Gregory R. Carmichael Department of Chemical & Biochemical Engineering

1. Recent Advances in Chemical Weather Forecasting in Support of Atmospheric Chemistry Field Experiments Gregory R. Carmichael Department of Chemical & Biochemical Engineering Center for Global & Regional Environmental Research and the University of Iowa

3. Models are an Integral Part of Field Experiments • Flight planning • Provide 4-Dimensional context of the observations • Facilitate the integration of the different measurement platforms • Evaluate processes (e.g., role of biomass burning, heterogeneous chemistry….) • Evaluate emission estimates (bottom-up as well as top-down)

4. Satellite data in near-real time: MOPITT TOMS SEAWIFS AVHRR LIS TRACE-P EXECUTION Stratospheric intrusions FLIGHT PLANNING Long-range transport from Europe, N. America, Africa ASIAN OUTFLOW 3D chemical model forecasts: - ECHAM - GEOS-CHEM - Iowa/Kyushu - Meso-NH Boundary layer chemical/aerosol processing DC-8 P-3 PACIFIC • Emissions • Fossil fuel • Biomass burning • Biosphere, dust ASIA PACIFIC

5. ACE-Asia (NSF) & TRACE-P (NASA) Spring 2001 Experiments NASA/GTE DC-8

6. Ace-Asia April/May 2001

8. NASA GTE TRACE-P Mar’01-Apr’01 • Two aircrafts – DC8 and P3 • Chemical evolution during continental outflow, biomass burning, dust outbreaks, and urban plumes • 22 flights out of Hong Kong, Okinawa and Tokyo • O3, CO, SOx, NOx, HOx, RH and J • 100m to 12000m China

10. Model OverviewRegional Transport Model: STEM • Structure: Modular (on-line and off-line mode) • Meteorology: RAMS - MM5 - ECMWF - NCEP • Emissions: Anthropogenic, biogenic and natural • Chemical mechanism: SAPRC’99 (Carter,2000) • 93 Species, 225 reactions, explicit VOC treatment • Photolysis: NCAR-TUV 4.1 (30 reactions) • Resolution: Flexible 80km x 80km for regional and 16km x 16km for urban

11. Photochemistry: STEM-TUV Y. Tang (CGRER), 2002

14. Regional Emission Estimates:Anthropogenic Sources Industrial and Power Sector Coal, Fuel Oil, NG SO2, NOx, VOC, and Toxics Domestic Sector Coal, Biofuels, NG/LPG SO2, CO, and VOC Transportation Sector Gasoline, Diesel, CNG/LPG NOx, and VOC

15. Regional Emission Estimates:Natural Sources Biomass Burning In-field and Out-field combustion CO, NOx, VOC, and SPM Volcanoes SO2, and SPM Dust Outbreaks SPM

16. The Emissions Vary Greatly by Region – Reflecting Many Social/Economic Factors

17. The TRACE-P/Ace-Asia emission inventory shows the important sources of each type of air pollutant in Asia

18. For Southeast Asia and Indian Sub-Continent Original Fire Count(FC) data(AVHRR) 5-day Fire Count Moving Averaged Fire Count data (Level 2) “Fill-up” Zero Fire Counts using Moving Average(MA) Satellite Coverage Cloudiness Precipitation(NCEP) “Fill-up” Zero Fire Count using TOMS AI Mask Grid (Landcover) Mask Grid (Never Fire) “Extinguish” Fire Count using Mask Grids AI Adjusted Fire Count data (Level 3) Regress. Coeff.(AI/FC) Regional Emission Estimates:Biomass Burning Emissions

19. Open Burning Emissions of CO – Based on AVHRR Fire-count Data

20. Comparison of country surveys with various AVHRR fire-count adjustments reveals problem areas for further investigation Xinjiang Mongolia fire count > country surveys India fire count < country surveys Vietnam Indonesia It remains difficult to make the link between satellite observations of fire and atmospheric emissions

22. The Importance of Fossil, Biofuels and Open Burning Varies by Region

23. Uncertainty analysis has revealed wide differencesin our knowledge of the emissions of particularspecies in particular parts of Asia …

24. March 9 --forecast 3/9 Example of Forecast Used in Flight Planning

25. Propane data from Blake et al.

27. Frontal outflow of biomass burning plumes E of Hong Kong Biomass burning CO forecast (G.R. Carmichael, U. Iowa) Observed CO (G.W. Sachse, NASA/LaRC) Observed aerosol potassium (R. Weber, Georgia Tech)

28. DC8 #8 (2:30-3:30 GMT)

29. Using Measurements and Model – We Estimate Contributions of Fossil, Biofuel and Open Burning Sources

30. Testing Model:CO under-prediction under 1000m for TRACE-P ---WHY? What doe this tell us ? CO data from Sacshe

31. Back Trajectories from High CO point. --- CO > 700 --- CO > 600 --- CO > 500 --- CO > 450 --- CO > 400

32. Back Trajectories from High CO point(Zoom & CO > 500 ppbv) --- CO > 700 --- CO > 600 --- CO > 500

33. Urban PhotochemistryOH Radical Cycle VOC + OH ---> Orgainic PM PM2.5 SOx [or NOx] + NH3 + OH ---> (NH4)2SO4 [or NH4NO3] Ozone Visibility Fine PM (Nitrate, Sulfate, Organic PM) .OH NOx + VOC + OH + hv ---> O3 Acid Rain Water Quality SO2 + OH ---> H2SO4 NOx + SOx + OH (Lake Acidification, Eutrophication) NO2 + OH ---> HNO3 Air Toxics OH <---> Air Toxics (POPs, Hg(II), etc.)

34. Urban/Regional Photochemistry • Tropospheric chemistry is characterized by reaction cycles • OH plays a key role in tropospheric chemistry • Reactions lead to removal as well as generation of pollutants • NOx to VOC ratio governs Ozone production

35. Urban/Regional PhotochemistryNOx-VOC-Ozone Cycle • Organic radical production and photolysis of NO2 • VOC’s and N-species compete for OH radical

36. Urban/Regional PhotochemistryNOx-VOC-Ozone Cycle • In polluted environment, CO contributes to O3 production

37. Urban/Regional PhotochemistryNOx-VOC-Ozone Cycle • HCHO – primary intermediate in VOC-HOx chemistry • Short lived and indicator of primary VOC emissions

39. Comparison of Observed and Modeled OH Provides a Direct Check on Models

40. Characterization of Urban PollutionFlight DC8-13 : 03/21/2001 Flight Path Back Traj. % Urban HCHO • 1000 ppbv of CO, 10 ppbv of HCHO, 100 ppbv of O3 • Fresh plumes out of Shanghai, < 0.5 day in age

41. We run back-trajectories from each 5 minute leg of merge data set. Keep track of each time a trajectory passes in the grid cell of the city and below 2 km. Classification of trajectory by the Source of Megacity. Age as determined by trajectory is also shown Before Big difference !!! We catch more number of fresh airmass from Shanghai and Seoul.

42. Comparing Modeled and Measured Ratios We extract all points associated with a specified city and plot measured ratios and plot modeled ratios.

43. Comparison of Modeled and Observed Results from China’s Mega Cities

44. Urban Photochemistry HCHO to CO Ratios Age in days calculated from back trajectories along the flight path Units: ppbv-HCHO/ ppbv-CO

45. Ratio Analysis by Back trajectory region category. (1) Only from 01-05GMT Japan Central China (Shanghai etc) ΔO3/ΔNOz

46. Urban Photochemistry NOx-VOC Sensitivity to O3 Production Less than 2 day old plumes VOC sensitive Model results along the flight path Megacity points from back trajectories Loss(N)/(Loss(N)+Loss(R)) NOx sensitive Model NOx (ppbv) Klienman et al., 2000

47. These Results Also Have Air Quality Management Implications

48. Rishiri DUST[μg/m3] Lev =10,30,60,90,120,150,180,210 10 227 8 8 8 6 6 6 Height[km] Height[km] Height[km] 4 4 4 2 2 2 E90 E120 E150 SO4 [μg/m3] Lev =1,3,6,9,12,15,18,21 1 21.2 0 0 0 Rishiri Tarukawa Sado Harbin Beijing Tsukuba BC[μg/m3] Lev =0.1,0.24,0.36,0.48,0.6,0.72,0.84,0.96,1.08 0.1 1.15 Hachijo N30 Qingdao ：BC+OC ：DUST OC[μg/m3] 0.1 3.48 Lev =0.1,0.4,0.8,1.2,1.6,2.0,2.4,2.8,3.2 Shanghai ：Sea salt 8 Ogasawara 6 Height[km] Nagasaki & Fukue 4 2 ：Sulfate 0 Okinawa Fukuoka Amami AOD E.Q. APRIL

49. Fly here to sample high O3

50. Analysis Framework Climate : Air Quality