Contribution of Primary and Secondary Sources to Organic Aerosol and PM2.5 at SEARCH Network Sites

Abstract

Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. Laboratory chamber experiments provide insights into the precursors of SOA, but field data must be used to test the approaches. This study investigates primary and secondary sources of organic carbon (OC) and determines their mass contribution to particulate matter 2.5 µm or less in aerodynamic diameter (PM_2.5) in Southeastern Aerosol Research and Characterization (SEARCH) network samples. Filter samples were taken during 20 24-hr periods between May and August 2005 at SEARCH sites in Atlanta, GA (JST); Birmingham, AL (BHM); Centerville, AL (CTR); and Pensacola, FL (PNS) and analyzed for organic tracers by gas chromatography-mass spectrometry. Contribution to primary OC was made using a chemical mass balance method and to secondary OC using a mass fraction method. Aerosol masses were reconstructed from the contributions of POA, SOA, elemental carbon, inorganic ions (sulfate [SO₄ ^2?], nitrate [NO₃ ^?], ammonium [NH₄ ⁺]), metals, and metal oxides and compared with the measured PM_2.5. From the analysis, OC contributions from seven primary sources and four secondary sources were determined. The major primary sources of carbon were from wood combustion, diesel and gasoline exhaust, and meat cooking; major secondary sources were from isoprene and monoterpenes with minor contributions from toluene and β-caryophyllene SOA. Mass concentrations at the four sites were determined using source-specific organic mass (OM)-to-OC ratios and gave values in the range of 12–42 µg m^?3. Reconstructed masses at three of the sites (JST, CTR, PNS) ranged from 87 to 91% of the measured PM_2.5 mass. The reconstructed mass at the BHM site exceeded the measured mass by approximately 25%. The difference between the reconstructed and measured PM_2.5 mass for nonindustrial areas is consistent with not including aerosol liquid water or other sources of organic aerosol.     

Searching for evidence of acid-catalyzed enhancement of secondary organic aerosol formation using ambient aerosol data

Laboratory experiments suggest that strong acids promote formation of enhanced levels of secondary organic aerosol (SOA), and organic aerosols may contribute to the health impacts of fine PM. We report results from examining hourly speciated fine particle data for evidence of ambient aerosol acidity-catalyzed SOA formation, as indicated by larger increases in the concentrations of organic aerosol mass occurring on days and in locations where more acidic aerosol (lower NH₄⁺/SO₄⁼ molar ratios) exists. Data sets from the southeastern U.S. were examined for which hourly acidity of PM_2.5 aerosols could be estimated, and for which hourly organic carbon (OC) content had been measured simultaneously. Within-day organic aerosol changes during selected periods were statistically related to concurrent aerosol acidity levels estimated from nitrate-corrected ammonium-to-sulfate ratios. Data from the Look Rock, TN, TVA/IMPROVE site for mid-July to mid-August 2004 showed average compositions frequently as acidic as NH₄HSO₄, however, no apparent increases in OC levels with increasing aerosol acidity were observed, even when [OC] changes were compared with time-delayed aerosol acidity estimates. SEARCH network data (2003–2004) for rural Centreville, AL (CTR) and Yorkville, GA (YRK) sites were also examined. Warm-season acidity levels were higher at CTR than at YRK, and daytime levels exceeded those at night at both sites. At the YRK site no consistent positive correlations were found between changes in OC or TC levels and aerosol acidity, even with time lags up to 6 h. Aerosol acidity at this site, however, is relatively low due to nearby agricultural sources of NH₃. In contrast, during selected periods from April to October 2004, at CTR, 6-h lagged OC changes were weakly correlated with daytime, nitrate-corrected NH₄⁺/SO₄⁼ molar ratios, but distinguishing this apparent relationship from meteorological effects on measured OC levels is challenging.     

Source apportionment of airborne particulate matter in Southeast Texas using a source-oriented 3D air quality model

A nested version of the source-oriented externally mixed UCD/CIT model was developed to study the source contributions to airborne particulate matter (PM) during a two-week long air quality episode during the Texas 2000 Air Quality Study (TexAQS 2000). Contributions to primary PM and secondary ammonium sulfate in the Houston–Galveston Bay (HGB) and Beaumont–Port Arthur (BPA) areas were determined.The predicted 24-h elemental carbon (EC), organic compounds (OC), sulfate, ammonium ion and primary PM_2.5 mass are in good agreement with filter-based observations. Predicted concentrations of hourly sulfate, ammonium ion, and primary OC from diesel and gasoline engines and biomass burning organic aerosol (BBOA) at La Porte, Texas agree well with measurements from an Aerodyne Aerosol Mass Spectrometer (AMS).The UCD/CIT model predicts that EC is mainly from diesel engines and majority of the primary OC is from internal combustion engines and industrial sources. Open burning contributes large fractions of EC, OC and primary PM_2.5 mass. Road dust, internal combustion engines and industries are the major sources of primary PM_2.5. Wildfire dominates the contributions to all primary PM components in areas near the fires. The predicted source contributions to primary PM are in general agreement with results from a chemical mass balance (CMB) model. Discrepancy between the two models suggests that further investigations on the industrial PM emissions are necessary.Secondary ammonium sulfate accounts for the majority of the secondary inorganic PM. Over 80% of the secondary sulfate in the 4 km domain is produced in upwind areas. Coal combustion is the largest source of sulfate. Ammonium ion is mainly from agriculture sources and contributions from gasoline vehicles are significant in urban areas.     

Estimations of primary and secondary organic carbon formation in PM2.5 aerosols of Santiago City,Chile

High concentration of fine airborne particulates is considered one of the major environmental pollutants in Santiago, the Chilean Capital city, which in 1997 was declared a PM₁₀ saturated zone. To date there is no control of the amounts of fine and coarse aerosols concentrations and the source and chemical characterizations of the PM_2.5 particulates in the carbonaceous fractions are not well known even though this fraction could be represented almost the 50% in mass of the PM_2.5.In this work, we present for the first time determinations of primary organic aerosol (POA) and secondary organic aerosol composition (SOA) fractions of the total mass of PM_2.5 particulates collected in the urban atmosphere of Santiago City. Our purpose is to know the anthropogenic contributions to the formation of SOA. To accomplish this we used the elemental carbon (EC) and organic carbon (OC) determinations developed by automatic monitoring stations installed in the city during the period 2002–2005, with a particular analysis of the summer time occurred in February 2004. Based on the EC tracer method, we have estimated the POA and SOA fraction and our data permit us to estimate the SOA reaching up to 20% of total organic aerosol matter, in good agreement to other measurements observed in large cities of Europe and U.S.A.     

Insights into the primary–secondary and regional–local contributions to organic aerosol and PM2.5 mass in Pittsburgh,Pennsylvania

This paper presents chemical mass balance (CMB) analysis of organic molecular marker data to investigate the sources of organic aerosol and PM_2.5 mass in Pittsburgh, Pennsylvania. The model accounts for emissions from eight primary source classes, including major anthropogenic sources such as motor vehicles, cooking, and biomass combustion as well as some primary biogenic emissions (leaf abrasion products). We consider uncertainty associated with selection of source profiles, selection of fitting species, sampling artifacts, photochemical aging, and unknown sources. In the context of the overall organic carbon (OC) mass balance, the contributions of diesel, wood-smoke, vegetative detritus, road dust, and coke-oven emissions are all small and well constrained; however, estimates for the contributions of gasoline-vehicle and cooking emissions can vary by an order of magnitude. A best-estimate solution is presented that represents the vast majority of our CMB results; it indicates that primary OC only contributes 27±8% and 50±14% (average±standard deviation of daily estimates) of the ambient OC in the summer and winter, respectively. Approximately two-thirds of the primary OC is transported into Pittsburgh as part of the regional air mass. The ambient OC that is not apportioned by the CMB model is well correlated with secondary organic aerosol (SOA) estimates based on the EC-tracer method and ambient concentrations of organic species associated with SOA. Therefore, SOA appears to be the major component of OC, not only in summer, but potentially in all seasons. Primary OC dominates the OC mass balance on a small number of nonsummer days with high OC concentrations; these events are associated with specific meteorological conditions such as local inversions. Primary particulate emissions only contribute a small fraction of the ambient fine-particle mass, especially in the summer.     

Primary and secondary carbonaceous species in PM2.5 samples in Milan (Italy)

Seasonal elemental carbon (EC) and organic carbon (OC) concentration levels in PM2.5 samples collected in Milan (Italy) are presented and discussed, enriching the world-wide database of carbonaceous species in fine particulate matter (PM). High-volume PM2.5 sampling campaigns were performed from August 2002 through December 2003 in downtown Milan at an urban background site. Compared to worldwide average concentrations, in Milan warm-season OC and both warm- and cold-season EC are relatively low; conversely, cold-season OC concentrations are rather high. Consequently, high values for the OC/EC ratio are observed, especially in the winter period. The relation between OC/EC ratio values and wind direction is investigated, pointing out that the highest ratios are associated to winds blowing from those nearby areas where wood consumption for domestic heating is larger. Information on the OC partitioning between its primary and secondary fraction are derived by means of the EC-tracer method and principal component analysis. In the warm-season, OC is mainly of secondary origin, secondary organic aerosol (SOA) accounting for about 84% of the particulate organic matter and 25–28% of the PM2.5 mass. For the cold season the full application of the EC-tracer method was not possible and the primary organic aerosol deriving from traffic could only be estimated. However, principal component analysis (PCA) suggest a prevailing primary origin for OC, thus raising the attention on space heating emissions, and on wood combustion in particular, for air quality control. The role of traffic emissions on PM2.5 concentration levels, as a primary source, are also assessed: EC and primary organic matter from traffic account for a warm-season 30% and a cold-season 7% of the total carbon in PM2.5, that is for about 10% and 6% of PM2.5 mass, respectively. This latter small primary contribution estimated for the cold-season points out that stationary sources, which were not thought to play a significant role on PM concentration levels, may conversely be as much responsible for ambient particulate pollution.     

Elemental and organic carbon in urban canyon and background environments in Budapest,Hungary

As part of an international research project, aerosol samples were collected by several filter-based devices on Nuclepore polycarbonate membrane, Teflon membrane and quartz fibre filters over separate daylight periods and nights, and on-line aerosol measurements were performed by TEOM and aethalometer within an urban canyon (kerbside) and at a near-city background site in Budapest, Hungary from 23 April–5 May 2002. Aerosol masses in PM2.0, PM10–2.0, PM2.5, PM10 size fractions and of TSP were determined gravimetrically; atmospheric concentrations of organic (OC) and elemental carbon (EC) for PM2.5 (or PM2.0), PM10 fractions and for TSP were measured by thermal–optical transmission method. Repeatability of the mass determination by Nuclepore filters seems to be 5–6%. Collections on Teflon filters yielded smaller mass on average by 8(±12)% than that for the Nuclepore filters. Quartz filters overestimated the PM10 mass in comparison with the Nuclepore filters due primarily to sampling artefacts on average by 10(±16)% at the kerbside. Tandem filter set-ups were utilised for correcting the sampling artefacts for OC by subtraction method. At the kerbside, the aerosol mass was made up on average of 35(±4)% of organic matter (OM) in the PM10 fraction, while the contribution of OM to the PM2.5 mass was 43(±9)%. At the background, OM also accounted for 43(±13)% of the PM2.0 mass. On average, EC made up 14(±6)%, 7(±2)% and 4.5(±1.1)% of the mass in the PM2.5, PM10 fractions and TSP, respectively, at the kerbside; while its contribution was only 2.1(±0.5)% in the PM2.0 fraction in the near-city background. Temporal variability for PM mass, OC and EC concentrations was related to road traffic, local meteorology and long-range transport of air masses. It was concluded that a direct coupling between the atmospheric concentration levels and vehicle circulation can be identified within the urban canyon, nevertheless, the local meteorology in particular and long-range transport of air masses have much more influence on the air quality than changes in the source intensity of road traffic. Concentration ratios of OC/EC were evaluated, and the amount of secondary organic aerosol (SOA) was estimated by using EC as tracer for the primary OC emissions. Mean contribution and standard deviation of the SOA to the OM in the PM2.5 size fraction at the kerbside over daylight periods and nights were of 37(±18) and 46(±16)%, respectively.     

Seasonal and spatial trends in the sources of fine particle organic carbon in Israel,Jordan, and Palestine

A study of carbonaceous particulate matter (PM) was conducted in the Middle East at sites in Israel, Jordan, and Palestine. The sources and seasonal variation of organic carbon, as well as the contribution to fine aerosol (PM_2.5) mass, were determined. Of the 11 sites studied, Nablus had the highest contribution of organic carbon (OC), 29%, and elemental carbon (EC), 19%, to total PM_2.5 mass. The lowest concentrations of PM_2.5 mass, OC, and EC were measured at southern desert sites, located in Aqaba, Eilat, and Rachma. The OC contribution to PM_2.5 mass at these sites ranged between 9.4% and 16%, with mean annual PM_2.5 mass concentrations ranging from 21 to 25 ug m^?3. These sites were also observed to have the highest OC to EC ratios (4.1–5.0), indicative of smaller contributions from primary combustion sources and/or a higher contribution of secondary organic aerosol. Biomass burning and vehicular emissions were found to be important sources of carbonaceous PM in this region at the non-southern desert sites, which together accounted for 30%–55% of the fine particle organic carbon at these sites. The fraction of measured OC unapportioned to primary sources (1.4 μgC m^?3 to 4.9 μgC m^?3; 30%–74%), which has been shown to be largely from secondary organic aerosol, is relatively constant at the sites examined in this study. This suggests that secondary organic aerosol is important in the Middle East during all seasons of the year.     

Indoor/Outdoor relationships, trends, and carbonaceous content of fine particulate matter in retirement homes of the Los Angeles Basin

Hourly indoor and outdoor fine particulate matter (PM2.5), organic and elemental carbon (OC and EC, respectively), particle number (PN), ozone (O3), carbon monoxide (CO), and nitrogen oxide (NOx) concentrations were measured at two different retirement communities in the Los Angeles, CA, area as part of the Cardiovascular Health and Air Pollution Study. Site A (group 1 [G1]) was operated from July 6 to August 20, 2005 (phase 1 [P1]) and from October 19 to December 10, 2005 (P2), whereas site B (group 2 [G2]) was operated from August 24 to October 15, 2005 (P1), and from January 4 to February 18, 2006 (P2). Overall, the magnitude of indoor and outdoor measurements was similar, probably because of the major influence of outdoor sources on indoor particle and gas levels. However, G2 showed a substantial increase in indoor OC, PN, and PM2.5 between 6:00 and 9:00 a.m., probably from cooking. The contributions of primary and secondary OC (SOA) to measured outdoor OC were estimated from collected OC and EC concentrations using EC as a tracer of primary combustion-generated OC (i.e., "EC tracer method"). The study average outdoor SOA accounted for 40% of outdoor particulate OC (40-45% in the summer and 32-40% in the winter). Air exchange rates (hr(-1)) and infiltration factors (Finf; dimensionless) at each site were also determined. Estimated Finf and measured particle concentrations were then used in a single compartment mass balance model to assess the contributions of indoor and/or outdoor sources to measured indoor OC, EC, PM2.5, and PN. The average percentage contributions of indoor SOA of outdoor origin to measured indoor OC were approximately 35% (during G1P1 and G1P2) and approximately 45% (for G2P1 and G2P2). On average, 36% (G2P1) to 44% (G1P1) of measured indoor OC was composed of outdoor-generated primary OC.     

Insights into the nature of secondary organic aerosol in Mexico City during the MILAGRO experiment 2006

This study targets understanding the secondary sources of organic aerosol in Mexico City during the Megacities Impact on Regional and Global Environment (MIRAGE) 2006 field campaign. Ambient PM_2.5 was collected daily at urban and peripheral locations. Particle-phase secondary organic aerosol (SOA) products of anthropogenic and biogenic precursor gases were measured by gas chromatography mass spectrometry. Ambient concentrations of SOA tracers were used to estimate organic carbon (OC) from secondary origins (SOC). Anthropogenic SOC was estimated as 20–25% of ambient OC at both sites, while biogenic SOC was less abundant, but was relatively twice as important at the peripheral site. The OC that was not attributed secondary sources or to primary sources in a previous study showed temporal consistency with biomass-burning events, suggesting the importance of secondary processing of biomass-burning emissions in the region. The best estimate of biomass-burning-related SOC was in the range of 20–30% of ambient OC during peak biomass burning events. Low-molecular weight (MW) alkanoic and alkenoic dicarboxylic acids (C₂–C₅) were also measured, of which oxalic acid was the most abundant. The spatial and temporal trends of oxalic acid differed from tracers for primary and secondary sources, suggesting that it had different and/or multiple sources in the atmosphere.     

Source apportionment of primary and secondary organic aerosols using positive matrix factorization (PMF) of molecular markers

Monthly average ambient concentrations of more than eighty particle-phase organic compounds, as well as total organic carbon (OC) and elemental carbon (EC), were measured from March 2004 through February 2005 in five cities in the Midwestern United States. A multi-variant source apportionment receptor model, positive matrix factorization (PMF), was applied to explore the average source contributions to the five sampling sites using molecular markers for primary and secondary organic aerosols (POA, SOA). Using the molecular makers in the model, POA and SOA were estimated for each month at each site. Three POA factors were derived, which were dominated by primary molecular markers such as EC, hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs), and which represented the following POA sources: urban primary sources, mobile sources, and other combustion sources. The three POA sources accounted for 57% of total average ambient OC. Three factors, characterized by the presence of reaction products of isoprene, α-pinene and β-caryophyllene, and displaying distinct seasonal trends, were consistent with the characteristics of SOA. The SOA factors made up 43% of the total average measured OC. The PMF-derived results are in good agreement with estimated SOA concentrations obtained from SOA to tracer yield estimates obtained from smog chamber experiments. A linear regression comparing the smog chamber yield estimates and the PMF SOA contributions had a regression slope of 1.01 ± 0.07 and an intercept of 0.19 ± 0.10 μg OC m^?3 (adjusted R² of 0.763, n = 58).     

Estimates of the contributions of biogenic and anthropogenic hydrocarbons to secondary organic aerosol at a southeastern US location

An organic tracer-based method containing laboratory and field study components was used to estimate the secondary organic aerosol (SOA) contributions of biogenic and anthropogenic hydrocarbons to ambient organic carbon (OC) concentrations in PM_2.5 during 2003 in Research Triangle Park, NC. In the laboratory, smog chamber experiments were conducted where isoprene, α-pinene, β-caryophyllene, and toluene were individually irradiated in the presence of NO_X. In each experiment, SOA was collected and analyzed for potential tracer compounds, whose concentrations were used to calculate a mass fraction of tracer compounds for each hydrocarbon. In the field, 33 PM_2.5 samples were collected and analyzed for (1) tracer compounds observed in the laboratory irradiations, (2) levoglucosan, a biomass burning tracer, and (3) total OC. For each of the four hydrocarbons, the SOA contributions to ambient OC concentrations were estimated using the tracer concentrations and the laboratory-derived mass fractions. The estimates show SOA formation from isoprene, α-pinene, β-caryophyllene, and toluene contributed significantly to the ambient OC concentrations. The relative contributions were highly seasonal with biomass burning in the winter accounting for more than 50% of the OC concentrations, while SOA contributions remained low. However, during the 6-month period between May and October, SOA from the precursor hydrocarbons contributed more than 40% of the measured OC concentration. Although the tracer-based method is subject to considerable uncertainty due to the simplification of replacing the complex set of chemical reactions responsible for SOA with a laboratory-derived single-valued mass fraction, the results suggest this approach can be used to identify major sources of SOA which can assist in the development of air quality models.     

Chemical composition and source apportionment of PM2.5 particles in the Sihwa area, Korea

To investigate the chemical characteristics of fine particles in the Sihwa area, Korea, atmospheric aerosol samples were collected using a dichotomous PM10 sampler and two URG PM2.5 cyclone samplers during five intensive sampling periods between February 1998 and February 1999. The Inductively Coupled Plasma (ICP)-Atomic Emission Spectrometry (AES)/ICP-Mass Spectrometry (MS), ion chromatograph (IC), and thermal manganese dioxide oxidation (TMO) methods were used to analyze the trace elements, ionic species, and carbonaceous species, respectively. Backward trajectory analysis, factor analysis, and a chemical mass balance (CMB) model were used to estimate quantitatively source contributions to PM2.5 particles collected in the Sihwa area. The results of PM2.5 source apportionment using the CMB7 receptor model showed that (NH4)2SO4 was, on average, the major contributor to PM2.5 particles, followed by nontraffic organic carbon (OC) emission, NH4NO3, agricultural waste burning, motor vehicle emission, road dust, waste incineration, marine aerosol, and others. Here, the nontraffic OC sources include primary anthropogenic OC emitted from the industrial complex zone, secondary OC, and organic species from distant sources. The source impact of waste incineration emission became significant when the dominant wind directions were from southwest and west sectors during the sampling periods. It was found that PM2.5 particles in the Sihwa area were influenced mainly by both anthropogenic local sources and long-range transport and transformation of air pollutants.     

Carbonaceous aerosol characteristics in outdoor and indoor environments of Nanchang, China, during summer 2009

A study of carbonaceous aerosol was initiated in Nanchang, a city in eastern China, for the first time. Daily and diurnal (daytime and nighttime) PM2.5 (particulate matter with aerodynamic diameter < or =2.5 microm) samples were collected at an outdoor site and in three different indoor environments (common office, special printing and copying office, and student dormitory) in a campus of Nanchang University during summer 2009 (5-20 June). Daily PM10 (particulate matter with aerodynamic diameter < or =10 microm) samples were collected only at the outdoor site, whereas PM2.5 samples were collected at both indoor and outdoor sites. Loaded PM2.5 and PM10 samples were analyzed for organic and elemental carbon (OC, EC) by thermal/optical reflectance following the Interagency Monitoring of Protected Visual Environments-Advanced (IMPROVE-A) protocol. Ambient mass concentrations of PM10 and PM2.5 in Nanchang were compared with the air quality standards in China and the United States, and revealed high air pollution levels in Nanchang. PM2.5 accounted for about 70% of PM10, but the ratio of OC and EC in PM2.5 to that in PM10 was higher than 80%, which indicated that OC and EC were mainly distributed in the fine particles. The variations of carbonaceous aerosol between daytime and nighttime indicated that OC was released and formed more rapidly in daytime than in nighttime. OC/EC ratios were used to quantify secondary organic carbon (SOC). The differences in SOC and SOC/OC between daytime and nighttime were useful in interpreting the secondary formation mechanism. The results of (1) OC and EC contributions to PM2.5 at indoor sites and the outdoor site; (2) indoor-outdoor correlation of OC and EC; (3) OC-EC correlation; and (4) relative contributions of indoor and outdoor sources to indoor carbonaceous aerosol indicated that OC indoor sources existed in indoor sites, with the highest OC emissions in I2 (the special printing and copying office), and that indoor EC originated from outdoor sources. The distributions of eight carbon fractions in emissions from the printer and copier showed obviously high OC1 (>20%) and OC2 (approximately 30%), and obviously low EC1-OP (a pyrolyzed carbon fraction) (<10%), when compared with other sources.     

Sources of atmospheric carbonaceous particulate matter in Pittsburgh,Pennsylvania

The organic carbon (OC)/elemental carbon (EC) tracer method is applied to the Pittsburgh, PA, area to estimate the contribution of secondary organic aerosol (SOA) to the monthly average concentration of organic particulate matter (PM) during 1995. An emissions inventory is constructed for the primary emissions of OC and EC in the area of interest. The ratio of primary emissions of OC to those of EC ranges between 2.4 in the winter months and 1.0 in the summer months. A mass balance model and ambient measurements were used to assess the accuracy of the emissions inventory. It is estimated to be accurate to within 50%. The results from this analysis show a strong monthly dependence of the SOA contribution to the total organic PM concentration, varying from near zero during winter months to as much as 50% of the total OC concentration in the summer.     

Source identification of atlanta aerosol by positive matrix factorization

Data characterizing daily integrated particulate matter (PM) samples collected at the Jefferson Street monitoring site in Atlanta, GA, were analyzed through the application of a bilinear positive matrix factorization (PMF) model. A total of 662 samples and 26 variables were used for fine particle (particles < or = 2.5 microm in aerodynamic diameter) samples (PM2.5), and 685 samples and 15 variables were used for coarse particle (particles between 2.5 and 10 microm in aerodynamic diameter) samples (PM10-2.5). Measured PM mass concentrations and compositional data were used as independent variables. To obtain the quantitative contributions for each source, the factors were normalized using PMF-apportioned mass concentrations. For fine particle data, eight sources were identified: SO4(2-) -rich secondary aerosol (56%), motor vehicle (22%), wood smoke (11%), NO(3-) -rich secondary aerosol (7%), mixed source of cement kiln and organic carbon (OC) (2%), airborne soil (1%), metal recycling facility (0.5%), and mixed source of bus station and metal processing (0.3%). The SO4(2-) -rich and NO(3-) -rich secondary aerosols were associated with NH(4+). The SO4(2-) -rich secondary aerosols also included OC. For the coarse particle data, five sources contributed to the observed mass: airborne soil (60%), NO(3-)-rich secondary aerosol (16%), SO4(2-) -rich secondary aerosol (12%), cement kiln (11%), and metal recycling facility (1%). Conditional probability functions were computed using surface wind data and identified mass contributions from each source. The results of this analysis agreed well with the locations of known local point sources.     

The Southeastern Aerosol Research and Characterization Study: Part II. Filter-based measurements of fine and coarse particulate matter mass and composition

The Southeastern Aerosol Research and Characterization Study (SEARCH) was implemented in 1998-1999 to provide data and analyses for the investigation of the sources, chemical speciation, and long-term trends of fine particulate matter (PM2.5) and coarse particulate matter (PM10-2.5) in the Southeastern United States. This work is an initial analysis of 5 years (1999-2003) of filter-based PM2.5 and PM10-2.5 data from SEARCH. We find that annual PM2.5 design values were consistently above the National Ambient Air Quality Standards (NAAQS) 15 microg/m3 annual standard only at monitoring sites in the two largest urban areas (Atlanta, GA, and North Birmingham, AL). Other sites in the network had annual design values below the standard, and no site had daily design values above the NAAQS 65 microg/m3 daily standard. Using a particle composition monitor designed specifically for SEARCH, we found that volatilization losses of nitrate, ammonium, and organic carbon must be accounted for to accurately characterize atmospheric particulate matter. In particular, the federal reference method for PM2.5 underestimates mass by 3-7% as a result of these volatilization losses. Organic matter (OM) and sulfate account for approximately 60% of PM2.5 mass at SEARCH sites, whereas major metal oxides (MMO) and unidentified components ("other") account for > or = 80% of PM10-2.5 mass. Limited data suggest that much of the unidentified mass in PM10-2.5 may be OM. For paired comparisons of urban-rural sites, differences in PM2.5 mass are explained, in large part, by higher OM and black carbon at the urban site. For PM10, higher urban concentrations are explained by higher MMO and "other." Annual means for PM2.5 and PM10-2.5 mass and major components demonstrate substantial declines at all of the SEARCH sites over the 1999-2003 period (10-20% in the case of PM2.5, dominated by 14-20% declines in sulfate and 11-26% declines in OM, and 14-25% in the case of PM10-2.5, dominated by 17-30% declines in MMO and 14-31% declines in "other"). Although declining national emissions of sulfur dioxide and anthropogenic carbon may account for a portion of the observed declines, additional investigation will be necessary to establish a quantitative assessment, especially regarding trends in local and regional emissions, primary carbon emissions, and meteorology.     

Comparison of different gas-phase mechanisms and aerosol modules for simulating particulate matter formation

The effects of two gas-phase chemical kinetic mechanisms, Regional Atmospheric Chemistry Mechanism version 2 (RACM2) and Carbon-Bond 05 (CB05), and two secondary organic aerosol (SOA) modules, the Secondary Organic Aerosoi Model (SORGAM) and AER/EPRI/Caltech model (AEC), on fine (aerodynamic diameter < or =2.5 microm) particulate matter (PM2.5) formation is studied. The major sources of uncertainty in the chemistry of SOA formation are investigated. The use of all major SOA precursors and the treatment of SOA oligomerization are found to be the most important factors for SOA formation, leading to 66% and 60% more SOA, respectively. The explicit representation of high-NO, and low-NOx gas-phase chemical regimes is also important with increases in SOA of 30-120% depending on the approach used to implement the distinct SOA yields within the gas-phase chemical kinetic mechanism; further work is needed to develop gas-phase mechanisms that are fully compatible with SOA formation algorithms. The treatment of isoprene SOA as hydrophobic or hydrophilic leads to a significant difference, with more SOA being formed in the latter case. The activity coefficients may also be a major source of uncertainty, as they may differ significantly between atmospheric particles, which contain a myriad of SOA, primary organic aerosol (POA), and inorganic aerosol species, and particles formed in a smog chamber from a single precursor under dry conditions. Significant interactions exist between the uncertainties of the gas-phase chemistry and those of the SOA module.     

Sources of Atmospheric Carbonaceous Particulate Matter in Pittsburgh,Pennsylvania

Abstract

The organic carbon (OC)/elemental carbon (EC) tracer method is applied to the Pittsburgh, PA, area to estimate the contribution of secondary organic aerosol (SOA) to the monthly average concentration of organic particu-late matter (PM) during 1995. An emissions inventory is constructed for the primary emissions of OC and EC in the area of interest. The ratio of primary emissions of OC to those of EC ranges between 2.4 in the winter months and 1.0 in the summer months. A mass balance model and ambient measurements were used to assess the accuracy of the emissions inventory. It is estimated to be accurate to within 50%. The results from this analysis show a strong monthly dependence on SOA contribution to the total organic PM concentration, varying from near zero during winter months to 50% or more of the total OC concentration in the summer.     

Assessment of secondary organic carbon in the Southeastern United States: a review

Organic carbon (OC) is one of the major components of ambient PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter) and a significant portion of OC is from secondary organic aerosol (SOA) formation in the southeastern United States. Various approaches (based on measurement and modeling results) are applied to estimate secondary organic carbon (SOC) and its origins in the region. SOC estimates by various methods are consistent as to clear seasonal variation (i.e., relatively higher SOC in summer) and little spatial variability (i.e., a regional characteristic of SOC). However, there are differences as to the origins of SOC. SOA organic tracer and emission-based modeling studies indicate that the biogenic origin of SOC is dominant in the Southeast, showing that biogenic-origin SOC accounts for 90% of SOC in summer and more than 70% even in other seasons. However, results from other studies suggest that the anthropogenic origin of SOC is dominant, significant amounts of anthropogenic-origin SOC, or important roles of anthropogenic pollutants for SOA formation, especially at urban areas, as strong correlations between water-soluble OC (an indicator of SOC) and anthropogenic pollutants, considerable amounts of fossil water-soluble OC, and significant contributions of fossil SOC (37-52% in summer months, 70-73% in winter months) are observed. Therefore, more studies are needed to reconcile the differences in the source attribution of SOC measurements.