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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