Sample records for secondary inorganic aerosols

  1. Investigating the annual behaviour of submicron secondary inorganic and organic aerosols in London

    NASA Astrophysics Data System (ADS)

    Young, D. E.; Allan, J. D.; Williams, P. I.; Green, D. C.; Flynn, M. J.; Harrison, R. M.; Yin, J.; Gallagher, M. W.; Coe, H.

    2014-07-01

    For the first time, the behaviour of non-refractory inorganic and organic submicron particulate through an entire annual cycle is investigated using measurements from an Aerodyne compact time-of-flight aerosol mass spectrometer (cToF-AMS) located at a UK urban background site in North Kensington, London. We show secondary aerosols account for a significant fraction of the submicron aerosol burden and that high concentration events are governed by different factors depending on season. Furthermore, we demonstrate that on an annual basis there is no variability in the extent of secondary organic aerosol (SOA) oxidation, as defined by the oxygen content, irrespective of amount. This result is surprising given the changes in precursor emissions and contributions as well as photochemical activity throughout the year; however it may make the characterisation of SOA in urban environments more straightforward than previously supposed. Organic species, nitrate, sulphate, ammonium, and chloride were measured during 2012 with average concentrations (±one standard deviation) of 4.32 (±4.42), 2.74 (±5.00), 1.39 (±1.34), 1.30 (±1.52) and 0.15 (±0.24) ?g m-3, contributing 43, 28, 14, 13 and 2% to the total submicron mass, respectively. Components of the organic aerosol fraction are determined using positive matrix factorisation (PMF) where five factors are identified and attributed as hydrocarbon-like OA (HOA), cooking OA (COA), solid fuel OA (SFOA), type 1 oxygenated OA (OOA1), and type 2 oxygenated OA (OOA2). OOA1 and OOA2 represent more and less oxygenated OA with average concentrations of 1.27 (±1.49) and 0.14 (±0.29) ?g m-3, respectively, where OOA1 dominates the SOA fraction (90%). Diurnal, monthly, and seasonal trends are observed in all organic and inorganic species, due to meteorological conditions, specific nature of the aerosols, and availability of precursors. Regional and transboundary pollution as well as other individual pollution events influence London's total submicron aerosol burden. High concentrations of non-refractory submicron aerosols in London are governed by particulate emissions in winter, especially nitrate and SFOA, whereas SOA formation drives the high concentrations during the summer. The findings from this work could have significant implications for modelling of urban air pollution as well as for the effects of atmospheric aerosols on health and climate.

  2. Investigating the annual behaviour of submicron secondary inorganic and organic aerosols in London

    NASA Astrophysics Data System (ADS)

    Young, D. E.; Allan, J. D.; Williams, P. I.; Green, D. C.; Flynn, M. J.; Harrison, R. M.; Yin, J.; Gallagher, M. W.; Coe, H.

    2015-06-01

    For the first time, the behaviour of non-refractory inorganic and organic submicron particulate through an entire annual cycle is investigated using measurements from an Aerodyne compact time-of-flight aerosol mass spectrometer (cToF-AMS) located at a UK urban background site in North Kensington, London. We show that secondary aerosols account for a significant fraction of the submicron aerosol burden and that high concentration events are governed by different factors depending on season. Furthermore, we demonstrate that on an annual basis there is no variability in the extent of secondary organic aerosol (SOA) oxidation, as defined by the oxygen content, irrespective of amount. This result is surprising given the changes in precursor emissions and contributions as well as photochemical activity throughout the year; however it may make the characterisation of SOA in urban environments more straightforward than previously supposed. Organic species, nitrate, sulphate, ammonium, and chloride were measured during 2012 with average concentrations (±1 standard deviation) of 4.32 (±4.42), 2.74 (±5.00), 1.39 (±1.34), 1.30 (±1.52), and 0.15 (±0.24) ?g m-3, contributing 44, 28, 14, 13, and 2 % to the total non-refractory submicron mass (NR-PM1) respectively. Components of the organic aerosol fraction are determined using positive matrix factorisation (PMF), in which five factors are identified and attributed as hydrocarbon-like OA (HOA), cooking OA (COA), solid fuel OA (SFOA), type 1 oxygenated OA (OOA1), and type 2 oxygenated OA (OOA2). OOA1 and OOA2 represent more and less oxygenated OA with average concentrations of 1.27 (±1.49) and 0.14 (±0.29) ?g m-3 respectively, where OOA1 dominates the SOA fraction (90%). Diurnal, monthly, and seasonal trends are observed in all organic and inorganic species due to meteorological conditions, specific nature of the aerosols, and availability of precursors. Regional and transboundary pollution as well as other individual pollution events influence London's total submicron aerosol burden. High concentrations of non-refractory submicron aerosols in London are governed by particulate emissions in winter, especially nitrate and SFOA, whereas SOA formation drives the high concentrations during the summer. The findings from this work could have significant implications for modelling of urban air pollution as well as for the effects of atmospheric aerosols on health and climate.

  3. Secondary inorganic aerosol formation and its shortwave direct radiative forcing in China

    NASA Astrophysics Data System (ADS)

    Huang, Xin

    2015-04-01

    Secondary inorganic aerosol (SIA), including sulfate, nitrate and ammonium, is an important part of fine particle. SIA plays a significant role in shortwave radiation transfer. Numerical simulation is usually used to study SIA formation and its climate effect. In this work, we used the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) to study SIA formation and its direct radiative forcing (DRF) over China. SO2 oxidation pathways related to mineral aerosol, including transition metal-catalyzed oxidation in aqueous phase and heterogeneous reactions, play an important role in sulfate production, but they are not well treated in current atmospheric models. In this work, we improved the WRF-Chem model by simulating the enhancement role of mineral aerosol in sulfate production. Firstly, we estimated mineral cations based on local measurements in order to well represent aqueous phase acidity. Secondly, we scaled the transition metal concentration to the mineral aerosol levels according to the existing observations and improved transition metal-catalyzed oxidation calculation. Lastly, heterogeneous reactions of acid gases on the surface of mineral aerosol were included in this simulation. Accuracy in the prediction of sulfate by the model was significantly improved and we concluded that mineral aerosol can facilitate SO2 oxidation and subsequent sulfate formation. It was demonstrated that, over China, mineral aerosol was responsible for 21.8% of annual mean sulfate concentration. The enhanced aqueous oxidation was more significant compared to the heterogeneous reactions. In winter, mineral aerosol was responsible for 39.6% of sulfate production. In summer, gaseous oxidation and aqueous oxidation of SO2 by hydrogen peroxide and ozone were the dominant pathways of sulfate formation. Mineral aerosol only contributed 11.9% to the total sulfate production. The increase in annual mean sulfate concentration due to mineral aerosol could reach up to over 6 ?g/m3 in northern China, middle and lower reaches of the Yangtze River and the Sichuan Basin. We integrated the updated ammonia emission inventory and improved model to simulate SIA formation and its DRF over China in 2006. At the top of the atmosphere (TOA), the annual mean DRF of SIA was -2.5 W/m2, in which sulfate, nitrate and ammonium contributed -1.5 W/m2, -0.4 W/m2 and -0.6 W/m2 respectively. At the surface, the annual mean DRF of sulfate, nitrate and ammonium were -2.1 W/m2, -0.5 W/m2 and -0.8 W/m2 respectively. In the atmosphere, the annual mean DRF of sulfate, nitrate and ammonium were +0.6 W/m2, +0.1 W/m2 and +0.2 W/m2 respectively. The DRF of SIA at TOA displayed a distinct seasonal variation. The national mean DRF reached its maximum of -3.4 W/m2 in summer. There were several reasons for the summer maximum. Firstly, enhanced atmospheric oxidizing capacity and increased ammonia emission in summer accelerated the formation of sulfate and ammonium. Secondly, high humidity favored the hygroscopic growth of SIA in summer. Lastly, shortwave radiation flux at the TOA peaked in summer. On the contrary, the hygroscopic growth of SIA was limited in winter. Simultaneously, the shortwave radiation flux decreased to the minimum in winter. Consequently, the national mean DRF reached its minimum of -1.7 W/m2 in winter. SIA could play an important part in climate change by offsetting BC's radiative heating effect in China.

  4. Dynamic model evaluation for secondary inorganic aerosol and its precursors over Europe between 1990 and 2009

    NASA Astrophysics Data System (ADS)

    Banzhaf, S.; Schaap, M.; Kranenburg, R.; Manders, A. M. M.; Segers, A. J.; Visschedijk, A. J. H.; Denier van der Gon, H. A. C.; Kuenen, J. J. P.; van Meijgaard, E.; van Ulft, L. H.; Cofala, J.; Builtjes, P. J. H.

    2015-04-01

    In this study we present a dynamic model evaluation of chemistry transport model LOTOS-EUROS (LOng Term Ozone Simulation - EURopean Operational Smog) to analyse the ability of the model to reproduce observed non-linear responses to emission changes and interannual variability of secondary inorganic aerosol (SIA) and its precursors over Europe from 1990 to 2009. The 20 year simulation was performed using a consistent set of meteorological data provided by RACMO2 (Regional Atmospheric Climate MOdel). Observations at European rural background sites have been used as a reference for the model evaluation. To ensure the consistency of the used observational data, stringent selection criteria were applied, including a comprehensive visual screening to remove suspicious data from the analysis. The LOTOS-EUROS model was able to capture a large part of the seasonal and interannual variability of SIA and its precursors' concentrations. The dynamic evaluation has shown that the model is able to simulate the declining trends observed for all considered sulfur and nitrogen components following the implementation of emission abatement strategies for SIA precursors over Europe. Both the observations and the model show the largest part of the decline in the 1990s, while smaller concentration changes and an increasing number of non-significant trends are observed and modelled between 2000 and 2009. Furthermore, the results confirm former studies showing that the observed trends in sulfate and total nitrate concentrations from 1990 to 2009 are lower than the trends in precursor emissions and precursor concentrations. The model captured well these non-linear responses to the emission changes. Using the LOTOS-EUROS source apportionment module, trends in the formation efficiency of SIA have been quantified for four European regions. The exercise has revealed a 20-50% more efficient sulfate formation in 2009 compared to 1990 and an up to 20% more efficient nitrate formation per unit nitrogen oxide emission, which added to the explanation of the non-linear responses. However, we have also identified some weaknesses in the model and the input data. LOTOS-EUROS underestimates the observed nitrogen dioxide concentrations throughout the whole time period, while it overestimates the observed nitrogen dioxide concentration trends. Moreover, model results suggest that the emission information of the early 1990s used in this study needs to be improved concerning magnitude and spatial distribution.

  5. Ionic composition of PM2.5 at urban sites of northern Greece: secondary inorganic aerosol formation.

    PubMed

    Voutsa, D; Samara, C; Manoli, E; Lazarou, D; Tzoumaka, P

    2014-04-01

    This study investigates the water-soluble ionic constituents (Na(+), K(+), NH4 (+), Ca(2+), Mg(2+), Cl(-), NO3 (-), SO4 (2-)) associated to PM2.5 particle fraction at two urban sites in the city of Thessaloniki, northern Greece, an urban traffic site (UT) and urban background site (UB). Ionic constituents represent a significant fraction of PM2.5 mass (29.6 at UT and 41.5 % at UB). The contribution of marine aerosol was low (<1.5 %). Secondary inorganic aerosols (SIA) represent a significant fraction of PM2.5 mass contributing to 26.9 ± 12.4 % and 39.2 ± 13.2 % at UT and UB sites, respectively. Nitrate and sulfate are fully neutralized by ammonium under the existing conditions. The ionic constituents were evaluated in relation to their spatial and temporal variation, their gaseous precursors, meteorological conditions, local and long-range transport. PMID:24363054

  6. 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 ...

  7. CCN activity of aliphatic amine secondary aerosol

    NASA Astrophysics Data System (ADS)

    Tang, X.; Price, D.; Praske, E.; Vu, D.; Purvis-Roberts, K.; Silva, P. J.; Cocker, D. R., III; Asa-Awuku, A.

    2014-01-01

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, ? ? 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3), contains less volatile compounds than the primary aliphatic amine (BA) aerosol. TMA + N2O5 form semi-volatile organics in low RH conditions that have ? ~ 0.20, indicative of slightly soluble organic material. As RH increases, several inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. Higher CCN activity (? > 0.3) was also observed for humid BA+N2O5 aerosols compared with dry aerosol (? ~ 0.2), as a result of the formation of inorganic salts such as NH4NO3 and butylamine nitrate (C4H11N · HNO3). Compared with TMA, BA+N2O5 reactions produce more volatile aerosols. The BA+N2O5 aerosol products under humid experiments were found to be very sensitive to the temperature within the stream-wise continuous flow thermal gradient CCN counter. The CCN counter, when set above a 21 °C temperature difference, evaporates BA+N2O5 aerosol formed at RH ? 30%; ? ranges from 0.4 to 0.7 and is dependent on the instrument supersaturation (ss) settings. The aerosol behaves non-ideally, hence simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems ? ranges from 0.2 < ? < 0.7. This work indicates that aerosols formed via nighttime reactions with amines are likely to produce hygroscopic and volatile aerosol whereas photochemical reactions with OH produce secondary organic aerosol of lower CCN activity. Thermal gradient CCN counters measurement will impact the observed CCN activity of volatile aerosol formed via a nitric acid pathway. The contributions of semi-volatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems.

  8. Secondary Inorganic Soluble Aerosol in Hong Kong: Continuous Measurements, Formation Mechanism Discussion and Improvement of an Observation-Based Model to Study Control Strategies

    NASA Astrophysics Data System (ADS)

    Xue, Jian

    Work in this thesis focuses on half-hourly or hourly measurements of PM2.5 secondary inorganic aerosols (SIA) in two locations in Hong Kong (HK) using a continuous system, PILS (Particle-into-Liquid System) coupled to two ion chromatographs. The high-resolution data sets allow the examination of SIA temporal dynamics in the scale of hours that the filter-based approach is incapable of providing. (1) Impacts of local emissions, regional transports and their interactions on chemical composition and concentrations of PM2.5 SIA and other ionic species were investigated at the Hong Kong University of Science and Technology (HKUST), a receptor site, under three synoptic conditions. (2) Chemical compositions and size characteristics of ionic species were investigated at Tung Chung, a new town area located in the Southwest part of HK. The sampling period was from 17 to 26 December 2009, covering both normal conditions and an aerosol episode. The three major secondary inorganic ions, SO42, NH4+ and NO 3-, accounted for 47 +/- 6% of PM2.5 mass. Further examination of size characteristics of NO3 - shows that fine mode NO3- is more likely to occur in environments when the fine particles are less acidic and the sea-salt aerosol contributions are low. (3) The ionic chemical composition of PM2.5 and meteorological parameters (e.g., temperature, RH) obtained at the HKUST site under all three different synoptic conditions are input into Aerosol Inorganic Model (AIM-III) for estimation of in situ pH through calculation of H+ amount and aerosol liquid water content (LWC). The second part of this thesis work is to improve an observation-based model (OBAMAP) for SIA, which was first developed by Dr. Zibing Yuan (2006) to evaluate the sensitivity of formation of nitrate ad sulfate to changes in the emissions of their precursors (i.e., NOx, SO2, and VOCs). The improvement work includes incorporating updated chemical mechanisms, thermodynamic equilibrium for gas-aerosol phase apportionment and size distribution of SIA. The new OBM for SIA is applied to hourly gaseous and particulate composition data measured during a wintertime pollution episode encountered in Tung Chung for probing effectiveness of different precursor control strategies. The OBM is demonstrated to provide a relatively simple and cost-effective tool for analyzing the increasing database of high time resolution measurements of VOCs and major aerosol ionic species. In this thesis, we propose a new production regime of SO4 2- in which oxidation of S(IV) is dominated by NO 2 and O3 in the aqueous phase. Simulated with a simplified version of OBAMAP, it is shown elevation of NOx favors productions of SO42- in this regime, especially under high-SO 2 conditions. We then study the importance of NO2-derived and O3-derived SO42- during haze episodes in PRD and during winter at urban/suburban locations in PRD. Our findings reveal these two pathways account for >70% of SO42- productions. Since production of NO2-derived SO4 2- is independent on solar actinic fluxes while production by other pathways is, NO2-derived SO42- plays a more important role under low solar actinic fluxes conditions, even during the night time. In addition, it is noted that high levels of NO2-derived SO42- can only be expected under high-SO2 conditions (like in PRD) because level of atmospheric SO2 is the limiting parameter. (Abstract shortened by UMI.)

  9. Using hourly measurements to explore the role of secondary inorganic aerosol in PM2.5 during haze and fog in Hangzhou, China

    NASA Astrophysics Data System (ADS)

    Jansen, Roeland Cornelis; Shi, Yang; Chen, Jianmin; Hu, YunJie; Xu, Chang; Hong, Shengmao; Li, Jiao; Zhang, Min

    2014-11-01

    This paper explores the role of the secondary inorganic aerosol (SIA) species ammonium, NH{4/+}, nitrate, NO{3/-}, and sulfate, SO{4/2-}, during haze and fog events using hourly mass concentrations of PM2.5 measured at a suburban site in Hangzhou, China. A total of 546 samples were collected between 1 April and 8 May 2012. The samples were analyzed and classified as clear, haze or fog depending on visibility and relative humidity (RH). The contribution of SIA species to PM2.5 mass increased to ˜50% during haze and fog. The mass contribution of nitrate to PM2.5 increased from 11% during clear to 20% during haze episodes. Nitrate mass exceeded sulfate mass during haze, while near equal concentrations were observed during fog episodes. The role of RH on the correlation between concentrations of SIA and visibility was examined, with optimal correlation at 60%-70% RH. The total acidity during clear, haze and fog periods was 42.38, 48.38 and 45.51 nmol m-3, respectively, indicating that sulfate, nitrate and chloride were not neutralized by ammonium during any period. The nitrate to sulfate molar ratio, as a function of the ammonium to sulfate molar ratio, indicated that nitrate formation during fog started at a higher ammonium to sulfate molar ratio compared to clear and haze periods. During haze and fog, the nitrate oxidation ratio increased by a factor of 1.6-1.7, while the sulfur oxidation ratio increased by a factor of 1.2-1.5, indicating that both gaseous NO2 and SO2 were involved in the reduced visibility.

  10. 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...

  11. Cloud condensation nuclei (CCN) activity of aliphatic amine secondary aerosol

    NASA Astrophysics Data System (ADS)

    Tang, X.; Price, D.; Praske, E.; Vu, D. N.; Purvis-Roberts, K.; Silva, P. J.; Cocker, D. R., III; Asa-Awuku, A.

    2014-06-01

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g., hydroxyl radical and nitrate radical). The particle can contain both secondary organic aerosol (SOA) and inorganic salts. The ratio of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, ?, ? 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3) contains less volatile compounds than the primary aliphatic amine (BA) aerosol. As relative humidity (RH) increases, inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. The humid BA + N2O5 aerosol products were found to be very sensitive to the temperature at which the measurements were made within the streamwise continuous-flow thermal gradient CCN counter; ? ranges from 0.4 to 0.7 dependent on the instrument supersaturation (ss) settings. The variance of the measured aerosol ? values indicates that simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems' ? ranges within 0.2 < ? < 0.7. This work indicates that aerosols formed via nighttime reactions with amines are likely to produce hygroscopic and volatile aerosol, whereas photochemical reactions with OH produce secondary organic aerosol of lower CCN activity. The contributions of semivolatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems.

  12. Effect of acidic seed on biogenic secondary organic aerosol growth

    NASA Astrophysics Data System (ADS)

    Czoschke, Nadine M.; Jang, Myoseon; Kamens, Richard M.

    Secondary organic aerosol (SOA) growth in the presence of acid aerosols was studied in twin 500 l Teflon bags and in a 4 m flow reactor. In Teflon bags, isoprene, acrolein and ?-pinene were all made to react individually with ozone and exposed to either acid or non-acid inorganic seed aerosols to determine the effect of acid-catalyzed heterogeneous reactions on SOA growth. ?-Pinene and ozone were made to react in a flow reactor to assess the immediate effect of mixing an acid aerosol with SOA at high and low relative humidity levels. In all cases, exposure to acid seed aerosol increased the amount of SOA mass produced. Fourier transform infrared spectra of the SOA in acid systems confirmed the transformation of carbonyl functional groups through acid-catalyzed heterogeneous reactions when SOAs formed in acidic environments or were exposed to acidic aerosols. Organic products initially produced from ozonation in the gas phase partition onto the inorganic seed aerosol and react heterogeneously with an acid catalyst forming low vapor pressure products. These acid-catalyzed heterogeneous reactions are implicated in generating the increased SOA mass observed in acidic aerosol systems as they transform predominantly gas phase compounds of high volatility into low vapor pressure predominantly particle phase products.

  13. Secondary Organic Aerosol Formation: New Insights

    Microsoft Academic Search

    R. M. Kamens; M. Jang; S. Lee; N. Czoschke; S. Leungsakul; D. Hu

    2003-01-01

    A discussion of some of the important issues related to secondary organic aerosol (SOA) formation is presented, and SOA formation is placed in a context of global fine aerosol sources. Outdoor smog chamber experiments are described for the purposes of exploring the effects of different types of background aerosols on SOA formation from the reaction of alpha -pinene with NOx

  14. Secondary Organic Aerosol Formation by Heterogeneous

    E-print Network

    Goddard III, William A.

    partitioning from gas to particle phase and, hence, increase the organic particulate material (OPM). Aerosol as to the likely aerosol-phase chemical reactions involving ab- sorbed gas-phase organic compounds. ThSecondary Organic Aerosol Formation by Heterogeneous Reactions of Aldehydes and Ketones: A Quantum

  15. Inorganic ammonium salts and carbonate salts are efficient catalysts for aldol condensation in atmospheric aerosols.

    PubMed

    Nozière, Barbara; Dziedzic, Pawel; Córdova, Armando

    2010-04-21

    In natural environments such as atmospheric aerosols, organic compounds coexist with inorganic salts but, until recently, were not thought to interact chemically. We have recently shown that inorganic ammonium ions, NH(4)(+), act as catalysts for acetal formation from glyoxal, a common atmospheric gas. In this work, we report that inorganic ammonium ions, NH(4)(+), and carbonate ions, CO(3)(2-), are also efficient catalysts for the aldol condensation of carbonyl compounds. In the case of NH(4)(+) this was not previously known, and was patented prior to this article. The kinetic results presented in this work show that, for the concentrations of ammonium and carbonate ions present in tropospheric aerosols, the aldol condensation of acetaldehyde and acetone could be as fast as in concentrated sulfuric acid and might compete with their reactions with OH radicals. These catalytic processes could produce significant amounts of polyconjugated, light-absorbing compounds in aerosols, and thus affect their direct forcing on climate. For organic gases with large Henry's law coefficients, these reactions could also result in a significant uptake and in the formation of secondary organic aerosols (SOA). This work reinforces the recent findings that inorganic salts are not inert towards organic compounds in aerosols and shows, in particular, that common ones, such as ammonium and carbonate salts, might even play important roles in their chemical transformations. PMID:20358081

  16. 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 a-pinene and isop...

  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. Evaporation of mixed inorganic/organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Zardini, A.; Riipinen, I.; Kulmala, M.; Bilde, M.

    2009-04-01

    Biogenic sources as well as human activities contribute large amounts of volatile organic compounds to the atmosphere. Upon oxidation, polyfunctional molecules such as dicarboxylic acids are formed. These molecules generally have lower vapor pressures than the parent molecules and are able to condense on existing particles or maybe even participate in formation of new particles in the atmosphere. Current knowledge about the thermodynamic properties governing this partitioning as well as the influence of the organic molecules on properties of aqueous solution droplets is poor. We have therefore developed a new method based on the HTDMA technique (Hygroscopicity Tandem Differential Mobility Analyzer) for determining the subcooled liquid state vapor pressure as well as other thermodynamic properties of secondary organic aerosol components. We have recently measured evaporation rates of aqueous solution droplets containing one dicarboxylic acid (C3 to C5) and water [1-2-3]. In this work we expand the list of organics and investigate more complicated systems such as dicarboxylic acid together with inorganic salts. In addition, we show the first results of evaporation of freshly produced organic particles in an environmental chamber. References: 1. Koponen IK, Thermodynamic properties of malonic, succinic, and glutaric acids: Evaporation rates and saturation vapor pressures. Environmental Science & Technology, 41(11), 3926-3933, 2007. 2. Riipinen I, A method for determining thermophysical properties of organic material in aqueous solutions: Succinic acid. Atmospheric Research, 82(3-4), 579-590, 2006. 3. Zardini AA et al., White light Mie resonance spectroscopy used to measure very low vapor pressures of substances in aqueous solution aerosol particles. Optics Express 14,6951-6962, 2006.

  19. Glass formation processes in mixed inorganic/organic aerosol particles.

    PubMed

    Dette, Hans P; Koop, Thomas

    2015-05-14

    Recent experiments suggest that organic aerosol particles may transform into a glassy state at room temperature under dry conditions. Information on glass forming processes in mixed inorganic/organic aerosol particles is sparse, however, because inorganic crystal nucleation is usually very likely in such mixtures. Here we investigate the glass transition temperatures Tg of various organics (trehalose, sucrose, citric acid, sorbitol, and glycerol as well as 3-MBTCA) in binary mixtures with either NaNO3 or NH4HSO4 at different mass fractions. The glassy samples were prepared with the MARBLES technique by atomizing dilute aqueous solutions into aerosol particles and subsequent diffusion drying. The resulting aerosol particles were collected and their phase behavior was investigated using differential scanning calorimetry. At small and intermediate inorganic mass fractions salt crystallization did not occur. Instead, the single-phase mixtures remained in an amorphous state upon drying such that determination of their Tg was possible. From these measurements the Tg value of pure NaNO3 and pure NH4HSO4 could be inferred through extrapolation, resulting in values of Tg(NaNO3) ? 290 K and Tg(NH4HSO4) ? 220 K. Upon drying of NH4HSO4/3-MBTCA mixtures, phase-separated samples formed in which the inorganic-rich and organic-rich phases each show an independent glass transition. Our measurements provide a route toward establishing Tg values of inorganic salts that usually crystallize readily, and they may explain the reported contradicting observations of NaNO3 aerosol particles to either crystallize or remain amorphous upon drying at room temperature. PMID:25490407

  20. Nonequilibrium atmospheric secondary organic aerosol formation and growth

    E-print Network

    Dabdub, Donald

    into which semivolatile organic compounds undergo instan- taneous equilibrium partitioning to growNonequilibrium atmospheric secondary organic aerosol formation and growth Véronique Perrauda roles in air quality, health effects, vis- ibility, and climate. Secondary organic aerosols (SOA) formed

  1. Organosulfate Formation in Biogenic Secondary Organic Aerosol

    EPA Science Inventory

    Organosulfates of isoprene, a-pinene, and ß-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...

  2. Evidence for organosulfates in secondary organic aerosol.

    PubMed

    Surratt, Jason D; Kroll, Jesse H; Kleindienst, Tadeusz E; Edney, Edward O; Claeys, Magda; Sorooshian, Armin; Ng, Nga L; Offenberg, John H; Lewandowski, Michael; Jaoui, Mohammed; Flagan, Richard C; Seinfeld, John H

    2007-01-15

    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 alpha-pinene and isoprene, in the presence or absence of sulfate seed aerosol, is investigated through a series of controlled chamber experiments in two separate laboratories. By using electrospray ionization-mass spectrometry, sulfate esters in SOA produced in laboratory photooxidation experiments are identified for the first time. Sulfate esters are found to account for a larger fraction of the SOA mass when the acidity of seed aerosol is increased, a result consistent with aerosol acidity increasing SOA formation. Many of the isoprene and alpha-pinene sulfate esters identified in these chamber experiments are also found in ambient aerosol collected at several locations in the southeastern U.S. It is likely that this pathway is important for other biogenic terpenes, and may be important in the formation of humic-like substances (HULIS) in ambient aerosol. PMID:17310716

  3. Formation of secondary aerosols: impact of the gas-phase chemical mechanism

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Sartelet, K.; Seigneur, C.

    2010-08-01

    The impact of two recent gas-phase chemical kinetic mechanisms (CB05 and RACM2) on the formation of secondary inorganic and organic aerosols is compared for simulations of PM2.5 over Europe between 15 July and 15 August 2001. The host chemistry transport model is Polair3D of the Polyphemus air-quality platform. Particulate matter is modeled with SIREAM, which is coupled to the thermodynamic model ISORROPIA and to the secondary organic aerosol module MAEC. Model performance is satisfactory with both mechanisms for speciated PM2.5. The monthly-mean difference of the concentration of PM2.5 is less than 1 ?g/m3 (6%) over the entire domain. Secondary chemical components of PM2.5 include sulfate, nitrate, ammonium and organic aerosols, and the chemical composition of PM2.5 is not significantly different between the two mechanisms. Monthly-mean concentrations of inorganic aerosol are higher with RACM2 than with CB05 (+16% for sulfate, +11% for nitrate, and +12% for ammonium), whereas the concentrations of organic aerosols are slightly higher with CB05 than with RACM2 (+26% for anthropogenic SOA and +1% for biogenic SOA). Differences in the inorganic and organic aerosols result primarily from differences in oxidant concentrations (OH, O3 and NO3). Nitrate formation tends to be HNO3-limited over land and differences in the concentrations of nitrate are due to differences in concentration of HNO3. Differences in aerosols formed from aromatics SVOC are due to different aromatics oxidation between CB05 and RACM2. The aromatics oxidation in CB05 leads to more cresol formation, which then leads to more SOA. Differences in the aromatics aerosols would be significantly reduced with the recent CB05-TU mechanism for toluene oxidation. Differences in the biogenic aerosols are due to different oxidant concentrations (monoterpenes) and different particulate organic mass concentrations affecting the gas-particle partitioning of SOA (isoprene).

  4. Aqueous phase processing of secondary organic aerosols

    Microsoft Academic Search

    Yao Liu; T. Tritscher; A. P. Praplan; P. F. Decarlo; B. Temime-Roussel; E. Quivet; N. Marchand; J. Dommen; U. Baltensperger; A. Monod

    2011-01-01

    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, alpha-pinene, and 1,3,5-trimethylbenzene (TMB) in the presence of NOx, leading to the formation

  5. Secondary Organic Aerosol Formation: New Insights

    NASA Astrophysics Data System (ADS)

    Kamens, R. M.; Jang, M.; Lee, S.; Czoschke, N.; Leungsakul, S.; Hu, D.

    2003-12-01

    A discussion of some of the important issues related to secondary organic aerosol (SOA) formation is presented, and SOA formation is placed in a context of global fine aerosol sources. Outdoor smog chamber experiments are described for the purposes of exploring the effects of different types of background aerosols on SOA formation from the reaction of ? -pinene with NOx in the presence of natural sunlight. Experiments were carried out by first adding 20 to 200 ? g/m3 of background aerosols (such as diesel soot, wood smog, and ammonium sulfate seed particles) into 190m3, 140m3, and 25m3 Teflon film outdoor chambers prior to the addition of ? -pinene and NOx. SOA formation was monitored using a scanning mobility particle sizer (TSI-SMPS). Gas and particle phase products were sampled over the course of experiments using denuders and filters. Chamber results indicated that condensed SOA can dramatically alter the chemical composition of primary diesel soot particles as they age in the atmosphere. Since particle phase aldehyde chemistry has recently been implicated as a potentially large source of SOA (Jang and Kamens, et al., Science 2002), aerosol growth by the heterogeneous reactions of different organic carbonyls in the presence/absence of acidified seed aerosols was studied in a flow reactor and 500-liter Teflon bag system under dark conditions. The results from unsaturated carbonyl and dicarbonyl experiments indicate large increases in SOA formation in the presence of acidified aerosols. This has implications for both biogenic and aromatic systems that generate SOA.

  6. Hygroscopicity frequency distributions of secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Suda, S. R.; Petters, M. D.; Matsunaga, A.; Sullivan, R. C.; Ziemann, P. J.; Kreidenweis, S. M.

    2012-02-01

    Secondary organic compounds are an important component of ambient aerosol and potentially lower the supersaturation that is required for individual particles to serve as cloud condensation nuclei (CCN). Secondary organic aerosol (SOA) formed from the oxidation of a single precursor can be composed of many different compounds and their overall CCN efficiency has been reported for many different SOA systems. An aerosol's CCN efficiency can be described by a single hygroscopicity parameter, ?. However, this ? comprises an unknown distribution of underlying ?-values resulting from each individual compound in the SOA mixture. Here we report on a new technique for characterizing this distribution of?. Precursor hydrocarbons were oxidized in an environmental chamber to form SOA, which was collected on filters and extracted using ethyl acetate. Extracts were then fractionated by reversed-phase high-performance liquid chromatography using gradient elution with acetonitrile and water. The eluate was atomized, the solvent was removed by evaporation, and the residual aerosol particles were analyzed as a function of retention time using scanning flow CCN analysis. Kappa-values generally decreased with component retention time, consistent with expected decreasing polarity. Averaged SOA?-values reconstructed by integrating over the chromatogram agreed well with values measured for SOA sampled directly from the environmental chamber, suggesting that?for SOA represents the volume-weighted average of the constituent compounds'?-values. We anticipate that our measured hygroscopicity distributions will serve as validation points for mechanistic models that seek to predict the generation and evolution of organic aerosol composition and properties in the atmosphere.

  7. Characterizing the formation of secondary organic aerosols

    SciTech Connect

    Lunden, Melissa; Black, Douglas; Brown, Nancy

    2004-02-01

    Organic aerosol is an important fraction of the fine particulate matter present in the atmosphere. This organic aerosol comes from a variety of sources; primary organic aerosol emitted directly from combustion process, and secondary aerosol formed in the atmosphere from condensable vapors. This secondary organic aerosol (SOA) can result from both anthropogenic and biogenic sources. In rural areas of the United States, organic aerosols can be a significant part of the aerosol load in the atmosphere. However, the extent to which gas-phase biogenic emissions contribute to this organic load is poorly understood. Such an understanding is crucial to properly apportion the effect of anthropogenic emissions in these rural areas that are sometimes dominated by biogenic sources. To help gain insight on the effect of biogenic emissions on particle concentrations in rural areas, we have been conducting a field measurement program at the University of California Blodgett Forest Research Facility. The field location includes has been used to acquire an extensive suite of measurements resulting in a rich data set, containing a combination of aerosol, organic, and nitrogenous species concentration and meteorological data with a long time record. The field location was established in 1997 by Allen Goldstein, a professor in the Department of Environmental Science, Policy and Management at the University of California at Berkeley to study interactions between the biosphere and the atmosphere. The Goldstein group focuses on measurements of concentrations and whole ecosystem biosphere-atmosphere fluxes for volatile organic compounds (VOC's), oxygenated volatile organic compounds (OVOC's), ozone, carbon dioxide, water vapor, and energy. Another important collaborator at the Blodgett field location is Ronald Cohen, a professor in the Chemistry Department at the University of California at Berkeley. At the Blodgett field location, his group his group performs measurements of the concentrations of important gas phase nitrogen compounds. Experiments have been ongoing at the Blodgett field site since the fall of 2000, and have included portions of the summer and fall of 2001, 2002, and 2003. Analysis of both the gas and particle phase data from the year 2000 show that the particle loading at the site correlates with both biogenic precursors emitted in the forest and anthropogenic precursors advected to the site from Sacramento and the Central Valley of California. Thus the particles at the site are affected by biogenic processing of anthropogenic emissions. Size distribution measurements show that the aerosol at the site has a geometric median diameter of approximately 100 nm. On many days, in the early afternoon, growth of nuclei mode particles (<20 nm) is also observed. These growth events tend to occur on days with lower average temperatures, but are observed throughout the summer. Analysis of the size resolved data for these growth events, combined with typical measured terpene emissions, show that the particle mass measured in these nuclei mode particles could come from oxidation products of biogenic emissions, and can serve as a significant route for SOA partitioning into the particle phase. During periods of each year, the effect of emissions for forest fires can be detected at the Blodgett field location. During the summer of 2002 emissions from the Biscuit fire, a large fire located in Southwest Oregon, was detected in the aerosol data. The results show that increases in particle scattering can be directly related to increased black carbon concentration and an appearance of a larger mode in the aerosol size distribution. These results show that emissions from fires can have significant impact on visibility over large distances. The results also reinforce the view that forest fires can be a significant source of black carbon in the atmosphere, which has important climate and visibility. Continuing work with the 2002 data set, particularly the combination of the aerosol and gas phase data, will continue to provide important information o

  8. Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Smith, D. F.; Li, W.; Edney, E. O.; Driscoll, D. J.; Speer, R. E.; Weathers, W. S.

    A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas-aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon-nitrogen oxide (HC/NO x) mixtures irradiated in the presence of fine (<2.5 ?m) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 ?m -3, followed by 1.09±0.27% for p-xylene at 6.4 ?g m -3, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 ?g m -3. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas-aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.

  9. Laboratory Measured Optical Properties of Inorganic and Organic Aerosols at Relative Humidities up to 95%

    Microsoft Academic Search

    Benjamin T. Brem; Francisco C. MenaGonzalez; Scott R. Meyers; Tami C. Bond; Mark J. Rood

    2011-01-01

    Relative humidity (RH) affects the liquid water contentof an aerosol, alteringits scattering and absorption of visible light, which is important for aerosol effects on visibility and climate. Particle light extinction, light scattering and light absorption coefficient values are reported here for laboratory-generated inorganic and organic carbon (OC) aerosols at RH values between 8% and 95%. Light scattering was measured with

  10. Laboratory-Measured Optical Properties of Inorganic and Organic Aerosols at Relative Humidities up to 95%

    Microsoft Academic Search

    Benjamin T. Brem; Francisco C. Mena Gonzalez; Scott R. Meyers; Tami C. Bond; Mark J. Rood

    2012-01-01

    Relative humidity (RH) affects the liquid water content of an aerosol, altering its scattering and absorption of visible light, which is important for aerosol effects on visibility and climate. Particle light extinction, light scattering, and light absorption coefficient values are reported here for laboratory-generated inorganic and organic carbon (OC) aerosols at RH values between 8% and 95%. Light scattering was

  11. Secondary organic aerosol formation: some new and exciting insights

    Microsoft Academic Search

    R. Kamens; M. Jang; S. Lee; N. Czoschke; B. Chandramouli; M. Jaoui; S. Leungsakul

    2003-01-01

    A discussion of some of the important issues related to secondary organic aerosol (SOA) formation is presented, and SOA formation is placed in a context of global fine aerosol sources. Outdoor smog chamber experiments, accompanied by modeling studies, are then described for the purpose of exploring the effects of different types of background aerosols on SOA from the reaction of

  12. Organosulfate formation in biogenic secondary organic aerosol.

    PubMed

    Surratt, Jason D; Gómez-González, Yadian; Chan, Arthur W H; Vermeylen, Reinhilde; Shahgholi, Mona; Kleindienst, Tadeusz E; Edney, Edward O; Offenberg, John H; Lewandowski, Michael; Jaoui, Mohammed; Maenhaut, Willy; Claeys, Magda; Flagan, Richard C; Seinfeld, John H

    2008-09-11

    Organosulfates of isoprene, alpha-pinene, and beta-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 series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (alpha-pinene, beta-pinene, d-limonene, l-limonene, alpha-terpinene, gamma-terpinene, terpinolene, Delta(3)-carene, and beta-phellandrene) and three monoterpenes (alpha-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, alpha-pinene, beta-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%. PMID:18710205

  13. Examination of the Effects of Sea Salt Aerosols on Southeast Texas Ozone and Secondary Organic Aerosol

    E-print Network

    Benoit, Mark David

    2013-02-06

    . There are many different types of aerosols, including dust particles, soot particles, and microscopic particles containing inorganic compounds such as sulfates. Most of these particles have natural origins, but many are anthropogenic. The eventual purpose...

  14. Los Angeles summer midday particulate carbon: Primary and secondary aerosol

    Microsoft Academic Search

    Barbara J. Turpin; James J. Huntzicker; Susan M. Larson; Glen R. Cass

    1991-01-01

    Aerosol sampling during photochemically active times across the Los Angeles Basin has provided evidence of secondary formation of organic aerosol from gas-phase precursors at midday. Ambient organic carbon\\/elemental carbon ratios exceeded the estimated ratio of organic carbon\\/elemental carbon in primary source emissions on most sampling days at all sites. The concentration of secondary organic aerosol was calculated by using ambient

  15. CARES Helps Explain Secondary Organic Aerosols

    ScienceCinema

    Zaveri, Rahul

    2014-06-02

    What happens when urban man-made pollution mixes with what we think of as pristine forest air? To know more about what this interaction means for the climate, the Carbonaceous Aerosol and Radiative Effects Study, or CARES, field campaign was designed in 2010. The sampling strategy during CARES was coordinated with CalNex 2010, another major field campaign that was planned in California in 2010 by the California Air Resources Board (CARB), the National Oceanic and Atmospheric Administration (NOAA), and the California Energy Commission (CEC). "We found two things. When urban pollution mixes with forest pollutions we get more secondary organic aerosols," said Rahul Zaveri, FCSD scientist and project lead on CARES. "SOAs are thought to be formed primarily from forest emissions but only when they interact with urban emissions. The data is saying that there will be climate cooling over the central California valley because of these interactions." Knowledge gained from detailed analyses of data gathered during the CARES campaign, together with laboratory experiments, is being used to improve existing climate models.

  16. Secondary organic aerosol formation from isoprene photooxidation.

    PubMed

    Kroll, Jesse H; Ng, Nga L; Murphy, Shane M; Flagan, Richard C; Seinfeld, John H

    2006-03-15

    Recent work has shown that the atmospheric oxidation of isoprene (2-methyl-1,3-butadiene, C5H8) leads to the formation of secondary organic aerosol (SOA). In this study, the mechanism of SOA formation by isoprene photooxidation is comprehensively investigated, by measurements of SOA yields over a range of experimental conditions, namely isoprene and NOx concentrations. Hydrogen peroxide is used as the radical precursor, substantially constraining the observed gas-phase chemistry; all oxidation is dominated by the OH radical, and organic peroxy radicals (RO2) react only with HO2 (formed in the OH + H2O2 reaction) or NO concentrations, including NOx-free conditions. At high NOx, yields are found to decrease substantially with increasing [NOx], indicating the importance of RO2 chemistry in SOA formation. Under low-NOx conditions, SOA mass is observed to decay rapidly, a result of chemical reactions of semivolatile SOA components, most likely organic hydroperoxides. PMID:16570610

  17. 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 (? ? 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.

  18. Formation of semivolatile inorganic aerosols in the Mexico City Metropolitan Area during the MILAGRO campaign

    E-print Network

    Karydis, V. A.

    One of the most challenging tasks for chemical transport models (CTMs) is the prediction of the formation and partitioning of the major semi-volatile inorganic aerosol components (nitrate, chloride, ammonium) between the ...

  19. Gasoline contributes more than diesel to secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Balcerak, Ernie

    2012-05-01

    Gasoline-powered vehicles contribute more to secondary organic aerosol formation than diesel-fueled vehicles do, a new study shows. Organic compounds in gasoline fuel and diesel exhaust can lead to the formation of secondary organic aerosols, which negatively affect air quality, visibility, and health and have impacts on climate; however, few studies have investigated the relative contribution of gasoline and diesel to secondary aerosols. Traffic studies have found that the ratio of gasoline-to diesel-powered vehicles changes on weekends. For instance, in the Los Angeles, Calif., area, diesel emissions are about 54% lower on weekends than on weekdays, though gasoline emissions are about the same.

  20. 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, ?-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 ?g 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 ?-pinene, whereas it affected that formed from TMB. For the two first precursors, the aqueous phase chemical composition of SOA was further investigated using offline measurements, i.e. ion chromatography coupled to a mass spectrometer (IC-MS) and an atmospheric pressure chemical ionization mass spectrometer (APCI-MS) equipped with high pressure liquid chromatography (HPLC-MS). These analyses showed that aqueous phase processing enhanced the formation of some compounds already present in the SOA, thus confirming the aging effect of aqueous phase processes. For isoprene experiments, additional new compounds, likely oligomers, were formed through aqueous phase photooxidation, and their possible origins are discussed.

  1. Mass Size Distributions and Precursor Gas Concentrations of Major Inorganic Ions in'Antarctic Aerosol

    Microsoft Academic Search

    Risto Hillamo; Ivo Allegrini; Roberto Sparapani; Veli-Matti Kerminen

    1998-01-01

    Mass size distributions of major inorganic ions in aerosol particles and their atmospheric precursor gases were studied at Terra Nova Bay in Antarctica (74° 41? 42?S, 164° 05?36 ?E) between January 30 and February 18, 1995. The mass size distributions of sulphate, the major inorganic ion, had two submicron and two supermicron modes. The accumulation mode (average mass median diameter

  2. Development and initial evaluation of a dynamic species-resolved model for gas phase chemistry and size-resolved gas\\/particle partitioning associated with secondary organic aerosol formation

    Microsoft Academic Search

    Robert J. Griffin; Donald Dabdub; John H. Seinfeld

    2005-01-01

    A module for predicting the dynamic evolution of the gas phase species and the aerosol size and composition distribution during formation of secondary organic aerosol (SOA) is presented. The module is based on the inorganic gas-aerosol equilibrium model Simulating the Composition of Atmospheric Particles at Equilibrium 2 (SCAPE2) and updated versions of the lumped Caltech Atmospheric Chemistry Mechanism (CACM) and

  3. A review of Secondary Organic Aerosol (SOA) formation from isoprene

    E-print Network

    Kroll, Jesse

    Recent field and laboratory evidence indicates that the oxidation of isoprene, (2-methyl-1,3-butadiene, C[subscript 5]H[subscript 8]) forms secondary organic aerosol (SOA). Global biogenic emissions of isoprene (600 Tg ...

  4. Secondary organic aerosol formation from road vehicle emissions

    NASA Astrophysics Data System (ADS)

    Pieber, Simone M.; Platt, Stephen M.; El Haddad, Imad; Zardini, Alessandro A.; Suarez-Bertoa, Ricardo; Slowik, Jay G.; Huang, Ru-Jin; Hellebust, Stig; Temime-Roussel, Brice; Marchand, Nicolas; Drinovec, Luca; Mocnik, Grisa; Baltensperger, Urs; Astorga, Covadogna; Prévôt, André S. H.

    2014-05-01

    Organic aerosol particles (OA) are a major fraction of the submicron particulate matter. OA consists of directly emitted primary (POA) and secondary OA (SOA). SOA is formed in-situ in the atmosphere via the reaction of volatile organic precursors. The partitioning of SOA species depends not only on the exposure to oxidants, but for instance also on temperature, relative humidity (RH), and the absorptive mass chemical composition (presence of inorganics) and concentration. Vehicle exhaust is a known source of POA and likely contributes to SOA formation in urban areas [1;2]. This has recently been estimated by (i) analyzing ambient data from urban areas combined with fuel consumption data [3], (ii) by examining the chemical composition of raw fuels [4], or (iii) smog chamber studies [5, 6]. Contradictory and thus somewhat controversial results in the relative quantity of SOA from diesel vs. gasoline vehicle exhaust were observed. In order to elucidate the impact of variable ambient conditions on the potential SOA formation of vehicle exhaust, and its relation to the emitted gas phase species, we studied SOA formed from the exhaust of passenger cars and trucks as a function of fuel and engine type (gasoline, diesel) at different temperatures (T 22 vs. -7oC) and RH (40 vs. 90%), as well as with different levels of inorganic salt concentrations. The exhaust was sampled at the tailpipe during regulatory driving cycles on chassis dynamometers, diluted (200 - 400x) and introduced into the PSI mobile smog chamber [6], where the emissions were subjected to simulated atmospheric ageing. Particle phase instruments (HR-ToF-AMS, aethalometers, CPC, SMPS) and gas phase instruments (PTR-TOF-MS, CO, CO2, CH4, THC, NH3 and other gases) were used online during the experiments. We found that gasoline emissions, because of cold starts, were generally larger than diesel, especially during cold temperatures driving cycles. Gasoline vehicles also showed the highest SOA formation. Furthermore, we observed that vehicle emissions and SOA are significantly affected by temperature and RH: doubling the RH in the chamber resulted in significantly increased SOA formation. Primary emissions and secondary aerosol formation from diesel and gasoline vehicles will be compared at different temperature and RH. Also the interaction and influence of inorganics on organics will be discussed. References: [1] Robinson, A.L., et al. (2007) Science 315, 1259. [2] Weitkamp, E.A., et al. (2007) Environ. Sci. Technol. 41, 6969. [3] Bahreini, R., et al. (2012) Geophys. Res. Lett. 39, L06805. [4] Gentner, D.R. et al. (2012) PNAS 109, 18318. [5] Gordon, T.D. et al. (2013) Atmos. Chem. Phys. Discuss 13, 23173. [6] Platt, S.M., et al. (2013) Atmos. Chem. Phys. Discuss. 12, 28343.

  5. Redox activity of naphthalene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    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 ?g 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. Similar attempts to predict redox behaviour of oxidised two-stroke engine exhaust particles by measuring 1,2-naphthoquinone, 1,4-naphthoquinone and 9,10-phenanthrenequinone predicted DTT decay rates only 4.9 ± 2.5% of those observed. Together, 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 ?g-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. As well, 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.

  6. Secondary organic aerosol model intercomparison based on secondary organic aerosol to odd oxygen ratio in Tokyo

    NASA Astrophysics Data System (ADS)

    Morino, Yu; Tanabe, Kiyoshi; Sato, Kei; Ohara, Toshimasa

    2014-12-01

    Improvement of secondary organic aerosol (SOA) models is critical for accurate understanding of the behavior and sources of atmospheric aerosols. Over the last decade, a number of SOA production pathways were discovered, and several new SOA models have been developed. However, few comparative studies of the performances of the various SOA models have been conducted. In this study, simulation data obtained with five SOA models (two yield models, a volatility basis set (VBS) model, a mechanistic model, and a near-explicit model) were compared. The performances of the models were evaluated by comparison of the simulated data with observed ratios of the SOA concentration to odd oxygen concentration ([SOA]/[Ox], where [Ox] = [O3] + [NO2]) in the Tokyo metropolitan area. In Tokyo, SOA concentrations have been shown to correlate well with Ox concentrations; thus, Tokyo is an appropriate location for this intercomparison study. All five models showed similar results for the concentrations of gaseous species, including ozone, reactive nitrogen, hydroxy radicals, and volatile organic compounds. In contrast, the simulated SOA concentrations varied substantially among the five models. The VBS model reproduced the observed [SOA]/[Ox] ratio well, whereas the other four models substantially underestimated the ratio. The sensitivity of the ratio to various input parameters differed substantially among the models, as did the volatility distribution of SOA and the source contributions of SOA, suggesting that the choice of SOA model is critical for accurate assessment of the atmospheric behavior and sources of SOA.

  7. Laboratory studies on secondary organic aerosol formation from terpenes

    Microsoft Academic Search

    Yoshiteru Iinuma; O Boge; Yunkun Miao; Berko Sierau; Thomas Gnauk; Hartmut Herrmann

    2005-01-01

    The formation of secondary organic aerosol (SOA) following the\\u000a ozonolysis of terpene has been investigated intensively in recent years.\\u000a The enhancement of SOA yields from the acid catalysed reactions of\\u000a organics on aerosol surfaces or in the bulk particle phase has been\\u000a receiving great attention. Recent studies show that the presence of\\u000a acidic seed particles increases the SOA yield significantly

  8. Organic and inorganic markers and stable C-, N-isotopic compositions of tropical coastal aerosols from megacity Mumbai: sources of organic aerosols and atmospheric processing

    NASA Astrophysics Data System (ADS)

    Aggarwal, S. G.; Kawamura, K.; Umarji, G. S.; Tachibana, E.; Patil, R. S.; Gupta, P. K.

    2013-05-01

    To better understand the sources of PM10 samples in Mumbai, India, aerosol chemical composition, i.e., total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions were studied together with specific markers such as methanesulfonate (MSA), oxalic acid (C2), azelaic acid (C9), and levoglucosan. The results revealed that biofuel/biomass burning and fossil fuel combustion are the major sources of the Mumbai aerosols. Nitrogen-isotopic (?15N) composition of aerosol total nitrogen, which ranged from 18.1 to 25.4‰, also suggests that biofuel/biomass burning is a predominate source in both the summer and winter seasons. Aerosol mass concentrations of major species increased 3-4 times in winter compared to summer, indicating enhanced emission from these sources in the winter season. Photochemical production tracers, C2 diacid and nssSO42-, do not show diurnal changes. Concentrations of C2 diacid and WSOC show a strong correlation (r2 = 0.95). In addition, WSOC to OC (or TC) ratios remain almost constant for daytime (0.37 ± 0.06 (0.28 ± 0.04)) and nighttime (0.38 ± 0.07 (0.28 ± 0.06)), suggesting that mixing of fresh secondary organic aerosols is not significant and the Mumbai aerosols are photochemically well processed. Concentrations of MSA and C9 diacid present a positive correlation (r2 = 0.75), indicating a marine influence on Mumbai aerosols in addition to local/regional influence. Backward air mass trajectory analyses further suggested that the Mumbai aerosols are largely influenced by long-range continental and regional transport. Stable C-isotopic ratios (?13C) of TC ranged from -27.0 to -25.4‰, with slightly lower average (-26.5 ± 0.3‰) in summer than in winter (-25.9 ± 0.3‰). Positive correlation between WSOC/TC ratios and ?13C values suggested that the relative increment in 13C of wintertime TC may be caused by prolonged photochemical processing of organic aerosols in this season. This study suggests that in winter, the tropical aerosols are more aged due to longer residence time in the atmosphere than in summer aerosols. However, these conclusions are based on the analysis of a limited number of samples (n=25) and more information on this topic may be needed from other similar coastal sites in future.

  9. Organic and inorganic markers and stable C-, N-isotopic compositions of tropical coastal aerosols from megacity Mumbai: sources of organic aerosols and atmospheric processing

    NASA Astrophysics Data System (ADS)

    Aggarwal, S. G.; Kawamura, K.; Umarji, G. S.; Tachibana, E.; Patil, R. S.; Gupta, P. K.

    2012-08-01

    To better understand the sources of PM10 samples from Mumbai, India, aerosol chemical compositions, i.e. total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions were studied together with specific markers such as methanesulfonate (MSA), oxalic acid (C2), azelaic acid (C9), and levoglucosan. The results revealed that biofuel/biomass burning and fossil fuel combustion are the major sources of the Mumbai aerosols. Nitrogen-isotopic (?15N) composition of aerosol total nitrogen, which ranged from 18.1 to 25.4‰, also suggest that biofuel/biomass burning is the dominant source in both summer and winter seasons. Aerosol mass concentrations of major species increased 3-4 times in winter compared to summer, indicating an enhanced emission from these sources in winter season. Photochemical production tracers, C2 diacid and nssSO42- do not show diurnal changes. Concentrations of C2 diacid and WSOC show a strong correlation (r2 = 0.95). In addition, WSOC to OC (or TC) ratios remain almost constant for day- (0.37 ± 0.06 (0.28 ± 0.04)) and nighttime (0.38 ± 0.07 (0.28 ± 0.06)), suggesting that mixing of fresh secondary organic aerosols is not significant rather the Mumbai aerosols are photochemically well processed. Concentrations of MSA and C9 diacid present a positive correlation (r2 = 0.75), indicating a marine influence on Mumbai aerosols in addition to local/regional influence. Backward air mass trajectory analyses further suggested that the Mumbai aerosols are largely influenced by long-range continental and regional transport. Stable C-isotopic ratios (?13C) of TC ranged from -27.0 to -25.4‰ with slightly lower average (-26.5 ± 0.3‰) in summer than in winter (-25.9 ± 0.3‰). Positive correlation between WSOC/TC ratios and ?13C values suggested that the increment in ?13C of wintertime TC may be caused by prolonged photochemical processing of organic aerosols in this season. This study suggests that in winter, the tropical aerosols are more aged due to longer residence time in the atmosphere than in the summer aerosols.

  10. High secondary aerosol contribution to particulate pollution during haze events in China

    NASA Astrophysics Data System (ADS)

    Huang, Ru-Jin; Zhang, Yanlin; Bozzetti, Carlo; Ho, Kin-Fai; Cao, Jun-Ji; Han, Yongming; Daellenbach, Kaspar R.; Slowik, Jay G.; Platt, Stephen M.; Canonaco, Francesco; Zotter, Peter; Wolf, Robert; Pieber, Simone M.; Bruns, Emily A.; Crippa, Monica; Ciarelli, Giancarlo; Piazzalunga, Andrea; Schwikowski, Margit; Abbaszade, Gülcin; Schnelle-Kreis, Jürgen; Zimmermann, Ralf; An, Zhisheng; Szidat, Sönke; Baltensperger, Urs; Haddad, Imad El; Prévôt, André S. H.

    2014-10-01

    Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution.

  11. High secondary aerosol contribution to particulate pollution during haze events in China.

    PubMed

    Huang, Ru-Jin; Zhang, Yanlin; Bozzetti, Carlo; Ho, Kin-Fai; Cao, Jun-Ji; Han, Yongming; Daellenbach, Kaspar R; Slowik, Jay G; Platt, Stephen M; Canonaco, Francesco; Zotter, Peter; Wolf, Robert; Pieber, Simone M; Bruns, Emily A; Crippa, Monica; Ciarelli, Giancarlo; Piazzalunga, Andrea; Schwikowski, Margit; Abbaszade, Gülcin; Schnelle-Kreis, Jürgen; Zimmermann, Ralf; An, Zhisheng; Szidat, Sönke; Baltensperger, Urs; El Haddad, Imad; Prévôt, André S H

    2014-10-01

    Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution. PMID:25231863

  12. Formation of halogen-induced secondary organic aerosol (XOA)

    NASA Astrophysics Data System (ADS)

    Kamilli, Katharina; Ofner, Johannes; Zetzsch, Cornelius; Held, Andreas

    2013-04-01

    Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with ?-pinene and 0.0004 for bromine with ?-pinene. This work was funded by German Research Foundation (DFG) under grants HE 5214/5-1 and ZE792/5-2. References: Cai, X., and Griffin, R. J.: Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms, J. Geophys. Res., 111, D14206/14201-D14206/14214, 2006. Ofner, J. Balzer, N., Buxmann, J., Grothe, H., Schmitt-Kopplin, Ph., Platt, U., and Zetzsch, C., Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms, Atmos. Chem. Phys. Discuss. 12, 2975-3017, 2012.

  13. Formation of secondary aerosols over Europe: comparison of two gas-phase chemical mechanisms

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Sartelet, K.; Seigneur, C.

    2011-01-01

    The impact of two recent gas-phase chemical kinetic mechanisms (CB05 and RACM2) on the formation of secondary inorganic and organic aerosols is compared for simulations of PM2.5 over Europe between 15 July and 15 August 2001. The host chemistry transport model is Polair3D of the Polyphemus air-quality platform. Particulate matter is modeled with a sectional aerosol model (SIREAM), which is coupled to the thermodynamic model ISORROPIA for inorganic species and to a module (MAEC) that treats both hydrophobic and hydrophilic species for secondary organic aerosol (SOA). Modifications are made to the gas-phase chemical mechanisms to handle the formation of SOA. In order to isolate the effect of the original chemical mechanisms on PM formation, the addition of reactions and chemical species needed for SOA formation was harmonized to the extent possible between the two gas-phase chemical mechanisms. Model performance is satisfactory with both mechanisms for speciated PM2.5. The monthly-mean difference of the concentration of PM2.5 is less than 1 ?g m-3 (6%) over the entire domain. Secondary chemical components of PM2.5 include sulfate, nitrate, ammonium and organic aerosols, and the chemical composition of PM2.5 is not significantly different between the two mechanisms. Monthly-mean concentrations of inorganic aerosol are higher with RACM2 than with CB05 (+16% for sulfate, +11% for nitrate, and +10% for ammonium), whereas the concentrations of organic aerosols are slightly higher with CB05 than with RACM2 (+22% for anthropogenic SOA and +1% for biogenic SOA). Differences in the inorganic and organic aerosols result primarily from differences in oxidant concentrations (OH, O3 and NO3). Nitrate formation tends to be HNO3-limited over land and differences in the concentrations of nitrate are due to differences in concentration of HNO3. Differences in aerosols formed from aromatic SVOC are due to different aromatic oxidation between CB05 and RACM2. The aromatic oxidation in CB05 leads to more cresol formation, which then leads to more SOA. Differences in the aromatic aerosols would be significantly reduced with the recent CB05-TU mechanism for toluene oxidation. Differences in the biogenic aerosols are due to different oxidant concentrations (monoterpenes) and different particulate organic mass concentrations affecting the gas-particle partitioning of SOA (isoprene). These results show that the formulation of a gas-phase chemical kinetic mechanism for ozone can have significant direct (e.g., cresol formation) and indirect (e.g., oxidant levels) effects on PM formation. Furthermore, the incorporation of SOA into an existing gas-phase chemical kinetic mechanism requires the addition of reactions and product species, which should be conducted carefully to preserve the original mechanism design and reflect current knowledge of SOA formation processes (e.g., NOx dependence of some SOA yields). The development of chemical kinetic mechanisms, which offer sufficient detail for both oxidant and SOA formation is recommended.

  14. Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene.

    PubMed

    Hao, Li-qing; Wang, Zhen-ya; Huang, Ming-qiang; Fang, Li; Zhang, Wei-jun

    2007-01-01

    Hydroxyl radical (.OH)-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols (SOA). It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride>sodium silicate and ammonium nitrate>ammonium sulfate. PMID:17969643

  15. Aerosol composition and sources during the Chinese Spring Festival: fireworks, secondary aerosol, and holiday effects

    NASA Astrophysics Data System (ADS)

    Jiang, Q.; Sun, Y. L.; Wang, Z.; Yin, Y.

    2015-06-01

    Aerosol particles were characterized by an Aerodyne aerosol chemical speciation monitor along with various collocated instruments in Beijing, China, to investigate the role of fireworks (FW) and secondary aerosol in particulate pollution during the Chinese Spring Festival of 2013. Three FW events, exerting significant and short-term impacts on fine particles (PM2.5), were observed on the days of Lunar New Year, Lunar Fifth Day, and Lantern Festival. The FW were shown to have a large impact on non-refractory potassium, chloride, sulfate, and organics in submicron aerosol (PM1), of which FW organics appeared to be emitted mainly in secondary, with its mass spectrum resembling that of secondary organic aerosol (SOA). Pollution events (PEs) and clean periods (CPs) alternated routinely throughout the study. Secondary particulate matter (SPM = SOA + sulfate + nitrate + ammonium) dominated the total PM1 mass on average, accounting for 63-82% during nine PEs in this study. The elevated contributions of secondary species during PEs resulted in a higher mass extinction efficiency of PM1 (6.4 m2 g-1) than during CPs (4.4 m2 g-1). The Chinese Spring Festival also provides a unique opportunity to study the impact of reduced anthropogenic emissions on aerosol chemistry in the city. Primary species showed ubiquitous reductions during the holiday period with the largest reduction being in cooking organic aerosol (OA; 69%), in nitrogen monoxide (54%), and in coal combustion OA (28%). Secondary sulfate, however, remained only slightly changed, and the SOA and the total PM2.5 even slightly increased. Our results have significant implications for controlling local primary source emissions during PEs, e.g., cooking and traffic activities. Controlling these factors might have a limited effect on improving air quality in the megacity of Beijing, due to the dominance of SPM from regional transport in aerosol particle composition.

  16. Preliminary characterization of submicron secondary aerosol in the amazon forest - ATTO station

    NASA Astrophysics Data System (ADS)

    Carbone, S.; Ferreira De Brito, J.; Andreae, M. O.; Pöhlker, C.; Chi, X.; Saturno, J.; Barbosa, H. M.; Artaxo, P.

    2014-12-01

    Biogenic secondary organic aerosol particles are investigated in the Amazon in the context of the GoAmazon Project. The forest naturally emits a large number of gaseous compounds; they are called the volatile organic compounds (VOCs). They are emitted through processes that are not totally understood. Part of those gaseous compounds are converted into aerosol particles, which affect the biogeochemical cycles, the radiation balance, the mechanisms involving cloud formation and evolution, among few other important effects. In this study the aerosol life-cycle is investigated at the ATTO station, which is located about 150 km northeast of Manaus, with emphasis on the natural organic component and its impacts in the ecosystem. To achieve these objectives physical and chemical aerosol properties have been investigated, such as the chemical composition with aerosol chemical speciation monitor (ACSM), nanoparticle size distribution (using the SMPS - Scanning Mobility Particle Sizer), optical properties with measurements of scattering and absorption (using nephelometers and aethalometers). Those instruments have been operating continuously since February 2014 together with trace gases (O3, CO2, CO, SO2 and NOx) analyzers and additional meteorological instruments. On average PM1 (the sum of black carbon, organic and inorganic ions) totalized 1.0±0.3 ?g m-3, where the organic fraction was dominant (75%). During the beginning of the dry season (July/August) the organic aerosol presented a moderate oxygenated character with the oxygen to carbon ratio (O:C) of 0.7. In the wet season some episodes containing significant amount of chloride and backward wind trajectories suggest aerosol contribution from the Atlantic Ocean. A more comprehensive analysis will include an investigation of the different oxidized fractions of the organic aerosol and optical properties.

  17. Calculations of Incremental Secondary Organic Aerosol

    E-print Network

    Dabdub, Donald

    - and aerosol- phase dynamics (5-7). In addition, further understanding of VOC oxidation paths has allowed, some products of VOC oxidation undergo further oxidation reactions that lead to the formation). In addition, if the VOC contains certain structural characteristics, oxidation also occurs via reaction

  18. SECONDARY ORGANIC AEROSOL FORMATION FROM THE IRRADIATION OF SIMULATED AUTOMOBILE EXHAUST

    EPA Science Inventory

    A laboratory study was conducted to evaluate the potential for secondary organic aerosol formation from emissions from automotive exhaust. The goal was to determine to what extent photochemical oxidation products of these hydrocarbons contribute to secondary organic aerosol (SO...

  19. Size distributions of inorganic and organic species in the atmospheric aerosol in Hungary

    Microsoft Academic Search

    E. Mészáros; T. Barcza; A. Gelencsér; J. Hlavay; Gy. Kiss; Z. Krivácsy; A. Molnár; K. Polyák

    1997-01-01

    Atmospheric aerosol samples were taken in different size intervals by means of a Berner-type cascade impactor. The samples were analyzed by using capillary electrophoresis, atomic absorption spectrometry as well as liquid and gas chromatography to determine the size distribution of water soluble inorganic and organic ionc, metallic elements, polycyclic aromatic hydrocarbons and n-alkanes, respectively. The size distributions of ammonium and

  20. The influence of meteorology on the organic and inorganic properties of aerosols in Hong Kong

    E-print Network

    Zheng, Mei

    The influence of meteorology on the organic and inorganic properties of aerosols in Hong Kong Mei by gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-mass spectrometry (ICP-boundary transport evaluations. Fingerprinting using chemical tracers in these particles allows the identification

  1. 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...

  2. Effect of Hydrophilic Organic Seed Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of ?-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.

  3. Effect of hydrophilic organic seed aerosols on secondary organic aerosol formation from ozonolysis of ?-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 ?-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 ?-pinene ozonolysis. The results show that only citric acid seed significantly enhances the absorption of ?-pinene SOA into the particle-phase. The other two seed particles have a negligible effect on the ?-pinene SOA yields, suggesting that ?-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

  4. Cluster analysis on mass spectra of biogenic secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Spindler, C.; Kiendler-Scharr, A.; Kleist, E.; Mensah, A.; Mentel, T.; Tillmann, R.; Wildt, J.

    2009-04-01

    Biogenic secondary organic aerosols (BSOA) are of high importance in the atmosphere. The formation of SOA from the volatile organic compound (VOC) emissions of selected trees was investigated in the JPAC (Jülich Plant Aerosol Chamber) facility. The VOC (mainly monoterpenes) were transferred into a reaction chamber where vapors were photo-chemically oxidized and formed BSOA. The aerosol was characterized by aerosol mass spectrometry (Aerodyne Quadrupol-AMS). Inside the AMS, flash-vaporization of the aerosol particles and electron impact ionization of the evaporated molecules cause a high fragmentation of the organic compounds. Here, we present a classification of the aerosol mass spectra via cluster analysis. Average mass spectra are produced by combination of related single mass spectra to so-called clusters. The mass spectra were similar due to the similarity of the precursor substances. However, we can show that there are differences in the BSOA mass spectra of different tree species. Furthermore we can distinguish the influence of the precursor chemistry and chemical aging. BSOA formed from plants exposed to stress can be distinguished from BSOA formed under non stressed conditions. Significance and limitations of the clustering method for very similar mass spectra will be demonstrated and discussed.

  5. Aerosol composition and sources during the Chinese Spring Festival: fireworks, secondary aerosol, and holiday effects

    NASA Astrophysics Data System (ADS)

    Jiang, Q.; Sun, Y. L.; Wang, Z.; Yin, Y.

    2014-08-01

    Aerosol particles were characterized by an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) along with various collocated instruments in Beijing, China to investigate the aerosol composition and sources during the Chinese Spring Festival, 2013. Three fireworks (FW) events exerting significant and short-term impacts on fine particles (PM2.5) were observed on the days of Lunar New Year, Lunar Fifth Day, and Lantern Festival. The FW showed major impacts on non-refractory potassium, chloride, sulfate, and organics in PM1, of which the FW organics appeared to be mainly secondary with its mass spectrum resembling to that of secondary organic aerosol (SOA). Pollution events (PEs) and clean periods (CPs) alternated routinely throughout the study. Secondary particulate matter (SPM = SOA + sulfate + nitrate + ammonium) dominated PM1 accounting for 63-82% during the nine PEs observed. The elevated contributions of secondary species during PEs resulted in a higher mass extinction efficiency of PM1 (6.4 m2 g-1) than that during CPs (4.4 m2 g-1). The Chinese Spring Festival also provides a unique opportunity to study the impacts of reduced anthropogenic emissions on aerosol chemistry in the city. The primary species showed ubiquitous reductions during the holiday period with the largest reduction for cooking OA (69%), nitrogen monoxide (54%), and coal combustion OA (28%). The secondary sulfate, however, remained minor change, and the SOA and the total PM2.5 even slightly increased. These results have significant implications that controlling local primary source emissions, e.g., cooking and traffic activities, might have limited effects on improving air quality during PEs when SPM that is formed over regional scales dominates aerosol particle composition.

  6. Secondary organic aerosol formation: some new and exciting insights

    NASA Astrophysics Data System (ADS)

    Kamens, R.; Jang, M.; Lee, S.; Czoschke, N.; Chandramouli, B.; Jaoui, M.; Leungsakul, S.

    2003-04-01

    A discussion of some of the important issues related to secondary organic aerosol (SOA) formation is presented, and SOA formation is placed in a context of global fine aerosol sources. Outdoor smog chamber experiments, accompanied by modeling studies, are then described for the purpose of exploring the effects of different types of background aerosols on SOA from the reaction of ?-pinene with NO_x in the presence of natural sunlight. Experiments were carried out by first adding 20 to 200 ug/m^3 of background aerosols, such as diesel soot, wood smog, and ammonium sulfate seed particles into 190m^3 or 25m^3 Teflon film outdoor chambers prior to the addition of ?-pinene and NOx. SOA formation was monitored using a scanning mobility particle sizer (TSI-SMPS). The gas and particle phase products were sampled over the course of experiments using denuders and filters. Chamber results indicated that the chemistry of background aerosols can dramatically impact the amounts of resulting SOA. Since particle phase aldehyde chemistry has recently been implicated as a potentially large source of SOA (Jang and Kamens et al., Science 2002), aerosol growth by the heterogeneous reactions of different organic carbonyls in the presence/absence of acidified seed aerosols was studied in a flow reactor and 500 liter Teflon bag system under dark conditions. The results from unsaturated carbonyl and dicarbonyl experiments indicate large increases in SOA formation in the presence of acidified aerosols. This has implications for both biogenic and aromatic systems that generate SOA. For this reason we have recently implemented an aromatic kinetics mechanism that links gas and particle phase reactions; initial simulation results will be presented.

  7. Three-dimensional simulations of inorganic aerosol distributions in east Asia during spring 2001

    NASA Astrophysics Data System (ADS)

    Tang, Youhua; Carmichael, Gregory R.; Seinfeld, John H.; Dabdub, Donald; Weber, Rodney J.; Huebert, Barry; Clarke, Antony D.; Guazzotti, Sergio A.; Sodeman, David A.; Prather, Kimberly A.; Uno, Itsushi; Woo, Jung-Hun; Yienger, James J.; Streets, David G.; Quinn, Patricia K.; Johnson, James E.; Song, Chul-Han; Grassian, Vicki H.; Sandu, Adrian; Talbot, Robert W.; Dibb, Jack E.

    2004-10-01

    In this paper, aerosol composition and size distributions in east Asia are simulated using a comprehensive chemical transport model. Three-dimensional aerosol simulations for the TRACE-P and ACE-Asia periods are performed and used to help interpret actual observations. The regional chemical transport model, STEM-2K3, which includes the on-line gas-aerosol thermodynamic module SCAPE II, and explicitly considers chemical aging of dust, is used in the analysis. The model is found to represent many of the important observed features. The Asian outflow during March and April of 2001 is heavily polluted with high aerosol loadings. Under conditions of low dust loading, SO2 condensation and gas phase ammonia distribution determine the nitrate size and gas-aerosol distributions along air mass trajectories, a situation that is analyzed in detail for two TRACE-P flights. Dust is predicted to alter the partitioning of the semivolatile components between the gas and aerosol phases as well as the size distributions of the secondary aerosol constituents. Calcium in the dust affects the gas-aerosol equilibrium by shifting the equilibrium balance to an anion-limited status, which benefits the uptake of sulfate and nitrate, but reduces the amount of aerosol ammonium. Surface reactions on dust provide an additional mechanism to produce aerosol nitrate and sulfate. The size distribution of dust is shown to be a critical factor in determining the size distribution of secondary aerosols. As much of the dust mass is found in the supermicron mode (70-90%), appreciable amounts of sulfate and nitrate are found in the supermicron particles. For sulfate the observations and the analysis indicate that 10-30% of sulfate is in the supermicron fraction during dust events; in the case of nitrate, more than 80% is found in the supermicron fraction.

  8. A Study on the Aqueous Formation of Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Sinclair, K.; Tsigaridis, K.

    2013-12-01

    The effect aerosols have on radiative forcing in the atmosphere is recognized as one of the largest uncertainties in the radiation budget. About 80% of organic aerosol mass in the atmosphere is estimated to be created though secondary processes. Recently, the aqueous formation of secondary organic aerosols (SOA) has become recognized as important when considering the source, transformation and radiative impacts of SOA. This work focuses on implementing a mechanism for aqueous SOA formation that can be used in atmospheric chemistry and models of all scales, from box to global. A box model containing a simplified chemical mechanism for the aqueous production of precursors of aqueous SOA (Myriokefalitakis et al. (2011) is coupled to gas-phase chemistry which uses the carbon bond mechanism (CBM) IV is presented. The model implements aqueous chemistry of soluble gases, both in-cloud and aerosol water, including organic compounds such as glyoxal and methylglyoxal, which have been shown as potentially significant sources for dissolved secondary organic aerosols. This mechanism implements aqueous phase mass transfer and molecular dissociation. The model's performance is evaluated against previous box model studies from the literature. A comparison is conducted between the detailed GAMMA model (McNeill et al., 2012), which is constrained with chamber experiments and the one developed here. The model output under different atmospheric conditions is explored and differences and sensitivities are assessed. The objective of this work is to create a robust framework for simulating aqueous phase formation of SOA and maximizing the computational efficiency of the model, while maintaining accuracy, in order to later use the exact mechanism in global climate simulations.

  9. 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...

  10. Aerosol Coupling in the Earths System (ACES): Linking Chemical Composition of Secondary Organic Aerosol to Hygroscopic Properties

    Microsoft Academic Search

    J. F. Hamilton; M. R. Alfarra; K. P. Wyche; T. Carr; A. C. Lewis; P. S. Monks; G. B. McFiggans; N. A. Good; M. Irwin; F. Turner; M. Ward

    2008-01-01

    The formation of secondary organic aerosol from the oxidation of reactive biogenic emissions is thought to be an important factor in global climate regulation. Biogenic Secondary Organic Aerosol (BSOA) can contribute to indirect radiative forcing by acting as cloud condensation nuclei. The potential of particles to act as CCN depends on their composition and hygroscopic properties. Sesquiterpenes, such as beta-caryophyllene,

  11. Marine Primary and Secondary Aerosol emissions related to seawater biogeochemistry

    NASA Astrophysics Data System (ADS)

    Sellegri, Karine; D'Anna, Barbara; Marchand, Nicolas; Charriere, Bruno; Sempere, Richard; Mas, Sebastien; Schwier, Allison; Rose, Clémence; Pey, Jorge; Langley Dewitt, Helen; Même, Aurélie; R'mili, Badr; George, Christian; Delmont, Anne

    2014-05-01

    Marine aerosol contributes significantly to the global aerosol load and consequently has an important impact on both the Earth's albedo and climate. Different factors influence the way they are produced from the sea water and transferred to the atmosphere. The sea state (whitecap coverage) and sea temperature influence the size and concentration of primarily produced particles but also biogeochemical characteristics of the sea water may influence both the physical and chemical fluxes. In order to study marine emissions, one approach is to use semicontrolled environments such as mesocosms. Within the SAM project (Sources of marine Aerosol in the Mediterranean), we characterize the primary Sea Salt Aerosol (SSA) and Secondary aerosol formation by nucleation during mesocosms experiments performed in May 2013 at the Oceanographic and Marine Station STARESO in western Corsica. We followed both water and air characteristics of three mesocosms containing an immerged part filled with 3,3 m3 of sea water and an emerged part filled with filtered natural air. Mesocosms were equipped with a pack of optical and physicochemical sensors and received different treatments: one of these mesocosms was left unchanged as control and the two others were enriched by addition of nitrates and phosphates respecting Redfield ratio (N:P = 16) in order to create different levels of phytoplanctonic activities. The set of sensors in each mesocosm was allowed to monitor the water temperature, conductivity, pH, incident light, fluorescence of chlorophyll a, and dissolved oxygen concentration. The mesocosms waters were daily sampled for chemical and biological (dissolved organic matter (i.e. DOC and CDOM), particulate matter and related polar compounds, transparent polysaccharides and nutrients concentration) and biological (chlorophyll a, virus, bacteria, phytoplankton and zooplankton concentrations) analyses. Secondary new particle formation was followed on-line in the emerged parts of the mesocosms, while a primary production by bubble bursting was simulated from a sample of sea water in a dedicated set-up every day. The size segregated aerosol number fluxes, cloud condensation nuclei (CCN) fluxes, and biological and organic contents were determined as a function of the sea water characteristics.

  12. Simultaneous online monitoring of inorganic compounds in aerosols and gases in an industrialized area

    NASA Astrophysics Data System (ADS)

    Khezri, Bahareh; Mo, Huan; Yan, Zhen; Chong, Shey-Ling; Heng, Aik Kian; Webster, Richard D.

    2013-12-01

    The automatic MARGA (monitor for aerosols and gases in ambient air) sampling system was used to measure the inorganic ions Cl-, NO3-, SO42-, Na+, NH4+, K+, Mg2+ and Ca2+ in the PM2.5 aerosol phase and the corresponding inorganic gases HCl, HNO2, SO2, HNO3 and NH3 present in the gas phase. Samples were collected and analyzed hourly for 3 months between April and June, 2011, from a sampling site in Singapore close to a heavy industrial area containing extensive petrochemical refineries. The data (hourly and daily average) were analyzed, compared and discussed based on the ratios of HNO2/HNO3 and NH3/NH4+, the levels of nitrate and sulfate, the total nitrogen, the distribution of particulate matter and gaseous compounds, and the acidity of the aerosols. SO2 was the most abundant gas that appeared in an order of magnitude higher concentration than the other trace gases, and correspondingly SO42- was found to be at least 3-10 times higher than other anionic aerosol species. The concentration of major ions in aerosol samples and the related gaseous compounds followed the order of: SO42- > NH4+ > NO3- > K+ > Na+ > Cl- > Ca2+ > Mg2+ and SO2 > NH3 > HNO2 > HNO3, respectively. The maximum values for many of the target analytes occurred during the hazy period in May when there was significant contamination from regional fires. The elevated levels of HNO2 compared to HNO3 and high levels of HNO3 were rationalized based on artifacts in the denuder sampling methodology.

  13. Influence of particle phase state on the hygroscopic behavior of mixed organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Hodas, N.; Zuend, A.; Mui, W.; Flagan, R. C.; Seinfeld, J. H.

    2014-12-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids, to phase-separated particles, to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40-90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids, (2) forcing a single phase, but accounting for non-ideal interactions through activity coefficient calculations, and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation between the inorganic and organic components is assumed at all RH values, with water-uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that a single simplified modeling approach cannot be used to capture the water-uptake behavior for the diversity of particle phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to contribute substantially to error in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing.

  14. Influence of particle-phase state on the hygroscopic behavior of mixed organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Hodas, N.; Zuend, A.; Mui, W.; Flagan, R. C.; Seinfeld, J. H.

    2015-05-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that no single simplified modeling approach can be used to capture the water-uptake behavior for the diversity of particle-phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to produce substantial errors in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing.

  15. Inorganic aerosols responses to emission changes in Yangtze River Delta, China.

    PubMed

    Dong, Xinyi; Li, Juan; Fu, Joshua S; Gao, Yang; Huang, Kan; Zhuang, Guoshun

    2014-05-15

    The new Chinese National Ambient Air Quality standards (CH-NAAQS) published on Feb. 29th, 2012 listed PM2.5 as criteria pollutant for the very first time. In order to probe into PM2.5 pollution over Yangtze River Delta, the integrated MM5/CMAQ modeling system is applied for a full year simulation to examine the PM2.5 concentration and seasonality, and also the inorganic aerosols responses to precursor emission changes. Total PM2.5 concentration over YRD was found to have strong seasonal variation with higher values in winter months (up to 89.9 ?g/m(3) in January) and lower values in summer months (down to 28.8 ?g/m(3) in July). Inorganic aerosols were found to have substantial contribution to PM2.5 over YRD, ranging from 37.1% in November to 52.8% in May. Nocturnal production of nitrate (NO3(-)) through heterogeneous hydrolysis of N2O5 was found significantly contribute to high NO3(-) concentration throughout the year. In winter, NO3(-) was found to increase under nitrogen oxides (NOx) emission reduction due to higher production of N2O5 from the excessive ozone (O3) introduced by attenuated titration, which further lead to increase of ammonium (NH4(+)) and sulfate (SO4(2-)), while other seasons showed decrease response of NO3(-). Sensitivity responses of NO3(-) under anthropogenic VOC emission reduction was examined and demonstrated that in urban areas over YRD, NO3(-) formation was actually more sensitive to VOC than NOx due to the O3-involved nighttime chemistry of N2O5, while a reduction of NOx emission may have counter-intuitive effect by increasing concentrations of inorganic aerosols. PMID:24631615

  16. Importance of global aerosol modeling including secondary organic aerosol formed from monoterpene

    NASA Astrophysics Data System (ADS)

    Goto, Daisuke; Takemura, Toshihiko; Nakajima, Teruyuki

    2008-04-01

    A global three-dimensional aerosol transport-radiation model, coupled to an atmospheric general circulation model (AGCM), has been extended to improve the model process for organic aerosols, particularly secondary organic aerosols (SOA), and to estimate SOA contributions to direct and indirect radiative effects. Because the SOA formation process is complicated and unknown, the results in different model simulations include large differences. In this work, we simulate SOA production assuming various parameterizations of (1) primary organic aerosols (POA) mass concentrations, (2) oxidant species concentrations, and (3) volatile organic compound (VOC) concentrations in the SOA formation through gas-to-particle conversion governed by equilibrium partitioning of monoterpene oxidation products. Comparisons of results from observations, other models, and our simulations with/without the SOA partitioning theory lead to some findings of the influence of SOA on the radiation and cloud fields. First, the SOA number concentrations control cloud droplet effective radii near water cloud tops in the tropics and can affect the estimation of the aerosol indirect radiative effect. Second, SOA simulation results strongly depend on POA concentrations and emission data, so that disregarding this dependence may lead to a significant underestimation of the aerosol radiative effect because most of other studies assume that the SOA production level in the preindustrial era is same as in the current level. The global annual mean production of SOA formed from monoterpene is evaluated in this study as 6.74 Tg a-1, and the global annual mean radiative forcings of the direct and indirect effects by SOA from monoterpene are calculated to be -0.01 and -0.19 W m-2, respectively.

  17. Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

    Microsoft Academic Search

    T. E. Kleindienst; D. F. Smith; W. Li; E. O. Edney; D. J. Driscoll; R. E. Speer; W. S. Weathers

    1999-01-01

    A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC\\/NOx) mixtures irradiated in the presence of fine (<2.5?m) particulate matter. The goal was to

  18. Secondary Organic Aerosol Formation from Anthropogenic Air Pollution: Rapid and Higher than Expected

    Microsoft Academic Search

    Rainer Volkamer; Jose L. Jimenez; Federico San Martini; Katja Dzepina; Qi Zhang; Dara Salcedo; Luisa T. Molina; Douglas R. Worsnop; Mario J. Molina

    2006-01-01

    In urban areas the sources of organic aerosol comprise primary emissions of organic aerosol (POA) and volatile organic compounds (VOCs) as precursors for secondary organic aerosol (SOA). SOA is formed from low volatility products of VOC oxidation. Recent field studies offer evidence that current models greatly underestimate SOA. State-of-the-art SOA models parameterize the results of simulation chamber experiments that bracket

  19. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    Microsoft Academic Search

    M. F. Heringa; P. F. Decarlo; R. Chirico; T. Tritscher; M. Clairotte; C. Mohr; M. Crippa; J. G. Slowik; L. Pfaffenberger; J. Dommen; E. Weingartner; A. S. H. Prévôt; U. Baltensperger

    2011-01-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 mum) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three

  20. BrO loss due to secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Buxmann, Joelle; Bleicher, Sergej; Zetzsch, Cornelius; Held, Andreas; Sommariva, Roberto; von Glasow, Roland; Platt, Ulrich; Ofner, Johannes

    2013-04-01

    One major source of heterogeneous released reactive halogen species (RHS) is primary aerosol from sea-salt particles, ejected by sea spray. Photoactivated RHS emissions, such as atomic Br and BrO radicals, can play a key role in the destruction of atmospheric ozone, influencing HOx and NOx chemistry. Through aerosol interaction they show potential indirect effects on global climate. The formation of RHS can be significantly reduced in the presence of organic aerosols. Additionally, halogen species were found to change the aerosol size distribution, the presence of functional groups and the optical properties. Furthermore, they may form halogenated species in the condensed phase of the organic aerosol - although the inhibition of the formation of RHS has not been quantified before. The interaction of secondary organic aerosols (SOA) from predominantly aliphatic (?-pinene) or aromatic (catechol and guaiacol) precursors and heterogeneously released halogens was studied in smog-chamber experiments. BrO and OClO released from salt aerosols were detected by a White system in combination with Differential Optical Absorption Spectroscopy (DOAS). The size and number distribution of aerosols from salt droplets (~150nm-1000nm) and from SOA (~5nm-150nm) was quantified by a SMPS (Scanning Mobility Particle Sizer) to obtain typical surface areas of 103?m2/cm3 and 2 x 102?m2/cm3, respectively. In the absence of SOA a BrO production rate per salt aerosol surface area of 5.2 x 1011 molec/cm2s =8500 pmol/m2s has been measured. This confirms model assumptions for BrO formation over the Dead Sea, where the Br2 flux of 80-154 pmol/m2s and HOBr flux= 800 pmol/m2s was increased by a factor of 20-30 to explain high BrO mixing ratios. In the presence of SOA from ?-pinene, catechol and guaiacol the formation rate was significantly reduced. In a first approximation, neglecting gas phase reactions, the BrO loss rate regarding the surface area of SOA was calculated to be 42 x 1011 molec/cm2s, 12 x 1011molec/cm2sand 10 x 1011molec/cm2 s for ?-pinene, catechol and guaiacol, respectively. In the presence of SOA about 150 ppt of OClO were formed, which is not completely understood yet, but acidification by organic acids might trigger a chlorine release. Model studies of the experiments including gas and particulate phase reactions will be presented in order to help explain reaction pathways and to estimate accommodation coefficients. In conclusion, we found a reduced formation of BrO in the presence of SOA, and therefore less Br-catalysed O3 destruction. We also show the first quantitative BrO loss rate due to SOA, where ?-pinene shows 4 times higher loss rate compared to catechol and guaiacol.

  1. 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 ?-pinene is used for NO3 oxidation of all terpenes. Reducing the yield for ?-pinene and limonene oxidation in line with recent measurements reduces the global fraction of SOA formed from NO3 oxidation products from 27% to about 21%. This study underscores the need for SOA to be represented in a more realistic way in global aerosol models in order to better reproduce observations of organic aerosol burdens in industrialised and biomass burning regions.

  2. Secondary Aerosol Formation in Urban and Industrial Plumes in the Eastern United States

    NASA Astrophysics Data System (ADS)

    Brock, C.; Degouw, J.; Weber, R.; Sullivan, A.; Peltier, R.; Bates, T.; Quinn, P.; Middlebrook, A.; Warneke, C.; Atlas, E.; Stohl, A.; Trainer, M.; Cooper, O.; Fehsenfeld, F.; Holloway, J.; Hubler, G.; Neuman, A.; Ryerson, T.

    2006-12-01

    Measurements of aerosol particle size distributions, of bulk, size resolved, and single particle composition, and of trace and reactive gas mixing ratios were made on the National Oceanic and Atmospheric Administration WP-3D aircraft downwind of mixed urban/industrial sources in the northeastern United States. Water-soluble organic carbon (WSOC) was found to be a proxy for organic aerosol (OA) mass. From these WSOC measurements, secondary OA (SOA) was found to exceed primary OA by more than an order of magnitude, and was highly correlated with anthropogenic CO. The magnitude and rate of SOA formation was consistent with that determined from measurements in the same region in 2002; the time constant for this SOA formation was ~1 day. In addition to SOA, particulate sulfate was produced with a time constant of ~3 days from the gas-phase oxidation of SO_2, which was ubiquitous but inhomogeneously distributed in the pollution plumes. In pollution plumes, sulfate and associated ammonium (not necessarily fully neutralized) dominated the composition when submicron particle mass concentrations exceeded 15 ?g m-3; at lower mass concentrations SOA dominated. In the mixed urban/industrial plumes sampled, the relative importance of inorganic and organic compounds to particle mass was governed in part by variations in the source strength of precursor gases. However, differences in the oxidation timescales of SO_2 and volatile organic compounds (VOCs) relative to their transport time are also important, and may explain much of the variability in previously published OA/sulfate ratios for this region. These observations indicate that, even with higher-than-expected SOA formation, in the northeastern United States the potential inorganic particulate mass represented by SO_2 emissions significantly exceeds the potential SOA mass from anthropogenic VOC emissions.

  3. Aerosol Size Distribution Response to Anthropogenically Driven Historical Changes in Biogenic Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Pierce, J. R.; D'Andrea, S.; Acosta Navarro, J. C.; Farina, S.; Scott, C.; Farmer, D. K.; Spracklen, D. V.; Riipinen, I.

    2014-12-01

    Emissions of biological volatile organic compounds (BVOC) have changed in the past millennium due to changes in land use, temperature and CO2 concentrations. A recent model reconstruction of BVOC emissions over the past millennium predicted the changes in the three dominant secondary organic aerosol (SOA) producing BVOC classes (isoprene, monoterpenes and sesquiterpenes). The reconstruction predicted that in global averages isoprene emissions have decreased (land-use changes to crop/grazing land dominate the reduction), while monoterpene and sesquiterpene emissions have increased (temperature increases dominate the increases); however, all three show both increases and decreases in certain regions due to competition between the various influencing factors. These BVOC changes have largely been anthropogenic in nature, and land-use change was shown to have the most dramatic effect by decreasing isoprene emissions. We use these modeled estimates of these three dominant BVOC classes' emissions from the years 1000 to 2000 to test the effect of anthropogenic changes to BVOC emissions on SOA formation and global aerosol size distributions using the GEOS-Chem-TOMAS global aerosol microphysics model. With anthropogenic emissions (e.g. SO2, NOx, primary aerosols) held at present day values and BVOC emissions changed from year 1000 to year 2000 values, decreases in the number concentration of particles of size Dp > 80 nm (N80) of >25% in year 2000 relative to year 1000 were predicted in regions with extensive land-use changes since year 1000. This change in N80 was predominantly driven by a shift towards crop/grazing land that produces less BVOC than the natural vegetation. Similar sensitivities to year 1000 vs. year 2000 BVOC emissions exist when anthropogenic emissions are turned off. This large decrease in N80 could be a largely overlooked and important anthropogenic aerosol effect on regional climates.

  4. Aerosol Inorganic Composition at a Tropical Site: Discrepancies Between Filter-Based Sampling and a Semi-Continuous Method

    Microsoft Academic Search

    Ivonne Trebs; Meinrat O. Andreae; Wolfgang Elbert; Olga L. Mayol-Bracero; Lydia L. Soto-García; Yinon Rudich; Alla H. Falkovich; Willy Maenhaut; Paulo Artaxo; René Otjes; Jacob Slanina

    2008-01-01

    The concentrations of the water-soluble inorganic aerosol species, ammonium (NH4 ), nitrate (NO3 ), chloride (Cl), and sulfate (SO4 ), were measured from September to November 2002 at a pasture site in the Amazon Basin (Rondônia, Brazil) (LBA-SMOCC). Measurements were conducted using a semi-continuous technique (Wet-annular denuder\\/Steam-Jet Aerosol Collector: WAD\\/SJAC) and three integrating filter-based methods, namely (1) a denuder-filter pack

  5. 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

  6. Anthropogenic Influence on Secondary Aerosol Formation and Total Water-Soluble Carbon on Atmospheric Particles

    NASA Astrophysics Data System (ADS)

    Gioda, Adriana; Mateus, Vinicius; Monteiro, Isabela; Taira, Fabio; Esteves, Veronica; Saint'Pierre, Tatiana

    2013-04-01

    On a global scale, the atmosphere is an important source of nutrients, as well as pollutants, because of its interfaces with soil and water. Important compounds in the gaseous phase are in both organic and inorganic forms, such as organic acids, nitrogen, sulfur and chloride. In spite of the species in gas form, a huge number of process, anthropogenic and natural, are able to form aerosols, which may be transported over long distances. Sulfates e nitrates are responsible for rain acidity; they may also increase the solubility of organic compounds and metals making them more bioavailable, and also can act as cloud condensation nuclei (CCN). Aerosol samples (PM2.5) were collected in a rural and industrial area in Rio de Janeiro, Brazil, in order to quantify chemical species and evaluate anthropogenic influences in secondary aerosol formation and organic compounds. Samples were collected during 24 h every six days using a high-volume sampler from August 2010 to July 2011. The aerosol mass was determined by Gravimetry. The water-soluble ionic composition (WSIC) was obtained by Ion Chromatography in order to determine the major anions (NO3-, SO4= and Cl-); total water-soluble carbon (TWSC) was determined by a TOC analyzer. The average aerosol (PM2.5) concentrations ranged from 1 to 43 ug/m3 in the industrial site and from 4 to 35 ug/m3 in the rural area. Regarding anions, the highest concentrations were measured for SO42- (10.6 ?g/m3-12.6 ?g/m3); where the lowest value was found in the rural site and the highest in the industrial. The concentrations for NO3- and Cl- ranged from 4.2 ?g/m3 to 9.3 ?g/m3 and 3.1 ?g/m3 to 6.4 ?g /m3, respectively. Sulfate was the major species and, like nitrate, it is related to photooxidation in the atmosphere. Interestingly sulfate concentrations were higher during the dry period and could be related to photochemistry activity. The correlations between nitrate and non-sea-salt sulfate were weak, suggesting different sources for these species. The secondary aerosol represented an important fraction of total compounds in PM2.5 ranged from 16 to 18% for (NH4)2SO4 and 6 to 8% for NH4NO3. The values for TWSC ranged from 0.28 to 6.35 ?g/m3 in the industrial area and 0.12 to 7.49 ?g/m3 for rural area. The similarity between the areas regarding secondary aerosols formation and water-soluble carbon compounds is probably due to the particle size.

  7. Effect of NOx on secondary organic aerosol concentrations.

    PubMed

    Lane, Timothy E; Donahue, Neil M; Pandis, Spyros N

    2008-08-15

    The secondary organic aerosol (SOA) module in PMCAMx, a three-dimensional chemical transport model, has been updated to incorporate NOx-dependent SOA yields. Under low-NOx conditions, the RO2 radicals react with other peroxy radicals to form a distribution of products with lower volatilities, resulting in higher SOA yields. At high-NOx conditions, the SOA yields are lower because aldehydes, ketones, and nitrates dominate the product distribution. Based on recent laboratory smog chamber experiments, high-NOx SOA parametrizations were created using the volatility basis-set approach.The organic aerosol (OA) concentrations in the Eastern US are simulated for a summer episode, and are compared to the available ambient measurements. Changes in NOx levels result in changes of both the oxidants (ozone, OH radical, etc.) and the SOA yields during the oxidation of the corresponding organic vapors. The NOx dependent SOA parametrization predicts a maximum average SOA concentration of 5.2 microg m(-3) and a domain average concentration of 0.6 microg m(-3). As the NOx emissions are reduced by 25%, the domain average SOA concentration does not significantly change, but the response is quite variable spatially. However, the predicted average SOA concentrations increase in northern US cities by around 3% but decrease in the rural southeast US by approximately 5%. A decrease of the average biogenic SOA by roughly 0.5 microg m(-3) is predicted for the southeast US for a 50% reduction in NOx emissions. PMID:18767660

  8. Secondary organic aerosol from polycyclic aromatic hydrocarbons in Southeast Texas

    NASA Astrophysics Data System (ADS)

    Zhang, Hongliang; Ying, Qi

    2012-08-01

    Recent chamber studies show that low-volatility gas phase precursors such as polycyclic aromatic hydrocarbons (PAHs) can be a significant source of secondary organic aerosol (SOA). In this work, formation of SOA from the photo-oxidation products of PAHs is added to the SOA modeling framework of the Community Multiscale Air Quality (CMAQ) model to determine the regional distribution of SOA products from PAHs (PAH-SOA) and the contributions from sources in Southeast Texas during the Texas Air Quality Study 2006 (TexAQS 2006). Results show that PAHs released from anthropogenic sources can produce SOA mass as much as 10% of that from the traditional light aromatics or approximately 4% of total anthropogenic SOA. In areas under the influence of wildfire emissions, the amount of PAH-SOA can be as much as 50% of the SOA from light aromatics. A source-oriented modeling framework is adopted to determine the major sources of PAH-SOA by tracking the emitted PAHs and their oxidation products in the gas and aerosol phases from different sources separately. Among the eight sources (vehicles, solvent utilization, residential wood, industries, natural gas combustion, coal combustion, wildfire and other sources) that are tracked in the model, wildfire, vehicles, solvent and industries are the major sources of PAH-SOA. Coal and natural gas combustion appear to be less important in terms of their contributions to PAH-SOA.

  9. Secondary Organic Aerosol Production from Cloud Processing of Glycolaldehyde

    NASA Astrophysics Data System (ADS)

    Perri, M. J.; Seitzinger, S.; Turpin, B. J.

    2008-12-01

    Organic particulate matter (PM) formed in the atmosphere (secondary organic aerosol; SOA) is a substantial yet poorly understood contributor to atmospheric PM. Cloud processing is a newly recognized SOA formation pathway. This study investigates the potential for aqueous glycolaldehyde oxidation to produce low volatility products that are retained in the particle phase upon cloud droplet evaporation, increasing PM concentrations aloft. To our knowledge, this is the first confirmation that aqueous oxidation of glycolaldehyde via the hydroxyl radical forms glyoxal and glycolic acid, as previously assumed. Subsequent reactions form formic acid, glyoxylic acid, and oxalic acid as expected. Unexpected products include malonic acid, succinic acid, and higher molecular weight compounds, including oligomers. Predictions of aerosol yields based on these bulk aqueous experiments are presented. Due to (1) the large source strength of glycolaldehyde from precursors such as isoprene and ethene, (2) its water solubility, and (3) the aqueous formation of low volatility products, we predict that cloud processing of glycolaldehyde is an important source of SOA and that incorporation of this SOA formation pathway in chemical transport models will help explain the current under- prediction of organic PM concentrations.

  10. Heterogeneous glyoxal oxidation: a potential source of secondary organic aerosol.

    PubMed

    Connelly, B M; De Haan, D O; Tolbert, M A

    2012-06-21

    Laboratory studies are described that suggest reactive uptake of glyoxal on particulate containing HNO(3) could contribute to the formation of secondary organic aerosol (SOA) in the upper troposphere (UT). Using a Knudsen cell flow reactor, glyoxal is observed to react on supercooled H(2)O/HNO(3) surfaces to form condensed-phase glyoxylic acid. This product was verified by derivatization and GC-MS analysis. The reactive uptake coefficient, ?, of glyoxal varies only slightly with the pressure of nitric acid, from ? = 0.5 to 3.0 × 10(-3) for nitric acid pressures between 10(-8) and 10(-6) Torr. The data do not show any dependence on temperature (181-201 K) or pressure of glyoxal (10(-7) to 10(-5) Torr). Using the determined reactive uptake kinetics in a simple model shows that glyoxal uptake to supercooled H(2)O/HNO(3) may account for 4-53% of the total organic mass fraction of aerosol in the UT. PMID:22510110

  11. Secondary organic aerosol coating of synthetic metal-oxide nanoparticles.

    PubMed

    Lee, Joohyung; Donahue, Neil M

    2011-06-01

    Secondary organic aerosol (SOA) from the ?-pinene + ozone reaction readily coats TiO(2) and CeO(2) metal-oxide nanoparticles in smog-chamber experiments under atmospherically relevant conditions. Otherwise identical experiments compared bare nanoparticles and nanoparticles coated with poly(acrylic acid) (PAA). The PAA-coated particles result in significantly higher new-particle formation rates, suggesting that the SOA vapors coat bare metal oxide more readily than the PAA. After particles begin to grow via SOA coating, however, all particles, independent of size or the presence of a metal-oxide core, grow with a rate proportional to their surface area, modified to account for gas-phase diffusion in the transition regime between the kinetic and bulk-flow regimes. This suggests that SOA condensational growth may be modeled based on the size distribution of the condensational sink in the atmosphere. PMID:21534558

  12. 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-only model suggested that differences in the volatility of the precursors were able to explain most of the variability observed in the SOA formation. For aircraft exhaust, the previous methods to simulate SOA formation from SVOC and IVOC performed poorly. A more physically-realistic modeling framework was developed, which was then used to show that SOA formation from aircraft exhaust was (a) higher for petroleum-based than synthetically derived jet fuel and (b) higher at lower engine loads and vice versa. All of the SOA data from combustion emissions experiments were used to determine source-specific parameterizations to model SOA formation from SVOC, IVOC and other unspeciated emissions. The new parameterizations were used to investigate their influence on the OA budget in the United States. Combustion sources were estimated to emit about 2.61 Tg yr-1 of SVOC, 1VOC and other unspeciated emissions (sixth of the total anthropogenic organic emissions), which are predicted to double SOA production from combustion sources in the United States. The contribution of SVOC and IVOC emissions to global SOA formation was assessed using a global climate model. Simulations were performed using a modified version of GISS GCM 11'. The modified model predicted that SVOC and IVOC contributed to half of the OA mass in the atmosphere. Their inclusion improved OA model-measurement comparisons for absolute concentrations, POA-SOA split and volatility (gas-particle partitioning) globally suggesting that atmospheric models need to incorporate SOA formation from SVOC and IVOC if they are to reasonably predict the abundance and properties of aerosols. This thesis demonstrates that SVOC/IVOC and possibly other unspeciated organics emitted by combustion sources are very important precursors of SOA and potentially large contributors to the atmospheric aerosol mass. Models used for research and policy applications need to represent them to improve model-predictions of aerosols on climate and health outcomes. The improved modeling frameworks developed in this dissertation are suitable for implementa

  13. Estimates of non-traditional secondary organic aerosols from aircraft SVOC and IVOC emissions using CMAQ

    NASA Astrophysics Data System (ADS)

    Woody, M. C.; West, J. J.; Jathar, S. H.; Robinson, A. L.; Arunachalam, S.

    2015-06-01

    Utilizing an aircraft-specific parameterization based on smog chamber data in the Community Multiscale Air Quality (CMAQ) model with the volatility basis set (VBS), we estimated contributions of non-traditional secondary organic aerosols (NTSOA) for aircraft emissions during landing and takeoff (LTO) activities at the Hartsfield-Jackson Atlanta International Airport. NTSOA, formed from the oxidation of semi-volatile and intermediate volatility organic compounds (S/IVOCs), is a heretofore unaccounted component of fine particulate matter (PM2.5) in most air quality models. We expanded a prerelease version of CMAQ with VBS implemented for the Carbon Bond 2005 (CB05) chemical mechanism to use the Statewide Air Pollution Research Center 2007 (SAPRC-07) chemical mechanism and added species representing aircraft S/IVOCs and corresponding NTSOA oxidation products. Results indicated that the maximum monthly average NTSOA contributions occurred at the airport and ranged from 2.4 ng m-3 (34 % from idle and 66 % from non-idle aircraft activities) in January to 9.1 ng m-3 (33 and 67 %) in July. This represents 1.7 % (of 140 ng m-3) in January and 7.4 % in July (of 122 ng m-3) of aircraft-attributable PM2.5 compared to 41.0-42.0 % from elemental carbon and 42.8-58.0 % from inorganic aerosols. As a percentage of PM2.5, impacts were higher downwind of the airport, where NTSOA averaged 4.6-17.9 % of aircraft-attributable PM2.5 and, considering alternative aging schemes, was as high as 24.0 % - thus indicating the increased contribution of aircraft-attributable SOA as a component of PM2.5. However, NTSOA contributions were generally low compared to smog chamber results, particularly at idle, due to the considerably lower ambient organic aerosol concentrations in CMAQ compared to those in the smog chamber experiments.

  14. Field Studies for Secondary Organic Aerosol in the Transboundary Air

    NASA Astrophysics Data System (ADS)

    Irei, S.; Takami, A.; Sadanaga, Y.; Nozoe, S.; Hayashi, M.; Hara, K.; Arakaki, T.; Hatakeyama, S.; Miyoshi, T.; Yokouchi, Y.; Bandow, H.

    2014-12-01

    To study formation of secondary organic aerosol (SOA) in the air outflowed from the Chinese continent and its fraction in an urban city located in downwind, we have conducted field studies at two background sites and one urban site in the western Japan: the Cape Hedo Aerosol and Atmospheric Monitoring Station (26.9?N, 128.3?E), the Fukue Atmospheric Monitoring Station (32.8?N, 128.7?E), and Fukuoka University (33.6?N, 130.4?E), respectively. During the studies, stable carbon isotope ratio (?13C) of low-volatile water-soluble organic carbon (LV-WSOC) was measured in 24 h collected filter samples of total suspended particulate matter. Concentration of fine organic aerosol and the proportion of the signal at m/z 44 (ions from the carboxyl group) in the organic mass spectra (f44) were also measured by Aerodyne aerosol mass spectrometers. Limited to the Fukue site only, mixing ratios of trace gas species, such as aromatic hydrocarbons, NOx, and NOy, were also measured using GC-FID and NOx and NOyanalyzers for estimation of photochemical age (t[OH]). A case study in December 2010 showed that plots of ?13C versus f44 showed systematic variations at Hedo and Fukue. However, their trends were opposite. At Fukue the trend was consistent in the plot of ?13C of LV-WSOC versus t[OH] estimated by the NOx/NOy or the hydrocarbon ratios, indicating influence of SOA. The systematic trends aforementioned qualitatively agreed with a binary mixture model of SOA with background LV-WSOC having the f44 of ~0.06 and the ?13C of -17‰ or higher, implication of some influence of primary emission associated with C4plants. Given that the LV-WSOC at the urban Fukuoka site was a binary mixture, a mass balance for ?13C was constructed below. In the equation, ?13CMix, ?13CLocal, ?13CTrans, and FLocal are ?13C of binary LV-WSOC mixture, ?13C of LV-WSOC from local emission origin, ?13C of LV-WSOC from transboundary pollution origin, and a fraction of LV-WSOC from local emission origin in the mixture, respectively. We applied d13C values at Fukuoka and Fukue to ?13CMix and ?13CTrans, respectively, and ?13C of -27‰ for vehicular emission to ?13CLocal. The preliminary results demonstrated that, except some negative FLocal, the majority of calculated FLocal ranged from 4% to 86% and the lower FLocal, the higher LV-WSOC concentration.

  15. Organic and inorganic gaseous chlorine concentrations in relation to the particle size distribution of chloride in the marine aerosol

    Microsoft Academic Search

    Walter W. Berg; John W. Winchester

    1977-01-01

    An intensive field sampling program has been carried out over the ocean in which 56 gas samples and 172 aerosol particle samples were analyzed for total organic chlorine and total inorganic chlorine gas and for particulate chlorine as a function of particle size. Sampling was conducted for 13- to 21-hour periods, March 5-14, 1976, 4 km from the north Florida

  16. Light absorption by secondary organic aerosol from ?-pinene: Effects of oxidants, seed aerosol acidity, and relative humidity

    NASA Astrophysics Data System (ADS)

    Song, Chen; Gyawali, Madhu; Zaveri, Rahul A.; Shilling, John E.; Arnott, W. Patrick

    2013-10-01

    is well known that light absorption from dust and black carbon aerosols has a warming effect on climate while light scattering from sulfate, nitrate, and sea salt aerosols has a cooling effect. However, there are large uncertainties associated with light absorption and scattering by different types of organic aerosols, especially in the near-UV and UV spectral regions. In this paper, we present the results from a systematic laboratory study focused on measuring light absorption by secondary organic aerosols (SOAs) generated from dark ?-pinene + O3 and ?-pinene + NOx + O3 systems in the presence of neutral and acidic sulfate seed aerosols. Light absorption was monitored using photoacoustic spectrometers at four different wavelengths: 355, 405, 532, and 870 nm. Significant light absorption at 355 and 405 nm was observed for the SOA formed from ?-pinene + O3 + NO3 system only in the presence of highly acidic sulfate seed aerosols under dry conditions. In contrast, no absorption was observed when the relative humidity was elevated to greater than 27% or in the presence of neutral sulfate seed aerosols. Organic nitrates in the SOA formed in the presence of neutral sulfate seed aerosols were found to be nonabsorbing, while the light-absorbing compounds are speculated to be aldol condensation oligomers with nitroxy organosulfate groups that are formed in highly acidic sulfate aerosols. Overall, these results suggest that dark ?-pinene + O3 and ?-pinene + NOx + O3 systems do not form light-absorbing SOA under typical atmospheric conditions.

  17. Aerosol mass spectrometer constraint on the global secondary organic aerosol budget

    NASA Astrophysics Data System (ADS)

    Spracklen, D. V.; Jimenez, J. L.; Carslaw, K. S.; Worsnop, D. R.; Evans, M. J.; Mann, G. W.; Zhang, Q.; Canagaratna, M. R.; Allan, J.; Coe, H.; McFiggans, G.; Rap, A.; Forster, P.

    2011-12-01

    The budget of atmospheric secondary organic aerosol (SOA) is very uncertain, with recent estimates suggesting a global source of between 12 and 1820 Tg (SOA) a-1. We used a dataset of aerosol mass spectrometer (AMS) observations from 34 different surface locations to evaluate the GLOMAP global chemical transport model. The standard model simulation (which included SOA from monoterpenes only) underpredicted organic aerosol (OA) observed by the AMS and had little skill reproducing the variability in the dataset. We simulated SOA formation from biogenic (monoterpenes and isoprene), lumped anthropogenic and lumped biomass burning volatile organic compounds (VOCs) and varied the SOA yield from each precursor source to produce the best overall match between model and observations. We assumed that SOA is essentially non-volatile and condenses irreversibly onto existing aerosol. Our best estimate of the SOA source is 140 Tg (SOA) a-1 but with a large uncertainty range which we estimate to be 50-380 Tg (SOA) a-1. We found the minimum in normalised mean error (NME) between model and the AMS dataset when we assumed a large SOA source (100 Tg (SOA) a-1) from sources that spatially matched anthropogenic pollution (which we term antropogenically controlled SOA). We used organic carbon observations compiled by Bahadur et al. (2009) to evaluate our estimated SOA sources. We found that the model with a large anthropogenic SOA source was the most consistent with these observations, however improvement over the model with a large biogenic SOA source (250 Tg (SOA) a-1) was small. We used a dataset of 14C observations from rural locations to evaluate our estimated SOA sources. We estimated a maximum of 10 Tg (SOA) a-1 (10 %) of the anthropogenically controlled SOA source could be from fossil (urban/industrial) sources. We suggest that an additional anthropogenic source is most likely due to an anthropogenic pollution enhancement of SOA formation from biogenic VOCs. Such an anthropogenically controlled SOA source would result in substantial climate forcing. We estimated a global mean aerosol direct effect of -0.26 ± 0.15 Wm-2 and indirect (cloud albedo) effect of -0.6+0.24-0.14 Wm-2 from anthropogenically controlled SOA. The biogenic and biomass SOA sources are not well constrained with this analysis due to the limited number of OA observations in regions and periods strongly impacted by these sources. To further improve the constraints by this method, additional OA observations are needed in the tropics and the Southern Hemisphere.

  18. Cloud condensation nuclei activity of isoprene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Engelhart, Gabriella J.; Moore, Richard H.; Nenes, Athanasios; Pandis, Spyros N.

    2011-01-01

    This work explores the cloud condensation nuclei (CCN) activity of isoprene secondary organic aerosol (SOA), likely a significant source of global organic particulate matter and CCN, produced from the oxidation with OH from HONO/HOOH photolysis in a temperature-controlled SOA chamber. CCN concentrations, activation diameter, and droplet growth kinetic information were monitored as a function of supersaturation (from 0.3% to 1.5%) for several hours using a cylindrical continuous-flow streamwise thermal gradient CCN counter connected to a scanning mobility particle sizer. The initial SOA concentrations ranged from 2 to 30 ?g m-3 and presented CCN activity similar to monoterpene SOA with an activation diameter of 35 nm for 1.5% supersaturation and 72 nm for 0.6% supersaturation. The CCN activity improved slightly in some experiments as the SOA aged chemically and did not depend significantly on the level of NOx during the SOA production. The measured activation diameters correspond to a hygroscopicity parameter ? value of 0.12, similar to ? values of 0.1 ± 0.04 reported for monoterpene SOA. Analysis of the water-soluble carbon extracted from filter samples of the SOA suggest that it has a ? of 0.2-0.3 implying an average molar mass between 90 and 150 g mol-1 (assuming a zero and 5% surface tension reduction with respect to water, respectively). These findings are consistent with known oxidation products of isoprene. Using threshold droplet growth analysis, the CCN activation kinetics of isoprene SOA was determined to be similar to pure ammonium sulfate aerosol.

  19. High Molecular Weight Dimer Esters in ?-Pinene Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Kristensen, Kasper; Cui, Tianqu; Zhang, Haofei; Gold, Avram; Glasius, Marianne; Surratt, Jason D.

    2014-05-01

    Monoterpenes, such as ?-pinene, constitute an important group of biogenic volatile organic compounds (BVOC). Once emitted into the atmosphere ?-pinene is removed by oxidization by the hydroxyl radical (OH), reactions with ozone (O3), and with nitrate radicals (NO3) resulting in the formation of first-generation oxidation products, such as semi-volatile carboxylic acids. In addition, higher molecular weight dimer esters originating from the oxidation of ?-pinene have been observed in both laboratory-generated and ambient secondary organic aerosols (SOA). While recent studies suggest that the dimers are formed through esterification between carboxylic acids in the particle phase, the formation mechanism of the dimer esters is still ambiguous. In this work, we present the results of a series of smog chamber experiments to assess the formation of dimer esters formed from the oxidation of ?-pinene. Experiments were conducted in the University of North Carolina (UNC) dual outdoor smog chamber facility to investigate the effect of oxidant species (OH versus O3), relative humidity (RH), and seed aerosol acidity in order to obtain a better understanding of the conditions leading to the formation of the dimer esters and how these parameters may affect the formation and chemical composition of SOA. The chemical composition of ?-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), and a total of eight carboxylic acids and four dimer esters were identified, constituting between 8 and 12 % of the total ?-pinene SOA mass.

  20. Influence of collecting substrates on the characterization of hygroscopic properties of inorganic aerosol particles.

    PubMed

    Eom, Hyo-Jin; Gupta, Dhrubajyoti; Li, Xue; Jung, Hae-Jin; Kim, Hyekyeong; Ro, Chul-Un

    2014-03-01

    The influence of six collecting substrates with different physical properties on the hygroscopicity measurement of inorganic aerosol particle surrogates and the potential applications of these substrates were examined experimentally. Laboratory-generated single salt particles, such as NaCl, KCl, and (NH4)2SO4, 1-5 ?m in size, were deposited on transmission electron microscopy grids (TEM grids), parafilm-M, Al foil, Ag foil, silicon wafer, and cover glass. The particle hygroscopic properties were examined by optical microscopy. Contact angle measurements showed that parafilm-M is hydrophobic, and cover glass, silicon wafer, Al foil, and Ag foil substrates are hydrophilic. The observed deliquescence relative humidity (DRH) values for NaCl, KCl, and (NH4)2SO4 on the TEM grids and parafilm-M substrates agreed well with the literature values, whereas the DRHs obtained on the hydrophilic substrates were consistently ?1-2% lower, compared to those on the hydrophobic substrates. The water layer adsorbed on the salt crystals prior to deliquescence increases the Gibb's free energy of the salt crystal-substrate system compared to the free energy of the salt droplet-substrate system, which in turn reduces the DRHs. The hydrophilic nature of the substrate does not affect the measured efflorescence RH (ERH) values. However, the Cl(-) or SO4(2-) ions in aqueous salt droplets seem to have reacted with Ag foil to form AgCl or Ag2SO4, respectively, which in turn acts as seeds for the heterogeneous nucleation of the original salts, leading to higher ERHs. The TEM grids were found to be most suitable for the hygroscopic measurements of individual inorganic aerosol particles by optical microscopy and when multiple analytical techniques, such as scanning electron microscopy-energy dispersive X-ray spectroscopy, TEM-EDX, and/or Raman microspectrometry, are applied to the same individual particles. PMID:24506470

  1. Chemical characterization of secondary organic aerosol from aromatic precursors in smog chamber experiments

    Microsoft Academic Search

    M. Kalberer; M. Sax; R. Zenobi; D. Paulsen; M. Steinbacher; A. Prevot; E. Weingartner; U. Baltensperger

    2003-01-01

    In a newly built smog chamber (27m^3 volume) at the Paul Scherrer Institute secondary organic aerosols were produced from photo-oxidation products of aromatic compounds. The aerosol composition as well as gas phase reaction products was analyzed. Aerosol collected on filter samples was analyzed with gas chromatography \\/ mass spectrometry GC\\/MS after derivatization of carbonyl, carboxyl and hydroxyl functional groups to

  2. Processes influencing secondary aerosol formation in the San Joaquin Valley during winter

    SciTech Connect

    Frederick W. Lurmann; Steven G. Brown; Michael C. McCarthy; Paul T. Roberts [Sonoma Technology, Inc., Petaluma, CA (United States)

    2006-12-15

    Air quality data collected in the California Regional PM10/PM2.5 Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM2.5) mass concentrations in California ({le} 188 {mu}g/m{sup 3} 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NOx)-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NOx and volatile organic compound (VOC) emissions plus background O{sub 3} levels are expected to determine NOx oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter. 59 refs., 11 figs., 1 tab.

  3. Formation of semivolatile inorganic aerosols in the Mexico City Metropolitan Area during the MILAGRO campaign

    NASA Astrophysics Data System (ADS)

    Karydis, V. A.; Tsimpidi, A. P.; Lei, W.; Molina, L. T.; Pandis, S. N.

    2011-12-01

    One of the most challenging tasks for chemical transport models (CTMs) is the prediction of the formation and partitioning of the major semi-volatile inorganic aerosol components (nitrate, chloride, ammonium) between the gas and particulate phases. In this work the PMCAMx-2008 CTM, which includes the recently developed aerosol thermodynamic model ISORROPIA-II, is applied in the Mexico City Metropolitan Area in order to simulate the formation of the major inorganic aerosol components. The main sources of SO2 (such as the Miguel Hidalgo Refinery and the Francisco Perez Rios Power Plant) in the Mexico City Metropolitan Area (MCMA) are located in Tula, resulting in high predicted PM1 (particulate matter with diameter less than 1 ?m) sulfate concentrations (over 25 ?g m-3) in that area. The average predicted PM1 nitrate concentrations are up to 3 ?g m-3 (with maxima up to 11 ?g m-3) in and around the urban center, mostly produced from local photochemistry. The presence of calcium coming from the Tolteca area (7 ?g m-3) as well as the rest of the mineral cations (1 ?g m-3 potassium, 1 ?g m-3 magnesium, 2 ?g m-3 sodium, and 3 ?g m-3 calcium) from the Texcoco Lake resulted in the formation of a significant amount of aerosol nitrate in the coarse mode with concentrations up to 3 ?g m-3 over these areas. PM1-10 (particulate matter with diameter between 1 and 10 ?m) chloride is also high and its concentration exceeds 2 ?g m-3 in Texcoco Lake. PM1 ammonium concentrations peak at the center of Mexico City (2 ?g m-3) and the Tula vicinity (2.5 ?g m-3). The performance of the model for the major inorganic PM components (sulfate, ammonium, nitrate, chloride, sodium, calcium, and magnesium) is encouraging. At the T0 measurement site, located in the Mexico City urban center, the average measured values of PM1 sulfate, nitrate, ammonium, and chloride are 3.5 ?g m-3, 3.5 ?g m-3, 2.1 ?g m-3, and 0.36 ?g m-3, respectively. The corresponding predicted values are 3.7 ?g m-3, 2.7 ?g m-3, 1.7 ?g m-3, and 0.25 ?g m-3. High sulfate concentrations are associated with the transport of sulfate from the Tula vicinity, while in periods where southerly winds are dominant; the concentrations of sulfate are low. The underprediction of nitrate can be attributed to the underestimation of OH levels by the model during the early morning. Ammonium is sensitive to the predicted sulfate concentrations and the nitrate levels. The performance of the model is also evaluated against measurements taken from a suburban background site (T1) located north of Mexico City. The average predicted PM2.5 (particulate matter with diameter less than 2.5 ?m) sulfate, nitrate, ammonium, chloride, sodium, calcium, and magnesium are 3.3, 3.2, 1.4, 0.5, 0.3, 1.2, and 0.15 ?g m-3, respectively. The corresponding measured concentrations are 3.7, 2.9, 1.5, 0.3, 0.4, 0.6, and 0.15 ?g m-3. The overprediction of calcium indicates a possible overestimation of its emissions and affects the partitioning of nitric acid to the aerosol phase resulting occasionally in an overprediction of nitrate. Additional improvements are possible by improving the performance of the model regarding the oxidant levels, and revising the emissions and the chemical composition of the fugitive dust. The hybrid approach in which the mass transfer to the fine aerosol is simulated using the bulk equilibrium assumption and to the remaining aerosol sections using a dynamic approach, is needed in order to accurately simulate the size distribution of the inorganic aerosols. The bulk equilibrium approach fails to reproduce the observed coarse nitrate and overpredicts the fine nitrate. Sensitivity tests indicate that sulfate concentration in Tula decreases by up to 0.5 ?g m-3 after a 50% reduction of SO2 emissions while it can increase by up to 0.3 ?g m-3 when NOx emissions are reduced by 50%. Nitrate concentration decreases by up to 1 ?g m-3 after the 50% reduction of NOx or NH3 emissions. Ammonium concentration decreases by up to 1 ?g m-3, 0.3 ?g m-3, and 0.1 ?g m-3 after the 50% reduction o

  4. Relationship between aerosol oxidation level and hygroscopic properties of laboratory generated secondary organic aerosol (SOA) particles

    NASA Astrophysics Data System (ADS)

    Massoli, P.; Lambe, A. T.; Ahern, A. T.; Williams, L. R.; Ehn, M.; Mikkilä, J.; Canagaratna, M. R.; Brune, W. H.; Onasch, T. B.; Jayne, J. T.; Petäjä, T.; Kulmala, M.; Laaksonen, A.; Kolb, C. E.; Davidovits, P.; Worsnop, D. R.

    2010-12-01

    Laboratory experiments investigated the relationship between oxidation level and hygroscopic properties of secondary organic aerosol (SOA) particles generated via OH radical oxidation in an aerosol flow reactor. The hygroscopic growth factor at 90% RH (HGF90%), the CCN activity ($\\kappa$ORG,CCN) and the level of oxidation (atomic O:C ratio) of the SOA particles were measured. Both HGF90% and $\\kappa$ORG,CCN increased with O:C; the HGF90% varied linearly with O:C, while $\\kappa$ORG,CCN mostly followed a nonlinear trend. An average HGF90% of 1.25 and $\\kappa$ORG,CCN of 0.19 were measured for O:C of 0.65, in agreement with results reported for ambient data. The $\\kappa$ORG values estimated from the HGF90% ($\\kappa$ORG,HGF) were 20 to 50% lower than paired $\\kappa$ORG,CCN values for all SOA particles except 1,3,5-trimethylbenzene (TMB), the least hygroscopic of the SOA systems. Within the limitations of instrumental capabilities, we show that differences in hygroscopic behavior among the investigated SOA systems may correspond to differences in elemental composition.

  5. Effect of the OH Radical Scavenger Hydrogen Peroxide on Secondary Organic Aerosol Formation from ?-Pinene Ozonolysis

    Microsoft Academic Search

    Kaytlin M. Henry; Neil M. Donahue

    2011-01-01

    Hydrogen peroxide (HOOH) is a potentially valuable hydroxyl radical (OH) scavenger in secondary organic aerosol experiments focused on ozonolysis yields. Here, we present results for ?-pinene ozonolysis. The OH scavenging produces solely HO2 radicals and the resulting high [HO2]\\/[RO2] ratio causes an increase in aerosol formation from ?-pinene ozonolysis, compared to experiments performed with butanol OH scavengers. The majority of

  6. The Formation of Secondary Organic Aerosol from the Isoprene + OH Reaction in the Absence of NOx

    EPA Science Inventory

    The reaction of isoprene (C5H8) with hydroxyl radicals has been studied in the absence of nitrogen oxides (NOx) to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog ch...

  7. 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...

  8. 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...

  9. 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...

  10. Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals

    E-print Network

    Kessler, Sean Herbert

    The immense complexity inherent in the formation of secondary organic aerosol (SOA)—due primarily to the large number of oxidation steps and reaction pathways involved—has limited the detailed understanding of its underlying ...

  11. The role of long-range transport and domestic emissions in determining atmospheric secondary inorganic particle concentrations across the UK

    NASA Astrophysics Data System (ADS)

    Vieno, M.; Heal, M. R.; Hallsworth, S.; Famulari, D.; Doherty, R. M.; Dore, A. J.; Tang, Y. S.; Braban, C. F.; Leaver, D.; Sutton, M. A.; Reis, S.

    2013-12-01

    Surface concentrations of secondary inorganic particle components over the UK have been analysed for 2001-2010 using the EMEP4UK regional atmospheric chemistry transport model. In early 2003 an episode of substantially elevated surface concentrations of ammonium nitrate was measured across the UK by the AGANET network. The EMEP4UK model was able accurately to represent both the long-term decadal surface concentrations and the episode in 2003. The latter was identified as consisting of three separate episodes, each of less than 1 month duration, in February, March and April. The primary cause of the elevated nitrate levels across the UK was meteorological, a persistent high pressure system, but whose varying location impacted the relative importance of transboundary vs. domestic emissions. Whilst long-range transport dominated the elevated nitrate in February, in contrast it was domestic emissions that mainly contributed to the March episode, and for the April episode both domestic emissions and long-range transport contributed. A prolonged episode such as the one in early 2003 can have substantial impact on annual average concentrations. The episode led to annual concentration differences at the regional scale of similar magnitude to those driven by long-term changes in precursor emissions over the full decade investigated here. The results demonstrate that a substantial part of the UK, particularly the south and south-east, may be close to or actually exceeding annual mean limit values because of import of inorganic aerosol components from continental Europe under specific conditions. The results reinforce the importance of employing multiple year simulations in the assessment of emissions reduction scenarios on PM concentrations and the need for international agreements to address the transboundary component of air pollution.

  12. Carbon in southeastern U.S. aerosol particles: Empirical estimates of secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Blanchard, Charles L.; Hidy, George M.; Tanenbaum, Shelley; Edgerton, Eric; Hartsell, Benjamin; Jansen, John

    Fine particles in the southeastern United States are rich in carbon: Southeastern Aerosol Research and Characterization (SEARCH) network measurements from 2001 through 2004 indicate that fine particles less than 2.5 ?m aerodynamic diameter (PM 2.5) at two inland urban sites, Atlanta, GA and Birmingham, AL, contain 9 and 11% black carbon (BC) by mass, respectively, on average. For neighboring rural or urban Gulf Coast sites, the range is 4-7% BC. Organic carbon (OC) ranges from 25 to 27% in the inland cities, and 19-24% at the rural or Gulf Coast locations. Evidence in the literature suggests that a substantial fraction of the OC found in the Southeast is produced by atmospheric chemical reactions of volatile organic compounds (VOCs). Estimation of the fraction of OC from primary and secondary sources is difficult from first principles, because the chemistry is complex and incompletely understood, and the emission sources are both anthropogenic and natural. As an alternative, measurement-based models can be used to estimate empirically the primary and secondary source contributions. Three complementary empirical models are described and applied using the SEARCH database. The methods include (a) a multiple regression model employing markers for primary and secondary carbon using gas and particle data, (b) a carbon mass balance using carbon and CO data, along with certain assumptions about the OC/CO ratios in primary emissions for different urban and rural conditions, and (c) exploitation of isotopic measurements of carbon along with the BC and OC data. Secondary organic carbon (SOC) represents ˜20-60% of mean OC, depending upon location and season. The results are sensitive to estimates of emissions of primary OC and BC.

  13. A Methodology for the Prediction of the Chemical Composition of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Barley, M.; Topping, D.; McFiggans, G.; Jenkin, M.

    2009-04-01

    Atmospheric aerosols have been identified by the Intergovernmental Panel on Climate Change in their recent reports (IPCC, 2007) as a key influence on climate change, but as also an influence about which we have minimal understanding. Atmospheric aerosols can contain a wide range of components but most are believed to be mainly composed of an inorganic part, an organic part and associated water. The inorganic component is relatively well understood and is composed of a limited number of ionic species. However, the organic component is much more complex as any of the thousands of organic compounds found in the atmosphere can potentially condense into the aerosol. A major contributor to the organic aerosol is believed to be from chemicals formed by atmospheric processes. Volatile organic compounds (VOC's) from both anthropogenic and biogenic sources (primary emissions), undergo progressive oxidation in the atmosphere and the products of these atmospheric reactions may contribute to the formation of secondary organic aerosol (SOA) particles. The oxidation process leads to increased functionalization of the VOC with a resulting increase in polarity and decrease in volatility. The less volatile components in this mixture may condense to form SOA particles by nucleation or by condensation onto particles (such as involatile primary emissions, or polymerised water soluble material) already present in the atmosphere. There is much speculation about the composition of SOA particles as complete analyses are not available. One approach is to model the formation of SOA using an explicit atmospheric chemistry scheme coupled to a condensation/absorption model. We will report on the use the Master Chemical Mechanism (MCM:- see http://mcm.leeds.ac.uk/MCM/) with a modified version of the Pankow absorption model to predict the chemical composition of SOA particles formed under a range of conditions. The MCM provided the atmospheric abundances of 3700 non-radical atmospheric chemical species in a trajectory model of a heavily polluted air parcel that arrived at Writtle (Essex) in the south of England at 18:00 on August 6th 2003 during the TORCH campaign. A similar set of abundances were simulated for an air-parcel arriving on August 12th with high concentrations of VOC's from biological sources. These two sets of atmospheric concentrations formed the inputs for the calculation of the chemical composition of anthropogenically dominated and biogenically dominated SOA respectively. The condensation of the oxidised VOC's were modelled using the following methodology:- 1) The model used was a modified version of the Pankow absorption model. 2) Estimated vapour pressures were used for all components and liquid phase ideality was assumed. 3) It was assumed that water condensed into the SOA alongside the organic components. 4) As liquid phase water is expected to be present the acid anhydrides predicted to be present in the atmosphere are expected to hydrolyse to their corresponding acids. 5) The presence of an involatile core onto which the organics can condense is assumed. Formation of SOA by condensation was modelled for both the anthropogenic and biogenic case over a range of temperatures, relative humidity and target mass (=core mass+SOA mass). This provided a range of SOA masses- particularly for the anthropogenic case where it was clear that the chemical composition of the SOA was strongly affected by the mass of SOA predicted. The results showed that anthropogenic SOA contained significant dicarboxylic acids derived from the hydrolysis of cyclic anhydrides while the biogenic SOA contained pinic acid (another dicarboxylic acid) and a range of multifunctional compounds dominated by hydroxyl and hydroperoxide groups.

  14. Secondary Electron Yield Measurements as a Means for Probing Organic Films on Aerosol Particles

    Microsoft Academic Search

    Paul J. Ziemann; Peter H. McMurry

    1998-01-01

    Secondary electron yields of salt particles (KCl and NaCl) coated with organic films (dioctyl sebacate and octacosane) were measured by impacting aerosol particles with monoenergetic electrons (10–600 eV) inside a particle beam apparatus. The results demonstrate that secondary electron yield measurements can be used to obtain information on the structure of organic films on aerosol particles. The technique relies upon

  15. 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.

  16. Heterogeneous ice nucleation on simulated secondary organic aerosol.

    PubMed

    Schill, Gregory P; De Haan, David O; Tolbert, Margaret A

    2014-02-01

    In this study, we have explored the phase behavior and the ice nucleation properties of secondary organic aerosol made from aqueous processing (aqSOA). AqSOA was made from the dark reactions of methylglyoxal with methylamine in simulated evaporated cloud droplets. The resulting particles were probed from 215 to 250 K using Raman spectroscopy coupled to an environmental cell. We find these particles are in a semisolid or glassy state based upon their behavior when exposed to mechanical pressure as well as their flow behavior. Further, we find that these aqSOA particles are poor depositional ice nuclei, in contrast to previous studies on simple mixtures of glassy organics. Additionally, we have studied the effect of ammonium sulfate on the phase, morphology, and ice nucleation behavior of the aqSOA. We find that the plasticizing effect of ammonium sulfate lowers the viscosity of the aqSOA, allowing the ammonium sulfate to effloresce within the aqSOA matrix. Upon humidification, the aqSOA matrix liquefies before it can depositionally nucleate ice, and the effloresced ammonium sulfate can act as an immersion mode ice nucleus. This change in the mode of nucleation is accompanied by an increase in the overall ice nucleation efficiency of the aqSOA particles. PMID:24410444

  17. Formation of semivolatile inorganic aerosols in the mexico city metropolitan area during the milagro campaign

    NASA Astrophysics Data System (ADS)

    Karydis, V. A.; Tsimpidi, A. P.; Lei, W.; Molina, L. T.; Pandis, S. N.

    2011-08-01

    One of the most challenging tasks for chemical transport models (CTMs) is the prediction of the formation and partitioning of the major semi-volatile inorganic aerosol components (nitrate, chloride, ammonium) between the gas and particulate phases. In this work the PMCAMx-2008 CTM, which includes the recently developed aerosol thermodynamic model ISORROPIA-II, is applied in the Mexico City Metropolitan Area in order to simulate the formation of the major inorganic aerosol components. The main sources of SO2 (such as the Miguel Hidalgo Refinery and the Francisco Perez Rios Power Plant) in the Mexico City Metropolitan Area (MCMA) are located in Tula, resulting in high predicted PM1 sulfate concentrations (over 25 ?g m-3) in that area. The average predicted PM1 nitrate concentrations are up to 3 ?g m-3 (with maxima up to 11 ?g m-3) in and around the urban center, mostly produced from local photochemistry. The presence of calcium coming from the Tolteca area (7 ?g m-3) as well as the rest of the mineral cations (1 ?g m-3 potassium, 1 ?g m-3 magnesium, 2 ?g m-3 sodium, and 3 ?g m-3 calcium) from the Texcoco Lake resulted in the formation of a significant amount of aerosol nitrate in the coarse mode with concentrations up to 3 ?g m-3 over these areas. PM1-10 chloride is also high and its concentration exceeds 2 ?g m-3 in Texcoco Lake. PM ammonium concentrations peak at the center of Mexico City (2 ?g m-3) and the Tula vicinity (2.5 ?g m-3). The performance of the model for the major inorganic PM components (sulfate, ammonium, nitrate, chloride, sodium, calcium, and magnesium) is encouraging. At T0, the average measured values of PM1 sulfate, nitrate, ammonium, and chloride are 3.6 ?g m-3, 3.6 ?g m-3, 2.1 ?g m-3, and 0.35 ?g m-3 respectively. The corresponding predicted values are 3.7 ?g m-3, 2.8 ?g m-3, 1.7 ?g m-3, and 0.25 ?g m-3. Additional improvements are possible by (i) using a day-dependent emission inventory, (ii) improving the performance of the model regarding the oxidant levels, and (iii) revising the emissions and the chemical composition of the fugitive dust. Sensitivity tests indicate that sulfate concentration in Tula decreases by up to 0.5 ?g m-3 after a 50 % reduction of SO2 emissions while it can increase by up to 0.3 ?g m-3 when NOx emissions are reduced by 50 %. Nitrate concentration decreases by up to 1 ?g m-3 after the 50 % reduction of NOx or NH3 emissions. Ammonium concentration decreases by up to 1 ?g m-3, 0.3 ?g m-3, and 0.1 ?g m-3 after the 50 % reduction of NH3, NOx, and SO2 emissions respectively.

  18. Reactive uptake of ammonia to secondary organic aerosols: kinetics of organonitrogen formation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liggio, J.; Staebler, R.; Li, S.-M.

    2015-06-01

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

  19. Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Chan, A. W. H.; Chan, M. N.; Surratt, J. D.; Chhabra, P. S.; Loza, C. L.; Crounse, J. D.; Yee, L. D.; Flagan, R. C.; Wennberg, P. O.; Seinfeld, J. H.

    2010-08-01

    Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C4-unsaturated aldehyde) under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other ?, ?-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are ?, ?-unsaturated and contain an additional methyl group on the ?-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO2) formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3-8), the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of ?, ?-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

  20. Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Chan, A. W. H.; Chan, M. N.; Surratt, J. D.; Chhabra, P. S.; Loza, C. L.; Crounse, J. D.; Yee, L. D.; Flagan, R. C.; Wennberg, P. O.; Seinfeld, J. H.

    2010-04-01

    Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C4-unsaturated aldehyde) under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other ?, ?-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are ?, ?-unsaturated and contain an additional methyl group on the ?-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO2) formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios, the SOA yields from isoprene high-NOxphotooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of ?, ?-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

  1. Dimers in ?-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

    NASA Astrophysics Data System (ADS)

    Kristensen, K.; Cui, T.; Zhang, H.; Gold, A.; Glasius, M.; Surratt, J. D.

    2014-04-01

    The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of ?-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of ?-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of ?-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of ?-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of ?-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total ?-pinene SOA mass. OH-initiated oxidation of ?-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of ?-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50-90%) relative to lower RH (30-50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from ?-pinene ozonolysis with respect to carboxylic acids and dimers. The results support the formation of the high-molecular weight dimers through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of ?-pinene. The high molecular weight and polar nature of dimers formed in the gas phase may explain increased particle number concentration as a result of homogenous nucleation. Since three of these dimers (i.e. pinyl-diaterpenyl dimer (MW 358), pinyl-diaterebyl dimer (MW 344) and pinonyl-pinyl dimer (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimers observed in this study can be used as tracers for the O3-initiated oxidation of ?-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility dimers result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

  2. Computation of Phase Equilibria, State Diagrams and Gas/Particle Partitioning of Mixed Organic-Inorganic Aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Peter, T.

    2009-04-01

    The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part 2: Consideration of phase separation effects by an XUNIFAC model, Atmos. Environ., 40, 6422-6436, 2006. Erdakos, G. B. and Pankow, J. F.: Gas/particle partitioning of neutral and ionizing compounds to single- and multi-phase aerosol particles. 2. Phase separation in liquid particulate matter containing both polar and low-polarity organic compounds, Atmos. Environ., 38, 1005-1013, 2004. Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559-4593, 2008.

  3. Mass yields of secondary organic aerosols from the oxidation of alpha-pinene and real plant emissions

    E-print Network

    Kroll, Jesse

    Biogenic volatile organic compounds (VOCs) are a significant source of global secondary organic aerosol (SOA); however, quantifying their aerosol forming potential remains a challenge. This study presents smog chamber ...

  4. 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...

  5. 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.

  6. Laboratory studies on secondary organic aerosol formation from terpenes.

    PubMed

    Iinuma, Yoshiteru; Böge, Olaf; Miao, Yunkun; Sierau, Berko; Gnauk, Thomas; Herrmann, Hartmut

    2005-01-01

    The formation of secondary organic aerosol (SOA) following the ozonolysis of terpene has been investigated intensively in recent years. The enhancement of SOA yields from the acid catalysed reactions of organics on aerosol surfaces or in the bulk particle phase has been receiving great attention. Recent studies show that the presence of acidic seed particles increases the SOA yield significantly (M. S. Jang and R. M. Kamens, Environ. Sci. Technol., 2001, 35, 4758, ref. 1; M. S. Jang, N. M. Czoschke, S. Lee and R. M. Kamens, Science, 2002, 298, 814, ref. 2; N. M. Czoschke, M. Jang and R. M. Kamens, Atmos. Environ., 2003, 37, 4287, ref. 3; M. S. Jang, B. Carroll, B. Chandramouli and R. M. Kamens, Environ. Sci. Technol., 2003, 37, 3828, ref. 4; Y. Iinuma, O. Böge, T. Gnauk and H. Herrmann, Atmos. Environ., 2004, 38, 761, ref. 5; S. Gao, M. Keywood, N. L. Ng, J. Surratt, V. Varutbangkul, R. Bahreini, R. C. Flagan and J. H. Seinfeld, J. Phys. Chem. A, 2004, 108, 10147, ref. 6). More detailed studies report the formation of higher molecular weight products in SOA (refs. 5 and 6; M. P. Tolocka, M. Jang, J. M. Ginter, F. J. Cox, R. M. Kamens and M. V. Johnston, Environ. Sci. Technol., 2004, 38, 1428, ref. 7; S. Gao, N. L. Ng, M. Keywood, V. Varutbangkul, R. Bahreini, A. Nenes, J. He, K. Y. Yoo, J. L. Beauchamp, R. P. Hodyss, R. C. Flagan and J. H. Seinfeld, Environ. Sci. Technol., 2004, 38, 6582, ref. 8) which could result in a non-reversible uptake of organics into the particle phase. Most of the past studies concentrated on the characterisation of the yields of enhanced SOA and its composition from ozonolysis of terpenes in the presence or absence of acidic and neutral seed particles. Recent findings from cyclohexene ozonolysis show that the presence of OH scavengers can also significantly influence the SOA yield. Our new results from the IfT chemistry department aerosol chamber on terpene ozonolysis in the presence of OH scavengers show that the presence of hydroxyl radical scavengers clearly reduces the amount of formed SOA. The OH scavenger strongly depletes the formation of oligomeric compounds in the particle phase in contrast to previous findings (M. D. Keywood, J. H. Kroll, V. Varatbangkul, R. Bahreini, R. C. Flagan and J. H. Seinfeld, Environ. Sci. Technol., 2004, 38, 3343, ref. 9). This result indicates that hydroxyl radicals play an important role in the formation of precursor compounds (e.g., hydroxy pinonaldehyde) for the particle phase heterogeneous acid catalysed reactions leading to the higher molecular weight compounds and thus the enhancement of SOA yields. Better understanding of the role of hydroxyl radicals in the formation of SOA is necessary to distinguish between the contribution of ozonolysis and hydroxyl radicals to the SOA yield. If the recent findings are a ubiquitous phenomenon in the atmosphere, current atmospheric and climate models might underestimate SOA formation yields, particle phase OC contents and its impact on the atmospheric radiation budget. PMID:16161789

  7. Source indicators of biomass burning associated with inorganic salts and carboxylates in dry season ambient aerosol in Chiang Mai Basin, Thailand

    NASA Astrophysics Data System (ADS)

    Tsai, Ying I.; Sopajaree, Khajornsak; Chotruksa, Auranee; Wu, Hsin-Ching; Kuo, Su-Ching

    2013-10-01

    PM10 aerosol was collected between February and April 2010 at an urban site (CMU) and an industrial site (TOT) in Chiang Mai, Thailand, and characteristics and provenance of water-soluble inorganic species, carboxylates, anhydrosugars and sugar alcohols were investigated with particular reference to air quality, framed as episodic or non-episodic pollution. Sulfate, a product of secondary photochemical reactions, was the major inorganic salt in PM10, comprising 25.9% and 22.3% of inorganic species at CMU and TOT, respectively. Acetate was the most abundant monocarboxylate, followed by formate. Oxalate was the dominant dicarboxylate. A high acetate/formate mass ratio indicated that primary traffic-related and biomass-burning emissions contributed to Chiang Mai aerosols during episodic and non-episodic pollution. During episodic pollution carboxylate peaks indicated sourcing from photochemical reactions and/or directly from traffic-related and biomass burning processes and concentrations of specific biomarkers of biomass burning including water-soluble potassium, glutarate, oxalate and levoglucosan dramatically increased. Levoglucosan, the dominant anhydrosugar, was highly associated with water-soluble potassium (r = 0.75-0.79) and accounted for 93.4% and 93.7% of anhydrosugars at CMU and TOT, respectively, during episodic pollution. Moreover, levoglucosan during episodic pollution was 14.2-21.8 times non-episodic lows, showing clearly that emissions from biomass burning are the major cause of PM10 episodic pollution in Chiang Mai. Additionally, the average levoglucosan/mannosan mass ratio during episodic pollution was 14.1-14.9, higher than the 5.73-7.69 during non-episodic pollution, indicating that there was more hardwood burning during episodic pollution. Higher concentrations of glycerol and erythritol during episodic pollution further indicate that biomass burning activities released soil biota from forest and farmland soils.

  8. Aqueous phase processing of secondary organic aerosol from isoprene photooxidation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Monod, A.; Tritscher, T.; Praplan, A. P.; DeCarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.

    2012-07-01

    Transport of reactive air masses into humid and wet areas is highly frequent in the atmosphere, making the study of aqueous phase processing of secondary organic aerosol (SOA) very relevant. We have investigated the aqueous phase processing of SOA generated from gas-phase photooxidation of isoprene using a smog chamber. The SOA collected on filters was extracted by water and subsequently oxidized in the aqueous phase either by H2O2 under dark conditions or by OH radicals in the presence of light, using a photochemical reactor. Online and offline analytical techniques including SMPS, HR-AMS, H-TDMA, TD-API-AMS, were employed for physical and chemical characterization of the chamber SOA and nebulized filter extracts. After aqueous phase processing, the particles were significantly more hygroscopic, and HR-AMS data showed higher signal intensity at m/z 44 and a lower signal intensity at m/z 43, thus showing the impact of aqueous phase processing on SOA aging, in good agreement with a few previous studies. Additional offline measurement techniques (IC-MS, APCI-MS2 and HPLC-APCI-MS) permitted the identification and quantification of sixteen individual chemical compounds before and after aqueous phase processing. Among these compounds, small organic acids (including formic, glyoxylic, glycolic, butyric, oxalic and 2,3-dihydroxymethacrylic acid (i.e. 2-methylglyceric acid)) were detected, and their concentrations significantly increased after aqueous phase processing. In particular, the aqueous phase formation of 2-methylglyceric acid and trihydroxy-3-methylbutanal was correlated with the consumption of 2,3-dihydroxy-2-methyl-propanal, and 2-methylbutane-1,2,3,4-tetrol, respectively, and an aqueous phase mechanism was proposed accordingly. Overall, the aging effect observed here was rather small compared to previous studies, and this limited effect could possibly be explained by the lower liquid phase OH concentrations employed here, and/or the development of oligomers observed during aqueous phase processing.

  9. The influence of meteorology on the organic and inorganic properties of aerosols in Hong Kong

    NASA Astrophysics Data System (ADS)

    Zheng, Mei; Guo, Zhigang; Fang, Ming; Kester, Dana R.

    2007-06-01

    The organic and inorganic species in total suspended particulates (TSP) collected from June to December in 1998 in Hong Kong were identified by gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-mass spectrometry (ICP-MS) to investigate the sources of Hong Kong aerosols and the mechanisms that control the chemical compositions and variations in the atmosphere. These samples were classified according to the climate: wet, dry under the influence of southerly winds from the sea (Dry-S) and dry under the influence of northerly winds from the continent (Dry-N). There were significant increases of materials from crustal, biogenic and pollution sources in the Dry-N period by a factor of 5, 4, and 2, respectively. Since the crustal tracers (e.g., Al, Fe) could be from coal flyash, the estimate of crustal material in the Dry-N period may include some materials from pollution source. Therefore, a positive correlation between crustal and pollution elements was observed. From the analysis of solvent-extractable organics (SEOC), microbial and meat cooking sources showed slight increase (1.2-fold). Higher levels of plant wax materials in the Dry-N period were probably due to the higher wind speed during the winter monsoon. The percentage of crustal material in TSP was 47% in the Dry-N period, and only 22% in the wet season and the Dry-S period. Plant wax materials (biogenic source) had a higher percentage in the Dry-N period (39% of SEOC) while microbial and meat cooking sources accounted for 49% of SEOC in the wet season. This study revealed that wind direction and precipitation had a significant influence not only on the concentrations but also on the chemical compositions and sources of Hong Kong aerosols.

  10. Sea salt aerosols as a reactive surface for inorganic and organic acidic gases in the arctic troposphere

    NASA Astrophysics Data System (ADS)

    Chi, J. W.; Li, W. J.; Zhang, D. Z.; Zhang, J. C.; Lin, Y. T.; Shen, X. J.; Sun, J. Y.; Chen, J. M.; Zhang, X. Y.; Zhang, Y. M.; Wang, W. X.

    2015-06-01

    Sea salt aerosols (SSA) are dominant particles in the arctic atmosphere and determine the polar radiative balance. SSA react with acidic pollutants that lead to changes of physical and chemical properties of their surface, which in turn alter their hygroscopic and optical properties. Transmission electron microscopy with energy-dispersive X-ray spectrometry was used to analyze morphology, composition, size, and mixing state of individual SSA at Ny-Ålesund, Svalbard in summertime. Individual fresh SSA contained cubic NaCl coated by certain amounts of MgCl2 and CaSO4. Individual partially aged SSA contained irregular NaCl coated by a mixture of NaNO3, Na2SO4, Mg(NO3)2, and MgSO4. The comparison suggests the hydrophilic MgCl2 coating in fresh SSA likely intrigued the heterogeneous reactions at the beginning of SSA and acidic gases. Individual fully aged SSA normally had Na2SO4 cores and an amorphous coating of NaNO3. Elemental mappings of individual SSA particles revealed that as the particles ageing Cl gradually decreased but the C, N, O, and S content increased. 12C14N- mapping from nanoscale secondary ion mass spectrometry indicates that organic matter increased in the aged SSA compared with the fresh SSA. 12C14N- line scans further show that organic matter was mainly concentrated on the aged SSA surface. These new findings indicate that this mixture of organic matter and NaNO3 on particle surfaces determines their hygroscopic and optical properties. These abundant SSA, whose reactive surfaces absorb inorganic and organic acidic gases in the arctic troposphere, need to be incorporated into atmospheric chemical models.

  11. Determination of sterols, estrogens and inorganic ions in waste water and size-segregated aerosol particles emitted from waste water treatment

    Microsoft Academic Search

    Melanie Beck; Michael Radke

    2006-01-01

    Concentrations of steroids and inorganic ions were measured in waste water of an aerated sand trap as well as in aerosol particles emitted from this tank at the waste water treatment plant (WWTP) of Bayreuth, Germany, in January and February 2003. The investigations comprised seven sterols, two estrogens, and several inorganic ions. Since an appropriate method for the determination of

  12. Secondary aerosol formation from atmospheric reactions of aliphatic amines

    NASA Astrophysics Data System (ADS)

    Murphy, S. M.; Sorooshian, A.; Kroll, J. H.; Ng, N. L.; Chhabra, P.; Tong, C.; Surratt, J. D.; Knipping, E.; Flagan, R. C.; Seinfeld, J. H.

    2007-05-01

    Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

  13. Secondary aerosol formation from atmospheric reactions of aliphatic amines

    NASA Astrophysics Data System (ADS)

    Murphy, S. M.; Sorooshian, A.; Kroll, J. H.; Ng, N. L.; Chhabra, P.; Tong, C.; Surratt, J. D.; Knipping, E.; Flagan, R. C.; Seinfeld, J. H.

    2007-01-01

    Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

  14. Secondary Organic Aerosol Formation from the Photooxidation of Naphthalene

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Chen, Y.; Wenger, J.

    2009-04-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous air pollutants that are released into the atmosphere as a by-product of combustion processes. The gas-phase PAHs can be chemically transformed via reaction with the hydroxyl radical to produce a range of oxidised organic compounds and other pollutants such as ozone and secondary organic aerosol (SOA). Epidemiological studies have established that exposure to this type of air pollution is associated with damaging effects on the respiratory and cardiovascular systems, and can lead to asthma, oxidative stress, health deterioration and even death. The major anthropogenic source of SOA in urban areas is believed to be aromatic hydrocarbons, which are present in automobile fuels and are used as solvents. As a result, research is currently being performed on the characterisation of SOA produced from aromatic hydrocarbons such as toluene, the xylenes and trimethylbenzenes. However, significant amounts of PAHs are also released into urban areas from automobile emissions and the combustion of fossil fuels for home heating. Naphthalene is regularly cited as the most abundant PAH in polluted urban air, with typical ambient air concentrations of 0.05 - 0.20 parts per billion (ppbV) in European cities, comparable to the xylenes. Since naphthalene reacts in an analogous manner to monocyclic aromatic compounds then it is also expected to make a significant contribution to ambient SOA. However, the yield and chemical composition of SOA produced from the atmospheric degradation of naphthalene is not well known. In this presentation, the effects of NOx level and relative humidity on the SOA formation from the phootooixdation of naphthalene will be presented. A series of experiments has been performed in a large atmospheric simulation chamber equipped with a gas chromatograph and analyzers for monitoring nitrogen oxides (NOx) and ozone. SOA formation from the photooxidation of naphthalene was measured using a scanning mobility particle sizer. The effect of NOx concentration on SOA formation was evaluated by varying the initial naphthalene and NOx concentrations. The results clearly show that a higher hydrocarbon to NOx ratio produces a higher yield of SOA. The SOA mass yields were also found to increase as the relative humidity was raised from 0 to 50%. A recently developed denuder-filter sampling technique was used to investigate the gas/particle partitioning behavior of the photooxidation products. This work is the first study of the formation of SOA from naphthalene and the results will be compared to those obtained from other aromatic compounds.

  15. Individual Aerosol Particles from Biomass Burning in Southern Africa Compositions and Aging of Inorganic Particles. 2; Compositions and Aging of Inorganic Particles

    NASA Technical Reports Server (NTRS)

    Li, Jia; Posfai, Mihaly; Hobbs, Peter V.; Buseck, Peter R.

    2003-01-01

    Individual aerosol particles collected over southern Africa during the SAFARI 2000 field study were studied using transmission electron microscopy and field-emission scanning electron microscopy. The sizes, shapes, compositions, mixing states, surface coatings, and relative abundances of aerosol particles from biomass burning, in boundary layer hazes, and in the free troposphere were compared, with emphasis on aging and reactions of inorganic smoke particles. Potassium salts and organic particles were the predominant species in the smoke, and most were internally mixed. More KCl particles occur in young smoke, whereas more K2SO4 and KNO3 particles were present in aged smoke. This change indicates that with the aging of the smoke, KCl particles from the fires were converted to K2SO4 and KNO3 through reactions with sulfur- and nitrogen- bearing species from biomass burning as well as other sources. More soot was present in smoke from flaming grass fires than bush and wood fires, probably due to the predominance of flaming combustion in grass fires. The high abundance of organic particles and soluble salts can affect the hygroscopic properties of biomass-burning aerosols and therefore influence their role as cloud condensation nuclei. Particles from biomass burning were important constituents of the regional hazes.

  16. Secondary Aerosol: Precursors and Formation Mechanisms. Technical Report on Grant

    SciTech Connect

    Weinstein-Lloyd, Judith B

    2009-05-04

    This project focused on studying trace gases that participate in chemical reactions that form atmospheric aerosols. Ammonium sulfate is a major constituent of these tiny particles, and one important pathway to sulfate formation is oxidation of dissolved sulfur dioxide by hydrogen peroxide in cloud, fog and rainwater. Sulfate aerosols influence the number and size of cloud droplets, and since these factors determine cloud radiative properties, sulfate aerosols also influence climate. Peroxide measurements, in conjunction with those of other gaseous species, can used to distinguish the contribution of in-cloud reaction to new sulfate aerosol formation from gas-phase nucleation reactions. This will lead to more reliable global climate models. We constructed and tested a new 4-channel fluorescence detector for airborne detection of peroxides. We integrated the instrument on the G-1 in January, 2006 and took a test flight in anticipation of the MAX-Mex field program, where we planned to fly under pressurized conditions for the first time. We participated in the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) - Megacity Aerosol EXperiment â?? Mexico City (MAX-Mex) field measurement campaign. Peroxide instrumentation was deployed on the DOE G-1 research aircraft based in Veracruz, and at the surface site at Tecamac University.

  17. No evidence for acid-catalyzed secondary organic aerosol formation in power plant plumes over metropolitan Atlanta, Georgia

    E-print Network

    Weber, Rodney

    No evidence for acid-catalyzed secondary organic aerosol formation in power plant plumes over that secondary organic aerosol formation via heterogeneous acid-catalyzed reactions within power plant plumes. S. Holloway, C. A. Brock, J. A. de Gouw, and E. L. Atlas (2007), No evidence for acid

  18. Spatial and Seasonal Trends in Biogenic Secondary Organic Aerosol

    E-print Network

    Zheng, Mei

    aerosol and PM2.5. SOA tracers in the particle phase can be produced by photochemical oxidation% monoterpenes (6). Atmospheric isoprene comprises about a third of the annual global VOC emission from allSOAtracersfromspecific VOCs can provide insight on sources and processes influ- encing SOA production and the spatial

  19. Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Tyndall, G.; Aumont, B.; Jimenez, J. L.; Lee-Taylor, J.; Orlando, J.

    2015-03-01

    This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOA). Typically only photolysis of smaller organic molecules (e.g. formaldehyde) for which explicit data exist is included in chemistry-climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from ?-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low- and high-NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after four days of chemical aging under those conditions (equivalent to eight days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields i.e ~15% (low-NOx) to ~45% (high-NOx) for ?-pinene, ~15% for toluene, ~25% for C12-alkane, and ~10% for C16-alkane. The small effect on low volatility n-alkanes such as C16-alkane is due to the rapid partitioning of early-generation products to the particle phase where they are assumed to be protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass seems increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas-phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an estimated SOA photolysis rate of JSOA=4 x 10-4JNO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40-60% for most species after ten days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle, and thus the amount of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales (less than 7 days) that are comparable to wet deposition.

  20. Size-segregated mass concentration and water soluble inorganic ions in an urban aerosol of the Central Balkans (Belgrade)

    NASA Astrophysics Data System (ADS)

    ?or?evi?, D.; Mihajlidi-Zeli?, A.; Reli?, D.; Ignjatovi?, Lj.; Huremovi?, J.; Stortini, A. M.; Gambaro, A.

    2012-01-01

    The distribution of nano/micron inorganic main ions in the size-segregated urban aerosol of Belgrade center was studied during the summer-autumn of 2008. The particle size distribution in the size ranges Dp ? 0.49 ?m, 0.49 ? Dp ? 0.95 ?m, 0.95 ? Dp ? 1.5 ?m, 1.5 ? Dp ? 3.0 ?m, 3.0 ? Dp ? 7.2 ?m and Dp ? 7.2 ?m was measured. The aerosol samples were submitted to gravimetric and chemical analyses. The obtained mean mass concentration of the PM fractions was in accordance with an urban aerosol distribution. The aerosol mass concentrations were determined by gravimetric measurements ( mGM) and, analyzed by ion chromatography for Na +, NH 4+, K +, Mg 2+, Ca 2+, Cl -, NO 3-, PO 43- and SO 42-. The mean random uncertainties associated with the determinations of Na +, NH 4+, K +, Mg 2+, Ca 2+, Cl -, NO 3- and SO 42- were assessed. The absolute highest concentration is found for SO 42- (1555.8 ± 973.6 ng m -3) in the range of Dp ? 0.49 ?m with an average participation of 8.19% to the total mass of the particles. The highest coefficients of correlation were found between NH 4+ and SO 42-. Principal component analysis, PCA, was used for the identification and evaluation of the contributions of the main emission sources to the contents of water soluble ions in the urban aerosol. The formation of (NH 4) 2SO 4 was found to be the dominant process. The influences of local urban (traffic) and regional industrial sources (nearby city Pan?evo) were identified and a contribution of marine aerosol was observed.

  1. SOURCE APPORTIONMENT OF PRIMARY AND SECONDARY CARBONACEOUS AEROSOL IN THE UNITED STATES USING MODELS AND MEASUREMENTS

    EPA Science Inventory

    In this presentation, three diagnostic evaluation methods of model performance for carbonaceous aerosol are reviewed. The EC-tracer method is used to distinguish primary and secondary carbon, radiocarbon data are used to distinguish fossil-fuel and contemporary carbon, and organ...

  2. The influence of HVAC systems on secondary organic aerosol formation Michael S. Waring1

    E-print Network

    Siegel, Jeffrey

    The influence of HVAC systems on secondary organic aerosol formation Michael S. Waring1 , Jeffrey A, ventilation, and air- conditioning (HVAC) system. This study models the influence of HVAC systems on SOA. The most influential HVAC parameters are the flow rates, particle filtration, and indoor temperature

  3. CCN Activity and Mixing Rules of Isoprene Secondary Organic Aerosol (SOA) and Sulfate

    E-print Network

    material produced by the oxidation of other VOC precursor gases, such as monoterpenes and small aromatic the gas-to-particle condensation of the low-volatility oxidation products of volatile organic compounds (VOCs), thereby forming a secondary organic aerosol (SOA). Globally, the dominant contributors to SOA

  4. Emission, oxidation, and secondary organic aerosol formation of volatile organic compounds as observed at Chebogue Point,

    E-print Network

    Silver, Whendee

    organic compounds (VOC) are oxidized in the troposphere. There are three possible final stages or out] Oxidation products of primary VOC emissions tend to become less volatile and more soluble becauseEmission, oxidation, and secondary organic aerosol formation of volatile organic compounds

  5. Naturally driven variability in the global secondary organic aerosol over a decade

    Microsoft Academic Search

    K. Tsigaridis; J. Lathière; M. Kanakidou; D. A. Hauglustaine

    2005-01-01

    In order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA

  6. Photochemical Aging of Secondary Organic Aerosol Particles Generated from the Oxidation of d-Limonene

    E-print Network

    Nizkorodov, Sergey

    oxidized volatile organic compounds (VOC). In the United States, on a regional scale, biogenic emissionsPhotochemical Aging of Secondary Organic Aerosol Particles Generated from the Oxidation of d of VOCs tend to be about 3 times higher than anthropogenic emissions. Monoterpenes, which are unsaturated

  7. Primary and secondary organics in the tropical Amazonian rainforest aerosols: chiral analysis of 2-methyltetraols.

    PubMed

    González, N J D; Borg-Karlson, A-K; Artaxo, P; Guenther, A; Krejci, R; Nozière, B; Noone, K

    2014-05-01

    This work presents the application of a new method to facilitate the distinction between biologically produced (primary) and atmospherically produced (secondary) organic compounds in ambient aerosols based on their chirality. The compounds chosen for this analysis were the stereomers of 2-methyltetraols, (2R,3S)- and (2S,3R)-methylerythritol, (l- and d-form, respectively), and (2S,3S)- and (2R,3R)-methylthreitol (l- and d-form), shown previously to display some enantiomeric excesses in atmospheric aerosols, thus to have at least a partial biological origin. In this work PM10 aerosol fractions were collected in a remote tropical rainforest environment near Manaus, Brazil, between June 2008 and June 2009 and analysed. Both 2-methylerythritol and 2-methylthreitol displayed a net excess of one enantiomer (either the l- or the d-form) in 60 to 72% of these samples. These net enantiomeric excesses corresponded to compounds entirely biological but accounted for only about 5% of the total 2-methyltetrol mass in all the samples. Further analysis showed that, in addition, a large mass of the racemic fractions (equal mixtures of d- and l-forms) was also biological. Estimating the contribution of secondary reactions from the isomeric ratios measured in the samples (=ratios 2-methylthreitol over 2-methylerythritol), the mass fraction of secondary methyltetrols in these samples was estimated to a maximum of 31% and their primary fraction to a minimum of 69%. Such large primary fractions could have been expected in PM10 aerosols, largely influenced by biological emissions, and would now need to be investigated in finer aerosols. This work demonstrates the effectiveness of chiral and isomeric analyses as the first direct tool to assess the primary and secondary fractions of organic aerosols. PMID:24777436

  8. Investigating the use of secondary organic aerosol as seed particles in simulation chamber experiments

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Rami Alfarra, M.; Wyche, K. P.; Ward, M. W.; Lewis, A. C.; McFiggans, G. B.; Good, N.; Monks, P. S.; Carr, T.; White, I. R.; Purvis, R. M.

    2011-06-01

    The use of ?-caryophyllene secondary organic aerosol particles as seeds for smog chamber simulations has been investigated. A series of experiments were carried out in the Manchester photochemical chamber as part of the Aerosol Coupling in the Earth System (ACES) project to study the effect of seed particles on the formation of secondary organic aerosol (SOA) from limonene photo-oxidation. Rather than use a conventional seed aerosol containing ammonium sulfate or diesel particles, a method was developed to use in-situ chamber generated seed particles from ?-caryophyllene photo-oxidation, which were then diluted to a desired mass loading (in this case 4-13 ?g m-3). Limonene was then introduced into the chamber and oxidised, with the formation of SOA seen as a growth in the size of oxidised organic seed particles from 150 to 325 nm mean diameter. The effect of the partitioning of limonene oxidation products onto the seed aerosol was assessed using aerosol mass spectrometry during the experiment and the percentage of m/z 44, an indicator of degree of oxidation, increased from around 5 to 8 %. The hygroscopicity of the aerosol also changed, with the growth factor for 200 nm particles increasing from less than 1.05 to 1.25 at 90 % RH. The detailed chemical composition of the limonene SOA could be extracted from the complex ?-caryophyllene matrix using two-dimensional gas chromatography (GC × GC) and liquid chromatography coupled to mass spectrometry. High resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) was used to determine exact molecular formulae of the seed and the limonene modified aerosol. The average O:C ratio was seen to increase from 0.32 to 0.37 after limonene oxidation products had condensed onto the organic seed.

  9. Investigating the use of secondary organic aerosol as seed particles in simulation chamber experiments

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Rami Alfarra, M.; Wyche, K. P.; Ward, M. W.; Lewis, A. C.; McFiggans, G. B.; Good, N.; Monks, P. S.; Carr, T.; White, I. R.; Purvis, R. P.

    2010-10-01

    The use of ?-caryophyllene secondary organic aerosol particles as seeds for smog chamber simulations has been investigated. A series of experiments were carried out in the Manchester photochemical chamber as part of the Aerosol Coupling in the Earth System (ACES) project to study the effect of seed particles on the formation of secondary organic aerosol (SOA) from limonene photo-oxidation. Rather than use a conventional seed aerosol containing ammonium sulphate or diesel particles, a method was developed to use in situ chamber generated seed particles from ?-caryophyllene photo-oxidation, which were then diluted to a desired mass loading (in this case 4-13 ?g m-3). Limonene was then introduced into the chamber and oxidised, with the formation of SOA seen as a growth in the size of oxidised organic seed particles from 150 to 325 nm mean diameter. The effect of the partitioning of limonene oxidation products onto the seed aerosol was assessed using aerosol mass spectrometry during the experiment and the percentage of m/z 44, an indicator of degree of oxidation, increased from around 5 to 8%. The hygroscopicity of the aerosol also changed, with the growth factor for 200 nm particles increasing from less than 1.05 to 1.25 at 90% RH. The detailed chemical composition of the limonene SOA could be extracted from the complex ?-caryophyllene matrix using two-dimensional gas chromatography (GC×GC) and liquid chromatography coupled to mass spectrometry. High resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) was used to determine exact molecular formulae of the seed and the limonene modified aerosol. The average O:C ratio was seen to increase from 0.32 to 0.37 after limonene oxidation products had condensed onto the organic seed.

  10. Light extinction by secondary organic aerosol: an intercomparison of three broadband cavity spectrometers

    NASA Astrophysics Data System (ADS)

    Varma, R. M.; Ball, S. M.; Brauers, T.; Dorn, H.-P.; Heitmann, U.; Jones, R. L.; Platt, U.; Pöhler, D.; Ruth, A. A.; Shillings, A. J. L.; Thieser, J.; Wahner, A.; Venables, D. S.

    2013-11-01

    Broadband optical cavity spectrometers are maturing as a technology for trace-gas detection, but only recently have they been used to retrieve the extinction coefficient of aerosols. Sensitive broadband extinction measurements allow explicit separation of gas and particle phase spectral contributions, as well as continuous spectral measurements of aerosol extinction in favourable cases. In this work, we report an intercomparison study of the aerosol extinction coefficients measured by three such instruments: a broadband cavity ring-down spectrometer (BBCRDS), a cavity-enhanced differential optical absorption spectrometer (CE-DOAS), and an incoherent broadband cavity-enhanced absorption spectrometer (IBBCEAS). Experiments were carried out in the SAPHIR atmospheric simulation chamber as part of the NO3Comp campaign to compare the measurement capabilities of NO3 and N2O5 instrumentation. Aerosol extinction coefficients between 655 and 690 nm are reported for secondary organic aerosols (SOA) formed by the NO3 oxidation of ?-pinene under dry and humid conditions. Despite different measurement approaches and spectral analysis procedures, the three instruments retrieved aerosol extinction coefficients that were in close agreement. The refractive index of SOA formed from the ?-pinene + NO3 reaction was 1.61, and was not measurably affected by the chamber humidity or by aging of the aerosol over several hours. This refractive index is significantly larger than SOA refractive indices observed in other studies of OH and ozone-initiated terpene oxidations, and may be caused by the large proportion of organic nitrates in the particle phase. In an experiment involving ammonium sulfate particles, the aerosol extinction coefficients as measured by IBBCEAS were found to be in reasonable agreement with those calculated using the Mie theory. The results of the study demonstrate the potential of broadband cavity spectrometers for determining the optical properties of aerosols.

  11. Light extinction by Secondary Organic Aerosol: an intercomparison of three broadband cavity spectrometers

    NASA Astrophysics Data System (ADS)

    Varma, R. M.; Ball, S. M.; Brauers, T.; Dorn, H.-P.; Heitmann, U.; Jones, R. L.; Platt, U.; Pöhler, D.; Ruth, A. A.; Shillings, A. J. L.; Thieser, J.; Wahner, A.; Venables, D. S.

    2013-07-01

    Broadband optical cavity spectrometers are maturing as a technology for trace gas detection, but only recently have they been used to retrieve the extinction coefficient of aerosols. Sensitive broadband extinction measurements allow explicit separation of gas and particle phase spectral contributions, as well as continuous spectral measurements of aerosol extinction in favourable cases. In this work, we report an intercomparison study of the aerosol extinction coefficients measured by three such instruments: a broadband cavity ring-down spectrometer (BBCRDS), a cavity-enhanced differential optical absorption spectrometer (CE-DOAS), and an incoherent broadband cavity-enhanced absorption spectrometer (IBBCEAS). Experiments were carried out in the SAPHIR atmospheric simulation chamber as part of the NO3Comp campaign to compare the measurement capabilities of NO3 and N2O5 instrumentation. Aerosol extinction coefficients between 655 and 690 nm are reported for secondary organic aerosols (SOA) formed by the NO3 oxidation of ?-pinene under dry and humid conditions. Despite different measurement approaches and spectral analysis procedures, the three instruments retrieved aerosol extinction coefficients that were in close agreement. The refractive index of SOA formed from the ?-pinene + NO3 reaction was 1.61, and was not measurably affected by the chamber humidity or by aging of the aerosol over several hours. This refractive index is significantly larger than SOA refractive indices observed in other studies of OH and ozone-initiated terpene oxidations, and may be caused by the large proportion of organic nitrates in the particle phase. In an experiment involving ammonium sulphate particles the aerosol extinction coefficients as measured by IBBCEAS were found to be in reasonable agreement with those calculated using Mie theory. The results of the study demonstrate the potential of broadband cavity spectrometers for determining the optical properties of aerosols.

  12. The analysis of chiral methyltetrols in atmospheric aerosols: A new look at Secondary Organic Aerosols from isoprene

    NASA Astrophysics Data System (ADS)

    Gonzalez Cantu, N. J.; Noziere, B.; Borg-Karlsson, A.; Pei, Y.; Petersson, J.; Krejci, R.; Artaxo, P.; Baltensperger, U.; Dommen, J.; Prevot, A. S.; Anthonsen, T.

    2010-12-01

    The quantities of Secondary Organic Aerosols (SOA) produced in the atmosphere by the transformations of organic gases are difficult to estimate, isoprene having possibly and important contribution, but also containing the most uncertainties. One of the main challenges in this topic is the limited information on real atmospheric SOA, as there was, until recently, no method to distinguish unambiguously between secondary and primary organic compounds in atmospheric aerosols. We have developed a new analytical method to make this distinction, based on separating the enantiomers of organic compounds (isomers mirror images of each other) in aerosols. In this work, this method is applied to the 2-methyltetrols, 2-methylerythritol and 2-methylthreitol, present in PM2.5 aerosols collected at Aspvreten, Sweden from May to November 2008. These compounds are currently considered as the main evidence supporting the presence of SOA from isoprene in the atmosphere. The results of our analyses show that these compounds are, at least in part, from biological (or “primary”) origin. In particular, 2-C-methyl-D-erythritol was 15 % in excess of the total mass of 2-methyltetrols in May-July, clearly indicating its biological origin, and consistent with its well-documented production by plants. Furthermore, the concentrations of the remaining racemic diastereoisomers (total 2-methylerythritol and total 2-methylthreitol) did not correlate with each other, implying that at least one of them, or both, were also from biological origin. This was supported by their lack of correlation with ozone at the site. While atmospheric (abiotic) reactions might have contributed, it can not be excluded that these compounds were mostly from biological origin, thus challenging the main evidence for the existence of SOA from isoprene in the atmosphere.

  13. Atmospheric chemistry in stereo: A new look at secondary organic aerosols from isoprene

    NASA Astrophysics Data System (ADS)

    Nozière, Barbara; González, Nélida J. D.; Borg-Karlson, Anna-Karin; Pei, Yuxin; Redeby, Johan Pettersson; Krejci, Radovan; Dommen, Josef; Prevot, Andre S. H.; Anthonsen, Thorleif

    2011-06-01

    Isoprene, a compound emitted by vegetation, could be a major contributor to secondary organic aerosols (SOA) in the atmosphere. The main evidence for this contribution were the 2-methylbutane-1,2,3,4-tetraols, or 2-methyltetrols (2-methylerythritol and 2-methylthreitol) present in ambient aerosols. In this work, the four stereoisomers of these tetraols were analyzed in aerosols from Aspvreten, Sweden. 2-C-methyl-D-erythritol was found in excess over its enantiomer in the Spring/Summer, by up to 29% in July. This clearly indicated some biological origins for this enantiomer, consistent with its well-documented production by plants and other living organisms. In addition, a minimum of 20 to 60% of the mass of racemic tetraols appeared from biological origin. Thus, the SOA mass produced by isoprene in the atmosphere is less than what indicated by the 2-methyltetrols in aerosols. Our results also demonstrate that stereochemical speciation can distinguish primary and secondary organic material in atmospheric aerosols.

  14. Closure study on measured and modeled optical properties for dry and hydrated laboratory inorganic aerosols with mixtures of dicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Deng, Junjun; Du, Ke; Wang, Wei; Rood, Mark J.

    2013-12-01

    A laboratory-based closure study was completed to compare measured and modeled optical properties and their dependence on controlled relative humidity (RH) for inorganic salts, dicarboxylic acids, and their mixtures. The closure between measured and modeled values of the light scattering coefficients were evaluated by calculating the average relative difference (ARD) values, which revealed agreement within 8.0% for the total scattering (?sp) and 14.8% for the back scattering (?bsp) values at dry RH conditions for all test aerosols. These ARD values were less than the total relative uncertainty based on the measurement and modeling approaches, indicating the achievement of closure for ?sp and ?bsp. Optical properties derived from ?sp including: (1) the hygroscopic growth factor, f?sp, (2) the backscatter ratio, b, and (3) the Ångström exponent, å, were also compared with measured values. The ARD values between corresponding measured and modeled results for these derived optical parameters ranged from 0.1% to 30.8%. The impact of particulate organic matter (POM) on optical and hygroscopic properties of the aerosols tested here was also compared to the aerosol optical and composition measurements that occurred during the New England Air Quality Study-Intercontinental Transport and Chemical Transformation field campaign. Such comparison confirmed that a larger POM mass fraction resulted in less hygroscopicity for both the ambient and the laboratory aerosols. This study evaluated closure between laboratory measurements and model calculations and validated the reliability of the measured and modeled results with the closure analysis. Therefore, Mie-Lorentz model can be used to calculate the optical properties and their dependence on RH for other aerosols with more confidence.

  15. Comprehensive characterisation of atmospheric aerosols in Budapest, Hungary: physicochemical properties of inorganic species

    Microsoft Academic Search

    Imre Salma; Willy Maenhaut; Éva Zemplén-Papp; Gyula Záray

    2001-01-01

    As part of an air pollution project in Budapest, aerosol samples were collected by stacked filter units and cascade impactors at an urban background site, two downtown sites, and within a road tunnel in field campaigns conducted in 1996, 1998 and 1999. Some criteria pollutants were also measured at one of the downtown sites. The aerosol samples were analysed by

  16. Individual aerosol particles from biomass burning in southern Africa: 2, Compositions and aging of inorganic particles

    Microsoft Academic Search

    Jia Li; Mihaly Posfai; Peter V. Hobbs; Peter R. Buseck

    2003-01-01

    (1) Individual aerosol particles collected over southern Africa during the SAFARI 2000 field study were studied using transmission electron microscopy and field-emission scanning electron microscopy. The sizes, shapes, compositions, mixing states, surface coatings, and relative abundances of aerosol particles from biomass burning, in boundary layer hazes, and in the free troposphere were compared, with emphasis on aging and reactions of

  17. Chemical characterization of secondary organic aerosol from aromatic precursors in smog chamber experiments

    NASA Astrophysics Data System (ADS)

    Kalberer, M.; Sax, M.; Zenobi, R.; Paulsen, D.; Steinbacher, M.; Prevot, A.; Weingartner, E.; Baltensperger, U.

    2003-04-01

    In a newly built smog chamber (27m^3 volume) at the Paul Scherrer Institute secondary organic aerosols were produced from photo-oxidation products of aromatic compounds. The aerosol composition as well as gas phase reaction products was analyzed. Aerosol collected on filter samples was analyzed with gas chromatography / mass spectrometry GC/MS after derivatization of carbonyl, carboxyl and hydroxyl functional groups to identify single compounds. In addition, the filters were analyzed with other analytical methods such as matrix assisted laser desorption / ionization mass spectrometry (MALDI) to gain insights into the overall mass distribution of the organic aerosol components and with diffuse reflectance infrared spectroscopy to estimate the importance of the different functional groups (such as carbonyl-, carboxyl-, or nitro-groups) present in the aerosol phase. Along with the aerosol analysis, the gas phase reaction products were analyzed off-line with GC/MS from samples collected on polyuretan foam plugs and on-line with proton transfer reaction mass spectrometry (PTRMS) with a high time resolution of about 2 minutes.

  18. Impacts of oxidation aging on secondary organic aerosol formation, particle growth rate, cloud condensation nuclei abundance, and aerosol climate forcing

    NASA Astrophysics Data System (ADS)

    Yu, F.; Luo, G.

    2014-12-01

    Particle composition measurements indicate that organic aerosol (OA) makes up ~20-90% of submicron particulate mass and secondary OA (SOA) accounts for a large fraction (~ 72 ±21%) of these OA masses at many locations around the globe. The volatility changes of secondary organic gases (SOG) associated with oxidation aging as well as the contribution of highly oxidized low volatile SOG (LV-SOG) to the condensational growth of secondary particles have been found to be important in laboratory and field measurements but are poorly represented in global models. A novel scheme to extend the widely used two-product SOA formation model, by adding a third product arising from the oxidation aging (i.e., LV-SOG) and considering the dynamic transfer of mass from higher to lower volatile products, has been developed and implemented into a global chemical transport model (GEOS-Chem) and a community atmosphere model (CESM-CAM5). The scheme requires only minor changes to the existing two-product SOA formation model and is computationally efficient. With the oxidation rate constrained by laboratory measurements, we show that the new scheme predicts a much higher SOA mass concentrations, improving the agreement with aerosol mass spectrometer SOA measurements. The kinetic condensation of LV-SOG on ultrafine particles, simulated by a size-resolved (sectional) advanced particle microphysics (APM) model incorporated into in GEOS-Chem and CAM5, increases the particle growth rate substantially and improves the agreement of simulated cloud condensation nuclei (CCN) concentrations with observations. Based on GEOS-Chem-APM simulations, the new SOA formation scheme increases global mean low troposphere SOA mass concentration by ~130% and CCN abundance by ~ 15%, and optical depth of secondary particles and coated black carbon and primary organic carbon particles by ~10%. As a result, aerosol radiative cooling effect (direct + first indirect) is enhanced by -0.9 W/m2, with large spatial variations. CAM5-APM simulations show similar magnitude of impacts. The implication of oxidation aging to net direct and indirect radiative forcing of anthropogenic aerosols based on both GEOS-Chem-APM and CAM5-APM will be discussed.

  19. Analysis of secondary organic aerosols from ozonolysis of isoprene by proton transfer reaction mass spectrometry

    NASA Astrophysics Data System (ADS)

    Inomata, Satoshi; Sato, Kei; Hirokawa, Jun; Sakamoto, Yosuke; Tanimoto, Hiroshi; Okumura, Motonori; Tohno, Susumu; Imamura, Takashi

    2014-11-01

    To understand the mechanism of formation of the secondary organic aerosols (SOAs) produced by the ozonolysis of isoprene, proton transfer reaction mass spectrometry (PTR-MS) was used to identify the semi-volatile organic compounds (SVOCs) produced in both the gaseous and the aerosol phases and to estimate the gas-aerosol partitioning of each SVOC in chamber experiments. To aid in the identification of the SVOCs, the products were also studied with negative ion-chemical ionization mass spectrometry (NI-CIMS), which can selectively detect carboxylic acids and hydroperoxides. The gaseous products were observed by on-line PTR-MS and NI-CIMS, whereas the SVOCs in SOAs collected on a filter were vaporized by heating the filter and were then analysed by off-line PTR-MS and NI-CIMS. The formation of oligomeric hydroperoxides involving a Criegee intermediate as a chain unit was observed in both the gaseous and the aerosol phases by NI-CIMS. PTR-MS also detected oligomeric hydroperoxides as protonated molecules from which a H2O molecule was eliminated, [M-OH]+. In the aerosol phase, oligomers involving formaldehyde and methacrolein as chain units were observed by PTR-MS in addition to oligomeric hydroperoxides. The gas-aerosol partitioning of each component was calculated from the ion signals in the gaseous and aerosol phases measured by PTR-MS. From the gas-aerosol partitioning, the saturated vapour pressures of the oligomeric hydroperoxides were estimated. Measurements by a fast-mobility-particle-sizer spectrometer revealed that the increase of the number density of the particles was complete within a few hundred seconds from the start of the reaction.

  20. Characterization of secondary organic aerosol particles using aerosol laser time-of-flight mass spectrometer coupled with FCM clustering algorithm

    NASA Astrophysics Data System (ADS)

    Huang, Mingqiang; Hao, Liqing; Guo, Xiaoyong; Hu, Changjin; Gu, Xuejun; Zhao, Weixiong; Wang, Zhenya; Fang, Li; Zhang, Weijun

    2013-01-01

    Experiments for formation of secondary organic aerosol (SOA) from photooxidation of 1,3,5-trimethylbenzene in the CH3ONO/NO/air mixture were carried out in the laboratory chamber. The size and chemical composition of the resultant individual particles were measured in real-time by an aerosol laser time of flight mass spectrometer (ALTOFMS) recently designed in our group. We also developed Fuzzy C-Means (FCM) algorithm to classify the mass spectra of large numbers of SOA particles. The study first started with mixed particles generated from the standards benzaldehyde, phenol, benzoic acid, and nitrobenzene solutions to test the feasibility of application of the FCM. The FCM was then used to extract out potential aerosol classes in the chamber experiments. The results demonstrate that FCM allowed a clear identification of ten distinct chemical particle classes in this study, namely, 3,5-dimethylbenzoic acid, 3,5-dimethylbenzaldehyde, 2,4,6-trimethyl-5-nitrophenol, 2-methyl-4-oxo-2-pentenal, 2,4,6-trimethylphenol, 3,5-dimethyl-2-furanone, glyoxal, and high-molecular-weight (HMW) components. Compared to offline method such as gas chromatography-mass spectrometry (GC-MS) measurement, the real-time ALTOFMS detection approach coupled with the FCM data processing algorithm can make cluster analysis of SOA successfully and provide more information of products. Thus ALTOFMS is a useful tool to reveal the formation and transformation processes of SOA particles in smog chambers.

  1. 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

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

    PubMed

    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

  3. Carbon in southeastern U.S. aerosol particles: Empirical estimates of secondary organic aerosol formation

    Microsoft Academic Search

    Charles L. Blanchard; George M. Hidy; Shelley Tanenbaum; Eric Edgerton; Benjamin Hartsell; John Jansen

    2008-01-01

    Fine particles in the southeastern United States are rich in carbon: Southeastern Aerosol Research and Characterization (SEARCH) network measurements from 2001 through 2004 indicate that fine particles less than 2.5?m aerodynamic diameter (PM2.5) at two inland urban sites, Atlanta, GA and Birmingham, AL, contain 9 and 11% black carbon (BC) by mass, respectively, on average. For neighboring rural or urban

  4. Fuel composition and secondary organic aerosol formation: gas-turbine exhaust and alternative aviation fuels.

    PubMed

    Miracolo, Marissa A; Drozd, Greg T; Jathar, Shantanu H; Presto, Albert A; Lipsky, Eric M; Corporan, Edwin; Robinson, Allen L

    2012-08-01

    A series of smog chamber experiments were performed to investigate the effects of fuel composition on secondary particulate matter (PM) formation from dilute exhaust from a T63 gas-turbine engine. Tests were performed at idle and cruise loads with the engine fueled on conventional military jet fuel (JP-8), Fischer-Tropsch synthetic jet fuel (FT), and a 50/50 blend of the two fuels. Emissions were sampled into a portable smog chamber and exposed to sunlight or artificial UV light to initiate photo-oxidation. Similar to previous studies, neat FT fuel and a 50/50 FT/JP-8 blend reduced the primary particulate matter emissions compared to neat JP-8. After only one hour of photo-oxidation at typical atmospheric OH levels, the secondary PM production in dilute exhaust exceeded primary PM emissions, except when operating the engine at high load on FT fuel. Therefore, accounting for secondary PM production should be considered when assessing the contribution of gas-turbine engine emissions to ambient PM levels. FT fuel substantially reduced secondary PM formation in dilute exhaust compared to neat JP-8 at both idle and cruise loads. At idle load, the secondary PM formation was reduced by a factor of 20 with the use of neat FT fuel, and a factor of 2 with the use of the blend fuel. At cruise load, the use of FT fuel resulted in no measured formation of secondary PM. In every experiment, the secondary PM was dominated by organics with minor contributions from sulfate when the engine was operated on JP-8 fuel. At both loads, FT fuel produces less secondary organic aerosol than JP-8 because of differences in the composition of the fuels and the resultant emissions. This work indicates that fuel reformulation may be a viable strategy to reduce the contribution of emissions from combustion systems to secondary organic aerosol production and ultimately ambient PM levels. PMID:22732009

  5. Primary and secondary organic aerosols in Fresno, California during wintertime: Results from high resolution aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Ge, Xinlei; Setyan, Ari; Sun, Yele; Zhang, Qi

    2012-10-01

    Organic aerosols (OA) were studied in Fresno, California, in winter 2010 with an Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). OA dominated the submicron aerosol mass (average = 67%) with an average concentration of 7.9?g m-3 and a nominal formula of C1H1.59N0.014O0.27S0.00008, which corresponds to an average organic mass-to-carbon ratio of 1.50. Three primary OA (POA) factors and one oxygenated OA factor (OOA) representative of secondary OA (SOA) were identified via Positive Matrix Factorization of the high-resolution mass spectra. The three POA factors, which include a traffic-related hydrocarbon-like OA (HOA), a cooking OA (COA), and a biomass burning OA (BBOA) released from residential heating, accounted for an average 57% of the OA mass and up to 80% between 6 - 9 P.M., during which enhanced emissions from evening rush hour traffic, dinner cooking, and residential wood burning were exacerbated by low mixed layer height. The mass-based size distributions of the OA factors were estimated based on multilinear analysis of the size-resolved mass spectra of organics. Both HOA and BBOA peaked at ˜140 nm in vacuum aerodynamic diameter (Dva) while OOA peaked at an accumulation mode of ˜460 nm. COA exhibited a unique size distribution with two size modes centering at ˜200 nm and 450 nm respectively. This study highlights the leading roles played by anthropogenic POA emissions, primarily from traffic, cooking and residential heating, in aerosol pollution in Fresno in wintertime.

  6. 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

  7. Quantitative evaluation of emission controls on primary and secondary organic aerosol sources during Beijing 2008 Olympics

    NASA Astrophysics Data System (ADS)

    Guo, S.; Hu, M.; Guo, Q.; Zhang, X.; Schauer, J. J.; Zhang, R.

    2013-08-01

    To assess the primary and secondary sources of fine organic aerosols after the aggressive implementation of air pollution controls during the 2008 Beijing Olympic Games, 12 h PM2.5 values were measured at an urban site at Peking University (PKU) and an upwind rural site at Yufa during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. The average PM2.5 concentrations were 72.5 ± 43.6 ?g m-3 and 64.3 ± 36.2 ?g m-3 (average ± standard deviation, below as the same) at PKU and Yufa, respectively, showing the lowest concentrations in recent years. Combining the results from a CMB (chemical mass balance) model and secondary organic aerosol (SOA) tracer-yield model, five primary and four secondary fine organic aerosol sources were compared with the results from previous studies in Beijing. The relative contribution of mobile sources to PM2.5 concentrations was increased in 2008, with diesel engines contributing 16.2 ± 5.9% and 14.5 ± 4.1% and gasoline vehicles contributing 10.3 ± 8.7% and 7.9 ± 6.2% to organic carbon (OC) at PKU and Yufa, respectively. Due to the implementation of emission controls, the absolute OC concentrations from primary sources were reduced during the Olympics, and the contributions from secondary formation of OC represented a larger relative source of fine organic aerosols. Compared with the non-controlled period prior to the Olympics, primary vehicle contributions were reduced by 30% at the urban site and 24% at the rural site. The reductions in coal combustion contributions were 57% at PKU and 7% at Yufa. Our results demonstrate that the emission control measures implemented in 2008 significantly alleviated the primary organic particle pollution in and around Beijing. However, additional studies are needed to provide a more comprehensive assessment of the emission control effectiveness on SOA formation.

  8. Determination of Secondary Organic Aerosol Products from the Photooxidation of Toluene and their Implications in Ambient PM 2.5

    Microsoft Academic Search

    T. E. Kleindienst; T. S. Conver; C. D. McIver; E. O. Edney

    2004-01-01

    A laboratory study was carried out to investigate the secondary organic aerosol products from photooxidation of the aromatic hydrocarbon toluene. The laboratory experiments consisted of irradiating toluene\\/propylene\\/NOx\\/air mixtures in a smog chamber operated inthe dynamic mode and collecting submicron secondary organic aerosol samples through a sampling train that consisted of an XAD denuder and a ZefluorTM filter. Oxidation products in

  9. Size-resolved airborne particulate oxalic and related secondary organic aerosol species in the urban atmosphere of Chengdu, China

    NASA Astrophysics Data System (ADS)

    Cheng, Chunlei; Wang, Gehui; Meng, Jingjing; Wang, Qiyuan; Cao, Junji; Li, Jianjun; Wang, Jiayuan

    2015-07-01

    Size-segregated (9-stages) airborne particles during winter in Chengdu city of China were collected on a day/night basis and determined for dicarboxylic acids (diacids), ketocarboxylic acids (ketoacids), ?-dicarbonyls, inorganic ions, and water-soluble organic carbon and nitrogen (WSOC and WSON). Diacid concentration was higher in nighttime (1831 ± 607 ng m- 3) than in daytime (1532 ± 196 ng m- 3), whereas ketoacids and dicarbonyls showed little diurnal difference. Most of the organic compounds were enriched in the fine mode (< 2.1 ?m) with a peak at the size range of 0.7-2.1 ?m. In contrast, phthalic acid (Ph) and glyoxal (Gly) presented two equivalent peaks in the fine and coarse modes, which is at least in part due to the gas-phase oxidation of precursors and a subsequent partitioning into pre-existing particles. Liquid water content (LWC) of the fine mode particles was three times higher in nighttime than in daytime. The calculated in-situ pH (pHis) indicated that all the fine mode aerosols were acidic during the sampling period and more acidic in daytime than in nighttime. Robust correlations of the ratios of glyoxal/oxalic acid (Gly/C2) and glyoxylic acid/oxalic acid (?C2/C2) with LWC in the samples suggest that the enhancement of LWC is favorable for oxidation of Gly and ?C2 to produce C2. Abundant K+ and Cl- in the fine mode particles and the strong correlations of K+ with WSOC, WSON and C2 indicate that secondary organic aerosols in the city are significantly affected by biomass burning emission.

  10. Contrasting diurnal variations in fossil and nonfossil secondary organic aerosol in urban outflow, Japan.

    PubMed

    Morino, Yu; Takahashi, Katsuyuki; Fushimi, Akihiro; Tanabe, Kiyoshi; Ohara, Toshimasa; Hasegawa, Shuichi; Uchida, Masao; Takami, Akinori; Yokouchi, Yoko; Kobayashi, Shinji

    2010-11-15

    Diurnal variations of fossil secondary organic carbon (SOC) and nonfossil SOC were determined for the first time using a combination of several carbonaceous aerosol measurement techniques, including radiocarbon (¹?C) determinations by accelerator mass spectrometry, and a receptor model (chemical mass balance, CMB) at a site downwind of Tokyo during the summer of 2007. Fossil SOC showed distinct diurnal variation with a maximum during daytime, whereas diurnal variation of nonfossil SOC was relatively small. This behavior was reproduced by a chemical transport model (CTM). However, the CTM underestimated the concentration of anthropogenic secondary organic aerosol (ASOA) by a factor of 4-7, suggesting that ASOA enhancement during daytime is not explained by production from volatile organic compounds that are traditionally considered major ASOA precursors. This result suggests that unidentified semivolatile organic compounds or multiphase chemistry may contribute largely to ASOA production. As our knowledge of production pathways of secondary organic aerosol (SOA) is still limited, diurnal variations of fossil and nonfossil SOC in our estimate give an important experimental constraint for future development of SOA models. PMID:20886860

  11. Aerosol Coupling in the Earths System (ACES): Linking Chemical Composition of Secondary Organic Aerosol to Hygroscopic Properties.

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Alfarra, M. R.; Wyche, K. P.; Carr, T.; Lewis, A. C.; Monks, P. S.; McFiggans, G. B.; Good, N. A.; Irwin, M.; Turner, F.; Ward, M.

    2008-12-01

    The formation of secondary organic aerosol from the oxidation of reactive biogenic emissions is thought to be an important factor in global climate regulation. Biogenic Secondary Organic Aerosol (BSOA) can contribute to indirect radiative forcing by acting as cloud condensation nuclei. The potential of particles to act as CCN depends on their composition and hygroscopic properties. Sesquiterpenes, such as beta-caryophyllene, have been proposed as SOA precursors due to their low volatility and highly reactive nature. One of the main problems with using smog chamber simulations to study SOA formation and properties is the need to use high concentrations of reactive organic species. This can result in higher SOA yields and a different composition than in the real atmosphere. As part of the Aerosol coupling in the Earth System (ACES) project, a series of novel experiments were carried out at the Manchester Aerosol Chamber. By using a high volume pump and a collapsible chamber, the entire contents of the chamber can be sampled rapidly onto a filter. Recent improvements in the sensitivity of analytical techniques have allowed us to use lower VOC precursor concentrations (20 ppb) than previous studies. Repetitive experiments were carried out and filter samples taken at different experiment times, 2, 4 and 6 hours, allowing the evolution of individual SOA components to be evaluated. Complementary proton transfer mass spectrometry was used to study the evolution of gas phase oxidation products. The composition of beta-caryophyllene SOA was studied using liquid chromatography coupled to mass spectrometry. Twelve components were identified based on MS2 fragmentation patterns. The SOA composition was found to be much simpler than seen for monoterpenes and no oligomers were found. Experiments at 42 ppb and 210 ppb, indicate that the distribution of products varied depending on the starting VOC concentration. Low concentrations resulted in a higher proportion of more polar species such as nor-caryophyllenic acid (172 g mol-1), indicating the importance of carrying out smog chamber studies as close to ambient concentrations as possible. Results obtained using an Aerodyne aerosol mass spectrometer showed that SOA formed using lower initial precursor concentration contained a higher fraction of m/z 44 (a typical marker for highly oxygenated organic molecules) compared to SOA produced using high precursor concentration. Ageing resulted in an increasingly complex OVOC profile compared to the simpler, early generation products, seen in the initial stages of the experiment. The hygroscopic properties of the beta-caryophyllene SOA were investigated using a hygroscopicity tandem differential mobility analyser (HTDMA) and a CCN counter. The evolution of the hygroscopic growth factor and the CCN activity were compared to the aerosol composition, giving an insight into how the oxidation processes altered the ability of the aerosol to take up water.

  12. Using multidimensional gas chromatography to group secondary organic aerosol species by functionality

    NASA Astrophysics Data System (ADS)

    Flores, Rosa M.; Doskey, Paul V.

    2014-10-01

    A carbon number-functionality grid (CNFG) for a complex mixture of secondary organic aerosol (SOA) precursors and oxidation products was developed from the theoretical retention index diagram of a multidimensional gas chromatographic (GC × 2GC) analysis of a mixture of SOA precursors and derivatized oxidation products. In the GC × 2GC analysis, comprehensive separation of the complex mixture was achieved by diverting the modulated effluent from a polar primary column into 2 polar secondary columns. Column stationary phases spanned the widest range of selectivity of commercially available GC analytic columns. In general, separation of the species by the polar primary column was by the number of carbon atoms in the molecule (when the homologous series of reference compounds was selected to have molecular volumes and functionalities similar to the target analytes) and the polar secondary columns provided additional separation according to functionality. An algebraic transformation of the Abraham solvation parameter model was used to estimate linear retention indices of solutes relative to elution of a homologous series of methyl diesters on the primary and secondary columns to develop the theoretical GC × 2GC retention diagram. Retention indices of many of the oxidation products of SOA precursors were estimated for derivatized forms of the solutes. The GC stationary phases selected for the primary column [(50%-Trifluoropropyl)-methylpolysiloxane] and secondary columns (90% Cyanopropyl Polysilphenylene-siloxane and Polyethylene Glycol in a Sol-Gel matrix) provided a theoretical separation of 33 SOA precursors and 98 derivatized oxidation products into 35 groups by molecular volume and functionality. Comprehensive analysis of extracts of vapor and aerosol samples containing semivolatile SOA precursors and oxidation products, respectively, is best accomplished by (1) separating the complex mixture of the vapor and underivatized aerosol extracts with a (50%-Trifluoropropyl)-methylpolysiloxane × 90% Cyanopropyl Polysilphenylene-siloxane × Polyethylene Glycol in a Sol-Gel matrix arrangement and (2) derivatizing the aerosol extract and reanalyzing the sample on the GC × 2GC column combination. Quantifying groupings and organic molecular species in time series of collections of vapor- and aerosol-phase atmospheric organic matter is a promising analytic technique for measuring production of SOA and evaluating transformations of SOA precursors.

  13. Airborne Measurements of Secondary Organic Aerosol Formation in the Oil Sands Region of Alberta

    NASA Astrophysics Data System (ADS)

    Liggio, J.; Hayden, K.; Liu, P.; Leithead, A.; Moussa, S. G.; Staebler, R. M.; Gordon, M.; O'brien, J.; Li, S. M.

    2014-12-01

    The Alberta oil sands (OS) region represents a strategic natural resource and is a key driver of economic development. Its rapid expansion has led to a need for a more comprehensive understanding of the associated potential cumulative environmental impacts. In summer 2013, airborne measurements of various gaseous and particulate substances were made in the Athabasca oil sands region between August 13 and Sept 7, 2013. In particular, organic aerosol mass and composition measurements were performed with a High Resolution Time of flight Aerosol Mass Spectrometer (HR-ToF-AMS) supported by gaseous measurements of organic aerosol precursors with Proton Transfer Reaction (PTR) and Chemical Ionization (CI) mass spectrometers. These measurement data on selected flights were used to estimate the potential for local anthropogenic OS emissions to form secondary organic aerosol (SOA) downwind of precursor sources, and to investigate the importance of the surrounding biogenic emissions to the overall SOA burden in the region. The results of several flights conducted to investigate these transformations demonstrate that multiple distinct plumes were present downwind of OS industrial sources, each with differing abilities to form SOA depending upon factors such as NOx level, precursor VOC composition, and oxidant concentration. The results indicate that approximately 100 km downwind of an OS industrial source most of the measured organic aerosol (OA) was secondary in nature, forming at rates of ~6.4 to 13.6 ?gm-3hr-1. Positive matrix factor (PMF) analysis of the HR-ToF-AMS data suggests that the SOA was highly oxidized (O/C~0.6) resulting in a measured ?OA (difference above regional background OA) of approximately 2.5 - 3 despite being 100 km away from sources. The relative contribution of biogenic SOA to the total SOA and the factors affecting SOA formation during a number of flights in the OS region will be described.

  14. A new atmospheric aerosol phase equilibrium model (UHAERO): organic systems

    NASA Astrophysics Data System (ADS)

    Amundson, N. R.; Caboussat, A.; He, J. W.; Martynenko, A. V.; Landry, C.; Tong, C.; Seinfeld, J. H.

    2007-09-01

    In atmospheric aerosols, water and volatile inorganic and organic species are distributed between the gas and aerosol phases in accordance with thermodynamic equilibrium. Within an atmospheric particle, liquid and solid phases can exist at equilibrium. Models exist for computation of phase equilibria for inorganic/water mixtures typical of atmospheric aerosols; when organic species are present, the phase equilibrium problem is complicated by organic/water interactions as well as the potentially large number of organic species. We present here an extension of the UHAERO inorganic thermodynamic model (Amundson et al., 2006c) to organic/water systems. Phase diagrams for a number of model organic/water systems characteristic of both primary and secondary organic aerosols are computed. Also calculated are inorganic/organic/water phase diagrams that show the effect of organics on inorganic deliquescence behavior. The effect of the choice of activity coefficient model for organics on the computed phase equilibria is explored.

  15. A new atmospheric aerosol phase equilibrium model (UHAERO): organic systems

    NASA Astrophysics Data System (ADS)

    Amundson, N. R.; Caboussat, A.; He, J. W.; Martynenko, A. V.; Landry, C.; Tong, C.; Seinfeld, J. H.

    2007-06-01

    In atmospheric aerosols, water and volatile inorganic and organic species are distributed between the gas and aerosol phases in accordance with thermodynamic equilibrium. Within an atmospheric particle, liquid and solid phases can exist at equilibrium. Models exist for computation of phase equilibria for inorganic/water mixtures typical of atmospheric aerosols; when organic species are present, the phase equilibrium problem is complicated by organic/water interactions as well as the potentially large number of organic species. We present here an extension of the UHAERO inorganic thermodynamic model (Amundson et al., 2006c) to organic/water systems. Phase diagrams for a number of model organic/water systems characteristic of both primary and secondary organic aerosols are computed. Also calculated are inorganic/organic/water phase diagrams that show the effect of organics on inorganic deliquescence behavior. The effect of the choice of activity coefficient model for organics on the computed phase equilibria is explored.

  16. Secondary organic aerosol formation from photooxidation of a mixture of dimethyl sulfide and isoprene

    NASA Astrophysics Data System (ADS)

    Chen, Tianyi; Jang, Myoseon

    2012-01-01

    Secondary organic aerosol (SOA) created from the photooxidation of a mixture of isoprene and dimethyl sulfide (DMS) was studied at different NO x concentrations (40-220 ppb) and humidities (12%, 42% and 80%) using a Teflon film indoor chamber. To study the effect of isoprene on DMS products, the major DMS photooxidation products, such as sulfuric acid, methanesulfonic acid (MSA) and methanesulfinic acid (MSIA), were quantified in both the presence and the absence of isoprene using a Particle-Into-Liquid-Sampler coupled with Ion Chromatography (PILS-IC). The resulting PILS-IC data showed that the DMS aerosol yield significantly decreased due to the photooxidation of isoprene. A 35.2% DMS aerosol yield reduction was observed due to 800 ppb isoprene in 185 ppb NO x and 140 ppb DMS. Among the aerosol-phase DMS oxidation products, MSA was the most sensitive to the presence of isoprene (e.g., 46% reduction). The DMS aerosol product analysis indicates that isoprene oxidation affects the pathways of MSA formation on the aerosol surface. Using a new approach that implements an Organic Carbon (OC) analyzer, the isoprene SOA yield ( Yiso) in the DMS/isoprene/NO x system was also estimated. The OC data showed that Yiso increased significantly with DMS compared to the Yiso without DMS. For example, Yiso with 80 ppb NO x and 840 ppb isoprene was increased by 124.6% due to 100 ppb DMS at RH = 42%. Our study suggests that the heterogeneous reactions of isoprene oxidation products with the highly acidic products (e.g., MSA and sulfuric acid) from DMS photooxidation can considerably contribute to the Yiso increase.

  17. 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 tendencies in the biogenic versus anthropogenic SOA responses.

  18. Particle size distribution of major inorganic species in atmospheric aerosols from Majorca (Spain)

    Microsoft Academic Search

    J. Mateu; R. Forteza; V. Cerdfi; M. Colom-Altés

    1995-01-01

    Atmospheric aerosols collected by means of a cascade impaction system at the campus of the University of the Balearic Islands (Majorca, Spain) from November 1993 to February 1994 were analysed for chloride, nitrate, sulphate, ammonium, calcium, magnesium, sodium and potassium. Based on particle size distribution, the species studied were classified into three groups: (a) concentration decrease with particle size (sulphate

  19. Fog scavenging of organic and inorganic aerosol in the Po Valley

    NASA Astrophysics Data System (ADS)

    Gilardoni, S.; Massoli, P.; Giulianelli, L.; Rinaldi, M.; Paglione, M.; Pollini, F.; Lanconelli, C.; Poluzzi, V.; Carbone, S.; Hillamo, R.; Russell, L. M.; Facchini, M. C.; Fuzzi, S.

    2014-07-01

    The interaction of aerosol with atmospheric water affects the processing and wet removal of atmospheric particles. Understanding such interaction is mandatory to improve model description of aerosol lifetime and ageing. We analyzed the aerosol-water interaction at high relative humidity during fog events in the Po Valley within the framework of the Agenzia Regionale per la Prevenzione e l'Ambiente (ARPA) - Emilia Romagna supersite project. For the first time in this area, the changes in particle chemical composition caused by fog are discussed along with changes in particle microphysics. During the experiment, 14 fog events were observed. The average mass scavenging efficiency was 70% for nitrate, 68% for ammonium, 61% for sulfate, 50% for organics, and 39% for black carbon. After fog formation, the interstitial aerosol was dominated by particles smaller than 200 nm Dva (vacuum aerodynamic diameter) and enriched in carbonaceous aerosol, mainly black carbon and water-insoluble organic aerosol. For each fog event, the size-segregated scavenging efficiency of nitrate and organic aerosol (OA) was calculated by comparing chemical species size distribution before and after fog formation. For both nitrate and OA, the size-segregated scavenging efficiency followed a sigmoidal curve, with values close to zero below 100 nm Dva and close to 1 above 700 nm Dva. OA was able to affect scavenging efficiency of nitrate in particles smaller than 300 nm Dva. A linear correlation between nitrate scavenging and particle hygroscopicity (?) was observed, indicating that 44-51% of the variability of nitrate scavenging in smaller particles (below 300 nm Dva) was explained by changes in particle chemical composition. The size-segregated scavenging curves of OA followed those of nitrate, suggesting that organic scavenging was controlled by mixing with water-soluble species. In particular, functional group composition and OA elemental analysis indicated that more oxidized OA was scavenged more efficiently than less oxidized OA. Nevertheless, the small variability of organic functional group composition during the experiment did not allow us to discriminate the effect of different organic functionalities on OA scavenging.

  20. Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer.

    PubMed

    Bahreini, R; Keywood, M D; Ng, N L; Varutbangkul, V; Gao, S; Flagan, R C; Seinfeld, J H; Worsnop, D R; Jimenez, J L

    2005-08-01

    The Aerodyne aerosol mass spectrometer (AMS) was used to characterize physical and chemical properties of secondary organic aerosol (SOA) formed during ozonolysis of cycloalkenes and biogenic hydrocarbons and photo-oxidation of m-xylene. Comparison of mass and volume distributions from the AMS and differential mobility analyzers yielded estimates of "effective" density of the SOA in the range of 0.64-1.45 g/cm3, depending on the particular system. Increased contribution of the fragment at m/z 44, C02+ ion fragment of oxygenated organics, and higher "delta" values, based on ion series analysis of the mass spectra, in nucleation experiments of cycloalkenes suggest greater contribution of more oxygenated molecules to the SOA as compared to those formed under seeded experiments. Dominant negative "delta" values of SOA formed during ozonolysis of biogenics indicates the presence of terpene derivative structures or cyclic or unsaturated oxygenated compounds in the SOA. Evidence of acid-catalyzed heterogeneous chemistry, characterized by greater contribution of higher molecular weight fragments to the SOA and corresponding changes in "delta" patterns, is observed in the ozonolysis of alpha-pinene. Mass spectra of SOA formed during photooxidation of m-xylene exhibit features consistent with the presence of furandione compounds and nitro organics. This study demonstrates that mixtures of SOA compounds produced from similar precursors result in broadly similar AMS mass spectra. Thus, fragmentation patterns observed for biogenic versus anthropogenic SOA may be useful in determining the sources of ambient SOA. PMID:16124302

  1. Chamber studies to simulate secondary organic aerosol formation from the Deepwater Horizon oil spill

    NASA Astrophysics Data System (ADS)

    Daumit, K. E.; Carrasquillo, A. J.; Cross, E. S.; Hunter, J. F.; Bahreini, R.; Middlebrook, A. M.; De Gouw, J. A.; Williams, L. R.; Worsnop, D. R.; Kroll, J. H.

    2011-12-01

    Because atmospheric organic species are generally emitted from a large number of sources, over wide spatial and temporal scales, it is generally challenging to ascribe ambient organic aerosol (OA) to the oxidation of specific secondary organic aerosol (SOA) precursors. However, the Deepwater Horizon (DWH) oil spill (April 20-July 15, 2010), provided the unique circumstance of a large, well-defined source of gas-phase organics introduced into a relatively clean atmosphere. Here we describe a laboratory simulation of SOA formation downwind of the DWH spill, via the oxidation of South Louisiana-light (SL) crude oil by OH radicals in an environmental chamber. Intermediate and semi-volatile fractions of the SL crude oil are vaporized and oxidized by gas-phase OH radicals (formed from the photolysis of HONO). The chemical composition is monitored as a function of OH exposure. When OH exposures are approximately matched, laboratory-generated SOA and OA measured downwind of the oil spill exhibit extremely similar aerosol mass spectra, in strong support of the hypothesis that the OA measured downwind of the DWH oil spill was secondary in nature. More generally, this agreement indicates that in cases when SOA precursors are well-constrained, chamber experiments can reasonably reproduce key properties of ambient OA. Results of chamber studies on sub-fractions of the SL crude oil, aimed at identifying the classes of oil components most responsible for SOA formation, will be discussed.

  2. Industrial sources of primary and secondary organic aerosols in two urban environments in Spain.

    PubMed

    Escudero, M; Viana, M; Querol, X; Alastuey, A; Díez Hernández, P; García Dos Santos, S; Anzano, J

    2015-07-01

    In urban areas, primary and secondary organic aerosols are typically considered to originate from vehicular traffic emissions. However, industrial emissions within or in the vicinity of urban areas may also be significant contributors to carbonaceous aerosol concentrations. This hypothesis was tested and validated in two urban areas in Spain. The observed unusual dominance of organic carbon (OC) over elemental carbon (EC), the analysis of the variability of OC, EC and OC/EC and their correlation with transport patterns suggested the presence of OC sources associated with industrial activities. A methodology based on chemical speciation of particulate matter (PM) followed by the application of receptor modelling techniques allowed for the identification of the specific industrial sources of OC, which were linked to primary OC emissions from a grain drying plant (cereal) and to secondary OC formation from paper production activities (paper mills), as well as from urban sources and biogenic emissions. This work presents an integrated approach to identifying and characterizing of industrial sources of carbonaceous aerosols in urban areas, aiming to improve the scarce body of literature currently available on this topic. PMID:25721527

  3. Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NOx concentration.

    PubMed

    Presto, Albert A; Hartz, Kara E Huff; Donahue, Neil M

    2005-09-15

    We report secondary organic aerosol (SOA) yields from the ozonolysis of alpha-pinene in the presence of NO and NO2. Experimental conditions are characterized by the [VOC]0/ [NOx]0 ratio (ppbC/ppb), which varies from approximately 1 to approximately 300. SOA yield is constant for [VOC]0/[NOx]0 > approximately 15 and decreases dramatically (by more than a factor of 4) as [VOC]0/[NOx]0 decreases. Aerosol production is completely suppressed in the presence of NO for [VOC]0/[NOx]0 < or = 4.5. Fouriertransform IR analysis of filter samples reveals that nitrate-containing species contribute significantly to the total aerosol mass at low [VOC]0/[NOx]0. Yield reduction is a result of the formation of a more volatile product distribution as [VOC]0/[NOx]0 decreases; we propose that the change in the product distribution is driven by changes in the gas-phase chemistry as NOx concentration increases. We also present two-product model parameters to describe aerosol production from the alpha-pinene/0/NOx system under both high- and low-NOx conditions. PMID:16201628

  4. 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.

  5. 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 meter. The m-xylene SOA yield ranges from 0.04 to 0.08 for aerosol in the range of 4.0 to 12.0 micrograms per cubic meter. These yields are generally comparable to those from photooxidation. In marine and industrial areas, SOA formation from the Cl- initiated oxidation of the studied common aromatics is likely to be most important in the early morning.

  6. Modeling Organic Aerosols during MILAGRO: Application of the CHIMERE Model and Importance of Biogenic Secondary Organic Aerosols

    SciTech Connect

    Hodzic, Alma; Jimenez, Jose L.; Madronich, Sasha; Aiken, Allison; Bessagnet, Bertrand; Curci, Gabriele; Fast, Jerome D.; Lamarque, J.-F.; Onasch, Timothy B.; Roux, Gregory; Schauer, James J.; Stone, Elizabeth A.

    2009-09-22

    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 have 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 first-generation oxidation of anthropogenic (i.e., aromatics, alkanes) and biogenic (i.e., monoterpenes and isoprene) 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 species, with a factor of 5-10 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. However, predicted SOA concentrations were unrealistically low when photochemistry was not active, especially overnight. These nighttime discrepancies were not significantly reduced when greatly enhanced partitioning to the aerosol phase was assumed. Model sensitivity results suggest that observed nighttime SOA concentrations are strongly influenced by the regional background (~2µg/m3) from biogenic origin, which is transported from the coastal regions into the Mexico City basin. The relative contribution of biogenic SOA to monthly mean SOA levels is estimated to be more than 30% within the city and up to 65-90% at the regional scale (even in the immediate vicinity of the city), which is consistent with measurements of modern carbon 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 to 10-20 Tons within the Mexico City metropolitan area during the daytime), and emphasize for the first time the role of biogenic precursors in this region, indicating that they cannot be neglected in modeling studies.

  7. Evidence of aqueous secondary organic aerosol formation from biogenic emissions in the North American Sonoran Desert

    PubMed Central

    Youn, Jong-Sang; Wang, Zhen; Wonaschütz, Anna; Arellano, Avelino; Betterton, Eric A.; Sorooshian, Armin

    2013-01-01

    This study examines the role of aqueous secondary organic aerosol formation in the North American Sonoran Desert as a result of intense solar radiation, enhanced moisture, and biogenic volatile organic compounds (BVOCs). The ratio of water-soluble organic carbon (WSOC) to organic carbon (OC) nearly doubles during the monsoon season relative to other seasons of the year. When normalized by mixing height, the WSOC enhancement during monsoon months relative to preceding dry months (May–June) exceeds that of sulfate by nearly a factor of 10. WSOC:OC and WSOC are most strongly correlated with moisture parameters, temperature, and concentrations of O3 and BVOCs. No positive relationship was identified between WSOC or WSOC:OC and anthropogenic tracers such as CO over a full year. This study points at the need for further work to understand the effect of BVOCs and moisture in altering aerosol properties in understudied desert regions. PMID:24115805

  8. Biogenic potassium salt particles as seeds for secondary organic aerosol in the Amazon.

    PubMed

    Pöhlker, Christopher; Wiedemann, Kenia T; Sinha, Bärbel; Shiraiwa, Manabu; Gunthe, Sachin S; Smith, Mackenzie; Su, Hang; Artaxo, Paulo; Chen, Qi; Cheng, Yafang; Elbert, Wolfgang; Gilles, Mary K; Kilcoyne, Arthur L D; Moffet, Ryan C; Weigand, Markus; Martin, Scot T; Pöschl, Ulrich; Andreae, Meinrat O

    2012-08-31

    The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt-rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest. PMID:22936773

  9. Physical Properties of Ambient and Laboratory-Generated Secondary Organic Aerosol

    SciTech Connect

    O'Brien, Rachel E.; Neu, Alexander; Epstein, Scott A.; MacMillan, Amanda; Wang, Bingbing; Kelly, Stephen T.; Nizkorodov, Sergey; Laskin, Alexander; Moffet, Ryan C.; Gilles, Mary K.

    2014-06-17

    The size and thickness of organic aerosol particles collected by impaction in five field campaigns were compared to those of laboratory generated secondary organic aerosols (SOA). Scanning transmission x-ray microscopy (STXM) was used to measure the total carbon absorbance (TCA) by individual particles as a function of their projection areas on the substrate. Because they flatten less upon impaction, particles with higher viscosity and surface tension can be identified by a steeper slope on a plot of TCA vs. size. The slopes of the ambient data are statistically similar indicating a small range of average viscosities and surface tensions across five field campaigns. Steeper slopes were observed for the plots corresponding to ambient particles, while smaller slopes were indicative of the laboratory generated SOA. This comparison indicates that ambient organic particles have higher viscosities and surface tensions than those typically generated in laboratory SOA studies.

  10. Gasoline emissions dominate over diesel in formation of secondary organic aerosol mass

    NASA Astrophysics Data System (ADS)

    Bahreini, R.; Middlebrook, A. M.; de Gouw, J. A.; Warneke, C.; Trainer, M.; Brock, C. A.; Stark, H.; Brown, S. S.; Dube, W. P.; Gilman, J. B.; Hall, K.; Holloway, J. S.; Kuster, W. C.; Perring, A. E.; Prevot, A. S. H.; Schwarz, J. P.; Spackman, J. R.; Szidat, S.; Wagner, N. L.; Weber, R. J.; Zotter, P.; Parrish, D. D.

    2012-03-01

    Although laboratory experiments have shown that organic compounds in both gasoline fuel and diesel engine exhaust can form secondary organic aerosol (SOA), the fractional contribution from gasoline and diesel exhaust emissions to ambient SOA in urban environments is poorly known. Here we use airborne and ground-based measurements of organic aerosol (OA) in the Los Angeles (LA) Basin, California made during May and June 2010 to assess the amount of SOA formed from diesel emissions. Diesel emissions in the LA Basin vary between weekdays and weekends, with 54% lower diesel emissions on weekends. Despite this difference in source contributions, in air masses with similar degrees of photochemical processing, formation of OA is the same on weekends and weekdays, within the measurement uncertainties. This result indicates that the contribution from diesel emissions to SOA formation is zero within our uncertainties. Therefore, substantial reductions of SOA mass on local to global scales will be achieved by reducing gasoline vehicle emissions.

  11. Primary and Secondary Aerosol Investigation from Different Sea-Waters in the Mediterranean Sea

    NASA Astrophysics Data System (ADS)

    D'anna, B.; Marchand, N.; Sellegri, K.; Sempéré, R.; Mas, S.; George, C.; Meme, A.; Frihi, A.; Pey, J.; Schwier, A.; Delmont, A.

    2014-12-01

    The Mediterranean Sea is a special marine environment characterized by low biological activity and high anthropogenic pressure. It is often difficult to discriminate the contribution of Primary and Secondary Aerosol formed at the sea-air interface from background level of the aerosol. We therefore decided to study the sea-air exchanges in a controlled environment provided by a 2m3simulation chamber, using freshly collected sea-water samples from the SEMEX site (43°15'64 N, 05°20'01 E) near Marseille bay. Two types of experiments were conducted for 4 weeks testing 3 different sea-waters. Primary sea-aerosol was generated by bubble-bursting method, then introduced in the simulation chamber and exposed to atmospheric oxidants (O3, OH) and light to simulated primary aerosol aging. A second set of experiments focused on secondary particle formation upon illumination and/or ozone exposure of the sea-water surface (15l of sea-water were deposited in a pyrex container located inside the simulation chamber). New particle formation was only observed for relatively high DOC level of the sea-water sample. Particles detection and analysis was followed by a PSM (1nm size), a CPC (2.5nm size), a SMPS (granulometry), a CCN chamber for hygroscopicity studies, a TOF-AMS (Aerodyne) for chemical analysis of the sub-micrometer fraction. Off-line analysis included TEM-EDX samples for morphology and size distribution studies and a hybrid quadrupole-orbitrap mass spectrometer (Thermo Fischer) for the molecular identification of the organic fraction. VOCs were measured on-line by PTR-HR-MS. The seawater samples were filtered at 60?m before use and were daily analyzed for chemical (colored dissolved organic matter, particulate matter and related polar compounds, transparent polysaccharides and nutrients concentration) and biological (chlorophyll a, virus, phytoplankton and zooplankton) analyses.

  12. 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 additional sources for this tracer at rural site and that it should be used with caution as meat cooking tracer in rural areas in the future. PMID:24262212

  13. Semi-volatile secondary organic aerosol in urban atmospheres: meeting a measurement challenge

    NASA Astrophysics Data System (ADS)

    Eatough, Delbert J.; Long, Russell W.; Modey, William K.; Eatough, Norman L.

    Ammonium nitrate and semi-volatile organic compounds are significant components of fine particles in urban atmospheres. These components, however, are not properly determined with current US EPA accepted methods such as the PM 2.5 FRM or other single filter samplers due to significant losses of semi-volatile material (SVM) from particles collected on the filter during sampling. Continuous PM 2.5 mass measurements are attempted using methods such as the R&P TEOM monitor. This method, however, heats the sample to remove particle-bound water which also results in evaporation of SVM. Research at Brigham Young University has resulted in samplers for both the integrated and continuous measurement of total PM 2.5, including the SVM. The PC-BOSS is a charcoal diffusion denuder based sampler for the determination of fine particulate chemical composition including the semi-volatile organic material. The RAMS is a modified TEOM monitor which includes diffusion denuders and Nafion dryers to remove gas phase material which can be absorbed by a charcoal sorbent filter. The RAMS then uses a "sandwich filter" consisting of a conventional particle collecting Teflon coated TX40 filter, followed by an activated charcoal sorbent filter which retains any semi-volatile ammonium nitrate or organic material lost from the particles collected on the TEOM monitor Teflon coated filter, thus allowing for determination of total PM 2.5 mass including the SVM. Recent research conducted by Brigham Young University using these two samplers has indicated the following about semi-volatile organic aerosol: The majority of semi-volatile fine particulate organic material is secondary organic aerosol. This semi-volatile organic aerosol is not retained on the heated filter of a regular TEOM monitor and hence is not measured by this sampling technique. In addition, secondary ammonium nitrate is also lost. Much of the semi-volatile organic aerosol is also lost during sampling from single filter samplers such as the PM 2.5 FRM sampler. The amount of semi-volatile organic aerosol lost from single filter samplers can vary from less than 1/3 that lost from heated TEOM filters during cold winter conditions to essentially all during warm summer conditions. Semi-volatile organic aerosol can only be reliably collected using an appropriate denuder sampler. Either a PM 2.5 FRM sampler or the IMPROVE sampler can be easily modified to a denuder sampler with filters which can be analyzed for semi-volatile OC, nonvolatile OC and EC using existing OC/EC analytical techniques. The research upon which these statements are based is summarized in this document.

  14. Secondary organic aerosol formation and composition from the photo-oxidation of methyl chavicol (estragole)

    NASA Astrophysics Data System (ADS)

    Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vázquez, M.; Borrás, E.; Ródenas, M.

    2014-06-01

    The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound (VOC) that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high-performance liquid chromatography mass spectrometry (HPLC-ITMS), high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18 and 29% for an initial VOC mixing ratio of 212 and 460 ppbv (parts per billion by volume) respectively; using a VOC:NOx ratio of ~5:1. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high-resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro-functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O:C ratios, where functionalisation rather than fragmentation is mainly observed as a result of the stability of the ring. The SOA species observed can be characterised as semi-volatile to low-volatility oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

  15. Key parameters controlling the formation of secondary organic aerosol in the aqueous phase (aqSOA)

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Lim, Y. B.; Sorooshian, A.; Turpin, B. J.

    2013-12-01

    Secondary organic aerosol formation in the aqueous phase of cloud (fog) droplets and aerosol particles (aqSOA) might contribute significantly to the total SOA burden and can help to explain the discrepancies in observed and predicted SOA properties. Ambient SOA often comprises highly oxidized material (high O/C ratio) composed of oligomers and dicarboxylic acids that do not have any known efficient gas phase sources. In order to implement aqSOA formation in models, the most important processes within the multiphase system have to be identified. We explore parameter ranges of physical key processes and aqSOA formation rates as a function of oxidant (OH) availability. The processes include (1) phase transfer of both SOA precursors and oxidants from the gas to the aqueous phase, (2) diffusion within the aqueous phase, and (3) aqueous phase reactions that result in aqSOA formation within the aqueous particles or droplets, respectively. Model results suggest that cloud aqSOA formation is oxidant-limited even if aqueous sources of the OH radical are taken into account. This limitation manifests itself as an apparent surface-dependence of aqSOA formation. Comparison to ambient data on organic mass (oxalate) formation in clouds as a function of cloud properties (drop surface area) exhibits similar trends. These findings imply that future cloud aqSOA parametrizations should include drop surface area and/or effective droplet radius instead of liquid water volume only. In aerosol particles, chemical aqueous OH sources result in higher OH concentrations due to the enhanced surface/volume ratio and higher solute concentrations that affect aqueous OH formation rates. Thus, aerosol aqSOA might scale either with the wet aerosol surface or volume, depending on oxidant availability.

  16. Effects of chemical aging on global secondary organic aerosol using the volatility basis set approach

    NASA Astrophysics Data System (ADS)

    Jo, D. S.; Park, R. J.; Kim, M. J.; Spracklen, D. V.

    2013-12-01

    A global 3-D chemical transport model (GEOS-Chem) is used with the volatility basis set (VBS) approach to examine the effects of chemical aging on global secondary organic aerosol (SOA) concentrations and budgets. We present full-year simulations and their comparisons with the global aerosol mass spectrometer (AMS) dataset, the Interagency Monitoring of Protected Visual Environments (IMPROVE) dataset from the United States, the European Monitoring and Evaluation Programme (EMEP) dataset from Europe, and water-soluble organic carbon observation data collected over East Asia. Using different chemical aging constants, we find that the model results with 4 × 10-11 cm3 molecule-1 s-1 are in better agreement with all observations relative to the model results with other aging constants, without aging, and with the two-product approach. The model simulations are improved when chemical aging is considered, especially for rural regions. However, the simulations still underestimate observed oxygenated organic aerosol (OOA) in urban areas. Two sensitivity simulations including semi-volatile primary organic aerosol (POA) were conducted. We find that including semi-volatile POA improves the model in terms of the hydrogen-like organic aerosol (HOA) to OOA ratio. However, the total OA concentrations are not improved. The total SOA production is considerably increased by 53%, from 26.0 to 39.9 Tg yr-1, after considering chemical aging, remaining lower than top-down estimates of SOA production. Direct radiative forcing (DRF) increases by -0.07 W m-2 due to the chemical aging of SOA, which is comparable to the mean DRF (-0.13 W m-2) of OA from the AeroCom multi-model study. This result indicates considerable global and, more importantly, regional climate implications. For example, the regional DRF change due to chemical aging of SOA in the eastern US is -0.29 W m-2, which is 4 times greater in magnitude than the global mean value.

  17. Calculating Equilibrium Phase Distribution during the Formation of Secondary Organic Aerosol Using COSMOtherm.

    PubMed

    Wang, Chen; Goss, Kai-Uwe; Lei, Ying Duan; Abbatt, Jonathan P D; Wania, Frank

    2015-07-21

    Challenges in the parametrization of compound distribution between the gas and particle phase contribute significantly to the uncertainty in the prediction of secondary organic aerosol (SOA) formation and are rooted in the complexity and variability of atmospheric condensed matter, which includes water, salts, and a multitude of organic oxidation products, often in two separated phases. Here, we explore the use of the commercial quantum-chemistry-based software COSMOtherm to predict equilibrium partitioning and Setchenow coefficients of a suite of oxidation products of ?-pinene ozonolysis in an aerosol that is assumed to separate into an organic-enriched phase and an electrolyte-enriched aqueous phase. The predicted coefficients are used to estimate the phase distribution of the organic compounds, water and ammonium sulfate, the resulting phase composition, and the SOA yield. Four scenarios that differ in terms of organic loading, liquid water content, and chemical aging are compared. The organic compounds partition preferentially to the organic phase rather than the aqueous phase for the studied aerosol scenarios, partially due to the salting-out effect. Extremely low volatile organic compounds are predicted to be the dominant species in the organic aerosols at low loadings and an important component at higher loadings. The highest concentration of oxidation products in the condensed phase is predicted for a scenario assuming the presence of non-phase-separated cloud droplets. Partitioning into an organic aerosol phase composed of the oxidation products is predicted to be similar to partitioning into a phase composed of a single organic surrogate molecule, suggesting that the calculation procedure can be simplified without major loss of accuracy. COSMOtherm is shown to produce results that are comparable to those obtained using group contribution methods. COSMOtherm is likely to have a much larger application domain than those group contribution methods because it is based on fundamental principles with little calibration. PMID:26079409

  18. Global aerosol modeling with the online NMMB/BSC Chemical Transport Model: sensitivity to fire injection height prescription and secondary organic aerosol schemes

    NASA Astrophysics Data System (ADS)

    Spada, Michele; Jorba, Oriol; Pérez García-Pando, Carlos; Tsigaridis, Kostas; Soares, Joana; Obiso, Vincenzo; Janjic, Zavisa; Baldasano, Jose M.

    2015-04-01

    We develop and evaluate a fully online-coupled model simulating the life-cycle of the most relevant global aerosols (i.e. mineral dust, sea-salt, black carbon, primary and secondary organic aerosols, and sulfate) and their feedbacks upon atmospheric chemistry and radiative balance. Following the capabilities of its meteorological core, the model has been designed to simulate both global and regional scales with unvaried parameterizations: this allows detailed investigation on the aerosol processes bridging the gap between global and regional models. Since the strong uncertainties affecting aerosol models are often unresponsive to model complexity, we choose to introduce complexity only when it clearly improves results and leads to a better understanding of the simulated aerosol processes. We test two important sources of uncertainty - the fires injection height and secondary organic aerosol (SOA) production - by comparing a baseline simulation with experiments using more advanced approaches. First, injection heights prescribed by Dentener et al. (2006, ACP) are compared with climatological injection heights derived from satellite measurements and produced through the Integrated Monitoring and Modeling System For Wildland Fires (IS4FIRES). Also global patterns of SOA produced by the yield conversion of terpenes as prescribed by Dentener et al. (2006, ACP) are compared with those simulated by the two-product approach of Tsigaridis et al. (2003, ACP). We evaluate our simulations using a variety of observations and measurement techniques. Additionally, we discuss our results in comparison to other global models within AEROCOM and ACCMIP.

  19. Investigating primary marine aerosol properties: CCN activity of sea salt and mixed inorganic-organic particles.

    PubMed

    King, Stephanie M; Butcher, Andrew C; Rosenoern, Thomas; Coz, Esther; Lieke, Kirsten I; de Leeuw, Gerrit; Nilsson, E Douglas; Bilde, Merete

    2012-10-01

    Sea spray particles ejected as a result of bubbles bursting from artificial seawater containing salt and organic matter in a stainless steel tank were sampled for size distribution, morphology, and cloud condensation nucleus (CCN) activity. Bubbles were generated either by aeration through a diffuser or by water jet impingement on the seawater surface. Three objectives were addressed in this study. First, CCN activities of NaCl and two types of artificial sea salt containing only inorganic components were measured to establish a baseline for further measurements of mixed organic-inorganic particles. Second, the effect of varying bubble residence time in the bulk seawater solution on particle size and CCN activity was investigated and was found to be insignificant for the organic compounds studied. Finally, CCN activities of particles produced from jet impingement were compared with those produced from diffuser aeration. Analyses indicate a considerable amount of organic enrichment in the jet-produced particles relative to the bulk seawater composition when sodium laurate, an organic surfactant, is present in the seawater. In this case, the production of a thick foam layer during impingement may explain the difference in activation and supports hypotheses that particle production from the two methods of generating bubbles is not equal. PMID:22809370

  20. Real-time continuous characterization of secondary organic aerosol derived from isoprene epoxydiols in downtown Atlanta, Georgia, using the Aerodyne Aerosol Chemical Speciation Monitor.

    PubMed

    Budisulistiorini, Sri Hapsari; Canagaratna, Manjula R; Croteau, Philip L; Marth, Wendy J; Baumann, Karsten; Edgerton, Eric S; Shaw, Stephanie L; Knipping, Eladio M; Worsnop, Douglas R; Jayne, John T; Gold, Avram; Surratt, Jason D

    2013-06-01

    Real-time continuous chemical measurements of fine aerosol were made using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) during summer and fall 2011 in downtown Atlanta, Georgia. Organic mass spectra measured by the ACSM were analyzed by positive matrix factorization (PMF), yielding three conventional factors: hydrocarbon-like organic aerosol (HOA), semivolatile oxygenated organic aerosol (SV-OOA), and low-volatility oxygenated organic aerosol (LV-OOA). An additional OOA factor that contributed to 33 ± 10% of the organic mass was resolved in summer. This factor had a mass spectrum that strongly correlated (r(2) = 0.74) to that obtained from laboratory-generated secondary organic aerosol (SOA) derived from synthetic isoprene epoxydiols (IEPOX). Time series of this additional factor is also well correlated (r(2) = 0.59) with IEPOX-derived SOA tracers from filters collected in Atlanta but less correlated (r(2) < 0.3) with a methacrylic acid epoxide (MAE)-derived SOA tracer, ?-pinene SOA tracers, and a biomass burning tracer (i.e., levoglucosan), and primary emissions. Our analyses suggest IEPOX as the source of this additional factor, which has some correlation with aerosol acidity (r(2) = 0.3), measured as H(+) (nmol m(-3)), and sulfate mass loading (r(2) = 0.48), consistent with prior work showing that these two parameters promote heterogeneous chemistry of IEPOX to form SOA. PMID:23638946

  1. Implementing a Volatility Basis Set Approach for Simulation of Secondary Organic Aerosol and its Climatic Impacts in CESM-CAM5

    NASA Astrophysics Data System (ADS)

    Glotfelty, T.; He, J.; Gantt, B.; Zhang, Y.

    2013-12-01

    Organic aerosols (OA) affect climate by serving as cloud condensation nuclei, which impact the cloud droplet number concentration (CDNC) and ultimately the radiation budget of the planet through aerosol direct and indirect effects. Accurately quantifying OA in climate models is important as they account for 20-90% of submicron aerosols. In order to better represent the formation of OA and their impact on climate, a volatility basis set (VBS) approach for the formation of secondary organic aerosols (SOA) has been implemented into the NCSU version of the Community Atmosphere Model version 5.1 (CAM5) in the Community Earth System Model (CESM). Compared to the officially released version of CESM/CAM5, the NCSU version used in this study features advanced inorganic aerosol treatments and aerosol activation parameterizations. In addition to the typical SOA precursors, SOA formation from semi-volatile primary organic aerosol (POA), polycyclic aromatic hydrocarbons, and glyoxal are being treated. To assess the performance of the improved model, two full year simulations of 2001 and 2010 will be conducted and evaluated against available observations including the total organic carbon (TOC) measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE), total carbon (TC) measurements from Speciation Trends Network (STN), and global aerosol mass spectrometer measurements of hydrocarbon-like aerosol (HOA) and oxygenated organic aerosol (OOA). Preliminary simulations for summer 2001 show that the VBS treatment increases the SOA concentration by 0.2 ?g m-3 on global average but by 0.6-9.7 ?g m-3 over Europe, East Asia, and North America. There is, however, a slight decrease in the SOA formed over rainforest areas; resulting from differences in SOA production from a single lumped precursor in the default treatment verses the species-dependent treatment in the VBS treatment. Compared to the baseline simulation, the simulation with the VBS treatment tends to improve TC predictions at the STN sites but deteriorate TOC predictions at the IMPROVE sites. The discrepancy between the evaluation at the largely rural IMPROVE and largely urban STN sites indicates the emissions from urban regions may be misrepresented by spatially interpolating emissions from a finer scales to a coarse resolution (0.9° by 1.25°) used in the simulation. The TOC and TC overpredictions with the VBS treatment may be caused in part by overestimations of POA emissions, as reflected by the > 83% overprediction of global HOA concentrations. The evaluation of SOA against global OOA data shows much smaller underpredictions (by 7% vs. 88%) with the VBS treatment. The additional SOA increases the global average column aerosol diameter and thus CDNC and the absolute value of shortwave cloud forcing. These results imply that OA have a strong impact on the climate system but improvements are needed in the representations of both the natural and anthropogenic emissions of organic species as well as the SOA formation mechanisms in global climate and Earth system models in order to reduce the uncertainties in the predicted climatic effects of aerosols.

  2. Formation of secondary organic aerosols from biogenic precursors: A case study over an Isoprene emitting forest.

    NASA Astrophysics Data System (ADS)

    Freney, Evelyn; Sellegri, Karine; Borbon, Agnès; Colomb, Aurelie; Delon, Claire; Jambert, Corinne; Durand, Pierre; Bourianne, Thierry; Gaimoz, Cecile; Feron, Anais; Triquette, Sylvain; Beekmann, Matthias; Sartelet, Karine; Dulcac, Francois

    2015-04-01

    Characterising the sources and formation patterns of atmospheric aerosols is fundamental to understanding the impact of anthropogenic emissions on the composition and physical properties of the atmosphere. Although, the contribution of urban anthropogenic aerosol particles is important (10 Tg C yr-1), the contribution of biogenic aerosols has been estimated to be as much as 90 Tg C yr-1 (Hallquist et al., 2009.). This large difference highlights the importance of understanding the formation mechanisms and sources of the biogenic aerosol in the atmosphere. An increasing number of studies have shown that the submicron aerosol mass concentration is dominated by organic aerosols in both rural and urban environments. In addition, there have been several studies showing that the combined emissions of both biogenic and anthropogenic VOC emissions can result in a higher yield of secondary organic aerosol (SOA) formation. Biogenic SOA is formed from the oxidation of biogenic volatile organic compounds that are emitted naturally from terrestrial vegetation. The most commonly emitted BVOCs include isoprene and monoterpenes (Kesslmeier and Staudt, 1999, Arneth et al., 2008). Despite their importance, the characterisation of BSOA from laboratory and field experiments is still poor and it is only recently that advances in measurement techniques providing more detailed analysis of these species is being provided. One of the reasons for the difficulty in characterising the abundance of these species, is their high temporal and spatial scales. As part of the ChArMEx (the Chemistry-Aerosol Mediterranean Experiment, http://charmex.lsce.ipsl.fr) experiment (SOP2a/SAFMED+) in July 2014, a number of research flights were performed over two forested areas in the south of France. These forested areas had different characteristics where one has mainly isoprene emitting vegetation, and the other is known to have more monoterpene emitting vegetation. The aims of these research flights were to characterise the gas-phase precursors responsible for the formation of biogenic SOA. The French ATR-42 aircraft was equipped with both gas-phase and aerosol phase measurements providing detailed measurements of aerosol chemistry (PTRMS, AMS) and physical properties (SMPS, CPC). During these measurements, we encountered suitable meteorological conditions to allow us to observe the formation of SOA from isoprene emissions and new particle formation from monoterpene emissions. These results provide an ideal case study that can be used to validate numerical models on the formation of SOA and new particles from biogenic emissions. Acknowledgements: ChArMEx is supported by CNRS/INSU, ADEME, Météo-France and CEA in the framework of the multidisciplinary programme MISTRALS (Mediterranean Integrated Studies aT Regional And Local Scales; http://www.mistrals-home.org). The contribution of OMP/SEDOO for the ChArMEx campaign web site (http://choc.sedoo.fr) was greatly appreciated. François Dulac and Eric Hamonou from LSCE are acknowledged for the campaign coordination and management.

  3. Effects of Chemical Aging on Global Secondary Organic Aerosol using the Volatility Basis Set Approach

    NASA Astrophysics Data System (ADS)

    Park, R.; Jo, D.; Kim, M.; Spracklen, D. V.; Hodzic, A.

    2014-12-01

    Organic aerosol (OA) constitutes significant mass fractions (20-90%) of total dry fine aerosols in the atmosphere. However, global models of OA have shown large discrepancies when compared to the observations because of the limited capability to simulate secondary OA (SOA). For reducing the discrepancies between observations and models, recent studies have shown that chemical aging reactions in the atmosphere are important because they can lead to decreases in organic volatility, resulting in increase of SOA mass yields. To efficiently simulate chemical aging of SOA in the atmosphere, we implemented the volatility basis set approach in a global 3-D chemical transport model (GEOS-Chem). We present full-year simulations and their comparisons with multiple observations - global aerosol mass spectrometer dataset, the Interagency Monitoring of Protected Visual Environments from the United States, the European Monitoring and Evaluation Programme dataset and water-soluble organic carbon observation data collected over East Asia. Using different input parameters in the model, we also explore the uncertainty of the SOA simulation for which we use an observational constraint to find the optimized values with which the model reduces the discrepancy from the observations. Finally, we estimate the effect of OA on climate using our best simulation results.

  4. 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) ?g 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) ?g m(-3)) than more volatile compounds with C*?10(7) ?g 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

  5. Transboundary Secondary Organic Aerosol in Western Japan: An Observed Limitation of the f44 Oxidation Indicator

    E-print Network

    Irei, Satoshi; Sadanaga, Yasuhiro; Miyoshi, Takao; Arakaki, Tekemitsu; Sato, Kei; Kaneyasu, Naoki; Bandow, Hiroshi; Hatakeyama, Shiro

    2015-01-01

    To obtain evidence for secondary organic aerosol formation during the long range transport of air masses over the East China Sea, we conducted field measurements in March 2012 at the Fukue atmospheric monitoring station, Nagasaki, in western Japan. The relative abundance of m/z 44 in fine organic aerosol mass spectra (f44) was measured by an Aerodyne aerosol chemical speciation monitor. The stable carbon isotope ratio (d13C) of low volatile water soluble organic carbon (LV-WSOC) in the daily filter samples of total suspended particulate matter was also analyzed using an elemental analyzer coupled with an isotope ratio mass spectrometer. Additionally, in situ measurements of NOx and NOy were performed using NOx and NOy analyzers. The measurements showed that, unlike the systematic trends observed in a previous field study, a scatter plot for d13C of LV-WSOC versus f44 indicated a random variation. Comparison of f44 with the photochemical age estimated by the NOx to NOy ratio revealed that the f44 values distri...

  6. Secondary organic aerosol production from aqueous photooxidation of glycolaldehyde: Laboratory experiments

    NASA Astrophysics Data System (ADS)

    Perri, Mark J.; Seitzinger, Sybil; Turpin, Barbara J.

    Organic particulate matter (PM) formed in the atmosphere (secondary organic aerosol; SOA) is a substantial yet poorly understood contributor to atmospheric PM. Aqueous photooxidation in clouds, fogs and aerosols is a newly recognized SOA formation pathway. This study investigates the potential for aqueous glycolaldehyde oxidation to produce low volatility products that contribute SOA mass. To our knowledge, this is the first confirmation that aqueous oxidation of glycolaldehyde via the hydroxyl radical forms glyoxal and glycolic acid, as previously assumed. Subsequent reactions form formic acid, glyoxylic acid, and oxalic acid as expected. Unexpected products include malonic acid, succinic acid, and higher molecular weight compounds, including oligomers. Due to (1) the large source strength of glycolaldehyde from precursors such as isoprene and ethene, (2) its water solubility, and (3) the aqueous formation of low volatility products (organic acids and oligomers), we predict that aqueous photooxidation of glycolaldehyde and other aldehydes in cloud, fog, and aerosol water is an important source of SOA and that incorporation of this SOA formation pathway in chemical transport models will help explain the current under-prediction of organic PM concentrations.

  7. Interpretation of Secondary Organic Aerosol Formation from Diesel Exhaust Photooxidation in an Environmental Chamber

    SciTech Connect

    Nakao, Shunsuke; Shrivastava, ManishKumar B.; Nguyen, Anh; Jung, Hee-Jung; Cocker, David R.

    2011-04-14

    Secondary organic aerosol (SOA) formation from diesel exhaust in a smog chamber was investigated. Particle volume measurement based on mobility diameter is shown to underestimate SOA formation from diesel exhaust due to the external void space of agglomerate particles, in which case mass-based measurement technique is necessary. Rapid determination of particle effective density as a function of particle mass was performed by an Aerosol Particle Mass analyzer – Scanning Mobility Particle Sizer (APM-SMPS) to obtain particle mass concentration and fractal dimension. Continuous aging of aerosol was observed in terms of atomic ratio (O/C), from 0.05 to 0.25 in 12 hours, underscoring the importance of multi-generational oxidation of low-volatile organic vapors emitted from diesel engine as the significant source of oxygenated SOA. Experimental conditions possibly have strong impacts on physical evolution of diesel particulates in a smog chamber. Higher particle effective densities were observed when raw exhaust was injected into a full bag as opposed to filling a bag with diluted exhaust using an ejector diluter. When longer transfer line was used for injecting diesel exhaust into the smog chamber, rapid particle coagulation was observed, leading to increasing particle volume concentration in dark while its mass concentration is decreasing.

  8. Secondary Organic Aerosol Formation and Organic Nitrate Yield from NO3 Oxidation of Biogenic Hydrocarbons

    PubMed Central

    2014-01-01

    The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (?-pinene, ?-pinene, ?-3-carene, limonene, sabinene, and ?-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m3 indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for ?-pinene to 38–65% for ?-3-carene and 86% for ?-caryophyllene at mass loading of 10 ?g m–3, suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location’s mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of ?-pinene, little organonitrate and no aerosol is formed. PMID:25229208

  9. Secondary organic aerosol formation from ozone-initiated reactions with nicotine and secondhand tobacco smoke

    NASA Astrophysics Data System (ADS)

    Sleiman, Mohamad; Destaillats, Hugo; Smith, Jared D.; Liu, Chen-Lin; Ahmed, Musahid; Wilson, Kevin R.; Gundel, Lara A.

    2010-11-01

    We used controlled laboratory experiments to evaluate the aerosol-forming potential of ozone reactions with nicotine and secondhand smoke. Special attention was devoted to real-time monitoring of the particle size distribution and chemical composition of SOA as they are believed to be key factors determining the toxicity of SOA. The experimental approach was based on using a vacuum ultraviolet photon ionization time-of-flight aerosol mass spectrometer (VUV-AMS), a scanning mobility particle sizer (SMPS) and off-line thermal desorption coupled to mass spectrometry (TD-GC-MS) for gas-phase byproducts analysis. Results showed that exposure of SHS to ozone induced the formation of ultrafine particles (<100 nm) that contained high molecular weight nitrogenated species ( m/ z 400-500), which can be due to accretion/acid-base reactions and formation of oligomers. In addition, nicotine was found to contribute significantly (with yields 4-9%) to the formation of secondary organic aerosol through reaction with ozone. The main constituents of the resulting SOA were tentatively identified and a reaction mechanism was proposed to elucidate their formation. These findings identify a new component of thirdhand smoke that is associated with the formation of ultrafine particles (UFP) through oxidative aging of secondhand smoke. The significance of this chemistry for indoor exposure and health effects is highlighted.

  10. Effects of NOx on the volatility of secondary organic aerosol from isoprene photooxidation

    SciTech Connect

    Xu, Lu; Kollman, Matthew S.; Song, Chen; Shilling, John E.; Ng, L. N.

    2014-01-28

    The effects of NOx on the volatility of the secondary organic aerosol (SOA) formed from isoprene photooxidation are investigated in environmental chamber experiments. Two types of experiments are performed. In HO2-dominant experiments, organic peroxy radicals (RO2) primarily react with HO2. In mixed experiments, RO2 reacts through multiple pathways. The volatility and oxidation state of isoprene SOA is sensitive to and displays a non-linear dependence on NOx levels. When initial NO/isoprene ratio is approximately 3 (ppbv:ppbv), SOA are shown to be most oxidized and least volatile, associated with the highest SOA yield. A High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) is applied to characterize the key chemical properties of aerosols. While the composition of SOA in mixed experiments does not change substantially over time, SOA become less volatile and more oxidized as oxidation progresses in HO2-dominant experiments. Analysis of the SOA composition suggests that the further reactions of organic peroxides and alcohols may produce carboxylic acids, which might play a strong role in SOA aging.

  11. Using proton transfer reaction mass spectrometry for online analysis of secondary organic aerosols.

    PubMed

    Hellén, Heidi; Dommen, Josef; Metzger, Axel; Gascho, Astrid; Duplissy, Jonathan; Tritscher, Torsten; Prevot, Andre S H; Baltensperger, Urs

    2008-10-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) is a useful tool in ambient trace gas analysis, especially for the analysis of oxygenated volatile organic compounds (OVOC). Many OVOCs are produced during photooxidation of volatile organic compounds and contribute to both the gas phase and secondary organic aerosols (SOA). The inlet system of the PTR-MS instrument was modified to allow also for the measurement of the particulate phase of an aerosol with a high time resolution. The new inlet consists mainly of a denuder to strip off the gas phase, and a heater (120/150 degrees C) to vaporize the aerosol particles. This inlet system was tested with pinonic acid particles generated with a nebulizer and SOA particles formed during the photooxidation of 1,3,5-trimethylbenzene and alpha-pinene with NO(x) in a smog chamber. The performance of this new technique is discussed and the partitioning coefficients for the oxidation products are estimated. PMID:18939569

  12. Secondary organic aerosol and the burning question of gasoline vs. diesel

    NASA Astrophysics Data System (ADS)

    Gentner, D. R.; Isaacman, G.; Worton, D. R.; Chan, A. W.; Dallmann, T. R.; Davis, L.; Liu, S.; Day, D. A.; Russell, L. M.; Wilson, K. R.; Weber, R.; Guha, A.; Harley, R. A.; Goldstein, A. H.

    2012-12-01

    Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to Secondary Organic Aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. Using novel gas chromatography and mass spectrometry methods, we analyzed liquid gasoline and diesel fuel collected across the state of California during Summer 2010 and used it to assess field data from the CalNex (California at the Nexus of Air Quality and Climate Change) Bakersfield supersite and the Caldecott Tunnel in Oakland, CA. We present the most comprehensive data to date on the chemical composition, mass distribution, emissions, and SOA formation potential of gasoline and diesel sources. We find that diesel exhaust is 7 times more efficient at forming aerosol than gasoline exhaust and emits twice as much gas-phase organic carbon per liter of fuel burned. Yet, both sources are important for air quality; depending on a region's fuel use, diesel is responsible for 65-90% of vehicular-derived SOA, with substantial contributions from both aromatic and aliphatic hydrocarbons. We assess our results in the context of other studies and discuss their implications for regional air pollution policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

  13. Soft ionization chemical analysis of secondary organic aerosol from green leaf volatiles emitted by turf grass.

    PubMed

    Jain, Shashank; Zahardis, James; Petrucci, Giuseppe A

    2014-05-01

    Globally, biogenic volatile organic compound (BVOC) emissions contribute 90% of the overall VOC emissions. Green leaf volatiles (GLVs) are an important component of plant-derived BVOCs, including cis-3-hexenylacetate (CHA) and cis-3-hexen-1-ol (HXL), which are emitted by cut grass. In this study we describe secondary organic aerosol (SOA) formation from the ozonolysis of dominant GLVs, their mixtures and grass clippings. Near-infrared laser desorption/ionization aerosol mass spectrometry (NIR-LDI-AMS) was used for chemical analysis of the aerosol. The chemical profile of SOA generated from grass clippings was correlated with that from chemical standards of CHA and HXL. We found that SOA derived from HXL most closely approximated SOA from turf grass, in spite of the approximately 5× lower emission rate of HXL as compared to CHA. Ozonolysis of HXL results in formation of low volatility, higher molecular weight compounds, such as oligomers, and formation of ester-type linkages. This is in contrast to CHA, where the hydroperoxide channel is the dominant oxidation pathway, as oligomer formation is inhibited by the acetate functionality. PMID:24666343

  14. Secondary aerosol formation from photochemical aging of aircraft exhaust in a smog chamber

    NASA Astrophysics Data System (ADS)

    Miracolo, M. A.; Hennigan, C. J.; Ranjan, M.; Nguyen, N. T.; Gordon, T. D.; Lipsky, E. M.; Presto, A. A.; Donahue, N. M.; Robinson, A. L.

    2011-05-01

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

  15. Seasonal variation of water-soluble inorganic species in the coarse and fine atmospheric aerosols at Dar es Salaam, Tanzania

    NASA Astrophysics Data System (ADS)

    Mkoma, Stelyus L.; Wang, Wan; Maenhaut, Willy

    2009-09-01

    The ionic composition of coarse, fine and total PM10 was investigated in aerosol samples collected from a kerbside in Dar es Salaam during the 2005 dry season and 2006 wet season. A "Gent" PM10 stacked filter unit sampler with sequential Nuclepore polycarbonate filters, providing coarse (8 ?m) and fine (0.4 ?m) size fractions, was deployed. The mean concentrations and associated standard deviation of fine, coarse and PM10 were, respectively, 17 ± 4, 52 ± 27, and 69 ± 29 ?g/m 3 during the 2005 dry season campaign and 13 ± 5, 34 ± 23 and 47 ± 25 ?g/m 3 for the 2006 wet season campaign. The higher PM mass concentrations during the dry season campaign are essentially due to soil dust dispersal, much biomass burning and temperature inversions. Chloride, Na + and Mg 2+ were the dominant ions in coarse fraction, indicating a significant influence of sea-salt aerosols. In the fine fraction, SO42- and NH4+ and K + were the most important ions. The mean equivalent PM2 NO3- concentration in the 2005 dry season campaign was two times higher than in the 2006 wet season campaign, probably due to reaction of NaCl (sea-salt) with HNO 3 as a result of higher levels of NO x during the dry season and/or reduced volatilization of NH 4NO 3 due to lower temperature in the dry season. The results from our water-soluble ions study strongly suggests that biomass burning and secondary aerosols make a significant contribution to fine particulate mass in Dar es Salaam atmosphere. Thus, burning of waste and biomass are thought to be the major causes for the atmospheric particulate pollution in Dar es Salaam during the dry season.

  16. Reactive processing of formaldehyde and acetaldehyde in aqueous aerosol mimics: Surface tension depression and secondary organic products

    E-print Network

    Li, Zhi; Sareen, Neha; McNeill, V Faye

    2011-01-01

    The reactive uptake of carbonyl-containing volatile organic compounds (cVOCs) by aqueous atmospheric aerosols is a likely source of particulate organic material. The aqueous-phase secondary organic products of some cVOCs are surface-active. Therefore, cVOC uptake can lead to organic film formation at the gas-aerosol interface and changes in aerosol surface tension. We examined the chemical reactions of two abundant cVOCs, formaldehyde and acetaldehyde, in water and aqueous ammonium sulfate (AS) solutions mimicking tropospheric aerosols. Secondary organic products were identified using Aerosol Chemical Ionization Mass Spectrometry (Aerosol-CIMS), and changes in surface tension were monitored using pendant drop tensiometry. Hemiacetal oligomers and aldol condensation products were identified using Aerosol-CIMS. A hemiacetal sulfate ester was tentatively identified in the formaldehyde-AS system. Acetaldehyde depresses surface tension to 65(\\pm2) dyn/cm in pure water and 62(\\pm1) dyn/cm in AS solutions. Surface t...

  17. Contribution of fungi to primary biogenic aerosols in the atmosphere: wet and dry discharged spores, carbohydrates, and inorganic ions

    NASA Astrophysics Data System (ADS)

    Elbert, W.; Taylor, P. E.; Andreae, M. O.; Pöschl, U.

    2007-09-01

    Biogenic aerosols play important roles in atmospheric chemistry physics, the biosphere, climate, and public health. Here, we show that fungi which actively discharge their spores with liquids into the air, in particular actively wet spore discharging Ascomycota (AAM) and actively wet spore discharging Basidiomycota (ABM), are a major source of primary biogenic aerosol particles and components. We present the first estimates for the global average emission rates of fungal spores. Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the spores of AAM and ABM may account for a large proportion of coarse particulate matter in tropical rainforest regions during the wet season (0.7-2.3 ?g m-3). For the particle diameter range of 1-10 ?m, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively wet discharged basidiospores (ABS). ABM emissions seem to account for most of the atmospheric abundance of mannitol (10-68 ng m-3), and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter (7-49 ng m-3), but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season (17-43 ng m-3), and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations. Based on the average abundance of mannitol reported for extratropical continental boundary layer air (~25 ng m-3), we have also calculated a value of ~17 Tg yr-1 as a first estimate for the global average emission rate of ABS over land surfaces, which is consistent with the typically observed concentrations of ABS (~10³-104 m-3; ~0.1-1 ?g m-3). The global average atmospheric abundance and emission rate of total fungal spores, including wet and dry discharged species, are estimated to be higher by a factor of about three, i.e. 1 ?g m-3 and ~50 Tg yr-1. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr-1 of anthropogenic primary organic aerosol; 12-70 Tg yr-1 of secondary organic aerosol) indicate that emissions from fungi should be taken into account as a significant global source of organic aerosol. The effects of fungal spores and related chemical components might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

  18. Naturally driven variability in the global secondary organic aerosol over a decade

    NASA Astrophysics Data System (ADS)

    Tsigaridis, K.; Lathière, J.; Kanakidou, M.; Hauglustaine, D. A.

    2005-07-01

    In order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA to temperature and moisture changes as well as to biogenic emission changes over a decade (1984-1993) has been evaluated. The considered emissions of biogenic non-methane volatile organic compounds (VOC) are driven by temperature, light and vegetation. They vary between 756 and 810 Tg Cy-1 and are therefore about 5.5 times higher than the anthropogenic VOC emissions. All secondary aerosols (sulphuric, nitrates and organics) are computed on-line together with the aerosol associated water. Over the studied decade, the computed natural variations (8%) in the chemical SOA production from biogenic VOC oxidation equal the chemical SOA production from anthropogenic VOC oxidation. Maximum values are calculated for 1990 (warmer and drier) and minimum values for 1986 (colder and wetter). The SOA computed variability results from a 7% increase in biogenic VOC emissions from 1986 to 1990 combined with 8.5% and 6% increases in the wet and dry deposition of SOA and leads to about 11.5% increase in the SOA burden of biogenic origin. The present study also demonstrates the importance of the hydrological cycle in determining the built up and fate of SOA in the atmosphere. It also reveals the existence of significant positive and negative feedback mechanisms in the atmosphere responsible for the non linear relationship between emissions of biogenic VOC and SOA burden.

  19. Naturally driven variability in the global secondary organic aerosol over a decade

    NASA Astrophysics Data System (ADS)

    Tsigaridis, K.; Lathière, J.; Kanakidou, M.; Hauglustaine, D. A.

    2005-03-01

    In order to investigate the variability of the secondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been applied. The response of the global budget of SOA to temperature and moisture changes as well as to biogenic emission changes over a decade (1984-1993) has been evaluated. The considered emissions of biogenic non-methane volatile organic compounds (VOC) are driven by temperature, light and vegetation. They vary between 756 and 810 TgC y-1 and are therefore about 5.5 times higher than the anthropogenic VOC emissions. All secondary aerosols (sulphuric, nitrates and organics) are computed on-line together with the aerosol associated water. Over the studied decade, the computed natural variations (8%) in the chemical SOA production from biogenic VOC oxidation equal the chemical SOA production from anthropogenic VOC oxidation. This computed variability results from a 7% increase in biogenic VOC emissions combined with 8.5% and 6% increases in the wet and dry deposition of SOA and leads to about 11.5% increase in the SOA burden of biogenic origin. The present study also demonstrates the importance of the hydrological cycle in determining the built up and fate of SOA in the atmosphere. It also reveals the existence of significant positive and negative feedback mechanisms in the atmosphere responsible for the non linear relationship between emissions of biogenic VOC and SOA burden.

  20. Simulation Chamber Investigations of Secondary Organic Aerosol Formation From Boreal Tree Emissions: Dependence on VOC Classes

    NASA Astrophysics Data System (ADS)

    Kiendler-Scharr, A.; Mentel, T. F.; Kleist, E.; Hohaus, T.; Mensah, A.; Spindler, C.; Tillmann, R.; Uerlings, R.; Dal Maso, M.; Rudich, Y.; Juergen, W.

    2008-12-01

    A considerable fraction of the organic aerosol component is of secondary origin, meaning it is formed through oxidation of volatile organic compounds (VOCs). Plant emissions, e.g. monoterpenes and sesquiterpenes, are a major source of VOCs in the troposphere. So far most laboratory and simulation chamber investigations on the potential to form secondary organic aerosols (SOA) from plant emissions focused on single VOCs such as a-pinene. In this study we investigated the formation and growth of SOA by ozonolysis and/or photo-oxidation of the VOCs emitted by several tree species such as spruce, pine and birch. The experiments were performed in the Plant chamber of the ICG-3 in Jülich under well defined conditions for the plant. VOC emissions were transferred to a reaction chamber which was operated as a continuously stirred tank reactor. SOA formation from the VOCs was initiated by an excess of ozone and OH radicals. The results are compared to a reference study with a-pinene as the only SOA precursor. Our results indicate that the general laboratory approach of studying the formation of SOA from single components can lead to a bias in both the mass yields and the mass spectral signatures observed. Plots of maximum SOA volumes versus the total amount of carbon fed into the reaction chamber led to approximately linear relationships. The intercepts of these plots were seen as threshold for SOA formation. It was observed that this threshold was lower for the mixture of VOCs emitted from spruce, pine, and birch than for a-pinene as single compound. We therefore conclude that the threshold for SOA formation from real plant mixtures may be much lower than the threshold obtained from laboratory experiments that were focussed on single VOCs. SOA formation from stress induced VOCs will be compared to non stress induced emissions. Possible feedbacks of climate change to VOC emissions and aerosol formation will be discussed based on our experimental observations.

  1. Surface Tension and Critical Supersaturations for Mixed Aerosol Particles Composed of Inorganic and Organic Compounds of Atmospheric Relevance

    NASA Astrophysics Data System (ADS)

    Zamora, I. R.; Jacobson, M. Z.

    2012-12-01

    The interaction between water vapor and aerosol particles in the atmosphere has implications on important processes. Among these are cloud droplet formation and growth, which impact cloud properties and therefore have an indirect effect on climate. A significant fraction of the dry submicron mass of atmospheric aerosols is composed of water-soluble organic carbon (WSOC). Although the WSOC fraction contains a large amount of compounds, most yet unidentified, it can be partitioned into three main categories in order to use a set of model substances to reproduce its behavior. In this study, we chose levoglucosan, succinic acid and Nordic Reference fulvic acid (NRFA) to represent the WSOC categories of neutral compounds, mono-/di-carboxylic acids, and polycarboxylic acids, respectively. We measured the surface tension of aqueous pure NRFA and of five of its mixtures at 298 K using the Wilhemy plate method. Langmuir adsorption parameters for the organic mixtures were extracted by fitting the surface tension measurements and corresponding solute concentrations to the Szyszkowski-Langmuir equation. The measured surface tension as a function of aqueous NRFA concentration was identical to that of Suwannee River (SR) and Waskish Peat fulvic acids below 0.02 g/L but up to 12% and 15% higher, respectively, at higher concentrations. Similar to previous findings by Aumann et al. (2010) with SRFA, the surface tension of a NRFA/inorganic salt solution was mainly controlled by the organic compound even when the salt comprised 75% of the added solute mass. This effect was observed for mixtures of NRFA with both sodium chloride and ammonium sulfate salts up to 5 g/L of NRFA. From 5 g/L to about 50 g/L of NRFA, the surface tension for both NRFA/salt mixtures stopped decreasing, remained constant at 52-53 mN/m and then started slowly increasing indicating that the salt component might start dominating at higher concentrations. For a solution of 25% NRFA / 75% levoglucosan, the surface tension lowering with increasing concentration was very similar to that of pure aqueous NRFA even to the maximum measured concentration of 50 g/L of NRFA. However, the surface tension of the NRFA/saccharide mixture exhibited a more linear decrease when plotted against ln(NRFA concentration) in the 0.1 to 50 g/L range. We also measured the surface tension of two additional mixtures based on chemical composition data for different aerosol types. The measured surface tension for the solution representing organic aerosols (40% NRFA / 40% succinic acid / 20% levoglucosan) was bounded by that of pure NRFA and the NRFA/levoglucosan mixture up to a concentration of ~28 g/L of NRFA, where it remained constant at around 46.6 mN/m until 80 g/L of NRFA. The solution representing biomass burning aerosols (25% NRFA/ 27% succinic acid / 18% levoglucosan / 30% ammonium sulfate) had a similar surface tension to pure NRFA up to a concentration of ~5 g/L of NRFA, from where the surface tension drop continued between that of pure NRFA and the NRFA/salt mixtures. Critical supersaturations as a function of dry particle diameter were estimated by using measured water activity as a function of concentration and surface tension data to calculate the maximum of each Köhler curve for the mixtures studied.

  2. Mass spectra deconvolution of low, medium, and high volatility biogenic secondary organic aerosol.

    PubMed

    Kostenidou, Evangelia; Lee, Byong-Hyoek; Engelhart, Gabriella J; Pierce, Jeffrey R; Pandis, Spyros N

    2009-07-01

    Secondary organic aerosol (SOA) consists of compounds with a wide range of volatilities and its ambient concentration is sensitive to this volatility distribution. Recent field studies have shown that the typical mass spectrum of ambient oxygenated organic aerosol (OOA) as measured by the Aerodyne Aerosol Mass Spectrometer (AMS) is quite different from the SOA mass spectra reported in smog chamber experiments. Part of this discrepancy is due to the dependence of SOA composition on the organic aerosol concentration. High precursor concentrations lead to higher concentrations of the more volatile species in the produced SOA while at lower concentrations the less volatile compounds dominate the SOA composition. alpha-Pinene, beta-pinene, d-limonene, and beta-caryophyllene ozonolysis experiments were performed at moderate concentration levels. Using a thermodenuder the more volatile SOA species were removed achieving even lower SOA concentration. The less volatile fraction was then chemically characterized by an AMS. The signal fraction of m/z44, and thus the concentration of C02+, is significantly higher for the less volatile SOA. High NO(x) conditions result in less oxidized SOA than low NO(x) conditions, while increasing relative humidity levels results in more oxidized products for limonene but has little effect on alpha-and beta-pinene SOA. Combining a smog chamber with a thermodenuder model employing the volatility basis-set framework, the AMS SOA mass spectrum for each experiment and for each precursor is deconvoluted into low, medium, and high volatility component mass spectra. The spectrum of the surrogate component with the lower volatility is quite similar to that of ambient OOA. PMID:19673280

  3. Aerosol-assisted atmospheric cold plasma deposition and characterization of superhydrophobic organic-inorganic nanocomposite thin films.

    PubMed

    Fanelli, Fiorenza; Mastrangelo, Anna M; Fracassi, Francesco

    2014-01-28

    A facile atmospheric pressure cold plasma process is presented to deposit a novel organic-inorganic hydrocarbon polymer/ZnO nanoparticles nanocomposite coating. Specifically, this method involves the utilization of an atmospheric pressure dielectric barrier discharge (DBD) fed with helium and the aerosol of a dispersion of oleate-capped ZnO nanoparticles (NPs) in n-octane. As assessed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, the deposited nanocomposite coating combines the chemical features of both the oleate-capped ZnO NPs and the polyethylene-like organic component originated from the plasma polymerization of n-octane. Additionally, scanning electron microscopy (SEM) and transmission scanning electron microscopy (TSEM) confirm the synthesis of hierarchical micro/nanostructured coatings containing quasi-spherical NPs agglomerates. The polyethylene-like polymer covers the NPs agglomerates to different extents and contributes to their immobilization in the three-dimensional network of the coating. The increase of both the deposition time (1-10 min) and the NPs concentration in the dispersion (0.5-5 wt %) has a significant effect on the chemical and morphological structure of the thin films and, in fact, results in the increase the ZnO NPs content, which ultimately leads to superhydrophobic surfaces (advancing and receding water contact angles higher than 160°) with low hysteresis due to the hierarchical multiscale roughness of the coating. PMID:24393041

  4. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    NASA Astrophysics Data System (ADS)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2012-02-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 ?m) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from ?-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA) observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25-0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, ?-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate experiments on the first two principal components (PCs), which explained 79% of the total variance. Projection of ambient SV-OOA spectra resolved by positive matrix factorization (PMF) showed that this approach could be useful to identify large contributions of the tested SOA sources to SV-OOA. The first results from this study indicate that the SV-OOA in Barcelona is strongly influenced by diesel emissions in winter while in summer at SIRTA at the southwestern edge of Paris SV-OOA is more similar to alpha-pinene SOA. However, contributions to the ambient SV-OOA from SOA sources that are not covered by the model can cause major interference and therefore future expansions of the PCA model with additional SOA sources is recommended.

  5. A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

    NASA Astrophysics Data System (ADS)

    Heringa, M. F.; Decarlo, P. F.; Chirico, R.; Tritscher, T.; Clairotte, M.; Mohr, C.; Crippa, M.; Slowik, J. G.; Pfaffenberger, L.; Dommen, J.; Weingartner, E.; Prévôt, A. S. H.; Baltensperger, U.

    2011-10-01

    Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 ?m) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from ?-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra in the m/z range 12-250 showing Pearson's r values >0.94 for the correlations between the different SOA types after 5 h of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxidized OA (SV-OOA) observed in the ambient aerosol. The atomic O : C ratios were found to be in the range of 0.25-0.55 with no major increase during the first 5 h of aging. On average, the diesel SOA showed the lowest O : C ratio followed by SOA from wood burning, ?-pinene and the scooter emissions. Grouping the fragment ions based on their carbon number revealed that the SOA source with the highest O : C ratio had the largest fraction of small ions. Fragment ions containing up to 3 carbon atoms accounted for 66%, 68%, 72% and 76% of the organic spectrum of the SOA produced by the diesel car, wood burner, ?-pinene and the scooter, respectively. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate experiments on the first two principal components (PCs), which explained 79% of the total variance. Projection of ambient SV-OOA spectra resolved by positive matrix factorization (PMF) showed that this approach could be useful to identify large contributions of the tested SOA sources to SV-OOA. The first results from this study indicate that the SV-OOA in Barcelona is strongly influenced by diesel emissions in winter while in summer at SIRTA at the southwestern edge of Paris SV-OOA is more similar to alpha-pinene SOA. However, contributions to the ambient SV-OOA from SOA sources that are not covered by the model can cause major interference and therefore future expansions of the PCA model with additional SOA sources is recommended.

  6. Composition of Secondary Organic Aerosols Produced by Photo-Oxidation of Biomass Burning Emissions in a Smog Chamber

    NASA Astrophysics Data System (ADS)

    Desyaterik, Y.; Sullivan, A.; Hennigan, C. J.; Robinson, A. L.; Collett, J. L.

    2009-12-01

    Knowledge of the chemical composition of atmospheric organic aerosols (OA) is essential for accurate representation of OA in air quality and climate models. Both the sources of OA and their properties and effects remain poorly understood. In particular, we still know relatively little about the atmospheric formation of secondary organic aerosols (SOA). There is growing interest in the impact of biomass burning emissions on air quality, human health, and radiative forcing. Through a series of experiments, we are working to quantify changes in the chemical composition of wood smoke particles as a result of photochemical aging under well-controlled laboratory conditions. One specific objective of this study is to identify markers for biomass burning SOA and test whether these markers can be used in atmospheric samples to quantify SOA formation from aging of biomass burning emissions. We analyzed SOA generated in a smog chamber by photooxidation of smoke produced by burning oak wood. In order to initiate photochemistry, the chamber was irradiated with UV light. Aqueous extracts of collected aerosol samples were analyzed with Electrospray Ionization Time-of-Flight Mass Spectrometry. The high mass accuracy of these measurements reduces ambiguity in the assignment of elemental compositions for observed ions. Analysis has shown that primary oak smoke aerosol includes products of the thermal decomposition of cellulose (levoglucosan, cyclotene etc.) and lignin (guaiacol and syringol derivatives, mostly aldehydes and alcohols). After 2 hours of aging at typical summertime hydroxyl radical concentrations, the aerosol mass increased 2.5 fold due to the production of secondary organic aerosol. Mass spectra of the secondary organic aerosol formed are dominated by organic nitrates (nitrophenol, nitrocresol, nitrocatechol, and nitroguaiacol) and aromatic acids (benzoic acid, mono and di-hydroxybenzoic acid). Both nitrates and acids most likely are formed due to oxidation of the lignin decomposition products (guaiacol and syringol derivatives) by reaction with OH and NO2. This research highlights the dynamic nature of fire emissions and atmospheric organic aerosols in general.

  7. Cloud processing of organic compounds: Secondary organic aerosol and nitrosamine formation

    NASA Astrophysics Data System (ADS)

    Hutchings, James W., III

    Cloud processing of atmospheric organic compounds has been investigated through field studies, laboratory experiments, and numerical modeling. Observational cloud chemistry studies were performed in northern Arizona and fog studies in central Pennsylvania. At both locations, the cloud and fogs showed low acidity due to neutralization by soil dust components (Arizona) and ammonia (Pennsylvania). The field observations showed substantial concentrations (20-5500 ng•L -1) of volatile organic compounds (VOC) in the cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase with half lives of approximately three hours. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction kinetics decreased with increasing organic carbon content, resulting in half lives of approximately 7 hours. The secondary organic aerosol (SUA) mass formation potential of cloud processing of BTEX was evaluated. SOA mass formation by cloud processing of BTEX, while strongly dependent on the atmospheric conditions, could contribute up to 9% of the ambient atmospheric aerosol mass, although typically ˜1% appears realistic. Field observations also showed the occurrence of N-nitrosodimethylamine (NDMA), a potent carcinogen, in fogs and clouds (100-340 ng•L -1). Laboratory studies were conducted to investigate the formation of NDMA from nitrous acid and dimethylamine in the homogeneous aqueous phase within cloud droplets. While NDMA was produced in the cloud droplets, the low yields (<1%) observed could not explain observational concentrations. Therefore heterogeneous or gaseous formation of NDMA with partitioning to droplet must be the source of aqueous NDMA. Box-model calculations tended to demonstrate a predominance of a gas phase formation mechanism followed by partitioning into the cloud droplets. The calculations were consistent with field measurements of gaseous and aqueous NDMA concentrations. Measurements and model calculations showed that while NDMA is eventually photolyzed, it might persist in the atmosphere for hours.

  8. Measurements and modeling of glyoxal: Insights into rural photochemistry and secondary organic aerosol production

    NASA Astrophysics Data System (ADS)

    Huisman, Andrew J.

    Glyoxal is important to atmospheric science as an indicator for oxidation chemistry and secondary organic aerosol formation. Global models indicate that the majority of glyoxal is biogenically derived, but few measurements of glyoxal are available in biogenically dominated regions. The Madison Laser-Induced Phosphorescence Instrument enables rapid measurements of glyoxal in such rural areas and facilitates new science with sensitive, selective, fast measurements of gas-phase glyoxal. We describe the development of this instrument and results from a deployment to a collaborative field campaign near Blodgett Forrest, CA. A photochemical box model was developed to evaluate the sources and sinks of glyoxal at the site and validated using laboratory data leading to two findings: (1) prompt formation of glyoxal from the reaction of isoprene + OH in the presence of NO; (2) model over-prediction of higher--generation glyoxal from isoprene by a factor of at least eight. Inclusion of these processes will alter mode] predictions of glyoxal and secondary aerosol due to the dominance of isoprene among biogenic emissions. A model incorporating these changes over-predicted glyoxal at the field site by a factor of 2 to 5. Vertical dilution, deposition, loss to aerosol, and transport were examined; no single process was able to reduce the over-prediction without introducing another problem such as incorrect diurnal profile. The ability of the box model to reproduce chamber but not ambient conditions suggests that the mechanistic representation of isoprene and 2--methyl--3--buten--2--ol (the dominant precursors of glyoxal at the site) should be examined in future studies with attention to the influence of the ratio of alkyl peroxy radical (RO2) to hydrogen dioxide radical (HO2). Comparison of measurements to results from the Community Multiscale Air Quality model show that the model correctly predicts ozone at the site but fails to match crucial aspects of radical and higher--generation chemistry, leading to excess glyoxal. Current generation global and regional models may place undue emphasis on the formation of aerosol from glyoxal from biogenic precursors as a result of similar over--predictions. Improvements to model photochemistry are suggested, likely leading to changes in predicted ozone.

  9. Plant and Soil Emissions of Amines and Amino Acids: A Source of Secondary Aerosol Precursors

    NASA Astrophysics Data System (ADS)

    Jackson, M. L.; Doskey, P. V.; Pypker, T. G.

    2011-12-01

    Ammonia (NH3) is the most abundant alkaline gas in the atmosphere and forms secondary aerosol by neutralizing sulfuric and nitric acids that are released during combustion of fossil fuels. Ammonia is primarily emitted by cropping and livestock operations. However, C2 and C3 amines (pKb 3.3-3.4), which are stronger bases than NH3 (pKb 4.7) have been observed in nuclei mode aerosol that is the precursor to secondary aerosol. Mixtures of amines and amino acids have been identified in diverse environments in aerosol, fog water, cloud water, the soluble fraction of precipitation, and in dew. Glycine (pKb 4.2), serine (pKb 4.8) and alanine (pKb 3.7 and 4.1 for the D and L forms, respectively) are typically the most abundant species. The only reported values of gas-phase glycine, serine and alanine were in marine air and ranged from 6-14 pptv. The origin of atmospheric amines and amino acids has not been fully identified, although sources are likely similar to NH3. Nitrate assimilation in plants forms glycine, serine, and L-alanine, while D-alanine is present in bacterial cell walls. Glycine is converted to serine during C3 plant photorespiration, producing CO2 and NH3. Bacteria metabolize glycine and alanine to methylamine and ethylamine via decarboxylation. Likely sources of amino acids are plants and bacteria, thus concentrations near continental sources are likely greater than those measured in marine air. The overall goal of the research is to examine seasonal variations and relationships between the exchange of CO2, NH3, amines, and amino acids with a corn/soybean rotation in the Midwest Corn Belt. The study presents gaseous profiles of organic amine compounds from various species of vegetation using a mist chamber trapping technique and analysis of the derivatized species by high pressure liquid chromatography with fluorescence detection. Amino acid and amine profiles were obtained for red oak (Quercus rubra), sugar maple (Acer saccharinum), white pine (Pinus strobus), paper birch (Betula papyrifera), northern white cedar (Thuja occidentalis), cool season turfgrass (Festuca sp., Poa sp., Agrostis sp., Lolium perrene), corn (Zea mays) and soybean (Glycine max) by drawing air through a chromatographic column packed with macerated leaves. The saturated air was scrubbed using a mist chamber containing 1% hydrochloric acid in ultrapure water. Diurnal variations in ambient levels were measured above a meadow, mixed hardwood forest, and a cornfield. The preliminary experiments indicate profiles of organic amine compounds vary by specie and the most volatile species are present in the gas-phase in ambient air.

  10. Secondary organic aerosol formation from gasoline vehicle emissions in a new mobile environmental reaction chamber

    NASA Astrophysics Data System (ADS)

    Platt, S. M.; El Haddad, I.; Zardini, A. A.; Clairotte, M.; Astorga, C.; Wolf, R.; Slowik, J. G.; Temime-Roussel, B.; Marchand, N.; Ježek, I.; Drinovec, L.; Mo?nik, G.; Möhler, O.; Richter, R.; Barmet, P.; Bianchi, F.; Baltensperger, U.; Prévôt, A. S. H.

    2012-10-01

    We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of aerosols from different emissions sources without limitation from the instruments or facilities available at any single site. The chamber can be mounted on a trailer for transport to host facilities or for mobile measurements. Photochemistry is simulated using a set of 40 UV lights (total power 4 KW). Characterisation of the emission spectrum of these lights shows that atmospheric photochemistry can be accurately simulated over a range of temperatures from -7-25 °C. A photolysis rate of NO2, JNO2, of (8.0 ± 0.7) × 10-3 molecules cm-3 s-1 was determined at 25 °C. Further, we present the first application of the mobile chamber and demonstrate its utility by quantifying primary organic aerosol (POA) emission and secondary organic aerosol (SOA) production from a Euro 5 light duty gasoline vehicle. Exhaust emissions were sampled during the New European Driving Cycle (NEDC), the standard driving cycle for European regulatory purposes, and injected into the chamber. The relative concentrations of oxides of nitrogen (NOx) and total hydrocarbon (THC) during the aging of emissions inside the chamber were controlled using an injection system developed as a part of the new mobile chamber set up. Total OA (POA + SOA) emission factors of (370 ± 18) × 10-3 g kg-1 fuel, or (14.6 ± 0.8) × 10-3 g km-1, after aging, were calculated from concentrations measured inside the smog chamber during two experiments. The average SOA/POA ratio for the two experiments was 15.1, a much larger increase than has previously been seen for diesel vehicles, where smog chamber studies have found SOA/POA ratios of 1.3-1.7. Due to this SOA formation, carbonaceous particulate matter (PM) emissions from a gasoline vehicle may approach those of a diesel vehicle of the same class. Furthermore, with the advent of emission controls requiring the use of diesel particle filters, gasoline vehicle emissions could become a far larger source of ambient PM than diesel vehicles. Therefore this large increase in the PM mass of gasoline vehicle aerosol emissions due to SOA formation has significant implications for our understanding of the contribution of on-road vehicles to ambient aerosols and merits further study.

  11. Ozonolysis of a series of biogenic organic volatile compounds and secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Bernard, François; Quilgars, Alain; Cazaunau, Mathieu; Grosselin, Benoît.; Daele, Véronique; Mellouki, Abdelwahid; Winterhalter, Richard; Moortgat, Geert K.

    2010-05-01

    Secondary organic aerosols are formed via nucleation of atmospheric organic vapours on pre-existing particles observed in various rural environments where the organic fraction represents the major part of the observed nano-particle (Kavouras and Stephanou, 2002; Kulmala et al., 2004a). However, nucleation of organic vapors appears to be unlikely thermodynamically in relevant atmospheric conditions (Kulmala et al., 2004b). In this work, a systematic study has been conducted to investigate the aerosol formation through the ozonolysis of a series of monotepenes using a newly developed aerosol flow reactor and the ICARE indoor simulation chamber. The nucleation thresholds have been determined for SOA formed through the reaction of ozone with a-Pinene, sabinene, myrcene and limonene in absence of any observable existing particles. The measurements were performed using the flow reactor combined to a particle counter (CPC 3022). Number concentrations of SOA have been measured for different concentration of consumed monoterpenes. The data obtained allow us to estimate the nucleation threshold for a range of 0.2 - 45 ppb of consumed monoterpenes. The nucleation threshold values obtained here (? 1 ppb of the consumed monoterpenes) have been found to be lower than the previously reported ones (Berndt et al., 2003; Bonn and Moortgat, 2003; Koch et al., 2000; Lee and Kamens, 2005). The ICARE simulation chamber has been used to study the mechanism of the reaction of ozone with various acyclic terpenes (myrcene, ocimene, linalool and a-farnesene) and to derive the SOA mass formation yield. The time-concentration profiles of reactants and products in gas-phase were obtained using in-situ Fourier Transform Infrared Spectroscopy. In addition, the number and mass concentrations of SOA have been monitored with a Scanning Mobility Particle Sizer. The chemical composition of the SOA formed has been tentatively characterised using Liquid Chromatography - Mass Spectrometry. The results obtained will be compared with those from the literature when available and discussed in terms of their atmospheric impact. Berndt, T., O. Böge and F. Stratmann (2003). Gas-phase ozonolysis of a-pinene: gaseous products and particle formation. Atmospheric Environment, 37: 3933-3945. Bonn, B. and G.K. Moortgat (2003). Sesquiterpene ozonolysis: Origin of atmospheric new particle formation from biogenic hydrocarbons. Journal of Geophysical Research, 30(11). Kavouras, I. and E.G. Stephanou (2002). Direct evidence of atmospheric secondary organic aerosol formation in forest atmosphere through heteromolecular nucleation. Environmental Science and Technology, 36: 5083-5091. Koch, S., R. Winterhalter, E. Uherek, A. Kolloff, P. Neeb and G.K. Moortagt (2000). Formation of new particles in the gas-phase ozonolysis of monoterpenes. Atmospheric Environment, 34: 4031-4042. Kulmala, M., V.-M. Kerminen, T. Anttila, A. Laaksonen and C.D. O'Dowd (2004b). Organic aerosol formation via sulphate cluster activation. Journal of Geophysical Research, 109(D04205): 1-7. Kulmala, M., H. Vehkamäki, T. Petäjä, M. Dal Maso, A. Lauri, V.-M. Kerminen, W. Birmili and P.H. McMurry (2004a). Formation and growth rates of ultra-fine atmospheric particles: a review of observations. Journal of Aerosol Science, 35: 143-176. Lee, S. and R.M. Kamens (2005). Particle nucleation from the reaction of a-pinene and O3. Atmospheric Environment, 39: 6822-6832.

  12. Secondary Organic Aerosol Produced from Aqueous Reactions of Phenols in Fog Drops and Deliquesced Particles

    NASA Astrophysics Data System (ADS)

    Smith, J.; Anastasio, C.

    2014-12-01

    The formation and evolution of secondary organic aerosol (SOA) in atmospheric condensed phases (i.e., aqueous SOA) can proceed rapidly, but relatively little is known of the important aqueous SOA precursors or their reaction pathways. In our work we are studying the aqueous SOA formed from reactions of phenols (phenol, guaiacol, and syringol), benzene-diols (catechol, resorcinol, and hydroquinone), and phenolic carbonyls (e.g., vanillin and syringaldehyde). These species are potentially important aqueous SOA precursors because they are released in large quantities from biomass burning, have high Henry's Law constants (KH = 103 -109 M-1 atm-1) and are rapidly oxidized. To evaluate the importance of aqueous reactions of phenols as a source of SOA, we first quantified the kinetics and SOA mass yields for 11 phenols reacting via direct photodegradation, hydroxyl radical (•OH), and with an excited organic triplet state (3C*). In the second step, which is the focus of this work, we use these laboratory results in a simple model of fog chemistry using conditions during a previously reported heavy biomass burning event in Bakersfield, CA. Our calculations indicate that under aqueous aerosol conditions (i.e., a liquid water content of 100 ?g m-3) the rate of aqueous SOA production (RSOA(aq)) from phenols is similar to the rate in the gas phase. In contrast, under fog/cloud conditions the aqueous RSOA from phenols is 10 times higher than the rate in the gas phase. In both of these cases aqueous RSOA is dominated by the oxidation of phenols by 3C*, followed by direct photodegradation of phenolic carbonyls, and then •OH oxidation. Our results suggest that aqueous oxidation of phenols is a significant source of SOA during fog events and also during times when deliquesced aerosols are present.

  13. Formation of hydroxyl radicals from photolysis of secondary organic aerosol material

    NASA Astrophysics Data System (ADS)

    Badali, K. M.; Zhou, S.; Aljawhary, D.; Antiñolo, M.; Chen, W. J.; Lok, A.; Mungall, E.; Wong, J. P. S.; Zhao, R.; Abbatt, J. P. D.

    2015-02-01

    This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA aerosol is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both ?-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are five times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over three times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA, the quantum yield for OH generation from ?-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloudwater and aerosol chemistry.

  14. Formation and chemical aging of secondary organic aerosol during the ?-caryophyllene oxidation

    NASA Astrophysics Data System (ADS)

    Tasoglou, A.; Pandis, S. N.

    2015-06-01

    The secondary organic aerosol (SOA) production during the oxidation of ?-caryophyllene by ozone (O3) and hydroxyl radicals (OH) and the subsequent chemical aging of the products during reactions with OH were investigated. Experiments were conducted with ozone and with hydroxyl radicals at low NOx (zero added NOx) and at high NOx (hundreds of parts per billion). The SOA mass yield at 10 ?g m-3 of organic aerosol was 27% for the ozonolysis, 20% for the reaction with OH at low NOx, and 38% at high NOx under dry conditions, 20 °C, and ozone excess. Parameterizations of the fresh SOA yields have been developed. The average fresh SOA atomic O : C ratio varied from 0.24 to 0.34 depending on the oxidant and the NOx level, while the H : C ratio was close to 1.5 for all systems examined. An average density of 1.06 ± 0.1 ?g m-3 of the ?-caryophyllene SOA was estimated. The exposure to UV light had no effect on the ?-caryophyllene SOA concentration and aerosol mass spectrometer (AMS) measurements. The chemical aging of the ?-caryophyllene SOA produced was studied by exposing the fresh SOA to high concentrations (107 molecules cm-3) of OH for several hours. These additional reactions increased the SOA concentration by 15-40% and O : C by approximately 25%. A limited number of experiments suggested that there was a significant impact of the relative humidity on the chemical aging of the SOA. The evaporation rates of ?-caryophyllene SOA were quantified by using a thermodenuder allowing us to estimate the corresponding volatility distributions and effective vaporization enthalpies.

  15. Role of secondary aerosols in haze formation in summer in the Megacity Beijing.

    PubMed

    Han, Tingting; Liu, Xingang; Zhang, Yuanhang; Qu, Yu; Zeng, Limin; Hu, Min; Zhu, Tong

    2015-05-01

    A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibilitysecondary organic aerosol) concentrations. The average values with standard deviation of SO4(2-), NO3(-), NH4(+) and SOA were 49.8 (±31.6), 31.4 (±22.3), 25.8 (±16.6) and 8.9 (±4.1)?g/m(3), respectively, during the haze episodes, which were 4.3, 3.4, 4.1, and 1.7 times those in the non-haze days. The SO4(2-), NO3(-), NH4(+), and SOA accounted for 15.8%, 8.8%, 7.3%, and 6.0% of the total mass concentration of PM10 during the non-haze days. The respective contributions of SNA species to PM10 rose to about 27.2%, 15.9%, and 13.9% during the haze days, while the contributions of SOA maintained the same level with a slight decrease to about 4.9%. The observed mass concentrations of SNA and SOA increased with the increase of PM10 mass concentration, however, the rate of increase of SNA was much faster than that of the SOA. The SOR (sulfur oxidation ratio) and NOR (nitrogen oxidation ratio) increased from non-haze days to hazy days, and increased with the increase of RH. High concentrations of aerosols and water vapor favored the conversion of SO2 to SO4(2-) and NO2 to NO3(-), which accelerated the accumulation of the aerosols and resulted in the formation of haze in Beijing. PMID:25968258

  16. Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Lewis, A. C.; Carey, T. J.; Wenger, J. C.; Garcia, E. Borrás. I.; Muñoz, A.

    2009-02-01

    Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1-5 TgC yr-1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

  17. Reactive oxidation products promote secondary organic aerosol formation from green leaf volatiles

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Lewis, A. C.; Carey, T. J.; Wenger, J. C.; Garcia, E. Borrás. I.; Muñoz, A.

    2009-06-01

    Green leaf volatiles (GLVs) are an important group of chemicals released by vegetation which have emission fluxes that can be significantly increased when plants are damaged or stressed. A series of simulation chamber experiments has been conducted at the European Photoreactor in Valencia, Spain, to investigate secondary organic aerosol (SOA) formation from the atmospheric oxidation of the major GLVs cis-3-hexenylacetate and cis-3-hexen-1-ol. Liquid chromatography-ion trap mass spectrometry was used to identify chemical species present in the SOA. Cis-3-hexen-1-ol proved to be a more efficient SOA precursor due to the high reactivity of its first generation oxidation product, 3-hydroxypropanal, which can hydrate and undergo further reactions with other aldehydes resulting in SOA dominated by higher molecular weight oligomers. The lower SOA yields produced from cis-3-hexenylacetate are attributed to the acetate functionality, which inhibits oligomer formation in the particle phase. Based on observed SOA yields and best estimates of global emissions, these compounds may be calculated to be a substantial unidentified global source of SOA, contributing 1-5 TgC yr-1, equivalent to around a third of that predicted from isoprene. Molecular characterization of the SOA, combined with organic mechanistic information, has provided evidence that the formation of organic aerosols from GLVs is closely related to the reactivity of their first generation atmospheric oxidation products, and indicates that this may be a simple parameter that could be used in assessing the aerosol formation potential for other unstudied organic compounds in the atmosphere.

  18. 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.

  19. Molecular corridors and kinetic regimes in the multiphase chemical evolution of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Berkemeier, T.; Schilling-Fahnestock, K.; Seinfeld, J.; Poeschl, U.

    2014-12-01

    The dominant component of atmospheric organic aerosol is that derived from the oxidation of volatile organic compounds (VOCs), so-called secondary organic aerosol (SOA). SOA consists of a multitude of organic compounds, only a small fraction of which has historically been identified. Formation and evolution of SOA is a complex process involving coupled chemical reaction and mass transport in the gas and particle phases. Current SOA models do not embody the full spectrum of reaction and transport processes nor do they identify the dominant rate-limiting steps in SOA formation. Based on molecular identification of SOA oxidation products, we show here that the chemical evolution of SOA from a variety of VOC precursors adheres to characteristic "molecular corridors" with a tight inverse correlation between volatility and molar mass. The slope of these corridors corresponds to the increase in molar mass required to decrease volatility by one order of magnitude (-dM/dlogC0). It varies in the range of 10-30 g mol-1 depending on the molecular size of the SOA precursor and the O:C ratio of the reaction products. Sequential and parallel reaction pathways of oxidation and dimerization or oligomerization progressing along these corridors pass through characteristic regimes of reaction-, diffusion-, or accommodation-limited multiphase chemical kinetics that can be classified according to reaction location, degree of saturation, and extent of heterogeneity of gas and particle phases. The molecular corridors and kinetic regimes help to constrain and described the properties of the products, pathways and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate.

  20. DROPLET PHASE (HETEROGENEOUS) AND GAS PHASE (HOMOGENEOUS) CONTRIBUTIONS TO SECONDARY AMBIENT AEROSOL FORMATION AS FUNCTIONS OF RELATIVE HUMIDITY

    EPA Science Inventory

    In previous publications (McMurry and Wilson, 1982; McMurry et al., 1981), techniques for determining the relative contributions of gas phase and liquid phase reactions to secondary ambient aerosol formation have been described. In this paper these methods are applied to more rec...

  1. Secondary organic aerosol formation from ethylene in the urban atmosphere of Hong Kong: A multiphase chemical modeling study

    Microsoft Academic Search

    X. H. Hilda Huang; H. S. Simon Ip; Jian Zhen Yu

    2011-01-01

    Ethylene is one of the most abundant anthropogenic volatile organic compounds (VOCs) in urban atmospheres. The potential of forming secondary organic aerosol (SOA) by this smallest alkene in urban environments has not previously been considered because of the general lack of attention to SOA formation through in-cloud processing of soluble oxidation products. Ethylene reacts with OH radicals to form glycolaldehyde

  2. Modeling the formamtion and aging of secondary organic aerosols in Los Angeles during CalNex 2010

    EPA Science Inventory

    Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of A...

  3. 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 ?-IEPOX and 3.4–5.5% for ?-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

  4. Final Report: Process Models of the Equilibrium Size & State of Organic/Inorganic Aerosols for the Development of Large Scale Atmospheric Models & the Analysis of Field Data

    SciTech Connect

    Wexler, Anthony Stein [UC Davis] [UC Davis; Clegg, Simon Leslie [UC Davis] [UC Davis

    2013-10-26

    Our work addressed the following elements of the Call for Proposals: (i) “to improve the theoretical representation of aerosol processes studied in ASP laboratory or field studies”, (ii) “to enhance the incorporation of aerosol process information into modules suitable for large-scale or global atmospheric models”, and (iii) “provide systematic experimental validation of process model predictions ... using data from targeted laboratory and field experiments”. Achievements to the end of 2012 are described in four previous reports, and include: new models of densities and surface tensions of pure (single solute) and mixed aqueous solutions of typical aerosol composition under all atmospheric conditions (0 to 100% RH and T > 150 K); inclusion of these models into the widely used Extended Aerosol Inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php); the addition of vapor pressure calculators for organic compounds to the E-AIM website; the ability of include user-defined organic compounds and/or lumped surrogates in gas/aerosol partitioning calculations; the development of new equations to represent the properties of soluble aerosols over the entire concentration range (using methods based upon adsorption isotherms, and derived using statistical mechanics), including systems at close to zero RH. These results are described in publications 1-6 at the end of this report, and on the “News” page of the E-AIM website (http://www.aim.env.uea.ac.uk/aim/info/news.html). During 2012 and 2013 we have collaborated in a combined observation and lab-based study of the water uptake of the organic component of atmospheric aerosols (PI Gannet Hallar, of the Desert Research Institute). The aerosol samples were analyzed using several complementary techniques (GC/MS, FT-ICR MS, and ion chromatography) to produce a very complete organic “speciation” including both polar and non-polar compounds. Hygroscopic growth factors of the samples were measured, and we have just completed comparisons of the data with our process model predictions based upon the inorganic and organic composition of the samples.

  5. Integrating phase and composition of secondary organic aerosol from the ozonolysis of ?-pinene.

    PubMed

    Kidd, Carla; Perraud, Véronique; Wingen, Lisa M; Finlayson-Pitts, Barbara J

    2014-05-27

    Airborne particles are important for public health, visibility, and climate. Predicting their concentrations, effects, and responses to control strategies requires accurate models of their formation and growth in air. This is challenging, as a large fraction is formed by complex reactions of volatile organic compounds, generating secondary organic aerosol (SOA), which grows to sizes important for visibility, climate, and deposition in the lung. Growth of SOA is particularly sensitive to the phase/viscosity of the particles and remains poorly understood. We report studies using a custom-designed impactor with a germanium crystal as the impaction surface to study SOA formed from the ozonolysis of ?-pinene at relative humidities (RHs) up to 87% at 297 ± 2 K (which corresponds to a maximum RH of 70-86% inside the impactor). The impaction patterns provide insight into changes in phase/viscosity as a function of RH. Attenuated total reflectance-Fourier transform infrared spectroscopy and aerosol mass spectrometry provide simultaneous information on composition changes with RH. The results show that as the RH at which the SOA is formed increases, there is a decrease in viscosity, accompanied by an increasing contribution from carboxylic acids and a decreasing contribution from higher molecular mass products. In contrast, SOA that is formed dry and subsequently humidified remains solid to high RH. The results of these studies have significant implications for modeling the growth, aging, and ultimately, lifetime of SOA in the atmosphere. PMID:24821796

  6. Direct photolysis of ?-pinene ozonolysis secondary organic aerosol: effect on particle mass and peroxide content.

    PubMed

    Epstein, Scott A; Blair, Sandra L; Nizkorodov, Sergey A

    2014-10-01

    Primary and secondary organic aerosols (POA and SOA) contain a complex mixture of multifunctional chemicals, many of which are photolabile. Much of the previous work that aimed to understand the chemical evolution (aging) of POA and SOA has focused on the reactive uptake of gas-phase oxidants by particles. By stripping volatile compounds and ozone from ?-pinene ozonolysis SOA with three 1-m-long denuders, and exposing the residual particles in a flow cell to near-ultraviolet (?>300 nm) radiation, we find that condensed-phase photochemistry can induce significant changes in SOA particle size and chemical composition. The particle-bound organic peroxides, which are highly abundant in ?-pinene ozonolysis SOA (22 ± 5% by weight), have an atmospheric photolysis lifetime of about 6 days at a 24-h average solar zenith angle (SZA) of 65° experienced at 34° latitude (Los Angeles) in the summer. In addition, the particle diameter shrinks 0.56% per day under these irradiation conditions as a result of the loss of volatile photolysis products. Experiments with and without the denuders show similar results, suggesting that condensed-phase processes dominate over heterogeneous reactions of particles with organic vapors, excess ozone, and gas-phase free radicals. These condensed-phase photochemical processes occur on atmospherically relevant time scales and should be considered when modeling the evolution of organic aerosol in the atmosphere. PMID:25165890

  7. 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.

  8. Optical properties of secondary organic aerosols generated by photooxidation of aromatic hydrocarbons

    PubMed Central

    Li, Kun; Wang, Weigang; Ge, Maofa; Li, Jiangjun; Wang, Dong

    2014-01-01

    The refractive index (RI) is the fundamental characteristic that affects the optical properties of aerosols, which could be some of the most important factors influencing direct radiative forcing. The secondary organic aerosols (SOAs) generated by the photooxidation of benzene, toluene, ethylbenzene and m-xylene (BTEX) under low-NOx and high-NOx conditions are explored in this study. The particles generated in our experiments are considered to be spherical, based on atomic force microscopy (AFM) images, and nonabsorbent at a wavelength of 532?nm, as determined by ultraviolet-visible light (UV-Vis) spectroscopy. The retrieved RIs at 532?nm for the SOAs range from 1.38–1.59, depending on several factors, such as different precursors and NOx levels. The RIs of the SOAs are altered differently as the NOx concentration increases as follows: the RIs of the SOAs derived from benzene and toluene increase, whereas those of the SOAs derived from ethylbenzene and m-xylene decrease. Finally, by comparing the experimental data with the model values, we demonstrate that the models likely overestimate the RI values of the SOA particles to a certain extent, which in turn overestimates the global direct radiative forcing of the organic particles. PMID:24815734

  9. Intermediate-volatility organic compounds: a large source of secondary organic aerosol.

    PubMed

    Zhao, Yunliang; Hennigan, Christopher J; May, Andrew A; Tkacik, Daniel S; de Gouw, Joost A; Gilman, Jessica B; Kuster, William C; Borbon, Agnes; Robinson, Allen L

    2014-12-01

    Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 ?g m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments. PMID:25375804

  10. [Estimate of the formation potential of secondary organic aerosol in Beijing summertime].

    PubMed

    Lü, Zi-Feng; Hao, Ji-Ming; Duan, Jing-Chun; Li, Jun-Hua

    2009-04-15

    Fractional aerosol coefficients (FAC) are used in conjunction with measurements of volatile organic compounds (VOC) during ozone episodes to estimate the formation potential of secondary organic aerosols (SOA) in the summertime of Beijing. The estimation is based on the actual atmospheric conditions of Beijing, and benzene and isoprene are considered as the precursors of SOA. The results show that 31 out of 70 measured VOC species are SOA precursors, and the total potential SOA formation is predicted to be 8.48 microg/m3, which accounts for 30% of fine organic particle matter. Toluene, xylene, pinene, ethylbenzene and n-undecane are the 5 largest contributors to SOA production and account for 20%, 22%, 14%, 9% and 4% of total SOA production, respectively. The anthropogenic aromatic compounds, which yield 76% of the calculated SOA, are the major source of SOA. The biogenic alkenes, alkanes and carbonyls produce 16%, 7% and 1% of SOA formation, respectively. The major components of produced SOA are expected to be aromatic compounds, aliphatic acids, carbonyls and aliphatic nitrates, which contribute to 72%, 14%, 11% and 3% of SOA mass, respectively. The SOA precursors have relatively low atmospheric concentrations and low ozone formation potential. Hence, SOA formation potential of VOC species, in addition to their atmospheric concentrations and ozone formation potential, should be considered in policy making process of VOCs control. PMID:19544991

  11. Optical properties of secondary organic aerosols generated by photooxidation of aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Li, Kun; Wang, Weigang; Ge, Maofa; Li, Jiangjun; Wang, Dong

    2014-05-01

    The refractive index (RI) is the fundamental characteristic that affects the optical properties of aerosols, which could be some of the most important factors influencing direct radiative forcing. The secondary organic aerosols (SOAs) generated by the photooxidation of benzene, toluene, ethylbenzene and m-xylene (BTEX) under low-NOx and high-NOx conditions are explored in this study. The particles generated in our experiments are considered to be spherical, based on atomic force microscopy (AFM) images, and nonabsorbent at a wavelength of 532 nm, as determined by ultraviolet-visible light (UV-Vis) spectroscopy. The retrieved RIs at 532 nm for the SOAs range from 1.38-1.59, depending on several factors, such as different precursors and NOx levels. The RIs of the SOAs are altered differently as the NOx concentration increases as follows: the RIs of the SOAs derived from benzene and toluene increase, whereas those of the SOAs derived from ethylbenzene and m-xylene decrease. Finally, by comparing the experimental data with the model values, we demonstrate that the models likely overestimate the RI values of the SOA particles to a certain extent, which in turn overestimates the global direct radiative forcing of the organic particles.

  12. Secondary organic aerosol formation from a large number of reactive man-made organic compounds.

    PubMed

    Derwent, Richard G; Jenkin, Michael E; Utembe, Steven R; Shallcross, Dudley E; Murrells, Tim P; Passant, Neil R

    2010-07-15

    A photochemical trajectory model has been used to examine the relative propensities of a wide variety of volatile organic compounds (VOCs) emitted by human activities to form secondary organic aerosol (SOA) under one set of highly idealised conditions representing northwest Europe. This study applied a detailed speciated VOC emission inventory and the Master Chemical Mechanism version 3.1 (MCM v3.1) gas phase chemistry, coupled with an optimised representation of gas-aerosol absorptive partitioning of 365 oxygenated chemical reaction product species. In all, SOA formation was estimated from the atmospheric oxidation of 113 emitted VOCs. A number of aromatic compounds, together with some alkanes and terpenes, showed significant propensities to form SOA. When these propensities were folded into a detailed speciated emission inventory, 15 organic compounds together accounted for 97% of the SOA formation potential of UK man made VOC emissions and 30 emission source categories accounted for 87% of this potential. After road transport and the chemical industry, SOA formation was dominated by the solvents sector which accounted for 28% of the SOA formation potential. PMID:20452649

  13. 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.

  14. 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.

  15. Evidence of Aqueous Secondary Organic Aerosol Formation from Biogenic Emissions in the North American Sonoran Desert

    NASA Astrophysics Data System (ADS)

    Sorooshian, A.; Youn, J.; Wang, Z.; Wonaschuetz, A.; Arellano, A. F.; Betterton, E. A.

    2013-12-01

    This study examines the role of aqueous secondary organic aerosol (SOA) formation in the North American Sonoran Desert as a result of intense solar radiation, enhanced moisture, and biogenic volatile organic compounds (BVOCs). The ratio of water-soluble organic carbon (WSOC) to organic carbon (OC) nearly doubles during the monsoon season relative to other seasons of the year. When normalized by mixing height, the WSOC enhancement during monsoon months relative to preceding dry months (May - June) exceeds that of sulfate by nearly a factor of ten. WSOC:OC and WSOC are most strongly correlated with moisture parameters, temperature, and concentrations of ozone and BVOCs. No positive relationship was identified between WSOC or WSOC:OC and anthropogenic tracers such as carbon monoxide over a full year. These results are especially of significance as recent modeling studies suggest that aqueous SOA formation is geographically concentrated in the eastern United States and likely unimportant in other areas such as the Southwest.

  16. Exposure of BEAS-2B cells to secondary organic aerosol coated on magnetic nanoparticles.

    PubMed

    Jang, Myoseon; Ghio, Andrew J; Cao, Gang

    2006-08-01

    Toxicological investigation suggests that exposures to complex secondary organic aerosol (SOA) products can result in adverse health effects in biological systems. However, the mechanism of adverse health effects is not yet understood. One of the major restrictions in studies of health effects of SOA is a particle exposure technique. In this study, we applied an innovative soft targeting technology using magnetic nanoparticles (MNP) to deliver SOAs onto target biological systems under a magnetic field. The exploratory exposure technology using MNP was demonstrated for the SOAs created from the reaction of ozone with alpha-pinene in an indoor Teflon film chamber. SOA increased the release of the proinflammatory mediator interleukin-8 by respiratory epithelial cells. These results support that MNP can effectively deliver SOAs to epithelial cells in vitro resulting in a significant biological effects. PMID:16918243

  17. A method to quantify organic functional groups and inorganic compounds in ambient aerosols using attenuated total reflectance FTIR spectroscopy and multivariate chemometric techniques

    NASA Astrophysics Data System (ADS)

    Coury, Charity; Dillner, Ann M.

    An attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopic technique and a multivariate calibration method were developed to quantify ambient aerosol organic functional groups and inorganic compounds. These methods were applied to size-resolved particulate matter samples collected in winter and summer of 2004 at three sites: a downtown Phoenix, Arizona location, a rural site near Phoenix, and an urban fringe site between the urban and rural site. Ten organic compound classes, including four classes which contain a carbonyl functional group, and three inorganic species were identified in the ambient samples. A partial least squares calibration was developed and applied to the ambient spectra, and 13 functional groups related to organic compounds (aliphatic and aromatic CH, methylene, methyl, alkene, aldehydes/ketones, carboxylic acids, esters/lactones, acid anhydrides, carbohydrate hydroxyl and ethers, amino acids, and amines) as well as ammonium sulfate and ammonium nitrate were quantified. Comparison of the sum of the mass measured by the ATR-FTIR technique and gravimetric mass indicates that this method can quantify nearly all of the aerosol mass on sub-micrometer size-segregated samples. Analysis of sample results shows that differences in organic functional group and inorganic compound concentrations at the three sampling sites can be measured with these methods. Future work will analyze the quantified data from these three sites in detail.

  18. A Comparison of Parameterizations of Secondary Organic Aerosol Production: Global Budget and Spatiotemporal Variability

    NASA Astrophysics Data System (ADS)

    Liu, J.; Chen, Z.; Horowitz, L. W.; Carlton, A. M. G.; Fan, S.; Cheng, Y.; Ervens, B.; Fu, T. M.; He, C.; Tao, S.

    2014-12-01

    Secondary organic aerosols (SOA) have a profound influence on air quality and climate, but large uncertainties exist in modeling SOA on the global scale. In this study, five SOA parameterization schemes, including a two-product model (TPM), volatility basis-set (VBS) and three cloud SOA schemes (Ervens et al. (2008, 2014), Fu et al. (2008) , and He et al. (2013)), are implemented into the global chemical transport model (MOZART-4). For each scheme, model simulations are conducted with identical boundary and initial conditions. The VBS scheme produces the highest global annual SOA production (close to 35 Tg·y-1), followed by three cloud schemes (26-30 Tg·y-1) and TPM (23 Tg·y-1). Though sharing a similar partitioning theory to the TPM scheme, the VBS approach simulates the chemical aging of multiple generations of VOCs oxidation products, resulting in a much larger SOA source, particularly from aromatic species, over Europe, the Middle East and Eastern America. The formation of SOA in VBS, which represents the net partitioning of semi-volatile organic compounds from vapor to condensed phase, is highly sensitivity to the aging and wet removal processes of vapor-phase organic compounds. The production of SOA from cloud processes (SOAcld) is constrained by the coincidence of liquid cloud water and water-soluble organic compounds. Therefore, all cloud schemes resolve a fairly similar spatial pattern over the tropical and the mid-latitude continents. The spatiotemporal diversity among SOA parameterizations is largely driven by differences in precursor inputs. Therefore, a deeper understanding of the evolution, wet removal, and phase partitioning of semi-volatile organic compounds, particularly above remote land and oceanic areas, is critical to better constrain the global-scale distribution and related climate forcing of secondary organic aerosols.

  19. Secondary Organic Aerosol Formation from the Photooxidation of Complex Hydrocarbon Mixtures: Composition, effect of SO2, and Relevance to Ambient Aerosol

    Microsoft Academic Search

    J. D. Surratt; S. Gao; E. Knipping; E. Edgerton; M. Shahgoli; J. H. Seinfeld; E. Edney; T. Kleindiesnt; M. Lewandowski; J. Offenberg; M. Jaoui

    2005-01-01

    Secondary organic aerosol (SOA) formation from single hydrocarbon precursors is commonly studied in smog chamber experiments to obtain SOA yield and organic composition data. However, very few complex air mixture experiments have been conducted to simulate possible conditions in ambient atmospheres. A six-phase experiment involving various combinations of alpha-pinene, toluene, isoprene, and SO2 were irradiated in the EPA's dynamic smog

  20. Quantitative evaluation of emission control of primary and secondary organic aerosol sources during Beijing 2008 Olympics

    NASA Astrophysics Data System (ADS)

    Guo, S.; Hu, M.; Guo, Q.; Zhang, X.; Schauer, J. J.; Zhang, R.

    2012-12-01

    To explore the primary and secondary sources of fine organic particles after the aggressive implementation of air pollution controls during 2008 Beijing Olympic Games, 12-h PM2.5 concentrations were measured at one urban and one upwind rural site during the CAREBeijing-2008 (Campaigns of Air quality REsearch in Beijing and surrounding region) summer field campaign. The PM2.5 concentrations were 72.5±43.6?g m3 and 64.3±36.2?g m-3 at the urban site and rural site, respectively, which were the lowest in recent years due to the implementation of drastic control measures and favorable weather conditions. Five primary and four secondary fine organic particle sources were quantified using a CMB (chemical mass balance) model and tracer-yield method. Compared with previous studies in Beijing, the contribution of vehicle emission increased, with diesel engines contributing 16.2±5.9% and 14.5±4.1% to the total organic carbon (OC) concentrations and gasoline vehicles accounting for 10.3±8.7% and 7.9±6.2% of the OC concentrations at two sites. Due to the implementation of emission control measures, the OC concentrations from important primary sources have been reduced, and secondary formation has become an important contributor to fine organic aerosols. Compared with the non-controlled period, primary vehicle contributions were reduced by 30% and 24% in the urban and regional area, and reductions in the contribution from coal combustion were 57% and 7%, respectively. These results demonstrate the emission control measures significantly alleviated the primary organic particle pollution in and around Beijing. However, the control effectiveness of secondary organic particles was not significant.

  1. Changes in Secondary Organic Aerosol burden from 1960-2010: a model study with the climate-aerosols ECHAM6-HAM2 model

    NASA Astrophysics Data System (ADS)

    Sousa Santos, Gabriela; Stanelle, Tanja; Bey, Isabelle

    2014-05-01

    Organic aerosols (OA) represent an important fraction of the total aerosol burden and include Primary Organic Aerosols (POA), which are directly emitted into the atmosphere and Secondary Organic Aerosols (SOA), which result from atmospheric oxidation of a number of gaseous precursors. Recent estimates indicate that SOA represent about 50% of the total OA burden (but only about 30 % of the OA surface concentration). In this study we explore the processes driving the changes in the production and burden of SOA from 1960 to 2010 with the global climate-aerosol model ECHAM6-HAM2. Between the 60s and 00s the global SOA production increases from 24 to 30 Tg/a, the burden increases from 0.56 Tg to 0.64 Tg. The increase takes mainly place in the main source regions of the Northern Hemisphere (tropical forested regions and highly polluted regions in Asia) and in South America. With a series of sensitivity simulations we distinguish between the roles of climate change (temperature, precipitation, radiation), land use change, changes in emissions of POA, and changes in emissions of anthropogenic precursors of SOA. We find that, while all regions show an increase in burden, the relative importance of each process is strongly region-dependent. In Europe, the increase in SOA is related to climate and land use changes. In Africa, the increase in SOA results from climate change and increase in POA emissions. In Asia, the increase is mainly due to increase in anthropogenic emissions.

  2. simpleGAMMA v1.0 - a reduced model of secondary organic aerosol formation in the aqueous aerosol phase (aaSOA)

    NASA Astrophysics Data System (ADS)

    Woo, J. L.; McNeill, V. F.

    2015-06-01

    There is increasing evidence that the uptake and aqueous processing of water-soluble volatile organic compounds (VOCs) by wet aerosols or cloud droplets is an important source of secondary organic aerosol (SOA). We recently developed GAMMA (Gas-Aerosol Model for Mechanism Analysis), a zero-dimensional kinetic model that couples gas-phase and detailed aqueous-phase atmospheric chemistry for speciated prediction of SOA and organosulfate formation in cloud water or aqueous aerosols. Results from GAMMA simulations of SOA formation in aerosol water (aaSOA) (McNeill et al., 2012) indicate that it is dominated by two pathways: isoprene epoxydiol (IEPOX) uptake followed by ring-opening chemistry (under low-NOx conditions) and glyoxal uptake. This suggested that it is possible to model the majority of aaSOA mass using a highly simplified reaction scheme. We have therefore developed a reduced version of GAMMA, simpleGAMMA. Close agreement in predicted aaSOA mass is observed between simpleGAMMA and GAMMA under all conditions tested (between pH 1-4 and RH 40-80 %) after 12 h of simulation. simpleGAMMA is computationally efficient and suitable for coupling with larger-scale atmospheric chemistry models or analyzing ambient measurement data.

  3. Quantification of Semi-Volatile gas-phase Organic Compounds (SVOCs) & Organic Aerosol species and the role of SVOCs in Secondary Organic Aerosol formation

    NASA Astrophysics Data System (ADS)

    Khan, M. H.; Holzinger, R.

    2013-12-01

    A Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS) with different sampling systems (multi-stage denuder for gas phase and impact on a collector for aerosol phase) has been deployed in summer 2013 during the Southern Oxidant and Aerosol Study (SOAS) at the SEARCH ground site, Centreville, Alabama for in-situ gas phase and aerosol measurements on an hourly time resolution. A bunch of DB-1 column (0.53 mm x 5.0 ?m) is used in the denuder for capturing the bulk of SVOCs and a collection-thermal-desorption (CTD) cell is used for collecting aerosol particles. Several hundreds semivolatile organic compounds (SVOCs) in gas phase and aerosol phases have been detected. The high mass resolution capabilities of ~5000, low detection limit (<0.05 pptv for gas species, <0.01 ng m-3 for aerosol species) and good physical and chemical characterization of SVOCs with the TD-PTR-MS allows constraining both, the quantity and the chemical composition. The SEARCH site was highly impacted by Biogenic Volatile Organic Compounds (BVOCs) and occasionally influenced by anthropogenic pollution. BVOCs and their oxidation products are capable of partitioning into the particle phase, so their simultaneous quantification in both phases has been used to determine the gas/particle-phase partitioning. Our results show the expected diurnal variation based on the changes of air temperature for many species. The results from this study give valuable insights into sources and processing of Secondary Organic Aerosols (SOAs) that can be used to improve parameterization algorithms in regional and global climate models.

  4. Secondary Organic Aerosol formation from isoprene photooxidation under dry conditions (CUMULUS project)

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, Lola; Siekmann, Frank; Giorio, Chiara; Temime-Roussel, Brice; Pangui, Edouard; Morales, Sébastien; Gratien, Aline; Ravier, Sylvain; Monod, Anne; Doussin, Jean-Francois

    2014-05-01

    Isoprene (2-methyl-1,3-butadiene, C5H8) is one of the most abundant non-methane hydrocarbons emitted into the troposphere. Its annual global emission has recently been estimated in the range of 440 to 660 TgC (Guenther et al., 2006). Because of its large concentrations and high reactivity with the hydroxyl radical (OH), isoprene can have a strong influence on tropospheric photochemistry. It has been determined recently that isoprene also plays a role in secondary organic aerosol (SOA) formation in the ambient atmosphere even if isoprene leads to low SOA yields. The aim of the present work was to study isoprene photo-oxidation with OH radical in order to investigate its oxidation products and resulting aerosol production. A special care was taken to the realism of the experiment: light source, NOx and OH levels and aging time (around 10 hours). Experiments were performed in the CESAM chamber (Wang et al., 2011) which was designed to investigate multiphase processes under realistic actinic flux, and accurate control of temperature. In each experiment, around 800 ppb of isoprene was injected in the chamber together with the OH source under dry conditions (<5 %RH) before irradiation. Gas-phase composition was analyzed in-situ by a Fourier Transform Infrared Spectrometer (FTIR), a Proton Transfer Reaction Mass Spectrometer (PTR-TOF-MS) and NOx and ozone analyzers. A Scanning Mobility Particle Sizer (SMPS) and an Aerodyne High Resolution Time-Of-Flight Aerosol Mass Spectrometer (HR-TOF-AMS) were also used to investigate SOA formation and composition. In all experiments, we noted a SOA production at the end of isoprene oxidation i.e. exhibiting a clear secondary products type growth. Several results (including SOA densities and yields, and O/C ratios) were obtained using SMPS and AMS data allowing us to characterize SOA formation and composition during the experiments. The characterization of the gaseous and particulate phases will be presented. While the SOA yields in the literature exhibit a general dispersion, the SOA yields obtained during the experiments are consistent with the lowest values found in the literature. Some assumptions concerning the cause of this dispersion, including the role of the irradiation source used, will be discussed. Guenther, A. et al. (2006). Atmos. Chem. Phys 6(11): 3181-3210. Wang, J. et al. (2011). Atmospheric Measurement Techniques 4(11): 2465-2494.

  5. The direct and indirect radiative effects of biogenic secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Scott, C. E.; Rap, A.; Spracklen, D. V.; Forster, P. M.; Carslaw, K. S.; Mann, G. W.; Pringle, K. J.; Kivekäs, N.; Kulmala, M.; Lihavainen, H.; Tunved, P.

    2013-06-01

    We use a global aerosol microphysics model in combination with an offline radiative transfer model to quantify the radiative effect of biogenic secondary organic aerosol (SOA) in the present day atmosphere. Through its role in particle growth and ageing, the presence of biogenic SOA increases the global annual mean concentration of cloud condensation nuclei (CCN; at 0.2% supersaturation) by 3.6-21.1%, depending upon the yield of SOA production, and the nature and treatment of concurrent primary carbonaceous emissions. This increase in CCN causes a rise in global annual mean cloud droplet number concentration (CDNC) of 1.9-5.2%, and a global mean first aerosol indirect effect (AIE) of between +0.01 W m-2 and -0.12 W m-2. The radiative impact of biogenic SOA is far greater when it also contributes to particle nucleation; using two organically-mediated mechanisms for new particle formation we simulate global annual mean AIEs of -0.22 W m-2 and -0.77 W m-2. The inclusion of biogenic SOA substantially improves the simulated seasonal cycle in the concentration of CCN sized particles observed at three forested sites. The best correlation is found when the organically-mediated nucleation mechanisms are applied, suggesting that the AIE of biogenic SOA could be as large as -0.77 W m-2. The radiative impact of SOA is sensitive to the presence of anthropogenic emissions. Lower background aerosol concentrations simulated with anthropogenic emissions from 1750 give rise to a greater fractional CCN increase and a more substantial indirect radiative effect from biogenic SOA. Consequently, the anthropogenic indirect radiative forcing between 1750 and the present day is sensitive to assumptions about the amount and role of biogenic SOA. We also calculate an annual global mean direct radiative effect (DRE) of between -0.08 W m-2 and -0.78 W m-2 in the present day, with uncertainty in the amount of SOA produced from the oxidation of biogenic volatile organic compounds (BVOCs) accounting for most of this range.

  6. The direct and indirect radiative effects of biogenic secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Scott, C. E.; Rap, A.; Spracklen, D. V.; Forster, P. M.; Carslaw, K. S.; Mann, G. W.; Pringle, K. J.; Kivekäs, N.; Kulmala, M.; Lihavainen, H.; Tunved, P.

    2014-01-01

    We use a global aerosol microphysics model in combination with an offline radiative transfer model to quantify the radiative effect of biogenic secondary organic aerosol (SOA) in the present-day atmosphere. Through its role in particle growth and ageing, the presence of biogenic SOA increases the global annual mean concentration of cloud condensation nuclei (CCN; at 0.2% supersaturation) by 3.6-21.1%, depending upon the yield of SOA production from biogenic volatile organic compounds (BVOCs), and the nature and treatment of concurrent primary carbonaceous emissions. This increase in CCN causes a rise in global annual mean cloud droplet number concentration (CDNC) of 1.9-5.2%, and a global mean first aerosol indirect effect (AIE) of between +0.01 W m-2 and -0.12 W m-2. The radiative impact of biogenic SOA is far greater when biogenic oxidation products also contribute to the very early stages of new particle formation; using two organically mediated mechanisms for new particle formation, we simulate global annual mean first AIEs of -0.22 W m-2 and -0.77 W m-2. The inclusion of biogenic SOA substantially improves the simulated seasonal cycle in the concentration of CCN-sized particles observed at three forested sites. The best correlation is found when the organically mediated nucleation mechanisms are applied, suggesting that the first AIE of biogenic SOA could be as large as -0.77 W m-2. The radiative impact of SOA is sensitive to the presence of anthropogenic emissions. Lower background aerosol concentrations simulated with anthropogenic emissions from 1750 give rise to a greater fractional CCN increase and a more substantial first AIE from biogenic SOA. Consequently, the anthropogenic indirect radiative forcing between 1750 and the present day is sensitive to assumptions about the amount and role of biogenic SOA. We also calculate an annual global mean direct radiative effect of between -0.08 W m-2 and -0.78 W m-2 in the present day, with uncertainty in the amount of SOA produced from the oxidation of BVOCs accounting for most of this range.

  7. Identification and quantification of individual chemical compounds in biogenic secondary organic aerosols using GCxGC-VUV/EI-HRTOFMS

    NASA Astrophysics Data System (ADS)

    Decker, M.; Worton, D. R.; Isaacman, G. A.; Chan, A. W.; Ruehl, C.; Zhao, Y.; Wilson, K. R.; Goldstein, A. H.

    2012-12-01

    Atmospheric aerosols have adverse effects on human health and air quality and affect radiative forcing and thus climate. While the organic fraction of aerosols is substantial, the sources and chemistry leading to the formation of secondary organic aerosols are very poorly understood. Characterizing individual compounds present in organic aerosol provides insights into the sources, formation mechanisms and oxidative transformations that have taken place. Fifteen aerosol samples collected over a 5 day period at the Blodgett Forest Research Station in the Sierra Nevada Mountains, part of the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) in July 2009, were analyzed using comprehensive two dimensional gas chromatography with high resolution time of flight mass spectrometry (GCxGC-HRTOFMS). Approximately 600 compounds were observed in each sample as significant peaks in the chromatogram. Of these, around a third were identified by matching the unique electron ionization (EI) mass spectrum of each compound to the NIST library of characteristic fragmentation patterns. One filter sample was also analyzed using vacuum ultraviolet ionization (VUV) instead of EI. This 'soft' ionization technique results in much less fragmentation yielding the molecular ion of each compound, from which the exact mass was determined. If the formula of the EI library matched compound equaled the high mass resolution VUV molecular weight within a certain tolerance (< 30 ppm), then the library match was considered confirmed; 226 compounds were identified in this way. Using the VUV technique 234 additional compounds that were not in the EI mass spectral database were assigned chemical formulas based on the observed molecular weights. The chemical formulas in conjunction with the location of the compound in the GCxGC chromatogram were used to provide further classification of these compounds based on their likely functionalization. The broad array of observed oxygenated compounds provide important constraints on the origins and secondary organic aerosol formation pathways in this region.

  8. Steady increase of secondary organic aerosol mass concentration and light extinction during the CARES 2010 Field Campaign

    NASA Astrophysics Data System (ADS)

    Gyawali, M. S.; Arnott, W. P.; Flowers, B. A.; Dubey, M. K.; Atkinson, D. B.; Song, C.; Zaveri, R. A.; Setyan, A.; Zhang, Q.; Mazzoleni, C.; Gorkowski, K.

    2011-12-01

    We present multispectral (355, 375, 405, 532, 870, 781, and 1047 nm) aerosol light absorption and scattering measurements for the 2010 Carbonaceous Aerosols and Radiative Effects (CARES) campaign in Sacramento, CA and the Sierra Nevada foothills. The short wavelength scattering at both sites gradually increased during the last 10 days of the campaign as diagnosed by a systematic increase in the Ångström exponent of scattering. The UV and near UV enhanced scattering was likely a consequence of the ultra and sub-micron aerosol which began to grow vigorously in the size range where scattering at shorter wavelengths begins to increase. Multispectral aerosol light absorption coefficients suggest the absence of short wavelength light absorption by brown carbon. Aerosol mass spectrometer data also shows the steady increase of secondary organic aerosol during the last 10 days of CARES. The time series of the measurements made between the two sites (T0 and T1) separated by the slope of the foothills are strikingly similar, except for isolated night time episodes of enhanced absorption at T0. This is possibly due to paving events or other nocturnal emissions markers

  9. Predicted change in global secondary organic aerosol concentrations in response to future climate, emissions, and land use change

    E-print Network

    Heald, C. L.; Henze, D. K.; Horowitz, L. W.; Feddema, Johannes J.; Lamarque, J. F.; Guenther, A.; Hess, P. G.; Vitt, F.; Seinfeld, J. H.; Goldstein, A. H.; Fung, I.

    2008-03-01

    Predicted change in global secondary organic aerosol concentrations in response to future climate, emissions, and land use change C. L. Heald,1,2 D. K. Henze,3 L. W. Horowitz,4 J. Feddema,5 J.-F. Lamarque,6 A. Guenther,6 P. G. Hess,6 F. Vitt,6 J. H...] and anthropogenic aromatics such as toluene and xylene [Odum et al., 1997; Jang and Kamens, 2001; Kleindienst et al., 2004]. Kroll et al. [2005, 2006] demonstrated that isoprene photooxidation leads to aerosol formation. Isoprene is the most abundantly emitted VOC...

  10. Diurnal variability of size-differentiated inorganic aerosols and their gas-phase precursors during January and February of 2003 near downtown Mexico City

    NASA Astrophysics Data System (ADS)

    Moya, Mireya; Grutter, Michel; Báez, Armando

    Size-differentiated atmospheric aerosol particles along with gas-phase precursors were measured at a site near downtown Mexico City (MER site) during January and February 2003 to provide information regarding the diurnal variability and partitioning of semi-volatile inorganic compounds between the gas phase and different-size particles. The aerosols were sampled with cascade impactors (MOUDI's) in the following periods: 1st (06:00-09:00 h, LST), 2nd (09:00-12:00 h, LST), 3rd (12:00-15:00 h, LST) and 4th (15:00-18:00 h, LST). The gas-phase measurements were continuously recorded with an open-path FTIR spectrometer. Overall, inorganic aerosol size/composition measurements observed a bimodal distribution: one mode was present in the accumulation size range (0.18-0.32 ?m, aerodynamic diameter) and the other in the coarse mode (over 1 ?m, aerodynamic diameter). During the morning sampling periods, the highest concentrations occurred mainly over the accumulation mode while during the afternoon sampling periods, concentration peaks were observed over both accumulation and coarse modes. More than half of the ammonium was found in the accumulation mode. The rest of the ions (sodium, chloride, sulfate, nitrate, calcium and potassium) were prominent in both modes. The significant presence of sodium and crustals (calcium and potassium) are explained in terms of the potential influence of the dry salt-lake of Texcoco and resuspended dust/soil, respectively. Based on the analysis of the time-resolved PM and gas-phase composition, the significant presence of gas-phase ammonia (>35 ppb) during the morning sampling periods was of importance in neutralizing the aerosol particles.

  11. Laboratory Studies of Processing of Carbonaceous Aerosols by Atmospheric Oxidants/Hygroscopicity and CCN Activity of Secondary & Processed Primary Organic Aerosols

    SciTech Connect

    Ziemann, P.J.; Arey, J.; Atkinson, R.; Kreidenweis, S.M.; Petters, M.D.

    2012-06-13

    The atmosphere is composed of a complex mixture of gases and suspended microscopic aerosol particles. The ability of these particles to take up water (hygroscopicity) and to act as nuclei for cloud droplet formation significantly impacts aerosol light scattering and absorption, and cloud formation, thereby influencing air quality, visibility, and climate in important ways. A substantial, yet poorly characterized component of the atmospheric aerosol is organic matter. Its major sources are direct emissions from combustion processes, which are referred to as primary organic aerosol (POA), or in situ processes in which volatile organic compounds (VOCs) are oxidized in the atmosphere to low volatility reaction products that subsequent condense to form particles that are referred to as secondary organic aerosol (SOA). POA and VOCs are emitted to the atmosphere from both anthropogenic and natural (biogenic) sources. The overall goal of this experimental research project was to conduct laboratory studies under simulated atmospheric conditions to investigate the effects of the chemical composition of organic aerosol particles on their hygroscopicity and cloud condensation nucleation (CCN) activity, in order to develop quantitative relationships that could be used to more accurately incorporate aerosol-cloud interactions into regional and global atmospheric models. More specifically, the project aimed to determine the products, mechanisms, and rates of chemical reactions involved in the processing of organic aerosol particles by atmospheric oxidants and to investigate the relationships between the chemical composition of organic particles (as represented by molecule sizes and the specific functional groups that are present) and the hygroscopicity and CCN activity of oxidized POA and SOA formed from the oxidation of the major classes of anthropogenic and biogenic VOCs that are emitted to the atmosphere, as well as model hydrocarbons. The general approach for this project was to carry out reactions of representative anthropogenic and biogenic VOCs and organic particles with ozone (O3), and hydroxyl (OH), nitrate (NO3), and chlorine (Cl) radicals, which are the major atmospheric oxidants, under simulated atmospheric conditions in large-volume environmental chambers. A combination of on-line and off-line analytical techniques were used to monitor the chemical and physical properties of the particles including their hygroscopicity and CCN activity. The results of the studies were used to (1) improve scientific understanding of the relationships between the chemical composition of organic particles and their hygroscopicity and CCN activity, (2) develop an improved molecular level theoretical framework for describing these relationships, and (3) establish a large database that is being used to develop parameterizations relating organic aerosol chemical properties and SOA sources to particle hygroscopicity and CCN activity for use in regional and global atmospheric air quality and climate models.

  12. Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes

    NASA Astrophysics Data System (ADS)

    Lee, Anita; Goldstein, Allen H.; Keywood, Melita D.; Gao, Song; Varutbangkul, Varuntida; Bahreini, Roya; Ng, Nga L.; Flagan, Richard C.; Seinfeld, John H.

    2006-04-01

    The ozonolyses of six monoterpenes (?-pinene, ?-pinene, 3-carene, terpinolene, ?-terpinene, and myrcene), two sesquiterpenes (?-humulene and ?-caryophyllene), and two oxygenated terpenes (methyl chavicol and linalool) were conducted individually in Teflon chambers to examine the gas-phase oxidation product and secondary organic aerosol (SOA) yields from these reactions. Particle size distribution and number concentration were monitored and allowed for the calculation of the SOA yield from each experiment, which ranged from 1 to 54%. A proton transfer reaction mass spectrometer (PTR-MS) was used to monitor the evolution of gas-phase products, identified by their mass to charge ratio (m/z). Several gas-phase oxidation products, formaldehyde, acetaldehyde, formic acid, acetone, acetic acid, and nopinone, were identified and calibrated. Aerosol yields, and the yields of these identified and calibrated oxidation products, as well as many higher m/z oxidation products observed with the PTR-MS, varied significantly between the different parent terpene compounds. The sum of measured oxidation products in the gas and particle phase ranged from 33 to 77% of the carbon in the reacted terpenes, suggesting there are still unmeasured products from these reactions. The observations of the higher molecular weight oxidation product ions provide evidence of previously unreported compounds and their temporal evolution in the smog chamber from multistep oxidation processes. Many of the observed ions, including m/z 111 and 113, have also been observed in ambient air above a Ponderosa pine forest canopy, and our results confirm they are consistent with products from terpene + O3 reactions. Many of these products are stable on the timescale of our experiments and can therefore be monitored in field campaigns as evidence for ozone oxidative chemistry.

  13. Aqueous photooxidation of ambient Po Valley Italy air samples: Insights into secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Kirkland, J. R.; Lim, Y. B.; Sullivan, A. P.; Decesari, S.; Facchini, C.; Collett, J. L.; Keutsch, F. N.; Turpin, B. J.

    2012-12-01

    In this work, we conducted aqueous photooxidation experiments with ambient samples in order to develop insights concerning the formation of secondary organic aerosol through gas followed by aqueous chemistry (SOAaq). Water-soluble organics (e.g., glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone) are formed through gas phase oxidation of alkene and aromatic emissions of anthropogenic and biogenic origin. Their further oxidation in clouds, fogs and wet aerosols can form lower volatility products (e.g., oligomers, organic acids) that remain in the particle phase after water evaporation, thus producing SOA. The aqueous OH radical oxidation of several individual potentially important precursors has been studied in the laboratory. In this work, we used a mist-chamber apparatus to collect atmospheric mixtures of water-soluble gases from the ambient air at San Pietro Capofiume, Italy during the PEGASOS field campaign. We measured the concentration dynamics after addition of OH radicals, in order to develop new insights regarding formation of SOA through aqueous chemistry. Specifically, batch aqueous reactions were conducted with 33 ml mist-chamber samples (TOC ~ 50-100?M) and OH radicals (~10-12M) in a new low-volume aqueous reaction vessel. OH radicals were formed in-situ, continuously by H2O2 photolysis. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS +/-), and ESI-MS with IC pre-separation (IC/ESI-MS-). Reproducible formation of pyruvate and oxalate were observed both by IC and ESI-MS. These compounds are known to form from aldehyde oxidation in the aqueous phase. New insights regarding the aqueous chemistry of these "more atmospherically-realistic" experiments will be discussed.

  14. Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility

    Microsoft Academic Search

    S. Zappoli; A. Andracchio; S. Fuzzi; M. C. Facchini; A. Gelencsér; G. Kiss; Z. Krivácsy; Á. Molnár; E. Mészáros; H.-C. Hansson; K. Rosman; Y. Zebühr

    1999-01-01

    A chemical mass balance of fine aerosol (<1.5?m AED) collected at three European sites was performed with reference to the water solubility of the different aerosol classes of components. The sampling sites are characterised by different pollution conditions and aerosol loading in the air. Aspvreten is a background site in central Sweden, K-puszta is a rural site in the Great

  15. Regional-scale modeling of secondary organic aerosol formation downwind from the DWH oil spill

    NASA Astrophysics Data System (ADS)

    Ahmadov, R.; McKeen, S. A.; Bahreini, R.; Brioude, J.; de Gouw, J. A.; Middlebrook, A. M.; Murphy, D. M.; Pollack, I. B.; Robinson, A. L.; Ryerson, T. B.; Trainer, M.; Warneke, C.

    2010-12-01

    In response to the Deepwater Horizon (DWH) oil spill disaster in the Gulf of Mexico, the NOAA P3 aircraft performed two flights over the Gulf of Mexico during 8th and 10th of June 2010 with multiple flight legs around the DWH site to quantify the atmospheric impact of the oil spill. The measurements detected high concentrations of volatile organic compounds (VOCs) and organic aerosols (OA) downwind of the spill site. Spatial characteristics of the observed OA distribution indicated a moderate secondary organic aerosol (SOA) formation in narrow plumes coincident with high concentrations of aromatic VOCs, and also a much broader and larger SOA plume somewhat removed from the spill site. These patterns can qualitatively be explained by a dependence of VOC species volatility on the distance to the DWH spill site, and SOA yield differences associated with lower volatility (C12-C20 alkanes) versus higher volatility VOC (C7-C11 alkanes and aromatics) that comprise the bulk of the spilled oil reaching the surface. In order to test this SOA formation hypothesis the WRF-CHEM model has been applied to the Gulf of Mexico for the period of P3 aircraft operations. Modifications to the original WRF-Chem formulation include the addition of hexadecane (n-C16) within the gas-phase mechanism, and a new volatility basis set approach to simulate SOA formation using the most recent SOA yields from available literature. Emissions of NOx and C6-C11 VOC species are constrained from the P3 aircraft observations. The model has been run with different horizontal resolutions, and different emission scenarios for C12-C20 VOCs that were inferred from the composition of oil collected near the DWH. Model results for SOA and total PM2.5 aerosol are compared with the observations collected aboard the P3 aircraft, and coastal PM2.5 monitors positioned downwind of the DWH spill site, in order to test the veracity of the model formulation and help constrain the conceptual model of SOA formation from DWH outlined above.

  16. Campholenic aldehyde ozonolysis: a possible mechanism for the formation of specific biogenic secondary organic aerosol constituents

    NASA Astrophysics Data System (ADS)

    Kahnt, A.; Iinuma, Y.; Mutzel, A.; Böge, O.; Claeys, M.; Herrmann, H.

    2013-08-01

    In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known ?-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon ?-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised with 2,4-dinitrophenylhydrazine (DNPH) followed by Liquid Chromatography/negative ion Electrospray Ionisation Time-of-Flight Mass Spectrometry analysis and were compared to the gas-phase compounds detected by online Proton-Transfer-Reaction Mass Spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and MS2 and MS3 fragmentation studies. Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving ?-pinene, ?-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m/z 201, C9H14O5 and m/z 215, C10H16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m/z 201 and 215 compounds were tentatively identified as a C9- and C10-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH-derivatives.

  17. Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents

    NASA Astrophysics Data System (ADS)

    Kahnt, A.; Iinuma, Y.; Mutzel, A.; Böge, O.; Claeys, M.; Herrmann, H.

    2014-01-01

    In the present study, campholenic aldehyde ozonolysis was performed to investigate pathways leading to specific biogenic secondary organic aerosol (SOA) marker compounds. Campholenic aldehyde, a known ?-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon ?-pinene ozonolysis. It was reacted with ozone in the presence and absence of an OH radical scavenger, leading to SOA formation with a yield of 0.75 and 0.8, respectively. The resulting oxidation products in the gas and particle phases were investigated employing a denuder/filter sampling combination. Gas-phase oxidation products bearing a carbonyl group, which were collected by the denuder, were derivatised by 2,4-dinitrophenylhydrazine (DNPH) followed by liquid chromatography/negative ion electrospray ionisation time-of-flight mass spectrometry analysis and were compared to the gas-phase compounds detected by online proton-transfer-reaction mass spectrometry. Particle-phase products were also analysed, directly or after DNPH derivatisation, to derive information about specific compounds leading to SOA formation. Among the detected compounds, the aldehydic precursor of terpenylic acid was identified and its presence was confirmed in ambient aerosol samples from the DNPH derivatisation, accurate mass data, and additional mass spectrometry (MS2 and MS3 fragmentation studies). Furthermore, the present investigation sheds light on a reaction pathway leading to the formation of terpenylic acid, involving ?-pinene, ?-pinene oxide, campholenic aldehyde, and terpenylic aldehyde. Additionally, the formation of diaterpenylic acid acetate could be connected to campholenic aldehyde oxidation. The present study also provides insights into the source of other highly functionalised oxidation products (e.g. m / z 201, C9H14O5 and m / z 215, C10H16O5), which have been observed in ambient aerosol samples and smog chamber-generated monoterpene SOA. The m / z 201 and 215 compounds were tentatively identified as a C9- and C10-carbonyl-dicarboxylic acid, respectively, based on reaction mechanisms of campholenic aldehyde and ozone, as well as detailed interpretation of mass spectral data, in conjunction with the formation of corresponding DNPH derivatives.

  18. Water uptake is independent of the inferred composition of secondary aerosols derived from multiple biogenic VOCs

    NASA Astrophysics Data System (ADS)

    Alfarra, M. R.; Good, N.; Wyche, K. P.; Hamilton, J. F.; Monks, P. S.; Lewis, A. C.; McFiggans, G.

    2013-12-01

    We demonstrate that the water uptake properties derived from sub- and super-saturated measurements of chamber-generated biogenic secondary organic aerosol (SOA) particles are independent of their degree of oxidation, determined using both online and offline methods. SOA particles are formed from the photooxidation of five structurally different biogenic VOCs, representing a broad range of emitted species and their corresponding range of chemical reactivity: ?-pinene, ?-caryophyllene, limonene, myrcene and linalool. The fractional contribution of mass fragment 44 to the total organic signal (f44) is used to characterise the extent of oxidation of the formed SOA as measured online by an aerosol mass spectrometer. Results illustrate that the values of f44 are dependent on the precursor, the extent of photochemical ageing as well as on the initial experimental conditions. SOA generated from a single biogenic precursor should therefore not be used as a general proxy for biogenic SOA. Similarly, the generated SOA particles exhibit a range of hygroscopic properties, depending on the precursor, its initial mixing ratio and photochemical ageing. The activation behaviour of the formed SOA particles show no temporal trends with photochemical ageing. The average ? values derived from the HTDMA and CCNc are generally found to cover the same range for each precursor under two different initial mixing ratio conditions. A positive correlation is observed between the hygroscopicity of particles of a single size and f44 for ?-pinene, ?-caryophyllene, linalool and myrcene, but not for limonene SOA. The investigation of the generality of this relationship reveals that ?-pinene, limonene, linalool and myrcene are all able to generate particles with similar hygroscopicity (?HTDMA ~0.1) despite f44 exhibiting a relatively wide range of values (~4 to 11%). Similarly, ?CCN is found to be independent of f44. The same findings are also true when sub- and super-saturated water uptake properties of SOA are compared to the averaged carbon oxidation state (OSC) determined using an offline method. These findings do not necessarily suggest that water uptake and chemical composition are not related. Instead, they suggest that either f44 and OSC do not represent the main dominant composition-related factors controlling water uptake of SOA particles, or they may emphasise the possible impact of semi-volatile compounds on limiting the ability of current state-of-the-art techniques to determine the chemical composition and water uptake properties of aerosol particles.

  19. Water uptake is independent of the inferred composition of secondary aerosols derived from multiple biogenic VOCs

    NASA Astrophysics Data System (ADS)

    Alfarra, M. R.; Good, N.; Wyche, K. P.; Hamilton, J. F.; Monks, P. S.; Lewis, A. C.; McFiggans, G. B.

    2013-04-01

    We demonstrate that the water uptake properties derived from sub- and super-saturated measurements of chamber-generated biogenic secondary organic aerosol (SOA) particles are independent of their degree of oxidation determined using both online and offline methods. SOA particles are formed from the photooxidation of five structurally different biogenic VOCs representing a broad range of emitted species and their corresponding range of chemical reactivity: ?-pinene, ?-caryophyllene, limonene, myrcene and linalool. The fractional contribution of mass fragment 44 to the total organic signal (f44) is used to characterise the extent of oxidation of the formed SOA as measured online by an aerosol mass spectrometer. Results illustrate that the values of f44 are dependent on the precursor, the extent of photochemical ageing as well as on the initial experimental conditions. SOA generated from a single biogenic precursor should therefore not be used as a general proxy for biogenic SOA. Similarly, the generated SOA particles exhibit a range of hygroscopic properties depending on the precursor, its initial mixing ratio and photochemical ageing. The activation behaviour of the formed SOA particles show no temporal trends with photochemical ageing. The average ? values derived from the HTDMA and CCNc are generally found to cover the same range for each precursor under two different initial mixing ratio conditions. A positive correlation is observed between the hygroscopicity of particles of a single size and f44 for ?-pinene, ?-caryophyllene, linalool and myrcene, but not for limonene SOA. The investigation of the generality of this relationship reveal that ?-pinene, limonene, linalool and myrcene are all able to generate particles with similar hygroscopicity (?HTDMA ~0.1) despite f44 exhibiting a relatively wide range of values (~4 to 11%). Similarly, ?CCN is found to be independent of f44. The same findings are also true when sub- and super-saturated water uptake properties of SOA are compared to the averaged carbon oxidation state (OSC) determined using an off-line method. These findings do not necessarily suggest that water uptake and chemical composition are not related. Instead, they suggest that either f44 and OSC do not represent the main dominant composition-related factors controlling water uptake of SOA particles, or they emphasise the possible impact of semi-volatile compounds on limiting the ability of current state-of-the-art techniques to determine the chemical composition and water uptake properties of aerosol particles.

  20. 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

  1. Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

    Microsoft Academic Search

    R. Chirico; P. F. Decarlo; M. F. Heringa; T. Tritscher; R. Richter; A. S. H. Prevot; J. Dommen; E. Weingartner; G. Wehrle; M. Gysel; M. Laborde; U. Baltensperger

    2010-01-01

    Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog

  2. Investigating the role of VOCs in secondary organic aerosol production during the PROPHET 2008 field intensive by proton transfer reaction linear ion trap (PTR-LIT) mass spectrometry

    Microsoft Academic Search

    L. H. Mielke; J. Slade; M. Alaghmand; M. Galloway; A. Kammrath; F. Keutsch; S. Bertman; M. Carroll; S. Griffith; R. Hansen; S. Dusanter; P. Stevens; A. Hansel; A. Wisthaler; D. Erickson; S. A. McLuckey; P. Shepson

    2009-01-01

    A major aim of the PROPHET 2008 field intensive conducted at the University of Michigan Biological Station was to more completely understand the local formation of secondary organic aerosol from oxidation of biogenic volatile organic compounds (BVOCs). This oxidation was monitored at every step including gas phase reactant VOCs, oxidants, reaction products, and finally aerosol number and size distribution. Several

  3. EFFECT OF RELATIVE HUMIDITY ON THE CHEMICAL COMPOSITION OF SECONDARY ORGANIC AEROSOL FORMED FROM REACTIONS OF 1-TETRADECENE AND O3. (R826235)

    EPA Science Inventory

    The chemical composition of secondary organic aerosol formed in an environmental chamber from ozonolysis of 1-tetradecene in humid and dry air was determined using a thermal desorption particle beam mass spectrometer (TDPBMS). The major products are ...

  4. SEASONAL AND REGIONAL VARIATIONS OF PRIMARY AND SECONDARY ORGANIC AEROSOLS OVER THE CONTINENTAL UNITED STATES: OBSERVATION-BASED ESTIMATES AND MODEL EVALUATION

    EPA Science Inventory

    Due to the lack of an analytical technique for directly quantifying the atmospheric concentrations of primary (OCpri) and secondary (OCsec) organic carbon aerosols, different indirect methods have been developed to estimate their concentrations. In this stu...

  5. 3rd hand smoking; heterogeneous oxidation of nicotine and secondary aerosol formation in the indoor environment

    NASA Astrophysics Data System (ADS)

    Petrick, Lauren; Dubowski, Yael

    2010-05-01

    Tobacco smoking is well known as a significant source of primary indoor air pollutants. However, only recently has it been recognized that the impact of Tobacco smoking may continue even after the cigarette has been extinguished (i.e., third hand smoke) due to the effect of indoor surfaces. These surfaces may affect the fate of tobacco smoke in the form of secondary reactions and pollutants, including secondary organic aerosol (SOA) formation. Fourier Transform Infrared spectrometry with Attenuated Total Reflection (FTIR-ATR) in tandem with a Scanning Mobility Particle Sizing (SMPS) system was used to monitor the ozonation of cellulose sorbed nicotine and resulting SOA formation. SOA formation began at onset of ozone introduction ([O3] = 60 ± 5 ppb) with a size distribution of dp ? 25 nm, and was determined to be a result of heterogeneous reaction (opposed to homogeneous). SOA yield from reacted surface nicotine was on the order of 10 %. Simultaneous to SOA monitoring, FTIR-ATR spectra showed surface changes in the nicotine film as the reaction progressed, revealing a pseudo first-order surface reaction rate of 0.0026 ± 0.0008 min-1. Identified surface oxidation products included: cotinine, myosmine, methylnicotinamide and nicotyrine. Surface reaction rate was found to be partially inhibited at high relative humidity. Given the toxicity of some of the identified products (e.g., cotinine has shown potential mutagenicity and teratogenicity) and that small particles may contribute to adverse health effects, the present study indicates that exposure to 3rd hand smoke ozonation products may pose additional health risks.

  6. Aqueous Oxidation of Green Leaf Volatiles as a Source of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Richards-Henderson, N. K.; Hansel, A.; Pham, A. T.; Vempati, H. S.; Valsaraj, K. T.; Anastasio, C.

    2013-12-01

    Vegetation emits volatile oxygenated hydrocarbons - the green leaf volatiles (GLVs) - which are formed from the biochemical conversion of linoleic and linolenic acids within plant cells. Stress or damage to vegetation can significantly elevate emission fluxes of these compounds, some of which are fairly water soluble. Aqueous-phase reactions of the GLVs with photochemically generated oxidants - such as hydroxyl radical (OH), singlet oxygen (1O2) and excited triplet states of organic compounds (3C*) _ might then form low-volatility products that can act as secondary organic aerosol (SOA). In order to determine if GLVs can be a significant source of secondary organic carbon in fogwater, studies of GLVs in laboratory solutions are needed to elucidate the oxidation kinetics and the corresponding SOA mass yields. In this study we are determining the second-order rate constants, and SOA mass yields, for five GLVs (cis-3-hexen-1-ol, cis-3-hexenylacetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol) reacting with OH,1O2 and 3C*. Experiments are performed at relevant fog water pHs, temperatures, and oxidant concentrations. Rate constants are determined using a relative rate approach in which the decay of GLVs and reference compounds are monitored as function of time by HPLC. The capacity of GLVs to form aqueous SOA was determined by following the formation of their decomposition products with HPLC-UV/DAD and HPLC-ESI/MS. SOA mass yields are measured gravimetrically from laboratory solutions containing atmospherically relevant concentrations of photooxidants and GLVs, and irradiated with simulated sunlight. We will use our results to assess the potential contribution of aqueous GLV reactions as a source of SOA in cloudy or foggy atmospheres.

  7. Partitioning of Semivolatile Organic Compounds in the Presence of a Secondary Organic Aerosol in a Controlled Atmosphere

    Microsoft Academic Search

    Keri B. Leach; Richard M. Kamens; Michael R. Strommen; Myoseon Jang

    1999-01-01

    The gas-particle partitioning of select semivolatile organic compounds (SOCs) was studied by injecting the SOCs into a 190 m3 Teflon film chamber containing a secondary organic aerosol (SOA) generated by volatilizing liquid a-pinene into an ozone-concentrated atmosphere. The concentration of total suspended particulates (TSP) and gas and particle-phase SOCs was measured over the course of three experiments spanning a temperature

  8. Effect of relative humidity on soot - secondary organic aerosol mixing: A case study from the Soot Aerosol Aging Study (PNNL-SAAS)

    NASA Astrophysics Data System (ADS)

    Sharma, N.; China, S.; Zaveri, R. A.; Shilling, J. E.; Pekour, M. S.; Liu, S.; Aiken, A. C.; Dubey, M. K.; Wilson, J. M.; Zelenyuk, A.; OBrien, R. E.; Moffet, R.; Gilles, M. K.; Gourihar, K.; Chand, D.; Sedlacek, A. J., III; Subramanian, R.; Onasch, T. B.; Laskin, A.; Mazzoleni, C.

    2014-12-01

    Atmospheric processing of fresh soot particles emitted by anthropogenic as well as natural sources alters their physical and chemical properties. For example, fresh and aged soot particles interact differently with incident solar radiation, resulting in different overall radiation budgets. Varying atmospheric chemical and meteorological conditions can result in complex soot mixing states. The Soot Aerosol Aging Study (SAAS) was conducted at the Pacific Northwest National Laboratory in November 2013 and January 2014 as a step towards understanding the evolution of mixing state of soot and its impact on climate-relevant properties. Aging experiments on diesel soot were carried out in a controlled laboratory chamber, and the effects of condensation and coagulation processes were systematically explored in separate sets of experiments. In addition to online measurement of aerosol properties, aerosol samples were collected for offline single particle analysis to investigate the evolution of the morphology, elemental composition and fine structure of sample particles from different experiments. Condensation experiments focused on the formation of ?-pinene secondary organic aerosol on diesel soot aerosol seeds. Experiments were conducted to study the aging of soot under dry (RH < 2%) and humid conditions (RH ~ 80%). We present an analysis of the morphology of soot, its evolution, and its correlation with optical properties, as the condensation of ?-pinene SOA is carried out for the two different RH conditions. The analysis was performed by using scanning electron microscopy, transmission electron microscopy, scanning transmission x-ray microscopy and atomic force microscopy for single particle characterization. In addition, particle size, mass, composition, shape, and density were characterized in-situ, as a function of organics condensed on soot seeds, using single particle mass spectrometer.

  9. Gaseous products and Secondary Organic Aerosol formation during long term oxidation of isoprene and methacrolein

    NASA Astrophysics Data System (ADS)

    Brégonzio-Rozier, L.; Siekmann, F.; Giorio, C.; Pangui, E.; Morales, S. B.; Temime-Roussel, B.; Gratien, A.; Michoud, V.; Ravier, S.; Tapparo, A.; Monod, A.; Doussin, J.-F.

    2014-09-01

    First- and higher-generation products from the oxidation of isoprene and methacrolein with OH radicals in the presence of NOx have been studied in a simulation chamber: (1) significant oxidation rates have been maintained for up to 7 h allowing the study of highly oxidized products, (2) gas-phase products distribution and yields are provided, and show good agreement with previous studies. Secondary organic aerosol (SOA) formation resulting from these experiments has also been investigated. Among the general dispersion exhibited by SOA mass yields from previous studies, the mass yields obtained here were consistent with the lowest values found in the literature, and more specifically in agreement with studies carried out with natural light or artificial lamps with emission spectrum similar to the solar one. An effect of light source is hence proposed to explain, at least in part, the discrepancies observed between different studies in the literature for both isoprene- and methacrolein-SOA mass yields. A high degree of similarity is shown in the comparison of SOA mass spectra from isoprene and methacrolein photooxidation, thus strengthening the importance of the role of methacrolein in SOA formation from isoprene photooxidation under our experimental conditions (i.e. presence of NOx and long term oxidation). Overall, if these results are further confirmed, SOA mass yields from both isoprene and methacrolein in the atmosphere could be lower than suggested by most of the current chamber studies.

  10. Chemical and Physical Approaches to Probing the Phase of Secondary Organic Aerosol (Invited)

    NASA Astrophysics Data System (ADS)

    Finlayson-Pitts, B. J.; Perraud, V. M.; Waring-Kidd, C.

    2013-12-01

    The viscosity and phase of secondary organic aerosol (SOA) are critical parameters for accurately predicting the growth of nuclei into the size range effective for light scattering and for altering cloud properties and lifetimes. Until relatively recently, it had been assumed that SOA was a liquid for which diffusion was sufficiently fast that quasi-equilibrium with the gas phase at the surface could be assumed. As a result, most models of SOA growth incorporated this assumption. However, discrepancies between model predicted SOA and field measurements suggested that there were either missing sources or incomplete model assumptions. A number of laboratory and field studies have now provided evidence that SOA may, at least under some circumstances, be a relatively high viscosity material that is better described as a semi-solid or amorphous tar-like substance. In this case, quasi-equilibrium does not apply and a kinetically-controlled, condensation type of mechanism may be more appropriate to describe SOA growth. We will describe the results of two types of laboratory approaches to probe SOA phase: (1) probing exchange between the gas phase and SOA using chemical markers, and (2) studying the impaction behavior of SOA in a custom-designed impactor. The implications for models of SOA growth will be presented.

  11. Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol.

    PubMed

    Mang, Stephen A; Henricksen, Dana K; Bateman, Adam P; Andersen, Mads P Sulbaek; Blake, Donald R; Nizkorodov, Sergey A

    2008-09-11

    The photodegradation of secondary organic aerosol (SOA) material by actinic UV radiation was investigated. SOA was generated via the dark reaction of ozone and d-limonene, collected onto quartz-fiber filters, and exposed to wavelength-tunable radiation. Photochemical production of CO was monitored in situ by infrared cavity ring-down spectroscopy. A number of additional gas-phase products of SOA photodegradation were observed by gas chromatography, including methane, ethene, acetaldehyde, acetone, methanol, and 1-butene. The absorption spectrum of SOA material collected onto CaF2 windows was measured and compared with the photolysis action spectrum for the release of CO, a marker for Norrish type-I photocleavage of carbonyls. Both spectra had a band at approximately 300 nm corresponding to the overlapping n --> pi* transitions in nonconjugated carbonyls. The effective extinction coefficient of freshly prepared SOA was estimated to be on the order of 15 L mol(-1) cm(-1) at 300 nm, implying one carbonyl group in every SOA constituent. The absorption by the SOA material slowly increased in the visible and near-UV during storage of SOA in open air in the dark, presumably as a result of condensation reactions that increased the degree of conjugation in the SOA constituents. These observations suggest that photolysis of carbonyl functional groups represents a significant sink for monoterpene SOA compounds in the troposphere, with an estimated lifetime of several hours over the continental United States. PMID:18700731

  12. Impact of propene on secondary organic aerosol formation from m-xylene.

    PubMed

    Song, Chen; Na, Kwangsam; Warren, Bethany; Malloy, Quentin; Cocker, David R

    2007-10-15

    Propene is widely used in smog chamber experiments to increase the hydroxyl radical (OH) level based on the assumption that the formation of secondary organic aerosol (SOA) from parent hydrocarbon is unaffected. A series of m-xylene/NO(x) photooxidation experiments were conducted in the presence of propene in the University of California CE-CERT atmospheric chamber facility. The experimental data are compared with previous m-xylene/N0(x) photooxidation work performed in the same chamber facility in the absence of propene (Song et al. Environ. Sci. Technol. 2005, 39, 3143-3149). The result shows that, for similar initial conditions, experiments with propene have lower reaction rates of m-xylene than those without propene, which indicates that propene reduces OH in the system. Furthermore, experiments with propene showed more than 15% reduction in SOA yield compared to experiments in the absence of propene. Additional experiments of m-xylene/ NO(x) with CO showed similar trends of suppressing OH and SOA formation. These results indicate that SOA from m-xylene/NO(x) photooxidation is strongly dependent on the OH level present, which provides evidence for the critical role of OH in SOA formation from aromatic hydrocarbons. PMID:17993138

  13. Secondary organic aerosol production from terpene ozonolysis. 1. Effect of UV radiation.

    PubMed

    Presto, Albert A; Hartz, Kara E Huff; Donahue, Neil M

    2005-09-15

    We report secondary organic aerosol (SOA) yields from the ozonolysis of alpha-pinene under both dark and UV-illuminated conditions. Exposure to UV light reduces SOA yield by 20-40%, with a maximum reduction in yield coinciding with a minimum in the amount of terpene consumed (15-30 ppb). The data are consistent with a constant absolute reduction in the yield of approximately 0.03. Gas chromatography mass spectrometry analysis of filter samples indicates that the major products found in alpha-pinene SOA include organic acids (e.g., pinic acid), keto acids (e.g., pinonic acid), and hydroxy keto acids (e.g., 10-hydroxypinonic acid). Analysis of filter-based results suggests that yield reduction is a result of the formation of a more volatile product distribution when experiments are conducted in the presence of UV light. These results implythat previous "dark bag" experiments may overestimate SOA generation from monoterpenes and also that SOA generation in the atmosphere may depend significantly on actinic flux. PMID:16201627

  14. A chamber study of secondary organic aerosol formation by linalool ozonolysis

    NASA Astrophysics Data System (ADS)

    Chen, Xi; Hopke, Philip K.

    The formation of secondary organic aerosol (SOA) produced from linalool ozonolysis was examined using a dynamic chamber system that allowed the simulation of ventilated indoor environments. Experiments were conducted under room temperature (22-23 °C) and air exchange rate of 0.67 h -1. An effort was made to maintain the product of the concentrations of the two reagents constant. The results suggest that under the conditions when the product of the two reagent concentrations was constant, the relative concentrations play an important role in determining the total SOA formed. A combination of concentrations somewhere in ozone limiting region will produce the maximum SOA concentration. The measured reactive oxygen species (ROS) concentrations at linalool and ozone concentrations relevant to prevailing indoor concentrations ranged from 0.71 to 2.53 nmol m -3 equivalents of H 2O 2. It was found that particle samples aged for 24 h lost a significant fraction of the ROS compared to fresh samples. The residual ROS concentrations were around 15-69%. Compared with other terpene species like ?-pinene that has one endocyclic unsaturated carbon bond, linalool was less efficient in potential SOA formation yields.

  15. Effect of bark beetle infestation on secondary organic aerosol precursor emissions.

    PubMed

    Amin, Hardik; Atkins, P Tyson; Russo, Rachel S; Brown, Aaron W; Sive, Barkley; Hallar, A Gannet; Huff Hartz, Kara E

    2012-06-01

    Bark beetles are a potentially destructive force in forest ecosystems; however, it is not known how insect attacks affect the atmosphere. The emissions of volatile organic compounds (VOCs) were sampled i.) from bark beetle infested and healthy lodgepole pine (Pinus contorta var. latifolia) trees and ii.) from sites with and without active mountain pine beetle infestation. The emissions from the trunk and the canopy were collected via sorbent traps. After collection, the sorbent traps were extracted with hexane, and the extracts were separated and detected using gas chromatography/mass spectroscopy. Canister samples were also collected and analyzed by a multicolumn gas chromatographic system. The samples from bark beetle infested lodgepole pine trees suggest a 5- to 20-fold enhancement in total VOCs emissions. Furthermore, increases in the ?-phellandrene emissions correlated with bark beetle infestation. A shift in the type and the quantity of VOC emissions can be used to identify bark beetle infestation but, more importantly, can lead to increases in secondary organic aerosol from these forests as potent SOA precursors are produced. PMID:22545866

  16. Effects of NOx on the volatility of secondary organic aerosol from isoprene photooxidation.

    PubMed

    Xu, Lu; Kollman, Matthew S; Song, Chen; Shilling, John E; Ng, Nga L

    2014-02-18

    The effects of NOx on the volatility of the secondary organic aerosol (SOA) formed from isoprene photooxidation are investigated in environmental chamber experiments. Two types of experiments are performed. In HO2-dominant experiments, organic peroxy radicals (RO2) primarily react with HO2. In mixed experiments, RO2 reacts through multiple pathways, including with NO, NO2, and HO2. The volatility and oxidation state of isoprene SOA are sensitive to and exhibit a nonlinear dependence on NOx levels. Depending on the NOx levels, the SOA formed in mixed experiments can be of similar or lower volatility compared to that formed in HO2-dominant experiments. The dependence of SOA yield, volatility, and oxidation state on the NOx level likely arises from gas-phase RO2 chemistry and succeeding particle-phase oligomerization reactions. The NOx level also plays a strong role in SOA aging. While the volatility of SOA in mixed experiments does not change substantially over time, SOA becomes less volatile and more oxidized as oxidation progresses in HO2-dominant experiments. PMID:24471688

  17. Modeling the multiday evolution and aging of secondary organic aerosol during MILAGRO 2006.

    PubMed

    Dzepina, Katja; Cappa, Christopher D; Volkamer, Rainer M; Madronich, Sasha; Decarlo, Peter F; Zaveri, Rahul A; Jimenez, Jose L

    2011-04-15

    In this study, we apply several recently proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at an altitude of ?3.5 km during three days of aging, in a way that is directly comparable to simulations in regional and global models. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) when using a non-aging SOA parameterization cannot explain the observed SOA concentrations in aged pollution, despite the increasing importance of the low-NO(x) channel. However, when using an aging SOA parameterization, V-SOA alone is similar to the regional aircraft observations, highlighting the wide diversity in current V-SOA formulations. When the SOA formed from oxidation of semivolatile and intermediate volatility organic vapors (SI-SOA) is computed following Robinson et al. (2007) the model matches the observed SOA mass, but its O/C is ?2× too low. With the parameterization of Grieshop et al. (2009), the total SOA mass is ?2× too high, but O/C and volatility are closer to the observations. Heating or dilution cause the evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs dilution. Lifting of the airmass to the free-troposphere during dry convection substantially increases SOA by condensation of semivolatile vapors; this effect is reduced by aging. PMID:21425791

  18. Effect of photolysis on secondary organic aerosol (SOA) formation and lifetime

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Madronich, S.; Kasibhatla, P. S.; Aumont, B.

    2014-12-01

    We investigate the effect of potentially important, but hitherto unexplored, gas- and particle-phase photolysis reactions on the lifetime and budgets of SOA. Recent laboratory studies showed that freshly formed SOA from e.g. monoterpenes have a lifetime of a few hours when exposed to UV radiation both in dry particles and aqueous solutions, suggesting that photolytic processing of secondary organic vapors and particles could be removing aerosols from the troposphere on timescales comparable to those of wet deposition. Photolytic reactions lead to fragmentation of molecules, changes in their properties (e.g. volatility, solubility, photo-bleaching) and thus their ability to form SOA or remain in the particle phase. These reactions are currently not included in 3D models, and as we are using more and more explicit SOA mechanisms in 3D models this issue comes to the forefront. Here, we use an explicit chemical model to estimate the effect of gas-phase photolysis on SOA formation for various precursors (biogenic and anthropogenic mixtures) and environments (low-, high-NOx). By comparison with laboratory studies, we estimate the relative importance of gas- vs. particle phase photolysis. This understanding is then parameterized within a global chemistry model to assess the potential effect on the SOA global budgets. The results confirm that photolytic reactions are an important loss process, which competes with the wet removal, but has however very different temporal and spatial patterns.

  19. Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons

    NASA Astrophysics Data System (ADS)

    Takekawa, Hideto; Minoura, Hiroaki; Yamazaki, Satoshi

    Photo-oxidation experiments on hydrocarbons were performed with a temperature-controlled smog chamber to study the temperature dependence of secondary organic aerosol (SOA) formation. A higher SOA yield was obtained at lower temperature and with a higher concentration of SOA generated. The relationship of SOA yield to temperature and SOA concentration is expressed by a gas/particle partitioning absorption model considered with temperature dependence. Under the condition of the same SOA concentration, the SOA yield at 283 K was approximately twice that at 303 K. It has been clarified experimentally that temperature is one of the most important factors in SOA formation. The experiments were performed not only with three aromatic hydrocarbons (toluene, m-xylene and 1,2,4-trimethylbenzene) and one biogenic alkene ( ?-pinene), but also with one alkane (n-undecane) on which few experiments for SOA formation have been performed. n-Undecane indicates a lower SOA yield than any other hydrocarbon investigated in this study.

  20. Heterogeneous chemistry of glyoxal on acidic solutions. An oligomerization pathway for secondary organic aerosol formation.

    PubMed

    Gomez, Mario E; Lin, Yun; Guo, Song; Zhang, Renyi

    2015-05-14

    The heterogeneous chemistry of glyoxal on sulfuric acid surfaces has been investigated at various acid concentrations and temperatures, utilizing a low-pressure fast flow laminar reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS). The uptake coefficient (?) of glyoxal ranges from (1.2 ± 0.06) × 10(-2) to (2.5 ± 0.01) × 10(-3) for 60-93 wt % H2SO4 at 253-273 K. The effective Henry's Law constant (H*) ranges from (98.9 ± 4.9) × 10(5) to (1.6 ± 0.1) × 10(5) M atm(-1) for 60-93 wt % at 263-273 K. Both the uptake coefficient and Henry's Law constant increase with decreasing acid concentration and temperature. Our results reveal a reaction mechanism of hydration followed by oligomerization for glyoxal on acidic media, indicating an efficient aqueous reaction of glyoxal on hygroscopic particles leading to secondary organic aerosol formation. PMID:25369518

  1. The heterogeneous OH oxidation of palmitic acid in single component and internally mixed aerosol particles: vaporization, secondary chemistry, and the role of particle phase

    Microsoft Academic Search

    V. F. McNeill; R. L. N. Yatavelli; J. A. Thornton; C. B. Stipe; O. Landgrebe

    2008-01-01

    We studied the OH oxidation of submicron aerosol particles consisting of pure palmitic acid (PA) or thin (near monolayer) coatings of PA on aqueous and effloresced inorganic salt particles. Experiments were performed as a function of particle size and OH exposure using a continuous-flow photochemical reaction chamber coupled to a chemical ionization mass spectrometer (CIMS) system, for detection of gas

  2. Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere.

    PubMed

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

    2015-07-21

    Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate 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 through 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-?-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 cold via H-abstraction by OH do not decompose to HMML, even if they are structurally identical to the MPAN-OH adduct. The SOA formation from HMML, from polyaddition of the lactone to organic compounds at the particle interface or in the condensed phase, is close to unity under dry conditions. However, the SOA yield is sensitive to particle liquid water and solvated ions. In hydrated inorganic particles, HMML reacts primarily with H2O to produce the monomeric 2-methylglyceric acid (2MGA) or with aqueous sulfate and nitrate to produce the associated organosulfate and organonitrate, respectively. 2MGA, a tracer for isoprene SOA, is semivolatile and its accommodation in aerosol water decreases with decreasing pH. Conditions that enhance the production of neutral 2MGA suppress SOA mass from the HMML channel. Considering the liquid water content and pH ranges of ambient particles, 2MGA will exist largely as a gaseous compound in some parts of the atmosphere. PMID:26095764

  3. Reactive Uptake of Ammonia to Secondary Organic Aerosols: Kinetics of Organonitrogen Formation

    NASA Astrophysics Data System (ADS)

    Liu, Yongchun; Liggio, John; Staebler, Ralf; Li, Shao-Meng

    2015-04-01

    Organonitrogen compounds originating from the heterogeneous uptake of NH3 or amines by secondary organic aerosol (SOA) has received significant attention recently. This is primarily due to its potential contribution to brown carbon (BrC), which can absorb solar radiation and affect climate. In addition, particle phase Organonitrogen species may represent a means of altering regional nitrogen cycles and/or nitrogen deposition patterns though the sequestering of ambient ammonia which is ultimately deposited downwind. Several reduced nitrogen forming heterogeneous reactions have previously been proposed, including Schiff base and/or Mannich reactions between NH3, ammonium salts or amines and organic carbonyl functional groups in particles. In order to assess and model the possible impact of Schiff base, Mannich or other N-forming reactions (via NH3) on the radiative forcing ability of ambient SOA and/or its impact on N-deposition, the kinetics of such heterogeneous reactions are required, and yet remain largely unknown. In the current study, the uptake kinetics of NH3 to form organonitrogen compounds in SOA derived from the ozonolysis of ?-pinene and the OH oxidation of m-xylene is reported for the first time from experiments performed in a 9 m3 smog chamber equipped with a High Resolution Time-of-Flight Aerosol Mass Spectrometer. The results demonstrate that particle bound organonitrogen compounds are mainly formed by NH3 uptake onto newly formed SOA (~1 hr), but relatively little onto more aged SOA. The uptake coefficients of NH3 to form organonitrogen compounds (between 0-150 min) are on the order of 10-4-10-3 and are prominently dependent upon particle acidity. Following 6 hours of reaction, the total organonitrogen mass contributed up to 10.0±1.5 wt% and 31.5±4.4 wt% to the total SOA mass from the ozonolysis of ?-pinene and OH oxidation of m-xylene. The influence of VOC precursors, seed particle acidity and gaseous NH3 concentration on the obtained uptake coefficients is described. The implications of the kinetics on atmospheric BrC and N-deposition are also discussed.

  4. Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

    NASA Astrophysics Data System (ADS)

    Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

    2014-05-01

    Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices, including diesel particulate filters (DPFs), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOCs). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle,~Urban Dynamometer Driving Schedule, and creep + idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photooxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary PM emissions and SOA production from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after 3 h of oxidation at typical urban VOC / NOx ratios (3 : 1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the nonmethane organic gas emissions that could not be speciated using traditional one-dimensional gas chromatography. The unspeciated organics - likely comprising less volatile species such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep + idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

  5. Gas-phase products and secondary organic aerosol formation from the ozonolysis and photooxidation of myrcene

    NASA Astrophysics Data System (ADS)

    Böge, Olaf; Mutzel, Anke; Iinuma, Yoshiteru; Yli-Pirilä, Pasi; Kahnt, Ariane; Joutsensaari, Jorma; Herrmann, Hartmut

    2013-11-01

    In this study, the ozone and OH-radical reactions of myrcene were investigated in an aerosol chamber (at 292-295 K and 50% relative humidity) to examine the gas-phase oxidation products and secondary organic aerosol (SOA) formation. The ozone reaction studies were performed in the presence and absence of CO, which serves as an OH radical scavenger. In the photooxidation experiments OH radicals were generated by photolysis of methyl nitrite. The ozonolysis of myrcene in the presence of CO resulted in a substantial yield of 4-vinyl-4-pentenal (55.3%), measured as m/z 111 plus m/z 93 using proton transfer reaction-mass spectrometry (PTR-MS) and confirmed unambiguously as C7H10O by denuder measurements and HPLC/ESI-TOFMS analysis of its 2,4-dinitrophenylhydrazine (DNPH) derivative. Additionally, the formation of two different organic dicarbonyls with m/z 113 and a molecular formula of C6H8O2 were observed (2.1%). The yields of these dicarbonyls were higher in the ozonolysis experiments without an OH scavenger (5.4%) and even higher (13.8%) in the myrcene OH radical reaction. The formation of hydroxyacetone as a direct product of the myrcene reaction with ozone with a molar yield of 17.6% was also observed. The particle size distribution and volume concentrations were monitored and facilitated the calculation of SOA yields, which ranged from 0 to 0.01 (ozonolysis in the presence of CO) to 0.39 (myrcene OH radical reaction). Terpenylic acid was found in the SOA samples collected from the ozonolysis of myrcene in the absence of an OH scavenger and the OH radical-initiated reaction of myrcene but not in samples collected from the ozonolysis in the presence of CO as an OH radical scavenger, suggesting that terpenylic acid formation involves the reaction of myrcene with an OH radical. A reaction mechanism describing the formation of terpenylic acid is proposed.

  6. Functional group composition of organic aerosol from combustion emissions and secondary processes at two contrasted urban environments

    NASA Astrophysics Data System (ADS)

    El Haddad, Imad; Marchand, Nicolas; D'Anna, Barbara; Jaffrezo, Jean Luc; Wortham, Henri

    2013-08-01

    The quantification of major functional groups in atmospheric organic aerosol (OA) provides a constraint on the types of compounds emitted and formed in atmospheric conditions. This paper presents functional group composition of organic aerosol from two contrasted urban environments: Marseille during summer and Grenoble during winter. Functional groups were determined using a tandem mass spectrometry approach, enabling the quantification of carboxylic (RCOOH), carbonyl (RCOR?), and nitro (RNO2) functional groups. Using a multiple regression analysis, absolute concentrations of functional groups were combined with those of organic carbon derived from different sources in order to infer the functional group contents of different organic aerosol fractions. These fractions include fossil fuel combustion emissions, biomass burning emissions and secondary organic aerosol (SOA). Results clearly highlight the differences between functional group fingerprints of primary and secondary OA fractions. OA emitted from primary sources is found to be moderately functionalized, as about 20 carbons per 1000 bear one of the functional groups determined here, whereas SOA is much more functionalized, as in average 94 carbons per 1000 bear a functional group under study. Aging processes appear to increase both RCOOH and RCOR? functional group contents by nearly one order of magnitude. Conversely, RNO2 content is found to decrease with photochemical processes. Finally, our results also suggest that other functional groups significantly contribute to biomass smoke and SOA. In particular, for SOA, the overall oxygen content, assessed using aerosol mass spectrometer measurements by an O:C ratio of 0.63, is significantly higher than the apparent O:C* ratio of 0.17 estimated based on functional groups measured here. A thorough examination of our data suggests that this remaining unexplained oxygen content can be most probably assigned to alcohol (ROH), organic peroxides (ROOH), organonitrates (RONO2) and/or organosulfates (ROSO3H).

  7. Emissions of black carbon, organic, and inorganic aerosols from biomass burning in North America and Asia in 2008

    E-print Network

    Jimenez, Jose-Luis

    assessment of the impact of aerosols emitted from boreal forest fires on the Arctic climate necessitates on the laserinduced incandescence technique on board the DC8 aircraft during the NASA ARCTAS campaign. Aircraft

  8. Secondary organic aerosol formation from low-NO(x) photooxidation of dodecane: evolution of multigeneration gas-phase chemistry and aerosol composition.

    PubMed

    Yee, Lindsay D; Craven, Jill S; Loza, Christine L; Schilling, Katherine A; Ng, Nga Lee; Canagaratna, Manjula R; Ziemann, Paul J; Flagan, Richard C; Seinfeld, John H

    2012-06-21

    The extended photooxidation of and secondary organic aerosol (SOA) formation from dodecane (C(12)H(26)) under low-NO(x) conditions, such that RO(2) + HO(2) chemistry dominates the fate of the peroxy radicals, is studied in the Caltech Environmental Chamber based on simultaneous gas and particle-phase measurements. A mechanism simulation indicates that greater than 67% of the initial carbon ends up as fourth and higher generation products after 10 h of reaction, and simulated trends for seven species are supported by gas-phase measurements. A characteristic set of hydroperoxide gas-phase products are formed under these low-NO(x) conditions. Production of semivolatile hydroperoxide species within three generations of chemistry is consistent with observed initial aerosol growth. Continued gas-phase oxidation of these semivolatile species produces multifunctional low volatility compounds. This study elucidates the complex evolution of the gas-phase photooxidation chemistry and subsequent SOA formation through a novel approach comparing molecular level information from a chemical ionization mass spectrometer (CIMS) and high m/z ion fragments from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Combination of these techniques reveals that particle-phase chemistry leading to peroxyhemiacetal formation is the likely mechanism by which these species are incorporated in the particle phase. The current findings are relevant toward understanding atmospheric SOA formation and aging from the "unresolved complex mixture," comprising, in part, long-chain alkanes. PMID:22424261

  9. Model analysis of secondary organic aerosol formation by glyoxal in laboratory studies: the case for photoenhanced chemistry.

    PubMed

    Sumner, Andrew J; Woo, Joseph L; McNeill, V Faye

    2014-10-21

    The reactive uptake of glyoxal by atmospheric aerosols is believed to be a significant source of secondary organic aerosol (SOA). Several recent laboratory studies have been performed with the goal of characterizing this process, but questions remain regarding the effects of photochemistry on SOA growth. We applied GAMMA (McNeill et al. Environ. Sci. Technol. 2012, 46, 8075-8081), a photochemical box model with coupled gas-phase and detailed aqueous aerosol-phase chemistry, to simulate aerosol chamber studies of SOA formation by the uptake of glyoxal by wet aerosol under dark and irradiated conditions (Kroll et al. J. Geophys. Res. 2005, 110 (D23), 1-10; Volkamer et al. Atmos. Chem. Phys. 2009, 9, 1907-1928; Galloway et al. Atmos. Chem. Phys. 2009, 9, 3331- 306 3345 and Geophys. Res. Lett. 2011, 38, L17811). We find close agreement between simulated SOA growth and the results of experiments conducted under dark conditions using values of the effective Henry's Law constant of 1.3-5.5 × 10(7) M atm(-1). While irradiated conditions led to the production of some organic acids, organosulfates, and other oxidation products via well-established photochemical mechanisms, these additional product species contribute negligible aerosol mass compared to the dark uptake of glyoxal. Simulated results for irradiated experiments therefore fell short of the reported SOA mass yield by up to 92%. This suggests a significant light-dependent SOA formation mechanism that is not currently accounted for by known bulk photochemistry, consistent with recent laboratory observations of SOA production via photosensitizer chemistry. PMID:25226456

  10. Observations of Secondary Organic Aerosol Production and Soot Aging under Atmospheric Conditions Using a Novel Environmental Aerosol Chamber 

    E-print Network

    Glen, Crystal

    2012-02-14

    carcinogenic materials (Dockery et al. 1993). ____________ This dissertation follows the style of Aerosol Science and Technology. 2 SOA is primarily formed by the vapor condensation of lower volatility products through volatile organic compound (VOC... compounds are present in the atmosphere (Goldstein and Galbally 2007). The uncertainty surrounding the atmospheric organic loading is amplified by the fact that each VOC may undergo numerous reactions involving pathways which produce a wide variety...

  11. Complex refractive indices in the near-ultraviolet spectral region of biogenic secondary organic aerosol aged with ammonia.

    PubMed

    Flores, J M; Washenfelder, R A; Adler, G; Lee, H J; Segev, L; Laskin, J; Laskin, A; Nizkorodov, S A; Brown, S S; Rudich, Y

    2014-06-14

    Atmospheric absorption by brown carbon aerosol may play an important role in global radiative forcing. Brown carbon arises from both primary and secondary sources, but the mechanisms and reactions of the latter are highly uncertain. One proposed mechanism is the reaction of ammonia or amino acids with carbonyl products in secondary organic aerosol (SOA). We generated SOA in situ by reacting biogenic alkenes (?-pinene, limonene, and ?-humulene) with excess ozone, humidifying the resulting aerosol, and reacting the humidified aerosol with gaseous ammonia. We determined the complex refractive indices (RI) in the 360-420 nm range for these aerosols using broadband cavity enhanced spectroscopy (BBCES). The average real part (n) of the measured spectral range of the NH3-aged ?-pinene SOA increased from n = 1.50 (±0.01) for the unreacted SOA to n = 1.57 (±0.01) after 1.5 h of exposure to 1.9 ppm NH3, whereas the imaginary component (k) remained below k < 0.001((+0.002)(-0.001)). For the limonene and ?-humulene SOA the real part did not change significantly, and we observed a small change in the imaginary component of the RI. The imaginary component increased from k = 0.000 to an average k = 0.029 (±0.021) for ?-humulene SOA, and from k < 0.001((+0.002)(-0.001)) to an average k = 0.032 (±0.019) for limonene SOA after 1.5 h of exposure to 1.3 and 1.9 ppm of NH3, respectively. Collected filter samples of the aged and unreacted ?-pinene SOA and limonene SOA were analyzed off-line by nanospray desorption electrospray ionization high resolution mass spectrometry (nano-DESI/HR-MS), and in situ using a Time-of-Flight Aerosol Mass Spectrometer (ToF-AMS), confirming that the SOA reacted and that various nitrogen-containing reaction products formed. If we assume that NH3 aging reactions scale linearly with time and concentration, which will not necessarily be the case in the atmosphere, then a 1.5 h reaction with 1 ppm NH3 in the laboratory is equivalent to 24 h reaction with 63 ppbv NH3, indicating that the observed aerosol absorption will be limited to atmospheric regions with high NH3 concentrations. PMID:24752662

  12. High-Resolution Electrospray Ionization Mass Spectrometry Analysis of Water Soluble Organic Aerosols Collected with a Particle into Liquid Sampler

    Microsoft Academic Search

    Adam P. Bateman; Sergey A. Nizkorodov; Julia Laskin; Alexander Laskin

    2010-01-01

    This work demonstrates the utility of a particle-into-liquid sampler (PILS) a technique traditionally used for identification of inorganic ions present in ambient or laboratory aerosols for the analysis of water soluble organic aerosol (OA) using high resolution electrospray ionization mass spectrometry (HR ESI-MS). Secondary organic aerosol (SOA) was produced from 0.5 ppm mixing ratios of limonene and ozone in a

  13. Influence Of Aerosol Water In The Organic Phase On The Mass, Properties And Source Apportionment Of Secondary Organic Aerosol In A Source-Oriented Model

    NASA Astrophysics Data System (ADS)

    Jathar, S.; Mahmud, A. A.; Pankow, J.; Kleeman, M.

    2013-12-01

    Secondary organic aerosol (SOA) is hygroscopic meaning that water partitions into the organic phase to a degree determined by the organic chemical composition and the ambient relative humidity. In addition to contributing to the SOA mass, the absorbed water also alters the mean molecular weight of the organic phase and the activity coefficients of SOA's constituent compounds, which in turn influences SOA's gas-particle partitioning. Classical SOA treatment in aerosol transport models does not account for water uptake and its subsequent impacts. In this work, we use the UCD/CIT source-oriented air quality model to simulate water uptake by OA on source-oriented particle types and assess its influence on the mass, properties and source-apportionment of SOA. The model is run for a summer month over two distinct regions: California and the Southeast United States. Internally mixed aerosol calculations predict partitioning of water into the condensed organic phase when the relative humidity is higher than 60%. Daily-averaged organic water concentrations are approximately ~0.5 ?g m-3 under typical conditions but depend strongly on relative humidity. On average, the model predicts a 100% increase in the combined SOA-water mass for every 10% increase in relative humidity above 60%. The water in the organic phase is sufficient to substantially change the mean molecular weight of the SOA-water mixture and the activity coefficients of the SOA constituents to push gas-particle equilibrium towards the particle phase. For simplicity, POA (being hydrophobic) and SOA (being hydrophilic) are treated as separate phases. Externally mixed aerosol calculations predict similar levels of particle water and SOA enhancement because the functional characteristics of the POA emitted from different sources does not yet influence SOA formation on those particles. Each externally mixed particle type therefore develops similar SOA composition. Tests of water uptake into the organic phase on the solubility of POA and SOA and composition of POA as a result of atmospheric aging are ongoing.

  14. The impact of recirculation, ventilation and filters on secondary organic aerosols generated by indoor chemistry

    NASA Astrophysics Data System (ADS)

    Fadeyi, M. O.; Weschler, C. J.; Tham, K. W.

    This study examined the impact of recirculation rates (7 and 14 h -1), ventilation rates (1 and 2 h -1), and filtration on secondary organic aerosols (SOAs) generated by ozone of outdoor origin reacting with limonene of indoor origin. Experiments were conducted within a recirculating air handling system that serviced an unoccupied, 236 m 3 environmental chamber configured to simulate an office; either no filter, a new filter or a used filter was located downstream of where outdoor air mixed with return air. For otherwise comparable conditions, the SOA number and mass concentrations at a recirculation rate of 14 h -1 were significantly smaller than at a recirculation rate of 7 h -1. This was due primarily to lower ozone concentrations, resulting from increased surface removal, at the higher recirculation rate. Increased ventilation increased outdoor-to-indoor transport of ozone, but this was more than offset by the increased dilution of SOA derived from ozone-initiated chemistry. The presence of a particle filter (new or used) strikingly lowered SOA number and mass concentrations compared with conditions when no filter was present. Even though the particle filter in this study had only 35% single-pass removal efficiency for 100 nm particles, filtration efficiency was greatly amplified by recirculation. SOA particle levels were reduced to an even greater extent when an activated carbon filter was in the system, due to ozone removal by the carbon filter. These findings improve our understanding of the influence of commonly employed energy saving procedures on occupant exposures to ozone and ozone-derived SOA.

  15. Quantifying the ionic reaction channels in the Secondary Organic Aerosol formation from glyoxal

    NASA Astrophysics Data System (ADS)

    Maxut, Aurelia; Nozière, Barbara; Rossignol, Stéphanie; George, Christian; Waxman, Eleanor Marie; Laskin, Alexander; Slowik, Jay; Dommen, Josef; Prévôt, André; Baltensperger, Urs; Volkamer, Rainer

    2014-05-01

    Glyoxal, a common organic gas in the atmosphere, has been identified in recent years as an important Secondary Organic Aerosol (SOA) precursor (Volkamer et al., 2007). But, unlike with other precursors, the SOA is largely produced by particle-phase reactions (Volkamer et al., 2009) and equilibria (Kampf et al. 2013) that are still not entirely characterized. Since 2009 series of smog chamber experiments have been performed within the Eurochamp program at the Paul Scherrer Institute, Switzerland, to investigate SOA formation from glyoxal. In these experiments, glyoxal was produced by the gas-phase oxidation of acetylene in the presence of seeds, the seed composition and other conditions being varied. The 2011 campaign resulted in the identification of salting processes controlling the glyoxal partitioning in the seeds (Kampf et al. 2013). This presentation will report results of the 2013 campaign focusing on the identification of the various reactions (ionic or photo-induced) contributing to the SOA mass. In particular, the contribution of the ionic reactions, i.e. mediated by NH4+, were investigated by quantifying the formation of imidazoles (imidazole, imidazole-2-carboxaldehyde, 2,2'-biimidazole) from the small condensation channel of glyoxal with ammonia. For this, the SOA produced were collected on quartz filters and analyzed by Orbitrap LC/MS (Q-Exactive Thermo Fisher). The formation of other products such as organic acids was also investigated to determine potential competing reactions. Time-resolved MOUDI sampling coupled with nano-DESY/ESI-MS/MS analysis was also used to identify nitrogen- and sulphur-containing products from all the reactions. The results obtained for a range of conditions will be presented and compared with recent mechanistic information on the ionic reaction channels (Nozière et al., in preparation, 2013). The implementation of all this new information into a glyoxal-SOA model will be discussed.

  16. Modeling the Multiday Evolution and Aging of Secondary Organic Aerosol During MILAGRO 2006

    SciTech Connect

    Dzepina, K.; Cappa, Christopher D.; Volkamer, Rainer M.; Madronich, Sasha; DeCarlo, Peter; Zaveri, Rahul A.; Jimenez, Jose L.

    2011-03-22

    In this study we apply several recently-proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at an altitude of ~3.5 km during three days of aging. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) when using the aromatic SOA parameterization of Ng et al. (2007) cannot explain the observed SOA concentrations in aged pollution, even as the low-NOx channel becomes more important away from the city. However, when using the aromatic SOA parameterization of Tsimpidi et al. (2010), V-SOA alone is similar to the regional aircraft observations, highlighting the wide diversity in current V-SOA formulations. When the SOA formed from oxidation of both semivolatile and intermediate volatility organic vapors (SI-SOA) is computed following Robinson et al. (2007) the model matches the observed SOA mass, but its O/C is too low by a factor of 2. With the parameterization of Grieshop et al. (2009) the total SOA mass is overpredicted by a factor of ~2 but O/C and volatility are closer to the observations. Heating or dilution of the air results in evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs. dilution. Finally, lifting of the airmass tothe free-troposphere during dry convection results in a substantial increase of SOA bycondensation of semivolatile vapors, with this effect being reduced by aging.

  17. Elucidating the Nature of Secondary Organic Aerosol by Optical and Mass Spectrometric Studies

    NASA Astrophysics Data System (ADS)

    Waring-Kidd, C.; Perraud, V. M.; Finlayson-Pitts, B. J.

    2012-12-01

    In the atmosphere, secondary organic aerosol (SOA) is formed by the reaction of volatile organic compounds (VOC) with diverse oxidants. Uptake of low (LVOC) and semi-volatile organic compounds (SVOC) leads to growth of the newly formed particles. While existing atmospheric models incorporate comprehensive gas-phase mechanisms to form these seed particles, they typically assume the SOA to be liquid, taking up LVOC's and SVOC's in a manner consistent with instantaneous equilibrium partitioning between the gas and condensed phases. However, recent studies from our laboratory and other groups have reported that laboratory-generated and ambient SOA often behave more like a high viscosity solid or tar. We report the design and application of a custom impactor designed to impact SOA directly onto an attenuated total internal reflection (ATR) crystal. The composition of the SOA is measured by a variety of techniques including infrared (ATR-IR) spectroscopy and atmospheric solids analysis probe mass spectrometry (ASAP-MS). A key feature of this approach is that the SOA on the ATR crystal can subsequently serve as a 'substrate' to further investigate the chemical and physical behavior of SOA. Once deposited on the crystal, the SOA was characterized by atomic-force and optical microscopy. The evaporation of SOA from a variety of precursors and reaction conditions was investigated using infrared spectroscopy (ATR-IR) and proton transfer mass spectrometry (PTR-MS). The uptake of atmospherically relevant organic compounds such as organic nitrates onto the SOA substrate was also studied. The results provide important insights into how to best describe the physical state of SOA from monoterpene oxidation under a variety of reaction conditions. The results will be discussed in the context of how the physical state impacts SOA growth and its atmospheric lifetime.

  18. Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

    SciTech Connect

    Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2012-05-17

    Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic mass was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.

  19. Secondary organic aerosol from sesquiterpene and monoterpene emissions in the United States.

    PubMed

    Sakulyanontvittaya, Tanarit; Guenther, Alex; Helmig, Detlev; Milford, Jana; Wiedinmyer, Christine

    2008-12-01

    Emissions of volatile organic compounds (VOC) from vegetation are believed to be a major source of secondary organic aerosol (SOA), which in turn comprises a large fraction of fine particulate matter in many areas. Sesquiterpenes are a class of biogenic VOC with high chemical reactivity and SOA yields. Sesquiterpenes have only recently been quantified in emissions from a wide variety of plants. In this study, a new sesquiterpene emission inventory is used to provide input to the Models-3 Community Multiscale Air Quality (CMAQ) model. CMAQ is used to estimate the contribution of sesquiterpenes and monoterpenes to SOA concentrations over the contiguous United States. The gas-particle partitioning module of CMAQ was modified to include condensable products of sesquiterpene oxidation and to update values of the enthalpy of vaporization. The resulting model predicts July monthly average surface concentrations of total SOA in the eastern U.S. ranging from about 0.2-0.8 microg m(-3). This is roughly double the amount of SOA produced in this region when sesquiterpenes are not included. Even with sesquiterpenes included, however, the model significantly underpredicts surface concentrations of particle-phase organic matter compared to observed values. Treating all SOA as capable of undergoing polymerization increases predicted monthly average surface concentrations in July to 0.4-1.2 microg m(-3), in closer agreement with observations. Using the original enthalpy of vaporization value in CMAQ in place of the values estimated from the recent literature results in predicted SOA concentrations of about 0.3-1.3 microg m(-3). PMID:19192798

  20. Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

    NASA Astrophysics Data System (ADS)

    Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

    2013-09-01

    The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter after three hours of oxidation inside the chamber at typical atmospheric oxidant levels. Therefore, the contribution of light duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photo-oxidizing exhaust from newer (LEV1 and LEV2) vehicles was only modestly lower (38%) than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions in non-methane organic gas emissions. These data suggest that a complex and non-linear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the time scale of these experiments, the mixture of organic vapors emitted by newer vehicles appear to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the non-methane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. These results for light-duty gasoline vehicles contrast with the results from a companion study of on-road heavy-duty diesel trucks; in that study late model (2007 and later) diesel trucks equipped with catalyzed diesel particulate filters emitted very little primary PM, and the photo-oxidized emissions produced negligible amounts of SOA.

  1. Spatial distributions of secondary organic aerosols from isoprene, monoterpenes, ?-caryophyllene, and aromatics over China during summer

    NASA Astrophysics Data System (ADS)

    Ding, Xiang; He, Quan-Fu; Shen, Ru-Qin; Yu, Qing-Qing; Wang, Xin-Ming

    2014-10-01

    Filter-based particle samples were simultaneously collected at 14 sites across 6 regions of China during the summer of 2012. These filters were analyzed for secondary organic aerosol (SOA) tracers from biogenic precursors (isoprene, monoterpenes, and ?-caryophyllene) and anthropogenic aromatics. The sum of all SOA tracers ranged from 29.9 to 371 ng m-3 with the majority from isoprene (123 ± 78.8 ng m-3), followed by monoterpenes (10.5 ± 6.64 ng m-3), ?-caryophyllene (5.07 ± 3.99 ng m-3), and aromatics (2.90 ± 1.52 ng m-3). The highest levels of biogenic SOA tracers were observed in East China, whereas the highest concentrations of the aromatic SOA tracer, 2,3-dihydroxy-4-oxopentanoic acid (DHOPA), occurred in North China. All biogenic SOA tracers exhibited positive correlations with temperature, most likely resulting from enhanced biogenic volatile organic compounds (BVOCs) emissions and photochemistry in high-temperature regions. Among the isoprene SOA tracers, the low-NOx products 2-methyltetrols were the largest by mass concentration. However, at certain urban sites, the contribution of the high-NOx product 2-methylglyceric acid was significantly higher, implying a greater influence of NOx on isoprene SOA formation in urban areas. For the monoterpene SOA tracers, the ratio of the first-generation products (cis-pinonic acid plus pinic acid) to the high-generation product (3-methyl-1,2,3-butanetricarboxylic acid) exhibited a negative correlation with the amount of high-generation products, indicating that this ratio could serve as an indicator of the aging of monoterpene SOA. The ratio ranged from 0.89 to 21.0, with an average of 7.00 ± 6.02, among the observation sites, suggesting that monoterpene SOA was generally fresh over China during the summer. As a typical anthropogenic SOA tracer, DHOPA exhibited higher levels at urban sites than at remote sites. These SOA tracers were further used to attribute SOA origins via the SOA-tracer method. The total concentrations of secondary organic carbon (SOC) and SOA were estimated to be in the range of 0.37 to 2.47 ?gC m-3 and 0.81 to 5.44 µg m-3, respectively, with the highest levels observed in the eastern regions of China. Isoprene (46 ± 14%) and aromatics (27 ± 8%) were the two major contributors to SOC in every region. In North China, aromatics were the largest SOA contributor. Our ground-based observations suggest that anthropogenic aromatics are important SOA precursors in China.

  2. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    NASA Astrophysics Data System (ADS)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.

    2015-06-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols (SOA) has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all primarily formed from the photo-oxidation of aromatic volatile organic compounds (VOC), in the gas phase and particulate matter (PM) together and PM alone was conducted. Since all of the target compounds are secondary products, their concentrations in the atmosphere are in the low ng m-3 range and consequently a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33‰, which is well within the range predicted by mass balance calculations. However, the observed carbon isotope ratios cover a range of nearly 9‰, and approximately 20% of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban centre with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This indicates that at high OH radical concentrations, photochemical formation or removal of nitrophenols can be faster than exchange between the two phases. The dependence between the concentrations and isotope ratios of the nitrophenols and meteorological conditions as well as pollution levels (NO2, O3, SO2 and CO) demonstrate that the influence of precursor concentrations on nitrophenol concentrations is far more important than the extent of photochemical processing.

  3. CCN spectra, hygroscopicity, and droplet activation kinetics of secondary organic aerosol resulting from the 2010 Deepwater Horizon oil spill.

    PubMed

    Moore, Richard H; Raatikainen, Tomi; Langridge, Justin M; Bahreini, Roya; Brock, Charles A; Holloway, John S; Lack, Daniel A; Middlebrook, Ann M; Perring, Anne E; Schwarz, Joshua P; Spackman, J Ryan; Nenes, Athanasios

    2012-03-20

    Secondary organic aerosol (SOA) resulting from the oxidation of organic species emitted by the Deepwater Horizon oil spill were sampled during two survey flights conducted by a National Oceanic and Atmospheric Administration WP-3D aircraft in June 2010. A new technique for fast measurements of cloud condensation nuclei (CCN) supersaturation spectra called Scanning Flow CCN Analysis was deployed for the first time on an airborne platform. Retrieved CCN spectra show that most particles act as CCN above (0.3 ± 0.05)% supersaturation, which increased to (0.4 ± 0.1)% supersaturation for the most organic-rich aerosol sampled. The aerosol hygroscopicity parameter, ?, was inferred from both measurements of CCN activity and from humidified-particle light extinction, and varied from 0.05 to 0.10 within the emissions plumes. However, ? values were lower than expected from chemical composition measurements, indicating a degree of external mixing or size-dependent chemistry, which was reconciled assuming bimodal, size-dependent composition. The CCN droplet effective water uptake coefficient, ?(cond), was inferred from the data using a comprehensive instrument model, and no significant delay in droplet activation kinetics from the presence of organics was observed, despite a large fraction of hydrocarbon-like SOA present in the aerosol. PMID:22356579

  4. Quantifying small molecules in secondary organic aerosol formed during the photo-oxidation of toluene with hydroxyl radicals

    NASA Astrophysics Data System (ADS)

    Hamilton, Jacqueline F.; Webb, Paul J.; Lewis, Alastair C.; Reviejo, Montserrat M.

    The composition of secondary organic aerosol (SOA) formed during the photo-oxidation of toluene in a large-volume smog chamber was determined using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (TD-GC×GC-TOF/MS). TD-GC×GC eliminated offline sample preparation and resulted in a single shot inventory of GC-amenable organic species within the aerosol. Seventy-four species were identified and quantified from chromatographic retention behaviour and mass spectral fragmentation. Functional groups resolved included organic acids, aromatics, dicarbonyls, furans, furanones, furandiones and pyranones. Concentrations of individual species were derived either directly from standards or from chemical surrogates. The major small organic molecule components by mass were formed via the peroxy-bicyclic reaction mechanism (e.g., 5-methyl-2(3H)-furanone=2972 ng m -3 or 0.861% of aerosol mass), although only around 10% of the total aerosol mass could be quantified. In addition, a large number of lower concentration species were observed with ambiguous chemical characteristics. Interpretation of their mass spectra suggests these species may be fragments of larger molecules broken down during the thermal desorption and separation stages.

  5. Atmospheric oxalic acid and related secondary organic aerosols in Qinghai Lake, a continental background site in Tibet Plateau

    NASA Astrophysics Data System (ADS)

    Meng, Jingjing; Wang, Gehui; Li, Jianjun; Cheng, Chunlei; Cao, Junji

    2013-11-01

    Summertime PM2.5 aerosols collected from Qinghai Lake (3200 m a.s.l.), a remote continental site in the northeastern part of Tibetan Plateau, were analyzed for dicarboxylic acids (C2-C11), ketocarboxylic acids and ?-dicarbonyals. Oxalic acid (C2) is the dominant dicarboxylic acid in the samples, followed by malonic, succinic and azelaic acids. Total dicarboxylic acids (231 ± 119 ng m-3), ketocarboxylic acids (8.4 ± 4.3 ng m-3), and ?-dicarbonyls (2.7 ± 2.1 ng m-3) at the Tibetan background site are 2-5 times less than those detected in lowland areas such as 14 Chinese megacities. Compared to those in other urban and marine areas enhancements in relative abundances of C2/total diacids and diacids-C/WSOC of the PM2.5 samples suggest that organic aerosols in the region are more oxidized due to strong solar radiation. Molecular compositions and air mass trajectories demonstrate that the above secondary organic aerosols in the Qinghai Lake atmosphere are largely derived from long-range transport. Ratios of oxalic acid, glyoxal and methylglyoxal to levoglucosan in PM2.5 aerosols emitted from household burning of yak dung, a major energy source for Tibetan in the region, are 30-400 times lower than those in the ambient air, which further indicates that primary emission from biomass burning is a negligible source of atmospheric oxalic acid and ?-dicarbonyls at this background site.

  6. Laboratory studies on optical properties of secondary organic aerosols generated during the photooxidation of toluene and the ozonolysis of ?-pinene

    NASA Astrophysics Data System (ADS)

    Nakayama, Tomoki; Matsumi, Yutaka; Sato, Kei; Imamura, Takashi; Yamazaki, Akihiro; Uchiyama, Akihiro

    2010-12-01

    It has recently been suggested that some organic aerosols can absorb solar radiation, especially at the shorter visible and UV wavelengths. Although quantitative characterization of the optical properties of secondary organic aerosols (SOAs) is required in order to confirm the effect of SOAs on the atmospheric radiation balance, the light absorption of SOAs has not yet been thoroughly investigated. In this study, we conducted laboratory experiments to measure the optical properties of SOAs generated during the photooxidation of toluene in the presence of NOx and the ozonolysis of ?-pinene. Extinction and scattering coefficients of the SOAs were measured by a cavity ring-down aerosol extinction spectrometer and an integrating nephelometer, respectively. Refractive indices of the SOAs were determined so that the measured particle size dependence of the extinction and scattering efficiencies could be reproduced by calculations using Mie scattering theory. As a result, significant light absorption was found at 355 nm for the toluene SOAs. In contrast, no significant absorption was found either at 355 or 532 nm for the ?-pinene SOAs. Using the obtained refractive index, mass absorption cross-section values of the toluene SOAs were calculated to be 0.3-3 m2 g-1 at 355 nm. The results indicate that light absorption by the SOAs formed from the photooxidation of aromatic hydrocarbons have a potential to influence the total aerosol light absorption, especially at UV wavelengths.

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

    Microsoft Academic Search

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

    2004-01-01

    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

  8. Laboratory Studies of Heterogeneous Reactions of HO2 Radical with Inorganic Aerosol Particles under the Ambient Conditions

    NASA Astrophysics Data System (ADS)

    Taketani, F.; Kanaya, Y.; Akimoto, H.

    2007-12-01

    The HO2 uptake coefficient for aerosol particles ((NH4)2SO4 and NaCl) under ambient conditions (760Torr and 296K) was measured using an aerosol flow tube(AFT) coupled with a chemical conversion/laser-induced fluorescence(CC/LIF) technique. The CC/LIF technique enabled experiments to be performed at almost the same HO2 radical concentration as that in the atmosphere(~108 molecules cm-3). HO2 radicals were injected into the AFT through a vertically movable Pyrex tube. Injector position dependent profiles of LIF intensity were measured as a function of aerosol concentration at various relative humilities(RH). The uptake coefficients of dry aerosol (NaCl and (NH4)2SO4) particles were < 0.05, while the uptake coefficients of wet particles of NaCl and (NH4)2SO4 were estimated to be 0.10 and 0.15, respectively, which suggested that heterogeneous loss was enhanced by the particle containing water. To estimate the contribution of heterogeneous loss of HO2 by aerosol, the diurnal variation of HO2 using a box-model calculation was demonstrated. As a result, the daytime maximum concentrations of HO2 were changed to 95 and 70 %, relative to an absence of heterogeneous loss for marine and urban areas, respectively.

  9. Limited influence of dry deposition of semivolatile organic vapors on secondary organic aerosol formation in the urban plume

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

    The dry deposition of volatile organic compounds (VOCs) and its impact on secondary organic aerosols (SOA) are investigated in the Mexico City plume. Gas-phase chemistry and gas-particle partitioning of oxygenated VOCs are modeled with the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) from C3 to C25 alkanes, alkenes, and light aromatics. Results 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. Dry deposition competes with the gas-particle uptake, and only gases with fewer than ~12 carbons dry deposit while longer species partition to SOA. Because dry deposition of submicron aerosols is slow, condensation onto particles protects organic gases from deposition, thus increasing their atmospheric burden and lifetime. In the absence of this condensation, ~50% of the regionally produced mass would have been dry deposited.

  10. Secondary Organic Aerosol Produced from Non-Measured Hydrocarbons Downwind from the Oil Spill in the Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    de Gouw, J. A.; Middlebrook, A. M.; Warneke, C.; Ahmadov, R.; Atlas, E. L.; Bahreini, R.; Blake, D. R.; Brock, C. A.; Brioude, J.; Fahey, D. W.; Fehsenfeld, F. C.; Gao, R.; Holloway, J. S.; Lueb, R.; McKeen, S. A.; Meagher, J. F.; Murphy, D. M.; Parrish, D. D.; Perring, A. E.; Pollack, I. B.; Ravishankara, A. R.; Robinson, A. L.; Ryerson, T. B.; Schwarz, J. P.; Spackman, J. R.; Srinivasan, A.; Watts, L.

    2010-12-01

    An extensively instrumented NOAA WP-3D research aircraft made airborne measurements of the gaseous and aerosol composition of air over the Deepwater Horizon (DWH) oil spill that occurred in April-July of 2010 in the Gulf of Mexico. A narrow plume of hydrocarbons was observed downwind from DWH that is attributed to the evaporation of fresh oil on the sea surface. A much wider plume of organic aerosol (OA) was attributed to secondary (SOA) formation from unmeasured, less volatile hydrocarbons that were emitted from a wider area around DWH. These observations provide compelling evidence for the importance of SOA formation from less volatile hydrocarbons, which has been proposed as a significant source of OA in the atmosphere.

  11. Molecular composition of aged secondary organic aerosol generated from a mixture of biogenic volatile compounds using ultrahigh resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Doussin, J.-F.; Giorio, C.; Mahon, B.; Wilson, E. M.; Maurin, N.; Pangui, E.; Venables, D. S.; Wenger, J. C.; Kalberer, M.

    2015-02-01

    Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidised molecules. Aerosol processing or further oxidation (ageing) of organic aerosol has been suggested to be responsible for their formation through heterogeneous uptake of oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several ageing processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography ultrahigh resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): ?-pinene, ?-pinene, ?3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated ageing was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O/C ratios of the SOA components. None of the ageing processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using ?-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH radical-initiated ?-pinene oxidation had a significantly higher overall OSC and O/C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidised species in ambient biogenic SOA.

  12. Nocturnal isoprene oxidation over the Northeast United States and its impact on reactive nitrogen partitioning and secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Brown, S. S.; de Gouw, J. A.; Warneke, C.; Ryerson, T. B.; Dubé, W. P.; Atlas, E.; Weber, R. K.; Neuman, J. A.; Roberts, J. M.; Swanson, A.; Flocke, F.; McKeen, S. A.; Brioude, J.; Sommariva, R.; Trainer, M.; Fehsenfeld, F. C.; Ravishankara, A. R.

    2008-12-01

    Isoprene is the largest single VOC emission to the atmosphere and is important to production of tropospheric oxidants and aerosol. Isoprene emissions are sunlight-dependent and undergo rapid photochemical oxidation during daylight hours. In regionally polluted areas, however, late-day isoprene emissions that remain in the atmosphere at sunset undergo oxidation by NO3, which is present only at night and whose production depends on the availability of NOx. These nighttime reactions provide a mechanism for degradation of biogenic VOC by an anthropogenic oxidant. The northeast United States is a region with large emissions of both isoprene and NOx. A recent aircraft study examined isoprene and its nocturnal oxidants in a series of night flights across this region. Substantial amounts of isoprene were observed after dark that were strongly anticorrelated with the presence of NO3. The products of photochemical oxidation of isoprene, methyl vinyl ketone and methacrolein, were more uniformly distributed, and could serve as tracers for the presence of isoprene at sunset, prior to its oxidation by NO3. Estimates of the mass of isoprene oxidized in darkness by NO3 based on these tracers shows that up to 20% of isoprene emissions in this regionally polluted area undergo nocturnal oxidation. The organic nitrates produced from the NO3 + isoprene reaction, though not directly measured, were estimated to account for 2 - 9% of total reactive nitrogen, and were large compared to other long-lived organic nitrates such as PAN. The mass of isoprene oxidized by NO3 was comparable to and correlated with the organic aerosol loading for flights with relatively low backgrounds of organic aerosol. On these flights, the contribution of nocturnally derived isoprene secondary organic aerosol was estimated at 1 - 15% of organic aerosol.

  13. Real refractive indices of ?- and ?-pinene and toluene secondary organic aerosols generated from ozonolysis and photo-oxidation

    NASA Astrophysics Data System (ADS)

    Kim, Hwajin; Barkey, Brian; Paulson, Suzanne E.

    2010-12-01

    The refractive index is the fundamental property controlling aerosol optical properties. Secondary organic aerosol (SOA) real refractive indices (mr) were derived from polar nephelometer measurements using parallel and perpendicular polarized 670 nm light, using a genetic algorithm method with Mie-Lorenz scattering theory and measured particle size distributions. The absolute error associated with the mr retrieval is ±0.03, and the instrument has sufficient sensitivity to achieve reliable retrievals for particles larger than about 200 nm. SOA generated by oxidizing ?-pinene, ?-pinene, and toluene with ozone and NOx/sunlight are explored. Retrieved refractive indices for the SOA vary between 1.38 and 1.61, depending on several factors. For ?- and ?-pinene ozonolysis, SOA mr ranges from 1.4 to 1.5 and, within the resolution of our method and bounds of our experiments, is not affected by the addition of an OH scavenger, and is only slightly dependent on the aerosol mass concentration. For photochemically generated SOA, mr generally increases as experiments progress, ranging from about 1.4 to 1.53 for ?-pinene, 1.38 to 1.53 for ?-pinene, and 1.4 to 1.6 for toluene. The pinene SOA mr appear to decrease somewhat toward the end of the experiments. Aspects of the data suggest aerosol mass concentration, oxidation chemistry, temperature, and aerosol aging may all influence the refractive index. There is more work to be done before recommendations can be made for atmospheric applications, but our calculations of the resulting asymmetry parameter indicate that a single value for SOA refractive index will not be sufficient to accurately model radiative transfer.

  14. 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 ?-pinene, ?-pinene, ?3-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. ?-pinene was the only monoterpene studied that showed a systematic decrease in both aerosol number concentration and mass concentration with increasing [NO2]. ?-pinene and ?3-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. ?-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 ?-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.

  15. Secondary Organic Aerosol Formation from the Photooxidation of Complex Hydrocarbon Mixtures: Composition, effect of SO2, and Relevance to Ambient Aerosol

    NASA Astrophysics Data System (ADS)

    Surratt, J. D.; Gao, S.; Knipping, E.; Edgerton, E.; Shahgoli, M.; Seinfeld, J. H.; Edney, E.; Kleindiesnt, T.; Lewandowski, M.; Offenberg, J.; Jaoui, M.

    2005-12-01

    Secondary organic aerosol (SOA) formation from single hydrocarbon precursors is commonly studied in smog chamber experiments to obtain SOA yield and organic composition data. However, very few complex air mixture experiments have been conducted to simulate possible conditions in ambient atmospheres. A six-phase experiment involving various combinations of alpha-pinene, toluene, isoprene, and SO2 were irradiated in the EPA's dynamic smog chamber at the National Exposure Research Laboratory in Raleigh, NC. Glass fiber filters and impactor plates were collected for each phase of the experiment to identify and quantify the nature of the SOA composition. The following suite of analytical techniques analyzed the resultant polar organic compounds and the high molecular weight species: liquid chromatography-electrospray ionization (ESI)-mass spectrometry, gas chromatography-mass spectrometry, ESI-ion trap mass spectrometry, matrix assisted laser desorption (MALDI)-time of flight mass spectrometry, and high-resolution mass spectrometry. When SO2 is present in the chamber, increases in the gravimetric aerosol mass concentration and in the abundance of polar organic compounds are observed, likely suggesting an acid catalysis effect stemming from the conversion of SO2 to H2SO4 that condenses onto aerosol formed. The addition of isoprene to a alpha-pinene/toluene mixture is found to lower the amount of aerosol produced and is also found to lower the abundance of organic compounds identified by the various analytical techniques. Lastly, many of the polar organic compounds identified and quantified here are also seen in the Southeastern Aerosol Research and Characterization (SEARCH) network during the summer of 2004. In particular, a sulfur and nitrogen containing organic species (MW = 295 gmol) is found to be the most abundant polar organic species identified in this field study (~28 % on average of the total identified organic mass). This species is also detected in the chamber experiment only when alpha-pinene and SO2 are both present in the chamber, suggesting that this abundant species is likely formed from monoterpene photooxidation. High-resolution mass spectrometry suggests the molecular formula for this species is C10H16NO7S.

  16. Modeling Atmospheric Secondary Organic Aerosol Dynamics through Chemistry, Emissions, and Partition Theory

    NASA Astrophysics Data System (ADS)

    Chang, Wayne Li-wen

    2011-12-01

    The detrimental impact on both human health and global climate of atmospheric particular matter (PM) is now well-established. Among the various classifications of PM, a significant portion is comprised of secondary organic aerosol (SOA). Despite its importance, there are still much uncertainty regarding the formation and evolution of SOA in the atmosphere, beginning with the oxidation of organic gases that leads to semi-volatile and low volatility products. The need to further improve the current knowledge SOA is made apparent by the observed large discrepancy between model predictions and field measurements of SOA. Proposed explanations behind the orders of magnitude underprediction of ambient SOA levels by state-of-the-art airshed models include: missing particle-forming oxidized organic products, unidentified SOA precursor emissions, and issues related to the fundamentals of current SOA partition theory, all of which are considered in this study to develop corresponding improvements to the latest airshed models. The model used in this study is the UCI-CIT airshed model, and the improvement scenario tests are set in the urban region of South Coast Air Basin of California. Recent chamber results have shown that the original implementation of alkane-derived SOA provided an underestimate for what was likely to be occurring in urban atmospheres. Thus, the original chemical mechanism is revised to include higher generation products of medium- and long-chain alkanes that can contribute to SOA in this study. Primary organic aerosol (POA) has been identified to be able to evaporate with dilution; therefore, test cases are developed that treat fractions of POA as semi-volatile, a source of SOA, rather than nonvolatile. While current atmospheric models assume that SOA are liquids into which semi-VOCs undergo equilibrium partitioning and grow the particles, recent laboratory and field experiments have shown otherwise. Hence, a new kinetics-driven partition theory is developed and analyzed against the original formulations. The results from the expanded chemical mechanism to include higher-generation products of alkane in the atmosphere shows that only the tetrahydrofurans will contribute to SOA and those contributions are only a small fraction compared to other SOA sources in the model, contrary to the prediction made based on chamber experiments and box models. In the tests for redistribution of POA as gas-phase parent VOCs sources, POA decreased with no commensurate increase in SOA. This is essentially due to the fact that the amount of mass that the POA can contribute is a small fraction of that already in the gas-phase parent VOC pool. Finally, using the newly developed kinetically determined SOA growth mechanism, to achieve the same level of predicted SOA levels as the original equilibrium approach requires 40--50% of SOA parent species to be allocated to the particle phase. The new formulation of SOA partition behavior based on kinetics will require the measurement of new input data and the corresponding parameterization for models in the future. The implication of this new approach should demand wider attention from the community.

  17. Airborne measurement of inorganic ionic components of fine aerosol particles using the particle-into-liquid sampler coupled to ion

    E-print Network

    many important roles in the environment, including visibility, Earth radiation budget and human health on board the NCAR C130 and NASA P-3B aircraft during the 2001 Aerosol Characterization Experiment (ACE)-Asia and the Transport and Chemical Evolution over the Pacific (TRACE-P) experiments, respectively. Concentrations of NH4

  18. Secondary aerosol formation in continental outflow conditions during ACE-Asia

    Microsoft Academic Search

    G. Buzorius; C. S. McNaughton; A. D. Clarke; B. Blomquist; K. Nielsen; F. J. Brechtel

    2004-01-01

    Ground-based aerosol size distribution measurements at the Gosan, Korea, sampling site during ACE-Asia showed occasionally elevated concentrations of nucleation mode aerosol particles, with subsequent growth to the Aitken mode. Similar results from aircraft and ship-based measurements at around the same time indicated that at least one event exhibited a broad spatial extent. One of the most pronounced events, with total

  19. Thermal desorption/tunable vacuum-ultraviolet time-of-flight photoionization aerosol mass spectrometry for investigating secondary organic aerosols in chamber experiments.

    PubMed

    Fang, Wenzheng; Gong, Lei; Shan, Xiaobin; Liu, Fuyi; Wang, Zhenya; Sheng, Liusi

    2011-12-01

    This paper describes thermal desorption/tunable vacuum-ultraviolet photoionization time-of-flight aerosol mass spectrometry (TD-VUV-TOF-PIAMS) for the real-time analysis of secondary organic aerosols (SOAs) in smog chamber experiments. SOAs are sampled directly from atmospheric pressure and are focused through an aerodynamic lens assembly into the mass spectrometer. Once the particles have entered the source region, they impact on a heater and are vaporized. The nascent vapor is then softly ionized by tunable VUV synchrotron radiation. TD-VUV-TOF-PIAMS was used in conjunction with the smog chamber to study SOA formation from the photooxidation of toluene with hydroxyl radicals. The ionization energies (IEs) of these SOA products are sometimes very different with each other. As the ideal photon source is tunable, its energy can be adjusted for each molecular to be ionized. The mass spectra obtained at different photon energies are then to be useful for molecular identification. Real-time analysis of the mass spectra of SOAs is compared with previous off-line measurements. These results illustrate the potential of TD-VUV-TOF-PIAMS for direct molecular characterization of SOAs in smog chamber experiments. PMID:22011279

  20. CCN Activity, Hygroscopicity, and Droplet Activation Kinetics of Secondary Organic Aerosol Resulting from the 2010 Gulf Oil Spill

    NASA Astrophysics Data System (ADS)

    Moore, R.; Lathem, T. L.; Cerully, K.; Bahreini, R.; Brock, C. A.; Langridge, J. M.; Middlebrook, A. M.; Nenes, A.; Calnex Science Team

    2010-12-01

    We present an analysis of the hygroscopicity and droplet activation kinetics of cloud condensation nuclei (CCN) sampled onboard the National Oceanic and Atmospheric Administration WP-3D aircraft downwind of the Deepwater Horizon oil spill site on June 8th and 10th, 2010. This set of measurements provides a unique case study for assessing in-situ the impact of fresh, hydrocarbonlike aerosols, which are expected to be formed via gas-to-particle conversion of the semi-volatile vapors released from oil evaporation. Similar hydrocarbon-rich aerosols constitute an important local emissions source in urban areas, but often coexist as an external/partially-internal mixture with more-oxidized, aged organic and sulfate aerosol. The DWH site provides the means to study the hygroscopic properties of these less-oxidized organic aerosols above a cleaner environmental background typical of marine environments in order to better discern their contribution to CCN activity and droplet growth. Measurements were performed with a Droplet Measurement Technologies Streamwise, Thermal-Gradient CCN counter, operating both as a counter (s=0.3%) and as a spectrometer (s=0.2-0.6%) using the newly-developed Scanning Flow CCN Analysis (SFCA) technique [1]. The instrument measures both the number concentration of particles able to nucleate droplets and also their resulting droplet sizes. The measured size information combined with a comprehensive computational fluid dynamics instrument model enables us to determine the rate of water uptake onto the particles and parameterize it in terms of an effective mass transfer coefficient [2], a key parameter needed to predict the number of activated droplets in ambient clouds. Non-refractory aerosol chemical composition was measured with an Aerodyne compact time-of-flight aerosol mass spectrometer. It was observed that the aerosols sampled downwind of the site on both days were composed predominantly of organics with a low degree of oxidation and low hygroscopicity (? ~ 0.05-0.1). It has been previously established for secondary organic aerosol that hygroscopicity increases with increasing oxidation (as characterized by the organic oxygen:carbon ratio) [3], and vice versa, and this dataset is used to evaluate this empirical finding. Particles measured in plumes downwind of the DWH site were seen to exhibit slow activation kinetics, consistent with a tenfold decrease in the mass transfer coefficient as compared to that of pure, ammonium sulfate. Observations of similar kinetic effects have been previously observed by Ruehl et al. in the California marine boundary layer and by Lathem and Nenes in fresh Canadian biomass burning plumes [2,4]. This study provides additional information about aerosol kinetic effects in this unique environment. [1] Moore, R. H. and A. Nenes. Aerosol Sci. Technol., 2009. [2] Lathem, T. L. and A. Nenes, in preparation. [3] Jimenez, J. L., et al. Science, 2010. [4] Ruehl, C., et al., Geophys. Res. Lett., 2009.

  1. Molecular characterization of polar organosulfates in secondary organic aerosol from the green leaf volatile 3-Z-hexenal

    NASA Astrophysics Data System (ADS)

    Safi Shalamzari, Mohammad; Kahnt, Ariane; Wang, Wu; Vermeylen, Reinhilde; Kleindienst, Tadeusz; Lewandovski, Michael; Maenhaut, Willy; Claeys, Magda

    2014-05-01

    Much information is available about secondary organic aerosol (SOA) formation from terpenes, including mono- and sesquiterpenes, and isoprene. However, information about SOA formation from green leaf volatiles (GLVs), an important class of biogenic volatile organic compounds, which are emitted when plants are wounded or attacked by insects, is very scarce. In the present study, we provide evidence that 3-Z-hexenal is a potential precursor for SOA through formation of organosulfates. Organosulfate formation from 3-Z-hexenal was studied by conducting smog chamber photooxidation experiments in the presence of NO and acidic ammonium seed aerosol, where OH radicals were generated from the NOx mediated photochemical chain reactions. The focus of the study was on the structural characterization of products, i.e., organosulfates (OSs) with a molecular weight (MW) of 226, which are also present in ambient fine aerosol from a forested site (K puszta, Hungary) at a substantial relative abundance that is comparable to that of the MW 216 isoprene-related OSs. Polar OSs are of climatic relevance because of their capacity to increase the hydrophilic properties of aerosols and as such their cloud-condensation nuclei effects. Two different liquid chromatography (LC) techniques were employed to separate the polar OSs: the first technique uses a reversed-phase trifunctionally bonded C18 stationary phase, whereas the second one is based on ion-pairing C18 LC using dibutylammonium acetate as ion-pairing reagent. With regard to mass spectrometry (MS) techniques, use was made of high-resolution MS to determine the accurate mass (measured mass, 225.00809; elemental composition, C6H9O7S) as well as linear ion trap MS to obtain detailed structural information. The MW 226 OSs were structurally characterized as sulfated derivatives of 3,4-dihydroxyhex-2-enoic acid with the sulfate group positioned at C-3 or C-4. The formation of these OSs is explained through photooxidation in the gas phase resulting in a hydroperoxide, followed by acid-catalyzed rearrangement into an epoxyhydroxide and subsequent sulfation of the epoxy group in the particle phase. This work was supported by the Belgian Federal Science Policy Office through the network project "Biogenic Influence on Oxidants and Secondary Organic Aerosol: theoretical, laboratory and modeling investigations (BIOSOA)" and the Research Foundation - Flanders (FWO).

  2. Carbonaceous and inorganic species in atmospheric aerosols during wintertime over urban and high-altitude sites in North India

    Microsoft Academic Search

    R. Rengarajan; M. M. Sarin; A. K. Sudheer

    2007-01-01

    Synchronous sampling of bulk-aerosols, carried out during wintertime from the two strategically located sites in North India, reveals that total suspended particulates (TSP) over an urban site (Hisar: 29.2°N 75.7°E; 219 m asl) ranged from 67 to 396 ?g m?3; in contrast, TSP at Manora Peak (a high-altitude station: 29.4°N 79.5°E; 1950 m asl) was relatively low (range: 13.7 to

  3. Photooxidation of 2-methyl-3-Buten-2-ol (MBO) as a potential source of secondary organic aerosol.

    PubMed

    Chan, Arthur W H; Galloway, Melissa M; Kwan, Alan J; Chhabra, Puneet S; Keutsch, Frank N; Wennberg, Paul O; Flagan, Richard C; Seinfeld, John H

    2009-07-01

    2-Methyl-3-buten-2-ol (MBO) is an important biogenic hydrocarbon emitted in large quantities by pine forests. Atmospheric photooxidation of MBO is known to lead to oxygenated compounds, such as glycolaldehyde, which is the precursor to glyoxal. Recent studies have shown that the reactive uptake of glyoxal onto aqueous particles can lead to formation of secondary organic aerosol (SOA). In this work, MBO photooxidation under high- and low-NO(x) conditions was performed in dual laboratory chambers to quantify the yield of glyoxal and investigate the potential for SOA formation. The yields of glycolaldehyde and 2-hydroxy-2-methylpropanal (HMPR), fragmentation products of MBO photooxidation, were observed to be lower at lower NO(x) concentrations. Overall, the glyoxal yield from MBO photooxidation was 25% under high-NO(x) and 4% under low-NO(x) conditions. In the presence of wet ammonium sulfate seed and under high-NO(x) conditions, glyoxal uptake and SOA formation were not observed conclusively, due to relatively low (< 30 ppb) glyoxal concentrations. Slight aerosol formation was observed under low-NO(x) and dry conditions, with aerosol mass yields on the order of 0.1%. The small amount of SOA was not related to glyoxal uptake, but is likely a result of reactions similar to those that generate isoprene SOA under low-NO(x) conditions. The difference in aerosol yields between MBO and isoprene photooxidation under low-NO(x) conditions is consistent with the difference in vapor pressures between triols (from MBO) and tetrols (from isoprene). Despite its structural similarity to isoprene, photooxidation of MBO is not expected to make a significant contribution to SOA formation. PMID:19673246

  4. Synthesis and Analysis of Putative Terpene Oxidation Products and the Secondary Organic Aerosol Particles that Form from Them

    NASA Astrophysics Data System (ADS)

    Ebben, C. J.; Strick, B. F.; Upshur, M.; Shrestha, M.; Velarde, L.; Lu, Z.; Wang, H.; Xiao, D.; Batista, V. S.; Martin, S. T.; Thomson, R. J.; Geiger, F. M.

    2013-12-01

    The terpenes isoprene and ?-pinene are abundant volatile organic compounds (VOCs) that are emitted by trees and oxidized in the atmosphere. However, the chemical processes involved in the formation of secondary organic aerosol (SOA) particles from VOCs are not well understood. In this work, we use a combined synthetic, analytical, and theoretical approach to gain a molecular level understanding of the chemistry involved in the formation of SOA particles from VOC precursors. To this end, we have synthesized putative products of isoprene and ?-pinene oxidation and the oligomers that form from them. Specifically, we have focused on the epoxide and 2-methyltetraols that form from isoprene oxidation by hydroxyl radicals, as well as products of ?-pinene ozonolysis. In our analysis, we utilize a spectroscopic technique called sum frequency generation (SFG). SFG is a coherent, surface-specific, vibrational spectroscopy that uses infrared and visible laser light fields, overlapped spatially and temporally at a surface, to probe vibrational transitions within molecules. Our use of this technique allows us to assess the chemical identity of aerosol-forming components at their surfaces, where interactions with the gas phase occur. The spectral responses from these compounds are compared to those of synthetic isoprene- and ?-pinene-derived aerosol particles, as well as natural aerosol particles collected in tropical and boreal forests to begin to predict the constituents that may be present at the surfaces of these particles. In addition, isotope editing is utilized to gain a better understanding of ?-pinene. The rigidity of this molecule makes it difficult to understand spectroscopically. The combination of synthesis with deuterium labeling, theory, and broadband and high-resolution SFG spectroscopy in the C-H and C-D stretching regions allow us to determine the orientation of this important molecule on a surface, which could have implications for its reactivity in the atmosphere. This work will also aid in spectroscopic assignments, which are difficult due to the presence of non-normal modes in the SFG spectra.

  5. Laboratory Studies of the Reactive Chemistry and Changing CCN Properties of Secondary Organic Aerosol, Including Model Development

    SciTech Connect

    Scot Martin

    2013-01-31

    The chemical evolution of secondary-organic-aerosol (SOA) particles and how this evolution alters their cloud-nucleating properties were studied. Simplified forms of full Koehler theory were targeted, specifically forms that contain only those aspects essential to describing the laboratory observations, because of the requirement to minimize computational burden for use in integrated climate and chemistry models. The associated data analysis and interpretation have therefore focused on model development in the framework of modified kappa-Koehler theory. Kappa is a single parameter describing effective hygroscopicity, grouping together several separate physicochemical parameters (e.g., molar volume, surface tension, and van't Hoff factor) that otherwise must be tracked and evaluated in an iterative full-Koehler equation in a large-scale model. A major finding of the project was that secondary organic materials produced by the oxidation of a range of biogenic volatile organic compounds for diverse conditions have kappa values bracketed in the range of 0.10 +/- 0.05. In these same experiments, somewhat incongruently there was significant chemical variation in the secondary organic material, especially oxidation state, as was indicated by changes in the particle mass spectra. Taken together, these findings then support the use of kappa as a simplified yet accurate general parameter to represent the CCN activation of secondary organic material in large-scale atmospheric and climate models, thereby greatly reducing the computational burden while simultaneously including the most recent mechanistic findings of laboratory studies.

  6. Contribution of fungi to primary biogenic aerosols in the atmosphere: active discharge of spores, carbohydrates, and inorganic ions by Asco- and Basidiomycota

    NASA Astrophysics Data System (ADS)

    Elbert, W.; Taylor, P. E.; Andreae, M. O.; Pöschl, U.

    2006-11-01

    Spores and related chemical compounds from actively spore-discharging Ascomycota (AAM) and actively spore-discharging Basidiomycota (ABM) are primary biogenic components of air particulate matter (characteristic size range 1-10 ?m). Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the forcible discharge of fungal spores may account for a large proportion of coarse air particulate matter in tropical rainforest regions during the wet season. For the particle diameter range of 1-10 ?m, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol, mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively discharged basidiospores (ABS), and that the literature-derived emission ratio of about 5 pg per ABS may be taken as a representative average. ABM emissions may account for most of the atmospheric abundance of mannitol, and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter, but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season, and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations. Based on the average abundance of mannitol in particulate matter, which is consistent with the above emission ratio and the observed abundance of ABS, we have also calculated a value of ~17 Tg yr-1 as a first estimate for the global average emission rate of ABS over land surfaces. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr-1 of anthropogenic primary organic aerosol; 12-70 Tg yr-1 of secondary organic aerosol) indicate that emissions from actively spore-discharging fungi should be taken into account as a significant source of organic aerosol. Their effects might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

  7. Biogenic secondary organic aerosol over the United States: Comparison of climatological simulations with observations

    Microsoft Academic Search

    Hong Liao; Daven K. Henze; John H. Seinfeld; Shiliang Wu; Loretta J. Mickley

    2007-01-01

    Understanding the effects of global climate change on regional air quality is central in future air quality planning. We report here on the use of the Goddard Institute for Space Studies (GISS) general circulation model (GCM) III to drive the GEOS-CHEM global atmospheric chemical transport model to simulate climatological present-day aerosol levels over the United States. Evaluation of model predictions

  8. Biogenic secondary organic aerosol over the United States: Comparison of climatological simulations with observations

    Microsoft Academic Search

    Hong Liao; Daven K. Henze; John H. Seinfeld; Shiliang Wu; Loretta J. Mickley

    2007-01-01

    (1) Understanding the effects of global climate change on regional air quality is central in future air quality planning. We report here on the use of the Goddard Institute for Space Studies (GISS) general circulation model (GCM) III to drive the GEOS-CHEM global atmospheric chemical transport model to simulate climatological present-day aerosol levels over the United States. Evaluation of model

  9. SMOG CHAMBER STUDIES OF SECONDARY ORGANIC AEROSOLS FROM IRRADIATED HYDROCARBONS UNDER AMBIENT CONDITIONS

    EPA Science Inventory

    Understanding the physics and chemistry of aerosols is fundamental to evaluating health risks and developing and evaluating atmospheric models. However, as noted in a recent NRC report only about 10% of the organics in PM2.5 have been identified. A significant portion of the un...

  10. Hydroxydicarboxylic Acids: Markers for Secondary Organic Aerosol from the Photooxidation of a-Pinene

    EPA Science Inventory

    Detailed organic analysis of fine (PM 2.5) rural aerosol collected during summer at K-puszta, Hungary, a mixed deciduous/coniferous forest site, shows the presence of polar oxygenated compounds that are also formed in laboratory irradiated a-pinene/NOx/air m...

  11. Naturally driven variability in the global secondary organic aerosol over a decade

    Microsoft Academic Search

    K. Tsigaridis; M. Kanakidou; D. A. Hauglustaine

    2005-01-01

    In order to investigate the variability of the sec- ondary organic aerosol (SOA) distributions and budget and provide a measure for the robustness of the conclusions on human induced changes of SOA, a global 3-dimensional chemistry transport model describing both the gas and the particulate phase chemistry of the troposphere has been ap- plied. The response of the global budget

  12. Global modelling of secondary organic aerosol from ?-pinene oxidation using a parameterization based on a detailed chemical mechanism

    NASA Astrophysics Data System (ADS)

    Ceulemans, Karl; Müller, Jean-Francois; Compernolle, Steven; Stavrakou, Jenny

    2010-05-01

    Monoterpenes are oxidized in the atmosphere by ozone and the hydroxyl and nitrate radicals. The condensable products resulting from these reactions contribute to Secondary Organic Aerosol (SOA). We have developed a detailed ?-pinene chemical mechanism BOREAM (Capouet et al. 2008), in which the primary gas phase chemistry is based on quantum-chemical results, structure activity relationships and experimental data. The secondary chemistry of the most important products is treated explicitly, while further chemistry is reduced by the aid of generic species classes. The partitioning between gas phase and SOA is modeled using Pankow's partitioning approach (Pankow 1994), with vapor pressures (Capouet and Müller 2006) and activity coefficients (Compernolle et al. 2009) obtained from group contribution methods. We will discuss the performance of BOREAM through comparison of model predictions for SOA formation with experimental SOA yields for a large number (>150) of photo-oxidation and dark ozonolysis experiments (Ceulemans et al. 2009). Although the BOREAM SOA yields are significantly higher than in several previous box modeling studies, a reasonable agreement is found in comparison with most laboratory measurements. For use in a global model, the detailed BOREAM chemistry is replaced by a parameterized scheme based on the two-product approach (Odum et al. 1996) with parameters obtained through regressions of full model simulations. The reduced scheme accounts for the dependence of SOA yield on the oxidant (ozone, OH or NO3) and the NOx regime. For example, the reaction of alpha-pinene with OH generates a peroxy radical which, upon reaction with either NO or HO2 leads to the formation of two condensable products. The branching ratios and partitioning coefficients are temperature dependent. We inserted the obtained parameterized scheme in the global model IMAGES, where it is used to represent the SOA formation due to the monoterpenes. For aromatics, isoprene and sesquiterpenes we use two-product parameterizations based on smog chamber studies. Irreversible SOA formation due to polymerization of short-chained aldehydes (glyoxal, methylglyoxal, etc.) and direct emission of POA are also considered. Monoterpenes are estimated to contribute about 20-40 TgOA/year globally, i.e. a factor 2-4 higher than in previous modeling studies. This large contribution stems from the high SOA yields (of the order of 50% in atmospheric conditions) obtained using BOREAM at low NOx in the the oxidation of ?-pinene by OH. These high yields result from the predicted formation of highly condensable polyfunctional compounds (e.g. hydroxy-dihydroperoxides). Possible uncertainties on these estimates will be discussed on the basis of sensitivity tests with the full mechanism. The calculated OA concentrations are compared with a large number of ground-based (IMPROVE, CARBOSOL, etc.) and aircraft (INTEX-A and ACE-1) measurements. Whereas a relatively good agreement is found over both Eastern and Western US, large OA underestimations are generally found over Europe, Africa and Asia. Possible causes will be discussed. Capouet, M. and J.-F. Müller, A group contribution method for estimating the vapour pressures of ?-pinene oxidation products, Atmos. Chem. Phys., 6, 1455-1467, 2006. Capouet, M., J.-F. Müller, K. Ceulemans, S. Compernolle, L. Vereecken, J. Peeters, Modeling aerosol formation in ?-pinene photooxidation experiments, J. Geophys. Res., 113, D02308, 2008. Ceulemans, K., S. Compernolle, J. Peeters, and J.-F. Müller, Evaluation of a detailed model of secondary aerosol formation from ?-pinene against dark ozonolysis experiments, submitted to Atmos. Environ., 2009. Compernolle, S., K. Ceulemans, and J.-F. Müller, Influence of non-ideality on aerosol growth, Atmos. Chem. Phys., 9, 1325-1337, 2009. Odum, J. R., T. Hoffmann, F. Bowman, D. Collins, R. C. Flagan, and J. H. Seinfeld, Gas/particle partitioning and secondary organic aerosol AMFs, Environ. Sci. Technol., 30, 2580-2585., 1996. Pankow, J. F., An absorption model of gas/particle partitio

  13. Including phase separation in a unified model to calculate partitioning of vapours to mixed inorganic-organic aerosol particles.

    PubMed

    Topping, David; Barley, Mark; McFiggans, Gordon

    2013-01-01

    A simple approach to calculate liquid-liquid phase separation has been developed based on the derivation of partitioning coefficients between multiple liquid phases and inclusion in a framework used to partition an arbitrary number of compounds between the vapour and particle phases in an atmospheric aerosol. The representation compares favourably with a more complex and expensive benchmark gas-particle thermodynamic model for simple well-constrained systems. The model has then been applied to consider liquid phase separation in multicomponent particles formed by the equilibration of organic products generated by a near-explicit model of VOC oxidation. Inclusion of phase separation decreases the predicted mass of condensed organic material by -10 to -50%, dependent on the concentration of semi-volatile components and ambient conditions in the model scenario. The current study considers only two liquid phases, but the framework can readily accommodate an arbitrary number, though this is beyond the scope of the current work. Uncertainty introduced by the omission of phase separation is far lower than existing uncertainties in pure component vapour pressures, where orders of magnitude differences in predicted mass are found, though the bias introduced when choosing a particular method for estimating the saturation vapour pressure will influence the magnitude of phase separation. The proposed technique is the first to be used to practically deal with the many hundreds or thousands of components present in the ambient atmospheric aerosol. PMID:24601007

  14. 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 ?g m-3 above ambient concentrations of 5 ?g 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 ?g m-3) and a large number of CIMS ions, indicating many different compounds were observed when a pine branch was placed in front of the PAM, while oak and kudzu branches resulted in lower enhancement. Processing of ambient air by OH led to significant reductions in the bounce of ambient particles, indicating an effect on their phase.

  15. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ? 100 ?M-C). OH radicals (3.5E-2 ?M [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have effective vapor pressures that are orders of magnitude lower when ammonium hydroxide is present (pH 7) than without (at lower pH). In Po Valley experiments, nitrogen-containing organics were prominent precursors and intermediates. Pyruvate and oxalate were among the products. Importantly, formation of aqSOA helps to explain the high O/C ratios found in atmospheric aerosols. While uncertainties remain large, global modeling suggests that aqSOA is comparable in magnitude to SOA formed through gas phase chemistry and vapor pressure driven partitioning (gasSOA).

  16. Evaluation by TCAM Model of Physical–Chemical Properties of Aerosol in Northern Italy

    Microsoft Academic Search

    Claudio Carnevale; Giovanna Finzi; Marialuisa Volta

    2008-01-01

    The chemical and size characterisation of aerosol in northern Italy was investigated by means of transport chemical aerosol\\u000a model (TCAM) multiphase model long-term simulations performed within the frame of the CityDelta-CAFE exercise. The results\\u000a show a high contribution of secondary inorganic compounds, in particular far from the Milan metropolitan area and in the large\\u000a rural area of the Po valley

  17. Apportionment of Primary and Secondary Organic Aerosols in Southern California During the 2005 Study of Organic Aerosols in Riverside (SOAR-1)

    EPA Science Inventory

    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 apportionment techniques....

  18. Hygroscopic properties of NaCl and NaNO3 mixture particles as reacted inorganic sea-salt aerosol surrogates

    NASA Astrophysics Data System (ADS)

    Gupta, D.; Kim, H.; Park, G.; Li, X.; Eom, H.-J.; Ro, C.-U.

    2014-12-01

    NaCl in fresh sea-salt aerosol (SSA) particles can partially or fully react with atmospheric NOx / HNO3, so internally mixed NaCl and NaNO3 aerosol particles can co-exist over a wide range of mixing ratios. Laboratory-generated, micrometer-sized NaCl and NaNO3 mixture particles at ten mixing ratios (mole fractions of NaCl (XNaCl) = 0.1 to 0.9) were examined systematically to observe their hygroscopic behavior, derive experimental phase diagrams for deliquescence and efflorescence, and understand the efflorescence mechanism. During the humidifying process, aerosol particles with the eutonic composition (XNaCl = 0.38) showed only one phase transition at their mutual deliquescence relative humidity (MDRH) of 67.9(± 0.5)%. On the other hand, particles with other mixing ratios showed two distinct deliquescence transitions, i.e., the eutonic component dissolved at MDRH and the remainder in the solid phase dissolved completely at their DRHs depending on the mixing ratios, resulting in a phase diagram composed of four different phases, as predicted thermodynamically. During the dehydration process, NaCl-rich particles (XNaCl > 0.38) showed two-stage efflorescence transitions: the first stage was purely driven by the homogeneous nucleation of NaCl and the second stage at the mutual efflorescence RH (MERH) of the eutonic components, with values in the range of 30.0-35.5%. Interestingly, aerosol particles with the eutonic composition (XNaCl = 0.38) also showed two-stage efflorescence with NaCl crystallizing first followed by heterogeneous nucleation of the remaining NaNO3 on the NaCl seeds. NaNO3-rich particles XNaCl ? 0.3) underwent single-stage efflorescence transitions at ERHs progressively lower than the MERH, because of the homogeneous nucleation of NaCl and the almost simultaneous heterogeneous nucleation of NaNO3 on the NaCl seeds. SEM/EDX elemental mapping indicated that the effloresced NaCl-NaNO3 particles at all mixing ratios were composed of a homogeneously crystallized NaCl moiety in the center, surrounded either by the eutonic component (for XNaCl > 0.38) or NaNO3 (for XNaCl ? 0.38). During the humidifying or dehydration process, the amount of eutonic composed part drives particle/droplet growth or shrinkage at the MDRH or MERH (second ERH), respectively, and the amount of remnant pure salts (NaCl or NaNO3 in NaCl- or NaNO3-rich particles, respectively) drives the second DRHs or first ERHs, respectively. Therefore, their behavior can be a precursor to the optical properties and direct radiative forcing for these atmospherically relevant mixture particles representing the coarse, reacted inorganic SSAs. In addition, the NaCl-NaNO3 mixture aerosol particles can maintain an aqueous phase over a wider RH range than the genuine SSA surrogate (i.e., pure NaCl particles), making their heterogeneous chemistry more probable.

  19. Hygroscopic properties of NaCl and NaNO3 mixture particles as reacted inorganic sea-salt aerosol surrogates

    NASA Astrophysics Data System (ADS)

    Gupta, D.; Kim, H.; Park, G.; Li, X.; Eom, H.-J.; Ro, C.-U.

    2015-03-01

    NaCl in fresh sea-salt aerosol (SSA) particles can partially or fully react with atmospheric NOx/HNO3, so internally mixed NaCl and NaNO3 aerosol particles can co-exist over a wide range of mixing ratios. Laboratory-generated, micrometer-sized NaCl and NaNO3 mixture particles at 10 mixing ratios (mole fractions of NaCl (XNaCl) = 0.1 to 0.9) were examined systematically to observe their hygroscopic behavior, derive experimental phase diagrams for deliquescence and efflorescence, and understand the efflorescence mechanism. During the humidifying process, aerosol particles with the eutonic composition (XNaCl = 0.38) showed only one phase transition at their mutual deliquescence relative humidity (MDRH) of 67.9 (±0.5)% On the other hand, particles with other mixing ratios showed two distinct deliquescence transitions; i.e., the eutonic component dissolved at MDRH, and the remainder in the solid phase dissolved completely at their DRHs depending on the mixing ratios, resulting in a phase diagram composed of four different phases, as predicted thermodynamically. During the dehydration process, NaCl-rich particles (XNaCl > 0.38) showed a two stage efflorescence transition: the first stage was purely driven by the homogeneous nucleation of NaCl and the second stage at the mutual efflorescence RH (MERH) of the eutonic components, with values in the range of 30.0-35.5%. Interestingly, aerosol particles with the eutonic composition (XNaCl = 0.38) also showed two-stage efflorescence, with NaCl crystallizing first followed by heterogeneous nucleation of the remaining NaNO3 on the NaCl seeds. NaNO3-rich particles (XNaCl ? 0.3) underwent single-stage efflorescence transitions at ERHs progressively lower than the MERH because of the homogeneous nucleation of NaCl and the almost simultaneous heterogeneous nucleation of NaNO3 on the NaCl seeds. SEM/EDX elemental mapping indicated that the effloresced NaCl-NaNO3 particles at all mixing ratios were composed of a homogeneously crystallized NaCl moiety in the center, surrounded either by the eutonic component (for XNaCl > 0.38) or NaNO3 (for XNaCl ? 0.38). During the humidifying or dehydration process, the amount of eutonic composed part drives particle/droplet growth or shrinkage at the MDRH or MERH (second ERH), respectively, and the amount of pure salts (NaCl or NaNO3 in NaCl- or NaNO3-rich particles, respectively) drives the second DRHs or first ERHs, respectively. Therefore, their behavior can be a precursor to the optical properties and direct radiative forcing for these atmospherically relevant mixture particles representing the coarse, reacted inorganic SSAs. In addition, the NaCl-NaNO3 mixture aerosol particles can maintain an aqueous phase over a wider RH range than pure NaCl particles as SSA surrogate, making their heterogeneous chemistry more probable.

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

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; ?usak, A.; Grgi?, 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.

  1. Modelling the formation and composition of secondary organic aerosol from ?- and ?-pinene ozonolysis using MCM v3

    NASA Astrophysics Data System (ADS)

    Jenkin, M. E.

    2004-09-01

    The formation and detailed composition of secondary organic aerosol (SOA) from the gas phase ozonolysis of ?- and ?-pinene has been simulated using the Master Chemical Mechanism version 3 (MCM v3), coupled with a representation of gas-to-aerosol transfer of semivolatile and involatile oxygenated products. A kinetics representation, based on equilibrium absorptive partitioning of ca. 200 semivolatile products, was found to provide an acceptable description of the final mass concentrations observed in a number of reported laboratory and chamber experiments, provided partitioning coefficients were increased by about two orders of magnitude over those defined on the basis of estimated vapour pressures. This adjustment is believed to be due, at least partially, to the effect of condensed phase association reactions of the partitioning products. Even with this adjustment, the simulated initial formation of SOA was delayed relative to that observed, implying the requirement for the formation of species of much lower volatility to initiate SOA formation. The inclusion of a simplified representation of the formation and gas-to-aerosol transfer of involatile dimers of 22 bi- and multifunctional carboxylic acids (in addition to the absorptive partitioning mechanism) allowed a much improved description of SOA formation for a wide range of conditions. The simulated SOA composition recreates certain features of the product distributions observed in a number of experimental studies, but implies an important role for multifunctional products containing hydroperoxy groups (i.e. hydroperoxides). This is particularly the case for experiments in which 2-butanol is used to scavenge OH radicals, because [HO2]/[RO2] ratios are elevated in such systems. The optimized mechanism is used to calculate SOA yields from ?- and ?-pinene ozonolysis in the presence and absence of OH scavengers, and as a function of temperature.

  2. Modelling the formation and composition of secondary organic aerosol from ?- and ?-pinene ozonolysis using MCM v3

    NASA Astrophysics Data System (ADS)

    Jenkin, M. E.

    2004-05-01

    The formation and detailed composition of secondary organic aerosol (SOA) from the gas phase ozonolysis of ?- and ?-pinene has been simulated using the Master Chemical Mechanism version 3 (MCM v3), coupled with a representation of gas-to-aerosol transfer of semivolatile and involatile oxygenated products. A kinetics representation, based on equilibrium absorptive partitioning of ca. 200 semivolatile products, was found to provide an acceptable description of the final mass concentrations observed in a number of reported laboratory and chamber experiments, provided partitioning coefficients were increased by about two orders of magnitude over those defined on the basis of estimated vapour pressures. This adjustment is believed to be due, at least partially, to the effect of condensed phase association reactions of the partitioning products. Even with this adjustment, the simulated initial formation of SOA was delayed relative to that observed, implying the requirement for the formation of species of much lower volatility to initiate SOA formation. The inclusion of a simplified representation of the formation and gas-to-aerosol transfer of involatile dimers of 22 bi- and multifunctional carboxylic acids (in addition to the absorptive partitioning mechanism) allowed a much improved description of SOA formation for a wide range of conditions. The simulated SOA composition recreates certain features of the product distributions observed in a number of experimental studies, but implies an important role for multifunctional products containing hydroperoxy groups (i.e. hydroperoxides). This is particularly the case for experiments in which 2-butanol is used to scavenge OH radicals, because [HO2]/[RO2] ratios are elevated in such systems. The optimized mechanism is used to calculate SOA yields from ?- and ?-pinene ozonolysis in the presence and absence of OH scavengers, and as a function of temperature.

  3. Investigation of the OH-initiated oxidation of aromatics in air: Gas phase and condensable products and hygroscopicity of secondary aerosol

    Microsoft Academic Search

    Jens Hjorth; Jyrki Viidanoja; Roberta Manca; Jean-Philippe Putaud; Davide Ferri; Niels R. Jensen; Bo R. Larsen; Rita Van Dingenen; Alessandro Dell' Acqua; Richard Winterhalter; Ezio Bolzacchini

    Summary Aromatic hydrocarbons are important constituents in polluted air. The atmospheric photo- oxidation of aromatic compounds, mainly initiated by reactions of the OH radical, has an impact on photochemical oxidant formation and is believed to be a major source of secondary aerosol (SOA) (Seinfeld and Pandis, 1998). The OH-initiated oxidation of benzene, toluene and benzaldehyde was studied in a 480

  4. SECONDARY ORGANIC CARBON AND AEROSOL YIELDS FROM THE IRRADIATIONS OF ISOPRENE AND á-PINENE IN THE PRESENCE OF NO X AND SO 2

    EPA Science Inventory

    A laboratory study was carried out to investigate the secondary organic carbon (SOC) yields of a-pinene and isoprene in the presence of SO2, which produces acidic aerosol in the system. Experiments were based on irradiating each hydrocarbon (HC) with NOx in ...

  5. Formation of Secondary Organic Aerosol from Irradiated a -Pinene/Tolueme/NOx Mixtures and the Effect of Isoprene and Sulfur Dioxide

    EPA Science Inventory

    Secondary organic aerosol (SOA) was generated by irradiating a series of a-pinene/toluene/NOx mixtures in the absence and presence of isoprene or sulfur dioxide. The purpose of the experiment was to evaluate the extent to which chemical perturbations to this base-case (a-pinene/...

  6. Towards the identification of molecular constituents associated with the surfaces of isoprene-derived secondary organic aerosol (SOA) particles

    NASA Astrophysics Data System (ADS)

    Ebben, C. J.; Strick, B. F.; Upshur, M. A.; Chase, H. M.; Achtyl, J. L.; Thomson, R. J.; Geiger, F. M.

    2014-03-01

    Secondary organic aerosol (SOA) particle formation ranks among the least understood chemical processes in the atmosphere, rooted in part in the lack of knowledge about chemical composition and structure at the particle surface, and little availability of reference compounds needed for benchmarking and chemical identification in pure and homogenous form. Here, we synthesize and characterize SOA particle constituents consisting of the isoprene oxidation products ?-, ?-, and cis- and trans-?-IEPOX (isoprene epoxide), as well as syn- and anti-2-methyltetraol. Paying particular attention to their phase state (condensed vs. vapor), we carry out a surface-specific and orientationally selective chemical analysis by vibrational sum frequency generation (SFG) spectroscopy of these compounds in contact with a fused silica window. Comparison to the vibrational SFG spectra of synthetic isoprene-derived SOA particle material prepared at the Harvard Environmental Chamber yields a plausible match with trans-?-IEPOX, suggesting it is an abundant species on their surfaces, while the other species studied here, if present, appear to be SFG inactive and thus likely to be localized in a centrosymmetric environment, e.g., the particle bulk. No match is found for authentic SOA particle material collected at the site of the Amazonian Aerosol Characterization Experiment (AMAZE-08) with the surface SFG spectra of the compounds surveyed here, yet we cannot rule out this mismatch being attributable to differences in molecular orientation. The implications of our findings for SOA formation are discussed in the context of condensational particle growth and reactivity.

  7. Effect of Secondary Organic Aerosol Coatings on Black Carbon Water Uptake, Cloud Condensation Nuclei Activity, and Particle Collapse

    NASA Astrophysics Data System (ADS)

    Holder, A. L.; Suda, S.; Hagler, G.; Hays, M. D.; Petters, M. D.

    2012-12-01

    The ability of black carbon aerosols to absorb water and act as a cloud condensation nuclei (CCN) directly controls their lifetime in the atmosphere as well as their impact on cloud formation, thus impacting the earth's climate. Black carbon emitted from most combustion processes is initially hydrophobic, thus requiring high critical supersaturations before these particles can serve as CCN. Due to atmospheric processing, black carbon particles can become internally mixed with hydrophilic material, altering the water uptake and CCN properties of the particle. We simulated this process by coating flame-generated black carbon particles with secondary organic aerosol produced from the reaction of decane and toluene with OH, and ?-caryophyllene with O3 in the presence of an OH scavenger. Particle coating thickness was determined by tandem differential mobility analysis. Hygroscopic properties of the coated particles were assessed using a hygroscopicity tandem differential mobility analyzer (HTDMA) operated at RH ~98% and a CCN counter. Additionally, a Single Particle Soot Photometer (SP2) was used to measure the black carbon mass and the coating thickness optically. The presence of a coating increased the black carbon particles' ability to uptake water in a fashion dependent upon the precursor compound. The critical supersaturation of 200 nm mobility diameter black carbon particles was dramatically reduced by trace amounts of coatings. Evidence of apparent particle collapse upon coating was observed in particles with reduced mobility diameters and large coating thicknesses, as measured by the SP2.

  8. Aging of secondary organic aerosol from small aromatic VOCs: changes in chemical composition, mass yield, volatility and hygroscopicity

    NASA Astrophysics Data System (ADS)

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2014-12-01

    Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form and transform SOA from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx. The effects of chemical aging on organic aerosol (OA) composition, mass yield, volatility and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state OSC) and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OS C ranged from -0.29 to 0.45 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.

  9. Contributions of isoprene, monoterpenes, ?-caryophyllene, and toluene to secondary organic aerosols in Hong Kong during the summer of 2006

    NASA Astrophysics Data System (ADS)

    Hu, Di; Bian, Qijing; Li, Teresa W. Y.; Lau, Alexis K. H.; Yu, Jian Zhen

    2008-11-01

    Isoprene, monoterpenes, ?-caryophyllene, and toluene are known to be important secondary organic aerosol (SOA) precursors. In this study, characteristic SOA tracers of these precursors were quantified in ambient samples of PM2.5 taken in Hong Kong and their contributions to SOA were estimated using a tracer-based method. Samples were collected every other day from four sampling sites during a field measurement campaign in the summer of 2006. Fourteen SOA tracers, along with 24 other polar oxygenated compounds, were identified and quantified using gas chromatography/ion trap mass spectrometry with prior trimethylsilylation. Concentrations of the individual tracers ranged from a few tenths to a few hundreds ng m-3. The tracer concentrations were found to be 1 order of magnitude higher on days under regional transport influences due to elevated oxidant levels than on days under mainly local emissions influences. Using the measured SOA tracer concentrations in the ambient aerosols and laboratory-derived tracer mass fractions reported by Kleindienst et al. (2007), we estimated that the average SOA attributable to isoprene, monoterpenes, ?-caryophyllene, and toluene was 8.83 ?g m-3 on days under regional transport influences versus 0.99 ?g m-3 on days under mainly local emissions influences, accounting for approximately 49% and 21%, respectively, of the ambient OC concentrations. The tracer-based estimates indicate that monoterpenes and ?-caryophyllene are significant contributors to ambient PM2.5 in the summer, which may be due to the high emissions of these biogenic hydrocarbons in Hong Kong.

  10. Volatility dependence of Henry's law constants of condensable organics: Application to estimate depositional loss of secondary organic aerosols

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    The water solubility of oxidation intermediates of volatile organic compounds that can condense to form secondary organic aerosol (SOA) is largely unconstrained in current chemistry-climate models. We apply the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere to calculate Henry's law constants for these intermediate species. Results show a strong negative correlation between Henry's law constants and saturation vapor pressures. Details depend on precursor species, extent of photochemical processing, and NOx levels. Henry's law constants as a function of volatility are made available over a wide range of vapor pressures for use in 3-D models. In an application using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) over the U.S. in summer, we find that dry (and wet) deposition of condensable organic vapors leads to major reductions in SOA, decreasing surface concentrations by ~50% (10%) for biogenic and ~40% (6%) for short chain anthropogenic precursors under the considered volatility conditions.

  11. 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 isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a "triangle plot" of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2 if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass resolution data is available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

  12. Cloud Condensation Nuclei Activity, Droplet Growth Kinetics and Hygroscopicity of Biogenic and Anthropogenic Secondary Organic Aerosol (SOA)

    NASA Astrophysics Data System (ADS)

    Zhao, Defeng; Buchholz, Angela; Kortner, Birthe; Schlag, Patrick; Rubach, Florian; Hendrik, Fucks; Kiendler-Scharr, Astrid; Tillmann, Ralf; Wahner, Andreas; Hallquist, Mattias; Flores, Michel; Rudich, Yinon; Glasius, Marianne; Kourtchev, Ivan; Kalberer, Markus; Mentel, Thomas

    2015-04-01

    Recent field data and model analysis show that secondary organic aerosol (SOA) formation is enhanced under anthropogenic influences (de Gouw et al. 2005, Spracklen et al. 2011). The interaction of biogenic VOCs (BVOCs) with anthropogenic emissions such as anthropogenic VOCs (AVOCs) could change the particle formation yields and the aerosol properties, as was recently demonstrated (Emanuelsson et al., 2013; Flores et al., 2014). However, the effect of the interaction of BVOCs with AVOCs on cloud condensation nuclei (CCN) activity and hygroscopicity of SOA remains elusive. Characterizing such changes is necessary in order to assess the indirect radiative forcing of biogenic aerosols that form under anthropogenic influence. In this study, we investigated the influence of AVOCs on CCN activation and hygroscopic growth of BSOA. SOA was formed from photooxidation of monoterpenes and aromatics as representatives of BVOCs and AVOCs, respectively. The hygroscopicity and CCN activation of BSOA were studied and compared with that of anthropogenic SOA (ASOA) and the mixture of ASOA and BSOA (ABSOA). We found that ASOA had a significantly higher hygroscopicity than BSOA at similar OH dose, which is attributed to a higher oxidation level of ASOA. While the ASOA fraction had an enhancing effect on the hygroscopicity of ABSOA compared to BSOA, the hygroscopicity of ABSOA cannot be explained by a linear combination of the pure ASOA and BSOA systems, indicating potentially additional non-linear effects such as oligomerization. However, in contrast to hygroscopicity, ASOA showed similar CCN activity as BSOA, in spite of its higher oxidation level. The ASOA fraction did not enhance the CCN activity of ABSOA. The discrepancy between hygroscopicity and CCN activity is discussed. In addition, BSOA, ABSOA and ASOA formed similar droplet size with ammonium sulfate in CCN at a given supersaturation, indicating none of these aerosols had a delay in the water uptake in the supersaturated condition. Our findings have important implications for the understanding of combined effect of AVOCs and BVOCs in SOA formation as well as on assessing their indirect radiative forcing. References: de Gouw, J. A., et al. (2005). J. Geophys. Res.-Atmos., 110(D16). Emanuelsson, E. U., et al. (2013). Atmos. Chem. Phys., 13: 2837-2855. Flores, J. M., et al., (2014).Atmos. Chem. Phys., 14: 5793-5806. Spracklen, D. V., et al. (2011). Atmos. Chem. Phys., 11: 12109-12136.

  13. Chemical coupling between acid gases and water-soluble inorganic ions in size-segregated aerosols during Arabian Dust in Beirut

    NASA Astrophysics Data System (ADS)

    Saliba, Najat; Dada, Lubna; Baalbaki, Rima

    2015-04-01

    In the proximity of the Eastern Mediterranean region, the combination of two large desert areas; Arabian and African, with heavy oil industry and high insolation during summer delineate a unique location of atmospheric processes in the region. Once emitted, dust particles can be transported over long distances and/or remain suspended in the atmosphere for several days. The so-called remnant dust episodes in Beirut originate from both African and Arabian deserts. In this study, the gas and particle transformations and gas-to-particle conversion during Arabian-dust (Ar-D) events are assessed. The increase in primary and secondary gas concentrations during Ar-D days is ascribed to three contributing factors; (i) the regional-long-range transport (LRT), (ii) the drop in the average solar radiation leading to a slow primary-to-secondary conversion and secondary gas photo-degradation, and (iii) the enhancement of the recirculation and accumulation of the main pollutants during dusty days. In parallel, a respective mass increase by 137, 149 and 13% in the coarse (CPM), accumulation (ACC) and ultrafine (UF) fractions was measured and an increase in particle volume distribution was mostly noticed for particles ranging in sizes between 2.25 and 5 ?m. This lead to major changes in the inorganic chemical composition of all particle sizes. In particular, the enhanced presence of several types of nitrate and sulfate salts in the accumulation mode confirms that remnant dust episodes offer a favorable environment for gas-to-particle conversion and particle chemical transformations and growth.

  14. Chemical characterization of the inorganic fraction of aerosols and mechanisms of the neutralization of atmospheric acidity in Athens, Greece

    NASA Astrophysics Data System (ADS)

    Karageorgos, E. T.; Rapsomanikis, S.

    2007-06-01

    The PM10 mass concentration levels and inorganic chemical composition were determined on 12-h resolution sampling during August 2003 and March 2004, in the centre of Athens, Greece. The August 2003 campaign mean PM10 mass concentration, obtained by Beta Attenuation at 5 m above ground in Athinas Street, was 56 ?g m-3 while the corresponding value for March 2004 was 92 ?g m-3. In both campaigns the E.U. imposed daily limit of 50 ?g m-3 was exceeded on several days. During the March campaign, in Athinas Street, additionally obtained DSFU-PM10 (PM10-2.5+PM2.5) gravimetric mass concentrations (mean: 121 ?g m-3) in the "breathing zone", at 1.5 m above ground were significantly higher compared to the respective mean PM10 mass concentrations obtained by the same method at 25 m above ground, in a second site (AEDA; mean: 86 ?g m-3) also in the centre of the city. The above findings suggest that, for a realistic estimation of the exposure of citizens to particulate matter, PM10 sampling in the "breathing zone" (1.5-3 m above ground) is necessary. Such data are presented for the first time for the centre of Athens. In both campaigns, calcium was found to be the predominant component of the coarse fraction while crust-related aluminosilicates and iron were the other major components. The above elements constitute the most important components of the fine fraction, together with the predominant sulphur. All toxic metals were found in concentrations below the established air quality limits, and most of them in lower concentrations compared to older studies. Lead in particular, appeared mostly in the fine fraction and in very low concentrations compared to studies dating more than a decade back. The predominant ions of the coarse fraction have been found to be Ca2+, NO3-, Na+ and Cl-, while SO42-, Ca2+ and NH4+ were the major ionic components of the fine fraction. In the fine particles, a low molar ratio of NH4+/SO42- indicated an ammonium-poor ambient air, and together with inter-ionic correlations suggested that atmospheric ammonia is the major neutralizing agent of sulfate, while being insufficient to neutralize it to full extend. The formation of NH4NO3 is therefore not favored and additional contribution to the neutralization of acidity has been shown to be provided by Ca2+ and Mg2+. In the coarse particle fraction, the predominantly abundant Ca2+ has been found to correlate well with NO3- and SO42-, indicating its role as important neutralizing agent in this particle size range. The proximity of the location under study to the sea explains the important concentrations of salts with marine origin like NaCl and MgCl2 that were found in the coarse fraction, while chloride depletion in the gaseous phase was found to be limited to the fine particulate fraction. Total analyzed inorganic mass (elemental+ionic) was found to be ranging between approximately 25-33% of the total coarse particle mass and 35-42% of the total fine particle mass.

  15. Chemical characterization of the inorganic fraction of aerosols and mechanisms of the neutralization of atmospheric acidity in Athens, Greece

    NASA Astrophysics Data System (ADS)

    Karageorgos, E. T.; Rapsomanikis, S.; Wåhlin, P.

    2006-12-01

    Mass concentration levels and the inorganic chemical composition of PM10 (two fractions; PM10-2.5 and PM2.5) were determined during August 2003 and March 2004, in the centre of Athens, Greece. August 2003 monthly mean PM10 mass concentration, at 5 m above ground, was 56 ?g/m3 and the EU imposed daily limit of 50 ?g/m3 was exceeded on 16 occasions. The corresponding monthly mean for March 2004 was 92 ?g/m3 and the aforementioned daily limit was exceeded on 23 occasions. The PM10 (PM10-2.5+PM2.5) mass concentrations at 1.5 m above ground were found to be approximately 20% higher compared to the respective PM10 measured at 5 m. Consequently, for a realistic estimation of the exposure of citizens to particulate matter, PM10 sampling at a height of 1.5-3 m above ground, in the "breathing zone" is necessary. Such data are presented for the first time for the centre of Athens. In both campaigns, calcium was found to be the predominant component of the coarse fraction while crust-related aluminosilicates and iron were found to be the other major components of the same fraction. The above elements constitute the most important components of the fine fraction, together with the predominant sulphur. Toxic metals were found to be below the air quality limits and in lower concentrations compared to older studies, with the exception of Cu and V for which some increase was observed. Pb, in particular, appeared mostly in the fine fraction and in very low concentrations compared to studies dating more than a decade back. The major ions of the coarse fraction have been found to be Ca2+, NO3- and Cl-, while SO4-2, Ca2+ and NH4+ were the major ionic components of the fine fraction. The low molar ratio of NH4+/SO4-2 indicated an ammonium-poor ambient air, where atmospheric ammonia is not sufficient to neutralize all acidity and the formation of NH4NO3 does not occur to a significant extend. Calcium predominated the coarse fraction and its good correlations with NO3- and SO4-2 indicated its role as an important neutralizing agent of atmospheric acidity in this particle size range. In the fine fraction, both Ca2+ and NH4+ participate in the neutralizing processes with NH4+ being the major neutralizing agent of SO4-2. Chloride depletion from NaCl or MgCl2 was not found to occur to a significant extend. Total analyzed inorganic mass (elemental+ionic) was found to be ranging between approximately 25-33% of the total coarse particle mass and 35-42% of the total fine particle mass.

  16. Aerosolized BC-819 Inhibits Primary but Not Secondary Lung Cancer Growth

    PubMed Central

    Hasenpusch, Günther; Pfeifer, Corinna; Aneja, Manish Kumar; Wagner, Kai; Reinhardt, Dietrich; Gilon, Michal; Ohana, Patricia; Hochberg, Avraham; Rudolph, Carsten

    2011-01-01

    Despite numerous efforts, drug based treatments for patients suffering from lung cancer remains poor. As a promising alternative, we investigated the therapeutic potential of BC-819 for the treatment of lung cancer in mouse tumor models. BC-819 is a novel plasmid DNA which encodes for the A-fragment of Diphtheria toxin and has previously been shown to successfully inhibit tumor growth in human clinical study of bladder carcinoma. In a first set of experiments, we examined in vitro efficacy of BC-819 in human lung cancer cell-lines NCI-H460, NCI-H358 and A549, which revealed >90% reduction of cell growth. In vivo efficacy was examined in an orthotopic mouse xenograft lung cancer model and in a lung metastasis model using luminescent A549-C8-luc adenocarcinoma cells. These cells resulted in peri- and intra-bronchiolar tumors upon intrabronchial application and parenchymal tumors upon intravenous injection, respectively. Mice suffering from these lung tumors were treated with BC-819, complexed to branched polyethylenimine (PEI) and aerosolized to the mice once per week for a period of 10 weeks. Using this regimen, growth of intrabronchially induced lung tumors was significantly inhibited (p?=?0.01), whereas no effect could be observed in mice suffering from lung metastasis. In summary, we suggest that aerosolized PEI/BC-819 is capable of reducing growth only in tumors arising from the luminal part of the airways and are therefore directly accessible for inhaled BC-819. PMID:21687669

  17. Emissions of biogenic volatile organic compounds and subsequent photochemical production of secondary organic aerosol in mesocosm studies of temperate and tropical plant species

    NASA Astrophysics Data System (ADS)

    Wyche, K. P.; Ryan, A. C.; Hewitt, C. N.; Alfarra, M. R.; McFiggans, G.; Carr, T.; Monks, P. S.; Smallbone, K. L.; Capes, G.; Hamilton, J. F.; Pugh, T. A. M.; MacKenzie, A. R.

    2014-12-01

    Silver birch (Betula pendula) and three Southeast Asian tropical plant species (Ficus cyathistipula, Ficus benjamina and Caryota millis) from the pantropical fig and palm genera were grown in a purpose-built and environment-controlled whole-tree chamber. The volatile organic compounds emitted from these trees were characterised and fed into a linked photochemical reaction chamber where they underwent photo-oxidation under a range of controlled conditions (relative humidity or RH ~65-89%, volatile organic compound-to-NOx or VOC / NOx ~3-9 and NOx ~2 ppbV). Both the gas phase and the aerosol phase of the reaction chamber were monitored in detail using a comprehensive suite of on-line and off-line chemical and physical measurement techniques. Silver birch was found to be a high monoterpene and sesquiterpene but low isoprene emitter, and its emissions were observed to produce measurable amounts of secondary organic aerosol (SOA) via both nucleation and condensation onto pre-existing seed aerosol (YSOA 26-39%). In contrast, all three tropical species were found to be high isoprene emitters with trace emissions of monoterpenes and sesquiterpenes. In tropical plant experiments without seed aerosol there was no measurable SOA nucleation, but aerosol mass was shown to increase when seed aerosol was present. Although principally isoprene emitting, the aerosol mass produced from tropical fig was mostly consistent (i.e. in 78 out of 120 aerosol mass calculations using plausible parameter sets of various precursor specific yields) with condensation of photo-oxidation products of the minor volatile organic compounds (VOCs) co-emitted; no significant aerosol yield from condensation of isoprene oxidation products was required in the interpretations of the experimental results. This finding is in line with previous reports of organic aerosol loadings consistent with production from minor biogenic VOCs co-emitted with isoprene in principally isoprene-emitting landscapes in Southeast Asia. Moreover, in general the amount of aerosol mass produced from the emissions of the principally isoprene-emitting plants was less than would be expected from published single-VOC experiments, if co-emitted species were solely responsible for the final SOA mass. Interpretation of the results obtained from the fig data sets leaves room for a potential role for isoprene in inhibiting SOA formation under certain ambient atmospheric conditions, although instrumental and experimental constraints impose a level of caution in the interpretation of the results. Concomitant gas- and aerosol-phase composition measurements also provide a detailed overview of numerous key oxidation mechanisms at work within the systems studied, and their combined analysis provides insight into the nature of the SOA formed.

  18. Simultaneous study of gas phase and secondary organic aerosols' chemical composition

    E-print Network

    Paris-Sud XI, Université de

    of oxygenated Semi-Volatile Organic Compounds (SVOCs). SVOCs partition between gas and particulate phases or biogenic Volatile Organic Compounds (VOCs) with atmospheric oxidants (OH, O3, NO3) leading to the formation and particulate phases simultaneously and allowing : - Characterization of secondary compounds partitioning

  19. Functionalization vs. fragmentation: n-aldehyde oxidation mechanisms and secondary organic aerosol formation.

    PubMed

    Chacon-Madrid, Heber J; Presto, Albert A; Donahue, Neil M

    2010-11-14

    Because of their relatively well-understood chemistry and atmospheric relevance, aldehydes represent a good model system for carbon-carbon fragmentation reactions in organic-aerosol aging mechanisms. Small aldehydes such as ethanal and propanal react with OH radicals under high NO(x) conditions to form formaldehyde and ethanal, respectively, with nearly unit yield. CO(2) is formed as a coproduct. This path implies the formation of the C(n-1) aldehyde, or an aldehyde with one fewer methylene group than the parent. However, as the carbon number of the n-aldehyde increases, reaction with the carbon backbone becomes more likely and the C(n-1) formation path becomes less important. In this work we oxidized n-pentanal, n-octanal, n-undecanal and n-tridecanal with OH radicals at high NO(x). The C(n-1) aldehyde molar yields after the peroxyl radical + NO reaction were 69 ± 15, 36 ± 10, 16 ± 5 and 4 ± 1%, respectively. Complementary structure-activity relationship calculations of important rate constants enable estimates of branching ratios between several intermediates of the C(n)n-aldehyde reaction with OH: C(n) peroxyacyl nitrate versus C(n) alkoxyacyl radical formation, C(n-1) alkyl nitrate versus C(n-1) alkoxy radical, and C(n-1) aldehyde formation versus isomerization products. We also measured SOA mass yields, which we compare with analogous n-alkanes to understand the effect of fragmentation on organic-aerosol formation. PMID:20856967

  20. Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Jimenez, J. L.; Madronich, S.; Canagaratna, M. R.; Decarlo, P. F.; Kleinman, L.; Fast, J.

    2010-06-01

    It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to estimate the potential contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic precursors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ("ROB") and Grieshop et al. (2009) ("GRI") are compared and evaluated against surface and aircraft measurements. The 3-D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, and for the first time also with oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (2-4 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total measured SOA at the surface during the day and is somewhat larger than that from commonly measured aromatic VOCs, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively downwind. Similar to aircraft observations, the predicted OA/?CO ratio for the ROB case increases from 20-30 ?g sm-3 ppm-1 up to 60-70 ?g sm-3 ppm-1 between a fresh and 1-day aged air mass, while the GRI case produces a 30% higher OA growth than observed. The predicted average O/C ratio of total OA for the ROB case is 0.16 at T0, substantially below observed value of 0.5. A much better agreement for O/C ratios and temporal variability (R2=0.63) is achieved with the updated GRI treatment. Both treatments show a deficiency in regard to POA ageing with a tendency to over-evaporate POA upon dilution of the urban plume suggesting that atmospheric HOA may be less volatile than assumed in these parameterizations. This study highlights the important potential role of S/IVOC chemistry in the SOA budget in this region, and highlights the need for further improvements in available parameterizations. The agreement observed in this study is not sufficient evidence to conclude that S/IVOC are the major missing SOA source in megacity environments. The model is still very underconstrained, and other possible pathways such as formation from very volatile species like glyoxal may explain some of the mass and especially increase the O/C ratio.

  1. Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

    SciTech Connect

    Hodzic, Alma; Jimenez, Jose L.; Madronich, Sasha; Canagaratna, M. R.; DeCarlo, Peter F.; Kleinman, Lawrence I.; Fast, Jerome D.

    2010-06-21

    It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of traditional anthropogenic and biogenic VOC precursors. In this study, the 3D regional air quality model CHIMERE is applied to quantify the contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic vapors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to explicitly include the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ("ROB") and Grieshop et al. (2009) ("GRI") are compared and evaluated against surface and aircraft measurements. For the first time, 3D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, but also against and oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (3-6 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. The predicted anthropogenic POA levels are found to agree within 20% with the observed HOA concentrations for both the ROB and GRI simulations, consistent with the interpretation of the emissions inventory by previous studies. The impact of biomass burning POA within the city is underestimated in comparison to the AMS BBOA, presumably due to insufficient nighttime smoldering emissions. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total SOA at the surface during the day and is somewhat larger than that from aromatics, especially at the T1 site at the edge of the city. The downwind SOA production from the continued multi-generation S/IVOC oxidation products actively continues. Similar to aircraft observations, the predicted OA/DCO ratio for the ROB case increases from 20-30 mg sm-3 ppm-1 up to 60-70 mg sm-3 ppm-1 between a fresh and 1-day aged air mass, while the GRI case produces a 30-40% higher OA growth than observed. The predicted average O/C ratio of total OA for the ROB case is 0.16 at T0, substantially below observed value of 0.5. A much better agreement for O/C ratios and temporal variability (R2=0.63) is achieved with the updated GRI treatment. Both treatments show a deficiency in regard to POA evolution with a tendency to over-evaporate POA upon dilution of the urban plume suggesting that atmospheric HOA may be less volatile than assumed in these parameterizations. This study highlights the very important potential role of S/IVOC chemistry in the SOA budget in this region, and highlights the need for improvements in current parameterizations. We note that other proposed pathways of SOA formation such as formation from very volatile species like glyoxal were not included in our simulations, which can also contribute SOA mass and especially increase the O/C ratio.

  2. Modeling organic aerosols in a megacity: Potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

    SciTech Connect

    Hodzic, A.; Kleinman, L.; Jimenez, J. L.; Madronich, S.; Canagaratna, M. R.; DeCarlo, P. F.; Fast, J.

    2010-06-01

    It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to estimate the potential contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic precursors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ('ROB') and Grieshop et al. (2009) ('GRI') are compared and evaluated against surface and aircraft measurements. The 3-D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, and for the first time also with oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (2-4 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total measured SOA at the surface during the day and is somewhat larger than that from commonly measured aromatic VOCs, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively downwind. Similar to aircraft observations, the predicted OA/{Delta}CO ratio for the ROB case increases from 20-30 {micro}g sm{sup -3} ppm{sup -1} up to 60-70 {micro}g sm{sup -3} ppm{sup -1} between a fresh and 1-day aged air mass, while the GRI case produces a 30% higher OA growth than observed. The predicted average O/C ratio of total OA for the ROB case is 0.16 at T0, substantially below observed value of 0.5. A much better agreement for O/C ratios and temporal variability (R{sup 2} = 0.63) is achieved with the updated GRI treatment. Both treatments show a deficiency in regard to POA ageing with a tendency to over-evaporate POA upon dilution of the urban plume suggesting that atmospheric HOA may be less volatile than assumed in these parameterizations. This study highlights the important potential role of S/IVOC chemistry in the SOA budget in this region, and highlights the need for further improvements in available parameterizations. The agreement observed in this study is not sufficient evidence to conclude that S/IVOC are the major missing SOA source in megacity environments. The model is still very underconstrained, and other possible pathways such as formation from very volatile species like glyoxal may explain some of the mass and especially increase the O/C ratio.

  3. Morphology of mixed primary and secondary organic particles and the adsorption of spectator organic gases during aerosol formation

    PubMed Central

    Vaden, Timothy D.; Song, Chen; Zaveri, Rahul A.; Imre, Dan; Zelenyuk, Alla

    2010-01-01

    Primary organic aerosol (POA) and associated vapors can play an important role in determining the formation and properties of secondary organic aerosol (SOA). If SOA and POA are miscible, POA will significantly enhance SOA formation and some POA vapor will incorporate into SOA particles. When the two are not miscible, condensation of SOA on POA particles forms particles with complex morphology. In addition, POA vapor can adsorb to the surface of SOA particles increasing their mass and affecting their evaporation rates. To gain insight into SOA/POA interactions we present a detailed experimental investigation of the morphologies of SOA particles formed during ozonolysis of ?-pinene in the presence of dioctyl phthalate (DOP) particles, serving as a simplified model of hydrophobic POA, using a single-particle mass spectrometer. Ultraviolet laser depth-profiling experiments were used to characterize two different types of mixed SOA/DOP particles: those formed by condensation of the oxidized ?-pinene products on size-selected DOP particles and by condensation of DOP on size-selected ?-pinene SOA particles. The results show that the hydrophilic SOA and hydrophobic DOP do not mix but instead form layered phases. In addition, an examination of homogeneously nucleated SOA particles formed in the presence of DOP vapor shows them to have an adsorbed DOP coating layer that is ?4 nm thick and carries 12% of the particles mass. These results may have implications for SOA formation and behavior in the atmosphere, where numerous organic compounds with various volatilities and different polarities are present. PMID:20194795

  4. The characterisation of secondary organic aerosol formed during the photodecomposition of 1,3-butadiene in air containing nitric oxide

    NASA Astrophysics Data System (ADS)

    Angove, D. E.; Fookes, C. J. R.; Hynes, R. G.; Walters, C. K.; Azzi, M.

    The formation of secondary organic aerosol (SOA) at yields of 0.4-0.5% and having a geometric mean diameter <100 nm has been observed during indoor environmental chamber experiments on 1.0-2.2 ppmv 1,3-butadiene in the presence of 0.5-1.1 ppmv NO. The SOA was collected on glass fibre filters, some of which were acetylated using a pyridine/acetic anhydride mixture immediately after collection. Analysis of the SOA by Fourier transform infrared spectroscopy (FTIR) resulted in bands assigned to OH stretching in alcoholic and carboxylic hydroxyl groups, NO stretching in NO 3 and C dbnd O stretching at 1728 cm -1, the latter indicative of formate esters rather than aldehydes or ketones. Initial NMR spectra showed a broad polymeric-like feature, which separated into peaks representative of monomeric units as the SOA hydrolysed over 3 days. Subsequent GC-MS and NMR analyses were used to identify 18 species, which represented 75-80% of the SOA mass. Some of the unidentified mass is probably composed of organic nitrates. Low vapour pressure (?10 -7 Torr) species detected were glycerol, threitol, erythritol and isomeric forms tentatively identified as threonic and erythronic acid nitrate. Gel permeation chromatography of acetylated SOA gave a polymer molecular weight distribution range up to ˜4.0×10 5 g mol -1, with a peak molecular weight of 6.12×10 4 g mol -1. A chemical mechanism for the formation of endogenous seed aerosol directly from 1,3-butadiene is presented. It is proposed that the SOA is polymeric and composed of C1-C4 oxygenated species, including formate esters and hemiacetal formates.

  5. Aging of secondary organic aerosol generated from the ozonolysis of ?-pinene: effects of ozone, light and temperature

    NASA Astrophysics Data System (ADS)

    Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Camredon, M.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Temime-Roussel, B.; Monod, A.; Aumont, B.; Doussin, J. F.

    2014-09-01

    A series of experiments was conducted in the CESAM simulation chamber to investigate the evolution of the physical and chemical properties of secondary organic aerosol (SOA) during different forcing. The present experiments represent a first attempt to comprehensively investigate the influence of oxidative processing, photochemistry, and diurnal temperature cycling upon SOA properties. SOA generated from the ozonolysis of ?-pinene were exposed to (1) elevated ozone concentrations, (2) light (under controlled temperature conditions), or (3) light and heat (6 °C light-induced temperature increase), and the resultant changes in SOA optical properties (i.e. absorption and scattering), hygroscopicity and chemical composition were measured using a suite of instrumentation interfaced to the CESAM chamber. The complex refractive index (CRI) was derived from integrated nephelometer measurements at 525 nm wavelength, using Mie scattering calculations and measured number size distributions. The particle size growth factor (GF) was measured with a hygroscopic tandem differential mobility analyzer (H-TDMA). An aerosol mass spectrometer (AMS) was used for the determination of the f44 / f43 and O : C ratio of the particles bulk. No change in SOA size or chemical composition was observed during O3 and light exposure at constant temperature; in addition, GF and CRI of the SOA remained constant with forcing. By contrast, illumination of the SOA in the absence of temperature control led to an increase in the real part of the CRI from 1.35 (±0.03) to 1.49 (±0.03), an increase of the GF from 1.04 (±0.02) to 1.14 (±0.02) and an increase of the f44 / f43 ratio from 1.73 (±0.03) to 2.23 (±0.03). These surprising results suggest that SOA properties may be governed more by local temperature fluctuations than by oxidative processing and photochemistry.

  6. Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Madronich, S.; Aumont, B.; Baker, A.; Camredon, M.; Hodzic, A.; Tyndall, G. S.; Apel, E.; Zaveri, R. A.

    2011-12-01

    The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 ?g m-3, and SOA peaking at 10-15 ?g m-3 during mid-day. The majority (?75%) of the model SOA stems from reaction products of the large n-alkanes, used here as surrogates for all emitted hydrocarbons of similar volatility, with the remaining SOA originating mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by ?-hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

  7. Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

    NASA Astrophysics Data System (ADS)

    Lee-Taylor, J.; Madronich, S.; Aumont, B.; Camredon, M.; Hodzic, A.; Tyndall, G. S.; Apel, E.; Zaveri, R. A.

    2011-06-01

    The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 ?g m-3, and SOA peaking at 10-15 ?g m-3 during mid-day. The majority (?75 %) of the model SOA stems from the large n-alkanes, with the remainder mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by ?-hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

  8. Explicit modeling of organic chemistry and secondary organic aerosol partitioning for Mexico City and its outflow plume

    SciTech Connect

    Lee-Taylor, J.; Madronich, Sasha; Aumont, B.; Baker, A.; Camredon, M.; Hodzic, Alma; Tyndall, G. S.; Apel, Eric; Zaveri, Rahul A.

    2011-12-21

    The evolution of organic aerosols (OA) in Mexico City and its outflow is investigated with the nearly explicit gas phase photochemistry model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere), wherein precursor hydrocarbons are oxidized to numerous intermediate species for which vapor pressures are computed and used to determine gas/particle partitioning in a chemical box model. Precursor emissions included observed C3-10 alkanes, alkenes, and light aromatics, as well as larger n-alkanes (up to C25) not directly observed but estimated by scaling to particulate emissions according to their volatility. Conditions were selected for comparison with observations made in March 2006 (MILAGRO). The model successfully reproduces the magnitude and diurnal shape for both primary (POA) and secondary (SOA) organic aerosols, with POA peaking in the early morning at 15-20 ug m-3, and SOA peaking at 10-15 ?g m-3 during mid-day. The majority (> 75%) of the model SOA stems from the large n-alkanes, with the remainder mostly from the light aromatics. Simulated OA elemental composition reproduces observed H/C and O/C ratios reasonably well, although modeled ratios develop more slowly than observations suggest. SOA chemical composition is initially dominated by *- hydroxy ketones and nitrates from the large alkanes, with contributions from peroxy acyl nitrates and, at later times when NOx is lower, organic hydroperoxides. The simulated plume-integrated OA mass continues to increase for several days downwind despite dilution-induced particle evaporation, since oxidation chemistry leading to SOA formation remains strong. In this model, the plume SOA burden several days downwind exceeds that leaving the city by a factor of >3. These results suggest significant regional radiative impacts of SOA.

  9. Secondary aerosol formation in the planetary boundary layer: observations on board on a Zeppelin and analysis by back plume approach

    NASA Astrophysics Data System (ADS)

    Kazanas, Konstantinos; Rubach, Florian; Tillmann, Ralf; Mentel, Thomas; Elbern, Hendrik; Wahner, Andreas; Zeppelin Pegasos-Team 2012

    2014-05-01

    The airship Zeppelin NT is an airborne platform capable of flying at low speed throughout the entire planetary boundary layer (PBL), thus the Zeppelin is an ideal platform to study regional processes in the lowest layers of the atmosphere with high spatial resolution. Atmospheric aerosol as a medium long lived tracer substance is of particular interest due to its influence on the global radiation budget. Due to its lifetime of up to several days secondary aerosol at a certain location can result from local production or from transport processes. Flight patterns during the PEGASOS campaign 2012 in the Po Valley included vertical profiles and transects through regions of interest We analysed one flight with North-South transects between the Apennin and San Pietro Capofiume and one flight with vertical profiles near the supersite San Pietro Capofiume to shed light on local production and transport processes. Model analyses were performed by using 12 hour back plumes for selected points of measurements to determine the regions which contributed to the air mass under observation. This analysis was done using the EURopean Air pollution Dispersion and Inverse Modelling (EURAD-IM) system. As a novel method, adjoint (backward) plumes are applied to identify the spread of originating air masses in terms of horizontal and vertical extension, and the influence of precursor species. Flight patterns include 5 points of measurement along the transect on 21.06.2012 and the lowest (ca. 80m), highest (ca. 708m), and medium height (299 to 464m) of 7 vertical profiles on the 20.06.2012.

  10. Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs)

    NASA Astrophysics Data System (ADS)

    Chan, A. W. H.; Kautzman, K. E.; Chhabra, P. S.; Surratt, J. D.; Chan, M. N.; Crounse, J. D.; Kürten, A.; Wennberg, P. O.; Flagan, R. C.; Seinfeld, J. H.

    2009-01-01

    Current atmospheric models do not include secondary organic aerosol (SOA) production from gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs). Recent studies have shown that primary semivolatile emissions, previously assumed to be inert, undergo oxidation in the gas phase, leading to SOA formation. This opens the possibility that low-volatility gas-phase precursors are a potentially large source of SOA. In this work, SOA formation from gas-phase photooxidation of naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in the Caltech dual 28-m3 chambers. Under high-NOx conditions and aerosol mass loadings between 10 and 40 ?g m

  11. Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs)

    NASA Astrophysics Data System (ADS)

    Chan, A. W. H.; Kautzman, K. E.; Chhabra, P. S.; Surratt, J. D.; Chan, M. N.; Crounse, J. D.; Kürten, A.; Wennberg, P. O.; Flagan, R. C.; Seinfeld, J. H.

    2009-05-01

    Current atmospheric models do not include secondary organic aerosol (SOA) production from gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs). Recent studies have shown that primary emissions undergo oxidation in the gas phase, leading to SOA formation. This opens the possibility that low-volatility gas-phase precursors are a potentially large source of SOA. In this work, SOA formation from gas-phase photooxidation of naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in the Caltech dual 28-m3 chambers. Under high-NOx conditions and aerosol mass loadings between 10 and 40 ?g m-3, the SOA yields (mass of SOA per mass of hydrocarbon reacted) ranged from 0.19 to 0.30 for naphthalene, 0.19 to 0.39 for 1-MN, 0.26 to 0.45 for 2-MN, and constant at 0.31 for 1,2-DMN. Under low-NOx conditions, the SOA yields were measured to be 0.73, 0.68, and 0.58, for naphthalene, 1-MN, and 2-MN, respectively. The SOA was observed to be semivolatile under high-NOx conditions and essentially nonvolatile under low-NOx conditions, owing to the higher fraction of ring-retaining products formed under low-NOx conditions. When applying these measured yields to estimate SOA formation from primary emissions of diesel engines and wood burning, PAHs are estimated to yield 3-5 times more SOA than light aromatic compounds over photooxidation timescales of less than 12 h. PAHs can also account for up to 54% of the total SOA from oxidation of diesel emissions, representing a potentially large source of urban SOA.

  12. Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield

    DOE PAGESBeta

    Lambe, A. T.; Chhabra, P. S.; Onasch, T. B.; Brune, W. H.; Hunter, J. F.; Kroll, J. H.; Cummings, M. J.; Brogan, J. F.; Parmar, Y.; Worsnop, D. R.; et al

    2015-01-01

    We performed a systematic intercomparison study of the chemistry and yields of secondary organic aerosol (SOA) generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0 × 108 to 2.2 × 1010 molec cm?3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2 × 106 to 2 × 107 molec cm?3 over exposure times of several hours. The OH concentration in themore »chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. In most cases, for a specific SOA type the most-oxidized chamber SOA and the least-oxidized flow reactor SOA have similar mass spectra, oxygen-to-carbon and hydrogen-to-carbon ratios, and carbon oxidation states at integrated OH exposures between approximately 1 × 1011 and 2 × 1011 molec cm?3 s, or about 1–2 days of equivalent atmospheric oxidation. This observation suggests that in the range of available OH exposure overlap for the flow reactor and chambers, SOA elemental composition as measured by an aerosol mass spectrometer is similar whether the precursor is exposed to low OH concentrations over long exposure times or high OH concentrations over short exposure times. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.« less

  13. WRF\\/CHEM modeling of impacts of weather conditions modified by urban expansion on secondary organic aerosol formation over Pearl River Delta

    Microsoft Academic Search

    Xuemei Wang; Zhiyong Wu; Guixiong Liang

    2009-01-01

    In this paper, the online Weather Research and Forecasting and Chemistry (WRF\\/CHEM) model, coupled with urban canopy (UCM) and biogenic-emission models, is used to explore impacts of urban expansion on secondary organic aerosols (SOA) formation. Two scenarios of urban maps are used in WRF\\/CHEM to represent early 1990s (pre-urbanization) and current urban distribution in the Pearl River Delta (PRD). Month-long

  14. 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

  15. 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

  16. Effects of Relative Humidity on Ozone and Secondary Organic Aerosol Formation from the Photooxidation of Benzene and Ethylbenzene

    NASA Astrophysics Data System (ADS)

    Jia, L.; Xu, Y.

    2012-12-01

    The formation of ozone and secondary organic aerosol from benzene-NOx and ethylbenzene-NOx irradiations was investigated under different levels of relative humidity (RH) in a smog chamber. The results show that the increase in RH can greatly reduce the maximum O3 by the transformation of -NO2 and -ONO2-containing products into the particle phase. In benzene irradiations, the SOA number concentration increases over 26 times as RH rises from <5% to 80%, and the intensity of the bands of -OH, -C=O and C-OH from SOA samples also greatly increases with RH. In ethylbenzene irradiations, ethylglyoxal favors the formation of monohydrate, which limits the RH effects. During evaporating processes, the lost substances have similar structures for both benzene and ethylbenzene. This demonstrates that ethyl-containing substances are very stable and difficult to evaporate. For benzene some of glyoxal hydrates are left to form C-O-C and C=O-containing species like hemiacetal and acetal after evaporation, whereas for ethylbenzene, glyoxal favors cross reactions with ethylglyoxal during the evaporating process. It is concluded that the increase in RH can irreversibly enhance the yields of SOA from both benzene and ethylbenzene.

  17. Secondary organic aerosol from aqueous reactions of green leaf volatiles with organic triplet excited states and singlet molecular oxygen.

    PubMed

    Richards-Henderson, Nicole K; Pham, Andrew T; Kirk, Benjamin B; Anastasio, Cort

    2015-01-01

    Vegetation emits a class of oxygenated hydrocarbons--the green leaf volatiles (GLVs)--under stress or damage. Under foggy conditions GLVs might be a source of secondary organic aerosol (SOA) via aqueous reactions with hydroxyl radical (OH), singlet oxygen ((1)O2*), and excited triplet states ((3)C*). To examine this, we determined the aqueous kinetics and SOA mass yields for reactions of (3)C* and (1)O2* with five GLVs: methyl jasmonate (MeJa), methyl salicylate (MeSa), cis-3-hexenyl acetate (HxAc), cis-3-hexen-1-ol (HxO), and 2-methyl-3-butene-2-ol (MBO). Second-order rate constants with (3)C* and (1)O2* range from (0.13-22) × 10(8) M(-1) s(-1) and (8.2-60) × 10(5) M(-1) s(-1) at 298 K, respectively. Rate constants with (3)C* are independent of temperature, while values with (1)O2* show significant temperature dependence (Ea = 20-96 kJ mol(-1)). Aqueous SOA mass yields for oxidation by (3)C* are (84 ± 7)%, (80 ± 9)%, and (38 ± 18)%, for MeJa, MeSa, and HxAc, respectively; we did not measure yields for other conditions because of slow kinetics. The aqueous production of SOA from GLVs is dominated by (3)C* and OH reactions, which form low volatility products at a rate that is approximately half that from the parallel gas-phase reactions of GLVs. PMID:25426693

  18. Characterization of polar compounds and oligomers in secondary organic aerosol using liquid chromatography coupled to mass spectrometry.

    PubMed

    Hamilton, Jacqueline F; Lewis, Alastair C; Carey, Trevor J; Wenger, John C

    2008-01-15

    A generic method has been developed for the analysis of polar compounds and oligomers in secondary organic aerosol (SOA) formed during atmospheric simulation chamber experiments. The technique has been successfully applied to SOA formed in a variety of systems, ranging from ozonolysis of biogenic volatile organic compounds to aromatic photooxidation. An example application of the method is described for the SOA produced from the reaction of ozone with cis-3-hexenyl acetate, an important biogenic precursor. A range of solvents were tested as extraction media, and water was found to yield the highest recovery. Extracts were analyzed using reversed-phase liquid chromatography coupled to ion trap mass spectrometry. In order to determine correct molecular weight assignments and increase sensitivity for less polar species, a series of low-concentration mobile-phase additives were used (NaCl, LiBr, NH4OH). Lithium bromide produced better fragmentation patterns, with more structural information than in the other cases with no reduction in sensitivity. The main reaction products identified in the particle-phase were 3-acetoxypropanal, 3-acetoxypropanoic acid, and 3-acetoxypropane peroxoic acid and a series of dimers and trimers up to 500 Da. Structural identification of oligomers indicates the presence of linear polyesters possibly formed via esterfication reactions or decomposition of peroxyhemiacetals. PMID:18081325

  19. FT-IR quantification of the carbonyl functional group in aqueous-phase secondary organic aerosol from phenols

    NASA Astrophysics Data System (ADS)

    George, Kathryn M.; Ruthenburg, Travis C.; Smith, Jeremy; Yu, Lu; Zhang, Qi; Anastasio, Cort; Dillner, Ann M.

    2015-01-01

    Recent findings suggest that secondary organic aerosols (SOA) formed from aqueous-phase reactions of some organic species, including phenols, contribute significantly to particulate mass in the atmosphere. In this study, we employ a Fourier transform infrared (FT-IR) spectroscopic technique to identify and quantify the functional group makeup of phenolic SOA. Solutions containing an oxidant (hydroxyl radical or 3,4-dimethoxybenzaldehyde) and either one phenol (phenol, guaiacol, or syringol) or a mixture of phenols mimicking softwood or hardwood emissions were illuminated to make SOA, atomized, and collected on a filter. We produced laboratory standards of relevant organic compounds in order to develop calibrations for four functional groups: carbonyls (Cdbnd O), saturated C-H, unsaturated C-H and O-H. We analyzed the SOA samples with transmission FT-IR to identify and determine the amounts of the four functional groups. The carbonyl functional group accounts for 3-12% of the SOA sample mass in single phenolic SOA samples and 9-14% of the SOA sample mass in mixture samples. No carbonyl functional groups are present in the initial reactants. Varying amounts of each of the other functional groups are observed. Comparing carbonyls measured by FT-IR (which could include aldehydes, ketones, esters, and carboxylic acids) with eight small carboxylic acids measured by ion chromatography indicates that the acids only account for an average of 20% of the total carbonyl reported by FT-IR.

  20. Overview of the inorganic and organic composition of size-segregated aerosol in Rondônia, Brazil, from the biomass-burning period to the onset of the wet season

    Microsoft Academic Search

    Sandro Fuzzi; Stefano Decesari; Maria Cristina Facchini; Fabrizia Cavalli; Lorenza Emblico; Mihaiela Mircea; Meinrat O. Andreae; Ivonne Trebs; András Hoffer; Pascal Guyon; Paulo Artaxo; Luciana V. Rizzo; Luciene L. Lara; Theotonio Pauliquevis; Willy Maenhaut; Nico Raes; Xuguang Chi; Olga L. Mayol-Bracero; Lydia L. Soto-García; Magda Claeys; Ivan Kourtchev; Jenny Rissler; Erik Swietlicki; Emilio Tagliavini; Gal Schkolnik; Alla H. Falkovich; Yinon Rudich; Gilberto Fisch; Luciana V. Gatti

    2007-01-01

    The aerosol characterization experiment performed within the Large-Scale Biosphere-Atmosphere Experiment in Amazonia–Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) field experiment carried out in Rondônia, Brazil, in the period from September to November 2002 provides a unique data set of size-resolved chemical composition of boundary layer aerosol over the Amazon Basin from the intense biomass-burning period to the onset of the

  1. Aging of secondary organic aerosol generated from the ozonolysis of ?-pinene: effects of ozone, light and temperature

    NASA Astrophysics Data System (ADS)

    Denjean, C.; Formenti, P.; Picquet-Varrault, B.; Camredon, M.; Pangui, E.; Zapf, P.; Katrib, Y.; Giorio, C.; Tapparo, A.; Temime-Roussel, B.; Monod, A.; Aumont, B.; Doussin, J. F.

    2015-01-01

    A series of experiments was conducted in the CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) simulation chamber to investigate the evolution of the physical and chemical properties of secondary organic aerosols (SOAs) during different forcings. The present experiments represent a first attempt to comprehensively investigate the influence of oxidative processing, photochemistry, and diurnal temperature cycling upon SOA properties. SOAs generated from the ozonolysis of ?-pinene were exposed under dry conditions (< 1% relative humidity) to (1) elevated ozone concentrations, (2) light (under controlled temperature conditions) or (3) light and heat (6 °C light-induced temperature increase), and the resultant changes in SOA optical properties (i.e. absorption and scattering), hygroscopicity and chemical composition were measured using a suite of instrumentation interfaced to the CESAM chamber. The complex refractive index (CRI) was derived from integrated nephelometer measurements of 525 nm wavelength, using Mie scattering calculations and measured number size distributions. The particle size growth factor (GF) was measured with a hygroscopic tandem differential mobility analyzer (H-TDMA). An aerosol mass spectrometer (AMS) was used for the determination of the f44 / f43 and O : C ratio of the particles bulk. No change in SOA size or chemical composition was observed during O3 and light exposure at constant temperature; in addition, GF and CRI of the SOA remained constant with forcing. On the contrary, illumination of SOAs in the absence of temperature control led to an increase in the real part of the CRI from 1.35 (±0.03) to 1.49 (±0.03), an increase of the GF from 1.04 (±0.02) to 1.14 (±0.02) and an increase of the f44 / f43 ratio from 1.73 (±0.03) to 2.23 (±0.03). The simulation of the experiments using the master chemical mechanism (MCM) and the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) shows that these changes resulted from the evaporation of semi-volatile and less oxidized SOA species induced by the relatively minor increases in temperature (~ 6 °C). These surprising results suggest that ?-pinene-O3 SOA properties may be governed more by local temperature fluctuations than by oxidative processing and photochemistry.

  2. Characterization of Secondary Organic Aerosols (SOA) from oxidation of biogenic volatile organic compounds (VOCs) using stable isotopes

    NASA Astrophysics Data System (ADS)

    Derseh, R. F.; Larson, T. E.; Perkins, G.; Mora, C. I.; Mazzoleni, L. R.; Putman, A.; Rahn, T.

    2010-12-01

    Recently it was shown that concurrent measurements of the mixing ratio and ?13C values of atmospheric volatile organic compounds (VOCs) can be used to provide information on the extent of chemical processing these VOCs have undergone in the troposphere (Rudolph et al., 2003). As an extension to this approach, we combine the measurement of gas and particulate phase carbon isotope compositions to study the formation of secondary organic aerosol (SOA) from the ozonolysis reaction of different monoterpenes. Different monoterpenes (?-pinene, ?-pinene and limonene) and ozone were injected in to a 1.5 m3 indoor chamber and let to react without the presence of light and OH scavenger under dry conditions. Gas phase samples were collected in MiniVac canisters (400 ml), at a time interval of 30 min. Aerosol samples were collected on quartz fiber filters (Pallflex® Filters) at a flow rate of 9.5 l/min for 3 h. All filters were pretreated at a temperature of 800 °C overnight before sampling. A customized sample pre-concentration system was used for gas phase samples to concentrate the VOC before injecting to a gas chromatograph (Agilent Technologies) coupled to an isotope ratio mass spectrometer (IsoPrime) via a combustion interface (GC-C-IRMS). Prior to the isotopic measurement individual monoterpenes were positively identified using a quadruple mass spectrometer attached to the Gas chromatograph. ?13C of total SOA was measured using an elemental analyzer coupled to the isotope ratio mass spectrometer. In general, the ?13C of SOA formed from ozonolysis of ? -pinene was slightly lower than ?13C of the precursor. The general variability in the isotopic composition of SOA from different monoterpenes and the change in isotopic composition of the gas phase monoterpenes during the ozonolysis experiment will be discussed. Reference Rudolph, J., Anderson, R.S., Czapiewski, K.V., Czuba, E., Ernst, D., Gillespie, T., Huang, L., Rigby, C., & Thompson, A.E. (2003). The stable carbon isotope ratio of biogenic emissions of isoprene and the potential use of stable isotope ratio measurements to study photochemical processing of isoprene in the atmosphere Journal of Atmospheric Chemistry, 44 (1), 39-55.

  3. Atmospheric submicron aerosol composition and particulate organic nitrate formation in a boreal forestland-urban mixed region

    NASA Astrophysics Data System (ADS)

    Hao, L. Q.; Kortelainen, A.; Romakkaniemi, S.; Portin, H.; Jaatinen, A.; Leskinen, A.; Komppula, M.; Miettinen, P.; Sueper, D.; Pajunoja, A.; Smith, J. N.; Lehtinen, K. E. J.; Worsnop, D. R.; Laaksonen, A.; Virtanen, A.

    2014-12-01

    The Puijo aerosol-cloud observation station is a unique measurement site for its location in the mixed region between the boreal forestland and the municipality of Kuopio, Finland. A measurement campaign was carried out at the station during fall 2010. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-Tof-AMS) was deployed to characterize the atmospheric submicron aerosols. Positive matrix factorization (PMF) was applied to the unified high-resolution mass spectra organic species with NO+ and NO2+ ions to discover the intrinsic relationships between the organic and inorganic species and their daily cycles. On average, the submicron aerosols in this study were dominated by organic and sulfate species, composing 48.2 and 28.7% of total observed aerosol mass, respectively, with smaller contributions from ammonium (9.3%), nitrate (4.9%), chloride (0.8%) and BC (8.1%). The sources of these species included the primary emissions originating from the city area, secondary formation from both natural and anthropogenic emissions and regional transport. The PMF analysis succeeded in separating the mixed organic and inorganic spectra into three distinct organic and one inorganic factors. For organic factors, the semi-volatile oxygenated organic aerosol (SVOOA) and low-volatility oxygenated OA (LVOOA) accounted for 54.8 and 36.3% of total organic masses, respectively, while the hydrocarbon-like organic aerosol (HOA) accounted for 8.9% of total organics, with its main source from urban emissions. The inorganic factor is identified as NH4NO3, comprising 6.9% of the fitted aerosol mass by PMF. Based on the PMF results, the nitrate species were separated into organic and inorganic components, with the organic nitrates contributing one-third of the total nitrate mass. The results highlight both anthropogenic and biogenic emissions as important atmospheric aerosol sources in a forest-urban mixed region.

  4. Exploration of Inorganic C and N Assimilation by Soil Microbes with Time-of-Flight Secondary Ion Mass Spectrometry†

    PubMed Central

    Cliff, John B.; Gaspar, Daniel J.; Bottomley, Peter J.; Myrold, David D.

    2002-01-01

    Stable C and N isotopes have long been used to examine properties of various C and N cycling processes in soils. Unfortunately, relatively large sample sizes are needed for accurate gas phase isotope ratio mass spectrometric analysis. This limitation has prevented researchers from addressing C and N cycling issues on microbially meaningful scales. Here we explored the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) to detect 13C and 15N assimilation by individual bacterial cells and to quantify N isotope ratios in bacterial samples and individual fungal hyphae. This was accomplished by measuring the relative abundances of mass 26 (12C14N?) and mass 27 (13C14N? and 12C15N?) ions sputtered with a Ga+ probe from cells adhered to an Si contact slide. TOF-SIMS was successfully used to locate and quantify the relative 15N contents of individual hyphae that grew onto Si contact slides in intimate contact with a model organomineral porous matrix composed of kaolin, straw fragments, and freshly deposited manure that was supplemented with 15NO3?. We observed that the 15N content of fungal hyphae grown on the slides was significantly lower in regions where the hyphae were influenced by N-rich manure than in regions influenced by N-deficient straw. This effect occurred over distances of tens to hundreds of microns. Our data illustrate that TOF-SIMS has the potential to locate N-assimilating microorganisms in soil and to quantify the 15N content of cells that have assimilated 15N-labeled mineral N and shows promise as a tool with which to explore the factors controlling microsite heterogeneities in soil. PMID:12147508

  5. 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 ?g 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.

  6. Evaluation of a quantitative structure-property relationship (QSPR) for predicting mid-visible refractive index of secondary organic aerosol (SOA).

    PubMed

    Redmond, Haley; Thompson, Jonathan E

    2011-04-21

    In this work we describe and evaluate a simple scheme by which the refractive index (? = 589 nm) of non-absorbing components common to secondary organic aerosols (SOA) may be predicted from molecular formula and density (g cm(-3)). The QSPR approach described is based on three parameters linked to refractive index-molecular polarizability, the ratio of mass density to molecular weight, and degree of unsaturation. After computing these quantities for a training set of 111 compounds common to atmospheric aerosols, multi-linear regression analysis was conducted to establish a quantitative relationship between the parameters and accepted value of refractive index. The resulting quantitative relationship can often estimate refractive index to ±0.01 when averaged across a variety of compound classes. A notable exception is for alcohols for which the model consistently underestimates refractive index. Homogenous internal mixtures can conceivably be addressed through use of either the volume or mole fraction mixing rules commonly used in the aerosol community. Predicted refractive indices reconstructed from chemical composition data presented in the literature generally agree with previous reports of SOA refractive index. Additionally, the predicted refractive indices lie near measured values we report for ? = 532 nm for SOA generated from vapors of ?-pinene (R.I. 1.49-1.51) and toluene (R.I. 1.49-1.50). We envision the QSPR method may find use in reconstructing optical scattering of organic aerosols if mass composition data is known. Alternatively, the method described could be incorporated into in models of organic aerosol formation/phase partitioning to better constrain organic aerosol optical properties. PMID:21399787

  7. Evaluation of the Volatility Basis-Set Approach for Modeling Primary and Secondary Organic Aerosol in the Mexico City Metropolitan Area

    NASA Astrophysics Data System (ADS)

    Tsimpidi, A. P.; Karydis, V. A.; Pandis, S. N.; Zavala, M.; Lei, W.; Molina, L. T.

    2007-12-01

    Anthropogenic air pollution is an increasingly serious problem for public health, agriculture, and global climate. Organic material (OM) contributes ~ 20-50% to the total fine aerosol mass at continental mid-latitudes. Although OM accounts for a large fraction of PM2.5 concentration worldwide, the contributions of primary and secondary organic aerosol have been difficult to quantify. In this study, new primary and secondary organic aerosol modules were added to PMCAMx, a three dimensional chemical transport model (Gaydos et al., 2007), for use with the SAPRC99 chemistry mechanism (Carter, 2000; ENVIRON, 2006) based on recent smog chamber studies (Robinson et al., 2007). The new modeling framework is based on the volatility basis-set approach (Lane et al., 2007): both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The emission inventory, which uses as starting point the MCMA 2004 official inventory (CAM, 2006), is modified and the primary organic aerosol (POA) emissions are distributed by volatility based on dilution experiments (Robinson et al., 2007). Sensitivity tests where POA is considered as nonvolatile and POA and SOA as chemically reactive are also described. In all cases PMCAMx is applied in the Mexico City Metropolitan Area during March 2006. The modeling domain covers a 180x180x6 km region in the MCMA with 3x3 km grid resolution. The model predictions are compared with Aerodyne's Aerosol Mass Spectrometry (AMS) observations from the MILAGRO Campaign. References Robinson, A. L.; Donahue, N. M.; Shrivastava, M. K.; Weitkamp, E. A.; Sage, A. M.; Grieshop, A. P.; Lane, T. E.; Pandis, S. N.; Pierce, J. R., 2007. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259-1262. Gaydos, T. M.; Pinder, R. W.; Koo, B.; Fahey, K. M.; Pandis, S. N., 2007. Development and application of a three- dimensional aerosol chemical transport model, PMCAMx. Atmospheric Environment 41, 2594-2611. Carter, W.P.L., 2000. Programs and Files Implementing the SAPRC-99 Mechanism and its Associates Emissions Processing Procedures for Models-3 and Other Regional Models. January 31, 2000. http://pah.cert.ucr.edu/~carter/SAPRC99.htm. Environ, 2006. User's guide to the comprehensive air quality model with extensions (CAMx). Version 4.30. Report prepared by ENVIRON International Corporation, Novato, CA. Lane, T.E.; Donahue, N. M.; Pandis, S. N. 2007. Simulating Secondary Organic Aerosol Formation using the Votality Basis-Set Approach in a Chemical Transport Model, in preperation. CAM (Comision Ambiental Metropolitana) 2006: Inventario de Emisiones 2004 de la Zona Metropolitana del Valle de Mexico, Mexico. Robinson, A. L.; Donahue, N. M.; Shrivastava, M. K.; Weitkamp, E. A.; Sage, A. M.; Grieshop, A. P.; Lane, T. E.; Pandis, S. N.; Pierce, J. R., 2007. Rethinking organic aerosols: semivolatile emissions and photochemical aging. Science 315, 1259-1262.

  8. Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

    NASA Astrophysics Data System (ADS)

    Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prévôt, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

    2010-12-01

    Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the third vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC < 0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.10 to 0.19. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.21 to 0.37.

  9. Impact of aftertreatment devices on primary emissions and secondary organic aerosol formation potential from in-use diesel vehicles: results from smog chamber experiments

    NASA Astrophysics Data System (ADS)

    Chirico, R.; Decarlo, P. F.; Heringa, M. F.; Tritscher, T.; Richter, R.; Prevot, A. S. H.; Dommen, J.; Weingartner, E.; Wehrle, G.; Gysel, M.; Laborde, M.; Baltensperger, U.

    2010-06-01

    Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the final vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC<0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, primary particles with a mobility diameter above 5 nm were 300±19 cm-3, and only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.097 to 0.190. Five hours of oxidation led to a more oxidized OA with an O/C range of 0.208 to 0.369.

  10. Primary and secondary biomass burning aerosols determined by proton nuclear magnetic resonance (H-NMR) spectroscopy during the 2008 EUCAARI campaign in the Po Valley (Italy)

    NASA Astrophysics Data System (ADS)

    Paglione, M.; Saarikoski, S.; Carbone, S.; Hillamo, R.; Facchini, M. C.; Finessi, E.; Giulianelli, L.; Carbone, C.; Fuzzi, S.; Moretti, F.; Tagliavini, E.; Swietlicki, E.; Eriksson Stenström, K.; Prévôt, A. S. H.; Massoli, P.; Canaragatna, M.; Worsnop, D.; Decesari, S.

    2013-12-01

    Atmospheric organic aerosols are generally classified into primary and secondary (POA and SOA) according to their formation processes. An actual separation, however, is challenging when the timescales of emission and of gas-to-particle formation overlap. The presence of SOA formation in biomass burning plumes leads to scientific questions about whether the oxidized fraction of biomass burning aerosol is rather of secondary or primary origin, as some studies would suggest, and about the chemical compositions of oxidized biomass burning POA and SOA. In this study, we apply nuclear magnetic resonance (NMR) spectroscopy to investigate the functional group composition of fresh and aged biomass burning aerosols during an intensive field campaign in the Po Valley, Italy. The campaign was part of the EUCAARI project and was held at the rural station of San Pietro Capofiume in spring 2008. Factor analysis applied to the set of NMR spectra was used to apportion the wood burning contribution and other organic carbon (OC) source contributions, including aliphatic amines. Our NMR results, referred to the polar, water-soluble fraction of OC, show that fresh wood burning particles are composed of polyols and aromatic compounds, with a sharp resemblance with wood burning POA produced in wood stoves, while aged samples are clearly depleted of alcohols and are enriched in aliphatic acids with a smaller contribution of aromatic compounds. The comparison with biomass burning organic aerosols (BBOA) determined by high resolution aerosol mass spectrometry (HR-TOF-AMS) at the site shows only a partial overlap between NMR BB-POA and AMS BBOA, which can be explained by either the inability of BBOA to capture all BB-POA composition, especially the alcohol fraction, or the fact that BBOA account for insoluble organic compounds unmeasured by the NMR. Therefore, an unambiguous composition for biomass burning POA could not be derived from this study, with NMR analysis indicating a higher O / C ratio compared to that measured for AMS BBOA. The comparison between the two techniques substantially improves when adding factors tracing possible contributions from biomass burning SOA, showing that the operational definitions of biomass burning organic aerosols are more consistent between techniques when including more factors tracing chemical classes over a range of oxidation levels. Overall, the non-fossil total carbon fraction was 50-57%, depending on the assumptions on the 14C content of non-fossil carbon, and the fraction of organic carbon estimated to be oxidized organic aerosol (OOA) from HR-TOF-AMS measurements was 73-100% modern.

  11. Primary and secondary biomass burning aerosols determined by proton nuclear magnetic resonance (1H-NMR) spectroscopy during the 2008 EUCAARI campaign in the Po Valley (Italy)

    NASA Astrophysics Data System (ADS)

    Paglione, M.; Saarikoski, S.; Carbone, S.; Hillamo, R.; Facchini, M. C.; Finessi, E.; Giulianelli, L.; Carbone, C.; Fuzzi, S.; Moretti, F.; Tagliavini, E.; Swietlicki, E.; Eriksson Stenström, K.; Prévôt, A. S. H.; Massoli, P.; Canaragatna, M.; Worsnop, D.; Decesari, S.

    2014-05-01

    Atmospheric organic aerosols are generally classified as primary and secondary (POA and SOA) according to their formation processes. An actual separation, however, is challenging when the timescales of emission and gas-to-particle formation overlap. The presence of SOA formation in biomass burning plumes leads to scientific questions about whether the oxidized fraction of biomass burning aerosol is rather of secondary or primary origin, as some studies would suggest, and about the chemical compositions of oxidized biomass burning POA and SOA. In this study, we apply nuclear magnetic resonance (NMR) spectroscopy to investigate the functional group composition of fresh and aged biomass burning aerosols during an intensive field campaign in the Po Valley, Italy. The campaign was part of the EUCAARI project and was held at the rural station of San Pietro Capofiume in spring 2008. Factor analysis applied to the set of NMR spectra was used to apportion the wood burning contribution and other organic carbon (OC) source contributions, including aliphatic amines. Our NMR results, referred to the polar, water-soluble fraction of OC, show that fresh wood burning particles are composed of polyols and aromatic compounds, with a sharp resemblance to wood burning POA produced in wood stoves, while aged samples are clearly depleted of alcohols and are enriched in aliphatic acids with a smaller contribution of aromatic compounds. The comparison with biomass burning organic aerosols (BBOA) determined by high-resolution aerosol mass spectrometry (HR-TOF-AMS) at the site shows only a partial overlap between NMR BB-POA and AMS BBOA, which can be explained by either the inability of BBOA to capture all BB-POA composition, especially the alcohol fraction, or the fact that BBOA account for insoluble organic compounds unmeasured by the NMR. Therefore, an unambiguous composition for biomass burning POA could not be derived from this study, with NMR analysis indicating a higher O / C ratio compared to that measured for AMS BBOA. The comparison between the two techniques substantially improves when adding factors tracing possible contributions from biomass burning SOA, showing that the operational definitions of biomass burning organic aerosols are more consistent between techniques when including more factors tracing chemical classes over a range of oxidation levels. Overall, the non-fossil total carbon fraction was 50-57%, depending on the assumptions about the 14C content of non-fossil carbon, and the fraction of organic carbon estimated to be oxidized organic aerosol (OOA) from HR-TOF-AMS measurements was 73-100% modern.

  12. Measuring Uptake Coefficients and Henry's Law Constants of Gas-Phase Species with Models for Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Fairhurst, M. C.; Waring-Kidd, C.; Ezell, M. J.; Finlayson-Pitts, B. J.

    2014-12-01

    Volatile organic compounds (VOC) are oxidized in the atmosphere and their products contribute to secondary organic aerosol (SOA) formation. These particles have been shown to have effects on visibility, climate, and human health. Current models typically under-predict SOA concentrations from field measurements. Underestimation of these concentrations could be a result of how models treat particle growth. It is often assumed that particles grow via instantaneous thermal equilibrium partitioning between liquid particles and gas-phase species. Recent work has shown that growth may be better represented by irreversible, kinetically limited uptake of gas-phase species onto more viscous, tar-like SOA. However, uptake coefficients for these processes are not known. The goal of this project is to measure uptake coefficients and solubilities for different gases onto models serving as proxies for SOA and determine how they vary based on the chemical composition of the gas and the condensed phase. Experiments were conducted using two approaches: attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and a flow system coupled to a mass spectrometer. The ATR crystal was coated with the SOA proxy and the gas-phase species introduced via a custom flow system. Uptake of the gas-phase species was characterized by measuring the intensity of characteristic IR bands as a function of time, from which a Henry's law constant and initial estimate of uptake coefficients could be obtained. Uptake coefficients were also measured in a flow system where the walls of the flow tube were coated with the SOA proxy and gas-phase species introduced via a moveable inlet. Uptake coefficients were derived from the decay in gas-phase species measured by mass spectrometry. The results of this work will establish a structure-interaction relationship for uptake of gases into SOA that can be implemented into regional and global models.

  13. Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

    PubMed

    Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

    2015-04-21

    Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ?OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ?OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ?OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 ?g mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol. PMID:25797024

  14. Fourier Transform Infrared Spectroscopy for Identification and Quantification of Organic Functional Groups in Aqueous Phase