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.     

Evaluating inter-continental transport of fine aerosols: (1) Methodology,global aerosol distribution and optical depth

Our objectives are to evaluate inter-continental source-receptor relationships for fine aerosols and to identify the regions whose emissions have dominant influence on receptor continents. We simulate sulfate, black carbon (BC), organic carbon (OC), and mineral dust aerosols using a global coupled chemistry-aerosol model (MOZART-2) driven with NCEP/NCAR reanalysis meteorology for 1997–2003 and emissions approximately representing year 2000. The concentrations of simulated aerosol species in general agree within a factor of 2 with observations, except that the model tends to overestimate sulfate over Europe in summer, underestimate BC and OC over the western and southeastern (SE) U.S. and Europe, and underestimate dust over the SE U.S. By tagging emissions from ten continental regions, we quantify the contribution of each region's emissions on surface aerosol concentrations (relevant for air quality) and aerosol optical depth (AOD, relevant for visibility and climate) globally. We find that domestic emissions contribute substantially to surface aerosol concentrations (57–95%) over all regions, but are responsible for a smaller fraction of AOD (26–76%). We define “background” aerosols as those aerosols over a region that result from inter-continental transport, DMS oxidation, and emissions from ships or volcanoes. Transport from other continental source regions accounts for a substantial portion of background aerosol concentrations: 36–97% for surface concentrations and 38–89% for AOD. We identify the Region of Primary Influence (RPI) as the source region with the largest contribution to the receptor's background aerosol concentrations (or AOD). We find that for dust Africa is the RPI for both aerosol concentrations and AOD over all other receptor regions. For non-dust aerosols (particularly for sulfate and BC), the RPIs for aerosol concentrations and AOD are identical for most receptor regions. These findings indicate that the reduction of the emission of non-dust aerosols and their precursors from an RPI will simultaneously improve both air quality and visibility over a receptor region.     

Present and potential future contributions of sulfate,black and organic carbon aerosols from China to global air quality,premature mortality and radiative forcing

Aerosols are harmful to human health and have both direct and indirect effects on climate. China is a major contributor to global emissions of sulfur dioxide (SO₂), a sulfate (SO₄^2?) precursor, organic carbon (OC), and black carbon (BC) aerosols. Although increasingly examined, the effect of present and potential future levels of these emissions on global premature mortality and climate change has not been well quantified. Through both direct radiative effects and indirect effects on clouds, SO₄^2? and OC exert negative radiative forcing (cooling) while BC exerts positive forcing (warming). We analyze the effect of China's emissions of SO₂, SO₄^2?, OC and BC in 2000 and for three emission scenarios in 2030 on global surface aerosol concentrations, premature mortality, and radiative forcing (RF). Using global models of chemical transport (MOZART-2) and radiative transfer (GFDL RTM), and combining simulation results with gridded population data, mortality rates, and concentration–response relationships from the epidemiological literature, we estimate the contribution of Chinese aerosols to global annual premature mortality and to RF in 2000 and 2030. In 2000, we estimate these aerosols cause approximately 470 000 premature deaths in China and an additional 30 000 deaths globally. In 2030, aggressive emission controls lead to a 50% reduction in premature deaths from the 2000 level to 240 000 in China and 10 000 elsewhere, while under a high emissions scenario premature deaths increase 50% from the 2000 level to 720 000 in China and to 40 000 elsewhere. Because the negative RF from SO₄^2? and OC is larger than the positive forcing from BC, Chinese aerosols lead to global net direct RF of ?74 mW m^?2 in 2000 and between ?15 and ?97 mW m^?2 in 2030 depending on the emissions scenario. Our analysis indicates that increased effort to reduce greenhouse gases is essential to address climate change as China's anticipated reduction of aerosols will result in the loss of net negative radiative forcing.     

Secondary organic aerosol importance in the future atmosphere

In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted.According to our present-day model simulations, isoprene oxidation produces 4.6 Tg SOA yr⁻¹, that is less than half of the 12.2 Tg SOA yr⁻¹ formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8 Tg at present to 2.0 Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere.     

Urban impacts on regional carbonaceous aerosols: Case study in central Texas

Rural and background sites provide valuable information on the concentration and optical properties of organic, elemental, and water-soluble organic carbon (OC, EC, and WSOC), which are relevant for understanding the climate forcing potential of regional atmospheric aerosols. To quantify climate- and air quality-relevant characteristics of carbonaceous aerosol in the central United States, a regional background site in central Texas was chosen for long-term measurement. Back trajectory (BT) analysis, ambient OC, EC, and WSOC concentrations and absorption parameters are reported for the first 15 months of a long-term campaign (May 2011–August 2012). BT analysis indicates consistent north–south airflow connecting central Texas to the Central Plains. Central Texas aerosols exhibited seasonal trends with increased fine particulate matter (<2.5 μm aerodynamic diameter, PM_2.5) and OC during the summer (PM_2.5 = 10.9 μg m^?3 and OC = 3.0 μg m^?3) and elevated EC during the winter (0.22 μg m^?3). When compared to measurements in Dallas and Houston, TX, central Texas OC appears to have mixed urban and rural sources. However, central Texas EC appears to be dominated by transport of urban emissions. WSOC averaged 63% of the annual OC, with little seasonal variability in this ratio. To monitor brown carbon (BrC), absorption was measured for the aqueous WSOC extracts. Light absorption coefficients for EC and BrC were highest during summer (EC MAC = 11 m² g^?1 and BRC MAE₃₆₅ = 0.15 m² g^?1). Results from optical analysis indicate that regional aerosol absorption is mostly due to EC with summertime peaks in BrC attenuation. This study represents the first reported values of WSOC absorption, MAE₃₆₅, for the central United States.

Implications:Background concentration and absorption measurements are essential in determining regional potential radiative forcing due to atmospheric aerosols. Back trajectory, chemical, and optical analysis of PM_2.5 was used to determine climatic and air quality implications of urban outflow to a regional receptor site, representative of the central United States. Results indicate that central Texas organic carbon has mixed urban and rural sources, while elemental carbon is controlled by the transport of urban emissions. Analysis of aerosol absorption showed black carbon as the dominant absorber, with less brown carbon absorption than regional studies in California and the southeastern United States.     

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.     

Correlations between fine particulate matter (PM2.5) and meteorological variables in the United States: Implications for the sensitivity of PM2.5 to climate change

We applied a multiple linear regression (MLR) model to study the correlations of total PM_2.5 and its components with meteorological variables using an 11-year (1998–2008) observational record over the contiguous US. The data were deseasonalized and detrended to focus on synoptic-scale correlations. We find that daily variation in meteorology as described by the MLR can explain up to 50% of PM_2.5 variability with temperature, relative humidity (RH), precipitation, and circulation all being important predictors. Temperature is positively correlated with sulfate, organic carbon (OC) and elemental carbon (EC) almost everywhere. The correlation of nitrate with temperature is negative in the Southeast but positive in California and the Great Plains. RH is positively correlated with sulfate and nitrate, but negatively with OC and EC. Precipitation is strongly negatively correlated with all PM_2.5 components. We find that PM_2.5 concentrations are on average 2.6 μg m^?3 higher on stagnant vs. non-stagnant days. Our observed correlations provide a test for chemical transport models used to simulate the sensitivity of PM_2.5 to climate change. They point to the importance of adequately representing the temperature dependence of agricultural, biogenic and wildfire emissions in these models.     

Carbonaceous aerosol over a Pinus taeda forest in Central North Carolina,USA

Organic aerosol is the least understood component of ambient fine particulate matter (PM_2.5). In this study, organic and elemental carbon (OC and EC) within ambient PM_2.5 over a three-year period at a forested site in the North Carolina Piedmont are presented. EC exhibited significant weekday/weekend effects and less significant seasonal effects, in contrast to OC, which showed strong seasonal differences and smaller weekend/weekday effects. Summer OC concentrations are about twice as high as winter concentrations, while EC was somewhat higher in the winter. OC was highly correlated with EC during cool periods when both were controlled by primary combustion sources. This correlation decreased with increasing temperature, reflecting higher contributions from secondary organic aerosol, likely of biogenic origin. PM_2.5 radiocarbon data from the site confirms that a large fraction of the carbon in PM_2.5 is indeed of biogenic origin, since modern (non-fossil fuel derived) carbon accounted for 80% of the PM_2.5 carbon over the course of a year. OC and EC exhibited distinct diurnal profiles, with summertime OC peaking in late evening and declining until midday. During winter, OC peaked during the early morning hours and again declined until midday. Summertime EC peaked during late morning hours except on weekends. Wintertime EC often peaked in late PM or early AM hours due to local residential wood combustion emissions. The highest short term peaks in OC and EC were associated with wildfire events. These data corroborate recent source apportionment studies conducted within 20 km of our site, where oxidation products of isoprene, α-pinene, and β-caryophyllene were identified as important precursors to organic aerosols. A large fraction of the carbon in rural southeastern ambient PM_2.5 appears to be of biogenic origin, which is probably difficult to reduce by anthropogenic controls.     

Future land use and land cover influences on regional biogenic emissions and air quality in the United States

A regional modeling system was applied with inputs from global climate and chemistry models to quantify the effects of global change on future biogenic emissions and their impacts on ozone and biogenic secondary organic aerosols (BSOA) in the US. Biogenic emissions in the future are influenced by projected changes in global and regional climates and by variations in future land use and land cover (LULC). The modeling system was applied for five summer months for the present-day case (1990–1999, Case 1) and three future cases covering 2045–2054. Individual future cases were: present-day LULC (Case 2); projected-future LULC (Case 3); and future LULC with designated regions of tree planting for carbon sequestration (Case 4). Results showed changing future meteorology with present-day LULC (Case 2) increased average isoprene and monoterpene emission rates by 26% and 20% due to higher temperature and solar insolation. However when LULC was changed together with climate (Case 3), predicted isoprene and monoterpene emissions decreased by 52% and 31%, respectively, due primarily to projected cropland expansion. The reduction was less, at 31% and 14% respectively, when future LULC changes were accompanied by regions of tree planting (Case 4). Despite the large decrease in biogenic emission, future average daily maximum 8-h (DM8H) ozone was found to increase between +8 ppbv and +10 ppbv due to high future anthropogenic emissions and global chemistry conditions. Among the future cases, changing LULC resulted in spatially varying future ozone differences of ?5 ppbv to +5 ppbv when compared with present-day case. Future BSOA changed directly with the estimated monoterpene emissions. BSOA increased by 8% with current LULC (Case 2) but decreased by 45%–28% due to future LULC changes. Overall, the results demonstrated that on a regional basis, changes in LULC can offset temperature driven increases in biogenic emissions, and, thus, LULC projection is an important factor to consider in the study of future regional air quality.     

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.     

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.     

Contributions of biogenic volatile organic compounds to the formation of secondary organic aerosols over Mt. Tai,Central East China

To better understand the contribution of biogenic volatile organic compounds to the formation of secondary organic aerosol (SOA) in high mountain regions, ambient aerosols were collected at the summit of Mt. Tai (1534 m, a.s.l.), Central East China (CEC) during the Mount Tai Experiment 2006 campaign (MTX2006) in early summer. Biogenic SOA tracers for the oxidation of isoprene, α/β-pinene, and β-caryophyllene were measured using gas chromatography/mass spectrometry. Most of the biogenic SOA tracers did not show clear diurnal variations, suggesting that they are formed during long-range atmospheric transport or over relatively long time scales. Although isoprene- and α/β-pinene-derived SOA tracers did not correlate with levoglucosan (a biomass burning tracer), β-caryophyllinic acid showed a good correlation with levoglucosan, indicating that crop residue burning may be a source for this acid. Total concentrations of isoprene oxidation products are much higher than those of α/β-pinene and β-caryophyllene oxidation products. The averaged ratio of isoprene to α/β-pinene oxidation products (R_iso/pine) was 4.9 and 6.7 for the daytime and nighttime samples, respectively. These values are among the highest in the aerosols reported in different geographical regions, which may be due to the large isoprene fluxes and relatively high levels of oxidants such as OH in CEC. Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) derived from isoprene, α/β-pinene, and β-caryophyllene to be 0.42–3.1 μgC m^?3 (average 1.6 μgC m^?3) during the daytime and 0.11–4.2 μgC m^?3 (1.7 μgC m^?3) during the nighttime. These values correspond to 2.9–23% (10%) and 3.2–28% (9.8%) of the total OC concentrations, in which isoprene-derived SOC accounts for 58% and 63% of total SOC during the daytime and nighttime, respectively. This study suggests that isoprene is a more significant precursor for biogenic SOA than α/β-pinene and β-caryophyllene at high altitudes in CEC.     

Regional scale modelling of particulate matter in the UK,source attribution and an assessment of uncertainties

The models HARM and ELMO are used to investigate the importance of different source categories contributing to total PM₁₀ (SIA, SOA and primary particulate matter) across the UK and the impact of uncertainties on both present day and future concentration estimates. Modelled concentrations of SIA (secondary inorganic aerosol) are compared against data from the UK's Nitric Acid and Aerosol Network and SOA (secondary organic aerosol) against measurements made at the Bush Estate, Edinburgh. These data indicate that the HARM/ELMO modelling approach comes close to achieving mass closure. Comparison with national maps of total PM₁₀ indicate that the models underestimate particulate matter concentrations around large conurbations, probably due to the localised nature of emissions of primary particulates in these areas and model scale. The models are used to attribute particulate matter to different source and size categories, assessing the relative importance of primaries, SIA and SOA; the contributions of anthropogenic and biogenic precursors of SOA; the relative importance of PM_coarse (PM₁₀–PM_2.5) and PM_fine (PM_2.5) and UK vs. other EMEP area sources. The implications of these attributions for emissions control policies are discussed. The impact of uncertainties in emissions of the sources of primaries, SIA and SOA are explored. For primary PM₁₀ and SOA this has been achieved through emissions scaling and for SIA using the GLUE (Generalised Likelihood Uncertainty Estimation) approach. The selection of acceptable model parameter sets has been based on the need to retain the capability to model deposition of S and N species. The impact of uncertainty on estimates of present day SIA concentrations is illustrated for sites in the Nitric Acid and Aerosol Network. A more limited assessment for 2010 has been carried out at the national scale, illustrating that inclusion of uncertainty can change modelled concentrations from no exceedance of current air quality objectives, to one of exceedance over large areas of south and east England.     

Atmospheric composition change: Climate–Chemistry interactions

Chemically active climate compounds are either primary compounds like methane (CH₄), removed by oxidation in the atmosphere, or secondary compounds like ozone (O₃), sulfate and organic aerosols, both formed and removed in the atmosphere. Man-induced climate–chemistry interaction is a two-way process: Emissions of pollutants change the atmospheric composition contributing to climate change through the aforementioned climate components, and climate change, through changes in temperature, dynamics, the hydrological cycle, atmospheric stability, and biosphere-atmosphere interactions, affects the atmospheric composition and oxidation processes in the troposphere. Here we present progress in our understanding of processes of importance for climate–chemistry interactions, and their contributions to changes in atmospheric composition and climate forcing. A key factor is the oxidation potential involving compounds like O₃ and the hydroxyl radical (OH). Reported studies represent both current and future changes. Reported results include new estimates of radiative forcing based on extensive model studies of chemically active climate compounds like O₃, and of particles inducing both direct and indirect effects. Through EU projects like ACCENT, QUANTIFY, and the AeroCom project, extensive studies on regional and sector-wise differences in the impact on atmospheric distribution are performed. Studies have shown that land-based emissions have a different effect on climate than ship and aircraft emissions, and different measures are needed to reduce the climate impact. Several areas where climate change can affect the tropospheric oxidation process and the chemical composition are identified. This can take place through enhanced stratospheric–tropospheric exchange of ozone, more frequent periods with stable conditions favoring pollution build up over industrial areas, enhanced temperature induced biogenic emissions, methane releases from permafrost thawing, and enhanced concentration through reduced biospheric uptake. During the last 5–10 years, new observational data have been made available and used for model validation and the study of atmospheric processes. Although there are significant uncertainties in the modeling of composition changes, access to new observational data has improved modeling capability. Emission scenarios for the coming decades have a large uncertainty range, in particular with respect to regional trends, leading to a significant uncertainty range in estimated regional composition changes and climate impact.     

Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies

Natural emissions adopted in current regional air quality modeling are updated to better describe natural background ozone and PM concentrations for North America. The revised natural emissions include organosulfur from the ocean, NO from lightning, sea salt, biogenic secondary organic aerosol (SOA) precursors, and pre-industrial levels of background methane. The model algorithm for SOA formation was also revised. Natural background ozone concentrations increase by up to 4 ppb in annual average over the southeastern US and Gulf of Mexico due to added NO from lightning while the revised biogenic emissions produced less ozone in the central and western US. Natural PM_2.5 concentrations generally increased with the revised natural emissions. Future year (2018) simulations were conducted for several anthropogenic emission reduction scenarios to assess the impact of the revised natural emissions on anthropogenic emission control strategies. Overall, the revised natural emissions did not significantly alter the ozone responses to the emissions reductions in 2018. With revised natural emissions, ozone concentrations were slightly less sensitive to reducing NOx in the southeastern US than with the current natural emissions due to higher NO from lightning. The revised natural emissions have little impact on modeled PM_2.5 responses to anthropogenic emission reductions. However, there are substantial uncertainties in current representations of natural sources in air quality models and we recommend that further study is needed to refine these representations.     

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.     

Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM_2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5–4 km) and between 4 and 27% at the urban scale (4–100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM_2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.     

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.     

Overview of surface measurements and spatial characterization of submicrometer particulate matter during the DISCOVER-AQ 2013 campaign in Houston,TX

The sources of submicrometer particulate matter (PM₁) remain poorly characterized in the industrialized city of Houston, TX. A mobile sampling approach was used to characterize PM₁ composition and concentration across Houston based on high-time-resolution measurements of nonrefractory PM₁ and trace gases during the DISCOVER-AQ Texas 2013 campaign. Two pollution zones with marked differences in PM₁ levels, character, and dynamics were established based on cluster analysis of organic aerosol mass loadings sampled at 16 sites. The highest PM₁ mass concentrations (average 11.6 ± 5.7 µg/m³) were observed to the northwest of Houston (zone 1), dominated by secondary organic aerosol (SOA) mass likely driven by nighttime biogenic organonitrate formation. Zone 2, an industrial/urban area south/east of Houston, exhibited lower concentrations of PM₁ (average 4.4 ± 3.3 µg/m³), significant organic aerosol (OA) aging, and evidence of primary sulfate emissions. Diurnal patterns and backward-trajectory analyses enable the classification of airmass clusters characterized by distinct PM sources: biogenic SOA, photochemical aged SOA, and primary sulfate emissions from the Houston Ship Channel. Principal component analysis (PCA) indicates that secondary biogenic organonitrates primarily related with monoterpenes are predominant in zone 1 (accounting for 34% of the variability in the data set). The relevance of photochemical processes and industrial and traffic emission sources in zone 2 also is highlighted by PCA, which identifies three factors related with these processes/sources (~50% of the aerosol/trace gas concentration variability). PCA reveals a relatively minor contribution of isoprene to SOA formation in zone 1 and the absence of isoprene-derived aerosol in zone 2. The relevance of industrial amine emissions and the likely contribution of chloride-displaced sea salt aerosol to the observed variability in pollution levels in zone 2 also are captured by PCA.

Implications: This article describes an urban-scale mobile study to characterize spatial variations in submicrometer particulate matter (PM₁) in greater Houston. The data set indicates substantial spatial variations in PM₁ sources/chemistry and elucidates the importance of photochemistry and nighttime oxidant chemistry in producing secondary PM₁. These results emphasize the potential benefits of effective control strategies throughout the region, not only to reduce primary emissions of PM₁ from automobiles and industry but also to reduce the emissions of important secondary PM₁ precursors, including sulfur oxides, nitrogen oxides, ammonia, and volatile organic compounds. Such efforts also could aid in efforts to reduce mixing ratios of ozone.