1. Eric Edgerton, ARA, Inc. PM Model Performance Workshop Chapel Hill, NC February 10, 2004 SEARCH: Overview of Data for Model Performance Evaluation Photo

2. SEARCH: Southeastern Aerosol Research and Characterization Study Oak Grove (OAK) Centreville (CTR) Pensacola (PNS) Yorkville (YRK) Jefferson Street (JST) North Birmingham (BHM) Gulfport (GFP) Outlying Landing Field #8 (OLF) rural urban suburban

3. SEARCH Objectives  Develop a Particulate Matter Climatology for 8 Sites  Understand Composition and its Variability –Year to Year, Season to Season (1999-2005) –Rural vs. Urban –Coastal vs. Inland  Test, Improve, and Deploy Measurement Methods for Pollutant Gases and Continuous PM Components  Estimate Source Contributions Understand Formation Processes  Provide Comprehensive Data Set for Use in SIP Development  Collaborate with States and Others

4. SEARCH Measurements - Continuous CategoryObservables Temporal Resolution Trace GasesO 3, NO, NO 2, HNO 3, NH x, NOy, CO, SO 2, CO 2 1 min. Fine ParticlesMass, BC, B scat SO 4 2-,NO 3, NH 4 + TC 1 min. or 60 min. (TC) Surface Met. T, RH, BP, WS, WD SR, precip. 1 min.

5. SEARCH Measurements - Discrete CategoryAnalytes Frequency (2000-2005) PM 2.5 MassDaily PM 2.5 SO 4 2-,NO 3 -, NH 4 + OC, EC, Trace Elem. 1/3 PM coarse Mass1/3 PM coarse SO 4 2-,NO 3 -, NH 4 + Trace Elem. 1/6 PM coarse OC, EC1/6 (2 sites) Trace GasNH 3 (started 10/1/03)1/3

6. Need to Benchmark Continuous Data with Filter Data

7. Example of SEARCH Continuous PM Data Validation Process – Raw Scatter

8. Example of SEARCH Continuous PM Data Validation Process – Raw Ratio Cont./Flt.

9. Example of SEARCH Continuous PM Data Validation Process – Adjusted Scatter

10. Example of SEARCH Continuous PM Data Validation Process – Adjusted Time Series

11. Time Series of Hourly SO 4 2- JST – August 2002 0 5 10 15 20 25 8/23/02 0:00 8/23/02 12:00 8/24/02 0:00 8/24/02 12:00 8/25/02 0:00 8/25/02 12:00 8/26/02 0:00 8/26/02 12:00 8/27/02 0:00 8/27/02 12:00 8/28/02 0:00 8/28/02 12:00 8/29/02 0:00 8/29/02 12:00 8/30/02 0:00 8/30/02 12:00 8/31/02 0:00 8/31/02 12:00 9/1/02 0:00 9/1/02 12:00 9/2/02 0:00 9/2/02 12:00 9/3/02 0:00 9/3/02 12:00 9/4/02 0:00 9/4/02 12:00 9/5/02 0:00 9/5/02 12:00 9/6/02 0:00 9/6/02 12:00 9/7/02 0:00 9/7/02 12:00 9/8/02 0:00 ARA SO4PILS SO4 SO4 (ug/m3)

12. Time Series of Hourly NO 3 - JST – August 2002 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 8/23/02 0:00 8/23/02 12:00 8/24/02 0:00 8/24/02 12:00 8/25/02 0:00 8/25/02 12:00 8/26/02 0:00 8/26/02 12:00 8/27/02 0:00 8/27/02 12:00 8/28/02 0:00 8/28/02 12:00 8/29/02 0:00 8/29/02 12:00 8/30/02 0:00 8/30/02 12:00 8/31/02 0:00 8/31/02 12:00 9/1/02 0:00 9/1/02 12:00 9/2/02 0:00 9/2/02 12:00 9/3/02 0:00 9/3/02 12:00 9/4/02 0:00 9/4/02 12:00 9/5/02 0:00 9/5/02 12:00 9/6/02 0:00 9/6/02 12:00 9/7/02 0:00 9/7/02 12:00 9/8/02 0:00 ARA NO3PILS NO3 NO3 (ug/m3)

13. Continuous vs. Filter Data 24-Hr Averages (JST) MAE = median abs. error; MAPE = median abs. % error

14. Filter-based and Continuous PM coarse JST: March-April 2003 (units are µg/m 3 )

15. Filter-based and Continuous PM coarse JST: October 2003 (units are µg/m3)

16. Diurnal CO, NOy, O3 Profiles at Jefferson Street January 2002 (left), August 2002 (right)

17. Diurnal PM 2.5 Profiles at Jefferson Street January 2002 (left), August 2002 (right)

18. SO2 Oxidation Rates

19. 151 86 44 25 55 150 57/53 CFPPs in Vicinity of Yorkville (distances in km)

20. SO2 and NOy 8/20/02 Event

21. SO2 vs. NOy 8/20/02 Event

22. Trajectory and CEM data point to Plant Bowen Plant Bowen CEM Data Bowen

23. SO2 and SO4 8/20/02 Event

24. SO4 vs. SO2, 8/20/02 Event Estimated transit time of 2.8 hours yields conversion rate of 2.5%/hour

25. Mean SO 2 conversion rate by season and time of day

26. Urban vs. Biomass (ER) CO NOy (ppb/ppm) PM2.5 (ug/m3/ppm) TC (ug/m3/ppm) Urban137 (12)38 (9)11(2) Biomass23 (13)220 (60)69 (19) U/B6.00.170.16 Urban data from Jefferson Street, Atlanta, GA SEARCH Site

27. Comparison of ERs with Literature Values

28. Ammonia First Look (4 th Quarter 2003)

29. SEARCH NH 3 Measurements Oak Grove Centreville Pensacola Yorkville Jefferson St. N.Birmingham Gulfport OLF rural urban suburban 24-hour denuder (1/3 day) all sites Starting 10/1/03 Continuous at Yorkville (9/15/03) and Oak Grove (7/1/04)

30. SEARCH NH 3 and %NHy 4 th Quarter 2003 urban- industrial urban-res./ind. rural- forested rural- forested rural- agricultural urban- residential urban- residential suburban

31. Hourly NH 3 and particulate-NH 4 + Yorkville, GA – November 2003

32. Continuous NH 3 vs. Wind Direction Yorkville, GA – November 2003

33. The Smoking Chicken 2 km 1 km Poultry operations within several km of Yorkville (crosshair) line up with NH 3 spikes.

36. Continuous NH 4 + and NO 3 - vs. Wind Direction Yorkville, GA - November 2003

37. Continuous NH 4 + and NO 3 - Oak Grove 11/11/03

38. Comparison of ERs with Literature Values

39. http://www.firedetect.ssd.nesdis.noaa.gov/index.htm HMS Fire and Smoke Summary for 2345 10/21/03 Emissions from Biomass Burning Oak Grove

40. Bsp (m -1 ) WD and B sp for Oak Grove – 10/21/03

41. Comparison of ERs with Literature Values

42. Ammonium Sulfate

43. Continuous PM at Jefferson Street August 16, 2001

44. SO4, xsNH4 and Molar Ratio

45. Background adjusted Molar Ratio

46. Sources of Carbon

47. Emission Ratios for CO2 and NOy JST 11/16-17/01

48. Emission Ratios for PM 2.5, TC and BC JST 11/16-17/01

49. Summary of Observed (ER) CO JST, Atlanta NOyPM2.5TCBC ppb/ppmug/m3-ppm n18 Mean0.1380.1520.088 0.026 s.d.0.0090.0220.015 0.005 CV (%)6.514.517.019.2

50. Simplified Carbon Source Matrix and Applicable Tools

51. Sources of Primary OC in PM 2.5 (F) (F/M ?) (F) (M) (Secondary F/M?)

52. Primary Carbon Speciation Sites SEARCH & EPA-STN STN-Urban STN-Rural STN-Suburban SEARCH-Urban SEARCH Rural SEARCH-Suburban

53. Carbon-14 and OC Data Atlanta, GA (JST) 0 4 8 12 16 20 7/1/20017/4/20017/7/2001 7/10/20017/13/20017/16/20017/19/20017/22/20017/25/20017/28/20017/31/20018/21/2001 11/13/200111/17/200111/18/2001 12/4/200112/5/2001 12/17/200112/20/200112/26/200112/29/2001 1/4/20021/7/2002 1/10/20021/13/20021/16/20021/19/2002 OC (ug/m3) 0 0.2 0.4 0.6 0.8 1 F Modern OCF Modern 0.59 0.62

54. OC Source Matrix Atlanta, GA – January * 2000 Data: Zheng et al., ES&T, 2002. Primary* Secondary Total # Modern 64 <5 61 +/-5 Fossil 36 <5 39 +/-5 # from 14 Cdata

55. OC Source Matrix Atlanta, GA – July 2001 * Zheng et al. Source Apportionment of Fine Particles at Atlanta, GA, AAAR 2002 Primary* Secondary Total # Modern <5 >50 59 +/-5 Fossil 40* <5 41 +/-5 # from 14 C data

56. Five-year Trends

57. Annual Average Speciated PM 2.5

58. PMcoarse at Jefferson Street, GA (Inorganic Species Account for < 50% of Mass)

59. Plant (Carbon) Material in PMcoarse Sample Centreville, AL 3700x

60. PMcoarse Speciation with OC and EC OM= OC*1.4, or OC*1.7, or OC*2.0

61. Continuous NOy, PM 2.5, TEOM PM coarse JST: January 21, 2004

62. FRM versus Best Estimate: Composition Recipes FRM Equivalent –Include Field Blank (0.3 µg/m 3 ) –Use components from Teflon filter (PCM1) and front Quartz filter (PCM3) Best Estimate –Blank correct all components –Add volatile NO3 –Add volatile NH4 (equiv. to NO3) –Add estimated volatile OC (backup Quartz)

63. SEARCH FRM Equivalent and Best Estimate PM 2.5 Composition (percent) Jefferson Street, Atlanta, GA 1999-2002 Average FRM Equivalent mass = 17.7 ug/m 3 Average Best Estimate mass = 19.0 ug/m 3

64. Use Of SEARCH “Best Estimate” Fractions For DV Calculations Future-year PM 2.5 design values are calculated using a combination of observed data and PM modeling results For this analysis, RRFs were calculated based on 1996 and 2010 IAQR modeling results from REMSAD To examine the uncertainties associated with the use of speciation measurements we calculated the 2010 DVs using –FRM base values and fractions –FRM base values and “best estimate” fractions

65. Use of SEARCH “Best Estimate” Fractions For DV Calculations FDVs calculated for all 8 SEARCH sites, with and without assumption that 50% of “other” is PBW associated with nitrates and sulfates Over the four combinations, 2010 FDVs differ by as much as 0.5  gm -3 For example: 11.9 12.3 14.5 16.4 11.8 12.0 14.4 16.1 12.012.113.6Pensacola 12.212.513.8Yorkville 14.614.717.1Atlanta 16.316.618.5Birmingham FRMBEOBSFRM PBW BE PBW

66. Use of SEARCH “Best Estimate” Fractions For DV Calculations Considering the best estimate fraction for each species separately, the largest differences come from nitrate For the Birmingham site: FRMBE Sulfate only16.616.2 Nitrate only16.617.4 Organics only16.6 Black carbon only16.616.5 Other inorganics only16.616.5 Unattributed mass only16.616.0

67. Summary SEARCH network will provide comprehensive PM/trace gas data through 2005 Filter data needed to characterize continuous PM technologies –Data adjustments –Data uncertainty Carbon speciation work underway (primary vs.secondary, Modern vs. Fossil) NH3 measurements begun in the SE –Primary species: high and variable near sources, expect lower and less variable near sinks Combination of continuous PM and Gas measurements shows promise –SO4 neutralization variability –Contributions from biomass burning –gas/particle conversion Differences between FRM Equivalent and Best Estimate are Significant and Need to be Understood –Model Evaluation –FDVs