SEARCH & VISTAS Special Studies RPO National Technical Meeting St. Louis, MO November 5, 2003

Outline SEARCH Overview Data Quality for Continuous PM Carbon Collaboration NH 3 Measurements Biomass Emissions In-Plume Oxidation Rates SO 4 Neutralization Other

SEARCH SouthEastern Aerosol Research and CHaracterization Study Jefferson Street Site (JST) Atlanta, GA Yorkville Site (YRK) Yorkville, GA

Oak Grove Centreville Pensacola Yorkville Jefferson Street North Birmingham Gulfport OLF #8 rural urban suburban SEARCH Network

SEARCH Measurements - Continuous CategoryObservables Temporal Resolution Trace Gases O 3, NO, NO 2, HNO 3, NH x, NOy, CO, SO 2, CO 2 1 min. Fine Particles Mass, BC, B scat SO 4 2-,NO 3, NH 4 + TC <10 min. or 60 min. Surface Met. T, RH, BP, WS, WD SR, precip. 1 min. Hg (2 sites)Hg(0), RGM, TPM60 min.

SEARCH Measurements - Discrete CategoryAnalyte(s) Frequency ( ) PM 2.5 MassDaily PM 2.5 SO 4 2-,NO 3, NH 4 + OC, EC Trace Elements 1/3 PM coarse Mass1/3 PM coarse SO 4 2-,NO 3, NH 4 + Trace Elements 1/6 PM coarse OC, EC1/6 (2 sites) Note: all measurements blank corrected

Comparisons of Continuous and Discrete PM Measurements in SEARCH

SEARCH TEOM Configuration Nafion drier 30C Heavy insulation (thermal shock) Filter change every 3 days

Yorkville TEOM vs. FRM 2002 Median absolute difference = 0.84 ug/m3 Median absolute % difference = 6.8 No seasonality

ARA Continuous SO4 Harvard SO4 analyzer –Denuders to remove SO2 (carbonate) and reduced S gases (C monolith) –Reduction of SO4 to SO2 on hot SS (850+C) –Automated zeroing every 90 minutes –1-minute data acquisition Mean and s.d. each averaging interval

ARA Continuous NO3/NH4 3-channel analyzer for NH4 and NO3 NH4 via oxidation to NO on hot Pt NO3 via reduction to NO on Mo Remove gas phase species with acid/base denuders and C monolith Detection via NO-ozone CL 1-minute data acquisition

Time Series of 24-Hr SO /2/20028/3/20028/4/20028/5/20028/6/20028/7/20028/8/20028/9/2002 8/10/20028/11/20028/12/20028/13/20028/14/20028/15/20028/16/20028/17/20028/18/20028/19/20028/20/20028/21/20028/22/20028/23/20028/24/20028/25/20028/26/20028/27/20028/28/20028/29/20028/30/20028/31/2002 9/1/20029/2/20029/3/20029/4/20029/5/20029/6/20029/7/20029/8/2002 Filter SO4PILS SO4ARA SO4 SO4 (ug/m3)

Time Series of Hourly SO /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)

Continuous vs. Filter SO 4 2- at Yorkville (using CE = 0.82)

Hourly SO 4 2- PILS vs. ARA Continuous Atlanta, GA - August 2002 (using CE = 0.86)

Time Series of 24-hr NH 4 + NH4 (ug/m3)

Time Series of Hourly NH /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 NH4PILS NH4 NH4 (ug/m3)

Scattergram of Hourly NH 4 +

Time Series of 24-hr NO 3 -

Time Series of Hourly NO /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)

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

Ongoing Comparison Work in VISTAS Millbrook Site –R&P 8400S (SO4) vs. HSPH SO4 –R&P 8400N (NO3) vs. ARA NO3 –R&P 5400 (EC) vsAethalometer (BC) –ARA NH4 vs. STN NH4

SEARCH/ARIES Collaboration on Carbonaceous Aerosol Historical Samples ( SEARCH/Improve/STN) –Composite Monthly or Seasonal Quartz Filters –Detailed Speciation (GC/MS) –CMB analysis for major sources Planned Samples ( SEARCH 4 sites/VISTAS 5 –Collect hi-vol samples 4 SEARCH sites, 5 VISTAS sites –Detailed Speciation/CMB and 14 C for Selected Events

Primary Carbon Source Attribution Sample Matrix January -December = 4 one-month composite; one for each quarter 6= 2 six-month composite; summer & winter 3= 2 three-month composite; summer &winter D= 30 daily samples ; July’01 & Jan’02

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

Simplified Organic Carbon Source Matrix Combination of CMB and C-14 data allows calculation of secondary OC by difference.

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

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 > /-5 Fossil 40* <5 41 +/-5 # from 14 C data

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 Continuous at Yorkville (9/15/03) and Oak Grove (1/15/04)

Total Reduced Nitrogen (NH x ) Diagram

Continuous NH 3 vs Denuder NH 3 24 Hour Samples Gaseous NH 3 is deduced by subtracting particulate NH 4 from NH x

NH 3 Time-Series 9/12/03 – 9/30/03 Yorkville, GA SEARCH Site Gaseous NH 3 is deduced by subtracting particulate NH 4 from TRN

HNO 3, NH 3, NH 4 NO 3 Event 9/24/03 – 9/27/03 Yorkville, GA SEARCH Site

1-hour NH x vs. Wind Direction

1.8 km 2.3 km 4.5 km The Smoking Chicken

HMS Fire and Smoke Summary for /21/03 Emissions from Biomass Burning Oak Grove

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

CO and NOy at Oak Grove – 10/21/03

NOy vs. CO Oak Grove Event – 10/21/03

Comparison of ERs with Literature Values

Field Observations of SO2 Oxidation Rates in Coal Fired Power Plant Plumes E. S. Edgerton, B. E. Hartsell, C. J. Waid, ARA, Inc. J. J. Jansen, Southern Company D. Alan Hansen, EPRI AAAR 2003 Anaheim, CA October 22, 2003

SO2 and SO4 8/20/02 Event

Daytime Pattern of Observed Oxidation (n = 28)

Continuous PM at Jefferson Street August 16, 2001

SO4, xsNH4 and Molar Ratio

Background adjusted Molar Ratio

SEARCH/VISTAS Collaboration on Characterization of Meteorology and its Relationships to Fine Particle Mass and Visibility in the VISTAS Region

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