[1] The seasonal and spatial variations of source contributions of 112 composite fine particulate matter (PM2.5) samples collected in the Southeastern Aerosol Research and Characterization Study (SEARCH) monitoring network during 2001–2005 using molecular marker-based chemical mass balance (CMB-MM) model were determined. The lowest PM2.5 concentration occurs in January with higher values in warm months (maxima in July at four inland sites versus October at the coastal sites). Sulfate shows a similar pattern and plays a primary role in PM2.5 seasonality. Carbonaceous material (organic matter plus EC) exhibits less seasonality, but more spatial variations between the inland and coastal sites. Compared with the data at coastal sites, source attributions of diesel exhaust, gasoline exhaust, other organic matter (other OM), secondary sulfate, nitrate, and ammonium in PM2.5 mass at inland sites are higher. The difference in source attributions of wood combustion, meat cooking, vegetative detritus, and road dust among the eight sites is not significant. Contributions of eight primary sources to fine OC are wood burning (17 ± 19%), diesel exhaust (9 ± 4%), gasoline exhaust (5 ± 7%), meat cooking (5 ± 5%), road dust (2 ± 3%), vegetative detritus (2 ± 2%), cigarette smoke (2 ± 2% at four urban sites), and coke production (2 ± 1% only at BHM). Primary and secondary sources explain 82–100% of measured PM2.5 mass at the eight sites, including secondary ionic species (SO42−, NH4+, and NO3−; 41.4 ± 5.7%), identified OM (24.9 ± 11.3%), “other OM” (unexplained OM, 23.3 ± 10.3%), and “other mass” (11.4 ± 9.6%). Vehicle exhaust from both diesel and gasoline contributes the lowest fraction to PM2.5 mass in July and higher fractions at BHM and JST than other sites. Wood combustion, in contrast, contributes significantly to a larger fraction in winter than in summer. Road dust shows relatively high levels in July and April across the eight sites, while minor sources such as meat cooking and other sources (e.g., vegetative detritus, coke production, and cigarette smoke) show relatively small seasonal and spatial variations in the SEARCH monitoring network.
[1] Fine particles (PM2.5) were collected using filter-based high-volume samplers during summer-winter 2008 at a rural site in the central Pearl River Delta (PRD), south China, to determine typical secondary organic aerosol (SOA) tracers from significant biogenic (isoprene, monoterpenes, and sesquiterpenes) and anthropogenic (aromatics) precursors. Average isoprene SOA tracers were significantly higher during summer (126 ng m−3) than during fall-winter (25.1 ng m−3), owing largely to the higher isoprene emission and reaction rates in summer. Average monoterpene SOA tracers during summer (11.6 ng m−3) and fall-winter (16.4 ng m−3) showed much less difference compared to isoprene SOA tracers, probably resulting from the counteracting effects of temperature on the precursor emission/tracer formation and on gas/particle partitioning. The concentrations of the aromatics' SOA tracer (2,3-dihydroxy-4-oxopentanoic acid) ranged from 1.70 to 52.0 ng m−3 with an average of 15.1 ng m−3, which was the highest reported in ambient air. The secondary organic carbon (SOC) estimated by the SOA-tracer method averaged 3.07 μg C m−3 in summer and 2.00 μg C m−3 in fall-winter, contributing 38.4% and 8.7% to OC, respectively. During summer, aromatics-SOC and isoprene-SOC reached 2.25 ± 1.5 μg C m−3 and 0.64 ± 0.7 μg C m−3 and accounted for 76% and 18% of the estimated SOC, respectively, while during fall-winter, aromatics-SOC (1.64 ± 1.4 μg C m−3) was dominant with a share of 79% in total estimated SOC. These results indicated that anthropogenic aromatics were dominant SOC precursors in the highly industrialized and urbanized PRD region. During summer, SOC levels estimated by elemental carbon (EC) tracer method were not only consistent with but also correlated well with those by SOA-tracer method. During fall-winter, however, SOC by SOA-tracer method was only about one third of that by EC-tracer method. Their gaps were significantly correlated with the biomass burning tracer levoglucosan, indicating that input from biomass burning emission with very high ratios of OC/EC during fall-winter would result in an overestimate of SOC by EC-tracer method. Therefore cautions should be taken when estimating SOC by EC-tracer method, especially when biomass burning exhibits significant influences.
Secondary organic aerosol (SOA) in the southeastern US is investigated by analyzing the spatial-temporal distribution of water-soluble organic carbon (WSOC) and other PM2.5 components from 900 archived 24-h Teflon filters collected at 15 urban or rural EPA Federal Reference Method (FRM) network sites throughout 2007. Online measurements of WSOC at an urban/rural-paired site in Georgia in the summer of 2008 are contrasted to the filter data. Based on FRM filters, excluding biomass-burning events (levoglucosan < 50 ng m 3), WSOC and sulfate were highly correlated with PM2.5 mass (r2~0.7). Both components comprised a large mass fraction of PM2.5 (13% and 31%, respectively, or ~25% and 50% for WSOM and ammonium sulfate). Sulfate and WSOC both tracked ambient temperature throughout the year, suggesting the temperature effects were mainly linked to faster photochemistry and/or synoptic meteorology and less due to enhanced biogenic hydrocarbon emissions. FRM WSOC, and to a lesser extent sulfate, were spatially homogeneous throughout the region, yet WSOC was moderately enhanced (27%) in locations of greater predicted isoprene emissions in summer. A Positive Matrix Factorization (PMF) analysis identified two major source types for the summer WSOC; 22% of the WSOC were associated with ammonium sulfate, and 56% of the WSOC were associated with brown carbon and oxalate. A small urban excess of FRM WSOC (10%) was observed in the summer of 2007, however, comparisons of online WSOC measurements at one urban/rural pair (Atlanta/Yorkville) in August 2008 showed substantially greater difference in WSOC (31%) relative to the FRM data, suggesting a low bias for urban filters. The measured Atlanta urban excess, combined with the estimated boundary layer heights, gave an estimated Atlanta daily WSOC production rate in August of 0.55 mgC m 2 h 1 between mid-morning and mid-afternoon. This study characterizes the regional nature of fine particles in the southeastern US, confirming the importance of SOA and the roles of both biogenic and anthropogenic emissions.