Evaluation of Commercially available Passive Samplers for Pollutant Saturation Monitoring in Wilmington, CA Brooks Mason

Overview What is passive sampling? Commercial Passive Sampling Media Environmental Justice Project Task I- Chamber Evaluations Task II- Pilot Study Task III- Harbor Communities Monitoring Study

What is Passive Sampling? Collection of various chemical compounds utilizing adsorbents Chemical adsorbents Physical adsorbents Virtually maintenance free Requires no pumps, moving parts, electricity, maintenance

Passive Sampling Cont. Time integrated measurement High Sensitivity Poor Resolution Relies on an experimentally calculated sampling rate

Ogawa & Company Passive Sampler Symmetrical Design allows for two simultaneous measurements Utilizes chemical adsorbent Pads for the collection of NOx, NO2, and SO2 Triethanol Amine Sampling Rate is Temperature and Humidity Dependent

Radiello Passive Sampler Utilizes a cylindrical diffusive body to increase surface area, sampling rate Aldehydes DNPH Hydrogen Sulfide Zinc Acetate VOC Carbograph 4

Importance of Chemical Species Aromatics, 1,3-butadiene, and Aldehydes react with NOx to produce Ozone and are hazardous to human and ecosystem health SO2 emissions produce secondary aerosols and contribute to ecosystem acidity H2S is hazardous to human health and produces a foul odor

Environmental Justice Project Eric Fujita, PI; Barbara Zielinska, Co-PI; Dave Campbell Task I (3/06-11/06) Evaluate Passive monitors for NOx, H2S, BTEX, 1,3-butadiene, formaldehyde, acetaldehyde, acrolein in a controlled atmospheric chamber Task II (8/06) Evaluate Passive monitors for NOx, H2S, BTEX, 1,3-butadiene, formaldehyde, acetaldehyde, acrolein in the study area (Wilmington, CA) Task III (2/07-11/07) Harbor Communities Monitoring Study 25 Sites Other measurements include minivol particulate sampling, photoaccousitic black carbon analyzers, dusttrak, qtrak, PID, basic meteorological, quality assurance

Task I - exp Aldehyde Samplers Sampling Ports Fan Temp/RH

Task I - exp Chamber Exposure Information 7 Day Exposures Nominal Concentration based on Wilmington Average Sampler Type Analyte Conc. Validation Analysis Method Ogawa NO2 NO2 25 ppb Horriba NO/NOx Analyzer Colorimetry for Nitrite Ogawa NOx NOx 54 ppb Radiello Aldehyde Formaldehyde 5 ppb Waters DNPH/HPLC HPLC/UV Acrolein 2 ppb Radiello VOC BTEX Canister GC/MS TD/GC/MS 1,3-Butadiene Radiello H2S H2S N/A Visible Spectrometry

Task I Results *Acrolein Validation Method highly inaccurate Species 7d Passive 7d Validation 7d P:V Ratio 7d %RSD   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 10% H2S 1.989 2.00 2% *Acrolein Validation Method highly inaccurate *VOC data is forthcoming due to 1,3 butadiene

Task II exp Task II Study Site Objectives 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 exp Passive Measurement Validation Method Ogawa NOx Ogawa SO2 Radiello H2S Radiello VOC Radiello Aldehyde Validation Method AQMD NOx Box AQMD Continuous SO2 N/A (7) 24 hour Canisters (7) 24 hour DNPH

Task II Results Ogawa NO2,NOx Ogawa SO2 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 79% [NO2] - No Fan 14.12 0.38 17.2 82% [NO2] - Fan 14.36 0.83 83% Ogawa SO2 Passive/SCAQMD [SO2] - No Fan 1.39 0.16 1.7 [SO2] - Fan 1.18 0.01 69%

Task II Results Radiello H2S Radiello Aldehyde Pollutant Average average deviation unit   SCAQMD Mean Passive/SCAQMD [H2S] - No Fan 0.31 0.10 (ppb) na [H2S] - Fan 0.26 0.06 Radiello Aldehyde DNPH Mean Passive/DNPH Formaldehyde - No Fan 1.23 0.03 (ppbv) 1.10 112% Formaldehyde - Fan 1.27 0.09 116% Acetaldehyde - No Fan 0.59 0.01 1.04 57% Acetaldehyde - Fan 0.02 total Acrolein - No Fan 0.05 0.21 23% total Acrolein - Fan 12%

Task II Results Radiello VOC Pollutant Average average deviation unit   Canister Mean Canister/DNPH 1,3-Butadiene - No Fan 0.05 0.009 (ppbv) 0.04 128% 1,3-Butadiene - Fan 0.003 129% Benzene - No Fan 0.29 0.024 0.37 78% Benzene- Fan 0.002 79% Toluene - No Fan 1.31 0.161 1.09 120% Toluene - Fan 1.19 0.117 110% Ethylbenzene - No Fan 0.17 0.011 0.13 125% Ethylbenzene - Fan 0.18 0.004 131% m,p Xylene - No Fan 0.46 0.029 0.45 103% m,p Xylene - Fan 0.49 0.006 109% o Xylene - No Fan 0.010 100% o Xylene - Fan 0.20 107%

Task III exp Harbor Communities Monitoring Study 4 seasonal saturation monitoring campaigns for 1 month each, 2007 Winter 2/13/07 – 3/13/07 finished 23 sites measure NOx, SO2, VOC, and Aldehyde 6 sites for measurement of NO2 3 sites for measurement of H2S 1 QA site with triplicate passive measurements and validation measurements

DRI Core DRI Core + continuous Res1 DRI Passive only SCAQMD (tentative) Port of Los Angeles OCN FD13 Port of Long Beach Res2 HES Res3 Res4 Revised 1/16/07 W710 Res6 Res5 E710 Res7 BFL E110 SE Res8 RES9 Res10 FD49 AQMD Res11 Note: DRI’s sampling locations are preliminary and are subject to change. PLAB

Task III Initial Results

Task III Initial Results

Task III Initial Results

Task III Initial Results

Task III Initial Results

Conclusions Radiello and Ogawa passive samplers have shown throughout all experiments to be precise, accurate, and sensitive. Low wind speeds have little effect on the sampling rate for all sampler types Future work Identify sampling rate for 1,3-butadiene in chamber exposures Identify effect of storage time on recovery Develop a method for passive collection of aldehydes using PFPH with analysis by thermal desorption GC/MS

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