Evaluation of secondary organic aerosol formation in winter

Three different methods are used to predict secondary organic aerosol (SOA) concentrations in the San Joaquin Valley of California during the winter of 1995–1996 [Integrated Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as a tracer of primary organic carbon. The second method relies on a Lagrangian trajectory model that simulates the formation, transport, and deposition of secondary organic aerosol. The model includes a recently developed gas–particle partitioning mechanism. Results from both methods are in good agreement with the chemical speciation of organic aerosol during IMS95 and suggest that most of the OC measured during IMS95 is of primary origin. Under suitable conditions (clear skies, low winds, low mixing heights) as much as 15–20 μg C m⁻³ of SOA can be produced, mainly due to oxidation of aromatics. The low mixing heights observed during the winter in the area allow accumulation of SOA precursors and the acceleration of SOA formation. Clouds and fog slow down the production of secondary compounds, reducing their concentrations by a factor of two or three from the above maximum levels. In addition, it appears that there is significant diurnal variation of SOA concentration. A strong dependence of SOA concentrations on temperature is observed, along with the existence of an optimal temperature for SOA formation.     

Searching for evidence of acid-catalyzed enhancement of secondary organic aerosol formation using ambient aerosol data

Laboratory experiments suggest that strong acids promote formation of enhanced levels of secondary organic aerosol (SOA), and organic aerosols may contribute to the health impacts of fine PM. We report results from examining hourly speciated fine particle data for evidence of ambient aerosol acidity-catalyzed SOA formation, as indicated by larger increases in the concentrations of organic aerosol mass occurring on days and in locations where more acidic aerosol (lower NH₄⁺/SO₄⁼ molar ratios) exists. Data sets from the southeastern U.S. were examined for which hourly acidity of PM_2.5 aerosols could be estimated, and for which hourly organic carbon (OC) content had been measured simultaneously. Within-day organic aerosol changes during selected periods were statistically related to concurrent aerosol acidity levels estimated from nitrate-corrected ammonium-to-sulfate ratios. Data from the Look Rock, TN, TVA/IMPROVE site for mid-July to mid-August 2004 showed average compositions frequently as acidic as NH₄HSO₄, however, no apparent increases in OC levels with increasing aerosol acidity were observed, even when [OC] changes were compared with time-delayed aerosol acidity estimates. SEARCH network data (2003–2004) for rural Centreville, AL (CTR) and Yorkville, GA (YRK) sites were also examined. Warm-season acidity levels were higher at CTR than at YRK, and daytime levels exceeded those at night at both sites. At the YRK site no consistent positive correlations were found between changes in OC or TC levels and aerosol acidity, even with time lags up to 6 h. Aerosol acidity at this site, however, is relatively low due to nearby agricultural sources of NH₃. In contrast, during selected periods from April to October 2004, at CTR, 6-h lagged OC changes were weakly correlated with daytime, nitrate-corrected NH₄⁺/SO₄⁼ molar ratios, but distinguishing this apparent relationship from meteorological effects on measured OC levels is challenging.     

A chamber study of secondary organic aerosol formation by linalool ozonolysis

The formation of secondary organic aerosol (SOA) produced from linalool ozonolysis was examined using a dynamic chamber system that allowed the simulation of ventilated indoor environments. Experiments were conducted under room temperature (22–23 °C) and air exchange rate of 0.67 h^?1. An effort was made to maintain the product of the concentrations of the two reagents constant. The results suggest that under the conditions when the product of the two reagent concentrations was constant, the relative concentrations play an important role in determining the total SOA formed. A combination of concentrations somewhere in ozone limiting region will produce the maximum SOA concentration. The measured reactive oxygen species (ROS) concentrations at linalool and ozone concentrations relevant to prevailing indoor concentrations ranged from 0.71 to 2.53 nmol m^?3 equivalents of H₂O₂. It was found that particle samples aged for 24 h lost a significant fraction of the ROS compared to fresh samples. The residual ROS concentrations were around 15–69%. Compared with other terpene species like α-pinene that has one endocyclic unsaturated carbon bond, linalool was less efficient in potential SOA formation yields.     

An absorption model of the gas/aerosol partitioning involved in the formation of secondary organic aerosol

A partitioning model is developed to allow the modeling of the dynamics of secondary organic aerosol (SOA) formation. The gas/aerosol partitioning is assumed to be governed by equilibrium partitioning into an absorptive, well-mixed liquid (or at least amorphous) organic matter (om) phase. The model is represented using a set of coupled linear equations. It may be especially applicable when photochemical smog is being formed in the summer. The model permits (indeed, it requires) partitioning of a given compound i to occur even when i is present at a level below its saturation vapor pressure. During early periods of SOA formation, to determine the partitioning for each compound of interest, the model must be solved iteratively for each time and location of interest. Iteration is required because the partitioning is assumed to be governed by mole fraction concentrations in the om phase, and because prior to solving the problem, one does not know the total number of mols of condensed compounds in the om phase. During later stages of SOA formation, if the amount and general composition of the SOA begin to become constant, the partitioning coefficient of each of the compounds will also stabilize, and an iterative solution will be less needed.     

Model evidence for a significant source of secondary organic aerosol from isoprene

We investigate how a recently suggested pathway for production of secondary organic aerosol (SOA) affects the consistency of simulated organic aerosol (OA) mass in a global three-dimensional model of oxidant-aerosol chemistry (GEOS-Chem) versus surface measurements from the interagency monitoring of protected visual environments (IMPROVE) network. Simulations in which isoprene oxidation products contribute to SOA formation, with a yield of 2.0% by mass reduce a model bias versus measured OA surface mass concentrations. The resultant increase in simulated OA mass concentrations during summer of 0.6–1.0 μg m⁻³ in the southeastern United States reduces the regional RMSE to 0.88 μg m⁻³ from 1.26 μg m⁻³. Spring and fall biases are also reduced, with little change in winter when isoprene emissions are negligible.     

An examination of oxidant amounts on secondary organic aerosol formation and aging

The effect of HO_x radicals (OH and HO₂) and ozone (O₃) on aerosol formation and aging has been studied. Experiments were performed in presence as well as in absence of oxygen in a flow-through chamber at 299 K for three organic precursor gases, isoprene, α-pinene and m-xylene. The HO_x source was the UV photolysis of humidified air or nitrogen and was measured with a GTHOS (Ground-based Tropospheric Hydrogen Oxides Sensor). The precursor gases concentration was monitored with an online GC-FID. The aerosol mass was then quantified by a Tapered Element Oscillating Microbalance (TEOM). Typical oxidant mixing ratios were (0–4.5) ppm for O₃, 200 pptv for OH and 3 ppbv for HO₂. A simple kinetics model is used to infer the aerosol production mechanism. In the present of O₃ (or O₂), the SOA yields were 0.46, 0.036 and 0.12 for α-pinene with an initial concentration of 100 ppbv (RH = 37%), isoprene with an initial concentration of 177 ppbv (RH = 50%) and m-xylene with an initial concentration of 100 ppbv (RH = 37%), respectively. When the chosen precursor gases reacted with HO_x in the absence of O₃, the maximum SOA yields were significantly increased by factors of 1.6 for isoprene 1.1 for α-pinene, and 3 for m-xylene respectively. The comparison of the calculated and measured potential aerosol mass concentrations as function of time shows that presence of ozone or oxygen can influence the aerosol yield and the absence of ozone or oxygen in the system resulted in high concentrations of its organic aerosol products.     

Source apportionment of secondary organic aerosol during a severe photochemical smog episode

The UCD/CIT air quality model was modified to predict source contributions to secondary organic aerosol (SOA) by expanding the Caltech Atmospheric Chemistry Mechanism to separately track source apportionment information through the chemical reaction system as precursor species react to form condensable products. The model was used to predict source contributions to SOA in Los Angeles from catalyst-equipped gasoline vehicles, non-catalyst equipped gasoline vehicles, diesel vehicles, combustion of high sulfur fuel, other anthropogenic sources, biogenic sources, and initial/boundary conditions during the severe photochemical smog episode that occurred on 9 September 1993. Gasoline engines (catalyst+non-catalyst equipped) were found to be the single-largest anthropogenic source of SOA averaged over the entire model domain. The region-wide 24-h average concentration of SOA produced by gasoline engines was predicted to be 0.34 μg m⁻³ with a maximum 24-h average concentration of 1.81 μg m⁻³ downwind of central Los Angeles. The region-wide 24-h average concentration of SOA produced by diesel engines was predicted to be 0.02 μg m⁻³, with a maximum 24-h average concentration of 0.12 μg m⁻³ downwind of central Los Angeles. Biogenic sources are predicted to produce a region-wide 24-h average SOA value of 0.16 μg m⁻³, with a maximum 24-h average concentration of 1.37 μg m⁻³ in the less-heavily populated regions at the northern and southern edges of the air basin (close to the biogenic emissions sources). SOA concentrations associated with anthropogenic sources were weakly diurnal, with slightly lower concentrations during the day as mixing depth increased. SOA concentrations associated with biogenic sources were strongly diurnal, with higher concentrations of aqueous biogenic SOA at night when relative humidity (RH) peaked and little biogenic SOA formation during the day when RH decreased.     

High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene

The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C₅H₈) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS) in the mass range m/z = 50–1000. The chemical composition of SOA is complex, with more than 1000 assigned peaks observed in the positive and negative ion mode spectra. Only a small fraction of peaks correspond to known products of isoprene oxidation, such as pyruvic acid, glycolic acid, methylglyoxal, etc. The absolute majority of the detected peaks correspond to highly oxidized oligomeric constituents of SOA, with an average O:C molar ratio of 0.6. The corresponding organic mass (OM) to organic oxygen (OO) ratio is 2.4. Approximately 8% of oxygen atoms in SOA are in the form of peroxides, as quantified with an iodide test. Double bond equivalency (DBE) factors, representing the sum of all double bonds and rings, increase by 1 for every 1–2 additional carbon atoms in the molecule. The number of unoxidized CC double bonds is estimated to be less than 10%; the remaining DBE is due to CO carbonyl groups. Kendrick analysis suggests that the prevalent oligomer building blocks are small carbonyls with a C₁–C₂ skeleton. Formaldehyde (CH₂O) is identified as the most common repetitive building block in the observed oligomeric compounds.     

成都市夏季大气挥发性有机物污染及其对二次有机气溶胶生成的贡献

于2014年7月8日至8月13日在成都市城区和工业区选取两个点位开展挥发性有机物(VOCs)样品采集工作,分析结果显示,成都市夏季城区大气中VOCs质量浓度在34.1~458.8μg/m3,平均值为(137.3±91.8)μg/m3;工业区大气中VOCs质量浓度在26.7~474.9μg/m3,平均值为(135.9±103.5)μg/m3。早高峰时段(7:00~10:00)两个点位VOCs的浓度水平均高于其他时段,说明VOCs浓度受机动车排放的影响较为明显。用·OH消耗速率和臭氧生成潜势评估VOCs大气化学反应活性,结果显示,芳香烃和烯烃是影响大气化学反应活性的关键组分。城区和工业区的二次有机气溶胶(SOA)的生成潜势分别为4.859、4.559μg/m3,芳香烃不仅是臭氧生成潜势的关键活性组分,同时也是SOA的重要前体物。     

Mass spectrometric study of secondary organic aerosol formed from the photo-oxidation of aromatic hydrocarbons

From measurements by an Aerodyne Aerosol Mass Spectrometer (AMS), secondary organic aerosol (SOA) formed in laboratory chambers is believed to be less oxidized than well-oxidized ambient organic aerosol (OA). However, the mass spectrum of SOA formed from the photo-oxidation of aromatic hydrocarbons has not been sufficiently studied by using AMS though these reactions are potential sources of urban SOA. In this study, we studied SOA formed from the photo-oxidation of seven aromatic hydrocarbons by using Time-of-Flight AMS. Strong mass signals from SOA were found at m/z 43 (m43) and 44 (m44) in all the experiments. The m44 to total organic aerosol mass ratio (m44/OA) increased with irradiation time. For example, the m44/OA ratio increased from 10.6% to 13.3% during irradiation for 11 h in an experiment with toluene. The average m44/OA ratios were determined to be 5.8–17.1% for all the experiments. The m44/OA decreased and the m43/OA increased with increasing number of alkyl substituents of precursor aromatic hydrocarbons. This is because low-reactive ketones are preferentially produced rather than aldehydes with increasing number of alkyl substituents. The m44/OA ratios of the benzene and monoalkylbenzene oxidation were 12.2–17.1% and were close to those of well-oxidized ambient OA. These findings are consistent with the hypothesis that the photo-oxidation of aromatic hydrocarbons is a potential source of urban SOA. In addition to oxygenated organic compounds, organic nitrogen oxides were also shown to be present in SOA by high-resolution mass spectra.     

Carbonaceous aerosol in urban and rural European atmospheres: estimation of secondary organic carbon concentrations

Aerosol samples from urban, rural and coastal areas in Europe were analysed for carbonaceous content by a thermaloptical transmission method. The fraction of particulate organic carbon with a secondary origin in gas/particle conversion of volatile organic compounds was estimated from the minimum ratio between particulate organic and black carbon, which occurred during periods of reduced photochemical activity. Values calculated by this method ranged from a minimum of 17%, in Birmingham, UK, during winter, to a maximum of 78% at a rural coastal area, in Portugal, with air masses transported directly from the ocean. A clear seasonal dependence was observed at both rural and urban environments, with minimum secondary organic carbon production during winter.     

Contribution of primary and secondary sources to organic aerosol and PM2.5 at SEARCH network sites

Chemical tracer methods for determining contributions to primary organic aerosol (POA) are fairly well established, whereas similar techniques for secondary organic aerosol (SOA), inherently complicated by time-dependent atmospheric processes, are only beginning to be studied. Laboratory chamber experiments provide insights into the precursors of SOA, but field data must be used to test the approaches. This study investigates primary and secondary sources of organic carbon (OC) and determines their mass contribution to particulate matter 2.5 microm or less in aerodynamic diameter (PM2.5) in Southeastern Aerosol Research and Characterization (SEARCH) network samples. Filter samples were taken during 20 24-hr periods between May and August 2005 at SEARCH sites in Atlanta, GA (JST); Birmingham, AL (BHM); Centerville, AL (CTR); and Pensacola, FL (PNS) and analyzed for organic tracers by gas chromatography-mass spectrometry. Contribution to primary OC was made using a chemical mass balance method and to secondary OC using a mass fraction method. Aerosol masses were reconstructed from the contributions of POA, SOA, elemental carbon, inorganic ions (sulfate [SO4(2-)], nitrate [NO3-], ammonium [NH4+]), metals, and metal oxides and compared with the measured PM2.5. From the analysis, OC contributions from seven primary sources and four secondary sources were determined. The major primary sources of carbon were from wood combustion, diesel and gasoline exhaust, and meat cooking; major secondary sources were from isoprene and monoterpenes with minor contributions from toluene and beta-caryophyllene SOA. Mass concentrations at the four sites were determined using source-specific organic mass (OM)-to-OC ratios and gave values in the range of 12-42 microg m(-3). Reconstructed masses at three of the sites (JST, CTR, PNS) ranged from 87 to 91% of the measured PM2.5 mass. The reconstructed mass at the BHM site exceeded the measured mass by approximately 25%. The difference between the reconstructed and measured PM2.5 mass for nonindustrial areas is consistent with not including aerosol liquid water or other sources of organic aerosol.     

Insights into the nature of secondary organic aerosol in Mexico City during the MILAGRO experiment 2006

This study targets understanding the secondary sources of organic aerosol in Mexico City during the Megacities Impact on Regional and Global Environment (MIRAGE) 2006 field campaign. Ambient PM_2.5 was collected daily at urban and peripheral locations. Particle-phase secondary organic aerosol (SOA) products of anthropogenic and biogenic precursor gases were measured by gas chromatography mass spectrometry. Ambient concentrations of SOA tracers were used to estimate organic carbon (OC) from secondary origins (SOC). Anthropogenic SOC was estimated as 20–25% of ambient OC at both sites, while biogenic SOC was less abundant, but was relatively twice as important at the peripheral site. The OC that was not attributed secondary sources or to primary sources in a previous study showed temporal consistency with biomass-burning events, suggesting the importance of secondary processing of biomass-burning emissions in the region. The best estimate of biomass-burning-related SOC was in the range of 20–30% of ambient OC during peak biomass burning events. Low-molecular weight (MW) alkanoic and alkenoic dicarboxylic acids (C₂–C₅) were also measured, of which oxalic acid was the most abundant. The spatial and temporal trends of oxalic acid differed from tracers for primary and secondary sources, suggesting that it had different and/or multiple sources in the atmosphere.     

Evaluation of the optimum volatile organic compounds control strategy considering the formation of ozone and secondary organic aerosol in Seoul, Korea

The characteristics of volatile organic compounds (VOCs) and their annual trends in Seoul, Korea were investigated, with their optimal control strategy suggested. The annual concentration of VOCs (96.2–121.1 ppbC) has shown a decreasing trend from 2004 to 2008, suggesting the control strategy via the “Special Measures for Metropolitan Air Quality Improvement,” which was implemented in 2005, has been successful. The contributions of individual VOC to the production of ambient ozone and secondary organic aerosol (SOA) are discussed to assess the adequacy of current control strategies. The contribution of aromatics (C6–C10) to the production of ozone accounted for 38.7–46.3 % of the total ozone production, followed by low carbon alkanes (C2–C6) (27.0–35.9 %). The total SOA formation potential of VOCs was found to range from 2.5 to 3.5 μg m^?3, mainly as a result of aromatics (C6–C10) (over 85 %). Considering the contributions from ozone and SOA production, it was concluded that solvent use was the most important emission source, followed by vehicle exhaust emissions. Thus, the current emission control strategy focused on these two emission sources is appropriate to reduce the VOCs related pollution level of the Seoul Metropolitan Region. Still, an additional control strategy, such as controlling the emissions from meat cooking, which is an emission source of high carbon alkanes (C7–C10), needs to be considered to further reduce the VOCs related pollution level in Seoul.     

Estimates of heterogeneous formation of secondary organic aerosol during a wood smoke episode in Houston,Texas

Observational data, collected during a wood smoke episode in Houston, Texas, were used to assess the extent to which acid-catalyzed reactions of carbonyls might contribute to secondary organic aerosol (SOA) formation. The wood smoke episode was chosen for this analysis because of relatively high concentrations of acidic aerosol, coupled with high concentrations of SOA precursors during the episode. Photochemical modeling, coupled with ambient measurements, indicated that acid aerosol-mediated organic aerosol formation reactions, not accounted for in most current photochemical models, may have led to SOA formation of up to a few μg m⁻³. In photochemical simulations, acid-mediated organic aerosol formation was modeled by calculating the rate of impingement of aldehyde molecules on acidic particles, and then assuming that a fraction of the impingements resulted in reaction. For reaction probabilities on the order of 0.005–0.0005, the model predicted SOA concentrations were consistent with estimates of SOA based on observations. In addition, observed concentrations of particulate phase ammonium during the episode were consistent with high concentrations of the types of organic acids that would be formed through acid-catalyzed reactions of carbonyls. Although there are substantial uncertainties in the estimates of heterogeneous SOA formation, collectively, these data and modeling analyses provide evidence for the importance of acid-catalyzed SOA formation reactions.     

Estimates of the contributions of biogenic and anthropogenic hydrocarbons to secondary organic aerosol at a southeastern US location

An organic tracer-based method containing laboratory and field study components was used to estimate the secondary organic aerosol (SOA) contributions of biogenic and anthropogenic hydrocarbons to ambient organic carbon (OC) concentrations in PM_2.5 during 2003 in Research Triangle Park, NC. In the laboratory, smog chamber experiments were conducted where isoprene, α-pinene, β-caryophyllene, and toluene were individually irradiated in the presence of NO_X. In each experiment, SOA was collected and analyzed for potential tracer compounds, whose concentrations were used to calculate a mass fraction of tracer compounds for each hydrocarbon. In the field, 33 PM_2.5 samples were collected and analyzed for (1) tracer compounds observed in the laboratory irradiations, (2) levoglucosan, a biomass burning tracer, and (3) total OC. For each of the four hydrocarbons, the SOA contributions to ambient OC concentrations were estimated using the tracer concentrations and the laboratory-derived mass fractions. The estimates show SOA formation from isoprene, α-pinene, β-caryophyllene, and toluene contributed significantly to the ambient OC concentrations. The relative contributions were highly seasonal with biomass burning in the winter accounting for more than 50% of the OC concentrations, while SOA contributions remained low. However, during the 6-month period between May and October, SOA from the precursor hydrocarbons contributed more than 40% of the measured OC concentration. Although the tracer-based method is subject to considerable uncertainty due to the simplification of replacing the complex set of chemical reactions responsible for SOA with a laboratory-derived single-valued mass fraction, the results suggest this approach can be used to identify major sources of SOA which can assist in the development of air quality models.     

Source apportionment of wintertime secondary organic aerosol during the California regional PM10/PM2.5 air quality study

The UCD/CIT air quality model with the Caltech Atmospheric Chemistry Mechanism (CACM) was used to predict source contributions to secondary organic aerosol (SOA) formation in the San Joaquin Valley (SJV) from December 15, 2000 to January 7, 2001. The predicted 24-day average SOA concentration had a maximum value of 4.26 μg m^?3 50 km southwest of Fresno. Predicted SOA concentrations at Fresno, Angiola, and Bakersfield were 2.46 μg m^?3, 1.68 μg m^?3, and 2.28 μg m^?3, respectively, accounting for 6%, 37%, and 4% of the total predicted organic aerosol. The average SOA concentration across the entire SJV was 1.35 μg m^?3, which accounts for approximately 20% of the total predicted organic aerosol. Averaged over the entire SJV, the major SOA sources were solvent use (28% of SOA), catalyst gasoline engines (25% of SOA), wood smoke (16% of SOA), non-catalyst gasoline engines (13% of SOA), and other anthropogenic sources (11% of SOA). Diesel engines were predicted to only account for approximately 2% of the total SOA formation in the SJV because they emit a small amount of volatile organic compounds relative to other sources. In terms of SOA precursors within the SJV, long-chain alkanes were predicted to be the largest SOA contributor, followed by aromatic compounds. The current study identifies the major known contributors to the SOA burden during a winter pollution episode in the SJV, with further enhancements possible as additional formation pathways are discovered.