1. Organic Carbon Aerosol in the Free Troposphere: Insights from ACE-Asia and ICARTT Fall AGU December 8, 2005 Colette L. Heald, Daniel J. Jacob, Rokjin J. Park, Solène Turquety, Rynda C. Hudman Rodney J. Weber, Rick Peltier, Amy Sullivan, Lynn M. Russell, Barry J. Huebert, John H. Seinfeld, Hong Liao Acknowledgements: NOAA-OGP, EPA-STAR, NSF-ATM

2. ORGANIC CARBON AEROSOL Reactive Organic Gases Oxidation by OH, O 3, NO 3 Direct Emission Fossil Fuel Biomass Burning Monoterpenes Nucleation or Condensation Aromatics ANTHROPOGENIC SOURCESBIOGENIC SOURCES OC FF: 45-80 TgC/yr BB: 10-30 TgC/yr Secondary Organic Aerosol (SOA): 8-40 TgC/yr *Numbers from IPCC [2001] Global Model Representation of SOA: 1.“Effective primary” yield 2.Two-product empirical fit to smog chamber data

3. FIRST SUGGESTIONS OF HIGH ORGANIC CARBON AEROSOL CONCENTRATIONS IN THE FREE TROPOSPHERE Single particles over NA [Murphy et al., Science, 1998] High organic loading in the UT TARFOX (E US) [Novakov et al., JGR, 1998] High organic loading in the FT

4. ACE-ASIA: OC AEROSOL MEASUREMENTS IN THE FREE TROPOSPHERE Mean Observations Mean Simulation (GEOS-Chem [Park et al., 2003]) Observations + High Levels of OC were observed in the FT during ACE-Asia by 2 independent measurement techniques. We cannot simulate this OC with current models. Seinfeld group Huebert group Russell group (ACE-Asia aircraft campaign conducted off of Japan during April/May 2001)

5. ACE-ASIA: MODEL REPRODUCES OTHER AEROSOL PROFILES GEOS-Chem simulates both the magnitude and shape of sulfate and EC concentrations throughout the troposphere  what is different about OC? Mean Observations Mean Simulation (GEOS-Chem) Secondary production Scavenging

6. ACE-ASIA: SECONDARY ORGANIC AEROSOL UNDERESTIMATED? Biogenic VOCs (eg. monoterpenes) Reactive Organic Gases Oxidation by OH, O 3, NO 3 Secondary Organic Aerosol Condensation of low vapour pressure ROGs on pre-existing aerosol SOA is a good candidate: condense more easily with colder temperature AND be produced in the FT (escape scavenging) GEOS-CHEM April Biogenic SOA FT observations ~ 4  g/m 3 Simulated biogenic SOA far too small! [Chung and Seinfeld, 2002] mechanism

7. ICARTT: COORDINATED ATMOSPHERIC CHEMISTRY CAMPAIGN OVER EASTERN NORTH AMERICA AND NORTH ATLANTIC IN SUMMER 2004 2004 fire season in North America: worst fire season on record in Alaska Multi-agency, International Collaboration Emissions derived from MODIS hot spots [Turquety et al., in prep] OC emissions from biomass burning were 4 times climatological average! OC: 1.4 TgC MOPITT Observations of CO Transport (July 17-19) [Turquety et al., in prep]

8. UNDERESTIMATE OF OC AEROSOL DURING ICARTT NOAA ITCT-2K4 flight tracks (R. Weber’s PILS instrument aboard) Observations GEOS-Chem Simulation Note: biomass burning plumes were removed OC aerosol underestimate observed over North America as well. SOA WSOMC OMC (=POA+SOA) OMC=organic molecular carbon (=1.4xOC) WS=water soluble (40-80% of total OC, primarily SOA)

9. EMISSIONS OF OC FROM BOREAL FIRES IN ALASKA/YUKON Fires over boreal regions generate enough energy to inject emissions into FT. Following Turquety et al. [in prep], we inject 60% of emissions directly into FT (3-5km) making these emissions a dominant source of OC in the FT. Injection of BB emissions into the FT increases the OC observed in the FT down-wind. However lack of correlation with CO in observations suggests that not all the OC can be attributed to the BB source. ITCT 2K4 OMC Observations (WS only) GEOS-Chem Simulation (with injected emiss) GEOS-Chem Simulation (with emission in BL)

10. INCLUDING ISOPRENE AS A SOURCE OF SOA Recent study: yield of SOA from isoprene is 0.9-3.0%[Kroll et al., 2005]. Isoprene oxidation products have been observed in the particulate phase [Claeys et al., 2004; Matsunaga et al., 2005] Applying smog chamber estimates [Kroll et al., 2005] to isoprene emissions inventories suggests a 50% increase in the SOA source over NA. GEIA Emissions July/August 2004 3% yield = 0.4 Tg SOA 10% yield = 0.8 Tg SOA

11. ISOPRENE SOA SOURCE: COMPARISON WITH OBSERVATIONS GEOS-Chem: 2-product SOA model IMPROVE (July-August 2004) GEOS-Chem: 10%terp+3%isop GEOS-Chem: 10%terp POA: 0.73 SOA: 0.45 POA: 0.73 SOA: 0.75 Isoprene SOA sources improves agreement with IMPROVE surface observations (improves spatial correlation) particularly in the East Observations (WS only) GEOS-Chem (2-product SOA) GEOS-Chem (10% terp SOA) GEOS-Chem (10%terp + 3%isop SOA) POA: 0.73 SOA: 1.16 ITCT-2K4 OMC

12. CLUES FROM CORRELATIONS WITH OTHER ICARTT SPECIES? BL (< 2km) FT (> 2km) Cloud-processing? [Lim et al., 2005] Weak correlation with biogenic tracer in the FT No correlation with aromatic SOA precursor Weak correlation with pollution In the FT No correlation with photochemically- produced O 3 In the FT No correlation with product of isoprene oxidation (Kroll et al. suggest MACR forms SOA) Note: BB plumes removed

13. IS SCAVENGING OF OC AEROSOLS OVERESTIMATED IN MODELS? Hydrophillic aerosols are wet scavenged assuming 100% solubility. Recent analysis of cloud events at Puy de Dome suggest scavenging efficiency of OC may be much lower [Sellegri et al., 2003]. A large decrease in scavenging efficiency increases OMC concentrations throughout the troposphere. To what degree are OC aerosols internally mixed? ITCT 2K4 OMC Observations GEOS-Chem Simulation (with scavenging  =0.14)

14. Chemistry leading to SOA production is not well understood! (And not represented in global models) BUT field observations can provide insights. Conclusions: 1.The large underestimate in OC aerosol concentrations observed during ACE-Asia cannot be explained by an underestimate in primary emissions 2.High OC concentrations in the FT observed during ICARTT can be partially explained by injection of aerosols from boreal fires in Alaska. 3.Including direct production of SOA from isoprene improves the correlation with surface observations during ICARTT. 4.OC concentrations in the FT are sensitive to efficiency of wet loss processes. How internally mixed are OC aerosols? 5.Many, many processes are not included in global models (SOA formation in clouds, polymerization reactions, heterogeneous reactions, etc.). To what degree can models represent OC aerosol concentrations (and the important biosphere-atmosphere feedbacks) using simple parameterizations? ORGANIC CARBON IN THE FT: AN ONGOING QUESTION