( 1 – 1 / 14.2688) = 18.407 ppmC

NMHC mass1 = NMHC conc 

###  NMHC dens 

###  VMIX 1 * 10 -6

= 18.407 * 16.33 17.44 * 3495 * 10 -6 = 1.0506 1.1220 g

Similarly, for Phase 2, DF = 22.152 and NMHC mass2 = 0

Similarly, for Phase 3, DF = 17.32632 and NMHC mass2 = 0.00256 g

4. SPECIATED HYDROCARBON MASS EMISSIONS CALCULATION

* * * *

4.4. SAMPLE CALCULATION

4.4.1 Exhaust emissions from a gasoline ve hicle are collected in three dilute exhaust sample bags and one dilution air (background) sample bag during the FTP. Gas chromatography is used to determine the benzene concentration of each bag sample. Calculate the weighted benzene mass emissions based on the following data:11 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 Test Phase HC e (ppbC) HC d (ppbC ) FID THC e (ppmC ) CH 4e (ppmC ) CO 2e (%) CO em (ppm) R a (%) VMIX (ft 3 ) D phase n (mile)

1 500 25 98 6 1.20 280 28 2846 3.584

2 100 25 22 4 0.95 87 25 4854 3.842

3 120 25 29 5 1.07 101 24 2840 3.586

For Phase 1:

DF = 13.47 / [CO 2e + (NMHC e + CH 4e + CO e ) * 10 -4 ] (see section 3, DF Calc.)

NMHC e = FID THC e - (r CH 4 * CH 4e ) = 98 ppmC - (1.04 * 6 ppmC) = 92 ppmC

CO = (1 - (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R a ) * CO em NOTE: If a CO instrument which m eets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted, CO em must be substituted directly for CO e . = (1 - (0.01925) * 1.2% - 0.000323 * 28%) * 280 ppm = 271 ppm

DF = 13.47 / [1.2% + (92 ppmC + 6 ppmC + 271 ppm) * 10 -4 ] = 10.89

HC conc = HC e - (HC d * (1 - (1 / DF))) = 500 ppbC - (25 ppbC * (1 - (1 / 10.89))) = 477 ppbC

Mol. Wt. of C 6 H 6 = (6 * 12.01115) + (6 * 1.00797) = 78.11472 g/mole

HC dens = (Mol. Wt. * conversion of liter to ft 3 ) / (Mol. Vol.) = (78.11472 g/mole * 28.316 liter/ft 3 ) / 24.055 liter/mole = 91.952 g/ft 3

HC mass n = (HC conc * HC dens * VMIX * 10 -6 ) / (Carbon No.)

HC mass 1 = (477 ppbC * 91.952 g/ft 3 * 2846 ft 3 * 10 -6 ) / 6 = 20.8 mg

Similarly, for Phase 2: HCc mass 2 = 5.7 mg12 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 and for Phase 3: HCc mass 3 = 4.2 mg

Therefore,



###        

           

   
phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm 

### D D HC HC 0.57 D D HC HC 0.43 HC

       

           

    miles 3.842 miles 3.586 mg 5.7 mg 4.2 0.57 miles 3.842 miles 3.584 mg 5.7 mg 20.8 0.43 HC

wm

HC wm = 2.3 mg/mile (benzene weighted mass emissions)

5. ALCOHOL MASS EMISSIONS CALCULATION

* * * *

5.4 SAMPLE CALCULATION

5.4.1 Alcohol emissions from an E85 fuel ed vehicle are collected in three sets of dilute exhaust impingers a nd one set of dilution air impingers during the FTP. Gas chromatography is used to determine the alcohol concentration in each impinger. This is the same vehicle test as the example in section 3.3. Calcul ate the weighted ethanol mass emissions based on the following data, along with the data presented in section 3.3:

Test Phase Ivol r (mL) Iconc e1 (μg/mL) Iconc e2 (μg/mL) Ivol em (liter) Iconc d1 (μg/mL) Iconc d2 (μg/mL) Ivol dm (liter) Itemp e ( o K) Itemp d ( o K)

1 15 4.984 0.106 8.18 0 0 31.16 294.26 294.26

2 15 0 0 14.65 0 0 31.16 294.26 294.26

3 15 0 0 8.67 0 0 31.16 294.26 294.26

Test Phase D phase n (mile) DF P B
(mm HG) VMIX (ft 3 3)

1 3.591 14.27 760 3495
2 3.846 22.15 760 5799 3 3.591 17.33 760 3484

* * * *13 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 6. CARBONYL MASS EMISSIONS CALCULATIONS

* * * *

6 .4. SAMPLE CALCULATION

6 .4.1 Carbonyl emissions from an E85 vehi cle are collected in three sets of dilute exhaust impingers and one se t of dilution air impingers during the FTP. HPLC is used to de termine the carbonyl mass in each impinger. This is the same vehicle test as the example in section 3.3. Calculate the weighted formaldehyde and acetaldehyde mass emissions based on the following data, along with the data presented in section 3.3:

Test Phase Ivol c (mLl) Formaldehyde Ivol em (liter) Acetaldehyde Ivol dm (liter) Itemp e ( o K) Itemp d ( o K) Iconc ce (μg/mL) Iconc cd (μg/mL) Iconc ce (μg/mL) Iconc cd (μg/mL)

1 4.4 0.387 0.006 8.47 4.114 0.006 8.23 294.26 294.26

2 4.4 0.048 0.016 15.35 0.013 0.009 13.88 294.26 294.26

3 4.4 0.016 0.006 9.01 0.012 0.005 8.16 294.26 294.26

Test Phase D phase n (mile) DF P B
(mm HG) VMIX (ft 3 3)

1 3.591 14.27 760 3495
2 3.846 22.15 760 5799 3 3.591 17.33 760 3484

* * * *

7 NONMHC MASS EMISIONS CALCULATION

* * * *

7.3 Sample Calculation

Continuing from the same E85 test used in the alcohol and ca rbonyl calculations:

Test Phase NMHC mass n (g) Ethanol mass n (g) Formaldehyde massn (g) Acetaldehyde mass n (g)

1 1.0506 1.1220 0.09271 0.0197 0.212

2 0 0 0.001457 0.000165

3 0.00256 0 0.000472 0.000329

and

NMHC dens = 16.33 17.44 g/ft 314 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 

##           



         



  RHO
dens mass1 dens ROH
dens mass1 dens mass1 mass1 r RHO RHO NMHC r ROH ROH NMHC NMHC NONMHC

NONMHC mass1 = 1.0506 1.1220 – 16.33 17.44 g/ft 3 * ( 0.9271 g / 27.116 (g/ft 3 )) * 0.756 – 16.33 17.44 g/ft 3 * ( 0.0197 g / 35.350 (g/ft 3 )) * 0 – 16.33 17.44 g/ft 3 * ( 0.212 g / 25.929 (g/ft 3 )) * 0.5 = 1.0506 1.1220 – 0.4221 0.4508 – 0 – 0.0668 0.0713 = 0.5617 0.5999 g

NONMHC mass2 = 0 – 16.33 17.44 g/ft 3 * ( 0 g / 27.116 (g/ft 3 )) * 0.756 – 16.33 17.44 g/ft 3 * ( 0.001457 g / 35.350 (g/ft 3 )) * 0 – 16.33 17.44 g/ft 3 * ( 0.000165 g / 25.929 (g/ft 3 )) * 0.5 = 0 – 0 – 0 – 0.0000525 = 0 g

Note: Results that are less than zero are reported as zero.

NONMHC mass3 = 0.00256 – 16.33 17.44 g/ft 3 * ( 0 g / 27.116 (g/ft 3 )) * 0.756 – 16.33 17.44 g/ft 3 * ( 0.000472 g / 35.350 (g/ft 3 )) * 0 – 16.33 17.44 g/ft 3 * ( 0.000329 g / 25.929 (g/ft 3 )) * 0.5 = 0.00256 – 0 – 0 – 0.000111 = 0.00249 g

8 WEIGHTED HYDROCARBON MASS EMISSIONS CALCULATION

* * * *

8.2 Sample calculation

Continuing from the previous example:

Test Phase NONMHC mass n (g) Ethanol mass n (g) Formaldehyde mass n (g) Acetaldehyde mass n (g) Distance (mile)

1 0.5999 0.5617 0.9271 0.019718 0.212 3.591

2 0 0 0.001457 0.000165 3.846

3 0.00249 0 0.000472 0.000329 3.591

     

         

    miles 3.846 miles 3.591 g 0 g 0.00249 0.57 miles 3.846 miles 3.591 g 0 g 0.5999 0.43 NONMHC

wm

     

         

    miles 3.846 miles 3.591 g 0 g 0.0024 0.57 miles 3.846 miles 3.591 g 0 g 0.5617 0.43 NONMHC

wm15 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 NONMHC wm = 0.03266 0.03488 g/mile Similarly, Ethanol wm = 0.05360 g/mile Similarly, Formaldehyde wm = 0.00137 g/mile Similarly, Acetaldehyde wm = 0.01231 g/mile

With all the above information, the weighted mass emissions of non-methane organic gas can be calculated: 

##       wm wm wm wm RHO ROH NONMHC NMOG

NMOG wm = 0.03266 0.03488 g/mile + 0.05360 g/mile + 0.00137 g/mile + 0.01231 g/mile = 0.09994 0.102 g/mile16 As Amended: December 6, 2012 Date of Hearing: November 15, 2012 APPENDIX 1

LIST OF COMPOUNDS

CAS # COMPOUND MIR

* * * *

Light End and Mid-Range Hydrocarbons (Listed in approximate elution order)

* * * *

03404-61-3 3-methyl-1-hexene 4.564.41

* * * *