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As a class of brown carbon, organonitrogen compounds originating from the heterogeneous uptake of NH3 by secondary organic aerosol (SOA) have received significant attention recently. In the current work, particulate organonitrogen formation during the ozonolysis of a-pinene and the OH oxidation of m-xylene in the presence of ammonia (34-125 ppb) was studied in a smog chamber equipped with a high resolution time-of-flight aerosol mass spectrometer and a quantum cascade laser instrument. A large diversity of nitrogen-containing organic (NOC) fragments was observed which were consistent with the reactions between ammonia and carbonyl-containing SOA. Ammonia uptake coefficients onto SOA which led to organonitrogen compounds were reported for the first time, and were in the range of ~ 10-3-10-2, decreasing significantly to < 10-5 after 6 h of reaction. At the end of experiments (~ 6 h) the NOC mass contributed 8.9 ± 1.7 and 31.5 ± 4.4 wt % to the total α-pinene- and m-xylene-derived SOA, respectively, and 4-15 wt % of the total nitrogen in the system. Uptake coefficients were also found to be positively correlated with particle acidity and negatively correlated with NH3 concentration, indicating that heterogeneous reactions were responsible for the observed NOC mass, possibly limited by liquid phase diffusion. Under these conditions, the data also indicate that the formation of NOC can compete kinetically with inorganic acid neutralization. The formation of NOC in this study suggests that a significant portion of the ambient particle associated N may be derived from NH3 heterogeneous reactions with SOA. NOC from such a mechanism may be an important and unaccounted for source of PM associated nitrogen. This mechanism may also contribute to the medium or long-range transport and wet/dry deposition of atmospheric nitrogen. [ABSTRACT FROM AUTHOR]

Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site (Pasadena) in June-July 2010 during CalNex (California Research at the Nexus of Air Quality and Climate Change) and a site in an oil and gas producing region (Uintah Basin) in January-February 2013 during UBWOS 2013 (Uintah Basin Winter Ozone Studies) will be discussed. Although the VOC (volatile organic compounds) compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 in UBWOS 2013 and 2.0 ± 1.0 ppb in Cal-Nex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 99 %). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Compared to the original MCM model that includes only ozonolysis of unsaturated organic compounds and OH oxidation of acetylene, when we updated yields of ozonolysis of alkenes and included OH oxidation of isoprene, vinyl alcohol chemistry, reaction of formaldehyde with HO2, oxidation of aromatics, and reaction of CH3O2 with OH, the model predictions for formic acid were improved by a factor of 6.4 in UBWOS 2013 and 4.5 in CalNex, respectively. A comparison of measured and modeled HCOOH= acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 19 and 45% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be 0-6 and 0-5% in UBWOS 2013 and CalNex, respectively. We observe that air-snow exchange processes and morning fog events may also contribute to ambient formic acid concentrations during UBWOS 2013 (~20% in total). In total, 53-59 in UBWOS 2013 and 50-55% in CalNex of secondary formation of formic acid remains unexplained. More work on formic acid formation pathways is needed to reduce the uncertainties in the sources and budget of formic acid and to narrow the gaps between measurements and model results. [ABSTRACT FROM AUTHOR]

Understanding of the atmosphere/forest canopy exchange of volatile organic compounds (VOCs) requires insight into the deposition, emission, and chemical reactions of VOCs below the canopy. Between 18 July and 9 August 2009, VOCs were measured with proton-transfer-reaction mass spectrometry (PTR-MS) at six heights between 1 and 6m beneath a 23m high mixed-forest canopy. Measured VOCs included methanol, isoprene, acetone, methacrolein and methyl vinyl ketone (MACR+MVK), monoterpenes, and sesquiterpenes. There are pronounced differences in the behaviour of isoprene and its by-products and that of the terpenes. Non-terpene mixing ratios increase with height, suggesting predominantly downward fluxes. In contrast, the terpene mixing ratios decrease with height, suggesting upward fluxes. A 1-D canopy model was used to compare results to measurements with and without surface deposition of isoprene and MACR+MVK and emissions of monoterpenes and sesquiterpenes. Results suggest deposition velocities of 2.7mms-1 for isoprene and 1.2mms-1 for MACR+MVK and daytime surface emission rates of 63 µgm-2 h-1 for monoterpenes. The modelled isoprene surface deposition is approximately 2% of the canopy-top isoprene emissions and the modelled emissions of monoterpenes comprise approximately 15 to 27% of the canopy-top monoterpene emissions to the atmosphere. These results suggest that surface monoterpene emissions are significant for forest canopy/atmosphere exchange for this mixed-forest location and surface uptake is relatively small for all the species measured in this study. [ABSTRACT FROM AUTHOR]

The mixed-phase relative rates approach for determining aerosol particle organic heterogeneous reaction kinetics is often performed utilizing mass spectral tracers as a proxy for particle-phase reactant concentration. However, this approach may be influenced by signal contamination from oxidation products during the experiment. In the current study, the mixed-phase relative rates technique has been improved by combining a positive matrix factor (PMF) analysis with electron ionization aerosol mass spectrometry (unit-mass resolution), thereby removing the influence of m/z fragments from reaction products on the reactant signals. To demonstrate the advantages of this approach, the heterogeneous reaction between OH radicals and citric acid (CA) was investigated using a photochemical flow tube coupled to a compact time-offlight aerosol mass spectrometer (C-ToF-AMS). The measured heterogeneous rate constant (k2) of citric acid toward OH was (3.31±0.29)×10-12 cm³ molecule-1 s-1 at 298K and (30±3) % relative humidity (RH) and was several times greater than the results utilizing individual m/z fragments. This phenomenon was further evaluated for particulate-phase organophosphates (triphenyl phosphate (TPhP), tris-1,3-dichloro-2-propyl phosphate (TDCPP) and tris-2-ethylhexyl phosphate (TEHP)), leading to k2 values significantly larger than previously reported. The results suggest that heterogeneous kinetics can be significantly underestimated when the structure of the products is highly similar to the reactant and when a non-molecular tracer is measured with a unit-mass resolution aerosol mass spectrometer. The results also suggest that the heterogeneous lifetime of organic aerosol in models can be overestimated due to underestimated OH uptake coefficients. Finally, a comparison of reported rate constants implies that the heterogeneous oxidation of aerosols will be dependent upon a number of factors related to the reaction system, and that a single rate constant for one system cannot be universally applied under all conditions. [ABSTRACT FROM AUTHOR]

Understanding of the atmosphere/forest canopy exchange of volatile organic compounds (VOCs) requires insight into deposition, emission, and chemical reactions of VOCs below the canopy. Currently, uncertainties in canopy processes, such as stomatal uptake, deposition, and sub-canopy chemistry, make it difficult to derive biogenic VOC emission inventories from canopy VOC concentration gradients. Between 18 July and 9 August 2009, VOCs were measured with proton-transfer-reaction mass spectrometry (PTR-MS) at 6 heights between 1 and 6 m beneath a 23 m high mixed-forest canopy. Measured VOCs included methanol, isoprene, acetone, methacrolein + methyl vinyl ketone (MACR+MVK), monoterpenes and sesquiterpenes. There are pronounced differences in the behaviour of isoprene and its by-products and that of the terpenes. Non-terpene fluxes are predominantly downward. In contrast, the terpene fluxes are significantly upward. A 1-dimensional canopy model was used to compare results to measurements with and without surface deposition of isoprene and MACR+MVK and emissions of monoterpenes and sesquiterpenes. Results suggest deposition velocities of 27 mm s-1 for isoprene and 12 mm s-1 for MACR+MVK and daytime surface emission rates of 63 μg m-2 h-1 for monoterpenes. The modelled isoprene surface deposition is approximately 2% of the canopy top isoprene emissions and the modelled emissions of monoterpenes comprise approximately 15 to 27% of the canopy-top monoterpene emissions to the atmosphere. These results suggest that surface monoterpene emissions are significant for forest canopy/atmosphere exchange for this mixed forest location and surface uptake is relatively small for all the species measured in this study. [ABSTRACT FROM AUTHOR]

Although black carbon (BC) is one of the key atmospheric particulate components driving climate change and air quality, there is no agreement on the terminology that considers all aspects of specific properties, definitions, measurement methods, and related uncertainties. As a result, there is much ambiguity in the scientific literature of measurements and numerical models that refer to BC with different names and based on different properties of the particles, with no clear definition of the terms. The authors present here a recommended terminology to clarify the terms used for BC in atmospheric research, with the goal of establishing unambiguous links between terms, targeted material properties and associated measurement techniques. [ABSTRACT FROM AUTHOR]

A large oxygenated organic uptake to aerosols was observed when exposing ambient urban air to inorganic acidic and non-acidic sulfate seed aerosol. For non-acidic seed aerosol the uptake was attributed to the direct dissolution of primary vehicle exhaust gases into the aqueous aerosol fraction, and was correlated to the initial seed sulphate mass. The uptake of primary oxygenated organic gases to aerosols in this study represents a significant amount of organic aerosol (OA) that may be considered primary when compared to that reported for primary organic aerosol (POA), but is considerably more oxygenated (O :C~0.3) than traditional POA. Consequently, a fraction of measured ambient oxygenated OA, which correlates with secondary sulphate, may in fact be of a primary, rather than secondary source. These results represent a new source of oxygenated OA on neutral aerosol and imply that the uptake of primary organic gases will occur in the ambient atmosphere, under dilute conditions, and in the presence of pre-existing SO4 aerosols which contain water. Conversely, under acidic seed aerosol conditions, oligomer formation was observed with the uptake of organics being enhanced by a factor of three or more compared to neutral aerosols, and in less than 2 min, representing an additional source of SOA to the atmosphere. This resulted in a trajectory in Van Krevelen space towards higher O:C (slope~-1.5), despite a lack of continual gas-phase oxidation in this closed system. The results demonstrate that high molecular weight species will form on acidic aerosols at the ambient level and mixture of organic gases, but are otherwise unaffected by subsequent aerosol neutralization, and that aerosol acidity will affect the organic O: C via aerosolphase reactions. These two processes, forming oxygenated POA under neutral conditions and SOA under acidic conditions can contribute to the total ambient OA mass and the evolution of ambient aerosol O:C ratios. This may be important for properly representing organic aerosol O:C ratios in air quality and climate models. [ABSTRACT FROM AUTHOR]

Measurements of submicron aerosol chemical composition were made over the central Arctic Ocean from 5 August to 8 September 2008 as a part of the Arctic Summer Cloud Ocean Study (ASCOS) using an aerosol mass spectrometer (AMS). The median levels of sulphate and organics for the entire study were 0.051 and 0.055 µgm-3, respectively. Positive matrix factorisation was performed on the entire mass spectral time series and this enabled marine biogenic and continental sources of particles to be separated. These factors accounted for 33% and 36% of the sampled ambient aerosol mass, respectively, and they were both predominantly composed of sulphate, with 47% of the sulphate apportioned to marine biogenic sources and 48% to continental sources, by mass. Within the marine biogenic factor, the ratio of methane sulphonate to sulphate was 0.25±0.02, consistent with values reported in the literature. The organic component of the continental factor was more oxidised than that of the marine biogenic factor, suggesting that it had a longer photochemical lifetime than the organics in the marine biogenic factor. The remaining ambient aerosol mass was apportioned to an organic-rich factor that could have arisen from a combination of marine and continental sources. In particular, given that the factor does not correlate with common tracers of continental influence, we cannot rule out that the organic factor arises from a primary marine source. [ABSTRACT FROM AUTHOR]

High time-resolved aircraft data, concurrent surface measurements and air quality model simulations were explored to diagnose the processes influencing aerosol chemistry under the influence of lake-breeze circulations in a polluted region of southwestern Ontario, Canada. The analysis was based upon horizontal aircraft transects conducted at multiple altitudes across an entire lake-breeze circulation. Air mass boundaries due to lake-breeze fronts were identified in the aircraft meteorological and chemical data, which were consistent with the frontal locations determined from surface analyses. Observations and modelling support the interpretation of a lake-breeze circulation where pollutants were lofted at a lake-breeze front, transported in the synoptic flow, caught in a downdraft over the lake, and then confined by onshore flow. The detailed analysis led to the development of conceptual models that summarize the complex 3-D circulation patterns and their interaction with the synoptic flow. The identified air mass boundaries, the interpretation of the lake-breeze circulation, and the air parcel circulation time in the lake-breeze circulation (3.0 to 5.0 h) enabled formation rates of organic aerosol (OA/ΔCO) and Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed to be determined. The formation rate for OA (relative to excess CO in ppmv) was found to be 11.6-19.4 µgm-3 ppmv-1 h-1 and the Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed formation rate was 5.0-8.8 %h-1. The formation rates are enhanced relative to regional background rates implying that lake-breeze circulations are an important dynamic in the formation of Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed and secondary organic aerosol. The presence of cumulus clouds associated with the lake-breeze fronts suggests that these enhancements could be due to cloud processes. Additionally, the effective confinement of pollutants along the shoreline may have limited pollutant dilution leading to elevated oxidant concentrations. [ABSTRACT FROM AUTHOR]

This paper presents the results of laboratory studies on the condensational uptake of gaseous organic compounds in the exhaust of a light-duty gasoline engine onto preexisting sulfate and nitrate seed particles. Significant condensation of the gaseous organic compounds in the exhaust occurs onto these inorganic particles on a time scale of 2- 5 min. The amount of condensed organic mass (COM) is proportional to the seed particle mass, suggesting that the uptake is due to dissolution determined by the equilibrium partitioning between gas phase and particles, not adsorption. The amount of dissolution in unit seed mass, S, decreases as a power function with increased dilution of the exhaust, ranging from 0.23 g g-1 at a dilution ratio of 81, to 0.025 g g-1 at a dilution ratio of 2230. It increases nonlinearly with increasing concentration of the total hydrocarbons in the gas phase (THC), rising from 0.12 g g-1 to 0.26 g g-1 for a CTHC increase of 1 to 18 µgm-3, suggesting that more organics are partitioned into the particles at higher gas phase concentrations. In terms of gas-particle partitioning, the condensational uptake of THC gases in gasoline engine exhaust can account for up to 30% of the total gas + particle THC. The organic mass spectrum of COM has the largest fragment at m/z 44, with mass ratios of mass fragments 43/44 and 57/44 at 0.59 and 2.91, much lower than those reported for gasoline engine primary organic aerosols. The mass fragment 44/total organic mass ratio of 0.097 indicates that COM contains large oxygenated components. By incorporating the present findings, regional air quality modelling results suggest that the condensational uptake of THC onto sulfate particles alone can be comparable to the primary particle mass under moderately polluted ambient conditions. These findings are important for modelling and regulating the air quality impacts of gasoline vehicular emissions. [ABSTRACT FROM AUTHOR]

Aerosol fluxes were measured above a mixed forest by Eddy Covariance (EC) with a Fast Mobility Particle Sizer (FMPS) at the Borden Forest Research Station in Ontario, Canada between 13 July and 12 August 2009. Chemically speciated flux measurements were made at a height of 29m at the same location between 19 July and 2 August, 2006 using a Quadrupole Aerosol Mass Spectrometer (Q-AMS). The Q-AMS measured an average sulphate deposition velocity of 0.3mm s-1 and an average nitrate deposition velocity of 4.8mm s-1. The FMPS, mounted at a height of 33m (approximately 10m above the canopy top) and housed in a temperature controlled enclosure, measured size-resolved particle concentrations from 3 to 410 nm diameter at a rate of 1Hz. For the size range 18< D <452 nm, 60% of fluxes were upward. The exchange velocity was between -0.5 and 2.0mm s-1, with median values near 0.5mm s-1 for all sizes between 22 and 310 nm. The size distribution of the apparent production rate of particles at 33m peaked at a diameter of 75 nm. Results indicate a decoupling of the above and below canopy spaces, whereby particles are stored in the canopy space at night, and are then diluted with cleaner air above during the day. [ABSTRACT FROM AUTHOR]

As part of the BAQS-Met 2007 field campaign, Aerodyne time-of-flight aerosol mass spectrometers (ToF-AMS) were deployed at two sites in southwestern Ontario from 17 June to 11 July 2007. One instrument was located at Harrow, ON, a rural, agriculture-dominated area approximately 40 km southeast of the Detroit/Windsor/Windsor urban area and 5 km north of Lake Erie. The second instrument was located at Bear Creek, ON, a rural site approximately 70 km northeast of the Harrow site and 50 km east of Detroit/Windsor. Positive matrix factorization analysis of the combined organic mass spectral dataset yields factors related to secondary organic aerosol (SOA), direct emissions, and a factor tentatively attributed to the reactive uptake of isoprene and/or condensation of its early generation reaction products. This is the first application of PMF to simultaneous AMS measurements at different sites, an approach which allows for self-consistent, direct comparison of the datasets. Case studies are utilized to investigate processing of SOA from (1) fresh emissions from Detroit/Windsor and (2) regional aerosol during periods of intersite flow. A strong correlation is observed between SOA/excess CO and photochemical age as represented by the NOx/NOy ratio for Detroit/Windsor outflow. Although this correlation is not evident for more aged air, measurements at the two sites during intersite transport nevertheless show evidence of continued atmospheric processing by SOA production. However, the rate of SOA production decreases with airmass age from an initial value of ∼10.1 µgm-3 Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. h-1 for the first ∼10 h of plume processing to near-zero in an aged airmass (i.e. after several days). The initial SOA production rate is comparable to the observed rate in Mexico City over similar timescales. [ABSTRACT FROM AUTHOR]

Ultrafine particle (UFP) number and size distributions were simultaneously measured at five urban and rural sites during the summer of 2007 in Ontario, Canada as part of the Border Air Quality and Meteorology Study (BAQS-Met 2007). Particle formation and growth events at these five sites were classified based on their strength and persistence as well as the variation in geometric mean diameter. Regional nucleation and growth events and local short-lived strong nucleation events were frequently observed at the near-border rural sites, upwind of industrial sources. Surprisingly, the particle number concentrations at one of these sites were higher than the concentrations at a downtown site in a major city, despite its high traffic density. Regional nucleation and growth events were favored during intense solar irradiance and in less polluted cooler drier air. The most distinctive regional particle nucleation and growth event during the campaign was observed simultaneously at all five sites, which were up to 350 km apart. Although the ultrafine particle concentrations and size distributions generally were spatially heterogeneous across the region, a more uniform spatial distribution of UFP across the five areas was observed during this regional nucleation event. Thus, nucleation events can cover large regions, contributing to the burden of UFP in cities and potentially to the associated health impacts on urban populations. Local short-lived nucleation events at the three near-border sites during this summer three-week campaign were associated with high SO2, which likely originated from US and Canadian industrial sources. Hence, particle formation in southwestern Ontario appears to often be related to anthropogenic gaseous emissions but biogenic emissions at times also contribute. Longer-term studies are needed to help resolve the relative contributions of anthropogenic and biogenic emissions to nucleation and growth in this region. [ABSTRACT FROM AUTHOR]

Submicron particles collected at Whistler, British Columbia, at 1020 m a.s.l. during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR) and X-ray fluorescence (XRF) techniques for organic functional groups (OFG) and elemental composition. Organic mass (OM) concentrations ranged from less than 0.5 to 3.1 μg m-3, with a project mean and standard deviation of 1.3±1.0 μg m-3 and 0.21±0.16 μg m-3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and <1% of the average organic aerosol composition, respectively. Measurements of volatile organic compounds (VOC), including isoprene and monoterpenes from biogenic VOC (BVOC) emissions and their oxidation products (methyl-vinylketone / methacrolein, MVK/MACR), were made using co-located proton transfer reaction mass spectrometry (PTR-MS). We present chemically-specific evidence of OFG associated with BVOC emissions. Positive matrix factorization (PMF) analysis attributed 65% of the campaign OM to biogenic sources, based on the correlations of one factor to monoterpenes and MVK/MACR. The remaining fraction was attributed to anthropogenic sources based on a correlation to sulfate. The functional group composition of the biogenic factor (consisting of 32% alkane, 25% carboxylic acid, 21% organic hydroxyl, 16% ketone, and 6% amine groups) was similar to that of secondary organic aerosol (SOA) reported from the oxidation of BVOCs in laboratory chamber studies, providing evidence that the magnitude and chemical composition of biogenic SOA simulated in the laboratory is similar to that found in actual atmospheric conditions. The biogenic factor OM is also correlated to dust elements, indicating that dust may act as a non-acidic SOA sink. This role is supported by the organic functional group composition and morphology of single particles, which were analyzed by scanning transmission X-ray microscopy near edge X-ray absorption fine structure (STXM-NEXAFS). [ABSTRACT FROM AUTHOR]

Ambient particulate matter (PM) samples were collected on quartz filters at a rural site in central Ontario during an intensive study in 2007. The concentrations of organic carbon (OC), pyrolysis organic carbon (POC), and elemental carbon (EC) were determined by thermal analysis. The concentrations are compared to the organic aerosol mass concentration (OM) measured with an Aerodyne C-ToF Aerosol Mass Spectrometer (AMS) and to the particle absorption coefficient (basp) obtained from a Radiance Research Particle Soot Absorption Photometer (PSAP). The total organic mass to organic carbon ratios (OM/OC) and specific attenuation coefficients (SAC=basp/EC) are derived. Proportionality of the POC mass with the oxygen mass in the aerosols estimated from the AMS offers a potential means to estimate OM/OC from thermal measurements only. The mean SAC for the study is 3.8±0.3 m2 g-1. It is found that the SAC is independent of or decrease with increasing particle mass loading, depending on whether or not the data are separated between aerosols dominated by more recent anthropogenic input and aerosols dominated by longer residence time or biogenic components. There is no evidence to support an enhancement of light absorption by the condensation of secondary material to particles, suggesting that present model simulations built on such an assumption may overestimate atmospheric warming by BC. [ABSTRACT FROM AUTHOR]

An Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed at the peak of Whistler Mountain (2182m above sea level), British Columbia, from 19 April to 16 May 2006, as part of the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign. The mass concentrations and size distributions of non-refractory submicron particle (NR-PM1) species (i.e., sulfate, nitrate, ammonium, chloride, and organics) were measured in situ at 10-min time resolution. The HR-ToF-AMS results agreed well with collocated measurements. The average concentration of non-refractory submicron particulate matter (NR-PM1; 1.9 μg m-3) is similar to those observed at other remote, high elevation sites in North America. Episodes of enhanced aerosol loadings were observed, due to influences of regional and trans-Pacific transport of air pollution. Organics and sulfate were the dominant species, on average accounting for 55% and 30%, respectively, of the NR-PM1 mass. The average size distributions of sulfate and ammonium both showed an accumulation mode peaking at ∼500 nm in vacuum aerodynamic diameter (Dva) while those of organic aerosol (OA) and nitrate peaked at ∼300 nm. The size differences suggested that sulfate and OA were mostly present in external mixtures from different source origins. We also quantitatively determined the elemental composition of OA using the high resolution mass spectra. Overall, OA at Whistler Peak was highly oxygenated, with an average organic-mass-to-organic-carbon ratio (OM/OC) of 2.28±0.23 and an atomic ratio of oxygen-to- carbon (O/C) of 0.83±0.17. The nominal formula for OA was C1H1.66N0.03O0.83 for the entire study. Two significant trans-Pacific dust events originated from Asia were observed at Whistler Peak during this study. While both events were characterized with significant enhancements of coarse mode particles and mineral contents, the composition and characteristics of NR-PM1 were significantly different between them. One trans-Pacific event occurred on 15 May 2006, during which ammonium sulfate contributed >90% of the total NR-PM1 mass. This event was followed by a high OA episode likely associated with regional emissions. In total, three enhanced regional OA events, each of which lasted 2-3 days, were observed during this study. In contrast to the two dust events, the regional OA events were generally characterized with higher OA/sulfate ratio, less oxidized OA, and lower OM/OC ratio. [ABSTRACT FROM AUTHOR]

Recent evidence has suggested that heterogeneous chemistry of oxygenated hydrocarbons, primarily carbonyls, plays a role in the formation of secondary organic aerosol (SOA); however, evidence is emerging that direct uptake of alkenes on acidic aerosols does occur and can contribute to SOA formation. In the present study, significant uptake of monoterpenes, oxygenated monoterpenes and sesquiterpenes to acidic sulfate aerosols is found under various conditions in a reaction chamber. Proton transfer mass spectrometry is used to quantify the organic gases, while an aerosol mass spectrometer is used to quantify the organic mass uptake and obtain structural information for heterogeneous products. Aerosol mass spectra are consistent with several mechanisms including acid catalyzed olefin hydration, cationic polymerization and organic ether formation, while measurable decreases in the sulfate mass on a per particle basis suggest that the formation of organosulfate compounds is also likely. A portion of the heterogeneous reactions appears to be reversible, consistent with reversible olefin hydration reactions. A slow increase in the organic mass after a fast initial uptake is attributed to irreversible reactions, consistent with polymerization and organosulfate formation. Uptake coefficients (γ) were estimated for a fast initial uptake governed by the mass accommodation coefficient (α) and ranged from 1×10-6-2.5×10-2. Uptake coefficients for a subsequent slower reactive uptake ranged from 1×10-7-1×10-4. These processes may potentially lead to a considerable amount of SOA from the various biogenic hydrocarbons under acidic conditions, which can be highly significant for freshly nucleated aerosols, particularly given the large array of atmospheric olefins. [ABSTRACT FROM AUTHOR]

Measurements of cloud condensation nuclei (CCN) were made in downtown Toronto during August and September, 2003. CCN measurements were performed at 0.58% supersaturation using a thermal-gradient diffusion chamber, whereas the aerosol size distribution and composition were simultaneously measured with a TSI SMPS and APS system and an Aerodyne Aerosol Mass Spectrometer (AMS), respectively. Aerosol composition data shows that the particles were predominately organic in nature, in particular for those with a vacuum aerodynamic diameter of <0.25µm. In this study, the largest contribution to CCN concentrations came from this size range, suggesting that the CCN are also organic-rich. Using the size and composition information, detailed CCN closure analyses were performed. In the first analysis, the particles were assumed to be internally mixed, the organic fraction was assumed to be insoluble, and the inorganic fraction was assumed to be ammonium sulfate. The AMS time-of-flight data were used for Köhler theory predictions for each particle size and composition to obtain the dry diameter required for activation. By so doing, this closure analysis yielded an average value of CCNpredicted/CCNobserved=1.12±0.05. However, several sample days showed distinct bimodal distributions, and a closure analysis was performed after decoupling the two particle modes. This analysis yielded an average value of CCNpredicted/CCNobserved=1.03±0.05. A sensitivity analysis was also performed to determine the aerosol/CCN closure if the organic solubility, droplet surface tension, or chamber supersaturation were varied. [ABSTRACT FROM AUTHOR]