California Environmental Protection Agency

AIR RESOURCES BOARD

CALIFORNIA NON-METHANE 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

Monitoring and Laboratory Division, Southern Laboratory Branch

Mobile Source Division

9528 Telstar Avenue

El Monte, California 91731

NOTE: Mention of any trade name 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 underline to indicate additions 

and strikeout to indicate deletions compared to the test procedures as last amended 

September 27, 2010. [No change] indicates proposed federal provisions that are also 

proposed for incorporation herein without change. Existing intervening text that is 

not amended in this rulemaking is indicated by “* * * *”. 
TABLE OF CONTENTS

A. General Applicability and Requirements A-1

B. Determination of Non-Methane Hydrocarbon Mass Emissions by Flame

Ionization Detection B-1

C. Method 1001: Determination of Alcohols in Automotive Source Samples by

Gas Chromatography C-1

D. Method 1002: Determination of C2 to C5 Hydrocarbons in Automotive

Source Samples by Gas Chromatography D-1

E. Method 1003: Determination of C6 to C12 Hydrocarbons in Automotive 

Source Samples by Gas Chromatography E-1

F. Method 1004: Determination of Aldehyde and Ketone Compounds in

Automotive Source Samples by High Performance Liquid Chromatography F-1

G. Determination of Non-Methane Organic Gas Mass Emissions G-1

APPENDICES

Appendix 1 - List of Light-End and Mid-Range Hydrocarbons 1-1

Appendix 2 - Definitions and Commonly Used Abbreviations 2-1

Appendix 3 - References 3-1
A-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Part A

GENERAL APPLICABILITY AND REQUIREMENTS

1. These test procedures shall apply to all 1993 and subsequent model-year transitional 

low-emission vehicles (TLEV), low-emission vehicles (LEV), ultra-low-emission vehicles 

(ULEV), and super-ultra-low-emission vehicles (SULEV) certifying to non-methane organic 

gas (NMOG) emission standards.

2. This document sets forth the analysis and calculation procedures that shall be performed to 

determine NMOG mass emissions. The document consists of the following parts: 

A. General Applicability and Requirements

B. Determination of Non-Methane Hydrocarbon Mass Emissions by Flame Ionization 

Detection 

C. Determination of Alcohols in Automotive Source Samples by Gas 

Chromatography (Method No. 1001) 

D. Determination of C2 to C5 Hydrocarbons in Automotive Source Samples by Gas 

Chromatography (Method No. 1002) 

E. Determination of C6 to C12 Hydrocarbons in Automotive Source Samples by Gas 

Chromatography (Method No. 1003) 

F. Determination of Aldehyde and Ketone Compounds in Automotive Source 

Samples by High Performance Liquid Chromatography (Method No. 1004).

G. Determination of NMOG Mass Emissions

Appendix 1 List of Light-End and Mid-Range Hydrocarbons

Appendix 2 Definitions and Commonly Used Abbreviations

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.

3. The 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:

Fuel NMHC by FID NMHC by GC Alcohols Carbonyls

Alcohol X X X

CNG X X

Diesel X X

Gasoline X X

LPG X X
A-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

The specified analyses shall be performed in accordance with the following parts of this 

document:

NMHC by FID-- Part B. Determination of Non-Methane Hydrocarbon Mass Emissions 

by Flame Ionization Detection

NMHC by GC-- Part D. Determination of C2 to C5 Hydrocarbons in Automotive 

Source Samples by Gas Chromatography (Method No. 1002); 

and 

Part E. Determination of C6 to C12 Hydrocarbons in Automotive 

Source Samples by Gas Chromatography (Method No. 1003) 

CARBONYLS-- Part F. Determination of Aldehyde and Ketone Compounds in 

Automotive Source Samples by High Performance Liquid 

Chromatography (Method No. 1004) 

ALCOHOLS -- Part C. Determination of Alcohols in Automotive Source Samples by 

Gas Chromatography (Method No. 1001)

4. For those manufacturers that 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 that are operated on fuels containing alcohols.

5. For 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 application. A 

density of 18.89 g/ft3 shall be used to determine the methane mass 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 the “California 

Exhaust Emission Standards and Test Procedures for 1988-2000 Model Passenger Cars, 

Light-Duty Trucks, and Medium-Duty Vehicles” and in the “California Exhaust Emission 

Standards and Test Procedures for 2001 and Subsequent Model Passenger Cars, Light-Duty 

Trucks, and Medium-Duty Vehicles.”

6. The 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.
B-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

PART B

DETERMINATION OF NON-METHANE HYDROCARBON MASS EMISSIONS

BY FLAME IONIZATION DETECTION

1. INTRODUCTION

1.1 This procedure describes a method for determining 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.

1.2 All definitions and abbreviations are contained in Appendix 2 of these test procedures.

2. TOTAL HYDROCARBON MEASUREMENT

2.1 A FID is used to measure total hydrocarbon concentration in vehicle exhaust in accordance with 

the Code of Federal Regulations [Ref.1]. SAE Recommended Practices J254 [Ref. 2] and J1094a 

[Ref. 3] are references on generally accepted gas analysis and constant volume sampling 

techniques. For Beckman 400 FIDs only, implementation of the recommendations outlined in 

SAE paper 770141[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.

3. METHANE MEASUREMENT

3.1 A GC combined with a FID constitute a methane analyzer and shall be used for direct 

measurement of methane concentrations. The SAE Recommended Practice J1151[Ref. 5] is a 

reference on generally accepted GC principles and analytical techniques for this specific 

application.

4. TOTAL HC FID RESPONSE TO METHANE

4.1 The 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 to NIST shall be analyzed by the 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:

rCH4 = FIDppm/SAMppm

where:
B-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

rCH4 = FID methane response factor.

FIDppm = FID reading in ppmC. 

SAMppm = the known methane concentration in ppmC.

 

The FID response to methane shall be checked at each calibration interval.

5. NMHC MASS EMISSION PER TEST PHASE

5.1 The following calculations shall be used to determine the NMHC mass emissions for each phase 

of the Federal Test Procedure. [Ref. 1].

5.2 Non-Alcohol Fueled All Vehicles

5.2.1 NMHCe = FID THCe - (rCH4 * CH4e )

NOTE: If NMHCe is calculated to be less than zero, then NMHCe = 0.

5.2.2 NMHCd = FID THCd - (rCH4 * CH4d )

NOTE: If NMHCd is calculated to be less than zero, then NMHCd = 0.

5.2.3 COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used 

and the conditioning column has been deleted, COem must be substituted directly for COe.

a) For gasoline, CH1.85 , where HCR = 1.85:

COe = (1 - 0.01925 * CO2e - 0.000323 * Ra ) * COem

b) For Phase 2 gasoline, CH1.94 , where HCR = 1.94:

COe = (1 - 0.01970 * CO2e - 0.000323 * Ra ) * COem

c) For LPG, CH 2.64, where HCR = 2.64:

COe = (1 - 0.02320 * CO2e - 0.000323 * Ra) * COem

d) For CNG, CH3.78, where HCR = 3.78:

COe = (1 - 0.02890 * CO2e - 0.000323 * Ra) * COem

5.2.4 ( )

( ) 4 CO2e NMHCe CH4e COe 10

x y 2 3.76 x y 4 z 2

x 100

DF − + + + ∗

















+ + ∗ + − ∗

=

(where fuel composition is CxHyOz as measured for the fuel used.; this expression is 

generally normalized so that x = 1)

a) For gasoline, CH1.85 , where x = 1, y = 1.85, and z = 0:

DF = 13.47 / [CO2e + (NMHCe + CH4e + COe ) * 10-4 ]
B-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

b) For Phase 2 gasoline, CH1.94 , x = 1, y = 1.94 and z = 0.017:

DF = 13.29 / [CO2e + (NMHCe + CH4e + COe ) * 10-4 ]

c) For LPG, CH 2.64 , where x = 1, y = 2.64, and z = 0:

DF = 11.68 / [CO2e + (NMHCe + CH4e + COe) * 10-4 ]

d) For CNG, CH3.78, where x = 1, y = 3.78, and z = 0.016:

DF = 9.83 / [CO2e + (NMHCe + CH4e + COe) * 10-4 ]

e) For E85, CH2.7841O0.3835, Where x = 1, y = 2.7841, and z = 0.3835:

DF = 12.4253 / [CO2e + (NMHCe + CH4e + COe) * 10-4 ]

5.2.5 The density of the NMHC is determined using the carbon:hydrogen ratio of the fuel,

CxHyOz, according to the following equation: 





 



 = ∗ +

24.055 liter/mole

28.316847 liter/ft3 NMHCdens (x 12.01115 y *1.00797)(g / mole)*

where: 12.01115 = atomic weight of carbon

1.00797 = atomic weight of hydrogen

5.3 Vehicles Operating on Fuels Containing Methanol

5.3.1 NMHCe = FID THCe - (rCH4 * CH4e) - (rCH3OH * CH3OHe)

NOTE: If NMHCe is calculated to be less than zero, then NMHCe = 0.

5.3.2 NMHCd = FID THCd - (rCH4 * CH4d) - (rCH3OH * CH3OHd)

NOTE: If NMHCd is calculated to be less than zero, then NMHCd = 0.

5.3.3 COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40 86.111 is used 

and the conditioning column has been deleted, COem must be substituted directly for COe .

a) For M100 (100% methanol), CH3OH, where HCR = 4:

COe = (1 - 0.03000 * CO2e - 0.000323 * Ra ) * COem

b) For M85 (85% methanol, 15% indolene), CH3.41 O0.72 , where 

HCR = 3.41:

COe = (1 - 0.02705 * CO2e - 0.000323 * Ra ) * COem

5.3.4 ( )

( ) 4 CO2e NMHCe CH4e COe CH3OHe HCHOe 10

x y 2 3.76 x y 4 z 2

x 100

DF − + + + + + ∗

















+ + ∗ + − ∗

=

(where fuel composition is CxHyOz as measured for the fuel used.)
B-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

a) For M100 (100% methanol), CH3OH, where x = 1, y = 4, and z = 1:

DF = 11.57 / [CO2e + (NMHCe+ CH4e + COe + CH3OHe + HCHOe ) * 10-4]

b) For M85 (85% methanol, 15% Indolene), CH3.41 O0.72 , where x = 1, 

y = 3.41, and z = 0.72:

DF = 12.02 / [CO2e + (NMHCe + CH4e + COe + CH3OHe + HCHOe) * 10-4] 

5.4 Vehicles Operating on Fuels Containing Ethanol

5.4.1 NMHCe = FID THCe - (rCH4 * CH4e) - (rC2H5OH * C2H5OHe)

NOTE: If NMHCe is calculated to be less than zero, then NMHCe = 0

5.4.2 NMHCd = FID THCd - (rCH4 * CH4d) - (rC2H5OH * C2H5OHd)

NOTE: If NMHCd is calculated to be less than zero, then NMHCd = 0

5.4.3 COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used 

and the conditioning column has been deleted, COem must be substituted directly for COe .

a) For E100 (100% ethanol), C2H5OH, where HCR = 3:

COe = (1 - 0.02500 * CO2e - 0.000323 * Ra ) * COem

5.4.4 ( )

( ) 4 CO2e NMHCe CH4e COe C2H5OHe HCHOe 10

x y 2 3.76 x y 4 z 2

x 100

DF − + + + + + ∗

















+ + ∗ + − ∗

= 

(where fuel composition is CxHyOz as measured for the fuel used.)

a) For E100 (100% ethanol), C2H5OH, where x = 1, y = 3, and z = 0.5:

DF = 12.29 / [CO2e + (NMHCe + CH4e + COe + C2 H5 OHe + HCHOe ) * 10-4 ]

5.5 All Vehicles

5.2.65.1 NMHCconc = NMHCe - NMHCd * [1 - (1 / DF)]

NOTE: If NMHCconc is calculated to be less than zero, then NMHCconc = 0

5.2.75.2 NMHCmassn = NMHCconc * NMHCdens * VMIX * 10-6

6. TOTAL WEIGHTED NMHC MASS EMISSIONS

6.1 All Vehicles

6.1.1 















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

NMHC NMHC 0.57

D D

NMHC NMHC NMHC 0.43
B-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

7. SAMPLE CALCULATIONS

7.1 Given the following data for a gasoline vehicle operated on phase 2 certification fuel, 

CH1.964O0.0182, calculate the weighted NMHC mass emission.

Test 

Phase

FID THCe

(ppmC)

FID THCd

(ppmC)

CH4e

(ppmC)

CH4d

(ppmC)

COem

(ppm)

CO2e

(%)

VMIX

(ft3)

Dphase n

(mile)

Ra

(%)

1 21.928

141.8

3.557

8.6

3.667

7.53

2.545

5.27

94.758

147.2

0.9581

1.19

2745

2846

3.610

3.583

38

2 3.826

13.0

3.533

8.4

2.694

5.68

2.490

5.10

16.516

20.8

0.5925

0.80

4700

4856

3.876

3.848

38

3 4.242

15.4

3.386

8.9

2.769

6.16

2.414

5.20

11.524

36.7

0.8225

1.04

2738

2839

3.611

3.586

38

For Phase 1:

NMHCe = FID THCe - (rCH4 * CH4e )

= 21.928 41.8 ppmC - (1.15 1.04 * 3.667 7.53 ppmC)

= 17.711 33.97 ppmC

NMHCd = FID THCd - (rCH4

 * CH4d )

= 3.557 8.6 ppmC - (1.15 1.04 * 2.545 5.27 ppmC)

= 0.630 3.12 ppmC

COe = (1 - 0.01925 * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used 

and the conditioning column has been deleted, COem must be substituted directly for COe .

= (1 - 0.01925 * 1.19% - 0.000323 * 38%) * 147.18 ppm

= 142.0 ppm

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 13.47 ÷ [CO2e + (NMHCe + CH4e + COe ) * 10-4]

DF = 13.2381 

 0.9581 + (17.711 ppmC + 3.667 ppmC + 94.758 ppmC) * 10-4

DF = 13.47 

 1.19% + (33.97 ppmC + 7.53 ppmC + 142.0 ppmC) * 10-4

= 11.15 13.653

NMHCconc = NMHCe - NMHCd * [1 - (1 ÷ DF)]

= 33.97 ppmC - 3.12 ppmC * [1- (1÷11.15)]
B-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

= 17.711 ppmC – 0.630 ppmC * [1 - (1 ÷ 13.653)]

= 17.127 31.13 ppmC





 



 = ∗ +

24.0547liter/mole

28.316847liter/ft3 NMHCdens (x 12.01115 y *1.00797)(g / mole) *

NMHCdens = (1 * 12.01115 + 1.964 *1.00797 )* (28.316847/24.055)

 = 16.470 g/ft3

NMHCmass n = NMHCconc * NMHCdens * VMIX * 10-6

= 17.127 31.13 ppmC * 16.4733 g/ft3 * 2745 2846 ft3 * 10-6

NMHCmass 1 = 0.7743 1.45 g

Similarly, for Phase 2: NMHCmass 2 = 0.0068 0.33 g

and for Phase 3: NMHCmass 3 = 0.0219 0.27 g

Therefore,

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

NMHC NMHC 0.57

D D

NMHC NMHC NMHC 0.43

















+

+

+ ∗ 















+

+ = ∗

3.586 miles 3.848 miles

0.27g 0.33g 0.57

3.583 miles 3.848 miles

1.45g 0.33g NMHC 0.43 wm

















+

+

+ ∗ 















+

+ = ∗

3.611 miles 3.876 miles

0.0217 g 0.0068g 0.57

3.610 miles 3.876 miles

0.768 g 0.0068 g NMHCwm 0.43

NMHCwm = 0.047 0.15 g/mile

7.2 Given the following data for a vehicle operating on 1085% methanol and 9015% gasoline 

(E10 M-85) CH2.7841O0.3835, calculate the weighted NMHC mass emission.

Test 

Phase

FID 

THCe

(ppmC)

FID 

THCd

(ppmC)

CH4e

(ppmC)

CH4d

(ppmc)

CH3OHe

(ppm)

COem

(ppm)

CO2e

(%)

VMIX

(ft3)

Dphase n

(mile)

Ra

(%)

HCHOe

(ppm)

1 88.5 5.5 17.76 2.82 72.9 303.2 1.28 2832 3.570 32 0.96

2 14.5 7.0 8.01 2.82 5.1 9.7 0.83 4827 3.850 32 0.10

3 21.8 7.7 10.13 2.93 7.4 18.2 1.13 2825 3.586 32 0.12
B-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Test 

Phase

FID 

THCe

(ppmC)

FID 

THCd

(ppmC)

CH4e

(ppmC)

CH4d

(ppmC)

COem

(ppm)

CO2e

(%)

VMIX

(ft3)

Dphase 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 this example, CH3OHd was assumed to be 0.0 ppmC for all three background bag samples.]

For Phase 1:

NMHCe = FID THCe - (rCH4 * CH4e) - (rCH3OH * CH3OHe)

= 14.398 88.5 ppmC - (1.15 1.04 * 2.215 17.76 ppmC) - (0.66*72.9 ppmC)

= 10.213 21.92 ppmC

NMHCd = FID THCd - (rCH4 * CH4d) - (rCH3OH * CH3OHd)

= 2.971 5.5 ppmC - (1.15 1.04 * 2.125 2.82 ppmC) - (0.66*0.0 ppmC)

= 0.527 2.57 ppmC

COe = (1 - 0.02705 * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the 

conditioning column has been deleted, COem must be substituted directly for COe .

= (1 - 0.02705 * 1.28% - 0.000323 * 32%) * 303.2 ppm

= 289.6 ppm

DF = 13.511 12.02 ÷ [CO2e + (NMHCe + CH4e + COe + CH3OHe + HCHOe) * 10-4] 

( ) 4 1.28% 21.92ppmC 17.76ppmC 289.6ppmC 72.9ppmC 0.96ppmC 10

12.02 − + + + + + ∗ =

( ) 4 0.9203 10.213ppmC 3.639ppmC 97.83ppmC 10

13.511 − + + + ∗ =

= 14.505 9.10

NMHCconc = NMHCe - NMHCd * [1 - (1 / DF)]

= 10.213 21.92 ppmC – 0.527 2.57 ppmC * [1 - (1 / 14.505 9.10)]

= 9.722 19.63 ppmC

NMHCmass n = NMHCconc * NMHCdens * VMIX * 10-6

NMHCmass 1 = 0.558 0.91 g
B-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Similarly, Phase 2: NMHCmass 2 = 0.0 g 

and for Phase 3: NMHCmass 3 = 0.10 0.040 g

Therefore,

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

NMHC NMHC 0.57

D D

NMHC NMHC NMHC 0.43

















+

+

+ ∗ 















+

+ = ∗

3.586 miles 3.850 miles

0.10g 0.00g 0.57

3.570 miles 3.850 miles

0.91g 0.00g NMHC 0.43 wm

















+

+

+ ∗ 















+

+ = ∗

3.581 miles 3.858 miles

0.040 g 0.00 g 0.57

3.590 miles 3.858 miles

0.558g 0.00 g NMHC 0.43 wm

NMHCwm = 0.06 g/mile

NMHCwm = 0.035 g/mile
C-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Part C

DETERMINATION OF ALCOHOLS

IN AUTOMOTIVE SOURCE SAMPLES 

BY GAS CHROMATOGRAPHY

METHOD NO. 1001

1. INTRODUCTION

1.1 This document describes a method of sampling and analyzing automotive source 

samples exhaust for alcohols in the range of 1 to 1200 μg per 15 mL of solution. 

The “target” alcohols that shall be analyzed and reported by this method are 

methanol and ethanol. These alcohols, when measured in concentrations above 

the LOD, shall be reported. 

1.2 This procedure is based on a method developed by the U. S. Environmental 

Protection Agency, (U.S. EPA) [Ref 6] which involves flowing diluted engine 

exhaust through deionized or purified water contained in glass impingers and 

analyzing this solution by gas chromatography .

1.3 The “target” alcohols (compounds of interest) that shall be measured by this 

method are methanol and ethanol in the range of 1 to 1200 μg per 15 mL of 

impinger solution. These alcohols, when measured in concentrations above the 

LOD, shall be reported.

1.3.1 For the purpose of calculating NMOG for vehicles tested on exhaust 

emission test fuel containing ethanol (see Part G, Determination of 

NMOG Mass Emissions):

1.3.1.1 The only alcohol that needs to be reported from this method is ethanol. 

1.3.1.2 The analysis of methanol is also within the scope of this analytical 

method and its measurement may provide meaningful information to the 

laboratory. However, its measurement is not required.

1.4 Other applicable forms of instrumentation and analytical techniques may be used 

if shown to yield results equivalent to those specified in this procedure and if 

approved in advance by the Executive Officer of the Air Resources Board.

1.5 All definitions and abbreviations are contained in Appendix 2 of these test 

procedures.
C-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

2. METHOD SUMMARY

2.1 The 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 autosampler. Separation of the sample mixture into its 

components is performed by a temperature-programmed capillary column. A FID 

is used for alcohol detection and quantification.

2.2 The computerized GC data system identifies the alcohol associated with each 

peak. The alcohol concentrations are determined by integrating the peak areas 

and using response factors determined from external standards.

3. INTERFERENCES AND LIMITATIONS

3.1 An interferent interfering compound is any component present in the sample with 

a retention time similar to that of any target alcohol described in this method. To 

reduce interference error, proof of chemical identity may require periodic 

confirmations using an alternate method and/or instrumentation, e.g., GC/MS.

3.2 The concentration of the alcohols in the range of interest is stable for up to six 

days as long as the samples are sealed and refrigerated at a temperature below 

40oF.

3.3 To avoid sample loss and/or contamination, samples should be analyzed or 

transferred from the impingers to tightly sealed storage bottles as soon as possible

after collection.

4. INSTRUMENTATION AND APPARATUS

4.1 For each mode of the CVS test, two sampling impingers, each containing a known 

amount of deionized or purified water (e.g. 15 mL for this procedure), are used to 

contain the sample.

4.1.1 A temperature-programmable GC, equipped with a DB-Wax type

Megabore column ([typically 30 m, 0.53 mm ID (Megabore), 1.0 μ film 

thickness]) and FID, is used. Other columns may be used, provided the 

alternate(s) can be demonstrated to the ARB to be equivalent or better 

with respect to precision, accuracy and resolution of all the target alcohols. 

4.1.2 A liquid injection autosampler is required.

4.1.3 A PC-controlled data acquisition system for quantifying peak areas is 

required.
C-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

5. REAGENTS AND MATERIALS

5.1 Methanol shall have a purity of 99.9 percent, or be high performance liquid

chromatography grade, EM Science or equivalent.

5.2 Ethanol shall be absolute, ACS reagent grade.

5.3 ASTM Type I purified or Type II deionized water shall be used.

5.4 Stock solutions are prepared gravimetrically or volumetrically by diluting 

methanol and ethanol with deionized or purified water, e.g., for this method a 

typical stock solution contains approximately 10 mg/mL of each target alcohol. 

Stock solutions must be replaced at least every six months.

5.4.1 A calibration standard within the expected concentration range of the 

samples is prepared by successive dilutions of the stock solution with 

deionized or purified water. ; 3 to 50 μg/mL is typical, depending on fuel 

type. Calibration standards must be replaced at least every week.

5.4.1.1 Typical calibration standards range from 3 to 100 μg/mL for exhaust 

emission testing, depending on fuel type.

5.4.1.2 Evaporative emission testing may require calibration standards as high as 

1000 μg/mL due to higher sample concentration.

5.4.1.3 Calibration standards must be replaced frequently to avoid degradation of 

the standard. Standards with concentrations of 100 μg/mL or less should 

be replaced weekly. 

5.4.2 A control standard containing all target alcohols is prepared by successive 

dilutions of a stock solution different from that of used in Section 5.4.1. 

This standard, at an approximate concentration of the samples, is used to 

monitor the precision of the analysis of each target alcohol. Control 

standards must be replaced at least every week.

5.4.3 Standards used for linearity and LOD determinations (Section 8) are also 

prepared by successive dilutions of an appropriate level stock solution.

5.4.4 Standards may also be purchased (e.g., NIST).

5.4.5 All standards should be refrigerated at a temperature below 40oF during 

storage.
C-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

5.5 Gas requirements.

5.5.1 Air shall be “Zero” grade (<1 ppmC total hydrocarbon contamination) or 

better.

5.5.2 Nitrogen shall have a minimum purity of 99.998 percent.

5.5.3 Helium shall have a minimum purity of 99.995 percent.

5.5.4 Hydrogen shall have a minimum purity of 99.995 percent.

6. PROCEDURE

6.1 Each of the graduated sampling impingers is filled with 15 mL of deionized or 

purified water.

6.2 The impingers are placed in an ice bath during the sample collection.

6.3 After sampling, the solution contained in each impinger is transferred to a vial and 

sealed.

6.3.1 Samples shall be refrigerated at a temperature below 40o

F if immediate 

analysis is not feasible, or if reanalysis at a later date may be required.

6.4 One microliter aliquots of unmodified samples are injected via autosampler into a 

GC. Suggested Typical standard operating conditions for the GC are:

Column: DB-Wax, 30 m, 0.53 mm ID, 1.0μ film thickness 

Carrier gas flow: Helium at 5 mL/min 

Make-up gas flow: Nitrogen at 25 mL/min 

Detector: FID, hydrogen at 30 mL/min and air at 300 mL/min 

Injector: Packed column injector with Megabore adapter insert; 

on-column injection 

Column temperature: 50oC (1 min),

50oC to 70oC (5oC/min),

70oC to 110oC (15oC/min),

110oC (4 min) 

Data system: PC-based data acquisition system

6.5 Samples containing compounds having concentrations above the documented 

range of instrument linearity must be diluted and reanalyzed.

6.6 The peak integrations are corrected as necessary in the data system. Any 

misplaced baseline segments are corrected in the reconstructed chromatogram.
C-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

6.7 The peak identifications provided by the computer are checked and corrected if 

necessary.

7. CALCULATIONS

7.1 The concentration of each target alcohol, in μg/mL, is determined by the 

following calculation that compares relates the sample peak area to with that of an 

external standard:

Concentration (μg/mL)sample = Peak Areasample x Response Factor

where the response factor (RF) is calculated during the calibration by:

( )

standard

standard μg mL

Peak Area

Concentration

RF =

7.2 Sample batches that span a broad concentration range (several orders of 

magnitude) should use more than one calibration level. 

7.2.1 Each sample concentration would then be calculated by using a standard 

of similar concentration to calculate the response factor, as in Section 7.1.

7.2.2 A multipoint calibration curve calculated by the GC software (e.g., Varian 

Star 6.0) may be used instead of the one-point calibration described in 

Section 7.1. 

7.3 This concentration is then used to calculate the total amount of alcohol in each 

impinger:

Mass (μg) = Concentration (μg/mL) x Impinger volume (mL)

7.4 An internal standard method may also be used. 

8. QUALITY CONTROL

8.1 Blank Run - A deionized or purified water blank is run each analysis day. All 

target alcohol concentrations from the blank analysis must be below the LOD 

before the analysis may proceed. 

8.1.1 If the blank shows a peak greater than the limit of detection (LOD) in the 

region of interest, the source of the contamination must be investigated 

and remedied.

8.2 Calibration Run - The calibration standard is analyzed each analysis day to 

generate the response factor used to quantify the sample concentrations.
C-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

8.3 Control Standard Run - The quality control standard is analyzed at least once each 

analysis day. Measurements of all target alcohols in the control standard must fall 

within the control limits to ensure the validity of the sample analyses that day. To 

meet this requirement, it may be necessary to inspect and repair the GC, and rerun 

the calibration and/or control standards.

8.4 Control Charts - A quality control chart is maintained for each analyte in the 

control standard. The control charts, used on a daily basis, establish that the 

method is “in-control”. The following describes how to construct a typical 

control chart:

1. Obtain at least 20 daily control standard results;

2. Calculate the control standard mean concentration and standard deviation 

for the target analyte; and

3. Create a control chart for the target analyte by placing the concentration 

on the Y-axis and the date on the X-axis. Establish upper and lower 

warning limits at either two standard deviations (2s) or 5 percent, 

whichever is greater, above and below the average concentration. 

Establish an upper and lower control limits at either three standard 

deviations (3s) or 5 percent, whichever is greater, above and below the 

average concentration.

4. A control standard measurement is considered to be out-of-control when 

the analyzed value exceeds the control limit or two successive control 

standard measurements of the same analyte exceed the warning limit.

5. If 20 control standard results are not yet available to create a control chart 

(e.g., the control standard was expended and replaced with a different 

concentration standard prior to obtaining 20 points with the new standard), 

measurements must be within 10% of the theoretical concentration.

The measured concentrations of all target analytes contained in the control 

standard must be within the control limits (“in-control”) for the sample results to 

be considered acceptable.

8.5 Duplicates - A duplicate analysis of one sample is performed at least once per 

analysis day. The relative percent difference (RPD) is calculated for each 

duplicate run:

( ) 100

Average of duplicate and original measurements

Difference between duplicate and original measurements

RPD % = ∗

For each compound, the allowable RPD depends on the average concentration 

level for the duplicate runs, as shown in the following table:
C-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Average Measurement for Duplicate Runs Allowable RPD (%)

1 to 10 times LOD 100

10 to 20 “ “ 30

20 to 50 “ “ 20

Greater than 50 “ “ 15

If the results of the duplicate analyses do not meet these criteria for all target 

alcohols, the sample may be reanalyzed. If reanalysis is not feasible or if the 

criteria are still not met on reanalysis, all sample results for that analysis day are 

invalid. 

8.6 Linearity - A multipoint calibration to confirm instrument linearity is performed 

for all target alcohols for new instruments, after making instrument modifications 

that can affect linearity, and at least once every year. The multipoint calibration 

consists of at least five concentration or mass loading levels, each above the LOD, 

distributed over the range of expected sample concentration. 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.

8.7 Limit of Detection - The LOD for the target alcohols must be determined for new 

instruments, after making instrument modifications that can affect the LOD and at 

least once every year. To make the calculations, it is necessary to perform a 

multipoint calibration consisting of at least four “low” concentration levels, each 

above the expected LOD, with at least five replicate determinations of the lowest 

concentration standard. A linear regression is performed and the standard 

deviation (in area counts) of the lowest concentration standard determined. The 

standard deviation is converted to concentration units using the slope of the linear 

regression:

s = sa ÷ m 

where m is the slope of the linear regression, s is the standard deviation (in 

concentration units) of the lowest concentration standard and sa is the standard 

deviation (in area counts) of the lowest concentration standard.

The LOD must be calculated using the following equation [Ref. 12]:

LOD = t ∗ s

where s is the standard deviation (in concentration units) of at least five replicate 

determinations of the lowest concentration standard and t is the t-factor for 99 

percent confidence for a one-sided normal (Gaussian) distribution. The number of 

degrees of freedom is equal to the number of replicates, minus one. An abbreviated 

t–table is:
C-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Degrees of Freedom t-value

4 3.7

5 3.4

6 3.1

7 3.0

The lowest standard must be of a concentration of one to five times the estimated 

LOD. 

8.7.1 The maximum allowable LOD for each alcohol is 0.10 μg/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 the maximum allowable 

LOD, the calculated laboratory LOD, or any level in between. 

8.7.2 For the purpose of calculating the total mass of all species, the 

concentrations of the compounds below the LOD are considered to be 

zero.
D-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Part D

DETERMINATION OF C2 TO C5 HYDROCARBONS

IN AUTOMOTIVE SOURCE SAMPLES BY GAS CHROMATOGRAPHY

METHOD NO. 1002

1. INTRODUCTION

1.1 This document describes a gas chromatographic method of analyzing measuring

C2 to C5 hydrocarbons (light-end hydrocarbons) in the ppbC range from 

automotive source samples. This method does not include sample collection 

procedures [Ref. 8]. The “target” hydrocarbons (compounds of interest) that shall 

be analyzed and reported by this method and Method 1003 are listed in Appendix 

1. All compounds on this list, when measured in concentrations above the LOD, 

shall be measured and reported (“targeted”) by either Method 1002 or Method 

1003. Each laboratory should divide the list into light-end (Method 1002) and 

mid-range (Method 1003) hydrocarbons in the manner that best suits the 

laboratory instrumentation. All compounds on the list not targeted by Method 

1002 must be targeted by Method 1003. 

1.2 Other applicable forms of instrumentation and analytical techniques may be used 

if shown to yield results equivalent to those specified in this procedure and if 

approved in advance by the Executive Officer of the Air Resources Board.

1.3 All definitions and abbreviations are contained in Appendix 2 of these test 

procedures.

2. METHOD SUMMARY

2.1 This is a method intended for routine analysis.

2.2 The samples are received by the laboratory in Tedlar Kynar® bags, which are 

sub-sampled into a GC for separation and analysis.

2.3 The gas chromatographic analysis is performed on an Alumina (Al203) PLOT 

column temperature programmed from 0oC to 200oC. An FID is used for 

detection and quantification.

2.4 The sample is injected into the GC by means of gas sampling valves. Separation 

of the sample hydrocarbon mixture into its components 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.
D-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

2.5 The computerized GC data acquisition system identifies the hydrocarbons 

associated with each peak. The hydrocarbon concentrations are determined by 

integrating the peak areas and using response factors determined from 

NIST-traceable standards.

3. INTERFERENCES AND LIMITATIONS

3.1 An interferent interfering compound is any component present in the sample with 

a retention time very similar to that of any target hydrocarbon described in this 

method. To reduce interference error, proof of chemical identity may require 

periodic confirmations using an alternate method and/or instrumentation, e.g., 

GC/MS, PID, different column, etc.

3.2 To 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 photochemically induced reactions of any reactive 

hydrocarbons. The compound 1,3-butadiene, resulting mostly during cold-start 

testing, is unstable. Therefore all cold-start samples must be analyzed within 8 

hours; all other samples must be analyzed within 24 hours, although analysis 

within 8 hours is recommended.

4. INSTRUMENTS AND APPARATUS

4.1 Tedlar Kynar® (polyvinylidene fluoride) bags, 2 4 mil in thickness, nominally 5 

to 10 liters in capacity and equipped with quick-connect fittings, are typically

used to contain the samples. Other sample collection containers, such as bags 

made of Tedlar® (polyvinyl fluoride) film or nickel-coated stainless steel 

canisters, may be used, provided they are made of non-reactive material and do 

not cause sample loss or contamination.

4.2 For manual sub-sampling 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 aliquot size is chosen based on considerations 

of instrument sensitivity and/or linearity.

4.3 A temperature-programmable GC equipped with a gas sampling valve system, a 

FID, and accessories is required.

4.4 An Alumina PLOT column (typically 50 m x 0.32 mm) is used. 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 the ARB

to be equivalent or better with respect to precision, accuracy and resolution of all 

the target hydrocarbons.

4.5 A sample trap capable of being cryogenically cooled may be used.
D-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

4.6 Data acquisition software is used to integrate peak areas to determine 

hydrocarbon concentrations.

5. REAGENTS AND MATERIALS

5.1 Helium shall have a minimum purity of 99.995 percent. Higher purity helium 

may be required to achieve the LOD required by Section 8.7.1.

5.2 Hydrogen shall have a minimum purity of 99.995 percent.

5.3 Air shall be “Zero” grade (<1 ppmC total hydrocarbon contamination) or better.

5.4 Nitrogen shall have a minimum purity of 99.998 percent.

5.5 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 linearity of the method. (See Section 8.6.) 

This propane standard must be a NIST-certified SRM or secondary NISTtraceable standard. A secondary standard is obtained by a comparison between a 

SRM and a candidate standard.

5.6 Control Standard - A quality control standard, containing at least ethene, propane, 

n-butane, and 2-methylpropene with concentrations between 0.2 and 3 ppmC 

based on a propane standard, is used for the following purposes:

1. Daily update of control charts, and

2. Daily determination of marker retention time windows.

5.7 A high concentration standard (higher than the calibration standard), containing 

the target hydrocarbons listed in Section 5.6, is used for linearity determinations. 

The high concentration 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.

5.8 A low concentration standard (one to five times the estimated LOD), containing 

the target hydrocarbons listed in Section 5.6, is used for LOD determinations. 

The low concentration 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.

5.8.1 In lieu of a low concentration standard, a higher concentration standard 

may be diluted.
D-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

5.9 Liquid nitrogen may be required to cool the cryogenic sample trap and column 

oven where applicable.

6. PROCEDURE

6.1 The gaseous sample is analyzed for the target hydrocarbons C2 through C5.

6.2 Suggested Typical standard operating conditions for the automated gas 

chromatograph are:

Helium carrier gas flow velocity: 30 cm/sec 2.2 mL/min at 2000C

Detector (0.010” FID)

Temperature: 2500C or higher

Nitrogen make-up gas flow: sufficient such that the total flow of 

helium plus nitrogen is 30 25 mL/min

Hydrogen gas flow: 30 25 mL/min

Air flow: 300 mL/min

Range 12, attenuation 8 (or another suitable value) 

Sample loop/valve temperature: 1500C (PLOT column)

Cryotrap temperature: -1800C (hold to trap hydrocarbons)

2000C (heat to release) hydrocarbons)

Precolumn oven temperature: 500C

Analytical column valve oven temperature: 1500C

Column Temperature Program: 00C (hold 37 min),

100C/min to 2000C (hold 15 min)

50C/min to 2000C

2000C (hold 35 min)

Detector temperature: 2500C

Injector temperature: 1500C

6.3 For automated systems, connect the samples to the GC and begin the analytical 

process. 

6.3.1 Samples may be injected manually by injecting an aliquot with a ground 

glass syringe. 

6.4 Introduce the sample into the carrier gas stream through the injection valve.

6.5 Each separated component exits from the column into the FID where a response is 

generated.

6.6 Concentrations of hydrocarbons are calculated using data acquisition/ processing 

software that uses calibration data from the NIST-traceable propane calibration 

standard.
D-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

6.7 For 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) or the sample must be 

diluted.

6.8 The peak integrations are corrected as necessary in the data system. Any 

misplaced baseline segments are corrected in the reconstructed chromatogram.

6.9 The peak identifications provided by the computer are checked and corrected if 

necessary.

6.10 Target compounds that 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 p-xylene, 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 p-xylene MIR value given in Appendix 1. 

6.11 The Alumina PLOT column is programmed to 200oC to assure all compounds are 

eluted before the next run.

7. CALCULATIONS

7.1 The target hydrocarbon concentrations, in ppbC, are calculated by the data system 

using propane as an external standard.

Concentrationsample (ppbC) = Peak Areasample x Response Factor

where the response factor (RF) is calculated during daily calibration by:

RF = Concentration of NIST-traceable propane standard, ppbC

 Area of propane peak

8. QUALITY CONTROL

8.1 Blank Run - A blank (pure nitrogen or helium) is run each analysis day. 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 defined as a check of the calibration standard run for 

contamination over all but the propane region of the chromatograph. The 

calibration standard must consist of only propane and make-up gas, with the 

concentration of all organic compounds except methane and propane below 2 

percent of the propane standard concentration. The weekly blank run will provide 

a check on contamination in the propane region of the chromatograph.
D-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

8.1.1 If the blank shows a peak greater than the limit of detection (LOD) in the 

region of interest, the source of contamination must be investigated and 

remedied.

8.2 Calibration Run - The calibration standard is analyzed each analysis day to 

generate the response factor used to quantify the sample concentrations.

8.3 Control Standard Run - The quality control standard is analyzed at least once each 

analysis day. Measurements of all compounds specified in Section 5.6 must fall 

within the control limits to ensure the validity of the sample analyses that day. To 

meet this requirement, it may be necessary to inspect and repair the GC, and rerun 

the calibration and/or control standards.

8.4 Control Charts - A quality control chart is maintained for each component of the 

control standard listed in Section 5.6. The control charts, used on a daily basis, 

establish that the method is “in- control.” The following describes how to 

construct a typical control chart: 

1. Obtain at least 20 daily control standard results;

2. Calculate the control standard mean concentration and standard deviation 

for the target hydrocarbon; and

3. Create a control chart for the target hydrocarbon by placing the 

concentration on the Y-axis and the date on the X-axis. Establish upper 

and lower warning limits at either two standard deviations (2s) or 5 

percent, whichever is greater, above and below the average concentration. 

Establish upper and lower control limits at either three standard deviations 

(3s) or 5 percent, whichever is greater, above and below the average 

concentration.

4. A control standard measurement is considered to be out-of-control when 

the analyzed value exceeds the control limit or two successive control 

standard measurements of the same analyte exceed the warning limit.

5. If 20 control standard measurements are not yet available to create a 

control chart (e.g., the control standard was expended and replaced prior to 

obtaining 20 points with the new standard), measurements must be within 

10% of the certified concentration. If the control standard is not a NIST 

standard, the cylinder should be certified by the laboratory against a NIST 

standard.

The measured concentrations of all target hydrocarbons contained in the control 

standard must be within the control limits (in-control) for the sample results to be 

considered acceptable.

8.5 Duplicates - A duplicate analysis of one sample is performed at least once per 

analysis day. The relative percent difference (RPD) is calculated for each 

duplicate run:
D-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

RPD (%) = |Difference between duplicate and original measurements| x 100

Average of duplicate and original measurements

For each compound specified in Section 5.6, the allowable RPD depends on the 

average concentration level for the duplicate runs, as shown in the following 

table:

Average Measurement for the Duplicate Runs Allowable RPD (%)

1 to 10 times LOD 100

10 to 20 “ “ 30

20 to 50 “ “ 20

Greater than 50 “ “ 15

If the results of the duplicate analyses do not meet these criteria for all compounds 

specified in Section 5.6, the sample may be reanalyzed. If reanalysis is not 

feasible or if the criteria are still not met on reanalysis, all sample results for that 

analysis day are invalid.

8.6 Linearity - A multipoint calibration to confirm instrument linearity is performed 

for the target hydrocarbons in the control standard for new instruments, after 

making instrument modifications that can affect linearity, and at least once every 

year 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 out-of-control, corrective action(s) must 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 standards 

is acceptable), each above the LOD, distributed over the range of expected sample 

concentration. 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.

8.7 Limit of Detection – The LOD for the target hydrocarbons in the control standard 

must be determined must be determined for new instruments and after making 

instrument modifications that can affect linearity and/or sensitivity and at least 

once every year 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 8.4, except using calibration standard 

area counts rather than control standard concentrations. When the calibration 

standard area counts are out-of-control, investigation and/or corrective action(s) 

must be taken. To make the calculations, it is necessary to perform a multipoint 

calibration consisting of at least four “low” concentration levels, each above the 

LOD, with at least five replicate determinations of the lowest concentration 
D-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

standard. A linear regression is performed and the standard deviation is converted 

to concentration units using the slope of the linear regression: 

s = sa ÷ m

where m is the slope of the linear regression, s is the standard deviation (in 

concentration units) of the lowest concentration standard and sa is the standard 

deviation (in area counts) of the lowest concentration standard.

The LOD must be calculated using the following equation [Ref. 12]:

LOD = t ∗ s

where s is the standard deviation (in concentration units) of at least five replicate 

determinations of the lowest concentration standard and t is the t-factor for 99 

percent confidence for a one-sided normal (Gaussian) distribution. The number of 

degrees of freedom is equal to the number of replicates, minus one. An abbreviated 

t-table is:

Degrees of Freedom t-value

4 3.7

5 3.4

6 3.1

7 3.0

The lowest standard must be of a concentration of one to five times the estimated 

LOD.

8.7.1 The maximum allowable LOD for each compound is 5 ppbC. 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 the maximum allowable 

LOD, the calculated laboratory LOD, or any level in between.

8.7.2 For the purpose of calculating the total mass of all species, the 

concentrations of all compounds below the LOD are considered to be zero.

8.8 Method 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 methods in the laboratory performing the 

analysis. The results obtained by the two methods should be compared and an 

acceptance criteria set for the relative percent difference. 
E-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Part E

DETERMINATION OF C6 TO C12 HYDROCARBONS

IN AUTOMOTIVE SOURCE SAMPLES BY GAS CHROMATOGRAPHY

METHOD NO. 1003

1. INTRODUCTION

1.1 This document describes a gas chromatographic method of analyzing measuring

C6 to C12 hydrocarbons (mid-range hydrocarbons) in the ppbC range from 

automotive source samples. This method does not include sample collection 

procedures [Ref. 7]. The target hydrocarbons (compounds of interest) that shall 

be analyzed and reported by this method and Method 1002 are listed in Appendix 

1. All compounds on this list, when measured in concentrations above the LOD, 

shall be measured and reported (“targeted”) by either Method 1002 or Method 

1003. Each laboratory should divide the list into light-end (Method 1002) and 

mid-range (Method 1003) hydrocarbons in the manner that best suits the 

laboratory instrumentation. All compounds on the list not targeted by Method 

1003 must be targeted by Method 1002. 

1.2 Other applicable forms of instrumentation and analytical techniques may be used 

if shown to yield results equivalent to those specified in this procedure and if 

approved in advance by the Executive Officer of the Air Resources Board.

1.3 All definitions and abbreviations are contained in Appendix 2 of these test 

procedures.

2. METHOD SUMMARY

2.1 This is a method intended for routine analysis.

2.2 The samples are received by the laboratory in Tedlar Kynar® bags, which are 

sub-sampled into a GC for separation and analysis.

2.3 The gas chromatographic analysis is performed through a temperatureprogrammed capillary column. A FID is used for detection.

2.4 The sample is injected into the GC by means of gas sampling valves. Separation 

of the sample hydrocarbon mixture into its components 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 hydrocarbons.

2.5 The computerized GC data acquisition system identifies the hydrocarbons 

associated with each peak. The hydrocarbon concentrations are determined by 
E-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

integrating the peak areas and using a response factor determined from 

NIST-traceable standards.

3. INTERFERENCES AND LIMITATIONS

3.1 An interferent interfering compound is any component present in the sample with 

a retention time similar to that of any target hydrocarbon described in this method. 

To reduce interference error, proof of chemical identity may require periodic 

confirmations using an alternate method and/or instrumentation, e.g., GC/MS, 

PID, different column, etc.

3.2 The concentration of hydrocarbons in the range of interest is stable for at least 24 

hours in the Tedlar sampling bags, provided the sample bags do not leak and are 

not exposed to bright light or excessive heat. Sampling bags must be shielded 

from direct sunlight to avoid photochemically induced reactions of any reactive 

hydrocarbons. Samples must be analyzed within 24 hours.

4. INSTRUMENTATION AND APPARATUS

4.1 Tedlar Kynar® (polyvinylidene fluoride) bags, 2 4 mil in thickness, nominally 5 

to 10 liters in capacity and equipped with quick-connect fittings, are typically

used to contain the samples. Other sample collection containers, such as bags 

made of Tedlar® (polyvinyl fluoride) film or nickel-coated stainless steel 

canisters, may be used, provided they are made of non-reactive material and do 

not cause sample loss or contamination.

4.2 For manual sub-sampling 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 aliquot size is chosen based on considerations 

of instrument sensitivity and/or linearity.

4.3 The GC is equipped with a FID, and a gas sampling valve system.

4.4 A non-polar capillary column [e.g., J&W Varian DB-1 (methylsiloxane), typically

60 m x 0.32 mm ID, film thickness 1.0 μ] is used. Other columns may be used, 

provided the alternate(s) can be demonstrated to the ARB to be equivalent or 

better with respect to precision, accuracy and resolution of all the target 

hydrocarbons. 

4.5 A sample trap capable of being cryogenically cooled may be used. 

4.6 A computer-controlled data acquisition system is required for quantifying peak 

areas.
E-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

5. REAGENTS AND MATERIALS

5.1 Helium shall have a minimum purity of 99.995 percent. Higher purity helium 

may be required to achieve the LOD required by Section 8.7.1.

5.2 Hydrogen shall have a minimum purity of 99.995 percent.

5.3 Air shall be “Zero” grade (<1 ppmC total hydrocarbon contamination) or better.

5.4 Nitrogen shall have a minimum purity of 99.998 percent.

5.5 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 linearity of the method. (See Section 8.6.) 

This propane standard must be a NIST-certified SRM or secondary NISTtraceable standard. A secondary standard is obtained by a comparison between a 

SRM and a candidate standard.

5.6 Control Standard - A quality control standard, containing at least n-hexane, 

n-octane, n-decane, benzene, toluene, and m- or p-xylene with concentrations 

between 0.2 and 1 ppmC based on a propane standard, is used for the following 

purposes:

1. Daily update of control charts, and

2. Daily determination of marker retention time windows.

5.7 A high concentration standard (higher than the calibration standard), containing 

the target hydrocarbons listed in Section 5.6, is used for linearity determinations. 

The high concentration 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.

5.8 A low concentration standard (one to five times the estimated LOD), containing 

the target hydrocarbons listed in Section 5.6, is used for LOD determinations. 

The low concentration 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.

5.8.1 In lieu of a low concentration standard, a higher concentration standard 

may be diluted.

5.9 Liquid nitrogen may be required to cool the cryogenic trap and column oven 

where applicable.
E-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

6. PROCEDURE

6.1 The gaseous sample is analyzed for the target hydrocarbons C5 through C12.

6.1 Typical operating conditions.

6.1.1 Suggested operating conditions for the manual GC are:

Helium carrier gas velocity: 30 cm/sec at 200oC 

Nitrogen make-up gas flow: sufficient such that the total flow of 

helium plus nitrogen is 30 mL/min 

Hydrogen gas flow (for FID): 30 mL/min 

“Zero” air gas flow (for FID): 300 mL/min 

Autozero FID at: 0.0 min 

Range 11, Attenuation 8 (or another suitable value) 

Sample valve temperature: 150oC 

Injector temperature: 150oC 

Column entrance port temperature: 95oC 

Detector temperature: 250oC 

Column temperature: Initial temperature 0oC;

10oC/min to 200oC

6.2.1.2 Suggested Typical operating conditions for the automated GC are:

Helium carrier gas flow flow velocity: 30 cm/sec 2.2 mL/min at 200oC

Detector (0.010” FID)

Temperature: 275oC or higher

Nitrogen make-up gas flow: sufficient such that the total flow of 

helium plus nitrogen is 30 25

mL/min 

Hydrogen gas flow (for FID): 30 25 mL/min 

“Zero” air gas flow (for FID): 300 mL/min 

Range 12, attenuation 8 (or another suitable value) 

Sample Autosampler valve temperature: 150oC 

Detector temperature: 300oC 

Injector temperature: 150oC

Cryotrap temperature: -180 oC (hold to trap hydrocabons)

200 oC (heat to release 

hydrocarbons)

Analytical column valve oven temperature: 150oC

Column temperature program: -40oC (hold 2.5 min)

3.6oC/min to 210oC

210oC (hold 5 min)

Initial temperature -50oC (5 min), 

5oC/min to 50oC, 

10oC/min to 200oC
E-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

6.2.1 Samples may be injected manually by injecting an aliquot with a ground 

glass syringe. 

6.32 Data Reduction

6.32.1 The results are calculated from the FID responses. 

6.32.2 The results are examined to see that the peaks are correctly integrated.

6.32.3 After running a particularly “dirty” sample, the analyst should run a blank 

before proceeding to the next sample as there may be sample carryover, or 

flush the sampling system with air.

6.32.4 The peak identifications provided by the computer are reviewed and, if 

necessary, corrected using the following procedure and criteria:

1. The relative retention indices from GC/MS analyses are used to 

help confirm peak identifications.

2. The primary peak identification is done by the computer using the 

relative retention times based on reference calibration runs.

3. Confirm that the relative peak heights of the sample run 

(“fingerprint”) match the typical fingerprint seen in past sample 

runs.

4. Compare the relative retention times of the sample peaks with 

those of reference runs.

5. Any peak with a reasonable doubt is labeled 'Unidentified'.

6.32.5 For 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) 

or the sample must be diluted.

6.32.6 The concentrations of the hydrocarbons are calculated using data 

acquisition/ processing software which uses calibration data from a 

NIST-traceable propane calibration standard.

6.32.7 Target compounds that 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 p-xylene, 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 MIR value given in Appendix 1.
E-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

7. CALCULATIONS

7.1 The target hydrocarbon concentrations, in ppbC, are calculated by the data system 

using propane as an external standard.

Concentrationsample (ppbC) = Peak Areasample ∗ Response Factor

where the Response Factor (RF) is calculated during daily calibration by:

Area of propane peak

Concentration of NIST traceable propane standard, ppbC RF − =

8. QUALITY CONTROL

8.1 Blank Run - A blank (pure nitrogen or helium) is run each analysis day. 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 defined as a check of the calibration standard run for 

contamination over all but the propane region of the chromatograph. The 

calibration standard must consist of only propane and make-up gas, with the 

concentration of all organic compounds except methane and propane below 2 

percent of the propane standard concentration. The weekly blank run will provide 

a check on contamination in the propane region of the chromatograph.

8.1.1 If the blank shows a peak greater than the limit of detection (LOD) in the 

region of interest, the source of the contamination must be investigated 

and remedied.

8.2 Calibration Run - The calibration standard is analyzed each analysis day to 

generate the response factor used to quantify the sample concentrations.

8.3 Control Standard Run - The quality control standard is analyzed at least once each 

analysis day. Measurements of all compounds specified in Section 5.6 must fall 

within the control limits to ensure the validity of the sample analyses that day. To 

meet this requirement, it may be necessary to inspect and repair the GC, and rerun 

the calibration and/or control standards.

8.4 Control Charts - A quality control chart is maintained for each component of the 

control standard listed in Section 5.6. The control charts, used on a daily basis, 

establish that the method is “in-control”. The following describes how to 

construct a typical control chart: 

1. Obtain at least 20 daily control standard results,

2. Calculate the control standard mean concentration and standard deviation 

for the target hydrocarbon, and
E-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

3. Create a control chart for the target hydrocarbon by placing the 

concentration on the Y-axis and the date on the X-axis. Establish upper 

and lower warning limits at either two standard deviations (2s) or 5 

percent, whichever is greater, above and below the average concentration. 

Establish upper and lower control limits at either three standard deviations 

(3s) or 5 percent, whichever is greater, above and below the average 

concentration.

4. A control standard measurement is considered to be out-of-control when 

the analyzed value exceeds the control limit or two successive control 

standard measurements of the same analyte exceed the warning limit.

5. If 20 control standard measurements are not yet available to create a 

control chart (e.g., the control standard was expended and replaced prior to 

obtaining 20 points with the new standard), measurements must be within 

10% of the certified concentration. If the control standard is not a NIST 

standard, the cylinder should be certified by the laboratory against a NIST 

standard.

The measured concentrations of all target hydrocarbons contained in the control 

standard must be within the control limits (in-control) for the sample results to be 

considered acceptable. 

8.5 Duplicates - A duplicate analysis of one sample is performed at least once per 

analysis day. The relative percent difference (RPD) is calculated for each 

duplicate run:

( ) 100

Average of duplicate and original measurements

| Difference between duplicate and original measurements | RPD % = ∗

For each compound specified in Section 5.6, the allowable RPD depends on the 

average concentration level for the duplicate runs, as shown in the following 

table:

Average Measurement for Duplicate Runs Allowable RPD (%)

1 to 10 times LOD 100

10 to 20 “ “ 30

20 to 50 “ “ 20

Greater than 50 “ “ 15

If the results of the duplicate analyses do not meet these criteria for all compounds 

specified in Section 5.6, the sample may be reanalyzed. If reanalysis is not 

feasible or if the criteria are still not met on reanalysis, all sample results for that 

analysis day are invalid.

8.6 Linearity - A multipoint calibration to confirm instrument linearity is performed 

for all target hydrocarbons in the control standard for new instruments, after 

making instrument modifications that can affect linearity, and at least once every 
E-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

year 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 out-of-control, corrective action(s) must 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 standards 

is acceptable), each above the LOD, distributed over the range of expected sample 

concentration. 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.

8.7 Limit of Detection - The LOD for the target hydrocarbons in the control standard 

must be determined for new instruments and after making instrument 

modifications that can affect linearity and/or sensitivity and at least once every 

year 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 8.4, except using calibration standard area 

counts rather than control standard concentrations. When the calibration standard 

area counts are out-of-control, investigation and/or corrective action(s) must be 

taken. To make the calculations, it is necessary to perform a multipoint 

calibration consisting of at least four “low” concentration levels, each above the 

LOD, with at least five replicate determinations of the lowest concentration 

standard. A linear regression is performed and the standard deviation (in area 

counts) of the lowest concentration standard determined. The standard deviation 

is converted to concentration units using the slope of the linear regression:

s = sa ÷ m 

where m is the slope of the linear regression, s is the standard deviation (in 

concentration units) of the lowest concentration standard and sa is the standard 

deviation (in area counts) of the lowest concentration standard.

The LOD must be calculated using the following equation [Ref. 12]:

LOD = t ∗ s

where s is the standard deviation (in concentration units) of at least five replicate 

determinations of the lowest concentration standard and t is the t-factor for 99 

percent confidence for a one-sided normal (Gaussian) distribution. The number of 

degrees of freedom is equal to the number of replicates, minus one. An abbreviated 

t-table is:
E-9

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Degrees of Freedom t-value

4 3.7

5 3.4

6 3.1

7 3.0

The lowest standard must be of a concentration of one to five times the estimated 

LOD.

8.7.1 The maximum allowable LOD for each compound is 5 ppbC. 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 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 the maximum allowable LOD, the 

calculated laboratory LOD, or any level in between.

8.7.2. For the purpose of calculating the total mass of all species, the 

concentrations of all compounds below the LOD are considered to be zero.

8.8 Method 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 methods in the laboratory performing the 

analysis. The results of the two analyses should be compared and an acceptance 

criteria set for the relative percent difference. 
F-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Part F

DETERMINATION OF ALDEHYDE AND KETONE COMPOUNDS

IN AUTOMOTIVE SOURCE SAMPLES

BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

METHOD NO. 1004

1. INTRODUCTION

1.1 This document describes a method of analyzing automotive source samples 

engine exhaust for aldehyde and ketone compounds (carbonyls) using impingers, 

containing acidified 2,4-dinitrophenylhydrazine (DNPH)-absorbing solution, or 

DNPH-impregnated cartridges. Carbonyl masses ranging between 0.02 to 200 μg 

are measured by this method. The “target” carbonyls (compounds of interest) that 

shall be analyzed measured and reported by this method are listed in Appendix 1. 

All of these carbonyl compounds, when measured in concentrations above the 

LOD, shall be reported.

1.1.1 For the purpose of calculating NMOG for vehicles tested on exhaust 

emission test fuel containing ethanol (see Part G, Determination of 

NMOG Mass Emissions):

1.1.1.1 The only carbonyl compounds that need to be reported from this method 

are formaldehyde and acetaldehyde. 

1.1.1.2 The additional carbonyls listed in Appendix 1 are within the scope of this 

analytical method and their measurement may provide meaningful 

information to the laboratory. However, their measurement is not 

required.

1.2 This procedure is derived from a method used by Hull [Ref. 10].

1.3 Other applicable forms of instrumentation and analytical techniques may be used 

if shown to yield results equivalent to those specified in this procedure and if 

approved in advance by the Executive Officer of the Air Resources Board.

1.4 All definitions and abbreviations are contained in Appendix 2 of these test 

procedures.

2. METHOD SUMMARY

2.1 The samples are received by the laboratory in sample collection cartridges or 

impingers. (See Section 4.2.) The DNPH reagent absorbing solution (2,4-DNPH)
F-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

complexes the carbonyl compounds into their diphenylhydrazone derivatives. 

The cartridges are then extracted eluted with 5 mL acetonitrile.

2.2 Separation and analysis are performed using a HPLC with an ultraviolet detector.

3. INTERFERENCES AND LIMITATIONS

3.1 An interferent interfering compound is any detectable compound present in the 

sample with a retention time very similar to that of any target carbonyl described 

in this method. To reduce interference error, proof of chemical identity may 

require periodic confirmations using an alternate method and/or instrumentation, 

e.g., alternative HPLC columns or mobile phase compositions.

3.2 If samples are not analyzed the same day as received, they must be refrigerated at 

a temperature below 40oF. 

3.2.1 Impinger solutions must first be transferred to glass bottles and sealed. 

Refrigerated samples are stable for up to 30 days.

3.2.2 If cartridges are not immediately extracted they must be refrigerated. 

3.2.3 Acrolein and crotonaldehyde have been shown to degrade in acidified 

DNPH cartridges; hence, it is recommended to extract the cartridges as 

soon as possible. The extract must be refrigerated.

3.2.4 Refrigerated cartridge sample extracts and impinger solutions are stable 

for up to 30 days.

3.3 When using the DuPont Zorbax or Supelco’s Supelcosil columns described in 

Section 4.1.5, methyl ethyl ketone (MEK) and butyraldehyde tend to coelute.

3.4 When using the Delta Bond column described in Section 4.1.5, formaldehyde 

tends to coelute with an unknown, non-carbonyl compound, and the tolualdehyde 

isomers tend to coelute. The guard column for the Delta Bond column must also 

be changed frequently in order to prevent the coelution of butyraldehyde and 

methacrolein and to prolong the life of the column.

3.3 The presence of NOx in exhaust samples depletes DNPH in the cartridges. 

Laboratories should develop criteria to validate test results by ensuring that 

enough DNPH is left to trap the carbonyl compounds.

4. INSTRUMENT AND APPARATUS

4.1 The HPLC analytical system consists of the following:

4.1.1 Dual high pressure pumps.
F-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

4.1.2 Automated gradient controller or pump module controller.

4.1.3 Temperature controller module for the column oven.

4.1.4 A liquid autosampler.

4.1.5 The primary system incorporates two DuPont Zorbax ODS or Supelco’s 

Supelcosil LC-18 columns (e.g., Supelco’s Supelcosil, typically 25cm x 

4.6mm, 5μ silica gel particles) in tandem and a guard column (e.g., 

Supelco’s Pelliguard, 2 cm long packed with LC18 5 μm pellicular beads). 

The secondary system incorporates a Delta Bond AK (4.6 mm ID x 200 

mm) packed column with a guard column 2 cm long packed with LC18 5 

μm pellicular beads or equivalent). Other columns may be used, provided 

the alternate(s) can be demonstrated to the ARB to be equivalent or better 

with respect to precision, accuracy and resolution of all target carbonyls. 

4.1.6 An ultraviolet/visible (UV/VIS) detector.

4.1.7 Data system for peak integration.

4.2 Samples are collected collection containers are in glass impingers or 

DNPH-impregnated cartridges.

5. REAGENTS AND MATERIALS

5.1 Acetonitrile, HPLC grade, (Burdick and Jackson or equivalent).

5.2 Water, HPLC grade, (Burdick and Jackson or equivalent).

5.3 Methanol, HPLC grade (Burdick and Jackson or equivalent).

5.4 Acidified DNPH-Silica cartridges (Waters Corp. or equivalent).

5.53 2,4-DNPH, purified, Radian Corporation or equivalent. Unpurified DNPH must 

be recrystallized twice from acetonitrile. The recrystallized DNPH is checked for

contaminants by injecting a dilute solution of DNPH in contaminant-free 

acetonitrile into the HPLC.

5.64 Sulfuric acid, or perchloric acid, analytical reagent grade, (Baker Analyzed or 

equivalent).

5. 75 The carbonyl/2,4-dinitrophenylhydrazone (DNPH) complexes [Ref. 11] listed in 

Table F1 may be purchased (e.g., Radian Corporation, in 1.2 mL ampules) or 

prepared in the laboratory. In-house standards must be recrystallized at least three 

times from 95 percent ethanol. 
F-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

TABLE F-1

PROPERTIES OF CARBONYL/2,4-DNPH COMPLEXES

Molecular Melting

Complex Weight (g/mole) Point oC

formaldehyde 210.15 165-166

acetaldehyde 224.18 152-153

acrolein 236.19 1651

acetone 238.20 125-127

propionaldehyde 238.20 144-145

butyraldehyde 252.23 119-120

hexanaldehyde 280.28 106-107

benzaldehyde 286.25 240-242

methyl ethyl ketone 252.53 117-118

methacrolein 250.21 200-201

crotonaldehyde 250.21 185-188

valeraldehyde 266.26 107-108

m-tolualdehyde 300.27 212

5.86 Stock Calibration Standard - A stock calibration standard is prepared by diluting 

the target carbonyl/2,4-DNPH complexes with acetonitrile. A typical stock 

calibration standard contains 3.0 μg/mL of each target carbonyl compound. Stock 

calibration standards of other concentrations may also be used. 

5.97 Working Standard - A working standard is prepared when required by diluting the 

stock calibration solution, making sure that the highest concentration of the 

standard is above the expected test level. Typically, the 3.0 μg/mL stock is 

diluted five times with acetonitrile in a volumetric flask to yield a 0.6 μg/mL 

solution.

5.108 Control Standard - A quality control standard, containing all target 

carbonyls/2,4-DNPH complexes within the typical concentration range of real 

samples, is analyzed to monitor the precision of the analysis of each target 

carbonyl. The control standard may be purchased, prepared in the laboratory 

from a stock solution different from the calibration standard, or prepared by batch 

mixing old samples, spiking it with a stock solution of target compounds, and 

stirring for a minimum of 2 hours. If necessary, the solution is filtered using filter 

paper to remove precipitation. All target compounds except acrolein have been 

found to be stable in the control standard.

5.119 Standards used for linearity and LOD determinations (Section 8) may be 

purchased or prepared by dilutions of an appropriate level stock solution.

 1

This compound has been known shown to decompose.
F-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

6. PROCEDURE

6.1 For systems collecting the samples via impingers, an absorbing solution is 

prepared by dissolving 0.11 - 0.13 grams of recrystallized DNPH in 1 L of HPLC 

grade acetonitrile. The absorbing solution should be prepared at least every two 

weeks. Each batch of acetonitrile used in this procedure is checked for 

oxygenated impurities by adding it to a contaminant-free dilute solution of DNPH 

and analyzing by HPLC. 

6.1.1 In the laboratory, pipette 15 mL of the DNPH absorbing solution into each 

of the 30 mL impingers for each emission test. Add 0.1 mL of 2.85 N 

sulfuric acid or 0.15 mL of 3.8 M perchloric acid to each impinger.

6.2 For systems collecting the samples via cartridges, DNPH-impregnated cartridges 

shall be sealed and refrigerated, at a temperature less than 40oF, upon receipt from 

manufacturer, until ready for use. 

6.2.1 At the exhaust volumes being sampled (1 L/min), a back-up cartridge may 

be required for CVS phase 1 or other high-concentration sample but no 

back-up cartridge is needed for CVS phases 2 and 3 or other lowconcentration samples.

6.3 After sampling uncap and place all impingers in preheated water at 70-80oC for 

30 minutes (min) to complete derivatization. Heating is not required when using 

perchloric acid.

6.3.1 For cartridges, remove the caps and extract with 5 mL acetonitrile, 

running the extract into glass storage bottles. 

6.4 Remove the impingers from the water bath and cool to room temperature. 

Replace any lost solvent by adding acetonitrile to the 15-mL mark.

6.4.1 Replacing lost solvent is not required when using an internal standard 

method (Section 7.4).

6.5 Transfer the solution from each impinger/cartridge to glass vials and seal with 

new septum screw caps.

6.6 Place the vials containing blank, working standard, control standard, and samples 

into the autosampler for subsequent injection into an HPLC. Suggested standard 

operating conditions for the HPLC are:

Primary Typical System:

Columns: 4.6 mm ID x 250 mm x 1/4 inches OD Dupont Zorbax 

ODS or Supelco Supelcosil (LC-18, 25cm x 4.6mm, 5μm

silica gel particles), - two columns in series, and a Supelco
F-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Pelliguard Gguard column – (2 cm long packed with C18 

5 μm pellicular beads)

Column temperature: 40oC

Detector: UV/VIS at 360 nm 

Sample volume: 10 μL 

Solvent A: acetonitrile 

Solvent B: 10 percent (volume/volume) methanol in water 

Solvent C: water

Flow: 1.2 mL/min

Program: 

50 percent A, 50 percent B, 45 percent C 0 (initial time)

65 percent A, 3.5 percent B, 31.5 percent C 0 to 30 2 min (linear ramp)

100 percent A, 0 percent B, 0 percent C 2 30 to 40 22 min (linear ramp)

100 percent A, 0 percent B, 0 percent C 40 to 42 min (hold)

50 percent A, 50 percent B, 45 percent C 22 42 to 45 37 min (linear ramp)

Under the above configuration, methyl ethyl ketone and butyraldehyde tend to

coelute. In order to report these compounds, it is necessary to analyze the samples 

using a secondary system. The tolualdehyde isomers (m-, p-, and o-) are separated 

using this configuration. The reporting of tolualdehyde is addressed in Section 7.4.

Secondary System:

Columns: Delta Bond AK C18 (4.6 mm ID x 200 mm x 1/4 in OD) 

packed column, Guard column - 2 cm long packed with 

C18 5 μm pellicular

Column temperature: 40oC

Detector: UV/VIS at 360 nm

Sample volume: 10 μL

Solvent A: acetonitrile

Solvent B: acetonitrile in water, 35 percent (v/v)

Flow: 1.5 mL/min

Program: 0 percent A, 100 percent B 0 (initial time)

23 percent A, 77 percent B 0 - 5.5 min

46 percent A, 54 percent B 5.5 - 13 min

0 percent A, 100 percent B 13 to 30 min

This secondary system is not used to report all compounds because formaldehyde 

tends to coelute with a non-carbonyl compound. If this coelution is resolved, the 

secondary system may be used alone to analyze all carbonyl compounds. The 

tolualdehyde isomers, however, are not separated with this configuration. The 

reporting of tolualdehyde is addressed in Section 7.4.

Data System: The outputs from the UV/VIS detector are sent to a PC-controlled 

data acquisition system.
F-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

6.7 If all target compounds are not separated using this configuration, a second HPLC 

with a different configuration must be used, in addition to the primary system, to 

separate the coeluting compounds.

6.87 The peak integrations are corrected as necessary in the data system. Any 

misplaced baseline segments are corrected in the reconstructed chromatogram.

6.98 Samples containing compounds having concentrations above the documented 

range of instrument linearity must be diluted and reanalyzed. 

7. CALCULATIONS

7.1 For each target carbonyl, the carbonyl mass is calculated from its 

carbonyl/2,4-DNPH mass.

7.2 The mass of each carbonyl compound, per impinger or cartridge, is determined by 

the following calculation:

 

Masssample = Peak Areasample ∗Response Factor ∗ Impinger(or Cartridge) volume(mL)∗B

where B is the ratio of the molecular weight of the carbonyl compound to its 

2,4-dinitrophenylhydrazone derivative and where the response factor (RF) for 

each carbonyl is calculated during the calibration by:

RF = Concentrationstandard ( μg 2,4-DNPH species/mL) 

Peak Areastandard

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

7.3.1 Under the conditions of the primary system in Section 6.6, the isomers are 

separated. The m-tolualdehyde response factor is applied to each peak and 

the sum reported as m-tolualdehyde.

7.3.2 Under the conditions of the secondary system described in Section 6.6, the 

isomers coelute. The m-tolualdehyde response factor is applied to the 

single tolualdehyde peak. This concentration is reported as mtolualdehyde.

7.4 An internal standard method may also be used.

8. QUALITY CONTROL

8.1 Blank Runs

8.1.1 Reagent Blanks - The solvents used are of the highest HPLC grade and are 

tested for impurities when a new lot number is used. If this lot number is 
F-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

found to be acceptable, (no carbonyls present at concentrations at or above 

the LOD), daily blank analysis is not performed.

8.1.2 Carbonyl/2,4-DNPH Purity - The carbonyl/ 2,4- DNPHs are checked for 

purity by their melting points and their chromatograms (See Table F-1). 

Analysis of the solution of carbonyl/2,4-DNPH must yield only the peak 

of interest. No contaminant peaks above the LOD should be observed.

8.1.3 Field Blanks – One cartridge is analyzed as a field blank for each emission 

test. If the field blank shows a peak greater than the limit of detection 

(LOD) in the region of interest, the source of the contamination must be 

investigated and remedied.

8.1.4 Cartridge Blanks - At least one cartridge per batch is analyzed as a batch 

blank. If the cartridge blank shows a peak greater than the limit of 

detection (LOD) in the region of interest, the source of the contamination 

must be investigated and remedied.

8.2 Calibration Run - The calibration standard is analyzed each analysis day to 

generate the response factors used to quantify the sample concentrations. 

8.3 Control Standard Run - The quality control standard is analyzed at least once each 

analysis day. Measurements of all target compounds in the control standard, 

except acrolein, must fall within the control limits to ensure the validity of the 

sample analyses that day. To meet this requirement, it may be necessary to rerun 

the calibration and control standards, and inspect and repair the HPLC.

8.4 Control Charts - A quality control chart is maintained for each component of the 

control standard. The control charts, used on a daily basis, establish that the 

method is “in- control.” The following describes how to construct a typical 

control chart: 

1. Obtain at least 20 daily control standard results,

2. Calculate the control standard mean concentration, and standard 

deviation(s) for the target analyte, and

3. Create a control chart for the target analyte 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.

4. Due to the low variability of the carbonyl control standard measurements, 

a control standard measurement is considered to be out-of-control when 

the analyzed value exceeds either the 3s limit, or the range of ± 10% of the 

mean control measurement, whichever is greater, or if two successive 

control standard measurements of the same analyte exceed the 2s limit.
F-9

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

5. If 20 control standard measurements are not yet available to create a 

control chart (e.g., the control standard was expended and replaced prior to 

obtaining 20 points with the new standard), measurements must be within 

10% of the assay (purchased) or theoretical (prepared in-house) 

concentration.

The measured concentrations of all target analytes contained in the control 

standard must be within the control limits (in-control) for the sample results to be 

considered acceptable. No control requirements have been established for 

acrolein, since it has been shown to degrade over time.

8.5 Duplicates - A duplicate analysis of one sample is performed at least once per 

analysis day. The relative percent difference (RPD) is calculated for each 

duplicate run:

( ) 100

Average of duplicate and original measurements

| Difference between duplicate and original measurements | RPD % = ∗

For each compound, the allowable RPD depends on the average concentration 

level for the duplicate runs, as shown in the following table:

Average Measurement for Duplicate Runs Allowable RPD (%)

1 to 10 times LOD 100 

10 to 20 “ “ 30

20 to 50 “ “ 20

Greater than 50 “ “ 15

If the results of the duplicate analyses do not meet these criteria for all target 

carbonyls, the sample may be reanalyzed. If reanalysis is not feasible or if the 

criteria are still not met on reanalysis, all sample results for that analysis day are 

invalid.

8.6 Linearity - A multipoint calibration to confirm instrument linearity is performed 

for all target analytes for new instruments, after making instrument modifications 

that can affect linearity, and at least once every year. The multipoint calibration 

consists of at least five concentration or mass loading levels (using smaller or 

larger volume sample sizes of existing standards is acceptable), each above the 

LOD, distributed over the range of expected sample concentration. Each 

concentration level is measured at least twice. A linear regression analysis is 

performed using concentration and average area counts to determine regression 

correlation coefficient (r). The r must be greater than 0.995 to be considered 

linear for one point calibrations.

8.7 Limit of Detection - The LOD for the target analytes must be determined for new 

instruments, after making instrument modifications which can affect the LOD and 

at least once per year. To make the calculations, it is necessary to perform a 
F-10

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

multipoint calibration consisting of at least four “low” concentration levels, each 

above the LOD, with at least five replicate determinations of the lowest 

concentration standard. A linear regression is performed and the standard 

deviation (in area counts) of the lowest concentration standard determined. The 

standard deviation is converted to concentration units using the slope of the linear 

regression:

s = sa ÷ m 

where m is the slope of the linear regression, s is the standard deviation (in 

concentration units) of the lowest concentration standard and sa is the standard 

deviation (in area counts) of the lowest concentration standard.

The LOD must be calculated using the following equation [Ref. 12]:

LOD = t ∗ s

where s is the standard deviation (in concentration units) of at least five replicate 

determinations of the lowest concentration standard and t is the t-factor for 99 

percent confidence for a one-sided normal (Gaussian) distribution. The number 

of degrees of freedom is equal to the number of replicates, minus one. An 

abbreviated t-table is:

Degrees of Freedom t-value

4 3.7

5 3.4

6 3.1

7 3.0

The lowest standard must be of a concentration of one to five times the estimated 

LOD.

8.7.1 The maximum allowable LOD is 0.0075 μg/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 the maximum allowable LOD, the 

calculated laboratory LOD, or any level in between.

8.7.2 For the purpose of calculating the total mass of all species, the 

concentrations of the compounds below the LOD are considered to be 

zero.
G-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Part G

DETERMINATION OF NMOG MASS EMISSIONS

1. INTRODUCTION

1.1 NMOG mass emissions consist of non-methane hydrocarbons and oxygenated 

hydrocarbons.

1.2 All definitions and abbreviations are set forth in Appendix 2 of these test 

procedures. 

2. NMOG WEIGHTED MASS EMISSIONS

2.1 NMOG weighted mass (wm) emissions shall be calculated as follows:

NMOGwm = ∑ NMHCwm +∑ROHwm +∑RHOwm

Non-methane hydrocarbon weighted mass emissions (NMHCwm) can be 

determined by either (FID or GC. If the FID method is used to calculate 

NMHCwm, refer to Part B of these test procedures entitled, “Determination of 

Non-Methane Hydrocarbon Mass Emissions by Flame Ionization Detection.” 

If the GC method is used to calculate NMHCwm, refer to section 43, 

“Speciated Hydrocarbon Mass Emissions Calculation,” contained herein. 

Carbonyl weighted mass emissions (RHOwm) are to be calculated according to 

section 65, “Carbonyl Mass Emissions Calculation,” contained herein. For 

alcohol fueled vehicles, alcohol weighted mass emissions (ROHwm) are to be 

calculated according to section 54, “Alcohol Mass Emissions Calculation,” 

contained herein. Dilution factors and mass emission are determined 

according to section 3, “Dilution Factors and Mass Emission Calculation,” 

contained herein.

If the FID method is used to determine the non-methane hydrocarbon 

weighted mass emissions, the NMHC sample measurement includes 

contributions from any oxygenated hydrocarbons that may be present in the 

sample. Therefore, the FID NMHC measurement must be corrected for the 

presence of alcohols and carbonyl compounds, to give a resultant value called 

non-oxygenated non-methane hydrocarbons (NONMHC). This correction 

may take place at the concentration level, for each sample and ambient 

background, or at the mass level, after NMHCmass and NMHCwm have been 

calculated. (The two operations are mathematically equivalent.) For the 

calculations presented in this document, the oxygenate correction is presumed 

to take place after NMHCmass and NMHCwm have been calculated.

2.2 NMOG weighted mass (wm) emissions, using the FID method, shall be 

calculated as follows:
G-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

(NMOGwm )FID = ∑NONMHCwm +∑ROHwm +∑RHOwm

NONMHCwm is calculated according to the following equations:

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

NONMHC NONMHC 0.57

D D

NONMHC NONMHC NONMHC 0.43

and

∑ ∑ ∗













 ∗ − ∗ 













 = − ∗ RHO

dens

mass n

ROH dens

dens

mass n

mass n mass n dens r RHO

RHO r NMHC

ROH

ROH NONMHC NMHC NMHC

where:

NMHCmass n = NMHCconc * NMHCdens

2.3 NMOG weighted mass (wm) emissions, using the GC method, shall be 

calculated as follows:

(NMOGwm )GC = ∑HCwm +∑ROHwm +∑RHOwm

In the GC method, the hydrocarbons are each measured individually and, 

therefore, the sum of species (∑HC) does not include methane or oxygenated 

compounds. Thus, this method does not need the corrections that the FID 

method requires.

3. DILUTION FACTOR AND NMHC MASS EMISSION CALCULATION

3.1 As shown in Part B, the dilution factor is determined using only the major 

constituents of the emission sample. The dilution factor is determined using 

the following equation:

( )

( ) 4

2e e 4e e CO NMHC CH CO 10

x y 2 3.76 x y 4 z 2

x 100

DF − + + + ∗

















+ + ∗ + − ∗

=

(where fuel composition is CxHyOz as measured for the fuel used; this 

expression is generally normalized so that x = 1)

3.2 The density of the NMHC is determined using the carbon:hydrogen ratio of 

the fuel, CxHyOz, according to the following equation: 
G-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012





 



 = ∗ +

24.0547liter/mole

28.316847liter/ft3 NMHCdens (x 12.01115 y *1.00797)(g / mole)*

where: 12.01115 = atomic weight of carbon

1.00797 = atomic weight of hydrogen

a) For gasoline, CH1.85, where x = 1, y = 1.85, and z = 0:

DF = 13.47 / [CO2e + (NMHCe + CH4e + COe) * 10-4]

NMHCdens = 16.33

b) For Phase 2 gasoline, CH1.94O0.017, where x = 1, y = 1.94 and z = 0.017,

DF = 13.295 / [CO2e + (NMHCe + CH4e + COe) * 10-4]

NMHCdens = 16.44

c) For LPG, CH2.64, where x = 1, y = 2.64, z = 0:

DF = 11.68 / [CO2e + (NMHCe + CH4e + COe) * 10-4]

NMHCdens = 17.27

d) For CNG, CH3.78O0.016, where x = 1, y = 3.78, and z = 0.016:

DF = 9.83 / [[CO2e + (NMHCe + CH4e + COe) * 10-4]

NMHCdens = 18.63

e) For E85, CH2.7841O0.3835, Where x = 1, y = 2.7841, and z = 0.3835:

DF = 12.4253 / [CO2e + (NMHCe + CH4e + COe) * 10-4]

NMHCdens = 17.44

3.3 Sample Calculation

A flex-fuel vehicle using E85 fuel CH2.7841O0.3835, where x = 1, y = 2.7841, 

and z = 0.3835:

Test 

Phase

FID 

THCe

(ppmC)

CH4e

(ppmC)

CO2e

(%)

COe

(ppm)

FID 

THCd

(ppmC)

CH4d

(ppmC)

CO2d

(%)

COd

(ppm)

VMIX

(ft3)

Dphase 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 3.591

FID response factor of methane is experimentally determined for each individual FID. 

The value of 1.15 used here is for example only. 

For phase 1:

NMHCe = FID THCe – r CH4 * CH4e 
G-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

= 27.230 – 1.15 * 6.918 

= 19.274 ppmC

DF = 12.4253 / [CO2e + (NMHCe + CH4e + COe) * 10-4]

= 12.4253 / [0.8564 + (19.274 + 6.918 + 117.801) * 10-4] 

= 14.2688 ppmC

NMHCd = FID THCd – r CH4 * CH4d

= 3.532 – 1.15 * 2.261 

= 0.9319 ppmC

NMHCconc = NMHCe –NMHCd* (1 – 1/DF) 

= 19.274 – 0.9319*( 1 – 1 / 14.2688) 

= 18.407 ppmC

NMHCmass1 = NMHCconc ∗ NMHCdens ∗ VMIX1 * 10-6

= 18.407 * 17.44 * 3495 * 10-6

= 1.1220 g

Similarly, for Phase 2, DF = 22.152 and NMHCmass2 = 0 

Similarly, for Phase 3, DF = 17.332 and NMHCmass2 = 0.0026 g 

34. SPECIATED HYDROCARBON MASS EMISSIONS CALCULATION

34.1 INTRODUCTION

Vehicular exhaust emissions are measured according to the FTP [Ref. 1]. For 

each of the three phases of the FTP, a tedlar sample collection bag, of 0.5 ft3

nominally 5 to 10 liters in capacity, is used to collect a dilute exhaust sample. 

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. A fourth 0.5 ft3 tedlar bag is used to collect a 

composite dilution air (background) sample from all three phases of the FTP. 

Since PVF and PVDF films contain plasticizer or volatile organic 

components, all of the films are conditioned in a vented oven at 250°F for 16 

hours before made into sample bags. All bag samples are analyzed according 

to Method No. 1002 (Part D of these test procedures) and Method No. 1003 

(Part E of these test procedures) to determine the dilute exhaust and dilution 

air concentrations of individual hydrocarbon compounds. The measured 

hydrocarbon compound concentrations are used in the following equations to 

calculate the weighted mass emissions of each hydrocarbon compound.

34.2 HC MASS EMISSIONS CALCULATION PER TEST PHASE

34.2.1 HCmass n = (HCconc ∗ HCdens ∗ VMIX ∗ 10-6) / (Carbon No.)
G-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

34.2.2 HCconc = HCe - (HCd ∗ (1 - (1 / DF)))

NOTE: If HCconc is calculated to be less than zero, then HCconc = 0.

34.3. WEIGHTED HC MASS EMISSIONS CALCULATION

34.3.1 















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

HC HC 0.57

D D

HC HC HC 0.43 

34.4. SAMPLE CALCULATION

34.4.1 Exhaust emissions from a gasoline vehicle 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:

Test 

Phase

HCe

(ppbC)

HCd

(ppbC)

FID THCe

(ppmC)

CH4e

(ppmC)

CO2e

(%)

COem

(ppm)

Ra

(%)

VMIX 

(ft3)

Dphase 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 / [CO2e + (NMHCe + CH4e + COe ) * 10-4 ] 

(see section 36, DF Calc.)

NMHCe = FID THCe - (rCH4 * CH4e )

= 98 ppmC - (1.04 * 6 ppmC)

= 92 ppmC

CO = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 

86.111 is used and the conditioning column has been deleted, COem must be 

substituted directly for COe .

= (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
G-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

HCconc = HCe - (HCd * (1 - (1 / DF)))

= 500 ppbC - (25 ppbC * (1 - (1 / 10.89)))

= 477 ppbC

Mol. Wt. of C6H6 = (6 * 12.01115) + (6 * 1.00797)

 = 78.11472 g/mole

HCdens = (Mol. Wt. * conversion of liter to ft3 ) / (Mol. Vol.)

= (78.11472 g/mole * 28.316 liter/ft3 ) / 24.055 liter/mole

= 91.952 g/ft3

HCmass n = (HCconc * HCdens * VMIX * 10-6

 ) / (Carbon No.)

HCmass 1 = (477 ppbC * 91.952 g/ft3 * 2846 ft3 * 10-6 ) / 6

= 20.8 mg

Similarly, for Phase 2: Hcmass = 5.7 mg

and for Phase 3: Hcmass = 4.2 mg

Therefore,

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

HC HC 0.57

D D

HC HC HC 0.43

 

















+

+

+ ∗ 















+

+ = ∗

3.586 miles 3.842 miles

4.2mg 5.7mg 0.57

3.584 miles 3.842 miles

20.8mg 5.7mg HC 0.43 wm

HCwm = 2.3 mg/mile (benzene weighted mass emissions)
G-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

45. ALCOHOL MASS EMISSIONS CALCULATION

45.1. INTRODUCTION

Vehicular emissions are measured according to the (FTP [Ref. 1]. For each of 

the three phases of the FTP, a set of two impingers is used to collect alcohol 

emissions in the dilute exhaust. A fourth set of two impingers is used to 

collect a composite dilution air (background) alcohol sample from all three 

phases of the FTP. All impingers are analyzed according to Method No. 1001 

to determine the alcohol concentration in each impinger. The measured 

alcohol concentrations are used in the following equations to calculate the 

weighted mass emissions of alcohol compounds.

45.2. ALCOHOL MASS EMISSIONS CALCULATION PER TEST PHASE

45.2.1 ROHmass n = (ROHconc ∗ ROHdens ∗ VMIX * 10-6

) / (Carbon No.)

45.2.2 ROHconc = ROHe - (ROHd * (1 - (1 / DF)))

NOTE: If ROHconc is calculated to be less than zero, then ROHconc = 0.

45.2.3 ROHe = (Imasse / Ivole) * (Mol. Vol. / Mol. Wt.)

45.2.4 Imasse = (Iconce1 + Iconce2) * DensROH * Ivolr

45.2.5 Ivole = Ivolem * (293.16oK / Itempe) * ( PB / 760 mm Hg) 

45.2.6 ROHd = (Imassd / Ivold) * (Mol. Vol. / Mol. Wt.)

45.2.7 Imassd = (Iconcd1 + Iconcd2) * DensROH * Ivolr

45.2.8 Ivold = Ivoldm * (293.16oK / Itempd) * (PB / 760 mm Hg)

45.3. WEIGHTED ALCOHOL MASS EMISSIONS CALCULATION

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

ROH ROH 0.57

D D

ROH ROH ROH 0.43 

45.4 SAMPLE CALCULATION

45.4.1 Alcohol emissions from an M85 E85 fueled vehicle are collected in 

three sets of dilute exhaust impingers and one set of dilution air 

impingers during the FTP. Gas chromatography is used to determine 

the methanol alcohol concentration in each impinger. This is the same 

vehicle test as the example in section 3.3. Calculate the weighted 

methanol mass emissions based on the following data, along with the 

data presented in section 3.3:
G-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Test 

Phase

Ivolr

(mL)

Iconce1

(μg/mL)

Iconce2

(μg/mL)

Ivolem

(liter)

Iconcd1

(μg/mL)

Iconcd2

(μg/mL)

Ivoldm

(liter)

Itempe

(

o

K)

Itempd

(

o

K)

1 15 4.984

2.24

0.106

0.05

8.18

3.90

0

0.07

0

0.01

31.16

13.50

294.26

295

294.26

294

2 15 0

0.29

0

0.06

14.65

6.50

0

0.07

0

0.01

31.16

13.50

294.26

297

294.26

294

3 15 0

0.32

0

0.02

8.67

4.00

0

0.07

0

0.01

31.16

13.50

294.26

298

294.26

294

Test Phase Dphase n

(mile)

DF PB 

(mm HG)

VMIX (ft3)

1 3.591 14.27 760 3495

2 3.846 22.15 760 5799

3 3.591 17.33 760 3484

Test 

Phase

FID 

THCe

(ppmC)

CH4e

(ppmC)

CO2e

(%)

COem

(ppm)

Ra

(%)

VMIX

(ft3)

Dphase n

(mile)

PB

(mmHg)

HCHOe

(ppm)

1 82 9 1.5 250 30 2834 3.581 760 0.81

2 19 5 0.7 20 32 4862 3.845 760 0.09

3 22 6 0.8 32 29 2835 3.583 760 0.10

Ethanol

For Phase 1:

Imasse = (Iconce1 + Iconce2) * DensROH * Ivolr

= (4.984 μg/mL + 0.106 μg/mL) * 15 mL

= 76.35 μg

= (2.24 μg/mL + 0.05 μg/mL) * 0.7914 g/mL * 

15 mL * 106 μg/g

= 27.2 μg

Mol. Wt. of C2H5OH = (2 * 12.01115) + (6 * 1.00797) + (1 * 15.9994)

= 46.06952 g/mole

Mol. Wt. of CH3OH = (1 * 12.01115) + (4 * 1.00797) + (1 * 15.9994)

= 32.0428 g/mole

Ivole = Ivolem * (293/16o K / Itempe ) * (PB / 760 mm Hg)

= 8.18 liter * (293.16oK / 294.26o K) * (760 mm Hg / 760 mm Hg)

= 8.15 liters

= 3.90 liter * (293.16oK / 295o K) * (760 mm Hg / 760 mm Hg)

= 3.88 liter

ROHe = (Imasse / Ivole ) * (Mol. Vol. / Mol. Wt.)
G-9

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

= (76.35 μg / 8.15 liter) * (24.055 liter/mole / 46.06952 g/mole)

= 4.89 ppm

= (27.2*10-6 g / 3.88 liter) * (24.055 liter/mole / 46.06952 g/mole)

= 5.27 ppmC

Imassd = (Iconcd1 + Iconcd2) * DensROH * Ivolr

= (0 μg/mL + 0μg/mL) * 15 mL

= 0 μg

= (0.07 μg/mL + 0.01 μg/mL) * 0.7914 g/ml * 15 ml * 106 μg/g

= 0.95 μg

Ivold = Ivoldm * (293.16o K / Itempd ) * ( PB / 760 mm Hg)

= 31.16 liter * (293.16oK / 294.26oK) * (760 mm Hg / 760 mm Hg)

= 31.04 liters

= 13.50 liter * (293.16oK / 294oK) * (760 mm Hg / 760 mm Hg)

= 13.46 liter

ROHd = (Imassd / Ivold) * (Mol. Vol. / Mol. Wt.)

= (0 μg / 31.46 liter) * (24.055 liter/mole / 46.06952 g/mole)

= 0 ppm

= (0.95*10-6 g/ 13.46 liter) * (24.055 liter/mole / 32.0428 g/mole)

= 0.05 ppmC

DF = 14.2688 (as calculated in section 3.3)

( ) 4

2 4 10

12.02 − + + + + + ∗ = CO e NMHCe CH e COe ROHe HCHOe

DF

(see section 6, DF Calc.)

NMHCe = FID THCe - (rCH4 * CH4e) - (rCH3OH * ROHe )

= 82 ppmC - (1.04 * 9 ppmC) - (0.66 * 5.27 ppmC)

= 69 ppmC

COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 

86.111 is used and the conditioning column has been deleted, COem must be 

substituted directly for COe .

 = (1 - (0.02705) * 1.5% - 0.000323 * 30%) * 250 ppm

 = 237 ppm
G-10

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

( ) 4 1.5% 69 ppmC 9ppmC 237 ppmC 5.27 ppmC 0.81ppm 10

12.02 DF − + + + + + ∗ =

ROHconc = ROHe - (ROHd * (1 - (1 / DF)))

= 4.89 ppm - (0 ppmC * (1 - (1 / 14.27)))

= 4.89 ppm

 = 5.27 ppmC - (0.05 ppmC * (1 - (1 / 7.84)))

 = 5.23 ppmC 

ROHdens = (Mol. Wt. * conversion of liter to ft3

) / (Mol. Vol.)

= (46.06952 g/mole * 28.316 liter/ft3) / 24.055 liter/mole

= 54.23007808 g/ft3

 = (32.0428 g/mole * 28.316 liter/ft) / 24.055 liter/mole

 = 37.719 g/ft3

VMIX = 3495 ft3 (from section 3.3)

ROHmass n = (ROHconc * ROHdens * VMIX * 10-6) / (Carbon No.)

ROHmass 1 = (4.89 ppmC * 54.23 g/ft3 * 3495 ft3 * 10-6) 

= 0.93 g

= (5.23 ppmC * 37.719 g/ft3 * 2834 ft3 * 10-6) / 1

 = 0.56 g

Similarly, for Phase 2: ROHmass 2 = 0 0.08 g

and for Phase 3: ROHmass 3 = 0 0.08 g

Therefore,

 

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

ROH ROH 0.57

D D

ROH ROH ROH 0.43

















+

+

+ ∗ 















+

+ = ∗

3.591 miles 3.846 miles

0g 0g 0.57

3.591 miles 3.846 miles

0.93 g 0g ROHwm 0.43

















+

+

+ ∗ 















+

+ = ∗

3.583 miles 3.845 miles

0.08mg 0.08mg 0.57

3.581 miles 3.845 miles

0.56mg 0.08mg ROHwm 0.43

ROHwm = 0.045 g/mile (ethanol weighted mass emissions)

ROHwm = 0.05 g (methanol weighted mass emissions)
G-11

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

56. CARBONYL MASS EMISSIONS CALCULATIONS

56.1. INTRODUCTION

Vehicular emissions are measured according to the FTP [Ref. 1]. For each of 

the three phases of the FTP, a set of two impingers (or cartridges) is used to 

collect carbonyl emissions in the dilute exhaust. A fourth set of two 

impingers (or cartridges) is used to collect a composite dilution air 

(background) carbonyl sample from all three phases of the FTP. All 

impingers (or cartridges) are analyzed according to Method No. 1004 to 

determine the mass of individual carbonyl compounds in each impinger (or 

cartridge). The measured carbonyl masses are used in the following equations 

to calculate the weighted mass emissions of each carbonyl compound.

56.2. CARBONYL MASS EMISSIONS CALCULATION PER TEST PHASE

56.2.1 RHOmass n = (RHOconc * RHOdens * VMIX * 10-6)

56.2.2 RHOconc = RHOe - (RHOd * (1 - (1 / DF)))

NOTE: If RHOconc is calculated to be less than zero, then RHOconc = 0.

56.2.3 RHOe = (Imasse / Ivole ) * (Mol. Vol. / Mol. Wt.)

56.2.4 Imasse = Iconcce *Ivolc

56.2.54 Ivole = Ivolem * (293.16oK / Itempe) * (PB / 760 mm Hg)

56.2.65 RHOd = (Imassd / Ivold) * (Mol. Vol. / Mol. Wt.) 

56.2.7 Imassd = Iconccd *Ivolc

56.2.86 Ivold = Ivoldm * (293.16oK / Itempd) * (PB / 760 mm Hg)

56.3. WEIGHTED CARBONYL MASS EMISSIONS CALCULATION

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

RHO RHO 0.57

D D

RHO RHO RHO 0.43

56.4. SAMPLE CALCULATION

56.4.1 Carbonyl emissions from a CNG an E85 vehicle are collected in three 

sets of dilute exhaust impingers and one set of dilution air impingers 

during the FTP. HPLC is used to determine the formaldehyde

carbonyl mass in each impinger. This is the same vehicle test as the 

example in section 3.3. Calculate the weighted formaldehyde and 
G-12

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

acetaldehyde mass emissions based on the following data, along with 

the data presented in section 3.3:

Test 

Phase

Ivolc

(ml)

Formaldehyde Ivolem

(liter)

Acetaldehyde Ivoldm

(liter)

Itempe

(

o

K)

Itempd

(

o

K) Iconcce

(μg/mL)

Iconccd

(μg/mL)

Iconcce

(μg/mL)

Iconccd

(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

Ivolr

(mL)

Imasse

(μg)

Ivolem

(liter)

Imassd

(μg)

Ivoldm

(liter)

Itempe

(

o

K)

Itempd

(

o

K)

1 15 2.45 8.49 0.17 31.57 295 292

2 15 0.76 14.55 0.17 31.57 298 292

3 15 0.64 4.00 0.17 31.57 298 292

Test Phase Dphase n

(mile)

DF PB 

(mm HG)

VMIX (ft3)

1 3.591 14.27 760 3495

2 3.846 22.15 760 5799

3 3.591 17.33 760 3484

Test 

Phase

FID 

THCe

(ppmC)

CH4e

(ppmC)

CO2e

(%)

COem

(ppm)

Ra

(%)

VMIX

(ft3)

Dphase n

(mile)

PB

(mmHg)

1 132 108 0.9 8 68 2866 3.581 760

2 4 3 0.1 4 67 4841 3.845 760

3 22 9 0.5 5 65 2837 3.583 760

Formaldehyde

For Phase 1:

Imasse = Iconcce *Ivolc

= 0.387 μg/mL * 4.4 mL

= 1.70 μg

Mol. Wt. of HCHO = (1 * 12.01115) + (2 * 1.00797) + (1 * 15.9994)

 = 30.0268 g/mole

Ivole = Ivolem * (293/16o K / Itempe ) * (PB / 760 mm Hg)

= 8.47 liter * (293.16oK / 294.26oK) * (760 mm Hg / 760 mm Hg)

= 8.44 liter

= 8.49 liter * (293.16oK / 295oK) * (760 mm Hg / 760 mm Hg)

= 8.44 liter
G-13

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

RHOe = (Imasse / Ivole ) * (Mol. Vol. / Mol. Wt.)

= (1.70 μg / 8.44 liter) * (24.055 liter/mole / 30.0268 g/mole)

= 0.16 ppm

= (2.45*10-6 g / 8.44 liter) * (24.055 liter/mole / 30.0268 g/mole)

= 233 ppb

Imassd = Iconccd * Ivolc

= 0.006 μg/mL * 4.4 mL

= 0.026 μg

Ivold = Ivoldm * (293.16oK / Itempd) * (PB / 760 mm Hg)

= 8.23 liter * (293.16oK / 294.26oK) * (760 mm Hg / 760 mm Hg)

= 8.20 liter

= 31.57 liter * (293.16oK / 292oK) * (760 mm Hg / 760 mm Hg)

= 31.70 liter

RHOd = (Imassd / Ivold ) * (Mol. Vol. / Mol. Wt.) 

= (0.026 μg / 8.20 liter) * (24.055 liter/mole / 30.0268 g/mole)

= 0.00258 ppm

= (0.17*10-6g / 31.70 liter)*(24.055 liter/mole / 30.0268 g/mole)

= 4 ppb

DF = 14.2688

DF = 9.77 / [CO2e + (NMHCe + CH4e + COe) * 10-4] 

(see section 6, DF Calc.)

NMHCe = FID THCe - (rCH4 * CH4e)

= 132 ppmC - (1.04 * 108 ppmC)

= 20 ppmC

COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 

86.111 is used and the conditioning column has been deleted, COem must be 

substituted directly for COe.

= (1 - 0.02890 * 0.9% - 0.000323 * 68%) * 8 ppm

= 7.6 ppm

DF = 9.77 / [0.9% + (20 ppmC + 108 ppmC + 7.6 ppm) * 10-4]

= 10.69

RHOconc = RHOe - (RHOd * (1 - (1 / DF)))
G-14

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

= 0.162 ppm - (0.00258 ppm * (1 - (1 / 14.27)))

= 0.1596 ppm

= 233 ppb - (4 ppb * (1 - (1 / 10.69)))

= 229 ppb

RHOdens = (Mol. Wt. * conversion of liter to ft3) / (Mol. Vol.)

= (30.0268 g/mole * 28.316 liter/ft3) / 24.055 liter/mole

= 35.35 g/ft3

VMIX = 3495 ft3

RHOmass n = (RHOconc * RHOdens * VMIX * 10-6)

RHOmass 1 = (0.1596 ppm * 35.35 g/ft3 * 3495 ft3 * 10-6 * 1000 mg/g)

= 19.718 mg

= (229 ppb * 35.35 g/ft3 * 2866 ft3 * 10-6)

= 23.2 mg

Similarly, for Phase 2: RHOmass 2 = 1.457 6.6 mg

and for Phase 3: RHOmass 3= 0.472 12.7 mg

Therefore,

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

RHO RHO 0.57

D D

RHO RHO RHO 0.43

















+

+

+ ∗ 















+

+ = ∗

3.591 miles 3.846 miles

0.472mg 1.457mg 0.57

3.591 miles 3.846 miles

19.718mg 1.457mg RHOwm 0.43

















+

+

+ ∗ 















+

+ = ∗

3.583 miles 3.845 miles

12.7mg 6.6mg 0.57

3.581 miles 3.845 miles

23.2mg 6.6mg RHO 0.43 wm

RHOwm = 1.371 3.2 mg/mi (formaldehyde weighted mass emissions)

Acetaldehyde

Similarly,

Phase 1: RHOmass 1 = 212 mg

Phase 2: RHOmass 2 = 0.165 mg

Phase 3: RHOmass 3 = 0.329 mg
G-15

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

















+

+

+ ∗ 















+

+ = ∗

3.591 miles 3.846 miles

0.329mg 0.165mg 0.57

3.591 miles 3.846 miles

212mg 0.165mg RHOwm 0.43

RHOwm = 0.0123 mg/mi (acetaldehyde weighted mass emissions)

5.4.2 Carbonyl emissions from a gasoline vehicle are collected in three sets 

of dilute exhaust cartridges and dilution air cartridges during the FTP. 

HPLC is used to determine the formaldehyde mass in each cartridge. 

Calculate the weighted formaldehyde mass emissions based on the 

following data: 

Test 

Phase

Iconcce

(μg/mL)

Iconccd

(μg/mL)

Iconcblk

(μg/mL)

Ivoldm

(liter)

Ivolem

(liter)

Itempe

(

o

K)

Itempd

(

o

K)

1 1.212 0.028 0.0 8.61 8.57 294.26 294.26

2 0.334 0.043 0.0 14.91 13.83 294.26 294.26

3 0.172 0.026 0.0 8.68 8.74 294.26 294.26

Test 

Phase

FID

THCe

(ppmC)

CH4e

(ppmC)

CO2e

(%)

COem

(ppm)

Ra

(%)

VMIX

(ft3)

Dphase n

(mile)

PB

(mmHg)

1 132 108 0.9 8 68 2866 3.581 760

2 4 3 0.1 4 67 4841 3.845 760

3 22 9 0.5 5 65 2837 3.583 760

For all three phases Ivolc = 4.4 mL

For Phase 1:

Imassd = (Iconccd – Iconcblk )*Ivolc

Imassd = (0.028 – 0.0) μg/mL * 4.4 mL = 0.1232 μg

Imasse = (Iconcce – Iconcblk )*Ivolc

Imasse = (1.212 – 0.0) μg/mL * 4.4 mL = 5.33 μg

Mol. Wt. of HCHO = (1 * 12.01115) + (2 * 1.00797) + (1 * 15.9994)

 = 30.0265 g/mole

Ivole = Ivolem * (293/16o K / Itempe ) * (PB / 760 mm Hg)
G-16

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

= 8.57 liter * (293.16oK / 294.26oK) * (760 mm Hg / 760 mm Hg)

= 8.54 liter

RHOe = (Imasse / Ivole ) * (Mol. Vol. / Mol. Wt.)

= (5.33*10-6 g / 8.54 liter) * (24.055 liter/mole / 30.0265 g/mole)

= 500 ppb

Ivold = Ivoldm * (293.16oK / Itempd ) * (PB / 760 mm Hg)

= 8.61 liter * (293.16oK / 294.26oK) * (760 mm Hg / 760 mm Hg)

= 8.58 liter

RHOd = (Imassd / Ivold ) * (Mol. Vol. / Mol. Wt.) 

= (0.1232*10-6g / 8.58 liter)*(24.055 liter/mole / 30.0265 g/mole)

= 11.5 ppb

DF = 9.77 / [CO2e + (NMHCe + CH4e + COe ) * 10-4 ]

(see section 6, DF Calc.)

NMHCe = FID THCe - (rCH4 * CH4e )

= 132 ppmC - (1.04 * 108 ppmC)

= 20 ppmC

COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 40, 

86.111 is used and the conditioning column has been deleted, COem must be 

substituted directly for COe.

= (1 - 0.02890 * 0.9% - 0.000323 * 68%) * 8 ppm

= 7.6 ppm

DF = 9.77 / [0.9% + ( 20 ppmC + 108 ppmC + 7.6 ppm) * 10-4 ]

= 10.69

RHOconc = RHOe - (RHOd * (1 - (1 / DF)))

= 500 ppb - (11.5 ppb * (1 - (1 / 10.69 )))

= 489.6 ppb (formaldehyde)

RHOdens = (Mol. Wt. * conversion of liter to ft3 ) / (Mol. Vol.)

= (30.0265 g/mole * 28.316 liter/ft3 ) / 24.055 liter/mole

= 35.35 g/ft3 

RHOmass n = (RHOconc * RHOdens * VMIX * 10-6 )

RHOmass 1 = (489.6 ppb * 35.35 g/ft3 * 2866 ft3 * 10-6 )

= 49.6 mg (formaldehyde)

Similarly, for Phase 2: RHOmass 2 = 12.9 mg
G-17

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

and similarly for Phase 3: RHOmass 3= 5.6 mg

Therefore,

)

D + D

RHO + RHO ) + 0.57 * (

D + D

RHO + RHO RHO = 0.43* (

phase 3 phase 2

mass 3 mass 2

phase1 phase 2

mass1 mass 2

wm

) 3.583 miles + 3.845 miles

5.6 mg +12.9 mg ) + 0.57 *( 3.581miles + 3.845 miles49.6 mg +12.9 mg RHOwm = 0.43*(

RHOwm = 5.04 mg/mi (formaldehyde weighted mass emissions)

6. DILUTION FACTOR CALCULATION

6.1. For Non-Alcohol Fueled Vehicles

6.1.1 ( )

( ) 4 CO2e NMHCe CH4e COe 10

x y 2 3.76 x y 4 z 2

x 100

DF − + + + ∗

















+ + ∗ + − ∗

= 

 (where fuel composition is CxHyOz as measured for the fuel used.)

6.1.2 COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 

40, 86.111 is used and the conditioning column has been deleted, 

COem must be substituted directly for COe .

a) For gasoline, CH1.85, where x = 1, y = 1.85, and z = 0:

DF = 13.47 / [CO2e + (NMHCe + CH4e + COe) * 10-4

COe = (1 - 0.01925 * CO2e - 0.000323 * Ra) * COem

b) For Phase 2 gasoline, CH1.94, where x = 1, y = 1.94 and z = 

0.017,

DF = 13.29 / [CO2e + (NMHCe + CH4e + COe) * 10-4

COe = (1 - 0.01970 * CO2e - 0.000323 * Ra) * COem

c) For LPG, CH2.64, where x = 1, y = 2.64, z = 0:

DF = 11.68 / [CO2e + (NMHCe + CH4e + COe) * 10-4

COe = (1 - 0.02320 * CO2e - 0.000323 * Ra) * COem

d) For CNG, CH3.78, where x = 1, y = 3.78, and z = 0.016:
G-18

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

DF = 9.83 / [[CO2e + (NMHCe + CH4e + COe) * 10-4]

COe = (1 - 0.02890 * CO2e - 0.000323 * Ra ) * COem

6.2. For Alcohol Fueled Vehicles:

6.2.1 ( )

( ) 4 CO2e NMHCe CH4e COe ROHe HCHOe 10

x y 2 3.76 x y 4 z 2

x 100

DF − + + + + + ∗

















+ + ∗ + − ∗

=

(where fuel composition is CxHyOz as measured for the fuel used.)

6.2.2 COe = (1 - (0.01 + 0.005 * HCR) * CO2e - 0.000323 * Ra ) * COem

NOTE: If a CO instrument which meets the criteria specified in CFR 

40, 86.111 is used and the conditioning column has been deleted, 

COem must be substituted directly for COe.

a) For M100 (100% methanol), CH3OH, where x = 1, y = 4, and z = 1:

DF = 11.57 / [CO2e + (NMHCe + CH4e + COe + ROHe + HCHOe) * 

10-4]

COe = (1 - 0.03000 * CO2e - 0.000323 * Ra ) * COem

b) For M85 (85% methanol, 15% indolene), CH3.41O0.72 , where x = 1, y 

= 3.41, and z = 0.72:

DF = 12.02 / [CO2e + (NMHCe + CH4e + COe + ROHe + HCHOe) * 

10-4]

COe = (1 - 0.02705 * CO2e - 0.000323 * Ra) * COem

c) For E100 (100% ethanol), C2H5OH, where x = 1, y = 3, and z = 0.5:

DF = 12.29 / [CO2e + (NMHCe + CH4e + COe + ROHe + HCHOe) * 

10-4] 

COe = (1 - 0.02500 * CO2e - 0.000323 * Ra ) * COem

7 NONMHC MASS EMISIONS CALCULATION

7.1 Non-oxygenated non-methane hydrocarbon is calculated from the FID NMHC 

measurement using the following equation:

∑ ∑ ∗













 ∗ − ∗ 













 = − ∗ RHO

dens

mass

ROH dens

dens

mass

mass mass dens r

RHO

RHO

r NMHC

ROH

ROH NONMHC NMHC NMHC

7.1.1 For the purpose of calculating NMOG for vehicles tested on exhaust 

emission test fuel containing ethanol:

7.1.1.1 The only alcohol included in the above calculation is ethanol.

7.1.1.2 The only carbonyl compounds included in the above calculation are 

formaldehyde and acetaldehyde.

7.2 FID Response Factors: 
G-19

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

FID response factors are experimentally determined for each individual FID. 

The following values are used in the sample calculations and are presented for 

example only. 

Oxygenated species Response factor*

(RF)

methanol 0.85

ethanol 0.756

formaldehyde 0

acetaldehyde 0.5

* Response factors are normalized to propane, i.e., propane has a response 

factor of 1.000.

7.3 Sample Calculation

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

Test Phase NMHCmass n

(g)

Ethanolmass n

(g)

Formaldehydemassn 

(g)

Acetaldehydemass n

(g)

1 1.1220 0.09271 0.0197 0.212

2 0 0 0.001457 0.000165

3 0.0026 0 0.000472 0.000329

and

NMHCdens = 17.44 g/ft3

∑ ∑ ∗













 ∗ − ∗ 













 = − ∗ RHO

dens

mass1

ROH dens

dens

mass1

mass1 mass1 dens r

RHO

RHO

r NMHC

ROH

ROH NONMHC NMHC NMHC

NONMHCmass1 = 1.1220 – 17.44 g/ft3 * ( 0.9271 g / 27.116 (g/ft3)) * 0.756 

– 17.44 g/ft3 * ( 0.0197 g / 35.350 (g/ft3)) * 0 

– 17.44 g/ft3 * ( 0.212 g / 25.929 (g/ft3)) * 0.5

= 1.1220 – 0.4508 – 0 – 0.0713

= 0.5999 g

NONMHCmass2 = 0 – 17.44 g/ft3 * ( 0 g / 27.116 (g/ft3)) * 0.756 

 – 17.44 g/ft3 * ( 0.001457 g / 35.350 (g/ft3)) * 0 

– 17.44 g/ft3 * ( 0.000165 g / 25.929 (g/ft3)) * 0.5

= 0 – 0 – 0 – 0.000055

= 0 g 
G-20

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

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

NONMHCmass3 = 0.0026 – 17.44 g/ft3 * ( 0 g / 27.116 (g/ft3)) * 0.756 

 – 17.44 g/ft3 * ( 0.000472 g / 35.350 (g/ft3)) * 0 

– 17.44 g/ft3 * ( 0.000329 g / 25.929 (g/ft3)) * 0.5

= 0.0026 – 0 – 0 – 0.000111

= 0.00249 g

8 WEIGHTED HYDROCARBON MASS EMISSIONS CALCULATION

8.1 Weighted NMOG is determined using the following equation:

NMOGwm = ∑NONMHCwm +∑ROHwm +∑RHOwm

where:

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

NONMHC NONMHC 0.57

D D

NONMHC NONMHC NONMHC 0.43 

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

ROH ROH 0.57

D D

ROH ROH ROH 0.43

















+

+

+ ∗ 















+

+ = ∗

phase3 phase2

mass3 mass2

phase1 phase2

mass1 mass2

wm D D

RHO RHO 0.57

D D

RHO RHO RHO 0.43

8.1.1 For the purpose of calculating NMOG for vehicles tested on exhaust 

emission test fuel containing ethanol:

8.1.1.1 The only alcohol included in the weighted NMOG calculation is 

ethanol.

8.1.1.2 The only carbonyl compounds included in the weighted NMOG

calculation are formaldehyde and acetaldehyde.

8.2 Sample calculation

Continuing from the previous example:

Test 

Phase

NONMHCmass 

n

(g)

Ethanolmass 

n

(g)

Formaldehydemass n

(g)

Acetaldehydemass n

(g)

Distance

(mile)

1 0.5999 0.9271 0.019718 0.212 3.591

2 0 0 0.001457 0.000165 3.846
G-21

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

3 0.00249 0 0.000472 0.000329 3.591





 





+

+  + ∗



 





+

+ = ∗

3.591miles 3.846 miles

0.00249 g 0 g 0.57

3.591miles 3.846 miles

0.5999 g 0 g NONMHC 0.43 wm

NONMHCwm = 0.03488 g/mile

Similarly, Ethanolwm = 0.05360 g/mile

Similarly, Formaldehydewm = 0.00137 g/mile

Similarly, Acetaldehydewm = 0.01231 g/mile

With all the above information, the weighted mass emissions of non-methane organic 

gas can be calculated:

NMOGwm = ∑NONMHCwm +∑ROHwm +∑RHOwm

NMOGwm = 0.03488 g/mile + 0.05360 g/mile + 0.00137 g/mile + 0.01231 g/mile

= 0.102 g/mile
CAS # COMPOUND MIR

1-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

APPENDIX 1

LIST OF COMPOUNDS

CAS # COMPOUND MIR

Alcohols

00067-56-1 methanol 0.71 0.67

00064-17-5 ethanol 1.69 1.53

Light End and Mid-Range Hydrocarbons

(Listed in approximate elution order)

00074-85-1 ethene 9.08 9.00

00074-86-2 ethyne 1.25 0.95

00074-84-0 ethane 0.31 0.28

00115-07-1 propene 11.58 11.66

00074-98-6 propane 0.56 0.49

00463-49-0 1,2-propadiene 12.16 8.45

00074-99-7 1-propyne 6.45 6.72

00075-28-5 2-methylpropane 1.35 1.23

00115-11-7 2-methylpropene 6.35 6.29

00106-98-9 1-butene 10.29 9.73

00106-99-0 1,3-butadiene 13.58 12.61

00106-97-8 n-butane 1.33 1.15

00624-64-6 trans-2-butene 13.91 15.16

00463-82-1 2,2-dimethylpropane 1.68 0.67

00107-00-6 1-butyne 6.20 6.11

00590-18-1 cis-2-butene 13.22 14.24

00563-45-1 3-methyl-1-butene 6.99

00078-78-4 2-methylbutane 1.68 1.45

00503-17-3 2-butyne 16.33 16.32

00109-67-1 1-pentene 7.79 7.21

00563-46-2 2-methyl-1-butene 6.51 6.40

00109-66-0 n-pentane 1.54 1.31

00078-79-5 2-methyl-1,3-butadiene 10.69 10.61

00646-04-8 trans-2-pentene 10.23 10.56

00558-37-2 3,3-dimethyl-1-butene 6.06 5.82

00627-20-3 cis-2-pentene 10.24 10.38

00689-97-4 1-buten-3-yne 11.09 10.48

00513-35-9 2-methyl-2-butene 14.45 14.08

00542-92-7 1,3-cyclopentadiene 7.61 6.98

00075-83-2 2,2-dimethylbutane 1.33 1.17

00142-29-0 cyclopentene 7.38 6.77

00691-37-2 4-methyl-1-pentene 6.26 5.68
CAS # COMPOUND MIR

1-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

00760-20-3 3-methyl-1-pentene 6.22 6.14

00287-92-3 cyclopentane 2.69 2.39

00079-29-8 2,3-dimethylbutane 1.14 0.97

01634-04-4 1-methyl-tert-butyl-ether 0.78 0.73

00691-38-3 4-methyl-cis-2-pentene 8.44 8.12

00107-83-5 2-methylpentane 1.80 1.50

00674-76-0 4-methyl-trans-2-pentene 8.44 8.12

00096-14-0 3-methylpentane 2.07 1.80

00763-29-1 2-methyl-1-pentene 5.18 5.26

00592-41-6 1-hexene 6.17 5.49

00110-54-3 n-hexane 1.45 1.24

13269-52-8 trans-3-hexene 8.16 7.57

07642-09-3 cis-3-hexene 8.22 7.61

04050-45-7 trans-2-hexene 8.44 8.62

00616-12-6 3-methyl-trans-2-pentene 8.44 13.17

00625-27-4 2-methyl-2-pentene 12.28 11.00

01120-62-3 3-methylcyclopentene 8.65 5.10

07688-21-3 cis-2-hexene 8.44 8.31

00637-92-3 1-ethyl-tert-butyl-ether 2.11 2.01

00922-62-3 3-methyl-cis-2-pentene 8.44 12.49

00590-35-2 2,2-dimethylpentane 1.22 1.12

00096-37-7 methylcyclopentane 2.42 2.19

00108-08-7 2,4-dimethylpentane 1.65 1.55

00464-06-2 2,2,3-trimethylbutane 1.32 1.11

07385-78-6 3,4-dimethyl-1-pentene 4.56 4.84

00693-89-0 1-methylcyclopentene 13.95 12.49

00071-43-2 benzene 0.81 0.72

03404-61-3 3-methyl-1-hexene 4.56 4.41

00562-49-2 3,3-dimethylpentane 1.32 1.20

00110-82-7 cyclohexane 1.46 1.25

00591-76-4 2-methylhexane 1.37 1.19

00565-59-3 2,3-dimethylpentane 1.55 1.34

00110-83-8 cyclohexene 5.45 5.00

00589-34-4 3-methylhexane 1.86 1.61

01759-58-6 trans-1,3-dimethylcyclopentane 2.15 1.94

02532-58-3 cis-1,3-dimethylcyclopentane 2.15 1.94

00617-78-7 3-ethylpentane 1.63 1.90

00822-50-4 trans-1,2-dimethylcyclopentane 1.99

00592-76-7 1-heptene 4.56 4.43

00540-84-1 2,2,4-trimethylpentane 1.44 1.26

14686-14-7 trans-3-heptene 6.96 6.32

00142-82-5 n-heptane 1.28 1.07

02738-19-4 2-methyl-2-hexene 6.96 9.47

03899-36-3 3-methyl-trans-3-hexene 6.96 9.72

14686-13-6 trans-2-heptene 7.33 7.14
CAS # COMPOUND MIR

1-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

00816-79-5 3-ethyl-2-pentene 6.96 9.75

00107-39-1 2,4,4-trimethyl-1-pentene 3.45 3.34

10574-37-5 2,3-dimethyl-2-pentene 6.96 9.74

06443-92-1 cis-2-heptene 6.96 7.16

00108-87-2 methylcyclohexane 1.99 1.70

00590-73-8 2,2-dimethylhexane 1.13 1.02

00107-40-4 2,4,4-trimethyl-2-pentene 5.85 6.29

01640-89-7 ethylcyclopentane 2.27 2.01

00592-13-2 2,5-dimethylhexane 1.68 1.46

00589-43-5 2,4-dimethylhexane 1.80 1.73

02815-58-9 1,2,4-trimethylcyclopentane 1.75 1.53

00563-16-6 3,3-dimethylhexane 1.57 1.24

00565-75-3 2,3,4-trimethylpentane 1.23 1.03

00560-21-4 2,3,3-trimethylpentane 1.57 1.02

00108-88-3 toluene 3.97 4.00

00584-94-1 2,3-dimethylhexane 1.34 1.19

00592-27-8 2-methylheptane 1.20 1.07

00589-53-7 4-methylheptane 1.48 1.25

00589-81-1 3-methylheptane 1.35 1.24

15890-40-1 (1a,2a,3b)-1,2,3-trimethylcyclopentane 1.75 1.63

00638-04-0 cis-1,3-dimethylcyclohexane 1.72 1.52

02207-04-7 trans-1,4-dimethylcyclohexane 1.75 1.47

03522-94-9 2,2,5-trimethylhexane 1.33 1.13

02613-65-2 trans-1-methyl-3-ethylcyclopentane 1.75 1.64

16747-50-5 cis-1-methyl-3-ethylcyclopentane 1.75 1.64

00111-66-0 1-octene 3.45 3.25

14850-23-8 trans-4-octene 5.90 4.81

00111-65-9 n-octane 1.11 0.90

13389-42-9 trans-2-octene 5.90 6.00

02207-03-6 trans-1,3-dimethylcyclohexane 1.72 1.52

07642-04-8 cis-2-octene 5.90 4.81

01069-53-0 2,3,5-trimethylhexane 1.33 1.22

02213-23-2 2,4-dimethylheptane 1.48 1.38

02207-01-4 cis-1,2-dimethylcyclohexane 1.75 1.41

01072-05-5 2,6-dimethylheptane 1.25 1.04

01678-91-7 ethylcyclohexane 1.75 1.47

00926-82-9 3,5-dimethylheptane 1.63 1.56

00100-41-4 ethylbenzene 2.79 3.04

03074-71-3 2,3-dimethylheptane 1.25 1.09

00108-38-3 m-&p-xylene 8.49 8.45

02216-34-4 4-methyloctane 1.08 0.95

03221-61-2 2-methyloctane 0.96 0.83

02216-33-3 3-methyloctane 1.25 0.99

00100-42-5 styrene (ethenylbenzene) 1.95 1.73

00095-47-6 o-xylene 7.49 7.64
CAS # COMPOUND MIR

1-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

00124-11-8 1-nonene 2.76 2.60

00111-84-2 n-nonane 0.95 0.78

00098-82-8 (1-methylethyl)benzene 2.32 2.52

15869-87-1 2,2-dimethyloctane 1.09 0.83

04032-94-4 2,4-dimethyloctane 1.09 1.03

02051-30-1 2,6-dimethyloctane 1.27 1.08

00103-65-1 n-propylbenzene 2.20 2.03

00620-14-4 1-methyl-3-ethylbenzene 6.61 7.39

00622-96-8 1-methyl-4-ethylbenzene 6.61 4.44

00108-67-8 1,3,5-trimethylbenzene 11.22 11.76

00611-14-3 1-methyl-2-ethylbenzene 6.61 5.59

00095-63-6 1,2,4-trimethylbenzene 7.18 8.87

00124-18-5 n-decane 0.83 0.68

00538-93-2 (2-methylpropyl)benzene 1.97 2.36

00135-98-8 (1-methylpropyl)benzene 1.97 2.36

00535-77-3 1-methyl-3-(1-methylethyl)benzene 5.92 7.10

00526-73-8 1,2,3-trimethylbenzene 11.26 11.97

00099-87-6 1-methyl-4-(1-methylethyl)benzene 5.92 4.44

00496-11-7 2,3-dihydroindene (indan) 3.17 3.32

00527-84-4 1-methyl-2-(1-methylethyl)benzene 5.92 5.49

00141-93-5 1,3-diethylbenzene 5.92 7.10

00105-05-5 1,4-diethylbenzene 5.92 4.43

01074-43-7 1-methyl-3-n-propylbenzene 5.92 7.10

01074-55-1 1-methyl-4-n-propylbenzene 5.92 4.43

00135-01-3 1,2-diethylbenzene 5.92 5.49

01074-17-5 1-methyl-2-n-propylbenzene 5.92 5.49

01758-88-9 1,4-dimethyl-2-ethylbenzene 8.86 7.55

00874-41-9 1,3-dimethyl-4-ethylbenzene 8.86 7.55

00934-80-5 1,2-dimethyl-4-ethylbenzene 8.86 7.55

02870-04-4 1,3-dimethyl-2-ethylbenzene 8.86 10.15

01120-21-4 n-undecane (hendecane) 0.74 0.61

00933-98-2 1,2-dimethyl-3-ethylbenzene 8.86 10.15

00095-93-2 1,2,4,5-tetramethylbenzene 8.86 9.26

01595-11-5 1-methyl-2-n-butylbenzene 5.35 4.73

00527-53-7 1,2,3,5-tetramethylbenzene 8.86 9.26

01074-92-6 1-(1,1-dimethylethyl)-2-methylbenzene 5.35 4.73

00488-23-3 1,2,3,4-tetramethylbenzene 8.86 9.26

00538-68-1 n-pentylbenzene 1.78 2.12

00098-19-1 1-(1,1-dimethylethyl)-3,5-DMbenzene 7.33 8.02

00091-20-3 naphthalene 3.26 3.34

00112-40-3 n-dodecane 0.66 0.55
CAS # COMPOUND MIR

1-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Carbonyl Compounds

00050-00-0 formaldehyde 8.97 9.46

00075-07-0 acetaldehyde 6.84 6.54

00107-02-8 acrolein 7.60 7.45

00067-64-1 acetone 0.43 0.36

00123-38-6 propionaldehyde 7.89 7.08

00123-72-8 butyraldehyde 6.74 5.97

00066-25-1 hexanaldehyde 4.98 4.35

00100-52-7 benzaldehyde 0.00

00078-93-3 methyl ethyl ketone (2-butanone) 1.49 1.48

00078-85-3 methacrolein 6.23 6.01

04170-30-3 crotonaldehyde 10.07 9.39

00110-62-3 valeraldehyde 5.76 5.08

00620-23-5 m-tolualdehyde 0.00
1-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

List of Compounds

(Listed by CAS number)

00050-00-0 formaldehyde

00064-17-5 ethanol

00066-25-1 hexanaldehyde

00067-56-1 methanol

00067-64-1 acetone

00071-43-2 benzene 

00074-84-0 ethane

00074-85-1 ethene

00074-86-2 ethyne

00074-98-6 propane 

00074-99-7 1-propyne 

00075-07-0 acetaldehyde

00075-28-5 2-methylpropane 

00075-83-2 2,2-dimethylbutane 

00078-78-4 2-methylbutane 

00078-79-5 2-methyl-1,3-butadiene 

00078-85-3 methacrolein

00078-93-3 methyl ethyl ketone (2-butanone)

00079-29-8 2,3-dimethylbutane 

00091-20-3 naphthalene 

00095-47-6 o-xylene 

00095-63-6 1,2,4-trimethylbenzene 

00095-93-2 1,2,4,5-tetramethylbenzene

00096-14-0 3-methylpentane 

00096-37-7 methylcyclopentane 

00098-19-1 1-(1,1-dimethylethyl)-3,5-dimethylbenzene

00098-82-8 (1-methylethyl)benzene 

00099-87-6 1-methyl-4-(1-methylethyl)benzene

00100-41-4 ethylbenzene 

00100-42-5 stryrene (ethenylbenzene)

00100-52-7 benzaldehyde

00103-65-1 n-propylbenzene 

00105-05-5 1,4-diethylbenzene 

00106-97-8 n-butane 

00106-98-9 1-butene 

00106-99-0 1,3-butadiene 

00107-00-6 1-butyne 

00107-02-8 acrolein

00107-39-1 2,4,4-trimethyl-1-pentene

00107-40-4 2,4,4-trimethyl-2-pentene

00107-83-5 2-methylpentane 

00108-08-7 2,4-dimethylpentane 
1-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

00108-38-3 m- & p-xylene 

00108-67-8 1,3,5-trimethylbenzene 

00108-87-2 methylcyclohexane 

00108-88-3 toluene 

00109-66-0 n-pentane 

00109-67-1 1-pentene 

00110-54-3 n-hexane

00110-62-3 valeraldehyde

00110-82-7 cyclohexane 

00110-83-8 cyclohexene 

00111-65-9 n-octane 

00111-66-0 1-octene 

00111-84-2 n-nonane 

00112-40-3 n-dodecane 

00115-07-1 propene 

00115-11-7 2-methylpropene 

00123-38-6 propionaldehyde

00123-72-8 butyraldehyde

00124-11-8 1-nonene 

00124-18-5 n-decane 

00135-01-3 1,2-diethylbenzene 

00135-98-8 (1-methylpropyl)benzene 

00141-93-5 1,3-diethylbenzene 

00142-29-0 cyclopentene 

00142-82-5 n-heptane 

00287-92-3 cyclopentane 

00463-49-0 1,2-propadiene 

00463-82-1 2,2-dimethylpropane 

00464-06-2 2,2,3-trimethylbutane 

00488-23-3 1,2,3,4-tetramethylbenzene

00496-11-7 2,3-dihydroindene (indan)

00503-17-3 2-butyne 

00513-35-9 2-methyl-2-butene 

00526-73-8 1,2,3-trimethylbenzene

00527-53-7 1,2,3,5-tetramethylbenzene

00527-84-4 1-methyl-2-(1-methylethyl)benzene

00535-77-3 1-methyl-3-(1-methylethyl)benzene

00538-68-1 n-pentylbenzene 

00538-93-2 (2-methylpropyl)benzene 

00540-84-1 2,2,4-trimethylpentane 

00542-92-7 1,3-cyclopentadiene 

00558-37-2 3,3-dimethyl-1-butene 

00560-21-4 2,3,3-trimethylpentane 

00562-49-2 3,3-dimethylpentane 

00563-16-6 3,3-dimethylhexane 

00563-45-1 3-methyl-1-butene 
1-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

00563-46-2 2-methyl-1-butene 

00565-59-3 2,3-dimethylpentane 

00565-75-3 2,3,4-trimethylpentane 

00584-94-1 2,3-dimethylhexane 

00589-34-4 3-methylhexane 

00589-43-5 2,4-dimethylhexane 

00589-53-7 4-methylheptane 

00589-81-1 3-methylheptane 

00590-18-1 cis-2-butene 

00590-35-2 2,2-dimethylpentane

00590-73-8 2,2-dimethylhexane 

00591-76-4 2-methylhexane 

00592-13-2 2,5-dimethylhexane 

00592-27-8 2-methylheptane 

00592-41-6 1-hexene 

00592-76-7 1-heptene 

00611-14-3 1-methyl-2-ethylbenzene 

00616-12-6 3-methyl-trans-2-pentene 

00617-78-7 3-ethylpentane 

00620-14-4 1-methyl-3-ethylbenzene 

00620-23-5 m-tolualdehyde

00622-96-8 1-methyl-4-ethylbenzene 

00624-64-6 trans-2-butene 

00625-27-4 2-methyl-2-pentene 

00627-20-3 cis-2-pentene 

00637-92-3 1-ethyl-tert-butyl-ether 

00638-04-0 cis-1,3-dimethylcyclohexane

00646-04-8 trans-2-pentene 

00674-76-0 4-methyl-trans-2-pentene 

00689-97-4 1-buten-3-yne

00691-37-2 4-methyl-1-pentene 

00691-38-3 4-methyl-cis-2-pentene 

00693-89-0 1-methylcyclopentene 

00760-20-3 3-methyl-1-pentene 

00763-29-1 2-methyl-1-pentene 

00816-79-5 3-ethyl-2-pentene 

00822-50-4 trans-1,2-dimethylcyclopentane

00874-41-9 1,3-dimethyl-4-ethylbenzene

00922-62-3 3-methyl-cis-2-pentene

00926-82-9 3,5-dimethylheptane 

00933-98-2 1,2-dimethyl-3-ethylbenzene

00934-80-5 1,2-dimethyl-4-ethylbenzene

01069-53-0 2,3,5-trimethylhexane 

01072-05-5 2,6-dimethylheptane

01074-17-5 1-methyl-2-n-propylbenzene

01074-43-7 1-methyl-3-n-propylbenzene
1-9

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

01074-55-1 1-methyl-4-n-propylbenzene

01074-92-6 1-(1,1-dimethylethyl)-2-methylbenzene

01120-21-4 n-undecane (hendecane)

01120-62-3 3-methylcyclopentene 

01595-11-5 1-methyl-2-n-butylbenzene

01634-04-4 1-methyl-tert-butyl-ether 

01640-89-7 ethylcyclopentane

01678-91-7 ethylcyclohexane 

01758-88-9 1,4-dimethyl-2-ethylbenzene

01759-58-6 trans-1,3-dimethylcyclopentane

02051-30-1 2,6-dimethyloctane

02207-01-4 cis-1,2-dimethylcyclohexane

02207-03-6 trans-1,3-dimethylcyclohexane

02207-04-7 trans-1,4-dimethylcyclohexane

02213-23-2 2,4-dimethylheptane 

02216-33-3 3-methyloctane 

02216-34-4 4-methyloctane

02532-58-3 cis-1,3-dimethylcyclopentane

02613-65-2 trans-1-methyl-3-ethylcyclopentane

02738-19-4 2-methyl-2-hexene 

02815-58-9 1,2,4-trimethylcyclopentane

02870-04-4 1,3-dimethyl-2-ethylbenzene

03074-71-3 2,3-dimethylheptane 

03221-61-2 2-methyloctane 

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

03522-94-9 2,2,5-trimethylhexane 

03899-36-3 3-methyl-trans-3-hexene 

04032-94-4 2,4-dimethyloctane 

04050-45-7 trans-2-hexene 

04170-30-3 crotonaldehyde

06443-92-1 cis-2-heptene 

07385-78-6 3,4-dimethyl-1-pentene 

07642-04-8 cis-2-octene 

07642-09-3 cis-3-hexene 

07688-21-3 cis-2-hexene 

10574-37-5 2,3-dimethyl-2-pentene 

13269-52-8 trans-3-hexene 

13389-42-9 trans-2-octene 

14686-13-6 trans-2-heptene 

14686-14-7 trans-3-heptene 

14850-23-8 trans-4-octene 

15869-87-1 2,2-dimethyloctane 

15890-40-1 (1a,2a,3b)-1,2,3-trimethylcyclopentane

16747-50-5 cis-1-methyl-3-ethylcyclopentane
2-1

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

APPENDIX 2

DEFINITIONS AND COMMONLY USED ABBREVIATIONS

I. The abbreviations and definitions set forth in this section apply to 

Parts A through G of these test procedures:

ASTM = American Society for Testing and Materials

Carbon No. = number of carbon atoms in the hydrocarbon or organic 

compound being measured.

CCR = California Code of Regulations

CH3OHd = the methanol concentration in the dilution air as determined 

from the dilution air methanol sample using the procedure 

specified in Method No. 1001, ppmC.

CH3OHe = the methanol concentration in the dilute exhaust as determined 

from the dilute exhaust methanol sample using the procedure 

specified in Method No. 1001, ppmC.

CH4d = the methane concentration in the dilution air, ppmC.

CH4e = the methane concentration in the dilute exhaust, ppmC.

C2H5OHd = the ethanol concentration in the dilution air as determined from 

the dilution air ethanol sample using the procedure specified in 

Method No. 1001, ppmC.

C2H5OHe = the ethanol concentration in the dilute exhaust as determined 

from the dilute exhaust ethanol sample using the procedure 

specified in Method No. 1001, ppmC.

CNG = compressed natural gas

COe = the carbon monoxide concentration in the dilute exhaust 

corrected for carbon dioxide and water removal, ppm.

COem = the carbon monoxide concentration in the dilute exhaust 

uncorrected for carbon dioxide and water removal, ppm.

CO2e = the carbon dioxide concentration in the dilute exhaust, %.

CVS = constant volume sampler
2-2

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Dphase 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.

DensROH = density of alcohol, g/mL.

DF = dilution factor (see Dilution Factor Calculation).

FID = flame ionization detector

FID 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.

FID THCe = the total hydrocarbon concentration including methane and 

methanol (for methanol-dueled engines) or ethanol (for 

ethanol-fueled engines) in the dilution exhaust as measured by 

the FID, ppmC.

FTP = Federal Test Procedure

GC = gas chromatograph

GC/MS = gas chromatography/mass spectrometry

HCconc = net concentration of an HC compound in the dilute exhaust 

corrected for background per test phase, ppbC.

HCd = composite concentration of an HC compound in the dilution air 

(background) for all three test phases as determined from the 

composite dilution air sample using the procedure specified in 

Method No. 1002 and Method No. 1003, ppbC.

HCdens = mass per unit volume of an HC compound corrected to 

standard conditions (293.16 K and 760 mm Hg) g/ft3.

HCe = concentration of an HC compound in the dilute exhaust per test 

phase as determined from the dilute exhaust sample using the 

procedure specific in Method No. 1002 and Method No. 1003, 

ppbC. 

HCmass n = mass emissions of an HC compound per test phase n (where n 

is either 1, 2, or 3), mg.
2-3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

HCwm = total weighted mass of an HC compound per mile, g/mile.

HCHOe = formaldehyde concentration in the dilute exhaust as determined 

from the dilute exhaust carbonyl sample using the procedure 

specified in Method No 1004, ppm.

HCR = the hydrogen-to-carbon ratio for the fuel used.

HPLC = high performance liquid chromatography

Iconcblk = concentration of the blank cartridge, μg/mL

Iconccd = total concentration of carbonyl compound extracted from both 

cartridges for the dilution air, μg/mL

Iconcce = total concentration of carbonyl compound extracted from both 

cartridges for the diluted exhaust, μg/mL

Iconcd1 = dilution air (background) alcohol concentration in the primary 

impinger for all three test phases as determined by the 

procedure specified in Method No. 1001, μg/mL.

Iconcd2 = dilution air (background) alcohol concentration in the 

secondary impinger for all three test phases as determined by 

the procedure specified in Method No. 1001, μg/mL.

Iconce1 = dilute exhaust alcohol concentration in the primary impinger 

per test phase as determined by the procedure specified in 

Method No. 1001, μg/mL.

Iconce2 = dilute exhaust alcohol concentration in the secondary impinger 

per test phase as determined by the procedure specified in 

Method No. 1001, μg/mL.

Imassd = total mass of an alcohol or carbonyl compound collected from 

the dilution air (background) in both primary and secondary 

impingers/cartridges for all three test phases as determined by 

the procedure specified in Method No. 1001 (alcohol) or 

Method No. 1004 (carbonyl), μg.

Imasse = total mass of an alcohol or carbonyl compound collected from 

the dilute exhaust in both primary and secondary 

impingers/cartridges per test phase as determined by the 

procedure specified in Method No. 1001 (alcohol) or Method 

No. 1004 (carbonyl), μg.
2-4

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

Itempd = dilution air temperature at the flowmeter inlet for 

impinger/cartridge sampling, oK.

Itempe = dilute exhaust temperature at the flowmeter inlet for 

impinger/cartridge sampling, oK.

Ivolc = elution volume of the cartridge, mL

(For example, Tthe cartridge is extracted with 5 mL 

acetonitrile, but 0.6 mL is retained in the cartridge, so the 

elution volume is 4.4 mL.) 

Ivold = total volume of dilution air (background) drawn through the 

impingers/cartridges for all three test phases corrected to 

standard conditions (293.16oK and 760 mm Hg), liter.

Ivoldm = total volume of dilution air (background) drawn through the 

impingers/cartridges for all three test phases as measured 

during testing, liter.

Ivole = total volume of dilute exhaust drawn through the 

impingers/cartridges per test phase corrected to standard 

conditions (293.16oK and 760 mm Hg), liter.

Ivolem = total volume of dilute exhaust drawn through the 

impingers/cartridges per test phase as measured during testing, 

liter.

Ivolr = volume of the reagent used in an impinger, mL.

LOD = limit of detection

LPG = liquified petroleum gas

Mol. Vol. = molecular volume which is 24.055 liter/mole at standard 

conditions (293.16oK and 760 mm Hg).

Mol. Wt. = molecular weight of the compound being measured, g/mole.

NIST = National Institute of Standards and Technology

NMHC = non-methane hydrocarbons

NMHCconc = the non-methane hydrocarbon concentration in the dilute 

exhaust corrected for background, ppmC.
2-5

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

NMHCd = the non-methane hydrocarbon concentration in the dilution air 

corrected for methane and alcohol removal, ppmC.

NMHCdens = the mass per unit volume of non-methane hydrocarbon 

corrected to standard conditions (16.33 g/ft3 at 293.16oK and 

760 mm Hg assuming a C:H ratio of 1:1.85 for gasoline; 16.78 

g/ft3 at 293.16o

K and 760 mm HG assuming a C:H ratio of 

1:1.94 for Phase 2 reformulated gasoline; 19.52 g/ft3 at 

293.16oK and 760 mm HG assuming a C:H ratio of 1:3.78 for 

natural gas; and 17.26 g/ft3 for LPG at 293.16oK and 760 mm 

Hg assuming a C:H ratio of 1:2.64), g/ft3 .

NMHCe = non-methane hydrocarbon concentration in the dilute exhaust 

corrected for methane and alcohol removal, ppmC.

NMHCmass n = the mass emission of non-methane hydrocarbon per test phase 

n (where n is either 1, 2, or 3), g.

NMHCwm = the total weighted mass of non-methane hydrocarbon per mile 

for all three phases of the FTP, g/mile.

NONMHCmass n = the mass emission of non-oxygenated non-methane 

hydrocarbon per test phase n (where n is either 1, 2, or 3), g.

NONMHCwm = the total weighted mass of non-oxygenated non-methane 

hydrocarbon per mile for all three phases of the FTP, g/mile.

NMOG = non-methane organic gases

PB = barometric pressure during testing, mm Hg.

PID = photoionization detector

PLOT = porous layer open tubular

Ra = the relative humidity of the ambient air, %.

rCH3OH = the FID response factor to methanol (see CFR 40, 

86.121-90(c)).

rCH4 = the FID response factor to methane (see Part B, “Determination 

of NMHC by FID”).

rC2H5OH = the FID response factor to ethanol (same procedure for 

methanol response factor, see CFR 40, 86.121-90(c)).
2-6

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

rROH = the FID response factor to an alcohol 

rRHO = the FID response factor to carbonyl compound 

RHO = generic symbol representing a carbonyl compound such as 

formaldehyde, acetaldehyde, acetone, etc.

RHOconc = net concentration of a carbonyl compound in the dilute exhaust 

corrected for background per test phase, ppm.

RHOd = composite concentration of a carbonyl compound in the 

dilution air (background) for all three test phases, ppm.

RHOdens = mass per unit volume of a carbonyl compound corrected to 

standard conditions (293.16oK and 760 mm Hg), g/ft3.

RHOe = concentration of a carbonyl compound in the dilute exhaust per 

test phase, ppm.

RHOmass n = mass emissions of a carbonyl compound per test phase n 

(where n is either 1, 2, or 3), g.

RHOwm = total weighted mass emissions of a carbonyl compound per 

mile, g/mile.

ROH = generic symbol representing an alcohol compound such as 

methanol or ethanol. 

ROHconc = net concentration of an alcohol compound in the dilute exhaust 

corrected for background per test phase, ppm.

ROHd = composite concentration of an alcohol compound in the 

dilution air (background) for all three test phases, ppm.

ROHdens = mass per unit volume of an alcohol compound corrected to 

standard conditions (293.16o

K and 760 mm Hg), g/ft3.

ROHe = concentration of an alcohol compound in the dilute exhaust per 

test phase, ppmC.

ROHmass n = mass emissions of an alcohol compound per test phase n 

(where n is either 1, 2, or 3), g.

ROHwm = total weighted mass emissions of an alcohol compound per 

mile, g/mile.
2-7

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

SAE = Society of Automotive Engineers

SRM = Standard Reference Material

VMIX = the total dilute exhaust volume measured per test phase and 

corrected to standard conditions (293.16oK and 760 mm Hg), 

ft3.
2-8

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012

II. The following list is commonly used measurement abbreviations:

g = gram

μg = microgram

m = meter

cm = centimeter

μm = micrometer

μ = micron

L = liter

mL = milliliter

μL = microliter

ppb = parts per billion.

ppbC = parts per billion carbon equivalent.

ppm = parts per million.

ppmC = parts per million carbon equivalent.
Appendix 3

As Amended: March 22, 2012

Board Hearing: January 26-27, 2012 3-1

APPENDIX 3

REFERENCES

[1] Code of Federal Regulations, Title 40, Part 86, Subpart B

[2] SAE J254, “Instrumentation and Techniques for Exhaust Gas 

Emissions Measurement”

[3] SAE J1094a, “Constant Volume Sampler System for Exhaust 

Emissions Measurement”

[4] SAE 770141, “Optimization of a Flame Ionization Detector for 

Determination of Hydrocarbons in Diluted Automotive Exhausts”. 

G.D. Reschke, Vehicle Emissions Laboratory, General Motors Proving 

Ground

[5] SAE J1154, “Methane Measurement Using Gas Chromatography,” 

(revised December 1991)

[6] U.S. Environmental Protection Agency, Characterization of Exhaust 

Emissions from Methanol and Gasoline Fueled Automobiles, EPA 

460/3-82-004.

[7] U.S. Environmental Protection Agency, Compendium of Methods for 

the Determination of Toxic Organic Compounds in Ambient Air, 

(Method T03-15) EPA-600/4-89-017 Research Triangle Park, North 

Carolina, June, 1989. 

[8] Standard Test Method for C1 through C6 Hydrocarbons in the 

Atmosphere by Gas Chromatography, American Standards for Testing 

Materials (ASTM) Standards on Chromatography (1981).

[9] U.S. Environmental Protection Agency, Compendium of Methods for 

the Determination of Toxic Organic Compounds in Ambient Air, 

(Method T03-15) EPA-600/4-84-041 Research Triangle Park, North 

Carolina, April, 1989. 

[10] Hull, L.A., Procedures for 2,4-Dinitrophenylhydrazone 

Aldehyde-Ketone Air Analysis, Internal Report at U.S. EPA.

[11] Shriner, R.L. and Fuson, R.C., Identification of Organic Compounds, 

2nd. Ed., John Wiley and Sons, Inc., 1940, p. 143.

[12] Keith, L. H., Taylor, J.K., et al, “Principles of Environmental 

Analysis”, Analytical Chemistry, Vol. 55, No. 14, December 1983.