1. Organics Analyses and Results
Chris Palmer
Department of Chemistry and Biochemistry

3. 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

4. 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

5. Ambient Levoglucosan

6. Levoglucosan Fraction
60-70
50-60

7. Levoglucosan Results

8. Levoglucosan Results

9. 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

10. 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)
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

12. 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

13. 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

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

15. Thiophenes Ambient Concentration (ng/m3)
Saarnio study ug/m3 PM2.5

16. 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?)

17. 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?

18. 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

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

20. 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
ppm from residential burners
Ambient levoglucosan decreased by 50%
Levo

21. 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

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

23. 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

24. 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

25. 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

26. 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