SCOS97-NARSTO VOC MeasurementsQuality Assurance Issues

Eric FujitaDivision of Atmospheric Sciences

Desert Research Institute

University and Community College System of Nevada

Reno, Nevada

SCOS97-NARSTO Data Analysis ConferenceDiamond Bar, CA

February 13-15, 2001

PAMS VOC Measurements During SCOS97-NARSTO

Sample Chemical Sampling Schedule

Site Location Collection Analysis Measurement Times Frequency Period

Ventura

Ventura - Emma Wood VCAPCD VCAPCD/AAC HC, carb 3-hr at 03, 06, 13, 17. 3rd day, IOP 6/16 to last IOP

El Rio VCAPCD VCAPCD/AAC HC, carb 3-hr at 03, 06, 13, 17. 3rd day, IOP 6/16 to last IOP

Simi Valley VCAPCD VCAPCD HC 3-hr at 03, 06, 13, 17. 3rd day, IOP 6/16 to last IOP

South Coast Air Basin

Hawthorne SCAQMD SCAQMD HC 3-hr at 00,03,06,09, 12.15.18,21 3rd day 7/6 to 9/28

Burbank SCAQMD SCAQMD HC, carb 3-hr at 00,03,06,09, 12.15.18,21 daily 7/15 to last IOP

Upland SCAQMD SCAQMD HC 3-hr at 00,03,06,09, 12.15.18,21 3rd day 7/6 to 9/28

Los Angeles - North Main ARB ARB HC 3-hr at 06, 13 3rd day 7/3 to 9/28

Banning SCAQMD SCAQMD HC, carb 3-hr at 00,03,06,09, 12.15.18,21 3rd day 7/6 to 9/28

Pico Rivera SCAQMD SCAQMD HC, carb 3-hr at 00,03,06,09, 12.15.18,21 daily 7/6 to last IOP

Azusa SCAQMD SCAQMD HC 3-hr at 00,03,06,09, 12.15.18,21 3rd day 7/6 to 9/28

San Diego

Mount Soledad SDAPCD SDAPCD HC, carb 3-hr at 03, 06, 13, 17. 3rd day, IOP 7/3 to 9/28

El Cajon SDAPCD SDAPCD HC, carb 3-hr at 03, 06, 13, 17. 3rd day, IOP 7/3 to 9/28

San Diego - Overland SDAPCD SDAPCD HC, carb 3-hr at 03, 06, 13, 17. 3rd day, IOP 7/3 to 9/28

San Diego - 12th Street ARB ARB HC 3-hr at 06, 13 3rd day 7/3 to 9/28

Alpine SDAPCD SDAPCD HC 3-hr at 03, 06, 13, 17. 3rd day, IOP 7/3 to 9/28

Supplemental VOC Measurements During SCOS97-NARSTO

Sample Chemical Sampling Schedule

Site Location Collection Analysis Measurement

Point Conception Cal Poly SLO DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

San Nicolas Island CE-CERT DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Santa Catalina Island USC DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Anaheim CE-CERT DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Burbank SCAQMD DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Los Angeles - ARCO Plaza CE-CERT BRC CO, CO2, CH4, MTBE, C2-C11 HC

Los Angeles - North Main CE-CERT BRC CO, CO2, CH4, MTBE, C2-C11 HC

Azusa CE-CERT BRC CO, CO2, CH4, MTBE, C2-C11 HC

Pine Mountain UCR DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Twenty-Nine Palms AAC AAC/AAC C2-C11 HC, C1-C7 carbonyls

Barstow DRI DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Tijuana-Rosarito Tracer ES&T DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Mexicali-ITM Tracer ES&T DRI/DRI CO, CO2, CH4, MTBE, C2-C11 HC, halocarbons, C1-C7 carbonyls

Supplemental VOC Measurements During SCOS97-NARSTO (continued)

Sample Chemical Sampling Schedule

Site Location Collection Analysis Measurement

Special Sampling

Simi Valley DGA DGA PAN, PPN, Perc

Azusa EPA/ManTech EPA/ManTech PAMS HC, HAPs, biogenic HC, MVK, methacrolein, and C4-C10 carbonyls

Azusa UCD UCD Multi-functional carbonyls

Azusa UCLA UCLA Total reactive carbon and HC

Azusa UCR UCR Biogenic HC & oxidation product

Azusa DGA DGA PAN, PPN, Perc

Pine Mountain UCR UCR Biogenic HC & oxidation product

Banning UCR UCR Biogenic HC & oxidation product

Lancaster DRI (Schorran) DRI (Schorran) Continous halocarbon

Barstow DRI (Schorran) DRI (Schorran) Continous halocarbon

Aircraft Samping

STI Aztec STI/CE-CERT BRC/AtmAA CO, CO2, CH4, MTBE, C2-C11 HC, C1-C7 carbonyls

UCD Cessna UCD/CE-CERT BRC/AtmAA CO, CO2, CH4, MTBE, C2-C11 HC, C1-C7 carbonyls

EOPACE Navajo SDAPCD SDAPCD C2-C11 HC, C1-C7 carbonyls

Gibbs Cessna SDAPCD SDAPCD C2-C11 HC, C1-C7 carbonyls

VOC Measurement Audits and Comparisons

Speciated Hydrocarbons

Participants: ARB, EPA, BRC, DRI, SDAPCD, SCAQMD, VCAPCD, BAAQMD, and AAC

Three sets of collocated ambient samples - morning sample from Los Angeles, afternoon sample from Azusa and late afternoon sample from Santa Monica.

Carbonyl Compounds Performance audit involving sampling from a standard mixture of carbonyl compounds

prepared in 33-liter tank by DRI. Participants - AtmAA, AAC, SCAQMD, VCAPCD, and SDAPCD

Field comparison at Azusa on September 23 and 24. Participants - DRI, AtmAA, AAC, SCAQMD, VCAPCD, and ManTech.

Other VOC Comparisons Biogenic compounds: Adsorbent tubes (UCR) with collocated canister samples (DRI and BRC)

at Riverside.

Halogenated compounds: Continuous GC/ECD (DGA) with canister samples (DRI - Zielinska and Schorran) at Azusa.

SCOS97-NARSTO Quality AssuranceHydrocarbon Performance Audits

• Participants

– Coordination, data compilation and analysis (Eric Fujita, DRI and Mike Miguel, ARB)

– DRI 12-port manifold canister sampling system (Larry Sheetz, DRI)

– Collection of ambient samples (Pat Harrington, ARB)

– Participating laboratories: ARB, U.S. EPA, Biopheric Research Corporation, Desert Research Institute, SDAPCD, SCAQMD, VCAPCD,BAAQMD, ManTech Environmental Technology, Atmospheric Analytical Consultants.

• Audit Samples

– Los Angeles N. Main (morning sample): AAC, ARB, BAAQMD, BRC, DRI, EPA, SCAQMD, SDAPCD, VCAPCD, ARB (duplicate), DRI (duplicate), EPA (duplicate).

– Azusa (afternoon sample): AAC, ARB, BAAQMD, BRC, DRI, EPA, SCAQMD, SDAPCD, VCAPCD, ARB (duplicate), DRI (duplicate), EPA (duplicate).

– Santa Monica (evening sample): BRC, DRI, EPA, SDAPCD, VCAPCD.

SCOS97-NARSTO Hydrocarbon AuditLos Angeles N. Main Ambient Sample – Functional Type and Totals

0

100

200

300

400

500

600

ARB

ARB-dAAC

BAAQMD

BRC

BRC dDRI

DRI-dEPA

SCAQMD la

b

SCAQMD A

uto

SDAPCD

VCAPCD

pp

bC

aromatics

olefins

paraffins

0

100

200

300

400

500

600

ARB

ARB-dAAC

BAAQMD

BRC

BRC-dDRI

DRI-dEPA

SCAQMD-la

b

SCAQMD-A

ut

SDAPCD

VCAPCD

pp

bC

idoxy

unid

other id

PAMS

SCOS97-NARSTO Hydrocarbon AuditAzusa Ambient Sample – Functional Type and Totals

0

50

100

150

200

250

300

350

400

450

ARB

ARB-dAAC

BAAQMD

BRCDRI

DRI-dEPA

EPA-d

SCAQMD la

b

SCAQMD A

uto

SDAPCD

VCAPCD

pp

bC

aromatics

olefins

paraffins

0

50

100

150

200

250

300

350

400

450

ARB

ARB-dAAC

BAAQMD

BRCDRI

DRI-dEPA

EPA-d

SCAQMD la

b

SCAQMD A

uto

SDAPCD

VCAPCD

pp

bC

idoxy

unid

other id

PAMS

SCOS97-NARSTO Hydrocarbon AuditSanta Monica Ambient Sample – Functional Type and Totals

0

50

100

150

200

BRC SDAPCD EPA VCAPCD DRI

pp

bC

aromatics

olefins

paraffins

0

50

100

150

200

BRC SDAPCD EPA VCAPCD DRI

pp

bC

idoxy

unid

other id

PAMS

SCOS97-NARSTO Hydrocarbon AuditAzusa Ambient Sample

Lab Slope R-sqLab/DRI Average

Lab/DRI StdDev

Number Obs.

Percent < detection

Percent Outliers

BRC 0.98 0.95 1.02 0.19 45 16.4 1.8

EPA 0.95 0.96 1.05 0.14 47 5.5 9.1

SCAQMD lab 1.02 0.99 0.95 0.13 37 21.8 10.9

SDAPCD 0.88 0.93 0.95 0.17 38 20.0 10.9

ARB 0.96 0.99 1.03 0.17 36 18.2 16.4

SCAQMD Auto-GC 1.08 0.98 1.00 0.15 46 0.0 16.4

VCAPCD 1.05 0.98 1.00 0.13 32 20.0 21.8

Mantech 1.00 0.95 0.97 0.16 32 14.5 27.3

BAAQMD 0.90 0.97 0.96 0.18 30 12.7 32.7

AAC 0.90 0.94 1.01 0.20 20 14.5 49.1

Outlier – Average above 1 ppbC with Lab/DRI ratio < 0.7 or >1.3Outliers excluded from regressions.

Azusa

0

5

10

15

20

25

30

0 10 20 30

DRI

AR

B

Azusa

0

5

10

15

20

25

30

0 10 20 30

DRI

BR

C

Azusa

0

5

10

15

20

25

30

0 10 20 30

DRI

SC

AQ

MD

- L

ab

Azusa

0

5

10

15

20

25

30

0 10 20 30

DRI

SC

AQ

MD

- A

uto

GC

Azusa

0

5

10

15

20

25

0 5 10 15 20 25

DRI

AA

C

Azusa

0

5

10

15

20

25

0 5 10 15 20 25

DRI

BA

AQ

MD

Azusa

0

10

20

30

40

50

60

0 20 40 60

DRI

SD

AP

CD

Azusa

0

5

10

15

20

25

30

0 10 20 30

DRI

VC

AP

CD

SCOS97-NARSTO Hydrocarbon AuditLos Angeles, N. Main Ambient Sample

Outlier – Average above 1 ppbC with Lab/DRI ratio < 0.7 or >1.3Outliers excluded from regressions.

Lab Slope R-sqLab/DRI Average

Lab/DRI StdDev

Number Obs.

Percent < detection

Percent Outliers

ARB 0.93 0.97 0.99 0.15 42 18.2 5.5

SCAQMD-lab 1.06 0.99 1.04 0.14 43 14.5 7.3

SDAPCD 0.94 0.96 0.96 0.15 40 18.2 9.1

BRC 0.95 0.99 0.99 0.11 44 7.3 12.7

VCAPCD 1.17 0.97 1.04 0.16 39 14.5 14.5

SCAQMD-Aut 1.14 0.98 1.08 0.21 46 0.0 16.4

EPA 1.00 0.95 1.04 0.16 44 3.6 16.4

Mantech 1.12 0.95 1.00 0.18 37 9.1 23.6

BAAQMD 0.90 0.97 0.95 0.20 34 9.1 29.1

AAC 0.76 0.92 0.94 0.23 24 14.0 38.0

Los Angeles

0

5

10

15

20

25

30

0 10 20 30

DRI

AR

B

Los Angeles

0

5

10

15

20

25

30

0 10 20 30

DRI

BR

C

Los Angeles

0

5

10

15

20

25

30

0 10 20 30

DRI

SC

AQ

MD

- L

ab

Los Angeles

0

5

10

15

20

25

30

0 10 20 30

DRI

SC

AQ

MD

- A

uto

GC

Los Angeles

0

5

10

15

20

25

30

0 10 20 30

DRI

AA

C

Los Angeles

0

5

10

15

20

25

30

0 10 20 30

DRI

BA

AQ

MD

Los Angeles

0

10

20

30

40

50

0 10 20 30 40 50

DRI

SD

AP

CD

Los Angeles

0

10

20

30

40

50

60

0 20 40 60

DRI

VC

AP

CD

SCOS97-NARSTO Hydrocarbon AuditAzusa Ambient Sample

Outlier – Average above 1 ppbC with Lab/DRI ratio < 0.7 or >1.3Outliers excluded from regressions.

Lab Slope R-sqLab/DRI Average

Lab/DRI StdDev

Number Obs.

Percent < detection

Percent Outliers

BRC 0.81 0.91 1.02 0.27 31 33.3 5.9

SDAPCD 0.72 0.66 1.06 0.20 9 58.8 23.5

VCAPCD 0.96 0.81 1.11 0.22 8 60.8 23.5

EPA 0.87 0.90 1.18 0.36 26 6.3 39.6

Santa Monica

0

1

2

3

4

5

0 1 2 3 4 5

DRI

BR

C

Santa Monica

0

1

2

3

4

5

0 1 2 3 4 5

DRI

EP

A

Santa Monica

0

1

2

3

4

5

0 1 2 3 4 5

DRI

Ma

nT

ech

Santa Monica

0

1

2

3

4

5

0 1 2 3 4 5

DRI

SD

AP

CD

PAMS, Azusa 1995/96

y = 1.06x

R2 = 0.92

0

300

600

900

1200

0 400 800 1200

DRI

SCA

QM

D

NHMC, Azusa 1995/96

y = 0.99x

R2 = 0.80

0

300

600

900

1200

1500

0 400 800 1200

DRISC

AQ

MD

DRI Data Azusa 1995/96 morning

y = 1.2325x

R2 = 0.9369

0

10

20

30

40

0 10 20 30 40

acetylene (ppbC)

ethy

lene

(pp

bC)

DRI Data Azusa 1995/96 afternoon

y = 0.865x

R2 = 0.8146

0

5

10

15

20

25

0 5 10 15 20 25

acetylene (ppbC)

ethy

lene

(pp

bC)

SCAQMD Data Azusa 1995/96 morning

y = 1.1349x

R2 = 0.6056

0

10

20

30

40

0 10 20 30 40

acetylene (ppbC)

ethy

lene

(pp

bC)

SCAQMD Data Azusa 1995/96 afternoon

y = 0.857x

R2 = 0.4539

0

5

10

15

20

0 5 10 15 20

acetylene (ppbC)

ethy

lene

(pp

bC)

DRI Data Los Angeles-N. Main 1995/96 morning

y = 1.3269x

R2 = 0.9764

0

20

40

60

0 20 40 60

acetylene (ppbC)

ethy

lene

(pp

bC)

DRI Data Los Angeles-N. Main 1995/96 afternoon

y = 1.1565x

R2 = 0.874

0

10

20

30

0 10 20 30

acetylene (ppbC)

ethy

lene

(pp

bC)

ARB Data Los Angeles-N. Main 1995/96 morning

y = 1.2887x

R2 = 0.9791

0

20

40

60

0 20 40 60

acetylene (ppbC)

ethy

lene

(pp

bC)

ARB Data Los Angeles-N. Main 1995/96 afternoon

y = 1.1277x

R2 = 0.8012

0

10

20

30

0 10 20 30

acetylene (ppbC)

ethy

lene

(pp

bC)

SCOS97-NARSTO Quality AssurancePerformance Audits for Sampling and Analysis of Carbonyl Compounds

• Participants

– Coordination, data compilation and analyis (Eric Fujita, DRI and Randy Pasek, ARB)

– Preparation and analysis of carbonyl standard (Greg Harshfield, DRI)

– Audit equipment (Larry Sheetz, DRI)

– Participating laboratories: SDAPCD, SCAQMD, VCAPCD, Atmospheric Assessment Associates (AtmAA), Atmospheric Analytical Consultants (AAC).

• Audit Sampling

– Standard mixture of four carbonyl compounds in 33 liter tank prepared by DRI.

– Standard mixture in 6-liter transfer canister and gas standard delivery system sent to participants

– Sample from standard mixture with ~ 200:1 dilution.

Gas Standard Delivery SystemPerformance Audits of Carbonyl Compound Measurements

Consists of a mass flow controller, a 6-liter stainless steel gas standard transfer canister, and a 3-way valve and tee assembly.

The flow controller is preset to provide a flow of 5.0 ml per minute.

Prior to shipment of the system, fittings and stainless steel sampling lines are cleaned with deionized water and baked at 170oC for 24 hours.

0

1

2

3

4

5

6

HCHO

CH3CHO

aceto

neM

EK

butanal

benza

ldeh

yde

ug/

sam

ple

DRI_1 SCAQMD_1 SCAQMD_2 SDAPCD_1

SDAPCD_2 SDAPCD_1 (bag) SDAPCD_2 (bag) DRI_2

SCOS97-NARSTO Carbonyl AuditSCAQMD and SDAPCD

SCOS97-NARSTO Carbonyl AuditAtmospheric Assessment Associates (AtmAA)

0

1

2

3

4

5

6

HCHO

CH3CHO

aceto

neM

EK

butanal

benza

ldeh

yde

ug/

sam

ple

DRI_1 DRI_1r AtmAA_1

AtmAA_1r AtmAA_2 AtmAA_1 (bag)

AtmAA_1r (bag) AtmAA_2 (bag) DRI_2

SCOS97-NARSTO Carbonyl AuditAtmospheric Analytical Consultants (AAC)

-1

0

1

2

3

4

5

6

HCHO

CH3CHO

aceto

neM

EK

butanal

benza

ldeh

yde

ug/

sam

ple

DRI_1 AAC_1 AAC_2 AAC_3 DRI_2

SCOS97-NARSTO Carbonyl AuditVentura County APCD

0

1

2

3

4

5

6

HCHO

CH3CHO

aceto

neM

EK

butanal

benza

ldeh

yde

ug/

sam

ple

DRI_1 VCAPCD DRI_2

Species Formula BRCDRI

ZielinskaDRI

Schorran DGAF12 (dichlorodifluoromethane) CCl2F2 884 780methylbromide CH3Br 100F11 (trichlorofluoromethane) CCl3F 352 330 366F113 (trichlorotrifluoroethane) Cl3CCF3 1110 1410 1126chloroform CCl3 56 50methyl chloroform CH3CCl3 654 630 868carbon tetrachloride CCl4 103 90 176trichloroethylene Cl2CCHCl 53 50 53chlorodibromomethane ClCHBr2 10perchloroethylene (tetra) Cl2CCCl2 775 770 823 434m-dichlorobenzene 1,3-Cl2C6H4 40p-dichlorobenzene 1,4-Cl2C6H4 390o-dichlorobenzene 1,2-Cl2C6H4 30

Ventura County APCDSCOS97-NARSTO Quality Assurance

Measurement Comparison of Halogenated Compounds

Laboratory Analysis Date Sample Type Analysis Method Sample IDIsoprene (ppbC)

Ratio to Grand Ave.

Mantech 9/12/97 Canister GC/MS X098 16.86 0.70Mantech 9/12/97 Canister GC/MS X098r 27.24 1.13DRI 8/7/97 Canister GC/FID X098 24.02 1.00DRI 8/12/97 Canister GC/FID X098r 24.30 1.01BRC 8/13/97 Canister GC/FID 4 23.00 0.96UCR 8/97 Carbotrap GC/MSD-SIM 1 25.95 1.08UCR 8/97 Carbotrap GC/MSD-SIM 2 24.40 1.02UCR 8/97 Carbotrap GC/MSD-SIM 3 27.49 1.15UCR 8/97 Carbotrap GC/MSD-SIM 4 27.26 1.14UCR 8/97 Carbotrap GC/MSD-SIM 5 28.87 1.20

AveragesMantech 22.05 0.92DRI 24.16 1.01BRC 23.00 0.96UCR 26.79 1.12Grand Average 24.00Standard Deviation 2.05Relative Percent Difference 8.6%

SCOS97-NARSTO Quality AssuranceMeasurement Comparison of Isoprene