Organics Analyses and Results Chris Palmer Department of Chemistry and Biochemistry

Organic Components of PM2.5 Combustion and pyrolysis products e.g. Levoglucosan - wood combustion Information rich Several source profiles available Autos, diesel, coal, etc. Not necessarily consistent Specific markers

Levoglucosan Analyses Total of 229 filters from four sites over 2 seasons (08-09 and 09-10) Levoglucosan is a well recognized marker for wood combustion

Ambient Levoglucosan

Levoglucosan Fraction 60-70 50-60

Levoglucosan Results

Levoglucosan Results

Sulfate Secondary sulfate is 10-20% of PM2.5 mass CMB does not identify a source for SO4 Woodsmoke (residential wood burning) 50% to 80% of PM2.5 mass Libby study shows relatively low sulfate What are other possible sources? Diesel transportation (low sulfur diesel) Residential oil burners Coal combustion

Organics Analysis Originally 8 samples (and one blank) from State Building Nov. 09 – Feb 10 16-54 μg/m3 PM2.5 Additional 25 samples (and one blank) analyzed Samples recommended by Robert Crawford (met data) 3.1-43.7 μg/m3 PM2.5 11/09 – 3/10 Omni Samples for fossil fuel burners sent for analysis DRI Analyses Hopanes and Steranes – 23 compounds representative of fossil fuel combustion: Original 8 filters plus OMNI samples PAHs – 94 compounds representative of combustion processes PAH analysis includes sulfur compounds dibenzothiophene and benzonaphthothiophene

Hopanes and Steranes Present in Fairbanks PM2.5 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 Omni results indicate high levels from certain coal combustion systems relative to residential oil Analysis of these results not complete

Dibenzothiophene Concentration in fuels (ppm) Dibenzothiophene (ppm) Fuel #1 15.5 Fuel #2 441 Waste Fuel 11.5 LSDF* 15.2 HSDF* 84.0 Not detected in Fairbanks coal

Thiophenes Fraction of PM2.5 (ppm) Recent results show much lower, but still significant, levels of thiophenes

Thiophenes Ambient Concentration (ng/m3) Saarnio study 11-30 ug/m3 PM2.5

Omni Results Neither thiophene detected in single experiments with fuel oils and waste oil Both thiophenes found in coal PM, but at much lower levels (1/100) than PAHs Inconsistent ratio of DBT/BNT (temperature?)

Thiophenes Summary Relatively high levels in Fairbanks PM, ambient air, and #2 fuel oil Implication that residential oil burners burning #2 fuel oil contribute to PM2.5 Thiophenes not detected in OMNI fuel oil studies Little or no data located on thiophenes in coal or coal combustion emissions. OMNI studies show low but detectable levels Fairbanks thiophene levels can not be explained by coal Do power plants supplement coal with #2 fuel oil? Are Omni studies representative of Fairbanks conditions?

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

Picene in Omni Studies Not detected in fuel oil emissions Detected at significant levels in most coal emissions

Picene Picene detected 31 of 33 Fairbanks samples Median 27.6 ppm, Maximum 69.3 ppm Results consistent between original and recent samples Zhang study in China 0-3.7 ppm from industrial boilers 72-284 ppm from residential burners Ambient levoglucosan decreased by 50% Levo

Picene Ambient concentration (ng/m3) Dehydroabietic acid increased by 51% during the first year of the changeout, and then returned to pre-changeout levels in the second year of the study Abietic acid increased by 35% over the entire study period Both resin acids did not consistently increase during the study Mingo Junction: 3.3 μg OC/m3; 3 to 10% of OC from coal combustion Faribanks averages ~12-15 μg OC/m3

Coal Analysis Fairbanks Coal ICP AES analysis for 30 elements Sulfur Content 1000-1200 ppm Arsenic, Strontium, etc. included No thiophenes detected

Retene Typically associated with wood smoke but also reported in coal combustion emissions Fairbanks PM Retene to Picene ratio 1.5 ± 0.5 Fairbanks levels similar to those reported for commercial coal boilers Omni results show signficant retene levels in coal emissions Retene to Picene ratio 0.03-0.4

Other PAHs Omni results for coal stoves 0.44 ± 0.02 Ratio of indeno[123-cd]pyrene to indeno[123-cd]pyrene + benzo[ghi]perylene Omni results for coal stoves 0.44 ± 0.02 Source IP/(IP+BghiP) Gasoline autos 0.18 Diesel autos 0.37 Coal combustion 0.56 Wood combustion 0.54 Fairbanks PM2.5 0.32 ± 0.07

Summary Levoglucosan continues to show relatively consistent >60% WS contribution Sulfur levels in coal and #2 fuel oil suggest these as sources Organic speciation results indicate substantial contributions from fossil fuel combustion Picene results strongly implicate coal combustion Suboptimal conditions: Residential burners give high picene Approximately 10% of OC could be from commercial coal burners Thiophene results may implicate fuel oil #2 but coal combustion may well contribute Ratio indicators implicate coal and wood combustion, mixed with residential oil or transportation sources

Further Study Reliable organic speciation for representative Fairbanks sources Study and comparison of OMNI PAH and Hopane/Sterane patterns to Fairbanks PM Preliminary efforts reveal no pattern similarities More volatile PAH are not present in Omni samples Correlation with Meteorological Parameters