MRPO Data Analysis Update

1. MRPO Data Analysis Update National RPO Technical Workgroup Meeting St. Louis, Nov. 4-6, 2003

2. MRPO Data Analysis Approach • 3-prong attack • Workgroup: State analysts and stakeholder members mine AQS data, examine specific issues (narrow focus) • Contractors: Tackle bigger projects and those requiring specialized expertise • In-house: Direct workgroup, develop new projects, focus on projects requiring more complex tools or analysis

3. Current Workgroup Projects • PM-Coarse: Characterize PM-coarse concentrations across region in terms of annual average, daily peaks, seasonal variation (Sarah Raymond, IDEM) • Continuous Speciation: Analyze continuous NO3, SO4, EC, OC data for diurnal patterns, weekday/weekend differences, EC/OC ratios, correlations with other criteria pollutants (Bill Adamski, WDNR, Sarah Raymond, IDEM) • PM2.5-O3 Relationship: Time series analysis of PM2.5 and O3 to explore how closely these 2 pollutants are linked (Mike Rizzo, R5 EPA)

4. Current Workgroup Projects (cont’d) • Indicator species: Examine O3 dependence on NOx and VOC with MAPPER (Bill Adamski, WDNR) • Monthly-Annual Averages: Develop regression model to predict annual average PM from selected monthly averages (Mike Lebeis, DTE) • Ion balance: Determine if aerosol is neutral, acidic, or basic (Joyce Gentry, MOG)

5. Contractor Projects • Review of Optical Data (ARS) • Analysis of Aircraft Data (Sonoma Tech) • Seney OC Speciation (Jamie Schauer) • Indicator Species, O3/Nox-VOC dependence, and sensitivity of PM to SO4 and NO3 reductions with ISORROPIA and SCAPE2 thermodynamic models (Charlie Blanchard) • Analysis of Recent Haze Data (Betty Pun, AER) • Source Apportionment of IMPROVE Data (DRI/Battelle) • Phase 1: SA of Eastern and Midwestern IMPROVE sites using PMF and UNMIX. Joint MRPO/Marama project, Battelle, completed 2002 • Phase 2: In-depth analysis of 4 sites using PMF, UNMIX, CMB, more species, more trajectory analysis. Focus on 2o sources, especially OC. DRI draft report 9/03.

9. Elevated Concentrations Correspond to PM Events

11. In-House MRPO Projects • GIS: Quantification of transboundary transport by back trajectory analysis • CART: Classification and regression tree analysis for PM forecasting and ozone ‘representativeness’ study • Spatial characterization of PM2.5 in urban areas • Ammonia data review

13. State-by-State Contributions to Class 1 Areas Avg. PM2.5 is the average PM2.5 concentration associated with the endpoints in each state of trajectories that originate at the indicated Class 1 area. Percent mass is calculated as

14. Midwest RPO Monitoring and Data Analysis Activities

15. St. Louis Supersite Continuation of St. Louis Supersite (cofunding by EPA) through June 2004. Comprehensive suite of measurements including criteria gases; continuous SO4, EC/OC, NO3, met; 1/6 day PM10, PM2.5, speciated PM2.5.

16. Organic Carbon Speciation at Seney • Organic carbon makes up about one-third of PM2.5 mass at Seney NWR. • OC on monthly composited filters analyzed for markers of various sources of organic carbon (gasoline- and diesel-fueled vehicles, wood burning, meat cooking, other combustion) • Source apportionment will examine relative importance of anthropogenic and biogenic sources to visibility impairment in this scenic wilderness • Isotope analysis on select species Seney National Wildlife Refuge, one of two Class 1 areas in Midwest RPO

17. Nitrogen Speciation at Bondville, IL • Continuous (15-minute) measurements of particle nitrate, particle sulfate, ammonium, and gaseous nitric acid, sulfur dioxide, nitrous acid, and ammonia • Operating in central, rural Illinois in agricultural area • Supplemented with denuder measurements, IMPROVE, meteorology, photolytic NO2, ozone • Will support thermodynamic models of particle formation and help determine when conditions for particle formation are limited by nitric acid and ammonia.  Particle humidification and collection chamber

19. New Monitoring Projects • Rural ammonia monitoring (with CENRAP) • 1/6 day denuder sampling at 8 sites for one year • Continuous ammonia at Bondville, plus 1 ‘roving’ monitor • Intercomparison of denuder, IC, and photoacoustic NH3 measurements • Denuder measurements include HNO3, SO2, particle NO3, SO4, and NH4

20. Equipment installation completed and sampling started Oct. 2003

22. New Monitoring Projects (cont’d) • Urban organic speciation • 1/6 day or more frequent sampling and analysis at 3 urban sites (Indianapolis, Detroit, Cincinnati) and 1 rural site (Bondville) • Includes drum sampling • Source apportionment of organic species will quantify contribution of vehicles, diesels, and wood-burning to urban and rural OC

24. Spatial and Seasonal Patterns of PM2.5 in Detroit

25. Goals • For both total mass and individual components of PM2.5: • Summarize annual average concentrations and show sites relative to each other; characterize background, upwind, central, and downwind sites. • In the same way, summarize seasonal variations • Determine whether an ‘urban excess’ exists, what species contribute to it, and whether it varies seasonally

26. Data Available • FRM data from 1999-2002 (note that most sites do not meet completeness criteria in early years) • 12 sites total in metro area • Only POC 1 data used • Speciation data from 2001-2003 • 5 sites, 2 shut down and 3 currently operating • Reconstructed mass calculating using IMPROVE algorithm • IMPROVE data for Bondville IL and Livonia IN were averaged for 2001-2002 to represent regional background concentrations. • Note slightly different analytical methods for OC/EC

27. Preliminary Conclusions—FRM Analysis • PM2.5 mass concentrations increase on a gradient from SW to NE through downtown Detroit, then decrease moving away from the city. All sites between Luna Pier (farthest upwind) and Linwood are above the NAAQS. • An ‘outer ring’ of suburban sites (Ann Arbor, Ypsilanti, Oak Park) have lower concentrations, just below the NAAQS. • Dearborn is the highest site, in keeping with its highly industrial location. • All FRM sites exhibit the same seasonal pattern of winter and summer peaks, spring and fall lows. Seasonal differences are generally only about 2 ug/m3. • Year-to-year changes are quite small (about 1 ug) and the relative differences among sites remain the same over the three years of data

28. Preliminary Conclusions—Speciation Data • Organic carbon makes up the biggest fraction of PM2.5 in Detroit (36%), followed closely by sulfate (31%) and nitrate (23%). EC and soil are 4% and 5%, respectively. • Organic carbon, elemental carbon, and soil show the largest changes from site to site. • Each species shows the same SW-NE gradient changes in concentration as does total PM2.5, increasing as you approach the center city, peaking at Dearborn, and decreasing as you move away from the city. • Dearborn has uncharacteristically high soil (2.5x other sites, unusual for PM2.5) and also significantly more OC than other sites

29. Preliminary Conclusions—Speciation Data • Strong seasonal behavior by sulfate (summer peak) and nitrate (winter peak). • Moderate seasonality (summer peak) by OC. • EC and soil show little seasonality. • Use caution comparing IMPROVE data with STN data, especially carbon (but this analysis is based on multiyear averages so differences have less effect)

30. Urban Excess • Annually, urban area contributes no sulfate, 1.6 ug/m3 nitrate, and 4.9 ug/m3 of OC to PM2.5, above regional background concentrations • Seasonally, the excess varies with the mass of the component, except for sulfate and soil. • OC excess is higher in summer and winter, nitrate excess is higher in winter, EC exhibits little seasonal difference • Sulfate excess is actually negative in the summer when sulfate is highest (i.e., the city is acting as a sink for sulfate). Likewise, soil excess is also negative in summer when soil is typically higher than other seasons.