monitoring network performance for nmhcs across 35 ...€¦ · monitoring network performance for...

PAMS AutoGC

Monitoring Network Performance for NMHCs

Across 35 Monitors in Texas

Carol J. [email protected]

August 10, 2016National Ambient Air Monitoring Conference

Orsat, LLC

www.orsat.com


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


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


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


Ethane to 1-Hexene

0.5 ppbv PAMS Standard

3.0 pA fs

C6+ Dimethylsiloxane (Boiling Point) Separation


n-Hexane to n-Dodecane

0.5 ppbv PAMS Standard

3.0 pA fs

Analytical Blank


PLOT column

Boiling point column

3.0 pA fs

3.0 pA fs

Ambient Air – PLOT Column


16.0 pA fs

Ambient Air – Boiling Point Column


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


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


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


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



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



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



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


Network

# of

Sites

Nominal

ppbv

NTC 13 5

EIMS 7 5

TCEQ 12 7


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



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


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



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


Summary

Requirements for Successful AutoGC

“

”

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



Carol J. Meyer

[email protected]

Orsat, LLC

www.orsat.com

monitoring network performance for nmhcs across 35 ...€¦ · monitoring network performance for...

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