Evaluation of Commercially available Passive Samplers for Pollutant

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

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

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

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

Ogawa & Company Passive Sampler n n Symmetrical Design allows for two simultaneous measurements Utilizes chemical adsorbent Pads for the collection of NOx, NO 2, and SO 2 n n Triethanol Amine Sampling Rate is Temperature and Humidity Dependent

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

Importance of Chemical Species n n n Aromatics, 1, 3 -butadiene, and Aldehydes react with NOx to produce Ozone and are hazardous to human and ecosystem health SO 2 emissions produce secondary aerosols and contribute to ecosystem acidity H 2 S is hazardous to human health and produces a foul odor

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

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

Task I - exp • Chamber Exposure Information • 7 Day Exposures • Nominal Concentration based on Wilmington Average Sampler Type Analyte Conc. Validation Analysis Method Ogawa NO 2 25 ppb Horriba NO/NOx Analyzer Colorimetry for Nitrite Ogawa NOx 54 ppb Horriba NO/NOx Analyzer Colorimetry for Nitrite Radiello Aldehyde Formaldehyde 5 ppb Waters DNPH/HPLC/UV Radiello Aldehyde Acrolein 2 ppb Waters DNPH/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 H 2 S 2 ppb N/A Visible Spectrometry

Task I Results Species 7 d Passive 7 d Validation 7 d P: V Ratio 7 d %RSD ppbv NO 18. 26 17. 20 106% 3% NO 2 21. 49 21. 80 99% 1% HCHO 5. 08 5. 20 98% 7% Acrolein 3. 19 3. 00 106% 10% H 2 S 1. 989 2. 00 99% 2% *Acrolein Validation Method highly inaccurate *VOC data is forthcoming due to 1, 3 butadiene

Task 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 exp n Passive Measurement n n n Ogawa NOx Ogawa SO 2 Radiello H 2 S Radiello VOC Radiello Aldehyde n Validation Method n n n AQMD NOx Box AQMD Continuous SO 2 N/A (7) 24 hour Canisters (7) 24 hour DNPH

Task II Results Ogawa NO 2, 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% [NO 2] - No Fan 14. 12 0. 38 (ppb) 17. 2 82% [NO 2] - Fan 14. 36 0. 83 (ppb) 17. 2 83% Average average deviation unit SCAQMD Mean Passive/SCAQMD [SO 2] - No Fan 1. 39 0. 16 (ppb) 1. 7 82% [SO 2] - Fan 1. 18 0. 01 (ppb) 1. 7 69% Ogawa SO 2 Pollutant

Task II Results Radiello H 2 S Pollutant Average average deviation unit SCAQMD Mean Passive/SCAQMD [H 2 S] - No Fan 0. 31 0. 10 (ppb) na na [H 2 S] - Fan 0. 26 0. 06 (ppb) na na unit DNPH Mean Passive/DNPH Radiello Aldehyde Pollutant Average average deviation 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%

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. 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 exp n Harbor Communities Monitoring Study 4 seasonal saturation monitoring campaigns for 1 month each, 2007 n Winter 2/13/07 – 3/13/07 finished n 23 sites measure NOx, SO 2, VOC, and Aldehyde n 6 sites for measurement of NO 2 n 3 sites for measurement of H 2 S n 1 QA site with triplicate passive measurements and validation measurements n

DRI Core + continuous Res 1 DRI Passive only SCAQMD (tentative) Port of Los Angeles OCN FD 13 Res 2 HES Res 4 Res 3 Res 6 Res 7 E 110 RES 9 Port of Long Beach Res 5 Res 8 Res 10 W 710 E 710 Revised 1/16/07 BFL SE FD 49 AQMD Res 11 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 n n n 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 n Identify sampling rate for 1, 3 -butadiene in chamber exposures n n 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 Mc. Daniel, and Mike Keith Questions?