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Aqueous multi-phase processes are significant contributors to organic aerosol (OA) mass in the atmosphere. This study characterizes the formation of water-soluble organic matter during the winter in the eastern United States through simultaneous measurements of water-soluble organic carbon in the gas and particle phases (WSOC

Transition metals are thought to be among the most toxic components in atmospheric particulate matter (PM) due to their role in catalyzing reactive oxygen species (ROS) formation. We show that precipitation of the transition metals Fe(II), Fe(III), and Mn(II) are thermodynamically favored in phosphate-based assays used to measure the oxidative potential (OP) – a surrogate for toxicity – of PM. Fe and Mn precipitation is likely to occur at extremely low metal concentrations ( 100 μM) with visible precipitates provide quasi-validation of the thermodynamic modeling. Oxidation of Fe(II) to Fe(III) is likely to be rapid in all in vitro OP assays, transforming Fe to a much less soluble form. Fe precipitates are likely to increase the rate of precipitation of other metals and possibly induce co-precipitation. These results have direct relevance for all PO4-based assays; the implications for studies of PM toxicity are discussed.

Cloud cycling plays a key role in the evolution of atmospheric particles and gases, producing secondary aerosol mass and transforming the optical properties and impacts of aerosols globally. In this study, bulk cloud water samples collected at Whiteface Mountain (Wilmington, NY) in the summer of 2017 were aerosolized, dried to 50% RH, and analyzed for the evaporative loss of water soluble organic carbon (WSOC) and for brown carbon (BrC) formation. Systematic WSOC evaporation occurred in all cloud water samples, while no evidence for drying induced BrC formation was observed. On average, 11% (±3%) of WSOC evaporated when the aerosolized cloud droplets were dried to 50% RH, though this represents a lower bound on the WSOC reversibly partitioned to clouds due to experimental constraints. To our knowledge, this represents the first direct measurements of organic evaporation from actual cloud water undergoing drying. Formate and acetate contributed 19%, on average, to the evaporated WSOC, while no oxalate evaporation occurred. GECKO-A model simulations were carried out to predict the production of WSOC compounds that reversibly partition to cloud water from photooxidation of an array of VOCs. The model results suggest that precursor VOC identity and oxidation regime (VOC:NOx) have a dramatic effect on the reversible partitioning of WSOC to cloud water and the abundance of aqSOA precursors, though the higher abundance of reversibly partitioned WSOC predicted by the model may be due to aqueous production of low-volatility material in the actual cloud samples. This study underscores the importance of the large fraction of unidentified compounds that contribute to WSOC in cloud water and their aqueous processing.

Liquid water is a dominant and critical tropospheric constituent. Over polluted land masses low level cumulus clouds interact with boundary layer aerosol. The planetary boundary layer (PBL) is the lowest atmospheric layer and is directly influenced by Earth's surface. Water-aerosol interactions are critical to processes that govern the fate and transport of trace species in the Earth system and their impacts on air quality, radiative forcing, and regional hydrological cycling. In the PBL, air parcels rise adiabatically from the surface, and anthropogenically influenced hygroscopic aerosols take up water and serve as cloud condensation nuclei (CCN) to form clouds. Water-soluble gases partition to liquid water in wet aerosols and cloud droplets and undergo aqueous-phase photochemistry. Most cloud droplets evaporate, and low volatility material formed during aqueous phase chemistry remains in the condensed phase and adds to aerosol mass. The resulting cloud-processed aerosol has different physicochemical properties compared to the original CCN. Organic species that undergo multiphase chemistry in atmospheric liquid water transform gases to highly concentrated, nonideal ionic aqueous solutions and form secondary organic aerosol (SOA). In recent years, SOA formation modulated by atmospheric waters has received considerable interest.Key uncertainties are related to the chemical nature of hygroscopic aerosols that become CCN and their interaction with organic species. Gas-to-droplet or gas-to-aqueous aerosol partitioning of organic compounds is affected by the intrinsic chemical properties of the organic species in addition to the pre-existing condensed phase. Environmentally relevant conditions for atmospheric aerosol are nonideal. Salt identity and concentration, in addition to aerosol phase state, can dramatically affect organic gas miscibility for many compounds, in particular when ionic strength and salt molality are outside the bounds of limiting laws. For example, Henry's law and Debye-Hückel theory are valid only for dilute aqueous systems uncharacteristic of real atmospheric conditions. Chemical theory is incomplete, and at ambient conditions, this chemistry plays a determining role in total aerosol mass and particle size, controlling factors for air quality and climate-relevant aerosol properties.Accurate predictive skill to understand the impacts of societal choices and policies on air quality and climate requires that models contain correct chemical mechanisms and appropriate feedbacks. Globally, SOA is a dominant contributor to the atmospheric organic aerosol burden, and most mass can be traced back to precursor gas-phase volatile organic compounds (VOCs) emitted from the biosphere. However, organic aerosol concentrations in the Amazon Rainforest, the largest emitter of biogenic VOCs, are generally lower than in U.S. national parks. The Interagency Monitoring of Protected Visual Environments (IMPROVE) air quality network, with sites located predominantly in national parks, provides the longest continuous record of organic aerosol measurements in the U.S. Analysis of IMPROVE data provides a useful chemical climatology of changing air resources in response to environmental rules and shifting economic trends. IMPROVE data provides an excellent test bed for case studies to assess model skill to accurately predict changes in organic aerosol concentrations in the context of a changing climate.

Transition metals in particulate matter (PM) are hypothesized to have enhanced toxicity based on their oxidative potential (OP). The acellular dithiothreitol (DTT) assay is widely used to measure the OP of PM and its chemical components. In our prior study, we showed that the DTT assay (pH 7.4, 0.1 M phosphate buffer, 37 °C) provides favorable thermodynamic conditions for precipitation of multiple metals present in PM. This study utilizes multiple techniques to characterize the precipitation of aqueous metals present at low concentrations in the DTT assay. Metal precipitation was identified using laser particle light scattering analysis, direct chemical measurement of aqueous metal removal, and microscopic imaging. Experiments were run with aqueous metals from individual metal salts and a well-characterized urban PM standard (NIST SRM-1648a, Urban Particulate Matter). Our results demonstrated rapid precipitation of metals in the DTT assay. Metal precipitation was independent of DTT but dependent on metal concentration. Metal removal in the chemically complex urban PM samples exceeded the thermodynamic predictions and removal seen in single metal salt experiments, suggesting co-precipitation and/or adsorption may have occurred. These results have broad implications for other acellular assays that study PM metals using phosphate buffer, and subsequently, the PM toxicity inferred from these assays.

This study characterizes the impact of the Chesapeake Bay and associated meteorological phenomena on aerosol chemistry during the second Ozone Water-Land Environmental Transition Study (OWLETS-2) field campaign, which took place from 4 June to 5 July 2018. Measurements of inorganic PM2.5 composition, gas-phase ammonia (NH3), and an array of meteorological parameters were undertaken at Hart-Miller Island (HMI), a land–water transition site just east of downtown Baltimore on the Chesapeake Bay. The observations at HMI were characterized by abnormally high NH3 concentrations (maximum of 19.3 µg m−3, average of 3.83 µg m−3), which were more than a factor of 3 higher than NH3 levels measured at the closest atmospheric Ammonia Monitoring Network (AMoN) site (approximately 45 km away). While sulfate concentrations at HMI agreed quite well with those measured at a regulatory monitoring station 45 km away, aerosol ammonium and nitrate concentrations were significantly higher, due to the ammonia-rich conditions that resulted from the elevated NH3. The high NH3 concentrations were largely due to regional agricultural emissions, including dairy farms in southeastern Pennsylvania and poultry operations in the Delmarva Peninsula (Delaware–Maryland–Virginia). Reduced NH3 deposition during transport over the Chesapeake Bay likely contributed to enhanced concentrations at HMI compared to the more inland AMoN site. Several peak NH3 events were recorded, including the maximum NH3 observed during OWLETS-2, that appear to originate from a cluster of industrial sources near downtown Baltimore. Such events were all associated with nighttime emissions and advection to HMI under low wind speeds (< 1 m s−1) and stable atmospheric conditions. Our results demonstrate the importance of industrial sources, including several that are not represented in the emissions inventory, on urban air quality. Together with our companion paper, which examines aerosol liquid water and pH during OWLETS-2, we highlight unique processes affecting urban air quality of coastal cities that are distinct from continental locations.

Mist chambers (MC) have been used for decades to sample water-soluble gases in atmospheric studies. Herein, we characterize the use of a mist chamber for the collection of oxygenated organic gases, with a focus on intermediate solubility compounds to better constrain the transition from low-to-high collection efficiency. The investigated compounds span a range in Henry's law constants (KH, 2.5 × 101 M atm−1 to 4.1 × 105 M atm−1) and include moieties abundant in tropospheric gases (carboxylic acids, alcohols, and carbonyls). Under the configuration used here, the MC achieved greater than 90% collection efficiency for compounds with KH > 4.9 × 102 M atm−1. This represents an improvement over prior MC characterizations, likely due to the increased number of intermediate solubility compounds investigated. We apply the MC collection efficiency to simulations of VOC photooxidation. The results indicate that the MC is likely to collect the majority of gas-phase oxidation products for ten different VOCs, with the highest collection efficiency (94%) predicted for the oxidation products of α-pinene under low-NOx conditions.

The urban heat island (UHI) is a widely observed phenomenon whereby urban environments have higher temperatures and different relative humidities than surrounding suburban and rural areas. Temperature (T) and relative humidity (RH) strongly affect the partitioning of semivolatile species found in the atmosphere, such as nitric acid, ammonia, and water. These species are inherently tied to aerosol pH, which is a key parameter driving some atmospheric chemical processes and environmental effects of aerosols. In this study, we characterized the effect of the UHI on aerosol pH in Baltimore, MD, and Chicago, IL. The T and RH differences that define the UHI lead to substantial differences in aerosol liquid water (ALW) content. The ALW differences produce urban aerosol pH that is systematically lower (more acidic) than rural aerosol pH for identical atmospheric composition. The UHI in Baltimore and Chicago are most intense during the summer and at night, with urban-rural aerosol pH differences in excess of 0.8 and 0.65 pH units, respectively. The UHI has been observed in cities of all sizes: the similarity of our results for cities with different climatologies and aerosol compositions suggests that these results have broad implications for chemistry occurring in and around urban atmospheres globally.

Recent laboratory studies have reported the formation of light-absorbing organic carbon compounds (brown carbon, BrC) in aqueous particles undergoing drying. Atmospheric particles undergo cycles of humidification and drying during vertical transport and through daily variations in temperature and humidity, which implies particle drying could potentially be an important source of BrC globally. In this work, we investigated BrC formation in ambient particles undergoing drying at a site in the eastern United States during summer. Aerosol BrC concentrations were linked to secondary organic aerosol (SOA) formation, consistent with seasonal expectations for this region. Measurements of water-soluble organic aerosol concentrations and light absorption (365 nm) were alternated between an unperturbed channel and a channel that dried particles to 41% or 35% relative humidity (RH), depending on the system configuration. The RH maintained in the dry channels was below most ambient RH levels observed throughout the study. We did not observe BrC formation in particles that were dried to either RH level. The results were consistent across two summers, spanning ~5 weeks of measurements that included a wide range of RH conditions and organic and inorganic aerosol loadings. This work suggests that mechanisms aside from humidification-drying cycles are more important contributors to ambient particle BrC loadings. The implications of this work on the atmospheric budget of BrC are discussed.

In humid locations of the Eastern U.S., sulfate is a surrogate for aerosol liquid water (ALW), a poorly measured particle constituent. Regional and seasonal variation in ALW&ndash, sulfate relationships offers a potential explanation to reconcile epidemiology and toxicology studies regarding particulate sulfur and health endpoints. ALW facilitates transfer of polar species from the gas phase to the particle phase and affects particle pH and metal oxidation state. Though abundant and a potential indicator of adverse health endpoints, ALW is largely removed in most particulate matter measurement techniques, including in routine particulate matter (PM2.5) networks that use federal reference method (FRM) monitors, which are used in epidemiology studies. We find that in 2004, a typical year in the available record, ambient ALW mass is removed during sampling and filter equilibration to standard laboratory conditions at most (94%) sites, up to 85% of the ambient water mass. The removal of ALW can induce the evaporation of other semi-volatile compounds present in PM2.5, such as ammonium nitrate and numerous organics. This produces an artifact in the PM mass measurements that is, importantly, not uniform in space or time. This suggests that PM2.5 epidemiology studies that exclude ALW are biased. This work provides a plausible explanation to resolve multi-decade discrepancies regarding ambient sulfate and health impacts in some epidemiological and toxicological studies.

Water-soluble organic carbon (WSOC) is a ubiquitous and significant fraction of fine particulate matter. Despite advances in aerosol thermodynamic equilibrium models, there is limited understanding on the comprehensive impacts of WSOC on aerosol acidity (pH). We address this limitation by studying submicron aerosols that represent the two extremes in acidity levels found in the atmosphere: strongly acidic aerosol from Baltimore, MD, and weakly acidic conditions characteristic of Beijing, China. These cases are then used to construct mixed inorganic–organic single-phase aqueous particles and thermodynamically analyzed by the Extended Aerosol Inorganics Model (E-AIM) and ISORROPIA models in combination with activity coefficient model AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficient) to evaluate the effects of WSOC on the H+ ion activity coefficients (γH+) and activity (pH). We find that addition of organic acids and nonacid organic species concurrently increases γH+ and aerosol liquid water. Under the highly acidic conditions typical of the eastern US (inorganic-only pH ∼1), these effects mostly offset each other, giving pH changes of ∼4.5), the nonacidic WSOC compounds had similarly minor effects on aerosol pH, but organic acids imparted the largest changes in pH compared to the inorganic-only simulations. Organic acids affect pH in the order of their pKa values (oxalic acid > malonic acid > glutaric acid). Although the inorganic-only pH was above the pKa value of all three organic acids investigated, pH changes in excess of 1 pH unit were only observed at unrealistic organic acid levels (aerosol organic acid concentrations > 35 µg m−3) in Beijing. The model simulations were run at 70 %, 80 %, and 90 % relative humidity (RH) levels and the effect of WSOC was inversely related to RH. At 90 % RH, WSOC altered aerosol pH by up to ∼0.2 pH units, though the effect was up to ∼0.6 pH units at 70 % RH. The somewhat offsetting nature of these effects suggests that aerosol pH is sufficiently constrained by the inorganic constituents alone under conditions where liquid–liquid phase separation is not anticipated to occur.

Measurements of PM2.5 chemical composition were carried out in Golden, CO during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field study. Chemical composition was dominated by organic compounds, which comprised an average of 75% of the PM2.5 mass throughout the study. Most of the organic matter was secondary (i.e., secondary organic aerosol, SOA), and appears to derive predominantly from regional sources, rather than the Denver metropolitan area. The concentration and composition of PM2.5 in Golden were strongly influenced by highly regular wind patterns and the site's close proximity to the mountains (~5 km). This second factor may be the cause of distinct differences between observations in Golden and those in downtown Denver, despite a distance between the sites of only ~15 km. Concentrations of aerosol nitrate, ammonium and elemental carbon increased significantly during the daytime when the winds were from the northeast, indicating a strong local source for these compounds. Local sources of dust appeared to minimally impact the Golden site, although this was not likely representative of other conditions in the Colorado Front Range. Conversely, dust that had undergone long-range transport from the southwestern U.S. likely impacted the entire Colorado Front Range, including Golden. During this event, water-soluble Ca2+ concentrations exceeded 1 µg m-3, and the PM2.5/PM10 ratio reached its lowest level throughout the study. The long-range transport of wildfire emissions also impacted the Colorado Front Range for 1-2 days during DISCOVER-AQ. The smoke event was characterized by high concentrations of organics and water-soluble K+. The results show a complex array of sources and atmospheric processes influence summertime PM in the Colorado Front Range.

Aerosol hygroscopicity was investigated using a novel dryer-humidifier system, coupled to a TSI-3563 nephelometer, to obtain the light scattering coefficient (σscat) as a function of relative humidity (RH) in hydration and dehydration modes. The measurements were performed in Porterville, CA (10 January to 6 February 2013), Baltimore, MD (3–30 July 2013), and Golden, CO (12 July to 10 August 2014). Observations in Porterville and Golden were part of the NASA-sponsored Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality project. The measured σscat under varying RH in the three sites was combined with ground aerosol extinction, PM2.5 mass concentrations, and particle composition measurements and compared with airborne observations performed during campaigns. The enhancement factor, f(RH), defined as the ratio of σscat(RH) at a certain RH divided by σscat at a dry value, was used to evaluate the aerosol hygroscopicity. Particles in Porterville showed low average f(RH = 80%) (1.42) which was attributed to the high carbonaceous loading in the region where residential biomass burning and traffic emissions contribute heavily to air pollution. In Baltimore, the high average f(RH = 80%) (2.06) was attributed to the large contribution of SO42− in the region. The lowest water uptake was observed in Golden, with an average f(RH = 80%) = 1.24 where organic carbon dominated the particle loading. Different empirical fits were evaluated using the f(RH) data. The widely used Kasten (gamma) model was found least satisfactory, as it overestimates f(RH) for RH

Atmospheric models that accurately describe the fate and transport of trace species for the right reasons aid in development of effective air quality management strategies that safeguard human health, in particular to mitigate the impacts of fine particulate matter (PM(2.5)). Controllable emissions from human activity facilitate formation of biogenic secondary organic aerosol (BSOA) to enhance the atmospheric PM(2.5) burden. Previous modeling with EPA’s Community Multiscale Air Quality (CMAQ) model predicted that anthropogenic primary organic aerosol (POA) emissions had the greatest impact on BSOA. Those experiments included formation processes from semi-volatile partitioning, but not interactions with aerosol liquid water (ALW), a ubiquitous PM constituent that modulates BSOA. We conduct 17 CMAQ summertime simulations with updated chemistry and evaluate changes in predicted BSOA mass due to removal of individual pollutants and source sectors from model inputs for the continental U.S. Among individual sectors, CMAQ predicts that SO(2) emissions from electricity generating point sources and mobile source NO(x) emissions have the largest impact on BSOA. Removal of anthropogenic NO(x), SO(2) and POA emissions during the simulated summertime period reduces nationally averaged BSOA by 23%, 14% and 8%, and PM(2.5) by 9.2%, 14% and 5.3% respectively. CMAQ-predicted ALW mass concentrations decrease by 10% and 35% in response to removal of NO(x) and SO(2) emissions. This work contributes to the understanding of ancillary benefits of existing and planned Federal NO(x) and SO(2) air quality rules through concurrent reductions in organic PM(2.5) mass.

Emissions of intermediate-volatility organic compounds (IVOCs) from five on-road diesel vehicles and one off-road diesel engine were characterized during dynamometer testing. The testing evaluated the effects of driving cycles, fuel composition and exhaust aftertreatment devices. On average, more than 90% of the IVOC emissions were not identified on a molecular basis, instead appearing as an unresolved complex mixture (UCM) during gas-chromatography mass-spectrometry analysis. Fuel-based emissions factors (EFs) of total IVOCs (speciated + unspeciated) depend strongly on aftertreatment technology and driving cycle. Total-IVOC emissions from vehicles equipped with catalyzed diesel particulate filters (DPF) are substantially lower (factor of 7 to 28, depending on driving cycle) than from vehicles without any exhaust aftertreatment. Total-IVOC emissions from creep and idle operations are substantially higher than emissions from high-speed operations. Although the magnitude of the total-IVOC emissions can vary widely, there is little variation in the IVOC composition across the set of tests. The new emissions data are combined with published yield data to investigate secondary organic aerosol (SOA) formation. SOA production from unspeciated IVOCs is estimated using surrogate compounds, which are assigned based on gas-chromatograph retention time and mass spectral signature of the IVOC UCM. IVOCs contribute the vast majority of the SOA formed from exhaust from on-road diesel vehicles. The estimated SOA production is greater than predictions by previous studies and substantially higher than primary organic aerosol. Catalyzed DPFs substantially reduce SOA formation potential of diesel exhaust, except at low speed operations.

The reversible nature of aqueous secondary organic aerosol (aqSOA) formation was characterized for the first time through direct atmospheric measurements. Water-soluble organic carbon in the gas and particle phases (WSOCg and WSOCp) was measured simultaneously to quantify aqSOA formation in Baltimore, Maryland. During the nighttime, aqSOA formation was evident as WSOCg increasingly partitioned to the particle phase with increasing relative humidity (RH). To characterize the reversible/irreversible nature of this aqSOA, the WSOCp measurement was alternated through an unperturbed ambient channel and through a “dried” channel maintained at ~40% RH (with 7 s residence time) to mimic the natural drying particles undergo throughout the day. Across the entire RH range encountered, there was no statistically significant difference in WSOCp concentrations through the dry and ambient channels, indicating that the aqSOA remained in the condensed phase upon the evaporation of aerosol water. This strongly suggests that the observed aqSOA was formed irreversibly.

Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 μg m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments.

The gas-particle partitioning of the primary organic aerosol (POA) emissions from fifty-one light-duty gasoline vehicles (model years 1987–2012) was investigated at the California Air Resources Board Haagen–Smit Laboratory. Each vehicle was operated over the cold-start unified cycle on a chassis dynamometer and its emissions were sampled using a constant volume sampler. Four independent yet complementary approaches were used to investigate POA gas-particle partitioning: sampling artifact correction of quartz filter data, dilution from the constant volume sampler into a portable environmental chamber, heating in a thermodenuder, and thermal desorption/gas chromatography/mass spectrometry analysis of quartz filter samples. This combination of techniques allowed gas-particle partitioning measurements to be made across a wide range of atmospherically relevant conditions – temperatures of 25–100 °C and organic aerosol concentrations of

Experiments were conducted to investigate light absorption of organic aerosol (OA) in fresh and photo-chemically aged biomass-burning emissions. The experiments considered residential hardwood fuel (oak) and fuels commonly consumed in wild-land and prescribed fires in the United States (pocosin pine and gallberry). Photo-chemical aging was performed in an environmental chamber. We constrained the light-absorption properties of the OA using conservative limiting assumptions, and found that both primary organic aerosol (POA) in the fresh emissions and secondary organic aerosol (SOA) produced by photo-chemical aging absorb light to a significant extent, and are categorized as brown carbon. This work presents the first direct evidence that SOA produced in aged biomass-burning emissions is absorptive. For the investigated fuels, SOA is less absorptive than POA in the long visible, but exhibits steeper wavelength-dependence (larger Absorption Ångström Exponent) and is more absorptive in the short visible and near-UV. Light absorption by SOA in biomass-burning emissions might be an important contributor to the global radiative forcing budget.

Experiments were performed to investigate the gas-particle partitioning of primary organic aerosol (POA) emissions from two medium-duty (MDDV) and three heavy-duty (HDDV) diesel vehicles. Each test was conducted on a chassis dynamometer with the entire exhaust sampled into a constant volume sampler (CVS). The vehicles were operated over a range of driving cycles (transient, high-speed, creep/idle) on different ultralow sulfur diesel fuels with varying aromatic content. Four independent yet complementary approaches were used to investigate POA gas-particle partitioning: artifact correction of quartz filter samples, dilution from the CVS into a portable environmental chamber, heating in a thermodenuder, and thermal desorption/gas chromatography/mass spectrometry (TD-GC-MS) analysis of quartz filter samples. During tests of vehicles not equipped with diesel particulate filters (DPF), POA concentrations inside the CVS were a factor of 10 greater than ambient levels, which created large and systematic partitioning biases in the emissions data. For low-emitting DPF-equipped vehicles, as much as 90% of the POA collected on a quartz filter from the CVS were adsorbed vapors. Although the POA emission factors varied by more than an order of magnitude across the set of test vehicles, the measured gas-particle partitioning of all emissions can be predicted using a single volatility distribution derived from TD-GC-MS analysis of quartz filters. This distribution is designed to be applied directly to quartz filter data that are the basis for existing emissions inventories and chemical transport models that have implemented the volatility basis set approach.

A new technique for measuring the primary organic aerosol (POA) emissions from internal combustion engines is presented. The method combines thermal-optical OC/EC analysis and thermal desorption gas chromatography mass spectrometry (TD-GC-MS) of quartz filter samples collected using a dilution sampler to quantify the total emissions of low-volatility organics and to distribute them across the volatility basis set. These data can be used in conjunction with partitioning theory to predict the gas-particle partitioning and thus the total amount of POA over the entire range of atmospheric conditions. The approach is evaluated using POA emissions data from two gas-turbine engines and one diesel generator. To evaluate the new method, we directly measured the effects of temperature and concentration on gas-particle partitioning of the emissions from each. Predictions based on the volatility distributions derived from the filter analyses are consistent with the direct partitioning measurements. The new approach r...

This paper compares measurements of gaseous and particulate emissions from a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS-2008 experiment: ARCTAS-A, based out of Fairbanks, Alaska, USA (3 April to 19 April 2008); ARCTAS-B based out of Cold Lake, Alberta, Canada (29 June to 13 July 2008); and ARCTAS-CARB, based out of Palmdale, California, USA (18 June to 24 June 2008). Approximately 500 smoke plumes from biomass burning emissions that varied in age from minutes to days were segregated by fire source region and urban emission influences. The normalized excess mixing ratios (NEMR) of gaseous (carbon dioxide, acetonitrile, hydrogen cyanide, toluene, benzene, methane, oxides of nitrogen and ozone) and fine aerosol particulate components (nitrate, sulfate, ammonium, chloride, organic aerosols and water soluble organic carbon) of these plumes were compared. A detailed statistical analysis of the different plume categories for different gaseous and aerosol species is presented in this paper. The comparison of NEMR values showed that CH4 concentrations were higher in air-masses that were influenced by urban emissions. Fresh biomass burning plumes mixed with urban emissions showed a higher degree of oxidative processing in comparison with fresh biomass burning only plumes. This was evident in higher concentrations of inorganic aerosol components such as sulfate, nitrate and ammonium, but not reflected in the organic components. Lower NOx NEMRs combined with high sulfate, nitrate and ammonium NEMRs in aerosols of plumes subject to long-range transport, when comparing all plume categories, provided evidence of advanced processing of these plumes.

Staged tests were conducted to measure the particle and vapor emissions from a CFM56-2B1 gasturbine engine mounted on a KC-135T Stratotanker airframe at different engine loads. Exhaust was sampled using a rake inlet installed 1-m downstream of the engine exit plane of a parked and chocked aircraft and a dilution sampler and portable smog chamber were used to investigate the particulate matter (PM) emissions. Total fine PM mass emissions were highest at low (4%) and high (85%) load and lower at intermediate loads (7% and 30%). PM mass emissions at 4% load are dominated by organics, while at 85% load elemental carbon is dominant. Quantifying the primary organic aerosol (POA) emissions is complicated by substantial filter sampling artifacts. Partitioning experiments reveal that the majority of the POA is semivolatile; for example, the POA emission factor changed by a factor of two when the background organic aerosol concentration was increased from 0.7 to 4 m gm �3 . Therefore, one cannot define a single non-volatile PM emission factor for aircraft exhaust. The gas- and particle-phase organic emissions were comprehensively characterized by analyzing canister, sorbent and filter samples with gas-chromatography/mass-spectrometry. Vapor-phase organic emissions are highest at 4% load and decrease with increasing load. Low-volatility organics (less volatile than a C12 nalkane) contributed 10e20% of the total organic emissions. The low-volatility organic emissions contain signatures of unburned fuel and aircraft lubricating oil but are dominated by an unresolved complex mixture (UCM) of presumably branched and cyclic alkanes. Emissions at all loads contain more low-volatility organic vapors than POA; thus secondary organic aerosol formation in the aging plume will likely exceed POA emissions.

A method for predicting volatility and polarity based on chromatographic information was developed and applied to the smog chamber ozonolysis of the sesquiterpene longifolene. The products were collected and analyzed using a GC × GC Thermal Desorption Aerosol Gas Chromatograph/Mass Spectrometer (2D-TAG) and a quadrupole Aerodyne Aerosol Mass Spectrometer (AMS). All the secondary organic aerosol (SOA) was produced within the first half hour of the experiment. However, the oxidation level of the organic aerosol, as inferred from the fraction of ion m/z 44, suggested continued evolution of the SOA over the subsequent hours. Measurements of speciated organic compounds using 2D-TAG confirm that the composition of the particles changed over the course of the experiment. Nearly 200 oxidation products (thought to be mostly ketones and acids) were observed with 2D-TAG, but most could not be identified definitively due to a lack of standards and the absence of likely sesquiterpene oxidation products in available mass spectral databases. To categorize the observed products, the vapor pressure and oxygen-to-carbon ratio (O/C) of observed compounds were estimated based on their two-dimensional chromatographic retention times relative to those of known standards, establishing a retention time correlation (RTC) method for using 2D-TAG to better constrain important modelling parameters. The product distribution continuously evolved in volatility and oxygenation during 5 h of oxidation. Using peak area as the best available proxy for mass, we conclude that the product mixture includes many non-negligible products; the most abundant 3 compounds accounted for only half of the total observed peak area and 80 % of peak area was spread across 15 compounds. The data provide evidence for three conclusions: (1) 2D-TAG provides valuable volatility and oxygenation information even in the absence of definitive species identification, (2) complex particle-phase chemistry causes continued evolution of particle composition after new particles formation, and (3) minor products contribute significantly to SOA from the ozonolysis of longifolene.

Field experiments were performed to investigate the effects of photo-oxidation on fine particle emissions from an in-use CFM56-2B gas turbine engine mounted on a KC-135 Stratotanker airframe. Emissions were sampled into a portable smog chamber from a rake inlet installed one-meter downstream of the engine exit plane of a parked and chocked aircraft. The chamber was then exposed to sunlight and/or UV lights to initiate photo-oxidation. Separate tests were performed at different engine loads (4, 7, 30, 85 %). Photo-oxidation created substantial secondary particulate matter (PM), greatly exceeding the direct PM emissions at each engine load after an hour or less of aging at typical summertime conditions. After several hours of photo-oxidation, the ratio of secondary-to-primary PM mass was on average 35 ± 4.1, 17 ± 2.5, 60 ± 2.2, and 2.7 ± 1.1 for the 4, 7, 30, and 85 % load experiments, respectively. The composition of secondary PM formed strongly depended on load. At 4 % load, secondary PM was dominated by secondary organic aerosol (SOA). At higher loads, the secondary PM was mainly secondary sulfate. A traditional SOA model that accounts for SOA formation from single-ring aromatics and other volatile organic compounds underpredicts the measured SOA formation by ~60 % at 4 % load and ~40 % at 85 % load. Large amounts of lower-volatiliy organic vapors were measured in the exhaust; they represent a significant pool of SOA precursors that are not included in traditional SOA models. These results underscore the importance of accounting for atmospheric processing when assessing the influence of aircraft emissions on ambient PM levels. Models that do not account for this processing will likely underpredict the contribution of aircraft emissions to local and regional air pollution.

Gas and particle-phase organic carbon compounds soluble in water (e.g., WSOC) were measured simultaneously in Atlanta throughout the summer of 2007 to investigate gas/particle partitioning of ambient secondary organic aerosol (SOA). Previous studies have established that, in the absence of biomass burning, particulate WSOC (WSOCp) is mainly from secondary organic aerosol (SOA) production. Comparisons between WSOCp, organic carbon (OC) and elemental carbon (EC) indicate that WSOCp was a nearly comprehensive measure of SOA in the Atlanta summertime. WSOCp and gas-phase WSOC (WSOCg) concentrations both exhibited afternoon maxima, indicating that photochemistry was a major route for SOA formation. An additional nighttime maximum in the WSOCg concentration indicated a dark source for oxidized organic gases, but this was not accompanied by detectable increases in WSOCp. To study SOA formation mechanisms, WSOC gas/particle partitioning was investigated as a function of temperature, RH, NOx, O3, and organic aerosol mass concentration. No clear relationship was observed between temperature and partitioning, possibly due to a simultaneous effect from other temperature-dependent processes. For example, positive temperature effects on emissions of biogenic SOA precursors and photochemical SOA formation may have accounted for the observed similar proportional increases of WSOCp and WSOCg with temperature. Relative humidity data indicated a linear dependence between partitioning and predicted fine particle liquid water. Lower NOx concentrations were associated with greater partitioning to particles, but WSOC partitioning had no visible relation to O3 or fine particle OC mass concentration. There was, however, a relationship between WSOC partitioning and the WSOCp concentration, suggesting a compositional dependence between partitioning semi-volatile gases and the absorbing organic aerosol. Combined, the overall results suggest two dominant SOA formation processes in urban Atlanta during summer. One was the photochemical production of SOA from presumably biogenic precursors that increased with the onset of sunrise and peaked in the afternoon. The other, which showed no apparent diurnal pattern, involved the partitioning of semi-volatile gases to liquid water, followed by heterogeneous reactions. The co-emission of water vapor and biogenic VOCs from vegetation may link these processes.

Ground-based measurements of meteorological parameters and water-soluble organic carbon in the gas(WSOCg) and particle (WSOCp) phases were carried out in Atlanta, Georgia, from May to September 2007. Fourteen separate events were observed throughout the summer in which WSOCp and water vapor concentrations were highly correlated (average WSOCp-water vapor r = 0.92); however, for the entire summer, no well-defined relationship existed between the two. The correlation events, which lasted on average 19 h, were characterized by a wide range of WSOCp and water vapor concentrations. Several hypotheses for the correlation are explored, including heterogeneous liquid phase SOA formation and the co-emission of biogenic VOCs and water vapor. The data provide supporting evidence for contributions from both and suggest the possibility of a synergistic effect between the co-emission of water vapor and VOCs from biogenic sources on SOA formation. Median WSOCp concentrations were also correlated with elemental carbon (EC), although this correlation extended over the entire summer. Despite the emission of water vapor from anthropogenic mobile sources and the WSOCp-EC correlation, mobile sources were not considered a potential cause for the WSOCp-water vapor correlations because of their low contribution to the water vapor budget. Meteorology could perhaps have influenced the WSOCp-EC correlation, but other factors are implicated as well. Overall, the results suggest that the temperature-dependent co-emission of water vapor through evapotranspiration and SOA precursor-VOCs by vegetation may be an important process contributing to SOA in some environments.

Measurements of atmospheric gases and fine particle chemistry were made in the Mexico City Metropolitan Area (MCMA) at a site ~30 km down wind of the city center. Ammonium nitrate (NH4NO3) dominated the inorganic aerosol fraction and showed a distinct diurnal signature characterized by rapid morning production and a rapid mid-day concentration decrease. Between the hours of 08:00–12:45, particulate water-soluble organic carbon (WSOC) concentrations increased and decreased in a manner consistent with that of NO3−, and the two were highly correlated (R2=0.88) during this time. A box model was used to analyze these behaviors and showed that, for both NO3− and WSOC, the concentration increase was caused primarily (~75–85%) by secondary formation, with a smaller contribution (~15–25%) from the entrainment of air from the free troposphere. For NO3−, a majority (~60%) of the midday concentration decrease was caused by dilution from boundary layer expansion, though a significant fraction (~40%) of the NO3− loss was due to particle evaporation. The WSOC concentration decrease was due largely to dilution (~75%), but volatilization did have a meaningful impact (~25%) on the decrease, as well. The results provide an estimate of ambient SOA evaporation losses and suggest that a significant fraction (~35%) of the fresh MCMA secondary organic aerosol (SOA) measured at the surface volatilized.

In this study, we characterize the CCN activity of the water-soluble organics in biomass burning aerosol. The aerosol after collection upon filters is dissolved in water using sonication. Hydrophobic and hydrophilic components are fractionated from a portion of the original sample using solid phase extraction, and subsequently desalted. The surface tension and CCN activity of these different samples are measured with a KSV CAM 200 goniometer and a DMT Streamwise Thermal Gradient CCN Counter, respectively. The measurements show that the strongest surfactants are isolated in the hydrophobic fraction, while the hydrophilics exhibit negligible surface tension depression. The presence of salts (primarily (NH4)2SO4) in the hydrophobic fraction substantially enhances surface tension depression; their synergistic effects considerably enhance CCN activity, exceeding that of pure (NH4)2SO4. From our analysis, average thermodynamic properties (i.e, molar volume) are determined for samples using our newly developed Köhler Theory Analysis (KTA) method. The molar mass of the hydrophilic and hydrophobic aerosol components is estimated to be 87±26 g mol−1 and 780±231 g mol−1, respectively. KTA also suggests that the relative proportion (in moles) of hydrophobic to hydrophilic compounds in the original sample to be 1:3. For the first time, KTA is applied to an aerosol with this level of complexity and displays its potential for providing physically-based constraints for GCM parameterizations of the aerosol indirect effect.

Dynamometer experiments were conducted to characterize the intermediate volatility organic compound (IVOC) emissions from a fleet of on-road gasoline vehicles and small off-road gasoline engines. IVOCs were quantified through gas chromatography/mass spectrometry analysis of adsorbent samples collected from a constant volume sampler. The dominant fraction (>80%, on average) of IVOCs could not be resolved on a molecular level. These unspeciated IVOCs were quantified as two chemical classes (unspeciated branched alkanes and cyclic compounds) in 11 retention-time-based bins. IVOC emission factors (mg kg-fuel(-1)) from on-road vehicles varied widely from vehicle to vehicle, but showed a general trend of lower emissions for newer vehicles that met more stringent emission standards. IVOC emission factors for 2-stroke off-road engines were substantially higher than 4-stroke off-road engines and on-road vehicles. Despite large variations in the magnitude of emissions, the IVOC volatility distribution and chemical characteristics were consistent across all tests and IVOC emissions were strongly correlated with nonmethane hydrocarbons (NMHCs), primary organic aerosol and speciated IVOCs. Although IVOC emissions only correspond to approximately 4% of NMHC emissions from on-road vehicles over the cold-start unified cycle, they are estimated to produce as much or more SOA than single-ring aromatics. Our results clearly demonstrate that IVOCs from gasoline engines are an important class of SOA precursors and provide observational constraints on IVOC emission factors and chemical composition to facilitate their inclusion into atmospheric chemistry models.

Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10-20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y(-1) of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations.

Molecular markers are organic species used to define fingerprints for source apportionment of ambient fine particulate matter. Traditionally, these markers have been assumed to be stable in the atmosphere. This work investigates the gas-particle partitioning of eight organic species used as molecular markers in receptor models for biomass burning (levoglucosan), motor vehicles (5α-cholestane, n-hexacosane, n-triacontane, 1,2-benz[a]anthracene, coronene), and meat cooking (cholesterol, oleic acid). Experiments were conducted using a thermodenuder to measure the evaporation of single component particles. The data were analyzed using the integrated volume method to determine saturation concentrations and enthalpies of vaporization for each compound. The results indicate that appreciable quantities (10%) of most of these markers exist in the gas phase under typical atmospheric conditions. Therefore, these species should be considered semivolatile. Predictions from a chemical kinetics model indicate that gas-particle partitioning has important effects on the atmospheric lifetime of these species. The atmospheric decay of semivolatile compounds proceeds much more rapidly than nonvolatile compounds because gas-phase oxidation induces evaporation of particle-phase material. Therefore, both gas-particle partitioning and chemical reactions need to be accounted for when semivolatile molecular markers are used for source apportionment studies.

Experiments were performed in an environmental chamber to characterize the effects of photo-chemical aging on biomass burning emissions. Photo-oxidation of dilute exhaust from combustion of 12 diff ...

We quantify the hygroscopic properties of particles freshly emitted from biomass burning and after several hours of photochemical aging in a smog chamber. Values of the hygroscopicity parameter, κ, were calculated from cloud condensation nuclei (CCN) measurements of emissions from combustion of 12 biomass fuels commonly burned in North American wildfires. Prior to photochemical aging, the κ of the fresh primary aerosol varied widely, between 0.06 (weakly hygroscopic) and 0.6 (highly hygroscopic). The hygroscopicity of the primary aerosol was positively correlated with the inorganic mass fraction of the particles. There was also a relationship between the hygroscopicity of the primary aerosol and the extent of oxygenation of the primary organic aerosol (POA), suggesting an influence of the POA composition on the primary aerosol hygroscopicity as well. Photochemical processing reduced the range of κ values to between 0.08 and 0.3. The changes in κ were driven by the photochemical production of secondary organic aerosol (SOA). SOA also contributed to growth of particles formed during nucleation events. Analysis of the nucleation mode particles enabled the first direct quantification of the hygroscopicity parameter κ for biomass burning SOA, which was on average 0.11, similar to values observed for biogenic SOA. Although initial CCN activity of biomass burning aerosol emissions are highly variable, after a few hours of photochemical processing κ converges to a value of 0.2 ± 0.1. Therefore, photochemical aging reduces the variability of biomass burning CCN, which should simplify analysis of the potential effects of biomass burning aerosol on climate.

This paper compares measurements of gaseous and particulate emissions from a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS-2008 experiment: ARCTAS-A, based out of Fairbanks, Alaska USA (3 April to 19 April 2008); ARCTAS-B based out of Cold Lake, Alberta, Canada (29 June to 13 July 2008); and ARCTAS-CARB, based out of Palmdale, California, USA (18 June to 24 June 2008). Extensive investigations of boreal fire plume evolution were undertaken during ARCTAS-B, where four distinct fire plumes that were intercepted by the aircraft over a range of down-wind distances (0.1 to 16 hr transport times) were studied in detail. Based on these analyses, there was no evidence for ozone production and a box model simulation of the data confirmed that net ozone production was slow (on average 1 ppbv h−1 in the first 3 h and much lower afterwards) due to limited NOx. Peroxyacetyl nitrate concentrations (PAN) increased with plume age and the box model estimated an average production rate of ~80 pptv h−1 in the first 3 h. Like ozone, there was also no evidence for net secondary inorganic or organic aerosol formation. There was no apparent increase in aerosol mass concentrations in the boreal fire plumes due to secondary organic aerosol (SOA) formation; however, there were indications of chemical processing of the organic aerosols. In addition to the detailed studies of boreal fire plume evolution, about 500 smoke plumes intercepted by the NASA DC-8 aircraft were segregated by fire source region. The normalized excess mixing ratios (i.e. ΔX/ΔCO) of gaseous (carbon dioxide, acetonitrile, hydrogen cyanide, toluene, benzene, methane, oxides of nitrogen (NOx), ozone, PAN) and fine aerosol particulate components (nitrate, sulfate, ammonium, chloride, organic aerosols and water soluble organic carbon) of these plumes were compared.

Smog chamber experiments were conducted to investigate the chemical and physical transformations of organic aerosol (OA) during photo-oxidation of open biomass burning emissions. The experiments were carried out at the US Forest Service Fire Science Laboratory as part of the third Fire Lab at Missoula Experiment (FLAME III). We investigated emissions from 12 different fuels commonly burned in North American wildfires. The experiments feature atmospheric and plume aerosol and oxidant concentrations; aging times ranged from 3 to 4.5 h. OA production, expressed as a mass enhancement ratio (ratio of OA to primary OA (POA) mass), was highly variable. OA mass enhancement ratios ranged from 2.9 in experiments where secondary OA (SOA) production nearly tripled the POA concentration to 0.7 in experiments where photo-oxidation resulted in a 30 % loss of the OA mass. The campaign-average OA mass enhancement ratio was 1.7 ± 0.7 (mean ± 1σ); therefore, on average, there was substantial SOA production. In every experiment, the OA was chemically transformed. Even in experiments with net loss of OA mass, the OA became increasingly oxygenated and less volatile with aging, indicating that photo-oxidation transformed the POA emissions. Levoglucosan concentrations were also substantially reduced with photo-oxidation. The transformations of POA were extensive; using levoglucosan as a tracer for POA, unreacted POA only contributed 17 % of the campaign-average OA mass after 3.5 h of exposure to typical atmospheric hydroxyl radical (OH) levels. Heterogeneous reactions with OH could account for less than half of this transformation, implying that the coupled gas-particle partitioning and reaction of semi-volatile vapors is an important and potentially dominant mechanism for POA processing. Overall, the results illustrate that biomass burning emissions are subject to extensive chemical processing in the atmosphere, and the timescale for these transformations is rapid.

[1] We present hygroscopic and cloud condensation nuclei (CCN) relevant properties of the water‐soluble fraction of Mexico City aerosol collected upon filters during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) campaign. Application of � ‐Kohler theory to the observed CCN activity gave a fairly constant hygroscopicity parameter (� = 0.28 ± 0.06) regardless of location and organic fraction. Kohler theory analysis was used to understand this invariance by separating the molar volume and surfactant contributions to the CCN activity. Organics were found to depress surface tension (10–15%) from that of pure water. Daytime samples exhibited lower molar mass (∼200 amu) and surface tension depression than nighttime samples (∼400 amu); this is consistent with fresh hygroscopic secondary organic aerosol (SOA) condensing onto particles during peak photochemical hours, subsequently aging during nighttime periods of high relative humidity. Changes in surface tension partially compensate for shifts in average molar volume to give the constant hygroscopicity observed, which implies the amount (volume fraction) of soluble material in the parent aerosol is the key composition parameter required for CCN predictions. This finding, if applicable elsewhere, may explain why CCN predictions are often found to be insensitive to assumptions of chemical composition and provides a very simple way to parameterize organic hygroscopicity in atmospheric models (i.e., � org = 0.28"WSOC). Special care should be given, however, to surface tension depression from organic surfactants, as its nonlinear dependence with organic fraction may introduce biases in observed (and predicted) hygroscopicity. Finally, threshold droplet growth analysis suggests the water‐soluble organics do not affect activation kinetics.

[1] Experiments were carried out in a smog chamber to investigate the oxidation of levoglucosan in biomass burning particles exposed to gas-phase hydroxyl radicals (OH). The experiments featured atmospherically-relevant particle and oxidant concentrations and both high and low relative humidity conditions. In every experiment, we observed levoglucosan decay in particles exposed to OH. The extent of decay ranged from ∼20% to ∼90% and was strongly correlated to the integrated OH exposure. Increased relative humidity did not enhance or impede reaction. Relative kinetics indicate that levoglucosan has an atmospheric lifetime of 0.7–2.2 days when biomass burning particles are exposed to 1 × 106 molecules cm−3 of OH (typical average summertime conditions). This implies that levoglucosan reacts with OH on a timescale similar to that of transport and deposition, which has important implications for the use of levoglucosan as a tracer for biomass burning emissions in source apportionment studies.

Hydroxyl radical (OH) uptake by organic aerosols, followed by heterogeneous oxidation, happens nearly at the collision frequency. Oxidation complicates the use of organic molecular markers such as hopanes for source apportionment, since receptor models assume markers are stable during transport. We report the oxidation kinetics of organic molecular markers (C(25)-C(32) n-alkanes, hopanes and steranes) in motor oil and primary organic aerosol emitted from a diesel engine at atmospherically relevant conditions inside a smog chamber. A thermal desorption aerosol gas chromatograph/mass spectrometer (TAG) and Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) were used to measure the changes in molecular comosition and bulk primary organic aerosol. From the measured changes in molecular composition, we calculated effective OH rate constants, effective relative rate constants, and effective uptake coefficients for molecular markers. Oxidation rates varied with marker volatility, with more volatile markers being oxidized at rates much faster than could be explained from heterogeneous oxidation. This rapid oxidation can be explained by significant gas-phase OH oxidation that dominates heterogeneous oxidation, resulting in overall oxidation lifetimes of 1 day or less. Based on our results, neglecting oxidation of molecular markers used for source apportionment could introduce significant error, since many common markers such as norhopane appear to be semivolatile under atmospheric conditions.

[1] This study characterizes the partitioning behavior of a significant fraction of the ambient organic aerosol through simultaneous measurements of gas and particle water-soluble organic carbon (WSOC). During the summer in Atlanta, WSOC gas/particle partitioning showed a strong RH dependence that was attributed to particulate liquid water. At elevated RH levels (>∼70%), a significant increase in WSOC partitioning to the particle phase was observed and followed the predicted water uptake by fine particles. The enhancement in particle-phase partitioning translated to increased median particle WSOC concentrations ranging from 0.3–0.9 μg C m−3. The results provide a detailed overview of the WSOC partitioning behavior in the summertime in an urban region dominated by biogenic emissions, and indicate that secondary organic aerosol formation involving partitioning to liquid water may be a significant aerosol formation route that is generally not considered.

An unanticipated wind shift led to the advection of plumes from two prescribed burning sites that impacted Atlanta, GA, producing a heavy smoke event late in the afternoon on February 28, 2007. Observed PM2.5 concentrations increased to over 140 microg/m3 and O3 concentrations up to 30 ppb in a couple of hours, despite the late hour in February when photochemistry is less vigorous. A detailed investigation of PM2.5 chemical composition and source apportionment analysis showed that the increase in PM2.5 mass was driven mainly by organic carbon (OC). However, both results from source apportionment and an observed nonlinear relationship between OC and PM2.5 potassium (K) indicate that the increased OC was not due solely to primary emissions. Most of the OC was water-soluble organic carbon (WSOC) and was dominated by hydrophobic compounds. The data are consistent with large enhancements in isoprenoid (isoprene and monoterpenes) and other volatile organic compounds emitted from prescribed burning that led to both significant O3 and secondary organic aerosol (SOA) production. Formation of oligomers from oxidation products of isoprenoid compounds or condensation of volatile organic compounds (VOCs) with multiple functional groups emitted during prescribed burning appears to be a major component of the secondary organic contributor of the SOA. The results from this study imply that enhanced emissions due to the fire itself and elevated temperature in the burning region should be considered in air quality models (e.g., receptor and emission-based models) to assess impacts of prescribed burning emissions on ambient air quality.

Aircraft measurements of fine inorganic aerosol composition were made with a particle-into-liquid sampler coupled to dual ion chromatographs (PILS-IC) as part of the NASA INTEX-NA study. The sampling campaign, which lasted from 1 July to 14 August 2004, centered over the eastern United States and Canada and showed that sulfate was the dominant inorganic species measured. The highest sulfate concentrations were observed at altitudes below 2 km, and back trajectory analyses showed a distinct difference between air masses that had or had not intercepted the Ohio River valley (ORV) region. Air masses encountered below 2 km with a history over the ORV had sulfate concentrations that were higher by a factor of 3.2 and total sulfur (S) concentrations higher by 2.5. The study's highest sulfate concentrations were found in these air masses. The sulfur of the ORV air masses was also more processed with a mean sulfate to total sulfur molar ratio of 0.5 compared to 0.3 in non-ORV measurements. Results from a second, independent trajectory model agreed well with those from the primary analysis. These ORV-influenced air masses were encountered on multiple days and were widely spread across the eastern United States and western Atlantic region.