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

2. 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

3. 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

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

5. 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

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

7. 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

8. 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

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

10. 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

11. 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

12. 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

13. 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

14. 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%

15. 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%

16. 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%

17. 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

18. 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

19. Task III Initial Results

20. Task III Initial Results

21. Task III Initial Results

22. Task III Initial Results

23. Task III Initial Results

24. 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

25. 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?