Sample records for secondary inorganic aerosols

  1. Factors determining the formation of secondary inorganic aerosol: a case study in the Po Valley (Italy)

    NASA Astrophysics Data System (ADS)

    Squizzato, S.; Masiol, M.; Brunelli, A.; Pistollato, S.; Tarabotti, E.; Rampazzo, G.; Pavoni, B.

    2013-02-01

    Physicochemical properties of aerosol were investigated by analyzing the inorganic water soluble content in PM2.5 samples collected in the eastern part of the Po Valley (Italy). In this area the EU limits for many air pollutants are frequently exceeded as a consequence of local sources and regional-scale transport of secondary inorganic aerosol precursors. Nine PM2.5-bound major inorganic ions (F-, Cl-, NO3-, SO42-, Na+, NH4+, K+, Mg2+, Ca2+) were monitored over one year in three sites categorized as semi-rural background, urban background and industrial. The acidic properties of the PM2.5 were studied by applying the recently developed E-AIM thermodynamic model 4 (Extended Aerosol Thermodynamics Model). The experimental data were also examined in relation to the levels of gaseous precursors of secondary inorganic aerosol (SO2, NOx, NO, NO2) and on the basis of some environmental conditions having an effect on the secondary aerosols generation processes. A chemometric procedure using cluster analysis on experimental [NH4+]/[SO42-] molar ratio and NO3- concentration has been applied to determine the conditions needed for ammonium nitrate formation in different chemical environments. Finally, some considerations on the secondary inorganic aerosol formation and the most relevant weather conditions concerning the sulfate-nitrate-ammonium system were also discussed. The obtained results and discussion can help in understanding the secondary aerosol formation dynamics in the Po Valley, which is one of the most critical regions for air pollution in southern Europe.

  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.

    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.

  3. Optical Properties of Mixed Black Carbon, Inorganic and Secondary Organic Aerosols

    SciTech Connect

    Paulson, S E

    2012-05-30

    Summarizes the achievements of the project, which are divided into four areas: 1) Optical properties of secondary organic aerosols; 2) Development and of a polar nephelometer to measure aerosol optical properties and theoretical approaches to several optical analysis problems, 3) Studies on the accuracy of measurements of absorbing carbon by several methods, and 4) Environmental impacts of biodiesel.

  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. H. J.; Denier van der Gon, H. A. C.; Kuenen, J. J. P.; van Meijgaard, E.; van Ulft, L. H.; Cofala, J.; Builtjes, P. J. H.

    2014-07-01

    In this study we present a dynamic model evaluation of the chemistry transport model LOTOS-EUROS 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 the regional climate model RACMO2. Observations at European rural background sites have been used as 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 day-to-day, 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 sulphur 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 1990's while smaller concentration changes and an increasing number of non-significant trends are observed and modelled between 2000-2009. Furthermore, the results confirm former studies showing that the observed trends in sulphate and total nitrate concentrations from 1990 to 2009 are significantly lower than the trends in precursor emissions and precursor concentrations. The model captured these non-linear responses to the emission changes well. Using the LOTOS-EUROS source apportionment module trends in formation efficiency of SIA have been quantified for four European regions. The exercise has revealed a 20-50% more efficient sulphate 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 to 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 1990's used in this study needs to be improved concerning magnitude and spatial distribution.

  5. The secondary formation of inorganic aerosols in the droplet mode through heterogeneous aqueous reactions under haze conditions

    NASA Astrophysics Data System (ADS)

    Wang, Xinfeng; Wang, Wenxing; Yang, Lingxiao; Gao, Xiaomei; Nie, Wei; Yu, Yangchun; Xu, Pengju; Zhou, Yang; Wang, Zhe

    2012-12-01

    Secondary inorganic aerosols play important roles in visibility reduction and in regional haze pollution. To investigate the characteristics of size distributions of secondary sulfates and nitrates as well as their formation mechanisms under hazes, size-resolved aerosols were collected using a Micro-Orifice Uniform Deposit Impactor (MOUDI) at an urban site in Jinan, China, in all four seasons (December 2007-October 2008). In haze episodes, the secondary sulfates and nitrates primarily formed in fine particles, with elevated concentration peaks in the droplet mode (0.56-1.8 ?m). The fine sulfates and nitrates were completely neutralized by ammonia and existed in the forms of (NH4)2SO4 and NH4NO3, respectively. The secondary formation of sulfates, nitrates and ammonium (SNA) was found to be related to heterogeneous aqueous reactions and was largely dependent on the ambient humidity. With rising relative humidity, the droplet-mode SNA concentration, the ratio of droplet-mode SNA to the total SNA, the fraction of SNA in droplet-mode particles and the mass median aerodynamic diameter of SNA presented an exponential, logarithmic or linear increase. Two heavily polluted multi-day haze episodes in winter and summer were analyzed in detail. The secondary sulfates were linked to heterogeneous uptake of SO2 followed by the subsequent catalytic oxidation by oxygen together with iron and manganese in winter. The fine nitrate formation was strongly associated with the thermodynamic equilibrium among NH4NO3, gaseous HNO3 and NH3, and showed different temperature-dependences in winter and summer.

  6. Secondary inorganic aerosol evaluation: Application of a transport chemical model in the eastern part of the Po Valley

    NASA Astrophysics Data System (ADS)

    Pecorari, Eliana; Squizzato, Stefania; Longo, Andrea; Visin, Flavia; Rampazzo, Giancarlo

    2014-12-01

    Secondary inorganic aerosol (SIA) represents an important component of fine particulate matter in Europe. A photochemical model has been used to assess the distribution of secondary inorganic ions (sulfate, nitrate and ammonium) in the eastern part of the Po Valley, close to Venice. Specific meteorological and environmental conditions and very highly urbanized and industrialized areas make this domain one of the most polluted in Europe. Several studies have been conducted to assess particulate matter (PM10 and PM2.5) areal distribution. However, SIA formation dynamics are still a research subject especially in the transition environments, where the changes in the orography and in the land-use can affect air mass movements and atmospheric composition. This paper is a first attempt to simulate SIA distribution by using a photochemical model in the sea/land Venice transition area. Moreover, a modeling approach with clean boundary conditions has been used to check local and regional influence on SIA levels in the domain. Results reveal that, despite the importance of regional influences, local formation processes are important in SIA distribution especially during warm periods. SO42- and NH4+ are more linked to emission sources distribution than NO3- that tends to be more diffused in the study area. The use of a photochemical model, suitably tested in a such complex area, can improve air pollution knowledge and can help in air quality decision making.

  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. Mechanism for production of secondary organic aerosols and their representation in atmospheric models. Final report

    SciTech Connect

    Seinfeld, J.H.; Flagan, R.C.

    1999-06-07

    This document contains the following: organic aerosol formation from the oxidation of biogenic hydrocarbons; gas/particle partitioning of semivolatile organic compounds to model inorganic, organic, and ambient smog aerosols; and representation of secondary organic aerosol formation in atmospheric models.

  9. Future premature mortality due to o3, secondary inorganic aerosols and primary PM in europe - sensitivity to changes in climate, anthropogenic emissions, population and building stock.

    PubMed

    Geels, Camilla; Andersson, Camilla; Hänninen, Otto; Lansø, Anne Sofie; Schwarze, Per E; Skjøth, Carsten Ambelas; Brandt, Jørgen

    2015-01-01

    Air pollution is an important environmental factor associated with health impacts in Europe and considerable resources are used to reduce exposure to air pollution through emission reductions. These reductions will have non-linear effects on exposure due, e.g., to interactions between climate and atmospheric chemistry. By using an integrated assessment model, we quantify the effect of changes in climate, emissions and population demography on exposure and health impacts in Europe. The sensitivity to the changes is assessed by investigating the differences between the decades 2000-2009, 2050-2059 and 2080-2089. We focus on the number of premature deaths related to atmospheric ozone, Secondary Inorganic Aerosols and primary PM. For the Nordic region we furthermore include a projection on how population exposure might develop due to changes in building stock with increased energy efficiency. Reductions in emissions cause a large significant decrease in mortality, while climate effects on chemistry and emissions only affects premature mortality by a few percent. Changes in population demography lead to a larger relative increase in chronic mortality than the relative increase in population. Finally, the projected changes in building stock and infiltration rates in the Nordic indicate that this factor may be very important for assessments of population exposure in the future. PMID:25749320

  10. 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.

  11. Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

    E-print Network

    Zender, Charles

    inorganic thermodynamic equilibrium, ammonia chemistry and dust and seasalt aerosols improve agreement1 Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions Chao Luo1 , Charles S. Zender1 , Huisheng

  12. 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.

  13. 7, 289349, 2007 Secondary aerosol

    E-print Network

    Paris-Sud XI, Université de

    sys- tematic study of aerosol formation from the atmospheric reactions of amines. Based5 on laboratory- abling us to estimate equilibrium constants for the reactions of amines with nitric acid.10 Though Chemistry and Physics Discussions Secondary aerosol formation from atmospheric reactions of aliphatic amines

  14. Secondary Organic Aerosol Formation by Heterogeneous

    E-print Network

    Goddard III, William A.

    Secondary Organic Aerosol Formation by Heterogeneous Reactions of Aldehydes and Ketones: A Quantum), for various short-chain aldehydes and ketones. We show that quantum mechanical gas- phase Gibbs free energies constants (reported as log K) of aerosol-phase chemical reactions, including hydration reactions and aldol

  15. Organic and Inorganic Aerosol Below-Cloud Scavenging by

    E-print Network

    Russell, Lynn

    Organic and Inorganic Aerosol Below-Cloud Scavenging by Suburban New Jersey Precipitation S T E V E removalprocessesassociatedwithprecipitation(or,ingeneral terms, scavenging). The changes in ambient particle distributions showed an average PM1.0 below-cloud scavenging coefficient of 7 Ã? 10-5 ( 3 Ã? 10-5 s-1, with variability associated

  16. Glass transition measurements in mixed organic and organic/inorganic aerosol particles

    NASA Astrophysics Data System (ADS)

    Dette, Hans Peter; Qi, Mian; Schröder, David; Godt, Adelheid; Koop, Thomas

    2014-05-01

    The recent proposal of a semi-solid or glassy state of secondary organic aerosol (SOA) particles has sparked intense research in that area. In particular, potential effects of a glassy aerosol state such as incomplete gas-to-particle partitioning of semi-volatile organics, inhibited chemical reactions and water uptake, and the potential to act as heterogeneous ice nuclei have been identified so far. Many of these studies use well-studied proxies for oxidized organics such as sugars or other polyols. There are, however, few measurements on compounds that do exist in atmospheric aerosol particles. Here, we have performed studies on the phase state of organics that actually occur in natural SOA particles arising from the oxidation of alpha-pinene emitted in boreal forests. We have investigated the two marker compounds pinonic acid and 3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA) and their mixtures. 3-MBCTA was synthesized from methyl isobutyrate and dimethyl maleate in two steps. In order to transfer these substances into a glassy state we have developed a novel aerosol spray drying technique. Dilute solutions of the relevant organics are atomized into aerosol particles which are dried subsequently by diffusion drying. The dried aerosol particles are then recollected in an impactor and studied by means of differential scanning calorimetry (DSC), which provides unambiguous information on the aerosols' phase state, i.e. whether the particles are crystalline or glassy. In the latter case DSC is used to determine the glass transition temperature Tg of the investigated samples. Using the above setup we were able to determine Tg of various mixtures of organic aerosol compounds as a function of their dry mass fraction, thus allowing to infer a relation between Tg and the O:C ratio of the aerosols. Moreover, we also studied the glass transition behavior of mixed organic/inorganic aerosol particles, including the effects of liquid-liquid phase separation upon drying.

  17. Modes in the size distributions of atmospheric inorganic aerosol

    NASA Astrophysics Data System (ADS)

    John, Walter; Wall, Stephen M.; Ondo, Joseph L.; Winklmayr, Wolfgang

    Ambient aerosol in the size range 0.075-16 ?m was sampled with Berner cascade impactors during the summer and fall intensive sampling periods of the Southern California Air Quality Study (SCAQS) of 1987. Deposits on the greased Tedlar stage substrates were extracted with deionized water and analyzed for inorganic anions and cations by ion chromatography. Stage mass data were inverted by a modified version of the Twomey nonlinear iterative algorithm and modes in the inverted size distributions were fitted with lognormal functions. Nine hundred size distributions of ionic species were obtained. Three modes, two submicron and one coarse, were sufficient to fit all of the size distributions. The smallest mode, at 0.2±0.1 ?m, aerodynamic diameter, is probably a condensation mode containing gas phase reaction products. A larger mode, at 0.7±0.2 ?m, is identified as a droplet mode. Evidence was obtained that the droplet mode grew out of the condensation mode by the addition of water and sulfate. During SCAQS, most of the inorganic particle mass was in the droplet mode except during a period of exceptionally low relative humidity. Nitrate was internally mixed with sulfate in the droplet mode. Since most of the aerosol fine mass is included in the ions analyzed, the observed condensation and droplet modes characterize the overall size distribution in the 0.1-1 ?m range, previously described by Whitby as a single accumulation mode.

  18. A study on major inorganic ion composition of atmospheric aerosols.

    PubMed

    Salve, P R; Krupadam, R J; Wate, S R

    2007-04-01

    Atmospheric aerosol samples were collected from Akola and Buldana region covering around 40 sqkm area during October-November 2002 and were analyzed for ten major inorganic ions namely F-, Cl-, NO3-, SO4(2-), PO4(2-), Na+, K+, Ca2+, Mg2+ and NH4+ using ion chromatographic technique. The average mass of aerosols was found to be 225.81 microg/m3 with standard deviation of 31.29 and average total water soluble load of total cations and anions was found to be 4.32 microg/m3. The concentration of ions in samples showed a general pattern as SO4(2-) > NO3- > Cl- > PO4(2-) > F- for anions and Na+ > Ca2+ > NH4+ > Mg2+ > K+ for cations. The overall composition of the aerosols was taken into account to identify the sources. The trend showed higher concentration of sodium followed by calcium, sulfate, nitrate, phosphate and ammoinum and found to be influenced by terrestrial sources. The presence of SO4(2-) and NO3- in aerosols may be due to re-suspension of soil particles. Ca2+, Mg2+ and Cl- are to be derived from soil materials. The presence of NH4+ may be attributed to the reaction of NH3 vapors with acidic gases may react or condense on an acidic particle surface of anthropogenic origin. The atmospheric aerosol is slightly acidic due to neutralization of basicity by SO2 and NO(x). PMID:17915758

  19. Chemistry of secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Yee, Lindsay Diana

    The photooxidation of volatile organic compounds (VOCs) in the atmosphere can lead to the formation of secondary organic aerosol (SOA), a major component of fine particulate matter. Improvements to air quality require insight into the many reactive intermediates that lead to SOA formation, of which only a small fraction have been measured at the molecular level. This thesis describes the chemistry of secondary organic aerosol (SOA) formation from several atmospherically relevant hydrocarbon precursors. Photooxidation experiments of methoxyphenol and phenolic compounds and C12 alkanes were conducted in the Caltech Environmental Chamber. These experiments include the first photooxidation studies of these precursors run under sufficiently low NOx levels, such that RO2 + HO2 chemistry dominates, an important chemical regime in the atmosphere. Using online Chemical Ionization Mass Spectrometery (CIMS), key gas-phase intermediates that lead to SOA formation in these systems were identified. With complementary particle-phase analyses, chemical mechanisms elucidating the SOA formation from these compounds are proposed. Three methoxyphenol species (phenol, guaiacol, and syringol) were studied to model potential photooxidation schemes of biomass burning intermediates. SOA yields (ratio of mass of SOA formed to mass of primary organic reacted) exceeding 25% are observed. Aerosol growth is rapid and linear with the organic conversion, consistent with the formation of essentially non-volatile products. Gas and aerosol-phase oxidation products from the guaiacol system show that the chemical mechanism consists of highly oxidized aromatic species in the particle phase. Syringol SOA yields are lower than that of phenol and guaiacol, likely due to unique chemistry dependent on methoxy group position. The photooxidation of several C12 alkanes of varying structure n-dodecane, 2-methylundecane, cyclododecane, and hexylcyclohexane) were run under extended OH exposure to investigate the effect of molecular structure on SOA yields and photochemical aging. Peroxyhemiacetal formation from the reactions of several multifunctional hydroperoxides and aldehyde intermediates was found to be central to organic growth in all systems, and SOA yields increased with cyclic character of the starting hydrocarbon. All of these studies provide direction for future experiments and modeling in order to lessen outstanding discrepancies between predicted and measured SOA.

  20. 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.

  1. CARES Helps Explain Secondary Organic Aerosols

    SciTech Connect

    Zaveri, Rahul

    2014-03-28

    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.

  2. Morphologies of mixed organic/inorganic/aqueous aerosol droplets.

    PubMed

    Song, Mijung; Marcolli, Claudia; Krieger, Ulrich K; Lienhard, Daniel M; Peter, Thomas

    2013-01-01

    Despite major progress in the understanding of properties of tropospheric aerosol particles, it remains challenging to understand their physical state and morphology. To obtain more detailed knowledge of the phases, phase transitions and morphologies of internally mixed organic/inorganic aerosol particles, we evaluated liquid-liquid phase separation (LLPS), deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of 33 organic/ammonium sulfate (AS)/H2O systems from our own and literature data. The organic fraction consists of single compounds or mixtures with up to ten aliphatic and/or aromatic components with carboxylic acid, hydroxyl, carbonyl, ether, and ester functionalities, covering O : C ratios between 0.29 and 1.33. Thirteen out of these 33 systems did not show LLPS for any of the studied organic-to-inorganic mixing ratios, sixteen underwent LLPS showing core-shell morphology, and four showed both core-shell and partially engulfed configurations depending on the organic-to-inorganic ratio and RH. In all cases the organic fractions of the systems with partially engulfed configurations consisted of dicarboxylic acids. AS in mixed organic/AS/H2O particles deliquesced between 70 and 84% RH. AS effloresced below 58% RH or remained in a one-liquid-phase state. AS in droplets with LLPS always showed efflorescence with ERH between 30 and 50% RH, providing clear evidence that the presence of LLPS facilitates AS efflorescence. Spreading coefficients of the organic-rich phase on the AS-rich phase for systems containing polyethylene glycol 400 (PEG-400) and a mixture of dicarboxylic acids are in agreement with the optically observed morphologies of droplets deposited on the hydrophobic substrate. Analysis of high resolution elastic Mie resonance spectra allowed the detection of LLPS for single levitated droplets consisting of PEG-400/AS/ H2O, whereas LLPS was difficult to detect in (2-methylglutaric acid + 3-methylglutaric acid + 2,2-dimethylsuccinic acid)/AS/H2O. Measured Mie spectra of PEG-400/AS/H2O at 93.5% and at 80.9% RH agreed with computed Mie spectra for a homogeneous and a core-shell configuration, respectively, confirming the results obtained from droplets deposited on a hydrophobic substrate. Based on the presented evidence, we therefore consider the core-shell morphology to be the prevalent configuration of liquid-liquid-phase-separated tropospheric organic/AS/H2O particles. PMID:24601008

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

    Microsoft Academic Search

    Daisuke Goto; Toshihiko Takemura; Teruyuki Nakajima

    2008-01-01

    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

  4. A COMPARATIVE REVIEW OF INORGANIC AEROSOL THERMODYNAMIC EQUILIBRIUM MODULES: SIMILARITIES, DIFFERENCES, AND THEIR LIKELY CAUSES

    EPA Science Inventory

    A comprehensive comparison of five inorganic aerosol thermodynamic equilibrium modules, MARS-A, SEQUILIB, SCAPE2, EQUISOLV II, and AIM2, was conducted for a variety of atmospheric concentrations of particulate matter (PM) constituents, relative humidities (RHs), and temperatures....

  5. Cloud Condensation Nuclei (CCN) Analysis of Biogenic Secondary Organic Aerosol

    E-print Network

    Collins, Gary S.

    Cloud Condensation Nuclei (CCN) Analysis of Biogenic Secondary Organic Aerosol Rachel L. Atlas1 Cloud condensation nuclei (CCN) are particles which water vapor condenses onto to form cloud droplets collection program. Chamber Experiments An aerosol's ability to act as a CCN is described by the Kohler

  6. 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 ...

  7. A Review of Secondary Organic Aerosol (SOA) Formation from Isoprene

    EPA Science Inventory

    Recent field and laboratory evidence indicates that the oxidation of isoprene forms secondary organic aerosol (SOA). Global biogenic emissions of isoprene (600 Tg yr-1) are sufficiently large the formation of SOA is even small yields results in substantial production ...

  8. Evaluation of biogenic emission flux and its impact on oxidants and inorganic aerosols in East Asia

    NASA Astrophysics Data System (ADS)

    Han, K. M.; Song, C. H.; Park, R. S.; Woo, J.; Kim, H.

    2010-12-01

    As a major precursor during the summer season, biogenic species are of primary importance in the ozone and SOAs (secondary organic aerosols) formations. Isoprene and mono-terpene also influence the level of inorganic aerosols (i.e. sulfate and nitrate) by controlling OH radicals. However, biogenic emission fluxes are highly uncertain in East Asia. While isoprene emission fluxes from the GEIA (Global Emissions Inventory Activity) and POET (Precursors of Ozone and their Effects in the Troposphere) inventories estimate approximately 20 Tg yr-1 in East Asia, those from the MEGAN (Model of Emissions of Gases and Aerosols from Nature) and MOHYCAN (MOdel for Hydrocarbon emissions by the CANopy) estimate approximately 10 Tg yr-1 and 5 Tg yr-1, respectively. In order to evaluate and/or quantify the magnitude of biogenic emission fluxes over East Asia, the tropospheric HCHO columns obtained from the GOME (Global Ozone Monitoring Experiment) observations were compared with the HCHO columns from the CMAQ (Community Multi-scale Air Quality) simulations over East Asia. In this study, US EPA Models-3/CMAQ v4.5.1 model simulation using the ACE-ASIA (Asia Pacific Regional Aerosol Characterization Experiment) emission inventory for anthropogenic pollutants and GEIA, POET, MEGAN, and MOHYCAN emission inventories for biogenic species was carried out in conjunction with the Meteorological fields generated from the PSU/NCAR MM5 (Pennsylvania state University/National Center for Atmospheric Research Meso-scale Model 5) model for the summer episodes of the year 2002. In addition to an evaluation of the biogenic emission flux, we investigated the impact of the uncertainty in biogenic emission inventory on inorganic aerosol formations and variations of oxidants (OH, O3, and H2O2) in East Asia. In this study, when the GEIA and POET emission inventories are used, the CMAQ-derived HCHO columns are highly overestimated over East Asia, particularly South China compared with GOME-derived HCHO columns. The CMAQ-derived HCHO columns using the MOHYCAN emission inventory have similar values with the GOME-derived HCHO columns over East Asia. Also, differences in biogenic emission fluxes lead to changes in the levels of nitrates by changing the OH radical concentrations.

  9. 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.

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

    EPA Science Inventory

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

  11. ATR-FTIR characterization of organic functional groups and inorganic ions in ambient aerosols at a rural site

    NASA Astrophysics Data System (ADS)

    Coury, Charity; Dillner, Ann M.

    An Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopic method was used to measure organic functional groups and inorganic ions at Tonto National Monument (TNM), an Interagency Monitoring of Protected Visual Environments (IMPROVE) sampling site in a rural area near Phoenix, Arizona. Functional groups and ions from common aerosol compound classes such as aliphatic and aromatic CH, methylene, methyl, aldehydes/ketones, carboxylic acids, ammonium sulfate and nitrate as well as functional groups from difficult to measure compound classes such as esters/lactones, acid anhydrides, carbohydrate hydroxyl and ethers, amino acids, and amines were quantified. On average, ˜33% of the PM 1.0 mass was composed of organic aerosol. The average (standard deviation) composition of the organic aerosol at TNM was 34% (6%) biogenic functional groups, 21% (5%) oxygenated functional groups, 28% (7%) aliphatic hydrocarbon functional groups (aliphatic CH, methylene and methyl) and 17% (1%) aromatic hydrocarbon functional groups. Compositional analysis, functional group correlations, and back trajectories were used to identify three types of events with source signatures: primary biogenic-influenced, urban-influenced, and regional background. The biogenic-influenced event had high concentrations of amino acids and carbohydrate hydroxyl and ether, as well as aliphatic CH and aromatic CH functional groups and qualitatively high levels of silicate. The urban-influenced events had back trajectories traveling directly from the Phoenix area and high concentrations of hydrocarbons, oxygenated functional groups, and inorganic ions. This aerosol characterization suggests that both primary emissions in Phoenix and secondary formation of aerosols from Phoenix emissions had a major impact on the aerosol composition and concentration at TNM. The regional background source had low concentrations of all functional groups, but had higher concentrations of biogenic functional groups than the urban source.

  12. A large source of low-volatility secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard; Sipilä, Mikko; Junninen, Heikki; Pullinen, Iida; Springer, Monika; Rubach, Florian; Tillmann, Ralf; Lee, Ben; Lopez-Hilfiker, Felipe; Andres, Stefanie; Acir, Ismail-Hakki; Rissanen, Matti; Jokinen, Tuija; Schobesberger, Siegfried; Kangasluoma, Juha; Kontkanen, Jenni; Nieminen, Tuomo; Kurtén, Theo; Nielsen, Lasse B.; Jørgensen, Solvejg; Kjaergaard, Henrik G.; Canagaratna, Manjula; Maso, Miikka Dal; Berndt, Torsten; Petäjä, Tuukka; Wahner, Andreas; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R.; Wildt, Jürgen; Mentel, Thomas F.

    2014-02-01

    Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene ?-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

  13. A large source of low-volatility secondary organic aerosol.

    PubMed

    Ehn, Mikael; Thornton, Joel A; Kleist, Einhard; Sipilä, Mikko; Junninen, Heikki; Pullinen, Iida; Springer, Monika; Rubach, Florian; Tillmann, Ralf; Lee, Ben; Lopez-Hilfiker, Felipe; Andres, Stefanie; Acir, Ismail-Hakki; Rissanen, Matti; Jokinen, Tuija; Schobesberger, Siegfried; Kangasluoma, Juha; Kontkanen, Jenni; Nieminen, Tuomo; Kurtén, Theo; Nielsen, Lasse B; Jørgensen, Solvejg; Kjaergaard, Henrik G; Canagaratna, Manjula; Maso, Miikka Dal; Berndt, Torsten; Petäjä, Tuukka; Wahner, Andreas; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R; Wildt, Jürgen; Mentel, Thomas F

    2014-02-27

    Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene ?-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally. PMID:24572423

  14. Improvement and further development in CESM/CAM5: gas-phase chemistry and inorganic aerosol treatments

    NASA Astrophysics Data System (ADS)

    He, J.; Zhang, Y.

    2014-09-01

    Gas-phase chemistry and subsequent gas-to-particle conversion processes such as new particle formation, condensation, and thermodynamic partitioning have large impacts on air quality, climate, and public health through influencing the amounts and distributions of gaseous precursors and secondary aerosols. Their roles in global air quality and climate are examined in this work using the Community Earth System Model version 1.0.5 (CESM1.0.5) with the Community Atmosphere Model version 5.1 (CAM5.1) (referred to as CESM1.0.5/CAM5.1). CAM5.1 includes a simple chemistry that is coupled with a 7-mode prognostic Modal Aerosol Model (MAM7). MAM7 includes classical homogenous nucleation (binary and ternary) and activation nucleation (empirical first-order power law) parameterizations, and a highly simplified inorganic aerosol thermodynamics treatment that only simulates particulate-phase sulfate and ammonium. In this work, a new gas-phase chemistry mechanism based on the 2005 Carbon Bond Mechanism for Global Extension (CB05_GE) and several advanced inorganic aerosol treatments for condensation of volatile species, ion-mediated nucleation (IMN), and explicit inorganic aerosol thermodynamics for sulfate, ammonium, nitrate, sodium, and chloride have been incorporated into CESM/CAM5.1-MAM7. Compared to the simple gas-phase chemistry, CB05_GE can predict many more gaseous species, and thus could improve model performance for PM2.5, PM10, PM components, and some PM gaseous precursors such as SO2 and NH3 in several regions as well as aerosol optical depth (AOD) and cloud properties (e.g., cloud fraction (CF), cloud droplet number concentration (CDNC), and shortwave cloud forcing, SWCF) on the global scale. The modified condensation and aqueous-phase chemistry could further improve the prediction of additional variables such as HNO3, NO2, and O3 in some regions, and new particle formation rate (J) and AOD on the global scale. IMN can improve the prediction of secondary PM2.5 components, PM2.5, and PM10 over Europe as well as AOD and CDNC on the global scale. The explicit inorganic aerosol thermodynamics using the ISORROPIA II model improves the prediction of all major PM2.5 components and their gaseous precursors in some regions as well as downwelling shortwave radiation, SWCF, and cloud condensation nuclei at a supersaturation of 0.5% on the global scale. For simulations of 2001-2005 with all the modified and new treatments, the improved model predicts that on global average, SWCF increases by 2.7 W m-2, reducing the normalized mean bias (NMB) of SWCF from -5.4 to 1.2%. Uncertainties in emissions can largely explain the inaccurate prediction of precursor gases (e.g., SO2, NH3, and NO) and primary aerosols (e.g., black carbon and primary organic matter). Additional factors leading to the discrepancies between model predictions and observations include assumptions associated with equilibrium partitioning for fine particles assumed in ISORROPIA II, irreversible gas/particle mass transfer treatment for coarse particles, uncertainties in model treatments such as dust emissions, secondary organic aerosol formation, multi-phase chemistry, cloud microphysics, aerosol-cloud interaction, dry and wet deposition, and model parameters (e.g., accommodation coefficients and prefactors of the nucleation power law) as well as uncertainties in model configuration such as the use of a coarse-grid resolution.

  15. 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.

  16. Persistent sensitivity of Asian aerosol to emissions of nitrogen oxides

    E-print Network

    Kharol, S. K.

    We use a chemical transport model and its adjoint to examine the sensitivity of secondary inorganic aerosol formation to emissions of precursor trace gases from Asia. Sensitivity simulations indicate that secondary inorganic ...

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. Effects of Organic-Inorganic Interactions on the Hygroscopicity of Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Lienhard, D.; Krieger, U. K.

    2013-12-01

    Aerosol hygroscopicity is an important property affecting size as well as phase transitions and viscosity of soluble or partially soluble particles following changes in ambient relative humidity (RH) and temperature. The effects of hygroscopic particle growth on the water contents and physical states of aerosol phases in turn may significantly affect multiphase chemistry, the direct effect of aerosols on climate, and the ability of specific particles to act as cloud condensation or ice nuclei. The hygroscopic growth of organic-inorganic mixtures in stable or metastable equilibrium with the RH of the surrounding air is governed by chemical thermodynamics and can be described, in principle, by adequate thermodynamic models. Organic-inorganic interactions involving dissolved ionic species in liquid (potentially highly viscous) phases tend to deviate substantially from ideal mixing and can lead to hygroscopicity behaviour deviating from simple linear additivity assumptions at given RH. The latter assumptions are employed in the Zdanovskii-Stokes-Robinson (ZSR) mixing rule, which is typically found to describe hygroscopic mass growth well in the RH range of completely liquid aerosol systems. We present a comparison and discussion of thermodynamic calculations based on the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and hygroscopic growth factor data from new measurements with an electrodynamic balance (EDB) as well as data from the literature. We focus on the different hygroscopicity features below the full deliquescence RH of multicomponent organic-inorganic systems. Experiments and model calculations are performed for different multicomponent systems showing varying degrees of organic-inorganic miscibility, including liquid-liquid phase separation, hygroscopicity, and hysteresis effects between metastable and stable gas-aerosol equilibria. It is found that depending on the hygroscopicity of the organic aerosol fraction and its miscibility with inorganic solutes, the water uptake prior to deliquescence can be substantial due to partial dissolution of electrolytes. This behaviour is not captured with a traditional ZSR parameterization, therefore, semi-empirical hygroscopicity parameterizations have been suggested recently. We show that the AIOMFAC-based equilibrium model is able to describe the causes of the water uptake based on solid-liquid and liquid-liquid equilibria between the coexisting aerosol phases. The model furthermore correctly accounts for the shift in the deliquescence RH of ammonium sulfate and other salts in aerosol mixtures, a thermodynamic effect caused by organic-inorganic interactions.

  2. 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...

  3. Secondary organic material formed by methylglyoxal in aqueous aerosol mimics

    E-print Network

    Meskhidze, Nicholas

    p. 1 Secondary organic material formed by methylglyoxal in aqueous aerosol mimics N. Sareen, A as a function of wavelength. Each aqueous solution initially contained 1.62 M methylglyoxal and: no salt, 5.1 M initially containing 1.62 M methylglyoxal and 3.1 M (NH4)2SO4 which was protected from light until analysis

  4. Spatial and Seasonal Trends in Biogenic Secondary Organic Aerosol

    E-print Network

    Zheng, Mei

    of fine particulate matter (PM2.5) were collected from May 2004 to April 2005 at one rural site and three than 2.5 µm (PM2.5), formed from primary emissions and through secondary formation, can lead aerosol and PM2.5. SOA tracers in the particle phase can be produced by photochemical oxidation

  5. Molecular transformations accompanying the aging of laboratory secondary organic aerosol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The aging of fresh secondary organic aerosol, generated by alpha-pinene ozonolysis in a flow tube reactor, was studied by passing it through a second reaction chamber where hydroxyl radicals were generated. Two types of experiments were performed: plug injection experiments where the particle mass a...

  6. Effect of Hydrophobic Primary Organic Aerosols on Secondary Organic Aerosol Formation from Ozonolysis of ?-Pinene

    SciTech Connect

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

    2007-10-16

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

  7. A Phase Equilibrium Model for Atmospheric Aerosols Containing Inorganic Electrolytes and Dicarboxylic Acids (UHAERO)

    NASA Astrophysics Data System (ADS)

    Martynenko, A. V.; Amundson, N.; Caboussat, A.; He, J.; Seinfeld, J. H.

    2006-12-01

    Atmospheric aerosols contain a significant fraction of organic compounds. While a variety of thermodynamic models have been developed to predict inorganic gas-aerosol equilibrium, the prediction of phase equilibrium for mixed inorganic/organic aerosols has gathered much less attention. Presented here is a phase equilibrium model for atmospheric aerosols containing inorganic electrolytes and dicarboxylic acids, including oxalic, malonic, succinic, glutaric, maleic, and malic acids. The computational framework of UHAERO is based on minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. The water update and deliquescence properties of aqueous solutions of dicarboxylic acids, and their mixtures with salts, are treated using a hybrid thermodynamic approach, namely the CSB model, in which existing models of inorganic (electrolyte) multicomponent solutions and water/organic mixtures are combined in a self consistent way. The model computes deliquescence behavior without any a priori specification of the relative humidities of deliquescence. Detailed phase diagrams of the sulfate/nitrate/ammonium/dicarboxylic acid/water system are presented as a function of relative humidity at 298.15K over the complete space of composition.

  8. The impact of long-range transport on secondary aerosol in Northeast Asia

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Carmichael, G. R.; Woo, J.; Zhang, Q.

    2013-12-01

    Long-range transport air pollution is an important issue in Northeast Asia. Large amounts of anthropogenic emissions of SO2 and NOx aggravate air pollution in the region. Most of the emissions come from the industrialized regions along the East China coast. China and Korea are changing their air quality standards for particle pollutant from PM10 to PM2.5 in 2012 and 2015, respectively. According to many previous studies, the long-rang transport of particle matter contributes to Korean air pollution problems, but there are many uncertainties regarding the impact of long range transport. Secondary inorganic aerosols (sulfate, nitrate and ammonium) are dominant ionic contributors to PM2.5. Especially high relative contributions of secondary aerosol appear under westerly wind cases at Korea. The secondary aerosols are produced by converting from SO2 and NOx during the long-range transport, but the contribution varies dramatically depending on season and wind pattern. So far, sulfate is the primary contributor to PM2.5, but nitrate levels are increasing because that NOx emissions in China are increasing dramatically since 2000 due to the growth in power, industry, and transport, while SO2 emissions are trending downward since 2005. We will present chemical characteristics of PM2.5 by westerly long-range transport focused on secondary aerosol, tracking their transport pattern, and production pathway in order to better understand regional air quality modeling of the long-range transport. This study will be performed based on the international study, MICS-Asia phase III, initiated with many researchers. Results using CMAQ with the modeling domain covering Northeast and Southeast China, Korea, and Japan with 15km resolution will be discussed.

  9. 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.

  10. PREDICTION OF MULTICOMPONENT INORGANIC ATMOSPHERIC AEROSOL BEHAVIOR. (R824793)

    EPA Science Inventory

    Many existing models calculate the composition of the atmospheric aerosol system by solving a set of algebraic equations based on reversible reactions derived from thermodynamic equilibrium. Some models rely on an a priori knowledge of the presence of components in certain relati...

  11. Indoor and outdoor concentrations of inorganic acidic aerosols and gases

    SciTech Connect

    Brauer, M.; Koutrakis, P.; Keeler, G.J.; Spengler, J.D. (Harvard Univ., Boston, MA (USA))

    1991-02-01

    Annular denuder-filter pack sampling systems were used to make indoor and outdoor measurements of aerosol strong H{sup +}, SO{sub 4}{sup 2{minus}}, NH{sub 4}{sup +}, NO{sub 3}{sup {minus}} and NO{sub 2}{sup {minus}}, and the gaseous pollutants SO{sub 2}, HNO{sub 3}, HONO and NH{sub 3} during summer and winter periods in Boston, Massachusetts. Outdoor levels of SO{sub 2}, HNO{sub 3}, H{sup +} and SO{sub 4}{sup 2{minus}} exceeded their indoor concentrations during both seasons. Winter indoor/outdoor ratios were lower than during the summer, probably due to lower air exchange rates during the winter period. During both monitoring periods, indoor/outdoor ratios of aerosol strong H{sub +} were 40-50% of the indoor/outdoor SO{sub 4}{sup 2{minus}} ratio. Since aerosol strong acidity is typically associated with SO{sub 4}{sup 2{minus}}, this finding is indicative of neutralization of the acidic aerosol by the higher indoor NH{sub 3} levels. Geometric mean indoor/outdoor NH{sub 3} ratios of 3.5 and 23 respectively were measured for the summer and winter sampling periods. For HONO, NH{sub 3}, NH{sub 4}{sup +} and NO{sub 2}{sup {minus}}, indoor concentrations were significantly higher than ambient levels. Indoor levels of NO{sub 3}{sup {minus}} were slightly less than outdoor concentrations.

  12. Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM

    SciTech Connect

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, Ditte; Rusanen, A.; Boy, Michael; Swietlicki, E.; Svenningsson, Birgitta; Zelenyuk, Alla; Pagels, J.

    2014-08-11

    We have developed the novel Aerosol Dynamics, gas- and particle- phase chemistry model for laboratory CHAMber studies (ADCHAM). The model combines the detailed gas phase Master Chemical Mechanism version 3.2, an aerosol dynamics and particle phase chemistry module (which considers acid catalysed oligomerization, heterogeneous oxidation reactions in the particle phase and non-ideal interactions between organic compounds, water and inorganic ions) and a kinetic multilayer module for diffusion limited transport of compounds between the gas phase, particle surface and particle bulk phase. In this article we describe and use ADCHAM to study: 1) the mass transfer limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), 2) the slow and almost particle size independent evaporation of ?-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.

  13. 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.

  14. Aerosol Precursor Emissions, Secondary Aerosol Production, and Climate-Forcing Gas Exchange in the Midwestern United States

    NASA Astrophysics Data System (ADS)

    Doskey, P. V.

    2009-12-01

    Aerosol precursors in the Midwest are generated from a myriad of sources including biogenic emissions of terpenes from the Ozarks region, anthropogenic emissions of volatile and semivolatile aliphatic and aromatic hydrocarbons from the St. Louis airshed, and agricultural emissions of ammonia (NH3), amines, and nitrogen oxides (NOx) from animal husbandry and cropping systems of the Midwest Corn Belt. The deciduous and coniferous forests of the Ozarks region are significant sources of isoprene, monoterpenes, and sesquiterpenes that are sensitive to rising CO2 levels and temperature and generate light-scattering, secondary organic aerosol (SOA). Application of nitrogen fertilizers stimulates emissions of ammonia (NH3), nitric oxide (NO), and nitrous oxide (N2O) from agricultural soils and crops. Nitric acid, generated through photooxidation of NO emissions from fossil fuel combustion in urban air and from soil emissions in agroecosystems, reacts rapidly with NH3 to generate light-scattering, secondary inorganic aerosol (SIA). The atmospheric lifetime of N2O is about 120 years, making the substance a potent greenhouse gas with a global warming potential of 290 for a time horizon of 20 years relative to CO2. Emissions of CO2, N2O, and SIA precursors from the Midwest Corn Belt and surrounding areas are likely to increase in the near future as pastureland and prairie is converted to grow corn and other biofuel crops to meet the demand for renewable fuels. Several large river systems transport nutrients from fertilized fields of the Midwest agroecosystem to the Gulf of Mexico where plankton growth is accelerated. Microbial decomposition of plankton detritus consumes oxygen and creates a hypoxic zone, which might be a significant source of N2O.The presentation will discuss gaps in our knowledge of the production of climate-forcing species in the Midwestern United States.

  15. 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.

  16. The Effect of Organic Compounds on the Hygroscopic Properties of Inorganic Aerosol

    NASA Astrophysics Data System (ADS)

    Krieger, U. K.; Zardini, A. A.; Marcolli, C.

    2006-12-01

    The hygroscopicity of the aerosols plays a major role for the direct and indirect effect on the climate. It is known that aerosols are often a mixture of inorganic and organic matter. A significant fraction of the organic matter is water soluble (WSOC) and affects light scattering, water uptake and phase transitions of multicomponent aerosols. Additionally, organic matter can act as a surfactant around an inorganic particle, affecting the evaporation-condensation time scale. This research project benefits from the combined measurements performed by two different instrumentations: the electrodynamic trap at IACETH, Zürich, Switzerland, and a Tandem Differential Mobility Analizer (TDMA) at the Paul Scherrer Institute, Switzerland. The Electrodynamic Trap consists of a chamber in which a levitated particle can experience all the atmospherically relevant conditions of temperature, pressure, and humidity. All these parameters can be continuously varied so that the hygroscopic curve of the aerosol particle can be measured. Additional tools help to better characterize the aerosol particle: 90 degrees angular scattering of lasers (for radius measurements) and intensity fluctuation of the scattered light with time (for phase changes detection). In this poster the results obtained through the electrodynamic balance technique will be shown and compared with the TDMA. In particular, bicomponent ammonium sulphate with adipic acid bicomponent particles are studied, with different mixing ratios. Particular emphasis is put on assessing the water uptake and the phase changes of the particles.

  17. SECONDARY ORGANIC AEROSOL FORMATION FROM THE OXIDATION OF AROMATIC HYDROCARBONS IN THE PRESENCE OF DRY SUBMICRON AMMONIUM SULFATE AEROSOL

    EPA Science Inventory

    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 ...

  18. Cloud condensation nuclei activity of isoprene secondary organic aerosol

    Microsoft Academic Search

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

    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%)

  19. Reactive intermediates revealed in secondary organic aerosol formation from isoprene

    PubMed Central

    Surratt, Jason D.; Chan, Arthur W. H.; Eddingsaas, Nathan C.; Chan, ManNin; Loza, Christine L.; Kwan, Alan J.; Hersey, Scott P.; Flagan, Richard C.; Wennberg, Paul O.; Seinfeld, John H.

    2010-01-01

    Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = ?-IEPOX + ?-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NOx conditions, respectively. Isoprene low-NOx SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NOx conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NOx SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO2 and NO2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models. PMID:20080572

  20. Formation of secondary organic aerosol in the Paris pollution plume and its impact on surrounding regions

    NASA Astrophysics Data System (ADS)

    Zhang, Q. J.; Beekmann, M.; Freney, E.; Sellegri, K.; Pichon, J. M.; Schwarzenboeck, A.; Colomb, A.; Bourrianne, T.; Michoud, V.; Borbon, A.

    2015-03-01

    Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plume of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI project, an intensive campaign was launched in the Greater Paris Region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind the Paris region. Slopes of the plume OA levels vs. Ox (= O3 + NO2) show secondary OA (SOA) formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. Simulated and observed slopes are in good agreement, when the most realistic "high-NOx" yields are used in the Volatility-Basis-Set scheme implemented into the model. In addition, these slopes are relatively stable from one day to another, which suggest that they are characteristic for the given megacity plume environment. Since OA within the plume is mainly formed from anthropogenic precursors (VOC and primary OA, POA), this work allows a specific evaluation of anthropogenic SOA and SOA formed from primary semi-volatile and intermediate volatile VOCs (SI-SOA) formation scheme in a model. For specific plumes, this anthropogenic OA build-up can reach about 10 ?g m-3. For the average of the month of July 2009, maximum increases occur close to the agglomeration for primary OA are noticed at several tens (for POA) to hundred (for SI-SOA) kilometers of distance from the Paris agglomeration.

  1. Secondary Organic Aerosol Production From Terpenes: Chemical Influences on Aerosol Yields

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Huff-Hartz, K.; Presto, A. A.; Pathak, R.; Robinson, A. L.; Pandis, S. N.

    2005-12-01

    Secondary Organic Aerosol (SOA) generation is caused by the production of relatively low vapor pressure products from higher vapor pressure precursors. Mono- and sesquiterpenes are recognized as major sources of biogenic SOA, especially following ozonolysis. SOA yields, however, depend on numerous factors. First is the widely accepted work of Pankow, Odom, and colleagues demonstrating that the partitioning of semi-volatile compounds depends strongly on the total mass of organic aerosol in a given system; extension of this theory leads us to refute the 'fallacy of the polluting tree'. Biogenic SOA yields in the absence of primary and secondary anthropogenic aerosol would be significantly lower than in polluted urban and regional environments. Other factors strongly influence SOA production. While the reaction mechanism following ozonolysis remains poorly defined, we have recently shown that SOA yields decline dramatically under high NOx conditions. However, continued oxidation, or aging, of semi-volatile organics in either phase will tend to further lower product vapor pressures, thus increasing aerosol yields. In addition to recent experimental results addressing all of these issues, we shall present a unifying framework for modeling semi-volatile partitioning and aerosol aging.

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

    EPA Science Inventory

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

  3. Secondary organic aerosol formation through cloud processing of aromatic VOCs

    NASA Astrophysics Data System (ADS)

    Herckes, P.; Hutchings, J. W.; Ervens, B.

    2010-12-01

    Field observations have shown substantial concentrations (20-5,500 ng L-1) of aromatic volatile organic compounds (VOC) in 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 laboratory conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase. 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 rates decreased with increasing organic carbon content. Kinetic data derived from these experiments were used as input to a multiphase box model in order to evaluate the secondary organic aerosol (SOA) mass formation potential of cloud processing of BTEX. Model results will be presented that quantify the SOA amounts from these aqueous phase pathways. The efficiency of this multiphase SOA source will be compared to SOA yields from the same aromatics as treated in traditional SOA models that are restricted to gas phase oxidation and subsequent condensation on particles.

  4. Investigating hygroscopic behavior and phase separation of organic/inorganic mixed phase aerosol particles with FTIR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zawadowicz, M. A.; Cziczo, D. J.

    2013-12-01

    Atmospheric aerosol particles can be composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have very well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. For example, the deliquescence relative humidity of pure ammonium sulfate is about 80% and its efflorescence point is about 35%. This behavior of ammonium sulfate is important to atmospheric chemistry because some reactions, such as the hydrolysis of nitrogen pentoxide, occur on aqueous but not crystalline surfaces. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosol are not typically a single inorganic salt, instead they often contain organic as well as inorganic species. Mixed inorganic/organic aerosol particles, while abundant in the atmosphere, have not been studied as extensively. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. This project investigates the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O:C ratios, including glycerol, 1,2,6-hexanetriol, 1,4-butanediol and 1,5-pentanediol have been investigated. This project aims to study gas-phase exchange in these aerosol systems to determine if exchange is impacted when phase separation occurs.

  5. Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy.

    PubMed

    Choi, Man Yee; Chan, Chak K

    2005-02-17

    The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets. PMID:16833412

  6. 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.

  7. Organic Aerosol Formation Photoenhanced by the Formation of Secondary Photo-sensitizers in ageing Aerosols

    NASA Astrophysics Data System (ADS)

    Aregahegn, Kifle; Nozière, Barbara; George, Christian

    2013-04-01

    Humankind is facing a changing environment possibly due to anthropogenic stress on the atmosphere. In this context, aerosols play a key role by affecting the radiative climate forcing, hydrological cycle, and by their adverse effect on health. The role of organic compounds in these processes is however still poorly understood because of their massive chemical complexity and numerous transformations. This is particularly true for Secondary Organic Aerosol (SOA), which are produced in the atmosphere by organic gases. Traditionally, the driving forces for SOA growth is believed to be the partitioning onto aerosol seeds of condensable gases, either emitted primarily or resulting from the gas phase oxidation of organic gases. However, even the most up-to-date models based on such mechanisms can not account for the SOA mass observed in the atmosphere, suggesting the existence of other, yet unknown formation processes. The present study shows experimental evidence that particulate phase chemistry produces photo-sensitizers that lead to photo-induced formation and growth of secondary organic aerosol in the near UV and the presence of volatile organic compounds (VOC) such as terpenes. By means of an aerosol flow tube reactor equipped with Scanning Mobility Particle Sizer (SMPS) having Kr-85 source aerosol neutralizer, Differential Mobility Analyser (DMA) and Condensation Particle Sizer (CPC), we identified that traces of the aerosol phase product of glyoxal chemistry as is explained in Gallway et al., and Yu et al., namely imidazole-2-carboxaldehyde (IC) is a strong photo-sensitizer when irradiated by near-UV in the presence of volatile organic compounds such as terpenes. Furthermore, the influence of pH, type and concentration of VOCs, composition of seed particles, relative humidity and irradiation intensity on particle growth were studied. This novel photo-sensitizer contributed to more than 30% of SOA growth in 19min irradiation time in the presence of terpenes in the system and has linear relationship with the irradiation intensity. These results demonstrate that, upon ageing, organic aerosols can produce photo-sensitizers which auto-photo-catalyses their SOA growth.

  8. 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.

  9. MATHEMATICAL MODEL FOR GAS/PARTICLE PARTITIONING OF SECONDARY ORGANIC AEROSOLS. (R824970)

    EPA Science Inventory

    A dynamic model is developed for gas-particle absorptive partitioning of semi-volatile organic aerosols. The model is applied to simulate a pair of m -xylene/NO x outdoor smog chamber experiments. In the presence of an inorganic seed aerosol a threshold ...

  10. A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Zardini, A. A.; Sjogren, S.; Marcolli, C.; Krieger, U. K.; Gysel, M.; Weingartner, E.; Baltensperger, U.; Peter, T.

    2008-03-01

    Atmospheric aerosols are often mixtures of inorganic and organic material. Organics can represent a large fraction of the total aerosol mass and are comprised of water-soluble and insoluble compounds. Increasing attention was paid in the last decade to the capability of mixed inorganic/organic aerosol particles to take up water (hygroscopicity). We performed hygroscopicity measurements of internally mixed particles containing ammonium sulfate and carboxylic acids (citric, glutaric, adipic acid) in parallel with an electrodynamic balance (EDB) and a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds were chosen to represent three distinct physical states. During hygroscopicity cycles covering hydration and dehydration measured by the EDB and the HTDMA, pure citric acid remained always liquid, adipic acid remained always solid, while glutaric acid could be either. We show that the hygroscopicity of mixtures of the above compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid in the ammonium sulfate/citric acid and in the ammonium sulfate/glutaric acid cases. However, we observe significant discrepancies compared to what is expected from bulk thermodynamics when a solid component is present. We explain this in terms of a complex morphology resulting from the crystallization process leading to veins, pores, and grain boundaries which allow for water sorption in excess of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.

  11. Bounce behavior of freshly nucleated biogenic secondary organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Virtanen, A.; Kannosto, J.; Kuuluvainen, H.; Arffman, A.; Joutsensaari, J.; Saukko, E.; Hao, L.; Yli-Pirilä, P.; Tiitta, P.; Holopainen, J. K.; Keskinen, J.; Worsnop, D. R.; Smith, J. N.; Laaksonen, A.

    2011-08-01

    The assessment of the climatic impacts and adverse health effects of atmospheric aerosol particles requires detailed information on particle properties. However, very limited information is available on the morphology and phase state of secondary organic aerosol (SOA) particles. The physical state of particles greatly affects particulate-phase chemical reactions, and thus the growth rates of newly formed atmospheric aerosol. Thus verifying the physical phase state of SOA particles gives new and important insight into their formation, subsequent growth, and consequently potential atmospheric impacts. According to our recent study, biogenic SOA particles produced in laboratory chambers from the oxidation of real plant emissions as well as in ambient boreal forest atmospheres can exist in a solid phase in size range >30 nm. In this paper, we extend previously published results to diameters in the range of 17-30 nm. The physical phase of the particles is studied by investigating particle bounce properties utilizing electrical low pressure impactor (ELPI). We also investigate the effect of estimates of particle density on the interpretation of our bounce observations. According to the results presented in this paper, particle bounce clearly decreases with decreasing particle size in sub 30 nm size range. The comparison measurements by ammonium sulphate and investigation of the particle impaction velocities strongly suggest that the decreasing bounce is caused by the differences in composition and phase of large (diameters greater than 30 nm) and smaller (diameters between 17 and 30 nm) particles.

  12. Bounce behavior of freshly nucleated biogenic secondary organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Virtanen, A.; Kannosto, J.; Joutsensaari, J.; Saukko, E.; Kuuluvainen, H.; Hao, L.; Yli-Pirilä, P.; Tiitta, P.; Holopainen, J. K.; Worsnop, D. R.; Smith, J. N.; Laaksonen, A.

    2011-03-01

    The assessment of the climatic impacts and adverse health effects of atmospheric aerosol particles requires detailed information on particle properties. However, very limited information is available on the morphology and phase state of secondary organic aerosol (SOA) particles. The physical state of particles greatly affects particulate-phase chemical reactions, and thus the growth rates of newly formed atmospheric aerosol particles. Thus verifying the physical phase state of SOA particles gives new and important insight into their formation, subsequent growth, and consequently potential atmospheric impacts. According to our recent study, biogenic SOA particles produced in laboratory chambers from the oxidation of real plant emissions as well as in ambient boreal forest atmospheres can exist in a solid phase in size range >30 nm. In this paper, we extend previously published results to diameters in the range of 17-30 nm. The physical phase of the particles is studied by investigating particle bounce properties utilizing electrical low pressure impactor (ELPI). We also investigate the effect of estimates of particle density on the interpretation of our bounce observations. According to the results presented in this paper, particle bounce clearly decreases with decreasing particle size in sub 30 nm size range. The decreasing bounce can be caused by the differences in composition and phase of large (diameters greater than 30 nm) and smaller (diameters between 17 and 30 nm) particles.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  14. Secondary Organic Aerosol Composition from C12 Alkanes.

    PubMed

    Schilling Fahnestock, Katherine A; Yee, Lindsay D; Loza, Christine L; Coggon, Matthew M; Schwantes, Rebecca; Zhang, Xuan; Dalleska, Nathan F; Seinfeld, John H

    2014-05-22

    The effects of structure, NOx conditions, relative humidity, and aerosol acidity on the chemical composition of secondary organic aerosol (SOA) are reported for the photooxidation of three C12 alkanes: n-dodecane, cyclododecane, and hexylcyclohexane. Acidity was modified through seed particle composition: NaCl, (NH4)2SO4, and (NH4)2SO4 + H2SO4. Off-line analysis of SOA was carried out by solvent extraction and gas chromatography-mass spectrometry (GC/MS) and direct analysis in real-time mass spectrometry. We report here 750 individual masses of SOA products identified from these three alkane systems and 324 isomers resolved by GC/MS analysis. The chemical compositions for each alkane system provide compelling evidence of particle-phase chemistry, including reactions leading to oligomer formation. Major oligomeric species for alkane SOA are peroxyhemiacetals, hemiacetals, esters, and aldol condensation products. Furans, dihydrofurans, hydroxycarbonyls, and their corresponding imine analogues are important participants in these oligomer-producing reactions. Imines are formed in the particle phase from the reaction of the ammonium sulfate seed aerosol with carbonyl-bearing compounds present in all the SOA systems. Under high-NO conditions, organonitrate products can lead to an increase of aerosol volume concentration by up to a factor of 5 over that in low-NO conditions. Structure was found to play a key role in determining the degree of functionalization and fragmentation of the parent alkane, influencing the mean molecular weight of the SOA produced and the mean atomic O:C ratio. PMID:24814371

  15. 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

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

    SciTech Connect

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

    2014-05-15

    China announced the Chinese National Ambient Air Quality standards (CH-NAAQS) on Feb. 29th, 2012, and PM2.5 is for the very first time included in the standards as a criteria pollutant. In order to probe into PM2.5 pollution over Yangtze River Delta, which is one of the major urban clusters hosting more than 80 million people in China, 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. Both simulation and observation demonstrated that, inorganic aerosols have substantial contributions 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. We also found that in winter NO3- was even increased 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 (SO42-), 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 VOC sensitive 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.

  17. 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

  18. OZONE-ISOPRENE REACTION: RE-EXAMINATION OF THE FORMATION OF SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

    The reaction of ozone and isoprene has been studied to examine physical and chemical characteristics of the secondary organic aerosol formed. Using a scanning mobility particle sizer, the volume distribution of the aerosol was found in the range 0.05 - 0.2 µm. The aerosol yield w...

  19. 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.

  20. Development of gas-phase chemistry, secondary organic aerosol, and aqueous-phase chemistry modules for PM modeling. Final report

    SciTech Connect

    Strader, R.; Gurciullo, C.S.; Pandis, S.N.; Kumar, N.; Lurmann, F.W.

    1998-10-30

    The Coordinating Research Council (CRC) is sponsoring a multi-phase study to develop improved air quality models for particulate matter (PM). Improved urban and regional scale PM air quality models are needed to develop reliable emission control strategies for areas that exceed the National Ambient Air Quality Standards (NAAQS) for PM-2.5 and PM-10, and for National Parks and other Class 1 areas with impaired visibility. This report describes the development and implementation of two process modules for PM models. These particular process modules are needed to simulate secondary aerosol species, which are often the dominate portion of PM-2.5 mass. The first module simulates the gas-phase atmospheric chemistry of the VOC/NO{sub x}/SO{sub 2}/ozone system and the formation of secondary organic aerosols. The module also simulates the formation of inorganic species, including sulfuric acid and nitric acid, that form important aerosol species: sulfate and nitrate; The second module simulates the aqueous-phase chemistry in fogs and clouds. This chemistry primarily enhances SO{sub 2} oxidation rates and leads to enhanced sulfate aerosol concentrations.

  1. Cloud condensation nucleus activity of secondary organic aerosol particles mixed with sulfate

    E-print Network

    Cloud condensation nucleus activity of secondary organic aerosol particles mixed with sulfate 2007; revised 30 July 2007; accepted 15 October 2007; published 21 December 2007. [1] The cloud environmental chamber. The organic component consisted of secondary organic aerosol (SOA) generated in the dark

  2. Predicting secondary organic aerosol formation rates in southeast Texas

    NASA Astrophysics Data System (ADS)

    Russell, Matthew; Allen, David T.

    2005-04-01

    Rates of secondary organic aerosol (SOA) formation, due to the reactions of aromatics and monoterpenes, were estimated for southeast Texas by incorporating a modified version of the Statewide Air Pollution Research Center's chemical mechanism (SAPRC99) into the Comprehensive Air Quality Model with extensions (CAMx version 3.10). The model included explicit representation of the reactions of five SOA precursors (?-pinene, ?-pinene, sabinene, d-limonene, and ?3-carene). Reactions of each SOA precursor with O3, OH radical, and NO3 radical were included. The model also included separate reactions for low- and high-SOA-yield aromatic groups with the OH radical. SOA yields in the mechanisms were estimated using compound-specific yield information (?SOA/?HC) derived from smog chamber experiments conducted by J. R. Odum and colleagues and R. J. Griffin and colleagues. The form of the SOA yield model was based on the work of J. R. Odum and colleagues and is a function of existing organic aerosol concentrations. Existing organic aerosol concentrations were estimated on the basis of ambient measurements of total organic carbon in southeast Texas. The reactions of monoterpenes (predominantly ?-pinene and ?-pinene) with ozone led to the most regional SOA formation, followed by monoterpenes with the nitrate radical. Aromatic-OH reactions led to less regional SOA formation compared to monoterpenes; however, this formation occurs close to the urban and industrial areas of Houston. In contrast, SOA formation due to the reactions of monoterpenes occurred in the forested areas north of the urban area. The results of this study are in qualitative agreement with estimates of SOA formation based on ambient data from the same time period.

  3. Secondary organic aerosol formation from acyclic, monocyclic, and polycyclic alkanes.

    PubMed

    Hunter, James F; Carrasquillo, Anthony J; Daumit, Kelly E; Kroll, Jesse H

    2014-09-01

    A large number of organic species emitted into the atmosphere contain cycloalkyl groups. While cyclic species are believed to be important secondary organic aerosol (SOA) precursors, the specific role of cyclic moieties (particularly for species with multiple or fused rings) remains uncertain. Here we examine the yields and composition of SOA formed from the reaction of OH with a series of C10 (cyclo)alkanes, with 0-3 rings, in order to better understand the role of multiple cyclic moieties on aerosol formation pathways. A chamber oxidation technique using high, sustained OH radical concentrations was used to simulate long reaction times in the atmosphere. This aging technique leads to higher yields than in previously reported chamber experiments. Yields were highest for cyclic and polycyclic precursors, though yield exhibited little dependence on number of rings. However, the oxygen-to-carbon ratio of the SOA was highest for the polycyclic precursors. These trends are consistent with aerosol formation requiring two generations of oxidation and 3-4 oxygen-containing functional groups in order to condense. Cyclic, unbranched structures are protected from fragmentation during the first oxidation step, with C-C bond scission instead leading to ring opening, efficient functionalization, and high SOA yields. Fragmentation may occur during subsequent oxidation steps, limiting yields by forming volatile products. Polycyclic structures can undergo multiple ring opening reactions, but do not have markedly higher yields, likely due to enhanced fragmentation in the second oxidation step. By contrast, C-C bond scission for the linear and branched structures leads to fragmentation prior to condensation, resulting in low SOA yields. The results highlight the key roles of multigenerational chemistry and susceptibility to fragmentation in the formation and evolution of SOA. PMID:25093758

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

    PubMed

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

    2013-04-16

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

  5. 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

  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. 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.

    2014-12-01

    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 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 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, vs. those in the smog chamber experiments.

  8. A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Zardini, A. A.; Sjogren, S.; Marcolli, C.; Krieger, U. K.; Gysel, M.; Weingartner, E.; Baltensperger, U.; Peter, T.

    2008-09-01

    Atmospheric aerosols are often mixtures of inorganic and organic material. Organics can represent a large fraction of the total aerosol mass and are comprised of water-soluble and insoluble compounds. Increasing attention was paid in the last decade to the capability of mixed inorganic/organic aerosol particles to take up water (hygroscopicity). We performed hygroscopicity measurements of internally mixed particles containing ammonium sulfate and carboxylic acids (citric, glutaric, adipic acid) in parallel with an electrodynamic balance (EDB) and a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds were chosen to represent three distinct physical states. During hygroscopicity cycles covering hydration and dehydration measured by the EDB and the HTDMA, pure citric acid remained always liquid, adipic acid remained always solid, while glutaric acid could be either. We show that the hygroscopicity of mixtures of the above compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid in the ammonium sulfate/glutaric acid system; deviations up to 10% in mass growth factor (corresponding to deviations up to 3.5% in size growth factor) are observed for the ammonium sulfate/citric acid 1:1 mixture at 80% RH. We observe even more significant discrepancies compared to what is expected from bulk thermodynamics when a solid component is present. We explain this in terms of a complex morphology resulting from the crystallization process leading to veins, pores, and grain boundaries which allow for water sorption in excess of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.

  9. Modeling Gas-phase Glyoxal and Associated Secondary Organic Aerosol Formation in a Megacity using WRF/Chem

    NASA Astrophysics Data System (ADS)

    Wang, K.; Hodzic, A.; Barth, M. C.; Jimenez, J. L.; Volkamer, R.; Ervens, B.; Zhang, Y.

    2011-12-01

    Organic aerosol (OA) as one of a major fine particulate matter in the atmosphere plays an important role in air pollution, human health, and climate forcing. OA is composed of directly emitted primary organic aerosol and chemically produced secondary organic aerosols (SOA). Despite much recent progress in understanding SOA formation, current air quality models cannot explain the magnitude and growth of atmospheric SOA, due to high uncertainties in sources, properties, and chemical reactions of precursors and formation pathways of SOA. Recent laboratory and modeling studies showed that glyoxal may serve as an important SOA precursor in the condensed solution of inorganic or organic aerosol particles (e.g., ammonium sulfate, fulvic acid, and amino acids). In this study, the Weather Research and Forecasting model with chemistry (WRF/Chem) is modified to account for the latest observed gas-phase yields of glyoxal from various volatile organic compounds (VOCs) and the associated SOA formation in the aqueous aerosol phase. The SOA formation in the aqueous aerosol phase is implemented using two approaches. In the first approach, two simplified parameterizations are used to represent the lumped particle-phase chemical processes under dark conditions and photochemical surface uptake. In the second approach, more detailed kinetic glyoxal reactions such as reversible glyoxal uptake, dimer formation of glyoxal, and oligomerization are treated and resolved explicitly. The updated WRF/Chem is assessed over the Mexico City and the surrounding region during March 2006 using the MILAGRO campaign data. Various observations such as organic matter from Aerodyne Aerosol Mass Spectrometer and VOCs from Proton-transfer Ion Trap Mass Spectrometry were compared. The preliminary results showed that the addition of the SOA formation from glyoxal in aqueous particles brings SOA predictions into a better agreement with field observations, in particular in presence of high relative humidity. The simulation with updated glyoxal yields gives a factor of 2 higher mixing ratio of glyoxal. The uncertainties in the model treatments as well as future work will also be discussed.

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

    NASA Astrophysics Data System (ADS)

    Li, Jia; Pósfai, MiháLy; Hobbs, Peter V.; Buseck, Peter R.

    2003-07-01

    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.

  11. 2-hydroxyterpenylic acid: an oxygenated marker compound for ?-pinene secondary organic aerosol in ambient fine aerosol.

    PubMed

    Kahnt, Ariane; Iinuma, Yoshiteru; Blockhuys, Frank; Mutzel, Anke; Vermeylen, Reinhilde; Kleindienst, Tadeusz E; Jaoui, Mohammed; Offenberg, John H; Lewandowski, Michael; Böge, Olaf; Herrmann, Hartmut; Maenhaut, Willy; Claeys, Magda

    2014-05-01

    An oxygenated MW 188 compound is commonly observed in substantial abundance in atmospheric aerosol samples and was proposed in previous studies as an ?-pinene-related marker compound that is associated with aging processes. Owing to difficulties in producing this compound in sufficient amounts in laboratory studies and the occurrence of isobaric isomers, a complete assignment for individual MW 188 compounds could not be achieved in these studies. Results from a comprehensive mass spectrometric analysis are presented here to corroborate the proposed structure of the most abundant MW 188 compound as a 2-hydroxyterpenylic acid diastereoisomer with 2R,3R configuration. The application of collision-induced dissociation with liquid chromatography/electrospray ionization-ion trap mass spectrometry in both negative and positive ion modes, as well as chemical derivatization to methyl ester derivatives and analysis by the latter technique and gas chromatography/electron ionization mass spectrometry, enabled a comprehensive characterization of MW 188 isomers, including a detailed study of the fragmentation behavior using both mass spectrometric techniques. Furthermore, a MW 188 positional isomer, 4-hydroxyterpenylic acid, was tentatively identified, which also is of atmospheric relevance as it could be detected in ambient fine aerosol. Quantum chemical calculations were performed to support the diastereoisomeric assignment of the 2-hydroxyterpenylic acid isomers. Results from a time-resolved ?-pinene photooxidation experiment show that the 2-hydroxyterpenylic acid 2R,3R diastereoisomer has a time profile distinctly different from that of 3-methyl-1,2,3-butanetricarboxylic acid, a marker for oxygenated (aged) secondary organic aerosol. This study presents a comprehensive chemical data set for a more complete structural characterization of hydroxyterpenylic acids in ambient fine aerosol, which sets the foundation to better understand the atmospheric fate of ?-pinene in future studies. PMID:24697354

  12. Secondary Aerosol Forming Potential of the Air Mass Arriving at Gosan ABC Superstation in Korea

    NASA Astrophysics Data System (ADS)

    Kang, E.; Brune, W. H.; Lee, M.

    2011-12-01

    Secondary aerosol forming potential of air masses was measured with the Potential Aerosol Mass (PAM) chamber at Gosan ABC superstation in Jeju, Korea in fall 2010 and spring 2011. PAM can be defined as the maximum aerosol mass that precursor gases can be oxidized to form particulate matter. The PAM chamber is a small flow-through photo-oxidation chamber that is irradiated with ultraviolet lamps. Rapid oxidation ensues in the extreme oxidizing environment, which measured values about 1~5 ppmv of O3 and 2 x 1011 ~ 6 x 1011 cm-s s of OH exposure. Previous studies using the PAM chamber were focused on the formation and the evolutionary change of chemical characteristics of secondary organic aerosol (SOA) by the photochemical aging in the controlled laboratory experiments with single Volatile Organic Carbons (VOCs). In this study, we applied the PAM chamber to the ambient air to study the overall potential of secondary aerosol formation in an air mass arriving in Gosan superstation. The OH exposure in this study was likely similar to that of 2 ~5 days aged air. The Aerosol number concentration and size distribution was measured by Scanning Mobility Particle Sizer (SMPS) in the range of 10 ~ 487 nm in diameter. Generation of secondary aerosol in PAM seemed to be highly correlated to the air mass trajectory; fresh continental plume originated from China had high secondary aerosol forming potential while aged continental plume passed through coastal region of China and Yellow sea had low secondary aerosol forming potential even the ambient aerosol mass concentration was high. In the presentation, we will describe the secondary aerosol forming potential of the air masses regarding to the availability of precursor gases and the transport pathway of air masses.

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

    E-print Network

    Jimenez, Jose-Luis

    Emissions of black carbon, organic, and inorganic aerosols from biomass burning in North America sampling was made in fresh plumes strongly impacted by wildfires in North America (Canada and California) in summer 2008 and in those transported from Asia (Siberia in Russia and Kazakhstan) in spring 2008. We

  14. Kinetic regimes for formation and aging of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Shiraiwa, Manabu; Berkemeier, Thomas; Schilling-Fahnestock, Katherine; Seinfeld, John; Pöschl, Ulrich

    2014-05-01

    Here we present a conceptual framework of kinetic regime and limiting cases for formation and aging of secondary organic aerosol (SOA). The limiting step of SOA formation can be identified following the developed classification scheme, which is based on three fundamental properties of oxidation products: the reaction location, the saturation ratio, and the heterogeneity in the gas and particle phases. Using the kinetic multi-layer model of gas-particle interactions (KM-GAP) (Shiraiwa et al., 2012), we have analyzed the experimental data of photooxidation of dodecane and subsequent SOA formation. We have found that the contribution of intermediate gas-phase oxidation products to SOA formation is most likely limited by gas-phase reaction, validating the assumption of instantaneous equilibrium partitioning. For semi-volatile and low volatility gas-phase oxidation products, partitioning into the particle phase can be limited by surface accommodation, and possibly by bulk diffusion when organic aerosols adopt glassy or amorphous solid state. The formation of low volatility particle-phase products, such as oligomers and other high molar mass compounds, may be limited by reaction and diffusion in the particle. The 2D evolution plot of molar mass vs. volatility is useful to overview SOA formation and aging. The average molar mass of the organic compounds can be used as a yardstick to estimate relative contribution of gas- vs. particle-phase chemistry to SOA formation. The relatively high values of measured average molar mass for ambient and laboratory-generated SOA imply the importance of particle-phase chemistry in SOA formation.

  15. An amorphous solid state of biogenic secondary organic aerosol particles.

    PubMed

    Virtanen, Annele; Joutsensaari, Jorma; Koop, Thomas; Kannosto, Jonna; Yli-Pirilä, Pasi; Leskinen, Jani; Mäkelä, Jyrki M; Holopainen, Jarmo K; Pöschl, Ulrich; Kulmala, Markku; Worsnop, Douglas R; Laaksonen, Ari

    2010-10-14

    Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90?billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate. PMID:20944744

  16. 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.

  17. Influence of environmental parameters on secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Warren, Bethany A.

    2008-07-01

    The influence of environmental parameters on secondary organic aerosol (SOA) was extensively investigated in the UC Riverside/CE-CERT environmental chamber. The presence of water vapor provided an additional SOA formation pathway during cyclohexene ozonolysis that increased SOA formation by ˜30%. The presence of dissolved salts had minimal impact as compared to the presence of water vapor. Temperature proved to be an important SOA formation parameter; aerosol formation increased by 3.5 times at 278K as compared to 300K for both alpha-pinene and cyclohexene isothermal ozonolysis. Changing experimental temperatures, in most cases led to a different gas-particle equilibrium, even after returning to the original temperature set point. A model, temperature influenced partitioning aerosol yield (TIPAY), was created to explain these results by incorporating a thermally labile component, a traditional gas to particle partitioning component, and an additional gas to particle partitioning component whose formation potential was temperature independent. Increasing light intensity, measured as the photolysis rate of NO2 to NO (k1), was found to increase SOA formation for the m-xylene/NOx photooxidation system. Irradiation source had a slight effect on total SOA formation as an irradiation spectrum more similar to natural light produced slightly more SOA than that with black lights, provides the wavelengths necessary for NO2 photolysis, at the same light intensity. Modeling of the gas phase chemistry with SAPRC07, supports the idea that the concentration of radical species OH and HO 2 greatly determine the amount of SOA formation. Building on SAPRC07, the SOA formation model PM-SAPRC08, was developed to determine the dominate gas phase reactions needed to predict SOA formation results for 100 experiments. While 7 simulations are tested, several of which are published routes, none adequately predicted SOA formation. Results of the influence of these environmental parameters provide a wealth of experimental data, along with model simulations that provide insight to SOA formation behavior and SOA formation mechanisms; essential to bridging the apparent disconnect between models of SOA production based on environmental chambers and that estimated from direct ambient measurements.

  18. 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

  19. Secondary organic aerosol formation in urban air: Temporal variations and possible contributions from unidentified hydrocarbons

    Microsoft Academic Search

    H. Matsui; M. Koike; N. Takegawa; Y. Kondo; R. J. Griffin; Y. Miyazaki; Y. Yokouchi; T. Ohara

    2009-01-01

    Quantitative evaluation of the performance of one of the most advanced mechanistic secondary organic aerosol (SOA) modules\\/models, the Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution 2 (MADRID2) in the three-dimensional Models-3\\/Community Multiscale Air Quality (CMAQ), in urban air is made. Model calculations are compared for the Tokyo, Japan, metropolitan area with measurements made using an Aerodyne quadrupole aerosol mass

  20. Secondary Organic Aerosol Formation in Urban Air: Temporal Variations and Possible Contributions from Unidentified Hydrocarbons

    Microsoft Academic Search

    H. Matsui; N. Takegawa; Y. Kondo; R. J. Griffin; Y. Miyazaki; Y. Yokouchi; T. Ohara

    2009-01-01

    Quantitative evaluation of the performance of one of the most advanced mechanistic secondary organic aerosol (SOA) modules\\/models Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution 2 (MADRID2) in the three-dimensional Models-3\\/Community Multiscale Air Quality (CMAQ), in urban air is made. Model calculations were compared for the Tokyo, Japan, metropolitan area with measurements made using an Aerodyne quadrupole aerosol mass spectrometer

  1. 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.

  2. Submicrometer aerosol in rural and urban backgrounds in southern Poland: primary and secondary components of PM1.

    PubMed

    Rogula-Koz?owska, Wioletta; Klejnowski, Krzysztof

    2013-01-01

    Diurnal samples of PM(1) (submicrometer particles, having aerodynamic diameters not greater than 1 ?m) were collected at an urban background site in Zabrze (from 01.08. to 31.12.2009) and a rural background site in Racibórz (from 01.08. to 31.12.2010). The samples were analyzed for carbon (organic and elemental), water soluble ions (Na(+), NH(4) (+), K(+), Mg(2+), Ca(2+), Cl(-), NO(3)(-), SO(4)(2-)) and concentrations of 21 elements by using, respectively, a Sunset Laboratory carbon analyzer, a Herisau Metrohm AG ion chromatograph, a PANalitycal Epsilon 5 spectrometer. To perform the monthly mass closure calculations for PM(1), the chemical components were categorized into organic matter (OM), elemental carbon (EC), secondary inorganic aerosol (SIA), crustal matter (CM), marine components (MC), other elements (OE) and unidentified matter (UM). The mass contributions of secondary (SOM) and primary (POM) organic matter to PM(1) were also estimated. In average, 50 % of PM(1) in Zabrze and 40 % in Racibórz were secondary aerosol coming from the transformations of its gaseous precursors. High concentrations and mass contributions of EC and OM to PM, and probable PM acidic nature in Zabrze, indicate particularly high hazard from the ambient submicrometer particles to the inhabitants of southern Poland. PMID:23104673

  3. The Correlation of Secondary Organic Aerosol with Odd Oxygen in Mexico City

    EPA Science Inventory

    Data from a mountain location intercepting the Mexico City emission plume demonstrate a strong correlation between secondary organic aerosol and odd-oxygen (O3 + NO2). The measured oxygenated-organic aerosol correlates with odd-oxygen measurements with an a...

  4. Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols

    Microsoft Academic Search

    Tzung-May Fu; Daniel J. Jacob; Folkard Wittrock; John P. Burrows; Mihalis Vrekoussis; Daven K. Henze

    2008-01-01

    We construct global budgets of atmospheric glyoxal and methylglyoxal with the goal of quantifying their potential for global secondary organic aerosol (SOA) formation via irreversible uptake by aqueous aerosols and clouds. We conduct a detailed simulation of glyoxal and methylglyoxal in the GEOS-Chem global 3-D chemical transport model including our best knowledge of source and sink processes. Our resulting best

  5. Secondary organic aerosol (SOA) formation through cloud processing: Aqueous photooxidation of glyoxal and methylglyoxal

    Microsoft Academic Search

    Ann Marie Grover Carlton

    2006-01-01

    This dissertation provides evidence supporting the hypothesis that secondary organic aerosol (SOA) is formed in the atmosphere through aqueous-phase reactions in clouds. Accurate prediction of SOA formation is critical because organic aerosol adversely affects health, visibility and climate. If in-cloud SOA formation is significant, then current models incorrectly predict the concentrations, atmospheric distributions, properties, behavior and effects of atmospheric organic

  6. Oxidation of ambient biogenic secondary organic aerosol by hydroxyl radicals: Effects on cloud condensation nuclei activity

    E-print Network

    Wong, J. P. S.

    Changes in the hygroscopicity of ambient biogenic secondary organic aerosols (SOA) due to controlled OH oxidation were investigated at a remote forested site at Whistler Mountain, British Columbia during July of 2010. ...

  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. 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...

  9. Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

    E-print Network

    Wood, E. C.

    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. ...

  10. 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...

  11. 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...

  12. Secondary organic aerosol from biogenic volatile organic compound mixtures

    NASA Astrophysics Data System (ADS)

    Hatfield, Meagan L.; Huff Hartz, Kara E.

    2011-04-01

    The secondary organic aerosol (SOA) yields from the ozonolysis of a Siberian fir needle oil (SFNO), a Canadian fir needle oil (CFNO), and several SOA precursor mixtures containing reactive and non-reactive volatile organic compounds (VOCs) were investigated. The use of precursor mixtures more completely describes the atmosphere where many VOCs exist. The addition of non-reactive VOCs such as bornyl acetate, camphene, and borneol had very little to no effect on SOA yields. The oxidation of VOC mixtures with VOC mass percentages similar to the SFNO produced SOA yields that became more similar to the SOA yield from SFNO as the complexity and concentration of VOCs within the mixture became more similar to overall SFNO composition. The SOA yield produced by the oxidation of CFNO was within the error of the SOA yield produced by the oxidation of SFNO at a similar VOC concentration. The SOA yields from SFNO were modeled using the volatility basis set (VBS), which predicts the SOA yields for a given mass concentration of mixtures containing similar VOCs.

  13. 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.

  14. Nonequilibrium Atmospheric Secondary Organic Aerosol Formation and Growth

    SciTech Connect

    Perraud, Veronique M.; Bruns, Emily A.; Ezell, Michael J.; Johnson, Stanley N.; Yu, Yong; Alexander, M. L.; Zelenyuk, Alla; Imre, D.; Chang, W. L.; Dabdub, Donald; Pankow, James F.; Finlayson-Pitts, Barbara J.

    2012-02-21

    Airborne particles play a critical role in air quality, human health effects, visibility and climate. Secondary organic aerosols (SOA) account for a significant portion of total airborne particles. They are formed in reactions of organic gases that produce low volatility and semi-volatile organic compounds (SVOCs). Current atmospheric models assume that SOA are liquids into which SVOCs undergo equilibrium partitioning and grow the particles. However a large discrepancy between model predictions and field measurements of SOA is commonly observed. We report here laboratory studies of the oxidation of a-pinene by ozone and nitrate radicals and show that particle composition is actually consistent with a kinetically determined growth mechanism, and not with equilibrium partitioning between the gas phase and liquid particles. If this is indeed a general phenomenon in air, the formulation of atmospheric SOA models will have to be revised to reflect this new paradigm. This will have significant impacts on quantifying the role of SOA in air quality, visibility, and climate.

  15. Light Absorption by Secondary Organic Aerosol from ?-Pinene: Effects of Oxidants, Seed Aerosol Acidity, and Relative Humidity

    SciTech Connect

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

    2013-10-25

    It 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 (SOA) generated from ozonolysis or NO3 oxidation of ?-pinene 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. Light absorption at 355 and 405 nm was observed by SOA generated from oxidation of ?-pinene in the presence of acidic sulfate seed aerosols, under dry conditions. No absorption was observed when the relative humidity was elevated to greater than 27%, or in the presence of neutral sulfate seed aerosols. The light-absorbing compounds are speculated to be aldol condensation oligomers with organosulfate and organic nitrate groups. The results of this study also indicate that organic nitrates from ?-pinene SOA formed in the presence of neutral sulfate seed aerosols do not appear to absorb near-UV and UV radiation.

  16. Modeling the formation of secondary organic aerosol within a comprehensive air quality model system

    Microsoft Academic Search

    Benedikt Schell; Ingmar J. Ackermann; Heinz Hass; Francis S. Binkowski; Adolf Ebel

    2001-01-01

    The Secondary Organic Aerosol Model (SORGAM) has been developed for use in comprehensive air quality model systems. Coupled to a chemistry-transport model, SORGAM is capable of simulating secondary organic aerosol (SOA) formation including the production of low-volatility products and their subsequent gas\\/particle partitioning. The current model formulation assumes that all SOA compounds interact and form a quasi-ideal solution. This has

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  19. Reactivity of Liquid and Semisolid Secondary Organic Carbon with Chloride and Nitrate in Atmospheric Aerosols.

    PubMed

    Wang, Bingbing; O'Brien, Rachel E; Kelly, Stephen T; Shilling, John E; Moffet, Ryan C; Gilles, Mary K; Laskin, Alexander

    2014-11-25

    Constituents of secondary organic carbon (SOC) in atmospheric aerosols are often mixed with inorganic components and compose a significant mass fraction of fine particulate matter in the atmosphere. Interactions between SOC and other condensed-phase species are not well understood. Here, we investigate the reactions of liquid-like and semisolid SOC from ozonolysis of limonene (LSOC) and ?-pinene (PSOC) with NaCl using a set of complementary microspectroscopic analyses. These reactions result in chloride depletion in the condensed phase, release of gaseous HCl, and formation of organic salts. The reactions attributed to acid displacement by SOC acidic components are driven by the high volatility of HCl. Similar reactions can take place in SOC/NaNO3 particles. The results show that an increase in SOC mass fraction in the internally mixed SOC/NaCl particles leads to higher chloride depletion. Glass transition temperatures and viscosity of PSOC were estimated for atmospherically relevant conditions. Data show that the reaction extent depends on SOC composition, particle phase state and viscosity, mixing state, temperature, relative humidity (RH), and reaction time. LSOC shows slightly higher potential to deplete chloride than PSOC. Higher particle viscosity at low temperatures and RH can hinder these acid displacement reactions. Formation of organic salts from these overlooked reactions can alter particle physiochemical properties and may affect their reactivity and ability to act as cloud condensation and ice nuclei. The release and potential recycling of HCl and HNO3 from reacted aerosol particles may have important implications for atmospheric chemistry. PMID:25386912

  20. 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.

  1. Physical state and acidity of inorganic sulfate can regulate the production of secondary organic material from isoprene photooxidation products.

    PubMed

    Kuwata, Mikinori; Liu, Yingjun; McKinney, Karena; Martin, Scot T

    2015-02-10

    The production of secondary organic material (SOM) by the reactive uptake of isoprene photooxidation products was investigated using partially to wholly neutralized sulfuric acid particles. The experiments were performed at a relative humidity (RH) of <5% and a temperature of 20 °C. The extent X of neutralization was adjusted from that of sulfuric acid (X = 0) to that of ammonium sulfate (X = 1). Significant SOM production was observed only for X < 0.7. The threshold of 0.7 corresponded to the transition point of the sulfate particles from aqueous to solid for <5% RH. The phase transition of inorganic sulfate therefore regulated the particle-phase reactions that produce isoprene SOM, at least for the investigated conditions. For aqueous particles, a decreasing extent of neutralization was associated with increasing production of SOM, including increased production of oligomers and organosulfates. These results can underpin treatments of phase-dependent SOM production within chemical transport models, thereby improving the accuracy of simulations of biogenic-anthropogenic interactions in the atmosphere and the associated impacts of aerosol particles on climate and air quality. PMID:25623937

  2. Impact of aerosol liquid water on secondary organic aerosol yields of irradiated toluene\\/propylene\\/NO x \\/(NH 4) 2SO 4\\/air mixtures

    Microsoft Academic Search

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

    2000-01-01

    Laboratory experiments were conducted to assess whether the presence of liquid water on pre-existing submicron ammonium sulfate aerosols affects yields of condensible organic compounds. Toluene\\/propylene\\/NOx\\/air mixtures were irradiated in the presence of submicron ammonium sulfate aerosol for a series of relative humidities and ammonium sulfate concentrations, generating aerosols containing organic and inorganic constituents with liquid water concentrations ranging from 4

  3. 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.

  4. 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 ...

  5. 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...

  6. Atmospheric oxidation of isoprene and 1,3-butadiene: influence of aerosol acidity and relative humidity on secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Lewandowski, M.; Jaoui, M.; Offenberg, J. H.; Krug, J. D.; Kleindienst, T. E.

    2014-11-01

    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 sample volume) and the percent change of secondary organic carbon (SOC). The measurements have used several precursor compounds representative of different classes of biogenic hydrocarbons including isoprene, monoterpenes, and sesquiterpenes. To date, isoprene has displayed the most pronounced increase in SOC, although few measurements have been conducted with anthropogenic hydrocarbons. In the present study, we examine several aspects of the effect of aerosol acidity on the secondary organic carbon formation from the photooxidation of 1,3-butadiene, as well as extending the previous analysis of isoprene. The photooxidation products measured in the absence and presence of acidic sulfate aerosols were generated either through photochemical oxidation of SO2 or by nebulizing mixtures of ammonium sulfate and sulfuric acid into a 14.5 m3 smog chamber system. The results showed that, like isoprene and ?-caryophyllene, 1,3-butadiene SOC yields linearly correlate with increasing acidic sulfate aerosol. The observed acid sensitivity of 0.11% SOC increase per nmol m-3 increase in H+ was approximately a factor of three less than that measured for isoprene. The results also showed that the aerosol yield decreased with increasing humidity for both isoprene and 1,3-butadiene, although to different degrees. Increasing the absolute humidity from 2 to 12 g m-3 reduced the 1,3-butadiene yield by 45% and the isoprene yield by 85%.

  7. Photolytic processing of secondary organic aerosols dissolved in cloud droplets

    SciTech Connect

    Bateman, Adam P.; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2011-05-26

    The effect of UV irradiation on the molecular composition of aqueous extracts of secondary organic aerosol (SOA) was investigated. SOA was prepared by the dark reaction of ozone and d-limonene at 0.05 - 1 ppm precursor concentrations and collected with a particle-into-liquid sampler (PILS). The PILS extracts were photolyzed by 300 - 400 nm radiation for up to 24 hours. Water-soluble SOA constituents were analyzed using high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) at different stages of photolysis for all SOA precursor concentrations. Exposure to UV radiation increased the average O/C ratio and decreased the average double bond equivalent (DBE) of the dissolved SOA compounds. Oligomeric compounds were significantly reduced by photolysis relative to the monomeric compounds. Direct pH measurements showed that compounds containing carboxylic acids increased upon photolysis. Methanol reactivity analysis revealed significant photodissociation of molecules containing carbonyl groups and formation of carboxylic acids. Aldehydes, such as limononaldehyde, were almost completely removed. The removal of carbonylswas confirmed by the UV-Vis absorption spectroscopy of the SOA extracts where the absorbance in the carbonyl n??* band decreased significantly upon photolysis. The effective quantum yield (the number of carbonyls destroyed per photon absorbed) was estimated as ~ 0.03. The concentration of peroxides did not change significantly during photolysis as quantified with an iodometric test. Although organic peroxides were photolyzed, the likely end products of photolysis were smaller peroxides, including hydrogen peroxide, resulting in a no net change in the peroxide content.

  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. Secondary Organic Aerosol Formation from Glyoxal: Effects of Seed Aerosol on Particle Composition

    NASA Astrophysics Data System (ADS)

    Slowik, Jay; Waxman, Eleanor; Coburn, Sean; Klein, Felix; Koenig, Theodore; Krapf, Manuel; Kumar, Nivedita; Wang, Siyuan; Baltensperger, Urs; Dommen, Josef; Prévôt, Andre; Volkamer, Rainer

    2014-05-01

    Conventional models of secondary organic aerosol (SOA) production neglect aqueous-phase processing mechanisms, thereby excluding potentially important SOA formation pathways. These missing pathways may be an important factor in the inability of current models to fully explain SOA yields and oxidation states. Molecules identified as important precursors to SOA generated through aqueous-phase include glyoxal, which is an oxidation product of numerous organic gases. Glyoxal SOA formation experiments were conducted in the PSI smog chamber as a function of seed composition, relative humidity (RH, 60 to 85%), and the presence/absence of gaseous ammonia, affecting particle acidity. In a typical experiment, the chamber was filled with the selected seed aerosol (NaCl, (NH4)2SO4, NaNO3, or K2SO4), after which glyoxal was generated by the brief (i.e. a few minutes) exposure of acetylene to UV light. The experiment was then allowed to proceed undisturbed for several hours. Each experiment consisted of several UV exposures, followed by a dilution phase at constant RH to investigate the gas/particle partitioning behavior of the generated SOA. Gas-phase glyoxal was monitored by an LED-CE-DOAS system, while the particle composition was measured using online aerosol mass spectrometry (Aerodyne HR-ToF-AMS) and offline analysis of collected filter samples. SOA composition was observed to depend strongly on seed type, with increased imidazole formation evident during experiments with (NH4)2SO¬4 and K2SO4 seeds relative to those with NaCl and NaNO3. Additionally, experiments conducted in the presence of ammonia showed large enhancements in both imidazole content and total SOA yield. Analysis of mass spectral markers indicates reversible uptake of glyoxal but irreversible particle-phase production of the imidazole-containing SOA. Positive matrix factorization (PMF) using the Multilinear Engine (ME-2) was applied to the AMS mass spectral time series to quantify factors related to reaction progress and product formation (e.g. glyoxal and different types of irreversibly-generated SOA). We will discuss glyoxal SOA yields and product distributions in terms of seed composition and ammonia effects.

  10. Deposition ice nucleation on fresh, cloud processed, internally mixed and oxidatively aged ?-pinene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Ladino Moreno, L.; Zhou, S.; Aljawhary, D.; Yakobi-Hancock, J.; Abbatt, J.

    2013-12-01

    There are many uncertainties related to role of organic aerosol (OA) as ice nuclei (IN). To that end, the ice nucleating abilities of fresh, cloud processed, internally mixed, and oxidatively aged secondary organic aerosol (SOA) particles were investigated with the University of Toronto continuous flow diffusion chamber (UT-CFDC) at temperatures relevant for cirrus cloud formation. Our SOA particles were produced by ?-pinene ozonolysis which took place in a flow tube (FT) and a smog chamber (SC). The FT-SOA particles mimicked freshly formed particles while the water soluble organic compound (WSOC) experiments from both the flow tube (FT-WSOC-SOA) and the smog chamber (SC-WSOC-SOA) capture the character of aged and cloud processed SOA particles. The FT-SOA particles exhibited low ice nucleation efficiency, i.e. relative humidities with respect to ice (RHi) of 152×4% and 157×4% were required to activate 0.1% of the aerosol particles in deposition mode at 223K and 218K, respectively. Similarly, the IN efficiencies of the FT-WSOC-SOA and SC-WSOC-SOA particles were found to be comparably low between 233K and 214K. However, if both the FT-WSOC-SOA and the SC-WSOC-SOA particles were pre-cooled at 233K prior to entering the UT-CFDC they nucleate ice at between 6 to 9% lower relative humidities, probably due to decreased viscosity. We also observed that an increase in the oxygen to carbon ratio (from 0.39 to 0.78) of the SC-WSOC-SOA particles from aqueous oxidative processing did not modify IN abilities. Finally, given that SOA is commonly mixed with inorganic salts, especially when arising through cloud processing, it was found that internally mixed particles of SC-WSOC-SOA and ammonium sulfate (AS) had a significantly higher RHi (140×5% at 219K) than pure AS particles of the same size (125×4%). Overall conclusions are that SOA-containing particles may act as IN only in regions where more efficient are not present. The SOA component will serve to suppress the IN abilities of efficient IN when internally mixed.

  11. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

    Reactive halogen species (RHS), such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. Model SOA from ?-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS released from simulated natural halogen sources like salt pans. Subsequently the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which result in new functional groups, changed UV/VIS absorption, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  12. Aerosol size distribution and radiative forcing response to anthropogenically driven historical changes in biogenic secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Emissions of biogenic volatile organic compounds (BVOCs) have changed in the past millennium due to changes in land use, temperature, and CO2 concentrations. Recent reconstructions of BVOC emissions have predicted that global isoprene emissions have decreased, while monoterpene and sesquiterpene emissions have increased; however, all three show regional variability due to competition between the various influencing factors. In this work, we use two modeled estimates of BVOC emissions from the years 1000 to 2000 to test the effect of anthropogenic changes to BVOC emissions on secondary organic aerosol (SOA) formation, global aerosol size distributions, and radiative effects using the GEOS-Chem-TOMAS (Goddard Earth Observing System; TwO-Moment Aerosol Sectional) global aerosol microphysics model. With anthropogenic emissions (e.g., SO2, NOx, primary aerosols) turned off 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 which led to regional increases in the combined aerosol radiative effect (direct and indirect) of > 0.5 W m-2 in these regions. We test the sensitivity of our results to BVOC emissions inventory, SOA yields, and the presence of anthropogenic emissions; however, the qualitative response of the model to historic BVOC changes remains the same in all cases. Accounting for these uncertainties, we estimate millennial changes in BVOC emissions cause a global mean direct effect of between +0.022 and +0.163 W m-2 and the global mean cloud-albedo aerosol indirect effect of between -0.008 and -0.056 W m-2. This change in aerosols, and the associated radiative forcing, could be a largely overlooked and important anthropogenic aerosol effect on regional climates.

  13. A thermal desorption mass spectrometer for freshly nucleated secondary aerosol particles

    NASA Astrophysics Data System (ADS)

    Held, A.; Gonser, S. G.

    2012-04-01

    Secondary aerosol formation in the atmosphere is observed in a large variety of locations worldwide, introducing new particles to the atmosphere which can grow to sizes relevant for health and climate effects of aerosols. The chemical reactions leading to atmospheric secondary aerosol formation are not yet fully understood. At the same time, analyzing the chemical composition of freshly nucleated particles is still a challenging task. We are currently finishing the development of a field portable aerosol mass spectrometer for nucleation particles with diameters smaller than 30 nm. This instrument consists of a custom-built aerosol sizing and collection unit coupled to a time-of-flight mass spectrometer (TOF-MS). The aerosol sizing and collection unit is composed of three major parts: (1) a unipolar corona aerosol charger, (2) a radial differential mobility analyzer (rDMA) for aerosol size separation, and (3) an electrostatic precipitator for aerosol collection. After collection, the aerosol sample is thermally desorbed, and the resulting gas sample is transferred to the TOF-MS for chemical analysis. The unipolar charger is based on corona discharge from carbon fibres (e.g. Han et al., 2008). This design allows efficient charging at voltages below 2 kV, thus eliminating the potential for ozone production which would interfere with the collected aerosol. With the current configuration the extrinsic charging efficiency for 20 nm particles is 32 %. The compact radial DMA similar to the design of Zhang et al. (1995) is optimized for a diameter range from 1 nm to 100 nm. Preliminary tests show that monodisperse aerosol samples (geometric standard deviation of 1.09) at 10 nm, 20 nm, and 30 nm can easily be separated from the ambient polydisperse aerosol population. Finally, the size-segregated aerosol sample is collected on a high-voltage biased metal filament. The collected sample is protected from contamination using a He sheath counterflow. Resistive heating of the filament allows temperature-controlled desorption of compounds of different volatility. We will present preliminary characterization experiments of the aerosol sizing and collection unit coupled to the mass spectrometer. Funding by the German Research Foundation (DFG) under grant DFG HE5214/3-1 is gratefully acknowledged. Han, B., Kim, H.J., Kim, Y.J., and Sioutas, C. (2008) Unipolar charging of ultrafine particles using carbon fiber ionizers. Aerosol Sci. Technol, 42, 793-800. Zhang, S.-H., Akutsu, Y., Russell, L.M., Flagan, R.C., and Seinfeld, J.H. (1995) Radial Differential Mobility Analyzer. Aerosol Sci. Technol, 23, 357-372.

  14. A Study of Stratospheric Aerosols and Their Effect on Inorganic Chlorine Partitioning Using Balloon, In Situ, and Satellite Observations

    NASA Technical Reports Server (NTRS)

    Osterman, G. B.; Salawitch, R. J.; Sen, B.; Toon, G. C.

    1999-01-01

    Heterogeneous reactions on the surface of aerosols lead to a decrease in the concentration of nitrogen radicals and an increase in the concentration of chlorine and hydrogen radical species. As a consequence, enhanced sulfate aerosol levels in the lower stratosphere resulting from volcanic eruptions lead to lower concentrations of ozone due to more rapid loss by chlorine and hydrogen radicals. This study focuses on continuing the effort to quantify the effect of sulfate aerosols on the partitioning of inorganic chlorine species at midlatitudes. The study begins with an examination of balloon-borne measurements of key chlorine species obtained by the JPL MkIV interferometer for different aerosol loading conditions. A detailed comparison of the response of HCl to variations in aerosol surface area observed by MkIV, ER-2 instruments, HALOE, and ATMOS is carried out by examining HCl vs CH4 correlation diagrams, since CH4 is the only tracer measured on each platform. Finally, the consistency between theory and observed changes in ClO and HCl due to variations in aerosol surface area is examined.

  15. 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

  16. Effect of OH radical scavengers on secondary organic aerosol formation from reactions of isoprene with ozone

    NASA Astrophysics Data System (ADS)

    Sato, Kei; Inomata, Satoshi; Xing, Jia-Hua; Imamura, Takashi; Uchida, Risa; Fukuda, Sayaka; Nakagawa, Kazumichi; Hirokawa, Jun; Okumura, Motonori; Tohno, Susumu

    2013-11-01

    In order to understand the effect of OH radical scavengers on secondary organic aerosol formation, aerosol yields from the isoprene ozonolysis were measured in the presence of sufficient amounts of OH radical scavengers. Cyclohexane, CO, n-hexane, and diethyl ether were used as the OH radical scavengers. The aerosol yield was determined to be 0.002-0.023 for experiments without OH radical scavengers in the aerosol mass range 2-120 ?g m-3. Similar aerosol yields were observed in experiments using cyclohexane. The aerosol yield observed with n-hexane was close to that observed without scavengers at 120 ?g m-3, but this aerosol yield was slightly lower than those observed in reactions without scavengers in the range 3-83 ?g m-3. The offline aerosol samples obtained in experiments with cyclohexane or n-hexane contained oxygenated hydrocarbons with six or more carbon atoms. Aerosol formation in experiments that used cyclohexane or n-hexane as the scavenger was enhanced. This was caused by the oxidation products of the OH radical scavengers, although the increase in the yield could not be quantified. The aerosol yields were 0.002-0.014 for experiments with CO and diethyl ether in the aerosol mass range 4-120 ?g m-3. The reaction of CO with OH radicals forms HO2 radicals, whereas the reactions of cyclohexane, n-hexane, and diethyl ether, respectively, with OH radicals form organic peroxy (RO2) radicals. Present results show that the aerosol yield is independent of the HO2/RO2 ratio or that it decreases with increasing HO2/RO2 ratio. Since the HO2 concentration is much higher than the RO2 concentration in the atmosphere, the results obtained using CO in this study will be a good approximation of the aerosol yield from the ozonolysis of isoprene in the atmosphere.

  17. simpleGAMMA - 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.

    2015-01-01

    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 cloudwater or aqueous aerosols. Results from GAMMA simulations of SOA formation in aerosol water (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 aqueous aerosol phase SOA 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.

  18. Secondary organic aerosol formation and source apportionment in Southeast Texas

    NASA Astrophysics Data System (ADS)

    Zhang, Hongliang; Ying, Qi

    2011-06-01

    The latest version of US EPA's Community Multi-scale Air Quality (CMAQ v4.7) model with the most recent update on secondary organic aerosol (SOA) formation pathways was adapted into a source-oriented modeling framework to determine the contributions of different emission sources to SOA concentrations from a carbon source perspective in Southeast Texas during the 2000 Texas Air Quality Study (TexAQS 2000) from August 25 to September 5, 2000. A comparison of the VOC and SOA predictions with observations shows that anthropogenic emissions of long chain alkanes and aromatics are likely underestimated in the EPA's Clean Air Interstate Rule (CAIR) inventory and the current SOA mechanism in CMAQ still under-predicts SOA. The peak SOA concentrations measured at La Porte are more accurately predicted by increasing the emissions of the anthropogenic SOA precursors by a factor of 5 although the overall precursor concentrations are better predicted by increasing the emissions by a factor of 2. A linear correlation between SOA and odd oxygen (?SOA/?O x = 23.0-28.4 ?g m -3/ppm O x) can be found when they are formed simultaneously in the air masses passing the urban Houston area on high SOA days. Based on the adjusted emissions (a factor of 2 increase in the alkane and aromatics precursor emissions), approximately 20% of the total SOA in the Houston-Galveston Bay area is due to anthropogenic sources. Solvent utilization and gasoline engines are the main anthropogenic sources. SOA from alkanes and aromatics accounts for approximately 2-4% and 5-9% of total SOA, respectively. The predicted overall anthropogenic SOA concentrations are not sensitive to the half-life time used to calculate the conversion rate of semi-volatile organic compounds to non-volatile oligomers in the particle phase. The main precursors of biogenic SOA are sesquiterpenes, which contribute to approximately 12-35% of total SOA. Monoterpenes contribute to 3-14% and isoprene accounts for approximately 6-9% of the total SOA. Oligomers from biogenic SOA account for approximately 30-58% of the total SOA, indicating that long range transport is an important source of SOA in this region.

  19. 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.

  20. Secondary organic aerosol formation from in-use motor vehicle emissions using a potential aerosol mass reactor.

    PubMed

    Tkacik, Daniel S; Lambe, Andrew T; Jathar, Shantanu; Li, Xiang; Presto, Albert A; Zhao, Yunliang; Blake, Donald; Meinardi, Simone; Jayne, John T; Croteau, Philip L; Robinson, Allen L

    2014-10-01

    Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ? 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ? 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas. PMID:25188317

  1. 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.

  2. 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.

  3. Widening the gap between measurement and modelling of secondary organic aerosol properties?

    NASA Astrophysics Data System (ADS)

    Good, N.; Topping, D. O.; Duplissy, J.; Gysel, M.; Meyer, N. K.; Metzger, A.; Turner, S. F.; Baltensperger, U.; Ristovski, Z.; Weingartner, E.; Coe, H.; McFiggans, G.

    2010-03-01

    The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of ?-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the sub-saturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation could be achieved widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from validated and extensively used instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood and the instrumentation extensively quality assured. It is impossible to say from the results presented here due to the differences in HTDMA data whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.

  4. 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.

  5. Physico-chemical properties of aerosols in Sao Paulo, Brazil and mechanisms of secondary organic aerosol formation.

    NASA Astrophysics Data System (ADS)

    Artaxo, Paulo; Ferreira de Brito, Joel; Varanda Rizzo, Luciana; Luiza Godoy, Maria; Godoy, Jose Marcus

    2013-04-01

    Megacities emissions are increasingly becoming a global issue, where emissions from the transportation sector play an increasingly important role. Sao Paulo is a megacity with a population of about 18 million people, 7 million cars and large-scale industrial emissions. As a result of the vehicular and industrial emissions, the air quality in Sao Paulo is bellow WMO standards for aerosol particles and ozone. Many uncertainties are found on gas- and particulate matter vehicular emission factors and their following atmospheric processes, e.g. secondary organic aerosol formation. Due to the uniqueness of the vehicular fuel in Brazil, largely based on ethanol use, such characterization currently holds further uncertainties. To improve the understanding of the role of this unique emission characteristics, we are running a source apportionment study in Sao Paulo focused on the mechanisms of organic aerosol formation. One of the goals of this study is a quantitative aerosol source apportionment focused on vehicular emissions, including ethanol and gasohol (both fuels used by light-duty vehicles). This study comprises four sampling sites with continuous measurements for one year, where trace elements and organic aerosol are being measured for PM2.5 and PM10 along with real-time NOx, O3, PM10 and CO measurements. Aerosol optical properties and size distribution are being measured on a rotation basis between sampling stations. Furthermore, a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) and an Aerosol Chemical Speciation Monitor (ACSM) are used to measure in real time VOCs and aerosol composition, respectively. Trace elements were measured using XRF and OC/EC analysis was determined with a Sunset OC/EC instrument. A TSI Nephelometer with 3 wavelengths measure light scattering and a MAAP measure black carbon. Results show aerosol number concentrations ranging between 10,000 and 35,000 cm-3, mostly concentrated in the nucleation and Aitken modes, with a peak in size at 80-120 nm. Average mass concentrations were measured at 11.5 ug/m3 and 30.7 ug/m3 for fine and coarse mode, respectively. The elemental analysis shows that Fe, Si and Al dominate the coarse mode indicating strong contribution from soil dust resuspension whereas sulfur dominates the fine mode (0.8 micrograms/m3). Scattering coefficients typically range between 20 and 150 Mm-1 at 637 nm, and absorption varied between 10 to 60 Mm-1 at 637 nm, respectively, both of them peaking at 7:00 local time, the morning rush hour. The corresponding single scattering albedo varies between 0.50 and 0.80, indicating a significant contribution of primary soot particles to the aerosol population. Organic aerosol accounts for 70% of the aerosol mass, with nitrates accounting for 11.7%, ammonia 8.4%, sulfate 8.2% and chlorine 1.6% pf PM1 measured by AMS techniques. Most of the organic aerosol were oxygenated. Several new particle formation events were observed, with a clear increase in organic aerosol and VOCs amounts associated with new particle formation. The study allows the characterization of a unique fueled fleet emissions and its impact on atmospheric chemistry, particle formation and other atmospheric dynamic processes. This work was funded by Petrobras S/A

  6. Formation of Secondary Organic Aerosols Through Photooxidation of Isoprene

    Microsoft Academic Search

    Magda Claeys; Bim Graham; Gyorgy Vas; Wu Wang; Reinhilde Vermeylen; Vlada Pashynska; Jan Cafmeyer; Pascal Guyon; Meinrat O. Andreae; Paulo Artaxo; Willy Maenhaut

    2004-01-01

    Detailed organic analysis of natural aerosols from the Amazonian rain forest showed considerable quantities of previously unobserved polar organic compounds, which were identified as a mixture of two diastereoisomeric 2-methyltetrols: 2-methylthreitol and 2-methylerythritol. These polyols, which have the isoprene skeleton, can be explained by OH radical-initiated photooxidation of isoprene. They have low vapor pressure, allowing them to condense onto preexisting

  7. Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    Reactive halogen species (RHS), such as X·, X2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. Model SOA from ?-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy), changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS)), or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

  8. Cloud forming potential of oligomers relevant to secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Xu, Wen; Guo, Song; Gomez-Hernandez, Mario; Zamora, Misti L.; Secrest, Jeremiah; Marrero-Ortiz, Wilmarie; Zhang, Annie L.; Collins, Don R.; Zhang, Renyi

    2014-09-01

    The hygroscopic growth factor (HGF) and cloud condensation nuclei (CCN) activity are measured for surrogates that mimic atmospherically relevant oligomers, including glyoxal trimer dihydrate, methyl glyoxal trimer dihydrate, sucrose, methyl glyoxal mixtures with sulfuric acid and glycolic acid, and 2,4-hexandienal mixtures with sulfuric acid and glycolic acid. For the single-component aerosols, the measured HGF ranges from 1.3 to 1.4 at a relative humidity of 90%, and the hygroscopicity parameter (?) is in the range of 0.06 to 0.19 on the basis of the measured CCN activity and 0.13 to 0.22 on the basis of the measured HGF, compared to the calculated values of 0.08 to 0.16. Large differences exist in the ? values derived using the measured HGF and CCN data for the multi-component aerosols. Our results reveal that, in contrast to the oxidation process, oligomerization decreases particle hygroscopicity and CCN activity and provides guidance for analyzing the organic species in ambient aerosols.

  9. Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions

    PubMed Central

    Gentner, Drew R.; Isaacman, Gabriel; Worton, David R.; Chan, Arthur W. H.; Dallmann, Timothy R.; Davis, Laura; Liu, Shang; Day, Douglas A.; Russell, Lynn M.; Wilson, Kevin R.; Weber, Robin; Guha, Abhinav; Harley, Robert A.; Goldstein, Allen H.

    2012-01-01

    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. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies. PMID:23091031

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

    E-print Network

    conducted in the Harvard Environmental Chamber (HEC). The CCN properties of ammonium sulfate particles mixedCCN Activity and Mixing Rules of Isoprene Secondary Organic Aerosol (SOA) and Sulfate For original material (mainly sulfate) within a single particle so that an understanding of the CCN activity of mixed

  11. Secondary organic aerosol yields from cloud-processing of isoprene oxidation products

    Microsoft Academic Search

    Barbara Ervens; Annmarie G. Carlton; Barbara J. Turpin; Katye E. Altieri; Sonia M. Kreidenweis; Graham Feingold

    2008-01-01

    While there is a growing understanding from laboratory studies of aqueous phase chemical processes that lead to secondary organic aerosol (SOA) formation in cloud droplets (SOAdrop), the contribution of aqueous phase chemistry to atmospheric SOA burden is yet unknown. Using a parcel model including a multiphase chemical mechanism, we show that SOAdrop carbon yields (Yc) from isoprene (1) depend strongly

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

    EPA Science Inventory

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

  13. A missing sink for gas-phase glyoxal in Mexico City: Formation of secondary organic aerosol

    Microsoft Academic Search

    Rainer Volkamer; Federico San Martini; Luisa T. Molina; Dara Salcedo; Jose L. Jimenez; Mario J. Molina

    2007-01-01

    (1) The sources of secondary organic aerosol (SOA) are highly uncertain. Direct measurements of gas-phase glyoxal in Mexico City are compared to experimentally constrained model predictions. Observed glyoxal concentrations are found significantly below those predicted. Additional glyoxal sources are likely and would increase these differences; an additional glyoxal sink must be operative. The model-measurement differences are fully resolved by a

  14. SEMI-VOLATILE SECONDARY AEROSOLS IN URBAN ATMOSPHERES: MEETING A MEASURED CHALLENGE

    EPA Science Inventory

    This presentation compares the results from various particle measurement methods as they relate to semi-volatile secondary aerosols in urban atmospheres. The methods include the PM2.5 Federal Reference Method; Particle Concentrator - BYU Organic Sampling System (PC-BOSS); the Re...

  15. Secondary organic aerosol formation from fossil fuel sources contribute majority of summertime organic mass at Bakersfield

    E-print Network

    Silver, Whendee

    ] Secondary organic aerosols (SOA), known to form in the atmosphere from oxidation of volatile organic from alkane and aromatic compounds, the two major classes of vehicle-emitted hydrocarbons, accounted for 65% OM (72% SOA). The alkane and aromatic SOA components were associated with 200 nm to 500 nm

  16. 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.

  17. 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

  18. Secondary organic aerosol formation through fog processing of VOCs

    NASA Astrophysics Data System (ADS)

    Herckes, P.; Hutchings, J. W.

    2010-07-01

    Volatile Organic Compounds (VOCs) including benzene, toluene, ethylbenzene and xylenes (BTEX) have been determined in highly concentrated amounts (>1 ug/L) in intercepted clouds in northern Arizona (USA). These VOCs are found in concentrations much higher than predicted by partitioning alone. The reactivity of BTEX in the fog/cloud aqueous phase was investigated through laboratory studies. BTEX species showed fast degradation in the aqueous phase in the presence of peroxides and light. Observed half-lives ranged from three and six hours, substantially shorter than the respective gas phase half-lives (several days). The observed reaction rates were on the order of 1 ppb/min but decreased substantially with increasing concentrations of organic matter (TOC). The products of BTEX oxidation reactions were analyzed using HPLC-UV and LCMS. The first generation of products identified included phenol and cresols which correspond to the hydroxyl-addition reaction to benzene and toluene. Upon investigating of multi-generational products, smaller, less volatile species are predominant although a large variety of products is found. Most reaction products have substantially lower vapor pressure and will remain in the particle phase upon droplet evaporation. The SOA generation potential of cloud and fog processing of BTEX was evaluated using simple calculations and showed that in ideal situations these reactions could add up to 9% of the ambient aerosol mass. In more conservative scenarios, the contribution of the processing of BTEX was around 1% of ambient aerosol concentrations. Overall, cloud processing of VOC has the potential to contribute to the atmospheric aerosol mass. However, the contribution will depend upon many factors such as the irradiation, organic matter content in the droplets and droplet lifetime.

  19. 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.

  20. 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.

  1. A comparison of summertime secondary organic aerosol source contributions at contrasting urban locations.

    PubMed

    Stone, Elizabeth A; Zhou, Jiabin; Snyder, David C; Rutter, Andrew P; Mieritz, Mark; Schauer, James J

    2009-05-15

    Primary and secondary sources contributing to atmospheric organic aerosol during the months of July and August were quantitatively assessed in three North American urban areas: Cleveland, Ohio, and Detroit, Michigan, in the Midwest region and Riverside, California, in the Los Angeles Air Basin. Organic molecular marker species unique to primary aerosol sources and secondarytracers derived from isoprene, alpha-pinene, beta-caryophyllene, and toluene were measured using gas chromatography-mass spectrometry. Source contributions from motor vehicles, biomass burning, vegetative detritus, and secondary organic aerosol (SOA) were estimated using chemical mass balance (CMB) modeling. In Cleveland, primary sources accounted for 37 +/- 2% of ambient organic carbon, measured biogenic and anthropogenic secondary sources contributed 46 +/- 6%, and other unknown sources contributed 17 +/- 4%. Similarly, Detroit aerosol was determined to be 44 +/- 5% primary and 37 +/- 3% secondary, while 19 +/- 7% was unaccounted for by measured sources. In Riverside, 21 +/- 3% of organic carbon came from primary sources, 26 +/- 5% was attributed to measured secondary sources, and 53 +/- 3% came from other sources that were expected to be secondary in nature. The comparison of samples across these two regions demonstrated that summertime SOA in the Midwestern United States was substantially different from the summertime SOA in the Los Angeles Air Basin and indicated the need to exert caution when generalizing about the sources and nature of SOA across different urban areas. Furthermore, the results of this study suggestthatthe contemporary understanding of SOA sources and formation mechanisms is satisfactory to explainthe majority of SOA in the Midwest Additional SOA sources and mechanisms of formation are needed to explain the majority of SOA in the Los Angeles Air Basin. PMID:19544838

  2. Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols

    NASA Astrophysics Data System (ADS)

    Yee, L. D.; Kautzman, K. E.; Loza, C. L.; Schilling, K. A.; Coggon, M. M.; Chhabra, P. S.; Chan, M. N.; Chan, A. W. H.; Hersey, S. P.; Crounse, J. D.; Wennberg, P. O.; Flagan, R. C.; Seinfeld, J. H.

    2013-02-01

    The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol), major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NOx (<10 ppb) conditions using H2O2 as the OH source. Secondary organic aerosol (SOA) yields (ratio of mass of SOA formed to mass of primary organic reacted) greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O:C) ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) measurements of the SOA in all three systems are ~0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010). An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach.

  3. Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols

    NASA Astrophysics Data System (ADS)

    Yee, L. D.; Kautzman, K. E.; Loza, C. L.; Schilling, K. A.; Coggon, M. M.; Chhabra, P. S.; Chan, M. N.; Chan, A. W. H.; Hersey, S. P.; Crounse, J. D.; Wennberg, P. O.; Flagan, R. C.; Seinfeld, J. H.

    2013-08-01

    The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol), major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NOx (< 10 ppb) conditions using H2O2 as the OH source. Secondary organic aerosol (SOA) yields (ratio of mass of SOA formed to mass of primary organic reacted) greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O : C) ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) measurements of the SOA in all three systems are ~ 0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010). An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach.

  4. A phase equilibrium model for atmospheric aerosols containing inorganic electrolytes and organic compounds (UHAERO), with application to dicarboxylic acids

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    Computation of phase and chemical equilibria of water-organic-inorganic mixtures is of significant interest in atmospheric aerosol modeling. A new version of the phase partitioning model, named UHAERO, is presented here, which allows one to compute the phase behavior for atmospheric aerosols containing inorganic electrolytes and organic compounds. The computational implementation of the model is based on standard minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. Water uptake and deliquescence properties of mixtures of aqueous solutions of salts and dicarboxylic acids, including oxalic, malonic, succinic, glutaric, maleic, malic, or methyl succinic acids, are based on a hybrid thermodynamic approach for the modeling of activity coefficients (Clegg and Seinfeld, 2006a, 2006b). UHAERO currently considers ammonium salts and the neutralization of dicarboxylic acids and sulfuric acid. Phase diagrams for sulfate/ammonium/water/dicarboxylic acid systems are presented as a function of relative humidity at 298.15 K over the complete space of compositions.

  5. FORMATION MECHANISMS FOR SECONDARY ORGANIC AEROSOL IN AMBIENT AIR

    EPA Science Inventory

    An laboratory and field research program is underway at the NERL to characterize secondary organic carbon in PM2.5 which is formed through chemical reactions in the atmosphere. Information from this study will provide critical data needed to improve the treatment of SO...

  6. Climate-relevant physical properties of molecular constituents for isoprene-derived secondary organic aerosol material

    NASA Astrophysics Data System (ADS)

    Upshur, M. A.; Strick, B. F.; McNeill, V. F.; Thomson, R. J.; Geiger, F. M.

    2014-10-01

    Secondary organic aerosol (SOA) particles, formed from gas-phase biogenic volatile organic compounds (BVOCs), contribute large uncertainties to the radiative forcing that is associated with aerosols in the climate system. Reactive uptake of surface-active organic oxidation products of BVOCs at the gas-aerosol interface can potentially decrease the overall aerosol surface tension and therefore influence their propensity to act as cloud condensation nuclei (CCN). Here, we synthesize and measure some climate-relevant physical properties of SOA particle constituents consisting of the isoprene oxidation products ?-, ?-, and cis- and trans-?-IEPOX (isoprene epoxide), as well as syn- and anti-2-methyltetraol. Following viscosity measurements, we use octanol-water partition coefficients to quantify the relative hydrophobicity of the oxidation products while dynamic surface tension measurements indicate that aqueous solutions of ?- and trans-?-IEPOX exhibit significant surface tension depression. We hypothesize that the surface activity of these compounds may enhance aerosol CCN activity, and that trans-?-IEPOX may be highly relevant for surface chemistry of aerosol particles relative to other IEPOX isomers.

  7. [Pollution characteristics of secondary water-soluble inorganic ions of PM2.5 in urban Chengdu, China].

    PubMed

    Li, You-ping; Zhou, Hong; Zhang Zhi-sheng; Wang, Qi-yuan; Luo, Lei

    2014-12-01

    A total of 131 samples of PM2.5 were collected at urban area of Chengdu from April, 2009 to January, 2010. The secondary water-soluble inorganic ions (NH4(+), NO3(-) and SO4(2-)) in PM2.5 were determined to study the pollution characteristics by Ion Chromatography method. The results showed the NH4(+), NO3(-) and SO4(2-) concentrations were (10.4 ± 8.6), (19.7 ± 14.6) and (32.8 ± 21.8) ?g x m(-3), accounting for (5.5 ± 2.8)%, (11.1 ± 3.5)% and (19.3 ± 6.4)% of PM2.5, respectively, and the sum of these three ions accounted for (35.9 ± 12.7)%. Meanwhile, the seasonal characteristics of secondary inorganic ions were obvious. The seasonal concentrations order of secondary inorganic components was SO4(2-) > NO3(-) > NH4(+) in summer and winter, and the proportion of secondary inorganic ions of PM2.5 was 39.4% in summer and 44.3% in winter. The results of Correlation Analysis showed that most of NH4(+), NO3(-) and SO4(2-) existed as NH4HSO4, (NH4 )2SO4 and NH4NO5 in Chengdu. And the average ratio of NO3(-)/SO4(2-) indicated that the main source of sulfur and nitrogen in the atmosphere was given priority to a fixed source. In addition, the sulfate oxidizing rate (SOR) and nitrate oxidizing rate (NOR) were 0.33 ± 0.12 and 0.19 ± 0.09, respectively. It showed that SO4(2-) and NO3(-) in PM2.5 were due to the secondary transformation. PMID:25826911

  8. Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Seinfeld, J. H.

    2012-05-01

    The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA). Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH), as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality) and EVAPORATION (for pure compound vapor pressures) with oxidation product information from the Master Chemical Mechanism (MCM) for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of ?-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH). Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, several simplified model approaches are tested with regard to computational costs and accuracy of predictions compared to the benchmark calculation. It is shown that forcing a liquid one-phase aerosol with or without consideration of non-ideal mixing bears the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, by more than 100% at RH values of 80% and by more than 200% at RH values of 95%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1) non-ideality in the condensed phase needs to be considered and (2) liquid-liquid phase separation is a consequence of considerable deviations from ideal mixing in solutions containing inorganic ions and organics that cannot be ignored. Computationally much more efficient calculations relying on the assumption of a complete organic/electrolyte phase separation below a certain RH successfully reproduce gas-particle partitioning in systems in which the average oxygen-to-carbon (O:C) ratio is lower than ~0.6, as in the case of ?-pinene SOA, and bear the potential for implementation in atmospheric chemical transport models and chemistry-climate models. A full equilibrium calculation is the method of choice for accurate offline (box model) computations, where high computational costs are acceptable. Such a calculation enables the most detailed predictions of phase compositions and provides necessary information on whether assuming a complete organic/electrolyte phase separation is a good approximation for a given aerosol system. Based on the group-contribution concept of AIOMFAC and O:C ratios as a proxy for polarity and hygroscopicity of organic mixtures, the results from the ?-pinene system are also discussed from a more general point of view.

  9. Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Seinfeld, J. H.

    2012-01-01

    The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA). Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH), as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality) and EVAPORATION (for pure compound vapor pressures) with oxidation product information from the Master Chemical Mechanism (MCM) for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of ?-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH). Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, different simplified model approaches are tested with regards to computational costs and accuracy of predictions compared to the benchmark calculation. Both forcing a liquid one-phase aerosol considering non-ideal mixing or assuming an ideal mixture bear the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, at high RH by more than 200%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1) non-ideality in the condensed phase needs to be considered and (2) liquid-liquid phase separation is a consequence of considerable deviations from ideal mixing in solutions containing inorganic ions and organics that cannot be ignored. Computationally much more efficient calculations relying on the assumption of a complete organic/electrolyte phase separation below a certain RH successfully reproduce gas-particle partitioning in systems in which the average oxygen-to-carbon (O:C) ratio is lower than ~0.6, as in the case of ?-pinene SOA, and bear the potential for implementation in atmospheric chemical transport models and chemistry-climate models. A full equilibrium calculation is the method of choice for accurate offline (box model) computations, where high computational costs are acceptable. Such a calculation enables the most detailed predictions of phase compositions and provides necessary information on whether assuming a complete organic/electrolyte phase separation is a good approximation for a given aerosol system. Based on the group-contribution concept of AIOMFAC and O:C ratios as a proxy for polarity and hygroscopicity of organic mixtures, the results from the ?-pinene system are also discussed from a more general point of view.

  10. The formation of secondary organic aerosol from the isoprene + OH reaction in the absence of NOx

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Lewandowski, M.; Offenberg, J. H.; Jaoui, M.; Edney, E. O.

    2009-04-01

    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 chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (?Hvapeff), the organic peroxide fraction, and the aerosol yield. The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols) were found to form in the absence of acidic sulfate aerosol. A re-evaluation of field samples in Research Triangle Park, North Carolina, during the summers of 2000 and 2001 indicated in the presence of the methyl butenediols from gas-phase denuder samples taken at the time. SOA/SOC (i.e., OM/OC) was found to average 1.9 in the absence of NOx. The effective enthalpy of vaporization was measured as 38.6 kJ mol-1, consistent with values that have previously been used in modeling studies. The yields in this work (using an independent technique than that previous) are lower than those of Kroll et al. (2006) for similar aerosol masses. SOC yields reported in this work range from 0.5-1.4% for carbon masses between 17 and 49 ?gC m-3.

  11. The formation of secondary organic aerosol from the isoprene + OH reaction in the absence of NOx

    NASA Astrophysics Data System (ADS)

    Kleindienst, T. E.; Lewandowski, M.; Offenberg, J. H.; Jaoui, M.; Edney, E. O.

    2009-09-01

    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 chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (?Hvapeff), organic peroxide fraction, and the aerosol yield. The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols) were found to form in the absence of acidic sulfate aerosol. However, reaction conditions did not favor the production of HO2 radicals, thus allowing RO2+RO2 reactions to proceed more readily than if higher HO2 levels had been generated. SOA/SOC (i.e. OM/OC) was found to average 1.9 in the absence of NOx. The effective enthalpy of vaporization was measured as 38.6 kJ mol-1, consistent with values used previously in modeling studies. The yields in this work (using an independent technique than used previously) are lower than those of Kroll et al. (2006) for similar aerosol masses. SOC yields reported in this work range from 0.5-1.4% for carbon masses between 17 and 49 ?gC m-3.

  12. Emissions and Secondary Organic Aerosol Production from Semivolatile and Intermediate Volatility Organic Compounds

    NASA Astrophysics Data System (ADS)

    Robinson, A. L.; Presto, A. A.; Miracolo, M. A.; Donahue, N. M.; Kroll, J. H.; Worsnop, D. R.

    2008-12-01

    Organic aerosols are a highly-dynamic system dominated by both variable gas-particle partitioning and chemical evolution. Important classes of organics include semivolatile and intermediate volatility organic compounds (SVOC and IVOC, respectively). SVOCs are compounds that exist in both the gas and particle phases at typical atmospheric conditions while IVOC are low-volatility vapors that exist exclusively in the gas phase. Both classes have saturation concentrations that are orders of magnitude lower than volatile organic compounds (VOC) that are the traditional subjects of atmosphere chemistry, such as monoterpenes, alkyl benzenes, etc. The SVOC and IVOC are poorly represented for in current atmospheric chemistry models. Source testing indicates that SVOC and IVOC emissions from biomass combustion, diesel engines and other sources exceed the primary organic aerosol emissions; thus the oxidation of these vapors could serve as a significant source of organic aerosol in the atmosphere. The formation of secondary organic aerosol (SOA) from the reactions between OH radicals and SVOCs and IVOCs was investigated in the Carnegie Mellon University smog chamber. Experiments were conducted with n-alkanes and emission surrogates (diesel fuel and lubricating oil). SVOC oxidation produces oxidized organic aerosol but little new organic aerosol mass. This behavior can be explained by the coupled effects of partitioning and aging. Oxidation of SVOC vapors creates low volatility species that partition into the condensed phase; this oxidation also reduces the SVOC vapor concentration which, in turn, requires particle-phase SVOC to evaporate to maintain phase equilibrium. In contrast, oxidation of IVOC results in sustained production of SOA consistent with a reaction with relatively slow kinetics and high mass yield. Aerosol Mass Spectrometer data indicates that the SOA formed from IVOC has a mass spectrum that is quite similar to the oxygenated organic aerosol factor observed in field studies.

  13. 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.

  14. The Potential of Amorphous Solid Secondary Organic Aerosol to Form Mixed-Phase and Cirrus Clouds

    NASA Astrophysics Data System (ADS)

    Knopf, D. A.; Wang, B.; Lambe, A. T.; Massoli, P.; Onasch, T. B.; Davidovits, P.; Worsnop, D. R.

    2012-12-01

    Atmospheric ice formation by heterogeneous nucleation, which results in cirrus and mixed-phase cloud formation, is one of the least understood processes affecting the global radiation budget, the hydrological cycle, and water vapor distribution. It is commonly assumed that inorganic particles such as mineral dust and solid ammonium sulfate represent important atmospheric ice nuclei (IN). However, a growing body of evidence suggests that secondary organic aerosols (SOA), which are ubiquitous in the atmosphere, exist in a solid (glassy) state. This implies that SOA may also play a role in ice cloud formation by acting as IN, but has not previously been experimentally verified. Here, we report observations of water uptake and ice nucleation via condensation, immersion, and deposition modes initiated by amorphous SOA particles at temperatures from T = 200 - 250 K and relative humidity (RH) from subsaturation conditions up to water saturation. SOA particles with oxygen-to-carbon (O/C) ratios ranging from 0.3 to 1.0 are generated from gas-phase OH oxidation of naphthalene in a flow reactor. At T > 230 K, water uptake at subsaturation conditions is correlated with SOA oxidation level (O/C ratio). This initial water uptake is followed by a moisture-induced phase transition and subsequent immersion freezing. At T < 230 K, the SOA forms ice via deposition nucleation at RH with respect to ice 10-15% below the homogeneous ice nucleation limit, with no apparent dependence on oxidation level. The SOA glass transition temperature (Tg) is estimated as a function of RH, temperature, and SOA oxidation level from corresponding measurements of particle density, hygroscopicity, and bounced fraction, the latter indicating particle phase state. Above Tg, water uptake and immersion freezing is observed when the particles are liquid or semi-solid. Below Tg, deposition ice nucleation is observed when the particles are solid. The data show that particle phase and viscosity govern the particles' response to temperature and RH and provide a straightforward interpretation for the observed different heterogeneous ice nucleation pathways and water uptake by the laboratory-generated SOA and previously investigated fulvic acid surrogate particles and organic dominated field-collected particles. These observations suggest that atmospheric ubiquitous SOA are potentially important for ice cloud formation and climate and should be investigated in future cloud resolving and climate modeling studies.

  15. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  17. Dicarboxylic acids, metals and isotopic compositions of C and N in atmospheric aerosols from inland China: implications for dust and coal burning emission and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Wang, G.; Xie, M.; Hu, S.; Tachibana, E.; Kawamura, K.

    2010-03-01

    Dicarboxylic acids (C2-C10), metals, elemental carbon (EC), organic carbon (OC), and stable isotopic compositions of total carbon (TC) and total nitrogen (TN) were determined for PM10 samples collected at three urban and one suburban sites of Baoji, an inland city of China, during winter and spring 2008. Oxalic acid (C2) was the dominant diacid, followed by succinic (C4) and malonic (C3) acids. Total diacids in the urban and suburban areas are 1546±203 and 1728±495 ng m-3 during winter and 1236±335 and 1028±193 ng m-3 during spring. EC in the urban and the suburban atmospheres are 17±3.8 and 8.0±2.1 ?g m-3 during winter and 20±5.9 and 7.1±2.7 ?g m-3 during spring whereas OC at the urban and suburban sites are 74±14 and 51±7.9 ?g m-3 in winter and 51±20 and 23±6.1 ?g m-3 in spring. Secondary organic carbon (SOC) accounted for 38±16% of OC in winter and 28±18% of OC in spring, suggesting an enhanced photochemical production of secondary organic aerosols in winter under an inversion layer development. Total metal elements in winter and spring are 34±10 and 61±27 ?g m-3 in the urban air and 18±7 and 32±23 ?g m-3 in the suburban air. A linear correlation (r2>0.8 in winter and r2>0.6 in spring) was found between primary organic carbon (POC) and Ca2+/Fe, together with a strong dependence of pH value on water-soluble inorganic carbon, suggesting fugitive dust as a major source of the airborne particles. Polycyclic aromatic hydrocarbons (PAHs), sulfate, and Pb in the samples well correlated each other (r2>0.6) in winter samples, suggesting an importance of emissions from coal burning for house heating. Stable carbon isotope compositions of TC (?13C) became higher with an increase in the concentration ratios of C2/OC due to aerosol aging. In contrast, nitrogen isotope compositions of TN (?15N) became lower with an increases in the mass ratios of NH4+/PM10 and NO3-/PM10 due to an enhanced adsorption and/or condensation of NH3 and HNO3 from gas phase onto solid phase.

  18. Dicarboxylic acids, metals and isotopic compositions of C and N in atmospheric aerosols from inland China: implications for dust and coal burning emission and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Wang, G.; Xie, M.; Hu, S.; Gao, S.; Tachibana, E.; Kawamura, K.

    2010-07-01

    Dicarboxylic acids (C2-C10), metals, elemental carbon (EC), organic carbon (OC), and stable isotopic compositions of total carbon (TC) and total nitrogen (TN) were determined for PM10 samples collected at three urban and one suburban sites of Baoji, an inland city of China, during winter and spring 2008. Oxalic acid (C2) was the dominant diacid, followed by succinic (C4) and malonic (C3) acids. Total diacids in the urban and suburban areas were 1546±203 and 1728±495 ng m-3 during winter and 1236±335 and 1028±193 ng m-3 during spring. EC in the urban and the suburban atmospheres were 17±3.8 and 8.0±2.1 ?g m-3 during winter and 20±5.9 and 7.1±2.7 ?g m-3 during spring, while OC at the urban and suburban sites were 74±14 and 51±7.9 ?g m-3 in winter and 51±20 and 23±6.1 ?g m-3 in spring. Secondary organic carbon (SOC) accounted for 38±16% of OC in winter and 28±18% of OC in spring, suggesting an enhanced photochemical production of secondary organic aerosols in winter under an inversion layer development. Total metal elements in winter and spring were 34±10 and 61±27 ?g m-3 in the urban air and 18±7 and 32±23 ?g m-3 in the suburban air. A linear correlation (r2>0.8 in winter and r2>0.6 in spring) was found between primary organic carbon (POC) and Ca2+/Fe, together with a strong dependence of pH value of sample extracts on water-soluble inorganic carbon, suggesting fugitive dust as an important source of the airborne particles. Polycyclic aromatic hydrocarbons (PAHs), sulfate, and Pb in the samples well correlated each other (r2>0.6) in winter, indicating an importance of emissions from coal burning for house heating. Stable carbon isotope compositions of TC (?13C) became higher with an increase in the concentration ratios of C2/OC due to aerosol aging. In contrast, nitrogen isotope compositions of TN (?15N) became lower with an increases in the mass ratios of NH4+/PM10 and NO3-/PM10, which is possibly caused by an enhanced adsorption and/or condensation of gaseous NH3 and HNO3 onto particles.

  19. Formation of brown carbon via reactions of ammonia with secondary organic aerosols from biogenic and anthropogenic precursors

    E-print Network

    Nizkorodov, Sergey

    occurs for a wide range of biogenic and anthropogenic aerosols. Aqueous reaction with ammonium ion coefficient a b s t r a c t Filter samples of secondary organic aerosols (SOA) generated from the ozone (O3 in color (limonene SOA). The aqueous phase reactions with dissolved ammonium (NH4 þ ) salts

  20. Laboratory studies on optical properties of secondary organic aerosols generated during the photooxidation of toluene and the ozonolysis of ?-pinene

    Microsoft Academic Search

    Tomoki Nakayama; Yutaka Matsumi; Kei Sato; Takashi Imamura; Akihiro Yamazaki; Akihiro Uchiyama

    2010-01-01

    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

  1. Emissions of Black Carbon, Organic, and Inorganic Aerosols From Biomass Burning in North America and Asia in 2008

    NASA Technical Reports Server (NTRS)

    Kondo, Y.; Matsui, H.; Moteki, N.; Sahu, L.; Takegawa, N.; Kajino, M.; Zhao, Y.; Cubison, M. J.; Jimenez, J. L.; Vay, S.; Diskin, G. S.; Anderson, B.; Wisthaler, A.; Mikoviny, T.; Fuelberg, H. E.; Blake, D. R.; Huey, G.; Weinheimer, A. J.; Knapp, D. J.; Brune, W. H.

    2011-01-01

    Reliable assessment of the impact of aerosols emitted from boreal forest fires on the Arctic climate necessitates improved understanding of emissions and the microphysical properties of carbonaceous (black carbon (BC) and organic aerosols (OA)) and inorganic aerosols. The size distributions of BC were measured by an SP2 based on the laser-induced incandescence technique on board the DC-8 aircraft during the NASA ARCTAS campaign. Aircraft sampling was made in fresh plumes strongly impacted by wildfires in North America (Canada and California) in summer 2008 and in those transported from Asia (Siberia in Russia and Kazakhstan) in spring 2008. We extracted biomass burning plumes using particle and tracer (CO, CH3CN, and CH2Cl2) data. OA constituted the dominant fraction of aerosols mass in the submicron range. The large majority of the emitted particles did not contain BC. We related the combustion phase of the fire as represented by the modified combustion efficiency (MCE) to the emission ratios between BC and other species. In particular, we derived the average emission ratios of BC/CO = 2.3 +/- 2.2 and 8.5 +/- 5.4 ng/cu m/ppbv for BB in North America and Asia, respectively. The difference in the BC/CO emission ratios is likely due to the difference in MCE. The count median diameters and geometric standard deviations of the lognormal size distribution of BC in the BB plumes were 136-141 nm and 1.32-1.36, respectively, and depended little on MCE. These BC particles were thickly coated, with shell/core ratios of 1.3-1.6. These parameters can be used directly for improving model estimates of the impact of BB in the Arctic.

  2. DETERMINATION OF SECONDARY ORGANIC AEROSOL PRODUCTS FROM THE PHOTOOXIDATION OF TOLUENE AND THEIR IMPLICATIONS IN AMBIENT PM2.5

    EPA Science Inventory

    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 in the dynamic mode...

  3. 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.

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

    Microsoft Academic Search

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

    2009-01-01

    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 m3 environmental chamber configured to simulate an office; either no filter, a

  5. Secondary Organic Aerosol Formation from m-Xylene in the Absence of NOx

    SciTech Connect

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

    2007-11-01

    Formation of secondary organic aerosol (SOA) from m-xylene photoxidation in the absence of NOx was investigated in a series of smog chamber experiments. Experiments were performed in dry air and in the absence of seed aerosol with H2O2 photolysis providing a stable hydroxyl radical (OH radical) source. SOA formation from this study is exceptionally higher than experiments with existence of NOx. The experiments with elevated HO2 levels indicate that organic hydroperoxide compounds should contribute to SOA formation. Nitrogen oxide (NO) is shown to reduce aerosol formation; the constant aerosol formation rate obtained before addition of NO and after consumption of NO strongly suggests that aerosol formation is mainly through reactions with OH and HO2 radicals. In addition, a density of 1.40 ± 0.1 g cm-3 for the SOA from the photooxidation of m-xylene in the absence of NOx has been measured, which is significantly higher than the currently used unit density.

  6. Secondary organic aerosol formation from the photo-oxidation of benzene

    NASA Astrophysics Data System (ADS)

    Borrás, Esther; Tortajada-Genaro, Luis Antonio

    2012-02-01

    The production of condensate compounds from the degradation of benzene by OH radical chemistry was studied. Secondary organic aerosol (SOA) formation was investigated in the EUPHORE ( European Photoreactor) simulation chambers. Experiments were performed under different OH-production conditions - addition of H 2O 2, NO or HONO -, in a high-volume reactor, with natural light and in the absence of seed aerosols. The consumption of precursor/reagents, the formation of gas-phase and particulate-phase products and the temporal evolution of aerosol were monitored. Several aerosol physical properties - mass concentration, overall aerosol yield, particle size distribution and density - were determined and found to be clearly dependent on OH radical production and NO x concentrations. Furthermore, the use of one and/or two products gas-particle partitioning absorption models allowed us to determine the aerosol yield curves. The SOA yield ranged from 1.6 to 9.7 %, with higher SOA formation under low-NO x conditions. Chemical characterization of the SOA was carried out, determining multi-oxygenated condensed organic compounds by a method based on the gas chromatography-mass spectrometry technique. Several ring-retaining and ring-cleavage products were identified and quantified. The compounds with the highest percentage contribution to the total aerosol mass were 4-nitrobenzene-1,2-diol, butenedioic acid, succinic acid and trans-trans-muconic. In addition, a multigenerational study was performed comparing with the photo-oxidations of phenol and catechol. The results showed that although the mass concentration of SOA produced was different, the physical and chemical properties were quite similar. Finally, we suggest a general mechanism to describe how changes in benzene degradation pathways - rate of OH generation and concentration of NO x - could justify the variation in SOA production and properties.

  7. Modeling secondary organic aerosol in an urban area: application to Paris, France

    NASA Astrophysics Data System (ADS)

    Couvidat, F.; Kim, Y.; Sartelet, K.; Seigneur, C.; Marchand, N.; Sciare, J.

    2012-09-01

    A secondary organic aerosol (SOA) model, H2O (Hydrophilic/Hydrophobic Organic), is evaluated over the Paris area. This model treats the formation of SOA with two kinds of surrogate species: hydrophilic species (which condense preferentially on an aqueous phase) and hydrophobic species (which condense only on an organic phase). These surrogates species are formed from the oxidation in the atmosphere of volatile organic compounds (VOC) by radicals (HO and NO3) and ozone. These VOC are either biogenic (isoprene, monoterpenes and sesquiterpenes) or anthropogenic (mainly aromatic compounds). This model includes the formation of aerosols from different precursors (biogenic precursors, aromatics), and semi-volatile organic compounds (SVOC) from traffic. The H2O aerosol model was incorporated into the Polyphemus air quality modeling platform and applied to the Paris area and evaluated by comparison to measurements performed during the Megapoli campaign in July 2009. The comparison to measurements in the suburbs and in the city center of Paris shows that the model gives satisfactory results for both elemental carbon (EC) and organic carbon (OC). However, the model gives a peak of OC concentrations in the morning due to high emissions from traffic, which does not appear in measurements. Uncertainties in the modeled temperature, which can affect the gas-particle partitioning, in the partitioning of primary SVOC or underestimation of primary organic aerosol (POA) evaporation by the model could explain the differences between model and measurements. Moreover, using a theoretical mechanism for the oxidation of primary SVOC and intermediate volatility organic compounds (IVOC), POA concentrations were found to be likely overestimated by models due to the use of simple partitioning constants (which do not take into account the affinity of a compound with the liquid aerosol solution) or due to the assumption that the organic aerosol solution is a one-phase ideal solution. The organic aerosol in the city center of Paris was found to be originating mostly from distant sources with only 30 to 38% due to local sources.

  8. Modeling secondary organic aerosol in an urban area: application to Paris, France

    NASA Astrophysics Data System (ADS)

    Couvidat, F.; Kim, Y.; Sartelet, K.; Seigneur, C.; Marchand, N.; Sciare, J.

    2013-01-01

    A secondary organic aerosol (SOA) model, H2O (Hydrophilic/Hydrophobic Organic), is evaluated over the Paris area. This model treats the formation of SOA with two kinds of surrogate species: hydrophilic species (which condense preferentially on an aqueous phase) and hydrophobic species (which condense only on an organic phase). These surrogates species are formed from the oxidation in the atmosphere of volatile organic compounds (VOC) by radicals (HO and NO3) and ozone. These VOC are either biogenic (isoprene, monoterpenes and sesquiterpenes) or anthropogenic (mainly aromatic compounds). This model includes the formation of aerosols from different precursors (biogenic precursors, aromatics), and semi-volatile organic compounds (SVOC) from traffic. The H2O aerosol model was incorporated into the Polyphemus air quality modeling platform and applied to the Paris area and evaluated by comparison to measurements performed during the Megapoli campaign in July 2009. The comparison to measurements in the suburbs and in the city center of Paris shows that the model gives satisfactory results for both elemental carbon (EC) and organic carbon (OC). However, the model gives a peak of OC concentrations in the morning due to high emissions from traffic, which does not appear in measurements. Uncertainties in the modeled temperature, which can affect the gas-particle partitioning, in the partitioning of primary SVOC or underestimation of primary organic aerosol (POA) evaporation by the model could explain the differences between model and measurements. Moreover, using a theoretical mechanism for the oxidation of primary SVOC and intermediate volatility organic compounds (IVOC), POA concentrations were found to be likely overestimated by models due to the use of simple partitioning constants (which do not take into account the affinity of a compound with the liquid aerosol solution) or due to the assumption that the organic aerosol solution is a one-phase ideal solution. The organic aerosol in the city center of Paris was found to be originating mostly from distant sources with only 30 to 38% due to local sources.

  9. Effect of Hydrophilic Organic Seed Aerosols on the Formation of Secondary Organic Aerosol from ?-Pinene Ozonolysis in Dry and Humid Conditions

    NASA Astrophysics Data System (ADS)

    Song, C.; Zaveri, R. A.; Alexander, L.; Newburn, M.

    2009-12-01

    Our previous study (Song et al., 2007) showed that hydrophobic primary organic aerosols (POA) could not enhance secondary organic aerosol (SOA) mass yield from ?-pinene ozonolysis, indicating that SOA species may not be well mixed with hydrophobic POA species. However, aerosol composition and properties of urban hydrophobic POA will change in the atmosphere. POA can be oxidized via heterogeneous uptake of oxidants such as hydroxyl radical (OH), ozone and nitrate radical (NO3). Some aerosol-phase organic monomers may undertake condensed-phase chemistry to form oligomers. As a result, urban POAs can gradually become hydrophilic over time. On the other hand, some atmospheric organic aerosols are already somewhat hydrophilic. For example, POA formed from biomass burning are already somewhat hydrophilic. These hydrophilic organic aerosols may act contrastingly to those hydrophobic POAs and could enhance the absorption of SOA species into the aerosol-phase by providing additional absorptive mass. In this study, we investigate the SOA formation from ?-pinene ozonolysis in the presence of various surrogates of oxidized/hydrophilic POAs such as fulvic acid, levoglucosan and glycerol. Fulvic acid serves as surrogates for aged oligomeric or polymeric substances in ambient organic aerosols; levoglucosan is used to resemble hydrophilic POAs from biomass burning; glycerol serves as a model hydrophilic organic aerosol. Each seed aerosol will be tested in both dry or humid conditions. Humidity will also be varied to exame the extent of the effect of aerosol-phase water on SOA yield. Organic species in the gas phase are measured with a Proton Transfer Reaction-Mass Spectrometer (PTR-MS) while the growth of aerosols and their composition are analyzed using a Scanning Mobility Particle Sizer (SMPS) and an Aerosol Mass Spectrometer (AMS), respectively. The data will be interpreted with the gas-particle partitioning theory, and the implications of our results on modeling SOA formation will be discussed.

  10. Comparison of abundances, compositions and sources of elements, inorganic ions and organic compounds in atmospheric aerosols from Xi'an and New Delhi, two megacities in China and India.

    PubMed

    Li, Jianjun; Wang, Gehui; Aggarwal, Shankar G; Huang, Yao; Ren, Yanqin; Zhou, Bianhong; Singh, Khem; Gupta, Prabhat K; Cao, Junji; Zhang, Rong

    2014-04-01

    Wintertime TSP samples collected in the two megacities of Xi'an, China and New Delhi, India were analyzed for elements, inorganic ions, carbonaceous species and organic compounds to investigate the differences in chemical compositions and sources of organic aerosols. The current work is the first time comparing the composition of urban organic aerosols from China and India and discussing their sources in a single study. Our results showed that the concentrations of Ca, Fe, Ti, inorganic ions, EC, PAHs and hopanes in Xi'an are 1.3-2.9 times of those in New Delhi, which is ascribed to the higher emissions of dust and coal burning in Xi'an. In contrast, Cl(-), levoglucosan, n-alkanes, fatty alcohols, fatty acids, phthalates and bisphenol A are 0.4-3.0 times higher in New Delhi than in Xi'an, which is attributed to strong emissions from biomass burning and solid waste incineration. PAHs are carcinogenic while phthalates and bisphenol A are endocrine disrupting. Thus, the significant difference in chemical compositions of the above TSP samples may suggest that residents in Xi'an and New Delhi are exposed to environmental hazards that pose different health risks. Lower mass ratios of octadecenoic acid/octadecanoic acid (C18:1/C18:0) and benzo(a)pyrene/benzo(e)pyrene (BaP/BeP) demonstrate that aerosol particles in New Delhi are photochemically more aged. Mass closure reconstructions of the wintertime TSP indicate that crustal material is the most abundant component of ambient particles in Xi'an and New Delhi, accounting for 52% and 48% of the particle masses, respectively, followed by organic matter (24% and 23% in Xi'an and New Delhi, respectively) and secondary inorganic ions (sulfate, nitrate plus ammonium, 16% and 12% in Xi'an and New Delhi, respectively). PMID:24496022

  11. 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.

  12. Analysis of secondary organic aerosol formation and aging using positive matrix factorization of high-resolution aerosol mass spectra: application to the dodecane low-NOx system

    NASA Astrophysics Data System (ADS)

    Craven, J. S.; Yee, L. D.; Ng, N. L.; Canagaratna, M. R.; Loza, C. L.; Schilling, K. A.; Yatavelli, R. L. N.; Thornton, J. A.; Ziemann, P. J.; Flagan, R. C.; Seinfeld, J. H.

    2012-12-01

    Positive matrix factorization (PMF) of high-resolution laboratory chamber aerosol mass spectra is applied for the first time, the results of which are consistent with molecular level MOVI-HRToF-CIMS aerosol-phase and CIMS gas-phase measurements. Secondary organic aerosol was generated by photooxidation of dodecane under low-NOx conditions in the Caltech environmental chamber. The PMF results exhibit three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition. The slope of the measured high-resolution aerosol mass spectrometer (HR-ToF-AMS) composition data on a Van Krevelen diagram is consistent with that of other low-NOx alkane systems in the same O : C range. Elemental analysis of the PMF factor mass spectral profiles elucidates the combinations of functionality that contribute to the slope on the Van Krevelen diagram.

  13. Formation and evolution of biogenic secondary organic aerosol over a forest site in Japan

    NASA Astrophysics Data System (ADS)

    Han, Yuemei; Iwamoto, Yoko; Nakayama, Tomoki; Kawamura, Kimitaka; Mochida, Michihiro

    2014-01-01

    composition of atmospheric aerosol particles was characterized using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer at a forest site in Japan during 20-30 August 2010. A major fraction of nonrefractory submicron aerosol particles consisted of organics (accounting for, on average, 46% of total mass), sulfate (41%), and ammonium (12%). Positive matrix factorization of high-resolution organic aerosol mass spectra identified two oxygenated organic aerosol (OOA) components: a highly oxidized, low-volatility OOA and a less oxidized, semivolatile OOA (SV-OOA), interpreted mainly as aged regional organic aerosol (OA) and as locally formed biogenic secondary OA (BSOA), respectively. The mass concentrations of SV-OOA increased prominently during the daytime, suggesting a strong photochemical production of BSOA on both nonevent and new particle formation event days. Increases of f44 (fraction of m/z 44 in OA mass spectrum), the fraction of CxOy+ fragment, and the O/C ratio after midday (around 13:00 local time) suggest that OA became increasingly oxygenated, which can be explained by the aging of freshly formed BSOA. Aqueous phase oxidation reactions under conditions of high relative humidity may have played a vital role in the aging of BSOA in this forest atmosphere. A substantial increase of the mass concentration of organics in the small size range (below 300 nm in vacuum aerodynamic diameter), without an increase in that of sulfate, suggests that the formation of BSOA made a dominant contribution to the presence of particles of cloud condensation nuclei size around the studied area.

  14. 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.

  15. Towards a quasi-complete reconstruction of past atmospheric aerosol load and composition (organic and inorganic) over Europe since 1920 inferred from Alpine ice cores

    NASA Astrophysics Data System (ADS)

    Preunkert, S.; Legrand, M.

    2013-07-01

    Seasonally resolved chemical ice core records available from the Col du Dôme glacier (4250 m elevation, French Alps), are here used to reconstruct past aerosol load and composition of the free European troposphere from before World War II to present. Available ice core records include inorganic (Na+, Ca2+, NH4+, Cl-, NO3-, and SO42-) and organic (carboxylates, HCHO, humic-like substances, dissolved organic carbon, water-insoluble organic carbon, and black carbon) compounds and fractions that permit reconstructing the key aerosol components and their changes over the past. It is shown that the atmospheric load of submicron aerosol has been increased by a factor of 3 from the 1921-1951 to 1971-1988 years, mainly as a result of a large increase of sulfate (a factor of 5), ammonium and water-soluble organic aerosol (a factor of 3). Thus, not only growing anthropogenic emissions of sulfur dioxide and ammonia have caused the enhancement of the atmospheric aerosol load but also biogenic emissions producing water-soluble organic aerosol. This unexpected change of biospheric source of organic aerosol after 1950 needs to be considered and further investigated in scenarios dealing with climate forcing by atmospheric aerosol.

  16. Towards a quasi-complete reconstruction of past atmospheric aerosol load and composition (organic and inorganic) over Europe since 1920 inferred from Alpine ice cores

    NASA Astrophysics Data System (ADS)

    Preunkert, S.; Legrand, M.

    2013-02-01

    Seasonally resolved chemical ice core records available from the Col du Dôme glacier (4250 m elevation, French Alps) are here revisited in view to reconstruct past aerosol load of the free European troposphere from prior World War II to present. The extended array of inorganic (Na+, Ca2+, NH4+, Cl-, NO3-, and SO42-) and organic (carboxylates, HCHO, HUmic LIke Substances, dissolved organic carbon, water insoluble organic carbon, and black carbon) compounds and fractions already investigated permit to examine the overall aerosol composition and its change over the past. It is shown that the atmospheric load of submicron aerosol has been increased by a factor of 3 from the 1921-1951 to 1971-1988 years, mainly as a result of a large increase of sulfate (a factor of 5), ammonium and water-soluble organic aerosol (a factor of 3). It is shown that not only growing anthropogenic emissions of sulfur dioxide and ammonia have caused the enhancement of the atmospheric aerosol load but also biogenic emissions producing water soluble organic aerosol. This unexpected change of biospheric source of organic aerosol after 1950 needs to be considered and further investigated in scenarii dealing with climate forcing by atmospheric aerosol.

  17. Hexagonal ice stability and growth in the presence of glyoxal and secondary organic aerosols.

    PubMed

    Daskalakis, Vangelis; Hadjicharalambous, Marios

    2014-09-01

    The presence of ice dominates the microphysics of formation of high altitude cirrus and polar stratospheric clouds, as well as the maturity of thunderstorms. We report on the hexagonal (1h) ice stability and growth in binary as well as multi-compound aerosols in atmospherically relevant conformations. The ubiquitous atmospheric trace gas glyoxal along with secondary organic aerosol (SOA) also in the presence of CO2 interacts with large ice 1h crystals of 1300-2000 water molecules. The crystals are subjected to phase transitions under superheating and supercooling conditions by Molecular Dynamics (MD) simulations. Density Functional Theory (DFT) based geometry optimization and vibrational frequency analysis are also employed for a smaller ice 1h cell of 12 water molecules. The interaction of the latter with each organic molecule reveals the extent of the mechanical stress exerted on the ordered ice structure. Full hydration of glyoxal promotes ice 1h stability and growth in wet aerosols, while partial hydration or full oxidation exerts a destabilizing effect on the ice 1h lattice. This behavior is associated with the ability of each organic phase to match the order of the ice 1h crystal. We propose that aqueous chemistry in wet aerosols may also have a strong effect on the microphysics of cloud formation. PMID:25033409

  18. Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms

    NASA Astrophysics Data System (ADS)

    Cai, Xuyi; Griffin, Robert J.

    2006-07-01

    The chlorine atom (Cl) is a potential oxidant of volatile organic compounds (VOCs) in the atmosphere and is hypothesized to lead to secondary organic aerosol (SOA) formation in coastal and industrialized areas. The purpose of this paper is to test this hypothesis and to quantify the SOA formation potentials of the common monoterpenes ?-pinene, ?-pinene, and d-limonene when oxidized by Cl in laboratory chamber experiments. Results indicate that the oxidation of these monoterpenes generates significant amounts of aerosol. The SOA yields of ?-pinene, ?-pinene, and d-limonene in this study are comparable to those when they are oxidized by ozone, by nitrate radical, and in photooxidation scenarios. For aerosol mass up to 30.0 ?g m-3, their yields reach approximately 0.20, 0.20, and 0.30, respectively. For d-limonene, data indicate two yield curves that depend on the initial concentration ratio of Cl precursor to d-limonene. It is argued theoretically that multiple SOA yield curves may be common for VOCs, depending on the initial concentration ratio of oxidant to VOC. SOA formation from the three typical monoterpenes when oxidized by Cl in the marine boundary layer, coastal areas, and inland industrialized areas could be a source of organic aerosol in the early morning.

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

    NASA Astrophysics Data System (ADS)

    Mentel, Th. F.; Kleist, E.; Andres, S.; Dal Maso, M.; Hohaus, T.; Kiendler-Scharr, A.; Rudich, Y.; Springer, M.; Tillmann, R.; Uerlings, R.; Wahner, A.; Wildt, J.

    2013-09-01

    Atmospheric aerosols impact climate by scattering and absorbing solar radiation and by acting as ice and cloud condensation nuclei. Biogenic secondary organic aerosols (BSOAs) comprise an important component of atmospheric aerosols. Biogenic volatile organic compounds (BVOCs) emitted by vegetation are the source of BSOAs. 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 BSOAs, and possibly their climatic effects. This raises questions of whether stress-induced changes in BSOA formation may attenuate or amplify effects of climate change. In this study we assess the potential impact of stress-induced BVOC emissions on BSOA formation for tree species typical for mixed deciduous and Boreal Eurasian forests. We studied the photochemical BSOA formation for plants infested by aphids in a laboratory setup under well-controlled conditions and applied in addition heat and drought stress. The results indicate that stress conditions substantially modify BSOA formation and yield. Stress-induced emissions of sesquiterpenes, methyl salicylate, and C17-BVOCs increase BSOA yields. Mixtures including these compounds exhibit BSOA yields between 17 and 33%, significantly higher than mixtures containing mainly monoterpenes (4-6% yield). Green leaf volatiles suppress SOA formation, presumably by scavenging OH, similar to isoprene. By classifying emission types, stressors and BSOA formation potential, we discuss 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.

  20. 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.

  1. 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.

  2. Influence of vapor wall loss in laboratory chambers on yields of secondary organic aerosol

    PubMed Central

    Zhang, Xuan; Cappa, Christopher D.; Jathar, Shantanu H.; McVay, Renee C.; Ensberg, Joseph J.; Kleeman, Michael J.; Seinfeld, John H.

    2014-01-01

    Secondary organic aerosol (SOA) constitutes a major fraction of submicrometer atmospheric particulate matter. Quantitative simulation of SOA within air-quality and climate models—and its resulting impacts—depends on the translation of SOA formation observed in laboratory chambers into robust parameterizations. Worldwide data have been accumulating indicating that model predictions of SOA are substantially lower than ambient observations. Although possible explanations for this mismatch have been advanced, none has addressed the laboratory chamber data themselves. Losses of particles to the walls of chambers are routinely accounted for, but there has been little evaluation of the effects on SOA formation of losses of semivolatile vapors to chamber walls. Here, we experimentally demonstrate that such vapor losses can lead to substantially underestimated SOA formation, by factors as much as 4. Accounting for such losses has the clear potential to bring model predictions and observations of organic aerosol levels into much closer agreement. PMID:24711404

  3. 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

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

    NASA Astrophysics Data System (ADS)

    Chen, Z.; Ren, X.; Brune, W. H.

    2007-12-01

    The effect of HOx radicals (OH and HO2) and ozone (O3) on secondary organic aerosol (SOA) formation and aging has been studied. Experiments were performed in the presence and in the absence of oxygen in a small chamber (~18 liters) for several organic precursor gases, including m-xylene, alpha-pinene and ethylbenzene. The HOx source was the UV photolysis of humidified air or nitrogen and was measured with the Penn State GTHOS (Ground-based Tropospheric Hydrogen Oxides Sensor). The precursor gases concentration was monitored with an online GC-FID. The aerosol mass was then quantified by a Tapered Element Oscillating Microbalance (TEOM). Typical oxidant mixing ratios were (0.??? -10) ppm for O3, (10-400) pptv for OH and (0.1-4) ppb for HO2. The SOA yields for different oxidant conditions will be discussed.

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

    NASA Astrophysics Data System (ADS)

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

    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 one or more of the following methods: instrumental neutron activation analysis, particle-induced X-ray emission analysis, a light reflection technique, gravimetry, thermal profiling carbon analysis and capillary electrophoresis. The quantities measured or derived include atmospheric concentrations of elements (from Na to U), of particulate matter, of black and elemental carbon, and total carbonaceous fraction, of some ionic species (e.g., nitrate and sulphate) in the fine ( <2 ?m equivalent aerodynamic diameter, EAD) or in both coarse (10- 2 ?m EAD) and fine size fractions, atmospheric concentrations of NO, NO 2, SO 2, CO and total suspended particulate matter, and meteorological parameters. The analytical results were used for characterisation of the concentration levels, elemental composition, time trends, enrichment of and relationships among the aerosol species in coarse and fine size fractions, for studying their fine-to-coarse concentration ratios, spatial and temporal variability, for determining detailed elemental mass size distributions, and for examining the extent of chemical mass closure.

  6. Dimer esters 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.

    2013-12-01

    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 dimer esters. A total of eight carboxylic acids and four dimer esters 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 dimer esters 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 dimer esters 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 dimer esters. SOA mass yield did not influence the chemical composition of SOA formed from ?-pinene ozonolysis with respect to carboxylic acids and dimer esters. The results support the formation of the high-molecular weight dimer esters through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of ?-pinene. The high molecular weight and polar nature of dimer esters formed in the gas-phase may explain increased particle number concentration as a~result of homogenous nucleation. Since three of these dimer esters (i.e., pinyl-diaterpenyl ester (MW 358), pinyl-diaterebyl ester (MW 344) and pinonyl-pinyl ester (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimer esters 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 esters result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

  7. 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.

    2013-09-01

    We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of different emission sources without limitation from the instruments or facilities available at any single site. 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 aging of emissions may be simulated over a range of temperatures (-7 to 25 °C). A photolysis rate of NO2, JNO2, of (8.0 ± 0.7) × 10-3 s-1 was determined at 25 °C. We demonstrate the utility of this new system by presenting results on the aging (OH = 12 × 106 cm-3 h) of emissions from a modern (Euro 5) gasoline car operated during a driving cycle (New European Driving Cycle, NEDC) on a chassis dynamometer in a vehicle test cell. Emissions from the entire NEDC were sampled and aged in the chamber. Total organic aerosol (OA; primary organic aerosol (POA) emission + secondary organic aerosol (SOA) formation) was (369.8-397.5)10-3 g kg-1 fuel, or (13.2-15.4) × 10-3 g km-1, after aging, with aged OA/POA in the range 9-15. A thorough investigation of the composition of the gas phase emissions suggests that the observed SOA is from previously unconsidered precursors and processes. This large enhancement in particulate matter mass from gasoline vehicle aerosol emissions due to SOA formation, if it occurs across a wider range of gasoline vehicles, would have significant implications for our understanding of the contribution of on-road gasoline vehicles to ambient aerosols.

  8. 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.

  9. 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.; Vásquez, M.; Borrás, E.; Ródenas, M.

    2013-12-01

    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 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 18-29% depending on initial precursor (VOC : NOx) mixing ratios. 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 characterized as semi-volatile to low volatile oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

  10. Acute Decreases in Proteasome Pathway Activity after Inhalation of Fresh Diesel Exhaust or Secondary Organic Aerosol

    PubMed Central

    Kipen, Howard M.; Gandhi, Sampada; Rich, David Q.; Ohman-Strickland, Pamela; Laumbach, Robert; Fan, Zhi-Hua; Chen, Li; Laskin, Debra L.; Zhang, Junfeng; Madura, Kiran

    2011-01-01

    Background Epidemiologic studies consistently demonstrate an association between acute cardiopulmonary events and changes in air pollution; however, the mechanisms that underlie these associations are not completely understood. Oxidative stress and inflammation have been suggested to play a role in human responses to air pollution. The proteasome is an intracellular protein degradation system linked to both of these processes and may help mediate air pollution effects. Objectives In these studies, we determined whether acute experimental exposure to two different aerosols altered white blood cell (WBC) or red blood cell (RBC) proteasome activity in human subjects. One aerosol was fresh diesel exhaust (DE), and the other freshly generated secondary organic aerosol (SOA). Methods Thirty-eight healthy subjects underwent 2-hr resting inhalation exposures to DE and separate exposures to clean air (CA); 26 subjects were exposed to DE, CA, and SOA. CA responses were subtracted from DE or SOA responses, and mixed linear models with F-tests were used to test the effect of exposure to each aerosol on WBC and RBC proteasome activity. Results WBC proteasome activity was reduced 8% (p = 0.04) after exposure to either DE or SOA and decreased by 11.5% (p = 0.03) when SOA was analyzed alone. RBCs showed similar 8–10% declines in proteasome activity (p = 0.05 for DE alone). Conclusions Air pollution produces oxidative stress and inflammation in many experimental models, including humans. Two experimental aerosols caused rapid declines in proteasome activity in peripheral blood cells, supporting a key role for the proteasome in acute human responses to air pollution. PMID:21163722

  11. Formation and Processing of Secondary Organic Aerosol from Catechol as a Model for Atmospheric HULIS

    NASA Astrophysics Data System (ADS)

    Ofner, Johannes; Krüger, Heinz-Ulrich; Grothe, Hinrich; Zetzsch, Cornelius

    2010-05-01

    A particular fraction of the secondary organic aerosol (SOA) termed HUmic Like Substances (HULIS) attracted attention only recently in atmospheric aerosol, initiating a discourse about their aromaticity and other properties, such as reactivity and hygroscopicity. A major portion of HULIS originates from volatile organic compounds, which are formed by abiotic oxidation reactions involving mainly OH radicals, ozone, nitrogen oxides and possibly halogens. Subsequently, the particles provide surface for heterogeneous reactions with atmospheric trace gases. Thus, aerosol smog-chamber studies with appropriate precursors are needed to generate SOA with HULIS qualities in situ inside the smog chamber and study their possible interactions. Catechol and guaiacol were chosen as aromatic precursors for synthetic HULIS production. The SOA was produced in a 700 L aerosol smog chamber, equipped with a solar simulator. SOA formation from each precursor was investigated at simulated environmental conditions (humidity, light, and presence of oxidizers) and characterized with respect to HULIS properties by particle classifiers, Fourier Transform IR spectroscopy (by long-path absorption and attenuated total reflection), UV/VIS spectroscopy, high-resolution mass-spectroscopy and temperature-programmed-desorption mass-spectrometry. High-resolution imaging was obtained using Field Emission Gun Scanning Electron Microscopy (FEGSEM). After HULIS formation the aerosol particles were exposed to atmospheric halogen species to study their processing with those trace gases, released by sea salt-activation. Those investigations show that aromatic precursors like catechol and guaiacol are suitable to form synthetic HULIS for laboratory-scale measurements with physical and chemical properties described in literature. However, sunlight and relative humidity play a major role in particle production and composition of functional groups, which are the anchor points for heterogeneous atmospheric chemistry. Possible reaction pathways of those synthetic particles with atmospheric halogen species could be identified forming gaseous and solid halogenated compounds.

  12. Secondary organic aerosol formation from fossil fuel sources contribute majority of summertime organic mass at Bakersfield

    NASA Astrophysics Data System (ADS)

    Liu, Shang; Ahlm, Lars; Day, Douglas A.; Russell, Lynn M.; Zhao, Yunliang; Gentner, Drew R.; Weber, Robin J.; Goldstein, Allen H.; Jaoui, Mohammed; Offenberg, John H.; Kleindienst, Tadeusz E.; Rubitschun, Caitlin; Surratt, Jason D.; Sheesley, Rebecca J.; Scheller, Scott

    2012-12-01

    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 chemical and physical properties of SOA at Bakersfield, California, a site influenced by anthropogenic and terrestrial biogenic emissions. Factor analysis was applied to the infrared and mass spectra of fine particles to identify sources and atmospheric processing that contributed to the organic mass (OM). We found that OM accounted for 56% of submicron particle mass, with SOA components contributing 80% to 90% of OM from 15 May to 29 June 2010. SOA formed from alkane and aromatic compounds, the two major classes of vehicle-emitted hydrocarbons, accounted for 65% OM (72% SOA). The alkane and aromatic SOA components were associated with 200 nm to 500 nm accumulation mode particles, likely from condensation of daytime photochemical products of VOCs. In contrast, biogenic SOA likely formed from condensation of secondary organic vapors, produced from NO3radical oxidation reactions during nighttime hours, on 400 nm to 700 nm sized primary particles, and accounted for less than 10% OM. Local petroleum operation emissions contributed 13% to the OM, and the moderate O/C (0.2) of this factor suggested it was largely of secondary origin. Approximately 10% of organic aerosols in submicron particles were identified as either vegetative detritus (10%) or cooking activities (7%), from Fourier transform infrared spectroscopic and aerosol mass spectrometry measurements, respectively. While the mass spectra of several linearly independent SOA components were nearly identical and external source markers were needed to separate them, each component had distinct infrared spectrum, likely associated with the source-specific VOCs from which they formed.

  13. Source contributions to primary and secondary inorganic particulate matter during a severe wintertime PM2.5 pollution episode in Xi'an, China

    NASA Astrophysics Data System (ADS)

    Wang, Dexiang; Hu, Jianlin; Xu, Yong; Lv, Di; Xie, Xiaoyang; Kleeman, Michael; Xing, Jia; Zhang, Hongliang; Ying, Qi

    2014-11-01

    Average PM2.5 concentrations of ?250 ?g m-3 and peak concentrations of ?500 ?g m-3 were observed in Xi'an, the largest city in Northwest China during an extreme event in January 2013. The source-oriented versions of the Community Multi-scale Air Quality (CMAQ) model with anthropogenic emissions from Emissions Database for Global Atmospheric Research (EDGAR) were used to study the source contributions of six different source categories including energy production, industries, transportation, residential activities, “other” (agriculture, biomass, waste burning, and biogenic sources), and windblown dust to primary and secondary inorganic PM2.5 (nitrate and sulfate) during this episode. The model generally captured the variation and magnitude of PM2.5 concentrations at monitoring sites. The monthly average concentration of the predicted PM2.5 in Xi'an was >200 ?g m-3, comparing favorably with the measurement of ?250 ?g m-3. Predicted concentrations of elemental carbon (EC), organic aerosol (OA), sulfate, nitrate, and ammonium were 6, 35, 18, 22, and 12 ?g m-3, respectively. Chemically unresolved PM2.5 components (PM2.5 Other) were ?80 ?g m-3. Industries and residential activities dominated EC, organic carbon (OC) and PM2.5 Other, contributing 85%, 95%, and 83%, respectively. Energy production (mainly coal combustion) was the dominating source for secondary nitrate, contributing 46%. Other local and upwind sources were also important, contributing 43% and 11% of total nitrate, respectively. Primary sulfate was ?10 ?g m-3 in vicinity surrounding point sources. Secondary sulfate from upwind sources was also important with concentrations of ?4-5 ?g m-3. Secondary sulfate formed by SO2 emitted from local sources was dominated by energy production. Based on the contributions of different sources to primary components and secondary nitrate and sulfate, the contributions of different sources to PM2.5 total mass in Xi'an during the extremely polluted months are: energy 5%, industries 58%, transportation 2%, residential activities 16%, dust 4%, and other (including other components, inexplicit sources, and upwind sources) 15%.

  14. Primary to secondary organic aerosol: evolution of organic emissions from mobile combustion sources

    NASA Astrophysics Data System (ADS)

    Presto, A. A.; Gordon, T. D.; Robinson, A. L.

    2014-05-01

    A series of smog chamber experiments were conducted to investigate the transformation of primary organic aerosol (POA) and formation of secondary organic aerosol (SOA) during the photooxidation of dilute exhaust from a fleet of gasoline and diesel motor vehicles and two gas-turbine engines. In experiments where POA was present in the chamber at the onset of photooxidation, positive matrix factorization (PMF) was used to determine separate POA and SOA factors from aerosol mass spectrometer data. A 2-factor solution, with one POA factor and one SOA factor, was sufficient to describe the organic aerosol for gasoline vehicles, diesel vehicles, and one of the gas-turbine engines. Experiments with the second gas-turbine engine required a 3-factor PMF solution with a POA factor and two SOA factors. Results from the PMF analysis were compared to the residual method for determining SOA and POA mass concentrations. The residual method apportioned a larger fraction of the organic aerosol mass as POA because it assumes that all mass at m / z 57 is associated with POA. The POA mass spectrum for the gasoline and diesel vehicles exhibited high abundances of the CnH2n+1 series of ions (m / z 43, 57, etc.) and was similar to the mass spectra of the hydrocarbon-like organic aerosol factor determined from ambient data sets with one exception, a diesel vehicle equipped with a diesel oxidation catalyst. POA mass spectra for the gas-turbine engines are enriched in the CnH2n-1 series of ions (m / z 41, 55, etc.), consistent with the composition of the lubricating oil used in these engines. The SOA formed from the three sources exhibits high abundances of m / z 44 and 43, indicative of mild oxidation. The SOA mass spectra are consistent with less-oxidized ambient SV-OOA (semivolatile oxygenated organic aerosols) and fall within the triangular region of f44 versus f43 defined by ambient measurements. However there is poor absolute agreement between the experimentally derived SOA mass spectra and ambient OOA factors, though this poor agreement should be expected based on the variability of ambient OOA factors. Van Krevelen analysis of the POA and SOA factors for gasoline and diesel experiments reveal slopes of -0.50 and -0.40, respectively. This suggests that the oxidation chemistry in these experiments is a combination of carboxylic acid and alcohol/peroxide formation, consistent with ambient oxidation chemistry.

  15. Investigating Primary Marine Aerosol Properties: CCN Activity of Sea Salt and Mixed Inorganic–Organic Particles

    PubMed Central

    2012-01-01

    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

  16. Aqueous glyoxal photooxidation in the presence of inorganic nitrogen: A potential source of organic nitrogen in aerosols and wet deposition

    NASA Astrophysics Data System (ADS)

    Kirkland, J. R.; Tan, Y.; Altieri, K. E.; Seitzinger, S.; Turpin, B. J.

    2010-12-01

    The sources of organic nitrogen in aerosols and atmospheric wet deposition are poorly understood, yet are important when assessing potential anthropogenic impacts on global nitrogen budgets. Nitrogen-containing organics are formed through gas phase photochemistry (e.g., involving NOx and isoprene). Imidazoles have been reported to form during smog chamber experiments involving glyoxal and ammonium sulfate seed particles. We hypothesize that nitrogen-containing organic compounds also form during cloud processing of water-soluble organic gases. Specifically, in this work we examine the possibility that organic nitrogen forms from GLY and inorganic nitrogen (NO3- or NH4+) at conditions found in daytime liquid clouds. We conducted batch aqueous reactions of GLY (1 mM) and OH radical (~10^-12 M) with and without nitric acid (1.7 mM) and ammonium sulfate (0.84 mM). OH radical was formed from the continuous photolysis of H2O2. Products were analyzed by ion chromatography (IC) and electrospray ionization mass spectrometry with pre-separation by IC (IC/ESI-MS). The addition of ammonium or nitrate had little effect on the concentrations of major system species (i.e., oxalate, glycolate) in the presence and absence of OH radical. Concentrations of inorganic nitrate and sulfate showed no significant change throughout light and dark experiments. ESI mass spectra with and without pre-separation by IC and ultra high resolution Fourier transform ion cyclotron resonance mass spectral analysis of samples will be examined and any evidence of organic nitrogen products will be discussed.

  17. Organic aerosol formation from the reactive uptake of isoprene epoxydiols (IEPOX) onto non-acidified inorganic seeds

    NASA Astrophysics Data System (ADS)

    Nguyen, T. B.; Coggon, M. M.; Bates, K. H.; Zhang, X.; Schwantes, R. H.; Schilling, K. A.; Loza, C. L.; Flagan, R. C.; Wennberg, P. O.; Seinfeld, J. H.

    2014-04-01

    The reactive partitioning of cis and trans ?-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans ?-IEPOX on AS seeds at liquid water contents of 40-75% of the total particle mass. OA formation from IEPOX is a kinetically limited process, thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis / trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm-1 (-50 / +100%). A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), possibly suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates, and amines in the particle organic composition. The results are consistent with weak correlations between IEPOX-derived OA and particle acidity or liquid water observed in field studies, as the chemical system is nucleophile-limited and not limited in water or catalyst activity.

  18. Organic aerosol formation from the reactive uptake of isoprene epoxydiols (IEPOX) onto non-acidified inorganic seeds

    NASA Astrophysics Data System (ADS)

    Nguyen, T. B.; Coggon, M. M.; Bates, K. H.; Zhang, X.; Schwantes, R. H.; Schilling, K. A.; Loza, C. L.; Flagan, R. C.; Wennberg, P. O.; Seinfeld, J. H.

    2013-10-01

    The reactive partitioning of cis and trans ?-IEPOX was investigated on hydrated inorganic seed particles, without the addition of acids. No organic aerosol (OA) formation was observed on dry ammonium sulfate (AS); however, prompt and efficient OA growth was observed for the cis and trans ?-IEPOX on AS seeds with liquid water contents of 40-75% of the total particle mass. OA formation from IEPOX is a kinetically-limited process; thus the OA growth continues if there is a reservoir of gas-phase IEPOX. There appears to be no differences, within error, in the OA growth or composition attributable to the cis/trans isomeric structures. Reactive uptake of IEPOX onto hydrated AS seeds with added base (NaOH) also produced high OA loadings, suggesting the pH-dependence for OA formation from IEPOX is weak for AS particles. No OA formation, after particle drying, was observed on seed particles where Na+ was substituted for NH4+. The Henry's Law partitioning of IEPOX was measured on NaCl particles (ionic strength ~9 M) to be 3 × 107 M atm-1. A small quantity of OA was produced when NH4+ was present in the particles, but the chloride (Cl-) anion was substituted for sulfate (SO42-), suggesting differences in nucleophilic strength of the anions. Online time-of-flight aerosol mass spectrometry and offline filter analysis provide evidence of oxygenated hydrocarbons, organosulfates and, notably, amines in the particle organic composition. The results help explain the substantial quantities of ambient IEPOX-derived OA observed under neutralized conditions. Experiments and models aimed at understanding OA production from IEPOX, or other epoxides, should consider the NH4+ activity, in conjunction with H+ activity (i.e., particle acidity) and nucleophile activity.

  19. 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.

  20. 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.

  1. Aqueous chemistry and yields of secondary organic aerosol formed from glyoxal and methylglyoxal in atmospheric waters

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Tan, Y.; Ortiz-Montalvo, D. L.; Turpin, B. J.

    2012-12-01

    Atmospherically abundant, volatile, water soluble organic compounds formed through gas-phase oxidation (e.g., glyoxal, methylglyoxal, and acetic acid) have great potential to form secondary organic aerosol via aqueous chemistry (SOAaq) in clouds, fogs and wet aerosols. In this work, detailed reaction mechanisms and a full kinetic model were developed for aqueous OH radical oxidation of methylglyoxal and acetic acid; they were validated, in part, with laboratory experiments (Tan et al., 2012). This new model was combined with the previous glyoxal model (Lim et al., 2010), and used to simulate atmospheric concentration dynamics and estimate SOAaq yields. At cloud relevant concentrations, the major photooxidation products are oxalic and pyruvic acids, and simulated molar SOA yields are ~76-77% for glyoxal and ~64-65% for methylglyoxal, regardless of our assumptions regarding the continued production of precursor (i.e., for both batch and continuously stirred tank reactor assumptions). In the presence of ammonium ion, organic acid salt formation is expected to decrease product vapor pressures and increase SOA yields. In the concentrated solutions encountered in wet aerosols, oligomers form via organic radical-radical reactions; simulated molar SOA yields are ~40% for both glyoxal and methylglyoxal.

  2. Chemical insights, explicit chemistry and yields of secondary organic aerosol from methylglyoxal and glyoxal

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Tan, Y.; Turpin, B. J.

    2013-02-01

    Atmospherically abundant, volatile water soluble organic compounds formed through gas phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3) and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud relevant concentrations (∼ 10-6-∼ 10-3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ∼ 120% for glyoxal and ∼ 80% for methylglyoxal. Oligomerization of unreacted aldehydes during droplet evaporation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (∼ 10 M), the major products are oligomers formed via organic radical-radical reactions, and simulated SOA yields (by mass) are ∼ 90% for both glyoxal and methylglyoxal.

  3. Secondary organic aerosol formation from m-xylene photooxidation: The role of the phenolic product

    NASA Astrophysics Data System (ADS)

    Nakao, S.; Qi, L.; Clark, C.; Sato, K.; Tang, P.; Cocker, D.

    2009-12-01

    Aromatic hydrocarbons comprise a significant fraction of volatile organic compounds in the urban atmosphere and their importance as precursors to secondary organic aerosols (SOA) has been widely recognized. However, SOA formation from aromatics is one of the least understood processes among all the classes of volatile organic compounds (VOCs) due to its complex multi-generation reactions. Phenolic compounds have been identified as one of the significant products from OH-initiated reaction of aromatic hydrocarbons and are suggested to have a very high potential of SOA formation (e.g., cresol isomers having SOA yield 9~42%, Henry et al., Atmos. Environ., 2008). We examined the effect of extent of oxidation of m-xylene on chemical composition and physical properties using m-xylene and xylenol as reactants in environmental chamber experiments. Chemical composition of SOA was investigated by Liquid Chromatography / Time of Flight Mass Spectrometer (LC/ToF-MS), and Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Physical properties of SOA such as density, volatility, and hygroscopicity were investigated by Aerosol Particle Mass Analyzer - Scanning Mobility Particle Sizer (APM-SMPS), Hygroscopicity/Volatility - Tandem Differential Mobility Analyzer (H/V-TDMA), respectively. Also SOA yields were obtained to evaluate the importance of xylenol as an intermediate product.

  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

    2013-11-01

    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. OH-initiated heterogeneous oxidation of internally-mixed squalane and secondary organic aerosol.

    PubMed

    Kolesar, Katheryn R; Buffaloe, Gina; Wilson, Kevin R; Cappa, Christopher D

    2014-03-18

    Recent work has established that secondary organic aerosol (SOA) can exist as an amorphous solid, leading to various suggestions that the addition of SOA coatings to existing particles will decrease the reactivity of those particles toward common atmospheric oxidants. Experimental evidence suggests that O3 is unable to physically diffuse through an exterior semisolid or solid layer thus inhibiting reaction with the core. The extent to which this suppression in reactivity occurs for OH has not been established, nor has this been demonstrated specifically for SOA. Here, measurements of the influence of adding a coating of ?-pinene+O3 SOA onto squalane particles on the OH-initiated heterogeneous oxidation rate are reported. The chemical composition of the oxidized internally mixed particles was monitored online using a vacuum ultraviolet-aerosol mass spectrometer. Variations in the squalane oxidation rate with particle composition were quantified by measurement of the effective uptake coefficient, ?eff, which is the loss rate of a species relative to the oxidant-particle collision rate. Instead of decreasing, the measured ?eff increased continuously as the SOA coating thickness increased, by a factor of ?2 for a SOA coating thickness of 42 nm (corresponding to ca. two-thirds of the particle mass). These results indicate that heterogeneous oxidation of ambient aerosol by OH radicals is not inhibited by SOA coatings, and further that condensed phase chemical pathways and rates in organic particles depend importantly on composition. PMID:24555558

  6. Molecular corridors represent the multiphase chemical evolution of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Berkemeier, T.; Schilling-Fahnestock, K. A.; Seinfeld, J. H.; Pöschl, U.

    2014-03-01

    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. The recent advent of soft ionization mass spectrometry methods now facilitates a more complete molecular identification of SOA than heretofore possible. Based on such novel measurements, 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. Sequential and parallel reaction oxidation and dimerization pathways progress along these corridors 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. These molecular corridors constrain the properties of unidentified products and reaction pathways and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate.

  7. Role of stabilized Criegee Intermediate in secondary organic aerosol formation from the ozonolysis of ?-cedrene

    NASA Astrophysics Data System (ADS)

    Yao, Lei; Ma, Yan; Wang, Lin; Zheng, Jun; Khalizov, Alexei; Chen, Mindong; Zhou, Yaoyao; Qi, Lu; Cui, Fenping

    2014-09-01

    Atmospheric ozonolysis of sesquiterpenes is an important source of secondary organic aerosols (SOA). The mechanisms by which Criegee Intermediates (CIs) react to form SOA precursors and the influence of environmental conditions, however, remain unclear. On the basis of environmental chamber experiments coupled with detailed characterization of gas-phase and particle-phase products, we present evidence that a significant fraction of CIs from ozonolysis of ?-cedrene are stabilized and bimolecular reactions of these stabilized CIs (SCIs) play a key role in the formation of SOA precursors. Ozonolysis experiments were conducted in a 4.5 m3 collapsible fluoropolymer chamber under various conditions in the presence of the OH radical and SCI scavengers. The size and mass of SOA particles produced during ozonolysis were measured directly and used for calculation of particle effective density and mass yield. Gaseous and particulate products were analyzed by several mass spectrometry methods. A total of 14 compounds in gas phase and 17 compounds in particle phase were tentatively identified. The major gas-phase products are secondary ozonides (SOZ) from intramolecular reactions of SCIs. Multifunctional organic acids are dominant particle-phase products. The measured density of aerosol particles is 1.04 ± 0.03 to 1.38 ± 0.03 g/cm3, and the aerosol mass yield is (23.7 ± 0.4)% to (46.4 ± 6.5)%, depending on reaction conditions. The presence of acetic acid, an SCI scavenger, inhibits new particle formation, but leads to increased aerosol mass yield. In contrast, the addition of SO2 dramatically enhances new particle formation and total aerosol yield. The calculated OH formation yield decreases from (62.4 ± 4.9)% to (9.0 ± 1.6)% upon addition of SCI scavengers CH3COOH and SO2, indicating that a large fraction of excited CIs are collisionally stabilized and unimolecular decomposition of SCIs via the hydroperoxide channel can be suppressed by bimolecular reactions. The reaction of SCIs with SO2 leads to the formation of sulfuric acid, an important nucleation precursor. From the consumption of SO2 added as SCI scavenger, a lower-limit yield of SCIs from ?-cedrene ozonolysis is estimated at ?88%. Our work underscores the key role of SCIs in SOA formation and observed composition of gas- and particle-phase products from ?-cedrene ozonolysis. Bimolecular reactions of sesquiterpene CIs with atmospherically relevant species (e.g. SO2, H2O) need to be considered when assessing the atmospheric relevance of ozonolysis of sesquiterpenes.

  8. Gas phase emissions from cooking processes and their secondary aerosol production potential

    NASA Astrophysics Data System (ADS)

    Klein, Felix; Platt, Stephen; Bruns, Emily; Termime-roussel, Brice; Detournay, Anais; Mohr, Claudia; Crippa, Monica; Slowik, Jay; Marchand, Nicolas; Baltensperger, Urs; Prevot, Andre; El Haddad, Imad

    2014-05-01

    Long before the industrial evolution and the era of fossil fuels, high concentrations of aerosol particles were alluded to in heavily populated areas, including ancient Rome and medieval London. Recent radiocarbon measurements (14C) conducted in modern megacities came as a surprise: carbonaceous aerosol (mainly organic aerosol, OA), a predominant fraction of particulate matter (PM), remains overwhelmingly non-fossil despite extensive fossil fuel combustion. Such particles are directly emitted (primary OA, POA) or formed in-situ in the atmosphere (secondary OA, SOA) via photochemical reactions of volatile organic compounds (VOCs). Urban levels of non-fossil OA greatly exceed the levels measured in pristine environments strongly impacted by biogenic emissions, suggesting a contribution from unidentified anthropogenic non-fossil sources to urban OA. Positive matrix factorization (PMF) techniques applied to ambient aerosol mass spectrometer (AMS, Aerodyne) data identify primary cooking emissions (COA) as one of the main sources of primary non-fossil OA in major cities like London (Allan et al., 2010), New York (Sun et al., 2011) and Beijing (Huang et al., 2010). Cooking processes can also emit VOCs that can act as SOA precursors, potentially explaining in part the high levels of oxygenated OA (OOA) identified by the AMS in urban areas. However, at present, the chemical nature of these VOCs and their secondary aerosol production potential (SAPP) remain virtually unknown. The approach adopted here involves laboratory quantification of PM and VOC emission factors from the main primary COA emitting processes and their SAPP. Primary emissions from deep-fat frying, vegetable boiling, vegetable frying and meat cooking for different oils, meats and vegetables were analysed under controlled conditions after ~100 times dilution. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a high resolution proton transfer time-of-flight mass spectrometer (PTR-ToF-MS) were used to quantify OA and VOC emissions, respectively. SOA production potential of the different emissions was quantified by introducing them into the PSI mobile smog chamber and a potential aerosol chamber (PAM) where they were photochemically aged. The measurements of primary emissions suggest that the COA factor identified in ambient atmospheric aerosols is mostly related to fat release from frying with vegetable oils or grilling fatty-meats. In contrast, vegetable cooking (boiling and frying) was associated with significant VOC emissions. The VOC emissions from frying consist mainly of aldehydes which are formed through breaking of fatty acids. Gas phase composition, emission factors and SAPP from all these processes will be presented. This work was supported by the Swiss National Science Foundation as well as the Swiss Federal Office for the Environment. The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement n.° 290605 (COFUND: PSI-FELLOW). J. Allan et al, Atmos. Chem. Phys. 10, 647-668 (2010) X.-F. Huang et al, Atmos. Chem. Phys. 10, 8933-8945 (2010) Y.-L. Sun et al, Atmos. Chem. Phys. 11, 1581-1602 (2011)

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

    NASA Astrophysics Data System (ADS)

    Li, Z.; Schwier, A. N.; Sareen, N.; McNeill, V. F.

    2011-07-01

    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(±2) dyn cm-1 in pure water and 62(±1) dyn cm-1 in AS solutions. Surface tension depression by formaldehyde in pure water is negligible; in AS solutions, a 9 % reduction in surface tension is observed. Mixtures of these species were also studied in combination with methylglyoxal in order to evaluate the influence of cross-reactions on surface tension depression and product formation in these systems. We find that surface tension depression in the solutions containing mixed cVOCs exceeds that predicted by an additive model based on the single-species isotherms.

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

    NASA Astrophysics Data System (ADS)

    Li, Z.; Schwier, A. N.; Sareen, N.; McNeill, V. F.

    2011-11-01

    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. Acetaldehyde depresses surface tension to 65(±2) dyn cm-1 in pure water (a 10% surface tension reduction from that of pure water) and 62(±1) dyn cm-1 in AS solutions (a 20.6% reduction from that of a 3.1 M AS solution). Surface tension depression by formaldehyde in pure water is negligible; in AS solutions, a 9% reduction in surface tension is observed. Mixtures of these species were also studied in combination with methylglyoxal in order to evaluate the influence of cross-reactions on surface tension depression and product formation in these systems. We find that surface tension depression in the solutions containing mixed cVOCs exceeds that predicted by an additive model based on the single-species isotherms.

  11. Secondary aspiration of aerosol particles into thin-walled nozzles facing the wind

    NASA Astrophysics Data System (ADS)

    Lipatov, G. N.; Grinshpun, S. A.; Semenyuk, T. I.; Sutugin, A. G.

    Problems of sampling aerosols from the turbulent atmosphere have been studied experimentally. The research was carried out with such particle sizes, type of samplers and sampling conditions that relate to those encountered in practical occupational hygiene and environmental monitoring. Distortion of the aerosol initial concentration was measured in a wind tunnel by a comparison method. Such distortions were caused by the external aspiration from a turbulent down flow using a vertical thin-walled cylindrical sampler. In addition, inertial errors themselves were determined by the limiting trajectory method. The difference between the results obtained with the help of the above methods showed the presence of secondary aspiration after the particles rebound from the outer nozzle surface for anisokinetical sampling. This fact was established by means of a set of special experiments with nozzles of various properties of the outer surface. Values of the rebound coefficient for Lycopodium particles aspirated into copper samplers over a range of diameters of 0.5-1 cm and anisokinetical coefficients (velocity ratio) of 1-40 were obtained. The conditions under which the efficiency of secondary aspiration is small were also defined.

  12. Aging of Secondary Organic Aerosol from ?-Pinene: Changes in Chemical Composition, Density and Morphology

    NASA Astrophysics Data System (ADS)

    Sarrafzadeh, M.; Hastie, D. R.

    2013-12-01

    Biogenic volatile organic compounds (VOC) are emitted in large quantities into the atmosphere. These VOC, which includes ?-pinene, can react to produce secondary organic aerosols (SOA), which contribute to a substantial fraction of ambient organic aerosols and are known to adversely affect visibility, climate and health. Despite this, the current knowledge regarding the SOA composition, their physical properties and the chemical aging processes they undergo in the atmosphere is limited. In this study, chemical aging of SOA generated from the photooxidation of ?-pinene was investigated in the York University smog chamber. The formation and aging of both gas and particle phase products were analyzed using an atmospheric pressure chemical ionization triple quadrupole mass spectrometer. The density of secondary organic matter was also simultaneously measured over the course of the aging experiments, allowing us to improve our understanding in changes in particle composition that may occur. In addition, particle phase and shape was investigated for generated particles from ?-pinene oxidation by scanning electron microscope (SEM). Results of this work, including particle density and morphology will be presented as well as comparisons of gas and particle phase products time profiles during aging.

  13. The effect of model spatial resolution on Secondary Organic Aerosol predictions

    NASA Astrophysics Data System (ADS)

    Wainwright, C.; Pierce, J. R.; Liggio, J.; Strawbridge, K.; Macdonald, A. M.; Leaitch, R.

    2012-04-01

    Between 20-90% of submicron aerosol mass throughout the continental boundary layer consists of secondary organic aerosol (SOA). As such, the ability of chemical transport models to accurately reproduce the continental boundary layer aerosol greatly depends on their ability to predict SOA. Although there has been much recent effort to better describe SOA formation mechanisms in models, little attention has been paid to the effects of model spatial resolution on SOA predictions. SOA predictability should improve with model resolution; however, it is unclear how finely resolved a model must be to make accurate predictions. The Whistler Aerosol and Cloud Study (WACS 2010), held between June 22nd and July 28th, 2010 and conducted at Whistler, BC, Canada provides a unique data set for testing simulated SOA predictions. The study consisted of intensive measurements of trace particles and gases in the atmosphere in a mountain valley. We test the ability of the global chemical transport model GEOS-chem (www.geos-chem.org) to predict the aerosol concentrations during this event and throughout the campaign. Simulations were performed using three different resolutions of the model: 4°x5° (~400 km), 2°x2.5° (~200 km) and 0.5°x0.667° (~50 km). The 4°x5° version of the model significantly under predicts organic aerosol (max organics ~1.5?g m-3when measurements were ~7?g m-3), while the 2°x2.5° and 0.5°x0.667° versions are much more closely compared with measurements (max organics ~5?gm-3). In addition to analysis at Whistler, data from the same simulations was used to perform a comparison across North America between the 4°x5° and 0.5°x0.667° versions of the model. It was found that, on average, the 0.5°x0.667° were significantly higher (~2-4 ?g m-3) for various places in North America (near sources and near coastlines), which suggests that sub-grid variability in temperature and semi-volatile partitioning causes the 4°x5° simulations to underpredict SOA concentrations relative to higher resolution simulations.

  14. Primary and secondary organics in tropical Amazonian rainforest aerosols: Chiral analysis of 2-methyltetrols

    SciTech Connect

    Gonzalez, Nelida; Borg-Karlson, Anna-Karin; Artaxo, Paulo; Guenther, Alex B.; Krejci, R.; Noziere, Barbara; Noone, Kevin

    2014-06-01

    This work presents the application of a newly developed method to facilitate the distinction between primary and secondary organic compounds in ambient aerosols based on their chiral analysis. The organic constituents chosen for chiral analysis are the four stereomers of the 2-methyltetrols, (2R,3S)- and (2S,3R)- methylerythritol and (2S,3S)- and (2R,3R)- methylthreitol. Ambient PM10 aerosol samples were collected between June 2008 and June 2009 near Manaus, Brazil, in a remote tropical rainforest environment of central Amazonia. The samples were analyzed for the presence of these four stereomers because qualitatively, in a previous study, they have been demonstrated to have partly primary origins. Thus the origin of these compounds may be primary and secondary from the biosynthesis and oxidation processes of isoprene within plants and also in the atmosphere. Using authentic standards, the quantified concentrations were in average 78.2 and 72.8 ng m-3 for (2R,3S)- and (2S,3R)- methylerythritol and 3.1 and 3.3 ng m-3 for (2S,3S)- and (2R,3R)- methylthreitol during the dry season and 7.1, 6.5, 2.0, and 2.2 ng m-3 during the wet season, respectively. Furthermore, these compounds were found to be outside the confidence interval for racemic mixtures (enantiomeric fraction, Ef = 0.5 -0.01) in nearly all the samples, with deviations of up to 32 % (Ef = 0.61) for (2R,3S)-methylerythritol and 47 % (Ef = 0.65) for (2S,3S)-methylthreitol indicating (99% confidence level) biologically-produced 2-methyltetrols. The minimum primary origin contribution ranged between 0.19 and 29.67 ng m-3 for the 2-methylerythritols and between 0.15 and 1.2 ng m-3 for the 2-methylthreitols. The strong correlation of the diatereomers (racemic 2-methylerythritol and 2-methylthreitol) in the wet season implied a secondary origin. Assuming the maximum secondary contribution in the dry season, the secondary fraction in the wet season was 81-99 % and in the dry season, 10 - 95 %. Nevertheless, from the total 2-methyltetrol mass, the secondary mass represented 31 % whereas the primary 69 %. These results could have been expected for PM10 aerosols and might be different for fine particles at the same site. In addition, correlations with isoprene emission estimates for this site only showed an anti-correlation with 2-methylthreitol suggesting their direct emission from biological activity. The present study reinforces the importance of the analysis of chiral organic compounds to correctly assess the contribution of primary biogenic emissions and isoprene oxidation products to biogenic secondary organic aerosol.

  15. Cloud Condensation Nucleus (CCN) Activation Properties of Biogenic Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Vanreken, T. M.; Ng, N. L.; Flagan, R. C.; Seinfeld, J. H.

    2004-12-01

    Organic compounds are known to comprise a significant fraction of the atmospheric aerosol population and have been found to contribute to the concentration of cloud condensation nuclei (CCN). Much of this organic material is secondary in nature; secondary organic aerosol (SOA) is formed when volatile organic compounds are oxidized to form less volatile products, which then condense into the aerosol phase. Many organic compounds found in the atmosphere, of both anthropogenic and biogenic origin, have been found to produce SOA. Such reactions typically result in complex mixtures of products, only a fraction of which have been identified. Thus while there have been several studies exploring the potential for organic particles to act as CCN (including some of the compounds identified in SOA products), there have been almost no direct investigation of the potential CCN activity of SOA. This paper presents the results of a series of experiments measuring directly the CCN activity of SOA produced by the ozonolysis of several common biogenic compounds. Six compounds were studied: five monoterpenes (? -pinene, ? -pinene, ? 3-carene, limonene, terpinolene) and one terpinoid alcohol (terpinen-4-ol). The chosen monoterpenes represent an estimated 87% of global monoterpene emissions, while the terpenoid alcohols make up approximately 25% of the other biogenic compounds capable of forming SOA. In each experiment, SOA was generated under controlled conditions at the Caltech indoor facility. Over several hours, CCN concentrations were measured at supersaturations ranging from 0.27% to 0.80%. These data are compared to simultaneous particle concentration and size distribution observations to determine the relationship between particle diameter and CCN activity. The analysis indicates considerable variation in CCN activity among the experiments; possible causes for such variability are explored.

  16. Molecular characterization of urban organic aerosol in tropical India: contributions of primary emissions and secondary photooxidation

    NASA Astrophysics Data System (ADS)

    Fu, P. Q.; Kawamura, K.; Pavuluri, C. M.; Swaminathan, T.; Chen, J.

    2010-03-01

    Organic molecular composition of PM10 samples, collected at Chennai in tropical India, was studied using capillary gas chromatography/mass spectrometry. Fourteen organic compound classes were detected in the aerosols, including aliphatic lipids, sugar compounds, lignin products, terpenoid biomarkers, sterols, aromatic acids, hydroxy-/polyacids, phthalate esters, hopanes, Polycyclic Aromatic Hydrocarbons (PAHs), and photooxidation products from biogenic Volatile Organic Compounds (VOCs). At daytime, phthalate esters were found to be the most abundant compound class; however, at nighttime, fatty acids were the dominant one. Di-(2-ethylhexyl) phthalate, C16 fatty acid, and levoglucosan were identified as the most abundant single compounds. The nighttime maxima of most organics in the aerosols indicate a land/sea breeze effect in tropical India, although some other factors such as local emissions and long-range transport may also influence the composition of organic aerosols. However, biogenic VOC oxidation products (e.g., 2-methyltetrols, pinic acid, 3-hydroxyglutaric acid and ?-caryophyllinic acid) showed diurnal patterns with daytime maxima. Interestingly, terephthalic acid was maximized at nighttime, which is different from those of phthalic and isophthalic acids. A positive relation was found between 1,3,5-triphenylbenzene (a tracer for plastic burning) and terephthalic acid, suggesting that the field burning of municipal solid wastes including plastics is a significant source of terephthalic acid. Organic compounds were further categorized into several groups to clarify their sources. Fossil fuel combustion (24-43%) was recognized as the most significant source for the total identified compounds, followed by plastic emission (16-33%), secondary oxidation (8.6-23%), and microbial/marine sources (7.2-17%). In contrast, the contributions of terrestrial plant waxes (5.9-11%) and biomass burning (4.2-6.4%) were relatively small. This study demonstrates that, in addition to fossil fuel combustion and biomass burning, the open-burning of plastics in urban area also contributes to the organic aerosols in South Asia.

  17. Spatial and temporal variability of ammonia and other inorganic aerosol species

    NASA Astrophysics Data System (ADS)

    Day, D. E.; Chen, X.; Gebhart, K. A.; Carrico, C. M.; Schwandner, F. M.; Benedict, K. B.; Schichtel, B. A.; Collett, J. L.

    2012-12-01

    Nitrogen deposition to the sensitive ecosystems in Rocky Mountain National Park (RMNP) has been increasing. Ammonia has been shown to be a large fraction of this nitrogen deposition, and sources in northeastern Colorado were found to be a significant contributor. In this work we report on the results from a small network of Radiello passive samplers to investigate the temporal and spatial variability of ammonia gas concentrations in northeastern Colorado. A URG denuder/filter-pack sampler was collocated with a Radiello passive sampler to provide a check on the accuracy of passive ammonia measurements and to provide information about complementary aerosol and trace gas species. These measurements showed seasonal variations in the concentrations of both particulate- and gas-phase aerosol components. The highest concentrations of ammonia occurred during summer months. These were almost twice the lowest concentrations, which occurred during spring and fall months. Ammonia also exhibited higher than expected concentrations during winter. There was considerable spatial variability in average ammonia concentrations, with May-August averages ranging from 3 ?g m-3 in rural grasslands to 4-11 ?g m-3 at suburban-urban sites to almost 30 ?g m-3 in an area of intensive livestock feeding and farming operations. The large ammonia gradients near sources are expected for this primary pollutant with high deposition rates. The overall concentrations in this region are significantly larger than those measured in RMNP, which were around 0.5 ?g m-3, and represent a large reservoir of ammonia that can be transported to RMNP with easterly winds.

  18. 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.

  19. 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.

  20. 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

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

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

    Secondary organic aerosol (SOA) formation from oxidation products of biogenic volatile organic compounds (BVOC) constitutes an important coupling between vegetation, atmospheric chemistry, and climate change. Such secondary organic aerosol components play an important role in particle formation in Boreal regions ((Laaksonen et al., 2008)), where biogenic secondary organic aerosols contribute to an overall negative radiative forcing, thus a negative feed back between vegetation and climate warming (Spracklen et al., 2008). Within the EUCAARI project we investigated SOA formation from mixtures of monoterpenes (and sesquiterpenes) as emitted typically from Boreal tree species in Southern Finland. The experiments were performed in the large photochemical reactor SAPHIR in Juelich at natural light and oxidant levels. Oxidation of the BVOC mixtures and SOA formation was induced by OH radicals and O3. The SOA was formed on the first day and then aged for another day. The resulting SOA was characterized by HR-ToF-AMS, APCI-MS, and filter samples with subsequent H-NMR, GC-MS and HPLC-MS analysis. The chemical evolution of the SOA is characterized by a fast increase of the O/C ratio during the formation process on the first day, stable O/C ratio during night, and a distinctive increase of O/C ratio at the second day. The increase of the O/C ratio on the second day is highly correlated to the OH dose and is accompanied by condensational growth of the particles. We will present simultaneous factor analysis of AMS times series (PMF, Ulbrich et al., 2009 ) and direct measurements of individual chemical species. We found that four factors were needed to represent the time evolution of the SOA composition (in the mass spectra) if oxidation by OH plays a mayor role. Corresponding to these factors we observed individual, representative molecules with very similar time behaviour. The correlation between tracers and AMS factors is astonishingly good as the molecular tracers represented only a very small mass fraction of the factors. There is indication that some factors grow at the cost of the other suggesting a set of successive generations of oxidation products. This conversion could proceed either by direct condensed phase processes or by an evaporation-oxidation-recondensation mechanism. On the other hand it seems that the factors evolve in parallel, representing products of multiple oxidation which appear on different time scales in the particulate phase. These findings will be discussed with respect to their importance for ageing processes of atmospheric organic aerosols. References Laaksonen, A., Kulmala, M., O'Dowd, C. D., Joutsensaari, J., Vaattovaara, P., Mikkonen, S., Lehtinen, K. E. J., Sogacheva, L., Dal Maso, M., Aalto, P., Petaja, T., Sogachev, A., Yoon, Y. J., Lihavainen, H., Nilsson, D., Facchini, M. C., Cavalli, F., Fuzzi, S., Hoffmann, T., Arnold, F., Hanke, M., Sellegri, K., Umann, B., Junkermann, W., Coe, H., Allan, J. D., Alfarra, M. R., Worsnop, D. R., Riekkola, M. L., Hyotylainen, T., and Viisanen, Y.: The role of VOC oxidation products in continental new particle formation, Atmospheric Chemistry and Physics, 8, 2657-2665, 2008 Spracklen, D. V., Bonn, B., and Carslaw, K. S.: Boreal forests, aerosols and the impacts on clouds and climate, Philosophical Transactions of the Royal Society a-Mathematical Physical and Engineering Sciences, 366, 4613-4626, 10.1098/rsta.2008.0201, 2008 Ulbrich, I. M., Canagaratna, M. R., Zhang, Q., Worsnop, D. R., and Jimenez, J. L.: Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data, Atmospheric Chemistry and Physics, 9, 2891-2918, 2009

  2. 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.

  3. 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.

  4. Secondary organic aerosol (SOA) formation through cloud processing: Aqueous photooxidation of glyoxal and methylglyoxal

    NASA Astrophysics Data System (ADS)

    Carlton, Ann Marie Grover

    This dissertation provides evidence supporting the hypothesis that secondary organic aerosol (SOA) is formed in the atmosphere through aqueous-phase reactions in clouds. Accurate prediction of SOA formation is critical because organic aerosol adversely affects health, visibility and climate. If in-cloud SOA formation is significant, then current models incorrectly predict the concentrations, atmospheric distributions, properties, behavior and effects of atmospheric organic aerosol. During cloud processing, water-soluble gas-phase oxidation products of reactive organic gases (e.g., aromatics and alkenes including, isoprene) partition into cloud droplets where they react further during regional transport to form low volatility compounds (e.g., carboxylic acids and oligomers) that remain, in part, in the particle phase upon droplet evaporation, adding to the atmospheric particulate matter (PM) burden. Batch photochemical reactions of glyoxal, methylglyoxal and pyruvic acid with hydrogen peroxide were conducted to validate and improve proposed in-cloud SOA formation pathways. This research verifies that aqueous photooxidation of these compounds yields oxalic acid and other compounds (e.g., oligomes) likely to contribute to SOA. Electro-spray ionization-mass spectrometry (ESI-MS) analysis provided evidence for oligomer formation. This work resolved a discrepancy in the literature regarding the aqueous-phase fate of methylglyoxal and pyruvic acid, providing a link between isoprene, a biogenic compound with a large (˜500 Tg yr-1) world-wide emission flux, and SOA. Experimental time series product concentrations were compared to predictions using proposed pathways and reaction rate constants from the literature. Not all products were predicted by the models and expected products did not match observed time profiles. Additional oxidation pathways for glyoxal and methylglyoxal were identified and modified aqueous-phase oxidation mechanisms were proposed. Modification led to substantially improved agreement between experimental measurements and model predictions. The improved mechanistic understanding regarding the SOA in-cloud formation pathway provided by this dissertation is needed to improve predictive air quality and climate models and to develop more effective air quality management plans. While the climactic importance of secondary sulfate production via cloud processing is well known, and organic aerosol is known to play a role in global climate, the potential importance of in-cloud SOA formation is only just beginning to be considered.

  5. Phase state is a limiting factor in hygroscopic growth of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Pajunoja, Aki; Virtanen, Annele

    2014-05-01

    Secondary organic aerosol (SOA) particles formed from oxidation products of volatile organic compounds (VOC) form a significant fraction of the total atmospheric particulate matter affecting climate both directly and indirectly. The dependence of hygroscopicity on particle composition is often represented with the single parameter ?, commonly used in global models to describe the hygroscopic properties of atmospheric aerosol particles. The physical phase state of SOA particles affects the partitioning of organic vapors and also may affect the uptake of water vapor and particle activation into cloud droplets. Thus, hygroscopic behaviour of SOA particles is affected by composition (i.e. oxidation state and molecular size) but also by phase of particles. In this study the following three distinct studies were performed: (1) particle bounced fraction (BF) measurements, which are qualitatively related to particle phase, as a function of relative humidity using an Aerosol Bounce Instrument (ABI). We assume that the particles with BF > 0 are solid or semisolid, and that particles with BF = 0 behave mechanically as liquids (2) water uptake measured in the sub-saturated region using hygroscopicity tandem differential mobility analyzer (HTDMA) by measuring the ratio of wet to dry particle diameter following exposure to water vapor at a controlled RH (3) cloud droplet formation in the supersaturated region using a cloud condensation nuclei counter (CCNc). Particle composition and oxidation state was measured with a compact time of flight aerosol mass spectrometer (c-ToF-AMS). In this study we show that at sub-saturation conditions water uptake by SOA particles is restricted due to the kinetic limitations. Diffusion and solubility limitations inhibit water uptake until the humidity is high enough for dissolution to occur. Our studies show that this 'threshold' humidity is dependent on particle composition, oxidation state, and average molecular size. Our laboratory results explain several observations both in laboratory and in the atmosphere that have reported discrepancies between SOA particle hygroscopicity measurements in subsaturated and in supersaturated conditions. The results reported here provide new information about one of the most central aerosol processes in the atmosphere.

  6. 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.

  7. Secondary organic aerosol formation from aqueous chemistry of glyoxal, methylglyoxal, and glycolaldehyde in atmospheric waters: Chemical insights and kinetic model studies

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Tan, Y.; Altieri, K. E.; Perri, M. J.; Carlton, A. G.; Seitzinger, S.; Turpin, B. J.

    2010-12-01

    Aqueous chemistry in clouds, fog and aerosol water is now considered an important source of secondary organic aerosol (SOA). Modeling studies confirm that the underlying chemistry is kinetically favorable. Laboratory studies have begun to validate and refine the aqueous chemical mechanisms. Field observations, such as the atmospheric abundance of oxalate, ubiquitous presence of high molecular weight or humic-like substances (HULIS), high ambient O/C ratios, and correlations between SOA and aerosol liquid water content provide atmospheric evidence for SOA formation through aqueous chemistry. In the aqueous phase, small and volatile (C2-C3) but water soluble organic compounds undergo radical (photooxidation) and non-radical (acid/base catalysis) reactions, or reactions with inorganic constituents (sulfate, nitrate or ammonia) to form low volatility products including organic acids, organic-inorganic complexes and oligomers. These products are expected to remain at least in part in the particle phase after water evaporation, forming SOA. While not traditionally considered to be SOA precursors, atmospherically abundant and water soluble organic compounds like glyoxal (C2), methylglyoxal (C3) and glycolaldehyde (C2) have great potential to form SOA via aqueous chemistry. This paper presents a unified reaction mechanism and full kinetic model for the aqueous-phase reaction of glyoxal, methylglyoxal, glycolaldehyde, pyruvic acid and acetic acid with OH radical and validates this mechanism, in part, with laboratory experiments. At cloud relevant concentrations (~1E-6 M), the major product is oxalic acid and formation is well predicted by the previous cloud model (Lim et al., 2005). As concentrations increase radical-radical reactions become increasingly important and yield higher molecular weight products. The full kinetic model suggests that SOA formed in aerosol water (where organic concentrations are > 1 M) is comprised of high molecular weight multifunctional compounds. Atmospheric aqueous chemistry can potentially explain the atmospheric formation of oxalate, oligomers and HULIS. The insights gained from the full kinetic model can be used to aid the development of simplified modules for incorporation of this SOA formation process into chemical transport models.

  8. 239,240Pu and inorganic substances in aerosols from the vicinity of a waste isolation pilot plant: the importance of resuspension.

    PubMed

    Arimoto, R; Kirchner, T; Webb, J; Conley, M; Stewart, B; Schoep, D; Walthall, M

    2002-10-01

    Aerosol samples were collected and analyzed to characterize the spatial and temporal variations in the concentrations of plutonium and selected inorganic substances in the atmosphere around the Waste Isolation Pilot Plant (WIPP). High-volume aerosol sampling was conducted at three sites: (1) On Site, (2) Near Field, and (3) Cactus Flats. 239,240Pu was determined by alpha spectrometry following chemical separations; mass loadings were determined gravimetrically. A separate set of low-volume aerosol samples was analyzed for major ions using ion chromatography and for trace elements by inductively-coupled plasma emission spectrometry and mass spectrometry. The average 239,240Pu activity concentrations in total suspended particle (TSP) samples (12 to 16 nBq m(-3)) were consistent with those previously reported, but they varied strongly with season, with the highest values generally in spring. Further, the 239,240Pu activity concentrations were comparable among the three sites, and therefore there was no evidence for elevated 239,240Pu activities due to WIPP operations. The fraction of the 239,240Pu activity concentrations in the PM10, samples (particles less than 10 microm diameter) relative to TSP was lower than the corresponding PM10/TSP ratios of either high-volume mass or several inorganics (sulfate, aluminum or lead), indicating that 239,240Pu tends to be on large particles. Aerosol mass loadings (microg m(-3)) and 239,240Pu activity concentrations were correlated for all sets of samples, but at On Site, the TSP samples showed higher mass to 239,240Pu ratios than the other sites. Thus activities or processes occurring at or near the WIPP site evidently produced aerosols that contributed to the mass loadings but contained less 239,244Pu than ambient aerosols. About 63% of the variability in 239,240Pu activity concentrations was explained by wind travel, sampling location, length of the sampling interval, and aerosol mass. 239,240Pu activity concentrations also were correlated with aluminum (an indicator of mineral dust), further implicating the resuspension of soils as an important determinant of 239,240Pu in aerosols. The 239,240Pu/Al ratios for the aerosols were higher than in soils, and this could be explained by the preferential binding of 239,240Pu to small soil particles that have large surface area to mass ratios and also have higher aluminum contents than larger particles. PMID:12240720

  9. Inorganic ion and nitrogen isotopic compositions of atmospheric aerosols at Yurihonjo, Japan: Implications for nitrogen sources

    NASA Astrophysics Data System (ADS)

    Kawashima, Hiroto; Kurahashi, Takahiro

    2011-11-01

    We studied the suspended particulate matter (SPM) collected in Akita Prefecture, Japan from April 2008 to January 2009 for inorganic ion composition and nitrogen isotopic ratio ( ?15N) of NH 4+ and NO 3-. The results showed an average SPM concentration of 15.6 ?g m -3. The seasonal trend for SPM was higher values in the spring, lower in the winter. The major cations were Na +, NH 4+, Ca 2+ and major anions were SO 42-, NO 3-, Cl -. The annual correlation coefficient of ions indicates a very high value with NH 4+ and SO 42- ( R = 0.93), NO 3- and K + ( R = 0.65), NO 3- and Ca 2+ ( R = 0.62). The high springtime values are the apparent result of the dust stream from Asia. Average ?15N-NH 4+ and ?15N-NO 3- were 16.1‰ and -0.69‰, respectively. ?15N-NH 4+ increased slightly in summer, and ?15N-NO 3- increased considerably in winter. The trends indicated conversely. The heavy ?15N-NH 4+ in summer appears to be from agricultural sources such as animal waste and fertilizer. In addition, according to the difference in isotopes of NO x sources as the precursor of NO 3-, the dominant origin of heavy ?15N-NO 3- in winter could be NO x emitted from fossil fuel combustion at low temperature. Moreover, the average ?15N-NO 3- seemed to be made to baseline (approximately 0%) by vehicle emissions at high temperature. These results are considered to be very reasonable.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

  12. 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.

  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. The chemical and microphysical properties of secondary organic aerosols from Holm Oak emissions

    NASA Astrophysics Data System (ADS)

    Lang-Yona, N.; Rudich, Y.; Mentel, Th. F.; Bohne, A.; Buchholz, A.; Kiendler-Scharr, A.; Kleist, E.; Spindler, C.; Tillmann, R.; Wildt, J.

    2010-08-01

    The Mediterranean region is expected to experience substantial climatic change in the next 50 years. But, possible effects of climate change on biogenic volatile organic compound (VOC) emissions as well as on the formation of secondary organic aerosols (SOA) produced from these VOC are yet unexplored. To address such issues, the effects of temperature on the VOC emissions of Mediterranean Holm Oak and small Mediterranean stand of Wild Pistacio, Aleppo Pine, and Palestine Oak have been studied in the Jülich plant aerosol atmosphere chamber. For Holm Oak the optical and microphysical properties of the resulting SOA were investigated. Monoterpenes dominated the VOC emissions from Holm Oak (97.5%) and Mediterranean stand (97%). Higher temperatures enhanced the overall VOC emission but with different ratios of the emitted species. The amount of SOA increased linearly with the emission strength with a fractional mass yield of 6.0±0.6%, independent of the detailed emission pattern. The investigated particles were highly scattering with no absorption abilities. Their average hygroscopic growth factor of 1.13±0.03 at 90% RH with a critical diameter of droplet activation was 100±4 nm at a supersaturation of 0.4%. All microphysical properties did not depend on the detailed emission pattern, in accordance with an invariant O/C ratio (0.57(+0.03/-0.1)) of the SOA observed by high resolution aerosol mass spectrometry. The increase of Holm oak emissions with temperature (?20% per degree) was stronger than e.g. for Boreal tree species (?10% per degree). The SOA yield for Mediterranean trees determined here is similar as for Boreal trees. Increasing mean temperature in Mediterranean areas could thus have a stronger impact on BVOC emissions and SOA formation than in areas with Boreal forests.

  15. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  16. 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. A.; Seinfeld, J. H.; Pöschl, U.

    2014-08-01

    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 describe the properties of the products, pathways, and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate.

  17. Reduction in biomass burning aerosol light absorption upon humidification: Roles of inorganically-induced hygroscopicity, particle collapse, and photoacoustic heat and mass transfer

    SciTech Connect

    lewis, Kristen A.; Arnott, W. P.; Moosmuller, H.; Chakrabarti, Raj; Carrico, Christian M.; Kreidenweis, Sonia M.; Day, Derek E.; Malm, William C.; Laskin, Alexander; Jimenez, Jose L.; Ulbrich, Ingrid M.; Huffman, John A.; Onasch, Timothy B.; Trimborn, Achim; Liu, Li; Mishchenko, M.

    2009-11-27

    Smoke particle emissions from the combustion of biomass fuels typical for the western and southeastern United States were studied and compared under high humidity and ambient conditions in the laboratory. The fuels used are Montana ponderosa pine (Pinus ponderosa), southern California chamise (Adenostoma fasciculatum), and Florida saw palmetto (Serenoa repens). Information on the non-refractory chemical composition of biomass burning aerosol from each fuel was obtained with an aerosol mass spectrometer and through estimation of the black carbon concentration from light absorption measurements at 870 nm. Changes in the optical and physical particle properties under high humidity conditions were observed for hygroscopic smoke particles containing substantial inorganic mass fractions that were emitted from combustion of chamise and palmetto fuels. Light scattering cross sections increased under high humidity for these particles, consistent with the hygroscopic growth measured for 100 nm particles in HTDMA measurements. Photoacoustic measurements of aerosol light absorption coefficients reveal a 20% reduction with increasing relative humidity, contrary to the expectation of light absorption enhancement by the liquid coating taken up by hygroscopic particles. This reduction is hypothesized to arise from two mechanisms: 1. Shielding of inner monomers after particle consolidation or collapse with water uptake; 2. The contribution of mass transfer through evaporation and condensation at high relative humidity to the usual heat transfer pathway for energy release by laser heated particles in the photoacoustic measurement of aerosol light absorption. The mass transfer contribution is used to evaluate the fraction of aerosol surface covered with liquid water solution as a function of RH.

  18. Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds

    E-print Network

    Seitzinger, Sybil

    source of organic aerosol and could explain the atmospheric presence of oxalic acid. Methylglyoxal of water-soluble organics (i.e., glyoxal, methylglyoxal, and glycolalde- hyde) can yield secondary organic]) is the main aqueous-phase oxidation prod- uct of methylglyoxal, a well-known isoprene [Talbot et al., 1995

  19. Epoxide as a Precursor to Secondary Organic Aerosol Formation from Isoprene Photooxidation in the Presence of Nitrogen Oxides

    EPA Science Inventory

    Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear...

  20. Supplemental Information : Secondary Organic Aerosol Production from Modern Diesel Engine Emissions, Shar Samy and1 Barbara Zielinska2

    E-print Network

    Meskhidze, Nicholas

    Supplemental Information : Secondary Organic Aerosol Production from Modern Diesel Engine Emissions emissions. For more detail on compositional and toxicity changes produced from further29 diesel engine use, including: engine age or total engine lifetime operation,23 differences in the initial in-chamber toluene

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

    EPA Science Inventory

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

  2. Secondary organic aerosols formed from oxidation of biogenic volatile organic compounds in the Sierra Nevada Mountains of California

    E-print Network

    Cohen, Ronald C.

    , polyols and alkanes to quantify oxidized BVOCs. Terpene and isoprene oxidation products were amongSecondary organic aerosols formed from oxidation of biogenic volatile organic compounds and terpenes, can be oxidized to form less volatile carbonyls, acids, and multifunctional oxygenated products

  3. Secondary organic aerosol formation from fossil fuel sources1 contribute majority of summertime organic mass at Bakersfield2

    E-print Network

    Russell, Lynn

    ; Abstract24 Secondary organic aerosols (SOA), known to form in the atmosphere from oxidation of25 May to 29 June 2010. SOA formed from alkane and32 aromatic compounds, the two major classes of vehicle-emitted hydrocarbons, accounted for 65%33 OM (72% SOA). The alkane and aromatic SOA components

  4. 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

  5. Relationship between Oxidation Level and Optical Properties of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Lambe, A. T.; Cappa, C. D.; Massoli, P.; Onasch, T. B.; Forestieri, S.; Martin, A. T.; Cummings, M. J.; Croasdale, D. R.; Brune, W. H.; Worsnop, D. R.; Davidovits, P.

    2013-12-01

    Brown carbon (BrC), which may include secondary organic aerosol (SOA), can be a significant climate-forcing agent via its optical absorption properties. However, the overall contribution of SOA to BrC remains poorly understood. Here, correlations between oxidation level and optical properties of SOA are examined. SOA was generated in a flow reactor in the absence of NOx by OH oxidation of gas-phase precursors used as surrogates for anthropogenic (naphthalene, tricyclo-[5.2.1.02,6]decane), biomass burning (guaiacol), and biogenic (?-pinene) emissions. SOA chemical composition was characterized with a time-of-flight aerosol mass spectrometer. SOA mass-specific absorption cross sections (MAC) and refractive indices were calculated from real-time cavity ring-down photoacoustic spectrometry measurements at 405 and 532 nm and from UV-vis spectrometry measurements of methanol extracts of filter-collected particles (300 to 600 nm). At 405 nm, SOA MAC values and imaginary refractive indices increased with increasing oxidation level and decreased with increasing wavelength, leading to negligible absorption at 532 nm. Real refractive indices of SOA decreased with increasing oxidation level. Comparison with literature studies suggests that under typical polluted conditions the effect of NOx on SOA absorption is small. SOA may contribute significantly to atmospheric BrC, with the magnitude dependent on both precursor type and oxidation level. Mass-specific absorption cross sections (MAC) of SOA at ? = 405 nm as a function of the O/C ratio

  6. Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

    SciTech Connect

    Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A.

    2013-05-10

    Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

  7. Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols.

    PubMed

    Lee, Hyun Ji Julie; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

    2013-06-01

    Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines, and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of water-soluble SOA generated from two monoterpenes, limonene and ?-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ?100 ppb ammonia in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (?0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for ?excitation = 420 ± 50 nm and ?emission = 475 ± 38 nm. The window of the strongest fluorescence shifted to ?excitation = 320 ± 25 nm and ?emission = 425 ± 38 nm for the ?-pinene-derived SOA. Both regions overlap with the EEM spectra of some of the fluorophores found in primary biological aerosols. Despite the low quantum yield, the aged SOA particles may have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols. PMID:23663151

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

    PubMed Central

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

    2014-01-01

    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

  10. 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.

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

    PubMed

    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

  12. Effect of chemical structure on secondary organic aerosol formation from C12 alkanes

    NASA Astrophysics Data System (ADS)

    Yee, L. D.; Craven, J. S.; Loza, C. L.; Schilling, K. A.; Ng, N. L.; Canagaratna, M. R.; Ziemann, P. J.; Flagan, R. C.; Seinfeld, J. H.

    2013-11-01

    The secondary organic aerosol (SOA) formation from four C12 alkanes (n-dodecane, 2-methylundecane, hexylcyclohexane, and cyclododecane) is studied in the Caltech Environmental Chamber under low-NOx conditions, in which the principal fate of the peroxy radical formed in the initial OH reaction is reaction with HO2. Simultaneous gas- and particle-phase measurements elucidate the effect of alkane structure on the chemical mechanisms underlying SOA growth. Reaction of branched structures leads to fragmentation and more volatile products, while cyclic structures are subject to faster oxidation and lead to less volatile products. Product identifications reveal that particle-phase reactions involving peroxyhemiacetal formation from several multifunctional hydroperoxide species are key components of initial SOA growth in all four systems. The continued chemical evolution of the particle-phase is structure-dependent, with 2-methylundecane SOA formation exhibiting the least extent of chemical processing and cyclododecane SOA achieving sustained growth with the greatest variety of chemical pathways. The extent of chemical development is not necessarily reflected in the oxygen to carbon (O : C) ratio of the aerosol as cyclododecane achieves the lowest O : C, just above 0.2, by the end of the experiment and hexylcyclohexane the highest, approaching 0.35.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  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. 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.

  19. 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.

  20. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: chemical characterization of the products

    NASA Astrophysics Data System (ADS)

    Grgi?, Irena; Kitanovski, Zoran; Krofli?, Ana; ?usak, Alen

    2014-05-01

    One of the largest primary sources of organic aerosol in the atmosphere is biomass burning (BB) (Laskin et al. 2009); in Europe its contribution to annual mean of PM10 is between 3 and 14 % (Maenhaut et al. 2012). During the process of wood burning many different products are formed via thermal degradation of wood lignin. Hardwood burning produces mainly syringol (2,6-dimetoxyphenol) derivatives, while softwood burning exclusively guaiacol (2-methoxyphenol) and its derivatives. Taking into account physical properties of methoxyphenols only, their concentrations in atmospheric waters might be underestimated. So, their aqueous phase reactions can be an additional source of SOA, especially in regions under significant influence of wood combustion. An important class of compounds formed during physical and chemical aging of the primary BBA in the atmosphere is nitrocatechols, known as strong absorbers of UV and Vis light (Claeys et al. 2012). Very recently, methyl-nitrocatechols were proposed as suitable markers for highly oxidized secondary BBA (Iinuma et al. 2010, Kitanovski et al. 2012). In the present work, the formation of SOA through aqueous phase photooxidation and nitration of guaiacol was examined. The key objective was to chemically characterize the main low-volatility products and further to check their possible presence in the urban atmospheric aerosols. The aqueous phase reactions were performed in a thermostated reactor under simulated sunlight in the presence of H2O2 and nitrite. Guaiacol reaction products were first concentrated by solid-phase extraction (SPE) and then subjected to semi-preparative liquid chromatography.The main product compounds were fractionated and isolated as pure solids and their structure was further elucidated by using nuclear magnetic resonance spectroscopy (1H, 13C and 2D NMR) and direct infusion negative ion electro-spray ionization tandem mass spectrometry (( )ESI-MS/MS). The main photonitration products of guaiacol (4-nitroguaiacol, 6-nitroguaiacol and 4,6-dinitroguaiacol) were examined for their presence in winter aerosol samples by using an optimized HPLC-(-)ESI-MS/MS. 4-nitroguaiacol and 4,6-dinitroguaiacol were unambiguously identified in winter PM10 from Ljubljana, Slovenia, whereas the absence of 6-nitroguaiacol was further explained with the help of long-term reaction monitoring. To our knowledge, our study represents the first report on the identification of 4,6-dinitroguaiacol in ambient aerosols. Laskin, A. et al. (2009) Environ. Sci. Technol. 43, 3764-3771. Maenhaut, W. et al. (2012) Sci. Tot. Environ. 437, 226-236. Claeys, M. et al. (2012) Environ. Chem. 9, 273-284. Iinuma, Y. et al. (2010) Environ. Sci. Technol. 44, 8453-8459. Kitanovski, Z. et al. (2012)J. Chromatogr. A 1268, 35-43.

  1. Secondary organic aerosol formation of relevance to the marine boundary layer

    NASA Astrophysics Data System (ADS)

    Cai, Xuyi

    The chlorine atom (Cl) is a potential oxidant of volatile organic compounds (VOCs) in the atmosphere and is hypothesized to lead to secondary organic aerosol (SOA) formation in coastal areas. The purpose of this dissertation is to test this hypothesis and quantify the SOA formation potentials of some representative biogenic and anthropogenic hydrocarbons when oxidized by Cl in laboratory chamber experiments. The chosen model compounds for biogenic and anthropogenic hydrocarbons in this study are three monoterpenes (alpha-pinene, beta-pinene, and d-limonene) and two aromatics (m-xylene and toluene), respectively. Results indicate that the oxidation of these monoterpenes and aromatics generates significant amounts of aerosol. The SOA yields of alpha-pinene, beta-pinene, and d-limonene obtained in this study are comparable to those when they are oxidized by ozone, by nitrate radical, and in photooxidation scenarios. For aerosol mass up to 30.0 mug m-3, their yields reach approximately 0.20, 0.20, and 0.30, respectively. The SOA yields for m-xylene and toluene are found to be in the range of 0.035 to 0.12 for aerosol concentrations up to 19 mug m-3. For d-limonene and toluene, data indicate two yield curves that depend on the initial concentration ratios of Cl precursor to hydrocarbon hydrocarbon. Zero-dimensional calculations based on these yields show that SOA formation from the five model compounds when oxidized by Cl in the marine boundary layer could be a significant source of SOA in the early morning. In addition, the mechanistic reaction pathways for Cl oxidation of alpha-pinene, beta-pinene, d-limonene, and toluene with Cl have been developed within the framework of the Caltech Atmospheric Chemistry Mechanisms (CACM). Output from the developed mechanisms is combined with an absorptive partitioning model to predict precursor decay curves and time-dependent SOA concentrations in experiments. Model calculations are able to match (in general within general +/- 50%) final measured SOA concentrations. Species predicted to dominate SOA composition include carboxylic acids and organic peroxides. Finally, the influence of surface tension on the formation of SOA is investigated using a size-dependent absorptive partitioning model that accounts for the influence of surface tension on the gas/particle partitioning of semi-volatile organic compounds (the Kelvin effect). Results from numerical simulations indicate that if non-polar organic species constitute a significant fraction of pre-existing aerosol (PA), the Kelvin effect on SOA formation may be negligible. However, if PA is dominated by polar organic compounds, the Kelvin effect on SUA formation is significant when the PA initial diameter is smaller than approximately 100 nm (decreasing SUA formation from specific compounds by as much as a factor of 2.5). If the PA is an aqueous aerosol, the Kelvin effect on SOA formation is most important (decreasing SOA formation from specific compounds by as much as a factor of 10).

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

    NASA Astrophysics Data System (ADS)

    Hayes, P. L.; Carlton, A. G.; Baker, K. R.; Ahmadov, R.; Washenfelder, R. A.; Alvarez, S.; Rappenglück, B.; Gilman, J. B.; Kuster, W. C.; de Gouw, J. A.; Zotter, P.; Prévôt, A. S. H.; Szidat, S.; Kleindienst, T. E.; Offenberg, J. H.; Jimenez, J. L.

    2014-12-01

    Four different parameterizations for the formation and evolution of secondary organic aerosol (SOA) are evaluated using a 0-D box model representing the Los Angeles Metropolitan Region during the CalNex 2010 field campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model-measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model/measurement agreement for mass concentration. When comparing the three parameterizations, the Grieshop et al. (2009) parameterization more accurately reproduces both the SOA mass concentration and oxygen-to-carbon ratio inside the urban area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the parameterizations over-predict urban SOA formation at long photochemical ages (? 3 days) compared to observations from multiple sites, which can lead to problems in regional and global modeling. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Polycyclic aromatic hydrocarbons (PAHs) are less important precursors and contribute less than 4% of the SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16-27, 35-61, and 19-35%, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71 (±3) %. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 ?g m-3 is also present due to the long distance transport of highly aged OA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr-1 of SOA globally, or 17% of global SOA, 1/3 of which is likely to be non-fossil.

  3. Oxidation of gaseous elemental mercury in the presence of secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Rutter, A. P.; Shakya, K. M.; Lehr, R.; Schauer, J. J.; Griffin, R. J.

    2012-11-01

    Gaseous elemental mercury (GEM; Hg0(g)) was oxidized by ozone and secondary hydroxyl radicals generated by the chemistry associated with the formation of secondary organic aerosols. The reaction was investigated in a 9-m3 Teflon® batch reactor. The losses of GEM in ozone-only experiments compared well with numerical model predictions based on published reaction rates, and a second order rate analysis gave a reaction rate of (7.4 ± 0.5) × 10-19 cm3 molecules-1 s-1, which was statistically indistinct from recent publications. Furthermore, the net oxidation of GEM observed in the SOA reaction system agreed well with a numerical model based on the GEM-ozone reaction rate determined in this study and a published GEM-OH oxidation rate. Recent modeling studies of mercury atmospheric cycling have found that use of laboratory-based GEM-ozone reaction rate coefficients caused overestimation of GEM oxidation, while theoretical studies cast doubt over the viability of the GEM-ozone oxidation reaction in the real atmosphere. The results presented here suggest that the reaction is viable in the atmosphere and that recent published reaction rates for GEM and ozone are pertinent for use in atmospheric models. An average of GEM-ozone rates determined during this and recent studies was 6.9 ± 0.9 × 10-19 cm3 molecules-1 s-1. This value is recommended for use in future modeling studies.

  4. Climate-relevant physical properties of molecular constituents relevant for isoprene-derived secondary organic aerosol material

    NASA Astrophysics Data System (ADS)

    Upshur, M. A.; Strick, B. F.; McNeill, V. F.; Thomson, R. J.; Geiger, F. M.

    2014-06-01

    Secondary organic aerosol (SOA) particles, formed from gas-phase biogenic volatile organic compounds (BVOCs), contribute large uncertainties to the radiative forcing that is associated with aerosols in the climate system. Reactive uptake of surface-active organic oxidation products of BVOCs at the gas-aerosol interface can potentially decrease the overall aerosol surface tension and therefore influence their propensity to act as cloud condensation nuclei (CCN). Here, we synthesize and measure some climate-relevant physical properties of SOA particle constituents consisting of the isoprene oxidation products ?-, ?-, and cis- and {trans-?-IEPOX (isoprene epoxide), as well as syn- and anti-2-methyltetraol. Following viscosity measurements, we use octanol-water partition coefficients to quantify the relative hydrophobicity of the oxidation products while dynamic surface tension measurements indicate that aqueous solutions of ?- and trans-?-IEPOX exhibit significant surface tension depression. We hypothesize that the surface activity of these compounds may enhance aerosol CCN activity, and that trans-?-IEPOX may be highly relevant for surface chemistry of aerosol particles relative to other IEPOX isomers.

  5. [Secondary aerosol formation through photochemical reactions estimated by using air quality monitoring data in the downtown of Pudong, Shanghai].

    PubMed

    Cui, Hu-xiong; Wu, Ya-ming; Duan, Yu-sen; Fu, Qing-yan; Zhang, Yi-hua; Wang, Dong-fang; Wang, Qian

    2013-05-01

    Analyses of diurnal patterns of PM10 in the downtown of Pudong, Shanghai have been performed in this study at different daily ozone maximum concentrations (O(3,max)) from May to October, 2010. In order to evaluate secondary aerosol formation at different ozone levels, CO was used as a tracer for primary aerosol, and 0(3, max) was used as an index for photochemical activity. Results show that along with increasing of O3 concentration, the concentration of primary and secondary aerosol was increased respectively from 0. 036 to 0.044 mg x m(-3) and from 0.018 to 0.055 mg x m(-3). The ratio of secondary to primary aerosol was increased from 49.8% to 124.5%. Furthermore, along with the increase of O(3, max) the forming time of O(3,max) and secondary aerosol was changed respectively from 13:00 to 14:00 and from 11:00-20:00 to 09:00-20:00. At the same time, the chemical composition of PM2.5 was different at different photochemical levels. PM(2.5) was composed of 12.0% organic carbon (OC), 18.7% sulfate (SO4(2-1)), 13.1% nitrate (NO3-) and 4.5% element carbon (EC) when O(3, max) was < 0.10 mg x m(-3) and PM2.5 was composed of 20.0% organic carbon (OC), 22.9% sulfate, 23.1% nitrate and 4.7% element carbon (EC) with O(3, max) > 0. 20 mg x m(-3). These results approved that the photochemical reactivity promoted the production of SO4(2-), NO3- and OC. PMID:23914560

  6. 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.

  7. 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

    NASA Astrophysics Data System (ADS)

    Fuzzi, Sandro; Decesari, Stefano; Facchini, Maria Cristina; Cavalli, Fabrizia; Emblico, Lorenza; Mircea, Mihaiela; Andreae, Meinrat O.; Trebs, Ivonne; Hoffer, AndráS.; Guyon, Pascal; Artaxo, Paulo; Rizzo, Luciana V.; Lara, Luciene L.; Pauliquevis, Theotonio; Maenhaut, Willy; Raes, Nico; Chi, Xuguang; Mayol-Bracero, Olga L.; Soto-GarcíA, Lydia L.; Claeys, Magda; Kourtchev, Ivan; Rissler, Jenny; Swietlicki, Erik; Tagliavini, Emilio; Schkolnik, Gal; Falkovich, Alla H.; Rudich, Yinon; Fisch, Gilberto; Gatti, Luciana V.

    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 wet season. Three main periods were clearly distinguished on the basis of the PM10 concentration trend during the experiment: (1) dry period, with average PM10 well above 50 ?g m-3; (2) transition period, during which the 24-hour-averaged PM10 never exceeded 40 ?g m-3 and never dropped below 10 ?g m-3; (3) and wet period, characterized by 48-hour-averaged concentrations of PM10 below 12 ?g m-3 and sometimes as low as 2 ?g m-3. The trend of PM10 reflects that of CO concentration and can be directly linked to the decreasing intensity of the biomass-burning activities from September through November, because of the progressive onset of the wet season. Two prominent aerosol modes, in the submicron and supermicron size ranges, were detected throughout the experiment. Dry period size distributions are dominated by the fine mode, while the fine and coarse modes show almost the same concentrations during the wet period. The supermicron fraction of the aerosol is composed mainly of primary particles of crustal or biological origin, whereas submicron particles are produced in high concentrations only during the biomass-burning periods and are mainly composed of organic material, mostly water-soluble, and ˜10% of soluble inorganic salts, with sulphate as the major anion. Size-resolved average aerosol chemical compositions are reported for the dry, transition, and wet periods. However, significant variations in the aerosol composition and concentrations were observed within each period, which can be classified into two categories: (1) diurnal oscillations, caused by the diurnal cycle of the boundary layer and the different combustion phase active during day (flaming) or night (smouldering); and (2) day-to-day variations, due to alternating phases of relatively wet and dry conditions. In a second part of the study, three subperiods representative of the conditions occurring in the dry, transition, and wet periods were isolated to follow the evolution of the aerosol chemical composition as a function of changes in rainfall rate and in the strength of the sources of particulate matter. The chemical data set provided by the SMOCC field experiment will be useful to characterize the aerosol hygroscopic properties and the ability of the particles to act as cloud condensation nuclei.

  8. Composition of Secondary Organic Aerosol from the Photolysis of 1-Nitronaphthalene

    NASA Astrophysics Data System (ADS)

    Wenger, J.; Healy, R.; Chen, Y.; Kalberer, M.; Kourtchev, I.

    2012-12-01

    Nitro-substituted polycyclic aromatic hydrocarbons are of interest due to their associated mutagenic and carcinogenic effects. 1-Nitronaphthalene is emitted directly from combustion processes such as vehicle exhaust, but is also formed through the reaction of naphthalene with the hydroxyl or nitrate radical in the presence of NOx. Photolysis has previously been demonstrated to be the major degradation pathway for 1-nitronaphthalene in the troposphere. In this study, a series of simulation chamber experiments has been performed to investigate the chemical composition of secondary organic aerosol (SOA) formed through the direct photolysis of 1-nitronaphthalene using an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS, TSI). SOA forms rapidly with a yield of up to 50% depending on precursor concentration and photolysis rate. Along with expected products such as naphthoquinone and nitronaphthol, condensed species exhibiting mass spectra consistent with the presence of four aromatic rings were also observed. It is proposed that these species may be formed through dimerization of naphthoxy radicals generated during the photolysis process. Further evidence to support this mechanism was obtained when 1-nitronaphthalene was photolyzed in the presence of excess nitrobenzene. Dimers were then formed containing three aromatic rings, consistent with the reaction of phenoxy and naphthoxy radicals. The molecular formulae of the dimers were also confirmed by collecting SOA on filters and analysing the extracts off-line using an LTQ Orbitrap Velos mass spectrometer (Thermo-Fisher Scientific), fitted with a TriVersa NanoMate chip-based electrospray ionization source (Advion Biosystems). The rapid formation of condensable dimers through the self-reaction of naphthoxy radicals represents a previously unreported potential pathway to SOA formation. Analogous mechanisms may also be important for other nitrated polycyclic aromatic hydrocarbons.

  9. 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.

  10. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    NASA Astrophysics Data System (ADS)

    Birdsall, A. W.; Miner, C. R.; Mael, L. E.; Elrod, M. J.

    2014-12-01

    Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters, and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied with experimental methods. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of similar magnitudes, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  11. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    NASA Astrophysics Data System (ADS)

    Birdsall, A. W.; Miner, C. R.; Mael, L. E.; Elrod, M. J.

    2014-08-01

    Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of a similar magnitude, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity-dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  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. Formation and aging of secondary organic aerosol from isoprene photooxidation during cloud condensation-evaporation cycles

    NASA Astrophysics Data System (ADS)

    Giorio, C.; Siekmann, F.; Bregonzio, L.; Temime-Roussel, B.; Ravier, S.; Tapparo, A.; Kalberer, M.; Doussin, J.; Monod, A.

    2013-12-01

    Biogenic volatile organic compounds (BVOCs) can be oxidized in the gas phase to form more water-soluble compounds which could partition into atmospheric water droplets. Oxidation processes in the liquid phase could produce high molecular weight and less volatile compounds which can partly remain in the particle phase after water evaporation (Ervens et al., 2011). This work investigates the formation and composition of secondary organic aerosol (SOA) from the photooxidation of isoprene (the most abundant BVOC) and methacrolein (its main first-generation oxidation product). The experiments were performed during the CUMULUS (CloUd MULtiphase chemistry of organic compoUndS in the troposphere) campaigns at the 4.2 m3 stainless steel CESAM chamber at LISA, specifically designed to investigate multiphase processes (Wang et al., 2011). In each experiment, 500/1000 ppb of isoprene or methacrolein were injected in the chamber together with HONO before irradiation. Gas phase oxidation products have been analyzed on-line by a Proton Transfer Reaction Mass Spectrometer (PTR-MS) and a Fourier Transform Infrared Spectrometer (FTIR) together with NOx and O3 analyzers. SOA formation and composition has been followed on-line with a Scanning Mobility Particle Sizer (SMPS) and an Aerodyne High Resolution Time-Of-Flight Aerosol Mass Spectrometer (HR-TOF-AMS). Particular attention has been focused on the study of SOA formation and aging during cloud condensation-evaporation cycles simulated in the smog chamber. In all experiments, we noted that water soluble gas-phase oxidation products readily partition into cloud droplets accompanied by a prompt SOA production during cloud formation which partly persists after cloud evaporation. Ervens, B. et al. (2011) Atmos. Chem. Phys. 11, 11069 11102. Wang, J. et al. (2011) Atmos. Measur. Tech. 4, 2465 2494.

  14. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: a kinetic study

    NASA Astrophysics Data System (ADS)

    Krofli?, Ana; Grgi?, Irena

    2014-05-01

    It is well known that atmospheric aerosols play a crucial role in the Earth's climate and public health (Pöschl 2005). Despite a great effort invested in the studies of secondary organic aerosol (SOA) budget, composition, and its formation mechanisms, there is still a gap between field observations and atmospheric model predictions (Heald et al. 2005, Hallquist et al. 2009, and Lim et al. 2010). The insisting uncertainties surrounding SOA formation and aging thus gained an increasing interest in atmospheric aqueous phase chemistry; they call for more complex and time consuming studies at the environmentally relevant conditions allowing confident extrapolation to desired ambient conditions. In addition to the adverse health effects of atmospheric particulate matter (PM) as such, toxicity is also attributed to nitro-aromatic and other organic compounds which have already been detected in real aerosol samples (Traversi et al. 2009). Moreover, low-volatility aromatic derivatives are believed to form at least partly in the aerosol aqueous phase and not only in the gas phase from where they partition into water droplets (Ervens et al. 2011). Two nitro derivatives of biomass burning tracer guaiacol have recently been found in winter PM10 samples from the city of Ljubljana, Slovenia, and aqueous photonitration reaction was proposed as their possible production pathway (Kitanovski et al. 2012). In this study the kinetics of guaiacol nitration in aqueous solution was investigated in the presence of H2O2 and NO2¯ upon simulated solar irradiation (Xenon lamp, 300 W). During the experiment the DURAN® flask with the reaction mixture was held in the thermostated bath and thoroughly mixed. The reaction was monitored for 44 hours at different temperatures. Guaiacol and its main nitro-products (4-nitroguaiacol, 4-NG; 6-nitroguaiacol, 6-NG; and 4,6-dinitroguaiacol, 4,6-DNG) were quantified in every aliquot, taken from the reaction mixture, by use of high pressure liquid chromatography (HPLC). The reaction kinetics was determined and the temperature dependence of pseudo-first order rate constants was described by the Arrhenius equation. The guaiacol lifetime in the atmosphere at low temperature was predicted afterwards. Last but not least, the long-term reaction monitoring explained the absence of 6-NG in real aerosol samples analyzed by Kitanovski et al. (2012). Pöschl, U. (2005) Angew. Chem. Int. Ed. 44, 7520-7540. Heald, C.L. et al. (2005) Geophys. Res. Lett. 32, L18809-L18812. Hallquist, M. et al. (2009) Atmos. Chem. Phys. 9, 5155-5236. Lim Y.B. et al. (2010) Atmos. Chem. Phys. 10, 10521-10539. Traversi, D. et al. (2009) Environ. Int. 35, 905-910. Ervens, B. et al. (2011) Atmos. Chem. Phys. 11, 11069-11102. Kitanovski, Z. et al. (2012) J. Chromatogr. A 1268, 35-43.

  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 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.

  17. 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.

  18. Novel methods for predicting gas-particle partitioning during the formation of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Wania, F.; Lei, Y. D.; Wang, C.; Abbatt, J. P. D.; Goss, K.-U.

    2014-08-01

    Several methods have been presented in the literature to predict an organic chemical's equilibrium partitioning between the water insoluble organic matter (WIOM) component of aerosol and the gas phase, Ki, WIOM as a function of temperature. They include (i) polyparameter linear free energy relationships calibrated with empirical aerosol sorption data, as well as (ii) the solvation models implemented in SPARC and (iii) the quantum-chemical software Cosmotherm, which predict solvation equilibria from molecular structure alone. We demonstrate that these methods can be used to predict Ki, WIOM for large numbers of individual molecules implicated in secondary organic aerosol (SOA) formation, including those with multiple functional groups. Although very different in their theoretical foundations, these methods give remarkably consistent results for the products of the reaction of normal alkanes with OH, i.e. their partition coefficients Ki, WIOM generally agree within one order of magnitude over a range of more than ten orders of magnitude. This level of agreement is much better than that achieved by different vapour pressure estimation methods that are more commonly used in the SOA community. Also, in contrast to the agreement between vapour pressure estimates, that between the Ki, WIOM estimates does not deteriorate with increasing number of functional groups. Furthermore, these partitioning coefficients Ki, WIOM are found to predict the SOA mass yield in chamber experiments of the oxidation of normal alkanes as good or better than a vapour pressure based method. If a Ki, WIOM prediction method was based on one or more surrogate molecules representing the solvation properties of the mixed OM phase of SOA, the choice of those molecule(s) was found to have a relatively minor effect on the predicted Ki, WIOM, as long as the molecule(s) are not very polar. This suggests that a single surrogate molecule, such as 1-octanol or a hypothetical SOA structure proposed by Kalberer et al. (2004), may often be sufficient to represent the WIOM component of the SOA phase, greatly simplifying the prediction. The presented methods could substitute for vapour pressure based methods in studies such as the explicit modeling of SOA formation from single precursor molecules in chamber experiments or the assignment of SOA-forming molecules to volatility basis sets.

  19. Novel methods for predicting gas-particle partitioning during the formation of secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Wania, F.; Lei, Y. D.; Wang, C.; Abbatt, J. P. D.; Goss, K.-U.

    2014-12-01

    Several methods have been presented in the literature to predict an organic chemical's equilibrium partitioning between the water insoluble organic matter (WIOM) component of aerosol and the gas phase, Ki,WIOM, as a function of temperature. They include (i) polyparameter linear free energy relationships calibrated with empirical aerosol sorption data, as well as (ii) the solvation models implemented in SPARC and (iii) the quantum-chemical software COSMOtherm, which predict solvation equilibria from molecular structure alone. We demonstrate that these methods can be used to predict Ki,WIOM for large numbers of individual molecules implicated in secondary organic aerosol (SOA) formation, including those with multiple functional groups. Although very different in their theoretical foundations, these methods give remarkably consistent results for the products of the reaction of normal alkanes with OH, i.e. their partition coefficients Ki,WIOM generally agree within one order of magnitude over a range of more than ten orders of magnitude. This level of agreement is much better than that achieved by different vapour pressure estimation methods that are more commonly used in the SOA community. Also, in contrast to the agreement between vapour pressure estimates, the agreement between the Ki,WIOM estimates does not deteriorate with increasing number of functional groups. Furthermore, these partitioning coefficients Ki,WIOM predicted SOA mass yields in agreement with those measured in chamber experiments of the oxidation of normal alkanes. If a Ki,WIOM prediction method was based on one or more surrogate molecules representing the solvation properties of the mixed OM phase of SOA, the choice of those molecule(s) was found to have a relatively minor effect on the predicted Ki,WIOM, as long as the molecule(s) are not very polar. This suggests that a single surrogate molecule, such as 1-octanol or a hypothetical SOA structure proposed by Kalberer et al. (2004), may often be sufficient to represent the WIOM component of the SOA phase, greatly simplifying the prediction. The presented methods could substitute for vapour-pressure-based methods in studies such as the explicit modelling of SOA formation from single precursor molecules in chamber experiments.

  20. Assessing the influence of secondary organic aerosols on long-range atmospheric PAH transport

    NASA Astrophysics Data System (ADS)

    Friedman, C. L.; Selin, N. E.

    2013-12-01

    We incorporate recent experimental findings on the synergy between secondary organic aerosols (SOA) and polycyclic aromatic hydrocarbons (PAHs) in a global atmospheric chemical transport model to test the influence of different gas-particle partitioning parameterizations on long-range atmospheric transport of PAHs. PAHs, byproducts of organic combustion, are toxic compounds that have been measured in areas distant from sources, such as the Arctic. Historically, the transport of PAHs in the atmosphere has been modeled by assuming that PAHs instantaneously and reversibly equilibrate between the gas phase and a particulate phase, with observed particulate fractions often times exceeding model results for unknown reasons. Recently obtained laboratory-based findings suggest PAHs become trapped in SOA particles during SOA formation and are thus prevented from evaporation and/or oxidation, possibly explaining discrepancies between observed and modeled particulate fractions. Here, we use the global atmospheric chemical transport model GEOS-Chem to investigate whether incorporation of pyrene, a four-ring PAH, into SOA upon formation better represents atmospheric long-range transport and gas-particle speciation of PAHs compared to our default partitioning scheme, in which PAHs instantaneously equilibrate between the gas phase, primary organic carbon aerosols (OC), and black carbon aerosols (BC). In general, we find that BC plays an important role in pyrene transport and gas-particle partitioning, with a model that includes BC producing the best match to observed seasonal variation and magnitude of pyrene particulate fraction. Incorporation of 100% of pyrene into SOA upon emission with fractional evaporation thereafter results in a reasonable match to observed total pyrene concentrations in the northern hemisphere mid-latitudes, but severely overestimates particulate fraction. Assuming that pyrene partitions to SOA following an octanol-air equilibrium partition coefficient upon emission with fractional evaporation thereafter similarly results in reasonable concentration results, but, in contrast, severely underestimates particulate fractions. Instantaneous equilibrium between the gas phase, OC, and BC is the only partitioning parameterization tested that simultaneously provides a good match to observed concentrations and particulate fractions. Other potential influences on pyrene long-range transport tested include spatiotemporal variability in gas-phase oxidant (hydroxyl radical) concentrations, spatiotemporal variability in SOA versus OC and BC, deposition efficiency of SOA versus OC and BC, and incorporation of particle-phase oxidation, with none of these parameterizations impacting PAH gas-particle partitioning as strongly as including BC in the model.

  1. Secondary Aerosol Formation in the planetary boundary layer observed by aerosol mass spectrometry on a Zeppelin NT

    NASA Astrophysics Data System (ADS)

    Rubach, Florian; Trimborn, Achim; Mentel, Thomas; 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). In combination with the high scientific payload of more than 1 ton, 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 its lifetime of up to several days secondaray aerosol at a certain location can result from local production or from transport processes. For aerosol measurements on a Zeppelin, a High-Resolution Time-of-Flight Aerosol Mass spectrometer (DeCarlo et al, 2006) was adapted to the requirements posed by an airborne platform. A weight reduction of over 20 % compared to the commercial instrument was achieved, while space occupation and footprint were each reduced by over 25 %. Within the PEGASOS project, the instrument was part of 10 measurement flight days over the course of seven weeks. Three flights were starting from Rotterdam, NL, seven flights were starting from Ozzano in the Po Valley, IT. Flight patterns included vertical profiles to study the dynamics of the PBL and cross sections through regions of interest to shed light on local production and transport processes. Analysis of data from transects between the Apennin and San Pietro Capofiume in terms of "residence time of air masses in the Po valley" indicates that aerosol nitrate has only local sources while aerosol sulfate is dominated by transport. The organic aerosol component has significant contributions of both processes. The local prodcution yields are commensurable with imultaneously observed precursor concentrations and oxidant levels. The PEGASOS project is funded by the European Commission under the Framework Programme 7 (FP7-ENV-2010-265148). DeCarlo, P.F. et al (2006), Anal. Chem., 78, 8281-8289.

  2. 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

  3. Formation of secondary organic aerosol and oligomers from the ozonolysis of enol ethers

    NASA Astrophysics Data System (ADS)

    Sadezky, A.; Chaimbault, P.; Mellouki, A.; Römpp, A.; Winterhalter, R.; Le Bras, G.; Moortgat, G. K.

    2006-06-01

    Formation of secondary organic aerosol has been observed in the gas phase ozonolysis of a series of enol ethers, among them several alkyl vinyl ethers (AVE, ROCH=CH2), such as ethyl, propyl, n-butyl, iso-butyl, t-butyl vinyl ether, and ethyl propenyl ether (EPE, C2H5OCH=CHCH3). The ozonolysis has been studied in a 570 l spherical glass reactor at atmospheric pressure (730 Torr) and temperature (296 K). Gas phase reaction products were investigated by in-situ FTIR spectroscopy, and secondary organic aerosol (SOA) formation was monitored by a scanning mobility particle sizer (SMPS). The chemical composition of the formed SOA was analysed by a hybrid mass spectrometer using electrospray ionization (ESI). The main stable gas phase reaction product is the respective alkyl formate ROC(O)H, formed with yields of 60 to 80%, implying that similar yields of the corresponding Criegee Intermediates (CI) CH2O2 for the AVE and CH3CHO2 for EPE are generated. Measured SOA yields are between 2 to 4% for all enol ethers. Furthermore, SOA formation is strongly reduced or suppressed by the presence of an excess of formic acid, which acts as an efficient CI scavenger. Chemical analysis of the formed SOA by ESI(+)/MS-TOF allows to identify oligomeric compounds in the mass range 200 to 800 u as its major constituents. Repetitive chain units are identified as CH2O2 (mass 46) for the AVE and C2H4O2 (mass 60) for EPE and thus have the same chemical compositions as the respective major Criegee Intermediates formed during ozonolysis of these ethers. The oligomeric structure and chain unit identity are confirmed by HPLC/ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF experiments, whereby successive and systematic loss of a fragment with mass 46 for the AVE (and mass 60 for EPE) is observed. It is proposed that the oligomer has the following basic structure of an oligoperoxide, -[CH(R)-O-O]n-, where R=H for the AVE and R=CH3 for the EPE. Oligoperoxide formation is thus suggested to be another, so far unknown reaction of stabilized Criegee Intermediates in the gas phase ozonolysis of oxygen-containing alkenes leading to SOA formation.

  4. Formation of secondary organic aerosol and oligomers from the ozonolysis of enol ethers

    NASA Astrophysics Data System (ADS)

    Sadezky, A.; Chaimbault, P.; Mellouki, A.; Römpp, A.; Winterhalter, R.; Le Bras, G.; Moortgat, G. K.

    2006-10-01

    Formation of secondary organic aerosol has been observed in the gas phase ozonolysis of a series of enol ethers, among them several alkyl vinyl ethers (AVE, ROCH=CH2), such as ethyl, propyl, n-butyl, iso-butyl, t-butyl vinyl ether, and ethyl propenyl ether (EPE, C2H5OCH=CHCH3). The ozonolysis has been studied in a 570 l spherical glass reactor at ambient pressure (730 Torr) and room temperature (296 K). Gas phase reaction products were investigated by in-situ FTIR spectroscopy, and secondary organic aerosol (SOA) formation was monitored by a scanning mobility particle sizer (SMPS). The chemical composition of the formed SOA was analysed by a hybrid mass spectrometer using electrospray ionization (ESI). The main stable gas phase reaction product is the respective alkyl formate ROC(O)H, formed with yields of 60 to 80%, implying that similar yields of the corresponding excited Criegee Intermediates (CI) CH2O2 for the AVE and CH3CHO2 for EPE are generated. Measured SOA yields are between 2 to 4% for all enol ethers. Furthermore, SOA formation is strongly reduced or suppressed by the presence of an excess of formic acid, which acts as an efficient CI scavenger. Chemical analysis of the formed SOA by ESI(+)/MS-TOF allows to identify oligomeric compounds in the mass range 200 to 800 u as its major constituents. Repetitive chain units are identified as CH2O2 (mass 46) for the AVE and C2H4O2 (mass 60) for EPE and thus have the same chemical compositions as the respective major Criegee Intermediates formed during ozonolysis of these ethers. The oligomeric structure and chain unit identity are confirmed by HPLC/ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF experiments, whereby successive and systematic loss of a fragment with mass 46 for the AVE (and mass 60 for EPE) is observed. It is proposed that the oligomer has the following basic structure of an oligoperoxide, -[CH(R)-O-O]n-, where R=H for the AVE and R=CH3 for the EPE. Oligoperoxide formation is thus suggested to be another, so far unknown reaction of stabilized Criegee Intermediates in the gas phase ozonolysis of oxygen-containing alkenes leading to SOA formation.

  5. 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.

    2013-09-01

    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 (DPF), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOC). 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, photo-oxidation 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 and secondary fine particulate matter 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 three hours 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 non-methane 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.

  6. Real-Time Observations of Secondary Aerosol Formation and Aging from Different Emission Sources and Environments

    NASA Astrophysics Data System (ADS)

    Ortega, A. M.; Palm, B. B.; Hayes, P. L.; Day, D. A.; Cubison, M.; Brune, W. H.; Hu, W.; Flynn, J. H.; Grossberg, N.; Lefer, B. L.; Rappenglueck, B.; Bon, D.; Graus, M.; Warneke, C.; Gilman, J.; Kuster, W.; De Gouw, J. A.; Jimenez, J. L.

    2013-12-01

    To investigate atmospheric processing of direct urban and wildfire emissions, we deployed a photochemical flow reactor (Potential Aerosol Mass, PAM) with submicron aerosol size and chemical composition measurements during FLAME-3, a biomass-burning study at USDA Fire Sciences Laboratory in Missoula, MT, and CalNex, a field study investigating the nexus of air quality and climate change at a receptor site in the LA-Basin at Pasadena, CA. The reactor produces OH concentrations up to 4 orders of magnitude higher than in ambient air, achieving equivalent aging of ~2 weeks in 5 minutes of processing. The OH exposure (OHexp) was stepped every 20 min in both field studies. Results show the value of this approach as a tool for in-situ evaluation of changes in OA concentration and composition due to photochemical processing. In FLAME-3, the average OA enhancement factor was 1.42 × 0.36 of the initial POA. Reactive VOCs, such as toluene, monoterpenes, and acetaldehyde, decreased with increased OHexp; however, formic acid, acetone, and some unidentified OVOCs increased after significant exposure. Net SOA formation in the photochemical reactor increased with OHexp, typically peaking around 3 days of equivalent atmospheric photochemical age (OHexp ~3.9e11 molecules cm-3 s), then leveling off at higher exposures. Unlike other studies, no decrease in OA is observed at high exposure, likely due to lower max OHexp in this study due to very high OH reactivity. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeded the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility species, and possibly of unidentified VOCs as SOA precursors in biomass burning smoke. Results from CalNex show enhancement of OA and inorganic aerosol from gas-phase precursors. The OA mass enhancement from aging was highest at night and correlated with trimethylbenzene concentrations, indicating the dominance of highly reactive VOC emissions as SOA precursors in the LA Basin. Aging in the reactor mimics atmospheric processing as the elemental composition of ambient and reactor measurements, when plotted in a Van Krevelen diagram, follow similar slopes; additionally, reactor measurements extend over a larger range of oxygen-to-carbon ratios (O/C) compared to that observed in the LA-Basin. While reactor aging always increases O/C, often beyond maximum ambient levels, we observe a transition from functionalization to fragmentation oxidation reactions at intermediate OHexp, with fragmentation dominating at very high OHexp. Maximum net SOA production is observed between 3-6 days of aging and decreases at higher exposures. A traditional SOA model with mostly aromatic precursors underpredicts the amount of SOA formed by an order-of-magnitude, which is consistent with model evaluations for ambient air at many polluted locations.

  7. Proposed chemical mechanisms leading to secondary organic aerosol in the reactions of aliphatic amines with hydroxyl and nitrate radicals

    NASA Astrophysics Data System (ADS)

    Price, Derek J.; Clark, Christopher H.; Tang, Xiaochen; Cocker, David R.; Purvis-Roberts, Kathleen L.; Silva, Philip J.

    2014-10-01

    The presence and importance of amines in the atmosphere, including aliphatic amines, continues to gain more attention. The atmospheric reaction mechanisms of these amines with key atmospheric radicals are important to predict both daytime and nighttime atmospheric chemistry. While previous studies have focused on the production of amine salts, this analysis looks at the importance of peroxy radical reactions to the formation of secondary organic aerosol. Atmospheric oxidation mechanisms are presented to explain the observed chemistry. A series of environmental chamber experiments were conducted in which aliphatic tertiary and secondary amines were reacted with either hydroxyl radical (OH) or nitrate radical (NO3). Chemical composition of the aerosol products was obtained with a High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a Particle Into Liquid Sampler Time of Flight Mass Spectrometer (PILS-ToF-MS), while the chemical composition of the gas-phase products was obtained with a Selected Ion Flow Tube Mass Spectrometer (SIFT-MS). A number of aerosol-phase mass spectra showed highly oxidized fragments at a much higher molecular weight (MW) than the amine precursor. It is proposed that these larger compounds are oligomers formed through peroxy radical reactions with hydrogen rearrangement. Another reaction pathway observed was the formation of amine salts. The relative importance of each pathway to the overall production of aerosol is found to be dependent on the type of amine and oxidant. For example, the oligomers were observed in the tertiary methyl amines, while the formation of amine salts was more prevalent in the secondary and tertiary ethyl amines.

  8. 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.

  9. 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.

  10. Detailed Chemical Characterization of Unresolved Complex Mixtures (UCM) inAtmospheric Organics: Insights into Emission Sources, Atmospheric Processing andSecondary Organic Aerosol Formation

    EPA Science Inventory

    Recent studies suggest that semivolatile organic compounds (SVOCs) are important precursors to secondary organic aerosol (SOA) in urban atmospheres. However, knowledge of the chemical composition of SVOCs is limited by current analytical techniques, which are typically unable to...

  11. 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 ...

  12. 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...

  13. Reduction in biomass burning aerosol light absorption upon humidification: roles of inorganically-induced hygroscopicity, particle collapse, and photoacoustic heat and mass transfer

    NASA Astrophysics Data System (ADS)

    Lewis, K. A.; Arnott, W. P.; Moosmüller, H.; Chakrabarty, R. K.; Carrico, C. M.; Kreidenweis, S. M.; Day, D. E.; Malm, W. C.; Laskin, A.; Jimenez, J. L.; Ulbrich, I. M.; Huffman, J. A.; Onasch, T. B.; Trimborn, A.; Liu, L.; Mishchenko, M. I.

    2009-07-01

    Smoke particle emissions from the combustion of biomass fuels typical for the western and southeastern United States were studied and compared under high humidity and ambient conditions in the laboratory. The fuels used are Montana ponderosa pine (Pinus ponderosa), southern California chamise (Adenostoma fasciculatum), and Florida saw palmetto (Serenoa repens). Information on the non-refractory chemical composition of biomass burning aerosol from each fuel was obtained with an aerosol mass spectrometer and through estimation of the black carbon concentration from light absorption measurements at 870 nm. Changes in the optical and physical particle properties under high humidity conditions were observed for hygroscopic smoke particles containing substantial inorganic mass fractions that were emitted from combustion of chamise and palmetto fuels. Light scattering cross sections increased under high humidity for these particles, consistent with the hygroscopic growth measured for 100 nm particles in HTDMA measurements. Photoacoustic measurements of aerosol light absorption coefficients reveal a 20% reduction with increasing relative humidity, contrary to the expectation of light absorption enhancement by the liquid coating taken up by hygroscopic particles. This reduction is hypothesized to arise from two mechanisms: 1. Shielding of inner monomers after particle consolidation or collapse with water uptake; 2. The contribution of mass transfer through evaporation and condensation at high relative humidity to the usual heat transfer pathway for energy release by laser-heated particles in the photoacoustic measurement of aerosol light absorption. The mass transfer contribution is used to evaluate the fraction of aerosol surface covered with liquid water solution as a function of RH.

  14. Reduction in biomass burning aerosol light absorption upon humidification: roles of inorganically-induced hygroscopicity, particle collapse, and photoacoustic heat and mass transfer

    NASA Astrophysics Data System (ADS)

    Lewis, K. A.; Arnott, W. P.; Moosmüller, H.; Chakrabarty, R. K.; Carrico, C. M.; Kreidenweis, S. M.; Day, D. E.; Malm, W. C.; Laskin, A.; Jimenez, J. L.; Ulbrich, I. M.; Huffman, J. A.; Onasch, T. B.; Trimborn, A.; Liu, L.; Mishchenko, M. I.

    2009-11-01

    Smoke particle emissions from the combustion of biomass fuels typical for the western and southeastern United States were studied and compared under high humidity and ambient conditions in the laboratory. The fuels used were Montana ponderosa pine (Pinus ponderosa), southern California chamise (Adenostoma fasciculatum), and Florida saw palmetto (Serenoa repens). Information on the non-refractory chemical composition of biomass burning aerosol from each fuel was obtained with an aerosol mass spectrometer and through estimation of the black carbon concentration from light absorption measurements at 870 nm. Changes in the optical and physical particle properties under high humidity conditions were observed for hygroscopic smoke particles containing substantial inorganic mass fractions that were emitted from combustion of chamise and palmetto fuels. Light scattering cross sections increased under high humidity for these particles, consistent with the hygroscopic growth measured for 100 nm particles in HTDMA measurements. Photoacoustic measurements of aerosol light absorption coefficients revealed a 20% reduction with increasing relative humidity, contrary to the expectation of light absorption enhancement by the liquid coating taken up by hygroscopic particles. This reduction is hypothesized to arise from two mechanisms: (1) shielding of inner monomers after particle consolidation or collapse with water uptake; (2) the lower case contribution of mass transfer through evaporation and condensation at high relative humidity (RH) to the usual heat transfer pathway for energy release by laser-heated particles in the photoacoustic measurement of aerosol light absorption. The mass transfer contribution is used to evaluate the fraction of aerosol surface covered with liquid water solution as a function of RH.

  15. Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: comparing laboratory and field studies

    E-print Network

    Kourtchev, I.; Fuller, S. J.; Giorio, C.; Healy, R. M.; Wilson, E.; O'Connor, I.; Wenger, J. C.; McLeod, M.; Aalto, J.; Ruuskanen, T. M.; Maenhaut, W.; Jones, R.; Venables, D. S.; Sodeau, J. R.; Kulmala, M.; Kalberer, M.

    2014-01-01

    et al.: Molecular composition of biogenic secondary organic aerosols Biosciences, Ithaca NY, USA). The Orbitrap MS instrument was calibrated using an Ultramark 1621 solution (Sigma- Aldrich, UK). The mass accuracy of the instrument was be- low 1.5 ppm... with a mass tolerance of ±5 ppm were calculated. The data filtering was performed using a Mathematica 8.0 (Wolfram Research Inc., UK) code developed in-house that employed several conservative rules and constraints similar to those used in previous...

  16. 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

  17. The roles of individual oxidants in secondary organic aerosol formation from ? 3-carene: 2. soa formation and oxidant contribution

    Microsoft Academic Search

    Christopher J Colville; Robert J Griffin

    2004-01-01

    This is Part 2 of a series of papers that address the role of individual oxidants in secondary organic aerosol (SOA) formation from the oxidation of ?3-carene. In the present paper, an equilibrium gas–particle partitioning model is developed and used in conjunction with the gas-phase chemical mechanism described in Part 1 to perform simulations of SOA formation from the oxidation

  18. 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

    2014-11-20

    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

  19. 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

  20. Nitrogen Containing Organic Compounds and Oligomers in Secondary Organic Aerosol Formed by Photooxidation of Isoprene

    SciTech Connect

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

    2011-07-06

    Electrospray ionization high-resolution mass spectrometry (ESI HR-MS) was used to probe molecular structures of oligomers in secondary organic aerosol (SOA) generated in laboratory experiments on isoprene photooxidation at low- and high-NOx conditions. Up to 80-90% of the observed products are oligomers and up to 33% are nitrogen-containing organic compounds (NOC). We observe oligomers with up to 8 monomer units in length. Tandem mass spectrometry (MSn) confirms NOC compounds are organic nitrates and elucidates plausible chemical building blocks contributing to oligomer formation. Most organic nitrates are comprised of methylglyceric acid units. Other important multifunctional C2-C5 monomer units are identified including methylglyoxal, hydroxyacetone, hydroxyacetic acid, glycolaldehyde, and 2-methyltetrols. The majority of the NOC oligomers contain only one nitrate moiety resulting in a low average N:C ratio of 0.019. Average O:C ratios of the detected SOA compounds are 0.54 under the low-NOx conditions and 0.83 under the high-NOx conditions. Our results underscore the importance of isoprene photooxidation as a source of NOC in organic particulate matter.

  1. High-Resolution Mass Spectroscopic Analysis of Secondary Organic Aerosol Generated by Ozonolysis of Isoprene

    SciTech Connect

    Nguyen, Tran B.; Bateman, Adam P.; Bones, David L.; Nizkorodov, Serguei; Laskin, Julia; Laskin, Alexander

    2010-02-01

    The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C5H8) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS). The chemical composition of SOA is complex, with more than 1000 assigned peaks observed in the positive and negative ion mode spectra. Only a small fraction of peaks corresponds to known products of isoprene oxidation, such as pyruvic acid, glycolic acid, methylglyoxal, etc. The absolute majority of the detected peaks correspond to highly oxidized oligomeric constituents of SOA, with an average O:C molar ratio of ~0.6. The corresponding organic mass (OM) to organic oxygen (OO) ratio is OM/OO?2.4. Approximately 8% of oxygen atoms in SOA are in the form of peroxides as quantified with an iodide test. Double bond equivalency (DBE) factors, representing the sum of all double bonds and rings, increase by 1 for every 2-3 additional carbon atoms in the molecule. The prevalent oligomer building blocks are therefore carbonyls or carboxylic acids with a C2-C3 skeleton. Kendrick analysis suggests that simple aldehydes, specifically formaldehyde, acetaldehyde, and methylglyoxal can serve as monomeric building blocks in the observed oligomers. The large number of reactive functional groups, especially organic peroxides and carbonyls, suggests that isoprene/O3 SOA should be prone to chemical and photochemical aging.

  2. Characterization of secondary organic aerosol generated from ozonolysis of ?-pinene mixtures

    NASA Astrophysics Data System (ADS)

    Amin, Hardik S.; Hatfield, Meagan L.; Huff Hartz, Kara E.

    2013-03-01

    In the atmosphere, multiple volatile organic compounds (VOCs) co-exist, and they can be oxidized concurrently and generate secondary organic aerosol (SOA). In this work, SOA is formed by the oxidation (in presence of excess ozone) of mixtures containing ?-pinene and other VOCs. The VOC mixtures were made so their composition approached a commercially-available ?-pinene-based essential oil, Siberian fir needle oil. The SOA products were sampled using filters, solvent extracted and analyzed by gas chromatography/mass spectrometry with trimethylsilyl derivatization. The individual product yields for SOA generated from ?-pinene changed upon the addition of other VOCs. An increase in concentration of non-reactive VOCs (bornyl acetate, camphene, and borneol) lead to a decrease in individual product yields of characteristic ?-pinene SOA products. Although these experiments were carried out under higher VOC and ozone concentrations in comparison to the atmosphere, this work suggests that the role of non-reactive VOCs should be explored in SOA products formation.

  3. Secondary organic aerosol formation in cloud and fog droplets: a literature evaluation of plausibility

    NASA Astrophysics Data System (ADS)

    Blando, James D.; Turpin, Barbara J.

    This paper investigates the hypothesis that cloud and fog processes produce fine organic particulate matter in the atmosphere. The evidence provided suggests that cloud and fog processes could be important contributors to secondary organic aerosol formation, and the contribution of this formation pathway should be further investigated. This conclusion is based on the following observations: (1) many organic vapors present in the atmosphere are sorbed by suspended droplets and have been measured in cloud and fog water, (2) organics participate in aqueous-phase reactions, and (3) organic particulate matter is sometimes found in the size mode attributed to cloud processing (i.e. the droplet mode). Specific compounds identified as potential precursors include aldehydes (e.g. formaldehyde, acetaldehyde, and propionaldehyde), acetone, alcohols (e.g. methanol, ethanol, 2-propanol, and phenol), monocarboxylic acids, and organic peroxides. Carboxylic acids (e.g. diacids and oxo-acids), glyoxal, esters, organosulfur compounds, polyols, amines and amino acids are potential products of cloud and fog processing.

  4. Filterable redox cycling activity: a comparison between diesel exhaust particles and secondary organic aerosol constituents.

    PubMed

    McWhinney, Robert D; Badali, Kaitlin; Liggio, John; Li, Shao-Meng; Abbatt, Jonathan P D

    2013-04-01

    The redox activity of diesel exhaust particles (DEP) collected from a light-duty diesel passenger car engine was examined using the dithiothreitol (DTT) assay. DEP was highly redox-active, causing DTT to decay at a rate of 23-61 pmol min(-1) ?g(-1) of particle used in the assay, which was an order of magnitude higher than ambient coarse and fine particulate matter (PM) collected from downtown Toronto. Only 2-11% of the redox activity was in the water-soluble portion, while the remainder occurred at the black carbon surface. This is in contrast to redox-active secondary organic aerosol constituents, in which upward of 90% of the activity occurs in the water-soluble fraction. The redox activity of DEP is not extractable by moderately polar (methanol) and nonpolar (dichloromethane) organic solvents, and is hypothesized to arise from redox-active moieties contiguous with the black carbon portion of the particles. These measurements illustrate that "Filterable Redox Cycling Activity" may therefore be useful to distinguish black carbon-based oxidative capacity from water-soluble organic-based activity. The difference in chemical environment leading to redox activity highlights the need to further examine the relationship between activity in the DTT assay and toxicology measurements across particles of different origins and composition. PMID:23470039

  5. Glyoxal in the Po Valley, Italy as a tracer for tropospheric ozone and secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Skog, K.; Keutsch, F. N.

    2012-12-01

    The Po Valley is one of the most polluted locations in Europe due to large anthropogenic emissions and frequent stagnation events. During June and July of 2012, the Madison Laser-Induced Phosphorescence instrument (Mad-LIP) measured glyoxal at the Pan-European Gas-AeroSOls-climate interaction Study (PEGASOS) ground site in San Pietro Capofiume, Italy. Glyoxal, formed via oxidation of volatile organic compounds (VOCs), has a lifetime of about two hours and is therefore a great tracer for the local tropospheric oxidative chemistry that also produces tropospheric ozone (O3). Glyoxal has also been proposed to significantly contribute to secondary organic aerosol (SOA), and other less volatile, oxidized compounds that may also contribute to SOA are formed by the same processes that form glyoxal. Data from this study will be compared to previous years at the measurement site and other field sites, both anthropogenic and biogenic in nature. Analysis will focus on glyoxal in the context of air mass source apportionment, and its role in the production of O3 and SOA.

  6. Secondary organic aerosol from ozone-initiated reactions with terpene-rich household products

    SciTech Connect

    Coleman, Beverly; Coleman, Beverly K.; Lunden, Melissa M.; Destaillats, Hugo; Nazaroff, William W.

    2008-01-01

    We analyzed secondary organic aerosol (SOA) data from a series of small-chamber experiments in which terpene-rich vapors from household products were combined with ozone under conditions analogous to product use indoors. Reagents were introduced into a continuously ventilated 198 L chamber at steady rates. Consistently, at the time of ozone introduction, nucleation occurred exhibiting behavior similar to atmospheric events. The initial nucleation burst and growth was followed by a period in which approximately stable particle levels were established reflecting a balance between new particle formation, condensational growth, and removal by ventilation. Airborne particles were measured with a scanning mobility particle sizer (SMPS, 10 to 400 nm) in every experiment and with an optical particle counter (OPC, 0.1 to 2.0 ?m) in a subset. Parameters for a three-mode lognormal fit to the size distribution at steady state were determined for each experiment. Increasing the supply ozone level increased the steady-state mass concentration and yield of SOA from each product tested. Decreasing the air-exchange rate increased the yield. The steady-state fine-particle mass concentration (PM1.1) ranged from 10 to> 300 mu g m-3 and yields ranged from 5percent to 37percent. Steady-state nucleation rates and SOA mass formation rates were on the order of 10 cm-3 s-1 and 10 mu g m-3 min-1, respectively.

  7. Secondary organic aerosol contributions to PM2.5 in Monterrey, Mexico: Temporal and seasonal variation

    NASA Astrophysics Data System (ADS)

    Mancilla, Yasmany; Herckes, Pierre; Fraser, Matthew P.; Mendoza, Alberto

    2015-02-01

    Air pollution caused by fine particles is a problem of great concern in the Monterrey Metropolitan Area (MMA) which is the third largest city and the second most important industrial center in Mexico. In this study, samples of fine particulate matter emissions with an aerodynamic diameter of less than 2.5 ?m (PM2.5) were collected for 12-hour periods during the spring and fall of 2011 and 2012. Eighty-three samples were analyzed for organic carbon (OC) and elemental carbon (EC). The carbonaceous fraction (OC + EC) accounted for 28-55% of the PM2.5 mass. The average OC/EC ratios ranged from 7.4 to 12.6, and OC and EC concentrations were statistically significant correlated (R2 = 0.81, p < 0.01). The secondary organic aerosol (SOA) contributions were determined using two approaches: the EC tracer method based on a primary OC/EC ratio derived from a tunnel study and the minimum observed OC/EC ratio. SOAs were determined to constitute, on average, 59-87% and 32-45% of the total OC and PM2.5, respectively. The relationship between O3 and wind speed indicated that pollutant levels were influenced by transport events during the spring, while stagnation events predominated during the fall campaigns. Statistically significant correlations were observed between OC and EC and gaseous species (CO, NOx, and SO2), indicating a contribution by combustion of fossil fuels to the carbonaceous material.

  8. Isoprene Forms Secondary Organic Aerosol Through Cloud Processing: A Model Study

    NASA Astrophysics Data System (ADS)

    Lim, H.; Turpin, B. J.; Carlton, A. G.

    2004-12-01

    Cloud processing of water-soluble organic vapors has been proposed as a pathway for the formation of organic particulate matter (PM) in the atmosphere (i.e., secondary organic aerosol; SOA). The simulations described below suggest that cloud processing of isoprene is a substantial contributor to atmospheric oxalic acid and SOA formation. Isoprene, a biogenic volatile organic compound (VOC) of global importance, forms highly water-soluble glyoxal, methylglyoxal, and glycolaldehyde in the gas phase. These carbonyls favorably partition into cloud droplets where they oxidize to organic acids (e.g., glyoxylic acid, glycolic acid, pyruvic acid, and oxalic acid). In this study we developed a box model to examine the importance of isoprene chemistry to in-cloud formation of SOA. The box model incorporates gas- and aqueous-phase chemistry and phase transfer of relevant water-soluble species. Simulations were conducted under clean conditions typical of the tropical Amazon (i.e., high emission flux of isoprene and low emissions of anthropogenic pollutants). Simulation results show that isoprene forms a substantial amount of organic acids through cloud processing. More than 80% of oxalic acid is expected to remain in the particle phase after cloud evaporation. This study suggests that cloud processing of isoprene is a substantial contributor to atmospheric water-soluble SOA that can alter the microphysics of cloud condensation nuclei (CCN). This work also discusses the sensitivity of the model to important model parameters.

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

    NASA Astrophysics Data System (ADS)

    Nguyen, Tran B.; Bateman, Adam P.; Bones, David L.; Nizkorodov, Sergey A.; Laskin, Julia; Laskin, Alexander

    2010-03-01

    The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C 5H 8) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS) in the mass range m/ z = 50-1000. The chemical composition of SOA is complex, with more than 1000 assigned peaks observed in the positive and negative ion mode spectra. Only a small fraction of peaks correspond to known products of isoprene oxidation, such as pyruvic acid, glycolic acid, methylglyoxal, etc. The absolute majority of the detected peaks correspond to highly oxidized oligomeric constituents of SOA, with an average O:C molar ratio of 0.6. The corresponding organic mass (OM) to organic oxygen (OO) ratio is 2.4. Approximately 8% of oxygen atoms in SOA are in the form of peroxides, as quantified with an iodide test. Double bond equivalency (DBE) factors, representing the sum of all double bonds and rings, increase by 1 for every 1-2 additional carbon atoms in the molecule. The number of unoxidized C dbnd C double bonds is estimated to be less than 10%; the remaining DBE is due to C dbnd O carbonyl groups. Kendrick analysis suggests that the prevalent oligomer building blocks are small carbonyls with a C 1-C 2 skeleton. Formaldehyde (CH 2O) is identified as the most common repetitive building block in the observed oligomeric compounds.

  10. 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.; Cazaunau, M.; Tapparo, A.; Monod, A.; Doussin, J.-F.

    2015-03-01

    First- and higher order-generation products formed from the oxidation of isoprene and methacrolein with OH radicals in the presence of NOx have been studied in a simulation chamber. Significant oxidation rates have been maintained for up to 7 h, allowing the study of highly oxidized products. Gas-phase product distribution and yields were obtained, and show good agreement with previous studies. Secondary organic aerosol (SOA) formation has also been investigated. SOA mass yields from previous studies show large discrepancies. 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 similar to the solar spectrum. Differences in light source are therefore proposed to explain partially the discrepancies observed between different studies in the literature for both isoprene- and methacrolein-SOA mass yields. There is a high degree of similarity between the 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). According to our results, SOA mass yields from both isoprene and methacrolein in the atmosphere could be lower than suggested by most of the current chamber studies.

  11. Modeling secondary organic aerosol formation from oxidation of ?-pinene, ?-pinene, and d-limonene

    NASA Astrophysics Data System (ADS)

    Chen, Jianjun; Griffin, Robert J.

    The biogenic species ?-pinene, ?-pinene, and d-limonene are among the most abundant monoterpenes emitted globally. They are also important precursors to secondary organic aerosol (SOA) formation in the atmosphere. This study involves the development of proposed oxidation mechanisms for these three species. Semi- and non-volatile oxidation products with the potential to lead to SOA formation are predicted explicitly. Simulation code that describes the gas-phase oxidation mechanisms including reactions that lead to ozone (O 3) formation is coupled to an equilibrium absorptive partitioning code. The coupled model is used to simulate both gas-phase chemistry and SOA formation associated with oxidation of these three species in chamber experiments involving single as well as multiple oxidants. For the partitioning model, required molecular properties of the oxidation products are taken from the literature or estimated based on structural characteristics. The predicted O 3 and SOA concentrations are typically within ±50% of measured values for most of the experiments except for the experiments with low initial hydrocarbon concentrations and the nitrate radical experiments with ?-pinene. The developed model will be used to update a gas-phase chemical mechanism and a SOA formation module used in a three-dimensional air quality model.

  12. The effects of increasing atmospheric ozone on biogenic monoterpene profiles and the formation of secondary aerosols

    NASA Astrophysics Data System (ADS)

    Pinto, Delia M.; Tiiva, Päivi; Miettinen, Pasi; Joutsensaari, Jorma; Kokkola, Harri; Nerg, Anne-Marja; Laaksonen, Ari; Holopainen, Jarmo K.

    Monoterpenes are biogenic volatile organic compounds (BVOCs) which play an important role in plant adaptation to stresses, atmospheric chemistry, plant-plant and plant-insect interactions. In this study, we determined whether ozonolysis can influence the monoterpenes in the headspace of cabbage. The monoterpenes were mixed with an air-flow enriched with 100, 200 or 400 ppbv of ozone (O 3) in a Teflon chamber. The changes in the monoterpene and O 3 concentrations, and the formation of secondary organic aerosols (SOA) were determined during ozonolysis. Furthermore, the monoterpene reactions with O 3 and OH were modelled using reaction kinetics equations. The results showed that all of the monoterpenes were unequally affected: ?-thujene, sabinene and D-limonene were affected to the greatest extend, whereas the 1,8-cineole concentration did not change. In addition, plant monoterpene emissions reduced the O 3 concentration by 12-24%. The SOA formation was dependent on O 3 concentration. At 100 ppbv of O 3, virtually no new particles were formed but clear SOA formation was observed at the higher ozone concentrations. The modelled results showed rather good agreements for ?-pinene and 1,8-cineole, whereas the measured concentrations were clearly lower compared to modelled values for sabinene and limonene. In summary, O 3-quenching by monoterpenes occurs beyond the boundary layer of leaves and results in a decreased O 3 concentration, altered monoterpene profiles and SOA formation.

  13. Secondary organic aerosol formation via the isolation of individual reactive intermediates: role of alkoxy radical structure.

    PubMed

    Carrasquillo, Anthony J; Hunter, James F; Daumit, Kelly E; Kroll, Jesse H

    2014-09-25

    The study of the chemistry underlying secondary organic aerosol (SOA) formation is complicated by the large number of reaction pathways and oxidation generations available to a given precursor species. Here we simplify such complexity to that of a single alkoxy radical (RO), by forming SOA via the direct photolysis of alkyl nitrite (RONO) isomers. Chamber experiments were conducted with 11 C10 RONO isomers to determine how the position of the radical center and branching of the carbon skeleton influences SOA formation. SOA yields served as a probe of RO reactivity, with lower yields indicating that fragmentation reactions dominate and higher yields suggesting the predominance of RO isomerization. The largest yields were from straight-chain isomers, particularly those with radical centers located toward the terminus of the molecule. Trends in SOA yields can be explained in terms of two major effects: (1) the relative importance of isomerization and fragmentation reactions, which control the distribution of products, and (2) differences in volatility among the various isomeric products formed. Yields from branched isomers, which were low but variable, provide insight into the degree of fragmentation of the alkoxy radicals; in the case of the two ?-substituted alkoxy radicals, fragmentation appears to occur to a greater extent than predicted by structure-activity relationships. Our results highlight how subtle differences in alkoxy radical structure can have major impacts on product yields and SOA formation. PMID:25148415

  14. 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

  15. Impact of Propene on Secondary Organic Aerosol Formation from m-Xylene

    SciTech Connect

    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 ofm-xylene/NOx photooxidation experiments were conducted in the presence of propene in the University of California CECERT atmospheric chamber facility. The experimental data are compared with previousm-xylene/NOx 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 ofm-xylene/NOx with CO showed similar trends of suppressing OH and SOA formation. These results indicate that SOA from m-xylene/NOx photooxidation is strongly dependent on the OH level present, which provides evidence for the critical role of OH in SOA formation from aromatic hydrocarbons.

  16. AEROSOL GROWTH IN A STEADY-STATE, CONTINUOUS FLOW CHAMBER: APPLICATION TO STUDIES OF SECONDARY AEROSOL FORMATION

    EPA Science Inventory

    An analytical solution for the steady-state aerosol size distribution achieved in a steady-state, continuous flow chamber is derived, where particle growth is occurring by gas-to-particle conversion and particle loss is occurring by deposition to the walls of the chamber. The s...

  17. 2-Hydroxyterpenylic acid: An oxygenated marker compound for a-pinene secondary organic aerosol in ambient fine aerosol

    EPA Science Inventory

    An oxygenated MW 188 compound is commonly observed in substantial abundance in atmospheric aerosol samples and was proposed in previous studies as an a-pinene-related marker compound that is associated with aging processes. Owing to difficulties in producing this compound in suff...

  18. Aerosols

    Atmospheric Science Data Center

    2013-04-17

    ... is needed for monitoring air quality and for understanding climate change. During the last weeks of March 2003, widespread aerosol ... MISR Team. Text acknowledgment: Clare Averill (Acro Service Corporation/Jet Propulsion Laboratory). Other formats available ...

  19. Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

    NASA Astrophysics Data System (ADS)

    Wood, E. C.; Canagaratna, M. R.; Herndon, S. C.; Kroll, J. H.; Onasch, T. B.; Kolb, C. E.; Worsnop, D. R.; Knighton, W. B.; Seila, R.; Zavala, M.; Molina, L. T.; Decarlo, P. F.; Jimenez, J. L.; Weinheimer, A. J.; Knapp, D. J.; Jobson, B. T.; Stutz, J.; Kuster, W. C.; Williams, E. J.

    2010-02-01

    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 better understood, we investigate the correlation of odd-oxygen ([Ox]?[O3]+[NO2]) and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 ?g m-3 ppm-1 (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 ?g m-3 ppm-1 in Mexico City, where typical values were near 120 ?g m-3 ppm-1. On several days in Mexico City, the [OOA]/[Ox] ratio decreased by a factor of ~2 between 08:00 and 13:00 LT. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not succesful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) can serve as a useful test of photochemical models using improved formulation mechanisms for SOA.

  20. Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

    NASA Astrophysics Data System (ADS)

    Wood, E. C.; Canagaratna, M. R.; Herndon, S. C.; Onasch, T. B.; Kolb, C. E.; Worsnop, D. R.; Kroll, J. H.; Knighton, W. B.; Seila, R.; Zavala, M.; Molina, L. T.; Decarlo, P. F.; Jimenez, J. L.; Weinheimer, A. J.; Knapp, D. J.; Jobson, B. T.; Stutz, J.; Kuster, W. C.; Williams, E. J.

    2010-09-01

    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 better understood, we investigate the correlation of odd-oxygen ([Ox]?[O3]+[NO2]) and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 ?g m-3/ppm (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 ?g m-3/ppm in Mexico City, where typical values were near 120 ?g m-3/ppm. On several days in Mexico City, the [OOA]/[Ox] ratio decreased by a factor of ~2 between 08:00 and 13:00 local time. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not succesful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) can serve as a useful test of photochemical models using improved formulation mechanisms for SOA.

  1. OH-Radical initiated ageing of biogenic secondary organic aerosols - A detailed chemical analysis

    NASA Astrophysics Data System (ADS)

    Müller, L.; Reinnig, M.-C.; Mentel, Th. F.; Tillmann, R.; Schlosser, E.; Wahner, A.; Saathoff, H.; Donahue, N. M.; Hoffmann, T.

    2009-04-01

    The chemical ageing[1] of secondary organic aerosol (SOA) was investigated in two series of experiments using on-line mass spectrometry and off-line high performance liquid chromatography mass spectrometry (HPLC-MS). In a set of photochemical experiments, performed in the large outdoor reaction chamber SAPHIR (Jülich, Germany), SOA was generated from a boreal mixture including mono- and sesquiterpenes (?-pinene, ?-pinene, ?3-carene, limonene, caryophyllene). During a long time experiment (30h) the generated SOA was exposed to OH-radicals and the chemical composition was analyzed on-line using atmospheric pressure ionization mass spectrometry (API-MS). The on-line method provides highly time resolved chemical information and therefore a direct insight into the temporal changes of SOA-composition. In parallel, filter samples analysed by HPLC-MS allow the enrichment of trace compounds and finally an unambiguous identification of individual substances. In addition, filter samples allow a direct comparison to samples from field studies. The ageing experiments showed a clear change in SOA composition. The compounds observed can be divided into two groups: A group of first generation SOA-compounds, generated by the OH oxidation of the terpenes and a group of second generation compounds, generated by the reaction of OH with SOA compounds. Among the second generation products, especially a tricarboxylic acid (3-methyl-1,2,3-butanetricarboxylic acid, m/z 203)[2] was observed to be a good marker compound for BSOA ageing. A further set of experiments was carried out in another large aerosol chamber facility, the AIDA chamber of the Research Centre Karlsruhe. In this dark chamber, the experiments focused on the OH-induced ageing of ?-pinene SOA and the influence of temperature. The results clearly show that the tricarboxylic acid is a distinctive marker for OH radical induced BSOA ageing and identify cis-pinonic acid as its precursor. To connect the results of the laboratory measurements with the ambient atmosphere, this paper also compares filter samples taken at the Finnish Forest Research Station in Hyytiälä to the filter samples obtained from SAPHIR/AIDA experiments. 1. Rudich, Y., N.M. Donahue, and T.F. Mentel (2007) Annual Review of Physical Chemistry 58: 321-352 2. Szmigielski, R., J.D. Surratt, Y. Gomez-Gonzalez, P. Van der Veken, I. Kourtchev, R. Vermeylen, F. Blockhuys, M. Jaoui, T.E. Kleindienst, M. Lewandowski, J.H. Offenberg, E.O. Edney, J.H. Seinfeld, W. Maenhaut, and M. Claeys (2007) Geophysical Research Letters 34(24)

  2. 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.

  3. Secondary Organic Aerosol Formation by Molecular-Weight Building Reactions of Biogenic Oxidation Products

    NASA Astrophysics Data System (ADS)

    Barsanti, K.; Guenther, A.; Matsunaga, S.; Smith, J.

    2006-12-01

    Understanding the chemical composition of atmospheric organic aerosols (OA) remains one of the significant challenges to accurately representing OA in air quality and climate models. Meeting this challenge will require further understanding of secondary organic aerosols (SOA), of which biogenic emissions are thought to be major precursors. Of recent interest is the significance of higher-molecular weight (MW) compounds (i.e., "oligomers"). Theoretical, laboratory, and field study results suggest that relatively volatile oxidation products may contribute to SOA formation through multi-phase MW- building reactions. The significance of such reactions for biogenic SOA formation, including for newly considered precursors such as isoprene, is explored in this work. Theoretical and field studies are employed to: 1) identify MW-building reactions that may contribute to SOA formation in the atmosphere, 2) identify MW-building reaction products in ambient samples, and 3) parameterize atmospheric SOA formation by MW-building reactions of biogenic oxidation products. Likely reactions of biogenic oxidation products include ester, amide, and peroxyhemiacetal formation. Each of the proposed reactions involves known oxidation productions of biogenic precursors (e.g., carboxylic acids and aldehydes) reacting with one another and/or other atmospheric constituents (e.g., sulfuric acid and ammonia) to form higher-MW/lower-volatility products that can condense to form SOA. It has been suggested that products of MW-building reactions can revert to the parent reactants during sampling and analysis. Thus, relatively volatile compounds detected in ambient particle samples in fact may be decomposition products of higher-MW products. The contribution of relatively volatile biogenic oxidation products to SOA via ester, amide, and peroxyhemiacetal formation, as determined by studies based on fundamental thermodynamics and gas/particle partitioning theory, will be discussed; in addition to evidence for such reactions based on field measurements. Finally, while the role of MW-building reactions in contributing to existing SOA has been considered previously, the role of such reactions in OA nucleation events also will be addressed.

  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. Characterization of low-temperature vapour pressure estimates for secondary organic aerosol applications

    NASA Astrophysics Data System (ADS)

    Schnitzler, Elijah G.; McDonald, Karen M.

    2012-09-01

    Many models of secondary organic aerosol (SOA) formation, adhering to gas-particle equilibrium partitioning theory, require known vapour pressures for low volatility products of volatile organic compound (VOC) oxidation. Since the majority of such products have yet to be isolated and analysed, few experimental determinations of pertinent vapour pressures have been achieved, and models are forced to rely on vapour pressure estimates, such as those available through the common, computer-based SPARC and MPBPWIN property calculators. Thus, the accuracy of the respective estimation methods must be measured and evaluated, in order to determine the consequences in the resulting models. However, published evaluations, and most models themselves, typically focus on moderate to high ambient temperatures, which may not be applicable year-round in colder regions, where the rate of VOC oxidation slows, while the vapour pressures of the products decrease, indicating an increased tendency to condense into the aerosol phase. In this paper, the accuracy of the SPARC and MPBPWIN methods is evaluated over a broad temperature range, from 248.15 to 298.15 K, in five degree intervals using a test set of 45 compounds. The results are reported in terms of mean average error (MAE) and mean bias error (MBE), and given for alcohol, carboxylic acid, aldehyde, and ketone compound classes at each temperature. Specific trends in MAE and MBE with regard to compound class and changing temperature are discussed. More generally, the evaluation indicates that SPARC, with MAE decreasing from 0.288 at 248.15 K to 0.165 at 298.15 K and MBE increasing from -0.180 at 248.15 K to a peak of -0.081 at 293.15 K, is more accurate at low to moderate temperatures than MPBPWIN, with MAE decreasing from 0.436 at 248.15 K to 0.272 at 298.15 K and MBE increasing from -0.328 at 248.15 K to -0.213 at 298.15 K. Decreasing accuracy at lower temperatures emphasizes a need for focused experimental and model efforts in this temperature range.

  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. Investigation of a Particle into Liquid Sampler to Study the Formation & Ageing of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Munoz, A.; Vazquez, M.; Rodenas, M.; Vera, T.; Borrás, E.

    2012-12-01

    The atmospheric oxidation of Volatile Organic Compounds (VOCs) in the presence of NOx results in the formation of tropospheric ozone and Secondary Organic Aerosol (SOA) [Hallquist et al., 2009]. Whilst SOA is known to affect both climate and human health, the VOC oxidation pathways leading to SOA formation are poorly understood [Solomon et al., 2007]. This is in part due to the vast number and the low concentration of SOA species present in the ambient atmosphere. It has been estimated as many as 10,000 to 100,000 VOCs have been detected in the atmosphere, all of which can undergo photo-chemical oxidation and contribute to SOA formation [Goldstein and Galbally, 2007]. Atmospheric simulation chambers such as the EUropean PHOtoREactor (EUPHORE) in Valencia, Spain, are often used to study SOA formation from a single VOC precursor under controlled conditions. SOA composition and formation can be studied using online techniques such as Aerosol Mass Spectrometry (AMS), which provide high time resolution but limited structural information [Zhang et al., 2007]. Offline techniques, such as collection onto filters, extraction and subsequent analysis, provide detailed SOA composition but only usually one or two samples per experiment. In this work we report time resolved SOA composition analysis using a Particle into Liquid Sampler (PILS) followed by Liquid Chromatography Ion-Trap Mass Spectrometry (LC-IT-MS/MS) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS/MS). Experiments were performed at EUPHORE investigating the formation and composition of Methyl Chavicol SOA. Methyl Chavicol (also known as Estragole) was identified as the highest floral emission from an oil palm plantation in Malaysian Borneo and has also been observed in US pine forests [Bouvier-Brown et al., 2009; Misztal et al., 2010]. Previous studies indicate a high SOA yield from Methyl Chavicol at around 40 % [Lee et al., 2006], however currently there have been very few literature reports of the atmospheric degradation of Methyl Chavicol. Methyl Chavicol oxidation was investigated using a series of photosmog and ozonolysis experiments with varying ratios of NOx:VOC. An extensive range of instruments were used to monitor radical and product formation [including: LIF (HOx intermediates), LOPAP (HONO), FT-IR, PTR-MS, GC-FID, and SMPS]. Samples were collected using the PILS at 30 minute intervals with filters taken at the end of each experiment for comparison. A number of key oxidation products have been identified. Time profiles can be used to determine the importance of first, second & higher oxidation products and may indicate which species are undergoing oxidation or heterogeneous reactions during aerosol ageing. This data will allow for modelled vs. measured SOA composition comparison, with the potential to determine the rates of reactions for the condensed phase oxidation products formed. References Bouvier-Brown et al., Atmos. Chem. Phys. 9, 2061-2074, 2009. Goldstein and Galbally, Environ. Sci. Technol. 41, 1514-1521, 2007. Hallquist et al., Atmos. Chem. Phys. 9, 5155-5236, 2009. Lee et al., J. Geophys. Res. 111, D17305, 2006. Misztal et al., Atmos. Chem. Phys. Discuss. 10, 1517-1557, 2010. Solomon et al., Climate Change 2007: IPCC Report. Cambridge, 2007. Zhang et al., Geophys. Res. Lett. 34, L13801, 2007.

  8. Understanding the anthropogenic influence on formation of biogenic secondary organic aerosols via analysis of organosulfates and related oxidation products

    NASA Astrophysics Data System (ADS)

    Nguyen, Q. T.; Christensen, M. K.; Cozzi, F.; Zare, A.; Hansen, A. M. K.; Kristensen, K.; Tulinius, T. E.; Madsen, H. H.; Christensen, J. H.; Brandt, J.; Massling, A.; Nøjgaard, J. K.; Glasius, M.

    2014-01-01

    Anthropogenic emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx) may affect concentration levels and composition of biogenic secondary organic aerosols (BSOA) through photochemical reactions with biogenic organic precursors to form organosulfates and nitrooxy organosulfates. We investigated this influence in a field study from 19 May-22 June 2011 at two sampling sites in Denmark. Within the study, we identified a substantial number of organic acids, organosulfates and nitrooxy organosulfates in the ambient urban curbside and semi-rural background air. A high degree of correlation in concentrations was found among a group of specific organic acids, organosulfates and nitrooxy organosulfates, which may originate from various precursors, suggesting a common mechanism or factor affecting their concentration levels at the sites. It was proposed that the formation of those species most likely occurred on a larger spatial scale with the compounds being long-range transported to the sites on the days with highest concentrations. The origin of the long-range transported aerosols was investigated using the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model in addition to modeled emissions of related precursors including isoprene and monoterpenes using the global Model of Emissions of Gases and Aerosols from Nature (MEGAN) and SO2 emissions using the European Monitoring and Evaluation Program (EMEP) database. The local impacts were also studied by examining the correlation between selected species which showed significantly enhanced concentrations at the urban curbside site and the local concentrations of various gases including SO2, ozone (O3), carbon monoxide (CO), NOx, aerosol acidity and other meteorological conditions. This investigation showed that an inter-play of the local parameters such as the aerosol acidity, NOx, relative humidity (RH), temperature and global radiation seemed to influence the concentration level of those species, via such as wet aerosol chemistry. The local impacts however seemed minor on the concentration levels of the studied compounds. The total concentrations of organosulfates and nitrooxy organosulfates contributed to approximately 0.7% of PM1 mass.

  9. 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.

  10. 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.

  11. Secondary organic aerosol formation from ozone reactions with single terpenoids and terpenoid mixtures

    NASA Astrophysics Data System (ADS)

    Waring, Michael S.; Wells, J. Raymond; Siegel, Jeffrey A.

    2011-08-01

    Ozone reacts with indoor-emitted terpenoids to form secondary organic aerosol (SOA). Most SOA research has focused on ozone reactions with single terpenoids or with consumer products, and this paper reports the results from an investigation of SOA formation from ozone reactions with both single terpenoids and mixtures of D-limonene, ?-pinene, and ?-terpineol. Transient experiments were conducted at low (25 ppb) and high (100 ppb) initial concentrations of ozone. The three terpenoids were tested singly and in combinations in a manner that controlled for their different reaction rates with ozone. The SOA formation was assessed by examining the evolution in time of the resulting number size-distributions and estimates of the mass concentrations. The results suggest that at higher ozone and terpenoid concentrations, SOA number formation follows a linear trend as a function of the initial rate of reaction. This finding was valid for both single terpenoids and mixtures. Generally speaking, higher ozone and terpenoid concentrations also led to larger geometric mean diameters and smaller geometric standard deviations of fitted lognormal distributions of the formed SOA. By assuming a density, mass concentrations were also assessed and did not follow as consistent of a trend. At low ozone concentration conditions, reactions with only D-limonene yielded the largest number concentrations of any experiment, even more than experiments with mixtures containing D-limonene and much higher overall terpenoid concentrations. This finding was not seen for high ozone concentrations. These experiments demonstrate quantifiable trends for SOA forming reactions of ozone and mixtures, and this work provides a framework for expanding these results to more complex mixtures and consumer products.

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

    NASA Astrophysics Data System (ADS)

    Kleeman, Michael J.; Ying, Qi; Lu, Jin; Mysliwiec, Mitchel J.; Griffin, Robert J.; Chen, Jianjun; Clegg, Simon

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

  13. 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.

  14. 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

  15. Physico-chemical characterization of secondary organic aerosol derived from catechol and guaiacol as a model substance for atmospheric humic-like substances

    NASA Astrophysics Data System (ADS)

    Ofner, J.; Krüger, H.-U.; Grothe, H.; Schmitt-Kopplin, P.; Whitmore, K.; Zetzsch, C.

    2010-07-01

    Secondary organic aerosol was produced from the aromatic precursors catechol and guaiacol by reaction with ozone in the presence and absence of simulated sunlight and humidity and investigated for its properties as a proxy for humic-like substances (HULIS). Beside a small particle size, a relatively low molecular weight and typical optical features in the UV/VIS spectral range, HULIS contain a typical aromatic and/or olefinic chemical structure and highly oxidized functional groups within a high chemical diversity. Various methods were used to characterize the secondary organic aerosols obtained: Fourier transform infrared spectroscopy (FTIR) demonstrated the formation of different carbonyl containing functional groups as well as structural and functional differences between aerosols formed at different environmental conditions. UV/VIS spectroscopy of filter samples showed that the particulate matter absorbs far into the visible range up to more than 500 nm. Ultrahigh resolved mass spectroscopy (ICR-FT/MS) determined O/C-ratios between 0.3 and 1 and main molecular weights between 200 and 500 Da. Temperature-programmed-pyrolysis mass spectroscopy identified carboxylic acids and lactones as major functional groups. Particle sizing using CNC-DMPS demonstrated the formation of small particles during a secondary organic aerosol formation process. Particle imaging using field-emission-gun scanning electron microscopy (FEG-SEM) showed spherical particles, forming clusters and chains. Hence, secondary organic aerosols from catechol and guaiacol are appropriate model substances for studies of the processing of aromatic secondary organic aerosols and atmospheric HULIS on the laboratory scale.

  16. 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.

  17. 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.

    2014-05-01

    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 (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm-3 h of OH exposure). 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 photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11-15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear 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 timescale of these experiments, the mixture of organic vapors emitted by newer vehicles appears to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the nonmethane 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. By comparing this study with a companion study of diesel trucks, we conclude that both primary PM emissions and SOA production for light-duty gasoline vehicles are much greater than for late-model (2007 and later) on-road heavy-duty diesel trucks.

  18. Effects of alkylate fuel on exhaust emissions and secondary aerosol formation of a 2-stroke and a 4-stroke scooter

    NASA Astrophysics Data System (ADS)

    Zardini, Alessandro A.; Platt, Stephen M.; Clairotte, Michael; El Haddad, Imad; Temime-Roussel, Brice; Marchand, Nicolas; Ježek, Irena; Drinovec, Luka; Mo?nik, Griša; Slowik, Jay G.; Manfredi, Urbano; Prévôt, André S. H.; Baltensperger, Urs; Astorga, Covadonga

    2014-09-01

    Regulated and unregulated emissions from a 2-stroke and a 4-stroke scooter were characterized during a legislative driving cycle in a certified laboratory. Scooter exhaust was analyzed at the tailpipe, in a dilution tunnel, and partly collected in a mobile smog chamber for photochemical ageing. We present evidence that the photochemically aged exhaust from a 2-stroke and a 4-stroke scooter produces considerable amounts of secondary organic aerosol: from 1.5 to 22.0 mg/km, and from 5.5 to 6.6 mg/km, respectively. Tests were repeated after replacing the standard petrol and synthetic lube oil with an alkylate fuel (with low content of aromatic compounds) and ultra-clean lube oil (low ash forming potential). We observed emission reduction (with some exceptions) for several gaseous and particulate phase species, in particular for carbon monoxide (from 8% up to 38% and from 31% to 50%, for the 2-stroke and the 4-stroke scooters, respectively), particulate mass (from 32% up to 75% for the 2-stroke scooter), aromatic compounds (89% and 97% for the 2-stroke and the 4-stroke scooter, respectively), and secondary organic aerosol (from 87% to 100% and 99% for the 2-stroke and the 4-stroke scooters, respectively). We attribute the organic aerosol reduction to the low content of aromatics in the alkylate fuel.

  19. Formation of brown carbon via reactions of ammonia with secondary organic aerosols from biogenic and anthropogenic precursors

    NASA Astrophysics Data System (ADS)

    Updyke, Katelyn M.; Nguyen, Tran B.; Nizkorodov, Sergey A.

    2012-12-01

    Filter samples of secondary organic aerosols (SOA) generated from the ozone (O3)- and hydroxyl radical (OH)-initiated oxidation of various biogenic (isoprene, ?-pinene, limonene, ?-cedrene, ?-humulene, farnesene, pine leaf essential oils, cedar leaf essential oils) and anthropogenic (tetradecane, 1,3,5-trimethylbenzene, naphthalene) precursors were exposed to humid air containing approximately 100 ppb of gaseous ammonia (NH3). Reactions of SOA compounds with NH3 resulted in production of light-absorbing "brown carbon" compounds, with the extent of browning ranging from no observable change (isoprene SOA) to visible change in color (limonene SOA). The aqueous phase reactions with dissolved ammonium (NH4+) salts, such as ammonium sulfate, were equally efficient in producing brown carbon. Wavelength-dependent mass absorption coefficients (MAC) of the aged SOA were quantified by extracting known amounts of SOA material in methanol and recording its UV/Vis absorption spectra. For a given precursor, the OH-generated SOA had systematically lower MAC compared to the O3-generated SOA. The highest MAC values, for brown carbon from SOA resulting from O3 oxidation of limonene and sesquiterpenes, were comparable to MAC values for biomass burning particles but considerably smaller than MAC values for black carbon aerosols. The NH3/NH4+ + SOA brown carbon aerosol may contribute to aerosol optical density in regions with elevated concentrations of NH3 or ammonium sulfate and high photochemical activity.

  20. 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.

  1. MODELING THE FORMATION OF SECONDARY ORGANIC AEROSOL WITHIN A COMPREHENSIVE AIR QUALITY MODEL SYSTEM

    EPA Science Inventory

    The aerosol component of the CMAQ model is designed to be an efficient and economical depiction of aerosol dynamics in the atmosphere. The approach taken represents the particle size distribution as the superposition of three lognormal subdistributions, called modes. The proces...

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  3. 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.

  4. 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.

  5. Organic and inorganic aerosol compositions in Ulaanbaatar, Mongolia, during the cold winter of 2007 to 2008: Dicarboxylic acids, ketocarboxylic acids, and ?-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Jung, Jinsang; Tsatsral, Batmunkh; Kim, Young J.; Kawamura, Kimitaka

    2010-11-01

    To investigate the distributions and sources of water-soluble organic acids in the Mongolian atmosphere, aerosol samples (PM2.5, n = 34) were collected at an urban site (47.92°N, 106.90°E, ˜1300 m above sea level) in Ulaanbaatar, the capital of Mongolia, during the cold winter. The samples were analyzed for water-soluble dicarboxylic acids (C2-C12) and related compounds (ketocarboxylic acids and ?-dicarbonyls), as well as organic carbon (OC), elemental carbon, water-soluble OC, and inorganic ions. Distributions of dicarboxylic acids and related compounds were characterized by a predominance of terephthalic acid (tPh; 130 ± 51 ng m-3, 19% of total detected organic acids) followed by oxalic (107 ± 28 ng m-3, 15%), succinic (63 ± 20 ng m-3, 9%), glyoxylic (55 ± 18 ng m-3, 8%), and phthalic (54 ± 27 ng m-3, 8%) acids. Predominance of terephthalic acid, which has not been reported previously in atmospheric aerosols, was mainly due to uncontrolled burning of plastic bottles and bags in home stoves for heating and waste incineration during the cold winter. This study demonstrated that most of the air pollutants were directly emitted from local sources such as heat and power plants, home stoves, and automobiles. Development of an inversion layer (<700 m above ground level) over the basin of Ulaanbaatar accelerated the accumulation of pollutants, causing severe haze episodes during the winter season.

  6. 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

    2013-04-01

    Terrestrial vegetation releases a great variety of volatile organic compounds (VOC) into the atmosphere. Monoterpenes, like myrcene, contribute significantly to this global biogenic VOC emission. In the atmosphere, monoterpenes rapidly undergo oxidation reactions by OH radicals (mainly during the daytime), NO3 radicals (mainly during the nighttime) and O3 to form multifunctional oxidation products. The products of these reactions are likely to be of low volatility and hence might lead to secondary organic aerosol (SOA) formation. In the present study, we report results from a series of chamber experiments performed in the LEAK chamber at TROPOS in which the gas-phase products and SOA yields obtained from myrcene O3 reactions with and without an OH radical scavenger as well as from the myrcene OH radical reaction in the presence of NOx have been measured. During the experiments the consumption of myrcene as well as the formation of gas-phase products was monitored using a proton transfer reaction mass spectrometer (PTR-MS). Ozone concentration was measured by an O3 monitor and the mixing ratios of nitrogen oxides were measured by a NOx monitor. Particle size distributions between 3-900 nm were monitored every 11 min using a differential mobility particle sizer (DMPS) system. In addition to the products observed by means of the PTR-MS by their m/z values, an identification of carbonylic compounds by their DNPH derivatives was performed. Beside low molecular mass products the formation of 4-vinyl-4-pentenal with a yield of 55 % in myrcene ozonolysis has been observed. The further oxidation of this major first generation product lead to the formation of two dicarbonylic products with m/z 113 and to SOA formation. The influence of the continuing oxidation of 4-vinyl-4-pentenal on SOA formation will be discussed in detail. The emergence of the gas-phase product hydroxyacetone as direct result of the myrcene ozone reaction will be mooted, because hydroxyacetone seems to be formed directly from the Criegee radical (dimethyl carbonyl oxide). Such an rearrangement of a Criegee radical is different from the currently discussed reaction pathways.

  7. Secondary organic aerosol formation during evaporation of droplets containing atmospheric aldehydes, amines, and ammonium sulfate.

    PubMed

    Galloway, Melissa M; Powelson, Michelle H; Sedehi, Nahzaneen; Wood, Stephanie E; Millage, Katherine D; Kononenko, Julia A; Rynaski, Alec D; De Haan, David O

    2014-12-16

    Reactions of carbonyl compounds in cloudwater produce organic aerosol mass through in-cloud oxidation and during postcloud evaporation. In this work, postcloud evaporation was simulated in laboratory experiments on evaporating droplets that contain mixtures of common atmospheric aldehydes with ammonium sulfate (AS), methylamine, or glycine. Aerosol diameters were measured during monodisperse droplet drying experiments and during polydisperse droplet equilibration experiments at 75% relative humidity, and condensed-phase mass was measured in bulk thermogravimetric experiments. The evaporation of water from a droplet was found to trigger aldehyde reactions that increased residual particle volumes by a similar extent in room-temperature experiments, regardless of whether AS, methylamine, or glycine was present. The production of organic aerosol volume was highest from droplets containing glyoxal, followed by similar production from methylglyoxal or hydroxyacetone. Significant organic aerosol production was observed for glycolaldehyde, acetaldehyde, and formaldehyde only at elevated temperatures in thermogravimetric experiments. In many experiments, the amount of aerosol produced was greater than the sum of all solutes plus nonvolatile solvent impurities, indicating the additional presence of trapped water, likely caused by increasing aerosol-phase viscosity due to oligomer formation. PMID:25409489

  8. Secondary Organic Aerosol from On- and Off-Road Combustion Emissions: Scientific and Policy Perspectives

    NASA Astrophysics Data System (ADS)

    Gordon, Timothy D.

    Combustion emissions from on-road sources such as light duty gasoline vehicles (LDGV), medium duty diesel vehicles (MDDV) and heavy duty diesel vehicles (HDDV) as well as small off-road engines (SORE) such those used in lawn and garden equipment are a major source of fine particulate matter (PM) pollution in the ambient atmosphere. Existing regulations have restricted direct PM emissions, especially for on-road sources; however, recent studies suggest that organic PM formed from the photo-oxidation of gaseous precursor emissions—so-called secondary organic aerosol (SOA)—contributes at least as much to the overall PM burden as PM "emitted from the tailpipe." A major limitation of many of these studies is that they attempt to induce from the behavior of simple emission surrogates (e.g., vaporized whole fuel) the behavior of actual combustion emissions from real world sources. This research investigates combustion emissions directly. The primary gas- and particle-phase emissions, SOA production and SOA yields from a range of different on-road and off-road combustion sources were characterized. LDGV, MDDV and HDDV were driven on chassis dynamometers over realistic, urban driving cycles. Off-road sources, including 2- and 4-stroke lawn and garden equipment and a diesel transportation refrigeration unit were tested using engine dynamometers operated over certification cycles. For nearly all gasoline engines (LDGV and SOREs), photo-oxidizing dilute combustion emissions for 3 hours produced at least as much SOA as the directly emitted primary PM. SOA increased net PM production for LDGV by a factor of 1-10, depending on the vehicle emission standard. SOA yields were found to increase with newer vehicles, which have lower primary emissions. SOA for diesel vehicles, while still large on an absolute basis, was a smaller fraction of the primary PM emissions (between 10-30%), due to the very high elemental carbon (EC) emissions from vehicles without diesel particulate filters (DPF). Aftertreatment systems utilizing a DPF and a diesel oxidation catalyst essentially eliminated primary PM and SOA. Among the off-road sources, SOA from 2-stroke emissions increased the net PM by roughly a factor of 2. Primary emission and SOA production factors from the various combustion sources tested in this work were combined with fuel consumption data for California's South Coast Air Basin (SoCAB) to determine the impact on the aggregate PM from on- and off-road sources in the region. These estimated impacts were compared to the PM values derived from the regulatory models EMFAC and OFFROAD. Our data indicate that PM from on-road gasoline sources is significantly under-represented by existing emissions models due to the dominant role of SOA. When SOA production is included, newer LDGV are one of the largest sources of PM in SoCAB. Furthermore, LDGV will become an even more important PM source once existing regulations requiring DPF retrofits on both on- and off-road diesel sources are implemented over the next few years. While on-road diesel vehicles are currently an important source of PM based on total fuel consumption, LDGV are responsible for a larger fraction of total PM. The primary and secondary PM contribution of off-road sources also appear to be high, but the magnitude remains highly uncertain, pending further experimental data. Evidence is presented that suggests that existing models may dramatically overpredict primary PM emissions from off-road sources. Regulators are strongly urged to consider the impact of SOA on net PM production.

  9. Seasonal variation of secondary organic aerosol in Nam Co, Central Tibetan Plateau

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Secondary organic aerosol (SOA) affects the earth's radiation balance and global climate. High-elevation areas are sensitive to global climate change. However, at present, SOA origins and seasonal variations are understudied in remote high-elevation areas. In this study, particulate samples were collected from July 2012 to July 2013 at the remote Nam Co (NC) site, Central Tibetan Plateau and analyzed for SOA tracers from biogenic (isoprene, monoterpenes and ?-caryophyllene) and anthropogenic (aromatics) precursors. Among these compounds, isoprene SOA (SOAI) tracers represented the majority (26.6 ± 44.2 ng m-3), followed by monoterpene SOA (SOAM) tracers (0.97 ± 0.57 ng m-3), aromatic SOA (SOAA) tracer (2,3-dihydroxy-4-oxopentanoic acid, DHOPA, 0.25 ± 0.18 ng m-3) and ?-caryophyllene SOA tracer (?-caryophyllenic acid, 0.09 ± 0.10 ng m-3). SOAI tracers exhibited high concentrations in the summer and low levels in the winter. The similar temperature dependence of SOAI tracers and isoprene emission suggested that the seasonal variation of SOAI at the NC site was mainly influenced by isoprene emission. The ratio of high-NOx to low-NOx products of isoprene (2-methylglyceric acid to 2-methyltetrols) was the highest in the winter and the lowest in the summer, due to the influence of temperature and relative humidity. The seasonal variation of SOAM tracers was impacted by monoterpenes emission and tracers partitioning. The similar temperature dependence of SOAM tracers and monoterpenes emission was only observed during winter to spring. SOAM tracer levels did not elevate with increased temperature in the summer, probably resulting from the counteraction of temperature effects on gas/particle partitioning and monoterpenes emission. The concentrations of DHOPA were 1-2 orders of magnitude lower than those reported in the urban regions of the world. Due to the transport of air pollutants from the adjacent Bangladesh and the eastern India, DHOPA presented relatively higher levels in the summer. In the winter when air masses mainly came from the northwestern India, mass fractions of DHOPA in total tracers increased, although its concentrations declined. The SOA-tracer method was applied to estimated secondary organic carbon (SOC) from these four precursors. The annual average of SOC was 0.22 ± 0.29 ?g C m-3, with the biogenic SOC (sum of isoprene, monoterpenes and ?-caryophyllene) accounting for 75%. In the summer, isoprene was the major precursor with its SOC contributions of 81%. In the winter when the emission of biogenic precursors largely dropped, the contributions of aromatic SOC increased. Our study implies that anthropogenic pollutants emitted in the Indian subcontinent could transport to the TP and have impact on SOC over the remote NC.

  10. Secondary organic aerosol formation from photo-oxidation of unburned fuel: experimental results and implications for aerosol formation from combustion emissions.

    PubMed

    Jathar, Shantanu H; Miracolo, Marissa A; Tkacik, Daniel S; Donahue, Neil M; Adams, Peter J; Robinson, Allen L

    2013-11-19

    We conducted photo-oxidation experiments in a smog chamber to investigate secondary organic aerosol (SOA) formation from eleven different unburned fuels: commercial gasoline, three types of jet fuel, and seven different diesel fuels. The goals were to investigate the influence of fuel composition on SOA formation and to compare SOA production from unburned fuel to that from diluted exhaust. The trends in SOA production were largely consistent with differences in carbon number and molecular structure of the fuel, i.e., fuels with higher carbon numbers and/or more aromatics formed more SOA than fuels with lower carbon numbers and/or substituted alkanes. However, SOA production from different diesel fuels did not depend strongly on aromatic content, highlighting the important contribution of large alkanes to SOA formation from mixtures of high carbon number (lower volatility) precursors. In comparison to diesels, SOA production from higher volatility fuels such as gasoline appeared to be more sensitive to aromatic content. On the basis of a comparison of SOA mass yields (SOA mass formed per mass of fuel reacted) and SOA composition (as measured by an aerosol mass spectrometer) from unburned fuels and diluted exhaust, unburned fuels may be reasonable surrogates for emissions from uncontrolled engines but not for emissions from engines with after treatment devices such as catalytic converters. PMID:24144104

  11. Investigation of isoprene OH initiated photo-oxidation mechanism and Secondary Organic Aerosol formation in presence of high nitrogen oxide

    NASA Astrophysics Data System (ADS)

    Elezi, Altin

    It is now well recognized that a wide variety of volatile organic compounds (VOCs) are emitted into the atmosphere from both biogenic and anthropogenic sources. Isoprene is the most abundant BVOCs in regional and global scale, emitted mainly from vegetation. The purpose of this work was to investigate isoprene OH initiated photo-oxidation mechanism and Secondary Organic Aerosol (SOA) formed during Smog Chamber experiments, in presence of high NOx level. The gas phase products of isoprene oxidation are analyzed using Ion Trap-Time Of Flight Mass Spectrometer. We used "de-synthesis of spectra" approach to separate the mass spectra for individual components. This enabled us to follow all major reaction products in course of experiment, quantify yields and calculate rate constant for MVK and MACR. Our experiments showed that photo-oxidation of isoprene leads to SOA formation but over delayed timescale. The role of methacrolein as an intermediate to aerosol formation is discussed and quantified. The contribution of methacrolein to total volume of aerosol formed is estimated to be 2% to 21%, which represents a small fraction of total volume formed and suggests that other contributors and pathways should be considered and elaborated. The role of hydroxycarbonyl compounds and their likely role in forming particulate matter is also investigated and discussed.

  12. Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds

    NASA Astrophysics Data System (ADS)

    Carlton, Annmarie G.; Turpin, Barbara J.; Lim, Ho-Jin; Altieri, Katye E.; Seitzinger, Sybil

    2006-03-01

    Aqueous-phase oxidation (in clouds and aerosols) is a potentially important source of organic aerosol and could explain the atmospheric presence of oxalic acid. Methylglyoxal, a water-soluble product of isoprene, oxidizes further in the aqueous phase to pyruvic acid. Discrepancies in the literature regarding the aqueous-phase oxidation of pyruvic acid create large uncertainties in the in-cloud yields of secondary organic aerosol (SOA) and oxalic acid. Resolving the fate of aqueous-phase pyruvic acid is critical to understanding SOA formation through cloud processing of water-soluble products of isoprene, other alkenes and aromatics. In this work, aqueous-phase photochemical reactions of pyruvic acid and hydrogen peroxide at pH values typical of clouds were conducted and demonstrated that photochemical oxidation of pyruvic acid yields glyoxylic, oxalic, acetic and formic acids. Oxalic and glyoxylic acids remain mostly in the particle phase upon droplet evaporation. Thus isoprene is an important precursor of in-cloud SOA formation.

  13. 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).

  14. Variations in atmospheric PM trace metal content in Spanish towns: Illustrating the chemical complexity of the inorganic urban aerosol cocktail

    Microsoft Academic Search

    Teresa Moreno; Xavier Querol; Andrés Alastuey; Mar Viana; Pedro Salvador; Ana Sánchez de la Campa; Begoña Artiñano; Jesús de la Rosa; Wes Gibbons

    2006-01-01

    The majority of the Spanish urban population breathe air containing inhalable ambient airborne particles at average concentrations of 30–46?gm?3 (PM10) and 20–30?gm?3 (PM2.5). Even though the average weight of inhaled urban aerosol is commonly similar, however, there can be large chemical differences between the ambient dusts from different towns, including the more bioreactive elements such as some metals. In this

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

    NASA Astrophysics Data System (ADS)

    Northcross, Amanda L.; Jang, Myoseon

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

  16. 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.

  17. One-year observations of size distribution characteristics of major aerosol constituents at a coastal receptor site in Hong Kong - Part 1: Inorganic ions and oxalate

    NASA Astrophysics Data System (ADS)

    Bian, Q.; Huang, X. H. H.; Yu, J. Z.

    2014-01-01

    Size distribution data of major aerosol constituents are essential in source apportioning of visibility degradation, testing and verification of air quality models incorporating aerosols. We report here one-year observations of mass size distributions of major inorganic ions (sulfate, nitrate, chloride, ammonium, sodium, potassium, magnesium and calcium) and oxalate at a coastal suburban receptor site in Hong Kong, China. A total of 43 sets of size segregated samples in the size range of 0.056-18 ?m were collected from March 2011 to February 2012. The size distributions of sulfate, ammonium, potassium and oxalate were characterized by a dominant droplet mode with a mass mean aerodynamic diameter (MMAD) in the range of ~0.7-0.9 ?m. Oxalate had a slightly larger MMAD than sulfate on days with temperatures above 22 °C as a result of the process of volatilization and repartitioning. Nitrate was mostly dominated by the coarse mode but enhanced presence in fine mode was detected on winter days with lower temperature and lower concentrations of sea salt and soil particles. This data set reveals an inversely proportional relationship between the fraction of nitrate in the fine mode and product of the sum of sodium and calcium in equivalent concentrations and the dissociation constant of ammonium nitrate (i.e., (1/[Na+] + 2[Ca2+]) × (1/Ke')). The seasonal variation observed for sea salt aerosol abundance, with lower values in summer and winter, is possibly linked with the lower marine salinities in these two seasons. Positive matrix factorization was applied to estimate the relative contributions of local formation and transport to the observed ambient sulfate level through the use of the combined datasets of size-segregated sulfate and select gaseous air pollutants. On average, the regional/super-regional transport of air pollutants was the dominant source at this receptor site, especially on high sulfate days, while local formation processes contributed approximately 30% of the total sulfate. This work provides field measurement-based evidence for importance of understanding both local photochemistry and regional/super-regional transport in order to properly simulate sulfate aerosols in air quality models.

  18. One-year observations of size distribution characteristics of major aerosol constituents at a coastal receptor site in Hong Kong - Part 1: Inorganic ions and oxalate

    NASA Astrophysics Data System (ADS)

    Bian, Q.; Huang, X. H. H.; Yu, J. Z.

    2014-09-01

    Size distribution data of major aerosol constituents are essential in source apportioning of visibility degradation, testing and verification of air quality models incorporating aerosols. We report here 1-year observations of mass size distributions of major inorganic ions (sulfate, nitrate, chloride, ammonium, sodium, potassium, magnesium and calcium) and oxalate at a coastal suburban receptor site in Hong Kong, China. A total of 43 sets of size-segregated samples in the size range of 0.056-18 ?m were collected from March 2011 to February 2012. The size distributions of sulfate, ammonium, potassium and oxalate were characterized by a dominant droplet mode with a mass mean aerodynamic diameter (MMAD) in the range of ~ 0.7-0.9 ?m. Oxalate had a slightly larger MMAD than sulfate on days with temperatures above 22 °C as a result of the process of volatilization and repartitioning. Nitrate was mostly dominated by the coarse mode but enhanced presence in fine mode was detected on winter days with lower temperature and lower concentrations of sea salt and soil particles. This data set reveals an inversely proportional relationship between the fraction of nitrate in the fine mode and product of the sum of sodium and calcium in equivalent concentrations and the dissociation constant of ammonium nitrate (i.e., (1/([Na+] + 2[Ca2+]) × (1/Ke')) when Pn_fine is significant (> 10%). The seasonal variation observed for sea salt aerosol abundance, with lower values in summer and winter, is possibly linked with the lower marine salinities in these two seasons. Positive matrix factorization was applied to estimate the relative contributions of local formation and transport to the observed ambient sulfate level through the use of the combined data sets of size-segregated sulfate and select gaseous air pollutants. On average, the regional/super-regional transport of air pollutants was the dominant source at this receptor site, especially on high-sulfate days while local formation processes contributed approximately 30% of the total sulfate. This work provides field-measurement-based evidence important for understanding both local photochemistry and regional/super-regional transport in order to properly simulate sulfate aerosols in air quality models.

  19. 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.

  20. Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol (MBO) Photooxidation: Evidence for Acid-Catalyzed Reactive Uptake of Epoxide

    NASA Astrophysics Data System (ADS)

    Surratt, J. D.; Zhang, H.; Worton, D. R.; Lewandowski, M.; Ortega, J.; Zhang, Z.; Lin, Y.; Park, J.; Kristensen, K.; Bhathela, N.; Campuzano-Jost, P.; Day, D. A.; Jimenez, J. L.; Jaoui, M.; Offenberg, J. H.; Kleindienst, T. E.; Gilman, J. B.; De Gouw, J. A.; Park, C.; Schade, G. W.; Frossard, A. A.; Russell, L. M.; Kaser, L.; Jud, W.; Hansel, A.; Karl, T.; Glasius, M.; Gold, A.; Seinfeld, J.; Guenther, A. B.

    2012-12-01

    2-methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied aerosol acidity levels. Results indicate SOA was enhanced with increasing aerosol acidity especially under low-NO conditions. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C5H12O6S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. This organosulfate species was also observed and correlated with aerosol acidity from ambient fine aerosol (PM2.5) samples that were collected from different field campaigns where MBO emissions are important, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Importantly, this compound can account for as high as 1% of the total organic aerosol mass in the atmosphere. It is hypothesized that MBO epoxide generated under low-NO conditions is the precursor to MBO SOA based upon the above results. Thus, the MBO epoxide was synthesized in high purity to investigate its potential to form SOA via reactive uptake in a series of controlled dark chamber studies. Our results suggest the MBO epoxide substantially forms SOA only in the presence of acidic seed aerosols. The chemical characterization results of the SOA constituents are consistent with field measurements in terms of the major SOA tracers.

  1. Gas phase precursors to anthropogenic secondary organic aerosol: Using the Master Chemical Mechanism to probe detailed

    E-print Network

    hydrocarbons Chemical ionisation reaction time-of-flight mass spectrometry a b s t r a c t A detailed gas-phase photochemical chamber box model, incorporating the Master Chemical Mechanism (MCMv3.1) degradation scheme during a series of aerosol chamber experiments in order to evaluate the mechanism under a variety of VOC

  2. 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...

  3. 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...

  4. 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

  5. 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

  6. GROWTH LAWS FOR THE FORMATION OF SECONDARY AMBIENT AEROSOLS: IMPLICATIONS FOR CHEMICAL CONVERSION MECHANISMS

    EPA Science Inventory

    The evolution of aerosol size distributions growing by gas-to-particle conversion has been observed recently in field and laboratory studies. A technique for extracting particle diameter growth rates from such data is presented. The functional dependence of these growth rates on ...

  7. Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of

    E-print Network

    Silver, Whendee

    19, 2012 (received for review July 22, 2012) Emissions from gasoline and diesel vehicles composition, mass distribu- tion, and organic aerosol formation potential of emissions from gasoline these emissions from gasoline and diesel vehicles is central to air quality mitigation policies in urban areas (2

  8. 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

  9. 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.

  10. Organic aerosols and inorganic species from post-harvest agricultural-waste burning emissions over northern India: impact on mass absorption efficiency of elemental carbon.

    PubMed

    Rajput, Prashant; Sarin, M M; Sharma, Deepti; Singh, Darshan

    2014-10-01

    Atmospheric PM2.5 (particulate matter with aerodynamic diameter of ? 2.5 ?m), collected from a source region [Patiala: 30.2 °N; 76.3 °E; 250 m above mean sea level] of emissions from post-harvest agricultural-waste (paddy-residue) burning in the Indo-Gangetic Plain (IGP), North India, has been studied for its chemical composition and impact on regional atmospheric radiative forcing. On average, organic aerosol mass accounts for 63% of PM2.5, whereas the contribution of elemental carbon (EC) is ?3.5%. Sulphate, nitrate and ammonium contribute up to ?85% of the total water-soluble inorganic species (WSIS), which constitutes ?23% of PM2.5. The potassium-to-organic carbon ratio from paddy-residue burning emissions (KBB(+)/OC: 0.05 ± 0.01) is quite similar to that reported from Amazonian and Savanna forest-fires; whereas non-sea-salt-sulphate-to-OC ratio (nss-SO4(2-)/OC: 0.21) and nss-SO4(2-)/EC ratio of 2.6 are significantly higher (by factor of 5 to 8). The mass absorption efficiency of EC (3.8 ± 1.3 m(2) g(-1)) shows significant decrease with a parallel increase in the concentrations of organic aerosols and scattering species (sulphate and nitrate). A cross plot of OC/EC and nss-SO4(2-)/EC ratios show distinct differences for post-harvest burning emissions from paddy-residue as compared to those from fossil-fuel combustion sources in south-east Asia. PMID:25124269

  11. 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).

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  14. 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....

  15. Variations in atmospheric PM trace metal content in Spanish towns: Illustrating the chemical complexity of the inorganic urban aerosol cocktail

    NASA Astrophysics Data System (ADS)

    Moreno, Teresa; Querol, Xavier; Alastuey, Andrés; Viana, Mar; Salvador, Pedro; Sánchez de la Campa, Ana; Artiñano, Begoña; de la Rosa, Jesús; Gibbons, Wes

    The majority of the Spanish urban population breathe air containing inhalable ambient airborne particles at average concentrations of 30-46 ?g m -3 (PM 10) and 20-30 ?g m -3 (PM 2.5). Even though the average weight of inhaled urban aerosol is commonly similar, however, there can be large chemical differences between the ambient dusts from different towns, including the more bioreactive elements such as some metals. In this context, we compare the source-apportioned trace metal content of airborne PM 10 and PM 2.5 collected daily over a 1-year period from six population centres in Spain: Barcelona, Alcobendas, Llodio, Huelva, Tarragona and Las Palmas de Gran Canaria. Total average trace metal (?TM) PM 10 and PM 2.5 contents vary by up to a factor of around 3, reaching a maximum of ?TM 10 811 ng m -3 and ?TM 2.5 503 ng m -3 at Llodio, an industrial but humid site with the lowest PM 10 mass levels but high contamination by Zn, Pb, Mn, Sn, Ni and Cr. In contrast, pollution at Huelva, although another industrially influenced site, instead emphasises Cu and As, whereas Barcelona, where traffic emissions and resuspension contribute to some of the highest average PM 10 levels in Spain, has unusually raised levels of Ti, V and Ba. Such variations in both daily and annual average PM bulk chemistry, particularly in potentially toxic trace metals concentrated in the finer aerosols (such as Cd, As, Pb, Hg and Ni), predict that PM health effects on resident populations from different towns are unlikely to be the same.

  16. Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: comparing laboratory and field studies

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Fuller, S. J.; Giorio, C.; Healy, R. M.; Wilson, E.; O'Connor, I. P.; Wenger, J. C.; McLeod, M.; Aalto, J.; Ruuskanen, T. M.; Maenhaut, W.; Jones, R.; Venables, D. S.; Sodeau, J. R.; Kulmala, M.; Kalberer, M.

    2013-11-01

    Numerous laboratory experiments have been performed in an attempt to mimic atmospheric secondary organic aerosol (SOA) formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. In this study, we generated SOA in a simulation chamber from the ozonolysis of ?-pinene and a biogenic volatile organic compound (BVOC) mixture containing ?- and ?-pinene, ?3-carene, and isoprene. The detailed molecular composition of laboratory-generated SOA was compared with that of background ambient aerosol collected at a boreal forest site (Hyytiälä, Finland) and an urban location (Cork, Ireland) using direct infusion nanoelectrospray ultrahigh resolution mass spectrometry. Kendrick Mass Defect and Van Krevelen approaches were used to identify and compare compound classes and distributions of the detected species. The laboratory-generated SOA contained a distinguishable group of dimers that was not observed in the ambient samples. The presence of dimers was found to be less pronounced in the SOA from the VOC mixtures when compared to the one component precursor system. The elemental composition of the compounds identified in the monomeric region from the ozonolysis of both ?-pinene and VOC mixtures represented the ambient organic composition of particles collected at the boreal forest site reasonably well, with about 70% of common molecular formulae. In contrast, large differences were found between the laboratory-generated BVOC samples and the ambient urban sample. To our knowledge this is the first direct comparison of molecular composition of laboratory-generated SOA from BVOC mixtures and ambient samples.

  17. Molecular composition of biogenic secondary organic aerosols using ultrahigh-resolution mass spectrometry: comparing laboratory and field studies

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Fuller, S. J.; Giorio, C.; Healy, R. M.; Wilson, E.; O'Connor, I.; Wenger, J. C.; McLeod, M.; Aalto, J.; Ruuskanen, T. M.; Maenhaut, W.; Jones, R.; Venables, D. S.; Sodeau, J. R.; Kulmala, M.; Kalberer, M.

    2014-02-01

    Numerous laboratory experiments have been performed in an attempt to mimic atmospheric secondary organic aerosol (SOA) formation. However, it is still unclear how close the aerosol particles generated in laboratory experiments resemble atmospheric SOA with respect to their detailed chemical composition. In this study, we generated SOA in a simulation chamber from the ozonolysis of ?-pinene and a biogenic volatile organic compound (BVOC) mixture containing ?- and ?-pinene, ?3-carene, and isoprene. The detailed molecular composition of laboratory-generated SOA was compared with that of background ambient aerosol collected at a boreal forest site (Hyytiälä, Finland) and an urban location (Cork, Ireland) using direct infusion nanoelectrospray ultrahigh-resolution mass spectrometry. Kendrick mass defect and van Krevelen approaches were used to identify and compare compound classes and distributions of the detected species. The laboratory-generated SOA contained a distinguishable group of dimers that was not observed in the ambient samples. The presence of dimers was found to be less pronounced in the SOA from the BVOC mixtures when compared to the one component precursor system. The molecular composition of SOA from both the BVOC mixture and ?-pinene represented the overall composition of the ambient sample from the boreal forest site reasonably well, with 72.3 ± 2.5% (n = 3) and 69.1 ± 3.0% (n = 3) common ions, respectively. In contrast, large differences were found between the laboratory-generated BVOC samples and the ambient urban sample. To our knowledge this is the first direct comparison of molecular composition of laboratory-generated SOA from BVOC mixtures and ambient samples.

  18. Organic aerosols

    SciTech Connect

    Penner, J.E.

    1994-01-01

    Organic aerosols scatter solar radiation. They may also either enhance or decrease concentrations of cloud condensation nuclei. This paper summarizes observed concentrations of aerosols in remote continental and marine locations and provides estimates for the sources of organic aerosol matter. The anthropogenic sources of organic aerosols may be as large as the anthropogenic sources of sulfate aerosols, implying a similar magnitude of direct forcing of climate. The source estimates are highly uncertain and subject to revision in the future. A slow secondary source of organic aerosols of unknown origin may contribute to the observed oceanic concentrations. The role of organic aerosols acting as cloud condensation nuclei (CCN) is described and it is concluded that they may either enhance or decrease the ability of anthropogenic sulfate aerosols to act as CCN.

  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.

    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.

  20. 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 ...

  1. Multi-generational oxidation model to simulate secondary organic aerosol in a 3-D air quality model

    NASA Astrophysics Data System (ADS)

    Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

    2015-02-01

    Multi-generational gas-phase oxidation of organic vapors can influence the abundance, composition and properties of secondary organic aerosol (SOA). Only recently have SOA models been developed that explicitly represent multi-generational SOA formation. In this work, we integrated the statistical oxidation model (SOM) into SAPRC-11 to simulate the multi-generational oxidation and gas/particle partitioning of SOA in the regional UCD/CIT air quality model. In SOM, evolution of organic vapors by reaction with the hydroxyl radical is defined by (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the organic molecule. These SOM parameter values were fit to laboratory "smog chamber" data for each precursor/compound class. The UCD/CIT model was used to simulate air quality over two-week periods in the South Coast Air Basin of California and the eastern United States. For the regions and episodes tested, the traditional two-product SOA model and SOM produce similar SOA concentrations but a modestly different SOA chemical composition. Predictions of the oxygen-to-carbon ratio qualitatively agree with those measured globally using aerosol mass spectrometers. Overall, the implementation of the SOM in a 3-D model provides a comprehensive framework to simulate the atmospheric evolution of OA.

  2. 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.

  3. 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.

  4. 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.

  5. Time scales for gas-particle partitioning equilibration of secondary organic aerosol formed from alpha-pinene ozonolysis.

    PubMed

    Saleh, Rawad; Donahue, Neil M; Robinson, Allen L

    2013-06-01

    Most chemical transport models assume instantaneous equilibrium to represent gas-particle partitioning of semivolatile organic aerosol. This approach has been challenged by recent studies suggesting that secondary organic aerosol (SOA) cannot reach equilibrium within atmospheric time scales. The emergent hypothesis is that gas-particle partitioning rates are limited by diffusion within the condensed phase, which is thought to be "glassy." Here, we investigate the equilibration time scales of SOA formed from ?-pinene ozonolysis by measuring the dynamic response to a modest step-change in temperature. Upon heating, equilibrium is disturbed, and the particles evaporate to restore equilibrium at the new temperature, which is attained when evaporation ceases. The SOA was formed at 10 °C and then heated to near room temperature (30 °C) so that the phase state (viscosity) of the condensed-phase after heating is similar to how it would be in the atmosphere. Experiments were performed in both a thermodenuder, with SOA loading of 350 ?g/m(3), and in a smog chamber, with SOA loading of 2-12 ?g/m(3). Both experiments show, contrary to previous findings, that the SOA achieves equilibrium with dynamic responses consistent with a mass accommodation coefficient of order 0.1. For typical atmospheric conditions, this translates into equilibration time scales on the order of minutes to tens of minutes, supporting the use of equilibrium partitioning in chemical transport models. PMID:23647198

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

    PubMed Central

    Jathar, Shantanu H.; Gordon, Timothy D.; Hennigan, Christopher J.; Pye, Havala O. T.; Pouliot, George; Adams, Peter J.; Donahue, Neil M.; Robinson, Allen L.

    2014-01-01

    Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10–20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y?1 of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations. PMID:25002466

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

    PubMed

    Jathar, Shantanu H; Gordon, Timothy D; Hennigan, Christopher J; Pye, Havala O T; Pouliot, George; Adams, Peter J; Donahue, Neil M; Robinson, Allen L

    2014-07-22

    Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10-20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y(-1) of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations. PMID:25002466

  8. Application of the Statistical Oxidation Model (SOM) to secondary organic aerosol formation from photooxidation of C12 Alkanes

    NASA Astrophysics Data System (ADS)

    Cappa, C. D.; Zhang, X.; Loza, C. L.; Craven, J. S.; Yee, L. D.; Seinfeld, J. H.

    2012-10-01

    Laboratory chamber experiments are the main source of data on the mechanism of oxidation and the secondary organic aerosol (SOA) forming potential of volatile organic compounds. Traditional methods of representing the SOA formation potential of an organic do not fully capture the dynamic, multi-generational nature of the SOA formation process. We apply the Statistical Oxidation Model (SOM) of Cappa and Wilson (2012) to model the formation of SOA from the formation of the four C12 alkanes, dodecane, 2-methyl undecane, cyclododecane and hexylcyclohexane, under both high- and low-NOx conditions, based upon data from the Caltech chambers. In the SOM, the evolution of reaction products is defined by the number of carbon (NC) and oxygen (NO) atoms, and the model parameters are (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the molecules. Optimal fitting of the model to chamber data is carried out using the measured SOA mass concentration and the aerosol O : C atomic ratio. The use of the kinetic, multi-generational SOM is shown to provide insights into the SOA formation process and to offer promise for application to the extensive library of existing SOA chamber experiments that is available.

  9. Application of the Statistical Oxidation Model (SOM) to Secondary Organic Aerosol formation from photooxidation of C12 alkanes

    NASA Astrophysics Data System (ADS)

    Cappa, C. D.; Zhang, X.; Loza, C. L.; Craven, J. S.; Yee, L. D.; Seinfeld, J. H.

    2013-02-01

    Laboratory chamber experiments are the main source of data on the mechanism of oxidation and the secondary organic aerosol (SOA) forming potential of volatile organic compounds. Traditional methods of representing the SOA formation potential of an organic do not fully capture the dynamic, multi-generational nature of the SOA formation process. We apply the Statistical Oxidation Model (SOM) of Cappa and Wilson (2012) to model the formation of SOA from the formation of the four C12 alkanes, dodecane, 2-methyl undecane, cyclododecane and hexylcyclohexane, under both high- and low-NOx conditions, based upon data from the Caltech chambers. In the SOM, the evolution of reaction products is defined by the number of carbon (NC) and oxygen (NO) atoms, and the model parameters are (1) the number of oxygen atoms added per reaction, (2) the decrease in volatility upon addition of an oxygen atom and (3) the probability that a given reaction leads to fragmentation of the molecules. Optimal fitting of the model to chamber data is carried out using the measured SOA mass concentration and the aerosol O:C atomic ratio. The use of the kinetic, multi-generational SOM is shown to provide insights into the SOA formation process and to offer promise for application to the extensive library of existing SOA chamber experiments that is available.

  10. SOA formation from partitioning and heterogeneous reactions: model study in the presence of inorganic species.

    PubMed

    Jang, Myoseon; Czoschke, Nadine M; Northcross, Amanda L; Cao, Gang; Shaof, David

    2006-05-01

    A predictive model for secondary organic aerosol (SOA) formation by both partitioning and heterogeneous reactions was developed for SOA created from ozonolysis of alpha-pinene in the presence of preexisting inorganic seed aerosols. SOA was created in a 2 m3 polytetrafluoroethylene film indoor chamber under darkness. Extensive sets of SOA experiments were conducted varying humidity, inorganic seed compositions comprising of ammonium sulfate and sulfuric acid, and amounts of inorganic seed mass. SOA mass was decoupled into partitioning (OM(P)) and heterogeneous aerosol production (OM(H)). The reaction rate constant for OM(H) production was subdivided into three categories (fast, medium, and slow) to consider different reactivity of organic products for the particle phase heterogeneous reactions. The influence of particle acidity on reaction rates was treated in a previous semiempirical model. Model OM(H) was developed with medium and strong acidic seed aerosols, and then extrapolated to OM(H) in weak acidic conditions, which are more relevant to atmospheric aerosols. To demonstrate the effects of preexisting glyoxal derivatives (e.g., glyoxal hydrate and dimer) on OM(H), SOA was created with a seed mixture comprising of aqueous glyoxal and inorganic species. Our results show that heterogeneous SOA formation was also influenced by preexisting reactive glyoxal derivatives. PMID:16719105

  11. Determination of external and internal mixing of organic and inorganic aerosol components from equilibrium water uptake by sub-micrometer particles.

    NASA Astrophysics Data System (ADS)

    Aklilu, Y.; Mozurkewich, M.

    2002-12-01

    The ability of a particle to gain and lose water with changes in relative humidity is fundamental to particle's effectiveness as a cloud condensation nucleus, chemical reactivity, atmospheric residence time and influence on global radiation balance. We describe a method developed to measure particle hygroscopicity over a range of relative humidities (RH) from 50% to 85%. Ambient aerosol particles were dried, monodisperse particles with diameters of usually 50 and 114 nm were selected, and their size distribution following humidification was measured. We measured particle hygroscopicity at Golden Ears Provincial Park and Eagle Ridge Mountain as part of the Pacific 2001 field study in the lower Fraser Valley in August of 2001. The humidified size distributions were sometimes monomodal and sometimes bimodal distribution with less and more hygroscopic peaks. The hygroscopicity of the monomodal particles varied between that of the less and more hygroscopic particles. The less hygroscopic particles were probably almost entirely organic in composition; they had consistent growth curves with wet/dry diameter ratios that increased from 1.04 at 50% relative humidity to 1.09 at 80% RH. These less hygroscopic particles constituted almost all the sampled aerosol at the forested site in Golden Ears Park and during the rainy periods at Eagle Ridge. At other times there were more hygroscopic particles, either as a single mixed mode or as a distinct mode in addition to the less hygroscopic particles. These showed little growth below 70% RH and pronounced growth above 70%. The increased water sorption above 70% RH is likely due to the particles containing (NH4)3H(SO4)2 or (NH4)2(SO4), as these salts deliquesce at 70% and 80% RH, respectively. Since the growth of these particles was less than expected for the pure salts, we conclude that these particles consisted of a mixture of the organic and inorganic components. An estimate of the relative organic fraction was made using the observed growth factors for mixed and organic particles and calculated growth factors for pure inorganic particles. The results indicate that the sampled particles contained a significant organic fraction. 50% of the more hygroscopic particles had organic fractions higher than 0.63, this value was 0.84 for monomodal particles. Bimodal distributions of the humidified particles clearly demonstrated external mixing of the aerosol. In addition, the width of the humidified distribution (spread factor) was also used as an indicator of varying composition. The most common result following humidification of particles was a single mode which frequently exhibited significant spread when humidified above 70% RH. The least amount of spread was observed for particles measured at Golden Ears Forest. At Eagle Ridge, lower spread factors were observed for particles with growth factors at the high or low end of the values observed. The highest spread factors were observed for particles with mid-range growth factors. These results indicate that while particles at Golden Ears Forest were largely single component particles, at Eagle Ridge particle had two sources whose hygroscopicity was approximated by the upper and lower growth factor values observed for the site.

  12. Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

    Sun, Y. L.; Zhang, Q.; Anastasio, C.; Sun, J.

    2010-05-01

    Recent work has shown that aqueous-phase reactions of phenolic compounds - phenol (C6H6O), guaiacol (C7H8O2), and syringol (C8H10O3) - can form secondary organic aerosol (SOA) at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS), an Ion Chromatography system (IC), and a Total Organic Carbon (TOC) analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C) ratios in the range of 0.80-1.06 and carbon oxidation states (=2×O/C-H/C) between -0.14 and +0.47. The organic mass-to-carbon (OM/OC) ratios determined by the HR-AMS (=2.21-2.55) agree well with values determined based on the SOA mass measured gravimetrically and the OC mass from the TOC analyzer. Both the O/C and OM/OC ratios of the phenolic SOA are similar to the values observed for ambient low-volatility oxygenated/secondary OA (LV-OOA). Oxalate is a minor, but ubiquitous, component of the SOA formed from all three phenolic precursors, accounting for 1.4-5.2% of the SOA mass, with generally higher yields in experiments with H2O2 added as an OH source compared to without. The AMS spectra show evidence for the formation of syringol and guaiacol dimers and higher oligomers via C-C and C-O coupling of phenoxyl radicals, which are formed through oxidation pathways such as abstraction of the phenolic hydrogen atom or OH addition to the aromatic ring. This latter pathway leads to hydroxylation of the aromatic ring, which is one mechanism that increases the degree of oxidation of the SOA products. Compared to direct photochemical reactions of the phenols, OH-initiated reactions favor the formation of smaller oxidation products but less dimers or higher oligomers. Two unique and prominent ions in the syringol and guaiacol SOA spectra, m/z 306 (C16H18O6+) and m/z 246 (C14H14O4+), respectively, are observed in ambient aerosols significantly influenced by wood combustion and fog processing. Our results indicate that cloud and fog processing of phenolic compounds, especially in areas with active biomass burning, might represent an important pathway for the formation of low-volatility and highly oxygenated organic species, which would remain in the particle phase after fog/cloud evaporation and affect the chemical and optical properties of atmospheric particles.

  13. Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry

    NASA Astrophysics Data System (ADS)

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

    2010-02-01

    Recent work has shown that aqueous-phase reactions of phenolic compounds - phenol (C6H6O), guaiacol (C7H8O2), and syringol (C8H10O3) - can form secondary organic aerosol (SOA) at high yields. Here we examine the chemical characteristics of this SOA and its formation mechanisms using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-AMS), an Ion Chromatograph (IC), and a Total Organic Carbon (TOC) analyzer. The phenolic SOA are highly oxygenated with oxygen-to-carbon (O/C) ratios in the range of 0.80-1.06 and carbon oxidation states