1. Organo-Sulfur and Receptor Modeling Status/Challenges Christopher Palmer Department of Chemistry and Biochemistry

2. CMB Summary State Building, 08-09 - Woodsmoke -Sulfate -No specific source identified for sulfate -Additional sulfur

3. Comparison to Libby, MT

4. CMB Summary www.epa.qld.gov.au/environmental_management/air/air_quality_monitoring / State Building 11/8/09–4/7/09 North Pole 1/25/09–4/7/09 RAMS 1/25/09–4/7/09 Peger Road 1/25/09–4/7/09 PM 2.5 Mass ± Std Deviation 25.3±15.318.9±14.38.2±2.116.8±10.3 Sample Days47212326 Ammonium Nitrate 2.1±0.7 8.1% 1.0±0.2 5.1% 0.9±0.1 10.5% 1.5±0.4 8.9% Sulfate 5.1±0.6 20.0% 1.9±0.2 9.8% 1.1±0.1 13.0% 2.8±0.3 16.7% Diesel Exhaust 0.3±0. 1 1.1% 0.2±0.05 0.8% N.D. 1.2±0.5 7.3% Automobile Exhaust 1.7±0.7 6.8% 0.7±0.3 3.7% N.D. 0.7±0.2 3.9% Woodsmoke 16.0±2.3 63.1% 15.0±2.0 79.8% 6.3±0.8 76.0% 10.6±1.6 62.7% Unexplained 0.2 0.8% 0.2 0.8% 0.04 0.5% 0.08 0.5%

5. CMB vs 14 C Date PM 2.5 Mass (μg/m 3 ) % PM 2.5 Resulting from Woodsmoke % Woodsmoke PM 2.5 Identified by CMB Model 12/14/08 39.059.6-71.870.8 12/17/08 34.949.8-60.062.8 12/23/08 47.543.6-52.582.3 12/29/08 66.045.3-54.563.9 1/7/09 63.742.2-50.862.0 1/25/09 26.753.2-64.169.3 2/9/09 12.342.5-51.172.0 2/15/09 29.641.7-50.347.3

6. Sulfate Secondary sulfate is 10-20% of PM 2.5 mass – CMB does not identify a source for SO 4 Woodsmoke (residential wood burning) – 45% ( 14 C) to 80% (CMB) of PM 2.5 mass – Libby study shows relatively low sulfate What are other possible sources? – Diesel transportation (low sulfur diesel) – Residential oil burners – Coal combustion

7. Organic Components of PM 2.5 Combustion and pyrolysis products – e.g. Levoglucosan - wood combustion Information rich Several source profiles available – Autos, diesel, coal, etc. – Not necessarily consistent – General – Suggest specific markers

8. Organics Analysis Eight samples (and one blank) from State Building site – Nov. 09 – Feb 10 – 16-54 ug/m 3 PM 2.5 DRI Analyses – Hopanes and Steranes – 23 compounds representative of fossil fuel combustion (file)file – PAHs – 66 compounds representative of combustion processes (file)file PAH analysis includes sulfur compounds dibenzothiophene and benzonaphthothiophene

9. Hopanes Steranes Fraction of PM 2.5 (ppm) 1. ROB, 2. Diesel, 3. Gasoline, 4. Bit Coal, 5. Fairbanks median

10. Hopanes Steranes Ambient concentration(ng/m 3 ) Zheng study median PM 2.5 13.3 ug/m 3

11. Hopanes Steranes Ratio of 17α (H) 21β (H) hopane to 22R-17α (H), 21β (H) homohopane Gasoline 3.7 Diesel 2.5 Coal – 0.1-2.6 Oros et al. – 4.28-9.19 Zhang et al. Fairbanks is 1.2 ± 0.4 – In the range reported by Oros et al. for coal

12. Hopanes and Steranes Present in Fairbanks PM 2.5 at relatively high levels Very high compared with coal profiles Typical to high compared with diesel vehicle profile Indicates a contribution from fossil fuel sources Not specific to any individual source

13. Thiophenes Fraction of PM 2.5 (ppm)

14. Thiophenes Ambient Concentration (ng/m 3 ) Saarnio study 11-30 ug/m 3 PM 2.5

15. Dibenzothiophene Concentration in fuels (ppm) Fuel Dibenzothiophene (ppm) Fuel #1 34.3 Fuel #2 461 Waste Fuel 21.7 LSDF 3 15.2 HSDF 3 84.0

16. Thiophenes Summary Relatively high levels in Fairbanks PM, ambient air, and #2 fuel oil Indication that residential oil burners burning #2 fuel oil contribute to PM 2.5 Little or no data located on thiophenes in coal or coal combustion emissions.

17. Picene PAH marker for coal combustion emissions – “unique to the organic carbon emissions from coal combustion” (Zhang) Relatively high concentrations from small residential burners (China) Typically low concentrations from commercial boilers – Conflicting published data – Coal type is significant

18. Picene Fraction of PM 2.5 Picene detected in all Fairbanks samples – Median 36.2 ppm, Maximum 69.3 ppm Zhang study in China – 0-3.7 ppm from industrial boilers – 72-284 ppm from residential burners

19. Picene Ambient concentration (ng/m 3 ) Mingo Junction: 3.3 ug OC/m 3 ; 3 to 10% of OC from coal combustion

20. Other PAHs Retene – Typically associated with wood smoke but also reported in coal combustion emissions – Fairbanks levels similar to those reported for commercial coal boilers Ratio of indeno[123-cd]pyrene to indeno[123- cd]pyrene + benzo[ghi]perylene SourceIP/(IP+BghiP) Gasoline autos0.18 Diesel autos0.37 Coal combustion0.56 Wood combustion0.54 Fairbanks PM 2.5 0.39 ± 0.02

21. Summary Organic speciation results indicate substantial contributions from fossil fuel combustion Picene results implicate coal combustion, under suboptimal conditions Thiophene results implicate residential fuel oil but could result from diesel vehicles or coal combustion Ratio indicators implicate coal combustion, residential oil combustion or mixed sources Sulfur may well be from coal or residential oil combustion

22. Further Study Organic speciation for representative Fairbanks sources – Filters from OMNI Full or targeted analysis of filters from other sites – Levoglucosan, picene, thiophenes – Sites differ in potential sources and in sulfate levels Comprehensive apportionment based on organic tracers – Contract with J.J. Schauer et al.?