PM_(2.5) source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

摘要

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_(2.5) (particulate matter with an aerodynamic diameter ＜2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_(2.5) mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromato-graphy/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27-38% of PM_(2.5) followed by biomass burning (21-24%) and motor vehicle exhaust (9-24%) at both sites, with 4-6% of PM_(2.5) attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13-23% deficit for PM_(2.5) mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.