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Sample records for aerosol soa tracers

  1. Organosulfates as Tracers for Secondary Organic Aerosol (SOA) Formation from 2-Methyl-3-Buten-2-ol (MBO) in the Atmosphere

    PubMed Central

    2012-01-01

    2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C5H12O6S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM2.5) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM2.5 collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA. PMID:22849588

  2. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; McKinney, K.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

    2015-10-01

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40 ‰) but varies substantially between locations, which is shown to reflect

  3. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    DOE PAGESBeta

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; et al

    2015-10-23

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown

  4. Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

    2015-04-01

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making it the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from

  5. Characterization of a real-time tracer for Isoprene Epoxydiols-derived Secondary Organic Aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    DOE PAGESBeta

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; et al

    2015-04-16

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene low-NO oxidation pathways, was quantified by applying Positive Matrix Factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of OA in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the SOAS study, 78% of IEPOX-SOA is accounted for the measured molecular tracers, making itmore » the highest level of molecular identification of an ambient SOA component to our knowledge. Enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O ( fC5H6O = C5H6O+/OA) across multiple field, chamber and source datasets. A background of ~ 1.7 ± 0.1‰ is observed in studies strongly influenced by urban, biomass-burning and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.8‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7‰). Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3‰) observed in non IEPOX-derived isoprene-SOA indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA

  6. Organosulfates as Tracers for Secondary Organic Aerosol (SOA) Formation from 2-Methyl-3-Buten-2 ol (MBO) in the Atmosphere

    EPA Science Inventory

    2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was exa...

  7. Molecular distributions and isotopic compositions of marine aerosols over the western North Atlantic: Dicarboxylic acids, ketoacids, α-dicarbonyls (glyoxal and methylglyoxal), fatty acids, sugars, and SOA tracers

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Ono, K.; Tachibana, E.; Quinn, P.; Bates, T. S.

    2013-12-01

    Marine aerosols were collected over the western North Atlantic from off the coast of Boston to Bermuda during the WACS (Western Atlantic Climate Study) cruise of R/V Ronald H. Brown in August 2012 using a high volume air sampler and pre-combusted quartz fiber filters. Aerosol filter samples (n=5) were analyzed for OC/EC, major inorganic ions, low molecular weight dicarboxylic acids and various secondary organic aerosol (SOA) tracers using carbon analyzer, ion chromatograph, GC/FID and GC/MS, respectively. Homologous series (C2-C12) of dicarboxylic acids (31-335 ng m-3) were detected with a predominance of oxalic acid. Total carbon and nitrogen and their stable isotope ratios were determined as well as stable carbon isotopic compositions of individual diacids using IRMS. Diacids were found to be the most abundant compound class followed by monoterpene-SOA tracers > isoprene-SOA tracers > sugar compounds > ketoacids > fatty alcohols > fatty acids > α-dicarbonyls > aromatic acids > n-alkanes. The concentrations of these compounds were higher in the coastal site and decreased in the open ocean. However, diacids stayed relatively high even in the remote ocean. Interestingly, contributions of oxalic acid to total aerosol carbon increased from the coast (2.3%) to the remote ocean (5.6%) during long-range atmospheric transport. Stable carbon isotopic composition of oxalic acid increased from the coast (-17.5‰) to open ocean (-12.4‰), suggesting that photochemical aging of organic aerosols occurred during the atmospheric transport over the ocean. Stable carbon isotope ratios of bulk aerosol carbon also increased from the coast near Boston to the open ocean near Bermuda.

  8. CONTRIBUTIONS OF TOLUENE AND Α -PINENE TO SOA FORMED IN AN IRRADIATED TOLUENE/Α-PINENE/NOX/AIR MIXTURE: COMPARISON OF RESULTS USING 14C CONTENT AND SOA ORGANIC TRACER METHODS

    EPA Science Inventory

    An organic tracer method, recently proposed for estimating individual contributions of toluene and α-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydro...

  9. Formation of Organic Tracers for Isoprene SOA under Acidic Conditions

    EPA Science Inventory

    The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC-MS methods. In addition to the known is...

  10. Molecular markers of biomass burning, fungal spores and biogenic SOA in the Taklimakan desert aerosols

    NASA Astrophysics Data System (ADS)

    Fu, Pingqing; Zhuang, Guoshun; Sun, Yele; Wang, Qiongzhen; Chen, Jing; Ren, Lujie; Yang, Fan; Wang, Zifa; Pan, Xiaole; Li, Xiangdong; Kawamura, Kimitaka

    2016-04-01

    Biogenic primary organic aerosols (POA) and secondary organic aerosols (SOA) are important organic constituents of atmospheric particulate matter (PM). In order to better understand the atmospheric abundances, molecular compositions and sources of the desert aerosols, biomass-burning tracers (e.g. levoglucosan), primary saccharides including fungal spore tracers, and SOA tracers from the oxidation of biogenic volatile organic compounds (e.g. isoprene, monoterpenes and sesquiterpene) have been studied in ambient aerosols from the Taklimakan desert, using gas chromatography-mass spectrometry. Results showed that the total concentrations of biomass-burning tracers at Hetian (177-359 ng m-3, mean 233 ng m-3 in PM2.5) in the south rim of the desert were much higher than those at Tazhong (1.9-8.8 ng m-3 in PM2.5 and 5.9-32 ng m-3 in TSP) in the central Taklimakan desert. Molecular markers of fungal spores were also detected in all the desert aerosols, highlighting the importance of primary bioaerosols in the Asian dust particles. A specific pattern of the dominance of 2-methylglyceric acid over 2-methyltetrols and C5-alkene triols was found in the Taklimakan desert aerosols, especially during the dust storm events, which is different from the 2-methyltetrols-dominated pattern in other ambient aerosols. Our results provide direct evidence on the biogenic POA and SOA tracers in the Taklimakan desert region, which help to better understand their impact on the aerosol chemistry in the down-wind regions.

  11. In situ Measurements of Gas- and Particle-Phase Organic Compounds: Insights for SOA Formation Mechanisms and Contributions of SOA to Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Zhao, Y.; Kreisberg, N. M.; Worton, D. R.; Isaacman, G. A.; Weber, R.; Liu, S.; Day, D. A.; Markovic, M. Z.; VandenBoer, T. C.; Russell, L. M.; Murphy, J. G.; Hering, S. V.; Goldstein, A. H.

    2011-12-01

    To investigate formation of secondary organic aerosol (SOA) and the contribution of SOA to organic aerosols, semi-volatile and intermediate-volatile organic compounds (SVOCs/IVOCs) in both gas and particle phases were measured using a modified Thermal Desorption Gas Chromatograph (TAG) instrument in Bakersfield, CA during the CALifornia at the NEXus between air quality and climate (CALNEX) campaign from 31 May through 27 June, 2010. More than 150 organic compounds were identified, spanning a wide range of volatility and functionality. Quantified compounds included organic tracers for primary and secondary organic sources, such as alkanes, PAHs, acids, hopanes and ketones. Hourly gas/particle partitioning was determined by a denuder difference method where the sample flow alternated every other sample through an active charcoal multi-channel denuder that efficiently removed gas-phase components. Gas/particle partitioning of three SOA tracers (phthalic acid, pinonaldehyde and 6, 10, 14-trimethyl-2-pentadecanone) was investigated to understand the formation mechanisms of SOA for different functional group classes in the ambient atmosphere. Comparison with Pankow gas/particle partitioning theory, observed particle-phase phthalic acid and pinonaldehyde, suggests formation by other mechanisms than gas-to-particle condensation. Source attribution is performed using Positive Matrix Factorization (PMF) analysis of speciated particle-phase TAG data along with total submicron organic aerosol (OA) measured by an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). SOA accounts for a major component of OA and the contribution of biogenic SOA to total SOA is comparable to anthropogenic SOA during nights.

  12. Formation of anthropogenic secondary organic aerosol (SOA) and its influence on biogenic SOA properties

    NASA Astrophysics Data System (ADS)

    Emanuelsson, E. U.; Hallquist, M.; Kristensen, K.; Glasius, M.; Bohn, B.; Fuchs, H.; Kammer, B.; Kiendler-Scharr, A.; Nehr, S.; Rubach, F.; Tillmann, R.; Wahner, A.; Wu, H.-C.; Mentel, Th. F.

    2013-03-01

    Secondary organic aerosol (SOA) formation from mixed anthropogenic and biogenic precursors has been studied exposing reaction mixtures to natural sunlight in the SAPHIR chamber in Jülich, Germany. In this study aromatic compounds served as examples of anthropogenic volatile organic compound (VOC) and a mixture of α-pinene and limonene as an example for biogenic VOC. Several experiments with exclusively aromatic precursors were performed to establish a relationship between yield and organic aerosol mass loading for the atmospheric relevant range of aerosol loads of 0.01 to 10 μg m-3. The yields (0.5 to 9%) were comparable to previous data and further used for the detailed evaluation of the mixed biogenic and anthropogenic experiments. For the mixed experiments a number of different oxidation schemes were addressed. The reactivity, the sequence of addition, and the amount of the precursors influenced the SOA properties. Monoterpene oxidation products, including carboxylic acids and dimer esters were identified in the aged aerosol at levels comparable to ambient air. OH radicals were measured by Laser Induced Fluorescence, which allowed for establishing relations of aerosol properties and composition to the experimental OH dose. Furthermore, the OH measurements in combination with the derived yields for aromatic SOA enabled application of a simplified model to calculate the chemical turnover of the aromatic precursor and corresponding anthropogenic contribution to the mixed aerosol. The estimated anthropogenic contributions were ranging from small (≈8%) up to significant fraction (>50%) providing a suitable range to study the effect of aerosol composition on the aerosol volatility (volume fraction remaining (VFR) at 343 K: 0.86-0.94). The aromatic aerosol had higher oxygen to carbon ratio O/C and was less volatile than the biogenic fraction. However, in order to produce significant amount of aromatic SOA the reaction mixtures needed a higher OH dose that also

  13. Improving the representation of secondary organic aerosol (SOA) in the MOZART-4 global chemical transport model

    NASA Astrophysics Data System (ADS)

    Mahmud, A.; Barsanti, K. C.

    2012-12-01

    The secondary organic aerosol (SOA) module in the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) has been updated by replacing existing two-product (2p) parameters with those obtained from two-product volatility basis set (2p-VBS) fits, and by treating SOA formation from the following volatile organic compounds (VOCs): isoprene, propene and lumped alkenes. Strong seasonal and spatial variations in global SOA distributions were demonstrated, with significant differences in the predicted concentrations between the base-case and updated model versions. The base-case MOZART-4 predicted annual average SOA of 0.36 ± 0.50 μg m-3 in South America, 0.31 ± 0.38 μg m-3 in Indonesia, 0.09 ± 0.05 μg m-3 in the USA, and 0.12 ± 0.07 μg m-3 in Europe. Concentrations from the updated versions of the model showed a~marked increase in annual average SOA. Using the updated set of parameters alone (MZ4-v1) increased annual average SOA by ~8%, ~16%, ~56%, and ~108% from the base-case in South America, Indonesia, USA, and Europe, respectively. Treatment of additional parent VOCs (MZ4-v2) resulted in an even more dramatic increase of ~178-406% in annual average SOA for these regions over the base-case. The increases in predicted SOA concentrations further resulted in increases in corresponding SOA contributions to annual average total aerosol optical depth (AOD) by <1% for MZ4-v1 and ~1-6% for MZ4-v2. Estimated global SOA production was ~6.6 Tg yr-1 and ~19.1 Tg yr-1 with corresponding burdens of ~0.24 Tg and ~0.59 Tg using MZ4-v1 and MZ4-v2, respectively. The SOA budgets predicted in the current study fall well within reported ranges for similar modeling studies, 6.7 to 96 Tg yr-1, but are lower than recently reported observationally-constrained values, 50 to 380 Tg yr-1. With MZ4-v2, simulated SOA concentrations at the surface were also in reasonable agreement with comparable modeling studies and observations. Concentrations of estimated organic aerosol (OA

  14. The influence of temperature and aerosol acidity on biogenic secondary organic aerosol tracers: Observations at a rural site in the central Pearl River Delta region, South China

    NASA Astrophysics Data System (ADS)

    Ding, Xiang; Wang, Xin-Ming; Zheng, Mei

    2011-02-01

    At a rural site in the central Pearl River Delta (PRD) region in south China, fine particle (PM 2.5) samples were collected during fall-winter 2007 to measure biogenic secondary organic aerosol (SOA) tracers, including isoprene SOA tracers (3-methyl-2,3,4-trihydroxy-1-butene, 2-methylglyceric acid, 2-methylthreitol and 2-methylerythritol), α-pinene SOA tracers ( cis-pinonic acid, pinic acid, 3-methyl-1,2,3-butanetricarboxylic acid, 3-hydroxyglutaric acid and 3-hydroxy-4,4-dimethylglutaric acid) and a sesquiterpene SOA tracer (β-caryophyllinic acid). The isoprene-, α-pinene- and sesquiterpene-SOA tracers averaged 30.8 ± 15.9, 6.61 ± 4.39, and 0.54 ± 0.56 ng m -3, respectively; and 2-methyltetrols (sum of 2-methylthreitol and 2-methylerythritol, 27.6 ± 15.1 ng m -3) and cis-pinonic acid (3.60 ± 3.76 ng m -3) were the dominant isoprene- and α-pinene-SOA tracers, respectively. 2-Methyltetrols exhibited significantly positive correlations ( p < 0.05) with ambient temperature, probably resulting from the enhanced isoprene emission strength and tracer formation rate under higher temperature. The significantly positive correlation ( p < 0.05) between 2-methyltetrols and the estimated aerosol acidity with a slope of 59.4 ± 13.4 ng m -3 per μmol [H +] m -3 reflected the enhancement of isoprene SOA formation by aerosol acidity, and acid-catalyzed heterogeneous reaction was probably the major formation pathway for 2-methyltetrols in the PRD region. 2-Methylglyceric acid showed poor correlations with both temperature and aerosol acidity. The α-pinene SOA tracers showed poor correlations with temperature, probably due to the counteraction between temperature effects on the precursor emission/tracer formation and gas/particle partitioning. Among the α-pinene SOA tracers, only cis-pinonic acid and pinic acid exhibited significant correlations with aerosol acidity with slopes of -11.7 ± 3.7 and -2.2 ± 0.8 ng m -3 per μmol [H +] m -3, respectively. The negative

  15. Seasonal variations of biogenic secondary organic aerosol tracers in Cape Hedo, Okinawa

    NASA Astrophysics Data System (ADS)

    Zhu, Chunmao; Kawamura, Kimitaka; Fu, Pingqing

    2016-04-01

    Secondary organic aerosol (SOA) substantially contributes to particulate organic matter affecting the regional and global air quality and the climate. Total suspended particle (TSP) samples were collected in October 2009 to February 2012 on a weekly basis at Cape Hedo, Okinawa, Japan in the western North Pacific Rim, an outflow region of Asian aerosols and precursors. The TSP samples were analyzed for SOA tracers derived from biogenic volatile organic compounds (BVOCs). Total isoprene-SOA tracers showed a maximum in summer (2.12 ± 2.02 ng m-3) and minimum in winter (1.16 ± 0.92 ng m-3). This seasonality is mainly controlled by isoprene emission from the local subtropical forest, followed by regional scale emission of isoprene from the surrounding seas and long-range transported air masses. Total monoterpene-SOA tracers peaked in March (3.38 ± 2.03 ng m-3) followed by October (2.95 ± 1.62 ng m-3). In contrast, sesquiterpene-SOA tracer, β-caryophyllinic acid, showed winter maximum (1.63 ± 1.18 ng m-3) and summer minimum (0.20 ± 0.46 ng m-3). The variations of the monoterpene- and sesquiterpene-SOA tracers are likely related to the continental outflow of oxidation products of BVOC. Using a tracer-based method, we estimated the total biogenic SOC of 0.25-157 ng m-3 (mean 35.8 ng m-3) that accounts for 0.01-9.8% (mean 2.7%) of aerosol organic carbon. Our study suggests that SOA formation in the western North Pacific Rim is involved with not only local but also regional emissions followed by long-range atmospheric transport.

  16. Elucidating the Chemical Complexity of Organic Aerosol Constituents Measured During the Southeastern Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Yee, L.; Isaacman, G. A.; Spielman, S. R.; Worton, D. R.; Zhang, H.; Kreisberg, N. M.; Wilson, K. R.; Hering, S. V.; Goldstein, A. H.

    2013-12-01

    Thousands of volatile organic compounds are uniquely created in the atmosphere, many of which undergo chemical transformations that result in more highly-oxidized and often lower vapor pressure species. These species can contribute to secondary organic aerosol, a complex mixture of organic compounds that is still not chemically well-resolved. Organic aerosol collected on filters taken during the Southeastern Oxidant and Aerosol Study (SOAS) constitute hundreds of unique chemical compounds. Some of these include known anthropogenic and biogenic tracers characterized using standardized analytical techniques (e.g. GC-MS, UPLC, LC-MS), but the majority of the chemical diversity has yet to be explored. By employing analytical techniques involving sample derivatization and comprehensive two-dimensional gas chromatography (GC x GC) with high-resolution-time-of-flight mass spectrometry (HR-ToF-MS), we elucidate the chemical complexity of the organic aerosol matrix along the volatility and polarity grids. Further, by utilizing both electron impact (EI) and novel soft vacuum ultraviolet (VUV) ionization mass spectrometry, a greater fraction of the organic mass is fully speciated. The GC x GC-HR-ToF-MS with EI/VUV technique efficiently provides an unprecedented level of speciation for complex ambient samples. We present an extensive chemical characterization and quantification of organic species that goes beyond typical atmospheric tracers in the SOAS samples. We further demonstrate that complex organic mixtures can be chemically deconvoluted by elucidation of chemical formulae, volatility, functionality, and polarity. These parameters provide insight into the sources (anthropogenic vs. biogenic), chemical processes (oxidation pathways), and environmental factors (temperature, humidity), controlling organic aerosol growth in the Southeastern United States.

  17. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2015-08-01

    A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black

  18. Impact of NOx on secondary organic aerosol (SOA) formation from β-pinene photooxidation

    NASA Astrophysics Data System (ADS)

    Sarrafzadeh, Mehrnaz; Pullinen, Iida; Springer, Monika; Kleist, Einhard; Tillmann, Ralf; Mentel, Thomas F.; Kiendler-Scharr, Astrid; Hastie, Donald R.; Wildt, Jürgen

    2016-04-01

    Secondary organic aerosols (SOA) generated from atmospheric oxidation of volatile organics contributes substantially to the global aerosol load. It has been shown that odd nitrogen (NOx) has a significant influence on the formation of this SOA. In this study, we investigated SOA formation from β-pinene photooxidation in the Jülich Plant Atmosphere Chamber (JPAC) under varying NOx conditions. At higher-NOx levels, the SOA yield was significantly suppressed by increasing the NOx concentration. However at lower-NOx levels the opposite trend, an increase in SOA with increasing NOx concentration, was observed. This increase was likely due to the increased OH concentration in the stirred flow reactor. By holding the OH concentration constant for all experiments we removed the potential effect of OH concentration on SOA mass growth. In this case increasing the NOx concentration only decreased the SOA yield. In addition, the impact of NOx on SOA formation was explored in the presence of ammonium sulfate seed aerosols. This suggested that SOA yield was only slightly suppressed under increasing NOx concentrations when seed aerosol was present.

  19. Present-day to 21st century projections of secondary organic aerosol (SOA) from a global climate-aerosol model with an explicit SOA formation scheme

    NASA Astrophysics Data System (ADS)

    Lin, G.; Penner, J. E.; Zhou, C.

    2014-12-01

    Secondary organic aerosol (SOA) has been shown to be an important component of non-refractory submicron aerosol in the atmosphere. The presence of SOA can influence the earth's radiative balance by contributing to the absorption and scattering of radiation and by altering the properties of clouds. Globally, a large fraction of SOA originates from biogenic volatile organic compounds (BVOCs), emissions of which depend on vegetation cover and climate. Temperature, CO2 concentration, and land use and land cover change have been shown to be major drivers of global isoprene emission changes in future climates. Additionally, the SOA concentration in the atmosphere not only depends on BVOC emissions, but is also controlled by anthropogenic emissions, temperature, precipitation and the oxidative capacity of the atmosphere. To project the change in SOA concentrations in the future requires a model that fully couples a BVOC emission model that represents these BVOC emission drivers, together with a sophisticated atmospheric model of SOA formation and properties. Recent studies have suggested that traditional parameterized SOA formation mechanisms that are tuned to fit smog chamber data do not fully account for the complexity and dynamics of real SOA system, calling into the question of the validity and completeness of previous SOA projections. In this study, we investigate the response of SOA mass to future physical climate change, to land cover and land use change, to changes in BVOCs emissions, and to changes in anthropogenic aerosol and gas species emissions for the year 2100, utilizing a global climate-aerosol model (CAM5-IMPACT): the NCAR Community Atmospheric Model (CAM5) coupled with a global aerosol model (IMPACT). The IMPACT model has sophisticated detailed process-based mechanisms describing aerosol microphysics and SOA formation through both gas phase and multiphase reactions. We perform sensitivity tests to isolate the relative roles of individual global change

  20. Seasonal variations of biogenic secondary organic aerosol tracers in ambient aerosols from Alaska

    NASA Astrophysics Data System (ADS)

    Haque, Md. Mozammel; Kawamura, Kimitaka; Kim, Yongwon

    2016-04-01

    We investigated total suspended particles (TSP) collected from central Alaska, USA for molecular compositions of secondary organic aerosol (SOA) derived from the oxidation of biogenic volatile organic compounds (BVOCs). Isoprene-, α-/β-pinene- and β-caryophyllene-SOA tracers were determined using gas chromatography-mass spectrometry. The concentration ranges of isoprene, α-/β-pinene and β-caryophyllene oxidation products were 0.02-18.6 ng m-3 (ave. 4.14 ng m-3), 0.42-8.24 ng m-3 (2.01 ng m-3) and 0.10-9 ng m-3 (1.53 ng m-3), respectively. Isoprene-SOA tracers showed higher concentrations in summer (ave. 8.77 ng m-3), whereas α-/β-pinene- and β-caryophyllene-SOA tracers exhibited highest levels in spring (3.55 ng m-3) and winter (4.04 ng m-3), respectively. β-Caryophyllinic acid and levoglucosan showed a positive correlation, indicating that biomass burning may be a major source for β-caryophyllene. We found that mean contributions of isoprene oxidation products to organic carbon (OC) and water-soluble organic (WSOC) (0.56% and 1.2%, respectively) were higher than those of α-/β-pinene (0.31% and 0.55%) and β-caryophyllene (0.08% and 0.13%). Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) produced from isoprene, α-/β-pinene and β-caryophyllene to be 0.66-718 ngC m-3 (ave. 159 ngC m-3), 7.4-143 ngC m-3 (35 ngC m-3) and 4.5-391 ngC m-3 (66.3 ngC m-3), respectively. Based on SOA tracers, this study suggests that isoprene is a more important precursor for the production of biogenic SOA than α-/β-pinene and β-caryophyllene in subarctic Alaska.

  1. Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Chhabra, P. S.; Chan, A. W. H.; Surratt, J. D.; Kroll, J. H.; Kwan, A. J.; McCabe, D. C.; Wennberg, P. O.; Sorooshian, A.; Murphy, S. M.; Dalleska, N. F.; Flagan, R. C.; Seinfeld, J. H.

    2007-10-01

    Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air.

  2. Volatility of Secondary Organic Aerosol (SOA) Formed from Photooxidation of Isoprene

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Kollman, M.; Xu, L.; Shilling, J. E.

    2012-12-01

    Isoprene is the most abundant non-methane hydrocarbon, so even a small aerosol yield may have a large effect on both local and global secondary organic aerosol (SOA) production. Previous studies have shown that isoprene SOA yields are higher under low-NOx conditions, and that volatility of isoprene SOA under low-NOx conditions is similar to a-pinene SOA. In this study, the volatility of SOA formed from the photooxidation of isoprene under different NOx conditions is investigated with a thermodenuder. Laboratory chamber experiments are performed under different NOx conditions at low RH (RH<5%) and without seed. H2O2 and HONO is used as OH precursor for low-NOx and high-NOx experiments, respectively. During each experiment, isoprene and selected gas-phase oxidation products are monitored with a Proton Transfer Reaction Mass Spectrometry (PTRMS).Particle-phase composition, mass, size distribution are measured with a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Scanning Mobility Particle Sizer (SMPS). The thermodenuder is upstream of the the HR-ToF-AMS and SMPS, modulating the aerosol composition with temperatures ranging from 30 to 200 oC. In general, the volatility of SOA decreases after peak SOA growth, indicating the formation of highly oxidized, low-volatility species with increased photochemical aging. The SOA yields obtained are in agreement with previous studies, with more SOA formed under low-NOx conditions. However, it is found that SOA formed under low-NOx conditions are more volatile. Preliminary results show that about 60% of low-NOx isoprene SOA and <40% of high-NOx isoprene SOA evaporates at 100 oC. Under high-NOx conditions, there is still 10% of aerosol mass remaining at 200 oC, suggesting that there are some very non-volatiles species in high-NOx isoprene SOA. The mass fraction of isoprene SOA remaining as a function of NOx and temperature will be presented. The mass spectra features of SOA at these conditions will also

  3. Small molecules as tracers in atmospheric secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Yu, Ge

    Secondary organic aerosol (SOA), formed from in-air oxidation of volatile organic compounds, greatly affects human health and climate. Although substantial research has been devoted to SOA formation and evolution, the modeled and lab-generated SOA are still low in mass and degree of oxidation compared to ambient measurements. In order to compensate for these discrepancies, the aqueous processing pathway has been brought to attention. The atmospheric waters serve as aqueous reaction media for dissolved organics to undergo further oxidation, oligomerization, or other functionalization reactions, which decreases the vapor pressure while increasing the oxidation state of carbon atoms. Field evidence for aqueous processing requires the identification of tracer products such as organosulfates. We synthesized the standards for two organosulfates, glycolic acid sulfate and lactic acid sulfate, in order to measure their aerosol-state concentration from five distinct locations via filter samples. The water-extracted filter samples were analyzed by LC-MS. Lactic acid sulfate and glycolic acid sulfate were detected in urban locations in the United States, Mexico City, and Pakistan with varied concentrations, indicating their potential as tracers. We studied the aqueous processing reaction between glyoxal and nitrogen-containing species such as ammonium and amines exclusively by NMR spectrometry. The reaction products formic acid and several imidazoles along with the quantified kinetics were reported. The brown carbon generated from these reactions were quantified optically by UV-Vis spectroscopy. The organic-phase reaction between oxygen molecule and alkenes photosensitized by alpha-dicarbonyls were studied in the same manner. We observed the fast kinetics transferring alkenes to epoxides under simulated sunlight. Statistical estimations indicate a very effective conversion of aerosol-phase alkenes to epoxides, potentially forming organosulfates in a deliquescence event and

  4. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, ground site

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2015-03-01

    A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2>0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0

  5. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: SOA Yield and Chemical Composition

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Qi, Li; Kacarab, Mary; Cocker, David

    2016-04-01

    Aromatic hydrocarbons account for 20%-30% of urban atmospheric VOCs and are major contributors to anthropogenic secondary organic aerosol (SOA). However, prediction of SOA from aromatic hydrocarbons as a function of structure, NOx concentration, and OH radical levels remains elusive. Innovative SOA yield and chemical composition evaluation approaches are developed here to investigate SOA formation from aromatic hydrocarbons. SOA yield is redefined in this work by adjusting the molecular weight of all aromatic precursors to the molecular weight of benzene (Yield'= Yieldi×(MWi/MWBenzene); i: aromatic hydrocarbon precursor). Further, SOA elemental ratio is calculated on an aromatic ring basis rather than the classic mole basis. Unified and unique characteristics in SOA formed from aromatic hydrocarbons with different alkyl groups (varying in carbon number and location on aromatic ring) are explored by revisiting fifteen years of UC Riverside/CE-CERT environmental chamber data on 129 experiments from 17 aromatic precursors at urban region relevant low NOx conditions (HC:NO 11.1-171 ppbC:ppb). Traditionally, SOA mass yield of benzene is much greater than that of other aromatic species. However, when adjusting for molecular weight, a similar yield is found across the 17 different aromatic precursors. More importantly, four oxygens per aromatic ring are observed in the resulting SOA regardless of the alkyl substitutes attached to the ring, which majorly affect H/C ratio in SOA. Therefore, resulting SOA bulk composition from aromatic hydrocarbons can be predicted as C6+nH6+2nO4 (n: alkyl substitute carbon number). Further, the dominating role of the aromatic ring carbons is confirmed by studying the chemical composition of SOA formed from the photooxidation of an aromatic hydrocarbon with a 13C isotopically labeled alkyl carbon. Overall, this study unveils the similarity in SOA formation from aromatic hydrocarbons enhancing the understanding of SOA formation from

  6. Improving the simulation of organic aerosols from anthropogenic and burning sources: a simplified SOA formation mechanism and the impact of trash burning

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Wiedinmyer, C.; Jimenez, J. L.

    2011-12-01

    Organic aerosols (OA) are an major component of fine aerosols, but their sources are poorly understood. We present results of two methods to improve OA predictions in anthropogenic pollution and biomass-burning impacted regions. (1) An empirical parameterization for secondary organic aerosol (SOA) formation in polluted air and biomass burning smoke is implemented into community chemistry-transport models (WRF/Chem and CHIMERE) and tested in this work, towards the goal of a computationally inexpensive method to calculate pollution and biomass burning SOA. This approach is based on the observed proportionality of SOA concentrations to excess CO and photochemical age of the airmass, as described in Hodzic and Jimenez (GMDD, 2011). The oxygen to carbon ratio in organic aerosols is also parameterizated vs. photochemical aged based on the ambient observations, and is used to estimate the aerosol hygroscopicity and CCN activity. The predicted SOA is assessed against observations from the Mexico City metropolitan area during the MILAGRO 2006 field experiment, and compared to previous model results using the more complex volatility basis approach (VBS) of Robinson et al.. The results suggest that the simplified approach reproduces the observed average SOA mass within 30% in the urban area and downwind, and gives better results than the original VBS. In addition to being much less computationally expensive than VBS-type methods, the empirical approach can also be used in regions where the emissions of SOA precursors are not yet available. (2) The contribution of trash burning emissions to primary and secondary organic aerosols in Mexico City are estimated, using a recently-developed emission inventory. Submicron antimony (Sb) is used as a garbage-burning tracer following the results of Christian et al. (ACP 2010), which allows evaluation of the emissions inventory. Results suggests that trash burning may be an appreciable source of organic aerosols in the Mexico City

  7. Characterization of Isoprene-Derived Secondary Organic Aerosol Formation at the Look Rock Site during the 2013 Southern Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S.; Li, X.; Bairai, S. T.; Hicks, W.; Renfro, J.; Corrigan, A. L.; Guzman, J. M.; Russell, L. M.; Liu, Y.; McKinney, K. A.; Zhang, X.; Cappa, C. D.; Zimmermann, K.; Bertram, T. H.; Canagaratna, M. R.; Croteau, D.; Worsnop, D. R.; Jayne, J. T.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2013-12-01

    Although isoprene is considered as the single largest source of secondary organic aerosol (SOA), the exact manner in which it forms remains unclear. Improving our fundamental understanding of isoprene-derived SOA will be key to improving existing air quality models, especially in the southeastern U.S. where models currently underestimate observations. Reactive epoxides, which include methacrylic acid epoxide (MAE) and isomeric isoprene epoxydiols (IEPOX), produced from the oxidation of isoprene have recently been demonstrated to lead to SOA through heterogeneous chemistry. Anthropogenic pollutants (NOx and SO2) have been shown to enhance isoprene-derived epoxides as a source of SOA. One of the major aims during SOAS was to examine how anthropogenic pollutants impact isoprene SOA formation and its climate-relevant properties. To address this aim, we deployed both an Aerodyne aerosol chemical speciation monitor (ACSM) and a chemical ionization high-resolution time-of-flight mass spectrometer (CI-HR-TOFMS) at the Look Rock (LRK) site in the Great Smoky Mountains National Park, TN, from June 1 to July 15, 2013. In addition, high-volume PM2.5 samplers collected daily (8AM-7AM), day (8AM-7PM), and night (8PM-7AM) samples onto quartz filters. On days that LRK was forecasted to have high isoprene, SO4 (sulfate), and NOx levels, PM2.5 were collected more frequently (8AM-11AM, 12PM-3PM, 4PM-7PM, and 8PM-7AM). Filters were analyzed for known isoprene-derived SOA tracers (2-methyltetrols, 2-methylglyceric acid, C5-alkene triols, 3-methyltetrahydrofuran-3,4-diols, and organosulfates) by gas chromatography/mass spectrometry and ultra performance liquid chromatography coupled to diode array detection and electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry. The average non-refractory PM1 mass measured by the ACSM was 3.87 μg m-3, with organic, sulfate, ammonium, nitrate and chloride contributing 64.4%, 24.1%, 7.6%, 3.8%, and 0.1%, respectively

  8. Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate change variability in the North Pacific Rim

    NASA Astrophysics Data System (ADS)

    Pokhrel, Ambarish; Kawamura, Kimitaka; Ono, Kaori; Seki, Osamu; Fu, Pingqing; Matoba, Sumio; Shiraiwa, Takayuki

    2016-04-01

    Monoterpene and isoprene secondary organic aerosol (SOA) tracers are reported for the first time in an Alaskan ice core to better understand the biological source strength before and after the industrial revolution in the Northern Hemisphere. We found significantly high concentrations of monoterpene- and isoprene-SOA tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylerythritol) in the ice core, which show historical trends with good correlation to each other since 1660s. They show positive correlations with sugar compounds (e.g., mannitol, fructose, glucose, inositol and sucrose), and anti-correlations with α-dicarbonyls (glyoxal and methylglyoxal) and fatty acids (e.g., C18:1) in the same ice core. These results suggest similar sources and transport pathways for monoterpene- and isoprene-SOA tracers. In addition, we found that concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) in the ice core have increased after the Great Pacific Climate Shift (late 1970s). They show positive correlations with α-dicarbonyls and fatty acids (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the marine boundary layer are recorded in the ice core from Alaska. Photochemical oxidation process for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations and retreat of sea ice in the Northern Hemisphere.

  9. Method of dispersing particulate aerosol tracer

    DOEpatents

    O'Holleran, Thomas P.

    1988-01-01

    A particulate aerosol tracer which comprises a particulate carrier of sheet silicate composition having a particle size up to one micron, and a cationic dopant chemically absorbed in solid solution in the carrier. The carrier is preferably selected from the group consisting of natural mineral clays such as bentonite, and the dopant is selected from the group consisting of rare earth elements and transition elements. The tracers are dispersed by forming an aqueous salt solution with the dopant present as cations, dispersing the carriers in the solution, and then atomizing the solution under heat sufficient to superheat the solution droplets at a level sufficient to prevent reagglomeration of the carrier particles.

  10. Seasonal variation of secondary organic aerosol tracers in Central Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Shen, R.-Q.; Ding, X.; He, Q.-F.; Cong, Z.-Y.; Yu, Q.-Q.; Wang, X.-M.

    2015-08-01

    Secondary organic aerosol (SOA) affects the earth's radiation balance and global climate. High-elevation areas are sensitive to global climate change. However, at present, SOA origins and seasonal variations are understudied in remote high-elevation areas. In this study, particulate samples were collected from July 2012 to July 2013 at the remote Nam Co (NC) site, Central Tibetan Plateau and analyzed for SOA tracers from biogenic (isoprene, monoterpenes and β-caryophyllene) and anthropogenic (aromatics) precursors. Among these compounds, isoprene SOA (SOAI) tracers represented the majority (26.6 ± 44.2 ng m-3), followed by monoterpene SOA (SOAM) tracers (0.97 ± 0.57 ng m-3), aromatic SOA (SOAA) tracer (2,3-dihydroxy-4-oxopentanoic acid, DHOPA, 0.25 ± 0.18 ng m-3) and β-caryophyllene SOA tracer (β-caryophyllenic acid, 0.09 ± 0.10 ng m-3). SOAI tracers exhibited high concentrations in the summer and low levels in the winter. The similar temperature dependence of SOAI tracers and isoprene emission suggested that the seasonal variation of SOAI tracers at the NC site was mainly influenced by the isoprene emission. The ratio of high-NOx to low-NOx products of SOAI (2-methylglyceric acid to 2-methyltetrols) was highest in the winter and lowest in the summer, due to the influence of temperature and relative humidity. The seasonal variation of SOAM tracers was impacted by monoterpenes emission and gas-particle partitioning. During the summer to the fall, temperature effect on partitioning was the dominant process influencing SOAM tracers' variation; while the temperature effect on emission was the dominant process influencing SOAM tracers' variation during the winter to the spring. SOAM tracer levels did not elevate with increased temperature in the summer, probably resulting from the counteraction of temperature effects on emission and partitioning. The concentrations of DHOPA were 1-2 orders of magnitude lower than those reported in the urban regions of the world

  11. Rethinking the global secondary organic aerosol (SOA) budget: stronger production, faster removal, shorter lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, Alma; Kasibhatla, Prasad S.; Jo, Duseong S.; Cappa, Christopher D.; Jimenez, Jose L.; Madronich, Sasha; Park, Rokjin J.

    2016-06-01

    Recent laboratory studies suggest that secondary organic aerosol (SOA) formation rates are higher than assumed in current models. There is also evidence that SOA removal by dry and wet deposition occurs more efficiently than some current models suggest and that photolysis and heterogeneous oxidation may be important (but currently ignored) SOA sinks. Here, we have updated the global GEOS-Chem model to include this new information on formation (i.e., wall-corrected yields and emissions of semi-volatile and intermediate volatility organic compounds) and on removal processes (photolysis and heterogeneous oxidation). We compare simulated SOA from various model configurations against ground, aircraft and satellite measurements to assess the extent to which these improved representations of SOA formation and removal processes are consistent with observed characteristics of the SOA distribution. The updated model presents a more dynamic picture of the life cycle of atmospheric SOA, with production rates 3.9 times higher and sinks a factor of 3.6 more efficient than in the base model. In particular, the updated model predicts larger SOA concentrations in the boundary layer and lower concentrations in the upper troposphere, leading to better agreement with surface and aircraft measurements of organic aerosol compared to the base model. Our analysis thus suggests that the long-standing discrepancy in model predictions of the vertical SOA distribution can now be resolved, at least in part, by a stronger source and stronger sinks leading to a shorter lifetime. The predicted global SOA burden in the updated model is 0.88 Tg and the corresponding direct radiative effect at top of the atmosphere is -0.33 W m-2, which is comparable to recent model estimates constrained by observations. The updated model predicts a population-weighed global mean surface SOA concentration that is a factor of 2 higher than in the base model, suggesting the need for a reanalysis of the contribution of

  12. Rethinking the global secondary organic aerosol (SOA) budget: stronger production, faster removal, shorter lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Kasibhatla, P. S.; Jo, D. S.; Cappa, C.; Jimenez, J. L.; Madronich, S.; Park, R. J.

    2015-11-01

    Recent laboratory studies suggest that secondary organic aerosol (SOA) formation rates are higher than assumed in current models. There is also evidence that SOA removal by dry and wet deposition occurs more efficiently than some current models suggest, and that photolysis and heterogeneous oxidation may be important (but currently ignored) SOA sinks. Here, we have updated the global GEOS-Chem model to include this new information on formation (i.e. wall-corrected yields and emissions of semi-volatile and intermediate volatility organic compounds) and on removal processes (photolysis and heterogeneous oxidation). We compare simulated SOA from various model configurations against ground, aircraft and satellite measurements to assess the extent to which these improved representations of SOA formation and removal processes are consistent with observed characteristics of the SOA distribution. The updated model presents a more dynamic picture of the lifecycle of atmospheric SOA, with production rates 4 times higher and sinks a factor of 3.7 more efficient than in the base model. In particular, the updated model predicts larger SOA concentrations in the boundary layer and lower concentrations in the upper troposphere, leading to better agreement with surface and aircraft measurements of organic aerosol compared to the base model. Our analysis thus suggests that the long-standing discrepancy in model predictions of the vertical SOA distribution can now be resolved, at least in part, by a stronger source and stronger sinks leading to a shorter lifetime. The predicted global SOA burden in the updated model is 0.95 Tg and the corresponding direct radiative forcing at top of the atmosphere is -0.35 W m-2, which is comparable to recent model estimates constrained by observations. The updated model predicts a population-weighed global mean surface SOA concentration that is a factor of 2 higher than in the base model, suggesting the need for a reanalysis of the contribution of

  13. Microspectroscopic Analysis of Anthropogenic- and Biogenic-Influenced Aerosol Particles during the SOAS Field Campaign

    NASA Astrophysics Data System (ADS)

    Ault, A. P.; Bondy, A. L.; Nhliziyo, M. V.; Bertman, S. B.; Pratt, K.; Shepson, P. B.

    2013-12-01

    During the summer, the southeastern United States experiences a cooling haze due to the interaction of anthropogenic and biogenic aerosol sources. An objective of the summer 2013 Southern Oxidant and Aerosol Study (SOAS) was to improve our understanding of how trace gases and aerosols are contributing to this relative cooling through light scattering and absorption. To improve understanding of biogenic-anthropogenic interactions through secondary organic aerosol (SOA) formation on primary aerosol cores requires detailed physicochemical characterization of the particles after uptake and processing. Our measurements focus on single particle analysis of aerosols in the accumulation mode (300-1000 nm) collected using a multi orifice uniform deposition impactor (MOUDI) at the Centreville, Alabama SEARCH site. Particles were characterized using an array of microscopic and spectroscopic techniques, including: scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and Raman microspectroscopy. These analyses provide detailed information on particle size, morphology, elemental composition, and functional groups. This information is combined with mapping capabilities to explore individual particle spatial patterns and how that impacts structural characteristics. The improved understanding will be used to explore how sources and processing (such as SOA coating of soot) change particle structure (i.e. core shell) and how the altered optical properties impact air quality/climate effects on a regional scale.

  14. Key parameters controlling OH-initiated formation of secondary organic aerosol in the aqueous phase (aqSOA)

    NASA Astrophysics Data System (ADS)

    Ervens, Barbara; Sorooshian, Armin; Lim, Yong B.; Turpin, Barbara J.

    2014-04-01

    Secondary organic aerosol formation in the aqueous phase of cloud droplets and aerosol particles (aqSOA) might contribute substantially to the total SOA burden and help to explain discrepancies between observed and predicted SOA properties. In order to implement aqSOA formation in models, key processes controlling formation within the multiphase system have to be identified. We explore parameters affecting phase transfer and OH(aq)-initiated aqSOA formation as a function of OH(aq) availability. Box model results suggest OH(aq)-limited photochemical aqSOA formation in cloud water even if aqueous OH(aq) sources are present. This limitation manifests itself as an apparent surface dependence of aqSOA formation. We estimate chemical OH(aq) production fluxes, necessary to establish thermodynamic equilibrium between the phases (based on Henry's law constants) for both cloud and aqueous particles. Estimates show that no (currently known) OH(aq) source in cloud water can remove this limitation, whereas in aerosol water, it might be feasible. Ambient organic mass (oxalate) measurements in stratocumulus clouds as a function of cloud drop surface area and liquid water content exhibit trends similar to model results. These findings support the use of parameterizations of cloud-aqSOA using effective droplet radius rather than liquid water volume or drop surface area. Sensitivity studies suggest that future laboratory studies should explore aqSOA yields in multiphase systems as a function of these parameters and at atmospherically relevant OH(aq) levels. Since aerosol-aqSOA formation significantly depends on OH(aq) availability, parameterizations might be less straightforward, and oxidant (OH) sources within aerosol water emerge as one of the major uncertainties in aerosol-aqSOA formation.

  15. Aqueous secondary organic aerosol (SOA) production from the oxidation of phenols by triplet excited state organics

    NASA Astrophysics Data System (ADS)

    Smith, J.; Yu, L.; Zhang, Q.; Anastasio, C.

    2011-12-01

    Recent literature has shown that atmospheric condensed-phase chemistry can play a significant role in the evolution of organic aerosols, including the formation of secondary organic aerosol (SOA). SOA formation from the oxidation of volatile organic compounds (VOCs) in the aqueous phase has largely focused on oxidations involving the hydroxyl radical and other oxidants, such as photochemically created triplet excited states, have not been fully investigated. Phenolic compounds are one of the primary carbon emission classes from biomass and wood combustion and have significant water solubility. Once in the aqueous phase, phenolic compounds can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted in large quantities from wood combustion. The oxidation of phenolic species in the condensed phase by triplet excited states can result in the production of SOA. A main goal of this study was to investigate bulk solution reaction kinetics under atmospherically relevant conditions in order to ascertain how these reactions can impact aqueous-phase SOA production. In our experiments, we studied the reactions of five phenols (phenol, guaiacol, syringol, catechol, and resorcinol) with the triplet state of 3,4-dimethoxybenzaldehyde (34-DMB) during simulated solar radiation. We have characterized the impacts of pH, ionic strength and reactant concentrations on the reaction behavior of this system. In addition, we analyzed the SOA formed using high-resolution aerosol mass spectrometry, ion chromatography, and liquid chromatography-mass spectrometry to infer the reaction mechanisms. Our evidence suggests that under atmospherically relevant conditions, triplet excited states can be the dominant oxidant of phenolics and contribute significantly to the total SOA budget.

  16. Investigation of the sources and seasonal variations of secondary organic aerosols in PM2.5 in Shanghai with organic tracers

    NASA Astrophysics Data System (ADS)

    Feng, Jialiang; Li, Man; Zhang, Pan; Gong, Shiyi; Zhong, Mian; Wu, Minghong; Zheng, Mei; Chen, Changhong; Wang, Hongli; Lou, Shengrong

    2013-11-01

    One hundred and forty seasonal PM2.5 samples were collected from January 2010 to January 2011 at one urban site and one suburban site simultaneously in a Chinese megacity, Shanghai, to study the concentrations and seasonal variation of secondary organic aerosols (SOA). Concentrations of water-soluble organic carbon (WSOC) were determined together with organic and elemental carbons. Thirteen organic tracers, including the tracer for biomass burning and tracers for SOA from isoprene, α-pinene, β-caryophyllene and toluene, were measured. EC-based method, WSOC-based method, tracer-based method and PMF modeling were used to estimate the seasonal contributions of secondary organic carbon (SOC) in Shanghai, and the results from the different methods were compared and evaluated. Biomass burning was the major contributor to the measured WSOC in the autumn sampling period, while SOA was the major contributor in the other seasons. The concentrations of the SOA tracers in summer were obviously higher than that in other seasons. It was found that SOC estimated with the tracer-based method accounted for only a small part of the SOC from the WSOC-based method in Shanghai, especially for the winter and spring sampling periods. PMF results showed that a large part of the SOC was associated with sulfate and nitrate but not with the SOA tracers.

  17. Surface-active and Light-absorbing Secondary Organic Aerosol (SOA) Material

    NASA Astrophysics Data System (ADS)

    McNeill, V. F.; Sareen, N.; Schwier, A. N.; Shapiro, E. L.

    2009-12-01

    We have observed the formation of light-absorbing, high-molecular-weight, and surface-active organics from methylgyloxal interacting with ammonium salts in aqueous aerosol mimics. Mixtures of methylglyoxal and glyoxal also form light-absorbing products and exhibit surface tension depression with a Langmuir-like dependence on initial methylglyoxal concentration. We used chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS) to characterize the product species. The results are consistent with aldol condensation products, carbon-nitrogen species, sulfur-containing compounds, and oligomeric species up to 759 amu. These observations have potentially significant implications for our understanding of the effects of SOA on climate, since a) SOA are typically treated as non-absorbing in climate models, and b) surface tension depression in aqueous aerosols by SOA material may result in increased cloud condensation nucleus (CCN) activity. Furthermore, surface film formation could affect aerosol heterogeneous chemistry. We will also discuss aerosol flow tube O3 oxidation experiments designed to determine the atmospheric lifetimes of the observed product compounds.

  18. Secondary Organic Aerosol Formation in the Captive Aerosol Growth and Evolution (CAGE) Chambers during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL

    NASA Astrophysics Data System (ADS)

    Leong, Y.; Karakurt Cevik, B.; Hernandez, C.; Griffin, R. J.; Taylor, N.; Matus, J.; Collins, D. R.

    2013-12-01

    Secondary organic aerosol (SOA) represents a large portion of sub-micron particulate matter on a global scale. The composition of SOA and its formation processes are heavily influenced by anthropogenic and biogenic activity. Volatile organic compounds (VOCs) that are emitted naturally from forests or from human activity serve as precursors to SOA formation. Biogenic SOA (BSOA) is formed from biogenic VOCs and is prevalent in forested regions like the Southeastern United States. The formation and enhancement of BSOA under anthropogenic influences such as nitrogen oxides (NOx), sulfur dioxide (SO2), and oxygen radicals are still not well understood. The lack of information on anthropogenic BSOA enhancement and the reversibility of SOA formation could explain the underprediction of SOA in current models. To address some of these gaps in knowledge, this study was conducted as part of the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL during the summer of 2013. SOA growth experiments were conducted in two Captive Aerosol Growth and Evolution (CAGE) outdoor chambers located at the SEARCH site. Ambient trace gas concentrations were maintained in these chambers using semi-permeable gas-exchange membranes, while studying the growth of injected monodisperse seed aerosol. The control chamber was operated under ambient conditions; the relative humidity and oxidant and NOx levels were perturbed in the second chamber. This design allows experiments to capture the natural BSOA formation processes in the southeastern atmosphere and to study the influence of anthropogenic activity on aerosol chemistry. Chamber experiments were periodically monitored with physical and chemical instrumentation including a scanning mobility particle sizer (SMPS), a cloud condensation nuclei counter (CCNC), a humidified tandem differential mobility analyzer (H-TDMA), and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The CAGE experiments focused on SOA

  19. Secondary Organic Aerosol (SOA) production from the Aqueous Reactions of Phenols and Triplet Aromatic Carbonyls

    NASA Astrophysics Data System (ADS)

    Smith, J.; Sun, Y.; Lu, Y.; Zhang, Q.; Anastasio, C.

    2010-12-01

    The phenolic compounds guaiacol, syringol and phenol have recently been shown to produce secondary organic aerosol (SOA) at high yields in the aqueous phase upon exposure to simulated sunlight and hydroxyl radical. These phenols are significant products from wood combustion that can readily enter atmospheric waters, such as aqueous aerosol particles and cloud/fog droplets. Once in the aqueous phase, phenols can react with the triplet excited states of non-phenolic aromatic carbonyls (NPCs), particle-bound organics that are also emitted from wood combustion. In this study, we examined the aqueous-phase production of SOA from the reaction of phenolic compounds with triplet excited state organics. These aqueous phase reactions were tested by illuminating solutions containing a phenolic compound and NPC under simulated sunlight at various concentrations and pH values. The phenolic compound is consumed during these reactions, following a first-order decay that varies with phenol concentration, phenol identity, and pH. The non-volatile product mass formed in our illuminated solutions was determined gravimetrically and by analysis with High Resolution Time of Flight Aerosol Mass Spectrometry (HR-AMS). The SOA mass yield was determined as the mass of non-volatile product formed per mass of phenolic consumed during illumination. We also used HR-AMS to analyze for elemental composition, carbon oxidation state, and oligomers in the SOA produced. Our results to date indicate that phenols can be rapidly oxidized by triplet excited states under environmentally relevant conditions and that the accompanying SOA mass yields are very high.

  20. Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Slowik, J.; Kampf, C.; Timkovsky, J.; Noziere, B.; Praplan, A.; Pffafenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A.; Baltensperger, U.; Volkamer, R.

    2012-04-01

    Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

  1. Secondary Organic Aerosol Formation from Glyoxal: photochemical versus dark uptake and reversible versus irreversible SOA formation

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Slowik, J. G.; Kampf, C. J.; Timkovsky, J.; Noziere, B.; Praplan, A. P.; Pfaffenberger, L.; Holzinger, R.; Hoffmann, T.; Dommen, J.; Prevot, A. S.; Baltensperger, U.; Volkamer, R.

    2011-12-01

    Glyoxal forms secondary organic aerosol (SOA) by partitioning to the aerosol aqueous phase according to Henry's law. The subsequent processing by heterogeneous and multiphase reactions shifts the partitioning towards aerosols. Currently it is not well understood whether these reactions result in reversible or irreversible SOA formation, and what parameters influence the rate limiting step of multiphase processing. We conducted a series of simulation chamber experiments at PSI in April and May 2011 to investigate processing under dark conditions, UV and/or visible light irradiated conditions, and in the presence and absence of OH radicals. Experiments used ammonium sulfate or ammonium sulfate/fulvic acid mixtures as seed aerosols, and were conducted between 50% and 85% relative humidity at approximately constant RH over the course of any given experiment. Glyoxal was produced photochemically from acetylene, using HONO photolysis as the OH radical source. Gas-phase glyoxal was measured by the CU LED-Cavity Enhanced-DOAS. The Thermal-Desorption Proton-Transfer-Reaction Mass Spectrometer (TD-PTR-MS) and Ion Chromatography Mass Spectrometer (IC-MS) monitored both gas and aerosol-phase organic reaction products. Particle composition was monitored by High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS), and HPLC-ESI MS/MS and LC-MS analysis of filter samples.

  2. Secondary Organic Aerosol (SOA) formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, T. F.

    2014-05-01

    Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene, and limonene) by OH dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR chamber in Jülich, Germany, at low NOx (0.01-1 ppbV) and low ozone (O3) concentration. OH concentration and OH reactivity were measured directly so that the overall reaction rates of organic compounds with OH were quantified. Multi-generation reaction process, particle growth, new particle formation, particle yield, and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction of OH with organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to be dominant after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates of monoterpene with OH or O3 indicates that generally, OH oxidation and ozonolysis had similar efficiency in particle growth. The SOA yield of

  3. Simulation of semi-explicit mechanisms of SOA formation from glyoxal in aerosol in a 3-D model

    NASA Astrophysics Data System (ADS)

    Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

    2014-06-01

    New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale. In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume

  4. Insights into secondary organic aerosol formation mechanisms from measured gas/particle partitioning of specific organic tracer compounds.

    PubMed

    Zhao, Yunliang; Kreisberg, Nathan M; Worton, David R; Isaacman, Gabriel; Weber, Robin J; Liu, Shang; Day, Douglas A; Russell, Lynn M; Markovic, Milos Z; VandenBoer, Trevor C; Murphy, Jennifer G; Hering, Susanne V; Goldstein, Allen H

    2013-04-16

    In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA. PMID:23448102

  5. Secondary Organic Aerosol (SOA) Formation from Hydroxyl Radical Oxidation and Ozonolysis of Monoterpenes

    NASA Astrophysics Data System (ADS)

    Zhao, Defeng; Kaminski, Martin; Schlag, Patrick; Fuchs, Hendrik; Acir, Ismail-Hakki; Bohn, Birger; Haeseler, Rolf; Kiendler-Scharr, Astrid; Rohrer, Franz; Tillmann, Ralf; Wang, Mingjin; Wegner, Robert; Wahner, Andreas; Mentel, Thomas

    2014-05-01

    Hydroxyl radical (OH) oxidation and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. The pure OH oxidation of monoterpenes, an important biogenic VOC class, has seldom been investigated. In order to elucidate the importance of the reaction pathyways of the OH oxidation and ozonolysis and their roles in particle formation and growth, we investigated the particle formation of several common monoterpenes (alpha-pinene, beta-pinene, and limonene) in the large atmosphere simulation chamber SAPHIR in Juelich, Germany. The experiments were conducted for both OH dominant and pure ozonolysis case (in the presence of CO as OH scavenger) at ambient relevant conditions (low OA, low VOC and low NOx concentration). OH and ozone (O3) concentrations were measured so that the oxidation rates of OH and O3 with precursors were quantified. The particle formation and growth, aerosol yield, multi-generation reaction process and aerosol composition were analyzed. Pure ozonolysis generated a large amount of particles indicating ozonolysis plays an important role in particle formation as well as OH oxidation. In individual experiments, particle growth rates did not necessarily correlate with OH or O3 oxidation rates. However, comparing the growth rates at similar OH or O3 oxidation rates shows that generally, OH oxidation and ozonolysis have similar efficiency in particle growth. Multi-generation products are shown to be important in the OH oxidation experiment based on aerosol yield "growth curve" (Ng et al., 2006). The reaction process of OH oxidation experiments was analyzed as a function of OH dose to elucidate the role of functionalization and fragmentation. A novel analysis was developed to link the particle formation with the reaction with OH, which was also used to examine the role of functionalization and fragmentation in the particle formation by OH oxidation. These analyses show

  6. Aerosol-halogen interaction: Change of physico-chemical properties of SOA by naturally released halogen species

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Balzer, N.; Buxmann, J.; Grothe, H.; Krüger, H.; Platt, U.; Schmitt-Kopplin, P.; Zetzsch, C.

    2011-12-01

    Reactive halogen species are released by various sources like photo-activated sea-salt aerosol or salt pans and salt lakes. These heterogeneous release mechanisms have been overlooked so far, although their potential of interaction with organic aerosols like Secondary Organic Aerosol (SOA), Biomass Burning Organic Aerosol (BBOA) or Atmospheric Humic LIke Substances (HULIS) is completely unknown. Such reactions can constitute sources of gaseous organo-halogen compounds or halogenated organic particles in the atmospheric boundary layer. To study the interaction of organic aerosols with reactive halogen species (RHS), SOA was produced from α-pinene, catechol and guaiacol using an aerosol smog-chamber. The model SOAs were characterized in detail using a variety of physico-chemical methods (Ofner et al., 2011). Those aerosols were exposed to molecular halogens in the presence of UV/VIS irradiation and to halogens, released from simulated natural halogen sources like salt pans, in order to study the complex aerosol-halogen interaction. The heterogeneous reaction of RHS with those model aerosols leads to different gaseous species like CO2, CO and small reactive/toxic molecules like phosgene (COCl2). Hydrogen containing groups on the aerosol particles are destroyed to form HCl or HBr, and a significant formation of C-Br bonds could be verified in the particle phase. Carbonyl containing functional groups of the aerosol are strongly affected by the halogenation process. While changes of functional groups and gaseous species were visible using FTIR spectroscopy, optical properties were studied using Diffuse Reflectance UV/VIS spectroscopy. Overall, the optical properties of the processed organic aerosols are significantly changed. While chlorine causes a "bleaching" of the aerosol particles, bromine shifts the maximum of UV/VIS absorption to the red end of the UV/VIS spectrum. Further physico-chemical changes were recognized according to the aerosol size-distributions or the

  7. Modeling Gas-Particle Partitioning of SOA: Effects of Aerosol Physical State and RH

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Seinfeld, J.

    2011-12-01

    Aged tropospheric aerosol particles contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. In liquid aerosol particles non-ideal mixing of all species determines whether the condensed phase undergoes liquid-liquid phase separation or whether it is stable in a single mixed phase, and whether it contains solid salts in equilibrium with their saturated solution. The extended thermodynamic model AIOMFAC is able to predict such phase states by representing the variety of organic components using functional groups within a group-contribution concept. The number and composition of different condensed phases impacts the diversity of reaction media for multiphase chemistry and the gas-particle partitioning of semivolatile species. Recent studies show that under certain conditions biogenic and other organic-rich particles can be present in a highly viscous, semisolid or amorphous solid physical state, with consequences regarding reaction kinetics and mass transfer limitations. We present results of new gas-particle partitioning computations for aerosol chamber data using a model based on AIOMFAC activity coefficients and state-of-the-art vapor pressure estimation methods. Different environmental conditions in terms of temperature, relative humidity (RH), salt content, amount of precursor VOCs, and physical state of the particles are considered. We show how modifications of absorptive and adsorptive gas-particle mass transfer affects the total aerosol mass in the calculations and how the results of these modeling approaches compare to data of aerosol chamber experiments, such as alpha-pinene oxidation SOA. For a condensed phase in a mixed liquid state containing ammonium sulfate, the model predicts liquid-liquid phase separation up to high RH in case of, on average, moderately hydrophilic organic compounds, such as first generation oxidation products of alpha-pinene. The computations also reveal that treating liquid phases as ideal

  8. Land cover maps, BVOC emissions, and SOA burden in a global aerosol-climate model

    NASA Astrophysics Data System (ADS)

    Stanelle, Tanja; Henrot, Alexandra; Bey, Isaelle

    2015-04-01

    It has been reported that different land cover representations influence the emission of biogenic volatile organic compounds (BVOC) (e.g. Guenther et al., 2006). But the land cover forcing used in model simulations is quite uncertain (e.g. Jung et al., 2006). As a consequence the simulated emission of BVOCs depends on the applied land cover map. To test the sensitivity of global and regional estimates of BVOC emissions on the applied land cover map we applied 3 different land cover maps into our global aerosol-climate model ECHAM6-HAM2.2. We found a high sensitivity for tropical regions. BVOCs are a very prominent precursor for the production of Secondary Organic Aerosols (SOA). Therefore the sensitivity of BVOC emissions on land cover maps impacts the SOA burden in the atmosphere. With our model system we are able to quantify that impact. References: Guenther et al. (2006), Estimates of global terrestrial isoprene emissions using MEGAN, Atmos. Chem. Phys., 6, 3181-3210, doi:10.5194/acp-6-3181-2006. Jung et al. (2006), Exploiting synergies of global land cover products for carbon cycle modeling, Rem. Sens. Environm., 101, 534-553, doi:10.1016/j.rse.2006.01.020.

  9. On the chemical nature of the oxygenated organic aerosol: implication in the formation and aging of α-pinene SOA in a Mediterranean environment, Marseille

    NASA Astrophysics Data System (ADS)

    El Haddad, I.; D'Anna, B.; Temime-Roussel, B.; Nicolas, M.; Boreave, A.; Favez, O.; Voisin, D.; Sciare, J.; George, C.; Jaffrezo, J.-L.; Wortham, H.; Marchand, N.

    2012-08-01

    Organic Aerosol (OA) measurements were conducted during summer 2008 at an urban background site, in Marseille, France's second city and the largest port in the Mediterranean, an urban industrialized environment known for its active photochemistry. PM2.5 was collected using high volume samplers and analyzed for elemental and organic carbon, major ions (NH4+, NO3- and SO42-), humic-like-substances, organic markers (i.e. primary tracers and α-pinene oxidation products), elemental composition and radiocarbon content (14C). The real-time chemical characterization of submicron particles was also achieved using a compact time of flight aerosol mass spectrometer. Positive matrix factorization conducted on the organic aerosol mass spectra matrix revealed four factors, including traffic emissions (hydrocarbon-like OA, HOA), industrial emissions, semi-volatile (SV-OOA) and low-volatile (LV-OOA) oxygenated organic aerosol (OOA) related to oxidation processes. The results obtained were in excellent agreement with chemical mass balance source apportionments conducted in conjunction with organic markers and elements. It appears that while primary emissions contributed only 22% to the total OA (of which 23% was associated with industrial processes), OOA constituted the overwhelming fraction. Radiocarbon measurements suggest that about 80% of this fraction was of non-fossil origin, assigned predominantly to biogenic secondary organic aerosol. Non-fossil carbon appears to especially dominate the LV-OOA fraction, an aged long-range-transported OOA, marginally affected by local anthropogenic SOA. We also examined the relation between OOA and α-pinene SOA obtained based on the levels of α-pinene oxidation products. α-pinene SOA showed good correlation with SV-OOA, suggesting that the compounds used for estimating α-pinene SOA appear to pertain mainly to the moderately oxidized fraction. In contrast, LV-OOA was found to be intimately related to HUmic LIke substances (HULIS

  10. Radiative forcing of organic aerosol in the atmosphere and on snow: incorporation of SOA and brown carbon

    NASA Astrophysics Data System (ADS)

    Lin, G.; Flanner, M.; Penner, J. E.

    2013-12-01

    Organic aerosols (OA) play an important role in climate change through their radiative forcing. Secondary organic aerosol (SOA) contributes a large portion of total organic aerosol, especially in remote regions. Organic aerosol has been shown to be an important source of solar-light absorption. However, very few global model calculations of the radiative forcing due to organic aerosol include SOA or the light-absorbing part of OA (brown carbon). Here, we use a global chemical transport model with a detailed SOA formation mechanism to investigate the change in SOA between present day and pre-industrial conditions. We employ a radiative transfer model to assess the radiative forcing associated with the change in SOA. We also reassess the radiative forcing of total OA by considering previously neglected brown carbon. In addition to the OA in the atmosphere, we examine for the first time the radiative forcing of OA deposited in snow and sea-ice by using the NCAR Community Land Model 4 (CLM4) for the land snow simulation and the Community Ice CodE 4 (CICE) for the sea-ice simulation. Anthropogenic emissions of NOx, CO, sulfate, biomass burning and fossil fuel organic aerosol are shown to influence the formation rate of SOA substantially, causing it to increase by 35 Tg/yr (41%) since pre-industrial times. The increase of SOA results in a direct forcing ranging from -0.12 to -0.34 Wm-2 and a first indirect forcing in warm phase clouds ranging from -0.24 to -0.32 Wm-2, with the range due to different assumed size distributions for SOA and different refractive indices. The global burden of primary organic aerosol (POA) is estimated to increase by 0.53 Tg since pre-industrial times. Based on different refractive indices assumed for brown carbon, the increase of POA leads to a direct forcing varying from -0.07 to -0.12 Wm-2. The change in total OA exerts a direct radiative forcing ranging from -0.17 to -0.46 Wm-2. Atmospheric absorption from brown carbon ranges from +0.13 to

  11. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, R. L.; Jang, M.

    2015-11-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+]) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of the photooxidation products and the sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (8 groups) and aerosol phase reactivity (6 groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid catalyzed reactions, and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx. The model is validated using isoprene photooxidation experiments performed in the dual, outdoor UF APHOR chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total OM formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC, and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H+] but is dynamically related to all three parameters. For VOC / NOx > 10, with increasing NOx both experimental and

  12. Simulating the SOA formation of isoprene from partitioning and aerosol phase reactions in the presence of inorganics

    NASA Astrophysics Data System (ADS)

    Beardsley, Ross L.; Jang, Myoseon

    2016-05-01

    The secondary organic aerosol (SOA) produced by the photooxidation of isoprene with and without inorganic seed is simulated using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model. Recent work has found the SOA formation of isoprene to be sensitive to both aerosol acidity ([H+], mol L-1) and aerosol liquid water content (LWC) with the presence of either leading to significant aerosol phase organic mass generation and large growth in SOA yields (YSOA). Classical partitioning models alone are insufficient to predict isoprene SOA formation due to the high volatility of photooxidation products and sensitivity of their mass yields to variations in inorganic aerosol composition. UNIPAR utilizes the chemical structures provided by a near-explicit chemical mechanism to estimate the thermodynamic properties of the gas phase products, which are lumped based on their calculated vapor pressure (eight groups) and aerosol phase reactivity (six groups). UNIPAR then determines the SOA formation of each lumping group from both partitioning and aerosol phase reactions (oligomerization, acid-catalyzed reactions and organosulfate formation) assuming a single homogeneously mixed organic-inorganic phase as a function of inorganic composition and VOC / NOx (VOC - volatile organic compound). The model is validated using isoprene photooxidation experiments performed in the dual, outdoor University of Florida Atmospheric PHotochemical Outdoor Reactor (UF APHOR) chambers. UNIPAR is able to predict the experimental SOA formation of isoprene without seed, with H2SO4 seed gradually titrated by ammonia, and with the acidic seed generated by SO2 oxidation. Oligomeric mass is predicted to account for more than 65 % of the total organic mass formed in all cases and over 85 % in the presence of strongly acidic seed. The model is run to determine the sensitivity of YSOA to [H+], LWC and VOC / NOx, and it is determined that the SOA formation of isoprene is most strongly related to [H

  13. Secondary Organic Aerosol Formation and Aging in a Flow Reactor in the Forested Southeast US during SOAS

    NASA Astrophysics Data System (ADS)

    Hu, W.; Palm, B. B.; Hacker, L.; Campuzano Jost, P.; Day, D. A.; Simoes de Sa, S.; Fry, J.; Ayres, B. R.; Draper, D. C.; Ortega, A. M.; Kiendler-Scharr, A.; Panujoka, A.; Virtanen, A.; Miettinen, P.; Krechmer, J.; Canagaratna, M. R.; Thompson, S.; Yatavelli, L. R.; Stark, H.; Worsnop, D. R.; Lechner, M.; Martin, S. T.; Farmer, D.; Brown, S. S.; Jimenez, J. L.

    2013-12-01

    A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area (Centreville Supersite) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 flow reactors (potential aerosol mass, PAM) were used to expose ambient air to oxidants and their output was analyzed by state-of-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a High-Resolution Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and for the first time, two different High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometers (HRToF-CIMS), and an SMPS. Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, O3 and NO3) to investigate SOA formation and aging. The OH exposure was estimated by 3 different methods (empirical parameterization, carbon monoxide consumption, and chemical box model). Effective OH exposures up to 7e12 molec cm-3 s were achieved, which is equivalent to over a month of aging in the atmosphere. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ambient OA by ≈ 30%, indicating shifting contributions of functionalization vs. fragmentation, which is similar to previous results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than the ambient OA. More SOA is typically formed during nighttime when terpenes are higher and lower during daytime when isoprene is higher. SOA formation is also observed after exposure of ambient air to O3 or NO3, although the amount and oxidation was lower than for OH exposure. Formation of organic nitrates in the NO3 reaction will be discussed. High SOA formation (above 40 μg m-3) and a large number of CIMS ions, indicating many different

  14. Organic Aerosol Formation in the Humid, Photochemically-Active Southeastern US: SOAS Experiments and Simulations

    NASA Astrophysics Data System (ADS)

    Sareen, N.; Lim, Y. B.; Carlton, A. G.; Turpin, B. J.

    2013-12-01

    Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized low volatility organic aerosol and, in some cases, light absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, health, and the environment. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols) leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify other precursors that are atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere at Brent, Alabama during the Southern Oxidant and Aerosol Study (SOAS). Four mist chambers in parallel collected ambient gases in a DI water medium at 20-25 LPM with a 4 hr collection time. Total organic carbon (TOC) values in daily composited samples were 64-180 μM. Aqueous OH radical oxidation experiments were conducted with these mixtures in a newly designed cuvette chamber to understand the formation of SOA through gas followed by aqueous chemistry. OH radicals (3.5E-2 μM [OH] s-1) were formed in-situ in the chamber, continuously by H2O2 photolysis. Precursors and products of these aqueous OH experiments were characterized using ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. ESI-MS results from a June 12th, 2013 sample showed precursors to be primarily odd, positive mode ions, indicative of the presence of non-nitrogen containing alcohols, aldehydes, organic peroxides, or epoxides. Products were seen in the negative mode and included organic acid ions like pyruvate

  15. A comparison of secondary organic aerosol (SOA) yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2

    NASA Astrophysics Data System (ADS)

    Draper, D. C.; Farmer, D. K.; Desyaterik, Y.; Fry, J. L.

    2015-05-01

    The effect of NO2 on secondary organic aerosol (SOA) formation from ozonolysis of α-pinene, β-pinene, Δ3-carene, and limonene was investigated using a dark flow-through reaction chamber. SOA mass yields were calculated for each monoterpene from ozonolysis with varying NO2 concentrations. Kinetics modeling of the first generation gas-phase chemistry suggests that differences in observed aerosol yields for different NO2 concentrations are consistent with NO3 formation and subsequent competition between O3 and NO3 to oxidize each monoterpene. α-pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. β-pinene and Δ3-carene produced fewer particles at higher [NO2], but both retained moderate mass yields. Limonene exhibited both higher number concentrations and greater mass concentrations at higher [NO2]. SOA from each experiment was collected and analyzed by HPLC-ESI-MS, enabling comparisons between product distributions for each system. In general, the systems influenced by NO3 oxidation contained more high molecular weight products (MW >400 amu), suggesting the importance of oligomerization mechanisms in NO3-initiated SOA formation. α-pinene, which showed anomalously low aerosol mass yields in the presence of NO2, showed no increase in these oligomer peaks, suggesting that lack of oligomer formation is a likely cause of α-pinene's near 0% yields with NO3. Through direct comparisons of mixed-oxidant systems, this work suggests that NO3 is likely to dominate nighttime oxidation pathways in most regions with both biogenic and anthropogenic influences. Therefore, accurately constraining SOA yields from NO3 oxidation, which vary substantially with the VOC precursor, is essential in predicting nighttime aerosol production.

  16. Examining the Effects of Anthropogenic Emissions on Isoprene-Derived Secondary Organic Aerosol Formation During the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, Ground Site

    EPA Science Inventory

    A suite of offline and real-time gas- and particle-phase measurements was deployed atLook Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formatio...

  17. Aged Organic Aerosol in the Upper Troposphere: Aging of boundary layer aerosol during and after convective transport and in-situ SOA formation during DC3. (Invited)

    NASA Astrophysics Data System (ADS)

    Campuzano Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Jimenez, J. L.; Hodzic, A.; Bela, M. M.; Barth, M. C.; Olson, J. R.; Crawford, J. H.; Brune, W. H.; Pollack, I. B.; Ryerson, T. B.; Blake, D. R.; Wisthaler, A.; Mikoviny, T.

    2013-12-01

    While aerosol scavenging in deep convection is efficient (comparable to soluble species like formaldehyde), significant transport of submicron aerosol was observed repeatedly during storms targeted in the course of the DC3 (Deep Convective Clouds and Chemistry ) campaign. The lofted aerosol was mostly organic, and even in fresh outflow was significantly more oxidized than the aerosol sampled in the source region of the convection. Organic aerosol (OA) sampled in both day-old outflow as well as in the background continental UT was in general significantly more oxidized than OA observed both in the fresh outflow, and in most lower tropospheric aerosol. This suggests either fast oxidative chemistry, and/or long residence times in the UT. Some of the potential factors contributing to this fast oxidation will be explored in this talk. A second source of UT OA was observed during several flights where gas-phase organics in the presence of NOx lead to the formation of secondary OA (SOA), including particulate organic nitrate. Most observations of this UT SOA during DC3 were made in fresh outflow. However, a unique opportunity to study the chemistry of this SOA formation in more detail with a box model presented itself in the flight on July 21st, 2012; here an initially near-particle-free UT airmass originating in the wake of a dissolving nighttime mesoscale convective system (MCS) was observed over several hours until new particle growth dominated by OA and particulate nitrate was measured.

  18. Oligomerization as a potential mechanism for Secondary Organic Aerosol (SOA) formation in clouds

    NASA Astrophysics Data System (ADS)

    Yasmeen, F.; Sauret, N.; Claeys, M.; Maria, P. C.; Massi, L.

    2009-04-01

    Electrospray ionization - mass spectrometry (ESI-MS) has been used to investigate oligomer formation in dark chamber experiments designed to study the polymerization conditions of common atmospheric photooxidation products without photochemical action. Methylglyoxal has been selected as the monomer considering, it is a gas-phase product from the atmospheric oxidation of isoprene and terpenes (biogenic sources) as well as of aromatic compounds (anthropogenic sources). Aqueous-phase oligomer formation of methylglyoxal has been investigated in a simulated cloud matrix, under dark conditions in view of its short life time (~1.6 hrs). A mechanistic pathway for the growth of oligomers via aldol condensation under cloud conditions and in the absence of UV-light and the OH radical is proposed here for the first time. Soluble oligomers (n=1-12) formed in the course of acid-catalyzed aldol condensation have been detected and identified by positive and negative ion ESI-MS, while their relative abundance is estimated from the full-scan mass spectra. In particular, oligomer abundances and their adduct formation was considered with special emphasis on the structural elucidation of these oligomers and their corresponding adduct products. The oligomer series starts with a β-hydroxy ketone via aldol condensation and oligomers are formed by multiple addition of C3H4O2 units (72 Da) to the parent β-hydroxy ketone. MS2 ion trap experiments have been performed to structurally characterize the oligomers. Oligomers could form under conditions encountered in clouds even at micromolar concentrations and thus could significantly result in secondary organic aerosol (SOA) after cloud droplet evaporation. Therefore, it is proposed that oligomer formation does not only occur during droplet evaporation when the concentrations of products increase but could as well be an in-cloud process and substantially enhance in-cloud SOA yields.

  19. Source apportionment using radiocarbon and organic tracers for PM2.5 carbonaceous aerosols in Guangzhou, South China: contrasting local- and regional-scale haze events.

    PubMed

    Liu, Junwen; Li, Jun; Zhang, Yanlin; Liu, Di; Ding, Ping; Shen, Chengde; Shen, Kaijun; He, Quanfu; Ding, Xiang; Wang, Xinming; Chen, Duohong; Szidat, Sönke; Zhang, Gan

    2014-10-21

    We conducted a source apportionment and investigated the atmospheric behavior of carbonaceous aerosols during hazy and normal days using radiocarbon ((14)C) and biomass burning/secondary organic aerosol (SOA) tracers during winter in Guangzhou, China. Haze episodes were formed either abruptly by local emissions or through the accumulation of particles transported from other areas. The average contributions of fossil carbon to elemental carbon (EC), water-insoluble organic carbon, and water-soluble organic carbon were 71 ± 10%, 40 ± 6% and 33 ± 3%, respectively. High contributions of fossil carbon to EC (80-90%) were observed for haze samples that were substantially impacted by local emissions, as were the highest (lowest) ratios for NO3(-)/SO4(2-) (OC/EC), which indicates that these particles mainly came from local vehicle exhaust. Low contributions of fossil carbon to EC (60-70%) were found for haze particles impacted by regional transport. Secondary organic carbon (SOC) calculated using SOA tracers accounts for only ∼ 20% of the SOC estimated by (14)C, which is probably because some important volatile organic carbons are not taken into account in the SOA tracer calculation method and because of the large discrepancy in ambient conditions between the atmosphere and smog chambers. A total of 33 ± 11% of the SOC was of fossil origin, a portion of which could be influenced by humidity. PMID:25264588

  20. The formation of SOA and chemical tracer compounds from the photooxidation of naphthalene and its methyl analogs in the presence and absence of nitrogen oxides

    EPA Science Inventory

    Laboratory smog chamber experiments have been carried out to investigate secondary organic aerosol (SOA)formation from the photooxidation of naphthalene and its methyl analogs, 1- and 2-methylnaphthalene (1-MN and 2- MN, respectively). Laboratory smog chamber irradiations were co...

  1. Artificial ultra-fine aerosol tracers for highway transect studies

    NASA Astrophysics Data System (ADS)

    Cahill, Thomas A.; Barnes, David E.; Wuest, Leann; Gribble, David; Buscho, David; Miller, Roger S.; De la Croix, Camille

    2016-07-01

    The persistent evidence of health impacts of roadway aerosols requires extensive information for urban planning to avoid putting populations at risk, especially in-fill projects. The required information must cover both highway aerosol sources as well as transport into residential areas under a variety of roadway configurations, traffic conditions, downwind vegetation, and meteorology. Such studies are difficult and expensive to do, but were easier in the past when there was a robust fine aerosol tracer uniquely tied to traffic - lead. In this report we propose and test a modern alternative, highway safety flare aerosols. Roadway safety flares on vehicles in traffic can provide very fine and ultra-fine aerosols of unique composition that can be detected quantitatively far downwind of roadways due to a lack of upwind interferences. The collection method uses inexpensive portable aerosol collection hardware and x-ray analysis protocols. The time required for each transect is typically 1 h. Side by side tests showed precision at ± 4%. We have evaluated this technique both by aerosol removal in vegetation in a wind tunnel and by tracking aerosols downwind of freeways as a function of season, highway configuration and vegetation coverage. The results show that sound walls for at-grade freeways cause freeway pollution to extend much farther downwind than standard models predict. The elevated or fill section freeway on a berm projected essentially undiluted roadway aerosols at distances well beyond 325 m, deep into residential neighborhoods. Canopy vegetation with roughly 70% cover reduced very fine and ultra-fine aerosols by up to a factor of 2 at distances up to 200 m downwind.

  2. SOA Formation from Glyoxal in the Aerosol Aqueous Phase: A case study from Mexico City using an explicit laboratory-based model

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Dzepina, K.; Lee-Taylor, J.; Ervens, B.; Volkamer, R.

    2012-04-01

    Glyoxal is an important contributor to secondary organic aerosol (SOA) formation via aerosol aqueous phase processing. This work takes a glyoxal-SOA model parameterization based on laboratory data and applies the box model to ambient measurements. For the Mexico City Metropolitan Area (MCMA) case study on April 9, 2003 the aerosol uptake and processing of glyoxal in aerosol water is investigated, and found able to rationalize the previously observed gas phase glyoxal imbalance (Volkamer et al., 2007) for the first time based on laboratory data. Our aerosol size distribution resolving model is constrained with time resolved distributions of aerosol chemical composition, and supports a surface limited uptake mechanism of glyoxal in Mexico City. We compare the AMS-measured OOA to SOA predictions using our glyoxal model combined with background aerosol, traditional VOC precursor (e.g., aromatics) SOA, and three parameterizations for SOA formation from S/IVOC, i.e., based on (1) Robinson et al., 2007, (2) Grieshop et al., 2009, and (3) GECKO-A (Lee-Taylor et al., 2011), which account for the bulk of SOA mass, but give very different results for the O/C ratio of predicted SOA. This presents to our knowledge the first comparison of a molecular perspective of S/IVOC ageing with empirical parameterizations. We compare the mass weighted O/C ratio from these different SOA sources to AMS-measured O/C ratios, in an attempt to use the rapidly increasing O/C to test for closure, and advance our understanding of aerosol ageing in Mexico City.

  3. Is dry deposition of semi-volatile organic gases a significant loss of secondary organic aerosols (SOA)?

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Aumont, B.; Knote, C. J.; Lee-Taylor, J. M.; Madronich, S.

    2013-12-01

    Dry deposition removal of semi-volatile organic compounds from the atmosphere and its impact on organic aerosol mass is currently under-explored and not well represented in chemistry-climate models, especially for the many complex partly oxidized organics involved in particle formation. The main reason for this omission is that current models use simplified SOA mechanisms that lump precursors and their products into volatility bins, therefore losing information on important properties of individual molecules (or groups) that are needed to calculate dry deposition. In this study, we apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate SOA formation and estimate the influence of dry deposition of gas-phase organics on SOA concentrations downwind of an urban area (Mexico City), as well as over a pine forest. SOA precursors considered here include short- and long-chain alkanes (C3-25), alkenes, light aromatics, isoprene and monoterpenes. We show that dry deposition of oxidized gases is not an efficient sink for anthropogenic SOA, as it removes <5% of SOA within the city's boundary layer and ~15% downwind. The effect on biogenic SOA is however significantly larger. We discuss reasons for these differences, and investigate separately the impacts on short and long-chain species. We show that the dry deposition is competing with the uptake of gases to the aerosol phase. In the absence of this condensation, ~50% of the regionally produced mass downwind of Mexico City would have been dry-deposited. However, because dry deposition of submicron aerosols is slow, condensation onto particles protects organic gases from deposition and therefore increases their atmospheric burden and lifetime. We use the explicit GECKO-A model to build an empirical parameterization for use in 3D models. Removal (dry and wet) of organic vapors depends on their solubility, and required Henry's law solubility coefficients were estimated for

  4. Cloud condensation nuclei activity, droplet growth kinetics, and hygroscopicity of biogenic and anthropogenic secondary organic aerosol (SOA)

    NASA Astrophysics Data System (ADS)

    Zhao, D. F.; Buchholz, A.; Kortner, B.; Schlag, P.; Rubach, F.; Fuchs, H.; Kiendler-Scharr, A.; Tillmann, R.; Wahner, A.; Watne, Å. K.; Hallquist, M.; Flores, J. M.; Rudich, Y.; Kristensen, K.; Hansen, A. M. K.; Glasius, M.; Kourtchev, I.; Kalberer, M.; Mentel, Th. F.

    2016-02-01

    Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively.

    We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κCCN, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH4)2SO4, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions.

    In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κHTDMA, of ASOA was distinctively higher (0.09-0.10) than that of BSOA (0.03-0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity.

    Closure analysis of CCN and HTDMA data showed κHTDMA was lower than κCCN by 30-70 %. Better closure was achieved for ASOA compared to BSOA. This

  5. Secondary Organic Aerosol (SOA) formation from the β-pinene + NO3 system: effect of humidity and peroxy radical fate

    NASA Astrophysics Data System (ADS)

    Boyd, C. M.; Sanchez, J.; Xu, L.; Eugene, A. J.; Nah, T.; Tuet, W. Y.; Guzman, M. I.; Ng, N. L.

    2015-01-01

    The formation of secondary organic aerosol (SOA) from the oxidation of β-pinene via nitrate radicals is investigated in the Georgia Tech Environmental Chamber facility (GTEC). Aerosol yields are determined for experiments performed under both dry (RH < 2%) and humid (RH = 50% and RH = 70%) conditions. To probe the effects of peroxy radical (RO2) fate on aerosol formation, "RO2 + NO3 dominant" and "RO2 + HO2 dominant" experiments are performed. Gas-phase organic nitrate species (with molecular weights of 215, 229, 231 and 245 amu) are detected by chemical ionization mass spectrometry and their formation mechanisms are proposed. The ions at m/z 30 (NO+) and m/z 46 (NO2+) contribute about 11% to the total organics signal in the typical aerosol mass spectrum, with NO+ : NO2+ ratio ranging from 6 to 9 in all experiments conducted. The SOA yields in the "RO2 + NO3 dominant" and "RO2 + HO2 dominant" experiments are comparable. For a wide range of organic mass loadings (5.1-216.1 μg m-3), the aerosol mass yield is calculated to be 27.0-104.1%. Although humidity does not appear to affect SOA yields, there is evidence of particle-phase hydrolysis of organic nitrates, which are estimated to compose 45-74% of the organic aerosol. The extent of organic nitrate hydrolysis is significantly lower than that observed in previous studies on photooxidation of volatile organic compounds in the presence of NOx. It is estimated that about 90 and 10% of the organic nitrates formed from the β-pinene + NO3 reaction are primary organic nitrates and tertiary organic nitrates, respectively. While the primary organic nitrates do not appear to hydrolyze, the tertiary organic nitrates undergo hydrolysis with a lifetime of 3-4.5 h. Results from this laboratory chamber study provide the fundamental data to evaluate the contributions of monoterpene + NO3 reaction to ambient organic aerosol measured in the southeastern United States, including the Southern Oxidant and Aerosol Study (SOAS) and the

  6. Secondary Organic Aerosol Formation and Aging in a Flow Reactor in the Forested Southeast US during SOAS

    NASA Astrophysics Data System (ADS)

    Hu, W.; Palm, B. B.; Hacker, L.; Campuzano Jost, P.; Day, D. A.; de Sá, S. S.; Ayres, B. R.; Draper, D.; Fry, J.; Ortega, A. M.; Kiendler-Scharr, A.; Pajunoja, A.; Virtanen, A.; Krechmer, J.; Canagaratna, M. R.; Thompson, S.; Yatavelli, R. L. N.; Stark, H.; Worsnop, D. R.; Martin, S. T.; Farmer, D.; Brown, S. S.; Jimenez, J. L.

    2015-12-01

    A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area in Centreville Supersite, AL (SEARCH network) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 oxidation flow reactors (OFR) were used to expose ambient air to oxidants and their output was analyzed by state-of-the-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a HR Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and Two HR-TOF Chemical Ionization Mass Spectrometers (HRToF-CIMS). Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, NO3 radicals and O3) to investigate the oxidation of BVOCs (including isoprene derived epoxydiols, IEPOX) and SOA formation and aging. Effective OH exposures up to 1×1013 molec cm-3 s were achieved, equivalent to over a month of aging in the atmosphere. Multiple oxidation products from isoprene and monoterpenes including small gas-phase acids were observed in OH OFR. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ~30% of ambient OA, indicating shifting contributions of functionalization vs. fragmentation, consistent with results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than ambient OA. More SOA is typically formed during nighttime when terpenes are higher and photochemistry is absent, and less during daytime when isoprene is higher, although the IEPOX pathway is suppressed in the OFR. SOA is also observed after exposure of ambient air to O3 or NO3, although the amounts and oxidation levels were lower than for OH. Formation of organic nitrates in the NO3 reaction will also be discussed.A major field campaign (Southern Oxidant and Aerosol

  7. Secondary organic aerosol (SOA) derived from isoprene epoxydiols: Insights into formation, aging and distribution over the continental US from the DC3 and SEAC4RS campaigns

    NASA Astrophysics Data System (ADS)

    Campuzano Jost, P.; Palm, B. B.; Day, D. A.; Hu, W.; Ortega, A. M.; Jimenez, J. L.; Liao, J.; Froyd, K. D.; Pollack, I. B.; Peischl, J.; Ryerson, T. B.; St Clair, J. M.; Crounse, J.; Wennberg, P. O.; Mikoviny, T.; Wisthaler, A.; Ziemba, L. D.; Anderson, B. E.

    2014-12-01

    Isoprene-derived SOA formation has been studied extensively in the laboratory. However, it is still unclear to what extent isoprene contributes to the overall SOA burden over the southeastern US, an area with both strong isoprene emissions as well as large discrepancies between modeled and observed aerosol optical depth. For the low-NO isoprene oxidation pathway, the key gas-phase intermediate is believed to be isoprene epoxide (IEPOX), which can be incorporated into the aerosol phase by either sulfate ester formation (IEPOX sulfate) or direct hydrolysis. As first suggested by Robinson et al, the SOA formed by this mechanism (IEPOX-SOA) has a characteristic fragmentation pattern when analyzed by an Aerodyne Aerosol Mass Spectrometer (AMS) with enhanced relative abundances of the C5H6O+ ion (fC5H6O). Based on data from previous ground campaigns and chamber studies, we have developed a empirical method to quantify IEPOX-SOA and have applied it to the data from the DC3 and SEAC4RS aircraft campaigns that sampled the SE US during the Spring of 2012 and the Summer of 2013. We used Positive Matrix Factorization (PMF) to extract IEPOX-SOA factors that show good correlation with inside or downwind of high isoprene emitting areas and in general agree well with the IEPOX-SOA mass predicted by the empirical expression. According to this analysis, the empirical method performs well regardless of (at times very strong) BBOA or urban OA influences. On average 17% of SOA in the SE US boundary layer was IEPOX-SOA. Overall, the highest concentrations of IEPOX-SOA were typically found around 1-2 km AGL, several hours downwind of the isoprene source areas with high gas-phase IEPOX present. IEPOX-SOA was also detected up to altitudes of 6 km, with a clear trend towards more aged aerosol at altitude, likely a combination of chemical aging and physical airmass mixing. The unique instrument package aboard the NASA-DC8 allows us to examine the influence of multiple factors (aerosol

  8. Natural organic compounds as tracers for biomass combustion in aerosols

    SciTech Connect

    Simoneit, B.R.T. |; Abas, M.R. bin |; Cass, G.R. |; Rogge, W.F. |; Mazurek, M.A.; Standley, L.J.; Hildemann, L.M.

    1995-08-01

    Biomass combustion is an important primary source of carbonaceous particles in the global atmosphere. Although various molecular markers have already been proposed for this process, additional specific organic tracers need to be characterized. The injection of natural product organic tracers to smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. The degree of alteration increases as the burn temperature rises and the moisture content of the fuel decreases. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular structures of the tracers are generally source specific. The homologous compound series and biomarkers present in smoke particles are derived directly from plant wax, gum and resin by volatilization and secondarily from pyrolysis of biopolymers, wax, gum and resin. The complexity of the organic components of smoke aerosol is illustrated with examples from controlled burns of temperate and tropical biomass fuels. Burning of biomass from temperate regions (i.e., conifers) yields characteristic tracers from diterpenoids as well as phenolics and other oxygenated species, which are recognizable in urban airsheds. The major organic components of smoke particles from tropical biomass are straight-chain, aliphatic and oxygenated compounds and triterpenoids. The precursor-to-product approach of organic geochemistry can be applied successfully to provide tracers for studying smoke plume chemistry and dispersion.

  9. Contribution of Primary and Secondary Sources to Organic Aerosol and PM2.5 at SEARCH Network Sites

    EPA Science Inventory

    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. La...

  10. A perspective on SOA generated in aerosol water from glyoxal and methylglyoxal and its impacts on climate-relevant aerosol properties

    NASA Astrophysics Data System (ADS)

    Sareen, N.; McNeill, V. F.

    2011-12-01

    In recent years, glyoxal and methylglyoxal have emerged to be potentially important SOA precursors with significant implications for climate-related aerosol properties. Here we will discuss how the chemistry of these and similar organic compounds in aerosol water can affect the aerosol optical and cloud formation properties. Aqueous-phase SOA production from glyoxal and methylglyoxal is a potential source of strongly light-absorbing organics, or "brown carbon". We characterized the kinetics of brown carbon formation from these precursors in mixtures of ammonium sulfate and water using UV-Vis spectrophotometry. This mechanism has been incorporated into a photochemical box model with coupled gas phase-aqueous aerosol chemistry. Methylglyoxal and related compounds also may impact an aerosol's ability to act as a cloud condensation nucleus. We recently showed via pendant drop tensiometry and aerosol chamber studies that uptake of methylglyoxal from the gas phase driven by aqueous-phase oligomerization chemistry is a potentially significant, previously unidentified source of surface-active organic material in aerosols. Results from pendant drop tensiometry showed significantly depressed surface tension in methylglyoxal-ammonium sulfate solutions. We further found that ammonium sulfate particles exposed to gas-phase methylglyoxal in a 3.5 m3 aerosol reaction chamber activate into cloud droplets at sizes up to 15% lower at a given supersaturation than do pure ammonium sulfate particles. The observed enhancement exceeds that predicted based on Henry's Law and our measurements of surface tension depression in bulk solutions, suggesting that surface adsorption of methylglyoxal plays a role in determining CCN activity. Methylglyoxal and similar gas-phase surfactants may be an important and overlooked source of enhanced CCN activity in the atmosphere. To characterize the SOA products formed in these solutions, an Aerosol Chemical Ionization Mass Spectrometer (CIMS) was used

  11. Secondary Organic Aerosol (SOA) Formation From the NO3 Radical Oxidation of Alpha- pinene

    NASA Astrophysics Data System (ADS)

    Perraud, V.; Yu, Y.; Bruns, E.; Ezell, M. J.; Johnson, S. N.; Alexander, M.; Zelenyuk, A.; Imre, D.; Finlayson-Pitts, B. J.

    2008-12-01

    Terpenes such as alpha-pinene, emitted in large quantities from vegetation into the troposphere, are well known to react with O3, OH and NO3 radicals leading to the formation of secondary organic aerosol, SOA. While particle formation and growth from the NO3 reaction with alpha-pinene have been reported by a number of groups, as have the gas phase products of this reaction, little is known about the chemical composition of the particles. We report studies of the composition of particles formed in the NO3 - alpha- pinene reaction using two reactors, a flow tube and a static chamber. Nitrate radicals were generated in the flow tube by the reaction of NO2 with O3 and in the static chamber by the thermal decomposition of N2O5. Particle formation and growth was monitored using SMPS and APS. A variety of analytical techniques were applied to measure the chemical composition, including FTIR of particles collected on ZnSe impactor discs, and GC-MS, ESI-MS, APCI-MS, HPLC-MS and HPLC-UV of samples collected on quartz fiber filters. In addition, particle mass spectrometer techniques including AMS and SPLAT provided real-time analysis. A number of organic nitrates were observed in the particles, along with carbonyl compounds and organic acids. Gas phase products measured using DNPH coated-cartridges included pinonaldehyde, formaldehyde, acetaldehyde and acetone. Results of studies in which concentrations of the reactants were varied will be presented and possible mechanisms and the atmospheric implications will be discussed.

  12. AEROSOL OPTICAL PROPERTIES AND BIOGENIC SOA: EFFECT ON HYGROSCOPIC PROPERTIES AND LIGHT ABSORPTION

    EPA Science Inventory

    This study will provide a comprehensive characterization of optical properties of biogenic SOA and their sensitivity to anthropogenic influence. Several parameters critical for climate modeling, such as absorption cross-section, single scattering albedo and sensitivity to R...

  13. Abundance of Biogenic and Anthropogenic SOA Tracers Compounds in Fine Particles during the Nucleation in Forests Experiment (NIFTy)

    NASA Astrophysics Data System (ADS)

    Jobson, B. T.; Wallace, W.; Westberg, H.; Hamilton, H.; Pryor, S. C.; Barthelmie, R.

    2008-12-01

    The Nucleation in Forests field experiment was conducted in May 2008 at the Morgan-Monroe State forest in Indiana to observe the nature and occurrence of new particle formation. As part of this experiment filter samples were collected at mid-canopy height using a MOUDI-110. The MOUDI sampler collected 10 size fractions from 0.056 um to 5.6 um. The filter samples were collected for 24 hours and analyzed by gas chromatography ion trap mass spectrometry for several anthropogenic and biogenic secondary organic aerosol tracer compounds including 2-methyltetrols from isoprene oxidation. The objective of the size resolved PM sampling was to determine if the growth of small particles that occurs during nucleation events was driven by biogenic or anthropogenic VOC photooxidation products. Results from this analysis will be presented.

  14. Reactive uptake of Isoprene-derived epoxydiols to submicron aerosol particles: implications for IEPOX lifetime and SOA formation

    NASA Astrophysics Data System (ADS)

    Thornton, J. A.; Gaston, C.; Riedel, T.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2014-12-01

    The reactive uptake of isoprene-derived epoxydiols (IEPOX) is thought to be a significant source of atmospheric secondary organic aerosol (SOA). However, the IEPOX reaction probability (γIEPOX) and its dependence upon particle composition remain poorly constrained. We report measurements of γIEPOX for trans-b-IEPOX, the predominant IEPOX isomer, on submicron particles as a function of composition, acidity, and relative humidity (RH). Particle acidity had the strongest effect. γIEPOX is more than 500 times larger on ammonium bisulfate (γ ~ 0.05) than on ammonium sulfate (γ ≤ 1 x 10-4). We could accurately predict γIEPOX using an acid-catalyzed, epoxide ring-opening mechanism and a high Henry's law coefficient (1.6 x 108 M/atm). Suppression of γIEPOX was observed in particles containing both ammonium bisulfate and polyethylene glycol (PEG-300), likely due to diffusion and solubility limitations within a PEG-300 coating, suggesting that IEPOX uptake could be self-limiting. Using the measured uptake kinetics, the predicted atmospheric lifetime of IEPOX is a few hours in the presence of highly acidic particles (pH < 0), but is greater than a day on less acidic particles (pH > 3). We connect these net reactive uptake measurements to chamber studies of the SOA yield from IEPOX multiphase chemistry and discuss the implications of these findings for modeling the anthropogenic influence upon SOA formation from isoprene.

  15. Ergosterol, arabitol and manitol as tracers for biological aerosols

    NASA Astrophysics Data System (ADS)

    Rudich, Y.; Burshtein, N.; Lang-Yona, N.

    2010-12-01

    Airborne fungi can cause a wide array of adverse responses in humans depending on the type and quantity present. Since dose and human response is highly individual, the sensitivity of a person exposed is also an important consideration. The abundance of bioaerosols in the ambient air and their health impacts depend on the season and on the environmental conditions. In order to quantify and identify fungi bioaerosols’ contribution to atmospheric aerosols and the impact to public health, it has been suggested to use chemicals that are typical of bioaerosols as biomarkers in chemical analysis of collected aerosols. An often used biomarker for determining the fungal biomass is ergosterol. Recently, Bauer et al. (2008) found that mannitol and arabitol concentrations are correlated with the fungal spore counts in atmospheric PM10. In this study, ergosterol, arabitol and mannitol were quantified in ambient aerosols collected in the Eastern Mediterranean region for 12 months in order to understand their annual and seasonal behavior and to test whether arabitol and mannitol are good predictors of fungi. Finally, correlations between ergosterol abundances with inorganic ions, humidity, temperature, and synoptic data in order to identify dominant sources of fungal spores were also studied. We will report on the measurements and the observed correlations between the different tracers.

  16. Influence of dry deposition of semi-volatile organic compounds (VOC) on secondary organic aerosol (SOA) formation in the Mexico City plume

    NASA Astrophysics Data System (ADS)

    Hodzic, Alma; Madronich, Sasha; Aumont, Bernard; Lee-Taylor, Julia; Karl, Thomas

    2013-04-01

    The dry deposition removal of organic compounds from the atmosphere and its impact on organic aerosol mass is currently unexplored and unaccounted for in chemistry-climate models. The main reason for this omission is that current models use simplified SOA mechanisms that lump precursors and their products into volatility bins, therefore losing information on other important properties of individual molecules (or groups) that are needed to calculate dry deposition. In this study, we apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate SOA formation and estimate the influence of dry deposition of VOCs on SOA concentrations downwind of Mexico City. SOA precursors considered here include short- and long-chain alkanes (C3-25), alkenes, and light aromatics. The results suggest that 90% of SOA produced in Mexico City originates from the oxidation and partitioning of long-chain (C>12) alkanes, while the regionally exported SOA is almost equally produced from long-chain alkanes and from shorter alkanes and light aromatics. We show that dry deposition of oxidized gases is not an efficient sink for SOA, as it removes <5% of SOA within the city's boundary layer and ~15% downwind. We discuss reasons for this limited influence, and investigate separately the impacts on short and long-chain species. We show that the dry deposition is competing with the uptake of gases to the aerosol phase, and because dry deposition of submicron aerosols is slow, condensation onto particles protects organic gases from deposition and therefore increases their atmospheric burden and lifetime. In the absence of this condensation, ~50% of the regionally produced mass would have been dry-deposited.

  17. Wintertime Secondary Organic Aerosol (SOA) Formation from Oxidation of Volatile Organic Compounds (VOCs) Associated with Oil and Gas Extraction

    NASA Astrophysics Data System (ADS)

    Murphy, S. M.; Soltis, J.; Field, R. A.; Bates, T. S.; Quinn, P.; De Gouw, J. A.; Veres, P. R.; Warneke, C.; Graus, M.; Gilman, J.; Lerner, B. M.; Koss, A.

    2013-12-01

    The Uintah Basin is located in a lightly populated area of Northeastern Utah near Dinosaur National Monument. Oil and gas extraction activities in the basin have dramatically increased in recent years due to the application of hydraulic fracturing. The Uintah Basin has experienced numerous high-ozone events during the past several winters with concentrations often exceeding 100 ppb. PM 2.5 monitoring by the city of Vernal, located at the edge of the basin, have shown wintertime concentrations in excess of the EPA 8-hour national standard, though the source and composition of particulates during these events is unclear. The Energy and Environment - Uintah Basin Winter Ozone Study (E&E UBWOS) was conducted during the winters of 2012 and 2013. During the study, intensive measurements of aerosol composition and speciated VOCs were made at a monitoring site near oil and gas extraction activities. Organic aerosol was found to be a major component of PM 2.5 and organic aerosol formation was highly correlated with the production of secondary VOC's. This correlation suggests that the organic aerosol is secondary in nature even though O:C ratios suggest a less oxidized aerosol than often observed in summertime SOA. The ozone levels and organic aerosol mass during 2012 were much lower than those observed in 2013. Calculations of the aerosol yield during both years will be presented along with an analysis of how well observed yields match predictions based on smog-chamber data. The potential for additional aerosol formation in the system will also be discussed.

  18. In-Situ Measurements of Aerosol Optical and Hygroscopic Properties at the Look Rock Site during SOAS 2013

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Zimmermann, K.; Bertram, T. H.; Corrigan, A. L.; Guzman, J. M.; Russell, L. M.; Budisulistiorini, S.; Li, X.; Surratt, J. D.; Hicks, W.; Bairai, S. T.; Cappa, C. D.

    2013-12-01

    One of the main goals of the Southern Oxidant and Aerosol Study (SOAS) is to characterize the climate-relevant properties of aerosols over the southeastern United States at the interface of biogenic and anthropogenic emissions. As part of the SOAS campaign, the UCD cavity ringdown/photoacoustic spectrometer was deployed to make in-situ measurements of aerosol light extinction, absorption and sub-saturated hygroscopicity at the Look Rock site (LRK) in the Great Smoky Mountains National Park, TN from June 1 to July 15, 2013. The site is influenced by substantial biogenic emissions with varying impacts from anthropogenic pollutants, allowing for direct examination of the optical and hygroscopic properties of anthropogenic-influenced biogenic secondary organic aerosols (SOA). During the experiment period, the average dry aerosol extinction (Bext), absorption (Babs) coefficients and single scattering albedo (SSA) at 532 nm were 30.3 × 16.5 Mm-1, 1.12 × 0.78 Mm-1 and 0.96 × 0.06. The Babs at 532 nm was well correlated (r2 = 0.79) with the refractory black carbon (rBC) number concentration determined by a single particle soot spectrometer (SP2). The absorption by black carbon (BC), brown carbon (BrC) and the absorption enhancement due to the 'lensing' effect were quantified by comparing the Babs of ambient and thermo-denuded aerosols at 405 nm and 532 nm. The optical sub-saturated hygroscopic growth factor was derived from extinction and particle size distribution measurements at dry and elevated relative humidity. In addition, to explore the extent to which ammonia mediated chemistry leads to BrC formation, as suggested in recent laboratory studies(1,2), we performed an NH3 perturbation experiment in-situ for 1 week during the study, in which ambient aerosols were exposed to approximately 100 ppb NH3 with a residence time of ~ 3hr. The broader implications of these observational data at LRK will be discussed in the context of the concurrent gas and aerosol chemical

  19. Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate variability in the North Pacific Rim

    NASA Astrophysics Data System (ADS)

    Pokhrel, A.; Kawamura, K.; Seki, O.; Ono, K.; Matoba, S.; Shiraiwa, T.

    2015-12-01

    180 m long ice core (ca. 343 years old) was drilled in the saddle of the Aurora Peak of Alaska, which is located southeast of Fairbanks (63.52°N; 146.54°W, elevation: 2,825 m). Samples were directly transported to the Institute of Low Temperature Science, Hokkaido University and have been analyzed for monoterpene- and isoprene-SOA tracers using gas chromatograph (GC; HP 6890) and mass spectrometry system (GC/MS; Agilent). Ice core collected from mountain glacier has not been explored for SOA yet. We found significantly high concentrations of these tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylrythritol), which show historical trends with good correlation with each other since 1665-2008. They show positive correlations with sugar compounds (e.g., mannitol, glucose, fructose, inositol, and sucrose), and anti-correlations with diacids (e.g., C9), w-oxocarboxylic (wC4-wC9), a-dicarbonyls and low molecular weight fatty acids (LFAs) (e.g., C18:1). LFAs show strong correlations with MSA- and nss-SO42- in the same ice core. These results suggest source regions of SOA tracers and ice core chemistry of Alaska. Concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) have increased in the ice core after the Great Pacific Climate Shift (late 1970's). They show positive correlations with a-dicarbonyls and LFAs (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the surface microlayer are recorded in the ice core. Photochemical oxidation processes for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations (e.g., North Pacific Index) and we can look at a whole range of environmental parameters in parallel with the robust reconstructed temperature changes in the Northern Hemisphere.

  20. ORGANIC AEROSOL FORMATION IN THE HUMID, PHOTOCHEMICALLY-ACTIVE SOUTHEASTERN US: SOAS EXPERIMENTS AND SIMULATIONS

    EPA Science Inventory

    A better understanding of SOA formation, properties and behavior in the humid eastern U.S. including dependence on anthropogenic emissions (RFA Q #1, 2). More accurate air quality prediction enabling more accurate air quality management (EPA Goal #1). Scientific insights co...

  1. Chemical characterization of the main secondary organic aerosol (SOA) products formed through aqueous-phase photonitration of guaiacol

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

    2014-04-01

    Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e. burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed in the atmospheric gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the low-volatility SOA products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of H2O2 and nitrite. The formed guaiacol reaction products were concentrated by using solid-phase extraction (SPE) and then purified by means of semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state 1H, 13C and 2D nuclear magnetic resonance (NMR) spectroscopy and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of UV and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  2. Molecular-level Analysis of Size Resolved Secondary Organic Aerosol (SOA) Samples from CALNEX Bakersfield Using High Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    O'Brien, R. E.; Laskin, A.; Laskin, J.; Weber, R.; Goldstein, A. H.

    2011-12-01

    This project focuses on analyzing the identities of molecules that comprise oligomers in size resolved aerosol fractions. Since oligomers are generally too large and polar to be measured by typical GC/MS analysis, soft ionization with high resolution mass spectrometry is used to extend the range of observable compounds. Samples collected with a microorifice uniform deposition impactor (MOUDI) during CALNEX Bakersfield in June 2010 have been analyzed with nanospray desorption electrospray ionization (nano-DESI) and an Orbitrap mass spectrometer. The nano-DESI is a soft ionization technique that allows molecular ions to be observed and the Orbitrap has sufficient resolution to determine the elemental composition of almost all species above the detection limit. A large fraction of SOA is made up of high molecular weight oligomers which are thought to form through acid catalyzed reactions of photo-chemically processed volatile organic compounds (VOC). The formation of oligomers must be influenced by the VOCs available, the amount of atmospheric sulfate and nitrate, and the magnitude of photo-chemical processing, among other potential influences. We present the elemental composition of chemical species in SOA in the 0.18 to 0.32 micron size range, providing the first multi-day data set for the study of these oligomers in atmospheric samples. Possible formation pathways and sources of observed compounds will be examined by comparison to other concurrent measurements at the site.

  3. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas-wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas-wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

  4. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2015-09-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool which explicitly represents SOA formation and gas/wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas/wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up to 0.35 yield unit due to the loss of organic vapors to chamber walls.

  5. SOA Measurements vs. Models: a Status Report

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; de Gouw, J. A.

    2009-12-01

    The advent of fast and more detailed organic aerosol (OA) and VOC measurements in the last decade has allowed clearer model-measurement comparisons for OA and secondary OA (SOA). Here we summarize the patterns emerging from studies to date.

  6. At least 8 studies have reported a large (x5-10) underestimation of SOA for polluted regions when using traditional models (those developed until ~2006) (Heald GRL05, Volkamer GRL06, Johnson ACP06, Kleinman ACP08, Matsui JGR09, Dzepina ACP09, Hodzic ACP09, Tsimpidi ACP09). This is especially obvious when models are evaluated with the ΔOA/ΔCO ratio.
  7. Close to pollution sources, discrepancies of an order-of-magnitude in SOA lead to smaller discrepancies (often x2-3) for total OA due to the presence of primary OA (de Gouw EST09). Such OA discrepancies have been repeatedly observed (e.g. Vutukuru JGR06, McKeen JGR07&09, Heald JGR07, Fast ACP09, Hodzic ACP09).
  8. The discrepancy is reduced when recently-updated yields for aromatics (Ng ACP07) and SOA from glyoxal (Volkamer GRL07) are used, and is eliminated when using SOA formation from S/IVOC (Robinson Sci07) although with an overprediction of SOA at long aging times (Dzepina ACP09; Hodzic ACP09b). It is not clear whether the urban discrepancy is removed for the right reasons.
  9. 4 evaluations of biogenic SOA formed in unpolluted regions find reasonable agreement between SOA from traditional models and field measurements (Tunved Sci06; Hodzic ACP09; Chen GRL09; Slowik ACPD09). One evaluation reports a significant underprediction (Capes ACP09), although the amount of precursor reacted was difficult to ascertain for that case. The difference with the systematic underprediction observed for anthropogenic SOA may be due to the lack of primary S/IVOC in biogenic emissions, or to other reasons (NOx, SO2, POA, etc.).
  10. Comparisons for biogenic SOA formed in polluted regions are more complex. Several studies have reported a lack of clear influence of biogenic VOCs in SOA

  11. Hourly Measurement of the Concentration and Gas-Particle Partitioning of Oxygenated Organic Tracers in Ambient Aerosol: First Results from Berkeley, CA and Rural Alabama

    NASA Astrophysics Data System (ADS)

    Isaacman, G. A.; Kreisberg, N. M.; Yee, L.; Chan, A.; Worton, D. R.; Hering, S. V.; Goldstein, A. H.

    2013-12-01

    Hourly and bi-hourly time-resolved measurements of organic tracer compounds in ambient aerosols have been successfully used to elucidate sources and formation pathways of atmospheric particulate matter. Here we extend the Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SVTAG), a custom in-situ instrument that collects, desorbs, and analyzes ambient aerosol and semi-volatile compounds with hourly time resolution, to include on-line derivatization and a second, parallel collection cell that provides simultaneous collection of both particle-phase and particle-plus-gas-phase organic compounds. By introducing a silylating agent upon desorption, SVTAG can measure highly oxygenated compounds that are not easily detected using traditional gas chromatography including most of the previously reported oxygenated tracers for biogenic and anthropogenic secondary organic aerosol. The use of a pair of matched collection cells with parallel sampling and serial analysis provides direct gas-particle partitioning information. One cell collects the total organic fraction of compounds with volatilities lower than a C13 hydrocarbon, while the other cell samples through an activated carbon denuder to selectively remove the gas-phase components. Taken together these provide a direct measurement of gas-particle partitioning to yield a check on classical absorption based partitioning theory while deviations from this theory provide constraints on other driving factors in aerosol formation chemistry, such as oligomerization, salt formation, and acidity. We present here the capabilities and utility of the dual cell SVTAG with derivatization, with chemical insights gained from initial tests on ambient Berkeley air and the first results from a rural site in Alabama obtained during the Southern Oxidant and Aerosol Study (SOAS). Tracers for varying isoprene oxidation pathways are used to explore the influence of anthropogenic emissions; concentrations of 2-methyltetrols and 2-methyl

  12. Gas-particle partitioning of organic acids during the Southern Oxidant and Aerosol Study (SOAS): measurements and modeling

    NASA Astrophysics Data System (ADS)

    Thompson, S.; Yatavelli, R.; Stark, H.; Kimmel, J.; Krechmer, J.; Day, D. A.; Isaacman, G. A.; Goldstein, A. H.; Khan, M. A. H.; Holzinger, R.; Lopez-Hilfiker, F.; Mohr, C.; Thornton, J. A.; Jayne, J. T.; Worsnop, D. R.; Jimenez, J. L.

    2014-12-01

    Gas-Particle partitioning measurements of organic acids were carried out during the Southern Oxidant and Aerosol Study (SOAS, June-July 2013) at the Centerville, AL Supersite in the Southeast US, a region with significant isoprene and terpene emissions. Organic acid measurements were made with a Chemical Ionization High Resolution Time-of-Flight Mass Spectrometer (HRToF-CIMS) with a Filter Inlet for Gases and AEROsols (FIGAERO) and acetate (CH3COO-) as the reagent ion. We investigate both individual species and bulk organic acids and partitioning to organic and water phases in the aerosol. Measured partitioning is compared to data from three other instruments that can also quantify gas-particle partitioning with high time resolution: another HRToF-CIMS using iodide (I-) as the reagent ion to ionize acids and other highly oxidized compounds, a Semivolatile Thermal Desorption Aerosol GC/MS (SV-TAG), and a Thermal Desorption Proton Transfer Time-of-Flight Mass Spectrometer (TD-PTRMS The partitioning measurements for three of the instruments are generally consistent, with results in the same range for most species and following similar temporal trends and diurnal cycles. The TD-PTRMS measures on average ½ the partitioning to the particle phase of the acetate CIMS. Both the measurements and the model of partitioning to the organic phase respond quickly to temperature, and the model agrees with the measured partitioning within the error of the measurement for multiple compounds, although many compounds do not match the modeled partitioning, especially at lower m/z. This discrepancy may be due to thermal decomposition of larger molecules into smaller ones when heated.

  13. Remote Sensing of Glyoxal as a New Atmospheric Tracer for VOC Chemistry and Secondary Organic Aerosol Formation in the Mexico City Metropolitan Area

    NASA Astrophysics Data System (ADS)

    Volkamer, R.; Molina, L. T.; Molina, M. J.; Shirley, T.; Lesher, R.; Brune, W.; Dzepina, K.; Jimenez, J.

    2004-12-01

    Air pollution in the Mexico City Metropolitan Area (MCMA) is intimately linked with the photochemical transformation of primary pollutants like VOC (volatile organic compounds) and NOx, which gives rise to the formation of secondary pollutants such as ozone and secondary organic aerosol (SOA) and their associated adverse effects on human health. As part of the field campaign held in the MCMA in April/May 2003, state-of-the-art measurement techniques including open-path Differential Optical Absorption Spectroscopy (DOAS), spectroradiometry, Aerosol Mass Spectrometry (AMS) and Laser Induced Fluorescence (LIF) were located at the National Center for Environmental Research and Training (CENICA) in Mexico City to characterize the gas-phase and aerosol-phase composition of relevance to the formation of ozone and SOA. A first-ever spectroscopic detection of glyoxal (DOAS) in the atmosphere is described. Glyoxal is shown to be a very useful new photochemical tracer for the chemistry of VOC. The time-resolved glyoxal measurements reveal a very efficient VOC oxidation process during morning hours, which is found to be relevant for overall smog formation later in the day. In combination with measurements of the radical precursor substances HONO, HCHO, ozone (DOAS), their respective J-values (spectroradiometry), OH- and HO2-radical concentrations (LIF), speciated aromatic hydrocarbons (DOAS) and chemical composition of the aerosol phase (AMS), the glyoxal data enables assessment of the role of VOC oxidation in the formation of secondary pollutants in the gas- and aerosol-phase by placing a lower limit on the extend of VOC turnover.

  14. Submicron aerosol organic functional groups, ions, and water content at the Centreville SEARCH site (Alabama), during SOAS campaign

    NASA Astrophysics Data System (ADS)

    Ruggeri, G.; Ergin, G.; Modini, R. L.; Takahama, S.

    2013-12-01

    The SOAS campaign was conducted from June 1 to July 15 of 2013 in order to understand the relationship between biogenic and anthropogenic emissions in the South East US1,2. In this study, the organic and inorganic composition of submicron aerosol in the Centreville SEARCH site was measured by Fourier Transform Infrared Spectroscopy (FTIR) and the Ambient Ion Monitor (AIM; URG Corporation), whereas the aerosol water content was measured with a Dry Ambient Aerosol Size Spectrometer (DAASS)3. Organic functional group analysis was performed on PM1 aerosol selected by cyclone and collected on teflon filters with a time resolution of 4-12 hours, using one inlet heated to 50 °C and the other operated either at ambient temperature or 70 °C 4. The AIM measured both condensed and gas phase composition with a time resolution of 1 hour, providing partitioning behavior of inorganic species such as NH3/NH4+, HNO3/NO3-. These measurements collectively permit calculation of pure-component vapor pressures of candidate organic compounds and activity coefficients of interacting components in the condensed phase, using models such as SIMPOL.15, E-AIM6, and AIOMFAC7. From these results, the water content of the aerosol is predicted, and a comparison between modeled and measured partitioning of inorganic compounds and water vapor are discussed, in addition to organic aerosol volatility prediction based on functional group analysis. [1]- Goldstein, A.H., et al., Biogenic carbon and anthropogenic pollutants combine to form a cooling haze over the southeastern United States. Proceedings of the National Academy of Sciences of the United States of America, 2009. 106(22), 8835-8840. [2]- Carlton, A.G., Turpin, B.J., 2013. Particle partitioning potential of organic compounds is highest in the Eastern US and driven by anthropogenic water. Atmospheric Chemistry and Physics Discussions 13, 12743-12770. [3]- Khlystov, A., Stanier, C.O., Takahama, S., Pandis, S.N., 2005. Water content of ambient

  15. Carbonaceous aerosol tracers in ice-cores record multi-decadal climate oscillations

    PubMed Central

    Seki, Osamu; Kawamura, Kimitaka; Bendle, James A. P.; Izawa, Yusuke; Suzuki, Ikuko; Shiraiwa, Takayuki; Fujii, Yoshiyuki

    2015-01-01

    Carbonaceous aerosols influence the climate via direct and indirect effects on radiative balance. However, the factors controlling the emissions, transport and role of carbonaceous aerosols in the climate system are highly uncertain. Here we investigate organic tracers in ice cores from Greenland and Kamchatka and find that, throughout the period covered by the records (1550 to 2000 CE), the concentrations and composition of biomass burning-, soil bacterial- and plant wax- tracers correspond to Arctic and regional temperatures as well as the warm season Arctic Oscillation (AO) over multi-decadal time-scales. Specifically, order of magnitude decreases (increases) in abundances of ice-core organic tracers, likely representing significant decreases (increases) in the atmospheric loading of carbonaceous aerosols, occur during colder (warmer) phases in the high latitudinal Northern Hemisphere. This raises questions about causality and possible carbonaceous aerosol feedback mechanisms. Our work opens new avenues for ice core research. Translating concentrations of organic tracers (μg/kg-ice or TOC) from ice-cores, into estimates of the atmospheric loading of carbonaceous aerosols (μg/m3) combined with new model constraints on the strength and sign of climate forcing by carbonaceous aerosols should be a priority for future research. PMID:26411576

  16. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: Explicit modeling of SOA formation from alkane and alkene oxidation

    DOE PAGESBeta

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-08

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chambermore » experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. Furthermore, this work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.« less

  17. Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

    NASA Astrophysics Data System (ADS)

    Riedel, T. P.; Lin, Y.-H.; Zhang, Z.; Chu, K.; Thornton, J. A.; Vizuete, W.; Gold, A.; Surratt, J. D.

    2015-10-01

    Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall-losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

  18. Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

    NASA Astrophysics Data System (ADS)

    Riedel, T. P.; Lin, Y.-H.; Zhang, Z.; Chu, K.; Thornton, J. A.; Vizuete, W.; Gold, A.; Surratt, J. D.

    2016-02-01

    Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

  19. Potential Aerosol Mass (PAM) flow reactor measurements of SOA formation in a Ponderosa Pine forest in the southern Rocky Mountains during BEACHON-RoMBAS

    NASA Astrophysics Data System (ADS)

    Palm, B. B.; Ortega, A. M.; Campuzano Jost, P.; Day, D. A.; Kaser, L.; Karl, T.; Jud, W.; Hansel, A.; Fry, J.; Brown, S. S.; Zarzana, K. J.; Dube, W. P.; Wagner, N.; Draper, D.; Brune, W. H.; Jimenez, J. L.

    2012-12-01

    A Potential Aerosol Mass (PAM) photooxidation flow reactor was used in combination with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer to characterize biogenic secondary organic aerosol (SOA) formation in a terpene-dominated forest during the July-August 2011 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) field campaign at the U.S. Forest Service Manitou Forest Observatory, Colorado, as well as in corresponding laboratory experiments. In the PAM reactor, a chosen oxidant (OH, O3, or NO3) was generated and controlled over a range of values up to 10,000 times ambient levels. High oxidant concentrations accelerated the gas-phase, heterogeneous, and possibly aqueous oxidative aging of volatile organic compounds (VOCs), inorganic gases, and existing aerosol, which led to repartitioning into the aerosol phase. PAM oxidative processing represented from a few hours up to ~20 days of equivalent atmospheric aging during the ~3 minute reactor residence time. During BEACHON-RoMBAS, PAM photooxidation enhanced SOA at intermediate OH exposure (1-10 equivalent days) but resulted in net loss of OA at long OH exposure (10-20 equivalent days), demonstrating the competing effects of functionalization vs. fragmentation (and possibly photolysis) as aging increased. PAM oxidation also resulted in f44 vs. f43 and Van Krevelen diagram (H/C vs. O/C) slopes similar to ambient oxidation, suggesting the PAM reactor employs oxidation pathways similar to ambient air. Single precursor aerosol yields were measured using the PAM reactor in the laboratory as a function of organic aerosol concentration and reacted hydrocarbon amounts. When applying the laboratory PAM yields with complete consumption of the most abundant VOCs measured at the forest site (monoterpenes, sesquiterpenes, MBO, and toluene), a simple model underpredicted the amount of SOA formed in the PAM reactor in the

  20. Temperature Effects on Secondary Organic Aerosol (SOA) from the Dark Ozonolysis and Photo-Oxidation of Isoprene.

    PubMed

    Clark, Christopher H; Kacarab, Mary; Nakao, Shunsuke; Asa-Awuku, Akua; Sato, Kei; Cocker, David R

    2016-06-01

    Isoprene is globally the most ubiquitous nonmethane hydrocarbon. The biogenic emission is found in abundance and has a propensity for SOA formation in diverse climates. It is important to characterize isoprene SOA formation with varying reaction temperature. In this work, the effect of temperature on SOA formation, physical properties, and chemical nature is probed. Three experimental systems are probed for temperature effects on SOA formation from isoprene, NO + H2O2 photo-oxidation, H2O2 only photo-oxidation, and dark ozonolysis. These experiments show that isoprene readily forms SOA in unseeded chamber experiments, even during dark ozonolysis, and also reveal that temperature affects SOA yield, volatility, and density formed from isoprene. As temperature increases SOA yield is shown to generally decrease, particle density is shown to be stable (or increase slightly), and formed SOA is shown to be less volatile. Chemical characterization is shown to have a complex trend with both temperature and oxidant, but extensive chemical speciation are provided. PMID:27175613

  21. Secondary organic aerosols over oceans via oxidation of isoprene and monoterpenes from Arctic to Antarctic

    PubMed Central

    Hu, Qi-Hou; Xie, Zhou-Qing; Wang, Xin-Ming; Kang, Hui; He, Quan-Fu; Zhang, Pengfei

    2013-01-01

    Isoprene and monoterpenes are important precursors of secondary organic aerosols (SOA) in continents. However, their contributions to aerosols over oceans are still inconclusive. Here we analyzed SOA tracers from isoprene and monoterpenes in aerosol samples collected over oceans during the Chinese Arctic and Antarctic Research Expeditions. Combined with literature reports elsewhere, we found that the dominant tracers are the oxidation products of isoprene. The concentrations of tracers varied considerably. The mean average values were approximately one order of magnitude higher in the Northern Hemisphere than in the Southern Hemisphere. High values were generally observed in coastal regions. This phenomenon was ascribed to the outflow influence from continental sources. High levels of isoprene could emit from oceans and consequently have a significant impact on marine SOA as inferred from isoprene SOA during phytoplankton blooms, which may abruptly increase up to 95 ng/m3 in the boundary layer over remote oceans. PMID:23880782

  22. Probing Molecular Associations of Secondary Organic Aerosol (SOA) Samples from CalNex 2010 with Nano-DESI High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    O'Brien, R. E.; Nguyen, T. B.; Laskin, A.; Laskin, J.; Hayes, P. L.; Liu, S.; Jimenez, J. L.; Russell, L. M.; Nizkorodov, S.; Goldstein, A. H.

    2012-12-01

    This project focuses on analyzing the identities of molecules that comprise oligomers in size resolved aerosol fractions. Since oligomers are generally too large and polar to be measured by typical GC/MS analysis, soft ionization with high resolution mass spectrometry is used to extend the range of observable compounds. Samples collected during CalNex 2010 in Bakersfield and Los Angeles and secondary organic aerosol (SOA) produced in a photochemical chamber by photooxidation of diesel (DSL) fuel and isoprene (ISO) under humid, high-NOx conditions have been analyzed with nanospray desorption electrospray ionization (nano-DESI) and a high-resolution Orbitrap mass spectrometer. The nano-DESI is a soft ionization technique that allows molecular ions to be observed and the Orbitrap has sufficient resolution to determine the elemental composition of almost all species above the detection limit. A large fraction of SOA is made up of high molecular weight oligomers which are thought to form through acid catalyzed reactions of photo-chemically processed volatile organic compounds (VOC). The formation of oligomers is influenced by the VOCs available, the amount of atmospheric sulfate and nitrate, and the magnitude of photo-chemical processing, among other potential influences. We present the elemental composition of chemical species in size resolved SOA samples with six-hour time resolution, providing the first time resolved data set for the study of these oligomers in atmospheric samples. We present a comparison of the degree of overlap between the ambient and chamber experiments as a novel method to examine sources for this fraction of SOA. Possible formation pathways and sources of observed compounds are analyzed by comparison to other concurrent measurements at the site.

  23. Influence of humidity, temperature, and radicals on the formation and thermal properties of secondary organic aerosol (SOA) from ozonolysis of β-pinene.

    PubMed

    Emanuelsson, Eva U; Watne, Ågot K; Lutz, Anna; Ljungström, Evert; Hallquist, Mattias

    2013-10-10

    The influence of water and radicals on SOAs produced by β-pinene ozonolysis was investigated at 298 and 288 K using a laminar flow reactor. A volatility tandem differential mobility analyzer (VTDMA) was used to measure the evaporation of the SOA, enabling the parametrization of its volatility properties. The parameters extracted included the temperature at which 50% of the aerosol had evaporated (T(VFR0.5)) and the slope factor (S(VFR)). An increase in S(VFR) indicates a broader distribution of vapor pressures for the aerosol constituents. Reducing the reaction temperature increased S(VFR) and decreased T(VFR0.5) under humid conditions but had less effect on T(VFR0.5) under dry conditions. In general, higher water concentrations gave lower T(VFR0.5) values, more negative S(VFR) values, and a reduction in total SOA production. The radical conditions were changed by introducing OH scavengers to generate systems with and without OH radicals and with different [HO2]/[RO2] ratios. The presence of a scavenger and lower [HO2]/[RO2] ratio reduced SOA production. Observed changes in S(VFR) values could be linked to the more complex chemistry that occurs in the absence of a scavenger and indicated that additional HO2 chemistry gives products with a wider range of vapor pressures. Updates to existing ozonolysis mechanisms with routes that describe the observed responses to water and radical conditions for monoterpenes with endocyclic and exocyclic double bonds are discussed. PMID:24001129

  24. Ozone reactivity of biogenic volatile organic compound (BVOC) emissions during the Southeast Oxidant and Aerosol Study (SOAS)

    NASA Astrophysics Data System (ADS)

    Park, J.; Guenther, A. B.; Helmig, D.

    2013-12-01

    Recent studies on atmospheric chemistry in the forest environment showed that the total reactivity by biogenic volatile organic compound (BVOC) emission is still not well understood. During summer 2013, an intensive field campaign (Southeast Oxidant and Aerosol Study - SOAS) took place in Alabama, U.S.A. In this study, an ozone reactivity measurement system (ORMS) was deployed for the direct determination of the reactivity of foliage emissions. The ORMS is a newly developed measurement approach, in which a known amount of ozone is added to the ozone-free air sample stream, with the ORMS measuring ozone concentration difference between before and after a glass flask flow tube reaction vessel (2-3 minutes of residence time). Emissions were also collected onto adsorbent cartridges to investigate the discrepancy between total ozone reactivity observation and reactivity calculated from identified BVOC. Leaf and canopy level experiments were conducted by deploying branch enclosures on the three dominant tree species at the site (i.e. liquidambar, white oak, loblolly pine) and by sampling ambient air above the forest canopy. For the branch enclosure experiments, BVOC emissions were sampled from a 70 L Teflon bag enclosure, purged with air scrubbed for ozone, nitrogen oxides. Each branch experiment was performed for 3-5 days to collect at least two full diurnal cycle data. In addition, BVOCs were sampled using glass tube cartridges for 2 hours during daytime and 3 - 4 hours at night. During the last week of campaign, the inlet for the ORMS was installed on the top of scaffolding tower (~30m height). The ozone loss in the reactor showed distinct diurnal cycle for all three tree species investigated, and ozone reactivity followed patterns of temperature and light intensity.

  25. Investigation of the tracers for plastic-enriched waste burning aerosols

    NASA Astrophysics Data System (ADS)

    Kumar, Sudhanshu; Aggarwal, Shankar G.; Gupta, Prabhat K.; Kawamura, Kimitaka

    2015-05-01

    To better identify the tracers for open-waste burning (OWB) aerosols, we have conducted aerosol sampling at 2 landfill sites, i.e., Okhla and Bhalswa in New Delhi. The metals such as, As, Cd, Sb and Sn, which have been observed almost negligible in remote aerosols, are found abundantly in these OWB aerosol samples (n = 26), i.e., 60 ± 65, 41 ± 53, 537 ± 847 and 1325 ± 1218 ng m-3, respectively. Samples (n = 20) collected at urban locations in New Delhi, i.e., at Employees' State Insurance (ESI) hospital and National Physical Laboratory (NPL) also show high abundances of these metals in the particles. Filter samples are also analyzed for water-soluble dicarboxylic acids (C2-C12) and related compounds (oxocarboxylic acids and α-dicarbonyls). Terephthalic acid (tPh) was found to account for more than 77% of total diacids determined in OWB aerosols. However, such a high abundance of tPh is not observed in aerosols collected at urban sites. Instead, phthalic acid (Ph) was found as the third/fourth most abundant diacid (∼3%) following C2 (>70%) and C4 (>12%) in these waste burning influenced urban aerosols. A possible secondary formation pathway of Ph by photo-degradation of phthalate ester (di-2-ethylhexyl phthalate) in plastic-waste burning aerosol is suggested. Ionic composition of OWB aerosols showed that Cl- is the most abundant ion (40 ± 8% of total ions determined). The correlation studies of the potential metals with the organic tracers of garbage burning, i.e., phthalic, isophthalic and terephthalic acids show that especially Sn can be used as marker for tracing the plastic-enriched waste burning aerosols.

  1. Aqueous Secondary Organic Aerosol (aqSOA) Formation By Radical Reactions: Model Studies Comparing the Role of OH Versus Organic Radicals

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Renard, P.; Reed Harris, A.; Vaida, V.; Monod, A.

    2014-12-01

    Chemical reactions in the aqueous phase are thought to significantly contribute to ambient aerosol mass under specific conditions. Results from many laboratory studies suggest that these reactions are efficiently initiated by the OH radical and lead to high molecular weight compounds (oligomers). Recent laboratory experiments have shown that methyl vinyl ketone (MVK) can form oligomers in high yield in aqueous solutions similar to aerosol water. Additional experiments have shown that the direct photolysis of pyruvic acid can generate organic radicals that initiate similar oligomer products upon oxidation of MVK (Renard et al., submitted). Sources of the OH radical in the aerosol aqueous phase include the direct uptake from the gas phase, Fenton reactions and, to a smaller extent, direct photolyses of hydrogen peroxide and nitrate. Recent model studies imply that under many conditions, aqSOA formation might be oxidant-limited since these OH(aq) sources are not sufficient to provide a continuous OH supply. This limitation can be (partially) removed if additional radical sources in the multiphase system are considered. Exemplary, we include the direct photolysis of aqueous pyruvic acid as a proxy for possible other radical sources. Model results will be shown and consequences for aqSOA formation and processing under ambient conditions will be discussed.

  2. SOA Measurements vs. Models: A Status Report

    NASA Astrophysics Data System (ADS)

    Jimenez, Jose-Luis; de Gouw, Joost; Hodzic, Alma

    2010-05-01

    The advent of fast and chemically-resolved organic aerosol (OA) and VOC measurements in the last decade has allowed more detailed model-measurement comparisons for OA and secondary OA (SOA). Large model underpredictions have been reported for SOA at many locations, but this is not always the case. Here we summarize the patterns emerging from studies to date, focusing on studies that use highly time and/or chemically resolved OA measurements. The model-measurement comparisons exhibit clear patterns depending on the region of the atmosphere. • At least 8 studies have reported a large (x5-10) underestimation of SOA for polluted regions when using traditional models (those developed until ~2006) (Heald GRL05, Volkamer GRL06, Johnson ACP06, Kleinman ACP08, Matsui JGR09, Dzepina ACP09, Hodzic ACP09, Tsimpidi ACP09). This is especially obvious when models are evaluated with the ΔOA/ΔCO ratio. • Close to pollution sources, discrepancies of an order-of-magnitude in SOA lead to smaller discrepancies (often x2-3) for total OA due to the presence of primary OA (de Gouw EST09). Such OA discrepancies have been repeatedly observed (e.g. Vutukuru JGR06, McKeen JGR07&09, Heald JGR07, Fast ACP09, Hodzic ACP09). • The discrepancy is reduced when recently-updated yields for aromatics (Ng ACP07) and SOA from glyoxal (Volkamer GRL07) are used, and is eliminated when using SOA formation from S/IVOC (Robinson Sci07) although with an overprediction of SOA at long aging times (Dzepina ACP09; Hodzic ACP10), especially with the Grieshop (ACP09) update of the Robison mechanism (Hodzic10). It is not clear whether the urban discrepancy is removed for the right reasons. • 4 evaluations of biogenic SOA formed in unpolluted regions find reasonable agreement between SOA from traditional models and field measurements (Tunved Sci06; Hodzic ACP09; Chen GRL09; Slowik ACPD09). One evaluation reports a significant underprediction (Capes ACP09), although the amount of precursor reacted was

  3. Characterization of ambient aerosols during the Southern Oxidant and Aerosol Study (SOAS) in Centreville, AL with a high-resolution time-of-flight aerosol mass spectrometer Basak Karakurt Cevik1, Yu Jun Leong1, Carlos Hernandez1, Robert Griffin1 1 Rice University, CEE Department, 6100 Main St., Houston, TX 77005, USA

    NASA Astrophysics Data System (ADS)

    Karakurt Cevik, B.; Leong, Y.; Hernandez, C.; Griffin, R. J.

    2013-12-01

    An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a Brechtel Manufacturing, Inc. particle-into-liquid sampler (PILS) were deployed at a rural location in Centreville, AL, from 1 June to 15 July 2013 as a part of the Southern Oxidant and Aerosol Study (SOAS). PILS samples were analyzed with Dionex ion chromatographs. The data will allow us to characterize the temporal characteristics of the concentrations and size distributions of non-refractory (NR) chemical species in the ambient submicron particles. Preliminary analysis of the data indicates that the sub-micron particulate matter is highly dominated by organic matter with a relatively high state of oxidation and it is followed by smaller contributions from sulfate and ammonium. In order to investigate the processes and sources that lead to observed aerosol concentrations at the site, the time series will be analyzed in conjunction with additional trace gas, aerosol, and meteorological measurements. The region is known to have high biogenic volatile organic compounds (VOCs) emissions and many of these biogenic VOCs (BVOCs) are important secondary organic aerosol (SOA) precursors. Preliminary data from the HR-ToF-AMS indicates the importance of oxidized organic aerosol during SOAS. The study will also focus on the importance of the SOA in the total organic fraction and the effect of atmospheric processing on the chemical composition of the organic fraction.

  4. Determination of aromatic tracer compounds for environmental tobacco smoke aerosol by two step laser mass spectrometry

    NASA Astrophysics Data System (ADS)

    Morrical, Brad D.; Zenobi, Renato

    Cigarette smoking is a major cause of indoor aerosol pollution. Determination of exposure to environmental tobacco smoke (ETS) aerosol is critical to understanding health effects. Sizing studies have shown that ETS has a size distribution that is efficiently deposited into the lungs and can therefore provide effective delivery of carcinogenic compounds into the human body. Two-step laser mass spectrometry is used to analyze aromatic compounds on aerosols collected from a smoking lobby. The determination and suitability of ETS tracers on aerosols is examined. Additionally, the transport of aerosol from the smoking lobby is examined to determine what effect deposition and dilution have on the mass spectrum observed. Results from the analysis of ETS, both from lobby samples and direct cigarette sampling, show that several unique peaks are present in the mass spectrum when compared to other combustion sources, such as automobiles and diesel trucks. In particular, ions at m/ z 118, 132, 146, and 160 are consistently present and are not found in other combustion sources. For the indoor environment, where chemical transformation is much less rapid than in the outdoor environment, these ions were found to be present as soon as the first smokers appeared and persisted over the course of the day. Aerosol samples taken in the morning prior to the presence of smokers in the lobby reveal the presence of skeletal PAHs, indicative of outdoor urban traffic aerosol penetration into the building.

  5. How will SOA change in the future?

    NASA Astrophysics Data System (ADS)

    Lin, Guangxing; Penner, Joyce E.; Zhou, Cheng

    2016-02-01

    Secondary organic aerosol (SOA) plays a significant role in the Earth system by altering its radiative balance. Here we use an Earth system model coupled with an explicit SOA formation module to estimate the response of SOA concentrations to changes in climate, anthropogenic emissions, and human land use in the future. We find that climate change is the major driver for SOA change under the representative concentration pathways for the 8.5 future scenario. Climate change increases isoprene emission rate by 18% with the effect of temperature increases outweighing that of the CO2 inhibition effect. Annual mean global SOA mass is increased by 25% as a result of climate change. However, anthropogenic emissions and land use change decrease SOA. The net effect is that future global SOA burden in 2100 is nearly the same as that of the present day. The SOA concentrations over the Northern Hemisphere are predicted to decline in the future due to the control of sulfur emissions.

  6. Concentration, distribution and variation of polar organic aerosol tracers in Ya'an, a middle-sized city in western China

    NASA Astrophysics Data System (ADS)

    Li, Li; Dai, Dongjue; Deng, Shihuai; Feng, Jialiang; Zhao, Min; Wu, Jun; Liu, Lu; Yang, Xiaohui; Wu, Sishi; Qi, Hui; Yang, Gang; Zhang, Xiaohong; Wang, Yingjun; Zhang, Yanzong

    2013-02-01

    PM2.5 (particulate matter with an aerodynamic diameter < 2.5 μm) and TSP (total suspended particulates) aerosol samples were collected in Ya'an, a middle-sized city with extensive wood resources in Southwestern China, to characterize the contribution of secondary organic aerosols (SOA) to the regional troposphere, the composition of the organic tracers as well as factors affecting their concentrations. A total of 34 samples were gathered on the Campus of Sichuan Agricultural University (SAU, urban site, in the city zone of Ya'an), while 49 samples were collected at Baima Spring Scenic Area (BSSA, forest site, situated about 30 km to the northeast of SAU) during June to July, 2010. Using GC/MS analysis with prior trimethylsilylation, organic tracers including isoprene oxidation products (2-methyltetrols, C5-alkene triols and 2-methylglyceric acid), α-/β-pinene oxidation products (norpinic acid, 3-hydroxyglutaric acid, 3-hydroxy-4,4-dimethylglutaric acid, and 3-methyl-1,2,3- butanetricarboxylic acid), a sesquiterpene oxidation product (β-caryophyllinic acid), sugars (glucose and fructose), sugar alcohols (arabitol, mannitol, erythritol, sorbitol and xylitol), anhydrosugars (levoglucosan, mannosan and galactosan) and malic acid were determined. The factors that could potentially affect the SOA tracer concentrations, i.e. trace gases (SO2, NOx, O3, NH3), aerosol acidity and meteorological parameters, were monitored. The results showed that the concentrations of total isoprene oxidation products were 72 and 82 ng/m3 at the two sampling locations, with 29 ± 18, 37 ± 9, 6 ± 2 ng/m3 at SAU and 57 ± 34, 33 ± 33, 4 ± 2 ng/m3 at BSSA for 2-methyltetrols, C5-alkene triols and 2-methylglyceric acid respectively. Compared with the concentrations of isoprene oxidation products, those of α-/β-pinene oxidation products and β-caryophyllinic acid were much lower, being 6 ± 33 and 0.5 ± 1.9 ng/m3 at SAU, and 9 ± 14 and 1.0 ± 1.2 ng/m3 at BSSA, respectively. The unique

  7. New tracer compounds for secondary organic aerosol formation from β-caryophyllene oxidation

    NASA Astrophysics Data System (ADS)

    van Eijck, Anna; Opatz, Till; Taraborrelli, Domenico; Sander, Rolf; Hoffmann, Thorsten

    2013-12-01

    Five products from β-caryophyllene oxidation (β-caryophyllonic acid (I), 3,3-dimethyl-2-(3-oxobutyl)cyclobutanecarboxylic acid (βCA198) (II), β-nocaryophyllonic acid (III), β-caryophyllinic acid (IV), and 2-(2-carboxyethyl)-3,3-dimethylcyclobutanecarboxylic acid (βCA200) (V)) were synthesized and their structures confirmed by nuclear magnetic resonance spectroscopy. Reaction chamber experiments with β-caryophyllene at two different ozone mixing ratios were performed and the carboxylic acid oxidation products in the particle phase were characterized by APCI-MS and HPLC-ESI-MS. All five synthesized acids were found as β-caryophyllene oxidation products in the reaction chamber aerosol. The main oxidation products of the reaction chamber experiments were β-14-hydroxynocaryophyllonic acid, β-nocaryophyllonic acid (III) and βCA198 (II). Product yields of the acids were estimated based on the chamber experiments and the application of the atmospheric chemistry box model CAABA/MECCA. Finally, ambient aerosol samples taken during the HUMPPA campaign in Hyytiälä, Finland in summer 2010 were analysed for the carboxylic acid β-caryophyllene oxidation products. All five synthesized compounds were detected and were quantified in the ambient aerosol samples. The major β-caryophyllene carboxylic acid oxidation products in the ambient air samples were β-nocaryophyllonic acid (III) and βCA198 (II) with concentrations in the range of about 0.2-14 ng m-3 and 0.8-6.8 ng m-3. The fact that the concentrations of these two acids in ambient aerosol are generally higher than the concentration of β-caryophyllinic acid (IV) (often used in previous studies as oxidation tracer) with a concentration of about 0.16 ng m-3 leads to the conclusion that these two acids are better suited as tracer compounds for β-caryophyllene secondary organic aerosol formation.

  8. Aircraft observations of water-soluble dicarboxylic acids in the aerosols over China

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Lin; Kawamura, Kimitaka; Qing Fu, Ping; Boreddy, Suresh K. R.; Watanabe, Tomomi; Hatakeyama, Shiro; Takami, Akinori; Wang, Wei

    2016-05-01

    Vertical profiles of dicarboxylic acids, related organic compounds and secondary organic aerosol (SOA) tracer compounds in particle phase have not yet been simultaneously explored in East Asia, although there is growing evidence that aqueous-phase oxidation of volatile organic compounds may be responsible for the elevated organic aerosols (OA) in the troposphere. Here, we found consistently good correlation of oxalic acid, the most abundant individual organic compounds in aerosols globally, with its precursors as well as biogenic-derived SOA compounds in Chinese tropospheric aerosols by aircraft measurements. Anthropogenically derived dicarboxylic acids (i.e., C5 and C6 diacids) at high altitudes were 4-20 times higher than those from surface measurements and even occasionally dominant over oxalic acid at altitudes higher than 2 km, which is in contrast to the predominance of oxalic acid previously reported globally including the tropospheric and surface aerosols. This indicates an enhancement of tropospheric SOA formation from anthropogenic precursors. Furthermore, oxalic acid-to-sulfate ratio maximized at altitudes of ˜ 2 km, explaining aqueous-phase SOA production that was supported by good correlations with predicted liquid water content, organic carbon and biogenic SOA tracers. These results demonstrate that elevated oxalic acid and related SOA compounds from both the anthropogenic and biogenic sources may substantially contribute to tropospheric OA burden over polluted regions of China, implying aerosol-associated climate effects and intercontinental transport.

  9. Evaluation of secondary organic aerosol formation in winter

    NASA Astrophysics Data System (ADS)

    Strader, Ross; Lurmann, Fred; Pandis, Spyros N.

    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.

  10. Total sugars in atmospheric aerosols: An alternative tracer for biomass burning

    NASA Astrophysics Data System (ADS)

    Scaramboni, C.; Urban, R. C.; Lima-Souza, M.; Nogueira, R. F. P.; Cardoso, A. A.; Allen, A. G.; Campos, M. L. A. M.

    2015-01-01

    Ambient aerosols were collected in an agro-industrial region of São Paulo State (Brazil) between May 2010 and February 2012 (n = 87). The atmosphere of the study region is highly affected by the emissions of gases and particles from sugar and fuel ethanol production, because part of the area planted with sugarcane is still burned before manual harvesting. This work proposes the quantification of total sugars as an alternative chemical tracer of biomass burning, instead of levoglucosan. The quantification of total sugars requires a small area of a filter sample and a simple spectrophotometer, in contrast to the determination of levoglucosan, which is much more complex and time-consuming. Total sugars concentrations in the aerosol ranged from 0.28 to 12.5 μg m-3, and (similarly to levoglucosan) the emissions were significantly higher at night and during the sugarcane harvest period, when most agricultural fires occur. The linear correlation between levoglucosan and total sugars (r = 0.612) was stronger than between levoglucosan and potassium (r = 0.379), which has previously been used as a biomass burning tracer. In the study region, potassium is used in fertilizers, and this, together with substantial soil dust resuspension, makes potassium unsuitable for use as a tracer. On average, ca. 40% of the total sugars was found in particles smaller than 0.49 μm. By including data from previous work, it was possible to identify from 35 to 42% of the total sugars, with biomass burning making the largest contribution. The high solubility in water of these sugars means that determination of their concentrations could also provide important information concerning the hydrophilic properties of atmospheric aerosols.

  11. Insight into the numerical challenges of implementing 2-dimensional SOA models in atmospheric chemical transport models

    NASA Astrophysics Data System (ADS)

    Napier, W. J.; Ensberg, J. J.; Seinfeld, J. H.

    2014-10-01

    The new generation of secondary organic aerosol (SOA) models that represent gas- and particle-phase chemistry and thermodynamic partitioning using discrete two-dimensional grids (e.g. SOM, 2D-VBS) cannot be efficiently implemented into three-dimensional atmospheric chemical transport models (CTMs) due to the large number of bins (tracers) required. In this study, we introduce a novel mathematical framework, termed the Oxidation State/Volatility Moment Method, that is designed to address these computational burdens so as to allow the new generation of SOA models to be implemented into CTMs. This is accomplished by mapping the two-dimensional grids onto probability distributions that conserve carbon and oxygen mass. Assessment of the Moment Method strengths (speed, carbon and oxygen conservation) and weaknesses (numerical drift) provide valuable insight that can guide future development of SOA modules for atmospheric CTMs.

  12. Composition and sources of organic tracers in aerosol particles of industrial central India

    NASA Astrophysics Data System (ADS)

    Giri, Basant; Patel, Khageshwar S.; Jaiswal, Nitin K.; Sharma, Saroj; Ambade, Balram; Wang, Wentao; Simonich, Staci L. Massey; Simoneit, Bernd R. T.

    2013-02-01

    Organic aerosols are important atmospheric components, and their formation and sources represent important aspects of urban air quality and health effects. Asia, including India, is the largest global source of aerosol particles due to regional natural advection (e.g. desert and soil dust) and anthropogenic activities (e.g. emissions from traffic, industry and burning of coal, biomass and agricultural waste) that generate vast amounts of particulate matter (PM) significantly contributing to climate change. This article reports on the distributions, concentrations, and sources of organic compounds (i.e., alkanes, carboxylic acids, carbonyl compounds, alcohols, plasticizers, PAHs, biomarkers) of PM in the ambient atmosphere of an extensively industrialized area of central India (Raipur, Chhattisgarh, a coal mega-burning region). The dominant components are emissions from fossil fuel utilization, burning of biomass and plastics, and fugitive sources. Speciation and variations of potential new tracer compounds identified are also described.

  13. Tracer-based estimation of secondary organic carbon in the Pearl River Delta, south China

    NASA Astrophysics Data System (ADS)

    Ding, Xiang; Wang, Xin-Ming; Gao, Bo; Fu, Xiao-Xin; He, Quan-Fu; Zhao, Xiu-Ying; Yu, Jian-Zhen; Zheng, Mei

    2012-03-01

    Fine particles (PM2.5) were collected using filter-based high-volume samplers during summer-winter 2008 at a rural site in the central Pearl River Delta (PRD), south China, to determine typical secondary organic aerosol (SOA) tracers from significant biogenic (isoprene, monoterpenes, and sesquiterpenes) and anthropogenic (aromatics) precursors. Average isoprene SOA tracers were significantly higher during summer (126 ng m-3) than during fall-winter (25.1 ng m-3), owing largely to the higher isoprene emission and reaction rates in summer. Average monoterpene SOA tracers during summer (11.6 ng m-3) and fall-winter (16.4 ng m-3) showed much less difference compared to isoprene SOA tracers, probably resulting from the counteracting effects of temperature on the precursor emission/tracer formation and on gas/particle partitioning. The concentrations of the aromatics' SOA tracer (2,3-dihydroxy-4-oxopentanoic acid) ranged from 1.70 to 52.0 ng m-3 with an average of 15.1 ng m-3, which was the highest reported in ambient air. The secondary organic carbon (SOC) estimated by the SOA-tracer method averaged 3.07 μg C m-3 in summer and 2.00 μg C m-3 in fall-winter, contributing 38.4% and 8.7% to OC, respectively. During summer, aromatics-SOC and isoprene-SOC reached 2.25 ± 1.5 μg C m-3 and 0.64 ± 0.7 μg C m-3 and accounted for 76% and 18% of the estimated SOC, respectively, while during fall-winter, aromatics-SOC (1.64 ± 1.4 μg C m-3) was dominant with a share of 79% in total estimated SOC. These results indicated that anthropogenic aromatics were dominant SOC precursors in the highly industrialized and urbanized PRD region. During summer, SOC levels estimated by elemental carbon (EC) tracer method were not only consistent with but also correlated well with those by SOA-tracer method. During fall-winter, however, SOC by SOA-tracer method was only about one third of that by EC-tracer method. Their gaps were significantly correlated with the biomass burning tracer

  14. SOA Pragmatism

    NASA Astrophysics Data System (ADS)

    Shan, Tony C.

    This paper presents a pragmatic approach composed of Methodology, Automation, Patterns, and Strategy (MAPS), to effectively manage the architecture design practices and solution development lifecycle of information systems in a service-oriented paradigm. The key challenges in SOA are discussed, such as architecture complexity, evolving technologies, immature governance, fragmented specification efforts, and disparate visual notations. This comprehensive framework aims to provide a mature integration of appropriate knowledge and capabilities to filter the inessential from the essential. In the Methodology dimension, a hybrid method, SOA philosophy, and a methodical approach are the key components. The Automation dimension covers tools, service lifecycle, and COTS mapping. The prominent elements of the Patterns dimension are data caching patterns, reference model, and open source reference implementation. Finally, the Strategy dimension addresses the strategy metamodel, technology architecture planning, and strategy roadmapping. In addition, a 9-point list of SOA wisdom is articulated, which gives best-practice guidelines to adopt and implement SOA pragmatically in large organizations from a practitioner's perspeoctive.

  15. Determination of isoprene-derived secondary organic aerosol tracers (2-methyltetrols) by HPAEC-PAD: Results from size-resolved aerosols in a tropical rainforest

    NASA Astrophysics Data System (ADS)

    Zhang, Zhi-Sheng; Engling, Guenter; Chan, Chuen-Yu; Yang, Yi-Hong; Lin, Mang; Shi, Si; He, Jun; Li, Yi-De; Wang, Xue-Mei

    2013-05-01

    Secondary organic aerosol (SOA) formed from oxidation of isoprene, the most abundant nonmethane hydrocarbon in the atmosphere, has been estimated to contribute significantly to the global aerosol burden. Measurement of isoprene-derived SOA molecular markers has become an effective method for the investigation of biogenic aerosol contributions in the atmosphere. The primary goals of this work are to present a new method based on high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) to quantify diastereoisomeric 2-methyltetrols (2-methylerythritol and 2-methylthreitol), marker compounds of isoprene-derived SOA, and thus to obtain better understanding regarding their abundance and size distribution specifically in a rainforest area. The 2-methyltetrol data, along with water-soluble inorganic ion concentrations, were obtained from size-segregated samples collected at a tropical rainforest site in South China during the period from May to June, 2010. The concentrations of 2-methyltetrols from selected samples measured by HPAEC-PAD showed good agreement with those measured by GC/MS. Overall, the HPAEC-PAD method provides a simple and fast, yet selective and sensitive, alternative to GC/MS for 2-methyltetrol determination, allowing for more efficient analysis of large sample numbers. The size distributions of 2-methylerythritol and 2-methylthreitol both exhibited a unimodal pattern, peaking in the particle size range of 0.44-1.0 μm, where their average concentrations were 11.7 and 4.2 ng m-3, respectively. A strong correlation between 2-methylerythritol and 2-methylthreitol was observed among the entire set of size-segregated samples, indicating their photochemical origin and similar formation mechanism regardless of particle sizes. Compared to the results obtained from previous chamber studies, the similar isomeric fraction of 2-methyltetrols obtained in this study and other field studies confirms their formation through

  16. Evaluation of Observed and Modelled Aerosol Lifetimes Using Radioactive Tracers of Opportunity and an Ensemble of 19 Global Models

    NASA Technical Reports Server (NTRS)

    Kristiansen, N. I.; Stohl, A.; Olivie, D. J. L.; Croft, B.; Sovde, O. A.; Klein, H.; Christoudias, T.; Kunkel, D.; Leadbetter, S. J.; Lee, Y. H.; Zhang, K.; Tsigaridis, K.; Bauer, S. E.; Faluvegi, G. S.; Shindell, D.

    2016-01-01

    Aerosols have important impacts on air quality and climate, but the processes affecting their removal from the atmosphere are not fully understood and are poorly constrained by observations. This makes modelled aerosol lifetimes uncertain. In this study, we make use of an observational constraint on aerosol lifetimes provided by radionuclide measurements and investigate the causes of differences within a set of global models. During the Fukushima Dai-Ichi nuclear power plant accident of March 2011, the radioactive isotopes cesium-137 (Cs-137) and xenon-133 (Xe-133) were released in large quantities. Cesium attached to particles in the ambient air, approximately according to their available aerosol surface area. Cs-137 size distribution measurements taken close to the power plant suggested that accumulation mode (AM) sulfate aerosols were the main carriers of cesium. Hence, Cs-137 can be used as a proxy tracer for the AM sulfate aerosol's fate in the atmosphere. In contrast, the noble gas Xe-133 behaves almost like a passive transport tracer. Global surface measurements of the two radioactive isotopes taken over several months after the release allow the derivation of a lifetime of the carrier aerosol. We compare this to the lifetimes simulated by 19 different atmospheric transport models initialized with identical emissions of Cs-137that were assigned to an aerosol tracer with each model's default properties of AM sulfate, and Xe-133 emissions that were assigned to a passive tracer. We investigate to what extent the modelled sulfate tracer can reproduce the measurements, especially with respect to the observed loss of aerosol mass with time. Modelled Cs-137and Xe-133 concentrations sampled at the same location and times as station measurements allow a direct comparison between measured and modelled aerosol lifetime. The e-folding lifetime e, calculated from station measurement data taken between 2 and 9 weeks after the start of the emissions, is 14.3 days (95

  17. Evaluation of observed and modelled aerosol lifetimes using radioactive tracers of opportunity and an ensemble of 19 global models

    NASA Astrophysics Data System (ADS)

    Kristiansen, N. I.; Stohl, A.; Olivié, D. J. L.; Croft, B.; Søvde, O. A.; Klein, H.; Christoudias, T.; Kunkel, D.; Leadbetter, S. J.; Lee, Y. H.; Zhang, K.; Tsigaridis, K.; Bergman, T.; Evangeliou, N.; Wang, H.; Ma, P.-L.; Easter, R. C.; Rasch, P. J.; Liu, X.; Pitari, G.; Di Genova, G.; Zhao, S. Y.; Balkanski, Y.; Bauer, S. E.; Faluvegi, G. S.; Kokkola, H.; Martin, R. V.; Pierce, J. R.; Schulz, M.; Shindell, D.; Tost, H.; Zhang, H.

    2015-09-01

    Aerosols have important impacts on air quality and climate, but the processes affecting their removal from the atmosphere are not fully understood and are poorly constrained by observations. This makes modelled aerosol lifetimes uncertain. In this study, we make use of an observational constraint on aerosol lifetimes provided by radionuclide measurements and investigate the causes of differences within a set of global models. During the Fukushima Dai-Ichi nuclear power plant accident of March 2011, the radioactive isotopes cesium-137 (137Cs) and xenon-133 (133Xe) were released in large quantities. Cesium attached to particles in the ambient air, approximately according to their available aerosol surface area. 137Cs size distribution measurements taken close to the power plant suggested that accumulation-mode (AM) sulphate aerosols were the main carriers for the cesium. Hence, 137Cs can be used as a proxy tracer for the AM sulphate aerosol's fate in the atmosphere. In contrast, the noble gas 133Xe behaves almost like a passive transport tracer. Global surface measurements of the two radioactive isotopes taken over several months after the release allow the derivation of a lifetime of the carrier aerosol. We compare this to the lifetimes simulated by 19 different atmospheric transport models initialized with identical emissions of 137Cs that were assigned to an aerosol tracer with each model's default properties of AM sulphate, and 133Xe emissions that were assigned to a passive tracer. We investigate to what extent the modelled sulphate tracer can reproduce the measurements, especially with respect to the observed loss of aerosol mass with time. Modelled 37Cs and 133Xe concentrations sampled at the same location and times as station measurements allow a direct comparison between measured and modelled aerosol lifetime. The e-folding lifetime τe, calculated from station measurement data taken between two and nine weeks after the start of the emissions, is 14.3 days

  18. Evaluation of observed and modelled aerosol lifetimes using radioactive tracers of opportunity and an ensemble of 19 global models

    NASA Astrophysics Data System (ADS)

    Kristiansen, N. I.; Stohl, A.; Olivié, D. J. L.; Croft, B.; Søvde, O. A.; Klein, H.; Christoudias, T.; Kunkel, D.; Leadbetter, S. J.; Lee, Y. H.; Zhang, K.; Tsigaridis, K.; Bergman, T.; Evangeliou, N.; Wang, H.; Ma, P.-L.; Easter, R. C.; Rasch, P. J.; Liu, X.; Pitari, G.; Di Genova, G.; Zhao, S. Y.; Balkanski, Y.; Bauer, S. E.; Faluvegi, G. S.; Kokkola, H.; Martin, R. V.; Pierce, J. R.; Schulz, M.; Shindell, D.; Tost, H.; Zhang, H.

    2016-03-01

    Aerosols have important impacts on air quality and climate, but the processes affecting their removal from the atmosphere are not fully understood and are poorly constrained by observations. This makes modelled aerosol lifetimes uncertain. In this study, we make use of an observational constraint on aerosol lifetimes provided by radionuclide measurements and investigate the causes of differences within a set of global models. During the Fukushima Dai-Ichi nuclear power plant accident of March 2011, the radioactive isotopes cesium-137 (137Cs) and xenon-133 (133Xe) were released in large quantities. Cesium attached to particles in the ambient air, approximately according to their available aerosol surface area. 137Cs size distribution measurements taken close to the power plant suggested that accumulation-mode (AM) sulfate aerosols were the main carriers of cesium. Hence, 137Cs can be used as a proxy tracer for the AM sulfate aerosol's fate in the atmosphere. In contrast, the noble gas 133Xe behaves almost like a passive transport tracer. Global surface measurements of the two radioactive isotopes taken over several months after the release allow the derivation of a lifetime of the carrier aerosol. We compare this to the lifetimes simulated by 19 different atmospheric transport models initialized with identical emissions of 137Cs that were assigned to an aerosol tracer with each model's default properties of AM sulfate, and 133Xe emissions that were assigned to a passive tracer. We investigate to what extent the modelled sulfate tracer can reproduce the measurements, especially with respect to the observed loss of aerosol mass with time. Modelled 137Cs and 133Xe concentrations sampled at the same location and times as station measurements allow a direct comparison between measured and modelled aerosol lifetime. The e-folding lifetime τe, calculated from station measurement data taken between 2 and 9 weeks after the start of the emissions, is 14.3 days (95

  19. Ångström coefficient as a tracer of the continental aerosols

    NASA Astrophysics Data System (ADS)

    Kusmierczyk-Michulec, Jolanta; Van Eijk, Alexander M. J.

    2007-09-01

    The variation of the extinction coefficient with wavelength can be presented as a power law function with a constant (related to the power factor) known as the Ångström coefficient. When the particle size distribution is dominated by small particles, usually associated with pollution, the Ångström coefficients are high; in clear conditions they are usually low. Long residence time of air masses over land and in particular the passage over large urban areas cause high concentrations of fine particles and thus high values of the Ångström coefficients. The opposite effect can be observed over water. The longer the time that the air masses spent over water the more evident is a change in the aerosol size distribution caused by the deposition of continental aerosols. As a result of this process the measured Ångström coefficient values become much smaller. Therefore this parameter is a good tracer for the concentration of aerosols originated over land. The relation between the Ångström coefficient and TOS (time over sea) is demonstrated on three data sets. The first data set includes measurements collected at the Irish Atlantic coast in 1994 and 1995, the second one, data collected within the Rough Evaporation Duct (RED) experiment that took place off Oahu, Hawaii in 2001. The third one represents data collected at the Baltic Sea during cruises in 1997and 1998.

  20. Modeling the formation and aging of secondary organic aerosols during CalNex 2010

    NASA Astrophysics Data System (ADS)

    Hayes, P. L.; Ortega, A. M.; Ahmadov, R.; McKeen, S. A.; Washenfelder, R. A.; Alvarez, S.; Rappenglueck, B.; Holloway, J. S.; Gilman, J. B.; Kuster, W. C.; De Gouw, J. A.; Zotter, P.; Prevot, A. S.; Kleindienst, T. E.; Offenberg, J. H.; Jimenez, J. L.

    2012-12-01

    Several traditional and recently proposed models are applied to predict the concentrations and properties of secondary organic aerosols (SOA) and organic gases at the Pasadena ground site during the CalNex campaign. The models are constrained with and compared against results from available observations. The CalNex campaign and specifically the Pasadena ground site featured a large and sophisticated suite of aerosol and gas phase instrumentation, and thus, it provides a unique opportunity to test SOA models under conditions of strong urban emissions at a range of low photochemical ages. The oxidation of volatile organic compounds (VOCs) using an updated traditional model cannot explain the observed ambient SOA, and under-predicts the measurements by a factor of ~40. Similarly, after accounting for the multi-generation oxidation of VOCs using a volatility basis set (VBS) approach as described by Tsimpidi et al. (2010), SOA is still under-predicted by a factor of ~8. For SOA formed from VOCs (V-SOA) the dominant precursors are aromatics (xylenes, toluene, and trimethylbenzenes). The model SOA formed from the oxidation of primary semivolatile and intermediate volatility organic compounds (P-S/IVOCs, producing SI-SOA) is also predicted using the parameterizations of Robinson et al. (2007) and Grieshop et al. (2009), and the properties of V-SOA + SI-SOA are compared against the measured O:C and volatility. We also compare the results of the different models against fossil/non-fossil carbon measurements as well as tracers of different SOA precursors. Potential Aerosol Mass (PAM) measurements of the SOA forming potential of the Pasadena air masses are also compared against that predicted by the models. The PAM analysis allows for model/measurement comparisons of SOA properties over a range of photochemical ages spanning almost two weeks. Using the V-SOA model, at low photochemical ages (< 1 day) the modeled PAM V-SOA is less than the measured PAM SOA, similar to the

  1. Isoprene Epoxydiols as Precursors to Secondary Organic Aerosol Formation: Acid-Catalyzed Reactive Uptake Studies with Authentic Compounds

    PubMed Central

    Lin, Ying-Hsuan; Zhang, Zhenfa; Docherty, Kenneth S.; Zhang, Haofei; Budisulistiorini, Sri Hapsari; Rubitschun, Caitlin L.; Shaw, Stephanie L.; Knipping, Eladio M.; Edgerton, Eric S.; Kleindienst, Tadeusz E.; Gold, Avram; Surratt, Jason D.

    2011-01-01

    Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NOx conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (> 99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7–6.4% for β-IEPOX and 3.4–5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C5-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NOx, isoprene-dominated regions influenced by the presence of acidic aerosols. PMID:22103348

  2. Modeling organic aerosols during MILAGRO: importance of biogenic secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Jimenez, J. L.; Madronich, S.; Aiken, A. C.; Bessagnet, B.; Curci, G.; Fast, J.; Lamarque, J.-F.; Onasch, T. B.; Roux, G.; Schauer, J. J.; Stone, E. A.; Ulbrich, I. M.

    2009-09-01

    tendency of the model to excessively evaporate the freshly formed SOA. Predicted SOA concentrations in our base case were extremely low when photochemistry was not active, especially overnight, as the SOA formed in the previous day was mostly quickly advected away from the basin. These nighttime discrepancies were not significantly reduced when greatly enhanced partitioning to the aerosol phase was assumed. Model sensitivity results suggest that observed nighttime OOA concentrations are strongly influenced by a regional background SOA (~1.5 μg/m3) of biogenic origin which is transported from the coastal mountain ranges into the Mexico City basin. The presence of biogenic SOA in Mexico City was confirmed by SOA tracer-derived estimates that have reported 1.14 (±0.22) μg/m3 of biogenic SOA at T0, and 1.35 (±0.24) μg/m3 at T1, which are of the same order as the model. Consistent with other recent studies, we find that biogenic SOA does not appear to be underestimated significantly by traditional models, in strong contrast to what is observed for anthropogenic pollution. The relative contribution of biogenic SOA to predicted monthly mean SOA levels (traditional approach) is estimated to be more than 30% within the city and up to 65% at the regional scale which may help explain the significant amount of modern carbon in the aerosols inside the city during low biomass burning periods. The anthropogenic emissions of isoprene and its nighttime oxidation by NO3 were also found to enhance the SOA mean concentrations within the city by an additional 15%. Our results confirm the large underestimation of the SOA production by traditional models in polluted regions (estimated as 10-20 tons within the Mexico City metropolitan area during the daily peak), and emphasize for the first time the role of biogenic precursors in this region, indicating that they cannot be neglected in urban modeling studies.

  3. Experimental Determination of Chemical Diffusion within Secondary Organic Aerosol Particles

    SciTech Connect

    Abramson, Evan H.; Imre, D.; Beranek, Josef; Wilson, Jacqueline; Zelenyuk, Alla

    2013-02-28

    Formation, properties, transformations, and temporal evolution of secondary organic aerosols (SOA) particles strongly depend on particle phase. Recent experimental evidence from a number of groups indicates that SOA is in a semi-solid phase, the viscosity of which remained unknown. We find that when SOA is made in the presence of vapors of volatile hydrophobic molecules the SOA particles absorb and trap them. Here, we illustrate that it is possible to measure the evaporation rate of these molecules that is determined by their diffusion in SOA, which is then used to calculate a reasonably accurate value for the SOA viscosity. We use pyrene as a tracer molecule and a-pinene SOA as an illustrative case. It takes ~24 hours for half the pyrene to evaporate to yield a viscosity of 10^8 Pa s for a-pinene. This viscosity is consistent with measurements of particle bounce and evaporation rates. We show that viscosity of 10^8 Pa s implies coalescence times of minutes, consistent with the findings that SOA particles are spherical. Similar measurements on aged SOA particles doped with pyrene yield a viscosity of 10^9 Pa s, indicating that hardening occurs with time, which is consistent with observed decrease in water uptake and evaporation rate with aging.

  4. SOA Precursors: A Comparison of Semi-Volatile and Water Soluble Organic Gases During SOAS

    NASA Astrophysics Data System (ADS)

    Carlton, A. M. G.; Sareen, N.; Turpin, B. J.

    2014-12-01

    It is well-established that a major pathway for secondary organic aerosol (SOA) formation is via the partitioning of semi-volatile products of gas-phase photochemical reactions into preexisting organic particulate matter. Semi-volatile partitioning theory is widely used while modeling SOA. Despite its significance, parameterizations based solely on this formation pathway are unable to reproduce trends in SOA mass, particularly high atmospheric O/C ratios and enrichment of organic aerosol aloft. Recent studies have also highlighted the importance of formation of SOA through reactions of water-soluble organic gases (WSOG) in atmospheric waters (clouds, fogs, and wet aerosols). In order to understand the relative magnitude of potential precursors to SOA via both formation pathways, we modeled semi-volatile and WSOG concentrations during the Secondary Organic and Aerosol Study (SOAS) conducted in Brent, Alabama during June-July 2013. CMAQ 5.0.1 is used to predict mixing ratios of semi-volatile gases and WSOG over the continental US for a 10 day time period during SOAS. Our modeling results indicate that WSOG concentrations are an order of magnitude greater, on average, than the sum of semi-volatile gases. Interestingly, concentrations of semi-volatile gases increase aloft, unlike concentrations of WSOG. These results suggest that the potential for SOA formation from WSOG was high, and provide support for efforts to accurately model that multiphase chemistry in order to develop more effective air quality management strategies.

  5. Use of multi-element tracers to source apportion mercury in south Florida aerosols

    NASA Astrophysics Data System (ADS)

    Graney, Joseph R.; Dvonch, J. Timothy; Keeler, Gerald J.

    The relative importance of local sources of mercury (Hg) in aerosols from urban areas in south Florida in relation to regional or global sources transported to the Everglades was investigated using a multi-element tracer approach. The sources of metals and Hg within aerosols were determined by integrating the collection of aerosols at seven locations with meteorology, source sampling, and statistical analysis. Sources include sea spray, soil dust from local carbonate bedrock and long range Saharan dust transport, regional scale transport of sulfate aerosols, and local point sources including oil-fired power plants, medical and waste incineration, and cement kilns. Using a principal components analysis-multiple linear regression (PCA-MLR) approach, 80% of the Hg in particulate form at the Thompson Park Everglades receptor site (THP) could be attributed to local sources. The key to the success of the source attribution at THP was collection of samples on a 12-h sampling basis in order to account for diurnal changes in meteorological conditions in south Florida associated with land-sea breeze development. Fifty-six±7% of the particulate Hg at THP was associated with elevated Zn concentrations which source sampling and surface meteorology indicate as emissions from municipal waste incineration located southeast of THP. Another 14±5% of the particulate Hg was associated with elevated Cu and Pb concentrations from sources SSE of THP. Eleven±1% of the particulate Hg originated from medical waste incineration sources and was associated with elevated levels of Cl and rapid SE to NW transport. Elevated concentrations of Si, Al, Fe, Mn, and K occurred on the same days at all sites, following passage of tropical storms over south Florida. PCA grouped these elements within a factor that is likely Saharan dust in origin, only 12±2% of the particulate Hg at THP could be attributed to this non-local source. Because the majority of the particulate Hg at THP can be attributed to

  6. Impacts of Anthropogenic Emissions in the Southeastern U.S. on Heterogeneous Chemistry of Isoprene-Derived Epoxides Leading to Secondary Organic Aerosol Formation (Invited)

    NASA Astrophysics Data System (ADS)

    Surratt, J. D.; Pye, H.; Lin, Y.; Budisulistiorini, S.; Zhang, H.; Marth, W.; Cui, T.; Arashiro, M.; Chu, K.; Zhang, Z.; Sexton, K.; Piletic, I.; Xie, Y.; Capps, S. L.; Luecken, D.; Hutzell, W. T.; Jaoui, M.; Canagaratna, M. R.; Croteau, D.; Jayne, J. T.; Worsnop, D. R.; Offenberg, J.; Kleindienst, T. E.; Lewandowski, M.; Edney, E.; Pinder, R. W.; Bartolotti, L.; Gold, A.

    2013-12-01

    Isoprene is a major source of secondary organic aerosol (SOA); however, the exact manner in which it forms SOA remains unclear. Improving our fundamental understanding of isoprene-derived SOA is key to improving existing air quality models, especially in the southeastern U.S. where models currently underestimate observations. By combining organic synthesis, computational calculations, mass spectrometry, smog chamber studies, and field measurements, we show that reactive epoxides, which include methacrylic acid epoxide (MAE) and isomeric isoprene epoxydiols (IEPOX), produced from the photochemical oxidation of isoprene are key to SOA formation. Furthermore, anthropogenic pollutants (NOx and SO2) enhance isoprene-derived epoxides as an SOA source. In the laboratory, we find that the reactive uptake of synthetic IEPOX and MAE standards onto acidified sulfate aerosol yields known isoprene-derived SOA tracers (2-methlytetrols, 2-methylglyceric acid, C5-alkene triols, 3-methyltetrahydrofuran-3,4-diols, dimers and organosulfates) that we measure in fine aerosol collected from multiple sites across the southeastern U.S. using gas chromatography/mass spectrometry (GC/MS) and liquid chromatography coupled to diode array detection and electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (LC/DAD-ESI-QTOFMS). Notably, IEPOX- and MAE-derived SOA tracers account for ~19% of the organic aerosol mass in Yorkville, GA. Moreover, real-time continuous chemical measurements of fine aerosol made using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) during summer 2011 and summer 2013 in Atlanta, GA, and Look Rock, TN, respectively, resolved an IEPOX-oxygenated organic aerosol (IEPOX-OOA) factor when applying positive matrix factorization (PMF) to the organic mass spectral time series. In Atlanta, this factor is found to account for ~33% of the fine OA mass and is correlated with IEPOX-derived SOA tracers (r2 = 0.6), sulfate (r2 = 0.5), and to some

  7. Exposure of BALB/c Mice to Diesel Engine Exhaust Origin Secondary Organic Aerosol (DE-SOA) during the Developmental Stages Impairs the Social Behavior in Adult Life of the Males

    PubMed Central

    Win-Shwe, Tin-Tin; Kyi-Tha-Thu, Chaw; Moe, Yadanar; Fujitani, Yuji; Tsukahara, Shinji; Hirano, Seishiro

    2016-01-01

    Secondary organic aerosol (SOA) is a component of particulate matter (PM) 2.5 and formed in the atmosphere by oxidation of volatile organic compounds. Recently, we have reported that inhalation exposure to diesel engine exhaust (DE) originated SOA (DE-SOA) affect novel object recognition ability and impair maternal behavior in adult mice. However, it is not clear whether early life exposure to SOA during the developmental stages affect social behavior in adult life or not. In the present study, to investigate the effects of early life exposure to DE-SOA during the gestational and lactation stages on the social behavior in the adult life, BALB/c mice were exposed to clean air (control), DE, DE-SOA and gas without any PM in the inhalation chambers from gestational day 14 to postnatal day 21 for 5 h a day and 5 days per week. Then adult mice were examined for changes in their social behavior at the age of 13 week by a sociability and social novelty preference, social interaction with a juvenile mouse and light-dark transition test, hypothalamic mRNA expression levels of social behavior-related genes, estrogen receptor-alpha and oxytocin receptor as well as of the oxidative stress marker gene, heme oxygenase (HO)-1 by real-time RT-PCR method. In addition, hypothalamic level of neuronal excitatory marker, glutamate was determined by ELISA method. We observed that sociability and social novelty preference as well as social interaction were remarkably impaired, expression levels of estrogen receptor-alpha, oxytocin receptor mRNAs were significantly decreased, expression levels of HO-1 mRNAs and glutamate levels were significantly increased in adult male mice exposed to DE-SOA compared to the control ones. Findings of this study indicate early life exposure of BALB/c mice to DE-SOA may affect their late-onset hypothalamic expression of social behavior related genes, trigger neurotoxicity and impair social behavior in the males. PMID:26834549

  8. Exposure of BALB/c Mice to Diesel Engine Exhaust Origin Secondary Organic Aerosol (DE-SOA) during the Developmental Stages Impairs the Social Behavior in Adult Life of the Males.

    PubMed

    Win-Shwe, Tin-Tin; Kyi-Tha-Thu, Chaw; Moe, Yadanar; Fujitani, Yuji; Tsukahara, Shinji; Hirano, Seishiro

    2015-01-01

    Secondary organic aerosol (SOA) is a component of particulate matter (PM) 2.5 and formed in the atmosphere by oxidation of volatile organic compounds. Recently, we have reported that inhalation exposure to diesel engine exhaust (DE) originated SOA (DE-SOA) affect novel object recognition ability and impair maternal behavior in adult mice. However, it is not clear whether early life exposure to SOA during the developmental stages affect social behavior in adult life or not. In the present study, to investigate the effects of early life exposure to DE-SOA during the gestational and lactation stages on the social behavior in the adult life, BALB/c mice were exposed to clean air (control), DE, DE-SOA and gas without any PM in the inhalation chambers from gestational day 14 to postnatal day 21 for 5 h a day and 5 days per week. Then adult mice were examined for changes in their social behavior at the age of 13 week by a sociability and social novelty preference, social interaction with a juvenile mouse and light-dark transition test, hypothalamic mRNA expression levels of social behavior-related genes, estrogen receptor-alpha and oxytocin receptor as well as of the oxidative stress marker gene, heme oxygenase (HO)-1 by real-time RT-PCR method. In addition, hypothalamic level of neuronal excitatory marker, glutamate was determined by ELISA method. We observed that sociability and social novelty preference as well as social interaction were remarkably impaired, expression levels of estrogen receptor-alpha, oxytocin receptor mRNAs were significantly decreased, expression levels of HO-1 mRNAs and glutamate levels were significantly increased in adult male mice exposed to DE-SOA compared to the control ones. Findings of this study indicate early life exposure of BALB/c mice to DE-SOA may affect their late-onset hypothalamic expression of social behavior related genes, trigger neurotoxicity and impair social behavior in the males. PMID:26834549

  9. Tests of regional elemental tracers of pollution aerosols. 1. Distinctness of regional signatures, stability during transport, and empirical validation

    SciTech Connect

    Lowenthal, D.H.; Wunschel, K.R.; Rahn, K.A. )

    1988-04-01

    The two major requirements for a successful regional tracer system are distinctness of signatures and stability of signatures during transport. Dissimilarity of the five regional signatures from eastern North America is shown by collinearity diagnostics and by apportionment of synthetic samples generated randomly. Stability of regional signatures during transport is shown first by use of tracer elements in coarse and fine aerosol to predict the maximum possible change of ratios from particle-size effects alone and then by examination of actual changes in signatures during transport from the Midwest to Underhill, VT. Two recent empirical validations of the tracer system are presented: qualitative agreement of pulses of mid-western aerosol in Vermont with pulses of perfluorocarbon tracer gas released in Ohio during CAPTEX '83 and reproduction of our three major northeastern and mid-western signatures by other investigators. The tracer system currently uses the seven elements As, Se, Sb, Zn, In, noncrustal Mn, and noncrustal V as measured by instrumental neutron activation.

  10. Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Rattanavaraha, Weruka; Chu, Kevin; Hapsari Budisulistiorini, Sri; Riva, Matthieu; Lin, Ying-Hsuan; Edgerton, Eric S.; Baumann, Karsten; Shaw, Stephanie L.; Guo, Hongyu; King, Laura; Weber, Rodney J.; Neff, Miranda E.; Stone, Elizabeth A.; Offenberg, John H.; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

    2016-04-01

    In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA) that contributes to fine particulate matter (PM2.5). Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2), oxides of nitrogen (NOx), and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH)-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM), ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS). Sample extracts were analyzed by gas chromatography-electron ionization-mass spectrometry (GC/EI-MS) with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH) network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM) ( ˜ 7 to ˜ 20 %). Isoprene-derived SOA tracers correlated with sulfate (SO42-) (r2 = 0.34, n = 117) but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML)-derived SOA tracers with nitrate radical production (P[NO3]) (r2 = 0.57, n = 40) were observed during nighttime, suggesting a potential role of the NO3 radical in

  11. Polar organic tracers in PM2.5 aerosols from forests in eastern China

    NASA Astrophysics Data System (ADS)

    Wang, W.; Wu, M. H.; Li, L.; Zhang, T.; Li, H. J.; Wang, Y. J.; Liu, X. D.; Sheng, G. Y.; Claeys, M.; Fu, J. M.

    2008-06-01

    Photooxidation products of biogenic volatile organic compounds, mainly isoprene and monoterpenes, are significant sources of atmospheric particulate matter in forested regions. The objectives of this study were to examine time trends and diurnal variations of polar organic tracers for the photooxidation of isoprene and α-pinene to investigate whether they are linked with meteorological parameters or trace gases and to estimate their regional carbon contributions. PM2.5 (particulate matter with an aerodynamic diameter <2.5 μm) aerosol samples were collected from forests in eastern China and compared with data from forested sites in Europe and America. Aerosol sampling was conducted at four sites located along a gradient of ecological succession in four different regions of China, i.e. Changbai Mountain Nature Reserve (boreal-temperate), Chongming National Forest Park (temperate), Dinghu Mountain Nature Reserve (subtropical) and Jianfengling Nature Reserve (tropical) during summer periods when the meteorological conditions are believed to be favorable for photochemical processes. Fifty PM2.5 samples were collected; seventeen organic compounds, organic carbon (OC), elemental carbon and trace gases were measured. Results indicate that the concentration trends of the secondary organic compounds reflected those of the trace gases and meteorological parameters. The 24-h average concentrations of isoprene oxidation products, α-pinene oxidation products, sugars and sugar alcohols vary systematically along gradients of ecological succession, except malic acid which may have both biogenic and anthropogenic sources. The maximum carbon contribution of isoprene and α-pinene oxidation products to the OC was 2.4% (293 ng/m3, Changbai day-time) and 0.3% (41.3 ng/m3, Changbai night-time), respectively.

  12. Polar organic tracers in PM2.5 aerosols from forests in eastern China

    NASA Astrophysics Data System (ADS)

    Wang, W.; Wu, M. H.; Li, L.; Zhang, T.; Liu, X. D.; Feng, J. L.; Li, H. J.; Wang, Y. J.; Sheng, G. Y.; Claeys, M.; Fu, J. M.

    2008-12-01

    Photooxidation products of biogenic volatile organic compounds, mainly isoprene and monoterpenes, are significant sources of atmospheric particulate matter in forested regions. The objectives of this study were to examine time series and diel variations of polar organic tracers for the photooxidation of isoprene and α-pinene to investigate whether they are linked with meteorological parameters or trace gases, and to determine their carbon contributions. In addition, the biogenic secondary organic carbon contributions from isoprene were estimated. PM2.5 (particulate matter with an aerodynamic diameter <2.5 μm) aerosol samples were collected from forests in eastern China and compared with data from forested sites in Europe and America. Aerosol sampling was conducted at four sites located along a gradient of ecological succession in four different regions, i.e. Changbai Mountain Nature Reserve (boreal-temperate), Chongming National Forest Park (temperate), Dinghu Mountain Nature Reserve (subtropical) and Jianfengling Nature Reserve in Hainan (tropical) during summer periods when the meteorological conditions are believed to be favorable for photochemical processes. Fifty PM2.5 samples were collected; eighteen organic compounds, organic carbon (OC), elemental carbon and trace gases were measured. Results indicate that the concentration trends of the secondary organic compounds reflected those of the trace gases and meteorological parameters. Very good correlations between the sum concentrations of isoprene oxidation products and atmospheric SO2, O3, NO2, NOx, as well as CO2, at the Changbai site were found. The secondary OC due to isoprene was relatively high in tropical Hainan (0.27 μgC/m3) where isoprene-emitting broadleaf species are dominant, but was comparable in boreal Changbai (0.32 μgC/m3) where coniferous species are prevalent. The contribution of malic acid, which may have both biogenic and anthropogenic sources, to the OC mass was comparable at the four

  13. Apportionment of primary and secondary organic aerosols in southern California during the 2005 study of organic aerosols in riverside (SOAR-1).

    PubMed

    Docherty, Kenneth S; Stone, Elizabeth A; Ulbrich, Ingrid M; DeCarlo, Peter F; Snyder, David C; Schauer, James J; Peltier, Richard E; Weber, Rodney J; Murphy, Shane M; Seinfeld, John H; Grover, Brett D; Eatough, Delbert J; Jimenez, Jose L

    2008-10-15

    Ambient sampling was conducted in Riverside, California during the 2005 Study of Organic Aerosols in Riverside to characterize the composition and sources of organic aerosol using a variety of state-of-the-art instrumentation and source apportionmenttechniques. The secondary organic aerosol (SOA) mass is estimated by elemental carbon and carbon monoxide tracer methods, water soluble organic carbon content, chemical mass balance of organic molecular markers, and positive matrix factorization of high-resolution aerosol mass spectrometer data. Estimates obtained from each ofthese methods indicate that the organic fraction in ambient aerosol is overwhelmingly secondary in nature during a period of several weeks with moderate ozone concentrations and that SOA is the single largest component of PM1 aerosol in Riverside. Average SOA/OA contributions of 70-90% were observed during midday periods, whereas minimum SOA contributions of approximately 45% were observed during peak morning traffic periods. These results are contraryto previous estimates of SOAthroughout the Los Angeles Basin which reported that, other than during severe photochemical smog episodes, SOA was lower than primary OA. Possible reasons for these differences are discussed. PMID:18983089

  14. Investigations of BVOC-SOA-cloud-climate feedbacks via interactive biogenic emissions using NorESM

    NASA Astrophysics Data System (ADS)

    Alterskjær, Kari; Egill Kristjansson, Jon; Grini, Alf; Iversen, Trond; Kirkevåg, Alf; Olivié, Dirk; Schulz, Michael; Seland, Øyvind

    2016-04-01

    Climate feedbacks represent a large source of uncertainty in future climate projections. One such feedback involves a change in emissions of biogenic volatile organic compounds (BVOCs) under global warming and a subsequent change in cloud radiative effects. Parts of the atmospheric BVOCs will oxidize in the atmosphere, which may reduce their volatility enough to form secondary organic aerosols (SOA). A changed SOA load will affect cloud radiative properties through aerosol-cloud interactions (ACI) and therefore act to reduce or enhance the temperature change resulting from greenhouse gases alone. In order to study this effect, a development version of the Norwegian Earth System Model (NorESM) has been extended to include explicit atmospheric particle nucleation and a treatment of SOA based on work by Risto Makkonen and collaborators. Biogenic sources of monoterpene and isoprene are interactively calculated by the Model of Emissions of Gases and Aerosols from Nature (MEGAN), version 2.1, incorporated into the Community Land Model, version 4.5. Monoterpene and isoprene are oxidized by O3, OH and NO3 to form SOA with a yield of 15 % and 5 % respectively. It is assumed that 50 % of the product from monoterpene ozonolysis is of low enough volatility to nucleate new particles. The remaining oxidized BVOCs condensate onto preexisting particles. The model improvements include three new tracers to account for both SOA and the BVOCs. This allows for transport of both SOA and precursor gases, making it possible for SOA to form above the surface layer of the model. The new SOA treatment also changes the size distribution of most model aerosols due to condensation. Preliminary results from 6-year simulations with prescribed sea surface temperatures show that the present day emissions of both isoprene (435.9 Tg/yr) and monoterpenes (121.4 Tg/yr) are within the range found in other studies. The resulting SOA production is on the order of 77 Tg/yr, also within the range found by

  15. Influence of Aerosol Acidity on the Chemical Composition of Secondary Organic Aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M.; Surratt, J. D.; Chan, A. W.; Schlling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J.

    2011-12-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI- TOFMS). A number of first- , second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  16. Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M. N.; Surratt, J. D.; Chan, A. W. H.; Schilling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E. O.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J. H.

    2011-02-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  17. Influence of aerosol acidity on the chemical composition of Secondary Organic Aerosol from β-caryophyllene

    NASA Astrophysics Data System (ADS)

    Chan, M. N.; Surratt, J. D.; Chan, A. W. H.; Schilling, K.; Offenberg, J. H.; Lewandowski, M.; Edney, E. O.; Kleindienst, T. E.; Jaoui, M.; Edgerton, E. S.; Tanner, R. L.; Shaw, S. L.; Zheng, M.; Knipping, E. M.; Seinfeld, J. H.

    2010-11-01

    The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increase of acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are identified as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

  18. Gravity-wave effects on tracer gases and stratospheric aerosol concentrations during the 2013 ChArMEx campaign

    NASA Astrophysics Data System (ADS)

    Chane Ming, Fabrice; Vignelles, Damien; Jegou, Fabrice; Berthet, Gwenael; Renard, Jean-Baptiste; Gheusi, François; Kuleshov, Yuriy

    2016-07-01

    Coupled balloon-borne observations of Light Optical Aerosol Counter (LOAC), M10 meteorological global positioning system (GPS) sondes, ozonesondes, and GPS radio occultation data, are examined to identify gravity-wave (GW)-induced fluctuations on tracer gases and on the vertical distribution of stratospheric aerosol concentrations during the 2013 ChArMEx (Chemistry-Aerosol Mediterranean Experiment) campaign. Observations reveal signatures of GWs with short vertical wavelengths less than 4 km in dynamical parameters and tracer constituents, which are also correlated with the presence of thin layers of strong local enhancements of aerosol concentrations in the upper troposphere and the lower stratosphere. In particular, this is evident from a case study above Ile du Levant (43.02° N, 6.46° E) on 26-29 July 2013. Observations show a strong activity of dominant mesoscale inertia GWs with horizontal and vertical wavelengths of 370-510 km and 2-3 km respectively, and periods of 10-13 h propagating southward at altitudes of 13-20 km during 27-28 July. The European Centre for Medium-Range Weather Forecasts (ECMWF) analyses also show evidence of mesoscale inertia GWs with similar horizontal characteristics above the eastern part of France. Ray-tracing experiments indicate the jet-front system as the main source of observed GWs. Using a simplified linear GW theory, synthetic vertical profiles of dynamical parameters with large stratospheric vertical wind maximum oscillations of ±40 mms-1 are produced for the dominant mesoscale GW observed at heights of 13-20 km. Parcel advection method reveals signatures of GWs in the ozone mixing ratio and the tropospheric-specific humidity. Simulated vertical wind perturbations of the dominant GWs and small-scale perturbations of aerosol concentration (aerosol size of 0.2-0.7 µm) are revealed to be in phase in the lower stratosphere. Present results support the importance of vertical wind perturbations in the GW-aerosol relationship

  19. Lessons Learned About Organic Aerosol Formation in the Southeast U.S. Using Observations and Modeling

    EPA Science Inventory

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA). In this work, modeling of isoprene SOA via heterogeneous uptake is explored and compared to observations from the Southern Oxidant and Aerosol Study (SOAS).

  20. Application of the tracer-aerosol gradient interpretive technique to sulfur attribution for the big bend regional aerosol and visibility observational study.

    PubMed

    Green, Mark; Kuhns, Hampden; Pitchford, Marc; Dietz, Russell; Ashbaugh, Lowell; Watson, Tom

    2003-05-01

    A simple data analysis method called the Tracer-Aerosol Gradient Interpretive Technique (TAGIT) is used to attribute particulate S and SO2 at Big Bend National Park in Texas and nearby areas to local and regional sources. Particulate S at Big Bend is of concern because of its effects on atmospheric visibility. The analysis used particulate S, SO2, and perfluorocarbon tracer data from six 6-hr sampling sites in and near Big Bend National Park. The data were collected in support of the Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study; the field portion was conducted from July through October 1999. Perfluorocarbon tracer was released continuously from a tower at Eagle Pass, TX, approximately 25 km northeast of two large coal-fired power plants (Carbon I and II) in Coahuila, Mexico, and approximately 270 km east-southeast of Big Bend National Park. The perfluorocarbon tracer did not properly represent the location of the emissions from the Carbon power plants for individual 6-hr sampling periods and attributed only 3% of the particulate S and 27% of the SO2 at the 6-hr sites in and near Big Bend to sources represented by the tracer. An alternative approach using SO2 to tag "local" sources such as the Carbon plants attributed 10% of the particulate S and 75% of the SO2 at the 6-hr sites to local sources. Based on these two approaches, most of the regional (65-86%) and a small fraction (19-31%) of the local SO2 was converted to particulate S. The analysis implies that substantial reductions in particulate S at Big Bend National Park cannot be achieved by only reducing emissions from the Carbon power plants; reduction of emissions from many sources over a regional area would be necessary. PMID:12774992

  1. Nonlinear Advection Algorithms Applied to Inter-related Tracers: Errors and Implications for Modeling Aerosol-Cloud Interactions

    SciTech Connect

    Ovtchinnikov, Mikhail; Easter, Richard C.

    2009-02-01

    Monotonicity constraints and gradient preserving flux corrections employed by many advection algorithms used in atmospheric models make these algorithms non-linear. Consequently, any relations among model variables transported separately are not necessarily preserved in such models. These errors cannot be revealed by traditional algorithm testing based on advection of a single tracer. New type of tests are developed and conducted to evaluate the preservation of a sum of several number mixing ratios advected independently of each other, as is the case, for example, in models using bin or sectional representation of aerosol or cloud particle size distribution. The tests show that when three tracers are advected in 1D uniform constant velocity flow, local errors in the sum can be on the order of 10%. When cloud-like interactions are allowed among the tracers, errors in total sum of three mixing ratios can reach up to 30%. Several approaches to eliminate the error are suggested, all based on advecting the sum as a separate variable and then normalizing mixing ratios for individual tracers to match the total sum. A simple scalar normalization preserves the total number mixing ratio and positive definiteness of the variables but the monotonicity constraint for individual tracers is no longer maintained. More involved flux normalization procedures are developed for the flux based advection algorithms to maintain the monotonicity for individual scalars and their sum.

  2. Phenols and hydroxy-PAHs (arylphenols) as tracers for coal smoke particulate matter: source tests and ambient aerosol assessments

    SciTech Connect

    Bernd R.T. Simoneit; Xinhui Bi; Daniel R. Oros; Patricia M. Medeiros; Guoying Sheng; Jiamo Fu

    2007-11-01

    Source tests were conducted to analyze and characterize diagnostic key tracers for emissions from burning of coals with various ranks. Coal samples included lignite from Germany, semibituminous coal from Arizona, USA, bituminous coal from Wales, UK and sample from briquettes of semibituminous coal, bituminous coal and anthracite from China. Ambient aerosol particulate matter was also collected in three areas of China and a background area in Corvallis, OR (U.S.) to confirm the presence of tracers specific for coal smoke. The results showed a series of aliphatic and aromatic hydrocarbons and phenolic compounds, including PAHs and hydroxy-PAHs as the major tracers, as well as a significant unresolved complex mixture (UCM) of compounds. The tracers that were found characteristic of coal combustion processes included hydroxy-PAHs and PAHs. Atmospheric ambient samples from Beijing and Taiyuan, cities where coal is burned in northern China, revealed that the hydroxy-PAH tracers were present during the wintertime, but not in cities where coal is not commonly used (e.g., Guangzhou, South China). Thus, the mass of hydroxy-PAHs can be apportioned to coal smoke and the source strength modeled by summing the proportional contents of EC (elemental carbon), PAHs, UCM and alkanes with the hydroxy-PAHs. 36 refs., 2 figs., 3 tabs.

  3. Assessment of biogenic secondary organic aerosol in the Himalayas

    NASA Astrophysics Data System (ADS)

    Stone, B. A.; Nguyen, T.; Pradhan, B.; Dangol, P.

    2012-12-01

    Biogenic contributions to secondary organic aerosol (SOA) in the Southeast Asian regional haze were assessed by measurement of particle-phase isoprene, monoterpene, and sesquiterpene photooxidation products in fine particles (PM2.5) at Godavari, Nepal, located in the Himalayas at an elevation of 1600 meters. Organic species were measured in solvent-extracts of filter samples using gas chromatography mass spectrometry (GCMS) and chemical derivatization. Molecular markers for primary aerosol sources—including motor vehicles, biomass burning, and detritus—and SOA tracers were measured. High concentrations of isoprene derivatives, particularly in the late summer months, point to biogenic SOA as a significant source of organic carbon in the Himalayan region. First-generation SOA products from alpha-pinene were detected in all samples, whereas multi-generation products were not, suggesting that monoterpenes were at an early stage of oxidation at Godavari. Biogenic SOA contributions to PM2.5 organic carbon in the 2005 monsoon and post-monsoon season ranged from 2-19% for isoprene, 1-5% for monoterpenes, and 1-4% for sesquiterpenes. Primary and secondary biogenic sources combined accounted for approximately half of observed organic aerosol, suggesting additional aerosol sources and/or precursors are significant in this region.

  4. Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides

    PubMed Central

    Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O. T.; Zhang, Zhenfa; Marth, Wendy J.; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G.; Vizuete, William; Xie, Ying; Luecken, Deborah J.; Piletic, Ivan R.; Edney, Edward O.; Bartolotti, Libero J.; Gold, Avram; Surratt, Jason D.

    2013-01-01

    Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NOx = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NOx. PMID:23553832

  5. Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides.

    PubMed

    Lin, Ying-Hsuan; Zhang, Haofei; Pye, Havala O T; Zhang, Zhenfa; Marth, Wendy J; Park, Sarah; Arashiro, Maiko; Cui, Tianqu; Budisulistiorini, Sri Hapsari; Sexton, Kenneth G; Vizuete, William; Xie, Ying; Luecken, Deborah J; Piletic, Ivan R; Edney, Edward O; Bartolotti, Libero J; Gold, Avram; Surratt, Jason D

    2013-04-23

    Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NO(x) = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NO(x). PMID:23553832

  6. Organic tracers of primary biological aerosol particles at subtropical Okinawa Island in the western North Pacific Rim

    NASA Astrophysics Data System (ADS)

    Zhu, Chunmao; Kawamura, Kimitaka; Kunwar, Bhagawati

    2015-06-01

    Primary biological aerosol particles (PBAPs) play an important role in affecting atmospheric physical and chemical properties. Aerosol samples were collected at Cape Hedo, Okinawa Island, Japan, from October 2009 to February 2012 and analyzed for five primary saccharides and four sugar alcohols as PBAP tracers. We detected high levels of sucrose in spring when blossoming of plants happens and prolifically emits pollen to the air. Concentrations of glucose, fructose, and trehalose showed levels higher than the other saccharides in spring in 2010. In comparison, primary saccharide levels were mutually comparable in spring, summer, and autumn in 2011, indicating the interannual variability of their local production in subtropical forests, which is driven by local temperature and radiation. High trehalose events were found to be associated with Asian dust outflows, indicating that Asian dust also contributes to PBAPs at Okinawa. Sugar alcohols peaked in summer and correlated with local precipitation and temperature, indicating high microbial activities. Positive matrix factorization analysis confirmed that the PBAPs are mainly derived from local vegetation, pollen, and fungal spores. A higher contribution of PBAP tracers to water-soluble organic carbon (WSOC) was found in summer (14.9%). The annual mean ambient loadings of fungal spores and PBAPs were estimated as 0.49 µg m-3 and 4.12 µg m-3, respectively, using the tracer method. We report, for the first time, year-round biomarkers of PBAP and soil dust and their contributions to WSOC in the subtropical outflow region of the Asian continent.

  7. Identification of oxidized organic atmospheric species during the Southern Oxidant and Aerosol Study (SOAS) using a novel Ion Mobility Time-of-Flight Chemical Ionization Mass Spectrometer (IMS-ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Krechmer, J.; Canagaratna, M.; Kimmel, J.; Junninen, H.; Knochenmuss, R.; Cubison, M.; Massoli, P.; Stark, H.; Jayne, J. T.; Surratt, J. D.; Jimenez, J. L.; Worsnop, D. R.

    2013-12-01

    We present results from the field deployment of a novel Ion Mobility Time-of-flight Chemical Ionization Mass Spectrometer (CI-IMS-TOF) during the Southern Oxidant and Aerosol Study (SOAS). IMS-TOF is a 2-dimensional analysis method, which separates gas-phase ions by mobility prior to determination of mass-to-charge ratio by mass spectrometry. Ion mobility is a unique physical property that is determined by the collisional cross section of an ion. Because mobility depends on size and shape, the IMS measurement is able to resolve isomers and isobaric compounds. Additionally, trends in IMS-TOF data space can be used to identify relationships between ions, such as common functionality or polymeric series. During SOAS we interfaced the IMS-TOF to a nitrate ion (NO3-) chemical ionization source that enables the selective ionization of highly oxidized gas phase species (those having a high O:C ratio) through clustering with the reagent ion. Highly oxidized products of terpenes and isoprene are important secondary organic aerosol precursors (SOA) that play an uncertain but important role in particle-phase chemistry. We present several case studies of atmospheric events during SOAS that exhibited elevated concentrations of sulfuric acid and/or organics. These events exhibited a rise in particle number and provide an opportunity to examine the role that organic species may have in local atmospheric new particle formation events. We also present the results from the field deployment and subsequent laboratory studies utilizing a Potential Aerosol Mass (PAM) flow reactor as the inlet for the CI-IMS-TOF. The reactor draws in ambient air and exposes it to high concentrations of the OH radical, created by photolysis O3 in the presence of water. The highly oxidized products are then sampled directly by the CI-IMS-TOF. We performed several experiments including placing pine and deciduous plants directly in front of the reactor opening and observed large increases in the number and

  8. SOA multiday growth: Model artifact or reality?

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J. M.; Madronich, S.; Aumont, B.; Hodzic, A.; Camredon, M.; Valorso, R.

    2013-12-01

    Simulations of SOA gas-particle partitioning with the explicit gas-phase chemical mechanism generator GECKO-A show significant SOA mass growth continuing for several days, even as the initial air parcel is diluted into the regional atmosphere. This result is a robust feature of our model and occurs with both anthropogenic and biogenic precursors. The growth originates from continuing oxidation of gas-phase precursors which persist in equilibrium with the particle phase. This result implies that sources of aerosol precursors could influence the chemical and radiative characteristics of the atmosphere over a wider region than previously imagined, and that SOA measurements near precursor sources may routinely underestimate this influence. It highlights the need to better understand the sink terms in the SOA budget.

  9. SOA from BVOCs in the Southeastern United States

    EPA Science Inventory

    Biogenic hydrocarbons contribute to organic aerosol in the southeast United States. In this work, we represent aerosol formation from the oxidation of isoprene and monoterpenes in CMAQ and compare to data from the Southeast Oxidants and Aerosol Study (SOAS). Sensitivity simulatio...

  10. Modeling SOA production from the oxidation of intermediate volatility alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-12-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapour pressure. This process was investigated using the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere). Results for the C8-C24 n-alkane series show the expected trends, i.e. (i) SOA yield grows with the carbon backbone of the parent hydrocarbon, (ii) SOA yields decreases with the decreasing pre-existing organic aerosol concentration, (iii) the number of generations required to describe SOA production increases when the pre-existing organic aerosol concentration decreases. Most SOA contributors were found to be not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA). Branched alkanes are more prone to fragment in the early stage of the oxidation than their corresponding linear analogues. Fragmentation is expected to alter both the yield and the mean oxidation state of the SOA. Here, GECKO-A is applied to generate highly detailed oxidation schemes for various series of branched and cyclised alkanes. Branching and cyclisation effects on SOA yields and oxidation states will be examined.

  11. To What Extent Can Biogenic SOA Be Controlled?

    EPA Science Inventory

    Anthropogenic pollution facilitates transformation of naturally emitted volatile organic compounds (VOCs) to the particle phase, enhancing the ambient concentrations of material commonly referred to as biogenic secondary organic aerosol (SOA). It is therefore conceivable that som...

  12. SOA FROM ISOPRENE OXIDATION PRODUCTS: MODEL SIMULATION OF CLOUD CHEMISTRY

    EPA Science Inventory

    Recent laboratory evidence supports the hypothesis that secondary organic aerosol (SOA) is formed in the atmosphere through aqueous-phase reactions in clouds. The results of batch photochemical reactions of glyoxal, methylglyoxal and hydrogen peroxide are presented. These labor...

  13. UNDERSTANDING REGIONAL OXIDATION CAPACITY BY COMPREHENSIVE OBSERVATIONS TO CONSTRAIN HYDROXYL RADICAL SOURCES AND SINKS DURING THE SOUTHERN OXIDANT AEROSOL STUDY (SOAS)

    EPA Science Inventory

    The proposed field measurements and data analysis will provide an important constraint to understand oxidation capacity in the Southeastern U.S. that determines SOA and photochemical ozone formation. Unexpectedly high levels of OH determining oxidation capacity have been co...

  14. Seasonal variation of levoglucosan in aerosols over the western North Pacific and its assessment as a biomass-burning tracer

    NASA Astrophysics Data System (ADS)

    Mochida, Michihiro; Kawamura, Kimitaka; Fu, Pingqing; Takemura, Toshihiko

    2010-09-01

    Levoglucosan is considered as a useful molecular tracer of biomass-burning aerosols in the atmosphere. To characterize the seasonal variation of its concentrations over the Pacific Ocean and to assess its usefulness as a tracer after long-range transport, we investigated long-term variations of levoglucosan over Chichi-jima in the western North Pacific, from 2001 to 2004. Organic carbon (OC), elemental carbon (EC) and D-glucose were analyzed for comparison. The seasonal variation of levoglucosan concentrations showed a maximum in the winter, which is consistent with the enhanced Asian outflow to the Pacific indicated by backward air-mass trajectories. The concentration levels of levoglucosan estimated from global aerosol model outputs in the winter are, on average, comparable to the observed levels, suggesting that a considerable fraction of levoglucosan did not decompose during long-range transport from the Asian continent by westerly/northwesterly winds. This result is supported by comparable ratios of levoglucosan to EC in Chichi-jima and the East Asian coastal region. Conversely, the measured concentrations of levoglucosan in the summer were significantly lower than the modeled one. This implies a degradation of levoglucosan in the air masses that stagnated over the Pacific, although uncertainties in the model estimate may also be partly responsible for this discrepancy. One possible degradation pathway is oxidation by OH radicals; the contribution of acid-catalyzed reactions needs further investigation.

  15. The Explicit-Cloud Parameterized-Pollutant Hybrid Approach for Aerosol-Cloud Interactions in Multiscale Modelling Framework Models: Tracer Transport Results

    SciTech Connect

    Gustafson, William I.; Berg, Larry K.; Easter, Richard C.; Ghan, Steven J.

    2008-05-30

    All estimates of aerosol indirect effects on the global energy balance have either completely neglected the influence of aerosol on convective clouds or treated the influence in a highly parameterized manner. Embedding cloud-resolving models (CRMs) within each grid cell of a global model provides a multiscale modelling framework for treating both the influence of aerosols on convective as well as stratiform clouds and the influence of all clouds on the aerosol, but treating the interactions explicitly by simulating all aerosol processes in the CRM would be computationally prohibitive. An alternate approach is to use horizontal statistics (e.g., cloud mass flux, cloud fraction, and precipitation) from the CRM simulation to drive a single-column parameterization of cloud effects on the aerosol and then use the aerosol profile to simulate aerosol effects on clouds within the CRM. Here we test this concept for vertical transport by clouds, using a CRM with tracer transport simulated explicitly to serve as a benchmark. We show that this parameterization, driven by the CRM’s cloud mass fluxes, reproduces the tracer transport by the CRM significantly better than a single column model that uses a conventional convective cloud parameterization.

  16. Global transformation and fate of SOA: Implications of low-volatility SOA and gas-phase fragmentation reactions

    NASA Astrophysics Data System (ADS)

    Shrivastava, Manish; Easter, Richard C.; Liu, Xiaohong; Zelenyuk, Alla; Singh, Balwinder; Zhang, Kai; Ma, Po-Lun; Chand, Duli; Ghan, Steven; Jimenez, Jose L.; Zhang, Qi; Fast, Jerome; Rasch, Philip J.; Tiitta, Petri

    2015-05-01

    Secondary organic aerosols (SOA) are large contributors to fine-particle loadings and radiative forcing but are often represented crudely in global models. We have implemented three new detailed SOA treatments within the Community Atmosphere Model version 5 (CAM5) that allow us to compare the semivolatile versus nonvolatile SOA treatments (based on some of the latest experimental findings) and to investigate the effects of gas-phase fragmentation reactions. The new treatments also track SOA from biomass burning and biofuel, fossil fuel, and biogenic sources. For semivolatile SOA treatments, fragmentation reactions decrease the simulated annual global SOA burden from 7.5 Tg to 1.8 Tg. For the nonvolatile SOA treatment with fragmentation, the burden is 3.1 Tg. Larger differences between nonvolatile and semivolatile SOA (up to a factor of 5) exist in areas of continental outflow over the oceans. According to comparisons with observations from global surface Aerosol Mass Spectrometer measurements and the U.S. Interagency Monitoring of Protected Visual Environments (IMPROVE) network measurements, the FragNVSOA treatment, which treats SOA as nonvolatile and includes gas-phase fragmentation reactions, agrees best at rural locations. Urban SOA is underpredicted, but this may be due to the coarse model resolution. All three revised treatments show much better agreement with aircraft measurements of organic aerosols (OA) over the North American Arctic and sub-Arctic in spring and summer, compared to the standard CAM5 formulation. This is mainly due to the oxidation of SOA precursor gases from biomass burning, not included in standard CAM5, and long-range transport of biomass burning OA at high altitudes. The revised model configurations that include fragmentation (both semivolatile and nonvolatile SOA) show much better agreement with MODerate resolution Imaging Spectrometers (MODIS) aerosol optical depth data over regions dominated by biomass burning during the summer

  17. Molecular Markers of Secondary Organic Aerosol in Mumbai, India.

    PubMed

    Fu, Pingqing; Aggarwal, Shankar G; Chen, Jing; Li, Jie; Sun, Yele; Wang, Zifa; Chen, Huansheng; Liao, Hong; Ding, Aijun; Umarji, G S; Patil, R S; Chen, Qi; Kawamura, Kimitaka

    2016-05-01

    Biogenic secondary organic aerosols (SOA) are generally considered to be more abundant in summer than in winter. Here, polar organic marker compounds in urban background aerosols from Mumbai were measured using gas chromatography-mass spectrometry. Surprisingly, we found that concentrations of biogenic SOA tracers at Mumbai were several times lower in summer (8-14 June 2006; wet season; n = 14) than in winter (13-18 February 2007; dry season; n = 10). Although samples from less than 10% of the season are extrapolated to the full season, such seasonality may be explained by the predominance of the southwest summer monsoon, which brings clean marine air masses to Mumbai. While heavy rains are an important contributor to aerosol removal during the monsoon season, meteorological data (relative humidity and T) suggest no heavy rains occurred during our sampling period. However, in winter, high levels of SOA and their day/night differences suggest significant contributions of continental aerosols through long-range transport together with local sources. The winter/summer pattern of SOA loadings was further supported by results from chemical transport models (NAQPMS and GEOS-Chem). Furthermore, our study suggests that monoterpene- and sesquiterpene-derived secondary organic carbon (SOC) were more significant than those of isoprene- and toluene-SOC at Mumbai. PMID:27045808

  18. Fungal spores overwhelm biogenic organic aerosols in a midlatitudinal forest

    NASA Astrophysics Data System (ADS)

    Zhu, Chunmao; Kawamura, Kimitaka; Fukuda, Yasuro; Mochida, Michihiro; Iwamoto, Yoko

    2016-06-01

    Both primary biological aerosol particles (PBAPs) and oxidation products of biogenic volatile organic compounds (BVOCs) contribute significantly to organic aerosols (OAs) in forested regions. However, little is known about their relative importance in diurnal timescales. Here, we report biomarkers of PBAP and secondary organic aerosols (SOAs) for their diurnal variability in a temperate coniferous forest in Wakayama, Japan. Tracers of fungal spores, trehalose, arabitol and mannitol, showed significantly higher levels in nighttime than daytime (p < 0.05), resulting from the nocturnal sporulation under near-saturated relative humidity. On the contrary, BVOC oxidation products showed higher levels in daytime than nighttime, indicating substantial photochemical SOA formation. Using tracer-based methods, we estimated that fungal spores account for 45 % of organic carbon (OC) in nighttime and 22 % in daytime, whereas BVOC oxidation products account for 15 and 19 %, respectively. To our knowledge, we present for the first time highly time-resolved results that fungal spores overwhelmed BVOC oxidation products in contributing to OA especially in nighttime. This study emphasizes the importance of both PBAPs and SOAs in forming forest organic aerosols.

  19. New Particle Formation and Secondary Organic Aerosol in Beijing

    NASA Astrophysics Data System (ADS)

    Hu, M.; Yue, D.; Guo, S.; Hu, W.; Huang, X.; He, L.; Wiedensohler, A.; Zheng, J.; Zhang, R.

    2011-12-01

    Air pollution in Beijing has been a major concern due to being a mega-city and green Olympic Games requirements. Both long term and intensive field measurements have been conducted at an Urban Air Quality Monitoring Station in the campus of Peking University since 2004. Aerosol characteristics vary seasonally depending on meteorological conditions and source emissions. Secondary compositions of SNA (sum of sulfate, nitrate, and ammonium) and SOA (secondary organic aerosol) become major fraction of fine particles, which may enhance aerosol impacts on visibility and climate change. The transformation processes of new particle formation (NPF) and secondary organic aerosol have been focused on. It was found that gaseous sulfuric acid, ammonia, and organic compounds are important precursors to NPF events in Beijing and H2SO4-NH3-H2O ternary nucleation is one of the important mechanisms. The contributions of condensation and neutralization of sulfuric acid, coagulation, and organics to the growth of the new particles are estimated as 45%, 34%, and 21%, respectively. Tracer-based method to estimate biogenic and anthropogenic SOA was established by using gas chromatography-mass spectrometry. Secondary organic tracers derived from biogenic (isoprene, α-pinene, β-caryophyllene) and anthropogenic (toluene) contributed 32% at urban site and 35% at rural site, respectively. Other source apportionment techniques were also used to estimate secondary organic aerosols, including EC tracer method, water soluble organic carbon content, chemical mass balance model, and AMS-PMF method.

  20. SOA YIELDS AND ORGANIC PRODUCT DISTRIBUTION FROM NATURAL HYDROCARBON/NOX IRRADIATIONS

    EPA Science Inventory

    Secondary organic aerosol (SOA) typically comprises one-quarter to one-third of the ambient aerosol mass in summertime urban atmospheres. In tropospheric environments, the main precursors of SOA come from aromatic and natural hydrocarbons. Recent work by various investigators...

  1. Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

    NASA Astrophysics Data System (ADS)

    Snyder, David C.; Rutter, Andrew P.; Worley, Chris; Olson, Mike; Plourde, Anthony; Bader, Rebecca C.; Dallmann, Timothy; Schauer, James J.

    2010-05-01

    Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM 2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5-4 km) and between 4 and 27% at the urban scale (4-100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM 2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.

  2. Source apportioning of primary and secondary organic carbon in summer PM2.5 in Hong Kong using positive matrix factorization of secondary and primary organic tracer data

    NASA Astrophysics Data System (ADS)

    Hu, Di; Bian, Qijing; Lau, Alexis K. H.; Yu, Jian Zhen

    2010-08-01

    The major inorganic constituents and organic tracer compounds in PM2.5 were used in positive matrix factorization (PMF) and chemical mass balance (CMB) models to apportion the primary and secondary source contributions to organic carbon (OC) in Hong Kong during the summer of 2006. Secondary organic aerosol (SOA) tracers of several biogenic and anthropogenic hydrocarbons were included in the PMF analysis. Their inclusion allowed the identification of two components of SOA among seven factors resolved by PMF. One SOA component was mainly associated with secondary sulfate and nitrate. The other SOA component, characterized by biogenic SOA tracers and mixed with biomass burning and vegetative detritus particles, was biomass burning-induced SOA. Secondary OC (SOC) apportioned by PMF (SOCPMF) was on average 6.84 μgC m-3 (65% of PM2.5 OC) on high pollution days under influence of significant regional transport (i.e., regional days) and 0.70 μgC m-3 (25% of PM2.5 OC) on days under the influence of mainly local emissions (i.e., local days). The biomass burning-induced SOA accounted for 20% of the total SOA on the regional days, underlining the importance of biomass burning aerosol source in this region. The average uncertainty for the SOCPMF estimates was ˜20% on the regional days and ˜120% on the local days. SOCPMF was compared with SOC determined by CMB (SOCCMB, i.e., unapportioned OC by CMB analysis) and a tracer-based method (SOCTBM) that apportioned SOC contributions by four hydrocarbon precursors including isoprene, monoterpenes, β-caryophyllene, and toluene. The three estimates of SOC closely tracked with each other among individual samples. The SOCCMB and SOCPMF estimates on the majority of the regional days differed from each other by less than 25%. Good correlations between contributions of SOC and individual primary OC sources apportioned by PMF and CMB further added to the credence to the PMF-derived estimation of secondary and primary OC source

  3. Natural products and altered derivatives as tracers for biomass combustion in aerosols

    SciTech Connect

    Simoneit, B.R.T.; Radzi bin Abas, M.; Cass, G.R.

    1995-12-01

    Biomass combustion is an important primary source of carbonaceous particles in the global atmosphere. Various molecular markers have been proposed for this process but additional specific tracers are needed. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by pyrolysis. Although the composition of organic matter in smoke particles is highly variable, the molecular structures of the tracers are generally source specific. Homologous compounds and biomarkers present in smoke are derived directly from plant wax, gum and resin by volatilization and secondarily from pyrolysis of biopolymers (e.g., lignin, cutin, suberin), wax, gum and resin. The component complexity is illustrated with examples from controlled bums of temperate and tropical biomass fuels. Conifer smoke contains characteristic tracers from diterpenoids as well as phenolics and other oxygenated species. These are recognizable in urban airsheds. The major organic components of smoke from tropical biomass are straight-chain, aliphatic and oxygenated compounds and triterpenoids. Several compounds are potential key indicators for combustion of such biomass. The precursor to product approach of organic geochemistry can be applied successfully to provide molecular tracers for studying smoke plume chemistry and dispersion.

  4. Thirteen years of observations on biomass burning organic tracers over Chichijima Island in the western North Pacific: An outflow region of Asian aerosols

    NASA Astrophysics Data System (ADS)

    Verma, Santosh Kumar; Kawamura, Kimitaka; Chen, Jing; Fu, Pingqing; Zhu, Chunmao

    2015-05-01

    East Asia is the world's greatest source region for the emission of anthropogenic aerosols and their precursors due to the rapid industrialization and intensive biomass burning (BB) activities. BB emits specific organic tracers such as levoglucosan, mannosan, and galactosan, which are produced by pyrolysis of cellulose and hemicellulose and then transported downwind to the western North Pacific by westerly winds. Here we present long-term observations of BB tracers over the remote Chichijima Island in the western North Pacific (WNP) from 2001 to 2013. Elevated concentrations of BB tracers by an order of magnitude were found in midautumn to midspring with winter maxima, which are strongly involved with the atmospheric transport by westerly winds from the Asian continent to the WNP, as supported by backward trajectory analyses. Throughout the observations, we found an increase in the averaged concentrations of BB tracers from 2006 to 2013, which is mainly caused by enhanced BB events in Asian urban and rural areas, as supported by enhanced fire/hot spots in East Asia via satellite images. We also found that the period of the high concentrations was prolonged from 2006 to 2013. Comparison between monthly averaged concentrations of BB tracers and backward air mass trajectories clearly demonstrates that the winter/spring maxima over Chichijima are involved with the seasonal shifting of atmospheric circulation followed by downwind transport of BB aerosols to the WNP. High abundances of BB tracers over the WNP indicate that BB-laden air masses can be transported to remote marine environments.

  5. High-time resolved measurements of biogenic and anthropogenic secondary organic aerosol precursors and products in urban air

    NASA Astrophysics Data System (ADS)

    Flores, Rosa M.; Doskey, Paul V.

    2016-04-01

    Volatile organic compounds (VOCs), which are present in the atmosphere entirely in the gas phase are directly emitted by biogenic (~1089 Tg yr-1) and anthropogenic sources (~185 Tg yr-1). However, the sources and molecular speciation of intermediate VOCs (IVOCs), which are for the most part also present almost entirely in the gas phase, are not well characterized. The VOCs and IVOCs participate in reactions that form ozone and semivolatile OC (SVOC) that partition into the aerosol phase. Formation and evolution of secondary organic aerosol (SOA) are part of a complex dynamic process that depends on the molecular speciation and concentration of VOCs, IVOCs, primary organic aerosol (POA), and the level of oxidants (NO3, OH, O3). The current lack of understanding of OA properties and their impact on radiative forcing, ecosystems, and human health is partly due to limitations of models to predict SOA production on local, regional, and global scales. More accurate forecasting of SOA production requires high-temporal resolution measurement and molecular characterization of SOA precursors and products. For the subject study, the IVOCs and aerosol-phase organic matter were collected using the high-volume sampling technique and were analyzed by multidimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-ToFMS). The IVOCs included terpenes, terpenoids, n-alkanes, branched alkanes, isoprenoids, alkylbenzenes, cycloalkylbenzenes, PAH, alkyl PAH, and an unresolved complex mixture (UCM). Diurnal variations of OA species containing multiple oxygenated functionalities and selected SOA tracers of isorprene, α-pinene, toluene, cyclohexene, and n-dodecane oxidation were also quantified. The data for SOA precursor and oxidation products presented here will be useful for evaluating the ability of molecular-specific SOA models to forecast SOA production in and downwind of urban areas.

  6. Seasonal and spatial variation of organic tracers for biomass burning in PM1 aerosols from highly insolated urban areas.

    PubMed

    van Drooge, B L; Fontal, M; Bravo, N; Fernández, P; Fernández, M A; Muñoz-Arnanz, J; Jiménez, B; Grimalt, J O

    2014-10-01

    PM1 aerosol characterization on organic tracers for biomass burning (levoglucosan and its isomers and dehydroabietic acid) was conducted within the AERTRANS project. PM1 filters (N = 90) were sampled from 2010 to 2012 in busy streets in the urban centre of Madrid and Barcelona (Spain) at ground-level and at roof sites. In both urban areas, biomass burning was not expected to be an important local emission source, but regional emissions from wildfires, residential heating or biomass removal may influence the air quality in the cities. Although both areas are under influence of high solar radiation, Madrid is situated in the centre of the Iberian Peninsula, while Barcelona is located at the Mediterranean Coast and under influence of marine atmospheres. Two extraction methods were applied, i.e. Soxhlet and ASE, which showed equivalent results after GC-MS analyses. The ambient air concentrations of the organic tracers for biomass burning increased by an order of magnitude at both sites during winter compared to summer. An exception was observed during a PM event in summer 2012, when the atmosphere in Barcelona was directly affected by regional wildfire smoke and levels were four times higher as those observed in winter. Overall, there was little variation between the street and roof sites in both cities, suggesting that regional biomass burning sources influence the urban areas after atmospheric transport. Despite the different atmospheric characteristics in terms of air relative humidity, Madrid and Barcelona exhibit very similar composition and concentrations of biomass burning organic tracers. Nevertheless, levoglucosan and its isomers seem to be more suitable for source apportionment purposes than dehydroabietic acid. In both urban areas, biomass burning contributions to PM were generally low (2 %) in summer, except on the day when wildfire smoke arrive to the urban area. In the colder periods the contribution increase to around 30 %, indicating that regional

  7. Enhanced secondary organic aerosols during fog episodes over typical location in Indo-Gangetic region

    NASA Astrophysics Data System (ADS)

    Kaul, D. S.; Tripathi, S. N.; Gupta, T.

    2011-12-01

    This study examines the reason of enhanced SOA yield during foggy days and hypothesizes likely production of SOA through aqueous phase chemistry during fog episodes. PM1 samples were collected from January 16, 2010 to February 20, 2010 at Kanpur to study the secondary organic aerosol (SOA) production during clear and foggy days. Of the 180 samples collected, 56 were from foggy days. Micro-Pulse Lidar Network (MPLNET), a part of National Aeronautic Space Administration (NASA), was used for identification of fog duration. Organic Carbon (OC), Elemental Carbon (EC) and water soluble organic carbon analysis were carried out by a EC-OC analyzer and a TOC analyzer, respectively. Trace gases and solar flux measurement were carried out by gas analyzers and a pyranometer (a part of NASA), respectively to identify the photo-chemical activity. Meteorological data were measured by atmospheric weather station. SOA was estimated during foggy and clear days using tracer method. Enhanced SOA was observed during foggy days, production of SOA was highest in the afternoon and lower during morning and evening. Peak of OC/EC ratio during foggy days occurred earlier indicating role of aqueous phase chemistry in addition to gas-particle portioning which is the prevalent mechanism of SOA production during clear days. The possible contribution of biomass burning to SOA which could otherwise confound the SOA estimate during foggy days was also examined by biomass tracer, potassium ion. The influence of biomass to SOA during foggy days was found to be negligible. This is so because organic carbon from biomass origin is highly hygroscopic and is scavenged by the fog droplets. The lesser average concentration of water soluble organic carbon during foggy days support the scavenging and removal of the biomass originated organic carbon. Evaporation of individual fog and subsequent increase of OC/EC ratio further supported the aqueous phase production of SOA. The temperature and relative humidity

  8. Can Sesquiterpene SOA be good CCN?

    NASA Astrophysics Data System (ADS)

    Asa-Awuku, A. A.; Tang, X.

    2011-12-01

    Secondary organic aerosol (SOA) particles are formed via gaseous reactions in the atmosphere and have the potential to impact climate and the hydrological cycle through their ability to act as cloud condensation nuclei (CCN). Beta-caryophyllene is a biogenic sesquiterpene emission and is known to react quickly and form low volatility products in the particulate phase. Previous work shows that the hygroscopic material in Beta-caryophyllene SOA may be semivolatile, and the less volatile component less hygroscopic. The less volatile component has been shown to impact the droplet growth kinetics. In this study, we revisit experiments at the University of California, Riverside Bourns College of Engineering- Center for Environmental Research and Technology (CE-CERT) dual 90 m3 indoor smog chamber, in which much lower concentration can be achieved. A suite of gas phase and particle phase instrumentation characterizes the thermodynamic aerosol properties and CCN activity. Hygroscopicity, volatility, particle size, number, mass, and composition and gas phase concentration are measured with, Gas chromatography-mass spectrometry (GC-MS), Scanning Mobility Particle Sizer (SMPS), tandem differential mobility analyzer (TDMA), and High Resolution Aerosol Mass Spectrometry (HR-AMS). In addition to chemical measurements aerosol physical properties are also reported. Experiments are conducted at different conditions to characterize the effect of hydroxyl radical, light, addition of another hydrocarbon precursor (isoprene) on SOA formation and characteristics.

  9. ß-CARYOPHYLLINIC ACID: AN ATMOSPHERIC TRACER FOR ß-CARYOPHYLLENE SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    The chemical compositions of ambient PM2.5 samples, collected in Research Triangle Park, North Carolina, USA, and a sample of secondary organic aerosol, formed by irradiating a mixture of the sesquiterpene, ß-caryophyllene, and oxides of nitrogen in a smog chamber, wer...

  10. EVIDENCE FOR ORGANOSULFATES IN SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    Recent work has shown that particle-phase reactions contribute to the formation of secondary organic aerosol (SOA), with enhancements of SOA yields in the presence of acidic seed aerosol. In this study, the chemical composition of SOA from the photooxidations of α-pinene and isop...

  11. Linear regression techniques for use in the EC tracer method of secondary organic aerosol estimation

    NASA Astrophysics Data System (ADS)

    Saylor, Rick D.; Edgerton, Eric S.; Hartsell, Benjamin E.

    A variety of linear regression techniques and simple slope estimators are evaluated for use in the elemental carbon (EC) tracer method of secondary organic carbon (OC) estimation. Linear regression techniques based on ordinary least squares are not suitable for situations where measurement uncertainties exist in both regressed variables. In the past, regression based on the method of Deming [1943. Statistical Adjustment of Data. Wiley, London] has been the preferred choice for EC tracer method parameter estimation. In agreement with Chu [2005. Stable estimate of primary OC/EC ratios in the EC tracer method. Atmospheric Environment 39, 1383-1392], we find that in the limited case where primary non-combustion OC (OC non-comb) is assumed to be zero, the ratio of averages (ROA) approach provides a stable and reliable estimate of the primary OC-EC ratio, (OC/EC) pri. In contrast with Chu [2005. Stable estimate of primary OC/EC ratios in the EC tracer method. Atmospheric Environment 39, 1383-1392], however, we find that the optimal use of Deming regression (and the more general York et al. [2004. Unified equations for the slope, intercept, and standard errors of the best straight line. American Journal of Physics 72, 367-375] regression) provides excellent results as well. For the more typical case where OC non-comb is allowed to obtain a non-zero value, we find that regression based on the method of York is the preferred choice for EC tracer method parameter estimation. In the York regression technique, detailed information on uncertainties in the measurement of OC and EC is used to improve the linear best fit to the given data. If only limited information is available on the relative uncertainties of OC and EC, then Deming regression should be used. On the other hand, use of ROA in the estimation of secondary OC, and thus the assumption of a zero OC non-comb value, generally leads to an overestimation of the contribution of secondary OC to total measured OC.

  12. SOA Aging and Oligomer Content and their Effect on the Volatility and Viscosity of SOA Particles Generated from Different Precursors

    NASA Astrophysics Data System (ADS)

    Wilson, J. M.; Zelenyuk, A.; Imre, D. G.; Beranek, J.

    2013-12-01

    Formation, properties, transformations and temporal evolution of secondary organic aerosol (SOA) particles strongly depend on particle phase and volatility. Our recent studies indicate that laboratory-generated alpha-pinene SOA particles are highly viscous semi-solids with viscosity characteristic of tars, and their evaporation rates are orders of magnitude slower than previously assumed. This is not surprising given that numerous studies provide evidence that SOA particles contain significant amounts of high molecular weight organic compounds (oligomers), which affect SOA phase and volatility. It is well known that oligomers can severely retard diffusion, mixing, and thus evaporation of smaller molecules. One of the most intriguing findings is that SOA fractional evaporation rates are nearly size independent. We begin by presenting our results of evaporation studies of particles composed of hexaethylene glycol (HEG), polyethylene glycols (PEGs) of different polymer chain length, and their mixtures. The data indicate that HEG particles exhibit the size-dependent evaporation expected for liquid droplets, while particles containing polymers with different chain lengths exhibit size-independent evaporation kinetics similar to those of SOA. We will then present the results of evaporation studies of SOA particles generated by oxidation of several different precursors, including alpha-pinene, isoprene, limonene, n-alkenes and cyclo-alkenes, from which we explore the relationship between SOA oligomer content and SOA volatility and viscosity. We, and others, also find that oligomer content in SOA increases with time, and with it we expect corresponding changes in viscosity and volatility. We will present the results of studies aimed at characterizing evaporation kinetics and the viscosity of SOA particles as a function of particle age. We will also present our findings on the effect of hydrophobic organics on SOA oligomer content, its volatility and viscosity.

  13. La-oxides as tracers for PuO{sub 2} to simulate contaminated aerosol behavior

    SciTech Connect

    Meyer, L.C.; Newton, G.J.; Cronenberg, A.W.; Loomis, G.G.

    1994-04-01

    An analytical and experimental study was performed on the use of lanthanide oxides (La-oxides) as surrogates for plutonium oxides (PuO{sub 2}) during simulated buried waste retrieval. This study determined how well the La-oxides move compared to PuO{sub 2} in aerosolized soils during retrieval scenarios. As part of the analytical study, physical properties of La-oxides and PuO{sub 2}, such as molecular diameter, diffusivity, density, and molecular weight are compared. In addition, an experimental study was performed in which Idaho National Engineering Laboratory (INEL) soil, INEL soil with lanthanides, and INEL soil with plutonium were aerosolized and collected in filters. Comparison of particle size distribution parameters from this experimental study show similarity between INEL soil, INEL soil with lanthanides, and INEL soil with plutonium.

  14. Investigation of the detailed chemical composition of organic aerosol in a South East Asian Rainforest

    NASA Astrophysics Data System (ADS)

    Hamilton, Jacqueline; Ward, Martyn; Rami Alfarra, M.; Lewis, Alastair; McFiggans, Gordon; Robinson, Niall

    2010-05-01

    The formation of secondary organic aerosol (SOA) in tropical regions is a key uncertainty in quantifying the effect of man made emissions on the climate. Large quantities of volatile organic compounds are emitted from natural biogenic sources in the tropics, including isoprene, monoterpenes and sequiterpenes. There are very few studies of the detailed chemical composition of organic aerosols in tropical rainforest regions, but these would provide information on the importance of primary versus secondary organic aerosols, the key VOC precursors, oxidation state and volatility. Particle samples were collected in a tropical rainforest at Danum Valley in Borneo as part of the OP3 field campaign in 2008. Twenty four hour filter samples were collected at the Global Atmospheric Watch station at a height of around 10 m and shipped back to the laboratory (below -4 °C) for offline analysis. The OA composition was studied using multiple high resolution chromatographic techniques including comprehensive two dimensional gas chromatography coupled to time of flight mass spectrometry (GCXGC-TOFMS) and liquid chromatography coupled to ion trap mass spectrometry (LC-MSn). The composition was directly compared to chamber generated SOA (as part of the Aerosol Coupling in the Earths System , ACES, experiment) to determine SOA tracers. A biogenic SOA tracer MS fragmentation library was constructed and a number of SOA components from limonene, linalool and -pinene were identified in the rainforest OA. Very high resolution mass spectrometry (Fourier Transform Ion Cyclotron Resonance FTICR-MS) allowed the O:C and H:C ratios to be determined and these will be compared to those obtained by aerosol mass spectrometry (AMS). In addition, the OA composition from the rainforest will be compared to other locations.

  15. Global transformation and fate of SOA: Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions

    SciTech Connect

    Shrivastava, ManishKumar B.; Easter, Richard C.; Liu, Xiaohong; Zelenyuk, Alla; Singh, Balwinder; Zhang, Kai; Ma, Po-Lun; Chand, Duli; Ghan, Steven J.; Jiminez, J. L.; Zhang, Qibin; Fast, Jerome D.; Rasch, Philip J.; Tiitta, P.

    2015-05-16

    Secondary organic aerosols (SOA) are large contributors to fine particle loadings and radiative forcing, but are often represented crudely in global models. We have implemented three new detailed SOA treatments within the Community Atmosphere Model version 5 (CAM5) that allow us to compare the semi-volatile versus non-volatile SOA treatments (based on some of the latest experimental findings) and also investigate the effects of gas-phase fragmentation reactions. For semi-volatile SOA treatments, fragmentation reactions decrease simulated SOA burden from 7.5 Tg to 1.8 Tg. For the non-volatile SOA treatment with fragmentation, the burden is 3.1 Tg. Larger differences between non-volatile and semi-volatile SOA (upto a factor of 5) correspond to continental outflow over the oceans. Compared to a global dataset of surface Aerosol Mass Spectrometer measurements and the US IMPROVE network measurements, the non-volatile SOA with fragmentation treatment (FragNVSOA) agrees best at rural locations. Urban SOA is under-predicted but this may be due to the coarse model resolution. All our three revised treatments show much better agreement with aircraft measurements of organic aerosols (OA) over the N. American Arctic and sub-Arctic in spring and summer, compared to the standard CAM5 formulation. This is due to treating SOA precursor gases from biomass burning, and long-range transport of biomass burning OA at elevated levels. The revised model configuration that include fragmentation (both semi-volatile and non-volatile SOA) show much better agreement with MODIS AOD data over regions dominated by biomass burning during the summer, and predict biomass burning as the largest global source of OA followed by biogenic and anthropogenic sources. The non-volatile and semi-volatile configuration predict the direct radiative forcing of SOA as -0.5 W m-2 and -0.26 W m-2 respectively, at top of the atmosphere, which are higher than previously estimated by most models, but in reasonable

  16. Aerosol transport and wet scavenging in deep convective clouds: A case study and model evaluation using a multiple passive tracer analysis approach

    NASA Astrophysics Data System (ADS)

    Yang, Qing; Easter, Richard C.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Fast, Jerome D.; Ghan, Steven J.; Wang, Hailong; Berg, Larry K.; Barth, Mary C.; Liu, Ying; Shrivastava, Manishkumar B.; Singh, Balwinder; Morrison, Hugh; Fan, Jiwen; Ziegler, Conrad L.; Bela, Megan; Apel, Eric; Diskin, Glenn S.; Mikoviny, Tomas; Wisthaler, Armin

    2015-08-01

    Wet scavenging of aerosols by continental deep convective clouds is studied for a supercell storm complex observed over Oklahoma during the Deep Convective Clouds and Chemistry campaign. A new passive-tracer-based transport analysis framework is developed to characterize convective transport using vertical profiles of several passive trace gases. For this case, the analysis estimates that observed passive gas mixing ratios in the upper troposphere convective outflow consist of 47% low level (<3 km) inflow air, 32% entrained midtroposphere air, and 21% upper troposphere air. The new analysis framework is used to estimate aerosol wet scavenging efficiencies. Observations yield high overall scavenging efficiencies of 81% for submicron aerosol mass. Organic, sulfate, and ammonium aerosols have similar wet scavenging efficiencies (80%-84%). The apparent scavenging efficiency for nitrate aerosol is much lower (57%), but the scavenging efficiency for nitrate aerosol plus nitric acid combined (84%) is close to the other species. Scavenging efficiencies for aerosol number are high for larger particles (84% for 0.15-2.5 µm diameter) but are lower for smaller particles (64% for 0.03-0.15 µm). The storm is simulated using the chemistry version of the Weather Research and Forecasting model. Compared to the observation-based analysis, the standard model strongly underestimates aerosol scavenging efficiencies by 32% and 41% in absolute differences for submicron mass and number. Adding a new treatment of secondary activation significantly improves simulated aerosol scavenging, producing wet scavenging efficiencies that are only 7% and 8% lower than observed efficiencies. This finding emphasizes the importance of secondary activation for aerosol wet removal in deep convective storms.

  17. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-08-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  18. Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

    NASA Astrophysics Data System (ADS)

    Aumont, B.; Valorso, R.; Mouchel-Vallon, C.; Camredon, M.; Lee-Taylor, J.; Madronich, S.

    2012-06-01

    The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8-C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.

  19. Ergosterol, arabitol and mannitol as tracers for biogenic aerosols in the eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Burshtein, N.; Lang-Yona, N.; Rudich, Y.

    2011-01-01

    Aerosols containing biological components can have a significant effect on human health by causing primarily irritation, infection and allergies. Specifically, airborne fungi can cause a wide array of adverse responses in humans depending on the type and quantity present. In this study we used chemical biomarkers for analyzing fungi-containing aerosols in the eastern Mediterranean region during the year 2009 in order to quantify annual fungal abundances. The prime marker for fungi used in this study was ergosterol, and its concentrations were compared with those of mannitol and arabitol which were recently suggested to also correlate with fungal spores concentrations (Bauer et al., 2008a). Back trajectory analysis, inorganic ions, humidity and temperature were used in an attempt to identify sources as well as the dependence on seasonal and environmental conditions. We found that the ambient concentrations of ergosterol, arabitol and mannitol range between 0 and 2.73 ng m-3, 1.85 and 58.27 ng m-3, 5.57 and 138.03 ng m-3, respectively. The highest levels for all biomarkers were during the autumn, probably from local terrestrial sources, as deduced from the inorganic ions and back trajectory analysis. Significant correlations were observed between arabitol and mannitol during the entire year except for the winter months. Both sugars correlated with ergosterol only during the spring and autumn. We conclude that mannitol and arabitol might not be specific biomarkers for fungi and that the observed correlations during spring and autumn may be attributed to high levels of vegetation during spring blossoms and autumn decomposing.

  20. Ergosterol, arabitol and mannitol as tracers for biogenic aerosols in the Eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Burshtein, N.; Yona, N. Lang; Rudich, Y.

    2010-11-01

    Aerosols containing biological components can have a significant effect on human health by causing primarily irritation, infection and allergies. Specifically, airborne fungi can cause a wide array of adverse responses in humans depending on the type and quantity present. In this study we used chemical biomarkers for analyzing fungi-containing aerosols in the eastern Mediterranean region during the year 2009 in order to quantify annual fungal abundances. The prime marker for fungi used in this study was ergosterol, and its concentrations were compared with those of mannitol and arabitol, which were recently suggested to also correlate with fungal spores concentrations (Bauer et al., 2008a). Back trajectory analysis, inorganic ions, humidity and temperature were used in an attempt to identify sources as well as the dependence on seasonal and environmental conditions. We found that the ambient concentrations of ergosterol, arabitol and mannitol range between 0 and 2.73 ng m-3, 1.85 and 58.27 ng m-3, 5.57 and 138.03 ng m-3, respectively. The highest levels for all biomarkers were during the autumn, probably from local terrestrial sources, as deduced from the inorganic ions and back trajectory analysis. Significant correlations were observed between arabitol and mannitol during the entire year except for the winter months. Both sugars correlated with ergosterol only during the spring and autumn. We conclude that mannitol and arabitol might not be specific biomarkers for fungi and that the observed correlations during spring and autumn may be attributed to high levels of vegetation during spring blossoms and autumn decomposition.

  1. Formation of 3-methyl-1,2,3-butanetricarboxylic acid via gas phase oxidation of pinonic acid - a mass spectrometric study of SOA aging

    NASA Astrophysics Data System (ADS)

    Müller, L.; Reinnig, M.-C.; Naumann, K. H.; Saathoff, H.; Mentel, T. F.; Donahue, N. M.; Hoffmann, T.

    2012-02-01

    This paper presents the results of mass spectrometric investigations of the OH-initiated oxidative aging of α-pinene SOA under simulated tropospheric conditions at the large aerosol chamber facility AIDA, Karlsruhe Institute of Technology. In particular, the OH-initiated oxidation of pure pinic and pinonic acid, two well-known oxidation products of α-pinene, was investigated. Two complementary analytical techniques were used, on-line atmospheric pressure chemical ionization/mass spectrometry (APCI/MS) and filter sampling followed by liquid chromatography/mass spectrometry (LC/ESI-MS). The results show that 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a very low volatile α-pinene SOA product and a tracer compound for terpene SOA, is formed from the oxidation of pinonic acid and that this oxidation takes place in the gas phase. This finding is confirmed by temperature-dependent aging experiments on whole SOA formed from α-pinene, in which the yield of MBTCA scales with the pinonic acid fraction in the gas phase. Based on the results, several feasible gas-phase radical mechanisms are discussed to explain the formation of MBTCA from OH-initiated pinonic acid oxidation.

  2. SOA Production From Cloud Processing of Glycolaldehyde

    NASA Astrophysics Data System (ADS)

    Perri, M. J.; Seitzinger, S. P.; Tan, Y.; Turpin, B. J.

    2007-12-01

    Recent studies suggest that aqueous cloud chemistry contributes to secondary organic aerosol (SOA) production. Gas phase primary precursors, such as ethene and isoprene, can oxidize in the interstitial spaces of clouds to form water-soluble species, including glycolaldehyde. These water-soluble products can partition into cloud droplets and undergo further oxidation (e.g., via hydroxyl radicals). If low-volatility products (e.g., oxalate) are formed, these products can remain in the particle phase following droplet evaporation, forming organic aerosol. Organic aerosol plays an important role in cloud microphysics, visibility, and human health, yet little is known about aqueous phase reaction pathways and products that contribute to SOA. The kinetics of aqueous phase glycolaldehyde oxidation were studied and products were identified. Hydroxyl radical was generated via continuous UV photolysis of hydrogen peroxide inside a glass photochemical vessel. The reaction of glycolaldehyde and hydroxyl radical was monitored in real-time via continuous electrospray ionization mass spectrometry (ESI-MS). Organic products (acids and aldehydes) formed and destroyed during the reaction were identified and quantified via negative and positive mode ionization. Based on ESI-MS data obtained, glycolaldehyde is oxidized via hydroxyl radical to glycolic acid, glyoxylic acid, and ultimately oxalic acid, as previously suggested. In addition, several unexpected higher molecular weight compounds were produced, and identification of these reaction products is currently underway. The results obtained from this study serve to validate and refine the aqueous SOA-producing pathway for glycolaldehyde in cloud chemistry models and can be used to increase the accuracy of SOA prediction in atmospheric air quality and climate models.

  3. The Tao of SOA

    NASA Astrophysics Data System (ADS)

    Shan, Tony C.

    This paper describes a comprehensive framework aiming to facilitate the effective adoption and operationalization of SOA in large enterprise computing environments, which consists of the Strategy, Automation, Methodology, Patterns, Lifecycle, and Engineering (SAMPLE) aspects. The major pain points in SOA are analyzed, such as the increasing dynamics, growing integration, proliferation of techniques, more heterogeneous platforms, disparate visual notations, intricate processes, disjointed operating models, and fragmented activities of WS-* specifications. The overarching SAMPLE model is designed to provide a sophisticated integration of appropriate capabilities and knowledge to filter the inessential from the essential. In the Strategy aspect, a metamodel, technology architecture planning, and strategy roadmapping are presented. The Automation aspect deals with tools, service lifecycle, and COTS mapping. The Methodology aspect covers a hybrid method, SOA principles, and a methodical process. The prominent elements of the Patterns aspect include data caching patterns, a reference model, and open source reference implementation. The Lifecycle aspect contains a methodical means to mature IT systems: review, refactoring, reengineering, and rearchitecting (R4). Finally, the Engineering aspect evolves the traditional software engineering and systems engineering practices to the service engineering discipline. Moreover, a 10-point list of SOA guidance is introduced from a practitioner’s standpoint, which gives best-practice guidelines to adopt and execute SOA practically in big organizations.

  4. Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

    EPA Science Inventory

    A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

  5. Effect of Vapor Pressure Scheme on Multiday Evolution of SOA in an Explicit Model

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Madronich, S.; Aumont, B.; Camredon, M.; Emmons, L. K.; Tyndall, G. S.; Valorso, R.

    2011-12-01

    Recent modeling of the evolution of Secondary Organic Aerosol (SOA) has led to the critically important prediction that SOA mass continues to increase for several days after emission of primary pollutants. This growth of organic aerosol in dispersing plumes originating from urban point sources has direct implications for regional aerosol radiative forcing. We investigate the robustness of predicted SOA mass growth downwind of Mexico City in the model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), by assessing its sensitivity to the choice of vapor pressure prediction scheme. We also explore the implications for multi-day SOA mass growth of glassification / solidification of SOA constituents during aging. Finally we use output from the MOZART-4 chemical transport model to evaluate our results in the regional and global context.

  6. Light absorption coefficient measurement of SOA using a UV-Visible spectrometer connected with an integrating sphere

    NASA Astrophysics Data System (ADS)

    Zhong, Min; Jang, Myoseon

    2011-08-01

    A method for measuring an aerosol light absorption coefficient ( B a) has been developed using a conventional UV-visible spectrometer equipped with an integrating sphere covering a wide range of wavelengths (280-800 nm). The feasibility of the proposed method was evaluated in both the transmittance mode (TUV-IS) and the reflective mode (RUV-IS) using the reference aerosol known for the cross-sectional area. The aerosol was collected on a conventional filter and measured for B a values. The resulting RUV-IS method was applied to measure light absorption of secondary organic aerosol (SOA). SOA was produced through photooxidation of different precursor hydrocarbons such as toluene, d-limonene and α-pinene in the presence of NO x (60-70 ppb) and inorganic seed aerosol using a 2-m 3 indoor Teflon film chamber. Of the three precursor hydrocarbons, the B a value of toluene SOA (0.574 m 2 g -1 at 350 nm) was the highest compared with B a values for α-pinene SOA (0.029 m 2 g -1) and d-limonene SOA (0.038 m 2 g -1). When d-limonene SOA or toluene SOA was internally mixed with neutral [(NH 4) 2SO 4] or acidic inorganic seed (NH 4HSO 4:H 2SO 4 = 1:1 by mole), the SOA showed 2-3 times greater B a values at 350 nm than the SOA with no seed. Aerosol aging with a light source for this study reduced B a values of SOA (e.g., on average 10% for toluene SOA and 30% for d-limonene SOA within 4 h). Overall, weak absorption appeared for chamber-generated SOA over wavelengths ranging from 280 to 550 nm, which fall into the sunlight spectrum.

  7. SOA VOLATILITY EVOLUTION: FORMATION AND OXIDATION OVER THE LIFECYCLE OF PM2.5

    EPA Science Inventory

    Secondary Organic Aerosols are a major, possibly dominant, source of organic PM2.5 that remain enigmatic. Enormous progress has been made in the past 15 years regarding SOA formation, starting with recognition that most SOA products are semivolatile, continuing to a...

  8. Contributions of Selected Biogenic and Aromatic Compounds to the Formation of Tropospheric Secondary Organic Aerosol over Several Sites in the United States

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Kleindienst, T. E.; Lewandowski, M.; Offenberg, J. H.; Corse, E. W.; Gerald, T.; Edney, E.

    2009-12-01

    The National Exposure Research Laboratory of the U.S. Environmental Protection Agency recently undertook an integrated laboratory and field research effort to better understand the contribution of biogenic and aromatic hydrocarbons to the formation of submicron ambient secondary organic aerosol (SOA). In the laboratory, isoprene, α-pinene, β-caryophyllene, 1,3-butadiene, 2-methyl-3-buten-2-ol, benzene, and toluene were individually irradiated under a wide range of conditions in a photochemical reaction chamber in the presence of nitrogen oxide (NOx). These hydrocarbons are thought to contribute to ambient SOA formation. In field studies conducted in Research Triangle Park, NC; Duke Forest in Chapel Hill, NC; Atlanta, GA; Pensacola, FL; Birmingham and Centerville, AL; Riverside, CA; Detroit, MI; Northbrook, East St. Louis and Bondville, IL; and Cincinnati, OH, ambient PM2.5 samples were collected for various periods between 2003 and 2006. The SOA collected from these laboratory experiments and the ambient PM2.5 samples were analyzed for organic carbon (OC) concentration and for organic tracer compounds by GC-MS using BSTFA derivatization for their identification and quantification. An organic tracer-based method was developed for estimating ambient SOA concentrations from individual SOA precursors to allow an assessment of SOA model predictions with ambient data. The results show that several major reaction products detected in SOA formed in the laboratory photooxidations were among the major compounds detected in field samples, effectively connecting laboratory and field results. Using the tracer-based method, the contributions of isoprene and monoterpenes to SOA formation show strong seasonal dependencies. However, no clear seasonal variations were observed for sesquiterpenes and aromatic hydrocarbons. The contribution of 2-methyl-3-buten-2-ol to ambient SOA was found to be not only season dependent but also higher in locations dominated by conifers, which are

  9. Fluid dynamic studies on scattering aerosol and its generation for application as tracer particles in supersonic flow measurements utilizing laser Doppler velocimeter

    NASA Technical Reports Server (NTRS)

    Mazumder, M. K.; Hoyle, B. D.; Kirsch, K. J.

    1974-01-01

    An experimental study on the particle-fluid interactions of scattering aerosols was performed using monodisperse aerosols of different particle sizes for the application of laser Doppler velocimeters in subsonic turbulence measurements. Particle response was measured by subjecting the particles to an acoustically excited oscillatory fluid velocity field and by comparing the ratio of particle velocity amplitude to the fluid velocity amplitude as a function of particle size and the frequency of oscillation. Particle velocity was measured by using a differential laser Doppler velocimeter. The test aerosols were fairly monodisperse with a mean diameter that could be controlled over the size range from 0.1 to 1.0 micron. Experimental results on the generation of a fairly monodisperse aerosol of solid particles and liquid droplets and on the aerosol response in the frequency range 100 Hz to 100 kHz are presented. It is indicated that a unit density spherical scatterer of 0.3 micron-diameter would be an optimum choice as tracer particles for subsonic air turbulence measurements.

  10. Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

    NASA Astrophysics Data System (ADS)

    Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

    2014-10-01

    Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

  11. Influence of continental outflow on aerosol chemical characteristics over the Arabian Sea during winter

    NASA Astrophysics Data System (ADS)

    Kumar, Ashwini; Sudheer, A. K.; Goswami, Vineet; Bhushan, Ravi

    2012-04-01

    The chemical composition of aerosol over the Arabian Sea was investigated during December 2007. Elemental Carbon (EC), Organic Carbon (OC), water soluble organic and inorganic constituents and crustal elements (Al, Fe, Ca, and Mg) were measured in total suspended particulate samples (TSP) collected from marine boundary layer of the Arabian Sea when the oceanic region is influenced by continental outflow. Anthropogenic and natural mineral aerosol originating from continental regions dominates the aerosol composition contributing ∼88% of total aerosol mass. The sea-salt aerosol comprises only ∼12% of TSP. The carbonaceous aerosol exhibits spatial trend similar to that of K+ suggesting major source could be biomass burning. Secondary organic aerosol (SOA) contribution estimated by EC-tracer method suggests that up to 67% of OC can be of secondary origin. Average water soluble organic carbon to OC ratio is ∼0.9, indicates significant formation of SOA during transport of continental air masses. These results demonstrate the dominance of continental aerosol over the Arabian Sea during wintertime where deposition may have major impact on surface ocean biogeochemistry.

  12. SOA Formation from Photooxidation of Individual PAHs and Mixtures

    NASA Astrophysics Data System (ADS)

    Chen, C. L.; Kacarab, M.; Tang, P.; Cocker, D. R., III

    2014-12-01

    Individual SOA experiments on PAHs such as naphthalene and methylnaphthalenes were conducted at the UCR CE-CERT environmental chamber. Measurements were made with a suite of instrumentation that includes HR-ToF-AMS, VTDMA, and APM-SMPS to comprehensively understand the chemical composition characteristics, volatility and density of particles. Our results indicated that the SOA yield from PAHs is large and the elemental and chemical composition analysis of HR-ToF-AMS revealed that oxygen-to-carbon ratio (O/C) increases with oxidation time and also suggested that the SOA from these three PAHs are mostly low volatility OOA. The density of aerosol formed from 1-methylnaphthalene photooxidation under high NOx condition was observed to decrease from 1.5 g/cm3 to 0.7 g/cm3 during the course of experiment. Transmission electron microscopy (TEM) of 1-methylnaphthalene SOA showed that the SOA coagulated after 5~6 hours photooxidation to form fractal-like particles. The sensitivity of SOA formation to varying HC mixtures is further explored. Serial mixtures of PAHs photooxidation experiments were conducted, including naphthalene, 1-methylnapthalene, 2-methylnaphtalene with m-xylene, and/or the surrogate mixture used to develop the Carter O3 reactivity scales. Preliminary results show that the SOA formation from m-xylene and naphthalene mixture photooxidation was found to be suppressed by m-xylene, and the volatility measured as volume remaining fraction (VRF) of the m-xylene and naphthalene mixture increases from 0.2 to 0.4, which indicates the volatility of mixture SOA is dominated by m-xylene SOA.

  13. Aerosol transport and wet scavenging in deep convective clouds: a case study and model evaluation using a multiple passive tracer analysis approach

    SciTech Connect

    Yang, Qing; Easter, Richard C.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Fast, Jerome D.; Ghan, Steven J.; Wang, Hailong; Berg, Larry K.; Barth, Mary; Liu, Ying; Shrivastava, ManishKumar B.; Singh, Balwinder; Morrison, H.; Fan, Jiwen; Ziegler, Conrad L.; Bela, Megan; Apel, Eric; Diskin, G. S.; Mikoviny, Tomas; Wisthaler, Armin

    2015-08-20

    The effect of wet scavenging on ambient aerosols in deep, continental convective clouds in the mid-latitudes is studied for a severe storm case in Oklahoma during the Deep Convective Clouds and Chemistry (DC3) field campaign. A new passive-tracer based transport analysis framework is developed to characterize the convective transport based on the vertical distribution of several slowly reacting and nearly insoluble trace gases. The passive gas concentration in the upper troposphere convective outflow results from a mixture of 47% from the lower level (0-3 km), 21% entrained from the upper troposphere, and 32% from mid-atmosphere based on observations. The transport analysis framework is applied to aerosols to estimate aerosol transport and wet-scavenging efficiency. Observations yield high overall scavenging efficiencies of 81% and 68% for aerosol mass (Dp < 1μm) and aerosol number (0.03< Dp < 2.5μm), respectively. Little chemical selectivity to wet scavenging is seen among observed submicron sulfate (84%), organic (82%), and ammonium (80%) aerosols, while nitrate has a much lower scavenging efficiency of 57% likely due to the uptake of nitric acid. Observed larger size particles (0.15 - 2.5μm) are scavenged more efficiently (84%) than smaller particles (64%; 0.03 - 0.15μm). The storm is simulated using the chemistry version of the WRF model. Compared to the observation based analysis, the standard model underestimates the wet scavenging efficiency for both mass and number concentrations with low biases of 31% and 40%, respectively. Adding a new treatment of secondary activation significantly improves simulation results, so that the bias in scavenging efficiency in mass and number concentrations is reduced to <10%. This supports the hypothesis that secondary activation is an important process for wet removal of aerosols in deep convective storms.

  14. SOA governance in healthcare organisations.

    PubMed

    Koumaditis, Konstantinos; Themistocleous, Marinos; Vassilakopoulos, Georgios

    2013-01-01

    Service Oriented Architecture (SOA) is increasingly adopted by many sectors, including healthcare. Due to the nature of healthcare systems there is a need to increase SOA adoption success rates as the non integrated nature of healthcare systems is responsible for medical errors that cause the loss of tens of thousands patients per year. Following our previous research [1] we propose that SOA governance is a critical success factor for SOA success in healthcare. Literature reports multiple SOA governance models that have limitations and they are confusing. In addition to this, there is a lack of healthcare specific SOA governance models. This highlights a literature void and thus the purpose of this paper is to proposed a healthcare specific SOA governance framework. PMID:23823423

  15. EPA STAR Grants Contribution to the SOAS Campaign

    EPA Science Inventory

    This poster explains how EPA Science to Achieve Results (STAR) grantees contributed to the summer 2013 inter-agency Southeast Atmosphere Study (SAS), specifically the Southern Oxidant and Aerosol Study (SOAS). There is also a brief explanation of EPA scientist involvement in this...

  16. The STAR Grants Contribution to the SOAS Campaign

    EPA Science Inventory

    The Southern Oxidant and Aerosol Study (SOAS) is a community-led field campaign that was part of the Southeast Atmosphere Study (SAS). As one of the largest field studies in decades to characterize air quality in the Southeastern United States, SAS is a collaborative project invo...

  17. Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

    EPA Science Inventory

    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,...

  18. Implications of Low Volatility SOA and Gas-Phase Fragmentation Reactions on SOA Loadings and their Spatial and Temporal Evolution in the Atmosphere

    SciTech Connect

    Shrivastava, ManishKumar B.; Zelenyuk, Alla; Imre, Dan; Easter, Richard C.; Beranek, Josef; Zaveri, Rahul A.; Fast, Jerome D.

    2013-04-27

    Recent laboratory and field measurements by a number of groups show that secondary organic aerosol (SOA) evaporates orders of magnitude slower than traditional models assume. In addition, chemical transport models using volatility basis set (VBS) SOA schemes neglect gas-phase fragmentation reactions, which are known to be extremely important. In this work, we present modeling studies to investigate the implications of non-evaporating SOA and gas-phase fragmentation reactions. Using the 3-D chemical transport model, WRF-Chem, we show that previous parameterizations, which neglect fragmentation during multi-generational gas-phase chemistry of semi-volatile/inter-mediate volatility organics ("aging SIVOC"), significantly over-predict SOA as compared to aircraft measurements downwind of Mexico City. In sharp contrast, the revised models, which include gas-phase fragmentation, show much better agreement with measurements downwind of Mexico City. We also demonstrate complex differences in spatial SOA distributions when we transform SOA to non-volatile secondary organic aerosol (NVSOA) to account for experimental observations. Using a simple box model, we show that for same amount of SOA precursors, earlier models that do not employ multi-generation gas-phase chemistry of precursors ("non-aging SIVOC"), produce orders of magnitude lower SOA than "aging SIVOC" parameterizations both with and without fragmentation. In addition, traditional absorptive partitioning models predict almost complete SOA evaporation at farther downwind locations for both "non-aging SIVOC" and "aging SIVOC" with fragmentation. In contrast, in our revised approach, SOA transformed to NVSOA implies significantly higher background concentrations as it remains in particle phase even under highly dilute conditions. This work has significant implications on understanding the role of multi-generational chemistry and NVSOA formation on SOA evolution in the atmosphere.

  19. Source apportionment of airborne particulate matter using inorganic and organic species as tracers

    NASA Astrophysics Data System (ADS)

    Wang, Yungang; Hopke, Philip K.; Xia, Xiaoyan; Rattigan, Oliver V.; Chalupa, David C.; Utell, Mark J.

    2012-08-01

    Source apportionment is typically performed on chemical composition data derived from particulate matter (PM) samples. However, many common sources no longer emit significant amounts of characteristic trace elements requiring the use of more comprehensive chemical characterization in order to fully resolve the PM sources. Positive matrix factorization (EPA PMF, version 4.1) was used to analyze 24-hr integrated molecular marker (MM), secondary inorganic ions, trace elements, carbonaceous species and light absorption data to investigate sources of PM2.5 in Rochester, New York between October 2009 and October 2010 to explore the role of specific MMs. An eight-factor solution was found for which the factors were identified as isoprene secondary organic aerosol (SOA), airborne soil, other SOA, diesel emissions, secondary sulfate, wood combustion, gasoline vehicle, and secondary nitrate contributing 6.9%, 12.8%, 3.7%, 7.8%, 45.5%, 9.1%, 7.9%, and 6.3% to the average PM2.5 concentration, respectively Concentrations of pentacosane, hexacosane, heptacosane, and octacosane in the gasoline vehicles factor were larger compared to diesel emissions. Aethalometer Delta-C was strongly associated with wood combustion. The compounds, n-heptacosanoic acid and n-octacosanoic acid, occasionally used in the past as tracers for road dust, were found to largely associate with SOA in this study. In comparison with a standard PMF analyses without MM, inclusion of them was necessary to resolve SOA and wood combustion factors in urban areas.

  20. Sources of primary and secondary organic aerosol and their diurnal variations.

    PubMed

    Zheng, Mei; Zhao, Xiuying; Cheng, Yuan; Yan, Caiqing; Shi, Wenyan; Zhang, Xiaolu; Weber, Rodney J; Schauer, James J; Wang, Xinming; Edgerton, Eric S

    2014-01-15

    PM(2.5), as one of the criteria pollutants regulated in the U.S. and other countries due to its adverse health impacts, contains more than hundreds of organic pollutants with different sources and formation mechanisms. Daytime and nighttime PM2.5 samples from the August Mini-Intensive Gas and Aerosol Campaign (AMIGAS) in the southeastern U.S. were collected during summer 2008 at one urban site and one rural site, and were analyzed for organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), and various individual organic compounds including some important tracers for carbonaceous aerosol sources by gas chromatography-mass spectrometry. Most samples exhibited higher daytime OC concentration, while higher nighttime OC was found in a few events at the urban site. Sources, formation mechanisms and composition of organic aerosol are complicated and results of this study showed that it exhibited distinct diurnal variations. With detailed organic tracer information, sources contributing to particulate OC were identified: higher nighttime OC concentration occurring in several occasions was mainly contributed by the increasing primary emissions at night, especially diesel exhaust and biomass burning; whereas sources responsible for higher daytime OC concentration included secondary organic aerosol (SOA) formation (e.g., cis-pinonic acid and non-biomass burning WSOC) together with traffic emissions especially gasoline engine exhaust. Primary tracers from combustion related sources such as EC, polycyclic aromatic hydrocarbons, and hopanes and steranes were significantly higher at the urban site with an urban to rural ratio between 5 and 8. However, this urban-rural difference for secondary components was less significant, indicating a relatively homogeneous distribution of SOA spatially. We found cholesterol concentrations, a typical tracer for meat cooking, were consistently higher at the rural site especially during the daytime, suggesting the likely

  1. Aerosol from Organic Nitrogen in the Southeast United States

    EPA Science Inventory

    Biogenic volatile organic compounds (BVOCs) contribute significantly to organic aerosol in the southeastern United States. During the Southern Oxidant and Aerosol Study (SOAS), a portion of ambient organic aerosol was attributed to isoprene oxidation and organic nitrogen from BVO...

  2. Smog chamber experiments to investigate Henry's law constants of glyoxal using different seed aerosols

    NASA Astrophysics Data System (ADS)

    Jakob, Ronit

    2014-05-01

    Aerosols play an important role in the chemistry and physics of the atmosphere. Hence, they have a direct as well as an indirect impact on the earth's climate. Depending on their formation, one distinguishes between primary and secondary aerosols[1]. Important groups within the secondary aerosols are the secondary organic aerosols (SOAs). In order to improve predictions about these impacts on the earth's climate the existing models need to be optimized, because they still underestimate SOA formation[2]. Glyoxal, the smallest α-dicarbonyl, not only acts as a tracer for SOA formation but also as a direct contributor to SOA. Because glyoxal has such a high vapour pressure, it was common knowledge that it does not take part in gas-particle partitioning and therefore has no impact on direct SOA formation. However, the Henry's law constant for glyoxal is surprisingly high. This has been explained by the hydration of the aldehyde groups, which means that a species with a lower vapour pressure is produced. Therefore the distribution of glyoxal between gas- and particle phase is atmospherically relevant and the direct contribution of glyoxal to SOA can no longer be neglected. A high salt concentration present in chamber seed aerosols leads to an enhanced glyoxal uptake into the particle. This effect is called "salting-in". The salting effect depends on the composition of the seed aerosol as well as the soluble compound. For very polar compounds, like glyoxal, a "salting-in" is observed[3]. Glyoxal particle formation during a smog chamber campaign at Paul-Scherrer-Institut (PSI) in Switzerland was examined using different seed aerosols such as ammonium sulfate, sodium chloride and sodium nitrate. The aim of this campaign was to investigate Henry's law constants for different seed aerosols. During the campaign filter samples were taken to investigate the amount of glyoxal in the particle phase. After filter extraction, the analyte was derivatized and measured using UHPLC

  3. Nitrated Secondary Organic Tracer Compounds in Biomass Burning Smoke

    NASA Astrophysics Data System (ADS)

    Iinuma, Y.; Böge, O.; Gräfe, R.; Herrmann, H.

    2010-12-01

    Natural and human-initiated biomass burning releases large amounts of gases and particles into the atmosphere, impacting climate, environment and affecting public health. Several hundreds of compounds are emitted from biomass burning and these compounds largely originate from the pyrolysis of biopolymers such as lignin, cellulose and hemicellulose. Some of compounds are known to be specific to biomass burning and widely recognized as tracer compounds that can be used to identify the presence of biomass burning PM. Detailed chemical analysis of biomass burning influenced PM samples often reveals the presence compounds that correlated well with levoglucosan, a known biomass burning tracer compound. In particular, nitrated aromatic compounds correlated very well with levoglucosan, indicating that biomass burning as a source for this class of compounds. In the present study, we present evidence for the presence of biomass burning originating secondary organic aerosol (BSOA) compounds in biomass burning influenced ambient PM. These BSOA compounds are typically nitrated aromatic compounds that are produced in the oxidation of precursor compounds in the presence of NOx. The precursor identification was performed from a series of aerosol chamber experiments. m-Cresol, which is emitted from biomass burning at significant levels, is found to be a major precursor compounds for nitrated BSOA compounds found in the ambient PM. We estimate that the total concentrations of these compounds in the ambient PM are comparable to biogenic SOA compounds in winter months, indicating the BSOA contributes important amounts to the regional organic aerosol loading.

  4. Primary sources and secondary formation of organic aerosols in Beijing, China.

    PubMed

    Guo, Song; Hu, Min; Guo, Qingfeng; Zhang, Xin; Zheng, Mei; Zheng, Jun; Chang, Chih Chung; Schauer, James J; Zhang, Renyi

    2012-09-18

    Ambient aerosol samples were collected at an urban site and an upwind rural site of Beijing during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. Contributions of primary particles and secondary organic aerosols (SOA) were estimated by chemical mass balance (CMB) modeling and tracer-yield method. The apportioned primary and secondary sources explain 73.8% ± 9.7% and 79.6% ± 10.1% of the measured OC at the urban and rural sites, respectively. Secondary organic carbon (SOC) contributes to 32.5 ± 15.9% of the organic carbon (OC) at the urban site, with 17.4 ± 7.6% from toluene, 9.7 ± 5.4% from isoprene, 5.1 ± 2.0% from α-pinene, and 2.3 ± 1.7% from β-caryophyllene. At the rural site, the secondary sources are responsible for 38.4 ± 14.4% of the OC, with the contributions of 17.3 ± 6.9%, 13.9 ± 9.1%, 5.6 ± 1.9%, and 1.7 ± 1.0% from toluene, isoprene, α-pinene, and β-caryophyllene, respectively. Compared with other regions in the world, SOA in Beijing is less aged, but the concentrations are much higher; between the sites, SOA is more aged and affected by regional transport at the urban site. The high SOA loading in Beijing is probably attributed to the high regional SOC background (~2 μg m(-3)). The toluene SOC concentration is high and comparable at the two sites, implying that some anthropogenic components, at least toluene SOA, are widespread in Beijing and represents a major factor in affecting the regional air quality. The aerosol gaseous precursor concentrations and temperature correlate well with SOA, both affecting SOA formation. The significant SOA enhancement with increasing water uptake and acidification indicates that the aqueous-phase reactions are largely responsible SOA formation in Beijing. PMID:22486583

  5. Hydroxy fatty acids in remote marine aerosols as microbial tracers: Long term study on β-hydroxy fatty acids from the remote marine Island, Chichi-Jima

    NASA Astrophysics Data System (ADS)

    Tyagi, P.

    2014-12-01

    To better understand the long-range atmospheric transport of microbial aerosols from Southeast Asia to the western North Pacific, marine aerosols were collected at a remote Island, Chichi-Jima on a biweekly basis during 1990-1993. These samples were investigated for the atmospheric abundances of hydroxy fatty acids (OH FAs). β-OH FAs are the major structural components of endotoxins in the outer membrane of Gram-negative bacteria (GNB) whereas w-OH FAs are present in cell walls of higher plants. Thus, we tested the applicability of the β-OH FAs (C10-C18) and ω-OH FAs (C16-C26) to assess the Gram-negative bacteria (GNB) and contribution of terrestrial higher plants, respectively. The average concentrations of β- and ω-OH FAs show pronounced seasonal variability with spring maximum (~301 ng/m-3 and ~ 272 ng/m-3, respectively). The concentrations of total OH FAs increased in winter/spring and decreased in summer/autumn, except for 1992-93. This seasonal trend can be interpreted by the atmospheric transport of microbial soil dust and higher plant metabolites from the Asian continent during winter/spring, when westerly winds dominate over the western North Pacific. The even carbon predominance of β- and ω-OH FAs (80 and 74 % of total) in marine aerosols could be explained by their significant contribution from GNB and terrestrial higher plants. These results have implications towards assessing the bacterial transport in the continental outflows. This study also confirms that β-OH FAs can be used as bacterial tracers in ambient aerosol samples.Keywords: β- and ω-hydroxy fatty acids, terrestrial biomarkers, marine aerosols, GC-MS

  6. Field and Laboratory Studies of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Coggon, Matthew Mitchell

    This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation. The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate. Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f42 and f 99) was found to coincide with periods of heavy (f 42 > 0.15; f99 > 0.04), moderate (0.05 < f42 < 0.15; 0.01 < f99 < 0.04), and negligible (f42 < 0.05; f99 < 0.01) ship influence. Application of

  7. Sources, properties, aging, and anthropogenic influences on OA and SOA over the Southeast US and the Amazon during SOAS, DC3, SEAC4RS, and GoAmazon

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; Campuzano Jost, P.; Hu, W.; Palm, B. B.; Thompson, S.; Krechmer, J.; Day, D. A.; Stark, H.; Peng, Z.; Ortega, A. M.; Isaacman, G. A.; Goldstein, A. H.; Holzinger, R.; de Sá, S. S.; Martin, S. T.; Alexander, M. L.; Guenther, A. B.; Canagaratna, M. R.; Massoli, P.; Kimmel, J.; Jayne, J. T.; Worsnop, D. R.; Brune, W. H.; Lee-Taylor, J. M.; Hodzic, A.; Madronich, S.; Offenberg, J. H.; Ferreira De Brito, J.; Artaxo, P.; Manzi, A. O.

    2014-12-01

    The SE US and the Amazon have large sources of biogenic VOCs and varying anthropogenic pollution impact, and often poor aerosol model performance. Recent results on the sources, properties, aging, and impact of anthropogenic pollution on OA and secondary OA (SOA) over these regions will be presented. SOA from IEPOX accounts for 14-17% of the OA on average over the SE US and extending up to 6 km. Higher IEPOX-SOA correlates with airmasses of high isoprene, IEPOX, sulfate, acidity, and lower NO. The IEPOX organosulfate accounts for ~10% of IEPOX-SOA over the SE US. The AMS ion C5H6O+ is shown to be a good marker of IEPOX-SOA, while total m/z 82 (as in ACSM) suffers larger interferences. The sinks of IEPOX-SOA via both OH oxidation and evaporation are slow. The low-volatility of IEPOX-SOA contrasts with the small semivolatile molecules that have so far been identified as its components, suggesting the importance of oligomerization. Urban SOA is estimated to account for 25% of the OA in the SE US using either the GEOS-Chem model or the measured 14C (using recent results that urban SOA (POA) is 30% (50%) non-fossil, mainly due to cooking emissions). An oxidation flow reactor (OFR) is used to investigate SOA formation by OH, O3, and NO3 in-situ. Largest SOA formation is always observed at night when monoterpenes (MT) are largest, and is underpredicted by SOA models that use MT as precursors but ignore partially-oxidized products. Closure results from models (VBS and GECKO-A) that account for the whole oxidation chain will be presented. The partitioning of organic acids is found to proceed rapidly in response to temperature changes, in contrast with recent reports of very slow equilibration. The agreement with absorptive partitioning theory is reasonable for most species, except small acids that may be formed by thermal decomposition during analysis. Partitioning data from four instruments is compared, with reasonable agreement in many cases including the rapid response

  8. Secondary Organic Aerosol Formation in Aerosol Water by Photochemical Reactions of Gaseous Mixture of Monoterpene and Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Lim, H.; Yi, S.; Park, J.; Cho, H.; Jung, K.

    2011-12-01

    There exist large uncertainties in model predictions for climate change and regional air quality. It could be caused by incomplete integration of secondary organic aerosol (SOA) formation in atmospheric chemical models. Recent laboratory studies have found SOA formation through chemical reactions on aerosol surface and in aerosol water. Water soluble organics formed by photochemical degradation of biogenic organics including isoprene and anthropogenic aromatics are predicted to form substantial amount of SOA through the newly found pathways. Although SOA formation in bulk aqueous solution was reported for laboratory experiments of various precursors (e.g., water soluble carbonyls and phenols), little is known for SOA formation in real aerosol water. In this study, photochemical reactions of the gaseous mixture of monoterpene and hydrogen peroxide were examined to investigate SOA formation through reactions in real aerosol phase water. SOA formation was conducted using a flow tube reactor (ID 30 cm x L 150 cm, FEP) and a smog chamber using FEP film in the presence of dry and wet seed particles. Acidity and chemical composition of seed aerosol were also controlled as important parameters influencing SOA formation. Particle size distribution and aerosol composition were analyzed to account for differences in SOA formation mechanisms and yields for dry and wet particles. The differences might be mainly associated with SOA formation in aerosol phase water. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2011-0000221).

  9. The contribution of secondary organic aerosol to PM2.5 concentrations in Pittsburgh

    NASA Astrophysics Data System (ADS)

    Cabada, J. C.; Pandis, S. N.; Robinson, A. L.; Subramanian, R.; Polidori, A.; Turpin, B.

    2002-12-01

    A major component of PM2.5 in the Eastern US is carbonaceous material. This organic particulate matter results from both direct emissions from sources such as automobiles, trucks and industries (primary), and from the oxidation of organic gases (secondary). Data from the Pittsburgh Air Quality Study are used to examine the contribution of secondary organic aerosol to the total organic aerosol loading measured in the city during 2001 and 2002. The contribution of secondary organic aerosol is estimated by using elemental carbon as a tracer for primary emissions of organic particulate matter (OC to EC ratio approach). A systematic method for the determination of the primary ratio has been developed based on the correlation of measurements of OC and EC to gaseous tracers of photochemical activity (O3) and primary emissions (CO, NOx). This method is applied to different sets of organic aerosols measurements (using an undenuded sampler, a denuded sampler and an in-situ carbon analyzer) for carbonaceous concentrations. Consistent results for the SOA fraction are obtained when the method is applied to the different sets of measurements for OC and EC. This approach indicates that between 20 and 40% of the organic particulate matter in Pittsburgh during the summer and fall of 2001 is secondary in origin while negligible contributions of SOA are estimated for the winter of 2001 and the spring of 2002.

  10. Characteristics and sources of carbonaceous aerosols from Shanghai, China

    NASA Astrophysics Data System (ADS)

    Cao, J.-J.; Zhu, C.-S.; Tie, X.-X.; Geng, F.-H.; Xu, H.-M.; Ho, S. S. H.; Wang, G.-H.; Han, Y.-M.; Ho, K.-F.

    2012-07-01

    An intensive investigation of carbonaceous PM2.5 and TSP from Pudong (China) was conducted as part of the MIRAGE-Shanghai Experiment in 2009. Data for organic and elemental carbon (OC and EC), organic species, including C17 to C40 n-alkanes and 17 polycyclic aromatic hydrocarbons (PAHs), and stable C isotopes OC (δ13COC) and EC (δ13CEC) were used to evaluate the aerosols' temporal variations and identify presumptive sources. High OC/EC ratios indicated a large fraction of secondary organic aerosol (SOA); high char/soot ratios indicated stronger contributions to EC from motor vehicles and coal combustion than biomass burning. Diagnostic ratios of PAHs indicated that much of the SOA was produced via coal combustion. Isotope abundances (δ13COC = -24.5 ± 0.8‰ and δ13CEC = -25.1 ± 0.6‰) indicated that fossil fuels were the most important source for carbonaceous PM2.5, with lesser impacts from biomass burning and natural sources. An EC tracer system and isotope mass balance calculations showed that the relative contributions to total carbon from coal combustion, motor vehicle exhaust, and SOA were 41%, 21%, and 31%: other primary sources such as marine, soil and biogenic emissions contributed 7%. Combined analyses of OC and EC, n-alkanes and PAHs, and stable carbon isotopes provide a new way to apportion the sources of carbonaceous particles.

  11. Effect of Hydrophobic Primary Organic Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of α-Pinene

    SciTech Connect

    Song, Chen; Zaveri, Rahul A.; Alexander, M. Lizabeth; Thornton, Joel A.; Madronich, Sasha; Ortega, John V.; Zelenyuk, Alla; Yu, Xiao-Ying; Laskin, Alexander; Maughan, A. D.

    2007-10-16

    Semi-empirical secondary organic aerosol (SOA) models typically assume a well-mixed organic aerosol phase even in the presence of hydrophobic primary organic aerosols (POA). This assumption significantly enhances the modeled SOA yields as additional organic mass is made available to absorb greater amounts of oxidized secondary organic gases than otherwise. We investigate the applicability of this critical assumption by measuring SOA yields from ozonolysis of α-pinene (a major biogenic SOA precursor) in a smog chamber in the absence and in the presence of dioctyl phthalate (DOP) and lubricating oil seed aerosol. These particles serve as surrogates for urban hydrophobic POA. The results show that these POA did not enhance the SOA yields. If these results are found to apply to other biogenic SOA precursors, then the semi-empirical models used in many global models would predict significantly less biogenic SOA mass and display reduced sensitivity to anthropogenic POA emissions than previously thought.

  12. Heterogeneous SOA yield from ozonolysis of monoterpenes in the presence of inorganic acid

    NASA Astrophysics Data System (ADS)

    Northcross, Amanda L.; Jang, Myoseon

    The secondary organic aerosol (SOA) yield of a series of montoerpenes was investigated to determine the relative amounts of organic mass, which can be attributed to mass produced by heterogeneous acid-catalyzed reactions. Five monoterpenes ( α-pinene, terpinolene, d-limonene, Δ2-carene, β-pinene) were studied using a 2 m 3 indoor Teflon chamber and SOA was created in the presence of both acidic and neutral inorganic seed aerosol. The relative humidity was varied to create differing acidic seed environments. The heterogeneous aerosol production was influenced by the seed mass concentration, the acidity of the inorganic seed aerosol, and also molecular structure of the monoterpene ozonolysis products. This study also can be incorporated with our previously presented model of the kinetic expression for SOA mass production from heterogeneous acid-catalyzed reactions.

  13. Role of methyl group number on SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions

    NASA Astrophysics Data System (ADS)

    Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

    2016-02-01

    Substitution of methyl groups onto the aromatic ring determines the secondary organic aerosol (SOA) formation from the monocyclic aromatic hydrocarbon precursor (SOA yield and chemical composition). This study links the number of methyl groups on the aromatic ring to SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions (HC/NO > 10 ppbC : ppb). Monocyclic aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from monocyclic aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low-NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from monocyclic aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests that, as more methyl groups are attached on the aromatic ring, SOA products from these monocyclic aromatic hydrocarbons become less oxidized per mass/carbon on the basis of SOA yield or chemical composition.

  14. Evolution of Asian aerosols during transpacific transport in INTEX-B

    SciTech Connect

    Dunlea, E. J.; DeCarlo, Peter; Aiken, Allison; Kimmel, Joel; Peltier, R. E.; Weber, R. J.; Tomlinson, Jason M.; Collins, Donald R.; Shinozuka, Yohei; McNaughton, C. S.; Howell, S. G.; Clarke, A. D.; Emmons, L.; Apel, Eric; Pfister, G. G.; van Donkelaar, A.; Martin, R. V.; Millet, D. B.; Heald, C. L.; Jimenez, J. L.

    2009-10-01

    Measurements of aerosol composition were made with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) on board the NSF/NCAR C-130 aircraft as part of the Intercontinental Chemical Transport Experiment Phase B 5 (INTEX-B) field campaign over the Eastern Pacific Ocean. The HR-ToF-AMS measurements of non-refractory submicron aerosol mass are shown to compare well with other aerosol instrumentation in the INTEX-B field study. Two case studies are described for pollution layers transported across the Pacific from the Asian continent, intercepted 3–4 days and 7–10 days downwind of Asia, respectively. Aerosol chemistry is shown to 10 be a robust tracer for air masses originating in Asia, specifically the presence of sulfate dominated aerosol is a distinguishing feature of Asian pollution layers that have been transported to the Eastern Pacific. We examine the time scales of processing for sulfate and organic aerosol in the atmosphere and show that our observations confirm a conceptual model for transpacific transport from Asia proposed by Brock et al. (2004). 15 Our observations of both sulfate and organic aerosol in aged Asian pollution layers are consistent with fast formation near the Asian continent, followed by washout during lofting and subsequent transformation during transport across the Pacific. Our observations are the first atmospheric measurements to indicate that although secondary organic aerosol (SOA) formation from pollution happens on the timescale of one day, 20 the oxidation of organic aerosol continues at longer timescales in the atmosphere. Comparisons with chemical transport models of data from the entire campaign reveal an under-prediction of SOA mass in the MOZART model, but much smaller discrepancies with the GEOS-Chem model than found in previous studies over the Western Pacific. No evidence is found to support a previous hypothesis for significant secondary 25 organic aerosol formation in the free troposphere.

  15. On the Interpretation of Oxygenated Organic Aerosols (and their Subtypes) Arising from Factor Analysis of Aerosol Mass Spectrometer Data

    NASA Astrophysics Data System (ADS)

    Jimenez, J. L.; Zhang, Q.; Canagaratna, M. R.; Ulbrich, I. M.; Ng, N. L.; Aiken, A. C.; Decarlo, P. F.; Kroll, J.; Mohr, C.; Allan, J. D.; Worsnop, D. R.

    2008-12-01

    Zhang et al. (ES&T 2005; ACP 2005) first performed factor analysis (FA) of Aerodyne Aerosol Mass Spectrometer (AMS) complete organic aerosol (OA) mass spectra. This study showed that an oxygenated organic aerosol (OOA) factor accounted for 2/3 of the OA mass at an urban site in Pittsburgh and strongly linked OOA to secondary organic aerosols (SOA). Many subsequent studies and the application of more powerful solution algorithms such as Positive Matrix Factorization (PMF) to the same FA problem have demonstrated the importance of OOA at most locations (e.g. Volkamer et al., GRL, 2006; Zhang et al., GRL, 2007; Lanz et al., ACP, 2007 and ES&T, 2008; Ulbrich et al., ACPD, 2008). Multiple studies have also identified several subtypes of OOA (e.g. OOA-1 and OOA-2). This type of analysis offers new insights because it provides some chemical resolution on the total OA mass with high time and size resolution, and bypasses the limitations of techniques that only analyze tracers and which may favor more reduced species. However the chemical resolution is limited and careful interpretation of the FA output is required, including the use of database spectra, time series of external tracers, tracer ratios, back-trajectory analyses, size- distribution analyses, etc. This presentation will address the interpretation of total OOA and its subfactors across a large range of locations in urban, suburban, rural, remote, and forested areas, and will compare with the results of other source apportionment techniques. Based on data from multiple datasets we conclude that (1) anthropogenic SOA in and downwind of urban areas is an important source of OOA; (2) motor vehicles, meat cooking, and trash burning are unlikely to be sources of primary OOA; (3) SOA from biogenic and biomass burning precursors are also clear sources of OOA; (4) primary biomass burning OA (P-BBOA) typically shows significant differences with ambient OOA factors; (5) heterogeneous oxidation of urban POA may give rise to

  16. Evidence for an unrecognized secondary anthropogenic source of organosulfates and sulfonates: gas-phase oxidation of polycyclic aromatic hydrocarbons in the presence of sulfate aerosol.

    PubMed

    Riva, Matthieu; Tomaz, Sophie; Cui, Tianqu; Lin, Ying-Hsuan; Perraudin, Emilie; Gold, Avram; Stone, Elizabeth A; Villenave, Eric; Surratt, Jason D

    2015-06-01

    In the present study, formation of aromatic organosulfates (OSs) from the photo-oxidation of polycyclic aromatic hydrocarbons (PAHs) was investigated. Naphthalene (NAP) and 2-methylnaphthalene (2-MeNAP), two of the most abundant gas-phase PAHs and thought to represent "missing" sources of urban SOA, were photochemically oxidized in an outdoor smog chamber facility in the presence of nonacidified and acidified sulfate seed aerosol. Effects of seed aerosol composition, acidity and relative humidity on OS formation were examined. Chemical characterization of SOA extracts by ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry revealed the formation of OSs and sulfonates from photo-oxidation in the presence of sulfate seed aerosol. Many of the organosulfur compounds identified in the smog chamber extracts were also measured in urban fine aerosol collected at Lahore, Pakistan, and Pasadena, USA, demonstrating that PAH photo-oxidation in the presence of sulfate aerosol is a hitherto unrecognized source of anthropogenic secondary organosulfur compounds, and providing new PAH SOA tracers. PMID:25879928

  17. Global mechanistic model of SOA formation: effects of different chemical mechanisms

    NASA Astrophysics Data System (ADS)

    Lin, G.; Penner, J. E.; Sillman, S.; Taraborrelli, D.; Lelieveld, J.

    2011-09-01

    Recent experimental findings indicate that Secondary Organic Aerosol (SOA) represents an important and, under many circumstances, the major fraction of the organic aerosol burden. Here, we use a global 3-d model (IMPACT) to test the results of different mechanisms for the production of SOA. The basic mechanism includes SOA formation from organic nitrates and peroxides produced from an explicit chemical formulation, using partition coefficients based on thermodynamic principles. We also include the formation of non-evaporative SOA from the reaction of glyoxal and methylglyoxal on aqueous aerosols and cloud droplets as well as from the reaction of epoxides on aqueous aerosols. A model simulation including these SOA formation mechanisms gives an annual global SOA production of 113.5 Tg. The global production of SOA is substantially decreased to 85.0 Tg yr-1 if the HOx regeneration mechanism proposed by Peeters et al. (2009) is used. Model predictions with and without this HOx regeneration scheme are compared with multiple surface observation datasets, namely: the Interagency Monitoring of Protected Visual Environments (IMPROVE) for the United States, the European Monitoring and Evaluation Programme (EMEP) as well as Aerosol Mass Spectrometry (AMS) data measured in both Northern Hemisphere and tropical forest regions. All model simulations realistically predict the organic carbon mass observed in the Northern Hemisphere, although they tend to overestimate the concentrations in tropical forest regions. This overestimate may result from an unrealistically high uptake rate of glyoxal and methylglyoxal on aqueous aerosols and in cloud drops. The modeled OC in the free troposphere is in agreement with measurements in the ITCT-2K4 aircraft campaign over the North America and in pollution layers in Asia during the INTEX-B campaign, although the model underestimates OC in the free troposphere during the ACE-Asia campaign off the coast of Japan.

  18. Influence of Aerosol Acidity on the Formation of Secondary Organic Aerosol from Biogenic Precursor Hydrocarbons

    EPA Science Inventory

    Secondary organic aerosol (SOA) formation and dynamics may be important factors for the role of aerosols in adverse health effects, visibility and climate change. Formation of SOA occurs when a parent volatile organic compound is oxidized to create products that form in a conden...

  19. Primary and secondary aerosols in Beijing in winter: sources, variations and processes

    NASA Astrophysics Data System (ADS)

    Sun, Yele; Du, Wei; Fu, Pingqing; Wang, Qingqing; Li, Jie; Ge, Xinlei; Zhang, Qi; Zhu, Chunmao; Ren, Lujie; Xu, Weiqi; Zhao, Jian; Han, Tingting; Worsnop, Douglas R.; Wang, Zifa

    2016-07-01

    Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and was mainly composed of organics (60 %), sulfate (15 %) and nitrate (11 %). Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA) factors from traffic, cooking, biomass burning (BBOA) and coal combustion (CCOA) emissions as well as two secondary OA (SOA) factors. POA dominated OA, on average accounting for 56 %, with CCOA being the largest contributor (20 %). Both CCOA and BBOA showed distinct polycyclic aromatic hydrocarbons (PAHs) spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 %) and biomass burning emissions (18 %). BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r2 = 0.93), and made a considerable contribution to OA in winter (9 %). An aqueous-phase-processed SOA (aq-OOA) that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH2SO2+) was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %). Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on aerosol composition, size

  20. Mechanism of the hydroxy radical oxidation of methacryoyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

    SciTech Connect

    Nguyen, Tran B.; Bates, Kelvin H.; Crounse, J. D.; Schwantes, Rebecca H.; Zhang, Xuan; Kjaergaard, Henrik G.; Surratt, Jason D.; Lin, Peng; Laskin, Alexander; Seinfeld, John H.; Wennberg, P. O.

    2015-01-01

    Methacryoyl peroxynitrate (MPAN), the acylperoxyl nitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation. Yet, the mechanism by which MPAN produces SOA via reaction with the hydroxyl radical (OH) is unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-α-lactone (HMML). The decomposition of the MPAN-OH adduct yields HMML + NO3 (~ 75%) and hydroxyacetone + CO + NO3 (~ 25%), out-competing its reaction with atmospheric oxygen. The production of other proposed SOA precursors, e.g., methacrylic acid epoxide (MAE), from MPAN and methacrolein are negligible (< 2 %). Furthermore, we show that the beta-alkenyl moiety of MPAN is critical for lactone formation. Alkyl radicals formed via OH abstraction nstead of addition are thermalized; thus, even if they are structurally identical to the MPAN-OH adduct, they do not decompose to HMML. The SOA formation from HMML, via polyaddition of the lactone to organic compounds, is close to unity under dry conditions. However, the SOA yield is sensitive to particle liquid water and solvated ions. In hydrated sulfate-containing particles, HMML reacts primarily with H2O and aqueous sulfate, producing monomeric 2-methylglyceric acid (2MGA) and the associated organosulfate. 2MGA, a tracer for isoprene SOA, is semivolatile and its volatility increases with decreasing pH in the aerosol water. Conditions that enhance the production of neutral 2MGA will suppress SOA mass from the HMML channel. Considering the liquid water content and pH ranges of ambient particles, MGA may exist largely as a gaseous compound in some parts of the atmosphere.

  1. Simulation of SOA formation and composition from oxidation of toluene and m-xylene in chamber experiments

    NASA Astrophysics Data System (ADS)

    Xu, J.; Liu, Y.; Nakao, S.; Cocker, D.; Griffin, R. J.

    2013-12-01

    Aromatic hydrocarbons contribute an important fraction of anthropogenic reactive volatile organic compounds (VOCs) in the urban atmosphere. Photo-oxidation of aromatic hydrocarbons leads to secondary organic products that have decreased volatilities or increased solubilities and can form secondary organic aerosol (SOA). Despite the crucial role of aromatic-derived SOA in deteriorating air quality and harming human health, its formation mechanism is not well understood and model simulation of SOA formation still remains difficult. The dependence of aromatic SOA formation on nitrogen oxides (NOx) is not captured fully by most SOA formation models. Most models predict SOA formation under high NOx levels well but underestimate SOA formation under low NOx levels more representative of the ambient atmosphere. Thus, it is crucial to investigate the NOx-dependent chemistry in aromatic photo-oxidation systems and correspondingly update SOA formation models. In this study, NOx-dependent mechanisms of toluene and m-xylene SOA formation are updated using the gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) coupled to a gas/aerosol partitioning model. The updated models were optimized by comparing to eighteen University of California, Riverside United States Environmental Protection Agency (EPA) chamber experiment runs under both high and low NOx conditions. Correction factors for vapor pressures imply uncharacterized aerosol-phase association chemistry. Simulated SOA speciation implies the importance of ring-opening products in governing SOA formation (up to 40%~60% for both aromatics). The newly developed model can predict strong decreases of m-xylene SOA yield with increasing NOx. Speciation distributions under varied NOx levels implies that the well-known competition between RO2 + HO2 and RO2 + NO (RO2 = peroxide bicyclic radical) may not be the only factor influencing SOA formation. The reaction of aromatic peroxy radicals with NO competing with its self

  2. Acid-catalyzed Heterogeneous Reactions in SOA Formation

    NASA Astrophysics Data System (ADS)

    Ng, N.; Keywood, M.; Varutbangkul, V.; Gao, S.; Loewer, E.; Surratt, J.; Richard, F. C.; John, S. H.

    2003-12-01

    The importance of heterogeneous reactions in secondary organic aerosol (SOA) formation has recently excited a great deal of interest in the aerosol community. Jang and Kamens (2001) showed enhanced aerosol yield from aldehydes, which can be produced by atmospheric photochemical reactions, in the presence of acidic seed. They suggest that the carbonyl functional groups of the aldehydes further react in the aerosol phase via hydration, polymerization, and hemiacetal/acetal formation with alcohols at an accelerated rate in the presence of acid. Jang et al. (2003) demonstrated similar results using a flow reactor and Czoschke et al. (in press) qualitatively showed increased yields for isoprene and alpha-pinene ozonolysis in the presence of acidic seed. While these findings are intriguing and important, the conditions under which the experiments were carried out were atmospherically unrealistic. A series of SOA formation experiments have been carried out in the Caltech Indoor Chamber Facility, which is comprised of dual 28 m3 FEP Teflon chambers, with the flexibility to carry out both dark ozonolysis and photochemical OH oxidation reactions. Cycloheptene and alpha-pinene were oxidized in the presence of neutral seed under dry (<10% RH) and humid (50% RH) conditions and in the presence of acidic seed under humid (50% RH) conditions. The SOA yields for these experiments will be presented, and the extent of the influence of acid-catalyzed reactions on SOA yield will be discussed. Reference List 1. Cocker, D. R. III. and R. C. Flagan and J. H. Seinfeld, State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environmental Science and Technology, 35, 2594-2601, 2001. 2. Czoschke, N. M., M. Jang, and R. M. Kamens, Effect of acid seed on biogenic sceondary organic aerosol growth, Atmospheric Environment, In press. 3. Jang, M., S. Lee, and R. M. Kamens, Organic aerosol growth by acid-catalyzed heterogeneous reactions of octanal in a flow reactor

  3. Model Representation of Secondary Organic Aerosol in CMAQ v4.7

    EPA Science Inventory

    Numerous scientific upgrades to the representation of secondary organic aerosol (SOA) are incorporated into the Community Multiscale Air Quality (CMAQ) modeling system. Additions include several recently identified SOA precursors: benzene, isoprene, and sesquiterpenes; and pathwa...

  4. Investigation of the Correlation between Odd Oxygen and Secondary Organic Aerosol in Mexico City and Houston

    EPA Science Inventory

    Many recent models underpredict secondary organic aerosol (SOA) particulate matter(PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much b...

  5. A highly resolved anion-exchange chromatographic method for determination of saccharidic tracers for biomass combustion and primary bio-particles in atmospheric aerosol

    NASA Astrophysics Data System (ADS)

    Iinuma, Yoshiteru; Engling, Guenter; Puxbaum, Hans; Herrmann, Hartmut

    An improved high-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection (PAD) method is developed and validated for simultaneous determination of atmospherically relevant sugar alcohols, monosaccharides, and monosaccharide anhydrides. The improved method enables the separation of levoglucosan and arabitol which were not or insufficiently separated by the previous HPAEC-PAD methods. Reproducibility of the method was tested for both standard solutions and atmospheric aerosol samples. The peak area relative standard deviation (RSD%) of standard solutions were found to be lower than 1.5% for consecutive analyses ( n = 3) and lower than 4% for day to day variation ( n = 9). The peak area RSD% of atmospheric samples with typical European wintertime monosaccharide concentrations ( n = 9) was found to be similar to that of standard solutions. Limits of detection ranged from 0.002 mg L -1 for inositol to 0.08 mg L -1 for fructose. The developed method offers a simple, reliable and cost effective determination of atmospheric tracers for biomass combustion and for selected bio-aerosol components at sub-nanogram per cubic-meter-air concentration levels for routine analysis.

  6. IDENTIFICATION AND QUANTIFICATION OF AEROSOL POLAR OXYGENATED COMPOUNDS BEARING CARBOXYLIC OR HYDROXYL GROUPS. 2. ORGANIC TRACER COMPOUNDS FROM MONOTERPENES

    EPA Science Inventory

    A comparison was made of polar organic compounds found in the field with those produced in secondary organic aerosol from laboratory irradiations of natural hydrocarbons and oxides of nitrogen. The field samples comprised atmospheric particulate matter (PM2.5) collect...

  7. Wavelength and NOx dependent complex refractive index of SOAs generated from the photooxidation of toluene

    NASA Astrophysics Data System (ADS)

    Nakayama, T.; Sato, K.; Matsumi, Y.; Imamura, T.; Yamazaki, A.; Uchiyama, A.

    2012-06-01

    Recently, secondary organic aerosols (SOAs) generated from anthropogenic volatile organic compounds have been proposed as a possible source of lightabsorbing organic compounds "brown carbon" in the urban atmosphere. However, the atmospheric importance of these SOAs remains unclear due to limited information about their optical properties. In this study, the complex refractive index (RI, m=n - ki) values at 405, 532, and 781 nm of the SOAs generated during the photooxidation of toluene (toluene-SOAs) under a variety of initial nitrogen oxide (NOx= NO + NO2) conditions were examined by photoacoustic spectroscopy (PAS) and cavity ring down spectroscopy (CRDS). The complex RI values obtained in the present study and reported in the literature indicate that the k value, which represents the light absorption of the toluene-SOAs steeply increased to shorter wavelengths at <405 nm, while the n value gradually increased to shorter wavelengths from 781 to 355 nm. The k values at 405 nm were found to increase from 1.8 × 10-3 to 7.2 × 10-3 with increasing initial NOx concentration from 109 to 571 ppbv. The nitrate to organics ratio of the SOAs determined using a highresolution time-of-flight aerosol mass spectrometer (H-ToF-AMS) also increased with increasing initial NOx concentration. The RI values of the SOAs generated during the photooxidation of 1,3,5-trimethylbenzene in the presence of NOx (1,3,5-TMB-SOAs) were also determined to investigate the influence of the chemical structure of the precursor on the optical properties of the SOAs, and it was found that the light absorption of the 1,3,5-TMB-SOAs is negligible at all of the wavelengths investigated (405, 532, and 781 nm). These results can be reasonably explained by the hypothesis that nitro-aromatic compounds such as nitro-cresols are the major contributors to the light absorption of the toluene-SOAs. Using the obtained RI values, mass absorption cross sections of the toluene-SOAs at 405 and 532 nm were estimated to

  8. Wavelength and NOx dependent complex refractive index of SOAs generated from the photooxidation of toluene

    NASA Astrophysics Data System (ADS)

    Nakayama, T.; Sato, K.; Matsumi, Y.; Imamura, T.; Yamazaki, A.; Uchiyama, A.

    2013-01-01

    Recently, secondary organic aerosols (SOAs) generated from anthropogenic volatile organic compounds have been proposed as a possible source of light-absorbing organic compounds, "brown carbon," in the urban atmosphere. However, the atmospheric importance of these SOAs remains unclear due to limited information about their optical properties. In this study, the complex refractive index (RI, m = n-ki values at 405, 532, and 781 nm of the SOAs generated during the photooxidation of toluene (toluene-SOAs) under a variety of initial nitrogen oxide (NOx = NO + NO2) conditions were examined by photoacoustic spectroscopy (PAS) and cavity ring-down spectroscopy (CRDS). The complex RI-values obtained in the present study and reported in the literature indicate that the k-value, which represents the light absorption of the toluene-SOAs, increased to shorter wavelengths at <532 nm, and the n-value also increased to shorter wavelengths from 781 to 355 nm. The k-values at 405 nm were found to increase from 0.0018 to 0.0072 with increasing initial NOx concentration from 109 to 571 ppbv. The nitrate to organics ratio of the SOAs determined using a high-resolution time-of-flight aerosol mass spectrometer (H-ToF-AMS) also increased with increasing initial NOx concentration. The RI-values of the SOAs generated during the photooxidation of 1,3,5-trimethylbenzene in the presence of NOx (1,3,5-TMB-SOAs) were also determined to investigate the influence of the chemical structure of the precursor on the optical properties of the SOAs, and it was found that the light absorption of the 1,3,5-TMB-SOAs is negligible at all of the wavelengths investigated (405, 532, and 781 nm). These results can be reasonably explained by the hypothesis that nitroaromatic compounds, such as nitrocresols, are the major contributors to the light absorption of the toluene-SOAs. Using the obtained RI-values, mass absorption cross sections of the toluene-SOAs at 405 nm were estimated to be 0.08-0.52 m2g-1 under

  9. Secondary organic aerosol formation and primary organic aerosol oxidation from biomass burning smoke in a flow reactor during FLAME-3

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L.

    2013-05-01

    We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A potential aerosol mass "PAM" flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~ 1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days aging in the atmosphere. VOC observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in an total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net SOA to POA ratio of biomass burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp ~ 3.9 × 1011 molecules cm-3 s-1), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeds the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility

  10. Multiphase, Multigeneration SOA Formation from Terpenes

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Zhang, J.; Tischuk, J. E.; Macsymiuk, C.

    2006-12-01

    Traditional representations of Secondary Organic Aerosol (SOA) formation typically focus on prompt products from the gas-phase reaction of a precursor with an oxidant. A well-studied example is that of terpenes, especially α-pinene, reacting with ozone. Typically, aerosol mass is measured as a function of the precursor consumed, and the mass fraction (yield) can be fit to an expression describing semi-volatile partitioning. Often an `Odum 2-product model' is used, with parameters fed directly into chemical transport models. Here we present chamber data for the reaction of ozone with limonene, which has 2 double bonds and thus 2 obvious generations of oxidation. We can represent the oxidation of limonene through two generations by using a volatility basis set, which describes the distribution of organic volatilities in the atmosphere over a range of 9 orders of magnitude. We represent the complete volatility distribution of oxidation products using the basis set, developing `volatility operators' for each step of the limonene oxidation. The conclusions are supported by data for ozonolysis of limonaketone as well as NMR analysis of SOA from limonene obtained in excess limonene vs excess ozone conditions. While ozone + terpene reactions make good laboratory models, a pressing question is how to constrain and represent multiple-generation oxidation of semivolatile vapors, which are mostly saturated. Given the enormous range of individual compounds comprising semivolatile organics, a condensed representation is essential. The volatility basis set and operators meet that need; we suggest preliminary gas-phase volatility operators for oxidation by OH radicals, depending on the O:C ratio of the organics. At low O:C, OH oxidation drives volatility downward, but as O:C approaches some limit (roughly 1), oxidation sharply increases volatility because the carbon backbone breaks, making light, volatile products. Operators are required for gas-phase, heterogeneous, and

  11. Naphthalene SOA: redox activity and naphthoquinone gas-particle partitioning

    NASA Astrophysics Data System (ADS)

    McWhinney, R. D.; Zhou, S.; Abbatt, J. P. D.

    2013-10-01

    Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox-active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. These results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10-4 m3 μg-1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. Also, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  12. Characterization of aerosol composition and sources in the greater Atlanta area by aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Xu, L.; Suresh, S.; Weber, R. J. J.; Baumann, K.; Edgerton, E. S.

    2014-12-01

    An important and uncertain aspect of biogenic secondary organic aerosol (SOA) formation is that it is often associated with anthropogenic pollution tracers. Prior studies in Atlanta suggested that 70-80% of the carbon in water-soluble organic carbon (WSOC) is modern, yet it is well-correlated with the anthropogenic CO. In this study, we deployed a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and an Aerosol Chemical Speciation Monitor (ACSM) at multiple sites in different seasons (May 2012-February 2013) to characterize the sources and chemical composition of aerosols in the greater Atlanta area. This area in the SE US is ideal to investigate anthropogenic-biogenic interactions due to high natural and anthropogenic emissions. These extensive field studies are part of the Southeastern Center for Air Pollution and Epidemiology study (SCAPE). The HR-ToF-AMS is deployed at four sites (~ 3 weeks each) in rotation: Jefferson Street (urban), Yorkville (rural), roadside site (near Highway 75/85), and Georgia Tech site (campus), with the urban and rural sites being part of the SEARCH network. We obtained seven HR-ToF-AMS datasets in total. During the entire measurement period, the ACSM is stationary at the GIT site and samples continuously. We perform positive matrix factorization (PMF) analysis on the HR-ToF-AMS and ACSM data to deconvolve the OA into different components. While the diurnal cycle of the total OA is flat as what have been previously observed, the OA factors resolved by PMF analysis show distinctively different diurnal trends. We find that the "more-oxidized oxygenated OA" (MO-OOA) constitutes a major fraction of OA at all sites. In summer, OA is dominated by SOA, e.g., isoprene-OA and OOA with different degrees of oxidation. In contrary, biomass burning OA is more prominent in winter data. By comparing HR-ToF-AMS and ACSM data during the same sampling periods, we find that the aerosol time series are highly correlated, indicating the

  13. Spatial and seasonal variations of isoprene secondary organic aerosol in China: Significant impact of biomass burning during winter

    PubMed Central

    Ding, Xiang; He, Quan-Fu; Shen, Ru-Qin; Yu, Qing-Qing; Zhang, Yu-Qing; Xin, Jin-Yuan; Wen, Tian-Xue; Wang, Xin-Ming

    2016-01-01

    Isoprene is a substantial contributor to global secondary organic aerosol (SOA). The formation of isoprene SOA (SOAI) is highly influenced by anthropogenic emissions. Currently, there is rare information regarding SOAI in polluted regions. In this study, one-year concurrent observation of SOAI tracers was undertaken at 12 sites across China for the first time. The tracers formed from the HO2-channel exhibited higher concentrations at rural sites, while the tracer formed from the NO/NO2-channel showed higher levels at urban sites. 3-Methyltetrahydrofuran-3,4-diols exhibited linear correlations with their ring-opening products, C5-alkenetriols. And the slopes were steeper in the southern China than the northern China, indicating stronger ring-opening reactions there. The correlation analysis of SOAI tracers with the factor determining biogenic emission and the tracer of biomass burning (levoglucosan) implied that the high level of SOAI during summer was controlled by biogenic emission, while the unexpected increase of SOAI during winter was largely due to the elevated biomass burning emission. The estimated secondary organic carbon from isoprene (SOCI) exhibited the highest levels in Southwest China. The significant correlations of SOCI between paired sites implied the regional impact of SOAI in China. Our findings implicate that isoprene origins and SOAI formation are distinctive in polluted regions. PMID:26842612

  14. Spatial and seasonal variations of isoprene secondary organic aerosol in China: Significant impact of biomass burning during winter

    NASA Astrophysics Data System (ADS)

    Ding, Xiang; He, Quan-Fu; Shen, Ru-Qin; Yu, Qing-Qing; Zhang, Yu-Qing; Xin, Jin-Yuan; Wen, Tian-Xue; Wang, Xin-Ming

    2016-02-01

    Isoprene is a substantial contributor to global secondary organic aerosol (SOA). The formation of isoprene SOA (SOAI) is highly influenced by anthropogenic emissions. Currently, there is rare information regarding SOAI in polluted regions. In this study, one-year concurrent observation of SOAI tracers was undertaken at 12 sites across China for the first time. The tracers formed from the HO2-channel exhibited higher concentrations at rural sites, while the tracer formed from the NO/NO2-channel showed higher levels at urban sites. 3-Methyltetrahydrofuran-3,4-diols exhibited linear correlations with their ring-opening products, C5-alkenetriols. And the slopes were steeper in the southern China than the northern China, indicating stronger ring-opening reactions there. The correlation analysis of SOAI tracers with the factor determining biogenic emission and the tracer of biomass burning (levoglucosan) implied that the high level of SOAI during summer was controlled by biogenic emission, while the unexpected increase of SOAI during winter was largely due to the elevated biomass burning emission. The estimated secondary organic carbon from isoprene (SOCI) exhibited the highest levels in Southwest China. The significant correlations of SOCI between paired sites implied the regional impact of SOAI in China. Our findings implicate that isoprene origins and SOAI formation are distinctive in polluted regions.

  15. How important are glassy SOA ice nuclei for the formation of cirrus clouds?

    NASA Astrophysics Data System (ADS)

    Zhou, C.; Penner, J. E.; Lin, G.; Liu, X.; Wang, M.

    2014-12-01

    Extremely low ice numbers (i.e. 5 - 100 / L) have been observed in the tropical troposphere layer (TTL) in a variety of field campaigns. Various mechanisms have been proposed to explain these low numbers, including the effect of glassy secondary organic aerosol acting as heterogeneous ice nuclei (IN). In this study, we explored these effects using the CAM5.3 model. SOA fields were provided by an offline version of the University of Michigan-IMPACT model, which has a detailed process-based mechanism that describes aerosol microphysics and SOA formation through both gas phase and multiphase reactions. The transition criterion of SOA to glassy heterogeneous IN follows the parameterization developed by Wang et al. 2012. With this parameterization, glassy SOA IN form mainly when the temperature (T) is lower than 210K. In the default CAM5.3 set-up in which only the fraction of Aitken mode sulfate aerosols with diameter larger than 100nm participate in the ice nucleation (Liu and Penner 2005 parameterization), glassy SOA IN are shown to decrease the ice number (Ni) by suppressing some of the homogeneous freezing at low temperatures thereby leading to an improved representation of the relationship between Ni and T compared to the observations summarized by Kramer et al. 2009. However, when we allow the total number of the Aitken mode sulfate particles to participate in homogeneous freezing, glassy SOA IN have only a small impact on the relationship between Ni and T. If the subgrid updraft velocity is decreased to 0.1 m/s (compared to 0.2 m/s in the default set-up), there is a large decrease of Ni, since homogeneous freezing is more easily suppressed by glassy SOA IN at these updrafts. We also present the effects of glassy SOA IN using an alternative ice nucleation scheme (Barahona and Nenes, 2009).

  16. Local source impacts on primary and secondary aerosols in the Midwestern United States

    NASA Astrophysics Data System (ADS)

    Jayarathne, Thilina; Rathnayake, Chathurika M.; Stone, Elizabeth A.

    2016-04-01

    Atmospheric particulate matter (PM) exhibits heterogeneity in composition across urban areas, leading to poor representation of outdoor air pollutants in human exposure assessments. To examine heterogeneity in PM composition and sources across an urban area, fine particulate matter samples (PM2.5) were chemically profiled in Iowa City, IA from 25 August to 10 November 2011 at two monitoring stations. The urban site is the federal reference monitoring (FRM) station in the city center and the peri-urban site is located 8.0 km to the west on the city edge. Measurements of PM2.5 carbonaceous aerosol, inorganic ions, molecular markers for primary sources, and secondary organic aerosol (SOA) tracers were used to assess statistical differences in composition and sources across the two sites. PM2.5 mass ranged from 3 to 26 μg m-3 during this period, averaging 11.2 ± 4.9 μg m-3 (n = 71). Major components of PM2.5 at the urban site included organic carbon (OC; 22%), ammonium (14%), sulfate (13%), nitrate (7%), calcium (2.9%), and elemental carbon (EC; 2.2%). Periods of elevated PM were driven by increases in ammonium, sulfate, and SOA tracers that coincided with hot and dry conditions and southerly winds. Chemical mass balance (CMB) modeling was used to apportion OC to primary sources; biomass burning, vegetative detritus, diesel engines, and gasoline engines accounted for 28% of OC at the urban site and 24% of OC at the peri-urban site. Secondary organic carbon from isoprene and monoterpene SOA accounted for an additional 13% and 6% of OC at the urban and peri-urban sites, respectively. Differences in biogenic SOA across the two sites were associated with enhanced combustion activities in the urban area and higher aerosol acidity at the urban site. Major PM constituents (e.g., OC, ammonium, sulfate) were generally well-represented by a single monitoring station, indicating a regional source influence. Meanwhile, nitrate, biomass burning, food cooking, suspended dust, and

  17. Global modeling of SOA formation from dicarbonyls, epoxides, organic nitrates and peroxides

    NASA Astrophysics Data System (ADS)

    Lin, G.; Penner, J. E.; Sillman, S.; Taraborrelli, D.; Lelieveld, J.

    2012-05-01

    Recent experimental findings indicate that secondary organic aerosol (SOA) represents an important and, under many circumstances, the major fraction of the organic aerosol burden. Here, we use a global 3-D model (IMPACT) to test the results of different mechanisms for the production of SOA. The basic mechanism includes SOA formation from organic nitrates and peroxides produced from an explicit chemical formulation, using partition coefficients based on thermodynamic principles together with assumptions for the rate of formation of low-volatility oligomers. We also include the formation of low-volatility SOA from the reaction of glyoxal and methylglyoxal on aqueous aerosols and cloud droplets as well as from the reaction of epoxides on aqueous aerosols. A model simulation including these SOA formation mechanisms gives an annual global SOA production of 120.5 Tg. The global production of SOA is decreased substantially to 90.8 Tg yr-1 if the HOx regeneration mechanism proposed by Peeters et al. (2009) is used. Model predictions with and without this HOx (OH and HO2 regeneration scheme are compared with multiple surface observation datasets, namely: the Interagency Monitoring of Protected Visual Environments (IMPROVE) for the United States, the European Monitoring and Evaluation Programme (EMEP), and aerosol mass spectrometry (AMS) data measured in both the Northern Hemisphere and tropical forest regions. All model simulations show reasonable agreement with the organic carbon mass observed in the IMPROVE network and the AMS dataset, however observations in Europe are significantly underestimated, which may be caused by an underestimation of primary organic aerosol emissions (POA) in winter and of emissions and/or SOA production in the summer. The modeled organic aerosol concentrations tend to be higher by roughly a factor of three when compared with measurements at three tropical forest sites. This overestimate suggests that more measurements and model studies are

  18. Summertime contributions of isoprene, monoterpenes, and sesquiterpene oxidation to the formation of secondary organic aerosol in the troposphere over Mt. Tai, Central East China during MTX2006

    NASA Astrophysics Data System (ADS)

    Fu, P. Q.; Kawamura, K.; Pochanart, P.; Tanimoto, H.; Kanaya, Y.; Wang, Z. F.

    2009-08-01

    To better understand the contribution of biogenic volatile organic compounds to the formation of secondary organic aerosol (SOA) in high mountain regions, ambient aerosols were collected at the summit of Mt. Tai (1534 m, a.s.l.), Central East China (CEC) during the Mount Tai eXperiment 2006 campaign (MTX2006) in early summer. Biogenic SOA tracers of isoprene, monoterpenes, and β-caryophyllene oxidation products were measured using gas chromatography/mass spectrometry. All the biogenic SOA tracers showed no clear diurnal variations, suggesting that they are formed during long-range atmospheric transport. Although isoprene- and monoterpene-derived SOA tracers did not correlate with levoglucosan (a biomass burning tracer), β-caryophyllinic acid showed a good correlation with levoglucosan, indicating that biomass burning may be a source for this compound. Total concentrations of isoprene oxidation products are much higher than those of monoterpene and β-caryophyllene oxidation products. The ratio of isoprene to monoterpene oxidation products (Riso/mono) was found to co-vary with ozone and NOx during the summer campaign. The average Riso/mono value was 6.94 at daytime and 10.0 at nighttime. These values are among the highest in the aerosols studied in different regions, which may be due to the large isoprene fluxes, high O3 and NOx levels and relatively high OH concentrations in CEC. Using a tracer-based method, we estimated the average concentrations of secondary organic carbon (SOC) derived from isoprene, monoterpenes, and β-caryophyllene to be 1.76 μgC m-3 at daytime and 1.85 μgC m-3 at nighttime. These values correspond to 11.2% and 11.0% of the total OC concentrations, in which isoprene-derived SOC are 7.4% and 8.0% at day- and night-time, respectively. This study suggests that isoprene is a more significant precursor for biogenic SOA than monoterpenes and β-caryophyllene in high altitude in CEC.

  19. Sources, Properties, Aging, and Anthropogenic Influences on OA and SOA over the Southeast US and the Amazon duing SOAS, DC3, SEAC4RS, and GoAmazon

    EPA Science Inventory

    The SE US and the Amazon have large sources of biogenic VOCs, varying anthropogenic pollution impacts, and often poor organic aerosol (OA) model performance. Recent results on the sources, properties, aging, and impact of anthropogenic pollution on OA and secondary OA (SOA) over ...

  20. Source apportionment of organic aerosol across Houston, TX during DISCOVER-AQ

    NASA Astrophysics Data System (ADS)

    Yoon, S.; Clark, A. E.; Ortiz, S. M.; Usenko, S.; Sheesley, R. J.

    2015-12-01

    As part of the ground-based sampling efforts during DISCOVER-AQ's Houston month-long campaign in September 2013, atmospheric particulate matter (PM) samples were collected at four sites: Moody Tower (urban), Manvel Croix (southern suburb), Conroe (northern suburb), and La Porte (urban industrial). The Houston metropolitan area, especially the Houston Ship Channel, is a densely industrialized urban city with large concentrations of petroleum refining, petrochemical manufacturing, and heavy traffic during peak hours. Due to these and other emission sources, the area is heavily impacted by ambient PM. This study will be looking at fine PM (diameter less than 2.5µm, PM2.5) from all four sites. PM2.5fraction is relevant for understanding fate and transport of organic contaminants and is widely known to negatively impact human health. Chemical analysis including radiocarbon (14C) and organic tracer measurements (polycyclic aromatic hydrocarbons, alkanes, hopanes, steranes, and levoglucosan) were used for source apportionment. The 14C measurements constrained CMB results to estimate both primary and secondary contributions to total organic carbon (TOC). Results indicate that Moody Tower had consistent primary motor vehicle exhaust contribution (18-27%) and a fossil secondary organic aerosol (SOA) contribution from 5-33% depending on atmospheric conditions. Conroe had a lower contribution of motor vehicle exhaust (5-10%) and similarly variable fraction of fossil SOA (4-25%). Manvel Croix had an interim motor vehicle contribution (9-15%) with a variable fossil SOA (5-30%). For contemporary OC, there was minimal contribution of wood smoke during examined weeks (0-9%) but larger contributor of biogenic SOA ranging from 40-75% at Moody Tower, 56-81% at Manvel Croix and 60-79% at Conroe. Overall, the motor vehicle contribution was consistent at each site during the analysis week, biogenic SOA was consistently high, while fossil SOA showed the most variability.

  1. Observing BVOC Emissions, Oxidation, Deposition, and Interactions with Anthropogenic Pollutants to Form SOA in the Southeast United States

    NASA Astrophysics Data System (ADS)

    Goldstein, A. H.; Isaacman, G. A.; Misztal, P. K.; Yee, L.; Olson, K. F.; Moss, J.; Kreisberg, N. M.; Hering, S. V.; Park, J. H.; Kaser, L.; Seco, R.; Guenther, A. B.; Su, L.; Mak, J. E.; Holzinger, R.; Hu, W.; Campuzano Jost, P.; Palm, B. B.; Day, D. A.; Jimenez, J. L.; Koss, A.; De Gouw, J. A.

    2014-12-01

    Our overarching goals in the SOAS 2013 campaign were to 1) quantify biogenic VOC emission and VOC deposition to understand the processes controlling these bi-directional exchanges, 2) observe a broad suite of primary VOC and their oxidation products in the field and in controlled laboratory experiments, and 3) investigate their fate to understand how anthropogenic pollution alters oxidation pathways and secondary organic aerosol (SOA) formation. We pursued these goals through measurement of atmospheric organics ranging from very volatile (using in-situ GC-MS and proton transfer reaction time-of-flight MS, PTR-ToF-MS) to semi-volatile gas and particle phase compounds (using the Semi-Volatile Thermal desorption Aerosol Gas chromatograph, SV-TAG). Measured concentrations and fluxes of VOCs at the top of the SEARCH tower were coordinated with concentration gradients and fluxes at the AABC flux tower site, and vertical profiles using the Long-EZ aircraft to provide equivalent observations across sites. These results are informed through measurements using the same instrument during the FIXIT controlled laboratory oxidation study at CalTech that investigated oxidation pathways of BVOC with varying levels of anthropogenic pollutants. Measurements by SV-TAG of particle-phase and total gas-plus-particle-phase compounds at the SEARCH tower provide hourly quantification of semi-volatile compounds, including the oxidation products of measured VOCs. Derivatization of hydroxyl groups prior to GC analysis allows analysis of highly oxidized chemicals, including most known tracers. Methyl tetrols, an oxidation product of isoprene, had a significant day-time gas-phase component, and their abundance was strongly correlated with particle-phase sulfate, indicative of anthropogenic influence on the formation or partitioning processes. Similar observations of pinic acid (monterpene oxidation product) and many other BVOC oxidation products were made in both the gas and particle phases

  2. EFFECT OF ACIDITY ON SECONDARY ORGANIC AEROSOL FORMATION FROM ISOPRENE

    EPA Science Inventory

    The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is c...

  3. Secondary organic aerosol formation of primary, secondary and tertiary Amines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Amines have been widely identified in ambient aerosol in both urban and rural environments and they are potential precursors for formation of nitrogen-containing secondary organic aerosols (SOA). However, the role of amines in SOA formation has not been well studied. In this wrok, we use UC-Riversid...

  4. Quantifying VOC-Reaction Tracers, Ozone Production, and Continuing Aerosol Production Rates in Urban and Far-Downwind Atmospheres

    NASA Technical Reports Server (NTRS)

    Chatfield, Robert; Ren, X.; Brune, W.; Fried, A.; Schwab, J.

    2008-01-01

    We have found a surprisingly informative decomposition of the complex question of smoggy ozone production (basically, [HO2] in a more locally determined field of [NO]) in the process of linked investigations of modestly smoggy Eastern North America (by NASA aircraft, July 2004) and rather polluted Flushing, NYC (Queens College, July, 2001). In both rural and very polluted situations, we find that a simple contour graph parameterization of the local principal ozone production rate can be estimated using only the variables [NO] and j(sub rads) [HCHO]: Po(O3) = c (j(sub rads) [HCHO])(sup a) [HCHO](sup b). Here j(sub rads) is the photolysis of HCHO to radicals, presumably capturing many harder-UV photolytic processes and the principle ozone production is that due to HO2; mechanisms suggest that ozone production due to RO2 is closely correlated, often suggesting a limited range of different proportionality factors. The method immediately suggests a local interpretation for concepts of VOC limitation and NOx limitation. We believe that the product j(sub rads) [HCHO] guages the oxidation rate of observed VOC mixtures in a way that also provides [HO2] useful for the principle ozone production rate k [HO2] [NO], and indeed, all ozone chemical production. The success of the method suggests that dominant urban primary-HCHO sources may transition to secondary plume-HCHO sources in a convenient way. Are there other, simple, near-terminal oxidized VOC's which help guage ozone production and aerosol particle formation? Regarding particles, we report on, to the extent NASA Research resources allow, on appealing relationships between far-downwind (Atlantic PBL) HCHO and very fine aerosol (including sulfate. Since j(sub rads) [HCHO] provides a time-scale, we may understand distant-plume particle production in a more quantitative manner. Additionally we report on a statistical search in the nearer field for relationships between glyoxals (important near-terminal aromatic and isoprene

  5. Effect of hydrophilic organic seed aerosols on secondary organic aerosol formation from ozonolysis of α-pinene.

    PubMed

    Song, Chen; Zaveri, Rahul A; Shilling, John E; Alexander, M Lizabeth; Newburn, Matt

    2011-09-01

    Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized volatile organic compound product will increase as the mass loading of preexisting organic aerosol increases. In a previous work, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the SOA yields from ozonolysis of α-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, a substantial faction of atmospheric aerosol is composed of polar, hydrophilic organic compounds. In this work, we investigate the effects of model hydrophilic organic aerosol (OA) species such as fulvic acid, adipic acid, and citric acid on the gas-particle partitioning of SOA from α-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of α-pinene SOA into the particle-phase. The other two seed particles have a negligible effect on the α-pinene SOA yields, suggesting that α-pinene SOA forms a well-mixed organic aerosol phase with citric acid and a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted OA species. PMID:21790137

  6. Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3-D model

    NASA Astrophysics Data System (ADS)

    Knote, C.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J.; Fast, J.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R.; Tyndall, G.; Washenfelder, R.; Waxman, E.; Zhang, Q.

    2013-10-01

    New pathways to form secondary organic aerosols (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and deliquesced aerosols where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include a detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aqueous-phase of aerosols. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. In all simulations the LA basin was found to be the hotspot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a simple uptake coefficient, as frequently employed in global modeling studies, leads to higher SOA contributions from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to be the main contributor to SOA mass compared to a volume process and reversible formation. We find that contribution of the latter is limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A kinetic limitation in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute >20% of glyoxal SOA mass, and the total mass formed (5.8% of total SOA in the LA

  7. Organic aerosol mixing observed by single-particle mass spectrometry.

    PubMed

    Robinson, Ellis Shipley; Saleh, Rawad; Donahue, Neil M

    2013-12-27

    We present direct measurements of mixing between separately prepared organic aerosol populations in a smog chamber using single-particle mass spectra from the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Docosane and docosane-d46 (22 carbon linear solid alkane) did not show any signs of mixing, but squalane and squalane-d62 (30 carbon branched liquid alkane) mixed on the time scale expected from a condensational-mixing model. Docosane and docosane-d46 were driven to mix when the chamber temperature was elevated above the melting point for docosane. Docosane vapors were shown to mix into squalane-d62, but not the other way around. These results are consistent with low diffusivity in the solid phase of docosane particles. We performed mixing experiments on secondary organic aerosol (SOA) surrogate systems finding that SOA derived from toluene-d8 (a surrogate for anthropogenic SOA (aSOA)) does not mix into squalane (a surrogate for hydrophobic primary organic aerosol (POA)) but does mix into SOA derived from α-pinene (biogenic SOA (bSOA) surrogate). For the aSOA/POA, the volatility of either aerosol does not limit gas-phase diffusion, indicating that the two particle populations do not mix simply because they are immiscible. In the aSOA/bSOA system, the presence of toluene-d8-derived SOA molecules in the α-pinene-derived SOA provides evidence that the diffusion coefficient in α-pinene-derived SOA is high enough for mixing on the time scale of 1 min. The observations from all of these mixing experiments are generally invisible to bulk aerosol composition measurements but are made possible with single-particle composition data. PMID:24131283

  8. Source apportionment and dynamic changes of carbonaceous aerosols during the haze bloom-decay process in China based on radiocarbon and organic molecular tracers

    NASA Astrophysics Data System (ADS)

    Liu, Junwen; Li, Jun; Liu, Di; Ding, Ping; Shen, Chengde; Mo, Yangzhi; Wang, Xinming; Luo, Chunling; Cheng, Zhineng; Szidat, Sönke; Zhang, Yanlin; Chen, Yingjun; Zhang, Gan

    2016-03-01

    Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities in China, yet few studies simultaneously focus on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56 ± 4 in BJ and 46 ± 5 % in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54 % in BJ, and 40, 15 and 46 % in GZ, respectively. Non-fossil fuel sources account for 52 in BJ and 71 % in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom-decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.

  9. Source apportionment and dynamic changes of carbonaceous aerosols during the haze bloom-decay process in China based on radiocarbon and organic molecular tracers

    NASA Astrophysics Data System (ADS)

    Liu, J.; Li, J.; Liu, D.; Ding, P.; Shen, C.; Mo, Y.; Wang, X.; Luo, C.; Cheng, Z.; Szidat, S.; Zhang, Y.; Chen, Y.; Zhang, G.

    2015-12-01

    Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities of China, yet seldom study simultaneously focuses on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), respectively, using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56 ± 4 % in BJ and 46 ± 5 % in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54 % in BJ, and 40, 15 and 46 % in GZ, respectively. Non-fossil fuel sources account for 52 % in BJ and 71 % in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom-decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.

  10. Photodegradation of SOA Prepared by Oxidation of d-Limonene by Ozone and NO3

    NASA Astrophysics Data System (ADS)

    Pan, X.; Xing, J.; Underwood, J. S.; Nizkorodov, S. A.

    2008-12-01

    Terpenes account for over 50% of biogenically emitted volatile organic compounds (VOC). Terpenes including limonene react with gas phase oxidants in the air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products spontaneously condense into particles. While in the atmosphere, SOA age via heterogeneous atmospheric chemistry, often with profound effects on the physical and chemical properties of the particles. The primary goal of this research is to study the photochemical aging of monoterpene-derived aerosol particles. SOA particles are generated in the lab by reacting limonene and oxidants including ozone and NO3 in a Teflon reaction chamber. The concentrations of limonene and oxidants were set to different levels in experiments. The particles are collected on filters and irradiated with light in the actinic region (>290 nm). The gas-phase photolysis products were studied using chemical ionization mass spectrometry (CIMS) in real time. The results show that the photodegradation of limonene SOA strongly depends on radiation wavelengths. SOA photodegradation mechanisms and their implications for photochemical aging of organic aerosols will be discussed.

  11. Effects of aging on organic aerosol from open biomass burning smoke in aircraft and laboratory studies

    NASA Astrophysics Data System (ADS)

    Cubison, M. J.; Ortega, A. M.; Hayes, P. L.; Farmer, D. K.; Day, D.; Lechner, M. J.; Brune, W. H.; Apel, E.; Diskin, G. S.; Fisher, J. A.; Fuelberg, H. E.; Hecobian, A.; Knapp, D. J.; Mikoviny, T.; Riemer, D.; Sachse, G. W.; Sessions, W.; Weber, R. J.; Weinheimer, A. J.; Wisthaler, A.; Jimenez, J. L.

    2011-12-01

    Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f60, the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f60~0.3% ± 0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f44 as a tracer for SOA and aged POA and a surrogate of organic O:C, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f60 and increasing f44 with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f60 signature. A statistically significant difference in f60 between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) = -0.01 to ~0.05, with a mean ΔOA/POA ~19%. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~8 ± 7 Tg OA yr-1 is estimated, of the order of 5 % of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden.

  12. Effects of aging on organic aerosol from open biomass burning smoke in aircraft and lab studies

    NASA Astrophysics Data System (ADS)

    Cubison, M. J.; Ortega, A. M.; Hayes, P. L.; Farmer, D. K.; Day, D.; Lechner, M. J.; Brune, W. H.; Apel, E.; Diskin, G. S.; Fisher, J. A.; Fuelberg, H. E.; Hecobian, A.; Knapp, D. J.; Mikoviny, T.; Riemer, D.; Sachse, G. W.; Sessions, W.; Weber, R. J.; Weinheimer, A. J.; Wisthaler, A.; Jimenez, J. L.

    2011-04-01

    Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f60, the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f60~0.3% ±0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f44 as a tracer for SOA and aged POA, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f60 and increasing f44 with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f60 signature. A statistically significant difference in f60 between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) =-0.01 to ~0.07, with a mean ΔOA/POA ~25%. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~9 Tg OA yr-1 is estimated, of the order of 5% of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden.

  13. Simulation of semi-explicit mechanisms of SOA formation from glyoxal in a 3D model

    NASA Astrophysics Data System (ADS)

    Knote, C. J.; Hodzic, A.; Jimenez, J. L.; Volkamer, R.; Orlando, J. J.; Baidar, S.; Brioude, J. F.; Fast, J. D.; Gentner, D. R.; Goldstein, A. H.; Hayes, P. L.; Knighton, W. B.; Oetjen, H.; Setyan, A.; Stark, H.; Thalman, R. M.; Tyndall, G. S.; Washenfelder, R. A.; Waxman, E.; Zhang, Q.

    2013-12-01

    Formation of secondary organic aerosols (SOA) through multi-phase processing of glyoxal has been proposed recently as a relevant contributor to SOA mass. Glyoxal has both anthropogenic and biogenic sources, and readily partitions into the aqueous-phase of cloud droplets and aerosols. Both reversible and irreversible chemistry in the liquid-phase has been observed. A recent laboratory study indicates that the presence of salts in the liquid-phase strongly enhances the Henry';s law constant of glyoxal, allowing for much more effective multi-phase processing. In our work we investigate the contribution of glyoxal to SOA formation on the regional scale. We employ the regional chemistry transport model WRF-chem with MOZART gas-phase chemistry and MOSAIC aerosols, which we both extended to improve the description of glyoxal formation in the gas-phase, and its interactions with aerosols. The detailed description of aerosols in our setup allows us to compare very simple (uptake coefficient) parameterizations of SOA formation from glyoxal, as has been used in previous modeling studies, with much more detailed descriptions of the various pathways postulated based on laboratory studies. Measurements taken during the CARES and CalNex campaigns in California in summer 2010 allowed us to constrain the model, including the major direct precursors of glyoxal. Simulations at convection-permitting resolution over a 2 week period in June 2010 have been conducted to assess the effect of the different ways to parameterize SOA formation from glyoxal and investigate its regional variability. We find that depending on the parameterization used the contribution of glyoxal to SOA is between 1 and 15% in the LA basin during this period, and that simple parameterizations based on uptake coefficients derived from box model studies lead to higher contributions (15%) than parameterizations based on lab experiments (1%). A kinetic limitation found in experiments hinders substantial contribution

  14. Ice Formation Potential of Laboratory Generated Biogenic and Anthropogenic-Biogenic SOA Particles

    NASA Astrophysics Data System (ADS)

    Knopf, D. A.; Alpert, P. A.; Charnawskas, J. C.; Lambe, A. T.; Massoli, P.; Onasch, T. B.; Davidovits, P.; Worsnop, D. R.

    2014-12-01

    Secondary organic aerosol (SOA) is ubiquitous in the atmosphere and may play an important role in cloud glaciation processes. We investigated several laboratory generated SOA particles systems for their initial water uptake and ice formation propensity as a function of temperature, T, relative humidity with respect to water, RH, relative humidity with respect to ice, RHice, and for different humidification rates, cRHice. This includes pure SOA particles formed from α-pinene, isoprene, and longifolene volatile organic compound precursors with and without the presence of sulfate seed particles as well as oxidized soot and soot-coated α-pinene and naphthalene SOA with varying O/C ratios and coating thicknesses. Micro-spectroscopic chemical imaging using scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) is used to characterize SOA, SOA-sulfate, SOA-soot particles generated in the Boston College potential aerosol mass (PAM) flow reactor in relation to their ice nucleation behavior. Water uptake is consistently observed on SOA particles at RH=75% and 95% for 262 and 228 K, respectively, followed by homogeneous ice nucleation applying atmospherically relevant cRHice=1 % min-1. When cRHice=25 % min-1, ice nucleation is delayed by about 30-40% RHice and cannot be explained by homogeneous ice nucleation. This implies diffusion limitation of water into these potentially glassy or semi-solid organic particles resulting in non-equilibrium between ambient RH and particle water activity. These data will aid in our understanding of the role of organic particle phase states in response to changes in T and RH which is crucial information for prediction of atmospheric ice nucleation.

  15. Formation of secondary organic aerosol from isoprene oxidation over Europe

    NASA Astrophysics Data System (ADS)

    Karl, M.; Tsigaridis, K.; Vignati, E.; Dentener, F.

    2009-01-01

    The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr-1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of particulate organic matter (POM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates POM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr-1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Tropospheric isoprene SOA production over Europe in summer more than doubles when, in addition to pre-existing carbonaceous aerosols, condensation of semi volatile vapours on ammonium and sulphate aerosols is considered. Consequently, smog chamber experiments on SOA formation should be

  16. Lead isotopes and trace metal ratios of aerosols as tracers of Pb pollution sources in Kanpur, India

    NASA Astrophysics Data System (ADS)

    Sen, Indra; Bizimis, Michael; Tripathi, Sachchida; Paul, Debajyoti; Tyagi, Swati; Sengupta, Deep

    2015-04-01

    The anthropogenic flux of Pb in the Earth's surface is almost an order of magnitude higher than its corresponding natural flux [1]. Identifying the sources and pathways of anthropogenic Pb in environment is important because Pb toxicity is known to have adverse effects on human health. Pb pollution sources for America, Europe, and China are well documented. However, sources of atmospheric Pb are unknown in India, particularly after leaded gasoline was phased out in 2000. India has a developing economy with a rapidly emerging automobile and high temperature industry, and anthropogenic Pb emission is expected to rise in the next decade. In this study, we report on the Pb- isotope compositions and trace metal ratios of airborne particulates collected in Kanpur, an industrial city in northern India. The Pb concentration in the airborne particulate matter varies between 14-216 ng/m3, while the other heavy metals vary by factor of 10 or less, e.g. Cd=0.3-3 ng/m3, As=0.4-3.5 ng/m3, Zn=36-161 ng/m3, and Cu=3-22 ng/m3. The 206Pb/207Pb, 208Pb/206Pb, and 208Pb/207Pb vary between 1.112 - 1.129, 2.123-2.141, and 2.409-2.424 respectively, and are highly correlated with each other (R2>0.9). Pb isotopes and trace metal data reveals that coal combustion is the major source of anthropogenic Pb in the atmosphere, with limited contribution from mining and smelting processes. We further conclude that combination of Pb isotope ratios and V/Pb ratios are powerful tracers for Pb source apportionment studies, which is otherwise difficult to differentiate based only on Pb systematics [1] Sen and Peucker-Ehrenbrink (2012), Environ. Sci. Technol.(46), 8601-8609

  17. Organosulfate Formation in Biogenic Secondary Organic Aerosol

    EPA Science Inventory

    Organosulfates of isoprene, α-pinene, and β-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive seri...

  18. Effect of Hydrophilic Organic Seed Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of α-Pinene

    SciTech Connect

    Song, Chen; Zaveri, Rahul A.; Shilling, John E.; Alexander, M. L.; Newburn, Matthew K.

    2011-07-26

    Gas-particle partitioning theory is widely used in atmospheric models to predict organic aerosol loadings. This theory predicts that secondary organic aerosol (SOA) yield of an oxidized VOC product will increase as the mass loading of preexisting organic aerosol increases. In a previous study, we showed that the presence of model hydrophobic primary organic aerosol (POA) had no detectable effect on the secondary organic aerosol (SOA) yields from ozonolysis of {alpha}-pinene, suggesting that the condensing SOA compounds form a separate phase from the preexisting POA. However, non-polar, hydrophobic POA may gradually become polar and hydrophilic as it undergoes oxidative aging while POA formed from biomass burning is already somewhat polar and hydrophilic. In this study, we investigate the effects of model hydrophilic POA such as fulvic acid, adipic acid and citric acid on the gas-particle partitioning of SOA from {alpha}-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of {alpha}-pinene SOA into the particle-phase. The other two POA seed particles have negligible effect on the {alpha}-pinene SOA yields, suggesting that {alpha}-pinene SOA forms a well-mixed organic aerosol phase with citric acid while a separate phase with adipic acid and fulvic acid. This finding highlights the need to improve the thermodynamics treatment of organics in current aerosol models that simply lump all hydrophilic organic species into a single phase, thereby potentially introducing an erroneous sensitivity of SOA mass to emitted POA.

  19. Aerosol Monosaccharide Anhydrides as Tracer Species for Identifying Wildfire Smoke Transport to California's Central Valley in August 2002

    NASA Astrophysics Data System (ADS)

    Abhyankar, M. S.; Dixon, R. W.

    2007-12-01

    The Biscuit fire burned close to 2,000 km2 of forested land in southwestern Oregon in July and August, 2002. August, 2002 also was a time in which PM2.5 concentrations were higher than typical in California Central Valley cities located several hundred kilometers to the southeast. The concentrations of two monosaccharide anhydrides, levoglucosan and mannosan, were measured in aerosol samples collected at four California Air Resource Board sites in Central Valley cities for the purpose of determining how the wildfire smoke affected air quality. Levoglucosan concentrations ranged from the detection limit of 18 ng m-3 to about 400 ng m-3. While days with high levoglucosan concentrations generally had above average to high PM2.5 concentrations, there were also days with high PM2.5 concentrations with low levoglucosan concentrations. Although mannosan was only detected in a small number of samples, the levoglucosan to mannosan ratios in these samples were consistent with smoke from softwood combustion. A wildfire source levoglucosan to PM2.5 concentration ratio was used to estimate the PM2.5 concentration originating from smoke. From this method, smoke was found to be a significant (greater than 10% of the total PM2.5 concentration) on occassions. The estimated smoke PM2.5 concentration always remained less than 10 μg m-3 and contributed to less than a third of the total PM2.5 concentration. Because the PM2.5 concentrations were higher than typical August values, either there were other factors leading to high PM2.5 concentrations in August 2002, or the smoke estimation method underestimated the smoke concentration.

  20. Secondary organic aerosol formation and primary organic aerosol oxidation from biomass-burning smoke in a flow reactor during FLAME-3

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Day, D. A.; Cubison, M. J.; Brune, W. H.; Bon, D.; de Gouw, J. A.; Jimenez, J. L.

    2013-11-01

    We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A "potential aerosol mass" (PAM) flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer-reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days of aging in the atmosphere, and allowing for us to extend the investigation of smoke aging beyond the oxidation levels achieved in traditional smog chambers. Volatile organic compound (VOC) observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net-SOA-to-POA ratio of biomass-burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp~3.9 × 1011 molecules cm-3 s), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors

  1. Ultrahigh-resolution FT-ICR mass spectrometry characterization of a-pinene ozonolysis SOA

    EPA Science Inventory

    Secondary organic aerosol (SOA) of α-pinene ozonolysis with and without hydroxyl radical scavenging hexane was characterized by ultrahigh-resolution. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Molecular formulas for more than 900 negative ions were i...

  2. Quantum Chemical Calculations Resolved Identification of Methylnitrocatechols in Atmospheric Aerosols.

    PubMed

    Frka, Sanja; Šala, Martin; Kroflič, Ana; Huš, Matej; Čusak, Alen; Grgić, Irena

    2016-06-01

    Methylnitrocatechols (MNCs) are secondary organic aerosol (SOA) tracers and major contributors to atmospheric brown carbon; however, their formation and aging processes in atmospheric waters are unknown. To investigate the importance of aqueous-phase electrophilic substitution of 3-methylcatechol with nitronium ion (NO2(+)), we performed quantum calculations of their favorable pathways. The calculations predicted the formation of 3-methyl-5-nitrocatechol (3M5NC), 3-methyl-4-nitrocatechol (3M4NC), and a negligible amount of 3-methyl-6-nitrocatechol (3M6NC). MNCs in atmospheric PM2 samples were further inspected by LC/(-)ESI-MS/MS using commercial as well as de novo synthesized authentic standards. We detected 3M5NC and, for the first time, 3M4NC. In contrast to previous reports, 3M6NC was not observed. Agreement between calculated and observed 3M5NC/3M4NC ratios cannot unambiguously confirm the electrophilic mechanism as the exclusive formation pathway of MNCs in aerosol water. However, the examined nitration by NO2(+) is supported by (1) the absence of 3M6NC in the ambient aerosols analyzed and (2) the constant 3M5NC/3M4NC ratio in field aerosol samples, which indicates their common formation pathway. The magnitude of error one could make by incorrectly identifying 3M4NC as 3M6NC in ambient aerosols was also assessed, suggesting the importance of evaluating the literature regarding MNCs with special care. PMID:27136117

  3. Organic Nitrate Contribution to New Particle Formation and Growth in Secondary Organic Aerosols from α-Pinene Ozonolysis.

    PubMed

    Berkemeier, Thomas; Ammann, Markus; Mentel, Thomas F; Pöschl, Ulrich; Shiraiwa, Manabu

    2016-06-21

    The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer (13)N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process. The direct reaction of α-pinene with NO3 was found to be less important for particle-phase organic nitrate formation. The nitrogen content of SOA particles decreased slightly upon increase of relative humidity up to 80%. The experiments show a tight correlation between organic nitrate content and SOA particle-number concentrations, implying that the condensing organic nitrates are among the extremely low volatility organic compounds (ELVOC) that may play an important role in the nucleation and growth of atmospheric nanoparticles. PMID:27219077

  4. Secondary organic aerosols - formation and ageing studies in the SAPHIR chamber

    NASA Astrophysics Data System (ADS)

    Spindler, Christian; Müller, Lars; Trimborn, Achim; Mentel, Thomas; Hoffmann, Thorsten

    2010-05-01

    Secondary organic aerosol (SOA) formation from oxidation products of biogenic volatile organic compounds (BVOC) constitutes an important coupling between vegetation, atmospheric chemistry, and climate change. Such secondary organic aerosol components play an important role in particle formation in Boreal regions ((Laaksonen et al., 2008)), where biogenic secondary organic aerosols contribute to an overall negative radiative forcing, thus a negative feed back between vegetation and climate warming (Spracklen et al., 2008). Within the EUCAARI project we investigated SOA formation from mixtures of monoterpenes (and sesquiterpenes) as emitted typically from Boreal tree species in Southern Finland. The experiments were performed in the large photochemical reactor SAPHIR in Juelich at natural light and oxidant levels. Oxidation of the BVOC mixtures and SOA formation was induced by OH radicals and O3. The SOA was formed on the first day and then aged for another day. The resulting SOA was characterized by HR-ToF-AMS, APCI-MS, and filter samples with subsequent H-NMR, GC-MS and HPLC-MS analysis. The chemical evolution of the SOA is characterized by a fast increase of the O/C ratio during the formation process on the first day, stable O/C ratio during night, and a distinctive increase of O/C ratio at the second day. The increase of the O/C ratio on the second day is highly correlated to the OH dose and is accompanied by condensational growth of the particles. We will present simultaneous factor analysis of AMS times series (PMF, Ulbrich et al., 2009 ) and direct measurements of individual chemical species. We found that four factors were needed to represent the time evolution of the SOA composition (in the mass spectra) if oxidation by OH plays a mayor role. Corresponding to these factors we observed individual, representative molecules with very similar time behaviour. The correlation between tracers and AMS factors is astonishingly good as the molecular tracers

  5. Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Fu, P. Q.; Kawamura, K.; Chen, J.; Charrière, B.; Sempéré, R.

    2013-02-01

    Organic molecular composition of marine aerosol samples collected during the MALINA cruise in the Arctic Ocean was investigated by gas chromatography/mass spectrometry. More than 110 individual organic compounds were determined in the samples and were grouped into different compound classes based on the functionality and sources. The concentrations of total quantified organics ranged from 7.3 to 185 ng m-3 (mean 47.6 ng m-3), accounting for 1.8-11.0% (4.8%) of organic carbon in the marine aerosols. Primary saccharides were found to be dominant organic compound class, followed by secondary organic aerosol (SOA) tracers formed from the oxidation of biogenic volatile organic compounds (VOCs) such as isoprene, α-pinene and β-caryophyllene. Mannitol, the specific tracer for airborne fungal spores, was detected as the most abundant organic species in the samples with a concentration range of 0.052-53.3 ng m-3 (9.2 ng m-3), followed by glucose, arabitol, and the isoprene oxidation products of 2-methyltetrols. Biomass burning tracers such as levoglucosan are evident in all samples with trace levels. On the basis of the tracer-based method for the estimation of fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 10.7% (up to 26.2%) of the OC in the marine aerosols was due to the contribution of fungal spores, followed by the contribution of isoprene SOC (mean 3.8%) and α-pinene SOC (2.9%). In contrast, only 0.19% of the OC was due to the photooxidation of β-caryophyllene. This study indicates that primary organic aerosols from biogenic emissions, both from long-range transport of mid-latitude aerosols and from sea-to-air emission of marine organics, as well as secondary organic aerosols formed from the photooxidation of biogenic VOCs are important factors controlling the organic chemical composition of marine aerosols in the Arctic Ocean.

  6. Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Fu, P. Q.; Kawamura, K.; Chen, J.; Charrière, B.; Sempéré, R.

    2012-08-01

    Organic molecular composition of marine aerosol samples collected during the MALINA cruise in the Arctic Ocean was investigated by gas chromatography/mass spectrometry. More than 110 individual organic compounds were determined in the samples and were grouped into different compound classes based on the functionality and sources. The concentrations of total quantified organics ranged from 7.3 to 185 ng m-3 (mean 47.6 ng m-3), accounting for 1.8-11.0% (4.8%) of organic carbon in the marine aerosols. Primary saccharides were found to be dominant organic compound class, followed by secondary organic aerosol (SOA) tracers formed from the oxidation of biogenic volatile organic compounds (VOCs) such as isoprene, α-pinene and β-caryophyllene. Mannitol, the specific tracer for airborne fungal spores, was detected as the most abundant organic species in the samples with a concentration range of 0.052-53.3 ng m-3 (9.2 ng m-3), followed by glucose, arabitol, and the isoprene oxidation products of 2-methyltetrols. Biomass burning tracers such as levoglucosan are evident in all samples with trace levels. On the basis of the tracer-based method for the estimation of fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 10.7% (up to 26.2%) of the OC in the marine aerosols was due to the contribution of fungal spores, followed by the contribution of isoprene SOC (mean 3.8%) and α-pinene SOC (2.9%). In contrast, only 0.19% of the OC was due to the photooxidation of β-caryophyllene. This study indicates that primary organic aerosols from biogenic emissions, both from long-range transport of mid-latitude aerosols and from sea-to-air emission of marine organics, as well as secondary organic aerosols formed from the photooxidation of biogenic VOCs are important factors controlling the organic chemical composition of marine aerosols in the Arctic Ocean.

  7. VOC emissions, evolutions and contributions to SOA formation at a receptor site in eastern China

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Hu, W. W.; Shao, M.; Wang, M.; Chen, W. T.; Lu, S. H.; Zeng, L. M.; Hu, M.

    2013-09-01

    Volatile organic compounds (VOCs) were measured by two online instruments (GC-FID/MS and PTR-MS) at a receptor site on Changdao Island (37.99° N, 120.70° E) in eastern China. Reaction with OH radical dominated chemical losses of most VOC species during the Changdao campaign. A photochemical-age-based parameterization method is used to calculate VOC emission ratios and to quantify the evolution of ambient VOCs. The calculated emission ratios of most hydrocarbons agree well with those obtained from emission inventory data, but determined emission ratios of oxygenated VOCs (OVOCs) are significantly higher than those from emission inventory data. The photochemical-age-based parameterization method is also used to investigate primary emissions and secondary formation of organic aerosol. The primary emission ratio of organic aerosol (OA) to CO is determined to be 14.9 μg m-3 ppm-1, and secondary organic aeorosols (SOA) are produced at an enhancement ratio of 18.8 μg m-3 ppm-1 to CO after 50 h of photochemical processing in the atmosphere. SOA formation is significantly higher than the level determined from VOC oxidation under both high-NOx (2.0 μg m-3 ppm-1 CO) and low-NOx conditions (6.5 μg m-3 ppm-1 CO). Polycyclic aromatic hydrocarbons (PAHs) and higher alkanes (> C10) account for as high as 17.4% of SOA formation, which suggests semi-volatile organic compounds (SVOCs) may be a large contributor to SOA formation during the Changdao campaign. The SOA formation potential of primary VOC emissions determined from field campaigns in Beijing and Pearl River Delta (PRD) is lower than the measured SOA levels reported in the two regions, indicating SOA formation is also beyond explainable by VOC oxidation in the two city clusters.

  8. Modeling regional secondary organic aerosol using the Master Chemical Mechanism

    NASA Astrophysics Data System (ADS)

    Li, Jingyi; Cleveland, Meredith; Ziemba, Luke D.; Griffin, Robert J.; Barsanti, Kelley C.; Pankow, James F.; Ying, Qi

    2015-02-01

    A modified near-explicit Master Chemical Mechanism (MCM, version 3.2) with 5727 species and 16,930 reactions and an equilibrium partitioning module was incorporated into the Community Air Quality Model (CMAQ) to predict the regional concentrations of secondary organic aerosol (SOA) from volatile organic compounds (VOCs) in the eastern United States (US). In addition to the semi-volatile SOA from equilibrium partitioning, reactive surface uptake processes were used to simulate SOA formation due to isoprene epoxydiol, glyoxal and methylglyoxal. The CMAQ-MCM-SOA model was applied to simulate SOA formation during a two-week episode from August 28 to September 7, 2006. The southeastern US has the highest SOA, with a maximum episode-averaged concentration of ∼12 μg m-3. Primary organic aerosol (POA) and SOA concentrations predicted by CMAQ-MCM-SOA agree well with AMS-derived hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA) urban concentrations at the Moody Tower at the University of Houston. Predicted molecular properties of SOA (O/C, H/C, N/C and OM/OC ratios) at the site are similar to those reported in other urban areas, and O/C values agree with measured O/C at the same site. Isoprene epoxydiol is predicted to be the largest contributor to total SOA concentration in the southeast US, followed by methylglyoxal and glyoxal. The semi-volatile SOA components are dominated by products from β-caryophyllene oxidation, but the major species and their concentrations are sensitive to errors in saturation vapor pressure estimation. A uniform decrease of saturation vapor pressure by a factor of 100 for all condensable compounds can lead to a 150% increase in total SOA. A sensitivity simulation with UNIFAC-calculated activity coefficients (ignoring phase separation and water molecule partitioning into the organic phase) led to a 10% change in the predicted semi-volatile SOA concentrations.

  9. Secondary organic aerosol: a comparison between foggy and nonfoggy days.

    PubMed

    Kaul, D S; Gupta, Tarun; Tripathi, S N; Tare, V; Collett, J L

    2011-09-01

    Carbonaceous species, meteorological parameters, trace gases, and fogwater chemistry were measured during winter in the Indian city of Kanpur to study secondary organic aerosol (SOA) during foggy and clear (nonfoggy) days. Enhanced SOA production was observed during fog episodes. It is hypothesized that aqueous phase chemistry in fog drops is responsible for increasing SOA production. SOA concentrations on foggy days exceeded those on clear days at all times of day; peak foggy day SOA concentrations were observed in the evening vs peak clear day SOA concentrations which occurred in the afternoon. Changes in biomass burning emissions on foggy days were examined because of their potential to confound estimates of SOA production based on analysis of organic to elemental carbon (OC/EC) ratios. No evidence of biomass burning influence on SOA during foggy days was found. Enhanced oxidation of SO(2) to sulfate during foggy days was observed, possibly causing the regional aerosol to become more acidic. No evidence was found in this study, either, for effects of temperature or relative humidity on SOA production. In addition to SOA production, fogs can also play an important role in cleaning the atmosphere of carbonaceous aerosols. Preferential scavenging of water-soluble organic carbon (WSOC) by fog droplets was observed. OC was found to be enriched in smaller droplets, limiting the rate of OC deposition by droplet sedimentation. Lower EC concentrations were observed on foggy days, despite greater stagnation and lower mixing heights, suggesting fog scavenging and removal of EC was active as well. PMID:21790145

  10. Rate constant and secondary organic aerosol yields for the gas-phase reaction of hydroxyl radicals with syringol (2,6-dimethoxyphenol)

    NASA Astrophysics Data System (ADS)

    Lauraguais, Amélie; Coeur-Tourneur, Cécile; Cassez, Andy; Seydi, Abdoulaie

    2012-08-01

    Syringol (2,6-dimethoxyphenol) is a potential marker compound for wood smoke emissions in the atmosphere. To investigate the atmospheric reactivity of this compound, the rate constant for its reaction with hydroxyl radicals (OH) has been determined in a simulation chamber (8 m3) at 294 ± 2 K, atmospheric pressure and low relative humidity (2-4%) using the relative rate method. The syringol and reference compound concentrations were followed by GC/FID (Gas chromatography/Flame Ionization Detection). The determined rate constant (in units of cm3 molecule-1 s-1) is ksyringol = (9.66 ± 1.11) × 10-11. The calculated atmospheric lifetime for syringol is 1.8 h, indicating that it is too reactive to be used as a tracer for wood smoke emissions. Secondary Organic Aerosol (SOA) formation from the OH reaction with syringol was also investigated. The initial mixing ratios for syringol were in the range 495-3557 μg m-3. The aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (M0) to the total reacted syringol concentration assuming a particle density of 1.4 g cm-3. The aerosol formation yield increases as the initial syringol concentration increases, and leads to aerosol yields ranging from 0.10 to 0.36. Y is a strong function of M0 and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. To our knowledge, this work represents the first investigation of the rate constant and SOA formation for the reaction of syringol with OH radicals. The atmospheric implications of this reaction are also discussed.

  11. A sub-decadal trend of diacids in atmospheric aerosols in East Asia

    NASA Astrophysics Data System (ADS)

    Kundu, S.; Kawamura, K.; Kobayashi, M.; Tachibana, E.; Lee, M.; Fu, P. Q.; Jung, J.

    2015-08-01

    The change of secondary organic aerosols (SOA) has been predicted to be highly uncertain in the future atmosphere in Asia. To better quantify the SOA change, we study a sub-decadal (2001-2008) trend of major surrogate compounds (C2-C10 diacids) of SOA in atmospheric aerosols from Gosan site in Jeju Island, South Korea. Gosan site is influenced by the pollution-outflows from East Asia. The molecular distribution of diacids was characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids in each year. The seasonal variations of diacids in each year were characterized by the highest concentrations of saturated diacids in spring and unsaturated diacids in winter. The consistent molecular distribution and seasonal variations are indicative of similar pollution sources for diacids in East Asia over a sub-decadal scale. However, the intensity of the pollution sources has increased as evidenced by the increases of major diacids at the rate of 3.9-47.4 % year-1 particularly in April. The temporal variations of atmospheric tracer compounds (CO, levoglucosan, 2-methyltetrols, pinic acid, glyoxylic acid, glyoxal and methylglyoxal) suggest that the increases of diacids are due to an enhanced precursor emissions associated with more anthropogenic than biogenic activities followed by their chemical processing in the atmosphere. The trends of diacids are opposite to the reported decreases of sulfate, nitrate and ammonium in the recent years in East Asia. This study demonstrates that recent pollution control strategies in East Asia could not decrease organic acidic species in the atmosphere. If the current rates of increases continue, the organic acid- and water-soluble fractions of SOA could increase significantly in the future atmosphere in East Asia.

  12. SOA Formation form the NO3 radicals Chemistry of Isoprene, Monoterpenes, Sesquiterpenes, Biogenic Oxygenated Compounds, and Aromatics

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Jaoui, M.; Docherty, K.; Corse, E.; Offenberg, J. H.; Lewandowski, M.

    2011-12-01

    Volatile organic compounds (VOCs) are oxidized in the atmosphere primarily by hydroxyl radicals (OH) during daylight hours but also by nitrate radicals (NO3) during overnight, photochemically inactive periods. While reactions with OH have received considerable attention with regard to gas-phase reaction products and secondary organic aerosol (SOA) formation, less is known about the mechanisms and products resulting from nighttime NO3 reactions despite their potential for SOA formation. To date, there have been limited studies on the chemical characteristics of aerosol reaction products formed from VOCs oxidation with NO3, and few SOA reaction products have been identified. Nighttime reactions have nevertheless been incorporated into some air quality models despite the limited information available and substantial uncertainties which still exist. The National Exposure Research Laboratory of the U.S. Environmental Protection Agency recently undertook an integrated laboratory research effort to better understand the contribution of NO3 reactions to nighttime SOA formation. Isoprene, methacrolein, a-pinene, b-pinene, d-limonene, b-caryophyllene, farnesene, a-humulene, 2-methyl-3-buten-2-ol, toluene, m-xylene, and naphthalene were reacted with NO3 under a wide range of conditions in a series of separate photochemical reaction chamber experiments. These hydrocarbons are thought to contribute to ambient SOA formation. NO3 was formed through thermal decomposition of N2O5. The yield, physical characteristics, and composition of SOA formed in each experiment was analyzed by a suite of instruments including a scanning mobility particle sizer, a Sunset Labs semi continuous EC-OC monitor, a volatility differential mobility analyzer, a direct insertion probe-mass spectrometer, a high resolution time-of-flight aerosol mass spectrometer, and a gas-chromatography-mass spectrometer. To understand the relative contributions of nighttime versus daytime VOCs reactions, a similar

  13. Characteristics and sources of carbonaceous aerosols from Shanghai, China

    NASA Astrophysics Data System (ADS)

    Cao, J.-J.; Zhu, C.-S.; Tie, X.-X.; Geng, F.-H.; Xu, H.-M.; Ho, S. S. H.; Wang, G.-H.; Han, Y.-M.; Ho, K.-F.

    2013-01-01

    An intensive investigation of carbonaceous PM2.5 and TSP (total suspended particles) from Pudong (China) was conducted as part of the MIRAGE-Shanghai (Megacities Impact on Regional and Global Environment) experiment in 2009. Data for organic and elemental carbon (OC and EC), organic species, including C17 to C40 n-alkanes and 17 polycyclic aromatic hydrocarbons (PAHs), and stable carbon isotopes OC (δ13COC) and EC (δ13CEC) were used to evaluate the aerosols' temporal variations and identify presumptive sources. High OC/EC ratios indicated a large fraction of secondary organic aerosol (SOA); high char/soot ratios indicated stronger contributions to EC from motor vehicles and coal combustion than biomass burning. Diagnostic ratios of PAHs indicated that much of the SOA was produced via coal combustion. Isotope abundances (δ13COC = -24.5 ± 0.8‰ and δ13CEC = -25.1 ± 0.6‰) indicated that fossil fuels were the most important source for carbonaceous PM2.5 (particulate matter less than 2.5 micrometers in diameter), with lesser impacts from biomass burning and natural sources. An EC tracer system and isotope mass balance calculations showed that the relative contributions to total carbon from coal combustion, motor vehicle exhaust, and SOA were 41%, 21%, and 31%; other primary sources such as marine, soil and biogenic emissions contributed 7%. Combined analyses of OC and EC, n-alkanes and PAHs, and stable carbon isotopes provide a new way to apportion the sources of carbonaceous particles.

  14. Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

    NASA Astrophysics Data System (ADS)

    Claeys, M.; Kourtchev, I.; Pashynska, V.; Vas, G.; Vermeylen, R.; Wang, W.; Cafmeyer, J.; Chi, X.; Artaxo, P.; Andreae, M. O.; Maenhaut, W.

    2010-04-01

    Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil) using a High-Volume dichotomous sampler (HVDS) and a Micro-Orifice Uniform Deposit Impactor (MOUDI). The samplings were conducted within the framework of the LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate) campaign, which took place from 9 September till 14 November 2002, spanning the late dry season (biomass burning), the transition period, and the onset of the wet season (clean conditions). In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including: (a) levoglucosan, a tracer for biomass burning, (b) malic acid, a tracer for the oxidation of semivolatile carboxylic acids, (c) tracers for secondary organic aerosol (SOA) from isoprene, i.e., the 2-methyltetrols (2-methylthreitol and 2-methylerythritol) and the C5-alkene triols [2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene], and (d) sugar alcohols (arabitol, mannitol, and erythritol), tracers for fungal spores. The results obtained for levoglucosan are covered first with the aim to address its contrasting behavior with that of malic acid, the isoprene SOA tracers, and the fungal spore tracers. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m-3 and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly

  15. Global modeling of SOA: the use of different mechanisms for aqueous-phase formation

    NASA Astrophysics Data System (ADS)

    Lin, G.; Sillman, S.; Penner, J. E.; Ito, A.

    2014-06-01

    There is growing interest in the formation of secondary organic aerosol (SOA) through condensed aqueous-phase reactions. In this study, we use a global model (IMPACT) to investigate the potential formation of SOA in the aqueous phase. We compare results from several multiphase process schemes with detailed aqueous-phase reactions to schemes that use a first-order gas-to-particle formation rate based on uptake coefficients. The predicted net global SOA production rate in cloud water ranges from 13.1 Tg yr-1 to 46.8 Tg yr-1 while that in aerosol water ranges from -0.4 Tg yr-1 to 12.6 Tg yr-1. The predicted global burden of SOA formed in the aqueous phase ranges from 0.09 Tg to 0.51 Tg. A sensitivity test to investigate two representations of cloud water content from two global models shows that increasing cloud water by an average factor of 2.7 can increase the net SOA production rate in cloud water by a factor of 4 at low altitudes (below approximately 900 hPa). We also investigated the importance of including dissolved Fe chemistry in cloud water aqueous reactions. Adding these reactions increases the formation rate of aqueous-phase OH by a factor of 2.6 and decreases the amount of global aqueous SOA formed by 31%. None of the mechanisms discussed here is able to provide a best fit for all observations. Rather, the use of an uptake coefficient method for aerosol water and a multi-phase scheme for cloud water provides the best fit in the Northern Hemisphere and the use of multiphase process scheme for aerosol and cloud water provides the best fit in the tropics. The model with Fe chemistry underpredicts oxalate measurements in all regions. Finally, the comparison of oxygen-to-carbon (O / C) ratios estimated in the model with those estimated from measurements shows that the modeled SOA has a slightly higher O / C ratio than the observed SOA for all cases.

  16. SOA Formation Potential of Emissions from Soil and Leaf Litter

    NASA Astrophysics Data System (ADS)

    Faiola, C. L.; Vanderschelden, G. S.; Wen, M.; Cobos, D. R.; Jobson, B. T.; VanReken, T. M.

    2013-12-01

    In the United States, emissions of volatile organic compounds (VOCs) from natural sources exceed all anthropogenic sources combined. VOCs participate in oxidative chemistry in the atmosphere and impact the concentrations of ozone and particulate material. The formation of secondary organic aerosol (SOA) is particularly complex and is frequently underestimated using state-of-the-art modeling techniques. We present findings that suggest emissions of important SOA precursors from soil and leaf litter are higher than current inventories would suggest, particularly under conditions typical of Fall and Spring. Soil and leaf litter samples were collected at Big Meadow Creek from the University of Idaho Experimental Forest. The dominant tree species in this area of the forest are ponderosa pine, Douglas-fir, and western larch. Samples were transported to the laboratory and housed within a 0.9 cubic meter Teflon dynamic chamber where VOC emissions were continuously monitored with a GC-FID-MS and PTR-MS. Aerosol was generated from soil and leaf litter emissions by pumping the emissions into a 7 cubic meter Teflon aerosol growth chamber where they were oxidized with ozone in the absence of light. The evolution of particle microphysical and chemical characteristics was monitored over the following eight hours. Particle size distribution and chemical composition were measured with a SMPS and HR-ToF-AMS respectively. Monoterpenes dominated the emission profile with emission rates up to 283 micrograms carbon per meter squared per hour. The dominant monoterpenes emitted were beta-pinene, alpha-pinene, and delta-3-carene in descending order. The composition of the SOA produced was similar to biogenic SOA formed from oxidation of ponderosa pine emissions and alpha-pinene. Measured soil/litter monoterpene emission rates were compared with modeled canopy emissions. Results suggest that during fall and spring when tree emissions are lower, monoterpene emissions within forests may be

  17. Chemical characterization of secondary organic aerosol constituents from isoprene ozonolysis in the presence of acidic aerosol

    NASA Astrophysics Data System (ADS)

    Riva, Matthieu; Budisulistiorini, Sri Hapsari; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

    2016-04-01

    Isoprene is the most abundant non-methane hydrocarbon emitted into Earth's atmosphere and is predominantly derived from terrestrial vegetation. Prior studies have focused largely on the hydroxyl (OH) radical-initiated oxidation of isoprene and have demonstrated that highly oxidized compounds, such as isoprene-derived epoxides, enhance the formation of secondary organic aerosol (SOA) through heterogeneous (multiphase) reactions on acidified sulfate aerosol. However, studies on the impact of acidified sulfate aerosol on SOA formation from isoprene ozonolysis are lacking and the current work systematically examines this reaction. SOA was generated in an indoor smog chamber from isoprene ozonolysis under dark conditions in the presence of non-acidified or acidified sulfate seed aerosol. The effect of OH radicals on SOA chemical composition was investigated using diethyl ether as an OH radical scavenger. Aerosols were collected and chemically characterized by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). Analysis revealed the formation of highly oxidized compounds, including organosulfates (OSs) and 2-methylterols, which were significantly enhanced in the presence of acidified sulfate seed aerosol. OSs identified in the chamber experiments were also observed and quantified in summertime fine aerosol collected from two rural locations in the southeastern United States during the 2013 Southern Oxidant and Aerosol Study (SOAS).

  18. Characterization and source apportionment of submicron aerosol with aerosol mass spectrometer during the PRIDE-PRD 2006 campaign

    NASA Astrophysics Data System (ADS)

    Xiao, R.; Takegawa, N.; Zheng, M.; Kondo, Y.; Miyazaki, Y.; Miyakawa, T.; Hu, M.; Shao, M.; Zeng, L.; Gong, Y.; Lu, K.; Deng, Z.; Zhao, Y.; Zhang, Y. H.

    2011-01-01

    oxygenated aerosol. The origin of HOA and OOA (the sum of LV-OOA and SV-OOA) has been further confirmed by the statistics that primary organic carbon (POC) and secondary organic carbon (SOC), estimated by the EC tracer method, were closely correlated with HOA and OOA, respectively. The results of the EC tracer method and of the PMF model revealed that primary organic aerosol (POA) constituted ~34-47% of OA mass and secondary organic aerosol (SOA) constituted ~53-66% of regional organic aerosol in PRD during summer reason. The presence of abundant SOA was consistent with water soluble organic carbon (WSOC) results (accounting for ~60% of OC on average) by Miyazaki et al. (2009) for the same campaign. OOA correlated well with WSOC at the BG site, indicating that most OOA were water soluble. More specifically, approximately 86% of LV-OOA and 61% of SV-OOA were estimated as water soluble species on the basis of carbon content comparison.

  19. Characterization and source apportionment of submicron aerosol with aerosol mass spectrometer during the PRIDE-PRD 2006 campaign

    NASA Astrophysics Data System (ADS)

    Xiao, R.; Takegawa, N.; Zheng, M.; Kondo, Y.; Miyazaki, Y.; Miyakawa, T.; Hu, M.; Shao, M.; Zeng, L.; Gong, Y.; Lu, K.; Deng, Z.; Zhao, Y.; Zhang, Y. H.

    2011-07-01

    oxygenated aerosol. The origin of HOA and OOA (the sum of LV-OOA and SV-OOA) has been further confirmed by the statistics that primary organic carbon (POC) and secondary organic carbon (SOC), estimated by the EC tracer method, were closely correlated with HOA and OOA, respectively. The results of the EC tracer method and of the PMF model revealed that primary organic aerosol (POA) constituted ~34-47 % of OA mass and secondary organic aerosol (SOA) constituted ~53-66 % of regional organic aerosol in PRD during summer season. The presence of abundant SOA was consistent with water soluble organic carbon (WSOC) results (accounting for ~60 % of OC on average) by Miyazaki et al. (2009) for the same campaign. OOA correlated well with WSOC at the BG site, indicating that most OOA were water soluble. More specifically, approximately 86 % of LV-OOA and 61 % of SV-OOA were estimated as water soluble species on the basis of carbon content comparison.

  20. Enhancing Trust in SOA Based Collaborative Environments

    NASA Astrophysics Data System (ADS)

    Boursas, Latifa; Bourimi, Mohamed; Hommel, Wolfgang; Kesdogan, Dogan

    Considering trust and privacy requirements for online and collaborative distance learning environments, this paper discusses potential extensions of SOA based applications to simultaneously support authentication and authorization services, and offering mutual trust to both learners and service providers. This study shows that the security mechanisms integrated in the SOA platform can be effectively extended and correlated with a trust model.

  1. Formation of secondary organic aerosol from isoprene oxidation over Europe

    NASA Astrophysics Data System (ADS)

    Karl, M.; Tsigaridis, K.; Vignati, E.; Dentener, F.

    2009-09-01

    The role of isoprene as a precursor to secondary organic aerosol (SOA) over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr-1 and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM) during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC) emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning) of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr-1). The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights in isoprene SOA formation mechanisms

  2. A Novel PTR-ToF-MS Inlet System for On-line Chemical Analysis of SOA

    NASA Astrophysics Data System (ADS)

    Eichler, Philipp; Müller, Markus; D'Anna, Barbara; Wisthaler, Armin

    2014-05-01

    Secondary organic aerosol (SOA) is formed from biogenic and anthropogenic precursors in the atmosphere. Because of its impact on human health and the environment there is a strong interest in understanding the chemistry of SOA formation and transformation. Its volatility, chemical complexity and reactivity and low ambient concentrations challenge the chemical analysis of SOA. Here we present a novel analytical setup for on-line measurements of SOA under ambient conditions by chemical ionization mass spectrometry. The method overcomes current limitations in the chemical analysis of SOA by combining on-line enrichment of the particle concentration and on-line mass spectrometric detection using soft chemical ionization. On-line sampling allows for highly time-resolved analysis of organic aerosol compounds and avoids potential sampling artifacts from sample pre-collection and pretreatment. The deployment of a soft ionization method minimizes the fragmentation of fragile organic aerosol compounds in the mass spectrometer. A proton-transfer-reaction time-of-flight mass-spectrometer (PTR-ToF-MS) is combined with a three-stage aerosol inlet system consisting of an activated carbon monolith denuder, an aerodynamic lens (ADL) and a thermodesorption unit. The denuder strips off gas-phase organic compounds and the ADL enriches the particle concentration in the sample flow. Ultimately, organic aerosol compounds are volatilized at 120 °C in the thermodesorption unit before being introduced into the PTR-ToF-MS system for chemical analysis. The ADL is designed to increase the particle concentration in the sample flow by a factor of up to 50 for particles in the size range between 50 and 1000 nm. This novel enrichment step enables the real-time in situ analysis of SOA at sub µg/m³-levels by PTR-ToF-MS. This work is funded through the PIMMS ITN, which is supported by the European Commission's 7th Framework Programme under grant agreement number 287382.

  3. The Effect of Aerosol Hygroscopicity and Volatility on Aerosol Optical Properties During Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Khlystov, A.; Grieshop, A. P.; Saha, P.; Subramanian, R.

    2014-12-01

    Secondary organic aerosol (SOA) from biogenic sources can influence optical properties of ambient aerosol by altering its hygroscopicity and contributing to light absorption directly via formation of brown carbon and indirectly by enhancing light absorption by black carbon ("lensing effect"). The magnitude of these effects remains highly uncertain. A set of state-of-the-art instruments was deployed at the SEARCH site near Centerville, AL during the Southern Oxidant and Aerosol Study (SOAS) campaign in summer 2013 to measure the effect of relative humidity and temperature on aerosol size distribution, composition and optical properties. Light scattering and absorption by temperature- and humidity-conditioned aerosols was measured using three photo-acoustic extinctiometers (PAX) at three wavelengths (405 nm, 532 nm, and 870 nm). The sample-conditioning system provided measurements at ambient RH, 10%RH ("dry"), 85%RH ("wet"), and 200 C ("TD"). In parallel to these measurements, a long residence time temperature-stepping thermodenuder (TD) and a variable residence time constant temperature TD in combination with three SMPS systems and an Aerosol Chemical Speciation Monitor (ACSM) were used to assess aerosol volatility and kinetics of aerosol evaporation. We will present results of the on-going analysis of the collected data set. We will show that both temperature and relative humidity have a strong effect on aerosol optical properties. SOA appears to increase aerosol light absorption by about 10%. TD measurements suggest that aerosol equilibrated fairly quickly, within 2 s. Evaporation varied substantially with ambient aerosol loading and composition and meteorology.

  4. Mechanisms of Formation of Secondary Organic Aerosols and Implications for Global Radiative Forcing

    SciTech Connect

    John H. Seinfeld

    2011-12-08

    Organic material constitutes about 50% of global atmospheric aerosol mass, and the dominant source of organic aerosol is the oxidation of volatile hydrocarbons, to produce secondary organic aerosol (SOA). Understanding the formation of SOA is crucial to predicting present and future climate effects of atmospheric aerosols. The goal of this program is to significantly increase our understanding of secondary organic aerosol (SOA) formation in the atmosphere. Ambient measurements indicate that the amount of SOA in the atmosphere exceeds that predicted in current models based on existing laboratory chamber data. This would suggest that either the SOA yields measured in laboratory chambers are understated or that all major organic precursors have not been identified. In this research program we are systematically exploring these possibilities.

  5. A sub-decadal trend in diacids in atmospheric aerosols in eastern Asia

    NASA Astrophysics Data System (ADS)

    Kundu, S.; Kawamura, K.; Kobayashi, M.; Tachibana, E.; Lee, M.; Fu, P. Q.; Jung, J.

    2016-01-01

    Change in secondary organic aerosols (SOAs) has been predicted to be highly uncertain in the future atmosphere in Asia. To better quantify the SOA change, we examine the sub-decadal (2001-2008) trend in major surrogate compounds (C2-C10 diacids) of SOA in atmospheric aerosols from Gosan site on Cheju Island, South Korea. The Gosan site is influenced by pollution outflows from eastern Asia. The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids in each year. The seasonal variations in diacids in each year were characterized by the highest concentrations of saturated diacids in spring and unsaturated diacids in winter. The consistent molecular distributions and seasonal variations along with significantly similar air mass transport patterns are indicative of similar pollution sources for diacids in eastern Asia on a sub-decadal scale. However, the intensity of the pollution sources has increased as evidenced by the increases in major diacids at the rate of 3.9-47.4 % per year, particularly in April. The temporal variations in atmospheric tracer compounds (carbon monoxide, levoglucosan, 2-methyltetrols, pinic acid, glyoxylic acid, glyoxal and methylglyoxal) suggest that the increases in diacids are due to enhanced precursor emissions associated with more anthropogenic than biogenic activities followed by the compounds' chemical processing in the atmosphere. The trends in diacids contrast with the reported decreases in sulfate, nitrate and ammonium in recent years in eastern Asia. This study demonstrates that recent pollution control strategies in eastern Asia were not able to decrease organic acidic species in the atmosphere. The increases in water-soluble organic acid fraction could modify the aerosol organic composition and its sensitivity to climate relevant physical properties.

  6. Characterizing the impact of urban emissions on regional aerosol particles: airborne measurements during the MEGAPOLI experiment

    NASA Astrophysics Data System (ADS)

    Freney, E. J.; Sellegri, K.; Canonaco, F.; Colomb, A.; Borbon, A.; Michoud, V.; Doussin, J.-F.; Crumeyrolle, S.; Amarouche, N.; Pichon, J.-M.; Bourianne, T.; Gomes, L.; Prevot, A. S. H.; Beekmann, M.; Schwarzenböeck, A.

    2014-02-01

    The MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) experiment took place in July 2009. The aim of this campaign was to study the aging and reactions of aerosol and gas-phase emissions in the city of Paris. Three ground-based measurement sites and several mobile platforms including instrument equipped vehicles and the ATR-42 aircraft were involved. We present here the variations in particle- and gas-phase species over the city of Paris, using a combination of high-time resolution measurements aboard the ATR-42 aircraft. Particle chemical composition was measured using a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), giving detailed information on the non-refractory submicron aerosol species. The mass concentration of black carbon (BC), measured by a particle absorption soot photometer (PSAP), was used as a marker to identify the urban pollution plume boundaries. Aerosol mass concentrations and composition were affected by air-mass history, with air masses that spent longest time over land having highest fractions of organic aerosol and higher total mass concentrations. The Paris plume is mainly composed of organic aerosol (OA), BC, and nitrate aerosol, as well as high concentrations of anthropogenic gas-phase species such as toluene, benzene, and NOx. Using BC and CO as tracers for air-mass dilution, we observe the ratio of ΔOA / ΔBC and ΔOA / ΔCO increase with increasing photochemical age (-log(NOx / NOy)). Plotting the equivalent ratios of different organic aerosol species (LV-OOA, SV-OOA, and HOA) illustrate that the increase in OA is a result of secondary organic aerosol (SOA) formation. Within Paris the changes in the ΔOA / ΔCO are similar to those observed during other studies in London, Mexico City, and in New England, USA. Using the measured SOA volatile organic compounds (VOCs) species together with organic aerosol formation

  7. EVALUATION OF SECONDARY ORGANIC AEROSOL FORMATION IN WINTER. (R823514)

    EPA Science Inventory

    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

  8. Estimating the direct and indirect effects of secondary organic aerosols using ECHAM5-HAM

    NASA Astrophysics Data System (ADS)

    O'Donnell, D.; Tsigaridis, K.; Feichter, J.

    2011-08-01

    Secondary organic aerosol (SOA) has been introduced into the global climate-aerosol model ECHAM5/HAM. The SOA module handles aerosols originating from both biogenic and anthropogenic sources. The model simulates the emission of precursor gases, their chemical conversion into condensable gases, the partitioning of semi-volatile condenable species into the gas and aerosol phases. As ECHAM5/HAM is a size-resolved model, a new method that permits the calculation of partitioning of semi-volatile species between different size classes is introduced. We compare results of modelled organic aerosol concentrations against measurements from extensive measurement networks in Europe and the United States, running the model with and without SOA. We also compare modelled aerosol optical depth against measurements from the AERONET network of grond stations. We find that SOA improves agreement between model and measurements in both organic aerosol mass and aerosol optical depth, but does not fully correct the low bias that is present in the model for both of these quantities. Although many models now include SOA, any overall estimate of the direct and indirect effects of these aerosols is still lacking. This paper makes a first step in that direction. The model is applied to estimate the direct and indirect effects of SOA under simulated year 2000 conditions. The modelled SOA spatial distribution indicates that SOA is likely to be an important source of free and upper tropospheric aerosol. We find a negative shortwave (SW) forcing from the direct effect, amounting to -0.31 Wm-2 on the global annual mean. In contrast, the model indicates a positive indirect effect of SOA of +0.23 Wm-2, arising from the enlargement of particles due to condensation of SOA, together with an enhanced coagulation sink of small particles. In the longwave, model results are a direct effect of +0.02 Wm-2 and an indirect effect of -0.03 Wm-2.

  9. Identification of significant precursor gases of secondary organic aerosols from residential wood combustion

    NASA Astrophysics Data System (ADS)

    Bruns, Emily A.; El Haddad, Imad; Slowik, Jay G.; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S. H.

    2016-06-01

    Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3–27% of the observed SOA, whereas for the first time we explain ~84–116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions.

  10. Identification of significant precursor gases of secondary organic aerosols from residential wood combustion

    PubMed Central

    Bruns, Emily A.; El Haddad, Imad; Slowik, Jay G.; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S. H.

    2016-01-01

    Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3–27% of the observed SOA, whereas for the first time we explain ~84–116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions. PMID:27312480

  11. Identification of significant precursor gases of secondary organic aerosols from residential wood combustion.

    PubMed

    Bruns, Emily A; El Haddad, Imad; Slowik, Jay G; Kilic, Dogushan; Klein, Felix; Baltensperger, Urs; Prévôt, André S H

    2016-01-01

    Organic gases undergoing conversion to form secondary organic aerosol (SOA) during atmospheric aging are largely unidentified, particularly in regions influenced by anthropogenic emissions. SOA dominates the atmospheric organic aerosol burden and this knowledge gap contributes to uncertainties in aerosol effects on climate and human health. Here we characterize primary and aged emissions from residential wood combustion using high resolution mass spectrometry to identify SOA precursors. We determine that SOA precursors traditionally included in models account for only ~3-27% of the observed SOA, whereas for the first time we explain ~84-116% of the SOA by inclusion of non-traditional precursors. Although hundreds of organic gases are emitted during wood combustion, SOA is dominated by the aging products of only 22 compounds. In some cases, oxidation products of phenol, naphthalene and benzene alone comprise up to ~80% of the observed SOA. Identifying the main precursors responsible for SOA formation enables improved model parameterizations and SOA mitigation strategies in regions impacted by residential wood combustion, more productive targets for ambient monitoring programs and future laboratories studies, and links between direct emissions and SOA impacts on climate and health in these regions. PMID:27312480

  12. Uncertainties in SOA Formation from the Photooxidation of α-pinene

    NASA Astrophysics Data System (ADS)

    McVay, R.; Zhang, X.; Aumont, B.; Valorso, R.; Camredon, M.; La, S.; Seinfeld, J.

    2015-12-01

    Explicit chemical models such as GECKO-A (the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) enable detailed modeling of gas-phase photooxidation and secondary organic aerosol (SOA) formation. Comparison between these explicit models and chamber experiments can provide insight into processes that are missing or unknown in these models. GECKO-A is used to model seven SOA formation experiments from α-pinene photooxidation conducted at varying seed particle concentrations with varying oxidation rates. We investigate various physical and chemical processes to evaluate the extent of agreement between the experiments and the model predictions. We examine the effect of vapor wall loss on SOA formation and how the importance of this effect changes at different oxidation rates. Proposed gas-phase autoxidation mechanisms are shown to significantly affect SOA predictions. The potential effects of particle-phase dimerization and condensed-phase photolysis are investigated. We demonstrate the extent to which SOA predictions in the α-pinene photooxidation system depend on uncertainties in the chemical mechanism.

  13. VOC species and emission inventory from vehicles and their SOA formation potentials estimation in Shanghai, China

    NASA Astrophysics Data System (ADS)

    Huang, C.; Wang, H. L.; Li, L.; Wang, Q.; Lu, Q.; de Gouw, J. A.; Zhou, M.; Jing, S. A.; Lu, J.; Chen, C. H.

    2015-10-01

    Volatile organic compound (VOC) species from vehicle exhausts and gas evaporation were investigated by chassis dynamometer and on-road measurements of nine gasoline vehicles, seven diesel vehicles, five motorcycles, and four gas evaporation samples. The secondary organic aerosol (SOA) mass yields of gasoline, diesel, motorcycle exhausts, and gas evaporation were estimated based on the mixing ratio of measured C2-C12 VOC species and inferred carbon number distributions. High aromatic contents were measured in gasoline exhausts and contributed comparatively more SOA yield. A vehicular emission inventory was compiled based on a local survey of on-road traffic in Shanghai and real-world measurements of vehicle emission factors from previous studies in the cities of China. The inventory-based vehicular organic aerosol (OA) productions to total CO emissions were compared with the observed OA to CO concentrations (ΔOA / ΔCO) in the urban atmosphere. The results indicate that vehicles dominate the primary organic aerosol (POA) emissions and OA production, which contributed about 40 and 60 % of OA mass in the urban atmosphere of Shanghai. Diesel vehicles, which accounted for less than 20 % of vehicle kilometers of travel (VKT), contribute more than 90 % of vehicular POA emissions and 80-90 % of OA mass derived by vehicles in urban Shanghai. Gasoline exhaust could be an important source of SOA formation. Tightening the limit of aromatic content in gasoline fuel will be helpful to reduce its SOA contribution. Intermediate-volatile organic compounds (IVOCs) in vehicle exhausts greatly contribute to SOA formation in the urban atmosphere of China. However, more experiments need to be conducted to determine the contributions of IVOCs to OA pollution in China.

  14. Effect of Ammonia on Glyoxal SOA in Inorganic Aqueous Seed Particles

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Volkamer, R. M.; Laskin, A.; Laskin, J.; Koenig, T. K.; Baltensperger, U.; Dommen, J.; Prevot, A. S.; Slowik, J.; Maxut, A.; Noziere, B.; Wang, S.; Yu, J.

    2014-12-01

    Glyoxal (C2H2O2) is a ubiquitous small molecule that is observed in the terrestrial biogenic, urban, marine and arctic atmosphere. It forms secondary organic aerosol (SOA) as a result of multiphase chemical reactions in water. The rate of these reactions is controlled by the effective Henry's law partitioning coefficient (Heff) which is enhanced in the presence of inorganic salts by up to 3 orders of magnitude (Kampf et al., 2013, ES&T). Aerosol particles are among the most concentrated salt solutions on Earth and the SOA formation rate in aerosol water is strongly modified by this 'salting-in' mechanism. We have studied the effect of gas-phase ammonia on the rate of SOA formation in real particles composed of different inorganic salts (sulfate, nitrate, chloride). A series of simulation chamber experiments were conducted at the Paul Scherrer Institut in Switzerland during Summer 2013. The SOA formation rate in experiments with added gas-phase ammonia (NH3) was found to be greatly accelerated compared to experiments without added NH3. Product analysis of particles included online HR-ToF-AMS and offline nano-DESI and LC-MS. We find that imidazole-like oligomer compounds dominate the observed products, rather than high-O/C oligomers containing solely C, H, and O. We further employed isotopically labelled di-substituted 13C glyoxal experiments in order to unambiguously link product formation to glyoxal (and separate it from chamber wall contamination). We present a molecular perspective on the reaction pathways and evaluate the effect of environmental parameters (RH, particle pH, seed chemical composition) on the formation of these imidazole-like oligomer compounds. The implications for SOA formation from photosensitized oxidation chemistry is discussed.

  15. Secondary aerosol formation from stress-induced biogenic emissions and possible climate feedbacks

    NASA Astrophysics Data System (ADS)

    Mentel, Th. F.; Kleist, E.; Andres, S.; Maso, M. D.; Hohaus, T.; Kiendler-Scharr, A.; Rudich, Y.; Springer, M.; Tillmann, R.; Uerlings, R.; Wahner, A.; Wildt, J.

    2013-03-01

    Atmospheric aerosols impact climate by scattering and absorbing solar radiation and by acting as ice and cloud condensation nuclei. Secondary organic aerosols (SOA) comprise an important component of atmospheric aerosols. Biogenic volatile organic compounds (BVOC) emitted by vegetation are a major source of SOA. Pathogens and insect attacks, heat waves and droughts can induce stress to plants that may impact their BVOC emissions, and hence the yield and type of formed SOA, and possibly their climatic effects. This raises questions whether stress-induced changes in SOA formation may attenuate or amplify effects of climate change. In this study we assess the potential impact of stress-induced BVOC emissions on SOA formation for tree species typical for mixed deciduous and Boreal Eurasian forests. We studied the photochemical SOA formation for infested plants in a laboratory setup under well-controlled conditions and applied in addition heat and drought stress. The results indicate that stress conditions substantially modify SOA formation. While sesquiterpenes, methyl salicylate, and C17-BVOC increase SOA yield, green leaf volatiles suppress SOA formation. By classifying emission types, stressors and SOA formation potential, we propose possible climatic feedbacks regarding aerosol effects. We conclude that stress situations for plants due to climate change should be considered in climate-vegetation feedback mechanisms.

  16. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

    PubMed

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

  17. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: Unified Method for Predicting Aerosol Composition and Formation.

    PubMed

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Kacarab, Mary; Cocker, David R

    2016-06-21

    Innovative secondary organic aerosol (SOA) composition analysis methods normalizing aerosol yield and chemical composition on an aromatic ring basis are developed and utilized to explore aerosol formation from oxidation of aromatic hydrocarbons. SOA yield and chemical composition are revisited using 15 years of University of California, Riverside/CE-CERT environmental chamber data on 17 aromatic hydrocarbons with HC:NO ranging from 11.1 to 171 ppbC:ppb. SOA yield is redefined in this work by normalizing the molecular weight of all aromatic precursors to the molecular weight of the aromatic ring [Formula: see text], where i is the aromatic hydrocarbon precursor. The yield normalization process demonstrates that the amount of aromatic rings present is a more significant driver of aerosol formation than the vapor pressure of the precursor aromatic. Yield normalization also provided a basis to evaluate isomer impacts on SOA formation. Further, SOA elemental composition is explored relative to the aromatic ring rather than on a classical mole basis. Generally, four oxygens per aromatic ring are observed in SOA, regardless of the alkyl substitutes attached to the ring. Besides the observed SOA oxygen to ring ratio (O/R ∼ 4), a hydrogen to ring ratio (H/R) of 6 + 2n is observed, where n is the number of nonaromatic carbons. Normalization of yield and composition to the aromatic ring clearly demonstrates the greater significance of aromatic ring carbons compared with alkyl carbon substituents in determining SOA formation and composition. PMID:27177154

  18. Modeling the role of alkanes, polycyclic aromatic hydrocarbons, and their oligomers in secondary organic aerosol formation.

    PubMed

    Pye, Havala O T; Pouliot, George A

    2012-06-01

    A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations over the United States. Oxidation of alkanes is predicted to produce more aerosol than oxidation of PAHs driven by relatively higher alkane emissions. SOA from alkanes and PAHs, although small in magnitude, can be a substantial fraction of the SOA from anthropogenic hydrocarbons, particularly in winter, and could contribute more if emission inventories lack intermediate volatility alkanes (>C(13)) or if the vehicle fleet shifts toward diesel-powered vehicles. The SOA produced from oxidation of alkanes correlates well with ozone and odd oxygen in many locations, but the lower correlation of anthropogenic oligomers with odd oxygen indicates that models may need additional photochemically dependent pathways to low-volatility SOA. PMID:22568386

  19. Oxidative potential of secondary organic aerosols produced from photooxidation of different hydrocarbons using outdoor chamber under ambient sunlight

    NASA Astrophysics Data System (ADS)

    Jiang, Huanhuan; Jang, Myoseon; Sabo-Attwood, Tara; Robinson, Sarah E.

    2016-04-01

    The oxidative potential of various secondary organic aerosols (SOA) was measured using dithiothreitol (DTT) assay to understand how organic aerosols react with cellular materials. SOA was produced via the photooxidation of four different hydrocarbons (toluene, 1,3,5-trimethylbenzene, isoprene and α-pinene) in the presence of NOx using a large outdoor photochemical smog chamber. The DTT consumption rate was normalized by the aerosol mass, which is expressed as DTTmass. Toluene SOA and isoprene SOA yielded higher DTTmass than 1,3,5-trimethylbenzene SOA or α-pinene SOA. In order to discover the correlation between the molecular structure and oxidative potential, the DTT responses of selected model compounds were also measured. Among them, conjugated aldehydes, quinones, and H2O2 showed considerable DTT response. To investigate the correlation between DTT response and cell responses in vitro, the expression of biological markers, i.e. IL-6, IL-8, and HMOX-1 were studied using small airway epithelial cells. Higher cellular expression of IL-8 was observed with toluene SOA exposure compared to 1,3,5-trimethylbenzene SOA exposure, which aligned with the results from DTT assay. Our study also suggests that within the urban atmosphere, the contribution of toluene SOA and isoprene SOA to the oxidative potential of ambient SOA will be more significant than that of α-pinene SOA.

  20. Modeling SOA formation from alkanes and alkenes in chamber experiments: effect of gas/wall partitioning of organic vapors.

    NASA Astrophysics Data System (ADS)

    Stéphanie La, Yuyi; Camredon, Marie; Ziemann, Paul; Ouzebidour, Farida; Valorso, Richard; Madronich, Sasha; Lee-Taylor, Julia; Hodzic, Alma; Aumont, Bernard

    2014-05-01

    Oxidation products of Intermediate Volatility Organic Compounds (IVOC) are expected to be the major precursors of secondary organic aerosols (SOA). Laboratory experiments were conducted this last decade in the Riverside APRC chamber to study IVOC oxidative mechanisms and SOA formation processes for a large set of linear, branched and cyclic aliphatic hydrocarbons (Ziemann, 2011). This dataset are used here to assess the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) (Aumont et al., 2005). The simulated SOA yields agree with the general trends observed in the chamber experiments. They are (i) increasing with the increasing carbon number; (ii) decreasing with increasing methyl branch number; and (iii) increasing for cyclic compounds compared to their corresponding linear analogues. However, simulated SOA yields are systematically overestimated regardless of the precursors, suggesting missing processes in the model. In this study, we assess whether gas-to-wall partitioning of organic vapors can explain these model/observation mismatches (Matsunaga and Ziemann, 2010). First results show that GECKO-A outputs better match the observations when wall uptake of organic vapors is taken into account. Effects of gas/wall partitioning on SOA yields and composition will be presented. Preliminary results suggest that wall uptake is a major process influencing SOA production in the Teflon chambers. References Aumont, B., Szopa, S., Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach. Atmos.Chem.Phys., 5, 2497-2517 (2005). P. J. Ziemann: Effects of molecular structure on the chemistry of aerosol formation from the OH-radical-initiated oxidation of alkanes and alkenes, Int. Rev.Phys.Chem., 30:2, 161-195 (2011). Matsunaga, A., Ziemann, P. J.: Gas-wall partitioning of organic compounds in a Teflon film

  1. CARES: Carbonaceous Aerosol and Radiative Effects Study Science Plan

    SciTech Connect

    Zaveri, RA; Shaw, WJ; Cziczo, DJ

    2010-05-27

    Carbonaceous aerosol components, which include black carbon (BC), urban primary organic aerosols (POA), biomass burning aerosols, and secondary organic aerosols (SOA) from both urban and biogenic precursors, have been previously shown to play a major role in the direct and indirect radiative forcing of climate. The primary objective of the CARES 2010 intensive field study is to investigate the evolution of carbonaceous aerosols of different types and their effects on optical and cloud formation properties.

  2. Evidence for ambient dark aqueous SOA formation in the Po Valley, Italy

    NASA Astrophysics Data System (ADS)

    Sullivan, Amy P.; Hodas, Natasha; Turpin, Barbara J.; Skog, Kate; Keutsch, Frank N.; Gilardoni, Stefania; Paglione, Marco; Rinaldi, Matteo; Decesari, Stefano; Facchini, Maria Cristina; Poulain, Laurent; Herrmann, Hartmut; Wiedensohler, Alfred; Nemitz, Eiko; Twigg, Marsailidh M.; Collett, Jeffrey L., Jr.

    2016-07-01

    Laboratory experiments suggest that water-soluble products from the gas-phase oxidation of volatile organic compounds can partition into atmospheric waters where they are further oxidized to form low volatility products, providing an alternative route for oxidation in addition to further oxidation in the gas phase. These products can remain in the particle phase after water evaporation, forming what is termed as aqueous secondary organic aerosol (aqSOA). However, few studies have attempted to observe ambient aqSOA. Therefore, a suite of measurements, including near-real-time WSOC (water-soluble organic carbon), inorganic anions/cations, organic acids, and gas-phase glyoxal, were made during the PEGASOS (Pan-European Gas-AeroSOls-climate interaction Study) 2012 campaign in the Po Valley, Italy, to search for evidence of aqSOA. Our analysis focused on four periods: Period A on 19-21 June, Period B on 30 June and 1-2 July, Period C on 3-5 July, and Period D on 6-7 July to represent the first (Period A) and second (Periods B, C, and D) halves of the study. These periods were picked to cover varying levels of WSOC and aerosol liquid water. In addition, back trajectory analysis suggested all sites sampled similar air masses on a given day. The data collected during both periods were divided into times of increasing relative humidity (RH) and decreasing RH, with the aim of diminishing the influence of dilution and mixing on SOA concentrations and other measured variables. Evidence for local aqSOA formation was only observed during Period A. When this occurred, there was a correlation of WSOC with organic aerosol (R2 = 0.84), aerosol liquid water (R2 = 0.65), RH (R2 = 0.39), and aerosol nitrate (R2 = 0.66). Additionally, this was only observed during times of increasing RH, which coincided with dark conditions. Comparisons of WSOC with oxygenated organic aerosol (OOA) factors, determined from application of positive matrix factorization analysis on the aerosol mass

  3. Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia,and Look Rock, Tennessee

    NASA Astrophysics Data System (ADS)

    Hapsari Budisulistiorini, Sri; Baumann, Karsten; Edgerton, Eric S.; Bairai, Solomon T.; Mueller, Stephen; Shaw, Stephanie L.; Knipping, Eladio M.; Gold, Avram; Surratt, Jason D.

    2016-04-01

    A year-long near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia, in 2012) and rural (Look Rock, Tennessee, in 2013) site in the southeastern US using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (up to 76 %) and sulfate (up to 31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the 1 year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (LV-OOA), isoprene-derived epoxydiols (IEPOX) OA (IEPOX-OA) and 91Fac (a factor dominated by a distinct ion at m/z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed up to 66 % of total OA mass. HOA was observed during the entire year only at the urban site (on average 21 % of OA mass). BBOA (15-33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly ( ˜ 27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27-41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m/z 75 is well correlated with the m/z 82 ion associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The

  4. Atmospheric oxidation of isoprene and 1,3-Butadiene: influence of aerosol acidity and Relative humidity on secondary organic aerosol

    EPA Science Inventory

    The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA)have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ per m3 air s...

  5. Measurements of secondary organic aerosol formed from OH-initiated photo-oxidation of isoprene using online photoionization aerosol mass spectrometry.

    PubMed

    Fang, Wenzheng; Gong, Lei; Zhang, Qiang; Cao, Maoqi; Li, Yuquan; Sheng, Liusi

    2012-04-01

    Isoprene is a significant source of atmospheric organic aerosol; however, the secondary organic aerosol (SOA) formation and involved chemical reaction pathways have remained to be elucidated. Recent works have shown that the photo-oxidation of isoprene leads to form SOA. In this study, the chemical composition of SOA from the OH-initiated photo-oxidation of isoprene, in the absence of seed aerosols, was investigated through the controlled laboratory chamber experiments. Thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) was used in conjunction with the environmental chamber to study SOA formation. The mass spectra obtained at different photon energies and the photoionization efficiency (PIE) spectra of the SOA products can be obtained in real time. Aided by the ionization energies (IE) either from the ab initio calculations or the literatures, a number of SOA products were proposed. In addition to methacrolein, methyl vinyl ketone, and 3-methyl-furan, carbonyls, hydroxycarbonyls, nitrates, hydroxynitrates, and other oxygenated compounds in SOA formed in laboratory photo-oxiadation experiments were identified, some of them were investigated for the first time. Detailed chemical identification of SOA is crucial for understanding the photo-oxidation mechanisms of VOCs and the eventual formation of SOA. Possible reaction mechanisms will be discussed. PMID:22397593

  6. Monoterpene SOA - Contribution of first-generation oxidation products to formation and chemical composition

    NASA Astrophysics Data System (ADS)

    Mutzel, Anke; Rodigast, Maria; Iinuma, Yoshiteru; Böge, Olaf; Herrmann, Hartmut

    2016-04-01

    Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was

  7. Development of new parameterizations for SOA production from SVOC and IVOC oxidation

    NASA Astrophysics Data System (ADS)

    Lemaire, Vincent; Coll, Isabelle; Camredon, Marie; Aumont, Bernard; Siour, Guillaume

    2014-05-01

    Recent experimental studies have demonstrated the partially volatile pattern of primary organic aerosol (POA) that is actually associated with organic species of so-called intermediate volatility (IVOCs), and by semi-volatile (SVOCs) species. Indeed, 50% to 75% of the total emitted mass of POA may be present in the atmospheric gas phase in accordance with the thermodynamic properties of its components (Shrivastava et al., 2006). During the processing of the emission plume, this gaseous material will then undergo photochemical oxidation, enhancing the production of secondary organic aerosol (SOA) (Robinson et al., 2007; Hodzic et al., 2010; Lee-Taylor et al., 2011). Considering POA as non volatile in Chemistry Transport Models (CTMs) could thus lead to an underestimation of SOA and an overestimation of POA (Aksoyoglu et al., 2011) and bias the temporal formation of the organic aerosol (Kroll et al., 2007; Presto et al., 2012). However, very rare experimental data exist on the fate of these species and their aerosol yield, but all existing studies have shown a significant SOA production (Presto et al., 2009; Miracolo et al., 2010; Lambe et al., 2012). Our works aims at including and testing in the CHIMERE CTM new parameterizations of SOA formation from the oxidation of IVOCs and SVOCs, arising from explicit 0D-model experiments. Our approach is based on the works of Aumont et al., (2013) who used the GECKO-A tool (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) to generate the explicit chemistry and gas-particle partitioning of superior alkanes and their oxidation products. Using this explicit scheme, Aumont et al., (2013) indeed produced 0D simulations of the oxidation of given SVOCs and IVOCs under different initial conditions of organic aerosol mass. We first focused on the chemistry of n-hexadecane. From the 0D-experiments, we tested the influence of the number of first generation surrogate species and the number of generation taken

  8. Illuminating the Atmospheric Oxidation Mechanisms, SOA Formation Pathways and Radical Yields of the Monoterpene Myrcene

    NASA Astrophysics Data System (ADS)

    Wyche, Kevin; Carr, Timo; Monks, Paul; Ellis, Andrew; Alfarra, Rami; McFiggans, Gordon; Hamilton, Jacqueline; Ward, Martyn; Boss, William; Camredon, Marie

    2010-05-01

    Biogenic Volatile Organic Compounds (BVOCs) are ubiquitous in the global troposphere, being emitted primarily from terrestrial plant life in significant quantities. Indeed, it is estimated that the total annual emission rate of all (non-methane) BVOCs is roughly ten times that of all anthropogenic volatile organic compounds (Guenther et al., 1995). With the exception of methane, the most dominant species of BVOC, in terms of emission strength, reactivity and their impact upon the atmosphere, are terpenes. Terpenes are a subdivision of BVOCs, composed primarily of hemiterpenes (C5), monoterpenes (C10), sesquiterpenes (C15) and diterpenes (C20). Under troposheric conditions terpenes react via complex and extensive gas phase oxidation pathways, have strong photochemical ozone creation potentials, constitute a significant radical source and are known to generate secondary organic aerosol (SOA) in high yields. At present there exists a certain lack of understanding regarding the oxidation mechanisms of certain terpenes and their role in SOA and radical formation. Consequently, as part of the NERC funded Aerosol Coupling in the Earth's System (ACES) and Total RAdical Production from the OZonolysis of alkenes (TRAPOZ) projects, a comprehensive series of simulation chamber experiments were conducted at the University of Manchester aerosol chamber facility, and at the EUropean PHOto REactor (EUPHORE) in order to investigate the gas phase degradation mechanisms, and SOA and radical formation potentials of a number of atmospherically significant terpenes. Both simulation chambers were highly instrumented during all experiments such that detailed and concomitant gas and aerosol phase measurements were made across a range of conditions. The work presented here describes the findings obtained from both photooxidation and ozonolysis experiments involving the common, but less well studied, aliphatic monoterpene, myrcene. The data presented include NOx and ozone measurements and

  9. Airborne observations of IEPOX-derived isoprene SOA in the Amazon during SAMBBA

    NASA Astrophysics Data System (ADS)

    Allan, J. D.; Morgan, W. T.; Darbyshire, E.; Flynn, M. J.; Williams, P. I.; Oram, D. E.; Artaxo, P.; Brito, J.; Lee, J. D.; Coe, H.

    2014-10-01

    Isoprene is a potentially highly significant but currently poorly quantified source of secondary organic aerosols (SOA). This is especially important in the tropics, where large rainforests act as significant sources of isoprene. Methylfuran, produced through thermal decomposition during analysis, has recently been suggested as a marker for isoprene SOA formation through the isoprene epoxydiol (IEPOX) route, which mostly occurs under low NOx conditions. This is manifested as a peak at m/z=82 in Aerodyne Aerosol Mass Spectrometer (AMS) data. Here we present a study of this marker measured during five flights over the Amazon rainforest on board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft during the South American Biomass Burning Analysis (SAMBBA) campaign. Cases where this marker is and is not present are contrasted and linked to the presence of acidic seed particles, lower NOx concentrations and higher humidities. There are also data to suggest a role of organic nitrogen in the particulate composition. Furthermore, an inspection of the vertical trends of the marker indicates that concentrations are highest at the top of the boundary layer (possibly due to semivolatile repartitioning) and that upwards through the free troposphere, the mass spectral profile evolves towards that of low volatility oxygenated aerosol. These observations offer insights into the behaviour of IEPOX-derived SOA formation above the Amazon rainforest and the suitability of methylfuran as a marker for this process.

  10. Organic Aerosols in Rural and Remote Atmospheric Environments: Insights from Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Jimenez, J.; Ulbrich, I.; Dunlea, E.; Decarlo, P.; Huffman, A.; Allan, J.; Coe, H.; Alfarra, R.; Canagaratna, M.; Onasch, T.; Jayne, J.; Worsnop, D.; Takami, A.; Miyoshi, T.; Shimono, A.; Hatakeyama, S.; Weimer, S.; Demerjian, K.; Drewnick, F.; Schneider, J.; Middlebrook, A.; Bahreini, R.; Cotrell, L.; Griffin, R.; Leaitch, R.; Li, S.; Hayden, K.; Rautiainen, J.

    2006-12-01

    primary emission tracers (e.g., EC and CO) suggest that dilution of urban POA is the main reason for its low concentration at rural/remote sites. In addition, case studies will be presented to evaluate the implications of intercontinental and regional transport of air pollution for the background organic aerosol composition at a high elevation site (the Whistler Mountain Summit, Canada) of North America. Finally, an attempt will be made to address the relative importance of secondary vs. primary organic aerosol (SOA vs. POA) and biogenic vs. anthropogenic OA.

  11. Field and Laboratory Studies of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Coggon, Matthew Mitchell

    This thesis is the culmination of field and laboratory studies aimed at assessing processes that affect the composition and distribution of atmospheric organic aerosol. An emphasis is placed on measurements conducted using compact and high-resolution Aerodyne Aerosol Mass Spectrometers (AMS). The first three chapters summarize results from aircraft campaigns designed to evaluate anthropogenic and biogenic impacts on marine aerosol and clouds off the coast of California. Subsequent chapters describe laboratory studies intended to evaluate gas and particle-phase mechanisms of organic aerosol oxidation. The 2013 Nucleation in California Experiment (NiCE) was a campaign designed to study environments impacted by nucleated and/or freshly formed aerosol particles. Terrestrial biogenic aerosol with > 85% organic mass was observed to reside in the free troposphere above marine stratocumulus. This biogenic organic aerosol (BOA) originated from the Northwestern United States and was transported to the marine atmosphere during periodic cloud-clearing events. Spectra recorded by a cloud condensation nuclei counter demonstrated that BOA is CCN active. BOA enhancements at latitudes north of San Francisco, CA coincided with enhanced cloud water concentrations of organic species such as acetate and formate. Airborne measurements conducted during the 2011 Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) were aimed at evaluating the contribution of ship emissions to the properties of marine aerosol and clouds off the coast of central California. In one study, analysis of organic aerosol mass spectra during periods of enhanced shipping activity yielded unique tracers indicative of cloud-processed ship emissions (m/z 42 and 99). The variation of their organic fraction (f42 and f 99) was found to coincide with periods of heavy (f 42 > 0.15; f99 > 0.04), moderate (0.05 < f42 < 0.15; 0.01 < f99 < 0.04), and negligible (f42 < 0.05; f99 < 0.01) ship influence. Application of

  12. Evidence for ambient dark aqueous SOA formation in the Po Valley, Italy

    NASA Astrophysics Data System (ADS)

    Sullivan, A. P.; Hodas, N.; Turpin, B. J.; Skog, K.; Keutsch, F. N.; Gilardoni, S.; Paglione, M.; Rinaldi, M.; Decesari, S.; Facchini, M. C.; Poulain, L.; Herrmann, H.; Wiedensohler, A.; Nemitz, E.; Twigg, M. M.; Collett, J. L., Jr.

    2015-12-01

    Laboratory experiments suggest that water-soluble products from the gas-phase oxidation of volatile organic compounds can partition into atmospheric waters where they are further oxidized to form low volatility products, providing an alternative route for oxidation in addition to further oxidation in the gas-phase. These products can remain in the particle phase after water evaporation forming what is termed as aqueous secondary organic aerosol (aqSOA). However, few studies have attempted to observe ambient aqSOA. Therefore, a suite of measurements, including near real-time WSOC (water-soluble organic carbon), inorganic anions/cations, organic acids, and gas-phase glyoxal, were made during the PEGASOS (Pan-European Gas-AeroSols-climate interaction Study) 2012 campaign in the Po Valley, Italy to search for evidence of aqSOA. Our analysis focused on two specific periods: Period A on 19-21 June and Period B on 3-5 July to represent the first and second halves of the study, respectively. The large scale circulation was predominately from the west in both periods. Plus back trajectory analysis suggested all sites sampled similar air masses during both periods allowing for comparison of Periods A and B. The data collected during both periods were divided into times of increasing relative humidity (RH) and decreasing RH with the aim of diminishing the influence of dilution and mixing on SOA concentrations and other measured variables. Evidence for local aqSOA formation was only observed during Period A. When this occurred, there was a correlation of WSOC with organic aerosol (R2 = 0.86), aerosol liquid water (R2 = 0.69), RH (R2 = 0.45), and aerosol nitrate (R2 = 0.71). Additionally, this was only observed during times of increasing RH, which coincided with dark conditions. Comparisons of WSOC with oxygenated organic aerosol (OOA) factors determined from application of positive matrix factorization analysis on the aerosol mass spectrometer observations of the submicron non

  13. Consideration of HOMs in α- and β-pinene SOA model

    NASA Astrophysics Data System (ADS)

    Gatzsche, Kathrin; Iinuma, Yoshiteru; Mutzel, Anke; Berndt, Torsten; Wolke, Ralf

    2016-04-01

    Secondary organic aerosol (SOA) is the major burden of the atmospheric organic particulate matter with 140 - 910 TgC yr‑1 (Hallquist et al., 2009). SOA particles are formed via the oxidation of volatile organic carbons (VOCs), where the volatility of the VOCs is lowered due to the increase in their functionalization as well as their binding ability. Therefore, gaseous compounds can either nucleate to form new particles or condense on existing particles. The framework of SOA formation under natural conditions is very complex, because there are a multitude of gas-phase precursors, atmospheric degradation processes and products after oxidation. A lacking understanding about chemical and physical processes associated with SOA formation makes modeling of SOA processes difficult, leading to discrepancy between measured and modeled global SOA burdens. The present study utilizes a parcel model SPACCIM (SPectral Aerosol Cloud Chemistry Interaction Model, Wolke et al., 2005) that couples a multiphase chemical model with a microphysical model. For SOA modeling a further development of SPACCIM was necessary. Therefore, two components are added (i) a gas-phase chemistry mechanism for the VOC oxidation and (ii) a partitioning approach for the gas-to-particle phase transfer. An aggregated gas-phase chemistry mechanism for α- and β-pinene was adapted from Chen and Griffin (2005). For the phase transfer an absorptive partitioning approach (Pankow, 1994) and a kinetic approach (Zaveri et al., 2014) are implemented. Whereby the kinetic approach serves some advantages. The organic aerosol can be resolved in different size sections, whereby the particle radius is involved in the partitioning equations. The phase state of the organic material and the reactivity of the organic compounds in the particle-phase directly influence the modeled SOA yields. Recently, highly oxidized multifunctional organic compounds (HOMs) were found in the gas phase from lab and field studies. They are

  14. Photochemical Aging of Organic Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Nizkorodov, S. A.; Bateman, A. P.; Dailo, M.; Do, T.; Mang, S. A.; Pan, X.; Underwood, J. S.; Walser, M. L.

    2007-05-01

    Secondary Organic Aerosol (SOA) particles are produced in the atmosphere as a result of oxidation of volatile organic compounds (VOC). Primary Organic Aerosol (POA) particles are directly emitted in the atmosphere by their sources. This research focuses on the mechanisms of direct photochemical processes taking place in model SOA and POA particles, the role of such processes in aging of organic aerosol particles, and the effect of photochemistry on particles' physicochemical properties. To address these questions, artificial SOA and POA particles are investigated with several laboratory-based approaches relying on cavity ring-down spectroscopy and mass-spectrometry. SOA particles generated by dark oxidation of d-Limonene, alpha-Pinene, and beta-Pinene by ozone are all found to absorb radiation in the tropospheric actinic window. The UV absorption photolyzes SOA constituents resulting in a release of small VOC molecules back in the gas-phase, and considerable change in SOA chemical composition. For terpenes featuring a terminal double bond, the main SOA photolysis products are invariably found to be formaldehyde and formic acid. Similar observations are obtained for products of ozonolysis of thin films of unsaturated fatty acids and self-assembled monolayers of unsaturated alkenes. For the case of fatty acids, a very detailed mechanism of ozonolysis and subsequent photolysis is proposed. The photolytic activity is primarily attributed to organic peroxides and aldehydes. These results convincingly demonstrate that photochemical processes occurring inside SOA and POA particles age the particles on time scales that are shorter than typical lifetimes of aerosol particles in the atmosphere.

  15. Probing the Evaporation Dynamics of Mixed SOA/Squalane Particles Using Size-Resolved Composition and Single-Particle Measurements.

    PubMed

    Robinson, Ellis Shipley; Saleh, Rawad; Donahue, Neil M

    2015-08-18

    An analysis of the formation and evaporation of mixed-particles containing squalane (a surrogate for hydrophobic primary organic aerosol, POA) and secondary organic aerosol (SOA) is presented. In these experiments, one material (D62-squalane or SOA from α-pinene + O3) was prepared first to serve as surface area for condensation of the other, forming the mixed-particles. The mixed-particles were then subjected to a heating-ramp from 22 to 44 °C. We were able to determine that (1) almost all of the SOA mass is comprised of material less volatile than D62-squalane; (2) AMS collection efficiency in these mixed-particle systems can be parametrized as a function of the relative mass fraction of the components; and (3) the vast majority of D62-squalane is able to evaporate from the mixed particles, and does so on the same time scale regardless of the order of preparation. We also performed two-population mixing experiments to directly test whether D62-squalane and SOA from α-pinene + O3 form a single solution or two separate phases. We find that these two OA types are immiscible, which informs our inference of the morphology of the mixed-particles. If the morphology is core-shell and dictated by the order of preparation, these data indicate that squalane is able to diffuse relatively quickly through the SOA shell, implying that there are no major diffusion limitations. PMID:26158746

  16. Smog chamber experiments to investigate Henry's law constants of glyoxal using different seed aerosols as well as imidazole formation in the presence of ammonia

    NASA Astrophysics Data System (ADS)

    Jakob, Ronit

    2015-04-01

    Aerosols play an important role in the chemistry and physics of the atmosphere. Hence, they have a direct as well as an indirect impact on the earth's climate. Depending on their formation, one distinguishes between primary and secondary aerosols[1]. Important groups within the secondary aerosols are the secondary organic aerosols (SOAs). In order to improve predictions about these impacts on the earth's climate the existing models need to be optimized, because they still underestimate SOA formation[2]. Glyoxal, the smallest α-dicarbonyl, not only acts as a tracer for SOA formation but also as a direct contributor to SOA. Because glyoxal has such a high vapour pressure, it was common knowledge that it does not take part in gas-particle partitioning and therefore has no impact on direct SOA formation. However, the Henry's law constant for glyoxal is surprisingly high. This has been explained by the hydration of the aldehyde groups, which means that a species with a lower vapour pressure is produced. Therefore the distribution of glyoxal between gas- and particle phase is atmospherically relevant and the direct contribution of glyoxal to SOA can no longer be neglected[3]. Besides this particulate glyoxal is able to undergo heterogeneous chemistry with gaseous ammonia to form imidazoles. This plays an important role for regions with aerosols exhibiting alkaline pH values for example from lifestock or soil dust because imidazoles as nitrogen containing compounds change the optical properties of aerosols[4]. A high salt concentration present in chamber seed aerosols leads to an enhanced glyoxal uptake into the particle. This effect is called "salting-in". The salting effect depends on the composition of the seed aerosol as well as the soluble compound. For very polar compounds, like glyoxal, a "salting-in" is observed[3]. Glyoxal particle formation during a smog chamber campaign at Paul-Scherrer-Institut (PSI) in Switzerland was examined using different seed aerosols

  17. Secondary organic aerosol in the global aerosol - chemical transport model Oslo CTM2

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Berntsen, T.; Myhre, G.; Isaksen, I. S. A.

    2007-11-01

    The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA). Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics). A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 69 Tg yr-1 by allowing semi-volatile species to partition to ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated. Allowing SOA to partition into ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to 9.4% of the total production. Total modelled organic aerosol (OA) values are found to represent a lower fraction of the measured values in winter (when primary organic aerosol (POA) is the dominant OA component) than in summer, which may be an indication that estimates of POA emissions are too low. Additionally, for measurement stations where the summer OA values are higher than in winter, the model generally underestimates the increase in summertime OA. In order to correctly model the observed increase in OA in summer, additional SOA sources or formation mechanisms may be necessary. The importance of NO3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%-60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas, if the yield of condensible oxidation products for β-pinene is used for NO3 oxidation of all terpenes. Reducing the yield

  18. Relationship between Oxidation Level and Optical Properties of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Lambe, A. T.; Cappa, C. D.; Massoli, P.; Onasch, T. B.; Forestieri, S.; Martin, A. T.; Cummings, M. J.; Croasdale, D. R.; Brune, W. H.; Worsnop, D. R.; Davidovits, P.

    2013-12-01

    Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo-[5.2.1.02,6]decane), biomass burning (guaiacol), and biogenic (α-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level. Mass-specific absorption cross sections (MAC) of SOA at λ = 405 nm as a function of the O/C ratio

  19. Characterization of Highly Oxidized Molecules in Fresh and Aged Biogenic Secondary Organic Aerosol.

    PubMed

    Tu, Peijun; Hall, Wiley A; Johnston, Murray V

    2016-04-19

    In this work, highly oxidized multifunctional molecules (HOMs) in fresh and aged secondary organic aerosol (SOA) derived from biogenic precursors are characterized with high-resolution mass spectrometry. Fresh SOA was generated by mixing ozone with a biogenic precursor (β-pinene, limonene, α-pinene) in a flow tube reactor. Aging was performed by passing the fresh SOA through a photochemical reactor where it reacted with hydroxyl radicals. Although these aerosols were as a whole not highly oxidized, molecular analysis identified a significant number of HOMs embedded within it. HOMs in fresh SOA consisted mostly of monomers and dimers, which is consistent with condensation of extremely low-volatility organic compounds (ELVOCs) that have been detected in the gas phase in previous studies and linked to SOA particle formation. Aging caused an increase in the average number of carbon atoms per molecule of the HOMs, which is consistent with particle phase oxidation of (less oxidized) oligomers already existing in fresh SOA. HOMs having different combinations of oxygen-to-carbon ratio, hydrogen-to-carbon ratio and average carbon oxidation state are discussed and compared to low volatility oxygenated organic aerosol (LVOOA), which has been identified in ambient aerosol based on average elemental composition but not fully understood at a molecular level. For the biogenic precursors and experimental conditions studied, HOMs in fresh biogenic SOA have molecular formulas more closely resembling LVOOA than HOMs in aged SOA, suggesting that aging of biogenic SOA is not a good surrogate for ambient LVOOA. PMID:27000653

  20. Phase state and humidity-induced phase transition studies of SOA particles from biogenic and anthropogenic precursors

    NASA Astrophysics Data System (ADS)

    Saukko, E.; Lambe, A. T.; Massoli, P.; Koop, T.; Wright, J. P.; Croasdale, D. R.; Pedernera, D. A.; Onasch, T. B.; Laaksonen, A.; Davidovits, P.; Worsnop, D. R.; Virtanen, A.

    2012-04-01

    There is mounting evidence showing that tropospheric secondary organic aerosol (SOA) may exist in a phase state other than liquid, namely semi-solid or solid amorphous. The solid or semi-solid, high viscosity material may have significantly higher lifetime in an oxidizing atmosphere than low viscosity liquid due to mass transfer limitations in the particle bulk. In this work we report a systematic study of the phase state of SOA particles produced by photo-oxidation of several volatile organic compound (VOC) precursors in a potential aerosol mass (PAM) flow tube reactor. The phase state of the particles was studied by their bounce behaviour upon impaction on a polished steel plate in a low pressure impactor. The SOA oxidation level (O/C) was determined by an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) The phase state for several types of SOA from different surrogate anthropogenic and biogenic precursors, produced at a wide range of oxidation conditions, were studied at a range of relative humidities. We report the solid or semi-solid phase state of SOA produced from cyclic and terpene precursors used in the study up to at least 50 % relative humidity. Furthermore, adding sulfur dioxide into the reaction chamber yielded liquefied particles, while particles formed from oxidation of pure organic precursor were solid or semi-solid. For a long-chain alkane precursor a liquid-like SOA at low oxidation level was produced, but upon increasing the oxidation level, the formed particles became more solid. While the bounce behaviour of the particles had no single explaining factor for all experiments, the precursor molar mass was seen to correlate with more solid phase at higher humidities in cases with cyclic or terpene precursor.

  1. Predicting secondary organic aerosol formation rates in southeast Texas

    NASA Astrophysics Data System (ADS)

    Russell, Matthew; Allen, David T.

    2005-04-01

    Rates of secondary organic aerosol (SOA) formation, due to the reactions of aromatics and monoterpenes, were estimated for southeast Texas by incorporating a modified version of the Statewide Air Pollution Research Center's chemical mechanism (SAPRC99) into the Comprehensive Air Quality Model with extensions (CAMx version 3.10). The model included explicit representation of the reactions of five SOA precursors (α-pinene, β-pinene, sabinene, d-limonene, and Δ3-carene). Reactions of each SOA precursor with O3, OH radical, and NO3 radical were included. The model also included separate reactions for low- and high-SOA-yield aromatic groups with the OH radical. SOA yields in the mechanisms were estimated using compound-specific yield information (ΔSOA/ΔHC) derived from smog chamber experiments conducted by J. R. Odum and colleagues and R. J. Griffin and colleagues. The form of the SOA yield model was based on the work of J. R. Odum and colleagues and is a function of existing organic aerosol concentrations. Existing organic aerosol concentrations were estimated on the basis of ambient measurements of total organic carbon in southeast Texas. The reactions of monoterpenes (predominantly α-pinene and β-pinene) with ozone led to the most regional SOA formation, followed by monoterpenes with the nitrate radical. Aromatic-OH reactions led to less regional SOA formation compared to monoterpenes; however, this formation occurs close to the urban and industrial areas of Houston. In contrast, SOA formation due to the reactions of monoterpenes occurred in the forested areas north of the urban area. The results of this study are in qualitative agreement with estimates of SOA formation based on ambient data from the same time period.

  2. Formation of brown carbon via reactions of ammonia with secondary organic aerosols from biogenic and anthropogenic precursors

    NASA Astrophysics Data System (ADS)

    Updyke, Katelyn M.; Nguyen, Tran B.; Nizkorodov, Sergey A.

    2012-12-01

    Filter samples of secondary organic aerosols (SOA) generated from the ozone (O3)- and hydroxyl radical (OH)-initiated oxidation of various biogenic (isoprene, α-pinene, limonene, α-cedrene, α-humulene, farnesene, pine leaf essential oils, cedar leaf essential oils) and anthropogenic (tetradecane, 1,3,5-trimethylbenzene, naphthalene) precursors were exposed to humid air containing approximately 100 ppb of gaseous ammonia (NH3). Reactions of SOA compounds with NH3 resulted in production of light-absorbing "brown carbon" compounds, with the extent of browning ranging from no observable change (isoprene SOA) to visible change in color (limonene SOA). The aqueous phase reactions with dissolved ammonium (NH4+) salts, such as ammonium sulfate, were equally efficient in producing brown carbon. Wavelength-dependent mass absorption coefficients (MAC) of the aged SOA were quantified by extracting known amounts of SOA material in methanol and recording its UV/Vis absorption spectra. For a given precursor, the OH-generated SOA had systematically lower MAC compared to the O3-generated SOA. The highest MAC values, for brown carbon from SOA resulting from O3 oxidation of limonene and sesquiterpenes, were comparable to MAC values for biomass burning particles but considerably smaller than MAC values for black carbon aerosols. The NH3/NH4+ + SOA brown carbon aerosol may contribute to aerosol optical density in regions with elevated concentrations of NH3 or ammonium sulfate and high photochemical activity.

  3. Limited Effect of Anthropogenic Nitrogen Oxides on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Knote, C. J.; Tilmes, S.; Emmons, L. K.; Lamarque, J. F.; Yu, P.

    2014-12-01

    Globally secondary organic aerosol (SOA) is mostly formed from biogenic vegetation emissions and as such is regarded as natural aerosol that cannot be reduced by emission control legislation. However, recent research implies that human activities facilitate SOA formation by affecting the amount of precursor emission, the chemical processing and the partitioning into the aerosol phase. Among the multiple human influences, nitrogen oxides (NO + NO2 = NOx) have been assumed to play a critical role in the chemical formation of low volatile compounds. The goal of this study is to improve the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-Chem) by implementing an updated 4-product Volatility Basis Set (VBS) scheme, and apply it to investigate the impact of anthropogenic NOx on SOA. We first compare three different SOA parameterizations: a 2-product model and the updated VBS model both with and without a SOA aging parameterization. Secondly we evaluate predicted organic aerosol amounts against surface measurement from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network and Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns. We then perform sensitivity experiments to examine how the SOA loading responds to a 50% reduction in anthropogenic NOx in different regions. We find limited SOA reductions of -2.3%, -5.6% and -4.0% for global, southeastern U.S. and Amazon NOx perturbations, respectively. To investigate the chemical processes in more detail, we also use a simplified box model with the same gas-phase chemistry and gas-aerosol partitioning mechanism as in CAM4-Chem to examine the SOA yields dependence on initial precursor emissions and background NOx level. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- versus high-NOx pathways, OH versus NO3-initiated oxidation) and to offsetting

  4. Photochemical evolution of organic aerosols observed in urban plumes from Hong Kong and the Pearl River Delta of China

    NASA Astrophysics Data System (ADS)

    Zhou, Shengzhen; Wang, Tao; Wang, Zhe; Li, Weijun; Xu, Zheng; Wang, Xinfeng; Yuan, Chao; Poon, C. N.; Louie, Peter K. K.; Luk, Connie W. Y.; Wang, Wenxing

    2014-05-01

    Organic aerosols influence human health and global radiative forcing. However, their sources and evolution processes in the atmosphere are not completely understood. To study the aging and production of organic aerosols in a subtropical environment, we measured hourly resolved organic carbon (OC) and element carbon (EC) in PM2.5 at a receptor site (Tung Chung, TC) in Hong Kong from August 2011 to May 2012. The average OC concentrations exhibited the highest values in late autumn and were higher during the daytime than at night. The secondary organic carbon (SOC) concentrations, which were estimated using an EC-tracer method, comprised approximately half of the total OC on average. The SOC showed good correlation with odd oxygen (Ox = O3 + NO2) in the summer and autumn seasons, suggestive of contribution of photochemical activities to the formation of secondary organic aerosols (SOA). We calculated production rates of SOA using the photochemical age (defined as -Log10(NOx/NOy)) in urban plumes from the Pearl River Delta (PRD) region and Hong Kong during pollution episodes in summer and autumn. The CO-normalized SOC increased with the photochemical age, with production rates ranging from 1.31 to 1.82 μg m-3 ppmv-1 h-1 in autumn and with a larger rate in summer (3.86 μg m-3 ppmv-1 h-1). The rates are in the range of the rates observed in the outflow from Mexico City, the eastern U.S. and Los Angeles. Microscopic analyses of the individual aerosol particles revealed large contrasts of aerosol physico-chemical properties on clean and smoggy days, with thick organic coatings internally mixed with inorganic sulfate for all particle sizes in the aged plumes from the PRD region.

  5. Science Opportunity Analyzer (SOA) Version 8

    NASA Technical Reports Server (NTRS)

    Witoff, Robert J.; Polanskey, Carol A.; Aguinaldo, Anna Marie A.; Liu, Ning; Hofstadter, Mark D.

    2013-01-01

    SOA allows scientists to plan spacecraft observations. It facilitates the identification of geometrically interesting times in a spacecraft s orbit that a user can use to plan observations or instrument-driven spacecraft maneuvers. These observations can then be visualized multiple ways in both two- and three-dimensional views. When observations have been optimized within a spacecraft's flight rules, the resulting plans can be output for use by other JPL uplink tools. Now in its eighth major version, SOA improves on these capabilities in a modern and integrated fashion. SOA consists of five major functions: Opportunity Search, Visualization, Observation Design, Constraint Checking, and Data Output. Opportunity Search is a GUI-driven interface to existing search engines that can be used to identify times when a spacecraft is in a specific geometrical relationship with other bodies in the solar system. This function can be used for advanced mission planning as well as for making last-minute adjustments to mission sequences in response to trajectory modifications. Visualization is a key aspect of SOA. The user can view observation opportunities in either a 3D representation or as a 2D map projection. Observation Design allows the user to orient the spacecraft and visualize the projection of the instrument field of view for that orientation using the same views as Opportunity Search. Constraint Checking is provided to validate various geometrical and physical aspects of an observation design. The user has the ability to easily create custom rules or to use official project-generated flight rules. This capability may also allow scientists to easily assess the cost to science if flight rule changes occur. Data Output allows the user to compute ancillary data related to an observation or to a given position of the spacecraft along its trajectory. The data can be saved as a tab-delimited text file or viewed as a graph. SOA combines science planning functionality unique to

  6. Molecular Characterization of Marine Organic Aerosols Collected during a Round-the-World Cruise

    NASA Astrophysics Data System (ADS)

    Fu, P.; Kawamura, K.; Miura, K.

    2010-12-01

    Total suspended particles (TSP) were collected on board the R/V Hakuho Maru during a round-the-world cruise (KH89-2) and were characterized for organic molecular compositions using solvent extraction/derivatization and gas chromatography/mass spectrometry technique. More than 140 organic species were detected in the marine aerosols and were grouped into 11 organic compound classes, including aliphatic lipids, anhydrosugars and sugar alcohols, lignin/resin acids, sterols, hopanes, polycyclic aromatic hydrocarbons, hydroxy-/polyacids, aromatic acids, as well as secondary organic aerosol (SOA) tracers from the photooxidation of biogenic volatile organic compounds. Concentrations of total quantified organics ranged from 0.94 to 98 ng m-3 (average 31 ng m-3) with higher concentrations in coastal regions (California Coast, South China Sea, and Western North Pacific) than in open marine areas (North Pacific and North Atlantic), suggesting that long-range atmospheric transport from the continents is the main source of marine organic aerosols. Isoprene SOA tracers, i.e., 2-methylglyceric acid, C5-alkene triols and 2-methyltetrols, were detected in all the samples (0.11-22 ng m-3, average 3.6 ng m-3) with higher concentrations in the tropical regions. They accounted for 0.48-29% of the total identified organics. Organic compounds were further categorized into several groups to clarify their sources. In the North Pacific and North Atlantic, secondary oxidation products (30-31%), fossil fuel combustion products (27-28%), as well as marine natural emissions (22-34%) were found as major contributors to the marine aerosols. In California Coast, North Indian Ocean and South China Sea, secondary oxidation products can contribute 44-55% of the total identified organics, followed by terrestrial natural emissions (12-27%), while biomass burning emissions were found to contribute only 1-2%. However, in the western North Pacific near the Asian continent, fossil fuel combustion (27%) and

  7. Heating-Induced Evaporation of Nine Different Secondary Organic Aerosol Types.

    PubMed

    Kolesar, Katheryn R; Li, Ziyue; Wilson, Kevin R; Cappa, Christopher D

    2015-10-20

    The volatility of the compounds comprising organic aerosol (OA) determines their distribution between the gas and particle phases. However, there is a disconnect between volatility distributions as typically derived from secondary OA (SOA) growth experiments and the effective particle volatility as probed in evaporation experiments. Specifically, the evaporation experiments indicate an overall much less volatile SOA. This raises questions regarding the use of traditional volatility distributions in the simulation and prediction of atmospheric SOA concentrations. Here, we present results from measurements of thermally induced evaporation of SOA for nine different SOA types (i.e., distinct volatile organic compound and oxidant pairs) encompassing both anthropogenic and biogenic compounds and O3 and OH to examine the extent to which the low effective volatility of SOA is a general phenomenon or specific to a subset of SOA types. The observed extents of evaporation with temperature were similar for all the SOA types and indicative of a low effective volatility. Furthermore, minimal variations in the composition of all the SOA types upon heating-induced evaporation were observed. These results suggest that oligomer decomposition likely plays a major role in controlling SOA evaporation, and since the SOA formation time scale in these measurements was less than a minute, the oligomer-forming reactions must be similarly rapid. Overall, these results emphasize the importance of accounting for the role of condensed phase reactions in altering the composition of SOA when assessing particle volatility. PMID:26393817

  8. Measurements of in-situ SOA Formation Using an Oxidation Flow Reactor at GoAmazon2014/5

    NASA Astrophysics Data System (ADS)

    Palm, B. B.; de Sá, S. S.; Campuzano Jost, P.; Day, D. A.; Hu, W.; Seco, R.; Park, J. H.; Guenther, A. B.; Kim, S.; Brito, J.; Wurm, F.; Artaxo, P.; Yee, L.; Isaacman-VanWertz, G. A.; Goldstein, A. H.; Souza, R. A. F. D.; Manzi, A. O.; Bustillos, J. O. V.; Tota, J.; Newburn, M. K.; Alexander, M. L. L.; Martin, S. T.; Brune, W. H.; Jimenez, J. L.

    2015-12-01

    During GoAmazon2014/5, ambient air was exposed to controlled concentrations of OH or O3 in-situ using an oxidation flow reactor (OFR). Oxidation ranged from hours-several weeks of aging. Oxidized air was sampled by several instruments (e.g., HR-AMS, ACSM, PTR-TOF-MS, SMPS, CCN) at both the T3 site (IOP1: Feb 1-Mar 31, 2014, and IOP2: Aug 15-Oct 15, 2014) and T2 site (between IOPs and into 2nd IOP). Oxidation of ambient air in the OFR led to significant and dynamic SOA formation. In general, more SOA was produced during the nighttime than daytime, and more in the dry season (IOP2) than wet season (IOP1). The maximum amount of SOA produced during nighttime from OH oxidation ranged from less than 1 µg/m3 to greater than 10 µg/m3. O3 oxidation of ambient air also led to SOA formation, although much less than from OH oxidation. Preliminary PMF factor analysis showed that the less-oxidized OOA (LO-OOA) factor was produced at up to several days OH aging, while at longer ages the more-oxidized OOA (MO-OOA) factor was formed and LO-OOA was depleted. HOA, BBOA, and IEPOX-SOA factors were not formed in the reactor, just depleted at high ages (though at different rates). More detailed PMF results will be presented. Variations in the amount of SOA formation often, but not always, correlated with measured gas-phase biogenic and/or anthropogenic SOA precursors (e.g., SV-TAG sesquiterpenes, PTR-TOFMS aromatics, isoprene, and monoterpenes). The SOA mass formed in the OFR was ~10x larger than could be explained by aerosol yields of measured primary VOCs, suggesting that most SOA was formed from intermediate sources such as S/IVOCs (e.g., VOC oxidation products or evaporated POA), consistent with previous OFR field and lab studies. To verify the SOA yields of VOCs under OFR experimental conditions, atmospherically-relevant concentrations of several VOCs were added individually into ambient air in the OFR and oxidized by OH or O3. SOA yields were similar to published chamber yields.

  9. Source-apportionment and model evaluation: experiences with the EMEP SOA model

    NASA Astrophysics Data System (ADS)

    Simpson, D.; Yttri, K. E.

    2009-04-01

    The EMEP MSC-W chemical transport model (Simpson et al., 2003) has been successfully used for the prediction of photochemical oxidants and various inorganic aerosol components (sulphate, nitrate, ammonium) for many years. The model generally performs well for such species, as should be expected for compounds whose emission sources and chemistry are fairly well know. For carbonaceous particulate matter (PCM) however the model has been found to give very different results in different parts of Europe, with typically poor performance in southern Europe, but rather good results in Northern Europe (Simpson et al., 2007). Earlier comparison with the results of source-apportionment studies from the CARBOSOL project (Gelencser et al., 2007, Simpson et al., 2007) has shown that the poor performance in southern Europe can partly be ascribed to difficulties with emissions from residential wood-burning, and partly due to an underestimate of the secondary organic aerosol (SOA) component. Such difficulties are expected for organic aerosols, a subject where the basic science is only partially understood, and where new experimental results continually lead to revisions in existing ideas concerning sources and formation mechanisms (e.g. Hallquist et al., 2009). In such a situation, it is essential that model results are evaluated as thoroughly as possible, and that where possible the various components of organic aerosol can be evaluated separately. A number of source-apportionment (SA) studies have recently become available in Europe, in which data on elemental carbon (EC), organic carbon (OC), 14C, levoglucosan, and various markers of primary organic carbon (cellulose, sugars/sugar-alcohols) have allowed estimates of various sources of carbonaceous particulate matter (PCM). As well as CARBOSOL, these studies include various sites in Switzerland (e.g. Lanz et al., 2008, Szidat et al., 2006), data are available from Gothenburg in Sweden (Szidat et al., 2008) and from southern

  10. VOC emissions, evolutions and contributions to SOA formation at a receptor site in Eastern China

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Hu, W. W.; Shao, M.; Wang, M.; Chen, W. T.; Lu, S. H.; Zeng, L. M.; Hu, M.

    2013-03-01

    Volatile organic compounds (VOCs) were measured by two online instruments (GC-FID/MS and PTR-MS) at a receptor site on Changdao Island (37.99° N, 120.70° E) in eastern China. Reaction with OH radical dominated the chemical loss of most VOC species during the Changdao campaign. A photochemical age based parameterization method is used to calculate VOC emission ratios and to quantify the evolution of ambient VOCs. The calculated emission ratios of most hydrocarbons agree well with those obtained from emission inventory, but the emission ratios of oxygenated VOCs (OVOCs) are significantly lower than those from emission inventory. The photochemical age based parameterization method is also used to investigate primary emissions and secondary formation of organic aerosol. The primary emission ratio of OA to CO are determined to be 14.9 μg m-3 ppm-1 and SOA are produced at an enhancement ratio of 18.8 μg m-3 ppm-1 to CO after 50 h of photochemical processing in the atmosphere. SOA formation is significantly higher than the level determined from VOC oxidation under both high-NOx (2.0 μg m-3 ppm-1 CO) and low-NOx condition (6.5 μg m-3 ppm-1 CO). Polycyclic aromatic hydrocarbons (PAHs) and higher alkanes (>C10) account for as high as 17.4% of SOA formation, which suggests semi-volatile organic compounds (SVOCs) may be a large contributor to SOA formation during the Changdao campaign. SOA formation potential of primary VOC emissions determined from both field campaigns and emission inventory in China are lower than the measured SOA levels reported in Beijing and Pearl River Delta (PRD), indicating SOA formation cannot be explained by VOC oxidation in this regions. SOA budget in China is estimated to be 5.0-13.7 Tg yr-1, with a fraction of at least 2.7 Tg yr-1 from anthropogenic emissions, which are much higher than the previous estimates from regional models.

  11. Chemistry of secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Yee, Lindsay Diana

    The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C12 alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NOx levels, such that RO2 + HO2 chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed. Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position. The photooxidation of several C12 alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the

  12. Evaporation Kinetics and Phase of Laboratory and Ambient Secondary Organic Aerosol

    SciTech Connect

    Vaden, Timothy D.; Imre, Dan G.; Beranek, Josef; Shrivastava, ManishKumar B.; Zelenyuk, Alla

    2011-02-08

    Field measurements of secondary organic aerosol (SOA) find higher mass loads than predicted by models, sparking intense efforts to find additional SOA sources but leaving the assumption of rapid SOA evaporation unchallenged. We characterized room-temperature evaporation of pure SOA and SOA formed in the presence of spectator organic vapors with and without aging. We find that it takes ~24 hrs for pure SOA particles to evaporate 75% of their mass, which is in sharp contrast to the ~10 minutes timescales predicted by models. The presence of spectator organic vapors and aging dramatically reduces the evaporation, and in some cases nearly stops it. For all cases, SOA evaporation behavior is size independent and does not follow the liquid droplet evaporation kinetics assumed by models.

  13. Photo-oxidation of pinonaldehyde at low NOx: from chemistry to organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Chacon-Madrid, H. J.; Henry, K. M.; Donahue, N. M.

    2013-03-01

    Pinonaldehyde oxidation by OH radicals under low-NOx conditions produces significant secondary organic aerosol (SOA) mass yields. Under concurrent UV illumination, mass yields are lower than high-NOx yields published earlier by our group. However, when OH radicals are produced via dark ozonolysis the SOA mass yields are comparable at high and low NOx. Because pinonaldehyde is a major first-generation gas-phase product of α-pinene oxidation by either ozone or OH radicals, its potential to form SOA serves as a molecular counterpoint to bulk SOA aging experiments involving SOA formed from α-pinene. Both the general tendency for aging reactions to produce more SOA and the sensitivity of the low-NOx products to UV photolysis observed in the bulk clearly occur for this single species as well. Photochemical oxidation of pinonaldehye and analogous first-generation terpene oxidation products are potentially a significant source of additional SOA in biogenically influenced air masses.

  14. Photochemistry of limonene secondary organic aerosol studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, Xiang

    Limonene is one of the most abundant monoterpenes in the atmosphere. Limonene easily reacts with gas-phase oxidants in air such as NO3, ozone and OH. Secondary organic aerosol (SOA) is formed when low vapor pressure products condense into particles. Chemicals in SOA particles can undergo further reactions with oxidants and with solar radiation that significantly change SOA composition over the course of several days. The goal of this work was to characterize radiation induced reaction in SOA. To perform experiments, we have designed and constructed an Atmospheric Pressure Chemical Ionization Mass Spectrometer (APCIMS) coupled to a photochemical cell containing SOA samples. In APCIMS, (H2O)nH 3O+ clusters are generated in a 63Ni source and react with gaseous organic analytes. Most organic chemicals are not fragmented by the ionization process. We have focused our attention on limonene SOA prepared in two different ways. The first type of SOA is produced by oxidation of limonene by ozone; and the second type of SOA is formed by the NO3-induced oxidation of limonene. They model the SOA formed under daytime and nighttime conditions, respectively. Ozone initiated oxidation is the most important chemical sink for limonene both indoors, where it is used for cleaning purposes, and outdoors. Terpenes are primarily oxidized by reactions with NO3 at night time. We generated limonene SOA under different ozone and limonene concentrations. The resulting SOA samples were exposed to wavelength-tunable radiation in the UV-Visible range between 270 nm and 630 nm. The results show that the photodegradation rates strongly depend on radiation wavelengths. Gas phase photodegradation products such as acetone, formaldehyde, acetaldehyde, and acetic acid were shown to have different production rates for SOA formed in different concentration conditions. Even for SOA prepared under the lowest concentrations, the SOA photodegradation was efficient. The conclusion is that exposure of SOA to

  15. Tracer Technique

    NASA Astrophysics Data System (ADS)

    Haba, H.; Motomura, S.; Kamino, S.; Enomoto, S.

    In radioactive tracer technique, radioactive nuclides are used to follow the behavior of elements or chemical species in chemical and other processes. This is realized by means of radioactivity measurement. In 1913, Hevesy and Paneth succeeded in determining the extremely low solubility of lead salts by using naturally occurring 210Pb as a radioactive tracer. As various radioactive nuclides became artificially available, this technique has been widely employed in studies of chemical equilibrium and reactions as well as in chemical analysis. It is also an essential technique in biochemical, biological, medical, geological, and environmental studies. Medical diagnosis and industrial process control are the fields of its most important practical application. In this chapter, fundamental ideas concerning radioactive tracers will be described followed by their application with typical examples. Detailed description on their application to life sciences and medicine is given in Vol. 4.

  16. Modeling Secondary Organic Aerosol Formation From Emissions of Combustion Sources

    NASA Astrophysics Data System (ADS)

    Jathar, Shantanu Hemant

    Atmospheric aerosols exert a large influence on the Earth's climate and cause adverse public health effects, reduced visibility and material degradation. Secondary organic aerosol (SOA), defined as the aerosol mass arising from the oxidation products of gas-phase organic species, accounts for a significant fraction of the submicron atmospheric aerosol mass. Yet, there are large uncertainties surrounding the sources, atmospheric evolution and properties of SOA. This thesis combines laboratory experiments, extensive data analysis and global modeling to investigate the contribution of semi-volatile and intermediate volatility organic compounds (SVOC and IVOC) from combustion sources to SOA formation. The goals are to quantify the contribution of these emissions to ambient PM and to evaluate and improve models to simulate its formation. To create a database for model development and evaluation, a series of smog chamber experiments were conducted on evaporated fuel, which served as surrogates for real-world combustion emissions. Diesel formed the most SOA followed by conventional jet fuel / jet fuel derived from natural gas, gasoline and jet fuel derived from coal. The variability in SOA formation from actual combustion emissions can be partially explained by the composition of the fuel. Several models were developed and tested along with existing models using SOA data from smog chamber experiments conducted using evaporated fuel (this work, gasoline, fischertropschs, jet fuel, diesels) and published data on dilute combustion emissions (aircraft, on- and off-road gasoline, on- and off-road diesel, wood burning, biomass burning). For all of the SOA data, existing models under-predicted SOA formation if SVOC/IVOC were not included. For the evaporated fuel experiments, when SVOC/IVOC were included predictions using the existing SOA model were brought to within a factor of two of measurements with minor adjustments to model parameterizations. Further, a volatility

  17. Phase, Viscosity, Morphology, and Room Temperature Evaporation Rates of SOA Particles Generated from Different Precursors, at Low and High Relative Humidities, and their Interaction with Hydrophobic Organics

    NASA Astrophysics Data System (ADS)

    Wilson, J. M.; Zelenyuk, A.; Imre, D. G.; Beranek, J.; Abramson, E.; Shrivastava, M.

    2012-12-01

    Formation, properties, transformations, and temporal evolution of secondary organic aerosol (SOA) particles strongly depend on particle phase. Semi-volatile molecules that comprise SOA particles were assumed to form a low viscosity solution that maintains equilibrium with the evolving gas phase by rapid evaporation condensation. However, studies by our group indicate that laboratory-generated alpha-pinene SOA particles and ambient SOA characterized in a recent field campaign are in a semi-solid, highly viscous phase, and their evaporation rates are orders of magnitude slower than predicted. We present the results of recent studies in which we have extended our work to include SOA particles generated by oxidation of a number of precursors including limonene, n-alkenes, cyclo-alkenes and isoprene. The resulting particles are characterized by their phase, morphology and room temperature evaporation rates. We conclude that, while the detailed properties of SOA particles depend of their precursor, all studied SOA particles are highly viscous semi-solids that exhibit very slow evaporation rates. Given that atmospheric relative humidity (RH) can change particle phase, it is important to investigate the effect of RH on the phase and evaporation kinetics of SOA particles. To this end SOA particles were generated at low and high (~90%) RH, and their evaporation kinetics and phase were characterized as a function of RH. In the ambient atmosphere SOA particles form in the presence of a mixture of different organic compounds, which are present at or below their equilibrium vapor pressure, and thus have been ignored. However, our data show that these compounds can adsorb to the surface of particles during SOA formation, becoming trapped in the highly viscous SOA, and affect particle properties. We examine the interaction between SOA particles and different hydrophobic organics representing typical anthropogenic emissions by making SOA in the presence of the vapors of these

  18. Origin of nitrocatechols and alkylated-nitrocatechols in atmospheric aerosol particles

    NASA Astrophysics Data System (ADS)

    Marchand, Nicolas; Sylvestre, Alexandre; Ravier, Sylvain; Detournay, Anais; Bruns, Emily; Temime-Roussel, Brice; Slowik, Jay; El Haddad, Imad; Prevot, Andre

    2013-04-01

    Biomass burning constitutes one of the major sources of aerosol particles in most of the environments during winter. If a lot of information is available in the literature on the primary fraction of biomass burning aerosol particles, almost nothing is known regarding the formation of Secondary Organic Aerosol (SOA) from the chemical mixture emitted by this source. Recently methylated nitrocatechol have been identified in atmospheric particles collected in winter. These compounds are strongly associated with biomass burning tracers such as levoglucosan and are suspected to be of secondary origin since they can be formed through the oxidation of cresol significantly emitted by biomass burning. However, nitrocatechols are particularly difficult to analyze using classical techniques like HPLC-MS or GC-MS. In the present study, we adopt a new analytical approach. Direct analysis in real time (DART), introduced by Cody et al. (2005), allows direct analysis of gases, liquids, solids and materials on surfaces. Thus, for particles collected onto filters, the sample preparation step is simplified as much as possible, avoiding losses and reducing to the minimum the analytical procedure time. Two analytic modes can be used. In positive mode, [MH]+ ions are formed by proton transfer reaction ; whereas in negative ionization mode, [MH]-, M- and [MO2]- ions are formed. DART source enables soft ionization and produces simple mass spectra suitable for analysis of complex matrices, like organic aerosol, in only a few seconds. For this study, the DART source was coupled to a Q-ToF mass spectrometer (Synapt G2 HDMS, Waters), with a mass resolution up to 40 000. The analysis of atmospheric aerosol samples, collected in Marseille during winter 2011 (APICE project), with the DART/Q-ToF approach highlighted the abundance of nitrocatechols and alkylated nitrocatechols. Their temporal trends were also very similar to those of levoglucosan or dihydroabietic acid well known tracers of biomass

  19. Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

    NASA Astrophysics Data System (ADS)

    Claeys, M.; Kourtchev, I.; Pashynska, V.; Vas, G.; Vermeylen, R.; Wang, W.; Cafmeyer, J.; Chi, X.; Artaxo, P.; Andreae, M. O.; Maenhaut, W.

    2010-10-01

    Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil) using a high-volume dichotomous sampler (HVDS) and a Micro-Orifice Uniform Deposit Impactor (MOUDI) within the framework of the 2002 LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate) campaign. The campaign spanned the late dry season (biomass burning), a transition period, and the onset of the wet season (clean conditions). In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including levoglucosan, malic acid, isoprene secondary organic aerosol (SOA) tracers and tracers for fungal spores. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m-3 and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly present in the fine mode, except during the wet period where it peaked in the coarse mode. Isoprene SOA tracers showed an average concentration of 250 ng m-3 during the dry period versus 157 ng m-3 during the transition period and 52 ng m-3 during the wet period. Malic acid and the 2-methyltetrols exhibited a different size distribution pattern, which is consistent with different aerosol formation processes (i.e., gas-to-particle partitioning in the case of malic acid and heterogeneous formation from gas-phase precursors in the case of the 2-methyltetrols). The 2-methyltetrols were mainly associated with the

  20. Atmospheric reactivity of hydroxyl radicals with guaiacol (2-methoxyphenol), a biomass burning emitted compound: Secondary organic aerosol formation and gas-phase oxidation products

    NASA Astrophysics Data System (ADS)

    Lauraguais, Amélie; Coeur-Tourneur, Cécile; Cassez, Andy; Deboudt, Karine; Fourmentin, Marc; Choël, Marie

    2014-04-01

    Methoxyphenols are low molecular weight semi-volatile polar aromatic compounds produced from the pyrolysis of wood lignin. The reaction of guaiacol (2-methoxyphenol) with hydroxyl radicals has been studied in the LPCA simulation chamber at (294 ± 2) K, atmospheric pressure, low relative humidity (RH < 1%) and under high-NOx conditions using CH3ONO as OH source. The aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer); the SOA yields were in the range from 0.003 to 0.87 and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. Transmission (TEM) and Scanning (SEM) Electron Microscopy observations were performed to characterize the physical state of SOA produced from the OH reaction with guaiacol; they display both liquid and solid particles (in an amorphous state). GC-FID (Gas Chromatography - Flame Ionization Detection) and GC-MS (Gas Chromatography - Mass Spectrometry) analysis show the formation of nitroguaiacol isomers as main oxidation products in the gas- and aerosol-phases. In the gas-phase, the formation yields were (10 ± 2) % for 4-nitroguaiacol (1-hydroxy-2-methoxy-4-nitrobenzene; 4-NG) and (6 ± 2) % for 3- or 6-nitroguaiacol (1-hydroxy-2-methoxy-3-nitrobenzene or 1-hydroxy-2-methoxy-6-nitrobenzene; 3/6-NG; the standards are not commercially available so both isomers cannot be distinguished) whereas in SOA their yield were much lower (≤0.1%). To our knowledge, this work represents the first identification of nitroguaiacols as gaseous oxidation products of the OH reaction with guaiacol. As the reactivity of nitroguaiacols with atmospheric oxidants is probably low, we suggest using them as biomass burning emission gas tracers. The atmospheric implications of the guaiacol + OH reaction are also discussed.

  1. Laboratory studies on secondary organic aerosol formation from crude oil vapors.

    PubMed

    Li, R; Palm, B B; Borbon, A; Graus, M; Warneke, C; Ortega, A M; Day, D A; Brune, W H; Jimenez, J L; de Gouw, J A

    2013-01-01

    Airborne measurements of aerosol composition and gas phase compounds over the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico in June 2010 indicated the presence of high concentrations of secondary organic aerosol (SOA) formed from organic compounds of intermediate volatility. In this work, we investigated SOA formation from South Louisiana crude oil vapors reacting with OH in a Potential Aerosol Mass flow reactor. We use the dependence of evaporation time on the saturation concentration (C*) of the SOA precursors to separate the contribution of species of different C* to total SOA formation. This study shows consistent results with those at the DWH oil spill: (1) organic compounds of intermediate volatility with C* = 10(5)-10(6) μg m(-3) contribute the large majority of SOA mass formed, and have much larger SOA yields (0.37 for C* = 10(5) and 0.21 for C* = 10(6) μg m(-3)) than more volatile compounds with C*≥10(7) μg m(-3), (2) the mass spectral signature of SOA formed from oxidation of the less volatile compounds in the reactor shows good agreement with that of SOA formed at DWH oil spill. These results also support the use of flow reactors simulating atmospheric SOA formation and aging. PMID:24088179

  2. The formation, properties and impact of secondary organic aerosol: current and emerging issues

    NASA Astrophysics Data System (ADS)

    Hallquist, M.; Wenger, J. C.; Baltensperger, U.; Rudich, Y.; Simpson, D.; Claeys, M.; Dommen, J.; Donahue, N. M.; George, C.; Goldstein, A. H.; Hamilton, J. F.; Herrmann, H.; Hoffmann, T.; Iinuma, Y.; Jang, M.; Jenkin, M.; Jimenez, J. L.; Kiendler-Scharr, A.; Maenhaut, W.; McFiggans, G.; Mentel, Th. F.; Monod, A.; Prévôt, A. S. H.; Seinfeld, J. H.; Surratt, J. D.; Szmigielski, R.; Wildt, J.

    2009-02-01

    Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with a description of the current state of knowledge on the global SOA budget and the atmospheric degradation mechanisms for SOA precursors. The topic of gas-particle partitioning theory is followed by an account of the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail; molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

  3. The formation, properties and impact of secondary organic aerosol: current and emerging issues

    NASA Astrophysics Data System (ADS)

    Hallquist, M.; Wenger, J. C.; Baltensperger, U.; Rudich, Y.; Simpson, D.; Claeys, M.; Dommen, J.; Donahue, N. M.; George, C.; Goldstein, A. H.; Hamilton, J. F.; Herrmann, H.; Hoffmann, T.; Iinuma, Y.; Jang, M.; Jenkin, M. E.; Jimenez, J. L.; Kiendler-Scharr, A.; Maenhaut, W.; McFiggans, G.; Mentel, Th. F.; Monod, A.; Prévôt, A. S. H.; Seinfeld, J. H.; Surratt, J. D.; Szmigielski, R.; Wildt, J.

    2009-07-01

    Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

  4. Relationship between oxidation level and optical properties of secondary organic aerosol.

    PubMed

    Lambe, Andrew T; Cappa, Christopher D; Massoli, Paola; Onasch, Timothy B; Forestieri, Sara D; Martin, Alexander T; Cummings, Molly J; Croasdale, David R; Brune, William H; Worsnop, Douglas R; Davidovits, Paul

    2013-06-18

    Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo[5.2.1.0(2,6)]decane), biomass burning (guaiacol), and biogenic (α-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level. PMID:23701291

  5. Effect of SO2 and Photolysis on Photooxidized Diesel Fuel Secondary Organic Aerosol Composition

    NASA Astrophysics Data System (ADS)

    MacMillan, A. C.; Blair, S. L.; Lin, P.; Laskin, A.; Laskin, J.; Nizkorodov, S.

    2014-12-01

    Diesel fuel (DSL) and sulfur dioxide (SO2) are important precursors to secondary organic aerosol (SOA) formation. DSL is often co-emitted with SO2 and NO2, thus it is important to understand the possible effects of SO2 on DSL SOA composition. Additionally, DSL SOA composition can be affected by photochemical aging processes such as photolysis. In this study, DSL SOA was first prepared under dry, high-NOx conditions with various concentrations of SO2 by photooxidation in a smog chamber. The SOA was then stripped of excess oxidants and gaseous organics with a denuder train and the resulting particles were photolyzed at various photolysis times in a quartz flow tube. The SOA composition, photochemical aging, properties, and mass concentration, before and after direct photolysis in the flow tube, were examined using several techniques. High-resolution mass spectrometry (HR-MS) was performed on DSL SOA samples to investigate the effect of SO2 on molecular level composition. SOA composition as a function of photolysis time was measured with an aerosol mass spectrometer (AMS). HR-MS results show that organosulfates are produced in DSL SOA. Both AMS and HR-MS results show that photolysis also has an effect on composition; though, this is more apparent in the HR-MS results than in the AMS results. In summary, both the presence of SO2 and solar radiation has an effect on DSL SOA composition.

  6. Enhancement in Secondary Organic Aerosol Formation in the Presence of Preexisting Organic Particle.

    PubMed

    Ye, Jianhuai; Gordon, Catherine A; Chan, Arthur W H

    2016-04-01

    Atmospheric models of secondary organic aerosol (SOA) typically assume organic species form a well-mixed phase. As a result, partitioning of semivolatile oxidation products into the particle phase to form SOA is thought to be enhanced by preexisting organic particles. In this work, the physicochemical properties that govern such enhancement in SOA yield were examined. SOA yields from α-pinene ozonolysis were measured in the presence of a variety of organic seeds which were chosen based on polarity and phase state at room temperature. Yield enhancement was only observed with seeds of medium polarities (tetraethylene glycol and citric acid). Solid hexadecanol seed was observed to enhance SOA yields only in chamber experiments with longer mixing time scales, suggesting that the mixing process for SOA and hexadecanol may be kinetically limited at shorter time scales. Our observations indicate that, in addition to kinetic limitations, intermolecular interactions also play a significant role in determining SOA yields. Here we propose for the first time to use the Hansen solubility framework to determine aerosol miscibility and predict SOA yield enhancement. These results highlight that current models may overestimate SOA formation, and parametrization of intermolecular forces is needed for accurate predictions of SOA formation. PMID:26963686

  7. Examining the role of NOx and acidity on organic aerosol formation through predictions of key isoprene aerosol species in the United States

    EPA Science Inventory

    Isoprene is a significant contributor to organic aerosol in the Southeastern United States. Later generation isoprene products, specifically isoprene epoxydiols (IEPOX) and methacryloylperoxynitrate (MPAN), have been identified as SOA precursors. The contribution of each pathway ...

  8. Mass spectral analysis of organic aerosol formed downwind of the Deepwater Horizon oil spill: field studies and laboratory confirmations.

    PubMed

    Bahreini, R; Middlebrook, A M; Brock, C A; de Gouw, J A; McKeen, S A; Williams, L R; Daumit, K E; Lambe, A T; Massoli, P; Canagaratna, M R; Ahmadov, R; Carrasquillo, A J; Cross, E S; Ervens, B; Holloway, J S; Hunter, J F; Onasch, T B; Pollack, I B; Roberts, J M; Ryerson, T B; Warneke, C; Davidovits, P; Worsnop, D R; Kroll, J H

    2012-08-01

    In June 2010, the NOAA WP-3D aircraft conducted two survey flights around the Deepwater Horizon (DWH) oil spill. The Gulf oil spill resulted in an isolated source of secondary organic aerosol (SOA) precursors in a relatively clean environment. Measurements of aerosol composition and volatile organic species (VOCs) indicated formation of SOA from intermediate-volatility organic compounds (IVOCs) downwind of the oil spill (Science2011, 331, doi 10.1126/science.1200320). In an effort to better understand formation of SOA in this environment, we present mass spectral characteristics of SOA in the Gulf and of SOA formed in the laboratory from evaporated light crude oil. Compared to urban primary organic aerosol, high-mass-resolution analysis of the background-subtracted SOA spectra in the Gulf (for short, "Gulf SOA") showed higher contribution of C(x)H(y)O(+) relative to C(x)H(y)(+) fragments at the same nominal mass. In each transect downwind of the DWH spill site, a gradient in the degree of oxidation of the Gulf SOA was observed: more oxidized SOA (oxygen/carbon = O/C ∼0.4) was observed in the area impacted by fresher oil; less oxidized SOA (O/C ∼0.3), with contribution from fragments with a hydrocarbon backbone, was found in a broader region of more-aged surface oil. Furthermore, in the plumes originating from the more-aged oil, contribution of oxygenated fragments to SOA decreased with downwind distance. Despite differences between experimental conditions in the laboratory and the ambient environment, mass spectra of SOA formed from gas-phase oxidation of crude oil by OH radicals in a smog chamber and a flow tube reactor strongly resembled the mass spectra of Gulf SOA (r(2) > 0.94). Processes that led to the observed Gulf SOA characteristics are also likely to occur in polluted regions where VOCs and IVOCs are coemitted. PMID:22788666

  9. Anthropogenic and biogenic organic compounds in summertime fine aerosols (PM2.5) in Beijing, China

    NASA Astrophysics Data System (ADS)

    Yang, Fan; Kawamura, Kimitaka; Chen, Jing; Ho, Kinfai; Lee, Shuncheng; Gao, Yuan; Cui, Long; Wang, Tieguan; Fu, Pingqing

    2016-01-01

    Ambient fine aerosol samples (PM2.5) were collected at an urban site (PKU) in Beijing and its upwind suburban site (Yufa) during the CAREBEIJING-2007 field campaign. Organic molecular compositions of the PM2.5 samples were studied for seven organic compound classes (sugars, lignin/resin acids, hydroxy-/polyacids, aromatic acids, biogenic SOA tracers, fatty acids and phthalates) using capillary GC/MS to better understand the characteristics and sources of organic aerosol pollution in Beijing. More than 60 individual organic species were detected in PM2.5 and were grouped into different compound classes based on their functional groups. Concentrations of total quantified organics at Yufa (469-1410 ng m-3, average 1050 ng m-3) were slightly higher than those at PKU (523-1390 ng m-3, 900 ng m-3). At both sites, phthalates were found as the most abundant compound class. Using a tracer-based method, the contributions of the biogenic secondary organic carbon (SOC) to organic carbon (OC) were 3.1% at PKU and 5.5% at Yufa, among which isoprene-SOC was the dominant contributor. In addition, most of the measured organic compounds were higher at Yufa than those at PKU, indicating a more serious pollution in its upwind region than in urban Beijing.

  10. Morphology of Mixed Primary and Secondary Organic Particles and the Adsorption of Spectator Organic Gases during Aerosol Formation

    SciTech Connect

    Vaden, Timothy D.; Song, Chen; Zaveri, Rahul A.; Imre, D.; Zelenyuk, Alla

    2010-04-13

    Traditional semi-empirical secondary organic aerosol (SOA) models assume that SOA mixes well with primary organic aerosols (POA), which significantly enhances the modeled SOA yields. These models further assume that the organic compounds in the gas phase do no condense on SOA as it forms. These assumptions were challenged through a detailed experimental investigation of the compositions and morphologies of SOA particles formed during ozonolysis of α-pinene in the presence of dioctyl phthalate (DOP) particles and DOP gas phase component using a single particle mass spectrometer. Ultraviolet (UV) laser depth-profiling experiments were used to characterize different types of mixed SOA/DOP particles: those formed by condensation of the oxidized α-pinene products on size-selected DOP particles and by condensation of DOP on size-selected α-pinene SOA particles. The results of these measurements conclusively show that the hydrophilic SOA and hydrophobic DOP do not mix, but instead form distinct phases. An examination of homogeneously-nucleated SOA particles formed in the presence of DOP shows them to be encapsulated by a thin DOP layer. Thus SOA can adsorb gas-phase DOP even though it has an extremely low vapor pressure (1.3×10-7 Torr), which has significant implications for SOA formation and fate in the atmosphere, where numerous organic compounds with various volatilities are present.

  11. SOAs for Scientific Applications: Experiences and Challenges

    PubMed Central

    Krishnan, Sriram; Bhatia, Karan

    2011-01-01

    Over the past several years, with the advent of the Open Grid Services Architecture (OGSA) (19) and the Web Services Resource Framework (WSRF) (25), Service-oriented Architectures (SOA) and Web service technologies have been embraced in the field of scientific and Grid computing. These new principles promise to help make scientific infrastructures simpler to use, more cost effective to implement, and easier to maintain. However, understanding how to leverage these developments to actually design and build a system remains more of an art than a science. In this paper, we present some positions learned through experience that provide guidance in leveraging SOA technologies to build scientific infrastructures. In addition, we present the technical challenges that need to be addressed in building an SOA, and as a case study, we present the SOA that we have designed for the National Biomedical Computation Resource (NBCR) (9) community. We discuss how we have addressed these technical challenges, and present the overall architecture, the individual software toolkits developed, the client interfaces, and the usage scenarios. We hope that our experiences prove to be useful in building similar infrastructures for other scientific applications. PMID:21308003

  12. SOAs for Scientific Applications: Experiences and Challenges.

    PubMed

    Krishnan, Sriram; Bhatia, Karan

    2009-04-01

    Over the past several years, with the advent of the Open Grid Services Architecture (OGSA) (19) and the Web Services Resource Framework (WSRF) (25), Service-oriented Architectures (SOA) and Web service technologies have been embraced in the field of scientific and Grid computing. These new principles promise to help make scientific infrastructures simpler to use, more cost effective to implement, and easier to maintain. However, understanding how to leverage these developments to actually design and build a system remains more of an art than a science. In this paper, we present some positions learned through experience that provide guidance in leveraging SOA technologies to build scientific infrastructures. In addition, we present the technical challenges that need to be addressed in building an SOA, and as a case study, we present the SOA that we have designed for the National Biomedical Computation Resource (NBCR) (9) community. We discuss how we have addressed these technical challenges, and present the overall architecture, the individual software toolkits developed, the client interfaces, and the usage scenarios. We hope that our experiences prove to be useful in building similar infrastructures for other scientific applications. PMID:21308003

  13. Optical Properties of Secondary Organic Aerosol from cis-3-Hexenol and cis-3-Hexenyl Acetate: Effect of Chemical Composition, Humidity, and Phase.

    PubMed

    Harvey, Rebecca M; Bateman, Adam P; Jain, Shashank; Li, Yong Jie; Martin, Scot; Petrucci, Giuseppe A

    2016-05-17

    Atmospheric aerosols play an important role in Earth's radiative balance directly, by scattering and absorbing radiation, and indirectly, by acting as cloud condensation nuclei (CCN). Atmospheric aerosol is dominated by secondary organic aerosol (SOA) formed by the oxidation of biogenic volatile organic compounds (BVOCs). Green leaf volatiles (GLVs) are a class of BVOCs that contribute to SOA, yet their role in the Earth's radiative budget is poorly understood. In this work we measured the scattering efficiency (at 450, 525, and 635 nm), absorption efficiency (between 190 and 900 nm), particle phase, bulk chemical properties (O:C, H:C), and molecular-level composition of SOA formed from the ozonolysis of two GLVs: cis-3-hexenol (HXL) and cis-3-hexenyl acetate (CHA). Both HXL and CHA produced SOA that was weakly absorbing, yet CHA-SOA was a more efficient absorber than HXL-SOA. The scatter efficiency of SOA from both systems was wavelength-dependent, with the stronger dependence exhibited by HXL-SOA, likely due to differences in particle size. HXL-SOA formed under both dry (10% RH) and wet (70% RH) conditions had the same bulk chemical properties (O:C), yet significantly different optical properties, which was attributed to differences in molecular-level composition. We have found that SOA derived from green leaf volatiles has the potential to affect the Earth's radiative budget, and also that bulk chemical properties can be insufficient to predict SOA optical properties. PMID:27074496

  14. High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization

    NASA Astrophysics Data System (ADS)

    Kundu, S.; Fisseha, R.; Putman, A. L.; Rahn, T. A.; Mazzoleni, L. R.

    2012-06-01

    The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA) was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH2, O and CH2O homologous series. The CH2 and O homologous series of the low molecular weight (MW) SOA (m/z < 300) are explained with a combination of functionalization and fragmentation of radical intermediates and reactive uptake of gas-phase carbonyls. They include isomerization and elimination reactions of Criegee radicals, reactions between alkyl peroxy radicals, and scission of alkoxy radicals resulting from the Criegee radicals. The presence of compounds with 10-15 carbon atoms in the first group (e.g. C11H18O6) provides evidence for SOA formation by the reactive uptake of gas-phase carbonyls during limonene ozonolysis. The high MW compounds (m/z > 300) were found to constitute a significant number fraction of the identified SOA components. The formation of high MW compounds was evaluated by molecular formula trends, fragmentation analysis of select high MW compounds and a comprehensive reaction matrix including the identified low MW SOA, hydroperoxides and Criegee radicals as building blocks. Although the formation of high MW SOA may occur via a variety of radical and non-radical reaction channels, the combined approach indicates a greater importance of the non-condensation reactions over aldol and ester condensation reaction channels. Among these hemi-acetal reactions appear to be most dominant followed by hydroperoxide and Criegee reaction channels.

  15. Indoor transient SOA formation from ozone + α-pinene reactions: Impacts of air exchange and initial product concentrations, and comparison to limonene ozonolysis

    NASA Astrophysics Data System (ADS)

    Youssefi, Somayeh; Waring, Michael S.

    2015-07-01

    The ozonolysis of reactive organic gases (ROG), e.g. terpenes, generates secondary organic aerosol (SOA) indoors. The SOA formation strength of such reactions is parameterized by the aerosol mass fraction (AMF), a.k.a. SOA yield, which is the mass ratio of generated SOA to oxidized ROG. AMFs vary in magnitude both among and for individual ROGs. Here, we quantified dynamic SOA formation from the ozonolysis of α-pinene with 'transient AMFs,' which describe SOA formation due to pulse emission of a ROG in an indoor space with air exchange, as is common when consumer products are intermittently used in ventilated buildings. We performed 19 experiments at low, moderate, and high (0.30, 0.52, and 0.94 h-1, respectively) air exchange rates (AER) at varying concentrations of initial reactants. Transient AMFs as a function of peak SOA concentrations ranged from 0.071 to 0.25, and they tended to increase as the AER and product of the initial reactant concentrations increased. Compared to our similar research on limonene ozonolysis (Youssefi and Waring, 2014), for which formation strength was driven by secondary ozone reactions, the AER impact for α-pinene was opposite in direction and weaker, while the initial reactant product impact was in the same direction but stronger for α-pinene than for limonene. Linear fits of AMFs for α-pinene ozonolysis as a function of the AER and initial reactant concentrations are provided so that future indoor models can predict SOA formation strength.

  16. Secondary organic aerosol from biogenic volatile organic compound mixtures

    NASA Astrophysics Data System (ADS)

    Hatfield, Meagan L.; Huff Hartz, Kara E.

    2011-04-01

    The secondary organic aerosol (SOA) yields from the ozonolysis of a Siberian fir needle oil (SFNO), a Canadian fir needle oil (CFNO), and several SOA precursor mixtures containing reactive and non-reactive volatile organic compounds (VOCs) were investigated. The use of precursor mixtures more completely describes the atmosphere where many VOCs exist. The addition of non-reactive VOCs such as bornyl acetate, camphene, and borneol had very little to no effect on SOA yields. The oxidation of VOC mixtures with VOC mass percentages similar to the SFNO produced SOA yields that became more similar to the SOA yield from SFNO as the complexity and concentration of VOCs within the mixture became more similar to overall SFNO composition. The SOA yield produced by the oxidation of CFNO was within the error of the SOA yield produced by the oxidation of SFNO at a similar VOC concentration. The SOA yields from SFNO were modeled using the volatility basis set (VBS), which predicts the SOA yields for a given mass concentration of mixtures containing similar VOCs.

  17. VOC characteristics, emissions and contributions to SOA formation during hazy episodes

    NASA Astrophysics Data System (ADS)

    Sun, Jie; Wu, Fangkun; Hu, Bo; Tang, Guiqian; Zhang, Junke; Wang, Yuesi

    2016-09-01

    Volatile organic compounds (VOC) are important precursors of secondary organic aerosols (SOA). The pollution processes in Beijing were investigated from 18th October to 6th November 2013 to study the characteristics, SOA formation potential and contributing factors of VOC during hazy episodes. The mean concentrations of VOC were 67.4 ± 33.3 μg m-3 on clear days and have 5-7-fold increase in polluted periods. VOC concentrations rapidly increased at a visibility range of 4-5 km with the rate of 25%/km in alkanes, alkenes and halocarbons and the rate of 45%/km in aromatics. Analysis of the mixing layer height (MLH); wind speed and ratios of benzene/toluene (B/T), ethylbenzene/m,p-xylene (E/X), and isopentane/n-pentane (i/n) under different visibility conditions revealed that the MLH and wind speed were the 2 major factors affecting the variability of VOC during clear days and that local emissions and photochemical reactions were main causes of VOC variation on polluted days. Combined with the fractional aerosol coefficient (FAC) method, the SOA formation potentials of alkanes, alkenes and aromatics were 0.3 ± 0.2 μg m-3, 1.1 ± 1.0 μg m-3 and 6.5 ± 6.4 μg m-3, respectively. As the visibility deteriorated, the SOA formation potential increased from 2.1 μg m-3 to 13.2 μg m-3, and the fraction of SOA-forming aromatics rapidly increased from 56.3% to 90.1%. Initial sources were resolved by a positive matrix factorization (PMF) model. Vehicle-related emissions were an important source of VOC at all visibility ranges, accounting for 23%-32%. As visibility declined, emissions from solvents and the chemical industry increased from 13.2% and 6.3% to 34.2% and 23.0%, respectively. Solvents had the greatest SOA formation ability, accounting for 52.5% on average on hazy days, followed by vehicle-related emissions (20.7%).

  18. Characterization of primary and secondary organic aerosols in Melbourne airshed: The influence of biogenic emissions, wood smoke and bushfires

    NASA Astrophysics Data System (ADS)

    Iinuma, Yoshiteru; Keywood, Melita; Herrmann, Hartmut

    2016-04-01

    Detailed chemical characterisation was performed for wintertime and summertime PM10 samples collected in Melbourne, Australia. The samples were analysed for marker compounds of biomass burning and biogenic secondary organic aerosol (SOA). The chemical analysis showed that the site was significantly influenced by the emissions from wintertime domestic wood combustion and summertime bushfires. Monosaccharide anhydrides were major primary biomass burning marker compounds found in the samples with the average concentrations of 439, 191, 57 and 3630 ngm-3 for winter 2004, winter 2005, summer 2005 and summer 2006, respectively. The highest concentration was determined during the summer 2006 bushfire season with the concentration of 15,400 ngm-3. Biomass burning originating SOA compounds detected in the samples include substituted nitrophenols, mainly 4-nitrocatechol (Mr 155), methyl-nitrocatechols (Mr 169) and dimethyl-nitrocatechols (Mr 183) with the sum concentrations as high as 115 ngm-3 for the wintertime samples and 770 ngm-3 for the bushfire influenced samples. In addition to this, elevated levels of biogenic SOA marker compounds were determined in the summertime samples influence by bushfire smoke. These marker compounds can be categorised into carboxylic acid marker compounds and heteroatomic organic acids containing nitrogen and sulfur. Carboxylic acid marker compounds can be largely attributed to oxidation products originating from 1,8-cineole, α-pinene and β-pinene that are main constituents of eucalyptus VOC emissions. Among those, diaterpenylic acid, terpenylic acid and daterebic acid were found at elevated levels in the bushfire influenced samples. Heteroatomic monoterpene SOA marker compounds (Mr 295, C10H17NO7S) were detected during both winter and summer periods. Especially high levels of these compounds were determined in the severe bushfire samples from summer 2006. Based on the results obtained from the chemical analysis and a macro tracer method

  19. The Relative Importance of Aqueous-Phase and Gas-Phase Phenol Oxidation as Sources of SOA (Invited)

    NASA Astrophysics Data System (ADS)

    Anastasio, C.; Smith, J.

    2010-12-01

    The oxidation of phenols is a source of secondary organic aerosol (SOA) in the gas phase as well as in aqueous phases (e.g., cloud and fog drops and water-containing aerosol particles). The relative importance of the gas- and aqueous-phase pathways depends largely on three factors: (1) the partitioning of phenols between the gaseous and condensed phases, (2) the rates of reaction in each phase, and (3) the yields of SOA in each phase. Our goal in this work is to determine the relative importance of these two pathways as sources of SOA. Using previously published rate constants, as well as newly determined kinetics and SOA yield data in the aqueous phase, we find that in a cloudy atmosphere both aqueous- and gas-phase sinks are significant for phenols with high vapor pressures (e.g., phenol itself), but that aqueous-phase sinks can dominate for phenols with lower vapor pressures (e.g., phenols with multiple hydroxy or methoxy substituents). In regions with wood combustion (a major source of phenols), our calculations indicate that destruction of phenols within wood smoke particles is very important and that reaction with particulate triplet excited states is a major sink.

  20. Ultraviolet Absorption by Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Madronich, S.; Lee-Taylor, J. M.; Hodzic, A.; Aumont, B.

    2014-12-01

    Secondary organic aerosols (SOA) are typically formed in the atmosphere by the condensation of a myriad of intermediates from the photo-oxidation of volatile organic compounds (VOCs). Many of these partly oxidized molecules have functional groups (chromophores) that absorb at the ultraviolet (UV) wavelengths available in the troposphere (λ ≳ 290 nm). We used the explicit chemical model GECKO-A (Generator of Explicit Chemistry and Kinetics for Organics in the Atmosphere) to estimate UV absorption cross sections for the gaseous and particulate components of SOA from different precursors (biogenic and anthropogenic) and formed in different environments (low and high NOx, day and night). Model predictions are evaluated with laboratory and field measurements of SOA UV optical properties (esp. mass absorption coefficients and single scattering albedo), and implications are presented for surface UV radiation trends, urban actinic flux modification, and SOA lifetimes.

  1. Primary to secondary organic aerosol: evolution of organic emissions from mobile combustion sources

    NASA Astrophysics Data System (ADS)

    Presto, A. A.; Gordon, T. D.; Robinson, A. L.

    2013-09-01

    A series of smog chamber experiments were conducted to investigate the transformation of primary organic aerosol (POA) and formation of secondary organic aerosol (SOA) during the photo-oxidation of dilute gasoline and diesel motor vehicle exhaust. In half of the experiments POA was present in the chamber at the onset of photo-oxidation. In these experiments positive matrix factorization (PMF) was used to determine separate POA and SOA factors from aerosol mass spectrometer data. A two-factor solution, with one POA factor and one SOA factor, was sufficient to describe the organic aerosol in all but one experiment. In the other half of the experiments, POA was not present at the onset of photo-oxidation; these experiments are considered "pure SOA" experiments. The POA mass spectrum was similar to the mass spectra of the hydrocarbon-like organic aerosol factor determined from ambient datasets with one exception, a diesel vehicle equipped with a diesel oxidation catalyst. The SOA in all experiments had a constant composition over the course of photo-oxidation, and did not appear to age with continued oxidation. The SOA mass spectra for the various gasoline and diesel vehicles were similar to each other, but markedly different than ambient oxidized organic aerosol factors. Van Krevelen analysis of the POA and SOA factors for gasoline and diesel experiments reveal slopes of -0.68 and -0.43, respectively. This suggests that the oxidation chemistry in these experiments is a combination of carboxylic acid and alcohol/peroxide formation, consistent with ambient oxidation chemistry. These experiments also provide insight to the mixing behavior of the POA and SOA. Analysis of the time series of the POA factor concentration and a basis-set model both indicate that for all but one of the vehicles tested here, the POA and SOA seem to mix and form a single organic aerosol phase.

  2. Cloud condensation nuclei activity of aliphatic amine secondary aerosol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

  3. Characterizing the Amount and Chemistry of Biogenic SOA Formation from Pine Forest Air Using a Flow Reactor

    NASA Astrophysics Data System (ADS)

    Palm, B. B.; Ortega, A. M.; Campuzano Jost, P.; Day, D. A.; Fry, J.; Zarzana, K. J.; Draper, D. C.; Brown, S. S.; Kaser, L.; Karl, T.; Jud, W.; Hansel, A.; Hodzic, A.; Dube, W. P.; Wagner, N. L.; Brune, W. H.; Jimenez, J. L.

    2013-12-01

    The amount and chemistry of biogenic secondary organic aerosol (SOA) formation was characterized as a function of oxidant exposure using a Potential Aerosol Mass (PAM) oxidative flow reactor, sampling air in a terpene- and MBO-dominated pine forest during the 2011 BEACHON-RoMBAS field campaign at the U.S. Forest Service Manitou Forest Experimental Observatory in the Colorado Rocky Mountains. In the reactor, a chosen oxidant (OH, O3, or NO3) was generated and stepped over a range of values up to 10,000 times ambient levels, accelerating the gas-phase and heterogeneous oxidative aging of volatile organic compounds (VOCs), inorganic gases, and preexisting aerosol. The resulting SOA formation was measured using an Aerodyne HR-ToF-AMS, a TSI SMPS and a PTR-TOF-MS. Oxidative processing in the flow reactor was equivalent to a few hours up to ~20 days of atmospheric aging during the ~4-min reactor residence time. During BEACHON-RoMBAS, OH oxidation led to a net production of up to several μg/m3 of SOA at intermediate exposures (1-10 equivalent days) but resulted in net loss of OA mass (up to ~30%) at higher OH exposures (10-20 equivalent days), demonstrating the competing effects of functionalization/condensation vs. fragmentation/evaporation reactions as OH exposure increased. O3 and NO3 oxidation led to smaller (up to 0.5 μg/m3) SOA production, and loss of SOA mass due to fragmentation reactions was not observed. OH oxidation resulted in f44 vs. f43 and Van Krevelen diagram (H:C vs. O:C) slopes similar to ambient oxidation, suggesting the flow reactor oxidation pathways are similar to those in ambient air. Organic nitrate SOA production was observed from NO3 radical oxidation only. New particle formation was observed from OH oxidation, but not O3 or NO3 oxidation under our experimental conditions. An enhancement of SOA production under the influence of anthropogenic pollution (Denver) was also observed. High-resolution AMS measurements showed that the O:C and H

  4. Volatile and intermediate volatility organic compounds in suburban Paris: variability, origin and importance for SOA formation

    NASA Astrophysics Data System (ADS)

    Ait-Helal, W.; Borbon, A.; Sauvage, S.; de Gouw, J. A.; Colomb, A.; Gros, V.; Freutel, F.; Crippa, M.; Afif, C.; Baltensperger, U.; Beekmann, M.; Doussin, J.-F.; Durand-Jolibois, R.; Fronval, I.; Grand, N.; Leonardis, T.; Lopez, M.; Michoud, V.; Miet, K.; Perrier, S.; Prévôt, A. S. H.; Schneider, J.; Siour, G.; Zapf, P.; Locoge, N.

    2014-10-01

    Measurements of gaseous and particulate organic carbon were performed during the MEGAPOLI experiments, in July 2009 and January-February 2010, at the SIRTA observatory in suburban Paris. Measurements comprise primary and secondary volatile organic compounds (VOCs), of both anthropogenic and biogenic origins, including C12-C16 n-alkanes of intermediate volatility (IVOCs), suspected to be efficient precursors of secondary organic aerosol (SOA). The time series of gaseous carbon are generally consistent with times series of particulate organic carbon at regional scale, and are clearly affected by meteorology and air mass origin. Concentration levels of anthropogenic VOCs in urban and suburban Paris were surprisingly low (2-963 ppt) compared to other megacities worldwide and to rural continental sites. Urban enhancement ratios of anthropogenic VOC pairs agree well between the urban and suburban Paris sites, showing the regional extent of anthropogenic sources of similar composition. Contrary to other primary anthropogenic VOCs (aromatics and alkanes), IVOCs showed lower concentrations in winter (< 5 ppt) compared to summer (13-27 ppt), which cannot be explained by the gas-particle partitioning theory. Higher concentrations of most oxygenated VOCs in winter (18-5984 ppt) suggest their dominant primary anthropogenic origin. The respective role of primary anthropogenic gaseous compounds in regional SOA formation was investigated by estimating the SOA mass concentration expected from the anthropogenic VOCs and IVOCs (I / VOCs) measured at SIRTA. From an integrated approach based on emission ratios and SOA yields, 38 % of the SOA measured at SIRTA is explained by the measured concentrations of I / VOCs, with a 2% contribution by C12-C16 n-alkane IVOCs. From the results of an alternative time-resolved approach, the average IVOC contribution to SOA formation is estimated to be 7%, which is half of the average contribution of the traditional aromatic compounds (15%). Both

  5. Secondary Organic Aerosol formation from isoprene photooxidation during cloud condensation-evaporation cycles

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, L.; Giorio, C.; Siekmann, F.; Pangui, E.; Morales, S. B.; Temime-Roussel, B.; Gratien, A.; Michoud, V.; Cazaunau, M.; DeWitt, H. L.; Tapparo, A.; Monod, A.; Doussin, J.-F.

    2015-07-01

    The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene/NOx/light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are two and four times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of two or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to water soluble volatile organic compounds (VOCs) dissolution in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

  6. Secondary organic aerosol formation from isoprene photooxidation during cloud condensation-evaporation cycles

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, L.; Giorio, C.; Siekmann, F.; Pangui, E.; Morales, S. B.; Temime-Roussel, B.; Gratien, A.; Michoud, V.; Cazaunau, M.; DeWitt, H. L.; Tapparo, A.; Monod, A.; Doussin, J.-F.

    2016-02-01

    The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene / NOx / light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are 2 and 4 times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of 2 or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to the dissolution of water soluble volatile organic compounds (VOCs) in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

  7. Significant Contributions of Isoprene to Summertime Secondary Organic Aerosol in Eastern United States.

    PubMed

    Ying, Qi; Li, Jingyi; Kota, Sri Harsha

    2015-07-01

    A modified SAPRC-11 (S11) photochemical mechanism with more detailed treatment of isoprene oxidation chemistry and additional secondary organic aerosol (SOA) formation through surface-controlled reactive uptake of dicarbonyls, isoprene epoxydiol and methacrylic acid epoxide was incorporated in the Community Multiscale Air Quality Model (CMAQ) to quantitatively determine contributions of isoprene to summertime ambient SOA concentrations in the eastern United States. The modified model utilizes a precursor-origin resolved approach to determine secondary glyoxal and methylglyoxal produced by oxidation of isoprene and other major volatile organic compounds (VOCs). Predicted OC concentrations show good agreement with field measurements without significant bias (MFB ∼ 0.07 and MFE ∼ 0.50), and predicted SOA reproduces observed day-to-day and diurnal variation of Oxygenated Organic Aerosol (OOA) determined by an aerosol mass spectrometer (AMS) at two locations in Houston, Texas. On average, isoprene SOA accounts for 55.5% of total predicted near-surface SOA in the eastern U.S., followed by aromatic compounds (13.2%), sesquiterpenes (13.0%) and monoterpenes (10.9%). Aerosol surface uptake of isoprene-generated glyoxal, methylglyoxal and epoxydiol accounts for approximately 83% of total isoprene SOA or more than 45% of total SOA. A domain wide reduction of NOx emissions by 40% leads to a slight decrease of domain average SOA by 3.6% and isoprene SOA by approximately 2.6%. Although most of the isoprene SOA component concentrations are decreased, SOA from isoprene epoxydiol is increased by ∼16%. PMID:26029963

  8. Secondary organic aerosol formation from fossil fuel sources contribute majority of summertime organic mass at Bakersfield

    EPA Science Inventory

    Secondary organic aerosols (SOA), known to form in the atmosphere from oxidation of volatile organic compounds (VOCs) emitted by anthropogenic and biogenic sources, are a poorly understood but substantial component of atmospheric particles. In this study, we examined the chemic...

  9. A two-dimensional volatility basis set - Part 2: Diagnostics of organic-aerosol evolution

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Kroll, J. H.; Pandis, S. N.; Robinson, A. L.

    2011-09-01

    We discuss the use of a two-dimensional volatility-oxidation space (2-D-VBS) to describe organic-aerosol chemical evolution. The space is built around two coordinates, volatility and the degree of oxidation, both of which can be constrained observationally or specified for known molecules. Earlier work presented the thermodynamics of organics forming the foundation of this 2-D-VBS, allowing us to define the average composition (C, H, and O) of organics, including organic aerosol (OA) based on volatility and oxidation state. Here we discuss how we can analyze experimental data, using the 2-D-VBS to gain fundamental insight into organic-aerosol chemistry. We first present a well-understood "traditional" secondary organic aerosol (SOA) system - SOA from α-pinene + ozone, and then turn to two examples of "non-traditional" SOA formation - SOA from wood smoke and dilute diesel-engine emissions. Finally, we discuss the broader implications of this analysis.

  10. A two-dimensional volatility basis set - Part 2: Diagnostics of organic-aerosol evolution

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Kroll, J. H.; Pandis, S. N.; Robinson, A. L.

    2012-01-01

    We discuss the use of a two-dimensional volatility-oxidation space (2-D-VBS) to describe organic-aerosol chemical evolution. The space is built around two coordinates, volatility and the degree of oxidation, both of which can be constrained observationally or specified for known molecules. Earlier work presented the thermodynamics of organics forming the foundation of this 2-D-VBS, allowing us to define the average composition (C, H, and O) of organics, including organic aerosol (OA) based on volatility and oxidation state. Here we discuss how we can analyze experimental data, using the 2-D-VBS to gain fundamental insight into organic-aerosol chemistry. We first present a well-understood "traditional" secondary organic aerosol (SOA) system - SOA from α-pinene + ozone, and then turn to two examples of "non-traditional" SOA formation - SOA from wood smoke and dilute diesel-engine emissions. Finally, we discuss the broader implications of this analysis.

  11. SOA Formation from the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol and Its Implications for PM2.5

    EPA Science Inventory

    The formation of secondary organic aerosol (SOA) generated by irradiating 2-methyl-3-buten-2-01 (MBO) in the presence and/or absence of NOx H2O2, and/or SO2 was examined. Experiments were conducted. in smog chambers operated either in dyna....

  12. Chemical characterization of biogenic SOA generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

    NASA Astrophysics Data System (ADS)

    Faiola, C. L.; Wen, M.; VanReken, T. M.

    2014-10-01

    The largest global source of secondary organic aerosol in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic VOC profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate, a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. VOCs emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA particle size distribution and chemical composition were measured using a scanning mobility particle sizer (SMPS) and Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS), respectively. The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+) m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, methyl jasmonate, is also presented. Elemental analysis results demonstrated an O:C range of baseline biogenic SOA between 0.3-0.47. The O:C of standard methyl jasmonate SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient datasets collected in forest environments.

  13. Chemical characterization of biogenic SOA generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

    DOE PAGESBeta

    Faiola, C. L.; Wen, M.; VanReken, T. M.

    2014-10-01

    The largest global source of secondary organic aerosol in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic VOC profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate, a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six differentmore » coniferous plant types. VOCs emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA particle size distribution and chemical composition were measured using a scanning mobility particle sizer (SMPS) and Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS), respectively. The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+) m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, methyl jasmonate, is also presented. Elemental analysis results demonstrated an O:C range of baseline biogenic SOA between 0.3–0.47. The O:C of standard methyl jasmonate SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient datasets collected in forest environments.« less

  14. Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

    SciTech Connect

    Matsui, H.; Koike, Makoto; Kondo, Yutaka; Fast, Jerome D.; Takigawa, M.

    2014-09-30

    Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimation of aerosol direct and indirect effects. In this study, we developed an aerosol module, designated Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can represent these parameters explicitly by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 µm to resolve both aerosol size (12 bins) and BC mixing state (10 bins) for a total of 120 bins. The particles with diameters from 1 to 40 nm are resolved using an additional 8 size bins to calculate NPF. The ATRAS module was implemented in the WRF-chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging and SOA processes over East Asia during the spring of 2009. BC absorption enhancement by coating materials was about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement was estimated to be 10 – 20% over northern East Asia and 20 – 35% over southern East Asia. A clear north-south contrast was also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increased CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increased CCN concentrations at lower supersaturations (larger particles) over southern East Asia. Application of ATRAS to East Asia also showed that the impact of each process on each optical and radiative parameter depended strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA

  15. Characterizing the impact of urban emissions on regional aerosol particles; airborne measurements during the MEGAPOLI experiment

    NASA Astrophysics Data System (ADS)

    Freney, E. J.; Sellegri, K.; Canonaco, F.; Colomb, A.; Borbon, A.; Michoud, V.; Doussin, J.-F.; Crumeyrolle, S.; Amarouch, N.; Pichon, J.-M.; Prévôt, A. S. H.; Beekmann, M.; Schwarzenböeck, A.

    2013-09-01

    The MEGAPOLI experiment took place in July 2009. The aim of this campaign was to study the aging and reactions of aerosol and gas-phase emissions in the city of Paris. Three ground-based measurement sites and several mobile platforms including instrument equipped vehicles and the ATR-42 aircraft were involved. We present here the variations in particle- and gas-phase species over the city of Paris using a combination of high-time resolution measurements aboard the ATR-42 aircraft. Particle chemical composition was measured using a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) giving detailed information of the non-refractory submicron aerosol species. The mass concentration of BC, measured by a particle absorption soot photometer (PSAP), was used as a marker to identify the urban pollution plume boundaries. Aerosol mass concentrations and composition were affected by air-mass history, with air masses that spent longest time over land having highest fractions of organic aerosol and higher total mass concentrations. The Paris plume is mainly composed of organic aerosol (OA), black carbon and nitrate aerosol, as well as high concentrations of anthropogenic gas-phase species such as toluene, benzene, and NOx. Using BC and CO as tracers for air-mass dilution, we observe the ratio of ΔOA / ΔBC and ΔOA / ΔCO increase with increasing photochemical age (-log(NOx / NOy). Plotting the equivalent ratios for the Positive Matrix Factorization (PMF) resolved species (LV-OOA, SV-OOA, and HOA) illustrate that the increase in OA is a result of secondary organic aerosol (SOA). Within Paris the changes in the ΔOA / ΔCO are similar to those observed during other studies in Mexico city, Mexico and in New England, USA. Using the measured VOCs species together with recent organic aerosol formation yields we predicted ~ 50% of the measured organics. These airborne measurements during the MEGAPOLI experiment show that urban emissions contribute to the formation of OA

  16. SOA approach to battle command: simulation interoperability

    NASA Astrophysics Data System (ADS)

    Mayott, Gregory; Self, Mid; Miller, Gordon J.; McDonnell, Joseph S.

    2010-04-01

    NVESD is developing a Sensor Data and Management Services (SDMS) Service Oriented Architecture (SOA) that provides an innovative approach to achieve seamless application functionality across simulation and battle command systems. In 2010, CERDEC will conduct a SDMS Battle Command demonstration that will highlight the SDMS SOA capability to couple simulation applications to existing Battle Command systems. The demonstration will leverage RDECOM MATREX simulation tools and TRADOC Maneuver Support Battle Laboratory Virtual Base Defense Operations Center facilities. The battle command systems are those specific to the operation of a base defense operations center in support of force protection missions. The SDMS SOA consists of four components that will be discussed. An Asset Management Service (AMS) will automatically discover the existence, state, and interface definition required to interact with a named asset (sensor or a sensor platform, a process such as level-1 fusion, or an interface to a sensor or other network endpoint). A Streaming Video Service (SVS) will automatically discover the existence, state, and interfaces required to interact with a named video stream, and abstract the consumers of the video stream from the originating device. A Task Manager Service (TMS) will be used to automatically discover the existence of a named mission task, and will interpret, translate and transmit a mission command for the blue force unit(s) described in a mission order. JC3IEDM data objects, and software development kit (SDK), will be utilized as the basic data object definition for implemented web services.

  17. THERMAL PROPERTIES OF SECONDARY ORGANIC AEROSOLS

    EPA Science Inventory

    Volume concentrations of steady-state secondary organic aerosol (SOA) were measured in several hydrocarbon/NOx irradiation experiments. These measurements were used to estimate the thermal behavior of the particles that may be formed in the atmosphere. These laborator...

  18. Aqueous phase processing of secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Liu, Yao; Tritscher, T.; Praplan, A. P.; Decarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.; Monod, A.

    2011-07-01

    The aging of secondary organic aerosol (SOA) by photooxidation in the aqueous phase was experimentally investigated. To simulate multiphase processes, the following experiments were sequentially performed in a smog chamber and in an aqueous phase photoreactor: (1) Gas-phase photooxidation of three different volatile organic compounds (VOC): isoprene, α-pinene, and 1,3,5-trimethylbenzene (TMB) in the presence of NOx, leading to the formation of SOA which was subjected to on-line physical and chemical analysis; (2) particle-to-liquid transfer of water soluble species of SOA using filter sampling and aqueous extraction; (3) aqueous-phase photooxidation of the obtained water extracts; and (4) nebulization of the solutions for a repetition of the on-line characterization. SOA concentrations in the chamber measured with a scanning mobility particle sizer (SMPS) were higher than 200 μg m-3, as the experiments were conducted under high initial concentrations of volatile organic compounds (VOC) and NOx. The aging of SOA through aqueous phase processing was investigated by measuring the physical and chemical properties of the particles online before and after processing using a high resolution time-of-flight aerosol mass spectrometer (AMS) and a hygroscopicity tandem differential mobility analyzer (H-TDMA). It was shown that, after aqueous phase processing, the particles were significantly more hygroscopic, and contained more fragmentation ions at m/z = 44 and less ions at m/z = 43, thus showing a significant impact on SOA aging for the three different precursors. Additionally, the particles were analyzed with a thermal desorption atmospheric pressure ionization aerosol mass spectrometer (TD-API-AMS). Comparing the smog chamber SOA composition and non processed nebulized aqueous extracts with this technique revealed that sampling, extraction and/or nebulization did not significantly impact the chemical composition of SOA formed from isoprene and α-pinene, whereas it

  19. Secondary Organic Aerosol Formation from Glyoxal: Effects of Seed Aerosol on Particle Composition

    NASA Astrophysics Data System (ADS)

    Slowik, Jay; Waxman, Eleanor; Coburn, Sean; Klein, Felix; Koenig, Theodore; Krapf, Manuel; Kumar, Nivedita; Wang, Siyuan; Baltensperger, Urs; Dommen, Josef; Prévôt, Andre; Volkamer, Rainer

    2014-05-01

    Conventional models of secondary organic aerosol (SOA) production neglect aqueous-phase processing mechanisms, thereby excluding potentially important SOA formation pathways. These missing pathways may be an important factor in the inability of current models to fully explain SOA yields and oxidation states. Molecules identified as important precursors to SOA generated through aqueous-phase include glyoxal, which is an oxidation product of numerous organic gases. Glyoxal SOA formation experiments were conducted in the PSI smog chamber as a function of seed composition, relative humidity (RH, 60 to 85%), and the presence/absence of gaseous ammonia, affecting particle acidity. In a typical experiment, the chamber was filled with the selected seed aerosol (NaCl, (NH4)2SO4, NaNO3, or K2SO4), after which glyoxal was generated by the brief (i.e. a few minutes) exposure of acetylene to UV light. The experiment was then allowed to proceed undisturbed for several hours. Each experiment consisted of several UV exposures, followed by a dilution phase at constant RH to investigate the gas/particle partitioning behavior of the generated SOA. Gas-phase glyoxal was monitored by an LED-CE-DOAS system, while the particle composition was measured using online aerosol mass spectrometry (Aerodyne HR-ToF-AMS) and offline analysis of collected filter samples. SOA composition was observed to depend strongly on seed type, with increased imidazole formation evident during experiments with (NH4)2SO¬4 and K2SO4 seeds relative to those with NaCl and NaNO3. Additionally, experiments conducted in the presence of ammonia showed large enhancements in both imidazole content and total SOA yield. Analysis of mass spectral markers indicates reversible uptake of glyoxal but irreversible particle-phase production of the imidazole-containing SOA. Positive matrix factorization (PMF) using the Multilinear Engine (ME-2) was applied to the AMS mass spectral time series to quantify factors related to

  20. Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

    SciTech Connect

    Madronich, Sasha

    2015-12-09

    The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

  1. Simulations of organic aerosol concentrations during springtime in the Guanzhong Basin, China

    NASA Astrophysics Data System (ADS)

    Feng, Tian; Li, Guohui; Cao, Junji; Bei, Naifang; Shen, Zhenxing; Zhou, Weijian; Liu, Suixin; Zhang, Ting; Wang, Yichen; Huang, Ru-jin; Tie, Xuexi; Molina, Luisa T.

    2016-08-01

    The organic aerosol (OA) concentration is simulated in the Guanzhong Basin, China from 23 to 25 April 2013 utilizing the WRF-CHEM model. Two approaches are used to predict OA concentrations: (1) a traditional secondary organic aerosol (SOA) module; (2) a non-traditional SOA module including the volatility basis-set modeling method in which primary organic aerosol (POA) is assumed to be semivolatile and photochemically reactive. Generally, the spatial patterns and temporal variations of the calculated hourly near-surface ozone and fine particle matters agree well with the observations in Xi'an and surrounding areas. The model also yields reasonable distributions of daily PM2.5 and elemental carbon (EC) compared to the filter measurements at 29 sites in the basin. Filter-measured organic carbon (OC) and EC are used to evaluate OA, POA, and SOA using the OC / EC ratio approach. Compared with the traditional SOA module, the non-traditional module significantly improves SOA simulations and explains about 88 % of the observed SOA concentration. Oxidation and partitioning of POA treated as semivolatile constitute the most important pathway for the SOA formation, contributing more than 75 % of the SOA concentrations in the basin. Residential emissions are the dominant anthropogenic OA source, constituting about 50 % of OA concentrations in urban and rural areas and 30 % in the background area. The OA contribution from transportation emissions decreases from 25 % in urban areas to 20 % in the background area, and the industry emission OA contribution is less than 6 %.

  2. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions.

    PubMed

    Gilardoni, Stefania; Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Pietrogrande, Maria Chiara; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-09-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the "brown" carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1-0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4-20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate. PMID:27551086

  3. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

    DOE PAGESBeta

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; George, Katheryn M.; Anastasio, Cort; Laskin, Julia; Dillner, Ann M.; Zhang, Qi

    2016-04-13

    Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as amore » function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to  ∼  2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values

  4. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

    NASA Astrophysics Data System (ADS)

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; George, Katheryn M.; Anastasio, Cort; Laskin, Julia; Dillner, Ann M.; Zhang, Qi

    2016-04-01

    Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ˜ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed

  5. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; George, K. M.; Anastasio, C.; Laskin, J.; Dillner, A. M.; Zhang, Q.

    2015-10-01

    Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday, winter solstice sunlight in northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated open-ring molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures C*) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C* values is observed

  6. Volatility of methylglyoxal cloud SOA formed through OH radical oxidation and droplet evaporation

    NASA Astrophysics Data System (ADS)

    Ortiz-Montalvo, Diana L.; Schwier, Allison N.; Lim, Yong B.; McNeill, V. Faye; Turpin, Barbara J.

    2016-04-01

    The volatility of secondary organic aerosol (SOA) formed through cloud processing (aqueous hydroxyl radical (radOH) oxidation and droplet evaporation) of methylglyoxal (MGly) was studied. Effective vapor pressure and effective enthalpy of vaporization (ΔHvap,eff) were determined using 1) droplets containing MGly and its oxidation products, 2) a Vibrating Orifice Aerosol Generator (VOAG) system, and 3) Temperature Programmed Desorption Aerosol-Chemical Ionization Mass Spectrometry (TPD Aerosol-CIMS). Simulated in-cloud MGly oxidation (for 10-30 min) produces an organic mixture of higher and lower volatility components with an overall effective vapor pressure of (4 ± 7) × 10-7 atm at pH 3. The effective vapor pressure decreases by a factor of 2 with addition of ammonium hydroxide (pH 7). The fraction of organic material remaining in the particle-phase after drying was smaller than for similar experiments with glycolaldehyde and glyoxal SOA. The ΔHvap,eff of pyruvic acid and oxalic acid + methylglyoxal in the mixture (from TPD Aerosol-CIMS) were smaller than the theoretical enthalpies of the pure compounds and smaller than that estimated for the entire precursor/product mix after droplet evaporation. After 10-30 min of aqueous oxidation (one cloud cycle) the majority of the MGly + radOH precursor/product mix (even neutralized) will volatilize during droplet evaporation; neutralization and at least 80 min of oxidation at 10-12 M radOH (or >12 h at 10-14 M) is needed before low volatility ammonium oxalate exceeds pyruvate.

  7. Mass Spectral Observations of Submicron Aerosol Particles and Production of Secondary Organic Aerosol at an Anthropogenically Influenced Site during the Wet Season of GoAmazon2014

    NASA Astrophysics Data System (ADS)

    de Sá, S. S.; Palm, B. B.; Campuzano Jost, P.; Day, D. A.; Hu, W.; Newburn, M. K.; Ferreira De Brito, J.; Artaxo, P.; Shilling, J. E.; Souza, R. A. F. D.; Manzi, A. O.; Alexander, M. L.; Jimenez, J. L.; Martin, S. T.

    2014-12-01

    As part of GoAmazon2014, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed to characterize the composition, size, and spectral markers present in submicron atmospheric aerosol particles at a site downwind of Manaus, Brazil, in the central Amazon basin. The focus was on the influence of biogenic-anthropogenic interactions on the measured aerosol particles, especially as related to the formation of secondary organic aerosol (SOA). Through a combination of meteorology, emissions, and chemistry, the research site was affected by biogenic emissions from the tropical rainforest that were periodically mixed with urban outflow from the Manaus metropolitan area. Results from the first intensive operation period, from 1 February to 31 March 2014, show that for the wet season the PM1 mass concentration had typical values on order of 1 to 2 μg/m3. The organic species were dominant, followed by sulfate. The mass-diameter distribution of the particle population had a prevailing mode between 300 and 400 nm (vacuum aerodynamic diameter, dva), and at times a smaller mode at finer size was also present. Highly oxidized organic material was frequently observed, characterized by a dominant peak at m/z 44. There was a diel trend in the elemental oxygen-to-carbon (O:C) ratio peaking in the afternoon. The analysis of the results aims at delineating the anthropogenic impact on the measurements. Multivariate statistical analysis by positive-matrix factorization (PMF) is applied to the time series of organic particle mass spectra. The factors and their loadings provide information on the relative and time-varying contributions of different sources and processes affecting the organic component of the aerosol particle phase. Relationships between AMS results and measurements from co-located instruments that provide information on anthropogenic and biogenic gas and particle tracers are investigated, toward the goal of improving the understanding of

  8. Using Multi-Isotope Tracer Methods to Understand the Sources of Nitrate in Aerosols, Fog and River Water in Podocarpus National Forest, Ecuador

    NASA Astrophysics Data System (ADS)

    Brothers, L. A.; Dominguez, G.; Fabian, P.; Thiemens, M. H.

    2008-12-01

    sulfate and nitrate concentrations in rain and fog water by standard methods to investigate water and nutrient pathways along with data from satellite and ground based remote sensing, observations and numerical models. We hope to pair this with a multi-isotope tracer method and NOAA Hysplit Back trajectories, and satellite imagery for information about the number of fires burning in the region to help identify sources of the high nitrate deposition.

  9. The remarkable effect of FeSO4 seed aerosols on secondary organic aerosol formation from photooxidation of α-pinene/NOx and toluene/NOx

    NASA Astrophysics Data System (ADS)

    Chu, Biwu; Hao, Jiming; Takekawa, Hideto; Li, Junhua; Wang, Kun; Jiang, Jingkun

    2012-08-01

    To investigate the effects of Fe(II) and Fe(III) ions on secondary organic aerosol (SOA) formation, we conducted a series of photooxidation experiments with α-pinene and toluene in the presence of nitric oxides (NOx) with/without FeSO4 or Fe2(SO4)3 seed aerosols. The FeSO4 seed aerosols suppressed SOA formation, while Fe2(SO4)3 seed aerosols did not display a noticeable effect on SOA formation. We did not observe effects of FeSO4 and Fe2(SO4)3 seed aerosols on gas phase compounds, including ozone, NOx, and hydrocarbons (HCs). The negative effect of Fe(II)-containing seed aerosols on SOA formation due to the reduction of condensable compounds (CCs) generated from hydrocarbon oxidation is discussed. The mean molecular weight of CCs reduced by Fe(II) is tentatively estimated to be larger than 300, indicating a possibility that many of the CCs reduced by Fe(II) are oligomers. Reduction of oligomer precursors may interrupt the oligomerization of other aldehyde products. If Fe(II) regeneration from photoreduction of Fe(III) is considered, the estimated mean molecular weight of the CCs reduced would be smaller. However, the negligible effect of Fe(III)-containing seed aerosols on SOA formation indicates that Fe(III) photoreduction is negligible in our experiments.

  10. Secondary Aerosol Formation from Oxidation of Aromatics Hydrocarbons by Cl atoms

    NASA Astrophysics Data System (ADS)

    Cai, X.; Griffin, R.

    2006-12-01

    Aerosol Formation From the Oxidation of Aromatic Hydrocarbons by Chlorine Atmospheric secondary organic aerosol (SOA) affects regional and global air quality. The formation mechanisms of SOA via the oxidation of volatile organic compounds by hydroxyl radicals, ozone, and nitrate radicals have been studied intensively during the last decade. Chlorine atoms (Cl) also have been hypothesized to be effective oxidants in marine and industrially influenced areas. Recent work by the authors has indicated that significant amounts of SOA are formed from the oxidation of monoterpenes by Cl. Aromatic hydrocarbons are important for generation of both SOA and ozone in urban areas because of their large emission rates and high reactivity. The goal of this work was to quantify the SOA formation potentials of two representative aromatic hydrocarbons through laboratory chamber experiments in which oxidation was initiated by Cl. The system constructed for this study includes an experimental chamber, a gas chromatograph for quantification of aromatic mixing ratios, a Scanning Mobility Particle Spectrometer to measure SOA size distributions, a zero air generator, and an illuminating system. The model aromatic hydrocarbons chosen for this study are toluene and m-xylene. Aerosol yields are estimated based on measured aerosol volume concentration, the concentration of consumed hydrocarbon, and estimation of wall loss of the newly formed aerosol. Toluene and m-xylene exhibit similar SOA yields from the oxidation initiated by Cl. The toluene SOA yield from Cl-initiated oxidation, however, depends on the ratio between the mixing ratios of the initial chlorine source and toluene in the chamber. For toluene experiments with higher such ratios, SOA yields vary from 0.05 to 0.079 for generated aerosol ranging from 4.2 to12.0 micrograms per cubic meter. In the lower ratio experiments, SOA yields are from 0.033 to 0.064, corresponding to generated aerosol from 3.0 to 11.0 micrograms per cubic

  11. Modeling organic aerosols during MILAGRO: application of the CHIMERE model and importance of biogenic secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Jimenez, J. L.; Madronich, S.; Aiken, A. C.; Bessagnet, B.; Curci, G.; Fast, J.; Lamarque, J. F.; Onasch, T. B.; Roux, G.; Ulbrich, I. M.

    2009-05-01

    The meso-scale chemistry-transport model CHIMERE is used to assess our understanding of major sources and formation processes leading to a fairly large amount of organic aerosols (OA, including primary OA (POA) and secondary OA (SOA)) observed in Mexico City during the MILAGRO field project (March 2006). Chemical analyses of submicron aerosols from aerosol mass spectrometers (AMS) indicate that organic particles found in the Mexico City basin contain a large fraction of oxygenated organic species (OOA) which have strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled here by the one-step oxidation of anthropogenic (i.e. aromatics, alkanes), biogenic (i.e. monoterpenes and isoprene), and biomass-burning SOA precursors and their partitioning into both organic and aqueous phases. The near-surface model evaluation shows that predicted OA correlates reasonably well with measurements during the campaign, however it remains a factor of 2 lower than the measured total OA. Fairly good agreement is found between predicted and observed POA within the city suggesting that anthropogenic and biomass burning emissions are reasonably captured. Consistent with previous studies in Mexico City, large discrepancies are encountered for SOA, with a factor of 2-10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two the sharp increase in SOA concentrations during the late morning at both urban and near-urban locations but the discrepancy increases rapidly later in the day, consistent with previous results, and is especially obvious when the column-integrated SOA mass is considered instead of the surface concentration. The increase in the missing SOA mass in the afternoon coincides with the sharp drop in POA suggesting a tendency of the model to excessively evaporate the freshly formed SOA. Predicted SOA concentrations in our base case

  12. SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data

    NASA Astrophysics Data System (ADS)

    McVay, Renee C.; Zhang, Xuan; Aumont, Bernard; Valorso, Richard; Camredon, Marie; La, Yuyi S.; Wennberg, Paul O.; Seinfeld, John H.

    2016-03-01

    Chemical mechanisms play an important role in simulating the atmospheric chemistry of volatile organic compound oxidation. Comparison of mechanism simulations with laboratory chamber data tests our level of understanding of the prevailing chemistry as well as the dynamic processes occurring in the chamber itself. α-Pinene photooxidation is a well-studied system experimentally, for which detailed chemical mechanisms have been formulated. Here, we present the results of simulating low-NO α-pinene photooxidation experiments conducted in the Caltech chamber with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) under varying concentrations of seed particles and OH levels. Unexpectedly, experiments conducted at low and high OH levels yield the same secondary organic aerosol (SOA) growth, whereas GECKO-A predicts greater SOA growth under high OH levels. SOA formation in the chamber is a result of a competition among the rates of gas-phase oxidation to low-volatility products, wall deposition of these products, and condensation into the aerosol phase. Various processes - such as photolysis of condensed-phase products, particle-phase dimerization, and peroxy radical autoxidation - are explored to rationalize the observations. In order to explain the observed similar SOA growth at different OH levels, we conclude that vapor wall loss in the Caltech chamber is likely of order 10-5 s-1, consistent with previous experimental measurements in that chamber. We find that GECKO-A tends to overpredict the contribution to SOA of later-generation oxidation products under high-OH conditions. Moreover, we propose that autoxidation may alternatively resolve some or all of the measurement-model discrepancy, but this hypothesis cannot be confirmed until more explicit mechanisms are established for α-pinene autoxidation. The key role of the interplay among oxidation rate, product volatility, and vapor-wall deposition in chamber experiments is

  13. Epoxide as a Precursor to Secondary Organic Aerosol Formation from Isoprene Photooxidation in the Presence of Nitrogen Oxides

    EPA Science Inventory

    Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear...

  14. Insights into the primary-secondary and regional-local contributions to organic aerosol and PM 2.5 mass in Pittsburgh, Pennsylvania

    NASA Astrophysics Data System (ADS)

    Subramanian, R.; Donahue, Neil M.; Bernardo-Bricker, Anna; Rogge, Wolfgang F.; Robinson, Allen L.

    This paper presents chemical mass balance (CMB) analysis of organic molecular marker data to investigate the sources of organic aerosol and PM 2.5 mass in Pittsburgh, Pennsylvania. The model accounts for emissions from eight primary source classes, including major anthropogenic sources such as motor vehicles, cooking, and biomass combustion as well as some primary biogenic emissions (leaf abrasion products). We consider uncertainty associated with selection of source profiles, selection of fitting species, sampling artifacts, photochemical aging, and unknown sources. In the context of the overall organic carbon (OC) mass balance, the contributions of diesel, wood-smoke, vegetative detritus, road dust, and coke-oven emissions are all small and well constrained; however, estimates for the contributions of gasoline-vehicle and cooking emissions can vary by an order of magnitude. A best-estimate solution is presented that represents the vast majority of our CMB results; it indicates that primary OC only contributes 27±8% and 50±14% (average±standard deviation of daily estimates) of the ambient OC in the summer and winter, respectively. Approximately two-thirds of the primary OC is transported into Pittsburgh as part of the regional air mass. The ambient OC that is not apportioned by the CMB model is well correlated with secondary organic aerosol (SOA) estimates based on the EC-tracer method and ambient concentrations of organic species associated with SOA. Therefore, SOA appears to be the major component of OC, not only in summer, but potentially in all seasons. Primary OC dominates the OC mass balance on a small number of nonsummer days with high OC concentrations; these events are associated with specific meteorological conditions such as local inversions. Primary particulate emissions only contribute a small fraction of the ambient fine-particle mass, especially in the summer.

  15. Research and design of logistical information system based on SOA

    NASA Astrophysics Data System (ADS)

    Zhang, Bo

    2013-03-01

    Through the study on the existing logistics information systems and SOA technology, based on the current situation of enterprise logistics management and business features, this paper puts forward a SOA-based logistics system design program. This program is made in the WCF framework, with the combination of SOA and the actual characteristics of logistics enterprises, is simple to realize, easy to operate, and has strong expansion characteristic, therefore has high practical value.

  16. Modeling Gas-phase Glyoxal and Associated Secondary Organic Aerosol Formation in a Megacity using WRF/Chem

    NASA Astrophysics Data System (ADS)

    Wang, K.; Hodzic, A.; Barth, M. C.; Jimenez, J. L.; Volkamer, R.; Ervens, B.; Zhang, Y.

    2011-12-01

    Organic aerosol (OA) as one of a major fine particulate matter in the atmosphere plays an important role in air pollution, human health, and climate forcing. OA is composed of directly emitted primary organic aerosol and chemically produced secondary organic aerosols (SOA). Despite much recent progress in understanding SOA formation, current air quality models cannot explain the magnitude and growth of atmospheric SOA, due to high uncertainties in sources, properties, and chemical reactions of precursors and formation pathways of SOA. Recent laboratory and modeling studies showed that glyoxal may serve as an important SOA precursor in the condensed solution of inorganic or organic aerosol particles (e.g., ammonium sulfate, fulvic acid, and amino acids). In this study, the Weather Research and Forecasting model with chemistry (WRF/Chem) is modified to account for the latest observed gas-phase yields of glyoxal from various volatile organic compounds (VOCs) and the associated SOA formation in the aqueous aerosol phase. The SOA formation in the aqueous aerosol phase is implemented using two approaches. In the first approach, two simplified parameterizations are used to represent the lumped particle-phase chemical processes under dark conditions and photochemical surface uptake. In the second approach, more detailed kinetic glyoxal reactions such as reversible glyoxal uptake, dimer formation of glyoxal, and oligomerization are treated and resolved explicitly. The updated WRF/Chem is assessed over the Mexico City and the surrounding region during March 2006 using the MILAGRO campaign data. Various observations such as organic matter from Aerodyne Aerosol Mass Spectrometer and VOCs from Proton-transfer Ion Trap Mass Spectrometry were compared. The preliminary results showed that the addition of the SOA formation from glyoxal in aqueous particles brings SOA predictions into a better agreement with field observations, in particular in presence of high relative humidity

  17. Slow aging in Secondary Organic Aerosol observed by Liquid Chromatography coupled with High-Resolution Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Bones, D. L.; Bateman, A. P.; Nguyen, T. B.; Laskin, J.; Laskin, A.; Nizkorodov, S.

    2009-12-01

    This study investigated long term changes in the chemical composition of model biogenic secondary organic aerosol (SOA) prepared via ozonolysis of the terpene limonene. This SOA has been observed to turn brown when exposed to NH4+. Our hypothesis is that the chromophoric compounds responsible for this color change are suspected to be imidazole-like or pyridinium-like compounds. These compounds are only present in small relative amounts, hence standard mass spectrometry is insufficient to unambiguously detect these compounds. However, a combination of HPLC and high resolution electrosp