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 ind icate 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 r ulemaking 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 C 2 to C 5 Hydrocarbons in Automotive Source Samples by Gas Chromatography D

- 1

E. Method 1003: Determination of C 6 to C 12 Hydrocarbons in Automoti ve 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

- 1A

- 1
As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 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

ga s (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 C 2 to C 5 Hydrocarbons in Automotive Source Samples by Gas Chromatography (Method No. 1002)

E. Determination of C 6 to C 12 Hydrocarbons in Automotive Source Samples by Gas Chromatography (Method No. 1003)

F. Determination of Aldehyde and Ketone Compounds in Automotive Source Samples by H igh 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 procedu res 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 XA

- 2
As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 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 C 2 to C 5 Hydrocarbons in Automotive Source Samples by Gas Chroma tography (Method No. 1002);

and

Part E. Determination of C 6 to C 12 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/ft 3 shall be used to determine the methane mass emissions. The methane mass emissions shall be multiplied by the appropriate methane reactivity adjus tment 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 Exh aust 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 , 201 2 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 abb reviations 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 f or 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 ca librated 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. Seve ral 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:

r CH 4 = FID ppm /SAM ppm

where:B

- 2
As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 r CH 4 = FID methane response factor.

FID ppm = FID reading in ppmC.

SAM ppm = 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 NMHC

e = FID THC

e - (r CH 4 * CH 4e )

NOTE: If NMHC

e is calculated to be less than zero, then NMHC

e = 0.

5.2.2 NMHC d = FID THC d - (r CH 4 * CH 4d )

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

5.2.3 CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e .

a) For gasoline, CH 1.85 , where HCR = 1.85:

CO

e = (1

- 0.01925 * CO 2e - 0.000323 * R

a ) * CO

em

b) For Phase 2 gasoline, CH 1.94 , where HCR = 1.94:

CO

e = (1

- 0.01970 * CO 2e - 0.000323 * R

a ) * CO

em

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

CO

e = (1

- 0.02320 * CO 2e - 0.000323 * R

a ) * CO

em

d) For CNG, CH 3.78 , where HCR = 3.78:

CO

e = (1

- 0.02890 * CO 2e - 0.000323 * R

a ) * CO

em

5.2.4 

## ( ) ( ) 4

e 4e e 2e 10 CO CH NMHC CO 2 z 4 y x 3.76 2 y x x 100

DF

− ∗ + + +        

− + ∗ + + ∗

=

(where fuel composition is C

x H y O

z as measured for the fuel used

. ; this expression is generally normalized so that x = 1 )

a) For gasoline, CH 1.85 , where x = 1, y = 1.85, and z = 0: DF = 13.47 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]B

- 3
As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 b) For Phase 2 gasoline, CH 1.94 , x = 1, y = 1.94 and z = 0.017: DF = 13.29 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

c) For LPG, CH 2.64 , where x = 1, y = 2.64, and z = 0: DF = 11.68 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

d) For CNG, CH 3.78 , where x = 1, y = 3.78, and z = 0.016: DF = 9.83 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

e) For E85, CH 2.7841 O 0.3835 , Where x = 1, y = 2.7841, and z = 0.3835: DF = 12.4253 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

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

, C

x H y O

z , according to the following equation:

     

+ ∗ = liter/mole 055

. 24 liter/ft3 316847

. 28
* mole) / g )( 00797

. 1 * y 01115

. 12 (x NMHC dens

where: 1 2.01115 = atomic weight of carbon

1.00797 = atomic weight of hydrogen

5.3 Vehicles Operating on Fuels Containing Methanol

5.3.1 NMHC

e = FID THC

e - (r CH 4 * CH 4e )

- (r CH 3 OH * CH 3 OH

e )

NOTE: If NMHC

e is calculated to be less than zero, then NMHC

e = 0.

5.3.2 NMHC d = FID THC d - (r CH 4 * CH 4d )

- (r CH 3 OH * CH 3 OH d )

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

5.3.3 CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40 86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e .

a) For M100 (100% methanol), CH 3 OH, where HCR = 4:

CO

e = (1

- 0.03000 * CO 2e - 0.000323 * R

a ) * CO

em

b) For M85 (85% methanol, 15% indolene), CH 3.41 O 0.72 , where

HCR = 3.41:

CO

e = (1

- 0.02705 * CO 2e - 0.000323 * R

a ) * CO

em

5.3.4 

## ( ) ( ) 4

e e 3 e 4e e 2e 10 HCHO OH CH CO CH NMHC CO 2 z 4 y x 3.76 2 y x x 100

DF

− ∗ + + + + +        

− + ∗ + + ∗

=

(where fuel composition is C

x H y O

z as measured for the fuel used.)B

- 4
As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 a) For M100 (100% methanol), CH 3 OH, where x = 1, y = 4, and z = 1: DF = 11.57 / [CO 2e + (NMHC

e + CH 4e + CO

e + CH 3 OH

e + HCHO

e ) * 10 - 4 ] b) For M85 (85% methanol, 15% Indolene), CH 3.41 O 0.72 , where x = 1, y = 3.41, and z = 0.72: DF = 12.02 / [CO 2e + (NMHC

e + CH 4e + CO

e + CH 3 OH

e + HCHO

e ) * 10 - 4 ]

5.4 Vehicles Operating on Fuels Containing Ethanol

5.4.1 NMHC

e = FID THC

e - (r CH 4 * CH 4e )

- (r C 2 H 5 OH * C 2 H 5 OH

e )

NOTE: If NMHC

e is calculated to be less than zero, then NMHC

e = 0

5.4.2 NMHC d = FID THC d - (r CH 4 * CH 4d )

- (r C 2 H 5 OH * C 2 H 5 OH d )

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

5.4.3 CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e . a) For E100 (100% ethanol), C 2 H 5 OH, where HCR = 3:

CO

e = (1

- 0.0 2500 * CO 2e - 0.000323 * R

a ) * CO

em

5.4.4 

## ( ) ( ) 4

e e 5 2 e 4e e 2e 10 HCHO OH H C CO CH NMHC CO 2 z 4 y x 3.76 2 y x x 100

DF

− ∗ + + + + +        

− + ∗ + + ∗

=

(where fuel composition is C

x H y O

z as measured for the fuel used.)

a) For E100 (100% ethanol), C 2 H 5 OH, where x = 1, y = 3, and z = 0.5: DF = 12.29 / [CO 2e + (NMHC

e + CH 4e + CO

e + C 2 H 5 OH

e + HCHO

e ) * 10 - 4 ]

5.5 All Vehicles

5. 2. 6 5.1 NMHC

conc = NMHC

e - NMHC d * [1

- (1 / DF)]

NOTE: If NMHC

conc is calculated to be less than zero, then NMHC

conc = 0

5. 2. 7 5.2 NMHC

mass n = NMHC

conc * NMHC dens * VMIX * 10 - 6

6. TOTAL WEIGHTED NMHC MASS EMISSIONS

6.1 All Vehicles

6.1.1        

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D NMHC NMHC 0.57 D D NMHC NMHC 0.43 NMHCB

- 5
As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 7. SAMPLE CALCULATIONS

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

CH 1.964 O 0.0182 , calculate the weighted NMHC mass emission.

Test

Phase FID THC

e (ppmC) FID THC d (ppmC) CH 4e (ppmC) CH 4d (ppmC) CO

em (ppm) CO 2e (%) VMIX (ft 3 ) D phase n (mile) R

a (%)

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:

NMHC

e = FID THC

e - (r CH 4 * CH 4e )

= 21.928 41.8 ppmC

- ( 1.15 1.04 * 3.667 7.53 ppmC)

= 17.711 33.97 ppmC

NMHC d = FID THC d - (r CH 4 * CH 4d )

= 3.557 8.6 ppmC

- ( 1.15 1.04 * 2.545 5.27 ppmC)

= 0.630 3.12 ppmC

CO

e = (1

- 0.01925 * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e .

= (1

- 0.01925 * 1.19%

- 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 ÷ [CO 2e + (NMHC

e + CH 4e + CO

e ) * 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

NMHC

conc = NMHC

e - NMHC d * [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 , 201 2 = 17.711 ppmC

– 0.630 ppmC * [1

- (1 ÷ 13.653)]

= 17.127 31.13 ppmC

     

+ ∗ = liter/mole 0547

. 24 liter/ft3 316847

. 28
* ) / )( 00797

. 1 * y 01115

. 12 (x NMHC dens mole g

NMHC dens = (1 * 12.01115 + 1.96 4 *1.00797 )* (28.316847/24.055 )

= 16.470 g/ft 3

NMHC

mass n = NMHC

conc * NMHC dens * VMIX * 10 - 6

= 17.127 31.13 ppmC * 16. 47 33 g/ft 3 * 2745 2846 ft 3 * 10 - 6

NMHC mass 1 = 0.7 743 1.45 g

Similarly, for Phase 2: NMHC mass 2 = 0.0068 0.33 g and for Phase 3: NMHC mass 3 = 0.021 9 0.27 g

Therefore,

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D NMHC NMHC 0.57 D D NMHC NMHC 0.43 NMHC



###        

+ +
∗ +        

+ +
∗ = miles 3.848 miles 3.586 g 0.33 g 0.27 0.57 miles 3.848 miles 3.583 g 0.33 g 1.45 0.43 NMHC

wm



###        

+ +
∗ +        

+ +
∗ = miles 3.876 miles 3.611 g 0.0068 g 0.0217 0.57 miles 3.876 miles 3.610 g 0.0068 g 0.768 0.43 NMHC

wm

NMHC

wm = 0.047 0.15 g/mile

7.2 Given the following data for a vehicle operating on 10 85 % m ethanol and 90 15 % gasoline ( E 10 M

- 85 ) CH 2.7841 O 0.3835 , calculate the weighted NMHC mass emission.

Test

Phase FID

THC

e (ppmC) FID

THC d (ppmC) CH 4e (ppmC) CH 4d (ppmc) CH 3 OH

e (ppm) CO

em (ppm) CO 2e (%) VMIX (ft 3 ) D phase n (mile) R

a (%) HCHO

e (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 0.12B

- 7 As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 Test

Phase FID

THC

e (ppmC) FID

THC d (ppmC) CH 4e (ppmC) CH 4d (ppmC) CO

em (ppm) CO 2e (%) VMIX (ft 3 ) D phase n (mile)

1 14.398 2.971 3.639 2.125 97.83 0.9203 3508 3.590

2 2.882 2.830 2.176 2.010 12.25 0.5935 6010 3.858

3 3.976 2.642 2.621 2.058 19.86 0.7624 3502 3.581

[For this example, CH 3 OH d was assumed to be 0.0 ppmC for all three background bag samples.]

For Phase 1:

NMHC

e = FID THC

e - (r CH 4 * CH 4e )

- (r CH 3 OH * CH 3 OH

e )

= 14.398 88.5 ppmC

- ( 1.15 1.04 * 2.215 17.76 ppmC)

- (0.66*72.9 ppmC)

= 10.213 21.92 ppmC

NMHC d = FID THC d - (r CH 4 * CH 4d )

- (r CH 3 OH * CH 3 OH d )

= 2.971 5.5 ppmC

- ( 1.15 1.04 * 2.125 2.82 ppmC)

- (0.66*0.0 ppmC)

= 0.527 2.57 ppmC

CO

e = (1

- 0.02705 * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e .

= (1

- 0.02705 * 1.28%

- 0.000323 * 32%) * 303.2 ppm = 289.6 ppm

DF = 13.511 12.02 ÷ [CO 2e + (NMHC

e + CH 4e + CO

e + CH 3 OH

e + HCHO

e ) * 10 - 4 ]



## ( ) 4 10 0.96ppmC 72.9ppmC ppmC 289.6 ppmC 17.76 ppmC 21.92 1.28% 12.02

− ∗ + + + + + =



## ( ) 4 10 ppmC 83

. 97 ppmC 639

. 3 ppmC 213

. 0 1 9203

. 0 13.511

− ∗ + + + =

= 14.505 9.10

NMHC

conc = NMHC

e - NMHC d * [1

- (1 / DF)]

= 10.213 21.92 ppmC

– 0.527 2.57 ppmC * [1

- (1 / 14.505 9.10 )]

= 9.722 19.63 ppmC

NMHC

mass n = NMHC

conc * NMHC dens * VMIX * 10 - 6

NMHC mass 1 = 0.55 8 0.91 gB

- 8
As Amended: March 22, 2012 Board Hearing: January 26

- 27 , 201 2 Similarly, Phase 2: NMHC mass 2 = 0.0 g

and for Phase 3: NMHC mass 3 = 0.10 0.040 g

Therefore,

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D NMHC NMHC 0.57 D D NMHC NMHC 0.43 NMHC



###        

+ +
∗ +        

+ +
∗ = miles 3.850 miles 3.586 g 0.00 g 0.10 0.57 miles 3.850 miles 3.570 g 0.00 g 0.91 0.43 NMHC

wm



###        

+ +
∗ +        

+ +
∗ = miles 3.858 miles 3.581 g 0.00 g 0.040 0.57 miles 3.858 miles 3.590 g 0.00 g 0.558 0.43 NMHC

wm

NMHC

wm = 0.06 g/mile

NMHC

wm = 0.035 g/mileC

- 1

As A mended: 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 e xhaust

emission test fuel containing ethanol (see Part G, Determinatio n of

NMOG Mass Emissions ) :

1.3.1.1 T he only alcohol that need s 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 A mended: 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 a nd 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. INTERFEREN CES AND LIMITATIONS

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

a retention time similar to that of a ny 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

40 o F.

3.3 To avoid sa mple 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 alcohol s.

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 A mended: 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 w eek.

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

emission test ing , 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. Standard s 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 40 o F during

storage.C

- 4

As A mended: 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 40 o F if immediate analysis is not feasible, or if reanalysis at a later date m ay 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: 50 o C (1 min)

, 50 o C to 70 o C (5 o C/min)

, 70 o C to 110 o C (15 o C/min)

, 110 o C (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 A mended: March 22, 2012 Board Hearing: January 26

- 27, 2012 6.7 The peak identifications provided by the computer are checked and corrected if

neces sary.

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 Area sample x Response Factor

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

( )

standard mL μg standard
Area Peak ion Concentrat 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 o f 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 proc eed.

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 A mended: 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 mainta ined 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 t he 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
ts measuremen original and duplicate of Average ts measuremen original and duplicate between Difference % 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 A mended: 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

inval id.

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 calibrat ion 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

conc entration 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 level s, 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 d eviation is converted to concentration units using the slope of the linear regression:

s = s a ÷ m

where m is the slope of the linear regression, s is the standard deviation (in concentration units) of the lowest concentration standard and s

a is th e standard deviation (in area counts) of the lowest concentration standard.

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



### s t LOD ∗ =

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 i s:C

- 8

As A mended: 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 repor ted. 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: Ja nuary 26

- 27, 2012 Part D

DETERMINATION OF C 2 TO C 5 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

C 2 to C 5 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 a re 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 techn iques 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

pro cedures.

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 (Al 2 0 3 ) PLOT column temperature programmed from 0 o C to 200 o C. 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 in to 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: Ja nuary 26

- 27, 2012 2.5 The computerized GC data acquis ition 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 confirmati ons 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 mus t 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 fitt ings, 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 requir ed.

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: Ja nuary 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 NIST

traceable 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 d eterminations. 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 analys is.

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

- traceabl e 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: Ja nuary 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 C 2 through C 5

.

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 200 0 C Detector (0.010” FID) Temperature: 250 0 C 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: 150 0 C (PLOT column) Cryotrap t emperature:

- 180 0 C ( hold to trap hydrocarbons )

200 0 C ( heat to release ) hydrocarbons ) Precolumn oven temperature: 50 0 C Analytical column valve oven temperature: 150 0 C Column Temperature Program: 0 0 C (hold 3 7 min)

, 10 0 C/min to 200 0 C (hold 15 min)

5 0 C/min to 200 0 C

200 0 C (hold 35 min) Detector temperature : 250 0 C Injector temperature: 150 0 C

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 f rom the NIST

- traceable propane calibration

standard.D

- 5

As Amended: March 22, 2012 Board Hearing: Ja nuary 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 200 o C to assure all com pounds 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.

Concentration sample (ppbC) = Peak Area sample 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 exce pt 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: Ja nuary 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 Contr ol 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 req uirement, 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 typ ical 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

conc entration 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 c ontrol 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 ne w 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 relativ e percent difference (RPD) is calculated for each duplicate run:D

- 7
As Amended: March 22, 2012 Board Hearing: Ja nuary 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 de pends 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, exce pt 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 d aily 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 standa rd 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” conc entration levels, each above the LOD, with at least five replicate determinations of the lowest concentrationD

- 8
As Amended: March 22, 2012 Board Hearing: Ja nuary 26

- 27, 2012 standard. A linear regression is performed and the standard deviation is converted to concentration units using the slope of the linear regressio n:

s = s a ÷ m

where m is the slope of the linear regression, s is the standard deviation (in concentration units) of the lowest concentration standard and s

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

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



### s t LOD ∗ =

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 cal culated 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 method s 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 C 6 TO C 12 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

C 6 to C 12 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 a re 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 a nd 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 temperature

programmed 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 co mputerized GC data acquisition system identifies the hydrocarbons associated with each peak. The hydrocarbon concentrations are determined byE

- 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. INTERFERENCE S 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 contai ners, 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 ba sed 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 puri ty 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 NIST

traceable 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

- h exane,

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 agai nst 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), containin g 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 ver ification 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 C 5 through C 12

.

6.1 Typical operating conditions.

6.1.1 Suggested operating conditions for the manual GC are: Helium carrier gas velocity: 30 cm/sec at 200 o C 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: 150 o C Injector temperature: 150 o C Column entrance port temperature: 95 o C Detector temperature: 250 o C Column temperature: Initial temperature 0 o C;

10 o C/min to 200 o C

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 200 o C Detector (0.010” FID) Temperature: 275 o C 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: 150 o C Detector temperature: 300 o C Injector temperature: 150 o C Cryotrap temperature:

- 180 o C ( hold to trap hydrocabons )

200 o C ( heat to release hydrocarbons ) Analytical column valve oven temperature: 150 o C Column temperature program:

- 40 o C ( hold 2.5 min)

3.6 o C/min to 210 o C

210 o C (hold 5 min) Initial temperature

- 50 o C (5 min),

5 o C/min to 50 o C,

10 o C/min to 200 o CE

- 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. 3 2 Data Reduction

6. 3 2 .1 The results are calculated from the FID responses.

6. 3 2 .2 The results are examined to see that the peaks are correctly integrated.

6. 3 2 .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 sampli ng system with air.

6. 3 2 .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 se en 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. 3 2 .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. 3 2 .6 The concentrations of the hydrocarbons are calculated using data

acq uisition/ processing software which uses calibration data from a

NIST

- traceable propane calibration standard.

6. 3 2 .7 Target compounds that coelute are reported as the major component, as determined by the analysis of several samples by GC/MS or other

meth ods. 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.E

- 6

As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 7. CAL CULATIONS

7.1 The target hydrocarbon concentrations, in ppbC, are calculated by the data system using propane as an external standard.

Concentration sample (ppbC) = Peak Area sample 

### ∗ Response Factor

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

peak propane of Area ppbC standard, propane traceable NIST of ion Concentrat 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 propa ne 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. Measu rements 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 cont rol 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 typi cal 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, andE

- 7

As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 3. Create a control chart for the target hydrocarbon by placing the

conce ntration 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 co ntrol 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 a t least once per analysis day. The relative percent difference (RPD) is calculated for each duplicate run:



## ( ) 100
ts measuremen original and duplicate of Average | ts measuremen original and duplicate between Difference | % 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 everyE

- 8

As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 year u nless 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 o r 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 conce ntration 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 th e 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 cha nged. 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 deter minations 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 th e linear regression:

s = s a ÷ m

where m is the slope of the linear regression, s is the standard deviation (in concentration units) of the lowest concentration standard and s

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

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



### s t LOD ∗ =

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 max imum 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 t his 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 e xhaust

emission test fuel containing ethanol ( see Part G

, Determination of

NMOG Mass Emissions ) :

1.1.1.1 T he 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 a nd 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 40 o F.

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 analytic al 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 Supelco s il , 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 pellicu lar 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 Sample s 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. 5 3 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. 6 4 Sulfuric acid, or perchloric acid, analytical reagent grade

, (Baker Analyzed or equivalent).

5. 7 5 The carbonyl/ 2,4

- dinitrophenylhydrazone ( DNPH ) co mplexes [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 o C

formaldehyde 210.15 165

- 166 acetaldehyde 224.18 152

- 153

acrolein 236.19 165 1

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

- 10 8

m

- tolualdehyde 300.27 212

5. 8 6 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. 9 7 Working Standard

- A working standard is prepared w hen 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. 10 8 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 mi nimum 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. 11 9 Standards used for linearity and LOD determinations (Se ction 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 t o each impinger.

6.2 For systems collecting the samples via cartridges, DNPH

- impregnated cartridges shall be sealed and refrigerated, at a temperature less than 40 o F, upon receipt from manufacturer, until ready for use.

6.2.1 At the exhaust volumes bei ng 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 low

concentration samples

.

6.3 After sampling uncap and place all impingers in preheated water at 70

- 80 o C 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 stan dard 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, 5 μ m silica gel particles ),

- two columns in series, and a SupelcoF

- 6
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 Pelliguard G g uard column

– ( 2 cm long packed with C18 5 μm pellicular beads ) Column temperature: 40 o C

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, 5 0 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, 5 0 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: 40 o C

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, h owever, 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. 8 7 The peak integrations are corrected as necessary in the data system. Any misplaced baseline segments are corrected in the reconstructed chromatogram.

6. 9 8 Samples containing compounds having concentrations above the documented range of instrument linearity must be diluted and reanalyzed.

7. CALCULATI ONS

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:



## ( ) ( ) B mL volume Cartridge or Impinger Factor Response Area Peak Mass sample sample ∗ ∗ ∗ =

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 = Concentration standard ( μg 2,4

- DNPH species/mL)

Peak Area standard

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 repo rted as m

tolualdehyde.

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 isF

- 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 b asis, 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 (p urchased) 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
ts measuremen original and duplicate of Average | ts measuremen original and duplicate between Difference | % 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 mak ing 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 acceptabl e), 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

correl ation 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 aF

- 10
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 multipoint calib ration 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 = s a ÷ m

where m is the slope of the linear regression, s is the standard deviation (in concentration units) of the lowest concentration standard and s

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

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



### s t LOD ∗ =

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:



## ∑ ∑ ∑ + + = wm wm wm wm RHO ROH NMHC NMOG

Non

- methane hydrocarbon weighted mass emissions (NMHC

wm ) can be determined by either ( FID or GC. If the FID method is used to calculate

NMHC

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

Non

- Methane Hydrocarbon Mass Emissions by Flame Ionization Detection.”

If the G C method is used to calculate NMHC

wm , refer to section 4 3

, “Speciated Hydrocarbon Mass Emissions Calculation

, ” contained herein. Carbonyl weighted mass emissions (RHO

wm ) are to be calculated according to

section 6 5

, “Carbonyl Mass Emissions Calculation

, ” contained herein. For alcohol fueled vehicles, alcohol weighted mass emissions (ROH

wm ) are to be calculated according to section 5 4

, “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 measu rement 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 no n

- methane hydrocarbons (NONMHC). This correction may take place at the concentration level, for each sample and ambient background, or at the mass level, after NMHC

mass and NMHC

wm 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 NMHC

mass and NMHC

wm 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 

## ( ) 

## ∑ ∑ ∑ + + = wm wm wm FID wm RHO ROH NONMHC NMOG

NONMHC

wm is calculated according to the following equation s :

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D NONMHC NONMHC 0.57 D D NONMHC NONMHC 0.43 NONMHC

and


### ∑ ∑ ∗        

∗

− ∗        

∗

− = RHO

dens

n mass dens ROH

dens

n mass dens n mass n mass r RHO RHO NMHC r ROH ROH NMHC NMHC NONMHC

where :

NMHC

mass n = NMHC

conc * NMHC d ens

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

calculated as follows:



## ( ) 

## ∑ ∑ ∑ + + = wm wm wm GC wm RHO ROH HC NMOG

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

, therefore, the sum of species (∑HC) do es 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

e 4e e 2e 10 CO CH NMHC CO 2 z 4 y x 3.76 2 y x x 100

DF

− ∗ + + +        

− + ∗ + + ∗

=

(where fuel composition is C

x H y O

z 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

, C

x H y O

z , according to the following equation:G

- 3
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012      

+ ∗ = liter/mole 0547

. 24 liter/ft3 316847

. 28
* mole) / g )( 00797

. 1 * y 01115

. 12 (x NMHC dens

where: 12.011 15 = atomic weight of carbon

1.00 797 = atomic weight of hydrogen

a) For gasoline, CH 1.85 , where x = 1, y = 1.85, and z = 0:

DF = 13.47 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

NMHC dens = 16.33

b) For Phase 2 gasoline, CH 1.94 O 0.017 , where x = 1, y = 1.94 and z = 0.017,

DF = 13.295 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

NMHC dens = 16.44

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

DF = 11.68 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

NMHC dens = 17.27

d) For CNG, CH 3.78 O 0.016 , where x = 1, y = 3.78, and z = 0.016:

DF = 9.83 / [[CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

NMHC dens = 18.63

e) For E85, CH 2.7841 O 0.3835 , Where x = 1, y = 2.7841, and z = 0.3835:

DF = 12.4253 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

NMHC dens = 17.44

3. 3 Sample Calculation

A flex

- fuel vehicle using E85 fuel CH 2.7841 O 0.3835 , where x = 1, y = 2.7841,

and z = 0.3835:

Test

Phase FID

THC

e (ppmC) CH 4e (ppmC) CO 2e (%) CO

e (ppm) FID

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

1 27.230 6.918 0.8564 117.801 3.532 2.261 0.0438 0.5224 3495 3.591

2 3.5459 2.357 0.5595 10.8229 3.476 2.247 0.4446 0.3322 5799 3.846

3 3.8510 2.590 0.7163 5.1538 3.396 2.188 0.4507 0.6752 3484 3.591

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:

NMHC

e = FID THC

e – r CH 4 * CH 4eG

- 4
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 = 27.230

– 1.15 * 6.918

= 19.274 ppmC

DF = 12.4253 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

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

= 14.2688 ppmC

NMHC d = FID THC d

– r CH 4 * CH 4d

= 3.532

– 1.15 * 2.261

= 0.9319 ppmC

NMHC

conc = NMHC

e – NMHC d * (1

– 1/DF)

= 19.274

– 0.9319 *( 1

– 1 / 14.2688)

= 18.407 ppm C

NMHC mass1 = NMHC

conc 

### ∗ NMHC dens 

### ∗ VMIX 1 * 10 - 6

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

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

Similarly, for Phase 3, DF = 17.332 and NMHC mass2 = 0.0026 g

3 4

. SPECIATED HYDROCARBON MASS EMISSIONS CALCULATION

3 4 .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 ft 3
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 ft 3 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 bef ore 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 hyd rocarbon compounds. The measured hydrocarbon compound concentrations are used in the following equations to calculate the weighted mass emissions of each hydrocarbon compound.

3 4 .2 HC MASS EMISSIONS CALCULATION PER TEST PHASE

3 4 .2.1 HC

mass n = (HC

conc 

### ∗ HC dens 

### ∗ VMIX 

### ∗ 10 - 6 ) / (Carbon No.)G

- 5

As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 3 4 .2.2 HC

conc = HC

e - (HC d 

### ∗ (1

- (1 / DF)))

NOTE: If HC

conc is calculated to be less than zero, then HC

conc = 0.

3 4 .3. WEIGHTED HC MASS EMISSIONS CALCULATION

3 4 .3.1        

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D HC HC 0.57 D D HC HC 0.43 HC

3 4 .4. SAMPLE CALCULATION

3 4 .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 FT P. 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 HC

e (ppbC) HC d (ppbC ) FID THC

e (ppmC ) CH 4e (ppmC ) CO 2e (%) CO

em (ppm) R

a (%) VMIX (ft 3 ) D phase n (mile)

1 500 25 98 6 1.20 280 28 2846 3.584

2 100 25 22 4 0.95 87 25 4854 3.842

3 120 25 29 5 1.07 101 24 2840 3.586

For Phase 1:

DF = 13.47 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ] (see section 3 6 , DF Calc.)

NMHC

e = FID THC

e - (r CH 4 * CH 4e )

= 98 ppmC

- (1.04 * 6 ppmC)

= 92 ppmC

CO = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

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

86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e .

= (1

- (0.01925) * 1.2%

- 0.000323 * 28%) * 280 ppm

= 271 ppm

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

= 10.89G

- 6
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 HC

conc = HC

e - (HC d * (1

- (1 / DF)))

= 500 ppbC

- (25 ppbC * (1

- (1 / 10.89)))

= 477 ppbC

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

= 78.11472 g/mole

HC dens = (Mol. Wt. * conversion of liter to ft 3 ) / (Mol. Vol.)

= (78.11472 g/mole * 28.316 liter/ft 3 ) / 24.055 liter/mole

= 91.952 g/ft 3

HC

mass n = (HC

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

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

= 20.8 mg

Similarly, for Phase 2: Hc
mass = 5.7 mg

an d for Phase 3: Hc
mass = 4.2 mg

Therefore,

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D HC HC 0.57 D D HC HC 0.43 HC



###        

+ +
∗ +        

+ +
∗ = miles 3.842 miles 3.586 mg 5.7 mg 4.2 0.57 miles 3.842 miles 3.584 mg 5.7 mg 20.8 0.43 HC

wm

HC

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

- 7
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 4 5

. ALCOHOL MASS EMISSIONS CALCULATION

4 5 .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 sam ple 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.

4 5 .2. ALCOHOL MASS EMISSIONS CALCULATION PER TEST PHASE

4 5 .2.1 ROH

mass n = (ROH

conc 

### ∗ ROH dens 

### ∗ VMIX * 10
- 6 ) / (Carbon No.)

4 5 .2.2 ROH

conc = ROH

e - (ROH d * (1

- (1 / DF)))

NOTE: If ROH

conc is calculated to be less than zero, then ROH

conc = 0.

4 5 .2.3 ROH

e = (Imass

e / Ivol

e ) * (Mol. Vol. / Mol. Wt.)

4 5 .2.4 Imass

e = (Iconc e1 + Iconc e2 ) * Dens ROH * Ivol

r

4 5 .2.5 Ivol

e = Ivol

em * (293.16 o K / Itemp

e ) * ( P B / 760 mm Hg)

4 5 .2.6 ROH d = (Imass d / Ivol d ) * (Mol. Vol. / Mol. Wt.)

4 5 .2.7 Imass d = (Iconc d1 + Iconc d2 ) * Dens ROH * Ivol

r

4 5 .2.8 Ivol d = Ivol dm * (293.16 o K / Itemp d ) * (P B / 760 mm Hg)

4 5 .3. WEIGHTED ALCOHOL MASS EMISSIONS CALCULATION

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D ROH ROH 0.57 D D ROH ROH 0.43 ROH

4 5 .4 SAMPLE CALCULATION

4 5 .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 th e example in section 3.3. Calculate the weighted

m ethanol 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 Ivol

r (mL) Iconc e1 (μg/mL) Iconc e2 (μg/mL) Ivol

em (liter) Iconc d1 (μg/mL) Iconc d2 (μg/mL) Ivol dm (liter) Itemp

e ( o K) Itemp d ( o K)

1 15 4.984

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 D phase n (mile) DF P B

(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

THC

e (ppmC ) CH 4e (ppmC ) CO 2e (%) CO

em (ppm) R

a (%) VMIX (ft 3 ) D phase n (mile) P B (mmHg) HCHO

e (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:

Imass
e = (Iconc e1 + Iconc e2 ) * Dens ROH * Ivol

r

= (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 * 10 6 μg/g

= 27.2 μg

Mol. Wt. of C 2 H 5 OH = (2 * 12.01115) + (6 * 1.00797) + (1 * 15.9994)

= 46.06952 g/mole

Mol. Wt. of CH 3 OH = (1 * 12.01115) + (4 * 1.00797) + (1 * 15.9994)

= 32.0428 g/mole

Ivol

e = Ivol

em * (293/16 o K / Itemp

e ) * (P B / 760 mm Hg)

= 8.18 liter * (293.16 o K / 294.26 o K ) * (760 mm Hg / 760 mm Hg)

= 8.1 5 liters

= 3.90 liter * (293.16 o K / 295 o K) * (760 mm Hg / 760 mm Hg)

= 3.88 liter

ROH

e = (Imass

e / Ivol

e ) * (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

Imass d = (Iconc d1 + Iconc d2 ) * Dens ROH * Ivol

r

= (0 μg/mL + 0μg/mL) * 15 mL

= 0 μg

= (0.07 μg/mL + 0.01 μg/mL) * 0.7914 g/ml * 15 ml * 10 6 μg/g

= 0.95 μg

Ivol d = Ivol dm * (293.16 o K / Itemp d ) * ( P B / 760 mm Hg)

= 31.16 liter * (293.16 o K / 294.26 o K) * (760 mm Hg / 760 mm Hg)

= 31.04 liters

= 13.50 liter * (293.16 o K / 294 o K) * (760 mm Hg / 760 mm Hg)

= 13.46 liter

ROH d = (Imass d / Ivol d ) * (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

4 2 10 02

. 12

− ∗ + + + + + =

e e e e e e HCHO ROH CO CH NMHC CO DF

(see section 6, DF Calc.)

NMHC

e = FID THC

e - (r CH 4 * CH 4e )

- (r CH 3 OH * ROH

e )

= 82 ppmC

- (1.04 * 9 ppmC)

- (0.66 * 5.27 ppmC)

= 69 ppmC

CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

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

86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e .

= (1

- (0.02705) * 1.5%

- 0.000323 * 30%) * 250 ppm

= 237 ppmG

- 10
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 

## ( ) 4 10 ppm 0.81 ppmC 5.27 ppmC 237 ppmC 9 ppmC 69 1.5% 12.02 DF

− ∗ + + + + + =

ROH

conc = ROH

e - (ROH d * (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

ROH dens = (Mol. Wt. * conversion of liter to ft 3 ) / (Mol. Vol.)

= (46.06952 g/mole * 28.316 liter/ft 3 ) / 24.055 liter/mole

= 54.23007808 g/ft 3

= (32.0428 g/mole * 28.316 liter/ft) / 24.055 liter/mole

= 37.719 g/ft 3

VMIX = 3495 ft 3 (from section 3.3)

ROH

mass n = (ROH

conc * ROH dens * VMIX * 10 - 6 ) / (Carbon No.)

ROH mass 1 = (4.89 ppmC * 54.23 g/ft 3 * 3495 ft 3 * 10 - 6 )

= 0.93 g

= (5.23 ppmC * 37.719 g/ft 3 * 2834 ft 3 * 10 - 6 ) / 1

= 0.56 g

Similarly, for Phase 2: ROH mass 2 = 0 0.08 g and for Phase 3: ROH mass 3 = 0 0.08 g

Therefore,

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D ROH ROH 0.57 D D ROH ROH 0.43 ROH



###        

+ +
∗ +        

+ +
∗ = miles 3.846 miles 3.591 g 0 g 0 0.57 miles 3.846 miles 3.591 g 0 g 0.93 0.43 ROH

wm



###        

+ +
∗ +        

+ +
∗ = miles 3.845 miles 3.583 mg 0.08 mg 0.08 0.57 miles 3.845 miles 3.581 mg 0.08 mg 0.56 0.43 ROH

wm

ROH

wm = 0.045 g/mile (ethanol weighted mass emissions)

ROH

wm = 0.05 g (methanol weighted mass emissions)G

- 11
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 5 6

. CARBONYL MASS EMISSIONS CALCULATIONS

5 6 .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 dilut ion 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 m asses are used in the following equations to calculate the weighted mass emissions of each carbonyl compound.

5 6 .2. CARBONYL MASS EMISSIONS CALCULATION PER TEST PHASE

5 6 .2.1 RHO

mass n = (RHO

conc * RHO dens * VMIX * 10 - 6 )

5 6 .2.2 RHO

conc = RHO

e - (RHO d * (1

- (1 / DF)))

NOTE: If RHO

conc is calculated to be less than zero, then RHO

conc = 0.

5 6 .2.3 RHO

e = (Imass

e / Ivol

e ) * (Mol. Vol. / Mol. Wt.)

5 6 .2.4 Imass
e = Iconc
ce *Ivol

c

5 6 .2. 5 4 Ivol

e = Ivol

em * (293.16 o K / Itemp

e ) * (P B / 760 mm Hg)

5 6 .2. 6 5 RHO d = (Imass d / Ivol d ) * (Mol. Vol. / Mol. Wt.)

5 6 .2. 7 Imass d = Iconc cd *Ivol

c

5 6 .2. 8 6 Ivol d = Ivol dm * (293.16 o K / Itemp d ) * (P B / 760 mm Hg)

5 6 .3. WEIGHTED CARBONYL MASS EMISSIONS CALCULATION

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D RHO RHO 0.57 D D RHO RHO 0.43 RHO

5 6 .4. SAMPLE CALCULATION

5 6 .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. Thi s is the same vehicle test as the example in section 3.3. Calculate the weighted formaldehyde andG

- 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 Ivol

c (ml) Formaldehyde Ivol

em (liter) Acetaldehyde Ivol dm (liter) Itemp

e ( o K) Itemp d ( o K) Iconc

ce (μg/mL) Iconc cd (μg/mL) Iconc

ce (μg/mL) Iconc cd (μg/mL)

1 4.4 0.387 0.006 8.47 4.114 0.006 8.23 294.26 294.26

2 4.4 0.048 0.016 15.35 0.013 0.009 13.88 294.26 294.26

3 4.4 0.016 0.006 9.01 0.012 0.005 8.16 294.26 294.26

Test

Phase Ivol

r (mL ) Imass

e (μg) Ivol

em (liter) Imass d (μg ) Ivol dm (liter) Itemp

e ( o K) Itemp d ( 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 D phase n (mile) DF P B

(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

THC

e (ppmC ) CH 4e (ppmC ) CO 2e (%) CO

em (ppm) R

a (%) VMIX (ft 3 ) D phase n (mile) P B (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:

Imass
e = Iconc
ce *Ivol

c

= 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

Ivol

e = Ivol

em * (293/16 o K / Itemp

e ) * (P B / 760 mm Hg)

= 8.47 liter * (293.16 o K / 29 4.26 o K) * (760 mm Hg / 760 mm Hg)

= 8.44 liter

= 8.49 liter * (293.16 o K / 295 o K) * (760 mm Hg / 760 mm Hg)

= 8.44 literG

- 13
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 RHO

e = (Imass

e / Ivol

e ) * (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

Imass d = Iconc cd * Ivol

c

= 0.006 μg/mL * 4.4 mL

= 0.026 μg

Ivol d = Ivol dm * (293.16 o K / Itemp d ) * (P B / 760 mm Hg)

= 8.23 liter * (293.16 o K / 294.26 o K) * (760 mm Hg / 760 mm Hg)

= 8.20 liter

= 31.57 liter * (293.16 o K / 292 o K) * (760 mm Hg / 760 mm Hg)

= 31.70 liter

RHO d = (Imass d / Ivol d ) * (Mol. Vol. / Mol. Wt.)

= ( 0.026 μg / 8.20 liter) * (24.055 liter/mole / 30.0268 g/mole)

= 0.00258 ppm

= (0.17*10 - 6 g / 31.70 liter)*(24.055 liter/mole / 30.0268 g/mole)

= 4 ppb

DF = 14.2688

DF = 9.77 / [CO 2e + (NMHC

e + CH 4e + CO e ) * 10 - 4 ] (see section 6, DF Calc.)

NMHC

e = FID THC

e - (r CH 4 * CH 4e )

= 132 ppmC

- (1.04 * 108 ppmC)

= 20 ppmC

CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted, CO

em must be substituted directly for CO

e .

= (1

- 0.02890 * 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

RHO

conc = RHO

e - (RHO d * (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)))

= 0.159 6 ppm

= 233 ppb

- (4 ppb * (1

- (1 / 10.69)))

= 229 ppb

RHO dens = (Mol. Wt. * conversion of liter to ft 3 ) / (Mol. Vol.)

= (30.0268 g/mole * 28.316 liter/ft 3 ) / 24.055 liter/mole

= 35.35 g/ft 3

VMIX = 3495 ft 3

RHO

mass n = (RHO

conc * RHO dens * VMIX * 10 - 6 )

RHO mass 1 = (0.1596 ppm * 35.35 g/ft 3 * 3495 ft 3 * 10 - 6 * 1000 mg/g)

= 19.7 18 mg

= (229 ppb * 35.35 g/ft 3 * 2866 ft 3 * 10 - 6 )

= 23.2 mg

Similarly, for Phase 2: RHO mass 2 = 1.457 6.6 mg and for Phase 3: RHO mass 3 = 0.472 12.7 mg

Therefore,

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D RHO RHO 0.57 D D RHO RHO 0.43 RHO



###        

+ +
∗ +        

+ +
∗ = miles 3.846 miles 3.591 mg 1.457 mg 0.472 0.57 miles 3.846 miles 3.591 mg 1.457 mg 19.718 0.43 RHO

wm



###        

+ +
∗ +        

+ +
∗ = miles 3.845 miles 3.583 mg 6.6 mg 12.7 0.57 miles 3.845 miles 3.581 mg 6.6 mg 23.2 0.43 RHO

wm

RHO

wm = 1.371 3.2 mg/mi (formaldehyde weighted mass emissions)

Acetaldehyde

Similarly,

Phase 1: RHO mass 1 = 212 mg

Phase 2: RHO mass 2 = 0.165 mg

Phase 3: RHO mass 3 = 0.329 mgG

- 15

As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 

###        

+ +
∗ +        

+ +
∗ = miles 3.846 miles 3.591 mg 0.165 mg 0.329 0.57 miles 3.846 miles 3.591 mg 0.165 mg 212 0.43 RHO

wm

RHO

wm = 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 Iconc ce ( μ g/mL) Iconc cd ( μ g/mL) Iconc blk ( μ g/mL) Ivol dm (liter) Ivol em (liter) Itemp e ( o K) Itemp d ( 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

THC e (ppmC) CH 4e (ppmC) CO 2e (%) CO em (ppm) R a (%) VMIX
(ft 3 ) D phase n (mile) P B (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:

Imass d = (Iconc cd

– Iconc blk )*Ivol

c

Imass d = (0.028

– 0.0) μ g/mL * 4.4 mL = 0.1232 μ g

Imass
e = (Iconc

ce – Iconc blk )*Ivol

c

Imass
e = (1.212

– 0.0) μ g/mL * 4.4 mL = 5.33 μ g

Mol. Wt. of HCHO = (1 * 12.01115) + (2 * 1.00797) + (1 * 15.9994)

= 30.0265 g/mole

Ivol

e = Ivol

em * (293/16 o K / Itemp

e ) * (P B / 760 mm Hg)G

- 16
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 = 8.57 liter * (293.16 o K / 294.26 o K) * (760 mm Hg / 760 mm Hg)

= 8.54 liter

RHO

e = (Imass

e / Ivol

e ) * (Mol. Vol. / Mol. Wt.)

= (5.33*10 - 6 g / 8.54 liter) * (24.055 liter/mole / 30.0265 g/mole)

= 500 ppb

Ivol d = Ivol dm * (293.16 o K / Itemp d ) * (P B / 760 mm Hg)

= 8.61 liter * (293.16 o K / 294.26 o K) * (760 mm Hg / 760 mm Hg)

= 8.58 liter

RHO d = (Imass d / Ivol d ) * (Mol. Vol. / Mol. Wt.)

= (0.1232*10 - 6 g / 8.58 liter)*(24.055 liter/mole / 30.0265 g/mole)

= 11.5 ppb

DF = 9.77 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ] (see section 6, DF Calc.)

NMHC

e = FID THC

e - (r CH 4 * CH 4e )

= 132 ppmC

- (1.04 * 108 ppmC)

= 20 ppmC

CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

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

86.111 is used and the condition ing column has been deleted, CO

em must be substituted directly for CO

e .

= (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

RHO

conc = RHO

e - (RHO d * (1

- (1 / DF)))

= 500 ppb

- (11.5 ppb * (1

- (1 / 10.69 )))

= 489.6 ppb (formaldehyde)

RHO dens = (Mol. Wt. * conversion of liter to ft 3 ) / (Mol. Vol.)

= (30.0265 g/mole * 28.316 liter/ft 3 ) / 24.055 liter/mole

= 35.35 g/ft 3

RHO

mass n = (RHO

conc * RHO dens * VMIX * 1 0 - 6 )

RHO mass 1 = (489.6 ppb * 35.35 g/ft 3 * 2866 ft 3 * 10 - 6 )

= 49.6 mg (formaldehyde)

Similarly, for Phase 2: RHO mass 2 = 12.9 mgG

- 17
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 and similarly for Phase 3: RHO mass 3 = 5.6 mg

Therefore,

) D + D RHO + RHO ( * 0.57 + ) D + D RHO + RHO ( * 0.43 = RHO

2 phase 3 phase 2 mass 3 mass

2 phase 1 phase 2 mass 1 mass

wm

) miles 3.845 + miles 3.583 mg 12.9 + mg 5.6 ( * 0.57 + ) miles 3.845 + 3.581miles mg 12.9 + mg 49.6 ( * 0.43 = RHO

wm

RHO

wm = 5.04 mg/mi (formaldehyde weighted mass emissions)

6. DILUTION FACTOR CALCULATION

6.1. For Non

- Alcohol Fueled Vehicles

6.1.1 

## ( ) ( ) 4

e 4e e 2e 10 CO CH NMHC CO 2 z 4 y x 3.76 2 y x x 100

DF

− ∗ + + +        

− + ∗ + + ∗

=

(where fuel composition is C

x H y O

z as measured for the fuel used.)

6.1.2 CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted,

CO

em must be substituted directly for CO

e .

a) For gasoline, CH 1.85 , where x = 1, y = 1.85, and z = 0: DF = 13.47 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4

CO

e = (1

- 0.01925 * CO 2e - 0.000323 * R

a ) * CO

em

b) For Phase 2 gasoline, CH 1.94 , where x = 1, y = 1.94 and z =
0.017, DF = 13.29 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4

CO

e = (1

- 0.01970 * CO 2e - 0.000323 * R

a ) * CO

em

c) For LPG, CH 2.64 , where x = 1, y = 2.64, z = 0: DF = 11.68 / [CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4

CO

e = (1

- 0.02320 * CO 2e - 0.000323 * R

a ) * CO

em

d) For CNG, CH 3.78 , 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 / [[CO 2e + (NMHC

e + CH 4e + CO

e ) * 10 - 4 ]

CO

e = (1

- 0.02890 * CO 2e - 0.000323 * R

a ) * CO

em

6.2. For Alcohol Fueled Vehicles :

6.2.1 

## ( ) ( ) 4

e e e 4e e 2e 10 HCHO ROH CO CH NMHC CO 2 z 4 y x 3.76 2 y x x 100

DF

− ∗ + + + + +        

− + ∗ + + ∗

=

(where fuel composition is C

x H y O

z as measured for the fuel used.)

6.2.2 CO

e = (1

- (0.01 + 0.005 * HCR) * CO 2e - 0.000323 * R

a ) * CO

em NOTE: If a CO instrument which meets the criteria specified in CFR 40, 86.111 is used and the conditioning column has been deleted,

CO

em must be substituted directly for CO

e .

a) For M100 (100% methanol), CH 3 OH, where x = 1, y = 4, and z = 1: DF = 11.57 / [CO 2e + (NMHC

e + CH 4e + CO

e + ROH

e + HCHO

e ) *

10
- 4 ]

CO

e = (1

- 0.03000 * CO 2e - 0.000323 * R

a ) * CO

em b) For M85 (85% methanol, 15% indolene), CH 3.41 O 0.72 , where x = 1, y = 3.41, and z = 0.72: DF = 12.02 / [CO 2e + (NMHC

e + CH 4e + CO

e + ROH

e + HCHO

e ) *

10
- 4 ]

CO

e = (1

- 0.02705 * CO 2e - 0.000323 * R

a ) * CO

em c) For E100 (100% ethanol), C 2 H 5 OH, where x = 1, y = 3, and z = 0.5:

DF = 12.29 / [CO 2e + (NMHC

e + CH 4e + CO

e + ROH

e + HCHO

e ) *

10
- 4 ]

CO

e = (1

- 0.02500 * CO 2e - 0.000323 * R

a ) * CO

em

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 dens ROH

dens mass dens mass mass r RHO RHO NMHC r ROH ROH NMHC NMHC NONMHC

7.1.1 For the purpose of calculating NMOG for vehicles tested on e xhaust

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 NMHC

mass n (g) Ethanol

mass n (g) Formaldehyde

massn (g) Acetaldehyde

mass 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

NMHC dens = 17.44 g/ft 3



## ∑ ∑ ∗        

∗

− ∗        

∗

− = RHO

dens mass1
dens ROH

dens mass1
dens mass1 mass1 r RHO RHO NMHC r ROH ROH NMHC NMHC NONMHC

NONMHC mass1 = 1.1220

– 17.44 g/ft 3 * ( 0.9271 g / 27.116 (g/ft 3 )) * 0.756

– 17.44 g/ft 3 * ( 0.0197 g / 35.350 (g/ft 3 )) * 0

– 17.44 g/ft 3 * ( 0.212 g / 25.929 (g/ft 3 )) * 0.5

= 1.1220

– 0.4508

– 0

– 0.0713

= 0.5999 g

NONMHC mass2 = 0

– 17.44 g/ft 3 * ( 0 g / 27.116 (g/ft 3 )) * 0.756

– 17.44 g/ft 3 * ( 0.001457 g / 35.350 (g/ft 3 )) * 0

– 17.44 g/ft 3 * ( 0.000165 g / 25.929 (g/ft 3 )) * 0.5

= 0

– 0

– 0

– 0.000055

= 0 gG

- 20
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 Note: Results that are l ess than zero are reported as zero.

NONMHC mass3 = 0.0026

– 17.44 g/ft 3 * ( 0 g / 27.116 (g/ft 3 )) * 0.756

– 17.44 g/ft 3 * ( 0.000472 g / 35.350 (g/ft 3 )) * 0

– 17.44 g/ft 3 * ( 0.000329 g / 25.929 (g/ft 3 )) * 0.5

= 0.0026

– 0

– 0

– 0.000111

= 0.00249 g

8 WEIGHTED HYDROCARBON MASS E M ISSIONS CALCULATION

8 .1 Weighted NMOG is determined using the following equation:



## ∑ ∑ ∑ + + = wm wm wm wm RHO ROH NONMHC NMOG

where:

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D NONMHC NONMHC 0.57 D D NONMHC NONMHC 0.43 NONMHC

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D ROH ROH 0.57 D D ROH ROH 0.43 ROH

       

+ +
∗ +        

+ +
∗ =

phase2 phase3 mass2 mass3

phase2 phase1 mass2 mass1

wm D D RHO RHO 0.57 D D RHO RHO 0.43 RHO

8.1.1 For the purpose of calculating NMOG for vehicles tested on e xhaust

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 NONMHC

mass

n (g) Ethanol

mass

n (g) Formaldehyde

mass n (g) Acetaldehyde

mass n (g) Distance (mile)

1 0.5999 0.9271 0.019718 0.212 3.591

2 0 0 0.001457 0.000165 3.846G

- 21
As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 3 0.00249 0 0.000472 0.000329 3.591

     

+ +
∗ +      

+ +
∗ = miles 3.846 miles 3.591 g 0 g 0.00249 0.57 miles 3.846 miles 3.591 g 0 g 0.5999 0.43 NONMHC

wm

NONMHC

wm = 0.03488 g/mile Similarly

, Ethanol

wm = 0.05360 g/mile Similarly

, Formaldehyde

wm = 0.00137 g/mile Similarly

, Acetaldehyde

wm = 0.01231 g/mile

With all the above information, the weighted mass emissions of n on

- methane organic gas can b e calculated:



## ∑ ∑ ∑ + + = wm wm wm wm RHO ROH NONMHC NMOG

NMOG

wm = 0.03488 g/mile + 0.05360 g/mile + 0.00137 g/mile + 0.01231 g/mile

= 0.102 g/mileCAS # 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 15.1 6

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

0068 9

- 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 5.68CAS # 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

- hexen e 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 7.14CAS # 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

- dimethylhexa ne 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

- dimethy lhexane 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 7.64CAS # 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

- met hylethyl)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

- diethy lbenzene 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 0.55CAS # 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 0.001

- 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 me thacrolein

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

- pent ene 00107

- 83

- 5 2

- methylpentane

00108

- 08

- 7 2,4

- dimethylpentane1

- 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

0 0463

- 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

- trimethylpen tane
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

- butene1

- 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

- t ert

- 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

- methylcyclopenten e 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

- propylbenzene1

- 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

- trim ethylcyclopentane

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

- dimethyloct ane 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

- meth yl

- 3

- ethylcyclopentane2

- 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

CH 3 OH d = the methanol concentration in the dilution air as determined from the dilution air methanol sample using the procedure

sp ecified in Method No. 1001, ppmC.

CH 3 OH

e = the methanol concentration in the dilute exhaust as determined from the dilute exhaust methanol sample using the procedure specified in Method No. 1001, ppmC.

CH 4d = the methane concentration in the dilution ai r, ppmC.

CH 4e = the methane concentration in the dilute exhaust, ppmC.

C 2 H 5 OH d = the ethanol concentration in the dilution air as determined from the dilution air ethanol sample using the procedure specified in Method No. 1001, ppmC.

C 2 H 5 OH

e = 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

CO

e = the carbon monoxide concentration in the dilute exhaust

corrected for carbon dioxide and water removal, ppm.

CO

em = the carbon monoxide concentration in the dilute exhaust uncorrected for carbon dioxide and water removal, ppm.

CO 2e = the carbon dioxide concentration in the dilute exhaust, %.

CVS = constant volume sa mpler2

- 2

As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 D phase 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.

Dens ROH = density of alcohol, g/mL.

DF = dilution factor (see Dilution Factor Calculation).

FID = flame ionization detector

FID THC d = 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 THC

e = the total hydrocarbon c oncentration 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 s pectrometry

HC

conc = net concentration of an HC compound in the dilute exhaust corrected for background per test phase, ppbC.

HC d = 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.

HC dens = mass per unit volume of an HC compound corrected to standard conditions (293.16 K and 760 mm Hg) g/ft 3

.

HC

e = 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.

HC

mass n = mass emissions of an HC compound per test phase n (wh ere n is either 1, 2, or 3), mg.2

- 3

As Amended: March 22, 2012 Board Hearing: January 26

- 27, 2012 HC

wm = total weighted mass of an HC compound per mile, g/mile.

HCHO

e = formaldehyde concentration in the dilute exhaust as determined from the dilute exhaust carbonyl sample using the procedure specified in Method No 100 4, ppm.

HCR = the hydrogen

- to

- carbon ratio for the fuel used.

HPLC = high performance liquid chromatography

Iconc blk = concentration of the blank cartridge, μg/mL

Iconc cd = total concentration of carbonyl compound extracted from both cartridges for the dilution air, μg/mL

Iconc
ce = total concentration of carbonyl compound extracted from both cartridges for the diluted exhaust, μg/mL

Iconc d1 = dilution air (background) alcohol concentration in the primary impinger for all three test phases as determ ined by the procedure specified in Method No. 1001, μg/mL.

Iconc d2 = 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.

Iconc e1 = dilut e exhaust alcohol concentration in the primary impinger per test phase as determined by the procedure specified in Method No. 1001, μg/mL.

Iconc e2 = dilute exhaust alcohol concentration in the secondary impinger per test phase as determined by the proced ure specified in Method No. 1001, μg/mL.

Imass d = 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 speci fied in Method No. 1001 (alcohol) or Method No. 1004 (carbonyl), μg.

Imass
e = 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 Itemp d = dilution air temperature at the flowmeter inlet for impinger/cartridge sampling, o K.

Itemp
e = dilute exhaust temperature at the flowmeter inlet for impinger/cartridge sampling, o K.

Ivol

c = elution volume of the cartridge, mL ( For example, T t he cartridge is extracted with 5 mL acetonitrile, but 0.6 mL is retained in the cartridge, so the

elution vo lume is 4.4 mL.)

Ivol d = total volume of dilution air (background) drawn through the impingers/cartridges for all three test phases corrected to standard conditions (293.16 o K and 760 mm Hg), liter.

Ivol dm = total volume of dilution air (background) dr awn through the impingers/cartridges for all three test phases as measured during testing, liter.

Ivol

e = total volume of dilute exhaust drawn through the impingers/cartridges per test phase corrected to standard conditions (293.16 o K and 760 mm Hg), lite r.

Ivol

em = total volume of dilute exhaust drawn through the impingers/cartridges per test phase as measured during testing,

liter.

Ivol

r = 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 (293.16 o K 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

NMHC

conc = 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 NMHC d = the non

- methane hydrocarbon concentration in the dilution air corrected for methane and alcohol removal, ppmC.

NMHC dens = the mass per unit volume of non

- methane hydrocarbon corrected to standard conditions (16.33 g/ft 3 at 293.16 o K and 760 mm Hg assuming a C:H ratio of 1:1.85 for gasoline; 16.78 g/ft 3 at 293.16 o K and 760 mm HG assuming a C:H ratio of 1:1.94 for Phase 2 reformulated gasol ine; 19.52 g/ft 3 at
293.16 o K and 760 mm HG assuming a C:H ratio of 1:3.78 for natural gas; and 17.26 g/ft 3 for LPG at 293.16 o K and 760 mm Hg assuming a C:H ratio of 1:2.64), g/ft 3

.

NMHC

e = non

- methane hydrocarbon concentration in the dilute exhaust corrected for methane and alcohol removal, ppmC.

NMHC

mass n = the mass emission of non

- methane hydrocarbon per test phase n (where n is either 1, 2, or 3), g.

NMHC

wm = the total weighted mass of non

- methane hydrocarbon per mile for all three phases of the FTP, g/mile.

NO N MHC

mass n = the mass emission of non

- oxygenated non

- methane hydrocarbon per test phase n (where n is either 1, 2, or 3), g.

NO N MHC

wm = 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

P B = barometric pressure during testing, mm Hg.

PID = photoionization detector

PLOT = porous layer open tubular

R
a = the relative humidity of the ambient air, %.

r CH 3 OH = the FID response factor to methanol (see CFR 40,

86.121

- 90(c)).

r CH 4 = the FID response factor to methane (see Part B, “Determination
of NMHC by FID”).

r C 2 H 5 OH = 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 r ROH = the FID response factor to an alcohol

r RHO = the FID response factor to carbonyl compound

RHO = generic symbol representing a carbonyl compound such as formaldehyde, acetaldehyde, acetone, etc.

RHO

conc = net concentration of a carbonyl compound in the dilute exhaust corrected for background per test phase, ppm.

RHO d = composite concentration of a carbonyl compound in the

diluti on air (background) for all three test phases, ppm.

RHO dens = mass per unit volume of a carbonyl compound corrected to standard conditions (293.16 o K and 760 mm Hg), g/ft 3

.

RHO

e = concentration of a carbonyl compound in the dilute exhaust per test phase, ppm.

RHO

mass n = mass emissions of a carbonyl compound per test phase n (where n is either 1, 2, or 3), g.

RHO

wm = total weighted mass emissions of a carbonyl compound per mile, g/mile.

ROH = generic symbol representing an alcohol compound such as

methanol or ethanol.

ROH

conc = net concentration of an alcohol compound in the dilute exhaust corrected for background per test phase, ppm.

ROH d = composite concentration of an alcohol compound in the dilution air (background) for all three test phases, ppm.

ROH dens = mass per unit volume of an alcohol compound corrected to standard conditions (293.16 o K and 760 mm Hg), g/ft 3

.

ROH

e = concentration of an alcohol compound in the dilute exhaust per

t est phase, ppmC.

ROH

mass n = mass emissions of an alcohol compound per test phase n (where n is either 1, 2, or 3), g.

ROH

wm = 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 (293.16 o K and 760 mm Hg),

ft 3

.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

c m = 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 C 1 through C 6 H ydrocarbons 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 Am bient 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., Id entification 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.