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PAMS AutoGC
Monitoring Network Performance for NMHCs
Across 35 Monitors in Texas
Carol J. Meyercarol@orsat.com
August 10, 2016National Ambient Air Monitoring Conference
Orsat, LLC
www.orsat.com
August 10, 2016National Ambient Air Monitoring Conference
TCEQ AutoGC Networks
AutoGC Sites in Operation by Year
Network # of Sites
Houston Regional Monitoring Group 4
Extended Industry Monitoring Sites 3
North Texas Commission 13
University of Texas CEER 4
Harris County Pollution Control 1
TCEQ 12
Total AutoGC Sites 37
August 10, 2016National Ambient Air Monitoring Conference
AutoGC Systems: Hourly Sample Collection
and Separation
Drier
Dry gas
Sample
Thermal Desorber Gas Chromatograph Data System
Basic System for the Separation of NMHCs from Ambient Air
August 10, 2016National Ambient Air Monitoring Conference
Additional Automation for Introduction of
Quality Control Samples
Automatic introduction of QC
samples
Dynamically diluted check
standard
Analytical blank
Manual dilution of multipoint
calibration curve
Dilution from 100 ppbv or 1
ppmv multi-component standard
C2-C6 Alumina PLOT Separation
August 10, 2016National Ambient Air Monitoring Conference
Ethane to 1-Hexene
0.5 ppbv PAMS Standard
3.0 pA fs
C6+ Dimethylsiloxane (Boiling Point) Separation
August 10, 2016National Ambient Air Monitoring Conference
n-Hexane to n-Dodecane
0.5 ppbv PAMS Standard
3.0 pA fs
Analytical Blank
August 10, 2016National Ambient Air Monitoring Conference
PLOT column
Boiling point column
3.0 pA fs
3.0 pA fs
Ambient Air – PLOT Column
August 10, 2016National Ambient Air Monitoring Conference
16.0 pA fs
Ambient Air – Boiling Point Column
August 10, 2016National Ambient Air Monitoring Conference
16.0 pA fs
3.0 pA fs
Quality Control Check Composition Purpose Frequency Acceptance Criteria
Retention Time Standard
(RTS)
Mixture containing all
target compounds
ideally between 1-5
ppbC
To help assess
retention time shifts
and optimize
processing methods
Twice a month
or weekly
100% of the compounds are
identified correctly in the
multicomponent RTS
Calibration Verification
Standard (CVS)
Mixture of 15 reference
compounds including
Propane and Benzene
used for calibration
To assess the
instrument drift and
ensure continued
instrument calibration
Daily 1) Propane and Benzene %
recoveries within 75% - 125%
and all other calibrants
within 55 - 145%
2) Data must be bracketed
by valid CVS
Method (Analytical) Blank Humidified, clean air To assess system
contribution to the
measurement
Daily 1) All target compounds <
2.0 ppbC
2) TNMHC < 20 ppbC
3) Data must be bracketed
by valid blanks
Precision Check Mixture used for CVS To assess analytical
precision
Weekly Propane and Benzene %RPD <
20% in two consecutive CVS
runs
Laboratory Calibration
Standard (LCS)
Mixture of 15 reference
compounds including
Propane and Benzene
used for calibration
Second source
standard, statically
blended 5 ppbv
Twice a month
or weekly
Propane and Benzene %
recoveries within 70-130%
Network Quality Control
August 10, 2016National Ambient Air Monitoring Conference
Recoveries in Daily Check Standard at 0.5 ppbv
National Ambient Air Monitoring Conference August 10, 2016
0
20
40
60
80
100
120
140
160
180
200
Eth
ane
Eth
yle
ne
Pro
pane
Pro
pyle
ne
Isobuta
ne
n-B
uta
ne
Acety
lene
trans-
2-B
ute
ne
1-B
ute
ne
cis
-2-B
ute
ne
Cyclo
penta
ne
Isopenta
ne
n-P
enta
ne
trans-
2-P
ente
ne
1-P
ente
ne
cis
-2-P
ente
ne
2,2
-Dim
eth
ylb
uta
ne
2,3
-Dim
eth
ylb
uta
ne
2-M
eth
ylp
enta
ne
3-M
eth
ylp
enta
ne
Isopre
ne
1-H
exene
n-H
exane
Meth
ylc
yclo
penta
ne
2,4
-Dim
eth
ylp
enta
ne
Benzene
Cyclo
hexane
2-M
eth
ylh
exane
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exane
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
epta
ne
Meth
ylc
yclo
hexane
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
cta
ne
Eth
ylb
enze
ne
m/p-X
yle
ne
Sty
rene
o-X
yle
ne
n-N
onane
Isopro
pylb
enzene
n-P
ropylb
enzene
m-e
thylt
olu
ene
p-E
thylt
olu
ene
1,3
,5-T
rim
eth
ylb
enzene
o-E
thylt
olu
ene
1,2
,4-T
rim
eth
ylb
enzene
n-D
ecane
1,2
,3-T
rim
eth
ylb
enzene
m-D
ieth
ylb
enze
ne
p-D
ieth
ylb
enzene
n-U
ndecane
n-D
odecane
% R
ecovery
Check Standard % Recovery - C3/C6 Average Response Factor
BP ColumnPLOT Column
Network Quality Control – 25 AutoGC Sites
National Ambient Air Monitoring Conference August 10, 2016
0.00
20.00
40.00
60.00
80.00
100.00
120.00
140.00
160.00
% R
ecovery
Daily CVS Recoveries - 25 AutoGC sites1 week N = 9
0.00
20.00
40.00
60.00
80.00
100.00
120.00
140.00
160.00
% R
ecovery
Weekly LCS Recoveries - 25 AutoGC sites6 weeks N = 7
TCEQ Performance Evaluation AuditFall 2014 - 12 AutoGCs
August 10, 2016National Ambient Air Monitoring Conference
0.0
20.0
40.0
60.0
80.0
100.0
120.0
140.0
160.0
180.0
Eth
ane
Eth
yle
ne
Pro
pan
e
Pro
pyl
ene
Iso
-Bu
tan
e
N-B
uta
ne
Ace
tyle
ne
Tran
s-2
-Bu
ten
e
1-B
ute
ne
Cis
-2-B
ute
ne
Cyc
lop
en
tan
e
Iso
-Pe
nta
ne
N-P
en
tan
e
1,3
-Bu
tad
ien
e
Tran
s-2
-Pe
nte
ne
1-P
ente
ne
Cis
-2-P
en
ten
e
2,2
-Dim
eth
ylb
uta
ne
2-M
eth
ylp
enta
ne
Iso
pre
ne
n-H
exa
ne
Me
thyl
cycl
op
en
tan
e
2,4
-Dim
eth
ylp
enta
ne
Be
nze
ne
Cyc
loh
exa
ne
2-M
eth
ylh
exan
e
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exan
e
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
ep
tan
e
Me
thyl
cycl
oh
exa
ne
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
ctan
e
Eth
ylb
en
zen
e
M&
P-X
ylen
e
Styr
ene
O-X
ylen
e
N-N
on
ane
Iso
pro
pyl
ben
zen
e
n-P
rop
ylb
enze
ne
1,3
,5-T
rim
eth
ylb
enze
ne
1,2
,4-T
rim
eth
ylb
enze
ne
n-D
ecan
e
1,2
,3-T
rim
eth
ylb
enze
ne
pp
bC
Measured ppbC
Average Lab Result
Average Theoretical
BP ColumnPLOT Column
August 10, 2016National Ambient Air Monitoring Conference
AECOM Performance Evaluation AuditsQ2 & Q4 2015 - 13 AutoGCs North Texas Network
0.0
20.0
40.0
60.0
80.0
100.0
120.0
Eth
ane
Eth
yle
ne
Pro
pan
e
Pro
pyl
ene
Iso
-Bu
tan
e
N-B
uta
ne
Ace
tyle
ne
Tran
s-2
-Bu
ten
e
1-B
ute
ne
Cis
-2-B
ute
ne
Cyc
lop
en
tan
e
Iso
-Pe
nta
ne
N-P
en
tan
e
1,3
-Bu
tad
ien
e
Tran
s-2
-Pe
nte
ne
1-P
ente
ne
Cis
-2-P
en
ten
e
2,2
-Dim
eth
ylb
uta
ne
2-M
eth
ylp
enta
ne
Iso
pre
ne
n-H
exa
ne
Me
thyl
cycl
op
en
tan
e
2,4
-Dim
eth
ylp
enta
ne
Be
nze
ne
Cyc
loh
exa
ne
2-M
eth
ylh
exan
e
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exan
e
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
ep
tan
e
Me
thyl
cycl
oh
exa
ne
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
ctan
e
Eth
ylb
en
zen
e
M&
P-X
ylen
e
Styr
ene
O-X
ylen
e
N-N
on
ane
Iso
pro
pyl
ben
zen
e
n-P
rop
ylb
enze
ne
1,3
,5-T
rim
eth
ylb
enze
ne
1,2
,4-T
rim
eth
ylb
enze
ne
n-D
ecan
e
1,2
,3-T
rim
eth
ylb
enze
ne
n-U
nd
eca
ne
pp
bC
Measured ppbC
Average Lab Result
Average Theoretical
BP ColumnPLOT Column
August 10, 2016National Ambient Air Monitoring Conference
AECOM Performance Evaluation AuditsQ2 & Q3 2015 - 7 AutoGCs Houston/Galveston Network
0.0
20.0
40.0
60.0
80.0
100.0
120.0
Eth
ane
Eth
yle
ne
Pro
pan
e
Pro
pyl
ene
Iso
-Bu
tan
e
N-B
uta
ne
Ace
tyle
ne
Tran
s-2
-Bu
ten
e
1-B
ute
ne
Cis
-2-B
ute
ne
Cyc
lop
en
tan
e
Iso
-Pe
nta
ne
N-P
en
tan
e
1,3
-Bu
tad
ien
e
Tran
s-2
-Pe
nte
ne
1-P
ente
ne
Cis
-2-P
en
ten
e
2,2
-Dim
eth
ylb
uta
ne
2-M
eth
ylp
enta
ne
Iso
pre
ne
n-H
exa
ne
Me
thyl
cycl
op
en
tan
e
2,4
-Dim
eth
ylp
enta
ne
Be
nze
ne
Cyc
loh
exa
ne
2-M
ethylhexan
e…
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exan
e
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
ep
tan
e
Me
thyl
cycl
oh
exa
ne
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
ctan
e
Eth
ylb
en
zen
e
M&
P-X
ylen
e
Styr
ene
O-X
ylen
e
N-N
on
ane
Iso
pro
pyl
ben
zen
e (
cum
en
e)
n-P
rop
ylb
enze
ne
1,3
,5-T
rim
eth
ylb
enze
ne
1,2
,4-T
rim
eth
ylb
enze
ne
n-D
ecan
e
1,2
,3-T
rim
eth
ylb
enze
ne
n-U
nd
eca
ne
pp
bC
Measured ppbC
Average Lab Results
Average Theoretical
BP ColumnPLOT Column
August 10, 2016National Ambient Air Monitoring Conference
Normalized Performance Audit Data Fall 2014 - Spring 2015 – 32 AutoGC Sites
0%
20%
40%
60%
80%
100%
120%
140%
Eth
ane
Eth
yle
ne
Pro
pane
Pro
pyle
ne
Iso-B
uta
ne
N-B
uta
ne
Acety
lene
Tra
ns-
2-B
ute
ne
1-B
ute
ne
Cis
-2-B
ute
ne
Cyclo
penta
ne
Iso-P
enta
ne
N-P
enta
ne
1,3
-Buta
die
ne
Tra
ns-
2-P
ente
ne
1-P
ente
ne
Cis
-2-P
ente
ne
2,2
-Dim
eth
ylb
uta
ne
2-M
eth
ylp
enta
ne
Isopre
ne
n-H
exane
Meth
ylc
yclo
penta
ne
2,4
-Dim
eth
ylp
enta
ne
Benzene
Cyclo
hexane
2-M
eth
ylh
exane
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exane
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
epta
ne
Meth
ylc
yclo
hexane
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
cta
ne
Eth
ylb
enzene
M&
P-X
yle
ne
Sty
rene
O-X
yle
ne
N-N
onane
Isopro
pylb
enze
ne
n-P
ropylb
enzene
1,3
,5-T
rim
eth
ylb
enze
ne
1,2
,4-T
rim
eth
ylb
enze
ne
n-D
ecane
1,2
,3-T
rim
eth
ylb
enze
ne
n-U
ndecane
% B
ias
BP ColumnPLOT Column
Network
# of
Sites
Nominal
ppbv
NTC 13 5
EIMS 7 5
TCEQ 12 7
August 10, 2016National Ambient Air Monitoring Conference
Minimum Detection Limits across 34 AutoGC
Systems 40 CFR part 136 Appendix B
Network # of Sites
NTC 13
EIMS 5
TCEQ 11
UT 4
HCPCS 1
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
Eth
ane
Eth
yle
ne
Pro
pan
e
Pro
pyl
ene
Iso
-Bu
tan
e
N-B
uta
ne
Tran
s-2
-Bu
ten
e
1-B
ute
ne
Cis
-2-B
ute
ne
Cyc
lop
en
tan
e
Iso
-Pe
nta
ne
N-P
en
tan
e
Tran
s-2
-Pe
nte
ne
1-P
ente
ne
Cis
-2-P
en
ten
e
2,2
-Dim
eth
ylb
uta
ne
Iso
pre
ne
n-H
exa
ne
Me
thyl
cycl
op
en
tan
e
2,4
-Dim
eth
ylp
enta
ne
Be
nze
ne
Cyc
loh
exa
ne
2-M
eth
ylh
exan
e
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exan
e
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
ep
tan
e
Me
thyl
cycl
oh
exa
ne
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
ctan
e
Eth
ylb
en
zen
e
M&
P-X
ylen
e
Styr
ene
O-X
ylen
e
N-N
on
ane
Iso
pro
pyl
ben
zen
e
n-P
rop
ylb
enze
ne
1,3
,5-T
rim
eth
ylb
enze
ne
1,2
,4-T
rim
eth
ylb
enze
ne
n-D
ecan
e
1,2
,3-T
rim
eth
ylb
enze
ne
pp
bC
BP ColumnPLOT Column
August 10, 2016National Ambient Air Monitoring Conference
Minimum Detection Limits over 10 years on a
Single AutoGC System 40 CFR part 136 Appendix B
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
Eth
ane
Eth
yle
ne
Pro
pan
e
Pro
pyl
ene
Iso
-Bu
tan
e
N-B
uta
ne
Tran
s-2
-Bu
ten
e
1-B
ute
ne
Cis
-2-B
ute
ne
Cyc
lop
en
tan
e
Iso
-Pe
nta
ne
N-P
en
tan
e
Tran
s-2
-Pe
nte
ne
1-P
ente
ne
Cis
-2-P
en
ten
e
2,2
-Dim
eth
ylb
uta
ne
Iso
pre
ne
n-H
exa
ne
Me
thyl
cycl
op
en
tan
e
2,4
-Dim
eth
ylp
enta
ne
Be
nze
ne
Cyc
loh
exa
ne
2-M
eth
ylh
exan
e
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exan
e
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
ep
tan
e
Me
thyl
cycl
oh
exa
ne
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
ctan
e
Eth
ylb
en
zen
e
M&
P-X
ylen
e
Styr
ene
O-X
ylen
e
N-N
on
ane
Iso
pro
pyl
ben
zen
e
n-P
rop
ylb
enze
ne
1,3
,5-T
rim
eth
ylb
enze
ne
1,2
,4-T
rim
eth
ylb
enze
ne
n-D
ecan
e
1,2
,3-T
rim
eth
ylb
enze
ne
pp
bC
10 Year Average Single Site
Average All Sites
BP ColumnPLOT Column
0.001
0.010
0.100
1.000
10.000
100.000
1000.000
10000.000
Eth
ane
Eth
yle
ne
Pro
pane
Pro
pyle
ne
Isobuta
ne
n-B
uta
ne
Acety
lene
trans-
2-B
ute
ne
1-B
ute
ne
cis
-2-B
ute
ne
Cyclo
penta
ne
Isopenta
ne
n-P
enta
ne
1,3
-Buta
die
ne
trans-
2-P
ente
ne
1-P
ente
ne
cis
-2-P
ente
ne
2,2
-Dim
eth
ylb
uta
ne
2,3
-Dim
eth
ylb
uta
ne
2-M
eth
ylp
enta
ne
3-M
eth
ylp
enta
ne
Isopre
ne
1-H
exene
n-H
exane
Meth
ylc
yclo
penta
ne
2,4
-Dim
eth
ylp
enta
ne
Benzene
Cyclo
hexane
2-M
eth
ylh
exane
2,3
-Dim
eth
ylp
enta
ne
3-M
eth
ylh
exane
2,2
,4-T
rim
eth
ylp
enta
ne
n-H
epta
ne
Meth
ylc
yclo
hexane
2,3
,4-T
rim
eth
ylp
enta
ne
Tolu
ene
2-M
eth
ylh
epta
ne
3-M
eth
ylh
epta
ne
n-O
cta
ne
Eth
ylb
enze
ne
m/p-X
yle
ne
Sty
rene
o-X
yle
ne
n-N
onane
Isopro
pylb
enzene
n-P
ropylb
enzene
m-e
thylt
olu
ene
p-E
thylt
olu
ene
1,3
,5-T
rim
eth
ylb
enzene
o-E
thylt
olu
ene
1,2
,4-T
rim
eth
ylb
enzene
n-D
ecane
1,2
,3-T
rim
eth
ylb
enzene
m-D
ieth
ylb
enze
ne
p-D
ieth
ylb
enzene
n-U
ndecane
n-D
odecane
ppbC
Ambient Data - C3/C6 Average Response Factor
BP ColumnPLOT Column
August 10, 2016National Ambient Air Monitoring Conference
Distribution of Ambient Data 3.5 Months – over 1900 measurements
35% < 1 ppbC
Chromatographic Data System
Capable of identification and quantitation of complex samples
Robust and simple calibration strategy
Output format for easy review of data
Event control for automation of quality control checks
Standard Operating Procedures
Daily operations for consistent data collection
Validation to handle deviations consistently
Data Quality Objectives
Well defined control limits
System for identifying and correcting failures
August 10, 2016National Ambient Air Monitoring Conference
Summary
Requirements for Successful AutoGC
National Ambient Air Monitoring Conference August 10, 2016
“
”
Acknowledgements
“Without data you are just another person with an opinion.” ---W. Edwards Deming
AECOM
Marty Hale
Scott Jenkins
University of Texas Austin
Dr. Dave Sullivan
Texas Commission on Environmental Quality
Cory Chism
Cindy Maresh
Patricia De La Cruz
Melanie Hotchkiss
August 10, 2016National Ambient Air Monitoring Conference
National Ambient Air Monitoring Conference August 10, 2016
Carol J. Meyer
carol@orsat.com
Orsat, LLC
www.orsat.com
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