Transcript Document
Photo SEARCH: Overview of Data for Model Performance Evaluation Eric Edgerton, ARA, Inc. PM Model Performance Workshop Chapel Hill, NC February 10, 2004 SEARCH: Southeastern Aerosol Research and Characterization Study rural urban suburban Yorkville (YRK) North Birmingham (BHM) Jefferson Street (JST) Centreville (CTR) Oak Grove (OAK) Outlying Landing Field #8 (OLF) Gulfport (GFP) Pensacola (PNS) 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 SEARCH Measurements - Continuous Category Observables Trace Gases O3, NO, NO2, HNO3, NHx, NOy, CO, SO2, CO2 Fine Particles Mass, BC, Bscat SO42-,NO3, NH4+ TC Surface Met. T, RH, BP, WS, WD SR, precip. Temporal Resolution 1 min. 1 min. or 60 min. (TC) 1 min. SEARCH Measurements - Discrete Frequency Category Analytes (2000-2005) PM2.5 Mass Daily PM2.5 SO42-,NO3-, NH4+ OC, EC, Trace Elem. 1/3 PMcoarse Mass 1/3 PMcoarse SO42-,NO3-, NH4+ Trace Elem. 1/6 PMcoarse OC, EC Trace Gas NH3 (started 10/1/03) 1/6 (2 sites) 1/3 Need to Benchmark Continuous Data with Filter Data Example of SEARCH Continuous PM Data Validation Process – Raw Scatter CONTINUOUS SO4 SO4 vs PCM1 Teflon 10 9 8 7 6 5 4 3 2 1 0 y = 0.59x + 0.31 2 R = 0.78 0 1 2 3 4 5 6 7 PCM1 TEFLON SO4 8 9 10 Example of SEARCH Continuous PM Data Validation Process – Raw Ratio Cont./Flt. Ratio of C-SO4/PCM1 SO4 1/ 1/ 2 2/ 002 1/ 3/ 200 1/ 2 2 4/ 002 1/ 2 5/ 00 1/ 2 2 6/ 002 1/ 2 7/ 00 1/ 2 2 8/ 002 1/ 2 9/ 002 1 10 /20 /1 02 11 /200 /1 2 12 /20 /1 02 /2 00 2 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 Example of SEARCH Continuous PM Data Validation Process – Adjusted Scatter CONTINUOUS SO4 SO4 vs PCM1 Teflon 10 9 8 7 6 5 4 3 2 1 0 y = 1.05x - 0.25 2 R = 0.87 0 1 2 3 4 5 6 7 PCM1 TEFLON SO4 8 9 10 Example of SEARCH Continuous PM Data Validation Process – Adjusted Time Series 20 15 10 5 PCM1 Tef SO4 C-SO4 Dec-02 Nov-02 Oct-02 Sep-02 Aug-02 Jul-02 Jun-02 May-02 Apr-02 Mar-02 Feb-02 0 Jan-02 Mass, ug/m3 C-SO4 and PCM1 Tef SO4 Time-Series Time Series of Hourly SO42JST – August 2002 25 ARA SO4 SO4 (ug/m3) 20 15 10 5 0 PILS SO4 Time Series of Hourly NO3JST – August 2002 3.5 ARA NO3 3.0 NO3 (ug/m3) 2.5 2.0 1.5 1.0 0.5 0.0 PILS NO3 Continuous vs. Filter Data 24-Hr Averages (JST) SO4 (30) Filter Mean 5.59 Mean 5.26 NH4 (19) 1.89 1.70 -10.2 0.29 12.6 NO3 (23) 0.45 0.33 -26.8 0.15 27.7 SO4 (36) Filter Mean 5.82 Mean 6.10 NH4 (32) 2.15 2.10 -2.1 0.20 9.6 NO3 (35) 0.45 0.54 22.0 0.13 34.5 PILS %E MAE MAPE -5.8 0.51 9.9 ARA %E MAE MAPE 4.8 0.43 8.5 MAE = median abs. error; MAPE = median abs. % error / 20 03 3/1 /20 03 0/2 00 3 3/1 3/2 00 3 3/1 6/2 00 3 3/1 9/2 00 3 3/2 2/2 00 3 3/2 5/2 00 3 3/2 8/2 00 3 3/3 1/2 00 3 4/3 /20 03 4/6 /20 03 4/9 /20 03 4/1 2/2 00 3 4/1 5/2 00 3 4/1 8/2 00 3 4/2 1/2 00 3 4/2 4/2 00 3 4/2 7/2 00 3 3/7 /20 03 3/4 3/1 12 9 TEOM PMc PMc Filter-based and Continuous PMcoarse JST: March-April 2003 21 21 Filter PMc TEOM PMc TEOM = 0.909*filter + 0.35 R2 = 0.952 18 18 15 15 6 6 3 3 0 0 0 3 6 (units are µg/m3) 1:1 line 12 9 9 filter PMc 12 15 18 21 Filter-based and Continuous PMcoarse JST: October 2003 18 18 TEOM PMc 1:1 line TEOM = 0.954*filter + 0.23 R2 = 0.959 15 15 12 12 TEOM PMc PMc Filter PMc 9 9 6 6 3 3 0 0 0 10/1/2003 10/4/2003 2 10/7/2003 10/10/2003 10/13/2003 10/16/2003 10/19/2003 10/22/2003 10/25/2003 10/28/2003 (units are µg/m3) 4 6 8 10 filter PMc 12 14 16 18 00 00 00 10 :0 0 11 :0 0 12 :0 0 13 :0 0 14 :0 0 15 :0 0 16 :0 0 17 :0 0 18 :0 0 19 :0 0 20 :0 0 21 :0 0 22 :0 0 23 :0 0 9: 1000 O3 800 80 600 60 400 40 200 20 0 0 NOy, O3 (ppb) . CO 8: 00 00 7: 0 00 NOy 6: 0 00 20 5: 200 00 40 4: 400 00 60 3: 600 00 80 2: 800 00 100 1: O3 CO (ppb) . CO NOy, O3 (ppb) . 1000 0: 00 10 :0 0 11 :0 0 12 :0 0 13 :0 0 14 :0 0 15 :0 0 16 :0 0 17 :0 0 18 :0 0 19 :0 0 20 :0 0 21 :0 0 22 :0 0 23 :0 0 9: 8: 00 00 7: 6: 00 00 5: 4: 00 00 3: 2: 00 00 1: 0: CO (ppb) . Diurnal CO, NOy, O3 Profiles at Jefferson Street January 2002 (left), August 2002 (right) NOy 100 3 3 0 0 9: 00 10 :0 0 11 :0 0 12 :0 0 13 :0 0 14 :0 0 15 :0 0 16 :0 0 17 :0 0 18 :0 0 19 :0 0 20 :0 0 21 :0 0 22 :0 0 23 :0 0 6 8: 00 6 7: 00 12 6: 00 12 5: 00 15 4: 00 15 3: 00 18 2: 00 Conc. (ug/m3) . 18 1: 00 9 OM BC SO4 NH4 NO3 0: 00 9: 00 10 :0 0 11 :0 0 12 :0 0 13 :0 0 14 :0 0 15 :0 0 16 :0 0 17 :0 0 18 :0 0 19 :0 0 20 :0 0 21 :0 0 22 :0 0 23 :0 0 8: 00 7: 00 6: 00 5: 00 4: 00 3: 00 2: 00 1: 00 0: 00 Conc. (ug/m3) . Diurnal PM2.5 Profiles at Jefferson Street January 2002 (left), August 2002 (right) 9 OM BC SO4 NH4 NO3 SO2 Oxidation Rates CFPPs in Vicinity of Yorkville (distances in km) 44 25 86 55 57/53 151 150 SO2 and NOy 8/20/02 Event 70 NOy SO2 60 50 40 30 20 10 0 8/20/2002 0:00 8/20/2002 4:00 8/20/2002 8:00 8/20/2002 12:00 8/20/2002 16:00 8/20/2002 20:00 SO2 vs. NOy 8/20/02 Event 70 SO2 = 4.69*NOy - 19.7 2 R = 0.991 60 SO2 (ppb) 50 40 30 20 10 0 0 5 10 15 NOy (ppb) 20 25 8/1 9/ 0 8/1 1 0: 00 9/ 0 8/1 1 3: 00 9/ 0 8/1 1 6: 00 9/ 8/1 01 9 :0 9/ 0 0 8/1 1 12 :0 9/ 0 0 8/1 1 15 : 9/ 01 00 8/1 18 : 9/ 01 00 8/2 21: 00 0/ 0 8/2 1 0: 00 0/ 0 8/2 1 3: 00 0/ 0 8/2 1 6: 00 0/ 8/2 01 9 :0 0/ 0 0 8/2 1 12 :0 0/ 0 0 8/2 1 15 : 0/ 01 00 8/2 18 : 0/ 01 00 8/2 21: 00 1/ 0 8/2 1 0: 00 1/ 0 8/2 1 3: 00 1/ 0 8/2 1 6: 00 1/ 8/2 01 9 :0 1/ 0 0 8/2 1 12 :0 1/ 0 0 8/2 1 15 : 1/ 01 00 8/2 18 : 1/ 01 00 21 :0 0 Bowen SO2/NOx Ratio (Molar) Plant Bowen CEM Data 6.0 5.5 3-hour average = 4.86 5.0 4.5 4.0 3.5 3.0 Trajectory and CEM data point to Plant Bowen SO2 and SO4 8/20/02 Event 70 5 SO2 SO4 ZERO 60 4 50 SO4 (ppb) SO2 (ppb) 3 40 30 2 20 1 10 0 8/20/2002 0:00 0 8/20/2002 4:00 8/20/2002 8:00 8/20/2002 12:00 8/20/2002 16:00 8/20/2002 20:00 SO4 vs. SO2, 8/20/02 Event 5 SO4 = 0.074*SO2 + 1.09 2 R = 0.982 4 SO4 (ppb) 3 2 1 0 0 10 20 30 40 50 60 SO2 (ppb) Estimated transit time of 2.8 hours yields conversion rate of 2.5%/hour Mean SO2 conversion rate by season and time of day 3 Fall-Winter Spring-Summer Conversion Rate (%) 2.5 2 1.5 1 0.5 0 5:00 7:00 9:00 11:00 13:00 Time Midpoint 15:00 17:00 19:00 Urban vs. Biomass (ER)CO NOy PM2.5 TC (ppb/ppm) (ug/m3/ppm) (ug/m3/ppm) Urban 137 (12) 38 (9) 11(2) Biomass 23 (13) 220 (60) 69 (19) 6.0 0.17 0.16 U/B Urban data from Jefferson Street, Atlanta, GA SEARCH Site Comparison of ERs with Literature Values FUEL NOy (as NO) ER (g/kg CO) SO2 PM2.5 TC* BC* Savannah/Grassland 60 5.4 83 57 3.1 Trop. Forest 15 5.5 88 64 6.4 non-Trop. Forest 28 9 121 78 5.2 Biofuels 27 3.5 92 51 7.6 Ag. Residues 27 4.3 42 36 7.5 This Study (Fires) This Study (Urban)# 28+/-14 147 +/-10 5.0 +/-2/7 195 +/- 54 63 +/- 14 n.d. 33 +/- 8 Andreae and Merlet. Global Geochem Cyclec 15(4):955-966. 2001. (A&M) * A&M TC and BC based on TSP # Based on Jefferson Street, Atlanta, GA SEARCH data 9.6 +/- 2.1 15 +/- 6.1 n.d. Ammonia First Look (4th Quarter 2003) SEARCH NH3 Measurements rural urban N.Birmingham 24-hour denuder (1/3 day) all sites Starting 10/1/03 Yorkville Centreville Oak Grove OLF Gulfport suburban Pensacola Jefferson St. Continuous at Yorkville (9/15/03) and Oak Grove (7/1/04) SEARCH NH3 and %NHy 4th Quarter 2003 3.0 2.5 80 ruralagricultural urbanindustrial NH3 % TRN 64 urban-res./ind. urbanresidential 1.5 ruralforested 1.0 urbanresidential ruralforested 48 % TRN NH3 (ppb) 2.0 suburban 32 16 0.5 0.0 0 BHM CTR JST YRK GFP OAK PNS OLF Hourly NH3 and particulate-NH4+ Yorkville, GA – November 2003 25 NH3 NH4 Conc. (ppb) 20 15 10 5 0 01-Nov-03 04-Nov-03 07-Nov-03 10-Nov-03 13-Nov-03 16-Nov-03 19-Nov-03 22-Nov-03 25-Nov-03 28-Nov-03 Continuous NH3 vs. Wind Direction Yorkville, GA – November 2003 12 300 n 10 250 8 200 6 150 4 100 2 50 0 0 0 18 36 54 72 90 108 126 144 162 180 WD 198 216 234 252 270 288 306 324 342 Count Mean NH3 (ppb) NH3 The Smoking Chicken 2 km 1 km Poultry operations within several km of Yorkville (crosshair) line up with NH3 spikes. Continuous NH4+ and NO3- vs. Wind Direction Yorkville, GA - November 2003 1.8 NO3 NH4 1.5 Conc. (ug/m3) . 1.2 0.9 0.6 0.3 0.0 0 18 36 54 72 90 108 126 144 162 180 198 216 234 252 270 288 306 324 342 Continuous NH4+ and NO3Oak Grove 11/11/03 2.0 NO3 NH4 Conc. (ug/m3) . 1.5 1.0 0.5 0.0 -0.5 11/11/03 0:00 11/11/03 6:00 11/11/03 12:00 11/11/03 18:00 Comparison of ERs with Literature Values FUEL NOy (as NO) ER (g/kg CO) SO2 PM2.5 TC* BC* Savannah/Grassland 60 5.4 83 57 3.1 Trop. Forest 15 5.5 88 64 6.4 non-Trop. Forest 28 9 121 78 5.2 Biofuels 27 3.5 92 51 7.6 Ag. Residues 27 4.3 42 36 7.5 This Study (Fires) This Study (Urban)# 28+/-14 147 +/-10 5.0 +/-2/7 195 +/- 54 63 +/- 14 n.d. 33 +/- 8 Andreae and Merlet. Global Geochem Cyclec 15(4):955-966. 2001. (A&M) * A&M TC and BC based on TSP # Based on Jefferson Street, Atlanta, GA SEARCH data 9.6 +/- 2.1 15 +/- 6.1 n.d. Emissions from Biomass Burning HMS Fire and Smoke Summary for 2345 10/21/03 Oak Grove http://www.firedetect.ssd.nesdis.noaa.gov/index.htm 360 WD and Bsp for Oak Grove – 10/21/03 Bsp 270 7.5E-05 180 5.0E-05 90 2.5E-05 -1) Bsp (m Bsp (m**-1) WDR (deg.) WDR 1.0E-04 0 10/21/03 0:00 0.0E+00 10/21/03 4:00 10/21/03 8:00 10/21/03 12:00 10/21/03 16:00 10/21/03 20:00 Comparison of ERs with Literature Values FUEL NOy (as NO) ER (g/kg CO) SO2 PM2.5 TC* BC* Savannah/Grassland 60 5.4 83 57 3.1 Trop. Forest 15 5.5 88 64 6.4 non-Trop. Forest 28 9 121 78 5.2 Biofuels 27 3.5 92 51 7.6 Ag. Residues 27 4.3 42 36 7.5 This Study (Fires) This Study (Urban)# 28+/-14 147 +/-10 5.0 +/-2/7 195 +/- 54 63 +/- 14 n.d. 33 +/- 8 Andreae and Merlet. Global Geochem Cyclec 15(4):955-966. 2001. (A&M) * A&M TC and BC based on TSP # Based on Jefferson Street, Atlanta, GA SEARCH data 9.6 +/- 2.1 15 +/- 6.1 n.d. Ammonium Sulfate Continuous PM at Jefferson Street August 16, 2001 50 15 SO4 NO3 NH4 PM2.5 SO4, NO3, NH4 (ug/m3) 9 30 6 20 3 10 0 0 8/16/01 0:00 8/16/01 2:00 8/16/01 4:00 8/16/01 6:00 8/16/01 8:00 8/16/01 10:00 8/16/01 12:00 8/16/01 14:00 8/16/01 16:00 8/16/01 18:00 8/16/01 20:00 8/16/01 22:00 PM2.5 (ug/m3) 40 12 SO4, xsNH4 and Molar Ratio 15 2.5 SO4 NH4 Ratio Ammonium sulfate 2.0 9 1.5 6 Ammonium bisulfate 3 0.5 Sulfuric acid 0 8/16/01 0:00 1.0 0.0 8/16/01 2:00 8/16/01 4:00 8/16/01 6:00 8/16/01 8:00 8/16/01 10:00 8/16/01 12:00 8/16/01 14:00 8/16/01 16:00 8/16/01 18:00 8/16/01 20:00 8/16/01 22:00 Molar Ratio SO4, NH4 (ug/m3) 12 Background adjusted Molar Ratio 14 2.5 SO4 adjRatio 12 2.0 1.5 8 adjRatio SO4 (ug/m3) 10 6 1.0 4 0.5 2 0 8/16/01 0:00 0.0 8/16/01 4:00 8/16/01 8:00 8/16/01 12:00 8/16/01 16:00 8/16/01 20:00 Sources of Carbon Emission Ratios for CO2 and NOy JST 11/16-17/01 600 CO2 NOy CO2 = 46.4*CO + 365 R2 = 0.79 CO (ppm), NOy (ppb) 500 400 300 NOy = 0.142*CO - 7.05 R2 = 0.91 200 100 0 0 500 1000 1500 2000 CO (ppb) 2500 3000 3500 Emission Ratios for PM2.5, TC and BC JST 11/16-17/01 120 PM2.5 BC PM2.5 = 0.0156*CO + 49.363 R2 = 0.79 TC 100 Conc. ug/m3 80 60 TC = 0.0093*CO + 12.5 R2 = 0.66 40 20 BC = 0.0025*CO + 0.89 R2 = 0.75 0 0 500 1000 1500 2000 CO (ppb) 2500 3000 3500 Summary of Observed (ER)CO JST, Atlanta NOy ppb/ppm n PM2.5 TC BC ug/m3-ppm ug/m3-ppm ug/m3-ppm 18 18 18 18 Mean 0.138 0.152 0.088 0.026 s.d. 0.009 0.022 0.015 0.005 6.5 14.5 17.0 CV (%) 19.2 Simplified Carbon Source Matrix and Applicable Tools Sources of Primary OC in PM2.5 (F) (M) (F) (F) (M) (M) (F/M ?) (Secondary F/M?) Primary Carbon Speciation Sites SEARCH & EPA-STN STN-Urban STN-Rural STN-Suburban SEARCH-Urban SEARCH Rural SEARCH-Suburban Carbon-14 and OC Data Atlanta, GA (JST) 1 20 OC F Modern 0.8 0.62 0.59 12 0.6 8 0.4 4 0.2 0 0 F Modern OC (ug/m3) 16 OC Source Matrix Atlanta, GA – January Primary* Secondary Total # Modern 64 <5 61 +/-5 Fossil 36 <5 39 +/-5 * 2000 Data: Zheng et al., ES&T, 2002. # from 14Cdata OC Source Matrix Atlanta, GA – July 2001 Primary* Secondary Total # Modern <5 >50 59 +/-5 Fossil 40* <5 41 +/-5 * Zheng et al. Source Apportionment of Fine Particles at Atlanta, GA, AAAR 2002 # from 14C data Five-year Trends JST -5 YRK BHM CTR PNS OLF GFP 1999 2000 2001 2002 2003 1999 2000 2001 2002 2003 1999 2000 2001 2002 2003 1999 2000 2001 2002 2003 1999 2000 2001 2002 2003 1999 2000 2001 2002 2003 1999 2000 2001 2002 2003 1999 2000 2001 2002 2003 ug/m3 Annual Average Speciated PM2.5 25 Other Major Metal Oxides 20 Organic Matter Elemental Carbon Ammonium Nitrate 15 Sulfate PM2.5 10 5 0 OAK PMcoarse at Jefferson Street, GA (Inorganic Species Account for < 50% of Mass) 12 PMcoarse (ug/m3) . 10 8 Other cNH4 cSO4 cNO3 cMMO 6 4 2 0 1999 2000 2001 2002 2003 5-Year mean Plant (Carbon) Material in PMcoarse Sample Centreville, AL 3700x PMcoarse Speciation with OC and EC OM= OC*1.4, or OC*1.7, or OC*2.0 Other 12% Other 19% cMMO 37% cMMO 38% OM1.7 39% OM1.4 33% cNO3 4% cNO3 4% cEC 3% cNH4 1% cSO4 3% cEC 3% Other 5% cMMO 38% OM2.0 46% cNO3 4% cEC 3% cNH4 1% cSO4 3% cNH4 1% cSO4 3% Continuous NOy, PM2.5, TEOM PMcoarse JST: January 21, 2004 240 60 NOy PM2.5 TEOM PMc 50 160 40 120 30 80 20 40 10 0 0:00 0 4:00 8:00 12:00 16:00 20:00 PM2.5, TEOM PMc, ug/m3 NOy, ppb . . 200 FRM versus Best Estimate: Composition Recipes • FRM Equivalent – Include Field Blank (0.3 µg/m3) – 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) SEARCH FRM Equivalent and Best Estimate PM2.5 Composition (percent) Jefferson Street, Atlanta, GA 1999-2002 Average FRM Equivalent mass = 17.7 ug/m3 Average Best Estimate mass = 19.0 ug/m3 1.7% 13.4% 14.7% 25.3% 27.3% 2.7% 2.5% 5.6% 1.1% 34.3% 33.7% 9.6% 9.1% 10.5% 8.5% Use Of SEARCH “Best Estimate” Fractions For DV Calculations • Future-year PM2.5 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 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: OBS FRM BE FRMPBW BEPBW Birmingham 18.5 16.6 16.3 16.4 16.1 Atlanta 17.1 14.7 14.6 14.5 14.4 Yorkville 13.8 12.5 12.2 12.3 12.0 Pensacola 13.6 12.1 12.0 11.9 11.8 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: FRM BE Sulfate only 16.6 16.2 Nitrate only 16.6 17.4 Organics only 16.6 16.6 Black carbon only 16.6 16.5 Other inorganics only 16.6 16.5 Unattributed mass only 16.6 16.0 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