Impacts of anthropogenic emissions and meteorology on spring ozone differences in San Antonio, Texas between 2017 and 2021.

San Antonio has been designated as ozone nonattainment under the current National Ambient Air Quality Standards (NAAQS). Ozone events in the city typically occur in two peaks, characterized by a pronounced spring peak followed by a late summer peak. Despite higher ozone levels, the spring peak has received less attention than the summer peak. To address this research gap, we used the Weather Research and Forecasting (WRF)-driven GEOS-Chem (WRF-GC) model to simulate San Antonio's ozone changes in the spring month of May from 2017 to 2021 and quantified the respective contributions from changes in anthropogenic emissions and meteorology. In addition to modeling, observations from the San Antonio Field Studies (SAFS), the Texas Commission on Environmental Quality (TCEQ) Continuous Ambient Monitoring Stations (CAMS), and the spaceborne TROPOspheric Monitoring Instrument (TROPOMI) are used to examine and validate changes in ozone and precursors. Results show that the simulated daytime mean surface ozone in May 2021 is 3.8 ± 0.6 ppbv lower than in May 2017, which is slightly less than the observed average differences of -5.3 ppbv at CAMS sites. The model predicted that the anthropogenic emission-induced changes contribute to a 1.4 ± 0.5 ppbv reduction in daytime ozone levels, while the meteorology-induced changes account for a 2.4 ± 0.6 ppbv reduction over 2017-2021. This suggests that meteorology plays a relatively more important role than anthropogenic emissions in explaining the spring ozone differences between the two years. We additionally identified (1) reduced NO2 and HCHO concentrations as chemical reasons, and (2) lower temperature, higher humidity, increased wind speed, and a stronger Bermuda High as meteorological reasons for lower ozone levels in 2021 compared to 2017. The quantification of the different roles of meteorology and ozone precursor concentrations helps understand the cause and variation of ozone changes in San Antonio over recent years.

Marine Submicron Aerosols from the Gulf of Mexico: Polluted and Acidic with Rapid Production of Sulfate and Organosulfates.

We measured submicron aerosols (PM1) at a beachfront site in Texas in Spring 2021 to characterize the "background" aerosol chemical composition advecting into Texas and the factors controlling this composition. Observations show that marine "background" aerosols from the Gulf of Mexico were highly processed and acidic; sulfate was the most abundant component (on average 57% of total PM1 mass), followed by organic material (26%). These chemical characteristics are similar to those observed at other marine locations globally. However, Gulf "background" aerosols were much more polluted; the average non-refractory (NR-) PM1 mass concentration was 3-70 times higher than that observed in other clean marine atmospheres. Anthropogenic shipping emissions over the Gulf of Mexico explain 78.3% of the total measured "background" sulfate in the Gulf air. We frequently observed haze pollution in the air mass from the Gulf, with significantly elevated concentrations of sulfate, organosulfates, and secondary organic aerosol associated with sulfuric acid. Analysis suggests that aqueous oxidation of shipping emissions over the Gulf of Mexico by peroxides in the particles might potentially be an important pathway for the rapid production of acidic sulfate and organosulfates during the haze episodes under acidic conditions.

Traffic, transport, and vegetation drive VOC concentrations in a major urban area in Texas.

The population of Texas has increased rapidly in the past decade. The San Antonio Field Study (SAFS) was designed to investigate ozone (O3) production and precursors in this rapidly changing, sprawling metropolitan area. There are still many questions regarding the sources and chemistry of volatile organic compounds (VOCs) in urban areas like San Antonio which are affected by a complex mixture of industry, traffic, biogenic sources and transported pollutants. The goal of the SAFS campaign in May 2017 was to measure inorganic trace gases, VOCs, methane (CH4), and ethane (C2H6). The SAFS field design included two sites to better assess air quality across the metro area: an urban site (Traveler's World; TW) and a downwind/suburban site (University of Texas at San Antonio; UTSA). The results indicated that acetone (2.52 ± 1.17 and 2.39 ± 1.27 ppbv), acetaldehyde (1.45 ± 1.02 and 0.93 ± 0.45 ppbv) and isoprene (0.64 ± 0.49 and 1.21 ± 0.85 ppbv; TW and UTSA, respectively) were the VOCs with the highest concentrations. Additionally, positive matrix factorization showed three dominant factors of VOC emissions: biogenic, aged urban mixed source, and acetone. Methyl vinyl ketone and methacrolein (MVK + MACR) exhibited contributions from both secondary photooxidation of isoprene and direct emissions from traffic. The C2H6:CH4 demonstrated potential influence of oil and gas activities in San Antonio. Moreover, the high O3 days during the campaign were in the NOx-limited O3 formation regime and were preceded by evening peaks in select VOCs, NOx and CO. Overall, quantification of the concentration and trends of VOCs and trace gases in a major city in Texas offers vital information for general air quality management and supports strategies for reducing O3 pollution. The SAFS campaign VOC results will also add to the growing body of literature on urban sources and concentrations of VOCs in major urban areas.

Solid organic-coated ammonium sulfate particles at high relative humidity in the summertime Arctic atmosphere.

SignificancePhysical and chemical properties of individual atmospheric particles determine their climate impacts. Hygroscopic inorganic salt particles mixed with trace amounts of organic material are predicted to be liquid under typical tropospheric conditions in the summertime Arctic. Yet, we unexpectedly observed a significant concentration of solid particles composed of ammonium sulfate with an organic coating under conditions of high relative humidity and low temperature. These particle properties are consistent with marine biogenic-derived new particle formation and growth, with particle collision hypothesized to result in the solid phase. This particle source is predicted to have increasing relevance in the context of declining Arctic sea ice and increasing open water, with impacts on clouds, and therefore climate.

Equal abundance of summertime natural and wintertime anthropogenic Arctic organic aerosols.

Aerosols play an important yet uncertain role in modulating the radiation balance of the sensitive Arctic atmosphere. Organic aerosol is one of the most abundant, yet least understood, fractions of the Arctic aerosol mass. Here we use data from eight observatories that represent the entire Arctic to reveal the annual cycles in anthropogenic and biogenic sources of organic aerosol. We show that during winter, the organic aerosol in the Arctic is dominated by anthropogenic emissions, mainly from Eurasia, which consist of both direct combustion emissions and long-range transported, aged pollution. In summer, the decreasing anthropogenic pollution is replaced by natural emissions. These include marine secondary, biogenic secondary and primary biological emissions, which have the potential to be important to Arctic climate by modifying the cloud condensation nuclei properties and acting as ice-nucleating particles. Their source strength or atmospheric processing is sensitive to nutrient availability, solar radiation, temperature and snow cover. Our results provide a comprehensive understanding of the current pan-Arctic organic aerosol, which can be used to support modelling efforts that aim to quantify the climate impacts of emissions in this sensitive region.

Contemporary sources dominate carbonaceous aerosol on the North Slope of Alaska.

As the Arctic continues to change and warm rapidly, it is increasingly important to understand the organic carbon (OC) contribution to Arctic aerosol. Biogenic sources of primary and secondary OC in the Arctic will be impacted by climate change, including warming temperatures and earlier snow and ice melt. This study focuses on identifying potential sources and regional influences on the seasonal concentration of organic aerosol through analysis of chemical and isotopic composition. Aerosol samples were collected at two sites on the North Slope of Alaska (Utqiagvik, UQK, and Oliktok Point, OLK, which is in an Arctic oilfield) over three summers from 2015 to 2017. The elemental carbon (EC) trends at each site were used to understand local combustion influences. Local sources drove EC concentrations at Oliktok Point, where high EC was attributed to oil and gas extraction activity, including diesel combustion emissions. Utqiagvik had very low EC in the summer. OC was more similar in concentration and well correlated between the two sites with high contributions of contemporary carbon by radiocarbon apportionment (UQK = 74%, OLK = 63%), which could include both marine and terrestrial sources of contemporary carbon (e.g. primary and secondary biogenic, biomass burning and/or associated SOA, and bioaerosols). OC concentrations are strongly correlated to maximum ambient temperatures on the NSA during the summer, which may have implications for predicting future OC aerosol concentrations in a warming Arctic. Biomass burning was determined to be an episodic influence at both sites, based on interpretation of combined aerosol composition, air mass trajectories, and remote sensing of smoke plumes. The results from this study overall strongly suggests contribution from regional sources of contemporary organic aerosol on the NSA, but additional analysis is needed to better constrain contributions from both biogenic sources (terrestrial and/or marine) and bioaerosol to better understand temperature-related aerosol processes in the Arctic.

Assessing the atmospheric fate of pesticides used to control mosquito populations in Houston, TX.

During the summer months, urban areas are literal hot spots of mosquito-borne disease transmission and air pollution. Public health authorities release aerosolized pesticides directly into the atmosphere to help control adult mosquito populations and thereby reduce the threat of diseases, such as Zika Virus. The primary adulticides (i.e. pesticides used to control adult mosquito populations) in Houston, TX are permethrin and malathion. These adulticides are typically sprayed at night using ultra-low volume sprayers. Particulate matter (PM) samples including total suspended and fine PM (PM < 2.5 µm in aerodynamic diameter) were collected at four ground-based sites across Houston in 2013 and include daytime, nighttime, and 24 h samples. Malathion is initially sprayed as coarse aerosol (5-25 µm), but is measured in fine aerosol (<2.5 µm) and coarse aerosol in the urban atmosphere. Particle size is relevant both for deposition velocities and for human exposure. Atmospheric permethrin concentrations measured in nighttime samples peak at 60 ng m-3, while malathion nighttime concentrations peak near 40 ng m-3. Malaoxon, an oxidation product of malathion, was also frequently detected at concentrations >10 ng m-3, indicating significant nighttime oxidation. Based on the loss of malathion and the increase in malaoxon, the atmospheric half-life of malathion in Houston was estimated at <12 h, which was significantly shorter than previous half-life estimates (∼days). Importantly, malaoxon is estimated to be 22-33 times more toxic to humans than malathion. Both the aerosol size and the half-life are critical for mosquito control, human exposure, and risk assessment of these routine pesticides.

Apportioned primary and secondary organic aerosol during pollution events of DISCOVER-AQ Houston.

Understanding the drivers for high ozone (O3) and atmospheric particulate matter (PM) concentrations is a pressing issue in urban air quality, as this understanding informs decisions for control and mitigation of these key pollutants. The Houston, TX metropolitan area is an ideal location for studying the intersection between O3 and atmospheric secondary organic carbon (SOC) production due to the diversity of source types (urban, industrial, and biogenic) and the on- and off-shore cycling of air masses over Galveston Bay, TX. Detailed characterization of filter-based samples collected during Deriving Information on Surface Conditions from Column and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) Houston field experiment in September 2013 were used to investigate sources and composition of organic carbon (OC) and potential relationships between daily maximum 8 h average O3 and PM. The current study employed a novel combination of chemical mass balance modeling defining primary (i.e. POC) versus secondary (i.e. SOC) organic carbon and radiocarbon (14C) for apportionment of contemporary and fossil carbon. The apportioned sources include contemporary POC (biomass burning [BB], vegetative detritus), fossil POC (motor vehicle exhaust), biogenic SOC and fossil SOC. The filter-based results were then compared with real-time measurements by aerosol mass spectrometry. With these methods, a consistent urban background of contemporary carbon and motor vehicle exhaust was observed in the Houston metropolitan area. Real-time and filter-based characterization both showed that carbonaceous aerosols in Houston was highly impacted by SOC or oxidized OC, with much higher contributions from biogenic than fossil sources. However, fossil SOC concentration and fractional contribution had a stronger correlation with daily maximum 8 h average O3, peaking during high PM and O3 events. The results indicate that point source emissions processed by on- and off-shore wind cycles likely contribute to peak events for both PM and O3 in the greater Houston metropolitan area.

Diesel Soot and Amine-Containing Organic Sulfate Aerosols in an Arctic Oil Field.

The rapid decrease in Arctic sea ice is motivating development and increasing oil and gas extraction activities. However, few observations of these local Arctic emissions exist, limiting the understanding of impacts on atmospheric composition and climate. To address this knowledge gap, the chemical composition of atmospheric aerosols was measured within the North Slope of Alaska oil fields during August and September 2016 using an aerosol time-of-flight mass spectrometer (ATOFMS) and a time-of-flight aerosol chemical speciation monitor (ToF-ACSM). Plumes from oil and gas extraction activities were characterized by soot internally mixed with sulfate (matching diesel soot) and organic carbon particles containing aminium sulfate salts. Sea spray aerosol at the coastal site was frequently internally mixed with sulfate and nitrate, from multiphase chemical processing from elevated NOx and SO2 within the oil field. Background (nonplume) air masses were characterized by aged combustion aerosol. No periods of "clean" (nonpolluted) Arctic air were observed. The composition of the nonrefractory aerosol measured with the ACSM was similar during plume and background periods and was consistent with the mass concentrations of nonrefractory particles measured by ATOFMS. Two ultrafine aerosol growth events were observed during oil field background periods and were correlated with fine mode amine-containing particles.

Urban Trees Are Sinks for Soot: Elemental Carbon Accumulation by Two Widespread Oak Species.

Urban trees could represent important short- and long-term landscape sinks for elemental carbon (EC). Therefore, we quantified foliar EC accumulation by two widespread oak tree species-Quercus stellata (post oak) and Quercus virginiana (live oak)-as well as leaf litterfall EC flux to soil from April 2017 to March 2018 in the City of Denton, Texas, within the Dallas-Fort Worth metropolitan area. Post oak trees accumulated 1.9-fold more EC (299 ± 45 mg EC m-2 canopy yr-1) compared to live oak trees (160 ± 31 mg EC m-2 canopy yr-1). However, in the fall, these oak species converged in their EC accumulation rates, with ∼70% of annual accumulation occurring during fall and on leaf surfaces. The flux of EC to the ground via leaf litterfall mirrored leaf-fall patterns, with post oaks and live oaks delivering ∼60% of annual leaf litterfall EC in fall and early spring, respectively. We estimate that post oak and live oak trees in this urban ecosystem potentially accumulate 3.5 t EC yr-1, equivalent to ∼32% of annual vehicular EC emissions from the city. Thus, city trees are significant sinks for EC and represent potential avenues for climate and air quality mitigation in urban areas.

Source apportionment of fine particulate matter organic carbon in Shenzhen, China by chemical mass balance and radiocarbon methods.

Chemical mass balance (CMB) modeling and radiocarbon measurements were combined to evaluate the sources of carbonaceous fine particulate matter (PM2.5) in Shenzhen, China during and after the 2011 summer Universiade games when air pollution control measurements were implemented to achieve air quality targets. Ambient PM2.5 filter samples were collected daily at two sampling sites (Peking University Shenzhen campus and Longgang) over 24 consecutive days, covering the controlled and uncontrolled periods. During the controlled period, the average PM2.5 concentration was less than half of what it was after the controls were lifted. Organic carbon (OC), organic molecular markers (e.g., levoglucosan, hopanes, polycyclic aromatic hydrocarbons), and secondary organic carbon (SOC) tracers were all significantly lower during the controlled period. After pollution controls ended, at Peking University, OC source contributions included gasoline and diesel engines (24%), coal combustion (6%), biomass burning (12.2%), vegetative detritus (2%), biogenic SOC (from isoprene, α-pinene, and ß-caryophyllene; 7.1%), aromatic SOC (23%), and other sources not included in the model (25%). At Longgang after the controls ended, similar source contributions were observed: gasoline and diesel engines (23%), coal combustion (7%), biomass burning (17.7%), vegetative detritus (1%), biogenic SOC (from isoprene, α-pinene, and ß-caryophyllene; 5.3%), aromatic SOC (13%), and other sources (33%). The contributions of the following sources were smaller during the pollution controls: biogenic SOC (by a factor of 10-16), aromatic SOC (4-12), coal combustion (1.5-6.8), and biomass burning (2.3-4.9). CMB model results and radiocarbon measurements both indicated that fossil carbon dominated over modern carbon, regardless of pollution controls. However, the CMB model needs further improvement to apportion contemporary carbon (i.e. biomass burning, biogenic SOC) in this region. This work defines the major contributors to carbonaceous PM2.5 in Shenzhen and demonstrates that control measures for primary emissions could significantly reduce secondary organic aerosol (SOA) formation.

Spatial and Temporal Distributions of Organophosphate Ester Concentrations from Atmospheric Particulate Matter Samples Collected across Houston, TX.

Atmospheric particulate matter (PM) samples were collected from four ground-based sites located in the Houston, TX (September 21-28, 2013) and were analyzed for 12 organophosphate esters (OPEs; current-use plasticizers and flame retardants). Samples analyzed included daytime, nighttime, and 24 h PM of <2.5 µm aerodynamic diameter (PM2.5) and total suspended particulate (TSP) samples. PM2.5 and TSP atmospheric ΣOPE concentrations varied over an order of magnitude and were statistically significantly different between urban and suburban and industrial sites. Additionally, significant temporal variability was also identified; for example, daytime atmospheric concentrations of 2-ethylhexyl diphenyl phosphate (EHDPP; 610 ± 220 pg m-3) measured in TSP samples were significantly higher than nighttime concentrations (280 ± 180 pg m-3; p = 0.03). Detailed discussions of the spatial and temporal distribution are given for Tris-(1-chloro-2-propyl) phosphate (TCiPP), EHDPP, tri-n-butyl phosphate (TnBP), and triphenyl phosphate (TPhP). Correlations to bulk measurements of carbonaceous PM including organic carbon, elemental carbon, and water-soluble organic carbon were used to understand potential sources and urban atmospheric transport. These results highlight the fundamental complexity associated with assessing OPE atmospheric concentrations across a large urban landscape and specific knowledge gaps at the intersection of consumer products and safety with environmental and human health.

Constraints on primary and secondary particulate carbon sources using chemical tracer and 14C methods during CalNex-Bakersfield.

The present study investigates primary and secondary sources of organic carbon for Bakersfield, CA, USA as part of the 2010 CalNex study. The method used here involves integrated sampling that is designed to allow for detailed and specific chemical analysis of particulate matter (PM) in the Bakersfield airshed. To achieve this objective, filter samples were taken during thirty-four 23-hr periods between 19 May and 26 June 2010 and analyzed for organic tracers by gas chromatography - mass spectrometry (GC-MS). Contributions to organic carbon (OC) were determined by two organic tracer-based techniques: primary OC by chemical mass balance and secondary OC by a mass fraction method. Radiocarbon (14C) measurements of the total organic carbon were also made to determine the split between the modern and fossil carbon and thereby constrain unknown sources of OC not accounted for by either tracer-based attribution technique. From the analysis, OC contributions from four primary sources and four secondary sources were determined, which comprised three sources of modern carbon and five sources of fossil carbon. The major primary sources of OC were from vegetative detritus (9.8%), diesel (2.3%), gasoline (<1.0%), and lubricating oil impacted motor vehicle exhaust (30%); measured secondary sources resulted from isoprene (1.5%), α-pinene (<1.0%), toluene (<1.0%), and naphthalene (<1.0%, as an upper limit) contributions. The average observed organic carbon (OC) was 6.42 ± 2.33 µgC m-3. The 14C derived apportionment indicated that modern and fossil components were nearly equivalent on average; however, the fossil contribution ranged from 32-66% over the five week campaign. With the fossil primary and secondary sources aggregated, only 25% of the fossil organic carbon could not be attributed. Whereas, nearly 80% of the modern carbon could not be attributed to primary and secondary sources accessible to this analysis, which included tracers of biomass burning, vegetative detritus and secondary biogenic carbon. The results of the current study contributes source-based evaluation of the carbonaceous aerosol at CalNex Bakersfield.

Spatial and Temporal Distribution of Current-Use Pesticides in Atmospheric Particulate Matter in Houston, Texas.

The atmospheric concentrations of seven current-use pesticides in particulate matter were determined at four locations throughout the Houston metropolitan area in TSP and PM2.5 samples from September 2013. Atmospheric concentrations in both TSP and PM2.5 ranged from below method detection limits (MDLs) to nearly 1100 pg m-3. The three compounds most frequently detected above MDLs were chlorothalonil, bifenthrin, and λ-cyhalothrin. Atmospheric chlorothalonil concentrations were above 800 pg m-3 in several TSP samples, but

Pressurized liquid extraction technique for the analysis of pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes in atmospheric particulate matter.

An analytical method has been developed for the pressurized liquid extraction (PLE) of a wide range of semi-volatile organic compounds (SVOCs) from atmospheric particulate matter. Approximately 130 SVOCs from eight compound classes were selected as molecular markers of (1) agricultural activity (30 current and historic-use pesticides), (2) industrial activity (18 PCBs), (3) consumer products and building materials (16 PBDEs, 11 OPEs), and (4) motor vehicle exhaust (22 PAHs, 16 alkanes, 9 hopanes, 8 steranes). Currently, there is no analytical method validated for the extraction of all eight compound classes in a single automated technique. The extraction efficiencies of varying solvents and solvent combinations at high temperatures and pressures were examined. Extracts were concentrated and analyzed by gas chromatography coupled with mass spectrometry. The optimized PLE method utilized methylene chloride:acetone (2:1 v/v) at 100 °C with three (5 min) static cycles, flush volume of 80%, and a 100 s N2 purge. Spike and recovery experiments (n=7) provided average percent recoveries for pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes of 88.8±4.0%, 86.9±2.6%, 83.8±2.9%, 101±6%, 90.3±6.1%, 74.4±8.8%, 104±8%, and 86.5±8.6%, respectively. The developed method was applied to atmospheric particulate matter samples collected in the greater Houston, TX metropolitan area. Ambient concentrations of eight classes of compounds (92 SVOCs) were reported in pg m(-3).

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 microm aerodynamic diameter, PM2.5) and OC during the summer (PM2.5 = 10.9 microg m(-3) and OC = 3.0 microg m(-3)) and elevated EC during the winter (0.22 microg 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 PM2.5 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.

Diagnostic air quality model evaluation of source-specific primary and secondary fine particulate carbon.

Ambient measurements of 78 source-specific tracers of primary and secondary carbonaceous fine particulate matter collected at four midwestern United States locations over a full year (March 2004-February 2005) provided an unprecedented opportunity to diagnostically evaluate the results of a numerical air quality model. Previous analyses of these measurements demonstrated excellent mass closure for the variety of contributing sources. In this study, a carbon-apportionment version of the Community Multiscale Air Quality (CMAQ) model was used to track primary organic and elemental carbon emissions from 15 independent sources such as mobile sources and biomass burning in addition to four precursor-specific classes of secondary organic aerosol (SOA) originating from isoprene, terpenes, aromatics, and sesquiterpenes. Conversion of the source-resolved model output into organic tracer concentrations yielded a total of 2416 data pairs for comparison with observations. While emission source contributions to the total model bias varied by season and measurement location, the largest absolute bias of -0.55 µgC/m(3) was attributed to insufficient isoprene SOA in the summertime CMAQ simulation. Biomass combustion was responsible for the second largest summertime model bias (-0.46 µgC/m(3) on average). Several instances of compensating errors were also evident; model underpredictions in some sectors were masked by overpredictions in others.

Temporal trends in motor vehicle and secondary organic tracers using in situ methylation thermal desorption GCMS.

Organic aerosol measurements with high temporal resolution can differentiate primary organic carbon (POC) from secondary organic carbon (SOC) and can be used to distinguish morning rush hour traffic emissions and subsequent photo-oxidation. In the current study, five hour filter samples were collected during the Summer Study for Organic Aerosols at Riverside (SOAR-1 in CA, USA) for analysis of organic molecular markers. To achieve the low detection limits required for the high temporal resolution data, a laboratory-based in situ methylation thermal desorption gas chromatography-mass spectrometry method was developed. This enabled the measurement of potential markers of SOC, including phthalic acid, along with markers for traffic emissions, including norhopane. The aromatic acids correlated well with unapportioned OC from a molecular marker chemical mass balance model (SOC-cmb; r(2) = 0.46-0.70) and SOC from the elemental carbon tracer method (SOC-ec; r(2) = 0.40-0.56). The aromatic acid/norhopane ratio increased substantially over the course of each day. The average mid-day phthalic acid ratio compared to previously published roadway emissions was a factor of 4 times higher, while the average 1,2,3-benzenetricarboxylic acid ratio was a factor of 40 times higher than roadway emissions. Using correlation plots of SOC-cmb and phthalic acid, it was estimated that 2.9 ± 0.6 µg m(-3) SOC was associated with mid-day aromatic acid production in Riverside.

Natural abundance 13C and 14C analysis of water-soluble organic carbon in atmospheric aerosols.

Water-soluble organic carbon (WSOC) constitutes a large fraction of climate-forcing organic aerosols in the atmosphere, yet the sources of WSOC are poorly constrained. A method was developed to measure the stable carbon isotope (δ(13)C) and radiocarbon (Δ(14)C) composition of WSOC for apportionment between fossil fuel and different biogenic sources. Synthetic WSOC test substances and ambient aerosols were employed to investigate the effect of both modern and fossil carbon contamination and any method-induced isotope fractionation. The method includes extraction of aerosols collected on quartz filters followed by purification and preparation for off-line δ(13)C and Δ(14)C determination. The preparative freeze-drying step for isotope analysis yielded recoveries of only ∼70% for ambient aerosols and WSOC probes. However, the δ(13)C of the WSOC isolates were in agreement with the δ(13)C of the unprocessed starting material, even for the volatile oxalic acid probe (6.59 ± 0.37‰ vs 6.33 ± 0.31‰; 2 sd). A (14)C-fossil phthalic acid WSOC probe returned a fraction modern biomass of <0.008 whereas a (14)C-modern sucrose standard yielded a fraction modern of >0.999, indicating the Δ(14)C-WSOC method to be free of both fossil and contemporary carbon contamination. Application of the δ(13)C/Δ(14)C-WSOC method to source apportion climate-affecting aerosols was illustrated be constraining that WSOC in ambient Stockholm aerosols were 88% of contemporary biogenic C3 plant origin.

Assessing the impact of industrial source emissions on atmospheric carbonaceous aerosol concentrations using routine monitoring networks.

Industrial sources can have a significant but poorly defined impact on ambient particulate matter concentrations in select areas. Detailed emission profiles are often not available and are hard to develop because of the diversity of emissions across time and space at large industrial complexes. A yearlong study was conducted in an industrial area in Detroit, MI, which combined real-time particle mass (tapered element oscillating microbalance) and black carbon (aetholometer) measurements with molecular marker measurements of monthly average concentrations as well as daily concentrations of select high pollution days. The goal of the study was to use the real-time data to define days in which the particulate matter concentration in the atmosphere was largely impacted by local source emissions and to use daily speciation data to derive emission profiles for the industrial source. When combined with motor vehicle exhaust, wood smoke and road dust profiles, the industrial source profile was used to determine the contribution of the local industrial source to the total organic carbon (OC) concentrations using molecular marker-chemical mass balance modeling (MM-CMB). The MM-CMB analysis revealed that the industrial source had minimal impact on the monthly average carbonaceous aerosol concentration, but contributed approximately 2 microg m(-3), or a little over one-third of the total OC, on select high-impact days.