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Abstract: The Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign conducted in the southeast United States (SEUS) during the summer of 2013 provided a singular opportunity to study local aerosol chemistry and investigate aerosol radiative properties and PM2.5 relationships, focusing on the complexities involved in simplifying the relationship into a linear regression. We utilize three Southeastern Aerosol Research and Characterization network sites and one Environmental Protection Agency Chemical Speciation Network station that afforded simultaneous Aerosol Robotic Network (AERONET) aerosol optical depth (AOD) and aerosol mass, chemistry, and light scattering monitoring. Prediction of AERONET AOD using linear regression of daily‐mean PM2.5 during the SEAC4RS campaign yielded r2 of 0.36–0.53 and highly variable slopes across four sites. There were further reductions in PM2.5 predictive skill using Moderate Resolution Imaging Spectroradiometer (MODIS) and Multi‐angle Imaging SpetroRadiometer (MISR) AOD data, which have shorter correlation lengths and times relative to surface PM2.5. Long‐term trends in aerosol chemistry and optical properties in the SEUS are also investigated and compared to SEAC4RS period data, establishing that the SEUS experienced significant reduction in aerosol mass, corresponding with changes in both aerosol chemistry and optical properties. These changes have substantial impact on the PM2.5‐AOD linear regression relationship and reinforce the need for long‐term aerosol observation stations in addition to concentrated field campaigns. [ABSTRACT FROM AUTHOR]

A yearlong near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia) and rural (Look Rock, Tennessee) site in the southeastern US using the Aerodyne aerosol chemical speciation monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (50-76 %) and inorganic sulfate (12-31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the one year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (OOA), isoprene-derived epoxydiol (IEPOX) OA (IEPOX-OA), and 91Fac OA (a factor dominated by a distinct ion at m=z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed 30-66% of total OA mass. HOA was also observed during the entire year only at the urban site (15-24% of OA mass). BBOA (15-33% of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly (~ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27-41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m=z 75 is proposed as an additional marker for IEPOX-OA, as it is shown to correlate well with the m=z 82 ion shown to be associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The contribution of 91Fac to the total OA mass was quite low at the urban site (~ 9 %), but was significant (21-23 %) at the rural site during warmer months. Comparison of 91Fac OA time series with SOA tracers measured from filter samples collected at Look Rock suggests that isoprene oxidation through a pathway other than IEPOX SOA chemistry may contribute to its formation. Other biogenic sources could also contribute to 91Fac, but there remains a need to resolve the exact source of this factor based on its significant contribution to rural OA mass. [ABSTRACT FROM AUTHOR]

Long-term (1999 to 2013) data from the Southeastern Aerosol Research and Characterization (SEARCH) network are used to characterize the effects of anthropogenic emission reductions on fine particle organic aerosol (OA) concentrations in the southeastern US. On average, 45 % (range 25 to 63 %) of the 1999 to 2013 mean organic carbon (OC) concentrations are attributed to combustion processes, including fossil-fuel use and biomass burning, through associations of measured OC with combustion products such as elemental carbon (EC), carbon monoxide (CO), and nitrogen oxides (NOx). The 2013 mean combustion-derived OC concentrations were 0.5 to 1.4 µg m-3 at the five sites operating in that year. Mean annual combustion-derived OC concentrations declined from 3.8 ± 0.2 µg m-3 (68 % of total OC) to 1.4 ± 0.1 µg m-3 (60 % of total OC) between 1999 and 2013 at the urban Atlanta, Georgia, site (JST) and from 2.9 ± 0.4 µg m-3 (39 % of total OC) to 0.7 ± 0.1 µg m-3 (30 % of total OC) between 2001 and 2013 at the urban Birmingham, Alabama, site (BHM). The urban OC declines coincide with reductions of motor-vehicle emissions between 2006 and 2010, which may have decreased mean OC concentrations at the urban SEARCH sites by > 2 µg m-3. BHM additionally exhibits a decline in OC associated with SO2 from 0.4 ± 0.04 µg m-3 in 2001 to 0.2 ± 0.03 µg m-3 in 2013, interpreted as the result of reduced emissions from industrial sources within the city. Analyses using non-soil potassium as a biomass-burning tracer indicate that biomass-burning OC occurs throughout the year at all sites. All eight SEARCH sites show an association of OC with sulfate (SO4) ranging from 0.3 to 1.0 µg m-3 on average, representing ~ 25 % of the 1999 to 2013 mean OC concentrations. Because the mass of OC associated with SO4 averages 20 to 30 % of the SO4 concentrations, the mean SO4-associated OC declined by ~ 0.5 to 1 µg m-3 as SO4 decreased throughout the SEARCH region. The 2013 mean SO4 concentrations of 1.7 to 2.0 µg m-3 imply that future decreases in mean SO4-associated OC concentrations would not exceed ~ 0.3 to 0.5 µg m-3. Seasonal OC concentrations, largely associated with ozone (O3), vary from 0.3 to 1.4 µg m-3 (~ 20 % of the total OC concentrations). [ABSTRACT FROM AUTHOR]

A variety of methods are used to measure the capability of particulate matter (PM) to catalytically generate reactive oxygen species (ROS) in vivo, also defined as the aerosol oxidative potential. A widely used measure of aerosol oxidative potential is the dithiothreitol (DTT) assay, which monitors the depletion of DTT (a surrogate for cellular antioxidants) as catalyzed by the redox-active species in PM. However, a major constraint in the routine use of the DTT assay for integrating it with the large-scale health studies is its labor-intensive and time-consuming protocol. To specifically address this concern, we have developed a semi-automated system for quantifying the oxidative potential of aerosol liquid extracts using the DTT assay. The system, capable of unattended analysis at one sample per hour, has a high analytical precision (Coefficient of Variation of 12% for standards, 4% for ambient samples), and reasonably low limit of detection (0.31 nmol min-1). Comparison of the automated approach with the manual method conducted on ambient samples yielded good agreement (slope = 1.08±0.12, r2 = 0.92, N = 9). The system was utilized for the Southeastern Center for Air Pollution and Epidemiology (SCAPE) to generate an extensive data set on DTT activity of ambient particles collected from contrasting environments (urban, road-side, and rural) in the southeastern US. We find that water-soluble PM2.5 DTT activity on a per air volume basis was spatially uniform and often well correlated with PM2.5 mass (r = 0.49 to 0.88), suggesting regional sources contributing to the PM oxidative potential in southeast US. However, the greater heterogeneity in the intrinsic DTT activity (per PM mass basis) across seasons indicates variability in the DTT activity associated with aerosols from sources that vary with season. Although developed for the DTT assay, the instrument can also be used to determine oxidative potential with other acellular assays. [ABSTRACT FROM AUTHOR]

Filter-based PM2.5 samples were chemically analyzed to investigate secondary organic aerosol (SOA) formation from isoprene in a rural atmosphere of the southeastern US influenced by both anthropogenic sulfur dioxide (SO2) and ammonia (NH3) emissions. Daytime PM2.5 samples were collected during summer 2010 using conditional sampling approaches based on pre-defined high and low SO2 or NH3 thresholds. Known molecular-level tracers for isoprene SOA formation, including 2-methylglyceric acid, 3-methyltetrahydrofuran-3,4-diols, 2-methyltetrols, C5-alkene triols, dimers, and organosulfate derivatives, were identified and quantified by gas chromatography cou pled to electron ionization mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). Mass concentrations of six isoprene low-NOx SOA tracers contributed to 12-19% of total organic matter (OM) in PM2.5 samples collected during the sampling period, indicating the importance of the hydroxyl radical (OH)-initiated oxidation (so-called photooxidation) of isoprene under low-NOx conditions that leads to SOA formation through reactive uptake of gaseous isoprene epoxydiols (IEPOX) in this region. IEPOX-derived SOA tracers were enhanced under high-SO2 sampling scenarios, suggesting that SO2 oxidation increases aerosol acidity of sulfate aerosols needed for enhancing heterogeneous oxirane ring opening reactions of IEPOX. No clear associations between isoprene SOA formation and high and low NH3 conditional samples were found. Furthermore, weak correlations between aerosol acidity and mass of IEPOX SOA tracers suggests that IEPOX-derived SOA formation might be modulated by other factors as well in addition to aerosol acidity. Positive correlations between sulfate aerosol loadings and IEPOX-derived SOA tracers for samples collected under all conditions indicates that sulfate aerosol could be a surrogate for surface area in the uptake of IEPOX onto preexisting aerosols. [ABSTRACT FROM AUTHOR]

Atmospheric deposition represents a major input of mercury to surface environments. The phase of mercury (gas or particle) has important implications for its removal from the atmosphere. We use long-term observations of reactive gaseous mercury (RGM), particle-bound mercury (PBM), fine particulate matter (PM2.5), and temperature at five sites in North America to derive an empirical gas-particle partitioning relationship log10 (K-1) = (10 ± 1) - (2500 ± 300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM2.5 in µg m-3, and T in Kelvin. This relationship is in the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition divalent mercury (Hg(II)). The resulting gas-phase fraction of Hg(II) ranges from over 90% in warm air with little aerosol to less than 10% in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by snow. Model comparison to Hg observations at surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. This and other model updates, including the correction of an outstanding algorithm error, to wet deposition improve the simulation of Hg wet deposition fluxes in the US relative to the previous version of the model. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II). [ABSTRACT FROM AUTHOR]

Fine particle (PM2.5) light absorption characteristics of aqueous extracts over wavelengths of 250 to 700nm were investigated based on two data sets; 24-h Federal Reference Method (FRM) filter extracts from 15 southeastern US monitoring sites over the year of 2007 (900 filters), and online measurements from a Particle-Into-Liquid Sampler deployed from July to mid-August 2009 in Atlanta, Georgia. Three main sources of soluble chromophores were identified, biomass burning, mobile source emissions, and compounds linked to Secondary Organic Aerosol (SOA) formation. Absorption spectra of aerosol solutions from different sources were similar. Angstrom exponents were ∼7±1 for biomass burning and non-biomass burning-impacted samples (delineated by a levoglucosan concentration of 50 ngm-3) at both rural and urban sites. The absorption coefficient from measurements averaged between wavelength 360 and 370nm (Abs365, in units m-1) was used as a measure of overall brown carbon absorptivity. Biomass-burning-impacted samples were highest during colder months and Abs365 was correlated with levoglucosan at all sites. During periods of little biomass burning in summer, light absorbing compounds were still ubiquitous and correlated with fine particle Water-Soluble Organic Carbon (WSOC), but comprised a much smaller fraction of the WSOC, where Abs365/WSOC (i.e., mass absorption efficiency) was typically ∼3 times higher in biomass burning-impacted samples. Factor analysis attributed 50% of the yearly average Abs365 to biomass burning sources. Brown carbon from primary urban emissions (mobile sources) was also observed and accounted for ∼10% of the regional yearly average Abs365. Summertime diurnal profiles of Abs365 and WSOC showed that morning to midday increases in WSOC from photochemical production were associated with a decrease in Abs365/WSOC. After noon this ratio substantially increased, indicating that either some fraction of the non-light absorbing fresh SOA was rapidly (within hours) converted to chromophores heterogeneously, or that SOA from gas-particle partitioning later in the day was more light-absorbing. Factor analysis associated ∼20 to 30% of Abs365 over 2007 with a secondary source that was highest in summer and also the main source for oxalic acid, suggesting that aqueous phase reactions may account for the light-absorbing fraction of WSOC observed throughout the southeastern US in summer. [ABSTRACT FROM AUTHOR]

Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM2.5), and temperature (T) at five sites in North America to derive an empirical gas-particle partitioning relationship log10(K−1) = (10±1)–(2500±300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM2.5 in μg m−3, and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semi-volatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II)., Earth and Planetary Sciences, Engineering and Applied Sciences

Single collection stations for wet or bulk deposition are generally inadequate to describe atmospheric inputs to watersheds in complex terrain. Atmospheric deposition is delivered by wet, dry and cloud deposition processes, and these processes are controlled by a wide range of landscape features, including canopy type and structure, topographic exposure, elevation and slope orientation. As a result, there can be a very high degree of spatial variability within a watershed, and a single sampling point, especially at low elevation, is unlikely to be representative. Atmospheric inputs at the watershed scale can be calculated from the whole watershed mass balance if the outputs and within-watershed sources and sinks are known with sufficient accuracy. Alternatively, indices of atmospheric deposition such as Pb accumulation in the forest floor and SO42- flux in throughfall can be used to characterize patterns of total deposition, and these indices can be used to model deposition to the entire watershedbased on known landscape features such as elevation and canopy type. [ABSTRACT FROM AUTHOR]

This study describes and analyzes measurements of 119 non-polar organic compounds in PM2.5 samples from three urban sites in the Southeastern Aerosol Research and Characterization (SEARCH) network: Jefferson Street in Atlanta, Georgia (JST), Birmingham, Alabama (BHM), and Hinton, Texas (HIN). Daily 24-h PM2.5 samples were collected on quartz-fiber filters from January 2006 through 2007 at HIN and from March 2006 through 2010 at JST and BHM. PM2.5 sampling at BHM and JST is ongoing. The measured species are associated with directly emitted particles and potentially serve as tracers of specific types of emissions. PM2.5 organic measurements include 28 n-alkanes (C15-C42), 18 iso-/anteiso-alkanes (C29-C37), 2 methyl alkanes, 3 branched alkanes, 5 cycloalkanes, 32 PAH compounds, 18 hopanes, 12 steranes, and 1 alkene, many of which are constituents of motor-vehicle exhaust and other anthropogenic PM2.5 emissions. Predominantly anthropogenic origins of the measured compounds are indicated by weekly and seasonal cycles that are identified with known emission patterns, especially for motor vehicle usage. Annual mean concentrations of each class of compounds declined by 60-90% from 2006 through 2009, then increased in 2010 to concentrations comparable to 2008. These changes are similar to 40% reductions of on-road and non-road motor-vehicle exhaust PM2.5 emissions between 2006 and 2010. Year-to-year variations in OC correlated with year-to-year variations in measured non-polar compound concentrations. Regression of OC against the sums of measured n-alkanes, iso-/anteiso-alkanes, PAHs, hopanes, and steranes indicates that 32 ± 7% of OC at BHM and 35 ± 4% of OC at JST derived from sources emitting the measured non-polar compounds. The reductions in measured concentrations of EC, OC, and non-polar OC species represent an important improvement in air quality in the southeastern U.S. that can be attributed by the long-term measurement program to PM2.5 emission reductions. [ABSTRACT FROM AUTHOR]

Unlabelled: The SEARCH study began in mid 1998 with a focus on particulate matter and gases in the southeastern United States. Eight monitoring sites, comprising four urban/nonurban pairs, are located inland and along the coast of the Gulf of Mexico. Downward trends in ambient carbon monoxide (CO), sulfur dioxide (SO2), and oxidized nitrogen species (NOy) concentrations averaged 1.2 +/- 0.4 to 9.7 +/- 1.8% per year from 1999 to 2010, qualitatively proportional to decreases of 4.7 to 7.9% per year in anthropogenic emissions of CO, SO2, and oxides of nitrogen (NOx) in the SEARCH region. Downward trends in mean annual sulfate (SO4) concentrations ranged from 3.7 +/- 1.1 to 6.2 +/- 1.1% per year approximately linear with, but not 1:1 proportional to, the 7.9 +/- 1.1% per year reduction in SO2 emissions from 1999 to 2010. The 95th percentile of the March-October peak daily 8-hr ozone (O3 concentrations decreased by 1.1 +/- 0.4 to 2.4 +/- 0.6 ppbv per year (1.5 +/- 0.6 to 3.1 +/- 0.8% per year); O3 precursor emissions of NOx and volatile organic compounds (VOC) decreased at rates of 4.7 and 3.3% per year, respectively. Ambient particulate nitrate (NO3) concentrations decreased by 0.6 +/- 1.2 to 5.8 +/- 0.9% per year modulated in comparison with mean annual ambient NOy concentration decreases ranging from 6.0 +/- 0.9 to 9.0 +/- 1.3% per year. Mean annual organic matter (OM) and elemental carbon (EC) concentrations declined by 3.3 +/- 0.8 to 6.5 +/- 0.3 and 3.2 +/- 1.4 to 7.8 +/- 0.7% per year. The analysis demonstrates major improvements in air quality in the Southeast from 1999 to 2010. Meteorological variations and incompletely quantified uncertainties for emission changes create difficulty in establishing unambiguous quantitative relationships between emission reductions and ambient air quality., Implications: Emissions and secondary pollutants show complex relationships that depend on year-to-year variations in dispersion and atmospheric chemistry. The observed response of 03 to NOx and VOC emissions in the Southeast implies that continuing reductions of precursor emissions, probably achieved through vehicle fleet turnover and emission control measures, will be needed to attain the National Ambient Air Quality Standard for O3. Reductions in fine particle concentrations have resulted from reductions of primary PM, especially EC and a portion of OM, and from reduction of gas precursors known to form particles, especially SO4 from SO2. Continued reduction of PM2.5 mass concentrations will require attention to organic constituents, which may be complicated by potentially unmanageable biogenic species present in the Southeast.

Unlabelled: The Southeastern Aerosol Research and Characterization (SEARCH) study, which has been in continuous operation from 1999 to 2012, was implemented to investigate regional and urban air pollution in the southeastern United States. With complementary data from other networks, the SEARCH measurements provide key knowledge about long-term urban/nonurban pollution contrasts and regional climatology affecting inland locations and sites along the Gulf of Mexico coastline. Analytical approaches ranging from comparisons of mean concentrations to the application of air mass trajectories and principal component analysis provide insight into local and area-wide pollution. Gases (carbon monoxide, sulfur dioxide, nitrogen oxides, ozone, and ammonia), fine particle mass concentration, and fine particle species concentrations (including sulfate, elementary carbon, and organic carbon) are affected by a combination of regional conditions and local emission sources. Urban concentrations in excess of regional baselines and intraurban variations of concentrations depend on source proximity, topography, and local meteorological processes. Regional-scale pollution events (95th percentile concentrations) involving more than 6 of the 8 SEARCH sites are rare (< 2% of days), while subregional events affecting 4-6 sites occur on approximately 10% of days. Regional and subregional events are characterized by widely coincident elevated concentrations of ozone, sulfate, and particulate organic carbon, driven by persistent synoptic-scale air mass stagnation and higher temperatures that favor formation of secondary species, mainly in the summer months. The meteorological conditions associated with regional stagnation do not favor long-range transport of polluted air masses during episodes. Regional and subregional pollution events frequently terminate with southward and eastward penetration of frontal systems, which may initially reduce air pollutant concentrations more inland than along the Gulf Coast., Implications: Regional distribution of emission sources and synoptic-scale meteorological influences favoring stagnation lead to high regionwide pollution levels. The regional influence is greatest with secondary species, including ozone (03) particulate sulfate (SO4), and particulate organic matter, some of which is produced by atmospheric oxidation of volatile organic compounds (VOCs) from vegetation and anthropogenic sources. Other species, many of which are from primary emissions, are more influenced by local sources, especially within the Atlanta, GA, and Birmingham, AL, metropolitan areas. Limited measurements of modern and fossil total carbon point to the importance of biological and biogenic emissions in the Southeast.

The objective of the National Dry Deposition Network is to determine patterns and trends of dry deposition for various sulfur and nitrogen species at roughly 50 locations throughout the continental USA. Each site is equipped for collection of continuous meteorological and ozone data and weekly average concentrations of SO4(2-), NO3-, SO2 and HNO3, using a three-stage filter pack. Results from 40 eastern US sites operational throughout 1989 show species-dependent variability from site to site, season to season, and day to night. Annual average concentrations of atmospheric SO4(2-), NO3-, SO2 and HNO3 ranged from 2.7 to 7.9, 0.2 to 3.9, 2.4 to 23.2 and 0.7 to 3.6 microg/m(-3), respectively. Seasonal variability was considerable for all constituents. Day/night data indicate that SO2 and HNO3, but not SO4(2-) and NO3-, are typically found at moderately to substantially lower concentrations at night, especially during spring and summer. Estimated dry deposition for SO2 and HNO3 appear to be much greater than for SO4(2-) and NO3-, respectively. Comparison of measured wet deposition and estimated dry deposition at numerous sites suggests that the two are similar in magnitude over much of the eastern USA.

Detailed chemical analyses reveal that acid precipitation (pH < 5.6) in the northeastern United States is caused by the strong mineral acids sulfuric and nitric. There is a large array of other proton sources in precipitation, weak acids and Bronsted acids; however, although these other acids contribute to the total acidity of precipitation, they have a minimal influence on the free acidity (ambient pH) of acid precipitation.