Brooks Mason

Evaluation of Commercially Evaluation of Commercially available Passive Samplers for available Passive Samplers for

Pollutant Saturation Pollutant Saturation Monitoring in Wilmington, CAMonitoring in Wilmington, CA

Brooks MasonBrooks Mason

OverviewOverview

What is passive sampling?What is passive sampling? Commercial Passive Sampling Commercial Passive Sampling MediaMedia

Environmental Justice ProjectEnvironmental Justice Project Task I- Chamber EvaluationsTask I- Chamber Evaluations Task II- Pilot StudyTask II- Pilot Study Task III- Harbor Communities Task III- Harbor Communities Monitoring StudyMonitoring Study

What is Passive What is Passive Sampling?Sampling?

Collection of Collection of various chemical various chemical compounds utilizing compounds utilizing adsorbentsadsorbents Chemical adsorbentsChemical adsorbents Physical adsorbentsPhysical adsorbents

Virtually Virtually maintenance freemaintenance free Requires no pumps, Requires no pumps, moving parts, moving parts, electricity, electricity, maintenancemaintenance

Passive Sampling Cont.Passive Sampling Cont.

Time integrated measurementTime integrated measurement High SensitivityHigh Sensitivity Poor ResolutionPoor Resolution

Relies on an experimentally Relies on an experimentally calculated sampling ratecalculated sampling rate

Ogawa & Company Passive Ogawa & Company Passive SamplerSampler

Symmetrical Design Symmetrical Design allows for two allows for two simultaneous simultaneous measurementsmeasurements

Utilizes chemical Utilizes chemical adsorbent Pads for adsorbent Pads for the collection of the collection of NOx, NO2, and SO2NOx, NO2, and SO2 Triethanol AmineTriethanol Amine

Sampling Rate is Sampling Rate is Temperature and Temperature and Humidity DependentHumidity Dependent

Radiello Passive Radiello Passive SamplerSampler

Utilizes a Utilizes a cylindrical cylindrical diffusive body to diffusive body to increase surface increase surface area, sampling area, sampling raterate

AldehydesAldehydes DNPHDNPH

Hydrogen SulfideHydrogen Sulfide Zinc AcetateZinc Acetate

VOCVOC Carbograph 4Carbograph 4

Importance of Chemical Importance of Chemical SpeciesSpecies

Aromatics, 1,3-Aromatics, 1,3-butadiene, and butadiene, and Aldehydes react with Aldehydes react with NOx to produce Ozone NOx to produce Ozone and are hazardous to and are hazardous to human and ecosystem human and ecosystem healthhealth

SO2 emissions produce SO2 emissions produce secondary aerosols and secondary aerosols and contribute to ecosystem contribute to ecosystem acidityacidity

H2S is hazardous to H2S is hazardous to human health and human health and produces a foul odorproduces a foul odor

Environmental Justice Environmental Justice ProjectProject

Eric Fujita, PI; Barbara Zielinska, Co-PI; Dave CampbellEric Fujita, PI; Barbara Zielinska, Co-PI; Dave Campbell Task I (3/06-11/06)Task I (3/06-11/06)

Evaluate Passive monitors for NOx, H2S, BTEX, Evaluate Passive monitors for NOx, H2S, BTEX, 1,3-butadiene, formaldehyde, acetaldehyde, 1,3-butadiene, formaldehyde, acetaldehyde, acrolein in a controlled atmospheric chamberacrolein in a controlled atmospheric chamber

Task II (8/06)Task II (8/06) Evaluate Passive monitors for NOx, H2S, BTEX, Evaluate Passive monitors for NOx, H2S, BTEX, 1,3-butadiene, formaldehyde, acetaldehyde, 1,3-butadiene, formaldehyde, acetaldehyde, acrolein in the study area (Wilmington, CA)acrolein in the study area (Wilmington, CA)

Task III (2/07-11/07)Task III (2/07-11/07) Harbor Communities Monitoring StudyHarbor Communities Monitoring Study

25 Sites25 Sites Other measurements include minivol particulate Other measurements include minivol particulate sampling, photoaccousitic black carbon analyzers, sampling, photoaccousitic black carbon analyzers, dusttrak, qtrak, PID, basic meteorological, dusttrak, qtrak, PID, basic meteorological, quality assurancequality assurance

Task I - expTask I - exp

Sampling Ports

Temp/RH

Aldehyde Samplers

Fan

Task I - expTask I - exp

Sampler Type Analyte Conc. Validation Analysis Method

Ogawa NO2 NO2 25 ppb Horriba NO/NOx Analyzer Colorimetry for Nitrite

Ogawa NOx NOx 54 ppb Horriba NO/NOx Analyzer Colorimetry for Nitrite

Radiello Aldehyde Formaldehyde 5 ppb Waters DNPH/HPLC HPLC/UV

Radiello Aldehyde Formaldehyde 5 ppb Waters DNPH/HPLC HPLC/UV

Radiello Aldehyde Acrolein 2 ppb Waters DNPH/HPLC HPLC/UV

Radiello VOC BTEX 2 ppb Canister GC/MS TD/GC/MS

Radiello VOC 1,3-Butadiene 2 ppb Canister GC/MS TD/GC/MS

Radiello H2S H2S 2 ppb N/A Visible Spectrometry

•Chamber Exposure Information

•7 Day Exposures

•Nominal Concentration based on Wilmington Average

Task I ResultsTask I Results

Species 7d Passive 7d Validation 7d P:V Ratio 7d %RSD

ppbv ppbv

NO 18.26 17.20 106% 3%

NO2 21.49 21.80 99% 1%

HCHO 5.08 5.20 98% 7%

Acrolein 3.19 3.00 106% 10%

H2S 1.989 2.00 99% 2%

*Acrolein Validation Method highly inaccurate

*VOC data is forthcoming due to 1,3 butadiene

Task II expTask II exp•Task II Study Site

•North Long Beach AQMD Station

•August 2006

•Objectives•Evaluate Replicate Precision and Accuracy of Passive Samplers under actual Environmental Conditions

•Evaluate effect of stagnant nightime air on sampling rate

Task II expTask II exp

Passive Passive MeasurementMeasurement Ogawa NOxOgawa NOx Ogawa SO2Ogawa SO2 Radiello H2SRadiello H2S Radiello VOCRadiello VOC Radiello AldehydeRadiello Aldehyde

Validation Validation MethodMethod AQMD NOx BoxAQMD NOx Box AQMD Continuous AQMD Continuous SO2SO2

N/AN/A (7) 24 hour (7) 24 hour CanistersCanisters

(7) 24 hour DNPH(7) 24 hour DNPH

Task II ResultsTask II Results

Ogawa NO2,NOx

Pollutant Average average deviation unit SCAQMD Mean Passive/ SCAQMD

[NO] - No Fan 8.14 0.54 (ppb) 10.8 75%

[NO] - Fan 8.51 0.49 (ppb) 10.8 79%

[NO2] - No Fan 14.12 0.38 (ppb) 17.2 82%

[NO2] - Fan 14.36 0.83 (ppb) 17.2 83%

Ogawa SO2

Pollutant Average average deviation unit SCAQMD Mean Passive/SCAQMD

[SO2] - No Fan 1.39 0.16 (ppb) 1.7 82%

[SO2] - Fan 1.18 0.01 (ppb) 1.7 69%


Radiello H2S

Pollutant Averageaverage

deviation unit SCAQMD

Mean Passive/SCAQMD

[H2S] - No Fan 0.31 0.10 (ppb) na na

[H2S] - Fan 0.26 0.06 (ppb) na na

Radiello Aldehyde


deviation unit DNPH Mean Passive/DNPH

Formaldehyde - No Fan 1.23 0.03 (ppbv) 1.10 112%

Formaldehyde - Fan 1.27 0.09 (ppbv) 1.10 116%

Acetaldehyde - No Fan 0.59 0.01 (ppbv) 1.04 57%

Acetaldehyde - Fan 0.59 0.02 (ppbv) 1.04 57%

total Acrolein - No Fan 0.05 0.01 (ppbv) 0.21 23%

total Acrolein - Fan 0.03 0.01 (ppbv) 0.21 12%


Radiello VOC


deviation unit Canister Mean Canister/DNPH

1,3-Butadiene - No Fan 0.05 0.009 (ppbv) 0.04 128%

1,3-Butadiene - Fan 0.05 0.003 (ppbv) 0.04 129%

Benzene - No Fan 0.29 0.024 (ppbv) 0.37 78%

Benzene- Fan 0.29 0.002 (ppbv) 0.37 79%

Toluene - No Fan 1.31 0.161 (ppbv) 1.09 120%

Toluene - Fan 1.19 0.117 (ppbv) 1.09 110%

Ethylbenzene - No Fan 0.17 0.011 (ppbv) 0.13 125%

Ethylbenzene - Fan 0.18 0.004 (ppbv) 0.13 131%

m,p Xylene - No Fan 0.46 0.029 (ppbv) 0.45 103%

m,p Xylene - Fan 0.49 0.006 (ppbv) 0.45 109%

o Xylene - No Fan 0.18 0.010 (ppbv) 0.18 100%

o Xylene - Fan 0.20 0.004 (ppbv) 0.18 107%

Task III expTask III exp

Harbor Communities Monitoring StudyHarbor Communities Monitoring Study 4 seasonal saturation monitoring 4 seasonal saturation monitoring campaigns for 1 month each, 2007campaigns for 1 month each, 2007

Winter 2/13/07 – 3/13/07 finishedWinter 2/13/07 – 3/13/07 finished 23 sites measure NOx, SO2, VOC, and 23 sites measure NOx, SO2, VOC, and AldehydeAldehyde

6 sites for measurement of NO26 sites for measurement of NO2 3 sites for measurement of H2S3 sites for measurement of H2S 1 QA site with triplicate passive 1 QA site with triplicate passive measurements and validation measurementsmeasurements and validation measurements

DRI Core

DRI Core + continuous

SCAQMD (tentative)

DRI Passive only

Port of Los Angeles

Port of Long Beach

Note: DRI’s sampling locations are preliminary and are subject to change.

Revised 1/16/07

FD13

Res1

OCN

HES

BFL

W710E710

SE

Res4

Res2

Res3

Res5Res6

FD49AQMD

Res11

RES9

E110

Res10

PLAB

Res8

Res7

Task III Initial Task III Initial ResultsResults

Week III VOC QA

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

bud13 benze tolue etbz mp_xyl o_xyl

Concentration (ppbv)

WeekIII Can

WeekIII Radiello


Week IV VOC QA

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

2.00

bud13 benze tolue etbz mp_xyl o_xyl

Concentration (ppbv)

WeekIV Can

WeekIV Radiello


Average VOC Concentration by Site

0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

1a-AQMD H1b-AQMD H1c-AQMD H

4-Sante Fe-PR1

5-Nursery6-Westside7-Berns Forklift

8-710 West9-710 East10-Superior11-LBPW

2-AQMD SW12-Gulf-PR213-Lakeme-PR3

14-Colon-PR415-McDonald-PR6

16-Pioneer-PR817-Marine-PR718-Emden-PR919-110 East

20-Fstreet-PR1021-McFarland-PR5

22-FireStation23-Elberon-PR11

ppbv

o_xyl

mp_xyl

etbz

tolue

benze

bud13


Average H2S Concentration by Site

0.000

0.100

0.200

0.300

0.400

0.500

0.600

0.700

0.800

0.900

1.000

1a-AQMD H 1b-AQMD H 1c-AQMD H18-Emden-PR9 20-Fstreet-PR10

ppbv


VOC, H2S Concentration vs. Week

0.00

0.50

1.00

1.50

2.00

2.50

I II III IV

Week (2/13/07-3/13/07)

bud13

benze

tolue

etbz

mp_xyl

o_xyl

H2S

ConclusionsConclusions Radiello and Ogawa passive samplers Radiello and Ogawa passive samplers have shown throughout all experiments have shown throughout all experiments to be precise, accurate, and sensitive.to be precise, accurate, and sensitive.

Low wind speeds have little effect on Low wind speeds have little effect on the sampling rate for all sampler typesthe sampling rate for all sampler types

Future workFuture work Identify sampling rate for 1,3-butadiene in Identify sampling rate for 1,3-butadiene in chamber exposureschamber exposures

Identify effect of storage time on recoveryIdentify effect of storage time on recovery Develop a method for passive collection of Develop a method for passive collection of aldehydes using PFPH with analysis by aldehydes using PFPH with analysis by thermal desorption GC/MSthermal desorption GC/MS

AcknowledgementsAcknowledgements

• California Air Resources BoardCalifornia Air Resources Board• Thanks to Barbara Zielinska, Thanks to Barbara Zielinska, Eric Fujita, Dave Campbell, Eric Fujita, Dave Campbell, Larry Sheetz, Katy Rempala, Larry Sheetz, Katy Rempala, Anna Cunningham, Mark McDaniel, Anna Cunningham, Mark McDaniel, and Mike Keithand Mike Keith

• Questions?Questions?

Documents

Brooks Mason