Recent Experiments with the Particle-Into-Liquid Sampler Rodney Weber, Yilin Ma, Amy Sullivan, K. Maxwell-Meier Doug Orsini, Chul Song - Georgia Tech - Outline PILS description. One instrument (PILS-IC), many compounds Highlights from aircraft studies Yosemite National Park (Jeff Collett et al.). Recent results measuring water-soluble OC

Particle-Into-Liquid-Sampler Schematic A method to continuously collect particles into a flowing liquid Vac. Pump Transport Liq. Flow Sample Air Flow: 10 to 20 L/min Steam Generator Drains Sample Water Continuous liquid flow at selectable rate; 30 nl/min to 2 ml/min. Concentrated liquid sample. Fast response time.

PILS-IC Measurements from Aircraft TRACE-P and ACE-ASIA Feb. 24 - April 10, 2001 March 30 - May 6, 2001 C 130 viewed from P3

TRACE-P and ACE-Asia TRACE-P: Feb. 24 - April 10, 2001 ACE-Asia: March 30 - May 6, 2001

Comparisons: Airborne Measurements of Fine Particles - Unique insights from rapid measurements - time Consistently lower concentrations on P3-B C-130: Low Turbulence Inlet P3-B: Standard Diffuser Inlet Ma et al., JGR, 2003

Major Sources of Inorganic Particles Compounds can interact when plumes are mixed KNO3, K2SO4 (NH4)2SO4, NH4NO3 CaCO3, MgCO3 NaCl

TRACE-P: Biomass Burning in Southeast Asia (Thailand) AVHRR Fire Counts For 3/7/01 Modeled BC emissions F10: 3/9/01 From Carmichael, U. Iowa, and Fuelberg, FSU

Characteristics of the Biomass Plume: Aircraft Soundings Urban/ Indust. Pass A Pass B K+ - light absorbing particles, r2 = 0.73 K+ - NO3-, r2 = 0.64 K+ - NH4+, r2 = 0.47 K+ - CO, r2 = 0.61 No correlation with Na+ (0.03) and Ca2+ (0.01)(sea salt and dust) All TRACE-P & ACE-Asia Data: Fine particulate K+ mainly in BB plume, (marker). Ma et al. JGR 2003

Fine Particulate Potassium Spatial Distribution and Relation to PM(fine) “Mass” TRACE-P Latitude > 25°N TRACE-P K+ concentrations K+ dK+/dSO42- High in biomass, low in fossil fuel plumes K+ found throughout TRACE-P experiment (and ACE-Asia) Most polluted plumes had highest fractions of K+/SO42- Biomass/biofuel burning a significant component of spring time Asian emissions

A Large Dust Event During ACE Asia http://daac.gsfc.nasa.gov/CAMPAIGN_DOCS/OCDST/asian_dust.html A Large Dust Event During ACE Asia SeaWiFS April 7/01

Fraction of Carbonate Replaced Reactions Between Acidic Gases and Fine Mineral Dust An accommodation coefficient dependence on RH? CaCO3 + 2HNO3  Ca(NO3)2 + H2O + CO2 CaCO3 + H2SO4 CaSO4 + H2O + CO2 CaCO3 + SO2 . . .  CaSO4 + … Fraction of Carbonate Replaced Inferred from Ion balance (cations-anions) Maxwell-Meier et al. 2004

W. J. Malm – National Park Service Measurements of a Suite of Compounds Is Useful Even in the US On the speciation and measurement of aerosol nitrate in regional aerosols J. L. Collett, T. Lee, X. Yu, and S. M. Kreidenweis Colorado State University W. J. Malm – National Park Service Funding: National Park Service

Similar results in Tokyo - Kondo et al. (PM2.5) NO3- Na+ Cl-

Studies of PM2.5 Water-Soluble Organic Carbon Broad Classification of Organic Compounds 6-minute measurement LOD 0.1 µgC/m3 WSOC is operationally defined as the fraction of OC in water at 0.01 to 0.025 gC/100L that passes through a 0.45 µm filter.

St Louis Midwest Supersite Amy Sullivan, Andrea Clements, Jay Turner, Minsuk Bae, and James Schauer Mean WSOC/OC: June, August, Oct.: 0.64, 0.61, 0.31 At times WSOC may be composed of more aged (oxidized) compounds. “Fresh” plumes are mainly water-insoluble OC. Need to chemically sub-divide the WSOC fraction of OC on-line.

Summary: Pros of Liquid Systems Many compounds detected with single instrument (i.e., ion chromatography) Anions: Cl-, NO2-, NO3-, SO42-, organic acids etc. Cations: Na+, NH4+, K+, Mg2+, Ca2+, (many situations where more than NH4+ important) Generally less susceptible to artifacts than integrated filters. Capable of measuring total (coarse + fine) or fine particles. “Easy” analysis, straight-forward calibrations, quantitative (ion balance). High sensitivity, order of ng/m3 (IC measurement) Amenable to a range of detectors

Summary: Cons of Liquid Systems No (or at least very limited) size resolving capabilities. Must deal with liquids, more complex less robust instrument. Must have a clean source of water. Possible interferences under unique conditions Houston TEXAQS, PILS-IC: not K+, likely an ethanolamine. May have there own set of artifacts.