1. Transport of ozone and reactive nitrogen during INTEX-B Thomas W. Walker M. Sc. thesis defence August 30, 2007 Photo from Environment Canada OMI Tropospheric O 3 column

2. NO x emission O 3 production O 3 transport Trans-Pacific transport of ozone and reactive nitrogen

3. NO x Catalyzes Ozone Production Ozone production efficiency increases with decreasing NO x PN's (PAN, MPAN, PPN, etc...) remove NO x from source regions and redistribute it to remote regions RC(O)OO + NO 2 RC(O)OONO 2

4. DC-8 (red): 10 flights C-130 (blue):12 flights Cessna (green):33 flights IONS (magenta):55 sondes Data Sources and Locations

5. Ozone Intercomparison Cessna in red, C-130 in blue Mean bias of 2.0 ppbv

6. GEOS-Chem version 7-04-10 GEOS-4 meteorological fields 4 o x5 o, 30 vertical levels NO x -O x -hydrocarbon chemistry Modifications to emissions Global CTM description

7. CDIAC scalars (2000-2003)‏ SCIAMACHY scalars (2003-2006)‏ Development of East Asian NO x emissions inventory 6.9 Tg yr -1 10.7 Tg yr -1 10.9 Tg yr -1 +1.6 Tg yr -1 +2.2 Tg yr -1

8. Evaluation of East Asian anthropogenic NO x emissions vs OMI: 14.3% model bias vs SCIAMACHY: 12.9% model bias r 2 > 0.8 against both instruments

9. Campaign average vertical profiles: O 3 11.6 ppbv5.7 ppbv-0.5 ppbv Mean bias, observation to baseline: Increase, relative to 2000 emissions: 3.0%2.8% Aircraft Baseline (2006) ‏ Streets (2000) ‏ No Asia No Lightning

10. Campaign average vertical profiles: NO y Aircraft Baseline (2006) ‏ Streets (2000) ‏ No Asia No Lightning

11. Sonde vertical profiles: O 3 5.4 ppbv9.1 ppbv Mean bias, observation to baseline (below 300 hPa): Aircraft Baseline (2006) ‏ Streets (2000) ‏ No Asia No Lightning

12. Tropospheric O 3 columns

13. Sources of O x production over the Pacific

14. Identifying transport pathways

15. Ozone flux into western Canada

18. Conclusions Remote sensing of trace gases: constrain and evaluate emissions Aircraft observations impacted by Asian anthropogenic emissions (LT) ‏ Lightning emissions (UT) ‏ Gross ozone production in E. Pacific depends on PN transport 35% of E. Pacific PN's originate in Asia >27% of O x production due to Asian PN's Events observed by aircraft Elevated O 3 (>95 ppbv), CO (>150 ppbv), and PAN (> 500 ppbv) ‏ Contributions from Asian emissions are high Flow directed northeastward, >19% from Asia

19. Future Directions Continued evaluation of INTEX-B in situ data Search for events indicative of transport to the Arctic Apply inverse model to constrain sensitivities to Asian source Evaluation of transport pathways using in situ and remote sensing data from ARCTAS

20. This work was supported by the Special Research Opportunity Program of the Natural Science and Engineering Research Council (NSERC) of Canada. Thomas Walker was supported by an NSERC Canadian Graduate Scholarship. The DC-8 and C-130 measurements were supported by NASA and NSF. Special thanks to: Randall Martin Dal's Atmospheric Composition Analysis Group INTEX-B colleagues Lauren Hughes Valerie Gapp

21. References Benkovitz, C. M., M. T. Scholtz, J. Pacyna, L. Tarrason, J. Dignon, E. C. Voldner, P. A. Spiro, J. A. Logan, and T. E. Graedel, Global gridded inventories for anthropogenic emissions of sulfur and nitrogen. JGR. 1996. Duncan, B. N., R. V. Martin, A. C. Staudt, R. Yevich, and J. A. Logan, Interannual and seasonal variability of biomass burning emissions constrained by satellite observations. JGR. 2003. Fu, T.-M., D. J. Jacob, P. I. Palmer, K. Chance, Y. X. Wang, B. Barletta, D. R. Blake, J. C. Stanton, and M. J. Pilling, Space-based formaldehyde measurements as constraints on volatile organic compound emissions in East and South Asia. JGR. 2007. Heald, C. L. et al. Asian outflow and trans-Pacific transport of carbon monoxide and ozone pollution: An integrated satellite, aircraft, and model perspective. JGR. 2003. Hudman, R.C. et al. Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California. JGR. 2004. Lobert, J. M., W. C. Keene, J. A. Logan, and R. Yevich, Global chlorine emissions from biomass burning: The reactive chlorine emissions inventory. JGR. 1999. Logan, J. A., An analysis of ozonesonde data for the troposphere: Recommendations for testing 3-D models and development of a gridded climatology for tropospheric ozone. JGR. 1999. Martin, R. V., et al., Evaluation of space-based constraints on global nitrogen oxide emissions with regional aircraft measurements over and downwind of eastern North America. JGR. 2006. McLinden, C. A., S. C. Olsen, B. J. Hannegan, O. Wild, M. J. Prather, and J. Sundet, Stratospheric Ozone in 3-D Models: A simple chemistry and the cross-tropopause flux. JGR. 2000. Pickering, K. E., Y. Wang, W.-K. Tao, C. Price, and J.-F. Muller, Vertical distributions of lightning NOx for use in regional and global chemical transport models. JGR. 1998. Price, C., and D. Rind, A simple lightning parametrization for calculating global lightning distributions. JGR. 1992. Wang, Y. H., D. J. Jacob, and J. A. Logan, Global simulation of tropospheric Ox-NOxhydrocarbon chemistry 1. Model formulation. JGR. 1998. Yevich, R., and J. A. Logan, An assessment of biofuel use and burning of agricultural waste in the developing world. Global Biogeochem. Cycles. 2003. Yienger, J. J., and H. Levy, II, Empirical model of global soil-biogenic NOx emissions. JGR. 1995. Zhang, Q., et al., NOx emission trends for China, 1995-2004: The view from the ground and the view from space. submitted to JGR., 2007.

22. Extra Slides

23. initiation: O 3 + hv--> O 2 + O( 1 D) ‏ O( 1 D) + M-->O + M H 2 O + O( 1 D) --> 2OH propagation: RH + OH O2 --> RO 2 + H 2 O[1] RO 2 + NO--> RO + NO 2 [2] RO + O 2 --> R'CHO + HO 2 [3] HO 2 + NO--> OH + NO 2 [4] NO 2 + hν O2 --> NO + O 3 termination: HO 2 + HO 2 --> H 2 O 2 + O 2 [5] NO 2 + OH + M--> HNO 3 + M[6] NONO 2 N2O5N2O5 HNO 3 PN NO x NO y

24. SCIAMACHY OMI ENVISAT, launched March 2002 10:00 local overpass time Global coverage in 6 days 30km along track X 60km across track +/- (5x10 14 molec cm -2 + 30%) NO 2 retrieval uncertainty AURA, launched July 2004 13:45 local overpass time Daily global coverage 13km X 24km at best NO 2 columns biased 15-30% low vs column measurements, 20-50% low inferred from ground measurements, and 40% lower than SCIAMACHY over industrial regions

25. OM I GEOS- Chem SCIAMACH Y GEOS- Chem Comparison of simulated and observed tropospheric NO2 columns