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Sample records for aerosol formation potential

  1. 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.

  2. Novel insight on photochemistry at interfaces: potential impact on Seconday Aerosol Formation?

    NASA Astrophysics Data System (ADS)

    Rossignol, S.; George, C.; Aregahegn, K.

    2014-12-01

    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 cannot 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), Differential Mobility Analyzer (DMA) and Condensation Particle Sizer (CPC), we identified that traces in the aerosol phase of glyoxal chemistry products, namely imidazole-2-carboxaldehyde (IC) are strong photo-sensitizers when irradiated with near-UV. In the presence of volatile organic compounds such as terpenes, this chemistry leads to a fast aerosol growth. Given the potential importance of this new photosensitized growth pathway for ambient OA, the related reaction mechanism was investigated at a molecular level. Bulk and flow tube experiments were performed to identify major products of the reaction of limonene with the triplet state of IC by direct (+/-)ESI-HRMS and UPLC/(+/-)HESI-HRMS analysis. Detection of recombination products of IC with limonene or with itself, in bulk and flow tube experiment ts, showed that IC is able to initiate a radical chemistry in the aerosol phase under realistic irradiation conditions. Furthermore, highly oxygenated limonene reaction products were detected, clearly explaining the observed OA growth. The chemistry of peroxy radicals derived from limonene upon addition of oxygen explains the formation of such low-volatile compounds without any traditional gas phase oxidant

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

    PubMed

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

    2009-04-15

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

  4. Aqueous aerosol SOA formation: impact on aerosol physical properties.

    PubMed

    Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Li, Ruizhi; McNeill, V Faye

    2013-01-01

    Organic chemistry in aerosol water has recently been recognized as a potentially important source of secondary organic aerosol (SOA) material. This SOA material may be surface-active, therefore potentially affecting aerosol heterogeneous activity, ice nucleation, and CCN activity. Aqueous aerosol chemistry has also been shown to be a potential source of light-absorbing products ("brown carbon"). We present results on the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties from GAMMA (Gas-Aerosol Model for Mechanism Analysis), a photochemical box model with coupled gas and detailed aqueous aerosol chemistry. The detailed aerosol composition output from GAMMA was coupled with two recently developed modules for predicting a) aerosol surface tension and b) the UV-Vis absorption spectrum of the aerosol, based on our previous laboratory observations. The simulation results suggest that the formation of oligomers and organic acids in bulk aerosol water is unlikely to perturb aerosol surface tension significantly. Isoprene-derived organosulfates are formed in high concentrations in acidic aerosols under low-NO(x) conditions, but more experimental data are needed before the potential impact of these species on aerosol surface tension may be evaluated. Adsorption of surfactants from the gas phase may further suppress aerosol surface tension. Light absorption by aqueous aerosol SOA material is driven by dark glyoxal chemistry and is highest under high-NO(x) conditions, at high relative humidity, in the early morning hours. The wavelength dependence of the predicted absorption spectra is comparable to field observations and the predicted mass absorption efficiencies suggest that aqueous aerosol chemistry can be a significant source of aerosol brown carbon under urban conditions. PMID:24601011

  5. Lower ionosphere large positive and negative ions are still puzzling: A potential role in ion induced aerosol formation

    NASA Astrophysics Data System (ADS)

    Arnold, Frank

    2016-04-01

    Inspired by greatly improved possibilities in future rocket borne high mass resolution ion mass spectrometry, previous pioneering rocket borne ion-mass spectrometer measurements, made by our MPIK-Heidelberg research group in the lower ionosphere, are revisited and reanalyzed. Here the focus is placed upon puzzling observations of lower ionosphere large positive and large negative ions. These have a role in lower ionosphere free electron removal. They also have a potential role in lower ionosphere aerosol and eventually even cloud formation. Measurements and model simulations are presented.

  6. Potential Organic Aerosol Formation from Biogenic Compounds: Model and Measurement analysis of the BEACHON-RoMBAS 2011 field data

    NASA Astrophysics Data System (ADS)

    Hodzic, A.; Lee-Taylor, J.; Aumont, B.; Madronich, S.; Palm, B. B.; Campuzano Jost, P.; Day, D. A.; Jimenez, J. L.; Karl, T.; Apel, E. C.; Kaser, L.; Hansel, A.

    2012-12-01

    The scientific understanding of the formation of organic aerosols (OA) from biogenic precursors and their ageing, especially in the presence of anthropogenic pollution, is still limited. The Rocky Mountain Biogenic Aerosol field Study (RoMBAS) took place in summer 2011 at the Manitou Forest Observatory in the Colorado Front Range as part of the NCAR Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen (BEACHON) project with the specific objective of characterizing the formation and growth of biogenic particles in the forest canopy that is dominated by terpene and MBO biogenic emissions. Here we present the results of the box model Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) that was applied at the measurement site to study local production of secondary OA (SOA), as well as the results of the 3D regional Weather Research and Forecasting model with chemistry (WRF/Chem) that was run at 4km horizontal resolution to simulate the regional transport and chemistry. First, we quantify the relative contribution of various biogenic and anthropogenic precursors to SOA levels that were measured by the Aerosol Mass Spectrometer (AMS). The GECKO-A model is initialized from measured VOC concentrations, and uses MEGAN biogenic emissions and WRF/Chem meteorological forcing. The predicted SOA daytime levels at the site of ~0.7-1.0 microg/m3 are consistent with the observations. The SOA production in GECKO from individual VOC precursors is estimated and compared with WRF/Chem predictions which are based on simplified two-product parameterizations as commonly used in regional models. The sensitivity of the SOA formation to the deposition of semi-volatile vapors, and to an increase in NOx and NO3 levels is also discussed for this site that is frequently influenced by advection of the anthropogenic plumes from Denver. Second, we examine how the organic vapors age after several days of atmospheric processing by

  7. Cloud Formation Potential of Biomass Burning Aerosol Surrogate-Particles Chemically Aged by OH

    NASA Astrophysics Data System (ADS)

    Slade, J. H.; Thalman, R. M.; Wang, J.; Li, Z. Q.; Knopf, D. A.

    2014-12-01

    Heterogeneous or multiphase reactions between trace gases such as OH and atmospheric aerosol can influence physicochemical properties of the particles including composition, morphology and lifetime. In this work, the cloud condensation nuclei (CCN) activity of laboratory-generated biomass burning aerosol (BBA) exposed to OH radicals is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type and OH exposure ([OH]×time) using a CCN counter coupled to a custom-built aerosol flow reactor (AFR). The composition of particles collected by a micro-orifice uniform deposit impactor (MOUDI) first subjected to different OH exposures is analyzed by Raman and scanning transmission X-ray microscopy coupled with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative compounds found in BBA that have different hygroscopicity, chemical functionalities, and reactivity with OH radicals. BBA surrogate-particles are generated following atomization of aqueous solutions with mass ratios LEV:MNC:KS of 1:0:0, 0:1:0, 0:0:1, 1:1:0, 0:1:1, 1:0:1, 1:1:1, and 1:0.03:0.3. OH radicals are generated in the AFR following photolysis of O3 in the presence of H2O using a variable intensity ultra-violet (UV) lamp, which allows equivalent atmospheric OH exposures from days to weeks. In addition, we investigate how κ changes i) in response to varying [O3] with and without OH, and ii) at a fixed OH exposure while varying RH. The impact of OH exposure on the CCN activity of BBA will be presented and its atmospheric implications will be discussed.

  8. Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

    SciTech Connect

    Hodzic, Alma; Jimenez, Jose L.; Madronich, Sasha; Canagaratna, M. R.; DeCarlo, Peter F.; Kleinman, Lawrence I.; Fast, Jerome D.

    2010-06-21

    It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of traditional anthropogenic and biogenic VOC precursors. In this study, the 3D regional air quality model CHIMERE is applied to quantify the contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic vapors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to explicitly include the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ("ROB") and Grieshop et al. (2009) ("GRI") are compared and evaluated against surface and aircraft measurements. For the first time, 3D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, but also against and oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (3-6 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. The predicted anthropogenic POA levels are found to agree within 20% with the observed HOA concentrations for both the ROB and GRI simulations, consistent with the interpretation of the emissions inventory by previous studies. The impact of biomass burning POA within the city is underestimated in comparison to the AMS BBOA, presumably due to insufficient nighttime smoldering emissions. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The production from anthropogenic and biomass burning

  9. Modeling organic aerosols in a megacity: Potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation

    SciTech Connect

    Hodzic, A.; Kleinman, L.; Jimenez, J. L.; Madronich, S.; Canagaratna, M. R.; DeCarlo, P. F.; Fast, J.

    2010-06-01

    It has been established that observed local and regional levels of secondary organic aerosols (SOA) in polluted areas cannot be explained by the oxidation and partitioning of anthropogenic and biogenic VOC precursors, at least using current mechanisms and parameterizations. In this study, the 3-D regional air quality model CHIMERE is applied to estimate the potential contribution to SOA formation of recently identified semi-volatile and intermediate volatility organic precursors (S/IVOC) in and around Mexico City for the MILAGRO field experiment during March 2006. The model has been updated to include explicitly the volatility distribution of primary organic aerosols (POA), their gas-particle partitioning and the gas-phase oxidation of the vapors. Two recently proposed parameterizations, those of Robinson et al. (2007) ('ROB') and Grieshop et al. (2009) ('GRI') are compared and evaluated against surface and aircraft measurements. The 3-D model results are assessed by comparing with the concentrations of OA components from Positive Matrix Factorization of Aerosol Mass Spectrometer (AMS) data, and for the first time also with oxygen-to-carbon ratios derived from high-resolution AMS measurements. The results show a substantial enhancement in predicted SOA concentrations (2-4 times) with respect to the previously published base case without S/IVOCs (Hodzic et al., 2009), both within and downwind of the city leading to much reduced discrepancies with the total OA measurements. Model improvements in OA predictions are associated with the better-captured SOA magnitude and diurnal variability. The predicted production from anthropogenic and biomass burning S/IVOC represents 40-60% of the total measured SOA at the surface during the day and is somewhat larger than that from commonly measured aromatic VOCs, especially at the T1 site at the edge of the city. The SOA production from the continued multi-generation S/IVOC oxidation products continues actively downwind. Similar

  10. Organic aerosol formation in citronella candle plumes

    PubMed Central

    Bothe, Melanie

    2010-01-01

    Citronella candles are widely used as insect repellants, especially outdoors in the evening. Because these essential oils are unsaturated, they have a unique potential to form secondary organic aerosol (SOA) via reaction with ozone, which is also commonly elevated on summer evenings when the candles are often in use. We investigated this process, along with primary aerosol emissions, by briefly placing a citronella tealight candle in a smog chamber and then adding ozone to the chamber. In repeated experiments, we observed rapid and substantial SOA formation after ozone addition; this process must therefore be considered when assessing the risks and benefits of using citronella candle to repel insects. PMID:20700379

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  12. Marine aerosol formation from biogenic iodine emissions.

    PubMed

    O'Dowd, Colin D; Jimenez, Jose L; Bahreini, Roya; Flagan, Richard C; Seinfeld, John H; Hämeri, Kaarle; Pirjola, Liisa; Kulmala, Markku; Jennings, S Gerard; Hoffmann, Thorsten

    2002-06-01

    The formation of marine aerosols and cloud condensation nuclei--from which marine clouds originate--depends ultimately on the availability of new, nanometre-scale particles in the marine boundary layer. Because marine aerosols and clouds scatter incoming radiation and contribute a cooling effect to the Earth's radiation budget, new particle production is important in climate regulation. It has been suggested that sulphuric acid derived from the oxidation of dimethyl sulphide is responsible for the production of marine aerosols and cloud condensation nuclei. It was accordingly proposed that algae producing dimethyl sulphide play a role in climate regulation, but this has been difficult to prove and, consequently, the processes controlling marine particle formation remains largely undetermined. Here, using smog chamber experiments under coastal atmospheric conditions, we demonstrate that new particles can form from condensable iodine-containing vapours, which are the photolysis products of biogenic iodocarbons emitted from marine algae. Moreover, we illustrate, using aerosol formation models, that concentrations of condensable iodine-containing vapours over the open ocean are sufficient to influence marine particle formation. We suggest therefore that marine iodocarbon emissions have a potentially significant effect on global radiative forcing.

  13. Marine aerosol formation from biogenic iodine emissions.

    PubMed

    O'Dowd, Colin D; Jimenez, Jose L; Bahreini, Roya; Flagan, Richard C; Seinfeld, John H; Hämeri, Kaarle; Pirjola, Liisa; Kulmala, Markku; Jennings, S Gerard; Hoffmann, Thorsten

    2002-06-01

    The formation of marine aerosols and cloud condensation nuclei--from which marine clouds originate--depends ultimately on the availability of new, nanometre-scale particles in the marine boundary layer. Because marine aerosols and clouds scatter incoming radiation and contribute a cooling effect to the Earth's radiation budget, new particle production is important in climate regulation. It has been suggested that sulphuric acid derived from the oxidation of dimethyl sulphide is responsible for the production of marine aerosols and cloud condensation nuclei. It was accordingly proposed that algae producing dimethyl sulphide play a role in climate regulation, but this has been difficult to prove and, consequently, the processes controlling marine particle formation remains largely undetermined. Here, using smog chamber experiments under coastal atmospheric conditions, we demonstrate that new particles can form from condensable iodine-containing vapours, which are the photolysis products of biogenic iodocarbons emitted from marine algae. Moreover, we illustrate, using aerosol formation models, that concentrations of condensable iodine-containing vapours over the open ocean are sufficient to influence marine particle formation. We suggest therefore that marine iodocarbon emissions have a potentially significant effect on global radiative forcing. PMID:12050661

  14. Sesquiterpene emissions from loblolly pine and their potential contribution to biogenic aerosol formation in the Southeastern US

    NASA Astrophysics Data System (ADS)

    Helmig, Detlev; Ortega, John; Guenther, Alex; Herrick, Jeffrey D.; Geron, Chris

    Sesquiterpene (SQT) and montoterpene (MT) emissions from loblolly pine ( Pinus taeda L.) were studied by branch enclosure experiments at Duke Forest in Chapel Hill, NC. Four SQT ( β-caryophyllene, α-bergamotene, α-humulene, β-farnesene), five MT ( α-pinene, β-pinene, β-myrcene, β-phellandrene, limonene), and the oxygenated MT linalool were identified. Emission rates of both compound classes increased exponentially with temperature, albeit SQT temperature coefficients (0.12-0.18 K -1) were higher than for MT (0.068-0.15 K -1), resulting in an increased contribution of SQT to the overall biogenic volatile organic compound (BVOC) flux during warm temperature conditions. The highly correlated variables of light and temperature conditions preclude a rigorous characterization of their individual roles in driving these emissions. However, the observations indicate that there may be both temperature-only and temperature/light-dependent components contributing to SQT emission variations. When normalized to 30 °C using the best-fit temperature algorithm, total SQT basal emission rate was 450 ng g -1 h -1. The potential contribution of SQT from all pine trees (based on the loblolly pine emission factors) to secondary, biogenic organic aerosol in 12 southeastern US states was estimated to be 7×10 6 kg for the month of September which constitutes an appreciable portion of the overall PM 2.5 emission budget.

  15. 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

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

    EPA Science Inventory

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Reactive halogen species (RHS) are very important due to their potential of stratospheric ozone depletion and surface ozone destruction. RHS seem to interact with precursors of secondary organic aerosol (SOA) similarly to common atmospheric oxidants like OH radicals and ozone. The potential interaction of RHS with preformed SOA has recently been studied (Ofner et al., 2012). Although aerosol formation from reaction of RHS with typical SOA precursors was previously studied (e.g. Cai et al., 2006), no data are available on bromine-induced aerosol formation from organic precursors yet. An aerosol smog-chamber was used to examine the halogen-induced secondary organic aerosol (XOA) formation under atmospheric conditions using simulated sunlight. With a concentration of 10 ppb for the organic precursor, 2 ppb for molecular chlorine, and 10 ppb for molecular bromine, the experimental setup is close to ambient conditions. By combined measurements of the aerosol size distribution, ozone and NOx mixing ratios, as well as the decay of the organic precursor, aerosol yields and aerosol growth rates were determined. The decay of the organic precursor was analyzed by capillary gas chromatography coupled with flame-ionization detection (GC-FID) and the aerosol size distribution was measured using a Scanning Mobility Particle Sizer (SMPS). Additionally, with the decay rate of the precursor and the calculated photolysis rates of molecular halogen species, based on the well-known spectrum of the solar simulator, mechanistic details on the XOA formation pathways can be determined. We observed XOA formation even at very low precursor and RHS concentrations with a diameter mode at 10-20 nm and a number concentration up to 1000000 particles cm-3. While the XOA formation from chlorine is very rapid, the interaction of bromine with the organic precursors is about five times slower. The aerosol yield reached maximum values of 0.01 for the reaction of chlorine with α-pinene and 0.0004 for

  18. MDIs: physics of aerosol formation.

    PubMed

    Clark, A R

    1996-03-01

    The aerosol clouds produced by metered dose inhalers are very dynamic and dramatic changes in both droplet size and velocity take place within the first few centimeters of the spray plume. It is the interaction of this dynamic cloud with the geometry of the mouth and oropharynx that controls the extent of oral deposition and hence the ability of the MDI to deliver a respiratory therapeutic to the lung. Oral deposition is controlled by inertial mechanisms and in order to develop meaningful in-vitro test methods consideration must be given to both the velocity and droplet size distribution of the cloud. The correct design of the inlet ports used to convey MDI clouds in aerosol sizing instruments is therefore crucial to the development of successful in-vitro methodologies. The use of large sampling chambers or the characterization of residual aerosol droplets is unlikely to produce meaning product comparisons or satisfactory product control data.

  19. The atmospheric aerosol-forming potential of whole gasoline vapor

    SciTech Connect

    Odum, J.R.; Jungkamp, T.P.W.; Griffin, R.J.

    1997-04-04

    A series of sunlight-irradiated, smog-chamber experiments confirmed that the atmosphere organic aerosol formation potential of whole gasoline vapor can be accounted for solely in terms of the aromatic fraction of the fuel. The total amount of secondary organic aerosol produced from the atmospheric oxidation of whole gasoline vapor can be represented as the sum of the contributions of the individual aromatic molecular constituents of the fuel. The urban atmospheric, anthropogenic hydrocarbon profile is approximated well by evaporated whole gasoline, and thus these results suggest that it is possible to model atmospheric secondary organic aerosol formation. 23 refs., 3 figs., 2 tabs.

  20. Investigation of the formation of benzoyl peroxide, benzoic anhydride, and other potential aerosol products from gas-phase reactions of benzoylperoxy radicals

    NASA Astrophysics Data System (ADS)

    Strollo, Christen M.; Ziemann, Paul J.

    2016-04-01

    The secondary organic aerosol (SOA) products of the reaction of benzaldehyde with Cl atoms and with OH radicals in air in the absence of NOx were investigated in an environmental chamber in order to better understand the possible role of organic peroxy radical self-reactions in SOA formation. SOA products and authentic standards were analyzed using mass spectrometry and liquid chromatography, and results show that the yields of benzoyl peroxide (C6H5C(O)OO(O)CC6H5) and benzoic anhydride (C6H5C(O)O(O)CC6H5), two potential products from the gas-phase self-reaction of benzoylperoxy radicals (C6H5C(O)OO·), were less than 0.1%. This is in contrast to results of recent studies that have shown that the gas-phase self-reactions of β-nitrooxyperoxy radicals formed from reactions of isoprene with NO3 radicals form dialkyl peroxides that contribute significantly to gas-phase and SOA products. Such reactions have also been proposed to explain the gas-phase formation of extremely low volatility dimers from autooxidation of terpenes. The results obtained here indicate that, at least for benzoylperoxy radicals, the self-reactions form only benzoyloxy radicals. Analyses of SOA composition and volatility were inconclusive, but it appears that the SOA may consist primarily of oligomers formed through heterogeneous/multiphase reactions possibly involving some combination of phenol, benzaldehyde, benzoic acid, and peroxybenzoic acid.

  1. Photochemical organonitrate formation in wet aerosols

    NASA Astrophysics Data System (ADS)

    Lim, Yong Bin; Kim, Hwajin; Kim, Jin Young; Turpin, Barbara J.

    2016-10-01

    Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal- and OH-containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 h irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen sulfates (CHNOS). These were also the dominant products formed in the dark chamber, indicating non-radical formation. In the humid chamber (> 70 % relative humidity, RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m / z- 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.

  2. Organosulfate Formation in Biogenic Secondary Organic Aerosol

    EPA Science Inventory

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

  3. Long-term aerosol and trace gas measurements in Eastern Lapland, Finland: the impact of Kola air pollution to new particle formation and potential CCN

    NASA Astrophysics Data System (ADS)

    Kyrö, Ella-Maria; Väänänen, Riikka; Kerminen, Veli-Matti; Virkkula, Aki; Asmi, Ari; Nieminen, Tuomo; Dal Maso, Miikka; Petäjä, Tuukka; Keronen, Petri; Aalto, Pasi; Riipinen, Ilona; Lehtipalo, Katrianne; Hari, Pertti; Kulmala, Markku

    2014-05-01

    Sulphur and primary emissions have been decreasing largely all over Europe, resulting in improved air quality and decreased direct radiation forcing by aerosols. The smelter industry in Kola Peninsula is one of largest sources of anthropogenic SO2 within the Arctic domain and since late 1990s the sulphur emissions have been decreasing rapidly (Paatero et al., 2008; Prank et al., 2010). New particle formation (NPF) is tightly linked with the oxidizing product of SO2, namely sulphuric acid (H2SO4), since it is known to be the key component in atmospheric nucleation (Sipilä et al., 2010). Thus, decreasing sulphur pollution may lead to less NPF. However, low values of condensation sink (CS), which is determined by the amount of pre-existing particles, favours NPF. We used 14 years (1998-2011) of aerosol number size distribution and trace gas data from SMEAR I station in Eastern Lapland, Finland, to investigate these relationships between SO2, NPF and CS. The station is a clean background station with occasional sulphur pollution episodes when the air masses arrive over Kola Peninsula. We found that while SO2 decreased by 11.3 % / year, the number of clear NPF event days was also decreasing by 9.9 % / year. At the same time, CS was decreasing also (-8.0 % / year) leading to formation of more particles per single NPF event (J3 increased by 29.7 % / year in 2006-2011) but the low vapour concentrations of H2SO4 (proxy decreased by 6.2 % / year) did not allow them to grow into climatically relevant sizes. Over the time, concentrations of potential CCN (cloud condensing nuclei) were also decreasing with more moderate pace, -4.0 % / year. The events started on average earlier after sunrise when the SO2 concentration during the start of the event was higher and NPF occurred more frequently in air masses which were travelling over Kola. Despite the total decrease in sulphur pollution originating from Kola there is currently no evidence of cleaning of the emissions, rather the

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the third vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC < 0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.10 to 0.19. Five hours of oxidation led to a more oxidized OA with an O/C range of 0

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

    Diesel particulate matter (DPM) is a significant source of aerosol in urban areas and has been linked to adverse health effects. Although newer European directives have introduced increasingly stringent standards for primary PM emissions, gaseous organics emitted from diesel cars can still lead to large amounts of secondary organic aerosol (SOA) in the atmosphere. Here we present results from smog chamber investigations characterizing the primary organic aerosol (POA) and the corresponding SOA formation at atmospherically relevant concentrations for three in-use diesel vehicles with different exhaust aftertreatment systems. One vehicle lacked exhaust aftertreatment devices, one vehicle was equipped with a diesel oxidation catalyst (DOC) and the final vehicle used both a DOC and diesel particulate filter (DPF). The experiments presented here were obtained from the vehicles at conditions representative of idle mode, and for one car in addition at a speed of 60 km/h. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the organic aerosol (OA) concentration and to obtain information on the chemical composition. For the conditions explored in this paper, primary aerosols from vehicles without a particulate filter consisted mainly of black carbon (BC) with a low fraction of organic matter (OM, OM/BC<0.5), while the subsequent aging by photooxidation resulted in a consistent production of SOA only for the vehicles without a DOC and with a deactivated DOC. After 5 h of aging ~80% of the total organic aerosol was on average secondary and the estimated "emission factor" for SOA was 0.23-0.56 g/kg fuel burned. In presence of both a DOC and a DPF, primary particles with a mobility diameter above 5 nm were 300±19 cm-3, and only 0.01 g SOA per kg fuel burned was produced within 5 h after lights on. The mass spectra indicate that POA was mostly a non-oxidized OA with an oxygen to carbon atomic ratio (O/C) ranging from 0.097 to 0

  6. Modeling of Crude Oil Evaporation: A Bottom-Up Approach to Prediction of Potential Secondary Organic Aerosol Formation Following Oil Spills

    NASA Astrophysics Data System (ADS)

    Drozd, G.; Worton, D. R.; Variano, E. A.; Goldstein, A. H.

    2014-12-01

    Releases of hydrocarbons from oil spills can have large environmental impacts in both the ocean and atmosphere. While evaporation of oil following a spill is mainly modeled simply as a mass loss mechanism, the resulting production of atmospheric pollutants can also be a major concern, particularly for continental releases, such as wrecks of train-tanker or river barges, and near-shore rig releases. Both may occur near population centers. The Deepwater Horizon (DWH) spill in the Gulf of Mexico in 2010 presented a unique opportunity to observe significant secondary organic aerosol (SOA) production due to a large oil spill. Following on these observations, we have conducted a series of measurements on evaporation of oil while explicitly accounting for changes in chemical composition occurring as a function of evaporation time. In this work we use GC×GC-VUV-HRTOFMS to achieve unprecedented characterization of oil composition from the Deepwater Horizon (DWH) oil spill, and how it changes with time following release. Roughly 75% of the total mass of the alkane mixture comprising the oil was classified according to degree of branching, number of cyclic rings, aromatic character, and molecular weight. Such detailed and comprehensive characterization of the DWH oil allows for bottom-up estimates of the relationship between oil volatility and composition. We developed an evaporative model, based solely on our composition measurements and thermodynamic data (vapor pressure, enthalpy of vaporization), rather than common boiling point parameterizations, which is in excellent agreement with published mass evaporation rates and allows for prediction of potential SOA production as a function of both wind speed (evaporation rate) and oil composition. Our measurements yield different oil volatility distributions than previously inferred; this suggests accurate prediction of SOA formation requires detailed oil composition measurements. A wind tunnel was used to verify model

  7. Organosulfate formation in biogenic secondary organic aerosol.

    PubMed

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

    2008-09-11

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

  8. Observational insights into aerosol formation from isoprene.

    PubMed

    Worton, David R; Surratt, Jason D; Lafranchi, Brian W; Chan, Arthur W H; Zhao, Yunliang; Weber, Robin J; Park, Jeong-Hoo; Gilman, Jessica B; de Gouw, Joost; Park, Changhyoun; Schade, Gunnar; Beaver, Melinda; Clair, Jason M St; Crounse, John; Wennberg, Paul; Wolfe, Glenn M; Harrold, Sara; Thornton, Joel A; Farmer, Delphine K; Docherty, Kenneth S; Cubison, Michael J; Jimenez, Jose-Luis; Frossard, Amanda A; Russell, Lynn M; Kristensen, Kasper; Glasius, Marianne; Mao, Jingqiu; Ren, Xinrong; Brune, William; Browne, Eleanor C; Pusede, Sally E; Cohen, Ronald C; Seinfeld, John H; Goldstein, Allen H

    2013-10-15

    Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO2) and hydroperoxyl (HO2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F(MAE formation)). The strong temperature dependence of F(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS; ~1 ng m(-3)) and MAE-derived organosulfates (MAE-OS; ~1 ng m(-3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m(-3)) relative to MAE-OS (<0.0005 ng m(-3)) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed that MAE forms 10-100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived products relative to IEPOX at the surface. In regions of high NOx, high isoprene emissions and strong vertical mixing the slower MPAN thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source. PMID:24004194

  9. 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.

  10. Formation and deposition of volcanic sulfate aerosols on Mars

    NASA Technical Reports Server (NTRS)

    Settle, M.

    1979-01-01

    The paper considers the formation and deposition of volcanic sulfate aerosols on Mars. The rate limiting step in sulfate aerosol formation on Mars is the gas phase oxidation of SO2 by chemical reactions with O, OH, and HO2; submicron aerosol particles would circuit Mars and then be removed from the atmosphere by gravitational forces, globally dispersed, and deposited over a range of equatorial and mid-latitudes. Volcanic sulfate aerosols on Mars consist of liquid droplets and slurries containing sulfuric acid; aerosol deposition on a global or hemispheric scale could account for the similar concentrations of sulfur within surficial soils at the two Viking lander sites.

  11. Characterizing the formation of secondary organic aerosols

    SciTech Connect

    Lunden, Melissa; Black, Douglas; Brown, Nancy

    2004-02-01

    combination of the aerosol and gas phase data, will continue to provide important information on the extent to which biogenic emissions contribute to secondary organic aerosol and may elucidate important interactions between anthropogenic and biogenic sources. The results of these studies, performed in the field, will contribute to the growing effort to produce robust models for particulate formation that are necessary for air quality planning and source apportionment.

  12. Sulfate aerosols and polar stratospheric cloud formation

    SciTech Connect

    Tolbert, M.A. )

    1994-04-22

    Before the discovery of the Antarctic ozone hole, it was generally assumed that gas-phase chemical reactions controlled the abundance of stratospheric ozone. However, the massive springtime ozone losses over Antarctica first reported by Farman et al in 1985 could not be explained on the basis of gas-phase chemistry alone. In 1986, Solomon et al suggested that chemical reactions occurring on the surfaces of polar stratospheric clouds (PSCs) could be important for the observed ozone losses. Since that time, an explosion of laboratory, field, and theoretical research in heterogeneous atmospheric chemistry has occurred. Recent work has indicated that the most important heterogeneous reaction on PSCs is ClONO[sub 2] + HCl [yields] Cl[sub 2] + HNO[sub 3]. This reaction converts inert chlorine into photochemically active Cl[sub 2]. Photolysis of Cl[sub 2] then leads to chlorine radicals capable of destroying ozone through very efficient catalytic chain reactions. New observations during the second Airborne Arctic Stratospheric Expedition found stoichiometric loss of ClONO[sub 2] and HCl in air processed by PSCs in accordance with reaction 1. Attention is turning toward understanding what kinds of aerosols form in the stratospheric, their formation mechanism, surface area, and specific chemical reactivity. Some of the latest findings, which underline the importance of aerosols, were presented at a recent National Aeronautics and Space Administration workshop in Boulder, Colorado.

  13. Modeling Secondary Organic Aerosol Formation From Emissions of Combustion Sources

    NASA Astrophysics Data System (ADS)

    Jathar, Shantanu Hemant

    -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

  14. 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.

  15. Secondary Organic Aerosol Formation from the Ozonolysis of Cycloalkenes

    NASA Astrophysics Data System (ADS)

    Keywood, M.; Varutbangkul, V.; Gao, S.; Brechtel, F.; Bahreini, R.; Flagan, R. C.; Seinfeld, J. H.

    2003-12-01

    Secondary organic aerosol (SOA) is ubiquitous in the atmosphere being present in both urban and remote locations and exerting influence on human health, visibility and climate. Despite its importance, our understanding of SOA formation still lacks essential elements, limiting our understanding of the effect of SOA on climate forcing. While there do exist experimental data on SOA yields from both biogenic and anthropogenic precursor compounds, it is difficult to extend these results to predict the aerosol-forming potential of precursor compounds not yet studied. In response to this, a series of chamber experiments were carried out in the Caltech Indoor Chamber Facility, where compounds from the cycloalkene and methyl-substituted cycloalkene families were oxidized by ozone in the dark. The reactions were carried out in dual 28 m3 teflon chambers at 20oC and relative humidity below 5%, in the presence of ammonium sulfate seed aerosol. Cyclohexane was used as a scavenger to prevent side oxidation reactions with OH radicals, generated during ozonolysis of the cycloalkene. While cycloalkenes may not be important precursors for SOA formation in the ambient atmosphere, the system was chosen for its simplicity relative to atmospherically relevant SOA precursors such as the biogenic monoterpenes and sesquiterpenes. Cycloalkenes may be seen as the simplified structures on which these more complicated compounds are based. The compounds reacted included the cycloalkenes: cyclopentene, cyclohexene, cycloheptene and cyclooctene, the methyl-substituted cycloalkenes: 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, 1-methy-1-cycloheptene and1-methyl-1-cylopentene, and other related classes of hydrocarbons: methylene cyclohexane and terpinolene. Data collected include aerosol yield, chemical composition and hygroscopic behaviour. The effect of the precursor hydrocarbon structure on these properties of the SOA will be discussed.

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

    EPA Science Inventory

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

  17. The influence of metallurgy on the formation of welding aerosols.

    PubMed

    Zimmer, Anthony T

    2002-10-01

    Recent research has indicated that insoluble ultrafine aerosols (ie., particles whose physical diameters are less than 100 nm) may cause adverse health effects due to their small size, and that toxicological response may be more appropriately represented by particle number or particle surface area. Unfortunately, current exposure criteria and the associated air-sampling techniques are primarily mass-based. Welding processes are high-temperature operations that generate substantial number concentrations of ultrafine aerosols. Welding aerosols are formed primarily through the nucleation of metal vapors followed by competing growth mechanisms such as coagulation and condensation. Experimental results and mathematical tools are presented to illustrate how welding metallurgy influences the chemical aspects and dynamic processes that initiate and evolve the resultant aerosol. This research suggests that a fundamental understanding of metallurgy and aerosol physics can be exploited to suppress the formation of undesirable chemical species as well as the amount of aerosol generated during a welding process.

  18. Aerosol formation yields from the reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, Cécile; Tomas, Alexandre; Guilloteau, Angélique; Henry, Françoise; Ledoux, Frédéric; Visez, Nicolas; Riffault, Véronique; Wenger, John C.; Bedjanian, Yuri

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers. Aerosol production was monitored using a scanning mobility particle sizer and loss of the precursor was determined by gas chromatography and infrared spectroscopy, whilst ozone concentrations were measured using a UV photometric analyzer. The overall organic aerosol yield ( Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses ( Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm -3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas-particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The results of this work are compared to similar studies reported in the literature.

  19. Incremental Reactivity Effects on Secondary Organic Aerosol Formation in Urban Atmospheres with and without Biogenic Influence

    NASA Astrophysics Data System (ADS)

    Kacarab, Mary; Li, Lijie; Carter, William P. L.; Cocker, David R., III

    2016-04-01

    Two different surrogate mixtures of anthropogenic and biogenic volatile organic compounds (VOCs) were developed to study secondary organic aerosol (SOA) formation at atmospheric reactivities similar to urban regions with varying biogenic influence levels. Environmental chamber simulations were designed to enable the study of the incremental aerosol formation from select anthropogenic (m‑Xylene, 1,2,4-Trimethylbenzene, and 1-Methylnaphthalene) and biogenic (α-pinene) precursors under the chemical reactivity set by the two different surrogate mixtures. The surrogate reactive organic gas (ROG) mixtures were based on that used to develop the maximum incremental reactivity (MIR) factors for evaluation of O3 forming potential. Multiple incremental aerosol formation experiments were performed in the University of California Riverside (UCR) College of Engineering Center for Environmental Research and Technology (CE-CERT) dual 90m3 environmental chambers. Incremental aerosol yields were determined for each of the VOCs studied and compared to yields found from single precursor studies. Aerosol physical properties of density, volatility, and hygroscopicity were monitored throughout experiments. Bulk elemental chemical composition from high-resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) data will also be presented. Incremental yields and SOA chemical and physical characteristics will be compared with data from previous single VOC studies conducted for these aerosol precursors following traditional VOC/NOx chamber experiments. Evaluation of the incremental effects of VOCs on SOA formation and properties are paramount in evaluating how to best extrapolate environmental chamber observations to the ambient atmosphere and provides useful insights into current SOA formation models. Further, the comparison of incremental SOA from VOCs in varying surrogate urban atmospheres (with and without strong biogenic influence) allows for a unique perspective on the impacts

  20. Incremental Reactivity Effects on Secondary Organic Aerosol Formation in Urban Atmospheres with and without Biogenic Influence

    NASA Astrophysics Data System (ADS)

    Kacarab, Mary; Li, Lijie; Carter, William P. L.; Cocker, David R., III

    2016-04-01

    Two different surrogate mixtures of anthropogenic and biogenic volatile organic compounds (VOCs) were developed to study secondary organic aerosol (SOA) formation at atmospheric reactivities similar to urban regions with varying biogenic influence levels. Environmental chamber simulations were designed to enable the study of the incremental aerosol formation from select anthropogenic (m-Xylene, 1,2,4-Trimethylbenzene, and 1-Methylnaphthalene) and biogenic (α-pinene) precursors under the chemical reactivity set by the two different surrogate mixtures. The surrogate reactive organic gas (ROG) mixtures were based on that used to develop the maximum incremental reactivity (MIR) factors for evaluation of O3 forming potential. Multiple incremental aerosol formation experiments were performed in the University of California Riverside (UCR) College of Engineering Center for Environmental Research and Technology (CE-CERT) dual 90m3 environmental chambers. Incremental aerosol yields were determined for each of the VOCs studied and compared to yields found from single precursor studies. Aerosol physical properties of density, volatility, and hygroscopicity were monitored throughout experiments. Bulk elemental chemical composition from high-resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) data will also be presented. Incremental yields and SOA chemical and physical characteristics will be compared with data from previous single VOC studies conducted for these aerosol precursors following traditional VOC/NOx chamber experiments. Evaluation of the incremental effects of VOCs on SOA formation and properties are paramount in evaluating how to best extrapolate environmental chamber observations to the ambient atmosphere and provides useful insights into current SOA formation models. Further, the comparison of incremental SOA from VOCs in varying surrogate urban atmospheres (with and without strong biogenic influence) allows for a unique perspective on the impacts

  1. Sulfate Formation on Mars by Volcanic Aerosols: A New Look

    NASA Astrophysics Data System (ADS)

    Blaney, D. L.

    1996-03-01

    Sulfur was measured at both Viking Lander sites in abundances of 5-9 wt % SO3. Because the sulfur was more concentrated in clumps which disintegrated and the general oxidized nature of the Martian soil, these measurements led to the assumption that a sulfate duricrust existed. Two types of models for sulfate formation have been proposed. One is a formation by upwardly migrating ground water. The other is the formation of sulfates by the precipitation of volcanic aerosols. Most investigators have tended to favor the ground water origin of sulfates on Mars. However, evidence assemble since Viking may point to a volcanic aerosol origin.

  2. Secondary organic aerosol formation by self-reactions of methylglyoxal and glyoxal in evaporating droplets.

    PubMed

    De Haan, David O; Corrigan, Ashley L; Tolbert, Margaret A; Jimenez, Jose L; Wood, Stephanie E; Turley, Jacob J

    2009-11-01

    Glyoxal and methylglyoxal are scavenged by clouds, where a fraction of these compounds are oxidized during the lifetime of the droplet. As a cloud droplet evaporates, the remaining glyoxal and methylglyoxal must either form low-volatility compounds such as oligomers and remain in the aerosol phase, or transfer back to the gas phase. A series of experiments on evaporating aqueous aerosol droplets indicates that over the atmospherically relevant concentration range for clouds and fog (4-1000 microM), 33 +/- 11% of glyoxal and 19 +/- 13% of methylglyoxal remains in the aerosol phase while the remainder evaporates. Measurements of aerosol density and time-dependent AMS signal changes are consistent with the formation of oligomers by each compound during the drying process. Unlike glyoxal, which forms acetal oligomers, exact mass AMS data indicates that the majority of methylglyoxal oligomers are formed by aldol condensation reactions, likely catalyzed by pyruvic acid, formed from methylglyoxal disproportionation. Our measurements of evaporation fractions can be used to estimate the global aerosol formation potential of glyoxal and methylglyoxal via self-reactions at 1 and 1.6 Tg C yr(-1), respectively. This is a factor of 4 less than the SOA formed by these compounds if their uptake is assumed to be irreversible. However, these estimates are likely lower limits for their total aerosol formation potential because oxidants and amines will also react with glyoxal and methylglyoxal to form additional low-volatility products.

  3. Formation of nitrogenated organic aerosols in the Titan upper atmosphere

    PubMed Central

    Imanaka, Hiroshi; Smith, Mark A.

    2010-01-01

    Many aspects of the nitrogen fixation process by photochemistry in the Titan atmosphere are not fully understood. The recent Cassini mission revealed organic aerosol formation in the upper atmosphere of Titan. It is not clear, however, how much and by what mechanism nitrogen is incorporated in Titan’s organic aerosols. Using tunable synchrotron radiation at the Advanced Light Source, we demonstrate the first evidence of nitrogenated organic aerosol production by extreme ultraviolet–vacuum ultraviolet irradiation of a N2/CH4 gas mixture. The ultrahigh-mass-resolution study with laser desorption ionization-Fourier transform-ion cyclotron resonance mass spectrometry of N2/CH4 photolytic solid products at 60 and 82.5 nm indicates the predominance of highly nitrogenated compounds. The distinct nitrogen incorporations at the elemental abundances of H2C2N and HCN, respectively, are suggestive of important roles of H2C2N/HCCN and HCN/CN in their formation. The efficient formation of unsaturated hydrocarbons is observed in the gas phase without abundant nitrogenated neutrals at 60 nm, and this is confirmed by separately using 13C and 15N isotopically labeled initial gas mixtures. These observations strongly suggest a heterogeneous incorporation mechanism via short lived nitrogenated reactive species, such as HCCN radical, for nitrogenated organic aerosol formation, and imply that substantial amounts of nitrogen is fixed as organic macromolecular aerosols in Titan’s atmosphere. PMID:20616074

  4. New aerosol particles formation in the Sao Paulo Metropolitan Area

    NASA Astrophysics Data System (ADS)

    Vela, Angel; Andrade, Maria de Fatima; Ynoue, Rita

    2016-04-01

    performance. For secondary aerosols, a simulation scenario (Case_1) with only emission of primary gases (biogenic and anthropogenic) is performed to evaluate its formation potential. The study period from 7th August to 6th September 2012 has been selected due to the avaliability of experimental data from the Narrowing the Uncertainties on Aerosol and Climate Changes in Sao Paulo State (NUANCE) project. Aerosol measurements consist basically on PM2.5 and PM10 concentration. OC, EC, ion, and aerosol mass size distribution measurements were also carried out in one of the measurement sites (IAG-USP). Results show that overall the emissions of primary gases coming mainly from vehicles have a potential to form new particles between 20 and 30% in relation to the baseline PM2.5 mass concentration found in the downtown SPMA. In addition, both the observed and predicted OC and EC at the IAG-USP measurement site make up the largest fraction of PM2.5 mass with contributions around 55 and 40%, respectively.

  5. An interfacial mechanism for cloud droplet formation on organic aerosols

    NASA Astrophysics Data System (ADS)

    Ruehl, Christopher R.; Davies, James F.; Wilson, Kevin R.

    2016-03-01

    Accurate predictions of aerosol/cloud interactions require simple, physically accurate parameterizations of the cloud condensation nuclei (CCN) activity of aerosols. Current models assume that organic aerosol species contribute to CCN activity by lowering water activity. We measured droplet diameters at the point of CCN activation for particles composed of dicarboxylic acids or secondary organic aerosol and ammonium sulfate. Droplet activation diameters were 40 to 60% larger than predicted if the organic was assumed to be dissolved within the bulk droplet, suggesting that a new mechanism is needed to explain cloud droplet formation. A compressed film model explains how surface tension depression by interfacial organic molecules can alter the relationship between water vapor supersaturation and droplet size (i.e., the Köhler curve), leading to the larger diameters observed at activation.

  6. Modeling comprehensive chemical composition of weathered oil following a marine spill to predict ozone and potential secondary aerosol formation and constrain transport pathways

    NASA Astrophysics Data System (ADS)

    Drozd, Greg T.; Worton, David R.; Aeppli, Christoph; Reddy, Christopher M.; Zhang, Haofei; Variano, Evan; Goldstein, Allen H.

    2015-11-01

    Releases of hydrocarbons from oil spills have large environmental impacts in both the ocean and atmosphere. Oil evaporation is not simply a mechanism of mass loss from the ocean, as it also causes production of atmospheric pollutants. Monitoring atmospheric emissions from oil spills must include a broad range of volatile organic compounds (VOC), including intermediate-volatile and semivolatile compounds (IVOC, SVOC), which cause secondary organic aerosol (SOA) and ozone production. The Deepwater Horizon (DWH) disaster in the northern Gulf of Mexico during Spring/Summer of 2010 presented a unique opportunity to observe SOA production due to an oil spill. To better understand these observations, we conducted measurements and modeled oil evaporation utilizing unprecedented comprehensive composition measurements, achieved by gas chromatography with vacuum ultraviolet time of flight mass spectrometry (GC-VUV-HR-ToFMS). All hydrocarbons with 10-30 carbons were classified by degree of branching, number of cyclic rings, aromaticity, and molecular weight; these hydrocarbons comprise ˜70% of total oil mass. Such detailed and comprehensive characterization of DWH oil allowed bottom-up estimates of oil evaporation kinetics. We developed an evaporative model, using solely our composition measurements and thermodynamic data, that is in excellent agreement with published mass evaporation rates and our wind-tunnel measurements. Using this model, we determine surface slick samples are composed of oil with a distribution of evaporative ages and identify and characterize probable subsurface transport of oil.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

    Atmospheric aerosols impact climate by scattering and absorbing solar radiation and by acting as ice and cloud condensation nuclei. Secondary organic aerosols (SOA) comprise an important component of atmospheric aerosols. Biogenic volatile organic compounds (BVOC) emitted by vegetation are a major source of SOA. Pathogens and insect attacks, heat waves and droughts can induce stress to plants that may impact their BVOC emissions, and hence the yield and type of formed SOA, and possibly their climatic effects. This raises questions whether stress-induced changes in SOA formation may attenuate or amplify effects of climate change. In this study we assess the potential impact of stress-induced BVOC emissions on SOA formation for tree species typical for mixed deciduous and Boreal Eurasian forests. We studied the photochemical SOA formation for infested plants in a laboratory setup under well-controlled conditions and applied in addition heat and drought stress. The results indicate that stress conditions substantially modify SOA formation. While sesquiterpenes, methyl salicylate, and C17-BVOC increase SOA yield, green leaf volatiles suppress SOA formation. By classifying emission types, stressors and SOA formation potential, we propose possible climatic feedbacks regarding aerosol effects. We conclude that stress situations for plants due to climate change should be considered in climate-vegetation feedback mechanisms.

  9. 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 ...

  10. Investigating secondary aerosol formation from agricultural amines and reduced sulfur compounds

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Gas phase amines and reduced sulfur compounds are often co-emitted from agricultural processes. Amines have been recently recognized as potentially major sources of agricultural aerosol formation, while the reduced sulfur compounds are largely ignored. There is a severe lack of knowledge and under...

  11. Atmospheric Degradation Initiated by OH Radicals of the Potential Foam Expansion Agent, CF3(CF2)2CH═CH2 (HFC-1447fz): Kinetics and Formation of Gaseous Products and Secondary Organic Aerosols.

    PubMed

    Jiménez, Elena; González, Sergio; Cazaunau, Mathieu; Chen, Hui; Ballesteros, Bernabé; Daële, Véronique; Albaladejo, José; Mellouki, Abdelwahid

    2016-02-01

    The assessment of the atmospheric impact of the potential foam expansion agent, CF3(CF2)2CH═CH2 (HFC-1447fz), requires the knowledge of its degradation routes, oxidation products, and radiative properties. In this paper, the gas-phase reactivity of HFC-1447fz with OH radicals is presented as a function of temperature, obtaining kOH (T = 263-358 K) = (7.4 ± 0.4) × 10(-13)exp{(161 ± 16)/T} (cm(3)·molecule(-1)·s(-1)) (uncertainties: ±2σ). The formation of gaseous oxidation products and secondary organic aerosols (SOAs) from the OH + HFC-1447fz reaction was investigated in the presence of NOx at 298 K. CF3(CF2)2CHO was observed at low- and high-NOx conditions. Evidence of SOA formation (ultrafine particles in the range 10-100 nm) is reported with yields ranging from 0.12 to 1.79%. In addition, the absolute UV (190-368 nm) and IR (500-4000 cm(-1)) absorption cross-sections of HFC-1447fz were determined at room temperature. No appreciable absorption in the solar actinic region (λ > 290 nm) was observed, leaving the removal by OH radicals as the main atmospheric loss process for HFC-1447fz. The major contribution of the atmospheric loss of HFC-1447fz is due to OH reaction (84%), followed by ozone (10%) and chlorine atoms (6%). Correction of the instantaneous radiative efficiency (0.36 W m(-2)·ppbv(-1)) with the relatively short lifetime of HFC-1447fz (ca. 8 days) implies that its global warming potential at a time horizon of 100 year is negligible (0.19) compared to that of HCFC-141b (782) and to that of modern foam-expansion blowing agents (148, 882, and 804 for HFC-152a, HFC-245fa and HFC-365mfc, respectively).

  12. Atmospheric Degradation Initiated by OH Radicals of the Potential Foam Expansion Agent, CF3(CF2)2CH═CH2 (HFC-1447fz): Kinetics and Formation of Gaseous Products and Secondary Organic Aerosols.

    PubMed

    Jiménez, Elena; González, Sergio; Cazaunau, Mathieu; Chen, Hui; Ballesteros, Bernabé; Daële, Véronique; Albaladejo, José; Mellouki, Abdelwahid

    2016-02-01

    The assessment of the atmospheric impact of the potential foam expansion agent, CF3(CF2)2CH═CH2 (HFC-1447fz), requires the knowledge of its degradation routes, oxidation products, and radiative properties. In this paper, the gas-phase reactivity of HFC-1447fz with OH radicals is presented as a function of temperature, obtaining kOH (T = 263-358 K) = (7.4 ± 0.4) × 10(-13)exp{(161 ± 16)/T} (cm(3)·molecule(-1)·s(-1)) (uncertainties: ±2σ). The formation of gaseous oxidation products and secondary organic aerosols (SOAs) from the OH + HFC-1447fz reaction was investigated in the presence of NOx at 298 K. CF3(CF2)2CHO was observed at low- and high-NOx conditions. Evidence of SOA formation (ultrafine particles in the range 10-100 nm) is reported with yields ranging from 0.12 to 1.79%. In addition, the absolute UV (190-368 nm) and IR (500-4000 cm(-1)) absorption cross-sections of HFC-1447fz were determined at room temperature. No appreciable absorption in the solar actinic region (λ > 290 nm) was observed, leaving the removal by OH radicals as the main atmospheric loss process for HFC-1447fz. The major contribution of the atmospheric loss of HFC-1447fz is due to OH reaction (84%), followed by ozone (10%) and chlorine atoms (6%). Correction of the instantaneous radiative efficiency (0.36 W m(-2)·ppbv(-1)) with the relatively short lifetime of HFC-1447fz (ca. 8 days) implies that its global warming potential at a time horizon of 100 year is negligible (0.19) compared to that of HCFC-141b (782) and to that of modern foam-expansion blowing agents (148, 882, and 804 for HFC-152a, HFC-245fa and HFC-365mfc, respectively). PMID:26704369

  13. 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 ...

  14. Laboratory Investigation of Organic Aerosol Formation from Aromatic Hydrocarbons

    DOE R&D Accomplishments Database

    Molina, Luisa T.; Molina, Mario J.; Zhang, Renyi

    2006-08-23

    Our work for this DOE funded project includes: (1) measurements of the kinetics and mechanism of the gas-phase oxidation reactions of the aromatic hydrocarbons initiated by OH; (2) measurements of aerosol formation from the aromatic hydrocarbons; and (3) theoretical studies to elucidate the OH-toluene reaction mechanism using quantum-chemical and rate theories.

  15. 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 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.

  16. Aerosol stability of infectious and potentially infectious reovirus particles.

    PubMed Central

    Adams, D J; Spendlove, J C; Spendlove, R S; Barnett, B B

    1982-01-01

    The aerosol stability of two particle forms, infectious and potentially infectious, of reovirus were examined under static conditions for a range of relative humidities at 21 and 24 degrees C. Virus aerosolization efficiency was determined for two methods of dissemination: Collison nebulizer and Chicago atomizer. Suspensions of Bacillus subtilis var. niger spores were added to reovirus preparations that included both particle forms and disseminated into a dynamic aerosol toroid to estimate the physical decay of the aerosols. At 90 to 100% relative humidity, both reovirus particle forms showed less than 10-fold loss of infectivity after 12 h of aging. At lower relative humidities the aerosol decay curve showed rapid initial decay followed by a markedly lower decay rate. Our findings reveal that reovirus particles are relatively stable in the airborne state. PMID:7149719

  17. New Particle Formation and Secondary Organic Aerosol in Beijing

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  18. Titan Aerosol Formation as a Sink for Stable Carbon and Nitrogen Isotopes

    NASA Astrophysics Data System (ADS)

    Trainer, Melissa G.; Stern, Jennifer C.; Sebree, Joshua A.; Gautier, Thomas J.; Fuentes, Javier A.; Domagal-Goldman, Shawn D.; Mandt, Kathleen E.

    2015-11-01

    Stable isotope ratios of major elements can be used to infer much about local- and global-scale processes on a planet. On Titan, aerosol production is a significant sink of carbon and nitrogen in the atmosphere, and isotopic fractionation of these elements may be introduced during the advanced organic chemistry that leads to the condensed phase products. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have measured the isotopic fractionation associated with the formation of Titan aerosol analogs via far-UV irradiation of several methane (CH4) and nitrogen (N2) mixtures.Our initial results probed the fractionation of the aerosol product, relative to the reactant gases, as a function of CH4 abundance [1]. Our results show that the direction of carbon isotope fractionation during aerosol formation is in contrast to the expected result if the source of the fractionation is a kinetic isotope effect. The resultant fractionation in nitrogen favored the light (14N) isotope in the aerosol, with N/C ratios varying from 0.13 - 0.31. Ongoing work includes probing the effects of pressure and temperature on the direction and magnitude of the stable isotope fractionation. We will present results alongside interpretation of the driving processes, as well as implications for Titan if similar fractionation occurred during aerosol formation in the atmosphere.[1] Sebree, J.A., Stern, J.C., Mandt, K.E., Domagal-Goldman, S.D., and Trainer, M.G.: 13C and 15N Fractionation of CH4/N2 Mixtures during Photochemical Aerosol Formation

  19. Volcanic sulfate aerosol formation in the troposphere

    NASA Astrophysics Data System (ADS)

    Martin, Erwan; Bekki, Slimane; Ninin, Charlotte; Bindeman, Ilya

    2014-11-01

    The isotopic composition of volcanic sulfate provides insights into the atmospheric chemical processing of volcanic plumes. First, mass-independent isotopic anomalies quantified by Δ17O and to a lesser extent Δ33S and Δ36S in sulfate depend on the relative importance of different oxidation mechanisms that generate sulfate aerosols. Second, the isotopic composition of sulfate (δ34S and δ18O) could be an indicator of fractionation (distillation/condensation) processes occurring in volcanic plumes. Here we present analyses of O- and S isotopic compositions of volcanic sulfate absorbed on very fresh volcanic ash from nine moderate historical eruptions in the Northern Hemisphere. Most of our volcanic sulfate samples, which are thought to have been generated in the troposphere or in the tropopause region, do not exhibit any significant mass-independent fractionation (MIF) isotopic anomalies, apart from those from an eruption of a Mexican volcano. Coupled to simple chemistry model calculations representative of the background atmosphere, our data set suggests that although H2O2 (a MIF-carrying oxidant) is thought to be by far the most efficient sulfur oxidant in the background atmosphere, it is probably quickly consumed in large dense tropospheric volcanic plumes. We estimate that in the troposphere, at least, more than 90% of volcanic secondary sulfate is not generated by MIF processes. Volcanic S-bearing gases, mostly SO2, appear to be oxidized through channels that do not generate significant isotopically mass-independent sulfate, possibly via OH in the gas phase and/or transition metal ion catalysis in the aqueous phase. It is also likely that some of the sulfates sampled were not entirely produced by atmospheric oxidation processes but came out directly from volcanoes without any MIF anomalies.

  20. Comparison of Aerosol Mass Spectrometer and Aerosol Chemical Speciation Monitor Measurements of Secondary Organic Aerosol Formation in Smog Chamber Studies

    NASA Astrophysics Data System (ADS)

    Croteau, P. L.; Hunter, J. F.; Daumit, K. E.; Carrasquillo, A. J.; Cross, E. S.; Canagaratna, M.; Jayne, J.; Worsnop, D. R.; Kroll, J. H.

    2012-12-01

    Thermal vaporization-electron impact ionization (TV-EI) mass spectrometry is a powerful tool for understanding the chemistry of secondary organic aerosol (SOA) formation and atmospheric aging. The Aerodyne Aerosol Mass Spectrometer (AMS) and recently developed Aerosol Chemical Speciation Monitor (ACSM) are two instruments that utilize the same TV-EI technique. The ACSM trades the particle sizing capability, sensitivity, speed, and resolution of the AMS for simplicity, affordability, and ease of operation - enabling stand-alone continuous sampling for extended periods of time. Here we present results of an intercomparison between a high-resolution AMS and an ACSM. Three well-studied SOA formation chamber experiments were conducted: isoprene photooxidation under high NOx conditions, m-xylene photooxidation under high NOx conditions, and α-pinene ozonolysis under low NOx conditions. Comparisons between time-series and mass spectra from these experiments, along with positive matrix factorization analysis results demonstrate that the ACSM, while it does not provide the same level of detail as an AMS, is a suitable tool for exploring the chemistry of SOA formation in chamber studies.

  1. 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 α-pinene, β-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 α-pinene, β-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 μg 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.

  2. Aerosolization, Chemical Characterization, Hygroscopicity and Ice Formation of Marine Biogenic Particles

    NASA Astrophysics Data System (ADS)

    Alpert, P. A.; Radway, J.; Kilthau, W.; Bothe, D.; Knopf, D. A.; Aller, J. Y.

    2013-12-01

    The oceans cover the majority of the earth's surface, host nearly half the total global primary productivity and are a major source of atmospheric aerosol particles. However, effects of biological activity on sea spray generation and composition, and subsequent cloud formation are not well understood. Our goal is to elucidate these effects which will be particularly important over nutrient rich seas, where microorganisms can reach concentrations of 10^9 per mL and along with transparent exopolymer particles (TEP) can become aerosolized. Here we report the results of mesocosm experiments in which bubbles were generated by two methods, either recirculating impinging water jets or glass frits, in natural or artificial seawater containing bacteria and unialgal cultures of three representative phytoplankton species, Thalassiosira pseudonana, Emiliania huxleyi, and Nannochloris atomus. Over time we followed the size distribution of aerosolized particles as well as their hygroscopicity, heterogeneous ice nucleation potential, and individual physical-chemical characteristics. Numbers of cells and the mass of dissolved and particulate organic carbon (DOC, POC), TEP (which includes polysaccharide-containing microgels and nanogels >0.4 μm in diameter) were determined in the bulk water, the surface microlayer, and aerosolized material. Aerosolized particles were also impacted onto substrates for ice nucleation and water uptake experiments, elemental analysis using computer controlled scanning electron microscopy and energy dispersive analysis of X-rays (CCSEM/EDX), and determination of carbon bonding with scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Regardless of bubble generation method, the overall concentration of aerosol particles, TEP, POC and DOC increased as concentrations of bacterial and phytoplankton cells increased, stabilized, and subsequently declined. Particles <100 nm generated by means of jets

  3. Aerosol formation in basaltic lava fountaining: Eyjafjallajökull volcano, Iceland

    NASA Astrophysics Data System (ADS)

    Ilyinskaya, Evgenia; Martin, Robert S.; Oppenheimer, Clive

    2012-10-01

    A short-lived episode of basaltic lava fountaining at Eyjafjallajökull volcano (March - April 2010) produced a low-altitude, ash-poor plume. We measured the composition of aerosol particles (sampled using a cascade impactor and filter packs), gases (sampled using filter packs), and volatile species scavenged by scoria and external water in order to investigate the formation and speciation of near-source aerosol (<2 min from emission). Samples were analyzed for volatile species (S, Cl and F) and metals (Na, K, Ca and Mg). The aerosol mass showed two unusual features: the prevalent size mode was finer than typically found in volcanic plumes (˜0.2μm, compared to >0.4 μm), and its composition was dominated by chloride rather than sulfate. We used two thermodynamic equilibrium models (E-AIM and HSC Chemistry v5.1) to show that the formation of particulate Cl- by condensation of HCl gas is more responsive to changes in ambient temperature than the oxidation of SO2 to SO42-, so that a low SO42-/Cl- ratio in aerosol particles is characteristic of volcanic emissions in cold climates. Field measurements suggested that the efficiency of SO2 to SO42- conversion inside the vent increased with lower explosivity. Volatiles adsorbed on the surface of scoria had significantly higher SO42-/halogen molar ratios than the aerosol samples. Several potential explanations for these differences are discussed.

  4. Secondary organic aerosol formation from road vehicle emissions

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    Organic aerosol particles (OA) are a major fraction of the submicron particulate matter. OA consists of directly emitted primary (POA) and secondary OA (SOA). SOA is formed in-situ in the atmosphere via the reaction of volatile organic precursors. The partitioning of SOA species depends not only on the exposure to oxidants, but for instance also on temperature, relative humidity (RH), and the absorptive mass chemical composition (presence of inorganics) and concentration. Vehicle exhaust is a known source of POA and likely contributes to SOA formation in urban areas [1;2]. This has recently been estimated by (i) analyzing ambient data from urban areas combined with fuel consumption data [3], (ii) by examining the chemical composition of raw fuels [4], or (iii) smog chamber studies [5, 6]. Contradictory and thus somewhat controversial results in the relative quantity of SOA from diesel vs. gasoline vehicle exhaust were observed. In order to elucidate the impact of variable ambient conditions on the potential SOA formation of vehicle exhaust, and its relation to the emitted gas phase species, we studied SOA formed from the exhaust of passenger cars and trucks as a function of fuel and engine type (gasoline, diesel) at different temperatures (T 22 vs. -7oC) and RH (40 vs. 90%), as well as with different levels of inorganic salt concentrations. The exhaust was sampled at the tailpipe during regulatory driving cycles on chassis dynamometers, diluted (200 - 400x) and introduced into the PSI mobile smog chamber [6], where the emissions were subjected to simulated atmospheric ageing. Particle phase instruments (HR-ToF-AMS, aethalometers, CPC, SMPS) and gas phase instruments (PTR-TOF-MS, CO, CO2, CH4, THC, NH3 and other gases) were used online during the experiments. We found that gasoline emissions, because of cold starts, were generally larger than diesel, especially during cold temperatures driving cycles. Gasoline vehicles also showed the highest SOA formation

  5. Ion-induced Aerosol-formation By Jet Aircraft: Implications For Contrail- and Cloud-formation

    NASA Astrophysics Data System (ADS)

    Eichkorn, S.; Wilhelm, S.; Arnold, F.

    Jet aircraft produced gaseous ions so called chemiions (CI) may promote the forma- tion of volatile aerosol particles (VAP). VAP are potentially important by acting as water vapor condensation nuclei in contrail- and perhaps even cloud-formation. This ion-induced VAP-formation proceeds via the formation of cluster ions which are suf- ficiently large to form stable VAP upon neutralisation by ion-ion recombination. Here we report the first measurements of large cluster ions in sulfur-poor and -rich exhaust plumes of jet aircraft in flight equipped with modern and old engines. Measurements were performed in the wake of an Airbus A340, a Boeing B707 and the German Re- search Aircraft ATTAS. Our measurements suggest that ion induced VAP-formation takes place and that gaseous sulphuric acid and gaseous low volatility organic com- pounds are involved. For modern engines burning fuel with a typical mean fuel sulfur content sulphuric acid seems to be the most abundant condensate in a contrail-free exhaust-plume.

  6. Predicting secondary organic aerosol formation rates in southeast Texas

    NASA Astrophysics Data System (ADS)

    Russell, Matthew; Allen, David T.

    2005-04-01

    Rates of secondary organic aerosol (SOA) formation, due to the reactions of aromatics and monoterpenes, were estimated for southeast Texas by incorporating a modified version of the Statewide Air Pollution Research Center's chemical mechanism (SAPRC99) into the Comprehensive Air Quality Model with extensions (CAMx version 3.10). The model included explicit representation of the reactions of five SOA precursors (α-pinene, β-pinene, sabinene, d-limonene, and Δ3-carene). Reactions of each SOA precursor with O3, OH radical, and NO3 radical were included. The model also included separate reactions for low- and high-SOA-yield aromatic groups with the OH radical. SOA yields in the mechanisms were estimated using compound-specific yield information (ΔSOA/ΔHC) derived from smog chamber experiments conducted by J. R. Odum and colleagues and R. J. Griffin and colleagues. The form of the SOA yield model was based on the work of J. R. Odum and colleagues and is a function of existing organic aerosol concentrations. Existing organic aerosol concentrations were estimated on the basis of ambient measurements of total organic carbon in southeast Texas. The reactions of monoterpenes (predominantly α-pinene and β-pinene) with ozone led to the most regional SOA formation, followed by monoterpenes with the nitrate radical. Aromatic-OH reactions led to less regional SOA formation compared to monoterpenes; however, this formation occurs close to the urban and industrial areas of Houston. In contrast, SOA formation due to the reactions of monoterpenes occurred in the forested areas north of the urban area. The results of this study are in qualitative agreement with estimates of SOA formation based on ambient data from the same time period.

  7. Aerosol Formation In The Free Troposphere: Aircraft and Laboratory Measurements of Ionic and Gaseous Aerosol Precursors

    NASA Astrophysics Data System (ADS)

    Arnold, F.

    Aerosol formation seems to be very efficient in the upper troposphere (UT) as in- dicated by the frequent presence of numerous very small and therefore very young aerosol particles. Aersosol formation proceeds via nucleation of supersaturated low volatility trace gases (LVG) involving either a homogeneous (HONU) or an ion- induced (INU) mechanism. LVG experience rapid removal by condenstation on prefer- ably pre-existing aerosol particles and therefore LVG must be formed locally in the UT by photochemical conversion of precursor gases. A prominent example is gaseous sulfuric acid which is formed from SO2. This SO2 originates at least in the northern hemisphere mostly from fossil fuel combustion at ground-level and to some part origi- nates also from jet aircraft cruising in the UT. Other conceivable LVG's are low volatil- ity organic compounds. After formation by nucleation new particles may experience condensational growth involving LVG. Alternatively new particles may experience scavenging by attachment to pre-existing larger particles. The LVG-concentration has a strong influence on the growth-rate of new particles and thereby on the possibil- ity for growth to the size of a cloud condensation nucleus. Unfortunately present knowledge on free tropospheric LVG is rather poor. Here will be reported free tropo- spheric aircraft-based measurements of ionic and gaseous aerosol-precursors. These include both measurements in the "background" FT as well as measurements in ex- haust plumes of jet aircraft cruising in the UT. Furthermore accompanying new labo- ratory investigations of INU and measurements behind aircraft jet engines at ground- level will also be adressed.

  8. Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO2 radical formation and aerosol growth

    NASA Astrophysics Data System (ADS)

    González Palacios, Laura; Corral Arroyo, Pablo; Aregahegn, Kifle Z.; Steimer, Sarah S.; Bartels-Rausch, Thorsten; Nozière, Barbara; George, Christian; Ammann, Markus; Volkamer, Rainer

    2016-09-01

    The multiphase chemistry of glyoxal is a source of secondary organic aerosol (SOA), including its light-absorbing product imidazole-2-carboxaldehyde (IC). IC is a photosensitizer that can contribute to additional aerosol ageing and growth when its excited triplet state oxidizes hydrocarbons (reactive uptake) via H-transfer chemistry. We have conducted a series of photochemical coated-wall flow tube (CWFT) experiments using films of IC and citric acid (CA), an organic proxy and H donor in the condensed phase. The formation rate of gas-phase HO2 radicals (PHO2) was measured indirectly by converting gas-phase NO into NO2. We report on experiments that relied on measurements of NO2 formation, NO loss and HONO formation. PHO2 was found to be a linear function of (1) the [IC] × [CA] concentration product and (2) the photon actinic flux. Additionally, (3) a more complex function of relative humidity (25 % < RH < 63 %) and of (4) the O2 / N2 ratio (15 % < O2 / N2 < 56 %) was observed, most likely indicating competing effects of dilution, HO2 mobility and losses in the film. The maximum PHO2 was observed at 25-55 % RH and at ambient O2 / N2. The HO2 radicals form in the condensed phase when excited IC triplet states are reduced by H transfer from a donor, CA in our system, and subsequently react with O2 to regenerate IC, leading to a catalytic cycle. OH does not appear to be formed as a primary product but is produced from the reaction of NO with HO2 in the gas phase. Further, seed aerosols containing IC and ammonium sulfate were exposed to gas-phase limonene and NOx in aerosol flow tube experiments, confirming significant PHO2 from aerosol surfaces. Our results indicate a potentially relevant contribution of triplet state photochemistry for gas-phase HO2 production, aerosol growth and ageing in the atmosphere.

  9. Secondary organic aerosol formation from idling gasoline passenger vehicle emissions investigated in a smog chamber

    NASA Astrophysics Data System (ADS)

    Nordin, E. Z.; Eriksson, A. C.; Roldin, P.; Nilsson, P. T.; Carlsson, J. E.; Kajos, M. K.; Hellén, H.; Wittbom, C.; Rissler, J.; Löndahl, J.; Swietlicki, E.; Svenningsson, B.; Bohgard, M.; Kulmala, M.; Hallquist, M.; Pagels, J. H.

    2013-06-01

    Gasoline vehicles have recently been pointed out as potentially the main source of anthropogenic secondary organic aerosol (SOA) in megacities. However, there is a lack of laboratory studies to systematically investigate SOA formation in real-world exhaust. In this study, SOA formation from pure aromatic precursors, idling and cold start gasoline exhaust from three passenger vehicles (EURO2-EURO4) were investigated with photo-oxidation experiments in a 6 m3 smog chamber. The experiments were carried out down to atmospherically relevant organic aerosol mass concentrations. The characterization instruments included a high-resolution aerosol mass spectrometer and a proton transfer mass spectrometer. It was found that gasoline exhaust readily forms SOA with a signature aerosol mass spectrum similar to the oxidized organic aerosol that commonly dominates the organic aerosol mass spectra downwind of urban areas. After a cumulative OH exposure of ~5 × 106 cm-3 h, the formed SOA was 1-2 orders of magnitude higher than the primary OA emissions. The SOA mass spectrum from a relevant mixture of traditional light aromatic precursors gave f43 (mass fraction at m/z = 43), approximately two times higher than to the gasoline SOA. However O : C and H : C ratios were similar for the two cases. Classical C6-C9 light aromatic precursors were responsible for up to 60% of the formed SOA, which is significantly higher than for diesel exhaust. Important candidates for additional precursors are higher-order aromatic compounds such as C10 and C11 light aromatics, naphthalene and methyl-naphthalenes. We conclude that approaches using only light aromatic precursors give an incomplete picture of the magnitude of SOA formation and the SOA composition from gasoline exhaust.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  12. 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.

  13. 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.

  14. Potential source regions and processes of aerosol in the summer Arctic

    NASA Astrophysics Data System (ADS)

    Heintzenberg, J.; Leck, C.; Tunved, P.

    2015-06-01

    Sub-micrometer particle size distributions measured during four summer cruises of the Swedish icebreaker Oden 1991, 1996, 2001, and 2008 were combined with dimethyl sulfide gas data, back trajectories, and daily maps of pack ice cover in order to investigate source areas and aerosol formation processes of the boundary layer aerosol in the central Arctic. With a clustering algorithm, potential aerosol source areas were explored. Clustering of particle size distributions together with back trajectories delineated five potential source regions and three different aerosol types that covered most of the Arctic Basin: marine, newly formed and aged particles over the pack ice. Most of the pack ice area with < 15% of open water under the trajectories exhibited the aged aerosol type with only one major mode around 40 nm. For newly formed particles to occur, two conditions had to be fulfilled over the pack ice: the air had spent 10 days while traveling over ever more contiguous ice and had traveled over less than 30% open water during the last 5 days. Additionally, the air had experienced more open water (at least twice as much as in the cases of aged aerosol) during the last 4 days before arrival in heavy ice conditions at Oden. Thus we hypothesize that these two conditions were essential factors for the formation of ultrafine particles over the central Arctic pack ice. In a comparison the Oden data with summer size distribution data from Alert, Nunavut, and Mt. Zeppelin, Spitsbergen, we confirmed the Oden findings with respect to particle sources over the central Arctic. Future more frequent broken-ice or open water patches in summer will spur biological activity in surface water promoting the formation of biological particles. Thereby low clouds and fogs and subsequently the surface energy balance and ice melt may be affected.

  15. Secondary organic aerosol formation from gasoline passenger vehicle emissions investigated in a smog chamber

    NASA Astrophysics Data System (ADS)

    Nordin, E. Z.; Eriksson, A. C.; Roldin, P.; Nilsson, P. T.; Carlsson, J. E.; Kajos, M. K.; Hellén, H.; Wittbom, C.; Rissler, J.; Löndahl, J.; Swietlicki, E.; Svenningsson, B.; Bohgard, M.; Kulmala, M.; Hallquist, M.; Pagels, J.

    2012-12-01

    Gasoline vehicles have elevated emissions of volatile organic compounds during cold starts and idling and have recently been pointed out as potentially the main source of anthropogenic secondary organic aerosol (SOA) in megacities. However, there is a lack of laboratory studies to systematically investigate SOA formation in real-world exhaust. In this study, SOA formation from pure aromatic precursors, idling and cold start gasoline exhaust from one Euro II, one Euro III and one Euro IV passenger vehicles were investigated using photo-oxidation experiments in a 6 m3 smog chamber. The experiments were carried out at atmospherically relevant organic aerosol mass concentrations. The characterization methods included a high resolution aerosol mass spectrometer and a proton transfer mass spectrometer. It was found that gasoline exhaust readily forms SOA with a signature aerosol mass spectrum similar to the oxidized organic aerosol that commonly dominates the organic aerosol mass spectra downwind urban areas. After 4 h aging the formed SOA was 1-2 orders of magnitude higher than the Primary OA emissions. The SOA mass spectrum from a relevant mixture of traditional light aromatic precursors gave f43 (mass fraction at m/z = 4 3) approximately two times higher than to the gasoline SOA. However O : C and H : C ratios were similar for the two cases. Classical C6-C9 light aromatic precursors were responsible for up to 60% of the formed SOA, which is significantly higher than for diesel exhaust. Important candidates for additional precursors are higher order aromatic compounds such as C10, C11 light aromatics, naphthalene and methyl-naphthalenes.

  16. 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 α-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 α-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

  17. 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.

    2015-08-01

    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 (SOAs). 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 α-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 4 days of chemical aging under those conditions (equivalent to 8 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 α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are 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 is 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 empirically estimated SOA photolysis rate of JSOA

  18. Measurements of aerosol chemistry during new particle formation events at a remote rural mountain site.

    PubMed

    Creamean, Jessie M; Ault, Andrew P; Ten Hoeve, John E; Jacobson, Mark Z; Roberts, Gregory C; Prather, Kimberly A

    2011-10-01

    Determining the major sources of particles that act as cloud condensation nuclei (CCN) represents a critical step in the development of a more fundamental understanding of aerosol impacts on cloud formation and climate. Reported herein are direct measurements of the CCN activity of newly formed ambient particles, measured at a remote rural site in the Sierra Nevada Mountains of Northern California. Nucleation events in the winter of 2009 occurred during two pristine periods following precipitation, with higher gas-phase SO(2) concentrations during the second period, when faster particle growth occurred (7-8 nm/h). Amines, as opposed to ammonia, and sulfate were detected in the particle phase throughout new particle formation (NPF) events, increasing in number as the particles grew to larger sizes. Interestingly, long-range transport of SO(2) from Asia appeared to potentially play a role in NPF during faster particle growth. Understanding the propensity of newly formed particles to act as CCN is critical for predicting the effects of NPF on orographic cloud formation during winter storms along the Sierra Nevada Mountain range. The potential impact of newly formed particles in remote regions needs to be compared with that of transported urban aerosols when evaluating the impact of aerosols on clouds and climate.

  19. 13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

    NASA Astrophysics Data System (ADS)

    Sebree, Joshua A.; Stern, Jennifer C.; Mandt, Kathleen E.; Domagal-Goldman, Shawn D.; Trainer, Melissa G.

    2016-05-01

    The ratios of the stable isotopes that comprise each chemical species in Titan's atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation - organic aerosol formation and subsequent deposition onto the surface of Titan - has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as 'tholins', via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

  20. Composition and formation of organic aerosol particles in the Amazon

    NASA Astrophysics Data System (ADS)

    Pöhlker, C.; Wiedemann, K.; Sinha, B.; Shiraiwa, M.; Gunthe, S. S.; Artaxo, P.; Gilles, M. K.; Kilcoyne, A. L. D.; Moffet, R. C.; Smith, M.; Weigand, M.; Martin, S. T.; Pöschl, U.; Andreae, M. O.

    2012-04-01

    We applied scanning transmission X-ray microscopy with near edge X-ray absorption fine structure (STXM-NEXAFS) analysis to investigate the morphology and chemical composition of aerosol samples from a pristine tropical environment, the Amazon Basin. The samples were collected in the Amazonian rainforest during the rainy season and can be regarded as a natural background aerosol. The samples were found to be dominated by secondary organic aerosol (SOA) particles in the fine and primary biological aerosol particles (PBAP) in the coarse mode. Lab-generated SOA-samples from isoprene and terpene oxidation as well as pure organic compounds from spray-drying of aqueous solution were measured as reference samples. The aim of this study was to investigate the microphysical and chemical properties of a tropical background aerosol in the submicron size range and its internal mixing state. The lab-generated SOA and pure organic compounds occurred as spherical and mostly homogenous droplet-like particles, whereas the Amazonian SOA particles comprised a mixture of homogeneous droplets and droplets having internal structures due to atmospheric aging. In spite of the similar morphological appearance, the Amazon samples showed considerable differences in elemental and functional group composition. According to their NEXAFS spectra, three chemically distinct types of organic material were found and could be assigned to the following three categories: (1) particles with a pronounced carboxylic acid (COOH) peak similar to those of laboratory-generated SOA particles from terpene oxidation; (2) particles with a strong hydroxy (COH) signal similar to pure carbohydrate particles; and (3) particles with spectra resembling a mixture of the first two classes. In addition to the dominant organic component, the NEXAFS spectra revealed clearly resolved potassium (K) signals for all analyzed particles. During the rainy season and in the absence of anthropogenic influence, active biota is

  1. Formation and evolution of molecular products in α-pinene secondary organic aerosol.

    PubMed

    Zhang, Xuan; McVay, Renee C; Huang, Dan D; Dalleska, Nathan F; Aumont, Bernard; Flagan, Richard C; Seinfeld, John H

    2015-11-17

    Much of our understanding of atmospheric secondary organic aerosol (SOA) formation from volatile organic compounds derives from laboratory chamber measurements, including mass yield and elemental composition. These measurements alone are insufficient to identify the chemical mechanisms of SOA production. We present here a comprehensive dataset on the molecular identity, abundance, and kinetics of α-pinene SOA, a canonical system that has received much attention owing to its importance as an organic aerosol source in the pristine atmosphere. Identified organic species account for ∼58-72% of the α-pinene SOA mass, and are characterized as semivolatile/low-volatility monomers and extremely low volatility dimers, which exhibit comparable oxidation states yet different functionalities. Features of the α-pinene SOA formation process are revealed for the first time, to our knowledge, from the dynamics of individual particle-phase components. Although monomeric products dominate the overall aerosol mass, rapid production of dimers plays a key role in initiating particle growth. Continuous production of monomers is observed after the parent α-pinene is consumed, which cannot be explained solely by gas-phase photochemical production. Additionally, distinct responses of monomers and dimers to α-pinene oxidation by ozone vs. hydroxyl radicals, temperature, and relative humidity are observed. Gas-phase radical combination reactions together with condensed phase rearrangement of labile molecules potentially explain the newly characterized SOA features, thereby opening up further avenues for understanding formation and evolution mechanisms of α-pinene SOA. PMID:26578760

  2. 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.

  3. Mitigating secondary aerosol generation potentials from biofuel use in the energy sector.

    PubMed

    Tiwary, Abhishek; Colls, Jeremy

    2010-01-01

    This paper demonstrates secondary aerosol generation potential of biofuel use in the energy sector from the photochemical interactions of precursor gases on a life cycle basis. The paper is divided into two parts-first, employing life cycle analysis (LCA) to evaluate the extent of the problem for a typical biofuel based electricity production system using five baseline scenarios; second, proposing adequate mitigation options to minimise the secondary aerosol generation potential on a life cycle basis. The baseline scenarios cover representative technologies for 2010 utilising energy crop (miscanthus), short rotation coppiced chips and residual/waste wood in different proportions. The proposed mitigation options include three approaches-biomass gasification prior to combustion, delaying the harvest of biomass, and increasing the geographical distance between the biomass plant and the harvest site (by importing the biofuels). Preliminary results indicate that the baseline scenarios (assuming all the biomass is sourced locally) bear significant secondary aerosol formation potential on a life cycle basis from photochemical neutralisation of acidic emissions (hydrogen chloride and sulphur dioxide) with ammonia. Our results suggest that gasification of miscanthus biomass would provide the best option by minimising the acidic emissions from the combustion plant whereas the other two options of delaying the harvest or importing biofuels from elsewhere would only lead to marginal reduction in the life cycle aerosol loadings of the systems.

  4. Mitigating secondary aerosol generation potentials from biofuel use in the energy sector.

    PubMed

    Tiwary, Abhishek; Colls, Jeremy

    2010-01-01

    This paper demonstrates secondary aerosol generation potential of biofuel use in the energy sector from the photochemical interactions of precursor gases on a life cycle basis. The paper is divided into two parts-first, employing life cycle analysis (LCA) to evaluate the extent of the problem for a typical biofuel based electricity production system using five baseline scenarios; second, proposing adequate mitigation options to minimise the secondary aerosol generation potential on a life cycle basis. The baseline scenarios cover representative technologies for 2010 utilising energy crop (miscanthus), short rotation coppiced chips and residual/waste wood in different proportions. The proposed mitigation options include three approaches-biomass gasification prior to combustion, delaying the harvest of biomass, and increasing the geographical distance between the biomass plant and the harvest site (by importing the biofuels). Preliminary results indicate that the baseline scenarios (assuming all the biomass is sourced locally) bear significant secondary aerosol formation potential on a life cycle basis from photochemical neutralisation of acidic emissions (hydrogen chloride and sulphur dioxide) with ammonia. Our results suggest that gasification of miscanthus biomass would provide the best option by minimising the acidic emissions from the combustion plant whereas the other two options of delaying the harvest or importing biofuels from elsewhere would only lead to marginal reduction in the life cycle aerosol loadings of the systems. PMID:19878969

  5. Formation of the Aerosol of Space Origin in Earth's Atmosphere

    NASA Technical Reports Server (NTRS)

    Kozak, P. M.; Kruchynenko, V. G.

    2011-01-01

    The problem of formation of the aerosol of space origin in Earth s atmosphere is examined. Meteoroids of the mass range of 10-18-10-8 g are considered as a source of its origin. The lower bound of the mass range is chosen according to the data presented in literature, the upper bound is determined in accordance with the theory of Whipple s micrometeorites. Basing on the classical equations of deceleration and heating for small meteor bodies we have determined the maximal temperatures of the particles, and altitudes at which they reach critically low velocities, which can be called as velocities of stopping . As a condition for the transformation of a space particle into an aerosol one we have used the condition of non-reaching melting temperature of the meteoroid. The simplified equation of deceleration without earth gravity and barometric formula for the atmosphere density are used. In the equation of heat balance the energy loss for heating is neglected. The analytical solution of the simplified equations is used for the analysis.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  7. Potential Climate Effects of Dust Aerosols' over West Africa

    NASA Astrophysics Data System (ADS)

    JI, Z.; Wang, G.; Pal, J. S.; Yu, M.

    2014-12-01

    Climate in West Africa is under the influence of the West African monsoon circulation and mineral dust emitted from the Sahara desert (which is the world's largest source of mineral dust emission). Dust aerosols alter the atmospheric radiative fluxes and act as cloud condensation nuclei in the process of emission, transportation and deposition. However, our understanding regarding how dust aerosols influence the present-day and future climate of West Africa is very limited. In this study, a regional climate model RegCM4.3.4-CLM4.5 is used to investigate the potential climatic effects of dust aerosols both in present (1981-2000) and future (2081-2100) periods over WA. First, the model performance and dust climatic effects are evaluated. The contribution of dust climatic effects under RCP8.5 scenario and their confounding effects with land use change are assessed. Our results indicate that the model can reproduce with reasonable accuracy the spatial and temporal distribution of climatology, aerosol optical depth and surface concentration over WA. The shortwave radiative forcing of dust is negative in the surface and positive in the atmosphere, with greater changes in JJA and MAM compared to those in SON and DJF. Over most of West Africa, cooling is the dominant effect on temperature. Their impact on precipitation features a dipole pattern, with decrease in the north and increase in the south of West Africa. Despite the dust-induced decrease of precipitation amount, dusts cause extreme precipitation to increase. To evaluate the uncertainties surrounding our modeling results, sensitivity experiments driven by ICBC from MIROC-ESM and CESM and their dynamic downscaling results are used for comparisons. Results from these sensitivity experiments indicate that the impact of dust aerosols on present and future climate is robust.

  8. Satellite observations and EMAC model calculations of sulfate aerosols from Kilauea: a study of aerosol formation, processing, and loss

    NASA Astrophysics Data System (ADS)

    Penning de Vries, Marloes; Beirle, Steffen; Brühl, Christoph; Dörner, Steffen; Pozzer, Andrea; Wagner, Thomas

    2016-04-01

    The currently most active volcano on Earth is Mount Kilauea on Hawaii, as it has been in a state of continuous eruption since 1983. The opening of a new vent in March 2008 caused half a year of strongly increased SO2 emissions, which in turn led to the formation of a sulfate plume with an extent of at least two thousand kilometers. The plume could be clearly identified from satellite measurements from March to November, 2008. The steady trade winds in the region and the lack of interfering sources allowed us to determine the life time of SO2 from Kilauea using only satellite-based measurements (no a priori or model information). The current investigation focuses on sulfate aerosols: their formation, processing and subsequent loss. Using space-based aerosol measurements by MODIS, we study the evolution of aerosol optical depth, which first increases as a function of distance from the volcano due to aerosol formation from SO2 oxidation, and subsequently decreases as aerosols are deposited to the surface. The outcome is compared to results from calculations using the EMAC (ECHAM/MESSy Atmospheric Chemistry) model to test the state of understanding of the sulfate aerosol life cycle. For this comparison, a particular focus is on the role of clouds and wet removal processes.

  9. Kick-starting aerosol formation on Titan with ion chemistry

    NASA Astrophysics Data System (ADS)

    Biennier, L.; Joalland, B.; Eddine, N. Jamal; Carles, S.; Guillemin, J.-C.

    2015-10-01

    The Cassini Huygens probe has revealed the presence of abundant and heavy ions in the upper atmosphere of Titan [1, 2]. These so-called macromolecules are now considered to be key intermediates in the production of aerosols observed at lower altitudes [3]. Under this scenario, macromolecules are formed and grow by gas phase ion-neutral reactions in the ionosphere. There they attach efficiently free electrons and recombine with positive ions leading to a rapid gain in mass. As they settle down in the cold atmosphere, they continue to grow until they reach a size where coagulation takes over. However, the composition of these macromolecules and their precise formation mechanisms are still largely unknown. It includes the first steps leading to the production of the macromolecules, which govern the growth rate.

  10. The role of anthropogenic species in Biogenic aerosol formation

    EPA Science Inventory

    Isoprene is a widely recognized source of organic aerosol in the southeastern United States. Models have traditionally represented isoprene-derived aerosol as semivolatile species formed from the initial isoprene + OH reaction. Recent laboratory and field studies indicate later g...

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

    PubMed Central

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

    2011-01-01

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

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

    PubMed

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

    2011-09-01

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

  13. 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

  14. Hydrocarbon nucleation and aerosol formation in Neptune's atmosphere.

    PubMed

    Moses, J I; Allen, M; Yung, Y L

    1992-10-01

    Photodissociation of methane at high altitude levels in Neptune's atmosphere leads to the production of complex hydrocarbon species such as acetylene (C2H2), ethane (C2H6), methylacetylene (CH3C2H), propane (C3H8), diacetylene (C4H2), and butane (C4H8). These gases diffuse to the lower stratosphere where temperatures are low enough to initiate condensation. Particle formation may not occur readily, however, as the vapor species become supersaturated. We present a theoretical analysis of particle formation mechanisms at conditions relevant to Neptune's troposphere and stratosphere and show that hydrocarbon nucleation is very inefficient under Neptunian conditions: saturation ratios much greater than unity are required for aerosol formation by either homogeneous, heterogeneous, or ion-induced nucleation. Homogeneous nucleation will not be important for any of the hydrocarbon species considered; however, both heterogeneous and ion-induced nucleation should be possible on Neptune for most of the above species. The relative effectiveness of heterogeneous and ion-induced nucleation depends on the physical and thermodynamic properties of the particular species, the abundance of the condensable species, the temperature at which the vapor becomes supersaturated, and the number and type of condensation nuclei or ions available. Typical saturation ratios required for observable particle formation rates on Neptune range from approximately 3 for heterogeneous nucleation of methane in the upper troposphere to greater than 1000 for heterogeneous nucleation of methylacetylene, diacetylene, and butane in the lower stratosphere. Thus, methane clouds may form slightly above, and stratospheric hazes far below, their saturation levels. When used in conjunction with the results of detailed models of atmospheric photochemistry, our nucleation models place realistic constraints on the altitude levels at which we expect hydrocarbon hazes or clouds to form on Neptune. PMID:11538166

  15. Hydrocarbon nucleation and aerosol formation in Neptune's atmosphere.

    PubMed

    Moses, J I; Allen, M; Yung, Y L

    1992-10-01

    Photodissociation of methane at high altitude levels in Neptune's atmosphere leads to the production of complex hydrocarbon species such as acetylene (C2H2), ethane (C2H6), methylacetylene (CH3C2H), propane (C3H8), diacetylene (C4H2), and butane (C4H8). These gases diffuse to the lower stratosphere where temperatures are low enough to initiate condensation. Particle formation may not occur readily, however, as the vapor species become supersaturated. We present a theoretical analysis of particle formation mechanisms at conditions relevant to Neptune's troposphere and stratosphere and show that hydrocarbon nucleation is very inefficient under Neptunian conditions: saturation ratios much greater than unity are required for aerosol formation by either homogeneous, heterogeneous, or ion-induced nucleation. Homogeneous nucleation will not be important for any of the hydrocarbon species considered; however, both heterogeneous and ion-induced nucleation should be possible on Neptune for most of the above species. The relative effectiveness of heterogeneous and ion-induced nucleation depends on the physical and thermodynamic properties of the particular species, the abundance of the condensable species, the temperature at which the vapor becomes supersaturated, and the number and type of condensation nuclei or ions available. Typical saturation ratios required for observable particle formation rates on Neptune range from approximately 3 for heterogeneous nucleation of methane in the upper troposphere to greater than 1000 for heterogeneous nucleation of methylacetylene, diacetylene, and butane in the lower stratosphere. Thus, methane clouds may form slightly above, and stratospheric hazes far below, their saturation levels. When used in conjunction with the results of detailed models of atmospheric photochemistry, our nucleation models place realistic constraints on the altitude levels at which we expect hydrocarbon hazes or clouds to form on Neptune.

  16. Formation of highly porous aerosol particles by atmospheric freeze-drying in ice clouds.

    PubMed

    Adler, Gabriela; Koop, Thomas; Haspel, Carynelisa; Taraniuk, Ilya; Moise, Tamar; Koren, Ilan; Heiblum, Reuven H; Rudich, Yinon

    2013-12-17

    The cycling of atmospheric aerosols through clouds can change their chemical and physical properties and thus modify how aerosols affect cloud microphysics and, subsequently, precipitation and climate. Current knowledge about aerosol processing by clouds is rather limited to chemical reactions within water droplets in warm low-altitude clouds. However, in cold high-altitude cirrus clouds and anvils of high convective clouds in the tropics and midlatitudes, humidified aerosols freeze to form ice, which upon exposure to subsaturation conditions with respect to ice can sublimate, leaving behind residual modified aerosols. This freeze-drying process can occur in various types of clouds. Here we simulate an atmospheric freeze-drying cycle of aerosols in laboratory experiments using proxies for atmospheric aerosols. We find that aerosols that contain organic material that undergo such a process can form highly porous aerosol particles with a larger diameter and a lower density than the initial homogeneous aerosol. We attribute this morphology change to phase separation upon freezing followed by a glass transition of the organic material that can preserve a porous structure after ice sublimation. A porous structure may explain the previously observed enhancement in ice nucleation efficiency of glassy organic particles. We find that highly porous aerosol particles scatter solar light less efficiently than nonporous aerosol particles. Using a combination of satellite and radiosonde data, we show that highly porous aerosol formation can readily occur in highly convective clouds, which are widespread in the tropics and midlatitudes. These observations may have implications for subsequent cloud formation cycles and aerosol albedo near cloud edges.

  17. Formation of highly porous aerosol particles by atmospheric freeze-drying in ice clouds

    PubMed Central

    Adler, Gabriela; Koop, Thomas; Haspel, Carynelisa; Taraniuk, Ilya; Moise, Tamar; Koren, Ilan; Heiblum, Reuven H.; Rudich, Yinon

    2013-01-01

    The cycling of atmospheric aerosols through clouds can change their chemical and physical properties and thus modify how aerosols affect cloud microphysics and, subsequently, precipitation and climate. Current knowledge about aerosol processing by clouds is rather limited to chemical reactions within water droplets in warm low-altitude clouds. However, in cold high-altitude cirrus clouds and anvils of high convective clouds in the tropics and midlatitudes, humidified aerosols freeze to form ice, which upon exposure to subsaturation conditions with respect to ice can sublimate, leaving behind residual modified aerosols. This freeze-drying process can occur in various types of clouds. Here we simulate an atmospheric freeze-drying cycle of aerosols in laboratory experiments using proxies for atmospheric aerosols. We find that aerosols that contain organic material that undergo such a process can form highly porous aerosol particles with a larger diameter and a lower density than the initial homogeneous aerosol. We attribute this morphology change to phase separation upon freezing followed by a glass transition of the organic material that can preserve a porous structure after ice sublimation. A porous structure may explain the previously observed enhancement in ice nucleation efficiency of glassy organic particles. We find that highly porous aerosol particles scatter solar light less efficiently than nonporous aerosol particles. Using a combination of satellite and radiosonde data, we show that highly porous aerosol formation can readily occur in highly convective clouds, which are widespread in the tropics and midlatitudes. These observations may have implications for subsequent cloud formation cycles and aerosol albedo near cloud edges. PMID:24297908

  18. Formation of highly porous aerosol particles by atmospheric freeze-drying in ice clouds.

    PubMed

    Adler, Gabriela; Koop, Thomas; Haspel, Carynelisa; Taraniuk, Ilya; Moise, Tamar; Koren, Ilan; Heiblum, Reuven H; Rudich, Yinon

    2013-12-17

    The cycling of atmospheric aerosols through clouds can change their chemical and physical properties and thus modify how aerosols affect cloud microphysics and, subsequently, precipitation and climate. Current knowledge about aerosol processing by clouds is rather limited to chemical reactions within water droplets in warm low-altitude clouds. However, in cold high-altitude cirrus clouds and anvils of high convective clouds in the tropics and midlatitudes, humidified aerosols freeze to form ice, which upon exposure to subsaturation conditions with respect to ice can sublimate, leaving behind residual modified aerosols. This freeze-drying process can occur in various types of clouds. Here we simulate an atmospheric freeze-drying cycle of aerosols in laboratory experiments using proxies for atmospheric aerosols. We find that aerosols that contain organic material that undergo such a process can form highly porous aerosol particles with a larger diameter and a lower density than the initial homogeneous aerosol. We attribute this morphology change to phase separation upon freezing followed by a glass transition of the organic material that can preserve a porous structure after ice sublimation. A porous structure may explain the previously observed enhancement in ice nucleation efficiency of glassy organic particles. We find that highly porous aerosol particles scatter solar light less efficiently than nonporous aerosol particles. Using a combination of satellite and radiosonde data, we show that highly porous aerosol formation can readily occur in highly convective clouds, which are widespread in the tropics and midlatitudes. These observations may have implications for subsequent cloud formation cycles and aerosol albedo near cloud edges. PMID:24297908

  19. Development of an aerosol microphysical module: Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS)

    SciTech Connect

    Matsui, H.; Koike, Makoto; Kondo, Yutaka; Fast, Jerome D.; Takigawa, M.

    2014-09-30

    Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimation of aerosol direct and indirect effects. In this study, we developed an aerosol module, designated Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can represent these parameters explicitly by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 µm to resolve both aerosol size (12 bins) and BC mixing state (10 bins) for a total of 120 bins. The particles with diameters from 1 to 40 nm are resolved using an additional 8 size bins to calculate NPF. The ATRAS module was implemented in the WRF-chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging and SOA processes over East Asia during the spring of 2009. BC absorption enhancement by coating materials was about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement was estimated to be 10 – 20% over northern East Asia and 20 – 35% over southern East Asia. A clear north-south contrast was also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increased CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increased CCN concentrations at lower supersaturations (larger particles) over southern East Asia. Application of ATRAS to East Asia also showed that the impact of each process on each optical and radiative parameter depended strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA

  20. 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.

  1. Organic nitrate aerosol formation via NO3 + biogenic volatile organic compounds in the southeastern United States

    NASA Astrophysics Data System (ADS)

    Ayres, B. R.; Allen, H. M.; Draper, D. C.; Brown, S. S.; Wild, R. J.; Jimenez, J. L.; Day, D. A.; Campuzano-Jost, P.; Hu, W.; de Gouw, J.; Koss, A.; Cohen, R. C.; Duffey, K. C.; Romer, P.; Baumann, K.; Edgerton, E.; Takahama, S.; Thornton, J. A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Mohr, C.; Wennberg, P. O.; Nguyen, T. B.; Teng, A.; Goldstein, A. H.; Olson, K.; Fry, J. L.

    2015-12-01

    Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are correlated with increase in gas- and aerosol-organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23-44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 1 % of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO3 + BVOCs.

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

    NASA Astrophysics Data System (ADS)

    Hutchings, James W., III

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

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

    SciTech Connect

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

    2011-07-26

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

  4. 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

  5. An investigation of a potential low bias in the MODIS aerosol products over Asia

    NASA Astrophysics Data System (ADS)

    McHardy, T. M.; Shi, Y.; Zhang, J.; Reid, J. S.; Campbell, J. R.; Hsu, N. Y. C.

    2015-12-01

    Heavy aerosol plumes can be misidentified as clouds in passive satellite-based aerosol retrievals due to their relatively high visible reflectivity. Thus, over regions such as China, where a higher frequency of heavy aerosol plumes is expected, regional aerosol optical depth analyses reported from passive satellite-based aerosol products may biased low. This fundamental error can be suppressed under certain conditions. In this study, with a synergistic use of satellite observations from MODIS, OMI and CALIOP, a low bias in the MODIS Dark Target (DT) and Deep Blue (DB) aerosol products is studied over Asia for the influence of dense aerosol plume undersampling. A new scheme has been developed for detecting heavy aerosol plumes by coupling OMI aerosol index retrievals with available CALIOP level 1B and cloud and aerosol profile data. Collocated CALIOP, MODIS and OMI data are then used to further investigate the potential low bias in the MODIS DT and DB aerosol products, in an attempt to quantify the measure of undersampling in the regional DT and DB archive. Our preliminary results show that DT and DB aerosol algorithms detect about half heavy aerosol loading when CALIPSO and OMI AI believe there are heavy absorbing aerosols.

  6. The Effect of Aerosol Formation on Stable Isotopes Ratio in Titan's Atmosphere

    NASA Astrophysics Data System (ADS)

    Gautier, Thomas; Trainer, Melissa G.; Sebree, Joshua; Wold, Allison; Stern, Jennifer

    2016-10-01

    The formation of large amounts of aerosol in Titan atmosphere induces a significant sink for carbon and nitrogen in the atmosphere. Due to the high complexity of the chemistry leading to aerosol formation, there may be isotopic fractionation along the formation pathways of the aerosol. So far several stable isotopes have been measured in Titan atmosphere including the 13C/12C, 15N/14N and D/H ratios for different gaseous species. However, the fractionation effect of the aerosol formation and its impact on atmospheric stable isotope ratios has yet to be fully understood. Two experimental studies were recently published on the stable carbon [1] and nitrogen [1,2] isotope fractionation during aerosol formation in N2-CH4 reactant mixture. To better constrain the fractionation effect of aerosol formation on the Titan atmosphere we have measured the isotopic fractionation induced in laboratory aerosol analogues produced exploring the space of parameters that are expected to have an effect on fractionation processes. Parameters studied include pressure and temperature of aerosol formation and the reactant gas phase composition, including the standard "Titan" mixture of CH4/N2 as well as other trace species such as benzene (C6H6).[1] Sebree, J.A., Stern, J.C., Mandt, K.E., Domagal-Goldman, S.D., and Trainer, M.G.: C and N Fractionation of CH /N Mixtures during Photochemical Aerosol Formation: Relevance to Titan, (2016) Icarus 270:421-428[2] Kuga, M., Carrasco, N., Marty, B., Marrochi, Y., Bernard, S., Rigaudier, T., Fleury, B., Tissandier, L.: Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles, (2014) EPSL 393:2-13

  7. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: Unified Method for Predicting Aerosol Composition and Formation.

    PubMed

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

    2016-06-21

    Innovative secondary organic aerosol (SOA) composition analysis methods normalizing aerosol yield and chemical composition on an aromatic ring basis are developed and utilized to explore aerosol formation from oxidation of aromatic hydrocarbons. SOA yield and chemical composition are revisited using 15 years of University of California, Riverside/CE-CERT environmental chamber data on 17 aromatic hydrocarbons with HC:NO ranging from 11.1 to 171 ppbC:ppb. SOA yield is redefined in this work by normalizing the molecular weight of all aromatic precursors to the molecular weight of the aromatic ring [Formula: see text], where i is the aromatic hydrocarbon precursor. The yield normalization process demonstrates that the amount of aromatic rings present is a more significant driver of aerosol formation than the vapor pressure of the precursor aromatic. Yield normalization also provided a basis to evaluate isomer impacts on SOA formation. Further, SOA elemental composition is explored relative to the aromatic ring rather than on a classical mole basis. Generally, four oxygens per aromatic ring are observed in SOA, regardless of the alkyl substitutes attached to the ring. Besides the observed SOA oxygen to ring ratio (O/R ∼ 4), a hydrogen to ring ratio (H/R) of 6 + 2n is observed, where n is the number of nonaromatic carbons. Normalization of yield and composition to the aromatic ring clearly demonstrates the greater significance of aromatic ring carbons compared with alkyl carbon substituents in determining SOA formation and composition. PMID:27177154

  8. Organosulfate formation during the uptake of pinonaldehyde on acidic sulfate aerosols

    NASA Astrophysics Data System (ADS)

    Liggio, John; Li, Shao-Meng

    2006-07-01

    Organosulfates are observed in studies of pinonaldehyde reactions with acidic sulfate aerosols using aerosol mass spectrometry, during which a significant fraction of the pinonaldehyde reaction products were found to consist of organosulfate compounds that account for 6-51% of the initial SO4= mass. Resultant aerosol mass spectra were consistent with proposed sulfate ester mechanisms, which likely form stable products. The existence of organosulfates was also confirmed in studies of the reaction system in bulk solution. The formation of organosulfates suggests that conventional inorganic SO4= chemical analysis may underestimate total SO4= mass in ambient aerosols.

  9. 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

    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.

  10. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-03-01

    Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10) and ketones (C3 and C9) on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s) at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point) were found to play a dominant role in determining the mode of nucleation (homogenous or heterogeneous) and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures) nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

  11. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-08-01

    Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10) and ketones (C3 and C9) on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s) at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point) were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous) and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures) nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

  12. Organic nitrate aerosol formation via NO3 + BVOC in the Southeastern US

    NASA Astrophysics Data System (ADS)

    Ayres, B. R.; Allen, H. M.; Draper, D. C.; Brown, S. S.; Wild, R. J.; Jimenez, J. L.; Day, D. A.; Campuzano-Jost, P.; Hu, W.; de Gouw, J.; Koss, A.; Cohen, R. C.; Duffey, K. C.; Romer, P.; Baumann, K.; Edgerton, E.; Takahama, S.; Thornton, J. A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Mohr, C.; Goldstein, A. H.; Olson, K.; Fry, J. L.

    2015-06-01

    Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOC) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are calculated and correlated to gas and aerosol organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol as measured by Aerosol Mass Spectrometry (AMS) and Thermal Dissociation - Laser Induced Fluorescence (TD-LIF) suggests a range of molar yield of aerosol phase monoterpene nitrates of 23-44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to terpenes and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 0.5 % of the total organic nitrate in the aerosol-phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading comparable to that of organic nitrate produced via NO3 + BVOC.

  13. Secondary Organic Aerosol formation from the gas-phase ozonolysis of 3-methylcatechol and 4-methylcatechol

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, Cécile; Foulon, Valentine; Laréal, Michel; Cassez, Andy; Zhao, Weixiong

    2010-05-01

    Secondary Organic Aerosol (SOA) formation during the ozonolysis of 3-methylcatechol (3-methyl-1,2-dihydroxybenzene) and 4-methylcatechol (3-methyl-1,2-dihydroxybenzene) was investigated using a simulation chamber (8 m3) at atmospheric pressure, room temperature (294 ± 2 K) and low relative humidity (5-10%). The initial mixing ratios were as follows (in ppb): 3-methylcatechol (194-1059), 4-methylcatechol (204-1188) and ozone (93-531). The ozone and methylcatechol concentrations were followed by UV photometry and GC-FID (Gas Chromatography - Flame ionization detector), respectively and the aerosol production was monitored using a SMPS (Scanning Mobility Particle Sizer). The SOA yields (Y) were determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted methylcatechol concentrations assuming a particle density of 1.4 g cm-3. The aerosol formation yield increases as the initial methylcatechol concentration increases, and leads to aerosol yields ranging from 32% to 67% and from 30% to 64% for 3-methylcatechol and 4-methylcatechol, respectively. Y is a strong function of Mo and the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. These data are comparable to those published in a recent study on secondary organic aerosol formation from catechol ozonolysis. To our knowledge, this work represents the first investigation of SOA formation from the ozone reaction with methylcatechols.

  14. Secondary Organic Aerosol Formation from the Photooxidation of Naphthalene

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

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

  15. The role of sulfate aerosol in the formation of cloudiness over the sea

    NASA Astrophysics Data System (ADS)

    Aloyan, A. E.; Yermakov, A. N.; Arutyunyan, V. O.

    2016-07-01

    We estimate the impact of sulfate aerosols on cloudiness formation over the sea in the middle troposphere and the involvement of these particles in the formation of polar stratospheric clouds (PSCs) in the lower stratosphere. The first of these problems is solved using a combined model of moist convection and the formation of cloudiness and sulfate aerosols in the troposphere and lower stratosphere over the sea, incorporating natural emissions of sulfur-containing compounds. We have found that a significant source of condensation nuclei in the troposphere is the photochemical transformation of biogenic dimethyl sulfide (in addition to NaCl). The results of numerical experiments indicate that the absence of sulfate aerosols hinders the cloudiness formation over the sea in the middle and upper troposphere. The problem of sulfate aerosol involvement in the formation of supercooled ternary solutions (STSs) (PSC Type Ib) in the lower stratosphere is solved using a mathematical model of global transport of multicomponent gas pollutants and aerosols in the atmosphere. Using the combined model, numerical experiments were performed for the winter season in both hemispheres. Sulfate aerosols were found to really participate in the formation of STS particles. Without their participation, the formation of STS particles in the lower stratosphere would be hindered. We present the results of numerical calculations and discuss the distribution of concentrations of gaseous nitric and sulfuric acids, as well as mass concentrations of these components in STS particles.

  16. Secondary Organic Aerosol formation from the gas-phase reaction of catechol with ozone

    NASA Astrophysics Data System (ADS)

    Coeur-Tourneur, C.; Tomas, A.; Guilloteau, A.; Henry, F.; Ledoux, F.; Visez, N.; Riffault, V.; Wenger, J. C.; Bedjanian, Y.; Foulon, V.

    2009-04-01

    The formation of secondary organic aerosol from the gas-phase reaction of catechol (1,2-dihydroxybenzene) with ozone has been studied in two smog chambers (at the LPCA in France and at the CRAC in Ireland). Aerosol production was monitored using a scanning mobility particle sizer. The overall organic aerosol yield (Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses (Mo) to the total reacted catechol concentrations, assuming a particle density of 1.4 g cm-3. Analysis of the data clearly shows that Y is a strong function of Mo and that secondary organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial catechol concentration, which leads to aerosol yields ranging from 17% to 86%. The aerosol yields determined in the LPCA and CRAC smog chambers were comparable and were also in accordance with those determined in a previous study performed in EUPHORE (EUropean PHOto REactor, Spain).

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  19. Real-Time Secondary Aerosol Formation Measurements using a Photooxidation Reactor (PAM) and AMS in Urban Air and Biomass Smoke

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    Recent field studies reveal large formation of secondary organic aerosol (SOA) under urban polluted ambient conditions, while SOA formation in biomass burning smoke appears to be variable but sometimes substantial. To study this formation in real-time, a Potential Aerosol Mass (PAM) photooxidation reactor was deployed with submicron aerosol size and chemical composition measurements during two studies: FLAME-3, a biomass-burning study at USDA Fire Sciences Laboratory in Missoula in 2009, MT and CalNex-LA in Pasadena, CA in 2010. A high-resolution aerosol mass spectrometer (HR-AMS) and a scanning mobility particle sizer (SMPS) alternated sampling unprocessed and PAM-processed aerosol. The PAM 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 intensity was also scanned every 20 min. in both field studies. Results show the value of PAM-AMS as a tool for in-situ evaluation of changes in OA concentration and composition due to SOA formation and POA oxidation. In FLAME-3, net SOA formation was variable among smokes from different biomasses; however, OA oxidation was always observed. The average SOA enhancement factor was 1.7 +/- 0.5 of the initial POA. Reactive VOCs such as toluene, monoterpenes, and acetaldehyde, as measured from a PIT-MS, decreased with increased PAM processing; however, formic acid, acetone, and some unidentified OVOCs increased after significant exposure to high oxidant levels suggesting multigenerational chemistry. Results from CalNex-LA show enhancement of SOA and inorganic aerosol from gas-phase precursors. This enhanced OA mass increase from PAM processing is maximum at night and correlates with trimethylbenzene concentrations, which indicates the dominance of short-lived SOA precursors in the LA Basin. A traditional SOA model with mostly aromatic precursors underpredicts the amount of SOA formed by about an order-of-magnitude, which

  20. Ambipolar potential formation in TMX

    SciTech Connect

    Correll, D.L.; Allen, S.L.; Casper, T.A.

    1981-05-05

    TMX experimental data on ambipolar potential control and on the accompanying electrostatic confinement are reported. New results on the radial dependence of the central-cell confining potential are given. Radial and axial particle losses as well as scaling of the central-cell axial confinement are discussed.

  1. Numerical simulation of advection fog formation on multi-disperse aerosols due to combustion-related pollutants

    NASA Technical Reports Server (NTRS)

    Hung, R. J.; Liaw, G. S.

    1980-01-01

    The effects of multi-disperse distribution of the aerosol population are presented. Single component and multi-component aerosol species on the condensation/nucleation processes which affect the reduction in visibility are described. The aerosol population with a high particle concentration provided more favorable conditions for the formation of a denser fog than the aerosol population with a greater particle size distribution when the value of the mass concentration of the aerosols was kept constant. The results were used as numerical predictions of fog formation. Two dimensional observations in horizontal and vertical coordinates, together with time-dependent measurements were needed as initial values for the following physical parameters: (1)wind profiles; (2) temperature profiles; (3) humidity profiles; (4) mass concentration of aerosol particles; (5) particle size distribution of aerosols; and (6) chemical composition of aerosols. Formation and dissipation of advection fog, thus, can be forecasted numerically by introducing initial values obtained from the observations.

  2. Increase in upper tropospheric and lower stratospheric aerosol levels and its potential connection with Asian pollution

    PubMed Central

    Vernier, J-P; Fairlie, T D; Natarajan, M; Wienhold, F G; Bian, J; Martinsson, B G; Crumeyrolle, S; Thomason, L W; Bedka, K M

    2015-01-01

    Satellite observations have shown that the Asian Summer Monsoon strongly influences the upper troposphere and lower stratosphere (UTLS) aerosol morphology through its role in the formation of the Asian Tropopause Aerosol Layer (ATAL). Stratospheric Aerosol and Gas Experiment II solar occultation and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) lidar observations show that summertime UTLS Aerosol Optical Depth (AOD) between 13 and 18 km over Asia has increased by three times since the late 1990s. Here we present the first in situ balloon measurements of aerosol backscatter in the UTLS from Western China, which confirm high aerosol levels observed by CALIPSO since 2006. Aircraft in situ measurements suggest that aerosols at lower altitudes of the ATAL are largely composed of carbonaceous and sulfate materials (carbon/sulfur elemental ratio ranging from 2 to 10). Back trajectory analysis from Cloud-Aerosol Lidar with Orthogonal Polarization observations indicates that deep convection over the Indian subcontinent supplies the ATAL through the transport of pollution into the UTLS. Time series of deep convection occurrence, carbon monoxide, aerosol, temperature, and relative humidity suggest that secondary aerosol formation and growth in a cold, moist convective environment could play an important role in the formation of ATAL. Finally, radiative calculations show that the ATAL layer has exerted a short-term regional forcing at the top of the atmosphere of −0.1 W/m2 in the past 18 years. Key Points Increase of summertime upper tropospheric aerosol levels over Asia since the 1990s Upper tropospheric enhancement also observed by in situ backscatter measurements Significant regional radiative forcing of −0.1 W/m2 PMID:26691186

  3. Secondary Organic Aerosol Formation from the Photooxidation of p- and o-Xylene

    SciTech Connect

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

    2007-11-01

    The formation of secondary organic aerosol (SOA) from the photooxidation of xylene isomers (m-, p-, and o-xylenes) has been extensively investigated. The dependence of SOA aerosol formation on the structure of xylene isomers in the presence of NO was confirmed. Generally, SOA formation of p-xylene was less than that ofm- and o-xylenes. This discrepancy varies significantly with initial NOx levels. In a NOx-free environment, the difference of aerosol formation between o- and p-xylenes becomes insignificant. Several chemical pathways for the SOA dependence on structure and NOx are explored, with the experimental findings indicating that organic peroxides may be a major key to explaining SOA formation from aromatic hydrocarbons.

  4. Satellite remote sensing of dust aerosol indirect effects on ice cloud formation.

    PubMed

    Ou, Steve Szu-Cheng; Liou, Kuo-Nan; Wang, Xingjuan; Hansell, Richard; Lefevre, Randy; Cocks, Stephen

    2009-01-20

    We undertook a new approach to investigate the aerosol indirect effect of the first kind on ice cloud formation by using available data products from the Moderate-Resolution Imaging Spectrometer (MODIS) and obtained physical understanding about the interaction between aerosols and ice clouds. Our analysis focused on the examination of the variability in the correlation between ice cloud parameters (optical depth, effective particle size, cloud water path, and cloud particle number concentration) and aerosol optical depth and number concentration that were inferred from available satellite cloud and aerosol data products. Correlation results for a number of selected scenes containing dust and ice clouds are presented, and dust aerosol indirect effects on ice clouds are directly demonstrated from satellite observations.

  5. The Role of Aerosol Composition in Arctic Cloud Formation

    NASA Astrophysics Data System (ADS)

    Brooks, S. D.; Hiranuma, N.; Moffet, R.; Laskin, A.; Gilles, M. K.; Glen, A.

    2010-12-01

    While it has been shown that aerosol size has a direct correlation with its ability to act as an ice nucleus, the role of the composition of freshly emitted and evolving aerosol in nucleation is poorly understood. Here we use combined measurements of ice nucleation and high resolution single particle composition to provide insight on the connection between aerosol composition in ice nucleation. These measurements were collected during the Indirect and Semidirect Aerosols Campaign (ISDAC) over Barrow, AK in the springtime of 2008. In-situ ice nucleation measurements were conducted using the Texas Continuous Flow Diffusion Chamber (CFDC). The composition of ambient particles as well as residuals of cloud droplets and ice crystals were studied on a particle by particle basis using computer controlled scanning electron microscopy with energy dispersive X-ray analysis (CCSEM/EDX) and scanning transmission X-Ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFAS). Observed IN concentrations varied from frequent values of 0.01 per liter to more than 10 per liters, depending on conditions and the availability of ice-nucleating aerosols. Ice crystals residuals collected in a fully glaciated cloud demonstrate that both particle chemistry and size requirement must be met for a particle to be an efficient ice nucleus. According to the STXM/NEXAFAS spectral maps, ice crystals residuals are characterized by insoluble cores of either large brown or black carbon (BBC) or carbonates coated by water soluble organics. In contrast, in ambient air samples collected from a biomass burning plume, many organic particles were also observed, but these were smaller and did not have insoluble cores. In-situ ice nucleation measurements show that these biomass particles have inferior ice nuclei ability, relative to those collected in the glaciated cloud. Taken together our measurements suggest that two key elements, a critical size (provided by BBC and/or carbonate

  6. 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.

  7. Incremental Reactivity Effects of Anthropogenic and Biogenic Volatile Organic Compounds on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Kacarab, M.; Li, L.; Carter, W. P. L.; Cocker, D. R., III

    2015-12-01

    Two surrogate reactive organic gas (ROG) mixtures were developed to create a controlled reactivity environment simulating different urban atmospheres with varying levels of anthropogenic (e.g. Los Angeles reactivity) and biogenic (e.g. Atlanta reactivity) influences. Traditional chamber experiments focus on the oxidation of one or two volatile organic compound (VOC) precursors, allowing the reactivity of the system to be dictated by those compounds. Surrogate ROG mixtures control the overall reactivity of the system, allowing for the incremental aerosol formation from an added VOC to be observed. The surrogate ROG mixtures were developed based on that used to determine maximum incremental reactivity (MIR) scales for O3 formation from VOC precursors in a Los Angeles smog environment. Environmental chamber experiments were designed to highlight the incremental aerosol formation in the simulated environment due to the addition of an added anthropogenic (aromatic) or biogenic (terpene) VOC. All experiments were conducted in the UC Riverside/CE-CERT dual 90m3 environmental chambers. It was found that the aerosol precursors behaved differently under the two altered reactivity conditions, with more incremental aerosol being formed in the anthropogenic ROG system than in the biogenic ROG system. Further, the biogenic reactivity condition inhibited the oxidation of added anthropogenic aerosol precursors, such as m-xylene. Data will be presented on aerosol properties (density, volatility, hygroscopicity) and bulk chemical composition in the gas and particle phases (from a SYFT Technologies selected ion flow tube mass spectrometer, SIFT-MS, and Aerodyne high resolution time of flight aerosol mass spectrometer, HR-ToF-AMS, respectively) comparing the two controlled reactivity systems and single precursor VOC/NOx studies. Incremental aerosol yield data at different controlled reactivities provide a novel and valuable insight in the attempt to extrapolate environmental chamber

  8. Simulations of aerosols and their effects on photolysis and ozone formation in Mexico City

    NASA Astrophysics Data System (ADS)

    Li, G.; Zavala, M.; Lei, W.; Karydis, V. A.; Tsimpidi, A. P.; Pandis, S.; Molina, L. T.

    2009-04-01

    Atmospheric aerosols, formed from natural and anthropogenic sources, are believed to be associated with adverse human effects at high levels in polluted urban areas. They also play a key role in climate through direct and indirect effects. Therefore, accurate simulations of aerosol composition and distribution in the atmospheric models are important in evaluating their impact on environment and climate. In the present study, a flexible gas phase chemical module with SAPRC mechanism and the CMAQ/models3 aerosol module developed by EPA have been implemented into the WRF-CHEM model. Additionally, to further improve the aerosol, especially the secondary organic aerosol (SOA) simulations, an advanced SOA module [Tsimpidi et al., 2009] has been incorporated into the WRF-CHEM model. The new SOA module is based on the volatility basis-set approach in which both primary and secondary organic components are assumed to be semivolatile and photochemically reactive [Lane et al., 2008]. Gas phase species and aerosol simulation results are compared with the available measurements obtained during the MILAGRO 2006 campaign. When the advanced SOA mechanism is employed, the SOA simulations are significantly improved. Furthermore, the aerosol impacts on the photochemistry in Mexico City have been evaluated using the FTUV [Tie et al., 2005]. Aerosol optical properties are calculated using the Mie theory and compared with available observations in Mexico City [Paredes-Miranda et al., 2008]. Aerosols, principally black carbon, reduce the photolysis frequencies of J[O3(1D)] and J[NO2] in the planetary boundary layer and hence decrease the ground-level ozone concentration. Our study demonstrates that the impact of aerosols on photochemistry is significant in polluted urban atmosphere. References: Lane, T. E., N. M. Donahue, and S. N. Pandis (2008), Simulating secondary organic aerosol formation using the volatility basis-set approach in a chemical transport model, PMCAMx, Atmos. Environ

  9. Heavy Ion Formation in Titan's Ionosphere: Magnetospheric Introduction of Free Oxygen and Source of Titan's Aerosols?

    NASA Technical Reports Server (NTRS)

    Sittler, E. C., Jr.; Hartle, R. E.; Cooper, J. F.; Johnson, R. E.; Coates, A.; dePater, imke; Strom, Daphne; Simoes, F.; Steele, A.; Robb, F.

    2007-01-01

    With the recent discovery of heavy ions, positive and negative, by the Cassini Plasma Spectrometer (CAPS) instrument in Titan's ionosphere, it reveals new possibilities for aerosol formation at Titan and the introduction of free oxygen to the aerosol chemistry from Saturn's magnetosphere with Enceladus as the primary oxygen source. One can estimate whether the heavy ions in the ionosphere are of sufficient number to account for all the aerosols, under what conditions are favorable for heavy ion formation and how they are introduced as seed particles deeper in Titan's atmosphere where the aerosols form and eventually find themselves on Titan's surface where unknown chemical processes can take place. Finally, what are the possibilities with regard to their chemistry on the surface with some free oxygen present in their seed particles?

  10. Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles

    NASA Astrophysics Data System (ADS)

    Tabazadeh, Azadeh

    Fatty acid salts and "humic" materials, found in abundance in atmospheric particles, are both anionic surfactants. Such materials are known to form organic aggregates or colloids in solution at very low aqueous concentrations. In a marine aerosol, micelle aggregates can form at a low fatty acid salt molality of ˜10 -3 m. In other types of atmospheric particles, such as biomass burning, biogenic, soil dust, and urban aerosols, "humic-like" materials exist in sufficient quantities to form micelle-like aggregates in solution. I show micelle formation limits the ability of surface-active organics in aerosols to reduce the surface tension of an atmospheric particle beyond about 10 dyne cm -1. A general phase diagram is presented for anionic surfactants to explain how surface-active organics can change the water uptake properties of atmospheric aerosols. Briefly such molecules can enhance and reduce water uptake by atmospheric aerosols at dry and humid conditions, respectively. This finding is consistent with a number of unexplained field and laboratory observations. Dry electron microscope images of atmospheric particles often indicate that organics may coat the surface of particles in the atmosphere. The surfactant phase diagram is used to trace the particle path back to ambient conditions in order to determine whether such coatings can exist on wet ambient aerosols. Finally, I qualitatively highlight how organic aggregate formation in aerosols may change the optical properties and chemical reactivity of atmospheric particles.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  13. Study of the CCN formation as a function of aerosol components

    NASA Astrophysics Data System (ADS)

    Fanourgakis, George S.; Myriokefalitakis, Stelios; Kanakidou, Maria

    2016-04-01

    Understanding the role of aerosols in Earth's climate through direct and indirect effects has attracted a lot of attention over the last years. Due to the chemical complexity of aerosols along with the variety of the primary emissions sources and the conversions from gas to particle in atmosphere, accurate predictions for the aerosols impact on a regional and global scale still remains a challenging problem. In this study, we examine the relative contribution of directly emitted particles in the atmosphere (primary particles) and particles formed from gas-to-particle conversion (secondary particles) to the global aerosols and to the cloud condensation nuclei (CCN) formation. The Chemistry Transport Model v4.0 (TM4-ECPL) coupled with an extended version of the aerosol micro-physics model M7, which describes microphysical processes (nucleation, coagulation, condensation of gas-phase species) for sulfate, black carbon, organic carbon sea salt, dust and various secondary organic aerosols, is here used. A systematic analysis on the CCN production as a function of the aerosol chemical composition is performed. The sensitivity of the results to physical parameters that affect the CCN formation and cannot be accurately determined, such as hygroscopicity, is investigated based on a detailed sensitivity analysis. This work has been supported by the European FP7 collaborative project BACCHUS (Impact of Biogenic versus Anthropogenic emissions on Clouds and Climate: towards a Holistic UnderStanding).

  14. 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.

    2014-10-01

    Emissions of biogenic volatile organic compounds (BVOC) have changed in the past millennium due to changes in land use, temperature and CO2 concentrations. Recent model reconstructions of BVOC emissions over the past millennium predicted changes in dominant secondary organic aerosol (SOA) producing BVOC classes (isoprene, monoterpenes and sesquiterpenes). The reconstructions predicted that global isoprene emissions have decreased (land-use changes to crop/grazing land dominate the reduction), while monoterpene and sesquiterpene emissions have increased (temperature increases dominate the increases); however, all three show regional variability due to competition between the various influencing factors. These BVOC changes have largely been anthropogenic in nature, and land-use change was shown to have the most dramatic effect by decreasing isoprene emissions. 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 SOA formation, global aerosol size distributions, and radiative effects using the GEOS-Chem-TOMAS global aerosol microphysics model. With anthropogenic emissions (e.g. SO2, NOx, primary aerosols) held at present day values and BVOC emissions changed from year 1000 to year 2000 values, decreases in the number concentration of particles of size Dp > 80 nm (N80) of >25% in year 2000 relative to year 1000 were predicted in regions with extensive land-use changes since year 1000 which led to regional increases in direct plus indirect aerosol radiative effect 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

  15. Potential Impacts of Pollution Aerosol and Dust Acting As Cloud-Nucleating Aerosol on Precipitation in the Colorado River Basin

    NASA Astrophysics Data System (ADS)

    Jha, V.; Cotton, W. R.; Carrio, G. G.

    2014-12-01

    The southwest US has huge demands on water resources. The Colorado River Basin (CRB) is potentially affected by anthropogenic aerosol pollution and dust acting as cloud-nucleating aerosol as well as impacting snowpack albedo.The specific objective of this research is to quantify the impacts of both dust and pollution aerosols on wintertime precipitation in the Colorado Mountains for the years 2005-2006. We examine the combined effects of anthropogenic pollution aerosol and dust serving as cloud condensation nuclei (CCN), ice nuclei (IN) and giant CCN(GCCN) on precipitation in the CRB. Anthropogenic pollution can enhance droplet concentrations, and decrease collision and coalescence and ice particle riming largely via the "spillover" effect. Dust can serve as IN and enhance precipitation in wintertime orographic clouds. Dust coated with sulfates or originating over dry lake beds can serve as GCCN which when wetted can result in larger cloud droplets and thereby enhance the warm-rain collision and coalescence process and ice particle riming. But smaller dust particles coated with sulfates, can decrease collision and coalescence and ice particle riming similar to anthropogenic pollution aerosols. The Colorado State University (CSU) Regional Atmospheric Modeling System (RAMS) version 6.0 is used for this study. RAMS was modified to ingest GEOS-CHEM output data and periodically update aerosol fields. GEOS-CHEM is a chemical transport model which uses assimilated meteorological data from the NASA Goddard Earth Observation System (GEOS). The aerosol data comprise a sum of hydrophobic and hydrophilic black carbon and organic aerosol, hydrophilic SOAs, hydrocarbon oxidation and inorganic aerosols (nitrate, sulfate and ammonium). In addition, a RAMS-based dust source and transport model is used. Preliminary analysis suggests pollution dominates over dust resulting in a decrease in precipitation via the spillover effect. Dust serving as GCCN and IN tend to enhance ice

  16. 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

  17. METAL AEROSOL FORMATION IN A LABORATORY SWIRL FLAME INCINERATOR

    EPA Science Inventory

    The paper describes experiments performed using an 82 kW (280,000 Btu/hr) refractory-lined horizontal tunnel combustor to examine the aerosol particle size distribution (PSD) produced by simulated nickel, cadmium, and lead wastes injected into an incineration environment. Metal c...

  18. Quantifying compositional impacts of ambient aerosol on cloud droplet formation

    NASA Astrophysics Data System (ADS)

    Lance, Sara

    It has been historically assumed that most of the uncertainty associated with the aerosol indirect effect on climate can be attributed to the unpredictability of updrafts. In Chapter 1, we analyze the sensitivity of cloud droplet number density, to realistic variations in aerosol chemical properties and to variable updraft velocities using a 1-dimensional cloud parcel model in three important environmental cases (continental, polluted and remote marine). The results suggest that aerosol chemical variability may be as important to the aerosol indirect effect as the effect of unresolved cloud dynamics, especially in polluted environments. We next used a continuous flow streamwise thermal gradient Cloud Condensation Nuclei counter (CCNc) to study the water-uptake properties of the ambient aerosol, by exposing an aerosol sample to a controlled water vapor supersaturation and counting the resulting number of droplets. In Chapter 2, we modeled and experimentally characterized the heat transfer properties and droplet growth within the CCNc. Chapter 3 describes results from the MIRAGE field campaign, in which the CCNc and a Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) were deployed at a ground-based site during March, 2006. Size-resolved CCN activation spectra and growth factor distributions of the ambient aerosol in Mexico City were obtained, and an analytical technique was developed to quantify a probability distribution of solute volume fractions for the CCN in addition to the aerosol mixing-state. The CCN were shown to be much less CCN active than ammonium sulfate, with water uptake properties more consistent with low molecular weight organic compounds. The pollution outflow from Mexico City was shown to have CCN with an even lower fraction of soluble material. "Chemical Closure" was attained for the CCN, by comparing the inferred solute volume fraction with that from direct chemical measurements. A clear diurnal pattern was observed for the CCN solute

  19. 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 ~ 50-100μM) 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.

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

    PubMed

    Dette, Hans P; Koop, Thomas

    2015-05-14

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

  1. Unique airborne measurements at the tropopause of Fukushima Xe-133, aerosol, and aerosol precursors indicate aerosol formation via homogeneous and cosmic ray induced nucleation

    NASA Astrophysics Data System (ADS)

    Schlager, Hans; Arnold, Frank; Aufmhoff, Heinfried; Minikin, Andreas; Baumann, Robert; Simgen, Hardy; Lindemann, Stefan; Rauch, Ludwig; Kaether, Frank; Pirjola, Liisa; Schumann, Ulrich

    2014-05-01

    We report unique airborne measurements, at the tropopause, of the Fukushima radio nuclide Xe-133, aerosol particles (size, shape, number concentration, volatility), aerosol precursor gases (particularly SO2, HNO3, H2O). Our measurements and accompanying model simulations indicate homogeneous and cosmic ray induced aerosol formation at the tropopause. Using an extremely sensitive detection method, we managed to detect Fukushima Xe-133, an ideal transport tracer, at and even above the tropopause. To our knowledge, these airborne Xe-133 measurements are the only of their kind. Our investigations represent a striking example how a pioneering measurement of a Fukshima radio nuclide, employing an extremely sensitive method, can lead to new insights into an important atmospheric process. After the Fukushima accidential Xe-133 release (mostly during 11-15 March 2011), we have conducted two aircraft missions, which took place over Central Europe, on 23 March and 11 April 2011. In the air masses, encountered by the research aircraft on 23 March, we have detected Fukushima Xe-133 by an extremely sensitive method, at and even above the tropopause. Besides increased concentrations of Xe-133, we have detected also increased concentrations of the gases SO2, HNO3, and H2O. The Xe-133 data and accompanying transport model simulations indicate that a West-Pacific Warm Conveyor Belt (WCB) lifted East-Asian planetary boundary layer air to and even above the tropopause, followed by relatively fast quasi-horizontal advection to Europe. Along with Xe-133, anthropogenic SO2, NOx (mostly released from East-Asian ground-level combustion sources), and warer vapour were also lifted by the WCB. After the lift, SO2 and NOx experienced efficient solar UV-radiation driven conversion to the important aerosol precursors gases H2SO4 and HNO3. Our investigations indicate that, increased concentrations of the gases SO2, HNO3, and H2O promoted homogeneous and cosmic ray induced aerosol formation at and

  2. Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Volkamer, R.

    2010-09-01

    This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m-3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7). Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  4. Aerosolized MMR vaccine: evaluating potential transmission of components to vaccine administrators and contacts of vaccinees.

    PubMed

    Diaz-Ortega, Jose-Luis; Bennett, John V; Castaneda, Deyanira; Martinez, David; Fernandez de Castro, Jorge

    2012-07-01

    Although numerous operative and immunological advantages accompany aerosol immunization, potential vaccine virus transmission from the aerosol device to vaccine administrators or from aerosol vaccinees to their contacts requires further study. We conducted a clinical and serological follow-up study of vaccine administrators and matched classroom or household contacts of young adults who received the MMR vaccines by aerosol or injection. Differences in incidence of clinical adverse events between vaccinees and contacts were not statistically significant. No seroresponses to any components of MMR vaccine were noted among 25 matched contacts of persons receiving injected vaccines, and only one equivocal seroresponse was noted among 25 matched contacts of aerosol recipients. No seroresponses were observed in 3 persons who administered aerosol vaccine. The composite findings of this study provide additional evidence of the safety of this approach.

  5. Formation of highly porous aerosol particles by atmospheric freeze-drying in ice clouds

    NASA Astrophysics Data System (ADS)

    Rudich, Yinon; Adler, Gabriela; Koop, Thomas; Taraniuk, Ilya; Moise, Tamar; Koren, Ilan; Heiblum, Reuven; Haspel, Carynelisa

    2014-05-01

    In cold high altitude cirrus clouds and anvils of high convective clouds in the tropics and mid-latitudes, ice partciles that are exposed to subsaturation conditions with respect to ice can sublimate, leaving behind residual modified aerosols. This freeze-drying process can occur in various types of clouds. In this talk we will describe experiements that simulate the atmospheric freeze-drying cycle of aerosols. We find that aerosols with high organic content can form highly porous particles (HPA) with a larger diameter and a lower density than the initial homogenous aerosol following ice subliation. We attribute this morphology change to phase separation upon freezing followed by a glass transition of the organic material that can preserve a porous structure follwoing ice sublimation. We find that the highly porous aerosol scatter solar light less efficiently than non-porous aerosol particles. A porous structure may explain the previously observed enhancement in ice nucleation efficiency of glassy organic particles. These observations may have implications for subsequent cloud formation cycles and aerosol albedo near cloud edges.

  6. Potential of polarization lidar to provide profiles of CCN- and INP-relevant aerosol parameters

    NASA Astrophysics Data System (ADS)

    Mamouri, R. E.; Ansmann, A.

    2015-12-01

    We investigate the potential of polarization lidar to provide vertical profiles of aerosol parameters from which cloud condensation nucleus (CCN) and ice nucleating particle (INP) number concentrations can be estimated. We show that height profiles of number concentrations of aerosol particles with radius > 50 nm (APC50, reservoir of favorable CCN) and with radius > 250 nm (APC250, reservoir of favorable INP), as well as profiles of the aerosol particle surface area concentration (ASC, used in INP parameterization) can be retrieved from lidar-derived aerosol extinction coefficients (AEC) with relative uncertainties of a factor of around 2 (APC50), and of about 25-50 % (APC250, ASC). Of key importance is the potential of polarization lidar to identify mineral dust particles and to distinguish and separate the aerosol properties of basic aerosol types such as mineral dust and continental pollution (haze, smoke). We investigate the relationship between AEC and APC50, APC250, and ASC for the main lidar wavelengths of 355, 532 and 1064 nm and main aerosol types (dust, pollution, marine). Our study is based on multiyear Aerosol Robotic Network (AERONET) photometer observations of aerosol optical thickness and column-integrated particle size distribution at Leipzig, Germany, and Limassol, Cyprus, which cover all realistic aerosol mixtures of continental pollution, mineral dust, and marine aerosol. We further include AERONET data from field campaigns in Morocco, Cabo Verde, and Barbados, which provide pure dust and pure marine aerosol scenarios. By means of a simple relationship between APC50 and the CCN-reservoir particles (APCCCN) and published INP parameterization schemes (with APC250 and ASC as input) we finally compute APCCCN and INP concentration profiles. We apply the full methodology to a lidar observation of a heavy dust outbreak crossing Cyprus with dust up to 8 km height and to a case during which anthropogenic pollution dominated.

  7. Formation and growth of indoor air aerosol particles as a result of D-limonene oxidation

    NASA Astrophysics Data System (ADS)

    Vartiainen, E.; Kulmala, M.; Ruuskanen, T. M.; Taipale, R.; Rinne, J.; Vehkamäki, H.

    Oxidation of D-limonene, which is a common monoterpene, can lead to new aerosol particle formation in indoor environments. Thus, products containing D-limonene, such as citrus fruits, air refresheners, household cleaning agents, and waxes, can act as indoor air aerosol particle sources. We released D-limonene into the room air by peeling oranges and measured the concentration of aerosol particles of three different size ranges. In addition, we measured the concentration of D-limonene, the oxidant, and the concentration of ozone, the oxidizing gas. Based on the measurements we calculated the growth rate of the small aerosol particles, which were 3-10 nm in diameter, to be about 6300nmh-1, and the losses of the aerosol particles that were due to the coagulation and condensation processes. From these, we further approximated the concentration of the condensable vapour and its source rate and then calculated the formation rate of the small aerosol particles. For the final result, we calculated the nucleation rate and the maximum number of molecules in a critical cluster. The nucleation rate was in the order of 105cm-3s-1 and the number of molecules in a critical-sized cluster became 1.2. The results were in agreement with the activation theory.

  8. Research highlights: laboratory studies of the formation and transformation of atmospheric organic aerosols.

    PubMed

    Borduas, Nadine; Lin, Vivian S

    2016-04-01

    Atmospheric particles are emitted from a variety of anthropogenic and natural precursors and have direct impacts on climate, by scattering solar irradiation and nucleating clouds, and on health, by causing oxidative stress in the lungs when inhaled. They may also form from gaseous precursors, creating complex mixtures of organic and inorganic material. The chemical composition and the physical properties of aerosols will evolve during their one-week lifetime which will consequently change their impact on climate and health. The heterogeneity of aerosols is difficult to model and thus atmospheric aerosol research strives to characterize the mechanisms involved in nucleating and transforming particles in the atmosphere. Recent advances in four laboratory studies of aerosol formation and aging are highlighted here.

  9. Organic aerosol formation from photochemical oxidation of diesel exhaust in a smog chamber.

    PubMed

    Weitkamp, Emily A; Sage, Amy M; Pierce, Jeffrey R; Donahue, Neil M; Robinson, Allen L

    2007-10-15

    Diluted exhaust from a diesel engine was photo-oxidized in a smog chamber to investigate secondary organic aerosol (SOA) production. Photochemical aging rapidly produces significant SOA, almost doubling the organic aerosol contribution of primary emissions after several hours of processing at atmospherically relevant hydroxyl radical concentrations. Less than 10% of the SOA mass can be explained using a SOA model and the measured oxidation of known precursors such as light aromatics. However, the ultimate yield of SOA is uncertain because it is sensitive to treatment of particle and vapor losses to the chamber walls. Mass spectra from an aerosol mass spectrometer (AMS) reveal that the organic aerosol becomes progressively more oxidized throughout the experiments, consistent with sustained, multi-generational production. The data provide strong evidence that the oxidation of a wide array of precursors that are currently not accounted for in existing models contributes to ambient SOA formation.

  10. Free amino acids in Antarctic aerosol: potential markers for the evolution and fate of marine aerosol

    NASA Astrophysics Data System (ADS)

    Barbaro, E.; Zangrando, R.; Vecchiato, M.; Piazza, R.; Cairns, W. R. L.; Capodaglio, G.; Barbante, C.; Gambaro, A.

    2015-05-01

    To investigate the impact of marine aerosols on global climate change it is important to study their chemical composition and size distribution. Amino acids are a component of the organic nitrogen in aerosols and particles containing amino acids have been found to be efficient ice nuclei. The main aim of this study was to investigate the L- and D-free amino acid composition as possible tracers of primary biological production in Antarctic aerosols from three different areas: two continental bases, Mario Zucchelli Station (MZS) on the coast of the Ross Sea, Concordia Station at Dome C on the Antarctic Plateau, and the Southern Ocean near the Antarctic continent. Studying the size distribution of amino acids in aerosols allowed us to characterize this component of the water-soluble organic carbon (WSOC) in marine aerosols near their source and after long-range transport. The presence of only free L-amino acids in our samples is indicative of the prevalence of phytoplanktonic material. Sampling at these three points allowed us to study the reactivity of these compounds during long-range transport. The mean total amino acid concentration detected at MZS was 11 pmol m-3, a higher percentage of amino acids were found in the fine fraction. The aerosol samples collected at Dome C had the lowest amino acid values (0.7 and 0.8 pmol m-3), and the coarse particles were found to have higher concentrations of amino acids compared to the coastal site. The amino acid composition in the aerosol collected at Dome C had also changed compared to the coastal site, suggesting that physical and chemical transformations had occurred during long range transport. During the sampling cruise on the R/V Italica on the Southern Ocean, high concentrations of amino acids were found in the total suspended particles, this we attribute to the presence of intact biological material (as microorganisms or plant material) in the sample.

  11. Substantial secondary organic aerosol formation in a coniferous forest: observations of both day and night time chemistry

    NASA Astrophysics Data System (ADS)

    Lee, A. K. Y.; Abbatt, J. P. D.; Leaitch, W. R.; Li, S.-M.; Sjostedt, S. J.; Wentzell, J. J. B.; Liggio, J.; Macdonald, A. M.

    2015-10-01

    Substantial biogenic secondary organic aerosol (BSOA) formation was investigated in a coniferous forest mountain region at Whistler, British Columbia. A largely biogenic aerosol growth episode was observed, providing a unique opportunity to investigate BSOA formation chemistry in a forested environment with limited influence from anthropogenic emissions. Positive matrix factorization of aerosol mass spectrometry (AMS) measurement identified two types of BSOA (BSOA-1 and BSOA-2), which were primarily generated by gas-phase oxidation of monoterpenes and perhaps sesquiterpenes. The temporal variations of BSOA-1 and BSOA-2 can be explained by gas-particle partitioning in response to ambient temperature and the relative importance of different oxidation mechanisms between day and night. While BSOA-1 will arise from gas-phase ozonolysis and nitrate radical chemistry at night, BSOA-2 is less volatile than BSOA-1 and consists of products formed via gas-phase oxidation by the OH radical and ozone during the day. Organic nitrates produced through nitrate radical chemistry can account for 22-33 % of BSOA-1 mass at night. The mass spectra of BSOA-1 and BSOA-2 have higher values of the mass fraction of m/z 91 (f91) compared to the background organic aerosol, and so f91 is used as an indicator of BSOA formation pathways. A comparison between laboratory studies in the literature and our field observations highlights the potential importance of gas-phase formation chemistry of BSOA-2 type materials that may not be captured in smog chamber experiments, perhaps due to the wall loss of gas-phase intermediate products.

  12. A kinetic mechanism for predicting secondary aerosol formation from the reactions of d-limonene in the presence of oxides of nitrogen and natural sunlight

    NASA Astrophysics Data System (ADS)

    Leungsakul, Sirakarn; Jeffries, Harvey E.; Kamens, Richard M.

    Among the monoterpenes, d-limonene is one of the most reactive, and has one of the highest particle formation potentials. Chamber experiments with d-limonene, nitric oxide, nitrogen dioxide, and diurnal natural sunlight are compared with simulation results from a first generation semi-explicit d-limonene daytime mechanism. The d-limonene model adequately predicts the timing of NO-NO 2 crossover, d-limonene decay, and the general trend of ozone formation, and particle mass accumulation. When experimental secondary organic aerosol (SOA) masses were greater than 1 mg m -3 the simulations tended to agree closely with the measured aerosol maxima. At lower SOA concentrations, the simulations tended to overpredict measured aerosol maxima by 25-50%. FTIR analysis and GC-ECD measurements indicate particle phase nitrates and peroxyacetyl nitrate (PAN) formation in the system. In the afternoon when temperatures are highest in the outdoor chambers, the slow rise of continuous ozone measurements suggests that PAN type compounds were decomposing to "bleed" NO 2 into the gas phase. Partitioning calculations also suggest that these types of compounds are off-gassing from the particle phase later in the afternoon as well, and provide an additional source of NO 2. Predicted aerosol yields with a commonly used two-parameter aerosol yield model are compared with experimental aerosol yields. The parameritized aerosol yield model had difficulty predicting most of the UNC chamber data. The explicit d-limonene mechanism developed in this study could reasonably simulate the aerosol formation trend in the Caltech chambers, but tended to overpredict SOA maxima.

  13. ACTRIS aerosol vertical profile data and observations: potentiality and first examples of integrated studies with models

    NASA Astrophysics Data System (ADS)

    Mona, Lucia; Benedetti, Angela; D'Amico, Giuseppe; Myhre, Cathrine Lund; Schulz, Michael; Wandinger, Ulla; Laj, Paolo; Pappalardo, Gelsomina

    2016-04-01

    The ACTRIS-2 project, funded by Horizon 2020, addresses the scope of integrating state-of-the-art European ground-based stations for long term observations of aerosols, clouds and short lived gases, capitalizing on the work of FP7-ACTRIS. It aims at achieving the construction of a user-oriented RI, unique in the EU-RI landscape for providing 4-D integrated high-quality data from near-surface to high altitude (vertical profiles and total-column) which are relevant to climate and air-quality research. ACTRIS-2 develops and implements, in a large network of stations in Europe and beyond, observational protocols that permit the harmonization of collected data and their dissemination. ACTRIS secures provision and dissemination of a unique set of data and data-products that would not otherwise be available with the same level of quality and standardization. This results from a 10-year plus effort in constructing a research infrastructure capable of responding to community needs and requirements, and has been engaged since the start of the FP5 EU commission program. ACTRIS ensures compliance with reporting requirements (timing, format, traceability) defined by the major global observing networks. EARLINET (European Aerosol research Lidar NETwork), the aerosol vertical profiling component of ACTRIS, is providing since May 2000 vertical profiles of aerosol extinction and backscatter over Europe. A new structure of the EARLINET database has been designed in a more user oriented approach reporting new data products which are more effective for specific uses of different communities. In particular, a new era is starting with the Copernicus program during which the aerosol vertical profiling capability will be fundamental for assimilation and validation purposes. The new data products have been designed thanks to a strong link with EARLINET data users, first of all modeling and satellite communities, established since the beginning of EARLINET and re-enforced within ACTRIS2

  14. 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.

  15. Organic aerosol formation from biogenic compounds over the Ponderosa pine forest in Colorado

    NASA Astrophysics Data System (ADS)

    Roux, Alma Hodzic; Lee-Taylor, Julia; Cui, Yuyan; Madronich, Sasha

    2013-05-01

    The secondary organic aerosol (SOA) formation and regional growth from biogenic precursors is of particular interest given their abundance in the atmosphere, and has been investigated during the Rocky Mountain Biogenic Aerosol field Study in 2011 in the pine forest canopy (dominated by terpene emissions) using both WRF/Chem 4km simulations and the GECKO-A explicit chemistry box-model runs. We have quantified the relative contribution of different biogenic precursors to SOA levels that were measured by the aerosol mass spectrometer at the site, and investigated the relative contribution of OH, O3 and NO3 chemistry to the formed SOA mass during day-and nighttime. Although, the local production and mass concentrations of submicron organic aerosols at the site seem relatively modest ˜1-2 ug/m3, we show that the optically active regional mass is increased as the SOA formation continues for several days in the background forest air. We investigate whether the simplified SOA parameterizations used in 3D models can capture this growth. In addition, preliminary comparisons of the number concentrations and the composition of ultrafine particles (8 - 30nm) from WRF/Chem simulations and TD-CIMS measurements are also discussed, and the contribution of organic aerosols to CCN formation is quantified.

  16. Organic peroxide and OH formation in aerosol and cloud water: laboratory evidence for this aqueous chemistry

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is well accepted as an atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2-C3) are precursors for SOAaq and products include organic acids, organic sulfates, and high molecular weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior. This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra high resolution Fourier Transform Ion Cyclotron Resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals, and epoxides, and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.

  17. Validation of MODIS aerosol retrievals and evaluation of potential cloud contamination in East Asia.

    PubMed

    Xia, Xiang-Ao; Chen, Hong-Bin; Wang, Pu-Cai

    2004-01-01

    MODIS aerosol retrievals onboard Terra/Aqua and ground truth data obtained from AERONET (Aerosol Robtic Network) solar direct radiance measurements are collocated to evaluate the quality of the former in East Asia. AERONET stations in East Asia are separated into two groups according to their locations and the preliminary validation results for each station. The validation results showed that the accuracy of MODIS aerosol retrievals in East Asia is a little worse than that obtained in other regions such as Eastern U.S., Western Europe, Brazil and so on. The primary reason is due to the improper aerosol model used in MODIS aerosol retrieval algorithm, so it is of significance to characterize aerosol properties properly according to long-term ground-based remote sensing or other relevant in situ observations in order to improve MODIS retrievals in East Asia. Cloud contamination is proved to be one of large errors, which is demonstrated by the significant relation between MODIS aerosol retrievals versus cloud fraction, as well as notable improvement of linear relation between satellite and ground aerosol data after potential cloud contamination screened. Hence, it is suggested that more stringent clear sky condition be set in use of MODIS aerosol data. It should be pointed out that the improvement might be offset by other error sources in some cases because of complex relation between different errors. Large seasonal variation of surface reflection and uncertainties associated with it result in large intercepts and random error in MODIS aerosol retrievals in northern inland of East Asia. It remains to be a big problem to retrieve aerosols accurately in inland characterized by relatively larger surface reflection than the requirement in MODIS aerosol retrieval algorithm.

  18. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    DOE PAGES

    Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; et al

    2016-03-08

    An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed formore » semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected) compared to daytime (average 0.9 µg m−3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of

  19. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    NASA Astrophysics Data System (ADS)

    Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; Kroll, Jesse H.; Peng, Zhe; Brune, William H.; Jimenez, Jose L.

    2016-03-01

    An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen-Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m-3 when LVOC fate corrected) compared to daytime (average 0.9 µg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic

  20. Secondary organic aerosol formation initiated from reactions between ozone and surface-sorbed squalene

    NASA Astrophysics Data System (ADS)

    Wang, Chunyi; Waring, Michael S.

    2014-02-01

    Previous research has shown that ozone reactions on surface-sorbed D-limonene can promote gas phase secondary organic aerosol (SOA) formation indoors. In this work, we conducted 13 steady state chamber experiments to measure the SOA formation entirely initiated by ozone reactions with squalene sorbed to glass, at chamber ozone of 57-500 ppb for two relative humidity (RH) conditions of 21% and 51%, in the absence of seed particles. Squalene is a nonvolatile compound that is a component of human skin oil and prevalent on indoor surfaces and in settled dust due to desquamation. The size distributions, mass and number secondary emission rates (SER), aerosol mass fractions (AMF), and aerosol number fractions (ANF) of formed SOA were quantified. The surface AMF and ANF are defined as the change in SOA mass or number formed, respectively, per ozone mass consumed by ozone-squalene reactions. All experiments but one exhibited nucleation and mass formation. Mass formation was relatively small in magnitude and increased with ozone, most notably for the RH = 51% experiments. The surface AMF was a function of the chamber aerosol concentration, and a multi-product model was fit using the 'volatility basis set' framework. Number formation was relatively strong at low ozone and low RH conditions. Though we cannot extrapolate our results because experiments were conducted at high air exchange rates, we speculate that this process may enhance particle number more than mass concentrations indoors.

  1. 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

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  3. Effects of temperature on the formation of secondary organic aerosol from amine precursors

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aerosol formation is directly influenced by meteorological properties such as temperature and relative humidity. Temperature, for example, directly affects the gas-to-particle partitioning of amine salts and semi-volatile organic amine products. These salts are formed in areas with high agricultur...

  4. The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth.

    PubMed

    DeWitt, H Langley; Hasenkopf, Christa A; Trainer, Melissa G; Farmer, Delphine K; Jimenez, Jose L; McKay, Christopher P; Toon, Owen B; Tolbert, Margaret A

    2010-10-01

    The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 × 10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S(8)) and sulfuric acid (H(2)SO(4)) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO(2) either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H(2)) or methane (CH(4)), increased the formation of S(8). With UV photolysis, formation of S(8) aerosols is highly dependent on the initial SO(2) pressure; and S(8) is only formed at a 2% SO(2) mixing ratio and greater in the absence of a reductant, and at a 0.2% SO(2) mixing ratio and greater in the presence of 1000 ppmv CH(4). We also found that organosulfur compounds are formed from the photolysis of CH(4) and moderate amounts of SO(2). The implications for sulfur aerosols on early Earth are discussed. Key Words: S-MIF-Archean atmosphere-Early Earth-Sulfur aerosols.

  5. On the importance of meteoric dust for the stratospheric aerosol and polar stratospheric cloud formation (Invited)

    NASA Astrophysics Data System (ADS)

    Borrmann, S.

    2013-12-01

    Aerosol particles originating from meteoric ablation at high altitudes appear after some time in the lower mesosphere and upper stratosphere. They can be transported to even lower altitudes by the down-welling in connection with the winter hemisphere polar vortices. At altitudes below 30 km these particles are a component of the stratospheric background aerosol and become involved in microphysical processes including polar stratospheric cloud formation (PSC). PSCs are believed to heterogeneously form on the sulfuric acid background aerosol. However at times of relative volcanic quiescence the number densities of such background aerosol particles decreases and PSC formation may become more dependent on the presence of the meteoric ablation dust. In this presentation at first a short review of laboratory experiments on cloud nucleation on meteoric dust is given, and literature results from atmospheric measurements are discussed. In the second section recent in-situ lower stratospheric measurements (up to 20 km altitude) within the Northern hemispheric polar vortex from the RECONCILE and ESSENCE campaigns (2010 and 2011) are presented. Here in-situ measurements of the non-volatility of submicron aerosol particles are described as well as results from a-posteriori analyses on particles sampled from flight altitudes (using EDX and electron microscopy).

  6. Evidence for the role of organics in aerosol particle formation under atmospheric conditions

    PubMed Central

    Metzger, Axel; Verheggen, Bart; Dommen, Josef; Duplissy, Jonathan; Prevot, Andre S. H.; Weingartner, Ernest; Riipinen, Ilona; Kulmala, Markku; Spracklen, Dominick V.; Carslaw, Kenneth S.; Baltensperger, Urs

    2010-01-01

    New particle formation in the atmosphere is an important parameter in governing the radiative forcing of atmospheric aerosols. However, detailed nucleation mechanisms remain ambiguous, as laboratory data have so far not been successful in explaining atmospheric nucleation. We investigated the formation of new particles in a smog chamber simulating the photochemical formation of H2SO4 and organic condensable species. Nucleation occurs at H2SO4 concentrations similar to those found in the ambient atmosphere during nucleation events. The measured particle formation rates are proportional to the product of the concentrations of H2SO4 and an organic molecule. This suggests that only one H2SO4 molecule and one organic molecule are involved in the rate-limiting step of the observed nucleation process. Parameterizing this process in a global aerosol model results in substantially better agreement with ambient observations compared to control runs. PMID:20133603

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

    NASA Astrophysics Data System (ADS)

    Chen, Xi; Hopke, Philip K.

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

  8. Limited Effect of Anthropogenic Nitrogen Oxides on Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Knote, C. J.; Tilmes, S.; Emmons, L. K.; Lamarque, J. F.; Yu, P.

    2014-12-01

    Globally secondary organic aerosol (SOA) is mostly formed from biogenic vegetation emissions and as such is regarded as natural aerosol that cannot be reduced by emission control legislation. However, recent research implies that human activities facilitate SOA formation by affecting the amount of precursor emission, the chemical processing and the partitioning into the aerosol phase. Among the multiple human influences, nitrogen oxides (NO + NO2 = NOx) have been assumed to play a critical role in the chemical formation of low volatile compounds. The goal of this study is to improve the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-Chem) by implementing an updated 4-product Volatility Basis Set (VBS) scheme, and apply it to investigate the impact of anthropogenic NOx on SOA. We first compare three different SOA parameterizations: a 2-product model and the updated VBS model both with and without a SOA aging parameterization. Secondly we evaluate predicted organic aerosol amounts against surface measurement from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network and Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns. We then perform sensitivity experiments to examine how the SOA loading responds to a 50% reduction in anthropogenic NOx in different regions. We find limited SOA reductions of -2.3%, -5.6% and -4.0% for global, southeastern U.S. and Amazon NOx perturbations, respectively. To investigate the chemical processes in more detail, we also use a simplified box model with the same gas-phase chemistry and gas-aerosol partitioning mechanism as in CAM4-Chem to examine the SOA yields dependence on initial precursor emissions and background NOx level. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- versus high-NOx pathways, OH versus NO3-initiated oxidation) and to offsetting

  9. Formation of secondary aerosols from gasoline vehicle exhausts when mixing with SO2

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Hu, Q.; Deng, W.; Zhang, Y.; Ding, X.; Fu, X.; Bernard, F.; Zhang, Z.; Lü, S.; He, Q.; Bi, X.; Chen, J.; Sun, Y.; Yu, J.; Peng, P.; Sheng, G.; Fu, J.

    2015-09-01

    Sulfur dioxide (SO2) can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs), but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhausts, is still poorly understood. Here we directly co-introduced gasoline vehicles exhausts (GVE) and SO2, a typical pollutant from coal burning, into a smog chamber to investigate the formation of secondary organic aerosols (SOA) and sulfate aerosols through photooxidation. In the presence of high concentration of SO2, new particle formation was enhanced while substantial sulfate was formed through the oxidation of SO2. The homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs), formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60-200 % in the presence of high concentration of SO2. This increase could largely be attributed to acid-catalyzed SOA formation, which was evidenced by the strong positive linear correlation (R2 = 0.97) between the SOA production factor and in-situ particle acidity calculated by AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) resolved OA's relatively lower oxygen-to-carbon (O : C) and higher hydrogen-to-carbon (H : C) molar ratios for the GVE/SO2 mixture, with a much lower estimated average carbon oxidation state (OSc) of -0.51 ± 0.06 than that of -0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be the major reason for the lower oxidation degree of SOA.

  10. Formation of secondary aerosols from gasoline vehicle exhaust when mixing with SO2

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Hu, Q.; Deng, W.; Zhang, Y.; Ding, X.; Fu, X.; Bernard, F.; Zhang, Z.; Lü, S.; He, Q.; Bi, X.; Chen, J.; Sun, Y.; Yu, J.; Peng, P.; Sheng, G.; Fu, J.

    2016-01-01

    Sulfur dioxide (SO2) can enhance the formation of secondary aerosols from biogenic volatile organic compounds (VOCs), but its influence on secondary aerosol formation from anthropogenic VOCs, particularly complex mixtures like vehicle exhaust, remains uncertain. Gasoline vehicle exhaust (GVE) and SO2, a typical pollutant from coal burning, are directly co-introduced into a smog chamber, in this study, to investigate the formation of secondary organic aerosols (SOA) and sulfate aerosols through photooxidation. New particle formation was enhanced, while substantial sulfate was formed through the oxidation of SO2 in the presence of high concentration of SO2. Homogenous oxidation by OH radicals contributed a negligible fraction to the conversion of SO2 to sulfate, and instead the oxidation by stabilized Criegee intermediates (sCIs), formed from alkenes in the exhaust reacting with ozone, dominated the conversion of SO2. After 5 h of photochemical aging, GVE's SOA production factor revealed an increase by 60-200 % in the presence of high concentration of SO2. The increase could principally be attributed to acid-catalyzed SOA formation as evidenced by the strong positive linear correlation (R2 = 0.97) between the SOA production factor and in situ particle acidity calculated by the AIM-II model. A high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) resolved OA's relatively lower oxygen-to-carbon (O : C) (0.44 ± 0.02) and higher hydrogen-to-carbon (H : C) (1.40 ± 0.03) molar ratios for the GVE / SO2 mixture, with a significantly lower estimated average carbon oxidation state (OSc) of -0.51 ± 0.06 than -0.19 ± 0.08 for GVE alone. The relative higher mass loading of OA in the experiments with SO2 might be a significant explanation for the lower SOA oxidation degree.

  11. Emission of sunscreen salicylic esters from desert vegetation and their contribution to aerosol formation

    NASA Astrophysics Data System (ADS)

    Matsunaga, S. N.; Guenther, A. B.; Potosnak, M. J.; Apel, E. C.

    2008-12-01

    Biogenic volatile organic compounds (BVOC) produced by plants are known to have an important role in atmospheric chemistry. However, our knowledge of the range of BVOCs produced by different plant processes is still expanding, and there remain poorly understood categories of BVOCs. In this study, emissions of a novel class of BVOC emissions were investigated in a desert region. Our study considered 8 species of common desert plants: blackbrush (Coleogyne ramosissima), desert willow (Chilopsis linearis), mesquite (Prosopis glandulosa), mondel pine (Pinus eldarica), pinyon pine (Pinus monophylla), cottonwood (Populus deltoides), saguaro cactus (Carnegiea gigantea) and yucca (Yucca baccata). The measurements focused on BVOCs with relatively high molecular weight (>C15) and/or an oxygenated functional group. Significantly high emission rates of two salicylic esters were found for blackbrush, desert willow and mesquite with emission rates of 3.1, 1.0 and 4.8μgC dwg-1 h-1, respectively (dwg; dry weight of the leaves in gram). The salicylic esters were identified as 2-ethylhexenyl salicylate (2-EHS) and 3,3,5-trimethylcyclohexenyl salicylate (homosalate) and are known as effective ultraviolet (UV) absorbers. We propose that the plants derive a protective benefit against UV radiation from the salicylic esters and that the emission process is driven by the physical evaporation of the salicylic esters due to the high ambient temperatures. In addition, the salicylic esters are predicted to be an effective precursor of secondary organic aerosol (SOA) because they probably produce oxidation products that can condense onto the aerosol phase. We estimated the contribution of the sunscreen esters themselves and their oxidation products on the SOA formation for the Las Vegas area using a BVOC emission model. The contribution was estimated to reach 50% of the biogenic terpenoid emission in the landscapes dominated by desert willow and mesquite and 13% in the Las Vegas area. The

  12. Potential emission flux to aerosol pollutants over Bengal Gangetic plain through combined trajectory clustering and aerosol source fields analysis

    NASA Astrophysics Data System (ADS)

    Kumar, D. Bharath; Verma, S.

    2016-09-01

    A hybrid source-receptor analysis was carried out to evaluate the potential emission flux to winter monsoon (WinMon) aerosols over Bengal Gangetic plain urban (Kolkata, Kol) and semi-urban atmospheres (Kharagpur, Kgp). This was done through application of fuzzy c-mean clustering to back-trajectory data combined with emission flux and residence time weighted aerosols analysis. WinMon mean aerosol optical depth (AOD) and angstrom exponent (AE) at Kol (AOD: 0.77; AE: 1.17) were respectively slightly higher than and nearly equal to that at Kgp (AOD: 0.71; AE: 1.18). Out of six source region clusters over Indian subcontinent and two over Indian oceanic region, the cluster mean AOD was the highest when associated with the mean path of air mass originating from the Bay of Bengal and the Arabian sea clusters at Kol and that from the Indo-Gangetic plain (IGP) cluster at Kgp. Spatial distribution of weighted AOD fields showed the highest potential source of aerosols over the IGP, primarily over upper IGP (e.g. Punjab, Haryana), lower IGP (e.g. Uttarpradesh) and eastern region (e.g. west Bengal, Bihar, northeast India) clusters. The emission flux contribution potential (EFCP) of fossil fuel (FF) emissions at surface (SL) of Kol/Kgp, elevated layer (EL) of Kol, and of biomass burning (BB) emissions at SL of Kol were primarily from upper, lower, upper/lower IGP clusters respectively. The EFCP of FF/BB emissions at Kgp-EL/SL, and that of BB at EL of Kol/Kgp were mainly from eastern region and Africa (AFR) clusters respectively. Though the AFR cluster was constituted of significantly high emission flux source potential of dust emissions, the EFCP of dust from northwest India (NWI) was comparable to that from AFR at Kol SL/EL.

  13. Halogen-induced organic aerosol (XOA): a study on ultra-fine particle formation and time-resolved chemical characterization.

    PubMed

    Ofner, Johannes; Kamilli, Katharina A; Held, Andreas; Lendl, Bernhard; Zetzsch, Cornelius

    2013-01-01

    The concurrent presence of high values of organic SOA precursors and reactive halogen species (RHS) at very low ozone concentrations allows the formation of halogen-induced organic aerosol, so-called XOA, in maritime areas where high concentrations of RHS are present, especially at sunrise. The present study combines aerosol smog-chamber and aerosol flow-reactor experiments for the characterization of XOA. XOA formation yields from alpha-pinene at low and high concentrations of chlorine as reactive halogen species (RHS) were determined using a 700 L aerosol smog-chamber with a solar simulator. The chemical transformation of the organic precursor during the aerosol formation process and chemical aging was studied using an aerosol flow-reactor coupled to an FTIR spectrometer. The FTIR dataset was analysed using 2D correlation spectroscopy. Chlorine induced homogeneous XOA formation takes place at even 2.5 ppb of molecular chlorine, which was photolysed by the solar simulator. The chemical pathway of XOA formation is characterized by the addition of chlorine and abstraction of hydrogen atoms, causing simultaneous carbon-chlorine bond formation. During further steps of the formation process, carboxylic acids are formed, which cause a SOA-like appearance of XOA. During the ozone-free formation of secondary organic aerosol with RHS a special kind of particulate matter (XOA) is formed, which is afterwards transformed to SOA by atmospheric aging or degradation pathways.

  14. NO3 radical, OH radical and O3-initiated secondary aerosol formation from aliphatic amines

    NASA Astrophysics Data System (ADS)

    Tang, Xiaochen; Price, Derek; Praske, Eric; Lee, Su Anne; Shattuck, Morgan A.; Purvis-Roberts, Kathleen; Silva, Philip J.; Asa-Awuku, Akua; Cocker, David R.

    2013-06-01

    Aliphatic amines enter the atmosphere from a variety of sources, and exist in both gas and particle phases in the atmosphere. Similar to ammonia, amines can form inorganic salts through acid-base reactions. However, the atmospheric behavior of amines with atmospheric oxidants (e.g. the nitrate radical (NO3), the hydroxyl radical (OH), O3) is still poorly understood. In this study, chamber experiments were conducted to explore the reaction between three aliphatic amines and HNO3/O3/NO3/OH. Effects of water vapor were also explored by conducting experiments under different relative humidity conditions (RH<0.1% to ˜40%). Results show that all three amines have a high potential to form secondary aerosol in reactions with NO3, and are affected by the presence of water vapor. DEA and BA are capable of forming a significant amount of stable inorganic salt at ppb level concentrations, while TMA tends to form mostly non-salt secondary organic aerosol under dry conditions. The OH photooxidation of amines has much lower secondary aerosol yield and is independent of relative humidity, while ozonolysis produced negligible amount of aerosol. Secondary aerosol from OH oxidation was composed of organic components only, due to the lack of acid source. This study shows that night time chemistry of aliphatic amines can produce secondary organic and inorganic aerosol mixtures, and the relative contribution of each component depends on the environment relative humidity.

  15. Substantial secondary organic aerosol formation in a coniferous forest: observations of both day- and nighttime chemistry

    NASA Astrophysics Data System (ADS)

    Lee, Alex K. Y.; Abbatt, Jonathan P. D.; Leaitch, W. Richard; Li, Shao-Meng; Sjostedt, Steve J.; Wentzell, Jeremy J. B.; Liggio, John; Macdonald, Anne Marie

    2016-06-01

    Substantial biogenic secondary organic aerosol (BSOA) formation was investigated in a coniferous forest mountain region in Whistler, British Columbia. A largely biogenic aerosol growth episode was observed, providing a unique opportunity to investigate BSOA formation chemistry in a forested environment with limited influence from anthropogenic emissions. Positive matrix factorization of aerosol mass spectrometry (AMS) measurement identified two types of BSOA (BSOA-1 and BSOA-2), which were primarily generated by gas-phase oxidation of monoterpenes and perhaps sesquiterpenes. The temporal variations of BSOA-1 and BSOA-2 can be explained by gas-particle partitioning in response to ambient temperature and the relative importance of different oxidation mechanisms between day and night. While BSOA-1 arises from gas-phase ozonolysis and nitrate radical chemistry at night, BSOA-2 is likely less volatile than BSOA-1 and consists of products formed via gas-phase oxidation by OH radical and ozone during the day. Organic nitrates produced through nitrate radical chemistry can account for 22-33 % of BSOA-1 mass at night. The mass spectra of BSOA-1 and BSOA-2 have higher values of the mass fraction of m/z 91 (f91) compared to the background organic aerosol. Using f91 to evaluate BSOA formation pathways in this unpolluted, forested region, heterogeneous oxidation of BSOA-1 is a minor production pathway of BSOA-2.

  16. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

    PubMed

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

  17. Direct evidence of atmospheric secondary organic aerosol formation in forest atmosphere through heteromolecular nucleation.

    PubMed

    Kavouras, Ilias G; Stephanou, Euripides G

    2002-12-01

    Atmospheric aerosols play a central role in climate and atmospheric chemistry. Organic matter frequently composes aerosol major fraction over continental areas. Reactions of natural volatile organic compounds, with atmospheric oxidants, are a key formation pathway of fine particles. The gas and particle atmospheric concentration of organic compounds directly emitted from conifer leaf epicuticular wax and of those formed through the photooxidation of alpha- and beta-pinene were simultaneously collected and measured in a conifer forest by using elaborated sampling and GC/ MS techniques. The saturation concentrations of acidic and carbonyl photooxidation products were estimated, by taking into consideration primary gas- and particle-phase organic species. Primary organic aerosol components represented an important fraction of the atmospheric gas-phase organic content Consequently, saturation concentrations of photooxidation products have been lowered facilitating new particle formation between molecules of photooxidation products and semi-volatile organic compounds. From the measured concentrations of the above-mentioned compounds, saturation concentrations (Csat,i) of alpha- and beta-pinene photooxidation products were calculated for nonideal conditions using a previously developed absorptive model. The results of these calculations indicated that primarily emitted organic species and ambient temperature play a crucial role in secondary organic aerosol formation. PMID:12523424

  18. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation.

    PubMed

    Shiraiwa, Manabu; Yee, Lindsay D; Schilling, Katherine A; Loza, Christine L; Craven, Jill S; Zuend, Andreas; Ziemann, Paul J; Seinfeld, John H

    2013-07-16

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

  19. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

    PubMed Central

    Shiraiwa, Manabu; Yee, Lindsay D.; Schilling, Katherine A.; Loza, Christine L.; Craven, Jill S.; Zuend, Andreas; Ziemann, Paul J.; Seinfeld, John H.

    2013-01-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process. PMID:23818634

  20. Urban stress-induced biogenic VOC emissions impact secondary aerosol formation in Beijing

    NASA Astrophysics Data System (ADS)

    Ghirardo, A.; Xie, J.; Zheng, X.; Wang, Y.; Grote, R.; Block, K.; Wildt, J.; Mentel, T.; Kiendler-Scharr, A.; Hallquist, M.; Butterbach-Bahl, K.; Schnitzler, J.-P.

    2015-08-01

    Trees can significantly impact the urban air chemistry by the uptake and emission of reactive biogenic volatile organic compounds (BVOCs), which are involved in ozone and particle formation. Here we present the emission potentials of "constitutive" (cBVOCs) and "stress-induced" BVOCs (sBVOCs) from the dominant broadleaf woody plant species in the megacity of Beijing. Based on an inventory of BVOC emissions and the tree census, we assessed the potential impact of BVOCs on secondary particulate matter formation in 2005 and 2010, i.e., before and after realizing the large tree-planting program for the 2008 Olympic Games. We found that sBVOCs, such as fatty acid derivatives, benzenoids and sesquiterpenes, constituted a significant fraction (∼ 15 %) of the total annual BVOC emissions, and we estimated that the overall annual BVOC budget may have doubled from ∼ 3.6 × 109 g C year-1 in 2005 to ∼ 7.1 × 109 g C year-1 in 2010 due to the increase in urban greens, while at the same time, the emission of anthropogenic VOCs (AVOCs) could be lowered by 24 %. Based on our BVOC emission assessment, we estimated the biological impact on SOA mass formation in Beijing. Compared to AVOCs, the contribution of biogenic precursors (2-5 %) for secondary particulate matter in Beijing was low. However, sBVOCs can significantly contribute (∼ 40 %) to the formation of total secondary organic aerosol (SOA) from biogenic sources; apparently, their annual emission increased from 1.05 μg m-3 in 2005 to 2.05 μg m-3 in 2010. This study demonstrates that biogenic and, in particular, sBVOC emissions contribute to SOA formation in megacities. However, the main problems regarding air quality in Beijing still originate from anthropogenic activities. Nevertheless, the present survey suggests that in urban plantation programs, the selection of plant species with low cBVOC and sBVOC emission potentials have some possible beneficial effects on urban air quality.

  1. Formation of Oxidized Organic Aerosol (OOA) through Fog Processing in the Po Valley

    NASA Astrophysics Data System (ADS)

    Gilardoni, S.; Paglione, M.; Rinaldi, M.; Giulianelli, L.; Massoli, P.; Hillamo, R. E.; Carbone, S.; Lanconelli, C.; Laaksonen, A. J.; Russell, L. M.; Poluzzi, V.; Fuzzi, S.; Facchini, C.

    2014-12-01

    Aqueous phase chemistry might be responsible for the formation of a significant fraction of the organic aerosol (OA) observed in the atmosphere, and could explain some of the discrepancies between OA concentration and properties predicted by models and observed in the environment. Aerosol - fog interaction and its effect on submicron aerosol properties were investigated in the Po Valley (northern Italy) during fall 2011, in the framework of the Supersite project (ARPA Emilia Romagna). Composition and physical properties of submicron aerosol were measured online by a High Resolution- Time of Flight - Aerosol Mass Spectrometer (HR-TOF-AMS), a Soot Photometer - Aerosol Mass Spectrometer (SP-AMS), and a Tandem Differential Mobility Particle Sizer (TDMPS). Organic functional group analysis was performed off-line by Hydrogen - Nuclear Magnetic Resonance (H-NMR) spectrometry and by Fourier Transform Infrared (FTIR) spectrometry. Aerosol absorption, scattering, and total extinction were measured simultaneously with a Particle Soot Absorption Photometer (PSAP), a Nephelometer, and a Cavity Attenuated Phase Shift Spectrometer particle extinction monitor (CAPS PMex), respectively. Water-soluble organic carbon in fog-water was characterized off-line by HR-TOF-AMS. Fourteen distinct fog events were observed. Fog dissipation left behind an aerosol enriched in particles larger than 400 nm, typical of fog and cloud processing, and dominated by secondary species, including ammonium nitrate, ammonium sulfate and oxidized OA (OOA). Source apportionment of OA allowed us to identify OOA as the difference between total OA and primary OA (hydrocarbon like OA and biomass burning OA). The formation of OOA through fog processing is proved by the correlation of OOA concentration with hydroxyl methyl sulfonate signal and by the similarity of OOA spectra with organic mass spectra obtained by re-aerosolization of fog water samples. The oxygen to carbon ratio and the hydrogen to carbon ratio of

  2. 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.

  3. Potential Impact of South Asian Anthropogenic Aerosols on Northern Hemisphere Climate

    NASA Astrophysics Data System (ADS)

    Bollasina, M. A.; Ming, Y.; Ramaswamy, V.

    2014-12-01

    South Asia has one of the world's highest aerosol loading due to the dramatic increase of anthropogenic emissions from the 1950s associated with rapid urbanization and population growth. The possible large-scale impact of the late 20th century increase of South Asian aerosol emissions on climate away from the source regions was studied by means of historical ensemble experiments with a state-of-the-art coupled climate model with fully interactive aerosols and a representation of both direct and indirect aerosol effects. The key characteristics of the northern hemisphere responses are examined separately for winter and summer, and show that regional aerosols induce significant planetary-scale teleconnection patterns. In both seasons, the large-scale aerosol imprint originates from substantial changes in the regional precipitation distribution. During the winter, in response to anomalous surface cooling in the northern Indian Ocean, aerosols cause a westward shift of convection over the eastern Indian Ocean and compensating subsidence to the west and over the Maritime continent. During the summer, aerosols are collocated with rainfall, and cause a widespread drying over South Asia mostly by indirect effects. In both cases, the impact of the regional diabatic heating anomaly propagates remotely by exciting a northern hemisphere wave-train which, enhanced by regional feedbacks, leads to remarkable changes in near-surface climate, including circulation and temperature, over Eurasia, the northern Pacific and North America. Depending on the region, the induced anomalies may have opposite signs between the two seasons, and may thus contribute to reinforcing or dampening those due greenhouse gases. These results underscore the potential influence of Asian aerosols on global climate, which is a compelling problem as regional aerosol loading will continue to be large in the coming decades.

  4. Ozone and secondary aerosol formation — Analysis of particle observations in the 2009 SHARP campaign

    NASA Astrophysics Data System (ADS)

    Cowin, J.; Yu, X.; Laulainen, N.; Iedema, M.; Lefer, B. L.; Anderson, D.; Pernia, D.; Flynn, J. H.

    2010-12-01

    Particulate matters (PM) play important roles in the formation and transformation of ozone. Although photooxidation of volatile organic compounds with respect to ozone formation in the gas phase is well understood, many unknowns still exist in heterogeneous mechanisms that process soot, secondary aerosols (both inorganic and organic), and key radical precursors such as formaldehyde and nitrous acid. Our main objective is to answer two key science questions: 1) will reduction of fine PM reduce ozone formation? 2) What sources of PM are most culpable? Are they from local chemistry or long-range transport? The field data collected in the 2009 Study of Houston Atmospheric Radical Precursors (SHARP) by our group at the Moody Tower consist of 1) real-time photolysis rates of ozone precursors, 2) particle size distributions, 3) organic carbon and elemental carbon, and 4) an archive of single particle samples taken with the Time Resolved Aerosol Collector (TRAC) sampler. The time resolution of the TRAC sampler is 30 minutes for routine measurements, and 15 minutes during some identified “events” (usually in the mid-afternoon) of high ozone and secondary organic or sulfate particle formation. The latter events last typically about an hour. Five ozone exceedance days occurred during the 6 weeks of deployment. Strong correlation between photochemical activities and organic carbon was observed. Initial data analysis indicates that secondary organic aerosol is a major component of the carbonaceous aerosols observed in Houston. Soot, secondary sulfate, seal salt, and mineral dust particles are determined from single particle analysis using scanning electron microscope and transmission electron microcopy coupled with energy dispersive X-ray spectroscopy. Compared with observations in 2000, the mass percentage of organics is higher (60 vs. 30%), and lower for sulfate (20% vs. 32%). On-going data analysis will focus on the composition, sources, and transformation of primary and

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  6. Potential of polarization lidar to provide profiles of CCN- and INP-relevant aerosol parameters

    NASA Astrophysics Data System (ADS)

    Mamouri, Rodanthi-Elisavet; Ansmann, Albert

    2016-05-01

    We investigate the potential of polarization lidar to provide vertical profiles of aerosol parameters from which cloud condensation nucleus (CCN) and ice nucleating particle (INP) number concentrations can be estimated. We show that height profiles of particle number concentrations n50, dry considering dry aerosol particles with radius > 50 nm (reservoir of CCN in the case of marine and continental non-desert aerosols), n100, dry (particles with dry radius > 100 nm, reservoir of desert dust CCN), and of n250, dry (particles with dry radius > 250 nm, reservoir of favorable INP), as well as profiles of the particle surface area concentration sdry (used in INP parameterizations) can be retrieved from lidar-derived aerosol extinction coefficients σ with relative uncertainties of a factor of 1.5-2 in the case of n50, dry and n100, dry and of about 25-50 % in the case of n250, dry and sdry. Of key importance is the potential of polarization lidar to distinguish and separate the optical properties of desert aerosols from non-desert aerosol such as continental and marine particles. We investigate the relationship between σ, measured at ambient atmospheric conditions, and n50, dry for marine and continental aerosols, n100, dry for desert dust particles, and n250, dry and sdry for three aerosol types (desert, non-desert continental, marine) and for the main lidar wavelengths of 355, 532, and 1064 nm. Our study is based on multiyear Aerosol Robotic Network (AERONET) photometer observations of aerosol optical thickness and column-integrated particle size distribution at Leipzig, Germany, and Limassol, Cyprus, which cover all realistic aerosol mixtures. We further include AERONET data from field campaigns in Morocco, Cabo Verde, and Barbados, which provide pure dust and pure marine aerosol scenarios. By means of a simple CCN parameterization (with n50, dry or n100, dry as input) and available INP parameterization schemes (with n250, dry and sdry as input) we finally compute

  7. 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

  8. 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.

  9. The Formation of Sulfate and Elemental Sulfur Aerosols Under Varying Laboratory Conditions: Implications for Early Earth

    NASA Technical Reports Server (NTRS)

    DeWitt, H. Langley; Hasenkopf, Christa A.; Trainer, Melissa G.; Farmer, Delphine K.; Jimenez, Jose L.; McKay, Christopher P.; Toon, Owen B.; Tolbert, Margaret A.

    2010-01-01

    The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 x 10(exp 9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO2) by UV light with lambda < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S8) and sulfuric acid (H2S04) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO2 either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H2) or methane (CH4), increased the formation of S8. With UV photolysis, formation of S8 aerosols is highly dependent on the initial SO2 pressure; and S8 is only formed at a 2% SO2 mixing ratio and greater in the absence of a reductant, and at a 0.2% SO2 mixing ratio and greater in the presence of 1000 ppmv CH4. We also found that organosulfur compounds are formed from the photolysis of CH4 and moderate amounts of SO2, The implications for sulfur aerosols on early Earth are discussed.

  10. Formation characteristics of aerosol particles from pulverized coal pyrolysis in high-temperature environments

    SciTech Connect

    Wei-Hsin Chen; Shan-Wen Du; Hsi-Hsien Yang; Jheng-Syun Wu

    2008-05-15

    The formation characteristics of aerosol particles from pulverized coal pyrolysis in high temperatures are studied experimentally. By conducting a drop-tube furnace, fuel pyrolysis processes in industrial furnaces are simulated in which three different reaction temperatures of 1000, 1200, and 1400{sup o}C are considered. Experimental observations indicate that when the reaction temperature is 1000{sup o}C, submicron particles are produced, whereas the particle size is dominated by nanoscale for the temperature of 1400{sup o}C. Thermogravimetric analysis of the aerosol particles stemming from the pyrolysis temperature of 1000{sup o}C reveals that the thermal behavior of the aerosol is characterized by a three-stage reaction with increasing heating temperature: (1) a volatile-reaction stage, (2) a weak-reaction stage, and (3) a soot-reaction stage. However, with the pyrolysis temperature of 1400{sup o}C, the volatile- and weak-reaction stages almost merge together and evolve into a chemical-frozen stage. The submicron particles (i.e., 1000{sup o}C) are mainly composed of volatiles, tar, and soot, with the main component of the nanoscale particles (i.e., 1400{sup o}C) being soot. The polycyclic aromatic hydrocarbons (PAHs) contained in the aerosols are also analyzed. It is found that the PAH content in generated aerosols decreases dramatically as the pyrolysis temperature increases. 31 refs., 9 figs., 1 tab.

  11. Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States

    PubMed Central

    Xu, Lu; Guo, Hongyu; Boyd, Christopher M.; Klein, Mitchel; Bougiatioti, Aikaterini; Cerully, Kate M.; Hite, James R.; Kreisberg, Nathan M.; Knote, Christoph; Olson, Kevin; Koss, Abigail; Goldstein, Allen H.; Hering, Susanne V.; de Gouw, Joost; Baumann, Karsten; Lee, Shan-Hu; Nenes, Athanasios; Weber, Rodney J.; Ng, Nga Lee

    2015-01-01

    Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43–70% of total measured organic aerosol (29–49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic−biogenic interactions and consequently improve air quality and climate simulations. PMID:25535345

  12. Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States.

    PubMed

    Xu, Lu; Guo, Hongyu; Boyd, Christopher M; Klein, Mitchel; Bougiatioti, Aikaterini; Cerully, Kate M; Hite, James R; Isaacman-VanWertz, Gabriel; Kreisberg, Nathan M; Knote, Christoph; Olson, Kevin; Koss, Abigail; Goldstein, Allen H; Hering, Susanne V; de Gouw, Joost; Baumann, Karsten; Lee, Shan-Hu; Nenes, Athanasios; Weber, Rodney J; Ng, Nga Lee

    2015-01-01

    Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43-70% of total measured organic aerosol (29-49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic-biogenic interactions and consequently improve air quality and climate simulations. PMID:25535345

  13. 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.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

    Huang, Xin

    2015-04-01

    Secondary inorganic aerosol (SIA), including sulfate, nitrate and ammonium, is an important part of fine particle. SIA plays a significant role in shortwave radiation transfer. Numerical simulation is usually used to study SIA formation and its climate effect. In this work, we used the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) to study SIA formation and its direct radiative forcing (DRF) over China. SO2 oxidation pathways related to mineral aerosol, including transition metal-catalyzed oxidation in aqueous phase and heterogeneous reactions, play an important role in sulfate production, but they are not well treated in current atmospheric models. In this work, we improved the WRF-Chem model by simulating the enhancement role of mineral aerosol in sulfate production. Firstly, we estimated mineral cations based on local measurements in order to well represent aqueous phase acidity. Secondly, we scaled the transition metal concentration to the mineral aerosol levels according to the existing observations and improved transition metal-catalyzed oxidation calculation. Lastly, heterogeneous reactions of acid gases on the surface of mineral aerosol were included in this simulation. Accuracy in the prediction of sulfate by the model was significantly improved and we concluded that mineral aerosol can facilitate SO2 oxidation and subsequent sulfate formation. It was demonstrated that, over China, mineral aerosol was responsible for 21.8% of annual mean sulfate concentration. The enhanced aqueous oxidation was more significant compared to the heterogeneous reactions. In winter, mineral aerosol was responsible for 39.6% of sulfate production. In summer, gaseous oxidation and aqueous oxidation of SO2 by hydrogen peroxide and ozone were the dominant pathways of sulfate formation. Mineral aerosol only contributed 11.9% to the total sulfate production. The increase in annual mean sulfate concentration due to mineral aerosol could reach up to over 6

  16. Carbonaceous aerosols observed at Ieodo Ocean Research Station and implication for the role of secondary aerosols in fog formation

    NASA Astrophysics Data System (ADS)

    Han, J.; Shin, B.; Hwang, G.; Kim, J.; Lee, M.; Shim, J.

    2014-12-01

    Carbonaceous components and soluble ions of PM2.5 were measured at Ieodo Ocean Research Station (IORS) from December 2004 to June 2008. IORS is a 40-m research tower and located in the East China Sea (32.07°N, 125.10°E). As IORS is distanced equally from South Korea, China, and Japan, it is an ideal place to monitor Asian outflows with the least influence of local emissions. The mean concentration of PM2.5 mass was 21.8 ± 14.9 μg/m3 with the maximum of 35.3 μg/m3 (March) and the minimum of 11.2 μg/m3 (September). The monthly variation of PM2.5 mass was similar to that of O3 due to meteorological conditions, which determines the degree of influence from nearby lands. Chinese outflows were mostly responsible for the enhancement of mass and major constituents of PM2.5 such as sulfate, OC, and EC. Their concentrations were the lowest in summer when aged marine air masses were dominant. It is noteworthy that sulfate was also enhanced when air mass passed through Japan, even though its concentration was not as high as that of Chinese outflows. In June, OC concentration was distinctively high with high OC/EC ratio of ~9.5. At IORS, June is characterized by the most frequent occurrence of fog and the lowest visibility with the highest relative humidity. In China, the clearing fire of agricultural residues is the major source of fine aerosols in June, leading to severe haze (e.g., Cheng et al., 2014). In addition, the aerosol optical depth was also observed to be the maximum over northeast Asia in June (Kim et al., 2007). Consequently, our results suggest that organic aerosol played a critical role in fog formation in the study region. References Cheng, Z., et al. (2014) Impact of biomass burning on haze pollution in the Yangtze River delta, China: a case study in summer 2011, Atmos. Chem. Phys., 14, 4573-4585, doi:10.5194/acp-14-4573-2014. Kim, S.-W., et al. (2007) Seasonal and monthly variations of columnar aerosol optical properties over east Asia determined from

  17. 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.

  18. 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.

  19. Rapid Formation of Molecular Bromine from Deliquesced NaBr Aerosol in the Presence of Ozone and UV Light

    EPA Science Inventory

    The formation of gas-phase bromine from aqueous sodium bromide aerosols is investigated through a combination of chamber experiments and chemical kinetics modeling. Experiments show that Br2(g) is produced rapidly from deliquesced NaBr aerosols in the presence of OH radicals prod...

  20. Insights into different nitrate formation mechanisms from seasonal variations of secondary inorganic aerosols in Shanghai

    NASA Astrophysics Data System (ADS)

    Tao, Ye; Ye, Xingnan; Ma, Zhen; Xie, Yuanyuan; Wang, Ruyu; Chen, Jianmin; Yang, Xin; Jiang, Shuqin

    2016-11-01

    The dominant mechanisms for the formation of fine particulate nitrate during four seasons were proposed by evaluating the correlations between [NO3-]/[SO42-] and [NH4+]/[SO42-]. Size-resolved aerosols were collected in Shanghai from April 2013 to January 2014. The concentration of fine particulate nitrate was below one tenth of the concentration of sulfate in summer, whereas fine particulate nitrate dominated over sulfate in winter. Influenced by aged sea salt aerosols, the molar ratio of [Na+]/[NH4+] reached 53 ± 49% and the depletion of chloride was very significant (0.83) during autumn. In spring, the increase of nitrate concentration became evident for [NH4+]/[SO42-]>2, indicating that sulfate is fully neutralized. During summertime, nighttime hydrolysis of N2O5 dominated the fine particulate nitrate formation. The thresholds of [NH4+]/[SO42-] for nitrate formation in autumn and winter were wrongly characterized by the linear regression between [NO3-]/[SO42-] and [NH4+]/[SO42-], because considerable amounts of Na2SO4 and NH4Cl were present. Replaced by free ammonium in the function equation, it was established that the winter and spring aerosols shared the same nitrate formation mechanism. On the basis of free sulfate, it was evident that both homogeneous neutralization and hydrolysis of N2O5 mechanisms were involved during autumn.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  2. Potential source identification for aerosol concentrations over a site in Northwestern India

    NASA Astrophysics Data System (ADS)

    Payra, Swagata; Kumar, Pramod; Verma, Sunita; Prakash, Divya; Soni, Manish

    2016-03-01

    The collocated measurements of aerosols size distribution (ASD) and aerosol optical thickness (AOT) are analyzed simultaneously using Grimm aerosol spectrometer and MICROTOP II Sunphotometer over Jaipur, capital of Rajasthan in India. The contrast temperature characteristics during winter and summer seasons of year 2011 are investigated in the present study. The total aerosol number concentration (TANC, 0.3-20 μm) during winter season was observed higher than in summer time and it was dominated by fine aerosol number concentration (FANC < 2 μm). Particles smaller than 0.8 μm (at aerodynamic size) constitute ~ 99% of all particles in winter and ~ 90% of particles in summer season. However, particles greater than 2 μm contribute ~ 3% and ~ 0.2% in summer and winter seasons respectively. The aerosols optical thickness shows nearly similar AOT values during summer and winter but corresponding low Angstrom Exponent (AE) values during summer than winter, respectively. In this work, Potential Source Contribution Function (PSCF) analysis is applied to identify locations of sources that influenced concentrations of aerosols over study area in two different seasons. PSCF analysis shows that the dust particles from Thar Desert contribute significantly to the coarse aerosol number concentration (CANC). Higher values of the PSCF in north from Jaipur showed the industrial areas in northern India to be the likely sources of fine particles. The variation in size distribution of aerosols during two seasons is clearly reflected in the log normal size distribution curves. The log normal size distribution curves reveals that the particle size less than 0.8 μm is the key contributor in winter for higher ANC.

  3. Transient secondary organic aerosol formation from limonene ozonolysis in indoor environments: impacts of air exchange rates and initial concentration ratios.

    PubMed

    Youssefi, Somayeh; Waring, Michael S

    2014-07-15

    Secondary organic aerosol (SOA) results from the oxidation of reactive organic gases (ROGs) and is an indoor particle source. The aerosol mass fraction (AMF), a.k.a. SOA yield, quantifies the SOA forming potential of ROGs and is the ratio of generated SOA to oxidized ROG. The AMF depends on the organic aerosol concentration, as well as the prevalence of later generation reactions. AMFs have been measured in unventilated chambers or steady-state flow through chambers. However, indoor settings have outdoor air exchange, and indoor SOA formation often occurs when ROGs are transiently emitted, for instance from emissions of cleaning products. Herein, we quantify "transient AMFs" from ozonolysis of pulse-emitted limonene in a ventilated chamber, for 18 experiments at low (0.28 h(-1)), moderate (0.53 h(-1)), and high (0.96 h(-1)) air exchange rates (AER) with varying initial ozone-limonene ratios. Transient AMFs increased with the amount of ROG reacted; AMFs also increased with decreasing AERs and increasing initial ozone-limonene ratios, which together likely promoted more ozone reactions with the remaining exocyclic bond of oxidized limonene products in the SOA phase. Knowing the AER and initial ozone-limonene ratio is crucial to predict indoor transient SOA behavior accurately.

  4. Simulating SAL formation and aerosol size distribution during SAMUM-I

    NASA Astrophysics Data System (ADS)

    Khan, Basit; Stenchikov, Georgiy; Weinzierl, Bernadett; Kalenderski, Stoitchko; Osipov, Sergey

    2015-04-01

    To understand the formation mechanisms of Saharan Air Layer (SAL), we combine model simulations and dust observations collected during the first stage of the Saharan Mineral Dust Experiment (SAMUM-I), which sampled dust events that extended from Morocco to Portugal, and investigated the spatial distribution and the microphysical, optical, chemical, and radiative properties of Saharan mineral dust. We employed the Weather Research Forecast model coupled with the Chemistry/Aerosol module (WRF-Chem) to reproduce the meteorological environment and spatial and size distributions of dust. The experimental domain covers northwest Africa including the southern Sahara, Morocco and part of the Atlantic Ocean with 5 km horizontal grid spacing and 51 vertical layers. The experiments were run from 20 May to 9 June 2006, covering the period of most intensive dust outbreaks. Comparisons of model results with available airborne and ground-based observations show that WRF-Chem reproduces observed meteorological fields as well as aerosol spatial distribution across the entire region and along the airplane's tracks. We evaluated several aerosol uplift processes and found that orographic lifting, aerosol transport through the land/sea interface with steep gradients of meteorological characteristics, and interaction of sea breezes with the continental outflow are key mechanisms that form a surface-detached aerosol plume over the ocean. Comparisons of simulated dust size distributions with airplane and ground-based observations are generally good, but suggest that more detailed treatment of microphysics in the model is required to capture the full-scale effect of large aerosol particles.

  5. Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NO x photooxidation system

    NASA Astrophysics Data System (ADS)

    Lu, Zifeng; Hao, Jiming; Takekawa, Hideto; Hu, Lanhua; Li, Junhua

    High concentrations (>15 μm 3 cm -3) of CaSO 4, Ca(NO 3) 2 and (NH 4) 2SO 4 were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO 4 and aqueous Ca(NO 3) 2), even at elevated concentrations. The presence of high concentrations of (NH 4) 2SO 4 aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH 4) 2SO 4 on SOA yield is found to be positively correlated with the (NH 4) 2SO 4 surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH 4) 2SO 4 seed aerosols.

  6. Program Abstracts: Formation and Growth of Atmospheric Aerosols

    SciTech Connect

    Peter H. McMurry; Markku Kulmala

    2006-09-07

    DOE provided $11,000 to sponsor the Workshop on New Particle Formation in the Atmosphere, which was held at The Riverwood Inn and Conference Center near Minneapolis, MN from September 7 to 9, 2006. Recent work has shown that new particle formation is an important atmospheric process that must be better understood due to its impact on cloud cover and the Earth's radiation balance. The conference was an informal gathering of atmospheric and basic scientists with expertise pertinent to this topic. The workshop included discussions of: • atmospheric modeling; • computational chemistry pertinent to clustering; • ions and ion induced nucleation; • basic laboratory and theoretical studies of nucleation; • studies on neutral molecular clusters; • interactions of organic compounds and sulfuric acid; • composition of freshly nucleated particles. Fifty six scientists attended the conference. They included 27 senior scientists, 9 younger independent scientists (assistant professor or young associate professor level), 7 postdocs, 13 graduate students, 10 women, 35 North Americans (34 from the U.S.), 1 Asian, and 20 Europeans. This was an excellent informal workshop on an important topic. An effort was made to include individuals from communities that do not regularly interact. A number of participants have provided informal feedback indicating that the workshop led to research ideas and possible future collaborations.

  7. FY 2010 Fourth Quarter Report: Evaluation of the Dependency of Drizzle Formation on Aerosol Properties

    SciTech Connect

    Lin, W; McGraw, R; Liu, Y; Wang, J; Vogelmann, A; Daum, PH

    2010-10-01

    Metric for Quarter 4: Report results of implementation of composite parameterization in single-column model (SCM) to explore the dependency of drizzle formation on aerosol properties. To better represent VOCALS conditions during a test flight, the Liu-Duam-McGraw (LDM) drizzle parameterization is implemented in the high-resolution Weather Research and Forecasting (WRF) model, as well as in the single-column Community Atmosphere Model (CAM), to explore this dependency.

  8. Biotic stress accelerates formation of climate-relevant aerosols in boreal forests

    NASA Astrophysics Data System (ADS)

    Joutsensaari, J.; Yli-Pirilä, P.; Korhonen, H.; Arola, A.; Blande, J. D.; Heijari, J.; Kivimäenpää, M.; Mikkonen, S.; Hao, L.; Miettinen, P.; Lyytikäinen-Saarenmaa, P.; Faiola, C. L.; Laaksonen, A.; Holopainen, J. K.

    2015-11-01

    Boreal forests are a major source of climate-relevant biogenic secondary organic aerosols (SOAs) and will be greatly influenced by increasing temperature. Global warming is predicted to not only increase emissions of reactive biogenic volatile organic compounds (BVOCs) from vegetation directly but also induce large-scale insect outbreaks, which significantly increase emissions of reactive BVOCs. Thus, climate change factors could substantially accelerate the formation of biogenic SOAs in the troposphere. In this study, we have combined results from field and laboratory experiments, satellite observations and global-scale modelling in order to evaluate the effects of insect herbivory and large-scale outbreaks on SOA formation and the Earth's climate. Field measurements demonstrated 11-fold and 20-fold increases in monoterpene and sesquiterpene emissions respectively from damaged trees during a pine sawfly (Neodiprion sertifer) outbreak in eastern Finland. Laboratory chamber experiments showed that feeding by pine weevils (Hylobius abietis) increased VOC emissions from Scots pine and Norway spruce seedlings by 10-50 fold, resulting in 200-1000-fold increases in SOA masses formed via ozonolysis. The influence of insect damage on aerosol concentrations in boreal forests was studied with a global chemical transport model GLOMAP and MODIS satellite observations. Global-scale modelling was performed using a 10-fold increase in monoterpene emission rates and assuming 10 % of the boreal forest area was experiencing outbreak. Results showed a clear increase in total particulate mass (local max. 480 %) and cloud condensation nuclei concentrations (45 %). Satellite observations indicated a 2-fold increase in aerosol optical depth over western Canada's pine forests in August during a bark beetle outbreak. These results suggest that more frequent insect outbreaks in a warming climate could result in substantial increase in biogenic SOA formation in the boreal zone and, thus

  9. Biotic stress accelerates formation of climate-relevant aerosols in boreal forests

    NASA Astrophysics Data System (ADS)

    Joutsensaari, J.; Yli-Pirilä, P.; Korhonen, H.; Arola, A.; Blande, J. D.; Heijari, J.; Kivimäenpää, M.; Mikkonen, S.; Hao, L.; Miettinen, P.; Lyytikäinen-Saarenmaa, P.; Faiola, C. L.; Laaksonen, A.; Holopainen, J. K.

    2015-04-01

    Boreal forests are a major source of climate-relevant biogenic secondary organic aerosols (SOA) and will be greatly influenced by increasing temperature. Global warming is predicted to increase emissions of reactive biogenic volatile organic compounds (BVOC) from vegetation directly, but will also induce large-scale insect outbreaks, which significantly increase emissions of reactive BVOC. Thus, climate change factors could substantially accelerate the formation of biogenic SOA in the troposphere. In this study, we have combined results from field and laboratory experiments, satellite observations and global scale modelling in order to evaluate the effects of insect herbivory and large-scale outbreaks on SOA formation and the Earth's climate. Field measurements demonstrated 11-fold and 20-fold increases in monoterpene and sesquiterpene emissions, respectively, from damaged trees during a pine sawfly (Neodiprion sertifer) outbreak in eastern Finland. Laboratory chamber experiments showed that feeding by pine weevils (Hylobius abietis) increased VOC emissions from Scots pine and Norway spruce seedlings by 10-50 fold resulting in 200-1000 fold increases in SOA masses formed via ozonolysis. The influence of insect damage on aerosol concentrations in boreal forests was studied with a global chemical transport model GLOMAP and MODIS satellite observations. Global scale modelling was performed using a 10-fold increase in monoterpene emission rates and assuming 10% of the boreal forest area was experiencing outbreak. Results showed a clear increase in total particulate mass (local max. 480%) and cloud condensation nuclei concentrations (45%). Satellite observations indicated a two-fold increase in aerosol optical depth (AOD) over western Canada's pine forests in August during a bark beetle outbreak. These results suggest that more frequent insect outbreaks in a warming climate could result in substantial increase in biogenic SOA formation in the boreal zone and, thus

  10. Influence of Aerosol Chemical Composition on Heterogeneous Ice Formation under Mid-Upper Troposphere Conditions

    NASA Astrophysics Data System (ADS)

    Kanji, Z. A.; Niemand, M.; Saathoff, H.; Möhler, O.; Chou, C.; Abbatt, J.; Stetzer, O.

    2011-12-01

    Aerosols are involved in cooling/warming the atmosphere directly via interaction with incoming solar radiation (aerosol direct effect), or via their ability to act as cloud condensation or ice nuclei (IN) and thus play a role in cloud formation (indirect effect). In particular, the physical properties of aerosols such as size and solubility and chemical composition can influence their behavior and fate in the atmosphere. Ice nucleation taking place via IN is termed as heterogeneous ice nucleation and can take place with via deposition (ice forming on IN directly from the vapor phase), condensation/immersion (freezing via formation of the liquid phase on IN) or condensation (IN colliding with supercooled liquid drops). This presentation shows how the chemical composition and surface area of various tropospherically relevant aerosols influence conditions of temperature (T) and relative humidity (RH) required for heterogeneous ice formation conditions in the mid-upper troposphere regime (253 - 220K)? Motivation for this comes first from, the importance of being able to predict ice formation accurately so as to understand the hydrological cycle since the ice is the primary initiator of precipitation forming clouds. Second, the tropospheric budget of water vapour, an especially active greenhouse gas is strongly influenced by ice nucleation and growth. Third, ice surfaces in the atmosphere act as heterogeneous surfaces for chemical reactions of trace gases (e.g., SO2, O3, NOx and therefore being able to accurately estimate ice formation rates and quantify ice surface concentrations will allow a more accurate calculation of trace gas budgets in the troposphere. Ice nucleation measurements were conducted using a self-developed continuous flow diffusion chamber and static chamber. A number of tropospherically relevant particulates with naturally-varying and laboratory-modified surface chemistry/structure were investigated for their ice formation efficiency based on highest

  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

  12. A Computational Approach to Understanding Aerosol Formation and Oxidant Chemistry in the Troposphere

    SciTech Connect

    Francisco, Joseph S.; Kathmann, Shawn M.; Schenter, Gregory K.; Dang, Liem X.; Xantheas, Sotiris S.; Garrett, Bruce C.; Du, Shiyu; Dixon, David A.; Bianco, Roberto; Wang, Shuzhi; Hynes, James T.; Morita, Akihiro; Peterson, Kirk A.

    2006-04-18

    An understanding of the mechanisms and kinetics of aerosol formation and ozone production in the troposphere is currently a high priority because these phenomena are recognized as two major effects of energy-related air pollution. Atmospheric aerosols are of concern because of their effect on visibility, climate, and human health. Equally important, aerosols can change the chemistry of the atmosphere, in dramatic fashion, by providing new chemical pathways (in the condensed phase) unavailable in the gas phase. The oxidation of volatile organic compounds (VOCs) and inorganic compounds (e.g., sulfuric acid, ammonia, nitric acid, ions, and mineral) can produce precursor molecules that act as nucleation seeds. The U.S. Department of Energy (DOE) Atmospheric Chemistry Program (ACP) has identified the need to evaluate the causes of variations in tropospheric aerosol chemical composition and concentrations, including determining the sources of aerosol particles and the fraction of such that are of primary and secondary origin. In particular, the ACP has called for a deeper understanding into aerosol formation because nucleation creates substantial concentrations of fresh particles that, via growth and coagulation, influence the Earth's radiation budget. Tropospheric ozone is also of concern primarily because of its impact on human health. Ozone levels are controlled by NOx and by VOCs in the lower troposphere. The VOCs can be either from natural emissions from such sources as vegetation and phytoplankton or from anthropogenic sources such as automobiles and oil-fueled power production plants. The major oxidant for VOCs in the atmosphere is the OH radical. With the increase in VOC emissions, there is rising concern regarding the available abundance of HOx species needed to initiate oxidation. Over the last five years, there have been four field studies aimed at initial measurements of HOx species (OH and HO? radicals). These measurements revealed HOx levels that are two to

  13. Photochemical Formation of Aerosol in Planetary Atmospheres: Photon and Water Mediated Chemistry of SO_2

    NASA Astrophysics Data System (ADS)

    Kroll, Jay A.; Donaldson, D. J.; Vaida, Veronica

    2016-06-01

    Sulfur compounds have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth's atmosphere. However, several discrepancies between modeling and observations of the Venusian atmosphere show there are still problems in our fundamental understanding of sulfur chemistry. This is of particular concern due to the important role sulfur compounds play in the formation of aerosols, which have a direct impact on planetary climates, including Earth's. We investigate the role of water complexes in the hydration of sulfur oxides and dehydration of sulfur acids and will present spectroscopic studies to document such effects. I will present recent work investigating mixtures of SO_2 and water that generate large quantities of aerosol when irradiated with solar UV light, even in the absence of traditional OH chemistry. I will discuss a proposed mechanism for the formation of sulfurous acid (H_2SO_3) and present recent experimental work that supports this proposed mechanism. Additionally, the implications that photon-induced hydration of SO_2 has for aerosol formation in the atmosphere of earth as well as other planetary atmospheres will be discussed.

  14. Aerosol formation by ozonolysis of α- and β-pinene with initial concentrations below 1 ppb

    NASA Astrophysics Data System (ADS)

    Saathoff, Harald; Naumann, Karl-Heinz; Möhler, Ottmar

    2014-05-01

    Secondary organic aerosols (SOA) from the oxidation of biogenic volatile organic compounds (BVOC) are a large fraction of the tropospheric aerosol especially over tropical continental regions. The dominant SOA forming compounds are monoterpenes of which pinene is the most abundant. The reactions of monoterpenes with OH radicals, NO3 radicals, and ozone yield secondary organic aerosol mass in highly variable yields. Despite the various studies on SOA formation the influence of temperature and precursor concentrations on SOA yields are still major uncertainties in tropospheric aerosol models. In previous studies we observed a negative temperature dependence of SOA yields for SOA from ozonolysis α-pinene and limonene (Saathoff et al., 2009). However, this study as well as most of the literature data for measured SOA yields is limited to terpene concentrations of several ppb and higher (e.g. Bernard et al., 2012), hence about an order of magnitude higher than terpene concentrations even near their sources. Monoterpene concentrations in and above tropical or boral forests reach values up to a few tenth of a ppb during daytime decreasing rapidly with altitude in the boundary layer (Kesselmeier et al. 2000; Boy et al., 2004). Therefore we investigated the yield of SOA material from the ozonolysis of α- and β-pinene under simulated tropospheric conditions in the large aerosol chamber AIDA on time scales of several hours and for terpene concentrations between 0.1 and 1 ppb. The temperatures investigated were 243, 274, and 296 K with relative humidities ranging from 25% to 41%. The organic aerosol was generated by controlled oxidation with an excess of ozone (220-930 ppb) and the aerosol yield is calculated from size distributions measured with differential mobility analysers (SMPS, TSI, 3071 & 3080N) in the size range between 2 and 820 nm. On the basis of the measured initial particle size distribution, particle number concentration (CPC, TSI, 3775, 3776, 3022), and

  15. Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

    2015-08-01

    In China, a rapid increase in passenger vehicles has led to the growing concern of vehicle exhaust as an important source of anthropogenic secondary organic aerosol (SOA) in megacities hard hit by haze. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) operated in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with relative humidity at around 50 %. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary organic aerosol (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at comparable OH exposure. This quite lower OH exposure than that in typical atmospheric conditions might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yields in this study were well fit by a one-product gas-particle partitioning model but quite lower than those of a previous study investigating SOA formation from three idling passenger vehicles (Euro 2-4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90 % of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C / ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a combination of carboxylic acid and alcohol/peroxide formation.

  16. Potentialities and Limits of ICESAT-2 Observation for Atmospheric Aerosol Investigation

    NASA Astrophysics Data System (ADS)

    Mona, L.; Amodeo, A.; D'Amico, G.

    2016-06-01

    ICESat-2(Ice, Cloud, and land Elevation Satellite-2), slated for launch in 2017, will continue the important observations of ice-sheet elevation change, sea-ice freeboard, and vegetation canopy height begun by ICESat in 2003. Among the other potential applications, ICESat-2 could provide some information about atmospheric aerosol over Polar Regions thanks to the lidar instrument. In this context, it is essential to demonstrate the ICESat-2 capability of providing vertical profiles of the aerosol backscatter coefficient and to define its potentialities and limits. First results of this investigation are reported and will be presented at the conference.

  17. Global aerosol formation and revised radiative forcing based on CERN CLOUD data

    NASA Astrophysics Data System (ADS)

    Gordon, H.; Carslaw, K. S.; Sengupta, K.; Dunne, E. M.; Kirkby, J.

    2015-12-01

    New particle formation in the atmosphere accounts for 40-70% of global cloud condensation nuclei (CCN). It is a complex process involving many precursors: sulphuric acid, ions, ammonia, and a wide range of natural and anthropogenic organic molecules. The CLOUD laboratory chamber experiment at CERN allows the contributions of different compounds to be disentangled in a uniquely well-controlled environment. To date, CLOUD has measured over 500 formation rates (Riccobono 2014, Kirkby 2015, Dunne 2015), under conditions representative of the planetary boundary layer and free troposphere. To understand the sensitivity of the climate to anthropogenic atmospheric aerosols, we must quantify historical aerosol radiative forcing. This requires an understanding of pre-industrial aerosol sources. Here we show pre-industrial nucleation over land usually involves organic molecules in the very first steps of cluster formation. The complexity of the organic vapors is a major challenge for theoretical approaches. Furthermore, with fewer sulphuric acid and ammonia molecules available to stabilize nucleating clusters in the pre-industrial atmosphere, ions from radon or galactic cosmic rays were probably more important than they are today. Parameterizations of particle formation rates determined in CLOUD as a function of precursor concentrations, temperature and ions are being used to refine the GLOMAP aerosol model (Spracklen 2005). The model simulates the growth, transport and loss of particles, translating nucleation rates to CCN concentrations. This allows us to better understand the effects of pre-industrial and present-day particle formation. I will present new results on global CCN based on CLOUD data, including estimates of anthropogenic aerosol radiative forcing, currently the most uncertain driver of climate change (IPCC 2013). References: Riccobono, F. et al, Science 344 717 (2014); Kirkby, J. et al, in review; Dunne, E. et al, in preparation; Spracklen, D. et al, Atmos

  18. Potential phosphorus recovery by struvite formation.

    PubMed

    Jaffer, Y; Clark, T A; Pearce, P; Parsons, S A

    2002-04-01

    Formation of struvite (MgNH4PO4 x 6H2O) at sewage treatment works can cause operational problems and decrease efficiency. Struvite has a commercial value and the controlled formation and recovery of it would be beneficial. A mass balance was conducted at full scale across the whole sewage treatment plant in order to identify a stream to conduct bench-scale struvite crystallisation studies. The most suitable stream was identified as the centrifuge liquors. The average flow of the liquor stream was 393 m3 d(-1) and the composition was as follows: 167 mg L(-1) phosphorus, 44 mg L(-1) magnesium, 615 mg L(-1) ammonium, 56 mg L(-1) calcium and 2580 mg L(-1) of alkalinity. The pH averaged at 7.6 and the stream had a predicted struvite precipitation potential of 140 mg L(-1). Struvite crystallisation occurred quickly during the trials, by raising the pH of the centrifuge liquors to 9.0 and dosing with magnesium. Up to 97% phosphorus removal as struvite was achieved. Struvite formation occurred when the molar ratio of magnesium:phosphorus was at least 1.05:1. Below this ratio phosphorus removals of 72% were observed, but not exclusively as struvite. Annual yields of struvite were calculated to be 42-100 tonnes a year, depending on the dose regime. Revenue from the sale of produced struvite could be between Pound Sterling8400 and Pound Sterling20,000 a year. PMID:12044083

  19. Aerosol and CCN properties at Princess Elisabeth station, East Antarctica: seasonality, new particle formation events and properties around precipitation events

    NASA Astrophysics Data System (ADS)

    Mangold, Alexander; Laffineur, Quentin; De Backer, Hugo; Herenz, Paul; Wex, Heike; Gossart, Alexandra; Souverijns, Niels; Gorodetskaya, Irina; Van Lipzig, Nicole

    2016-04-01

    Since 2010, several complementary ground-based instruments for measuring the aerosol composition of the Antarctic atmosphere have been operated at the Belgian Antarctic research station Princess Elisabeth, in Dronning Maud Land, East Antarctica (71.95° S, 23.35° E, 1390 m asl.). In addition, three ground-based remote sensing instruments for cloud and precipitation observations have been installed for continuous operation, including a ceilometer (cloud base height, type, vertical extent), a 24 Ghz micro-rain radar (vertical profiles of radar effective reflectivity and Doppler velocity), and a pyrometer (cloud base temperature). The station is inhabited from November to end of February and operates under remote control during the other months. In this contribution, the general aerosol and cloud condensation nuclei (CCN) properties will be described with a special focus on new particle formation events and around precipitation events. New particle formation events are important for the atmospheric aerosol budget and they also show that aerosols are not only transported to Antarctica but are also produced there, also inland. Aerosols are essential for cloud formation and therefore also for precipitation, which is the only source for mass gain of the Antarctic ice sheet. Measured aerosol properties comprise size distribution, total number, total mass concentration, mass concentration of light-absorbing aerosol and absorption coefficient and total scattering coefficient. In addition, a CCN counter has been operated during austral summers 2013/14, 2014/15 and 2015/16. The baseline total number concentration N-total was around some hundreds of particles/cm3. During new particle formation events N-total increased to some thousands of particles/cm3. Simultaneous measurements of N-total, size distribution and CCN number revealed that mostly the number of particles smaller than 100 nm increased and that the concentration of cloud condensation nuclei increased only very

  20. 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 α-pinene secondary organic aerosol (SOA) particles, and 3) the influence of chamber wall effects on the observed SOA formation in smog chambers.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  2. Nature, Origin, Potential Composition, and Climate Impact of the Asian Tropopause Aerosol Layer (ATAL)

    NASA Technical Reports Server (NTRS)

    Fairlie, T. D.; Vernier, J.-P.; Thomason, L. W.; Natarajan, M.; Bedka, K.; Wienhold, F.; Bian J.; Martinsson, B.

    2015-01-01

    Satellite observations from SAGE II and CALIPSO indicate that summertime aerosol extinction has more than doubled in the Asian Tropopause Aerosol Layer (ATAL) since the late 1990s. Here we show remote and in-situ observations, together with results from a chemical transport model (CTM), to explore the likely composition, origin, and radiative forcing of the ATAL. We show in-situ balloon measurements of aerosol backscatter, which support the high levels observed by CALIPSO since 2006. We also show in situ measurements from aircraft, which indicate a predominant carbonaceous contribution to the ATAL (Carbon/Sulfur ratios of 2- 10), which is supported by the CTM results. We show that the peak in ATAL aerosol lags by 1 month the peak in CO from MLS, associated with deep convection over Asia during the summer monsoon. This suggests that secondary formation and growth of aerosols in the upper troposphere on monthly timescales make a significant contribution to ATAL. Back trajectory calculations initialized from CALIPSO observations provide evidence that deep convection over India is a significant source for ATAL through the vertical transport of pollution to the upper troposphere.

  3. 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.

  4. Potential pathogenic bacteria in metalworking fluids and aerosols from a machining facility.

    PubMed

    Perkins, Sarah D; Angenent, Largus T

    2010-12-01

    The metalworking and machining industry utilizes recirculating metalworking fluids for integral aspects of the fabrication process. Despite the use of biocides, these fluids sustain substantial biological growth. Subsequently, the high-shear forces incurred during metalworking processing aerosolize bacterial cells and may cause dermatologic and respiratory effects in exposed workers. We quantified and identified the bacterial load for metalworking fluid and aerosol samples of a machining facility in the US Midwest during two seasons. To investigate the presence of potentially pathogenic bacteria in fluid and air, we performed 16S rRNA gene surveys. The concentration of total bacterial cells (including culturable and nonculturable cells) was relatively constant throughout the study, averaging 5.1 × 10⁸ cells mL⁻¹ in the fluids and 4.8 × 10⁵ cells m⁻³ in the aerosols. We observed bacteria of potential epidemiologic significance from several different bacterial phyla in both fluids and aerosols. Most notably, Alcaligenes faecalis was identified through both direct sequencing and culturing in every sample collected. Elucidating the bacterial community with gene surveys showed that metalworking fluids were the source of the aerosolized bacteria in this facility. PMID:20955193

  5. 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

  6. Secondary organic aerosol formation from the gas phase reaction of hydroxyl radicals with m-, o- and p-cresol

    NASA Astrophysics Data System (ADS)

    Henry, Françoise; Coeur-Tourneur, Cecile; Ledoux, Frédéric; Tomas, Alexandre; Menu, Dominique

    Secondary organic aerosol (SOA) formation during the atmospheric oxidation of cresols was investigated using a large smog chamber (8000 L), at atmospheric pressure, 294±2 K and low relative humidity (6-10%). Cresol oxidation was initiated by irradiation of cresol/CH 3ONO/NO/air mixtures. The cresol loss was measured by gas chromatography with a flame ionization detector (GC-FID) and the temporal evolution of the aerosol was monitored using a scanning mobility particle sizer (SMPS). The overall organic aerosol yield ( Y) was determined as the ratio of the suspended aerosol mass corrected for wall losses ( Mo) to the total reacted cresol concentrations assuming a particle density of 1.4 g cm -3. Analysis of the data clearly show that Y is a strong function of Mo and that SOA formation can be expressed by a one-product gas/particle partitioning absorption model. The aerosol formation is affected by the initial cresol concentration, which leads to aerosol yields from 9% to 42%. These results are in good agreement with a recent study performed on SOA formation from the photo-oxidation of o-cresol in a smog chamber. To our knowledge, the present work represents the first investigation of SOA formation from OH reaction with m- and p-cresol.

  7. Secondary Organic Aerosol Formation from 2-Methyl-3-Buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

    SciTech Connect

    Zhang, Haofei; Zhang, Zhenfa; Cui, Tianqu; Lin, Ying-Hsuan; Bhathela, Neil A.; Ortega, John; Worton, David; Goldstein, Allen H.; Guenther, Alex B.; Jimenez, Jose L.; Gold, Avram; Surratt, Jason D.

    2014-04-08

    Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to isoprene, MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide) was synthesized and tentatively proposed here to explain this enhancement. In the present study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosols. Major SOA constituents, 2,3-dihydroxyisopentanol (DHIP) and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosols collected from the BEACHON-RoMBAS field campaign during summer 2011, where MBO emissions are substantial. Our results support epoxides as potential products of MBO photooxidation leading to formation of atmospheric SOA and suggest that reactive uptake of epoxides may generally explain acid enhancement of SOA observed from other biogenic hydrocarbons.

  8. 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

  9. Molecular-scale evidence of aerosol particle formation via sequential addition of HIO3

    NASA Astrophysics Data System (ADS)

    Sipilä, Mikko; Sarnela, Nina; Jokinen, Tuija; Henschel, Henning; Junninen, Heikki; Kontkanen, Jenni; Richters, Stefanie; Kangasluoma, Juha; Franchin, Alessandro; Peräkylä, Otso; Rissanen, Matti P.; Ehn, Mikael; Vehkamäki, Hanna; Kurten, Theo; Berndt, Torsten; Petäjä, Tuukka; Worsnop, Douglas; Ceburnis, Darius; Kerminen, Veli-Matti; Kulmala, Markku; O'Dowd, Colin

    2016-09-01

    Homogeneous nucleation and subsequent cluster growth leads to the formation of new aerosol particles in the atmosphere. The nucleation of sulfuric acid and organic vapours is thought to be responsible for the formation of new particles over continents, whereas iodine oxide vapours have been implicated in particle formation over coastal regions. The molecular clustering pathways that are involved in atmospheric particle formation have been elucidated in controlled laboratory studies of chemically simple systems, but direct molecular-level observations of nucleation in atmospheric field conditions that involve sulfuric acid, organic or iodine oxide vapours have yet to be reported. Here we present field data from Mace Head, Ireland, and supporting data from northern Greenland and Queen Maud Land, Antarctica, that enable us to identify the molecular steps involved in new particle formation in an iodine-rich, coastal atmospheric environment. We find that the formation and initial growth process is almost exclusively driven by iodine oxoacids and iodine oxide vapours, with average oxygen-to-iodine ratios of 2.4 found in the clusters. On the basis of this high ratio, together with the high concentrations of iodic acid (HIO3) observed, we suggest that cluster formation primarily proceeds by sequential addition of HIO3, followed by intracluster restructuring to I2O5 and recycling of water either in the atmosphere or on dehydration. Our study provides ambient atmospheric molecular-level observations of nucleation, supporting the previously suggested role of iodine-containing species in the formation of new aerosol particles, and identifies the key nucleating compound.

  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

  11. Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

    NASA Technical Reports Server (NTRS)

    Guzman, Marcelo I.; Athalye, Richa R.; Rodriguez, Jose M.

    2012-01-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ?Gdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp -2)) > (R(sub x-)(exp -1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8-8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol - and ethanol-water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I- on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I- < Br- < Cl- over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

  12. Concentration effects and ion properties controlling the fractionation of halides during aerosol formation.

    PubMed

    Guzman, Marcelo I; Athalye, Richa R; Rodriguez, Jose M

    2012-06-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO(2), NaNO(3), NaClO(4), and NaIO(4). The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f(X(-))) and their correlation with ion properties. Although no correlation exists between f(X(-)) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(X(-)), dehydration free-energy ΔG(dehyd), and polarizability α, follows the order: R(X(-))(-2) > R(X(-))(-1) > R(X(-)) > ΔG(dehyd) > α. The same pure physical process is observed in H(2)O and D(2)O. The factor f(X(-)) does not change with pH (6.8-8.6), counterion (Li(+), Na(+), K(+), and Cs(+)) substitution effects, or solvent polarity changes in methanol- and ethanol-water mixtures (0 ≤ x(H(2)O) ≤ 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I(-) on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I(-) < Br(-) < Cl(-) over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

  13. Salting Constants of Small Organic Molecules in Aerosol-Relevant Salts and Application to Aerosol Formation in the Southeastern United States

    NASA Astrophysics Data System (ADS)

    Waxman, E.; Carlton, A. M. G.; Ziemann, P. J.; Volkamer, R. M.

    2014-12-01

    Secondary organic aerosol (SOA) formation from small water-soluble molecules such as glyoxal and methyl glyoxal is a topic of emerging interest. Results from recent field campaigns, e.g. Waxman et al. (2013, GRL) and Knote et al. (2014, ACP), show that these molecules can form significant SOA mass as a result of 'salting-in'. Salting-in happens when a molecule's solubility increases with salt concentration and salting-out is the reverse. Salting effects modify the solubility exponentially with increasing salt concentration, and thus the effective Henry's law constant can strongly modify partitioning, and multiphase chemical reaction rates in aerosol water. Moreover, the solubility in aerosol water cannot easily inferred based on the solubility in cloud water, as the salting effects could change the solubility by a factor of 104 or more. In this work, we have devised and applied a novel experimental setup to measure salting constants using an ion trap mass spectrometer. We focus on small, water soluble molecules like methyl glyoxal and similar compounds and measure salting constants for aerosol-relevant salts including ammonium sulfate, ammonium nitrate, and sodium chloride. The Setschenow salting-constant values are then used to parameterize the effects of salting in CMAQ. We present a series of sensitivity studies of the effects that inorganic aerosols have on the SOA formation from small soluble molecules in the southeastern United States.

  14. 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 α-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 α-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.

  15. Modeling secondary organic aerosol formation from oxidation of α-pinene, β-pinene, and d-limonene

    NASA Astrophysics Data System (ADS)

    Chen, Jianjun; Griffin, Robert J.

    The biogenic species α-pinene, β-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 α-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.

  16. Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Shiraiwa, M.; Yee, L. D.; Schilling, K.; Loza, C. L.; Craven, J. S.; Zuend, A.; Ziemann, P. J.; Seinfeld, J.

    2013-12-01

    Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosol (SOA). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multi-generation gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a mid-experiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. The results of the current work have a number of implications for SOA models. While the dynamics of an aerosol size distribution reflects the mechanism of growth, we demonstrate here that it provides a key constraint in interpreting laboratory and ambient SOA formation. This work, although carried out specifically for the long chain alkane, dodecane, is expected to be widely applicable to other major classes of SOA precursors. SOA consists of a myriad of organic compounds containing various functional groups, which can generally undergo heterogeneous/multiphase reactions forming low-volatility products such as oligomers and other high molecular mass compounds. If particle-phase chemistry is indeed

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  18. Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

    NASA Astrophysics Data System (ADS)

    Liu, T.; Wang, X.; Deng, W.; Hu, Q.; Ding, X.; Zhang, Y.; He, Q.; Zhang, Z.; Lü, S.; Bi, X.; Chen, J.; Yu, J.

    2015-04-01

    In China, fast increase in passenger vehicles has procured the growing concern about vehicle exhausts as an important source of anthropogenic secondary organic aerosols (SOA) in megacities hard-hit by haze. However, there are still no chamber simulation studies in China on SOA formation from vehicle exhausts. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with the relative humidity around 50%. After aging at an OH exposure of 5 × 106 molecules cm-3 h, the formed SOA was 12-259 times as high as primary OA (POA). The SOA production factors (PF) were 0.001-0.044 g kg-1 fuel, comparable with those from the previous studies at the quite similar OH exposure. This quite lower OH exposure than that in typical atmospheric condition might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yield data in this study were well fit by a one-product gas-particle partitioning model and quite lower than those of a previous study investigating SOA formation form three idling passenger vehicles (Euro 2-Euro 4). Traditional single-ring aromatic precursors and naphthalene could explain 51-90% of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C/ΔO : C ranged from -0.59 to -0.36, suggesting that the oxidation chemistry in these experiments was a

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

    NASA Astrophysics Data System (ADS)

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

    2010-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

  1. Size-resolved aerosol composition at an urban and a rural site in the Po Valley in summertime: implications for secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Sandrini, Silvia; van Pinxteren, Dominik; Giulianelli, Lara; Herrmann, Hartmut; Poulain, Laurent; Facchini, Maria Cristina; Gilardoni, Stefania; Rinaldi, Matteo; Paglione, Marco; Turpin, Barbara J.; Pollini, Francesca; Bucci, Silvia; Zanca, Nicola; Decesari, Stefano

    2016-09-01

    The aerosol size-segregated chemical composition was analyzed at an urban (Bologna) and a rural (San Pietro Capofiume) site in the Po Valley, Italy, during June and July 2012, by ion-chromatography (major water-soluble ions and organic acids) and evolved gas analysis (total and water-soluble carbon), to investigate sources and mechanisms of secondary aerosol formation during the summer. A significant enhancement of secondary organic and inorganic aerosol mass was observed under anticyclonic conditions with recirculation of planetary boundary layer air but with substantial differences between the urban and the rural site. The data analysis, including a principal component analysis (PCA) on the size-resolved dataset of chemical concentrations, indicated that the photochemical oxidation of inorganic and organic gaseous precursors was an important mechanism of secondary aerosol formation at both sites. In addition, at the rural site a second formation process, explaining the largest fraction (22 %) of the total variance, was active at nighttime, especially under stagnant conditions. Nocturnal chemistry in the rural Po Valley was associated with the formation of ammonium nitrate in large accumulation-mode (0.42-1.2 µm) aerosols favored by local thermodynamic conditions (higher relative humidity and lower temperature compared to the urban site). Nocturnal concentrations of fine nitrate were, in fact, on average 5 times higher at the rural site than in Bologna. The water uptake by this highly hygroscopic compound under high RH conditions provided the medium for increased nocturnal aerosol uptake of water-soluble organic gases and possibly also for aqueous chemistry, as revealed by the shifting of peak concentrations of secondary compounds (water-soluble organic carbon (WSOC) and sulfate) toward the large accumulation mode (0.42-1.2 µm). Contrarily, the diurnal production of WSOC (proxy for secondary organic aerosol) by photochemistry was similar at the two sites but

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  3. Photochemistry at interfaces: a source of radicals impacting on aerosol formation and properties

    NASA Astrophysics Data System (ADS)

    George, C.; D'anna, B.; Monge, M.; Dupart, Y.

    2011-12-01

    Recent findings confirm the presence of light absorbing organic material (HULIS, biomass burning particles, PAHs) in atmospheric aerosols... but also at the air/ocean interface. The presence of such light absorbing material allows photosensitised processes to occur. The latter may be sources of radicals in the troposphere that may alter its oxidation capacity (as for instance through the formation of HONO) or change the pathways leading to particle formation and ageing. We will exemplify such processes by presenting new data on the generation of radicals from dust particles or at the air/sea interface leading to particle formation in presence of SO2. These are recent findings that are questioning our current understanding of tropospheric photochemistry.

  4. Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

    DOE PAGES

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2015-07-24

    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 secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition 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 duringmore » photo-oxidation, and the final OA OSc ranged from -0.29 to 0.16 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 a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

  5. Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

    NASA Astrophysics Data System (ADS)

    Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; Nenes, A.; Donahue, N. M.; Pandis, S. N.

    2015-07-01

    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 secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition 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 OSc ranged from -0.29 to 0.16 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 a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.

  6. Impacts of Sulfate Seed Acidity and Water Content on Isoprene Secondary Organic Aerosol Formation.

    PubMed

    Wong, Jenny P S; Lee, Alex K Y; Abbatt, Jonathan P D

    2015-11-17

    The effects of particle-phase water and the acidity of pre-existing sulfate seed particles on the formation of isoprene secondary organic aerosol (SOA) was investigated. SOA was generated from the photo-oxidation of isoprene in a flow tube reactor at 70% relative humidity (RH) and room temperature in the presence of three different sulfate seeds (effloresced and deliquesced ammonium sulfate and ammonium bisulfate) under low NOx conditions. High OH exposure conditions lead to little isoprene epoxydiol (IEPOX) SOA being generated. The primary result is that particle-phase water had the largest effect on the amount of SOA formed, with 60% more SOA formation occurring with deliquesced ammonium sulfate seeds as compared to that on effloresced ones. The additional organic material was highly oxidized. Although the amount of SOA formed did not exhibit a dependence on the range of seed particle acidity examined, perhaps because of the low amount of IEPOX SOA, the levels of high-molecular-weight material increased with acidity. While the uptake of organics was partially reversible under drying, the results nevertheless indicate that particle-phase water enhanced the amount of organic aerosol material formed and that the RH cycling of sulfate particles may mediate the extent of isoprene SOA formation in the atmosphere. PMID:26460477

  7. Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Zhang, J.

    2003-12-01

    The formation of secondary particulate matter from the atmospheric oxidation of organic compounds can significantly contribute to the particulate burden, but the formation of organic secondary particulate matter is poorly understood. One way of producing organic secondary particulate matter is the oxidation of hydrocarbons with seven or more carbon atoms to get products with low vapor pressure. However, several recent reports suggest that relatively low molecular weight carbonyls can enter the particle phase by undergoing heterogeneous reactions. This may be a very important mechanism for the formation of organic secondary particulate matter. Atmospheric aldehydes are important carbonyls in the gas phase, which form via the oxidation of hydrocarbons emitted from anthropogenic and biogenic sources. In this poster, we report the results on particle growth by the heterogeneous reactions of hexanal. A 5 L Continuous Stirred Tank Reactor (CSTR) is set up to conduct the reactions in the presence of seed aerosol particles of deliquesced ammonia bisulfate. Hexanal is added into CSTR by syringe pump, meanwhile the concentrations of hexanal are monitored with High Pressure Liquid Chromatograph (HPLC 1050). A differential Mobility Analyzer (TSI 3071) set to an appropriate voltage is employed to obtain monodisperse aerosols, and another DMA associated with a Condensation Nuclear Counter (TSI 7610) is used to measure the secondary particle size distribution by the reaction in CSTR. This permits the sensitive determination of particle growth due to the heterogeneous reaction, very little growth occurs when hexanal added alone. Results for the simultaneous addition of hexanal and alcohols will also be presented.

  8. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    NASA Astrophysics Data System (ADS)

    Quan, Jiannong; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang; Liu, Yangang

    2015-12-01

    The effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60-80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO2 and NOx, accelerated the formation of secondary

  9. 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.; Močnik, 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

  10. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    DOE PAGES

    Quan, Jiannong; Liu, Yangang; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang

    2015-09-30

    In this study, the effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) bothmore » significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60–80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly due to high emission and low reaction rate; the occurrence of heterogeneous aqueous reactions in the late haze period, together with the accumulated high concentrations of precursor gases such as SO2 and NOx, accelerated the

  11. Effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events

    SciTech Connect

    Quan, Jiannong; Liu, Yangang; Liu, Quan; Li, Xia; Gao, Yang; Jia, Xingcan; Sheng, Jiujiang

    2015-09-30

    In this study, the effect of heterogeneous aqueous reactions on the secondary formation of inorganic aerosols during haze events was investigated by analysis of comprehensive measurements of aerosol composition and concentrations [e.g., particular matters (PM2.5), nitrate (NO3), sulfate (SO4), ammonium (NH4)], gas-phase precursors [e.g., nitrogen oxides (NOx), sulfur dioxide (SO2), and ozone (O3)], and relevant meteorological parameters [e.g., visibility and relative humidity (RH)]. The measurements were conducted in Beijing, China from Sep. 07, 2012 to Jan. 16, 2013. The results show that the conversion ratios of N from NOx to nitrate (Nratio) and S from SO2 to sulfate (Sratio) both significantly increased in haze events, suggesting enhanced conversions from NOx and SO2 to their corresponding particle phases in the late haze period. Further analysis shows that Nratio and Sratio increased with increasing RH, with Nratio and Sratio being only 0.04 and 0.03, respectively, when RH < 40%, and increasing up to 0.16 and 0.12 when RH reached 60–80%, respectively. The enhanced conversion ratios of N and S in the late haze period is likely due to heterogeneous aqueous reactions, because solar radiation and thus the photochemical capacity are reduced by the increases in aerosols and RH. This point was further affirmed by the relationships of Nratio and Sratio to O3: the conversion ratios increase with decreasing O3 concentration when O3 concentration is lower than <15 ppb but increased with increasing O3 when O3 concentration is higher than 15 ppb. The results suggest that heterogeneous aqueous reactions likely changed aerosols and their precursors during the haze events: in the beginning of haze events, the precursor gases accumulated quickly

  12. 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

  13. Secondary organic aerosol formation from isoprene photooxidation during cloud condensation-evaporation cycles

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene / NOx / light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are 2 and 4 times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of 2 or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to the dissolution of water soluble volatile organic compounds (VOCs) in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

  14. Primary emissions and secondary organic aerosol formation from the exhaust of a flex-fuel (ethanol) vehicle

    NASA Astrophysics Data System (ADS)

    Suarez-Bertoa, R.; Zardini, A. A.; Platt, S. M.; Hellebust, S.; Pieber, S. M.; El Haddad, I.; Temime-Roussel, B.; Baltensperger, U.; Marchand, N.; Prévôt, A. S. H.; Astorga, C.

    2015-09-01

    Incentives to use biofuels may result in increasing vehicular emissions of compounds detrimental to air quality. Therefore, regulated and unregulated emissions from a Euro 5a flex-fuel vehicle, tested using E85 and E75 blends (gasoline containing 85% and 75% of ethanol (vol/vol), respectively), were investigated at 22 and -7 °C over the New European Driving Cycle, at the Vehicle Emission Laboratory at the European Commission Joint Research Centre Ispra, Italy. Vehicle exhaust was comprehensively analyzed at the tailpipe and in a dilution tunnel. A fraction of the exhaust was injected into a mobile smog chamber to study the photochemical aging of the mixture. We found that emissions from a flex-fuel vehicle, fueled by E85 and E75, led to secondary organic aerosol (SOA) formation, despite the low aromatic content of these fuel blends. Emissions of regulated and unregulated compounds, as well as emissions of black carbon (BC) and primary organic aerosol (POA) and SOA formation were higher at -7 °C. The flex-fuel unregulated emissions, mainly composed of ethanol and acetaldehyde, resulted in very high ozone formation potential and SOA, especially at low temperature (860 mg O3 km-1 and up to 38 mg C kg-1). After an OH exposure of 10 × 106 cm-3 h, SOA mass was, on average, 3 times larger than total primary particle mass emissions (BC + POA) with a high O:C ratio (up to 0.7 and 0.5 at 22 and -7 °C, respectively) typical of highly oxidized mixtures. Furthermore, high resolution organic mass spectra showed high 44/43 ratios (ratio of the ions m/z 44 and m/z 43) characteristic of low-volatility oxygenated organic aerosol. We also hypothesize that SOA formation from vehicular emissions could be due to oxidation products of ethanol and acetaldehyde, both short-chain oxygenated VOCs, e.g. methylglyoxal and acetic acid, and not only from aromatic compounds.

  15. A strategy for characterizing the mixing state of immiscible aerosol components and the formation of multiphase aerosol particles through coagulation.

    PubMed

    Mitchem, Laura; Buajarern, Jariya; Ward, Andrew D; Reid, Jonathan P

    2006-07-20

    We demonstrate that the coagulation of two aerosol droplets of different chemical composition can be studied directly through the unique combination of optical tweezers and Raman spectroscopy. Multiple optical traps can be established, allowing the manipulation of multiple aerosol droplets. Spontaneous Raman scattering allows the characterization of droplet composition and mixing state, permitting the phase segregation of immiscible components in multiphase aerosol to be investigated with spatial resolution. Stimulated Raman scattering allows the integrity of the droplet and uniformity of refractive index to be probed. The combination of these spectroscopic probes with optical tweezers is shown to yield unprecedented detail in studies of the coagulation of decane and water droplets.

  16. Analytic formulation and parametrization of the kinetic potential theory for drizzle formation.

    PubMed

    McGraw, Robert; Liu, Yangang

    2004-09-01

    The kinetic potential of nucleation theory is extended to describe cloud droplet growth processes that can lead to drizzle formation. In this model drizzle formation is identified as a statistical barrier crossing phenomenon that transforms cloud droplets to much larger drizzle size with a rate dependent on turbulent diffusion, droplet collection efficiency, and properties of the underlying cloud droplet size distribution. Closed-form expressions for the kinetic potential, critical drop volume, barrier height, and both steady-state and transient barrier crossing drizzle rates are obtained in terms of measurable cloud properties. In an analogy with the theory of phase transformation, clouds are classified into two regimes: an activated metastable regime, in which there is a significant barrier and drizzle initiation resembles nucleation, and an unstable regime where kinetics dominates analogous to the spinodal regime of phase transformation. Observational evidence, including the threshold behavior of drizzle formation and the well-known effect that aerosols have on drizzle suppression, is shown to favor drizzle formation under activated conditions (more similar to nucleation than spinodal decomposition) and under transient conditions rather than steady state. These new applications of the kinetic potential theory should lead to more accurate parametrizations of aerosol-cloud interaction and improved algorithms for weather forecasting and climate prediction.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  20. 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 α-pinene oxidation product, is suggested to be a key intermediate in the formation of terpenylic acid upon α-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 α-pinene, α-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

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

    SciTech Connect

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

    2007-10-16

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

  2. Importance of Physico-Chemical Properties of Aerosols in the Formation of Arctic Ice Clouds

    NASA Astrophysics Data System (ADS)

    Keita, S. A.; Girard, E.

    2014-12-01

    Ice clouds play an important role in the Arctic weather and climate system but interactions between aerosols, clouds and radiation are poorly understood. Consequently, it is essential to fully understand their properties and especially their formation process. Extensive measurements from ground-based sites and satellite remote sensing reveal the existence of two Types of Ice Clouds (TICs) in the Arctic during the polar night and early spring. TIC-1 are composed by non-precipitating very small (radar-unseen) ice crystals whereas TIC-2 are detected by both sensors and are characterized by a low concentration of large precipitating ice crystals. It is hypothesized that TIC-2 formation is linked to the acidification of aerosols, which inhibit the ice nucleating properties of ice nuclei (IN). As a result, the IN concentration is reduced in these regions, resulting to a smaller concentration of larger ice crystals. Over the past 10 years, several parameterizations of homogeneous and heterogeneous ice nucleation have been developed to reflect the various physical and chemical properties of aerosols. These parameterizations are derived from laboratory studies on aerosols of different chemical compositions. The parameterizations are also developed according to two main approaches: stochastic (that nucleation is a probabilistic process, which is time dependent) and singular (that nucleation occurs at fixed conditions of temperature and humidity and time-independent). This research aims to better understand the formation process of TICs using a newly-developed ice nucleation parameterizations. For this purpose, we implement some parameterizations (2 approaches) into the Limited Area version of the Global Multiscale Environmental Model (GEM-LAM) and use them to simulate ice clouds observed during the Indirect and Semi-Direct Arctic Cloud (ISDAC) in Alaska. We use both approaches but special attention is focused on the new parameterizations of the singular approach. Simulation

  3. Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

    DOE PAGES

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-12-08

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for themore » no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

  4. Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

    DOE PAGES

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-08-28

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution ofmore » US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less

  5. 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 μg 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.

  6. Limited effect of anthropogenic nitrogen oxides on secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-12-01

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. Small differences are found for the no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9-5.6, 6.4-12.0 and 0.9-2.8 % for global, southeast US and Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

  7. Limited effect of anthropogenic nitrogen oxides on Secondary Organic Aerosol formation

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Unger, N.; Hodzic, A.; Emmons, L.; Knote, C.; Tilmes, S.; Lamarque, J.-F.; Yu, P.

    2015-08-01

    Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NOx = NO + NO2) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product Volatility Basis Set (VBS) scheme, including NOx-dependent SOA yields and aging parameterizations. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of two compared to Aerosol Mass Spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different region and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9 to 5.6, 6.4 to 12.0 and 0.9 to 2.8 % for global, the southeast US and the Amazon NOx perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NOx can be largely attributed to buffering in chemical pathways (low- and high-NOx pathways, O3 versus NO3-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.

  8. Instantaneous nitric oxide effect on secondary organic aerosol formation from m-xylene photooxidation

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Tang, Ping; Cocker, David R.

    2015-10-01

    Secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation is highly sensitive to NO concentration. The instantaneous effect of NO on SOA formation from m-xylene photooxidation is investigated in this work by data mining 10 years of aromatic hydrocarbon chamber experiments conducted in the UC Riverside/CE-CERT chamber. First, the effect of sub-ppb NO concentrations on SOA formation is explored. The relationship of SOA growth rate to 1) NO2/NO ratio; 2) instantaneous HC/NO; 3) absolute NO concentration; 4) peroxy radical reaction branching ratio and 5) hydroxyl radical concentration are illustrated. Second, continuous and stepwise NO, NO2 and HONO injection are applied to m-xylene photooxidation experiments to simulate continuous NO sources in an urban area. The influence of these reaction scenarios on radical concentrations and SOA formation is explored. [HO2rad ]/[RO2rad ] shows a strong correlation with SOA yields in addition to [rad OH]/[HO2rad ], [rad OH], [HO2rad ] and [RO2rad ]. Enhanced SOA formation is observed when low NO levels (<1 ppb) are artificially maintained by continuous or step-wise injection; consistent with earlier research, SOA formation is observed to be suppressed by large initial NO injections. It is proposed that NO at sub-ppb level enhances rad OH formation increasing HO2rad and RO2rad and therefore promoting SOA formation. Further, two NO pathways (one promoting and one suppressing SOA formation) and one extremely low NO phase (NO "free") are used to demonstrate the evolution of NO impact on SOA formation during photooxidation. This study implies that SOA yields from aromatic hydrocarbon and low NOx photooxidation is previously underestimated due to differences between traditional environmental chamber experiments and atmospheric reactivity.

  9. Halogen-induced organic aerosol (XOA) formation and decarboxylation of carboxylic acids by reactive halogen species - a time-resolved aerosol flow-reactor study

    NASA Astrophysics Data System (ADS)

    Ofner, Johannes; Zetzsch, Cornelius

    2013-04-01

    Reactive halogen species (RHS) are released to the atmosphere from various sources like photo-activated sea-salt aerosol and salt lakes. Recent studies (Cai et al., 2006 and 2008, Ofner et al., 2012) indicate that RHS are able to interact with SOA precursors similarly to common atmospheric oxidizing gases like OH radicals and ozone. The reaction of RHS with SOA precursors like terpenes forms so-called halogen-induced organic aerosol (XOA). On the other hand, RHS are also able to change the composition of functional groups, e.g. to initiate the decarboxylation of carboxylic acids (Ofner et al., 2012). The present study uses a 50 cm aerosol flow-reactor, equipped with a solar simulator to investigate the time-resolved evolution and transformation of vibrational features in the mid-infrared region. The aerosol flow-reactor is coupled to a home-made multi-reflection cell (Ofner et al., 2010), integrated into a Bruker IFS 113v FTIR spectrometer. The reactor is operated with an inlet feed (organic compound) and a surrounding feed (reactive halogen species). The moveable inlet of the flow reactor allows us to vary reaction times between a few seconds and up to about 3 minutes. Saturated vapours of different SOA precursors and carboxylic acids were fed into the flow reactor using the moveable inlet. The surrounding feed inside the flow reactor was a mixture of zero air with molecular chlorine as the precursor for the formation of reactive halogen species. Using this setup, the formation of halogen-induced organic aerosol could be monitored with a high time resolution using FTIR spectroscopy. XOA formation is characterized by hydrogen-atom abstraction, carbon-chlorine bond formation and later, even formation of carboxylic acids. Several changes of the entire structure of the organic precursor, caused by the reaction of RHS, are visible. While XOA formation is a very fast process, the decarboxylation of carboxylic acids, induced by RHS is rather slow. However, XOA formation

  10. 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 μg/m3-12.6 μg/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 μg/m3 to 9.3 μg/m3 and 3.1 μg/m3 to 6.4 μg /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

  11. Assessing the oxidative potential of isoprene-derived epoxides and secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Kramer, Amanda J.; Rattanavaraha, Weruka; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Lin, Ying-Hsuan

    2016-04-01

    Fine particulate matter (PM2.5) is known to contribute to adverse health effects, such as asthma, cardiopulmonary disease, and lung cancer. Secondary organic aerosol (SOA) is a major component of PM2.5 and can be enhanced by atmospheric oxidation of biogenic volatile organic compounds in the presence of anthropogenic pollutants, such as nitrogen oxides (NOx) and sulfur dioxide. However, whether biogenic SOA contributes to adverse health effects remains unclear. The objective of this study was to assess the potential of isoprene-derived epoxides and SOA for generating reactive oxygen species (ROS) in light of the recent recognition that atmospheric oxidation of isoprene in the presence of acidic sulfate aerosol is a major contributor to the global SOA burden. The dithiothreitol (DTT) assay was used to characterize the ROS generation by the isoprene-derived epoxides, trans-β-isoprene epoxydiol (trans-β-IEPOX) and methacrylic acid epoxide (MAE), and their hydrolysis products, the 2-methyltetrol diastereomers (2-MT), 2-methylglyceric acid (2-MG), their organosulfate derivatives, as well as an isoprene-derived hydroxyhydroperoxide (ISOPOOH). In addition, ROS generation potential was evaluated for total SOA produced from photooxidation of isoprene and methacrolein (MACR) as well as from the reactive uptake of trans-β-IEPOX and MAE onto acidified sulfate aerosol. The high-NOx regime, which yields 2-MG-, MAE- and MACR-derived SOA has a higher ROS generation potential than the low-NOx regime, which yields 2-MT, IEPOX- and isoprene-derived SOA. ISOPOOH has an ROS generation potential similar to 1,4-naphthoquinone (1,4-NQ), suggesting a significant contribution of aerosol-phase organic peroxides to PM oxidative potential. MAE- and MACR-derived SOA show equal or greater ROS generation potential than reported in studies on diesel exhaust PM, highlighting the importance of a comprehensive investigation of the toxicity of isoprene-derived SOA.

  12. Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface.

    PubMed

    Bernard, F; Ciuraru, R; Boréave, A; George, C

    2016-08-16

    In this study, we evaluated photosensitized chemistry at the air-sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1-10 mg L(-1)) as a proxy for dissolved organic matter, and nonanoic acid (0.1-10 mM), a fatty acid proxy which formed an organic film at the air-water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm(-3), illustrating the production of unsaturated compounds by chemical reactions at the air-water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air-sea interface in the production of atmospheric organic aerosol from photosensitized origins. PMID:27434860

  13. Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface.

    PubMed

    Bernard, F; Ciuraru, R; Boréave, A; George, C

    2016-08-16

    In this study, we evaluated photosensitized chemistry at the air-sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1-10 mg L(-1)) as a proxy for dissolved organic matter, and nonanoic acid (0.1-10 mM), a fatty acid proxy which formed an organic film at the air-water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm(-3), illustrating the production of unsaturated compounds by chemical reactions at the air-water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air-sea interface in the production of atmospheric organic aerosol from photosensitized origins.

  14. Photochemical aerosol formation in planetary atmospheres: A comparison between Pluto and Titan

    NASA Astrophysics Data System (ADS)

    Lavvas, Panayotis; Strobel, Darrell F.; Lellouch, Emmanuel; Gurwell, Mark A.; Cheng, Andrew F.; Summers, Michael; Gladstone, Randy

    2016-10-01

    The New Horizons mission observations have revealed us that Pluto's atmosphere is rich in photochemical hazes that extend to high altitudes above its surface [1], apparently similar to those observed in Titan's atmosphere [2].We use detailed models combining photochemistry and microphysics in order to simulate the aerosol formation and growth in Pluto's atmosphere, as performed for Titan's atmosphere [3]. Here we discuss the possible mechanisms leading to the formation of haze particles in Pluto's atmosphere, and we evaluate the contribution of different growth processes (e.g. coagulation vs. condensation) to the resulting particle properties.Moreover we investigate the role of these particles in the radiative balance of Pluto's atmosphere and we compare the resulting particle properties, with those retrieved for Titan's upper atmosphere based on Cassini observations [4]. We discuss the similarities and difference between Pluto's and Titan's aerosols.[1] Gladstone et al., 2016, Science, 351, 6271[2] West et al., 2015, Titan's Haze, in Titan, Interior, Surface, Atmosphere and Space environment, Cambridge University Press[3] Lavvas et al., 2013, PNAS, pnas.1217059110[4] Lavvas et al., 2015, DPS47, id.205.08

  15. Efficient Isoprene Secondary Organic Aerosol Formation from a Non-IEPOX Pathway.

    PubMed

    Liu, Jiumeng; D'Ambro, Emma L; Lee, Ben H; Lopez-Hilfiker, Felipe D; Zaveri, Rahul A; Rivera-Rios, Jean C; Keutsch, Frank N; Iyer, Siddharth; Kurten, Theo; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D; Shilling, John E; Thornton, Joel A

    2016-09-20

    With a large global emission rate and high reactivity, isoprene has a profound effect upon atmospheric chemistry and composition. The atmospheric pathways by which isoprene converts to secondary organic aerosol (SOA) and how anthropogenic pollutants such as nitrogen oxides and sulfur affect this process are subjects of intense research because particles affect Earth's climate and local air quality. In the absence of both nitrogen oxides and reactive aqueous seed particles, we measure SOA mass yields from isoprene photochemical oxidation of up to 15%, which are factors of 2 or more higher than those typically used in coupled chemistry climate models. SOA yield is initially constant with the addition of increasing amounts of nitric oxide (NO) but then sharply decreases for input concentrations above 50 ppbv. Online measurements of aerosol molecular composition show that the fate of second-generation RO2 radicals is key to understanding the efficient SOA formation and the NOx-dependent yields described here and in the literature. These insights allow for improved quantitative estimates of SOA formation in the preindustrial atmosphere and in biogenic-rich regions with limited anthropogenic impacts and suggest that a more-complex representation of NOx-dependent SOA yields may be important in models.

  16. Efficient Isoprene Secondary Organic Aerosol Formation from a Non-IEPOX Pathway.

    PubMed

    Liu, Jiumeng; D'Ambro, Emma L; Lee, Ben H; Lopez-Hilfiker, Felipe D; Zaveri, Rahul A; Rivera-Rios, Jean C; Keutsch, Frank N; Iyer, Siddharth; Kurten, Theo; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D; Shilling, John E; Thornton, Joel A

    2016-09-20

    With a large global emission rate and high reactivity, isoprene has a profound effect upon atmospheric chemistry and composition. The atmospheric pathways by which isoprene converts to secondary organic aerosol (SOA) and how anthropogenic pollutants such as nitrogen oxides and sulfur affect this process are subjects of intense research because particles affect Earth's climate and local air quality. In the absence of both nitrogen oxides and reactive aqueous seed particles, we measure SOA mass yields from isoprene photochemical oxidation of up to 15%, which are factors of 2 or more higher than those typically used in coupled chemistry climate models. SOA yield is initially constant with the addition of increasing amounts of nitric oxide (NO) but then sharply decreases for input concentrations above 50 ppbv. Online measurements of aerosol molecular composition show that the fate of second-generation RO2 radicals is key to understanding the efficient SOA formation and the NOx-dependent yields described here and in the literature. These insights allow for improved quantitative estimates of SOA formation in the preindustrial atmosphere and in biogenic-rich regions with limited anthropogenic impacts and suggest that a more-complex representation of NOx-dependent SOA yields may be important in models. PMID:27548285

  17. Diurnal Cycles of Aerosol Optical Properties at Pico Tres Padres, Mexico City: Evidences for Changes in Particle Morphology and Secondary Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Mazzoleni, C.; Dubey, M.; Chakrabarty, R.; Moosmuller, H.; Onasch, T.; Zavala, M.; Herndon, S.; Kolb, C.

    2007-12-01

    Aerosol optical properties affect planetary radiative balance and depend on chemical composition, size distribution, and morphology. During the MILAGRO field campaign, we measured aerosol absorption and scattering in Mexico City using the Los Alamos aerosol photoacoustic (LAPA) instrument operating at 781 nm. The LAPA was mounted on-board the Aerodyne Research Inc. mobile laboratory, which hosted a variety of gaseous and aerosol instruments. During the campaign, the laboratory was moved to different sites, capturing spatial and temporal variability. Additionally, we collected ambient aerosols on Nuclepore filters for scanning electron microscopy (SEM) analysis. SEM images of selected filters were taken to study particle morphology. Between March 7th and 19th air was sampled at the top of Pico Tres Padres, a mountain on the north side of Mexico City. Aerosol absorption and scattering followed diurnal patterns related to boundary layer height and solar insulation. We report an analysis of aerosol absorption, scattering, and morphology for three days (9th, 11th and 12th of March 2006). The single scattering albedo (SSA, ratio of scattering to total extinction) showed a drop in the tens-of-minutes-to-hour time frame after the boundary layer grew above the sampling site. Later in the day the SSA rose steadily reaching a maximum in the afternoon. The SEM images showed a variety of aerosol shapes including fractal-like aggregates, spherical particles, and other shapes. The absorption correlated with the CO2 signal and qualitatively with the fraction of fractal-like particles to the total particle count. In the afternoon the SSA qualitatively correlated with a relative increase in spherical particles and total particle count. These observed changes in optical properties and morphology can be explained by the dominant contribution of freshly emitted particles in the morning and by secondary particle formation in the afternoon. SSA hourly averaged values ranged from ~0.63 in

  18. Formation of secondary aerosols from biomass burning plumes: chamber simulation study

    NASA Astrophysics Data System (ADS)

    Wang, X.; Hu, Q.; Fang, Z.; Deng, W.

    2015-12-01

    Biomass burning contributed substantially to carbonaceous aerosols in China's ambient air, even in its highly industrialized megacities, based on recent source attributions by receptor modeling or by molecular and isotopic tracers. Although chemical evolution of biomass burning plumes in the ambient is a vital issue for the study of climatic and health effects, the understanding of secondary pollutants formation during the aging of biomass burning plumes is far from complete. Here we collected typical agriculture residues and forest plant branches in the Pearl River Delta in south China, and got them burned in laboratory-controlled conditions and introduced the plumes from burning these biomass directly into the GIGCAS indoor smog chamber with a reactor of 30 m3 to investigate the photochemical aging of the plumes. The inorganic trace gases, including SO2, NOx, NH3 and O3, were monitored online with chemiluminescence gas analyzers, precursor volatile organic compounds (VOCs) were monitor online with a PTR-ToF-MS and offline by a preconcentrator coupled with a gas chromatography-mass selective detector/flame ionization detector/electron capture detector (GC-MSD/FID/ECD), particle number concentrations and size distributions were obtained using a scanning mobility particle sizer (SMPS), and a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) was used to measure the chemical compositions and evolutions of submicron aerosols and to trace the change in the average element ratios of organics, like H/C, O/C, and N/C. The results from the study were summarized in the following aspects: 1) primary emission factors of gaseous and particulate pollutants from burning of typical biomass including agricultural remains and forest wood plants; 2) yields of secondary pollutants, including secondary inorganic and organic aerosols and gaseous products (like O3) during photochemical aging of biomass burning plumes; 3) relationship between the formed secondary

  19. 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.

  20. Advection fog formation and aerosols produced by combustion-originated air pollution

    NASA Technical Reports Server (NTRS)

    Hung, R. J.; Liaw, G. S.; Vaughan, O. H., Jr.

    1980-01-01

    The way in which pollutants produced by the photochemical reaction of NO(X) and SO(X) affect the quality of the human environment through such phenomena as the formation of advection fog is considered. These pollutants provide the major source of condensation nuclei for the formation of fog in highways, airports and seaports. Results based on the monodisperse, multicomponent aerosol model show that: (1) condensation nuclei can grow and form a dense fog without the air having attained supersaturation; (2) the mass concentration range for NO(X) is one-third that of SO(X); and (3) the greater the mass concentration, the particle concentration, and the radius of condensation nuclei, the denser the fog that is formed.

  1. Aerosol Plume during a Polluted Event Occuring Over Paris Area and its Potential Photochemical Effect

    NASA Astrophysics Data System (ADS)

    Randriamiarisoa, H.; Chazette, P.; Sanak, J.; Hauglustaine, D.

    2002-12-01

    As in many big cities, there are several pollution events in Paris area. A thorough understanding of the processes leading on the formation of pollutants and their transport during pollution episodes is necessary. One of the pertinent factors, which contributions on atmospheric chemistry and radiative effect are not yet well known, is the aerosol. ESQUIF (Etude et Simulation de la QUalité de l?air en Ile de France) is the first program dedicated to study such issues over the Paris area. It was carried out from summer 1998 to winter 2000 (Menut et al., 2000). To characterize all the properties of the urban aerosol, many campaigns were coordinated using both ground and airborne measurements (Chazette et al., 2000). We are focusing on the 31st of July 2000 where a well-defined polluted plume has been observed. Aerosol number concentrations in different size classes were measured and show that urban aerosol in Paris area is mainly submicronic. The absorbent part of the aerosol, mainly associated to the black carbon component, has been observed to be associated to particles with diameter less than 0.1 æm. The single scattering albedo has been assessed to be close to 0.85 leading to a significant influence on the photochemical chemistry. Indeed, a significant decrease of the daily maximum ozone concentration has been calculated using the INCA model and will be presented. ACKNOWLEDGEMENTS The Programme National de Chimie Atmosphérique, INSU supported this work. REFERENCES Chazette P., H. Randriamiarisoa, J. Sanak, C. Flamant, J. Pelon, M. Sicard, H. Cachier, F. Aulagnier, R. Sarda-Esteve, L. Gomes, S. Alfaro and A. Gaudichet (2001). ESQUIF 2000 : Aerosol survey over the Ile-de-France area, J. Aerosol Sci ., 32/suppl. 1, S439-S440. Menut, L., R. Vautard, C. Flamant, A. Abonnel, M. Beekmann, P. Chazette, P.H. Flamant, D. Gombert, D. Guédalia, D. Kley, M.P. Lefebvre, B. Lossec, D. Martin, G. Mégie, P. Perros, M. Sicard and G. Toupance (2000). Measurements and modelling

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    carbon (BC ~ 0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

  3. 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

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

    PubMed

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

    2012-08-01

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

  5. 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.

    2015-07-01

    This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA 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 α-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 5 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, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-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 cloud water and aerosol chemistry.

  6. Relationship Between Aerosol Number Size Distribution and Atmospheric Electric Potential Gradient in an Urban Area

    NASA Astrophysics Data System (ADS)

    Wright, Matthew; Matthews, James; Bacak, Asan; Silva, Hugo; Priestley, Michael; Percival, Carl; Shallcross, Dudley

    2016-04-01

    Small ions are created in the atmosphere by ground based radioactive decay and solar and cosmic radiation ionising the air. The ionosphere is maintained at a high potential relative to the Earth due to global thunderstorm activity, a current from the ionosphere transfers charge back to the ground through the weakly ionised atmosphere. A potential gradient (PG) exists between the ionosphere and the ground that can be measured in fair weather using devices such as an electric field mill. PG is inversely-proportional to the conductivity of the air and therefore to the number of ions of a given electrical mobility; a reduction of air ions will cause an increase of PG. Aerosols in the atmosphere act as a sink of air ions with an attachment rate dependent on aerosol size distribution and ion mobility. These relationships have been used to infer high particulate, and hence pollution, levels in historic datasets of atmospheric PG. A measurement campaign was undertaken in Manchester, UK for three weeks in July and August where atmospheric PG was measured with an electric field mill (JCI131, JCI Chilworth) on a second floor balcony, aerosol size distribution measured with a scanning mobility particle sizer (SMPS, TSI3936), aerosol concentration measured with a condensation particle counter (CPC, Grimm 5.403) and local meteorological measurements taken on a rooftop measurement site ~200 m away. Field mill and CPC data were taken at 1 s intervals and SMPS data in 2.5 minute cycles. Data were excluded for one hour either side of rainfall as rainclouds and droplets can carry significant charge which would affect PG. A quantity relating to the attachment of ions to aerosol (Ion Sink) was derived from the effective attachment coefficient of the aerosols. Further measurements with the field mill and CPC were taken at the same location in November 2015 when bonfire events would be expected to increase aerosol concentrations. During the summer measurements, particle number count (PNC

  7. 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.

  8. Potential chemical evolution of aerosols on Titan's surface: some new results on Titan's tholins

    NASA Astrophysics Data System (ADS)

    Coll, P.; Poch, O.; Ramirez, S. I.; Buch, A.; Brassé, C.; Raulin, F.

    2011-10-01

    Titan's environment hosts a complex organic chemistry that can be investigated from Earth-based laboratory experiments. One of the key astrobiological questions of Titan's environment is the fate of the organic aerosols produced in the atmosphere, after they are deposited on the surface. In the present study, we report the geological structures these aerosols may encounter in the light of the last observations of the Cassini-Huygens mission. We chose to quantify the production of some astrobiologically interesting molecules in putative ammonia-water bodies likely to be present at the surface or subsurface of Titan, as crater melt pools or cryolavas. After aerosol analogues (tholins) synthesis and surface hydrolysis simulation, some resulting products were identified and quantified. Tholins were found to be very reactive toward an oxygen source. Urea was identified as the main product of Titan's tholins hydrolysis in ammonia-water solutions, with a production yield in mass, ranging from 6 to 12% at 279 K after 10 weeks. Several amino acids - alanine, glycine and aspartic acid - and perhaps the uracil nucleobase were also produced with yields from 0.001 to 0.4%. The determination of production yields carried out by the present study is a major step into the characterization of potential aerosols evolution on Titan.

  9. Sulfate aerosol as a potential transport medium of radiocesium from the Fukushima nuclear accident.

    PubMed

    Kaneyasu, Naoki; Ohashi, Hideo; Suzuki, Fumie; Okuda, Tomoaki; Ikemori, Fumikazu

    2012-06-01

    To date, areas contaminated by radionuclides discharged from the Fukushima Dai-ichi nuclear power plant accident have been mapped in detail. However, size of the radionuclides and their mixing state with other aerosol components, which are critical in their removal from the atmosphere, have not yet been revealed. We measured activity size distributions of (134)Cs and (137)Cs in aerosols collected 47 days after the accident at Tsukuba, Japan, and found that the activity median aerodynamic diameters of (134)Cs and (137)Cs in the first sample (April 28-May 12) were 0.54 and 0.53 μm, respectively, and those in the second sample (May 12-26) were both 0.63 μm. The activity size distributions of these radiocesium were within the accumulation mode size range and almost overlapped with the mass size distribution of non-sea-salt sulfate aerosol. From the analysis of other aerosol components, we found that sulfate was the potential transport medium for these radionuclides, and resuspended soil particles that attached radionuclides were not the major airborne radioactive substances at the time of measurement. This explains the relatively similar activity sizes of radiocesium measured at various sites during the Chernobyl accident. Our results can serve as basic data for modeling the transport/deposition of radionuclides.

  10. Understanding the toxicological potential of aerosol organic compounds using informatics based screening

    NASA Astrophysics Data System (ADS)

    Topping, David; Decesari, Stefano; Bassan, Arianna; Pavan, Manuela; Ciacci, Andrea

    2016-04-01

    Exposure to atmospheric particulate matter is responsible for both short-term and long-term adverse health effects. So far, all efforts spent in achieving a systematic epidemiological evidence of specific aerosol compounds determining the overall aerosol toxicity were unsuccessful. The results of the epidemiological studies apparently conflict with the laboratory toxicological analyses which have highlighted very different chemical and toxicological potentials for speciated aerosol compounds. Speciation remains a problem, especially for organic compounds: it is impossible to conduct screening on all possible molecular species. At the same time, research on toxic compounds risks to be biased towards the already known compounds, such as PAHs and dioxins. In this study we present results from an initial assessment of the use of in silico methods (i.e. (Q)SAR, read-across) to predict toxicity of atmospheric organic compounds including evaluation of applicability of a variety of popular tools (e.g. OECD QSAR Toolbox) for selected endpoints (e.g. genotoxicity). Compounds are categorised based on the need of new experimental data for the development of in silico approaches for toxicity prediction covering this specific chemical space, namely the atmospheric aerosols. Whilst only an initial investigation, we present recommendations for continuation of this work.

  11. Characterization of carbonaceous aerosols at Mount Lu in South China: implication for secondary organic carbon formation and long-range transport.

    PubMed

    Li, Peng-hui; Wang, Yan; Li, Tao; Sun, Lei; Yi, Xianliang; Guo, Li-qiong; Su, Rui-hong

    2015-09-01

    In order to understand the sources and potential formation processes of atmospheric carbonaceous aerosols in South China, fine particle samples were collected at a high-elevation mountain site--Mount Lu (29°35' N, 115°59' E, 1165 m A.S.L.) during August-September, 2011. Eight carbonaceous fractions from particles were resolved following the IMPROVE thermal/optical reflectance protocol. During the observation campaign, the daily concentrations of PM2.5 at Mount Lu ranged from 7.69 to 116.39 μg/m(3), with an average of 58.76 μg/m(3). The observed average organic carbon (OC) and elemental carbon (EC) concentrations in PM2.5 were 3.78 and 1.28 μg/m(3), respectively. Secondary organic carbon (SOC) concentration, estimated by EC-tracer method, was 2.07 μg/m(3) on average, accounting for 45.0% of the total OC. The enhancement of secondary organic aerosol (SOA) formation was observed during cloud/fog processing, and heterogeneous acid-catalyzed reactions may have contributed to SOA formation as well. Back trajectory analysis indicated that air masses were mainly sourced from southern China during observation period, and this air mass source was featured by highest values of OC and effective carbon ratio (ECR). Relation of carbonaceous species and principal component analysis indicated that multiple sources contributed to the carbonaceous aerosols at Mount Lu.

  12. Comprehensive mapping and characteristic regimes of aerosol effects on the formation and evolution of pyro-convective clouds

    SciTech Connect

    Chang, D.; Cheng, Y.; Reutter, P.; Trentmann, J.; Burrows, S. M.; Spichtinger, P.; Nordmann, S.; Andreae, M. O.; Poschl, U.; Su, H.

    2015-09-21

    Here, a recent parcel model study (Reutter et al., 2009) showed three deterministic regimes of initial cloud droplet formation, characterized by different ratios of aerosol concentrations (NCN) to updraft velocities. This analysis, however, did not reveal how these regimes evolve during the subsequent cloud development. To address this issue, we employed the Active Tracer High Resolution Atmospheric Model (ATHAM) with full microphysics and extended the model simulation from the cloud base to the entire column of a single pyro-convective mixed-phase cloud. A series of 2-D simulations (over 1000) were performed over a wide range of NCN and dynamic conditions. The integrated concentration of hydrometeors over the full spatial and temporal scales was used to evaluate the aerosol and dynamic effects. The results show the following. (1) The three regimes for cloud condensation nuclei (CCN) activation in the parcel model (namely aerosol-limited, updraft-limited, and transitional regimes) still exist within our simulations, but net production of raindrops and frozen particles occurs mostly within the updraft-limited regime. (2) Generally, elevated aerosols enhance the formation of cloud droplets and frozen particles. The response of raindrops and precipitation to aerosols is more complex and can be either positive or negative as a function of aerosol concentrations. The most negative effect was found for values of NCN of ~ 1000 to 3000 cm–3. (3) The nonlinear properties of aerosol–cloud interactions challenge the conclusions drawn from limited case studies in terms of their representativeness, and ensemble studies over a wide range of aerosol concentrations and other influencing factors are strongly recommended for a more robust assessment of the aerosol effects.

  13. Comprehensive mapping and characteristic regimes of aerosol effects on the formation and evolution of pyro-convective clouds

    DOE PAGES

    Chang, D.; Cheng, Y.; Reutter, P.; Trentmann, J.; Burrows, S. M.; Spichtinger, P.; Nordmann, S.; Andreae, M. O.; Poschl, U.; Su, H.

    2015-09-21

    Here, a recent parcel model study (Reutter et al., 2009) showed three deterministic regimes of initial cloud droplet formation, characterized by different ratios of aerosol concentrations (NCN) to updraft velocities. This analysis, however, did not reveal how these regimes evolve during the subsequent cloud development. To address this issue, we employed the Active Tracer High Resolution Atmospheric Model (ATHAM) with full microphysics and extended the model simulation from the cloud base to the entire column of a single pyro-convective mixed-phase cloud. A series of 2-D simulations (over 1000) were performed over a wide range of NCN and dynamic conditions. Themore » integrated concentration of hydrometeors over the full spatial and temporal scales was used to evaluate the aerosol and dynamic effects. The results show the following. (1) The three regimes for cloud condensation nuclei (CCN) activation in the parcel model (namely aerosol-limited, updraft-limited, and transitional regimes) still exist within our simulations, but net production of raindrops and frozen particles occurs mostly within the updraft-limited regime. (2) Generally, elevated aerosols enhance the formation of cloud droplets and frozen particles. The response of raindrops and precipitation to aerosols is more complex and can be either positive or negative as a function of aerosol concentrations. The most negative effect was found for values of NCN of ~ 1000 to 3000 cm–3. (3) The nonlinear properties of aerosol–cloud interactions challenge the conclusions drawn from limited case studies in terms of their representativeness, and ensemble studies over a wide range of aerosol concentrations and other influencing factors are strongly recommended for a more robust assessment of the aerosol effects.« less

  14. Comprehensive Mapping and Characteristic Regimes of Aerosol Effects on the Formation and Evolution of Pyro-Convective Clouds

    SciTech Connect

    Chang, Di; Cheng, Yafang; Reutter, Philipp; Trentmann, Jrg; Burrows, Susannah M.; Spichtinger, Peter; Nordmann, Stephan; Andreae, M. O.; Poschl, U.; Su, Hang

    2015-09-21

    A recent parcel model study (Reutter et al., 2009) showed three deterministic regimes of initial cloud droplet formation characterized by ratios of aerosol concentrations (NCN) to updraft velocities. This analysis, however, did not reveal how these regimes evolve during the subsequent development of clouds. To address this issue, we employed the Active Tracer High Resolution Atmospheric Model with full microphysics and extended the model simulation from the cloud base to the entire column of a single pyro-convective mixed-phase cloud. A series of 2-D simulations (over 1000) were performed over a wide range of NCN and dynamic conditions. The integrated concentration of hydrometeors over the full spatial and temporal scales was used to evaluate the aerosol and dynamic effects. The results show that: (1) the three regimes for cloud condensation nuclei (CCN) activation in the parcel model (namely aerosol-limited, updraft-limited, and transitional regimes) still exist within our simulations, but the net production of raindrops and frozen particles occurs mostly within the updraft-limited regime. (2) Generally, elevated aerosols enhance the formation of cloud droplets and frozen particles. The response of raindrops and precipitation to aerosols is more complicated and can be either positive or negative as a function of aerosol concentrations. The most negative effect was found for a value of NCN of ~1000 to 3000 cm-3. (3) The employment of nonlinear (dynamic and microphysical) processes leads to a more complicated and unstable response of clouds to aerosol perturbation compared with the parcel model results. Therefore, conclusions drawn from limited case studies might require caveats regarding their representativeness, and high-resolution sensitivity studies over a wide range of aerosol concentrations and updraft velocities are highly recommended.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  16. Secondary organic aerosol formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compound (BVOC) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene and limonene) by OH-dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction) chamber in Jülich, Germany, at low NOx (0.01 ~ 1 ppbV) and low ozone (O3) concentration (< 20 ppbV). OH concentration and total OH reactivity (kOH) were measured directly, and through this the overall reaction rate of total organics with OH in each reaction system was quantified. Multi-generation reaction process, particle growth, new particle formation (NPF), particle yield and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH-dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction rate of OH with total organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to play an important role after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates

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

    PubMed

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

    2015-05-01

    A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibilityaerosol) concentrations. The average values with standard deviation of SO4(2-), NO3-, NH4+ and SOA were 49.8 (±31.6), 31.4 (±22.3), 25.8 (±16.6) and 8.9 (±4.1)μg/m3, respectively, during the haze episodes, which were 4.3, 3.4, 4.1, and 1.7 times those in the non-haze days. The SO4(2-), NO3-, NH4+, and SOA accounted for 15.8%, 8.8%, 7.3%, and 6.0% of the total mass concentration of PM10 during the non-haze days. The respective contributions of SNA species to PM10 rose to about 27.2%, 15.9%, and 13.9% during the haze days, while the contributions of SOA maintained the same level with a slight decrease to about 4.9%. The observed mass concentrations of SNA and SOA increased with the increase of PM10 mass concentration, however, the rate of increase of SNA was much faster than that of the SOA. The SOR (sulfur oxidation ratio) and NOR (nitrogen oxidation ratio) increased from non-haze days to hazy days, and increased with the increase of RH. High concentrations of aerosols and water vapor favored the conversion of SO2 to SO4(2-) and NO2 to NO3-, which accelerated the accumulation of the aerosols and resulted in the formation of haze in Beijing.

  18. Field Observation of Heterogeneous Formation of Secondary Organic Aerosols on Asian Mineral Dust Surfaces

    NASA Astrophysics Data System (ADS)

    Wang, G.

    2014-12-01

    This study investigated the heterogeneous formation mechanism of secondary organic aerosols (SOA) on dust surfaces by characterizing molecular compositions and size distributions of dicarboxylic acids, keto-carboxylic acids, a-dicarbonyls and inorganic ions in size-segregated aerosols (9-stages) in the urban atmosphere of Xi'an, China during dust storm periods and comparing with those in non-dust storm periods. In the presence of a dust storm, all the above mentioned SOA species in Xi'an are predominantly enriched on coarse particles (>2.1 µm). Oxalic acid well correlated with NO3- (r2=0.72, p<0.01) rather than SO42-. This phenomenon differs greatly from the observed particles during a non-dust storm period, which is characterized by an enrichment of the SOA on fine particles (<2.1 µm) with a strong correlation between C2 and SO42-. We propose a three-step formation pathway to explain these observations as follows. First, nitric acid and nitrogen oxides react with dust to form a liquid film on the surface via water vapor-absorption of calcium nitrate. Second, gaseous Gly and mGly partition into the aqueous-phase. Finally, the aqueous-phase Gly and mGly oxidize into glyoxylic acid (wC2), followed by a further oxidation into C2. To the best of our knowledge, we found for the first time the enrichments of glyoxal (Gly) and methylglyoxal (mGly) on dust surfaces. Our data indicate a more critical role of nitrate than sulfate in the heterogeneous formation process of SOA on dust surfaces. Mass ratio of C2 to wC2 was found to be higher in coarse particles than in fine particles during the dust storm events, which is due to low acidity condition of large particles that is favorable for conversion of wC2 to C2.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  1. Modeled aerosol nitrate formation pathways during wintertime in the Great Lakes region of North America

    NASA Astrophysics Data System (ADS)

    Kim, Yoo Jung; Spak, Scott N.; Carmichael, Gregory R.; Riemer, Nicole; Stanier, Charles O.

    2014-11-01

    Episodic wintertime particle pollution by ammonium nitrate is an important air quality concern across the Midwest U.S. Understanding and accurately forecasting PM2.5 episodes are complicated by multiple pathways for aerosol nitrate formation, each with uncertain rate parameters. Here, the Community Multiscale Air Quality model (CMAQ) simulated regional atmospheric nitrate budgets during the 2009 LADCO Winter Nitrate Study, using integrated process rate (IPR) and integrated reaction rate (IRR) tools to quantify relevant processes. Total nitrate production contributing to PM2.5 episodes is a regional phenomenon, with peak production over the Ohio River Valley and southern Great Lakes. Total nitrate production in the lower troposphere is attributed to three pathways, with 57% from heterogeneous conversion of N2O5, 28% from the reaction of OH and NO2, and 15% from homogeneous conversion of N2O5. TNO3 formation rates varied day-to-day and on synoptic timescales. Rate-limited production does not follow urban-rural gradients and NOx emissions due, to counterbalancing of urban enhancement in daytime HNO3 production with nocturnal reductions. Concentrations of HNO3 and N2O5 and nighttime TNO3 formation rates have maxima aloft (100-500 m), leading to net total nitrate vertical flux during episodes, with substantial vertical gradients in nitrate partitioning. Uncertainties in all three pathways are relevant to wintertime aerosol modeling and highlight the importance of interacting transport and chemistry processes during ammonium nitrate episodes, as well as the need for additional constraint on the system through field and laboratory experiments.

  2. Secondary Organic Aerosol Formation from Ultra-Low Super Ultra-Low and Partial Zero Emission Vehicle Exhaust

    NASA Astrophysics Data System (ADS)

    Robinson, A. L.; Zhao, Y.; Lambe, A. T.; Saleh, R.; Saliba, G.; Maldonado, H.; Sardar, S.; Frodin, B.; Drozd, G.; Goldstein, A. H.; Kroll, J. H.; Cross, E. S.; Franklin, J. P.

    2015-12-01

    Secondary organic aerosol (SOA) is the dominant component of organic aerosol in many urban areas during the summertime. On-road light duty gasoline vehicles (LDGV) have been indicated as a major source of SOA precursors. Emissions of the SOA-forming non methane hydrocarbons (NMHCs) from on-road LDGV have been substantially reduced along with more stringent emission standards, leading to reduced potential for SOA formation. However, recent smog chamber measurements reported that the reductions in SOA formation were less than those in NMHC emissions, indicating that newer, low emitting vehicles may emit a more efficient of SOA precursors. Vehicles that meet the ultra-low, super ultra-low and partial zero emission standards have substantially lower NMHC emissions than vehicles tested in past studies. To better understand the effects of more stringent emission controls on the SOA formation, we conducted experiments 13 vehicles recruited from the Southern California vehicle fleet (five ultra-low emission vehicles, four super ultra-low emission vehicles and four partial zero emission vehicles) at the California Air Resources Board Haagen-Smit Laboratory. In addition, we investigated several vehicles compliant with older emission standards have also been investigated here to bridge the previous studies. Dilute vehicle exhaust were photo-oxidized in a smog chamber with the VOC-to-NOx ratio adjusted to simulate the photochemistry in urban air. Application of literature data from single-ring aromatic compounds cannot explain the observed SOA during chamber experiments. The average ratios between estimated and measured SOA for vehicles under different emission standards ranged from 0.04 to 0.71. Comprehensive measurements of SOA precursor emissions were made, including NMHCs, intermediate volatility and semi-volatile organic compounds. This study presents results of SOA production from these low emitting vehicles and compares the results with recently published data. This

  3. 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: α-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 α-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.

  4. Formation of Brown Aqueous Secondary Organic Aerosol during Multiphase Cloud Simulations using the CESAM Chamber Facility

    NASA Astrophysics Data System (ADS)

    Hawkins, L. N.; Welsh, H.; De Haan, D. O.; Doussin, J. F.; Pednekar, R.; Caponi, L.; Pangui, E.; Gratien, A.; Cazaunau, M.; Formenti, P.; Pajunoja, A.

    2015-12-01

    We investigated the formation of aqueous brown carbon (aqBrC) from methylglyoxal and methylamine in multiphase reactions using the CESAM chamber facility at the University Paris-Est Creteil. Following reaction in the chamber, droplets and particles were sampled with a Particle-Into-Liquid-Sampler (PILS), a capillary waveguide cell for UV/visible spectroscopy, and a total organic carbon analyzer (TOC). Particle size distributions were measured with a scanning mobility particle sizer and used to determine the mass absorption coefficient (a normalized absorbance measurement). Absorption spectra were recorded while aerosol or gas phase aqBrC precursors were introduced into the humid chamber. Sampling was continuous during and after cloud events. The events lasted 5-10 minutes and produced measurable brown carbon signal at 365 nm. When lights were used, absorbance at 365 nm decreased steadily indicating photobleaching of aqBrC products or preferential formation of different, non-absorbing products. Although absorptivity increases prior to cloud formation, cloud events produce sharp increased in aqBrC absorptivity. While measurable absorbance at 365 nm indicates aqBrC formation, very little absorbance was recorded beyond 450 nm indicating that the products were not as oligomerized as products observed in prior work in multi-day, bulk phase simulations.

  5. In-cloud measurements highlight the role of aerosol hygroscopicity in cloud droplet formation

    NASA Astrophysics Data System (ADS)

    Väisänen, Olli; Ruuskanen, Antti; Ylisirniö, Arttu; Miettinen, Pasi; Portin, Harri; Hao, Liqing; Leskinen, Ari; Komppula, Mika; Romakkaniemi, Sami; Lehtinen, Kari E. J.; Virtanen, Annele

    2016-08-01

    The relationship between aerosol hygroscopicity and cloud droplet activation was studied at the Puijo measurement station in Kuopio, Finland, during the autumn 2014. The hygroscopic growth of 80, 120 and 150 nm particles was measured at 90 % relative humidity with a hygroscopic tandem differential mobility analyzer. Typically, the growth factor (GF) distributions appeared bimodal with clearly distinguishable peaks around 1.0-1.1 and 1.4-1.6. However, the relative contribution of the two modes appeared highly variable reflecting the probable presence of fresh anthropogenic particle emissions. The hygroscopicity-dependent activation properties were estimated in a case study comprising four separate cloud events with varying characteristics. At 120 and 150 nm, the activation efficiencies within the low- and high-GF modes varied between 0-34 and 57-83 %, respectively, indicating that the less hygroscopic particles remained mostly non-activated, whereas the more hygroscopic mode was predominantly scavenged into cloud droplets. By modifying the measured GF distributions, it was estimated how the cloud droplet concentrations would change if all the particles belonged to the more hygroscopic group. According to κ-Köhler simulations, the cloud droplet concentrations increased up to 70 % when the possible feedback effects on effective peak supersaturation (between 0.16 and 0.29 %) were assumed negligible. This is an indirect but clear illustration of the sensitivity of cloud formation to aerosol chemical composition.

  6. Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation.

    PubMed

    Percival, Carl J; Welz, Oliver; Eskola, Arkke J; Savee, John D; Osborn, David L; Topping, David O; Lowe, Douglas; Utembe, Steven R; Bacak, Asan; McFiggans, Gordon; Cooke, Michael C; Xiao, Ping; Archibald, Alexander T; Jenkin, Michael E; Derwent, Richard G; Riipinen, Ilona; Mok, Daniel W K; Lee, Edmond P F; Dyke, John M; Taatjes, Craig A; Shallcross, Dudley E

    2013-01-01

    Carbonyl oxides ("Criegee intermediates"), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al, Sci, Total Environ., 2006, 360, 5, Gäb et al., Nature, 1985, 316, 535, ref. 1-3). Recently it was shown that small Criegee intermediates, C.I.'s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204, ref. 4) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of 502 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipilä et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U. S. A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429, ref. 5-7). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007, ref. 8). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved

  7. Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation.

    PubMed

    Percival, Carl J; Welz, Oliver; Eskola, Arkke J; Savee, John D; Osborn, David L; Topping, David O; Lowe, Douglas; Utembe, Steven R; Bacak, Asan; McFiggans, Gordon; Cooke, Michael C; Xiao, Ping; Archibald, Alexander T; Jenkin, Michael E; Derwent, Richard G; Riipinen, Ilona; Mok, Daniel W K; Lee, Edmond P F; Dyke, John M; Taatjes, Craig A; Shallcross, Dudley E

    2013-01-01

    Carbonyl oxides ("Criegee intermediates"), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al, Sci, Total Environ., 2006, 360, 5, Gäb et al., Nature, 1985, 316, 535, ref. 1-3). Recently it was shown that small Criegee intermediates, C.I.'s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204, ref. 4) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of 502 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipilä et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U. S. A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429, ref. 5-7). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007, ref. 8). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved

  8. Sulfate Aerosol Formation and Oxidation Pathways on Haze Event over East Asia Region Focusing on Korea.

    NASA Astrophysics Data System (ADS)

    Choi, D.; Koo, Y. S.

    2014-12-01

    The aerosol transports from China largely contribute to high PM (Particulate Matter) concentration in Korea. Especially, secondary inorganic aerosol (SIA) such as nitrate, sulfate and ammonium are largely transported from China to Korea during haze event. The measured PM2.5 (Particle Matter with aerodynamic diameters less than 2.5㎛) concentrations at the supersite monitoring stations in Korea are normally over 100 ug/m3 and SIAs are major chemical species with more than 70% of PM2.5 during the event. According to our air quality forecast model, sulfate concentrations are largely under-predicted in winter and slightly over-predicted in summer. Those discrepancies between model predicted and observed sulfate concentrations are mainly due to uncertainties of precursor emissions of NOx, SO2, and VOCs (Volatile Organic Compounds) and chemical mechanism of the sulfate formation in the chemical forecast model of CMAQ (Community Multiscale Air Quality Model). Formation of sulfate is chemically linked to primary emissions of sulfur dioxide and to be abundancy of atmospheric oxidants such as hydroxyl radical, hydrogen peroxide, ozone, methyl hydroperoxide, and peroxyacetic acid. All of these oxidant species are formed via photochemical reactions with NOx and VOCs. The aim of this work is to investigate the dependency of sulfate formation on oxidant levels in winter and summer during episode event using CMAQ and its sulfate tracking probing tool. The sensitivity of the precursor emissions of SO2, NOx, VOCs and NH3 was also tested to understand the pathways of the sulfate formation. The results show that long range transport from China is a major factor to determine sulfate level in Korea during haze events and dominant mechanisms in the sulfate formation are the gas-phase OH and aqueous phase H2O2 reactions. NOx-SO2-VOCs chemical regimes for the sulfate formation is the VOCs limited regimes in Korea. The further details of the sensitivity run of the precursor emissions and

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

    PubMed Central

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    .2 μg m-3). Particle-phase sulfate is fairly correlated (r2~0.3) with both MAE- and IEPOX-derived SOA tracers, and more strongly correlated (r2~0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the methacrylic acid epoxide (MAE)-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2=0.38) and nitrate (r2=0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a~clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2~0.5 and ~0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

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

    NASA Astrophysics Data System (ADS)

    Grgić, Irena; Kitanovski, Zoran; Kroflič, Ana; Čusak, 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

  12. Kinetic potential and barrier crossing: a model for warm cloud drizzle formation.

    PubMed

    McGraw, Robert; Liu, Yangang

    2003-01-10

    The kinetic potential of nucleation theory is used to describe droplet growth processes in a cloud. Drizzle formation is identified as a statistical barrier-crossing phenomenon that transforms cloud droplets to drizzle size with a rate dependent on turbulent diffusion, droplet collection, and size distribution. Steady-state and transient drizzle rates are calculated for typical cloud conditions. We find drizzle more likely under transient conditions. The model quantifies an important indirect effect of aerosols on climate-drizzle suppression in clouds of higher droplet concentration.

  13. 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...

  14. Isotopic mass independent signature of black crusts: a proxy for atmospheric aerosols formation in the Paris area (France).

    NASA Astrophysics Data System (ADS)

    Genot, Isabelle; Martin, Erwan; Yang, David Au; De Rafelis, Marc; Cartigny, Pierre; Wing, Boswell; Le Gendre, Erwann; Bekki, Slimane

    2016-04-01

    In view of the negative forcing of the sulfate aerosols on climate, a more accurate understanding of the formation of these particles is crucial. Indeed, despite the knowledge of their effects, uncertainties remain regarding the formation of sulfate aerosols, particularly the oxidation processes of S-bearing gases. Since the discovery of oxygen and sulfur mass independent fractionation (O- and S-MIF) processes on Earth, the sulfate isotopic composition became essential to investigate the atmospheric composition evolution and its consequences on the climate and the biosphere. Large amount of S-bearing compounds (SO2 mainly) is released into the atmosphere by anthropogenic and natural sources. Their oxidation in the atmosphere generates sulfate aerosols, H2SO4, which precipitate on the earth surface mainly as acid rain. One consequence of this precipitation is the formation of black crust on buildings made of carbonate stones. Indeed the chemical alteration of CaCO3 by H2SO4 leads to gypsum (CaSO4·2H2O) concretions on building walls. Associated to other particles, gypsum forms black-crusts. Therefore, black crusts acts as 'sulfate aerosol traps', meaning that their isotopic composition reveals the composition and thus the source and formation processes of sulfate aerosols in the atmosphere in a specific region. In this study we collected 37 black crusts on a 300km NW-SE profile centered on Paris (France). In our samples, sulfate represent 40wt.% and other particles 60wt.% of the black crusts. After sulfate extraction from each samples we measured their O- and S-isotopes composition. Variations of about 10‰ in δ18O and δ34S are observed and both O-MIF (Δ17O from 0 to 1.4‰) and S-MIF (Δ33S from 0 to -0.3‰) compositions have been measured. In regards to these compositions we can discuss the source and formation (oxidation pathways) of the sulfate aerosols in troposphere above the Paris region that covers urban, rural and coastal environments. Furthermore

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

    NASA Astrophysics Data System (ADS)

    Beardsley, Ross L.; Jang, Myoseon

    2016-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Beardsley, R. L.; Jang, M.

    2015-11-01

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

  17. Cloud-Aerosol Drivers of Reflective Roof and Solar Power Potential Benefits Across Selected Indian Cities

    NASA Astrophysics Data System (ADS)

    Millstein, D.; Fischer, M. L.

    2013-12-01

    Application of reflective roof surfaces is an adaptive strategy for sustainable warm-climate human environments that can improve human comfort for un-conditioned buildings, energy consumption for conditioned buildings, the urban heat island effect, and potentially net radiation absorbed by the earth. Here, we evaluate the (1) potential radiative benefits of installing cool roofs and (2) incoming surface radiation available for solar power generation across selected Indian cities using a combination of satellite data (MODIS and MERRA) and a radiative transfer model (RRTMG). The radiative transfer model was run multiple times at each time step and location in order to separate the effects of clouds and aerosols on top of the atmosphere outgoing shortwave radiation reflected from roofs and on bottom of the atmosphere incoming shortwave radiation available for solar power generation. Modeled downwelling shortwave radiation at the surface was first validated against measurements obtained from urban rooftops during the 9-month (June, 2011-March, 2012) a joint Indian-US Ganges Valley Aerosol Experiment (GVAX) campaign. Results show that model bias at two Indian cities, Nainital (-4.2% average midday bias) and Pantnagar (0.5% average midday bias) was small compared to the radiative benefit obtained from a typical increase in surface reflectance (e.g., 0.3-0.6). Although both cities are located in the northern state of Uttarakhand, differences in terrain type, pollution burdens and cloudiness allow for validation of the model across a wide range of conditions. For example, Nainital is located in complex terrain at an altitude of ~2,000 meters near the Himalayan Mountains while Pantnagar is located in a flat plain at an altitude of ~300 meters. Pantnagar had a larger aerosol burden than Nainital as the average aerosol optical depth at Pantnagar (0.47) was larger than Nainital (0.33). Nainital was cloudier, with clouds observed on 62% of the days during the validation period

  18. 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

  19. 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.

    2015-12-01

    Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plumes of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) 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 of the Paris region. Two mechanisms of secondary OA (SOA) formation are used, both including SOA formation from oxidation and chemical aging of primary semivolatile and intermediate volatility organic compounds (SI-SOA) in the volatility basis set (VBS) framework. As for SOA formed from traditional VOC (volatile organic compound) precursors (traditional SOA), one applies chemical aging in the VBS framework adopting different SOA yields for high- and low-NOx environments, while another applies a single-step oxidation scheme without chemical aging. Two emission inventories are used for discussion of emission uncertainties. The slopes of the airborne OA levels versus Ox (i.e., O3 + NO2) show SOA formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. The simulated slopes were overestimated slightly by factors of 1.1, 1.7 and 1.3 with respect to those observed for the three airborne measurements, when the most realistic "high-NOx" yields for traditional SOA formation in the VBS scheme are used in the model. In addition, these slopes are relatively stable from one day to another, which suggests that they are characteristic for the given megacity plume environment. The configuration with increased primary

  20. Formation and characterization of fission-product aerosols under postulated HTGR accident conditions

    SciTech Connect

    Tang, I.N.; Munkelwitz, H.R.

    1982-07-01

    The paper presents the results of an experimental investigation on the formation mechanism and physical characterization of simulated nuclear aerosols that could likely be released during an HTGR core heat-up accident. Experiments were carried out in a high-temperature flow system consisting essentially of an inductively heated release source, a vapor deposition tube, and a filter assembly for collecting particulate matter. Simulated fission products Sr and Ba as oxides are separately impregnated in H451 graphite wafers and released at elevated temperatures into a dry helium flow. In the presence of graphite, the oxides are quantitatively reduced to metals, which subsequently vaporize at temperatures much lower than required for the oxides alone to vaporize in the absence of graphite. A substantial fraction of the released material is associated with particulate matter, which is collected on filters located downstream at ambient temperature. The release and transport of simulated fission product Ag as metal are also investigated.

  1. 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 ...

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

    EPA Science Inventory

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Kroflič, Ana; Grgić, 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

  5. oVOC production from tropospheric alkyne oxidation and contribution to aerosol formation and growth

    NASA Astrophysics Data System (ADS)

    Goodall, Iain

    2013-04-01

    Ethyne (C2H2) is one of the simplest volatile organic compounds (VOC) and is predominantly emitted via anthropogenic processes and reacts with nitrogen oxides (NOx) in the presence of sunlight to form tropospheric ozone (O3). The dominant oxidation product of ethyne is the dicarbonyl species glyoxal (CHOCHO), which is thought to be a significant contributor to secondary organic aerosol (SOA) formation via irreversible oligomerisation reactions upon the surface of hydrated aerosol particulates and within cloud droplets. A series of chamber experiments were performed at the EUPHORE facility (Valencia, Spain) to study the atmospheric oxidation of ethyne, to determine oxidation product yields and to monitor SOA formation and growth by dicarbonyl oligomerisation. A Proton Transfer Reaction-Time of Flight- Mass Spectrometer (PTR-ToF-MS) was deployed by the University of Leicester to monitor precursor decay and the subsequent evolution of any gas-phase oxidised volatile organic compounds (oVOC). This was further complemented by a Broadband Cavity Enhanced Absorption Spectrometer (BBCEAS) for specific dicarbonyl and NO2 measurements. Aqueous extracts of chamber SOA were taken from filters collected during the experiments and subsequently analysed offline. The work explores the yields of low molecular weight products of ethyne oxidation for light and dark reactions, with varying levels of NOx and OH. Novel experiments were performed under atmospherically relevant conditions utilising natural lighting rather than artificial lighting. Reaction yields have been assessed with the aim of contributing to the ethyne and glyoxal mechanisms in the Master Chemical Mechanism (MCM; http://mcm.leeds.ac.uk/MCM), and have been compared with previously reported values determined from experiments performed under artificial lighting conditions.

  6. Investigating the Formation of Ambient Secondary Organic Aerosol in Southeastern USA

    NASA Astrophysics Data System (ADS)

    Weber, R.; Sullivan, A.; Peltier, R.; Hennigan, C.; Yan, B.; Zheng, M.; Kaynak, B.; Russell, J.; Brock, C.; de Gouw, J.; Warneke, C.; Holloway, J.; Atlas, E.; Edgerton, E.

    2006-12-01

    It is well known that during periods of intense photochemistry the formation of secondary organic aerosol (SOA) is a major source for fine particle mass, and a significant contributor to poor air quality. This process is thought to be especially important in the southeastern United States due to high concentrations of both anthropogenic and biogenic precursor organic compounds. SOA formation, however, is poorly understood. Recent studies by a number of investigators in widely different urban regions show that model simulations based on SOA yields from smog chamber experiments under predict the organic aerosol by factors of roughly 5 to 15. These studies also show organic aerosol can be formed rapidly within 5 to 20 hours following emission. We have found similar results based on data collected from a suite of instrumentation deployed on the NOAA WP-3B aircraft during the New England Air Quality Study of August 2004. Throughout the mission plumes transported from New York City were intercepted various distances downwind. For plumes less that roughly 20 hrs old concentrations of water-soluble organic compounds (WSOC) in fine particles rapidly increased relative to carbon monoxide with increasing plume age. WSOC concentrations were 8 +/- 2 times higher than expected based on calculations using current SOA yields, and although WSOC was highly correlated with anthropogenic tracers, no correlation was found to biogenic VOCs. Subsequent measurements with the same suite of instruments over metropolitan Atlanta and a large region of north Georgia resulted in similar findings despite measured biogenic VOC concentrations higher by factors of 10 to 100. WSOC was only correlated with anthropogenic emissions, chemically aged air masses had WSOC concentrations relative to CO similar to that found in the northeast, and WSOC concentrations were roughly 5 +/- 1 times higher than that predicted by the Community Multi-scale Air Quality Model (CMAQ). In contrast, radiocarbon analysis

  7. 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

  8. Photo-oxidation of pinonaldehyde at low NOx: from chemistry to organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Chacon-Madrid, H. J.; Henry, K. M.; Donahue, N. M.

    2013-03-01

    Pinonaldehyde oxidation by OH radicals under low-NOx conditions produces significant secondary organic aerosol (SOA) mass yields. Under concurrent UV illumination, mass yields are lower than high-NOx yields published earlier by our group. However, when OH radicals are produced via dark ozonolysis the SOA mass yields are comparable at high and low NOx. Because pinonaldehyde is a major first-generation gas-phase product of α-pinene oxidation by either ozone or OH radicals, its potential to form SOA serves as a molecular counterpoint to bulk SOA aging experiments involving SOA formed from α-pinene. Both the general tendency for aging reactions to produce more SOA and the sensitivity of the low-NOx products to UV photolysis observed in the bulk clearly occur for this single species as well. Photochemical oxidation of pinonaldehye and analogous first-generation terpene oxidation products are potentially a significant source of additional SOA in biogenically influenced air masses.

  9. Formation of ozone and growth of aerosols in young smoke plumes from biomass burning: 1. Lagrangian parcel studies

    NASA Astrophysics Data System (ADS)

    Alvarado, Matthew James; Prinn, Ronald G.

    2009-05-01

    We have developed a new model of the gas- and aerosol-phase chemistry of biomass burning smoke plumes called Aerosol Simulation Program (ASP). Here we use ASP combined with a Lagrangian parcel model to simulate the chemistry in smoke plumes from three fires: the Otavi savannah fire in Namibia, an Alaska boreal forest fire, and the Timbavati savannah fire. Our model explained the observations of ozone in the Otavi and Alaska plumes fairly well, but our initial model simulation of the Timbavati plume underestimated the concentrations of ozone, OH, and secondary aerosol matter. The Timbavati simulation agrees with observations if we increase OH to equal its observed levels. Heterogeneous reactions of NO2 and SO2 could explain the needed higher concentrations of OH and the rapid formation of ozone, nitrate, and sulfate in the smoke plume if the uptake coefficients on smoke aerosols are large (O(10-3) and O(10-4), respectively). Uncharacterized organic species in the smoke plume were likely responsible for the rapid formation of aerosol organic carbon. The changes in the aerosol size distribution were dominated by plume dilution and condensational growth. The single scattering albedo of the modeled smoke increases from 0.866 to 0.902 over 1 h of aging. The change in aerosol scattering with relative humidity for the modeled fresh smoke matches observations up to 66% RH, but the model greatly overestimates the humidification factor at 80% RH (2.88 versus an observed value of 1.70-1.79). For the aged smoke, the modeled humidification factor is 1.22, slightly below the observed value of 1.40.

  10. 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...

  11. Enhanced UV Absorption in Carbonaceous Aerosols during MILAGRO and Identification of Potential Organic Contributors.

    NASA Astrophysics Data System (ADS)

    Mangu, A.; Kelley, K. L.; Marchany-Rivera, A.; Kilaparty, S.; Gunawan, G.; Gaffney, J. S.; Marley, N. A.

    2007-12-01

    ), and nitrated PAH compounds for comparison. Potential organic aerosol components are identified which contribute to the enhanced absorption observed in the field. The wavelength dependence of the mass specific absorption is obtained from these spectra and total carbon measurements. The wavelength dependence of the aerosol complex refractive index (m = n +ik) in the UV-visible spectral region is determined by application of the Kramers Kronig function. The importance of the aerosol absorption in the infrared spectral region to radiative forcing will be discussed. 1. Marley, N.A., J.S. Gaffney, J.C. Baird, C.A. Blazer, P.J. Drayton, and J.E. Frederick, Aerosol Sci. Technol., 34, 535-549, (2001). 2. N.A. Marley, J.S. Gaffney, and K.A. Orlandini, Chapter 7 in Humic/Fulvic Acids and Organic Colloidal Materials in the Environment, ACS Symposium Series 651, American Chemical Society, Washington, D.C., pp. 96-107, 1996. This work was conducted as part of the Department of Energy's Atmospheric Science Program as part of the Megacity Aerosol Experiment - Mexico City during MILAGRO. This research was supported by the Office of Science (BER), U.S. Department of Energy Grant No. DE-FG02-07ER64329. We also wish to thank Mexican Scientists and students for their assistance from the Instituto Mexicano de Petroleo (IMP) and CENICA.

  12. 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.

  13. Construction, Modeling and Testing of a Low-Flow, Large-Diameter Aerosol Flow System for the Study of the Formation and Reactions of Tropospheric Aerosols

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    A unique, high-volume, low-flow, stainless steel aerosol flow system for the study of the formation and reactions of aerosols relevant to the troposphere has been constructed, modeled and experimentally tested. The total flow tube length is 7.3 m which includes a 1.2 m section used for mixing. The flow tube is equipped with ultraviolet lamps for photolysis. The diameter of 0.45 m results in a smaller surface to volume ratio than is found in many other flow systems and reduces the contribution of wall reactions. The latter is also reduced by frequent cleaning of the flow tube walls which is feasible due to the ease of disassembly of the flow tube. Flow systems present a major advantage over chamber studies in that continuous sampling under stable conditions over long periods of time is possible, increasing the amount of sample available for analysis and permitting a wide variety of analytical techniques to be applied simultaneously. In this system, the large volume (1000 L) and low flow speed (2 cm/minute) result in a residence time of nearly an hour; and equally spaced sampling ports allow for time-resolved measurements of aerosol and gas-phase products. The central features of this system have been modeled using computational fluid dynamics software and experimentally probed using inert gases and aerosols. Instrumentation attached directly to this flow system includes a NOx analyzer, an ozone analyzer, relative humidity and temperature probes, a scanning mobility particle sizer (SMPS) spectrometer, an aerodynamic particle sizer (APS) spectrometer, GC-MS, integrating nephelometer, and FTIR. Particles are collected using impactors and filters, and analyzed by a variety of techniques including FTIR, electrospray ionization mass spectrometry (ESI-MS), atmospheric pressure chemical ionization mass spectrometry (APCI-MS), GC-MS, HPLC-UV and HPLC-MS. In addition, for selected studies, an aerosol mass spectrometer (AMS), a single particle mass spectrometer (SPLAT II) and

  14. In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

    NASA Astrophysics Data System (ADS)

    Palm, B. B.; Campuzano-Jost, P.; Ortega, A. M.; Day, D. A.; Kaser, L.; Jud, W.; Karl, T.; Hansel, A.; Hunter, J. F.; Cross, E. S.; Kroll, J. H.; Peng, Z.; Brune, W. H.; Jimenez, J. L.

    2015-11-01

    Ambient air was oxidized by OH radicals in an oxidation flow reactor (OFR) located in a montane pine forest during the BEACHON-RoMBAS campaign to study biogenic secondary organic aerosol (SOA) formation and aging. High OH concentrations and short residence times allowed for semi-continuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative time scales of condensation of low volatility organic compounds (LVOCs) onto particles, condensational loss to the walls, and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 4 μg m-3 when LVOC fate corrected) compared to daytime (average 1 μg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene + p-cymene concentrations, including a substantial increase just after sunrise at 07:00 LT. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 6 times more SOA was formed in the reactor from OH oxidation than

  15. Emissions of biogenic volatile organic compounds and subsequent formation of secondary organic aerosols in a Larix kaempferi forest

    NASA Astrophysics Data System (ADS)

    Mochizuki, T.; Miyazaki, Y.; Ono, K.; Wada, R.; Takahashi, Y.; Saigusa, N.; Kawamura, K.; Tani, A.

    2015-04-01

    We conducted simultaneous measurements of concentrations and above-canopy fluxes of isoprene and α-pinene, along with their oxidation products in aerosols in a Larix kaempferi (Japanese larch) forest in summer 2012. Vertical profiles of isoprene showed the maximum concentration near the forest floor with a peak around noon, whereas oxidation products of isoprene, i.e., methacrolein (MACR) and methyl vinyl ketone (MVK), showed higher concentrations near the canopy level of the forest. The vertical profile suggests large emissions of isoprene near the forest floor, likely due to Dryopteris crassirhizoma (a fern species), and the subsequent reaction within the canopy. The concentrations of α-pinene also showed highest values near the forest floor with maximums in the early morning and late afternoon. The vertical profiles of α-pinene suggest its large emissions from soil and litter in addition to emissions from L. kaempferi leaves at the forest site. Isoprene and its oxidation products in aerosols exhibited similar diurnal variations within the forest canopy, providing evidence for secondary organic aerosol (SOA) formation via oxidation of isoprene most likely emitted from the forest floor. Although high abundance of α-pinene was observed in the morning, its oxidation products in aerosols showed peaks in daytime, due to a time lag between the emission and atmospheric reactions of α-pinene to form SOA. Positive matrix factorization (PMF) analysis indicated that anthropogenic influence is the most important factor contributing to the elevated concentrations of molecular oxidation products of isoprene- (> 64%) and α-pinene-derived SOA (> 57%). The combination of the measured fluxes and vertical profiles of biogenic volatile organic compounds (BVOCs) suggests that the inflow of anthropogenic precursors/aerosols likely enhanced the formation of both isoprene- and α-pinene-SOA within the forest canopy even when the BVOC flux was relatively low. This study highlights

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

    DOE PAGES

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

    2016-02-08

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

  17. Seasonality of ultrafine and sub-micron aerosols and the inferences on particle formation processes

    NASA Astrophysics Data System (ADS)

    Cheung, H. C.; Chou, C. C.-K.; Chen, M.-J.; Huang, W.-R.; Huang, S.-H.; Tsai, C.-Y.; Lee, C. S.-L.

    2015-08-01

    The aim of this study is to investigate the seasonal variations in the physicochemical properties of atmospheric ultrafine particles (UFPs, d ≤ 100nm) and submicron particles (PM1, d ≤ 1 μm) in an East-Asian urban area, which are hypothesized to be affected by the interchange of summer and winter monsoons. An observation experiment was conducted at the TARO, an urban aerosol station in Taipei, Taiwan, from October 2012 to August 2013. The measurements included the mass concentration and chemical composition of UFPs and PM1, as well as the particle number concentration (PNC) and size distribution (PSD) with size range of 4-736 nm. The results indicate that the mass concentration of PM1 was elevated during cold seasons with peak level of 18.5 μg m-3 in spring, whereas the highest UFPs concentration was measured in summertime with a seasonal mean of 1.62 μg m-3. Moreover, chemical analysis revealed that the UFPs and PM1 were characterized by distinct composition; UFPs were composed mostly of organics, whereas ammonium and sulfate were the major constituents in PM1. The seasonal median of total PNCs ranged from 13.9 × 103 cm-3 in autumn to 19.4 × 103 cm-3 in spring. The PSD information retrieved from the corresponding PNC measurements indicates that the nucleation mode PNC (N4-25) peaked at 11.6 × 103 cm-3 in winter, whereas the Aitken mode (N25-100) and accumulation mode (N100-736) exhibited summer maxima at 6.0 × 103 and 3.1 × 103 cm-3, respectively. The shift in PSD during summertime is attributed to the enhancement in the photochemical production of condensable organic matter that, in turn, contributes to the growth of aerosol particles in the atmosphere. In addition, remarkable photochemical production of particles was observed in spring and summer seasons, which was characterized with averaged particle growth and formation rates of 4.3 ± 0.8 nm h-1 and 1.6 ± 0.8 cm-3 s-1, respectively. The prevalence of new particle formation (NPF) in summer is

  18. Formation of v-shaped potentials

    NASA Astrophysics Data System (ADS)

    Thiemann, H.; Singh, N.; Schunk, R. W.

    1983-06-01

    The V-shaped potential structures formed by the injection of a non-neutral electron current into a cold background plasma were simulated numerically. The injection disturbs the initial quasi-neutral plasma, leading to the excitation of strong turbulences which heat the plasma. This leads to expulsion of the plasma from the simulation region. Due to ambipolar electric fields the current injection is interrupted and the initial background plasma is extracted from the system. A particle composition with the characteristics of the two plasma reservoirs now represents the plasma in the simulation region. The interaction of the electron beam with this plasma excites turbulences of smaller amplitudes. A nearly constant time averaged potential drop with nonstationary distribution develops across the system. Single and multiple double layers may form for the duration of one ion plasma period.

  19. Kinetics of oxygenated product formation during the heterogeneous oxidation of organic aerosol

    NASA Astrophysics Data System (ADS)

    Kolesar, K. R.; Cappa, C. D.; Wilson, K. R.

    2014-12-01

    Oxidation of organic aerosols can lead to changes in their atmospheric lifetime, optical properties and health effects. Whereas much is known about the rates of reaction and subsequent branching ratios of gas-phase organic species, much less is known about their condensed phase counterparts. The determination of the kinetics and abundances of the oxidation products associated with condensed phase reactions is needed to understand the oxidation reaction pathways and their branching ratios. The Vacuum Ultraviolet Aerosol Mass Spectrometer (VUV-AMS) at the Chemical Dynamics Beamline at Lawrence Berkeley National Laboratory has been useful in determining the reaction rate constants for a number of condensed phase organic compounds with oxidants such as OH and O3. The relatively soft ionization in the VUV-AMS leads to substantially less fragmentation than other AMS instruments that use electron impact ionization, and therefore preserves a greater amount of molecular information about parent molecules. Previously, ketones formed from the heterogenous oxidation of model organic compounds have been identified and their formation kinetics quantified. However, other possible products, such as alcohols and organic peroxides, have not previously been identified in the VUV-AMS mass spectra or characterized as these are subject to greater fragmentation. Here, we present a method in which the fragmentation pattern is specified for each alcohol isomer formed from the oxidation of two model organic compounds, bis-2-ethylhexl sebacate and squalane. From this we are able to define unique m/z fragments for each isomer from which we derive information about alcohol and abundances. This study demonstrates additional methods for the analysis of mass spectra obtained with the VUV-AMS as well as provides insights into condensed phase oxidation kinetics.

  20. Formation of Anthropogenic and Biogenic Secondary Organic Aerosol at Bakersfield, CA

    NASA Astrophysics Data System (ADS)

    Liu, S.; Russell, L. M.; Day, D. A.; Zhao, Y.; Goldstein, A. H.; Weber, R.

    2011-12-01

    The source and chemistry of secondary organic aerosol (SOA) are major challenges remaining unresolved in the atmospheric science. To address this uncertainty, measurements were conducted at the Bakersfield (California, US) supersite during the CALNEX campaign in May and June of 2010. The submicron organic mass (OM), a major component of PM1 (65%), accounted for 70% of the OM in PM2.5. A majority of this submicron OM (80-90%) was composed of SOA, which is a mixture of components formed from anthropogenic and biogenic origins. These SOA components were distinguished and consistently identified from the factor analysis applied on the independent Fourier Transform Infrared Spectroscopy and High Resolution Time-of-Flight Aerosol Mass Spectrometry measurements. The SOA formed from motor vehicular emissions dominated the OM (65%). This SOA was likely composed of oxidation products from alkane (alkane SOA; 41% of the OM) and PAH (PAH SOA; 24% of the OM) compound classes. The alkane SOA tightly tracked the ozone mixing ratios, suggesting that this component was likely formed via the ozone-driven oxidation processes. The PAH SOA was likely formed by OH radical oxidation, consistent with the good correlation of the PAH SOA to sulfate, which is a surrogate for gas-phase OH oxidation under dry conditions. The petroleum operation SOA, a nearly missing component in the source inventory of PM2.5 in San Joaquin Valley, accounted for 14% of the OM. While the anthropogenic SOA components were formed during the daytime, the biogenic SOA (10-13% of the OM) was likely the product of NO3 radical oxidation of biogenic volatile organic compounds, which transported from the nearby mountain regions to the sampling site at night. The mass concentration of the SOA components could help improve the source inventory estimation of San Joaquin Valley, and the formation pathways of distinct SOA components were suggested in this work.

  1. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    NASA Technical Reports Server (NTRS)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  4. Secondary organic aerosol formation from the β-pinene+NO3 system: effect of humidity and peroxy radical fate

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

    The formation of secondary organic aerosol (SOA) from the oxidation of β-pinene via nitrate radicals is investigated in the Georgia Tech Environmental Chamber (GTEC) facility. Aerosol yields are determined for experiments performed under both dry (relative humidity (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, which likely correspond to molecular formulas of C10H17NO4, C10H15NO5, C10H17NO5, and C10H15NO6, respectively) are detected by chemical ionization mass spectrometry (CIMS) and their formation mechanisms are proposed. The NO+ (at m/z 30) and NO2+ (at m/z 46) ions contribute about 11 % to the combined organics and nitrate signals in the typical aerosol mass spectrum, with the NO+ : NO2+ ratio ranging from 4.8 to 10.2 in all experiments conducted. The SOA yields in the "RO2 + NO3 dominant" and "RO2 + HO2 dominant" experiments are comparable. For a wide range of organic mass loadings (5.1-216.1 μg m-3), the aerosol mass yield is calculated to be 27.0-104.1 %. Although humidity does not appear to affect SOA yields, there is evidence of particle-phase hydrolysis of organic nitrates, which are estimated to compose 45-74 % of the organic aerosol. The extent of organic nitrate hydrolysis is significantly lower than that observed in previous studies on photooxidation of volatile organic compounds in the presence of NOx. It is estimated that about 90 and 10 % of the organic nitrates formed from the β-pinene+NO3 reaction are primary organic nitrates and tertiary organic nitrates, respectively. While the primary organic nitrates do not appear to hydrolyze, the tertiary organic nitrates undergo hydrolysis with a lifetime of 3-4.5 h. Results from this laboratory chamber study provide the fundamental data to evaluate the

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

    PubMed

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

    2014-10-21

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

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

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, D.; Rusanen, A.; Boy, M.; Swietlicki, E.; Svenningsson, B.; Zelenyuk, A.; Pagels, J.

    2014-01-01

    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 α-pinene secondary organic aerosol (SOA) particles, and (3) the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed α-pinene SOA mass increase in the presence of NH3(g). Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. These salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating α-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar like amorphous phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if low-volatility and viscous oligomerized SOA material accumulates in the particle surface layer upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass transfer limited uptake of condensable organic compounds onto wall deposited particles or directly onto the Teflon chamber walls of smog chambers can have profound influence on the

  7. Rapid formation of molecular bromine from deliquesced NaBr aerosol in the presence of ozone and UV light

    NASA Astrophysics Data System (ADS)

    Nissenson, Paul; Wingen, Lisa M.; Hunt, Sherri W.; Finlayson-Pitts, Barbara J.; Dabdub, Donald

    2014-06-01

    The formation of gas-phase bromine from aqueous sodium bromide aerosols is investigated through a combination of chamber experiments and chemical kinetics modeling. Experiments show that Br2(g) is produced rapidly from deliquesced NaBr aerosols in the presence of OH radicals produced by ozone irradiated by UV light. The mechanisms responsible for the “bromine explosion” are examined using a comprehensive chemical kinetics Model of Aqueous, Gaseous, and Interfacial Chemistry (MAGIC). A sensitivity analysis on the model confirms that a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transfer is responsible for most of the observed bromine. However, the rate-limiting steps in the bromine explosion pathway vary, depending on the availability of ozone and bromide in the system. Interface reactions, an important source of bromine production under dark conditions, account for only a small fraction of total bromine under irradiation. Simulations performed with gaseous ozone and aerosol bromide concentrations typical of the marine boundary layer also show Br2(g) production, with BrO(g) and HOBr(g) as the dominant Br-containing products through this mechanism. Aerosol bromide is depleted after several hours of daylight, with photolysis of BrO(g) and HOBr(g) becoming major sources of Br atoms that continue generating Br2(g) after aerosol bromide is depleted.

  8. Aerosol and cloud condensation nuclei formation at Mt. Kleiner Feldberg, Germany

    NASA Astrophysics Data System (ADS)

    Kohl, R.; Bonn, B.; Bourtsoukidis, S.; Wex, H.; Stratmann, F.; Bingemer, H.; Haunold, W.; Jacobi, S.

    2012-04-01

    New particle formation in number and mass is a quite ubiquous phenomenon in the atmospheric boundary layer. However, different locations provide different mechanisms for the initial particle production steps. Investigating the formation aims usually in explaining two aspects, the initial formation process and the contribution to cloud condensation nuclei production. In this study we focus on the latter. Once these particles are formed they grow further on until they reach cloud effective sizes. This is the size, where those particles can affect local climate via the indirect aerosol effect. This study deals with the processes mentioned at Mt. Kleiner Feldberg (810 m a.s.l.) about 50 km northwest of Frankfurt activation diameters. We have been determined using a CCN-counter (DMT, Boulder, U.S.) [Roberts and Nenes, 2005] and a SMPS (TSI 3936) with a long DMA (TSI 3081) and a UCPC (TSI 3025A). Particles were assumed to be equal in chemical composition since the vast majority of particles were smaller than 300 nm in diameter, i.e. secondary of nature. Therefore, measured CCN concentrations were intercompared with section wise integrated particle number concentrations starting at the largest size towards the smaller ones. The best match of integrated and CCN concentration was assumed to be the activation diameter (Dp,active). With this set-up the activation diameters were determined for five supersaturations (0.1, 0.2 0.3, 0.4 and 0.6%) during a two weeks period. This resulted in the expected detcrease in activation size with increasing supersaturation from about 130±10 nm at 0.1% to 70±5 nm at 0.6% supersaturation. The empirically fitted kappa-value [Petters and Kreidenweis, 2007] was obtained as 0.16±0.03 indicating aerosols of lower water-solubility. Second, measurements of ice nuclei [Klein et al., 2010] were conducted once per day during the same time period, which indicate that IN concentrations, were about one per mill of the CCN. Interestingly the cross

  9. On the composition of ammonia-sulfuric-acid ion clusters during aerosol particle formation

    NASA Astrophysics Data System (ADS)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2015-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from < 2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm-3 (0.1 to 56 pptv), and a temperature range from -25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4] < 0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm/Δ n), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Δ m/Δn saturated between 1 and 1.4 for [NH3] / [H2SO4] > 10. Positively

  10. On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

    NASA Astrophysics Data System (ADS)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2014-05-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from <2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm-3, and a temperature range from -25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4]<0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm / Δn), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Δm / Δn saturated between 1 and 1.4 for [NH3] / [H2SO4]>10. Positively charged clusters grew on

  11. Hydrochloric acid aerosol formation by the interaction of hydrogen chloride with humid air

    NASA Technical Reports Server (NTRS)

    Rhein, R. A.

    1973-01-01

    The conditions in which hydrochloric acid aerosol is predicted by the interaction of hydrogen chloride gas with the water vapor in humid air are analyzed. The liquid gas phase equilibrium for the HCL-H2O system is expressed in terms of relative humidity and hydrogen chloride concentration as parts per million, units commonly used in pollution studies. Presented are the concentration (wt %) of HC1 in the aerosol and the concentration of aerosol (ppm) predicted.

  12. 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, α-pinene, and α-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.

  13. Potential of aerosolized rifampicin lipospheres for modulation of pulmonary pharmacokinetics and bio-distribution.

    PubMed

    Singh, Charan; Koduri, L V Seshu Kumar; Dhawale, Vaibhav; Bhatt, Tara Datt; Kumar, Rajdeo; Grover, Vikas; Tikoo, Kulbhushan; Suresh, Sarasija

    2015-11-30

    The aim of the present study was to establish the potential of rifampicin loaded phospholipid lipospheres carrier for pulmonary application. Lipospheres were prepared with rifampicin and phospholipid in the ratio of 1:1 using spray drying method. Further, lipospheres were evaluated for flow properties and surface area measurement. The formulated lipospheres were evaluated in vitro for aerodynamic characterization and in vivo for lung pharmacokinetics and biodistribution studies in Sprague Dawley rats. Powder flow properties finding suggested the free flowing nature of the lipospheres. In-vitro aerosol performance study indicated more than 80±5% of the emitted dose (ED) and 77.61±3% fine particles fraction (FPF). Mass median aerodynamic diameter (MMAD) and geometric standard deviation (GSD) were found to be 2.72±0.13 μm and 3.28±0.12, respectively. In-vitro aerosol performance study revealed the higher deposition at 3, 4 and 5 stages which simulates the trachea-primary bronchus, secondary and terminal bronchus of the human lung, respectively. The drug concentration from nebulized lipospheres in the non-targeted tissues was lesser than from rifampicin-aqueous solution. The pulmonary pharmacokinetic study demonstrated improved bioavailability, longer residence of drug in the lung and targeting factor of 8.03 for lipospheres as compared to rifampicin-aqueous solution. Thus, the results of the study demonstrated the potential of rifampicin lipospheres formulation would be of use as an alternative to existing oral therapy.

  14. 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...

  15. Formation of high-molecular-weight compounds via the heterogeneous reactions of gaseous C8-C10 n-aldehydes in the presence of atmospheric aerosol components

    NASA Astrophysics Data System (ADS)

    Han, Yuemei; Kawamura, Kimitaka; Chen, Qingcai; Mochida, Michihiro

    2016-02-01

    A laboratory study on the heterogeneous reactions of straight-chain aldehydes was performed by exposing n-octanal, nonanal, and decanal vapors to ambient aerosol particles. The aerosol and blank filters were extracted using methanol. The extracts were nebulized and the resulting compositions were examined using a high-resolution time-of-flight aerosol mass spectrometer. The mass spectral analysis showed that the exposures of the aldehydes to aerosol samples increased the peak intensities in the high mass range. The peaks in the mass spectra of the aerosol samples after exposure to different aldehydes were characterized by a homologous series of peak shifts due to the addition of multiple CH2 units. This result is explained by the formation of high-molecular-weight (HMW) compounds that contain single or multiple aldehyde moieties. The HMW fragment peaks for the blank filters exposed to n-aldehydes were relatively weak, indicating an important contribution from the ambient aerosol components to the formation of the HMW compounds. Among the factors affecting the overall interaction of aldehydes with atmospheric aerosol components, gas phase diffusion possibly limited the reactions under the studied conditions; therefore, their occurrence to a similar degree in the atmosphere is not ruled out, at least for the reactions involving n-nonanal and decanal. The major formation pathways for the observed HMW products may be the self-reactions of n-aldehydes mediated by atmospheric aerosol components and the reactions of n-aldehydes with organic aerosol components. The observed formation of HMW compounds encourages further investigations into their effects on the aerosol properties as well as the organic aerosol mass in the atmosphere.

  16. Combined trajectory clustering and aerosol fields analysis to evaluate the potential emission flux to aerosol pollutants in an urban and semi-urban atmospheres in eastern India

    NASA Astrophysics Data System (ADS)

    Kumar, B. D.; Verma, S.

    2015-12-01

    A hybrid source-receptor analysis was carried out to evaluate the potential emission flux to winter monsoon (WinMon) aerosols over eastern India urban (Kolkata, Kol) and semi-urban atmospheres (Kharagpur, Kgp). This was done through application of fuzzy c-mean clustering to back-trajectory data combined with emission flux and residence time weighted aerosols analysis. WinMon mean aerosol optical depth (AOD) and angstrom exponent (AE) at Kol were respectively slightly higher than and nearly equal to that at Kgp. Out of six source region clusters over Indian subcontinent and two over Indian oceanic region, the cluster mean AOD was the highest when associated with the mean path of air mass originating from the Bay of Bengal (BoB) and the Arabian sea (AS) clusters at Kol and that from the Indo-Gangetic plain (IGP)cluster at Kgp. Spatial distribution of weighted AOD fields showed the highest potential source of aerosols over the IGP, majorly over upper IGP (IGP-U), lower IGP (IGP-L) and eastern region (ER) clusters. The emission flux contribution potential (EFCP) of fossil fuel (FF) emissions at surface (SL) of Kol/Kgp , elevated layer (EL) of Kol, and of biomass burning (BB) emissions at SL of Kol were majorly from IGP-U, IGP-L and IGP-U/L clusters respectively. The EFCP of FF/BB emissions at Kgp-EL/SL, and that of BB at EL of Kol/Kgp were mainly from ER and Africa (AFR) clusters respectively. Though the AFR cluster was constituted of significantly high emission flux source potential of dust emissions, the EFCP of dust from NWI was comparable to that from AFR at Kol SL/EL.

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

    Secondary organic aerosol (SOA) formation from single hydrocarbon precursors is commonly studied in smog chamber experiments to obtain SOA yield and organic composition data. However, very few complex air mixture experiments have been conducted to simulate possible conditions in ambient atmospheres. A six-phase experiment involving various combinations of alpha-pinene, toluene, isoprene, and SO2 were irradiated in the EPA's dynamic smog chamber at the National Exposure Research Laboratory in Raleigh, NC. Glass fiber filters and impactor plates were collected for each phase of the experiment to identify and quantify the nature of the SOA composition. The following suite of analytical techniques analyzed the resultant polar organic compounds and the high molecular weight species: liquid chromatography-electrospray ionization (ESI)-mass spectrometry, gas chromatography-mass spectrometry, ESI-ion trap mass spectrometry, matrix assisted laser desorption (MALDI)-time of flight mass spectrometry, and high-resolution mass spectrometry. When SO2 is present in the chamber, increases in the gravimetric aerosol mass concentration and in the abundance of polar organic compounds are observed, likely suggesting an acid catalysis effect stemming from the conversion of SO2 to H2SO4 that condenses onto aerosol formed. The addition of isoprene to a alpha-pinene/toluene mixture is found to lower the amount of aerosol produced and is also found to lower the abundance of organic compounds identified by the various analytical techniques. Lastly, many of the polar organic compounds identified and quantified here are also seen in the Southeastern Aerosol Research and Characterization (SEARCH) network during the summer of 2004. In particular, a sulfur and nitrogen containing organic species (MW = 295 gmol) is found to be the most abundant polar organic species identified in this field study (~28 % on average of the total identified organic mass). This species is also detected in the chamber

  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

    2015-05-14

    The heterogeneous chemistry of glyoxal on sulfuric acid surfaces has been investigated at various acid concentrations and temperatures, utilizing a low-pressure fast flow laminar reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS). The uptake coefficient (γ) 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.

  19. Enhancement effect of relative humidity on the formation and regional respiratory deposition of secondary organic aerosol.

    PubMed

    Yu, Kuo-Pin; Lin, Chi-Chi; Yang, Shang-Chun; Zhao, Ping

    2011-07-15

    In this study, we investigated the effect of relative humidity (RH) on the formation of secondary organic aerosol (SOA) generated from the ozonolysis of d-limonene in an environmental chamber. The mass yield and the number concentration of SOA increased seven and eight times, respectively, when the RH increased from 18% to 82%. The measured total loss rates (apparent loss rates) of the number and mass concentration of SOA in the chamber ranged from 1.70 to 1.77 h(-1) and from 2.51 to 2.61 h(-1), respectively, at a controlled ventilation rate of 0.72±0.04 h(-1). The wall-deposition-loss-rate coefficient observed (1.00±0.02 h(-1)) was approximate to the estimated value based on Zhao and Wu's model which includes the factors of turbulence, Brownian diffusion, turbophoresis and surface roughness. According to the ICRP (International Commission on Radiological Protection) model, the inhaled SOA particles are deposited primarily in the alveoli of the lung. The integrated alveolar deposited dose of the mass (surface area) of SOA over 3h accounted for 74.0-74.8% (74.3-74.9%) of the total deposited dose at the investigated RH. Raising the RH resulted in the growth of SOA particle sizes and increment of the deposition dose but did not cause significant changes in the ratio of regional to the total respiratory deposition of SOA. PMID:21570180

  20. 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...

  1. The role of potential barrier formation in spacecraft charging

    NASA Technical Reports Server (NTRS)

    Purvis, C. K.

    1983-01-01

    The role of potential barrier formation in spacecraft charging at geosynchronous orbit is discussed. The evidence for, and understanding of, spacecraft charging and its hazards to spacecraft operation in the early 1970's are summarized. Theoretical and experimental advances which have changed the basic understanding of the role of barrier formation in charging phenomenology are described. Potential barriers are found to play a fundamental role in the dynamics of spacecraft charging. The consequences for structural and differential charging and for discharging are described.

  2. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-07-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  3. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-01-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  4. Impact of NOx and OH on secondary organic aerosol formation from β-pinene photooxidation

    NASA Astrophysics Data System (ADS)

    Sarrafzadeh, Mehrnaz; Wildt, Jürgen; Pullinen, Iida; Springer, Monika; Kleist, Einhard; Tillmann, Ralf; Schmitt, Sebastian H.; Wu, Cheng; Mentel, Thomas F.; Zhao, Defeng; Hastie, Donald R.; Kiendler-Scharr, Astrid

    2016-09-01

    In this study, the NOx dependence of secondary organic aerosol (SOA) formation from photooxidation of the biogenic volatile organic compound (BVOC) β-pinene was comprehensively investigated in the Jülich Plant Atmosphere Chamber. Consistent with the results of previous NOx studies we found increases of SOA yields with increasing [NOx] at low-NOx conditions ([NOx]0 < 30 ppb, [BVOC]0 / [NOx]0 > 10 ppbC ppb-1). Furthermore, increasing [NOx] at high-NOx conditions ([NOx]0 > 30 ppb, [BVOC]0 / [NOx]0 ˜ 10 to ˜ 2.6 ppbC ppb-1) suppressed the SOA yield. The increase of SOA yield at low-NOx conditions was attributed to an increase of OH concentration, most probably by OH recycling in NO + HO2 → NO2 + OH reaction. Separate measurements without NOx addition but with different OH primary production rates confirmed the OH dependence of SOA yields. After removing the effect of OH concentration on SOA mass growth by keeping the OH concentration constant, SOA yields only decreased with increasing [NOx]. Measuring the NOx dependence of SOA yields at lower [NO] / [NO2] ratio showed less pronounced increase in both OH concentration and SOA yield. This result was consistent with our assumption of OH recycling by NO and to SOA yields being dependent on OH concentrations. Our results furthermore indicated that NOx dependencies vary for different NOx compositions. A substantial fraction of the NOx-induced decrease of SOA yields at high-NOx conditions was caused by NOx-induced suppression of new particle formation (NPF), which subsequently limits the particle surface where low volatiles condense. This was shown by probing the NOx dependence of SOA formation in the presence of seed particles. After eliminating the effect of NOx-induced suppression of NPF and NOx-induced changes of OH concentrations, the remaining effect of NOx on the SOA yield from β-pinene photooxidation was moderate. Compared to β-pinene, the SOA formation from α-pinene photooxidation was only suppressed by

  5. Potential of lidar backscatter data to estimate solar aerosol radiative forcing

    NASA Astrophysics Data System (ADS)

    Wendisch, Manfred; Müller, Detlef; Mattis, Ina; Ansmann, Albert

    2006-02-01

    The potential to estimate solar aerosol radiative forcing (SARF) in cloudless conditions from backscatter data measured by widespread standard lidar has been investigated. For this purpose 132 days of sophisticated ground-based Raman lidar observations (profiles of particle extinction and backscatter coefficients at 532 nm wavelength) collected during two campaigns [the European Aerosol Research Lidar Network (EARLINET) and the Indian Ocean Experiment (INDOEX)] were analyzed. Particle extinction profiles were used as input for radiative transfer simulations with which to calculate the SARF, which then was plotted as a function of the column (i.e., height-integrated) particle backscatter coefficient (betac). A close correlation between the SARF and betac was found. SARF-betac parameterizations in the form of polynomial fits were derived that exhibit an estimated uncertainty of +/-(10-30)%. These parameterizations can be utilized to analyze data of upcoming lidar satellite missions and for other purposes. The EARLINET-based parameterizations can be applied to lidar measurements at mostly continental, highly industrialized sites with limited maritime influence (Europe, North America), whereas the INDOEX parameterizations rather can be employed in polluted maritime locations, e.g., coastal regions of south and east Asia.

  6. Potential of lidar backscatter data to estimate solar aerosol radiative forcing.

    PubMed

    Wendisch, Manfred; Müller, Detlef; Mattis, Ina; Ansmann, Albert

    2006-02-01

    The potential to estimate solar aerosol radiative forcing (SARF) in cloudless conditions from backscatter data measured by widespread standard lidar has been investigated. For this purpose 132 days of sophisticated ground-based Raman lidar observations (profiles of particle extinction and backscatter coefficients at 532 nm wavelength) collected during two campaigns [the European Aerosol Research Lidar Network (EARLINET) and the Indian Ocean Experiment (INDOEX)] were analyzed. Particle extinction profiles were used as input for radiative transfer simulations with which to calculate the SARF, which then was plotted as a function of the column (i.e., height-integrated) particle backscatter coefficient (beta(c)). A close correlation between the SARF and beta(c) was found. SARF-beta(c) parameterizations in the form of polynomial fits were derived that exhibit an estimated uncertainty of +/-(10-30)%. These parameterizations can be utilized to analyze data of upcoming lidar satellite missions and for other purposes. The EARLINET-based parameterizations can be applied to lidar measurements at mostly continental, highly industrialized sites with limited maritime influence (Europe, North America), whereas the INDOEX parameterizations rather can be employed in polluted maritime locations, e.g., coastal regions of south and east Asia.

  7. Glyoxal processing outside clouds: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Volkamer, R.

    2010-05-01

    This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions in aqueous aerosol particles that form secondary organic aerosol (SOA). Recent laboratory results on glyoxal reactions are reviewed and a consistent set of reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds to form (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles compared to cloud droplets and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry. The application of this new module in a chemical box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the atmospheric relevance of SOA formation from glyoxal. During day time a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ~5 μg m-3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5

  8. Size effects in aerosol particle interactions: the van der Waals potential and collision rates

    SciTech Connect

    Marlow, W H

    1980-01-01

    Three effects which are explicitly dependent on aerosol particle size are identified and discussed. They are focussed about the particle collision rate and how it relates to the properties of the gas, the particle, and the particle's interaction potential energy which play roles in particle-particle collision rates. By incorporating the conduction electronic free path effect for conductors into the frequency-dependent dielectric constants of silver and graphite, particle size effects in the Lifshitz-van der Waals potentials for identical pairs of 1 nm and 100 nm particles are evaluated. Water and tetradecane particle interaction potentials for the same size particles are also calculated to illustrate size effects due to the retardation of the interaction. These potentials are then used to calculate the enhancement of the particle collision rates above their values in the absence of any potential at various gas pressures. The roles of the interaction potential in collision among identical pairs of particles of differing compositions is also briefly discussed.

  9. Reactions Between Water Soluble Organic Acids and Nitrates in Atmospheric Aerosols: Recycling of Nitric Acid and Formation of Organic Salts

    SciTech Connect

    Wang, Bingbing; Laskin, Alexander

    2014-03-25

    Atmospheric particles often include a complex mixture of nitrate and secondary organic materials accumulated within the same individual particles. Nitrate as an important inorganic component can be chemically formed in the atmosphere. For instance, formation of sodium nitrate (NaNO3) and calcium nitrate Ca(NO3)2 when nitrogen oxide and nitric acid (HNO3) species react with sea salt and calcite, respectively. Organic acids contribute a significant fraction of photochemically formed secondary organics that can condense on the preexisting nitrate-containing particles. Here, we present a systematic microanalysis study on chemical composition of laboratory generated particles composed of water soluble organic acids and nitrates (i.e. NaNO3 and Ca(NO3)2) investigated using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and Fourier transform infrared micro-spectroscopy (micro-FTIR). The results show that water-soluble organic acids can react with nitrates releasing gaseous HNO3 during dehydration process. These reactions are attributed to acid displacement of nitrate with weak organic acids driven by the evaporation of HNO3 into gas phase due to its relatively high volatility. The reactions result in significant nitrate depletion and formation of organic salts in mixed organic acids/nitrate particles that in turn may affect their physical and chemical properties relevant to atmospheric environment and climate. Airborne nitrate concentrations are estimated by thermodynamic calculations corresponding to various nitrate depletions in selected organic acids of atmospheric relevance. The results indicate a potential mechanism of HNO3 recycling, which may further affect concentrations of gas- and aerosol-phase species in the atmosphere and the heterogeneous reaction chemistry between them.

  10. Evaluating the potential impact of marine organic aerosols on climate assessments

    NASA Astrophysics Data System (ADS)

    Meskhidze, N.; Gantt, B.; Xu, J.

    2011-12-01

    Natural aerosols influence clouds and the hydrological cycle by their ability to act as cloud condensation nuclei (CCN). Because the anthropogenic contribution to climate forcing represents the difference between the total forcing and that from natural aerosols, understanding background aerosols is necessary to evaluate the influences of anthropogenic aerosols on cloud reflectivity and persistence (so-called indirect radiative forcing) and on precipitation. The effects of marine organic aerosols on microphysical properties of shallow clouds are explored using the NCAR Community Atmosphere Model (CAM5.0), coupled with the PNNL Modal Aerosol Model. Organic enrichment of sea spray is estimated using newly developed wind speed dependent size-resolved source function, while production of secondary organic aerosol of marine origin is inferred from the ocean emissions of biogenic trace gases. Model-predicted abundance of CCN in remote marine atmosphere is compared to satellite and in-situ data. Simulations show that over biologically productive ocean waters organic aerosols of marine origin can contribute up to 20% increase in CCN (at a supersaturation of 0.2%) number concentrations. Corresponding changes associated with cloud properties (liquid water path and droplet number) can reduce global annual mean indirect radiative forcing of anthropogenic aerosol by 0.1 Wm-2 or 8%. This study suggests that neglecting the effects of marine organic aerosol in climate models could result in overprediction of aerosol indirect effect.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  12. Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of alpha-pinene degradation and secondary organic aerosol formation.

    PubMed

    Librando, Vito; Tringali, Giuseppe

    2005-05-01

    This paper studies the reaction products of alpha-pinene, beta-pinene, sabinene, 3-carene and limonene with OH radicals and of alpha-pinene with ozone using FT-IR spectroscopy for measuring gas phase products and HPLC-MS-MS to measure products in the aerosol phase. These techniques were used to investigate the secondary organic aerosol (SOA) formation from the terpenes. The gas phase reaction products were all quantified using reference compounds. At low terpene concentrations (0.9-2.1 ppm), the molar yields of gas phase reaction products were: HCHO 16-92%, HCOOH 10-54% (OH source: H2O2, 6-25 ppm); HCHO 127-148%, HCOOH 4-6% (OH source: CH3ONO, 5-8 ppm). At high terpene concentrations (4.1-13.2 ppm) the results were: HCHO 9-27%, HCOOH 15-23%, CH3(CO)CH3 0-14%, CH3COOH 0-5%, nopinone 24% (only from beta-pinene oxidation), limona ketone 61% (only from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source H2O2, 23-30 ppm); HCHO 76-183%, HCOOH 12-15%, CH3(CO)CH3 0-12%, nopinone 17% (from beta-pinene oxidation), limona ketone 48% (from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source CH3ONO, 14-16 ppm). Pinic acid, pinonic acid, limonic acid, limoninic acid, 3-caric acid, 3-caronic acid and sabinic acid were identified in the aerosol phase. On the basis of these results, we propose a formation mechanism for pinonic and pinic acid in the aerosol phase explaining how degradation products could influence SOA formation and growth in the troposphere.

  13. Emissions of biogenic volatile organic compounds and subsequent formation of secondary organic aerosols in a Larix kaempferi forest

    NASA Astrophysics Data System (ADS)

    Mochizuki, T.; Miyazaki, Y.; Ono, K.; Wada, R.; Takahashi, Y.; Saigusa, N.; Kawamura, K.; Tani, A.

    2015-10-01

    We conducted simultaneous measurements of concentrations and above-canopy fluxes of isoprene and α-pinene, along with their oxidation products in aerosols in a Larix kaempferi (Japanese larch) forest in summer 2012. Vertical profiles of isoprene showed the maximum concentration near the forest floor with a peak around noon, whereas oxidation products of isoprene, i.e., methacrolein (MACR) and methyl vinyl ketone (MVK), showed higher concentrations near the canopy level of the forest. The vertical profile suggests large emissions of isoprene near the forest floor, likely due to Dryopteris crassirhizoma (a fern species), and the subsequent reaction within the canopy. The concentrations of α-pinene also showed highest values near the forest floor, with maximums in the early morning and late afternoon. The vertical profiles of α-pinene suggest its large emissions from soil and litter in addition to emissions from L. kaempferi leaves at the forest site. Isoprene and its oxidation products in aerosols exhibited similar diurnal variations within the forest canopy, providing evidence of secondary organic aerosol (SOA) formation via oxidation of isoprene most likely emitted from the forest floor. Although high abundance of α-pinene was observed in the morning, its oxidation products in aerosols showed peaks in daytime, due to a time lag between the emission and atmospheric reactions of α-pinene to form SOA. Positive matrix factorization (PMF) analysis indicated that anthropogenic influence is the most important factor contributing to the elevated concentrations of molecular oxidation products of isoprene- (> 64 %) and α-pinene-derived SOA (> 57 %). The combination of the measured fluxes and vertical profiles of biogenic volatile organic compounds (BVOCs) suggests that the inflow of anthropogenic precursors/aerosols likely enhanced the formation of both isoprene SOA and α-pinene SOA within the forest canopy even when the BVOC flux was relatively low. This study

  14. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  15. Abundance of fluorescent biological aerosol particles at temperatures conducive to the formation of mixed-phase and cirrus clouds

    NASA Astrophysics Data System (ADS)

    Twohy, Cynthia H.; McMeeking, Gavin R.; DeMott, Paul J.; McCluskey, Christina S.; Hill, Thomas C. J.; Burrows, Susannah M.; Kulkarni, Gourihar R.; Tanarhte, Meryem; Kafle, Durga N.; Toohey, Darin W.

    2016-07-01

    Some types of biological particles are known to nucleate ice at warmer temperatures than mineral dust, with the potential to influence cloud microphysical properties and climate. However, the prevalence of these particle types above the atmospheric boundary layer is not well known. Many types of biological particles fluoresce when exposed to ultraviolet light, and the Wideband Integrated Bioaerosol Sensor takes advantage of this characteristic to perform real-time measurements of fluorescent biological aerosol particles (FBAPs). This instrument was flown on the National Center for Atmospheric Research Gulfstream V aircraft to measure concentrations of fluorescent biological particles from different potential sources and at various altitudes over the US western plains in early autumn. Clear-air number concentrations of FBAPs between 0.8 and 12 µm diameter usually decreased with height and generally were about 10-100 L-1 in the continental boundary layer but always much lower at temperatures colder than 255 K in the free troposphere. At intermediate temperatures where biological ice-nucleating particles may influence mixed-phase cloud formation (255 K ≤ T ≤ 270 K), concentrations of fluorescent particles were the most variable and were occasionally near boundary-layer concentrations. Predicted vertical distributions of ice-nucleating particle concentrations based on FBAP measurements in this temperature regime sometimes reached typical concentrations of primary ice in clouds but were often much lower. If convection was assumed to lift boundary-layer FBAPs without losses to the free troposphere, better agreement between predicted ice-nucleating particle concentrations and typical ice crystal concentrations was achieved. Ice-nucleating particle concentrations were also measured during one flight and showed a decrease with height, and concentrations were consistent with a relationship to FBAPs established previously at the forested surface site below. The vertical

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  17. The kinetics of aerosol particle formation and removal in NPP severe accidents

    NASA Astrophysics Data System (ADS)

    Zatevakhin, Mikhail A.; Arefiev, Valentin K.; Semashko, Sergey E.; Dolganov, Rostislav A.

    2016-06-01

    Severe Nuclear Power Plant (NPP) accidents are accompanied by release of a massive amount of energy, radioactive products and hydrogen into the atmosphere of the NPP containment. A valid estimation of consequences of such accidents can only be carried out through the use of the integrated codes comprising a description of the basic processes which determine the consequences. A brief description of a coupled aerosol and thermal-hydraulic code to be used for the calculation of the aerosol kinetics within the NPP containment in case of a severe accident is given. The code comprises a KIN aerosol unit integrated into the KUPOL-M thermal-hydraulic code. Some features of aerosol behavior in severe NPP accidents are briefly described.

  18. 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...

  19. Impacts of crystal metal on secondary aliphatic amine aerosol formation during dust storm episodes in Beijing

    NASA Astrophysics Data System (ADS)

    Liu, Qingyang; Bei, Yiling

    2016-03-01

    Trimethylamine (TMA) enters the atmosphere from a variety of sources and is a ubiquitous atmospheric organic base. The atmospheric reaction mechanism of TMA with key atmospheric oxidants is important to predict its distribution and environmental behavior in the particle phase. While previous studies have extensively focused on the production of particle amine salts (i.e. trimethylamine-N-oxide (TMAO)) using chamber experiments, the atmospheric behavior of TMAO in the environment is still poorly understood. Ambient fine particulate matter (PM2.5) was collected at two sampling sites in Beijing from March 10 to May 10, 2012. We analyzed the samples for water-soluble ions, crystal metals, TMA, and TMAO. Water-soluble ions (e.g. SO42-, NO3-, NH4+), TMA, and TMAO were measured using ion chromatography, while crystal metal (e.g. Al, Fe, Mn) in PM2.5 was quantified by inductively coupled plasma mass spectrometry (ICP-MS). Two dust storms (DS) occurred during the sampling period on March 28 and April 28. Mineral dust impacted PM2.5 mass and composition greatly during dust storm days, as it contributed approximately 1.2-4.0 times greater on dust storm days versus non-dust storm days. We found TMAO concentrations were highly associated with aluminum in PM2.5. Further, we applied the density functional theory (DFT) method to confirm that aluminum plays a catalytic effect in the reaction of TMA with ozone (O3). Our work improves understanding of the effect of crystal metals on secondary aliphatic amine aerosol formation in the atmosphere.

  20. Emission of sunscreen salicylic esters from desert vegetation and their contribution to aerosol formation

    NASA Astrophysics Data System (ADS)

    Matsunaga, S. N.; Guenther, A. B.; Potosnak, M. J.; Apel, E. C.

    2008-07-01

    Biogenic volatile organic compounds (BVOC) produced by plants are known to have an important role in atmospheric chemistry. However, our knowledge of the range of BVOCs produced by different plant processes is still expanding, and there remain poorly understood categories of BVOCs. In this study, emissions of a novel class of BVOC emissions were investigated in a desert region. Our study considered 8 species of common desert plants: blackbrush (Coleogyne ramosissima), desert willow (Chilopsis linearis), mesquite (Prosopis glandulosa), mondel pine (Pinus eldarica), pinyon pine (Pinus monophylla), cottonwood (Populus deltoides), saguaro cactus (Carnegiea gigantea) and yucca (Yucca baccata). The measurements focused on BVOCs with relatively high molecular weight (>C15) and/or an oxygenated functional group. Significantly high emission rates of two salicylic esters were found for blackbrush, desert willow and mesquite with emission rates of 1.4, 2.1 and 0.46 μgC dwg-1 h-1, respectively. The salicylic esters were identified as 2-ethylhexenyl salicylate (2-EHS) and 3,3,5-trimethylcyclohexenyl salicylate (homosalate) and are known as effective ultraviolet (UV) absorbers. We propose that the plants derive a protective benefit against UV radiation from the salicylic esters and that the emission process is driven by the physical evaporation of the salicylic esters due to the high ambient temperatures. In addition, the salicylic esters are predicted to be an effective precursor of secondary organic aerosol (SOA) because of their low vapor pressure due to a high number of carbon atoms (15 or 16) and the presence of three oxygen atoms. We estimated the contribution of the sunscreen esters themselves and their oxidation products on the SOA formation for the Las Vegas region using a BVOC emission model. The contribution was estimated to reach 90% of the biogenic SOA in the landscapes dominated by desert willow and mesquite and 25% in Las Vegas area.

  1. The variation of characteristics and formation mechanisms of aerosols in dust, haze, and clear days in Beijing

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Zhuang, Guoshun; Sun, Yele; An, Zhisheng

    A 4-year campaign from 2001 to 2004 monitoring PM 2.5 and TSP in the spring season in urban Beijing, China was performed to study the variation of characteristics and the different formation mechanisms of aerosols in dust, haze, and clear days. A total of 315 aerosol samples were collected and used in this study. The aerosols were more basic in dust days and more acidic in haze days. The ions presented in the order of SO42->Ca 2+≫ NO3->Cl -> NH4+>Na + in dust days, and of SO42-> NO3-> NH4+≫Cl ->Ca 2+>K + in haze days. Ions has been classified into three groups, "Na +, Mg 2+, Ca 2+", "K +, SO42-, Cl -", and " NO3-, NH4+", representing crust, pollution-crust, and pollution species, respectively. Crust and pollution ions were the main ion fractions in dust and haze days, respectively. The variation of Ca 2+/Al showed that the increase of dust in dust and haze days was from soil and construction, respectively. "CaCO 3, CaSO 4, and (NH 4) 2SO 4" and "(NH 4) 2SO 4, NH 4NO 3, and Ca(NO 3) 2" were the major species in dust and haze days, respectively. The formation of CaSO 4 on airborne soil particles and the formation of (NH 4) 2SO 4 and NH 4NO 3 were the predominant pathways of sulfate and nitrate formations in dust and haze days, respectively. Sulfate might be mainly formed through heterogeneous reactions in the aqueous surface layer on the pre-existing particles, while nitrate mainly through homogeneous gas-phase reactions in the spring season in Beijing. The formation of sulfate and nitrate was accelerated in dust and haze days.

  2. Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation.

    PubMed

    Krechmer, Jordan E; Coggon, Matthew M; Massoli, Paola; Nguyen, Tran B; Crounse, John D; Hu, Weiwei; Day, Douglas A; Tyndall, Geoffrey S; Henze, Daven K; Rivera-Rios, Jean C; Nowak, John B; Kimmel, Joel R; Mauldin, Roy L; Stark, Harald; Jayne, John T; Sipilä, Mikko; Junninen, Heikki; Clair, Jason M St; Zhang, Xuan; Feiner, Philip A; Zhang, Li; Miller, David O; Brune, William H; Keutsch, Frank N; Wennberg, Paul O; Seinfeld, John H; Worsnop, Douglas R; Jimenez, Jose L; Canagaratna, Manjula R

    2015-09-01

    Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10(-2) to 10 μg m(-3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr(-1) of SOA production, or 3.3% of global SOA. PMID:26207427

  3. Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation.

    PubMed

    Krechmer, Jordan E; Coggon, Matthew M; Massoli, Paola; Nguyen, Tran B; Crounse, John D; Hu, Weiwei; Day, Douglas A; Tyndall, Geoffrey S; Henze, Daven K; Rivera-Rios, Jean C; Nowak, John B; Kimmel, Joel R; Mauldin, Roy L; Stark, Harald; Jayne, John T; Sipilä, Mikko; Junninen, Heikki; Clair, Jason M St; Zhang, Xuan; Feiner, Philip A; Zhang, Li; Miller, David O; Brune, William H; Keutsch, Frank N; Wennberg, Paul O; Seinfeld, John H; Worsnop, Douglas R; Jimenez, Jose L; Canagaratna, Manjula R

    2015-09-01

    Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10(-2) to 10 μg m(-3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr(-1) of SOA production, or 3.3% of global SOA.

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

    NASA Astrophysics Data System (ADS)

    Roldin, P.; Eriksson, A. C.; Nordin, E. Z.; Hermansson, E.; Mogensen, D.; Rusanen, A.; Boy, M.; Swietlicki, E.; Svenningsson, B.; Zelenyuk, A.; Pagels, J.

    2014-08-01

    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 (MCMv3.2), 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 evaporation of liquid dioctyl phthalate (DOP) particles, (2) the slow and almost particle-size-independent evaporation of α-pinene ozonolysis secondary organic aerosol (SOA) particles, (3) the mass-transfer-limited uptake of ammonia (NH3) and formation of organic salts between ammonium (NH4+) and carboxylic acids (RCOOH), and (4) the influence of chamber wall effects on the observed SOA formation in smog chambers. ADCHAM is able to capture the observed α-pinene SOA mass increase in the presence of NH3(g). Organic salts of ammonium and carboxylic acids predominantly form during the early stage of SOA formation. In the smog chamber experiments, these salts contribute substantially to the initial growth of the homogeneously nucleated particles. The model simulations of evaporating α-pinene SOA particles support the recent experimental findings that these particles have a semi-solid tar-like amorphous-phase state. ADCHAM is able to reproduce the main features of the observed slow evaporation rates if the concentration of low-volatility and viscous oligomerized SOA material at the particle surface increases upon evaporation. The evaporation rate is mainly governed by the reversible decomposition of oligomers back to monomers. Finally, we demonstrate that the mass-transfer-limited uptake of condensable organic compounds

  5. Laboratory Simulation of Haze/Aerosol formation in warm and hot Jupiters

    NASA Astrophysics Data System (ADS)

    Gharib-Nezhad, Ehsan; Lyons, James R.; Wright, David P.

    2016-10-01

    During the transit of an exoplanet across its host star, transmitted starlight through exoplanet atmosphere is absorbed and scattered, and the recorded transit spectra reveal important chemical information. There are many detected exoplanets in which hazes/aerosols obscure the incident photons, and consequently, fewer photons are transmitted through the atmosphere, contributing to a flat/nearly flat transit spectrum. Here, we have carried out two complementary approaches to address haze formation. First, laboratory simulations of haze condensation in exoplanet atmospheres are carried out using an electric discharge tube. A mixture of likely gas species (i.e. H2, He, H2O, CH4, N2 and H2S) is inserted into a glass manifold on a vacuum line, at a pressure ~100-10 mbar, and depending on the exoplanet category (e.g., warm or hot Jupiters), the temperature is set. Applying a few kilovolts produces plasma in the discharge tube, and as a result, particles are formed. We use spectroscopic ellipsometry to measure the optical constants (complex refractive index) of the collected laboratory hazes. Then, chemical characterization is made using RBS (Rutherford Backscattering Spectroscopy) and XPS (X-ray Photoelectron Spectroscopy). Second, we developed a transit modeling code by which the transit spectra are generated using observational and laboratory data as an input. The model accounts for Mie scattering from haze particles in the vis-NIR spectral region, and Rayleigh scattering which comes from gases and particles (effective in UV-vis). The measured refractive indexes (real and imaginary part) describe the absorption and scattering in the vis-NIR transmission region, and, by generating transit spectra close to the observed ones from exoplanets, constraints on atmospheric chemical characterization can be revealed. Our laboratory results show that haze particles formed in the presence of water and with the solar C/O ratio = 0.5. The other outcome of our experiment is that

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

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

  7. 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

  8. A modeling perspective of the ChArMEx intensive campaign: origin of photo-oxidant and organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Cholakian, Arineh; Beekmann, Matthias; Siour, Guillaume; Coll, Isabelle; Colette, Augustin; Gros, Valerie; Marchand, Nicolas; Sciare, Jean; Colomb, Aurélie; Gheusi, François; Sauvage, Stéphane

    2016-04-01

    During the summers of 2013 and 2014, two three-week intensive campaigns took place over the western Mediterranean in order to investigate the origins of photo-oxidants as well as the sources and processes of formation of organic aerosols in this region. Within the frame of the MISTRAL/ChArMEx program, an extensive number of chemical compounds were investigated by means of ground-based and also airborne measurements. In this paper, a modeling perspective of the 2013 campaign is given, using the CHIMERE chemistry-transport model, dealing with two aspects: 1) representativeness of the simulations with respect to the complex orography of Cape Corsica, 2) evaluation of secondary organic aerosol simulations in the western Mediterranean region with different model configurations using a variety of experimental data. The model has been configured in a way to fit the specificities of this unique region. The base simulations are performed in a domain covering the entire Europe as well as the northern Africa with a low resolution (30 km). In order to take into account the orographic complexity of the area where the ground-based measurements were performed (Ersa, Cape Corsica), nested simulations with a high resolution (1km horizontal resolution) focused on this site were performed with the goal of increasing the representativeness of the simulations. Still, this resolution does not allow to correctly represent the altitude of the Cape Corsica measurement site (533 m asl). To solve this problem, a large number of grid cells in the vicinity of the measurements site, all having different altitudes, were used to find the extrapolated concentration of an indicative list of species towards the exact altitude of the aforementioned site and to estimate an orographic representativeness error, which was shown to be less important for organic aerosols among said species. Alongside the base simulations, other series of simulations using multiple configurations of the Volatility Basis Set

  9. Skin as a potential source of infectious foot and mouth disease aerosols.

    PubMed

    Dillon, Michael B

    2011-06-22

    This review examines whether exfoliated, virus-infected animal skin cells could be an important source of infectious foot and mouth disease virus (FMDV) aerosols. Infectious material rafting on skin cell aerosols is an established means of transmitting other diseases. The evidence for a similar mechanism for FMDV is: (i) FMDV is trophic for animal skin and FMDV epidermis titres are high, even in macroscopically normal skin; (ii) estimates for FMDV skin cell aerosol emissions appear consistent with measured aerosol emission rates and are orders of magnitude larger than the minimum infectious dose; (iii) the timing of infectious FMDV aerosol emissions is consistent with the timing of high FMDV skin concentrations; (iv) measured FMDV aerosol sizes are consistent with skin cell aerosols; and (v) FMDV stability in natural aerosols is consistent with that expected for skin cell aerosols. While these findings support the hypothesis, this review is insufficient, in and of itself, to prove the hypothesis and specific follow-on experiments are proposed. If this hypothesis is validated, (i) new FMDV detection, management and decontamination approaches could be developed and (ii) the relevance of skin cells to the spread of viral disease may need to be reassessed as skin cells may protect viruses against otherwise adverse environmental conditions.

  10. Simulating the formation of carbonaceous aerosol in a European Megacity (Paris) during the MEGAPOLI summer and winter campaigns

    NASA Astrophysics Data System (ADS)

    Fountoukis, C.; Megaritis, A. G.; Skyllakou, K.; Charalampidis, P. E.; Denier van der Gon, H. A. C.; Crippa, M.; Prévôt, A. S. H.; Freutel, F.; Wiedensohler, A.; Pilinis, C.; Pandis, S. N.

    2015-09-01

    We use a three dimensional regional chemical transport model (PMCAMx) with high grid resolution and high resolution emissions (4 km × 4 km) over the Paris greater area to simulate the formation of carbonaceous aerosol during a summer (July 2009) and a winter (January/February 2010) period as part of the MEGAPOLI (Megacities: Emissions, urban, regional, and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) campaigns. Model predictions of carbonaceous aerosol are compared against Aerodyne aerosol mass spectrometer and black carbon (BC) high time resolution measurements from three ground sites. PMCAMx predicts BC concentrations reasonably well reproducing the majority (70 %) of the hourly data within a factor of two during both periods. The agreement for the summertime secondary organic aerosol (OA) concentrations is also encouraging (mean bias = 0.1 μg m-3) during a photochemically intense period. The model tends to underpredict the summertime primary OA concentrations in the Paris greater area (by approximately 0.8 μg m-3) mainly due to missing primary OA emissions from cooking activities. The total cooking emissions are estimated to be approximately 80 mg d-1 per capita and have a distinct diurnal profile in which 50 % of the daily cooking OA is emitted during lunch time (12:00-14:00 LT) and 20 % during dinner time (20:00-22:00 LT). Results also show a large underestimation of secondary OA in the Paris greater area during wintertime (mean bias = -2.3 μg m-3) pointing towards a secondary OA formation process during low photochemical activity periods that is not simulated in the model.

  11. Simulating the formation of carbonaceous aerosol in a European Megacity (Paris) during the MEGAPOLI summer and winter campaigns

    NASA Astrophysics Data System (ADS)

    Fountoukis, Christos; Megaritis, Athanasios G.; Skyllakou, Ksakousti; Charalampidis, Panagiotis E.; Denier van der Gon, Hugo A. C.; Crippa, Monica; Prévôt, André S. H.; Fachinger, Friederike; Wiedensohler, Alfred; Pilinis, Christodoulos; Pandis, Spyros N.

    2016-03-01

    We use a three-dimensional regional chemical transport model (PMCAMx) with high grid resolution and high-resolution emissions (4 × 4 km2) over the Paris greater area to simulate the formation of carbonaceous aerosol during a summer (July 2009) and a winter (January/February 2010) period as part of the MEGAPOLI (megacities: emissions, urban, regional, and global atmospheric pollution and climate effects, and Integrated tools for assessment and mitigation) campaigns. Model predictions of carbonaceous aerosol are compared against Aerodyne aerosol mass spectrometer and black carbon (BC) high time resolution measurements from three ground sites. PMCAMx predicts BC concentrations reasonably well reproducing the majority (70 %) of the hourly data within a factor of two during both periods. The agreement for the summertime secondary organic aerosol (OA) concentrations is also encouraging (mean bias = 0.1 µg m-3) during a photochemically intense period. The model tends to underpredict the summertime primary OA concentrations in the Paris greater area (by approximately 0.8 µg m-3) mainly due to missing primary OA emissions from cooking activities. The total cooking emissions are estimated to be approximately 80 mg d-1 per capita and have a distinct diurnal profile in which 50 % of the daily cooking OA is emitted during lunch time (12:00-14:00 LT) and 20 % during dinner time (20:00-22:00 LT). Results also show a large underestimation of secondary OA in the Paris greater area during wintertime (mean bias = -2.3 µg m-3) pointing towards a secondary OA formation process during low photochemical activity periods that is not simulated in the model.

  12. Optimal schooling formations using a potential flow model

    NASA Astrophysics Data System (ADS)

    Tchieu, Andrew; Gazzola, Mattia; de Brauer, Alexia; Koumoutsakos, Petros

    2012-11-01

    A self-propelled, two-dimensional, potential flow model for agent-based swimmers is used to examine how fluid coupling affects schooling formation. The potential flow model accounts for fluid-mediated interactions between swimmers. The model is extended to include individual agent actions by means of modifying the circulation of each swimmer. A reinforcement algorithm is applied to allow the swimmers to learn how to school in specified lattice formations. Lastly, schooling lattice configurations are optimized by combining reinforcement learning and evolutionary optimization to minimize total control effort and energy expenditure.

  13. Trihalomethane formation potential of Kentucky River water. Water resources investigation

    SciTech Connect

    Rathbun, R.E.; White, K.D.; Evaldi, R.D.

    1992-01-01

    Trihalomethane compounds are chlorinated and brominated derivatives of methane that are formed when a natural water is disinfected with free chlorine to produce drinking water. These compounds result when the free chlorine used for disinfection reacts with the dissolved organic carbon of the water. The trihalomethane formation potential of water from the Kentucky River was determined for the period from July of 1988 through March of 1990. Multiple-linear regression analysis of the experimental data indicated that the trihalomethane formation potential was strongly dependent on the pH and dissolved organic carbon concentration and was only slightly dependent on the initial free-chlorine concentration.

  14. Formation of nitrogen- and sulfur-containing light-absorbing compounds accelerated by evaporation of water from secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey A.

    2012-01-01

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of d-limonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (<2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>105 L mol-1 cm-1 at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 103 cm2 g-1 - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH ˜ 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  15. Formation of Nitrogen- and Sulfur-Containing Light-Absorbing Compounds Accelerated by Evaporation of Water from Secondary Organic Aerosols

    SciTech Connect

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey

    2012-01-14

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of dlimonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (< 2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>10{sup 5} L mol{sup -1} cm{sup -1} at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 10{sup 3} cm{sup 2} g{sup -1} - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH {approx} 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  16. Formation of ozone and growth of aerosols in young smoke plumes from biomass burning: 2. Three-dimensional Eulerian studies

    NASA Astrophysics Data System (ADS)

    Alvarado, Matthew James; Wang, Chien; Prinn, Ronald G.

    2009-05-01

    Global-scale models of atmospheric chemistry (GACMs) "mix" biomass burning emissions into grid boxes with horizontal scales of 10-200 km. This ignores the complex nonlinear transformations that take place in the young smoke plumes. Here we use a new gas- and aerosol-phase chemistry model called Aerosol Simulation Program (ASP) and a 3-D Eulerian smoke plume model to simulate the fluid dynamics, radiative transfer, gas-phase chemistry, and aerosol-phase chemistry of the Timbavati smoke plume observed during SAFARI 2000. We then compare the results of the 3-D plume model with those of an Eulerian box model, which is used as an analog for the large grid boxes of GACMs. The 3-D plume model matched the observed plume injection height but required a large minimum horizontal diffusion coefficient to match the observed horizontal dispersion of the plume. Absorption and scattering by smoke aerosols reduced the modeled photolysis rates in the plume by 10-20%. Increasing the heterogeneous production of HONO and H2SO4 in the model and including uncharacterized organic species using monoterpenes as a proxy compound improves the model-observation match. Direct measurements of OH in the smoke plumes would be an excellent way to determine if heterogeneous production of HONO is taking place. The automatic dilution of smoke plume emissions into the large grid boxes of global models can result in large errors in predicted concentrations of O3, NOx and aerosol species downwind. We discuss several potential approaches that could reduce these errors.

  17. Investigation into the oxidative potential generated by the formation of particulate matter from incense combustion.

    PubMed

    Chuang, Hsiao-Chi; BéruBé, Kelly; Lung, Shih-Chun C; Bai, Kuan-Jen; Jones, Tim

    2013-01-15

    The formation of aerosols during combustion plays an important role in allowing released products to interreact, leading to an increase in particulate matter oxidative potential. This study investigated the physicochemistry of incense combustion-derived pollutants, which were emitted into the ambient air as solid and gas phases, followed by the determination of their oxidative potential. Upon combustion of a joss stick, approximately 60% of the mass of incense raw ingredients was released into the ambient air as combustion products including 349.51 mg/g PM(10), 145.48 mg/g CO and 0.16 mg/g NOx. Furthermore, incense combustion produced significant number of primary particles (<50 nm) at 0.99×10(5) 1/h. The NOx generated during incense combustion was able to react with CaCO(3) to produce the final product of Ca(NO(3))(2) in the ambient air. Moreover, coagulation could be a vital process for the growth of primary incense combustion particles through the intermixing with volatile organics. The incense particle's reactions with other combustion-derived products could be responsible for their significant oxidative capacity of 33.1-43.4% oxidative DNA damage. This study demonstrated that the oxidative potential of incense particles appeared to be related to the process of particle formation, and also provided novel data for the respiratory exposure assessment.

  18. Potential sensitivity of photosynthesis and isoprene emission to direct radiative effects of atmospheric aerosol pollution

    NASA Astrophysics Data System (ADS)

    Strada, S.; Unger, N.

    2015-09-01

    A global Earth system model is applied to quantify the impacts of direct anthropogenic aerosol effective radiative forcing on gross primary productivity (GPP) and isoprene emission. The impacts of different pollution aerosol sources (all anthropogenic, biomass burning and non-biomass burning) are investigated by performing sensitivity experiments. On the global scale, our results show that land carbon fluxes (GPP and isoprene emission) are not sensitive to pollution aerosols, even under a global decline in surface solar radiation (direct + diffuse) by ~ 9 %. At the regional scale, plant productivity (GPP) and isoprene emission show a robust but opposite sensitivity to pollution aerosols, in regions where complex canopies dominate. In eastern North America and Europe, anthropogenic pollution aerosols (mainly from non-biomass burning sources) enhance GPP by +8-12 % on an annual average, with a stronger increase during the growing season (> 12 %). In the Amazon basin and central Africa, biomass burning aerosols increase GPP by +2-5 % on an annual average, with a peak in the Amazon basin during the dry-fire season (+5-8 %). In Europe and China, anthropogenic pollution aerosols drive a decrease in isoprene emission of -2 to -12 % on the annual average. Anthropogenic aerosols affect land carbon fluxes via different mechanisms and we suggest that the dominant mechanism varies across regions: (1) light scattering dominates in the eastern US; (2) cooling in the Amazon basin; and (3) reduction in direct radiation in Europe and China.

  19. Laboratory studies of nitric acid hydrate and sulfuric acid aerosols: Implications for polar stratospheric cloud formation

    SciTech Connect

    Miller, R.E.

    1995-12-31

    The optical properties of atmospheric aerosols are important in a number of modeling and remote sensing applications. We have devised a new approach for determining the frequency dependent real and imaginary refractive indices directly from the observation of the infrared spectra of the aerosols. We have applied this method to the study of water ice aerosols and comparisons with previous measurements confirm that the method is sound and accurate. The temperature dependence of the refractive index of ice has also been measured over the range 130 K to 210 K, which includes the region of interest for the study of Polar Stratospheric Clouds (PSC`s). The method has also been applied to the study of nitric acid dehydrate (NAD) and nitric acid trihydrate (NAT). Sulfuric acid/nitric acid/water ternary systems are also being studied with the aim of determining the nature of the phases formed and the associated freezing points as a function of the concentrations of the acids.

  20. Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Nozière, Barbara; Ekström, Sanna; Alsberg, Tomas; Holmström, Sara

    2010-03-01

    Many atmospheric aerosols contain both organic compounds and inorganic material, such as sulfate salts. In this work, we show that these sulfates could trigger some chemical transformations of the organic compounds by producing sulfate radicals, SO4-, when exposed to UV light (280-320 nm). In particular, we show by mass spectrometry (LC/ESI-MSMS) that isoprene, methyl vinyl ketone, methacrolein, and α-pinene in irradiated sulfate solutions (ammonium and sodium sulfate) produce the same organosulfates as previously identified in aerosols, and even some that had remained unidentified until now. With a typical time constant of 9 h instead of 4600 days for esterifications, these radical reactions would be a plausible origin for the atmospheric organosulfates. These reactions also produced efficient surfactants, possibly resembling the long-chain organosulfates found in the experiments. Thus, photochemistry in mixed sulfate/organic aerosols could increase cloud condensation nuclei (CCN) numbers, which would be supported by previous atmospheric observations.

  1. Formation of Copper Zinc Tin Sulfide Thin Films from Colloidal Nanocrystal Dispersions via Aerosol-Jet Printing and Compaction.

    PubMed

    Williams, Bryce A; Mahajan, Ankit; Smeaton, Michelle A; Holgate, Collin S; Aydil, Eray S; Francis, Lorraine F

    2015-06-01

    A three-step method to create dense polycrystalline semiconductor thin films from nanocrystal liquid dispersions is described. First, suitable substrates are coated with nanocrystals using aerosol-jet printing. Second, the porous nanocrystal coatings are compacted using a weighted roller or a hydraulic press to increase the coating density. Finally, the resulting coating is annealed for grain growth. The approach is demonstrated for making polycrystalline films of copper zinc tin sulfide (CZTS), a new solar absorber composed of earth-abundant elements. The range of coating morphologies accessible through aerosol-jet printing is examined and their formation mechanisms are revealed. Crack-free albeit porous films are obtained if most of the solvent in the aerosolized dispersion droplets containing the nanocrystals evaporates before they impinge on the substrate. In this case, nanocrystals agglomerate in flight and arrive at the substrate as solid spherical agglomerates. These porous coatings are mechanically compacted, and the density of the coating increases with compaction pressure. Dense coatings annealed in sulfur produce large-grain (>1 μm) polycrystalline CZTS films with microstructure suitable for thin-film solar cells. PMID:25989610

  2. Characterization of vehicle emissions in São Paulo and the impacts on atmospheric chemistry and secondary aerosol formation

    NASA Astrophysics Data System (ADS)

    Ferreira De Brito, J.; Godoy, M.; Godoy, J.; Varanda Rizzo, L.; Artaxo, P.

    2012-12-01

    Megacities emissions are increasingly becoming a global issue, where emissions from the transportation sector play an important role. São Paulo, located in Southeast of Brazil, is a megacity with a population of 18 million people, 7 million cars and large-scale industrial emissions. As a result of the vehicular and industrial emissions, the air quality in São Paulo is considered one of the worst worldwide. Despite the large impact on human health and atmospheric chemistry/dynamics, 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 pattern, we are running a source apportionment study in São Paulo. 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) and diesel (heavy-duty vehicles). Whereas the latter shows usually much higher emission factors compared with ethanol or gasohol, heavy-duty vehicles have increasingly limited access within the São Paulo city limits, thus increasing the importance of light duty vehicles on air quality degradation. This study comprises four sampling sites, where trace elements and organic aerosol are being measured for PM2.5 and PM10 along with real-time NOx, ozone, 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 real-time VOC analysis and aerosol composition, respectively. Results show aerosol number concentrations ranging between 10^4 and 3.10^4 cm-3, mostly

  3. Expert consensus on an in vitro approach to assess pulmonary fibrogenic potential of aerosolized nanomaterials.

    PubMed

    Clippinger, Amy J; Ahluwalia, Arti; Allen, David; Bonner, James C; Casey, Warren; Castranova, Vincent; David, Raymond M; Halappanavar, Sabina; Hotchkiss, Jon A; Jarabek, Annie M; Maier, Monika; Polk, William; Rothen-Rutishauser, Barbara; Sayes, Christie M; Sayre, Phil; Sharma, Monita; Stone, Vicki

    2016-07-01

    The increasing use of multi-walled carbon nanotubes (MWCNTs) in consumer products and their potential to induce adverse lung effects following inhalation has lead to much interest in better understanding the hazard associated with these nanomaterials (NMs). While the current regulatory requirement for substances of concern, such as MWCNTs, in many jurisdictions is a 90-day rodent inhalation test, the monetary, ethical, and scientific concerns associated with this test led an international expert group to convene in Washington, DC, USA, to discuss alternative approaches to evaluate the inhalation toxicity of MWCNTs. Pulmonary fibrosis was identified as a key adverse outcome linked to MWCNT exposure, and recommendations were made on the design of an in vitro assay that is predictive of the fibrotic potential of MWCNTs. While fibrosis takes weeks or months to develop in vivo, an in vitro test system may more rapidly predict fibrogenic potential by monitoring pro-fibrotic mediators (e.g., cytokines and growth factors). Therefore, the workshop discussions focused on the necessary specifications related to the development and evaluation of such an in vitro system. Recommendations were made for designing a system using lung-relevant cells co-cultured at the air-liquid interface to assess the pro-fibrogenic potential of aerosolized MWCNTs, while considering human-relevant dosimetry and NM life cycle transformations. The workshop discussions provided the fundamental design components of an air-liquid interface in vitro test system that will be subsequently expanded to the development of an alternative testing strategy to predict pulmonary toxicity and to generate data that will enable effective risk assessment of NMs.

  4. Denitrification of the polar winter stratosphere: Implications of SAM II (Stratospheric Aerosol Measurement II) cloud formation temperatures

    SciTech Connect

    Hamill, P. ); Toon, O.B. )

    1990-03-01

    The authors use the Stratospheric Aerosol Measurement II (SAM II) extinction profiles and the associated temperature profiles to determine the amount of denitrification of the winter polar stratospheres. The authors see clear evidence of the denitrification process in the Antarctic data. There are indications in the Arctic data that denitrification mechanisms may be at work there also. At the latitudes observed by the SAM II satellite system, denitrification begins before the formation of extensive ice clouds and may be due to sedimentation of nitric acid particles. However, they cannot exclude the possibility of denitrification by type II PSC's at latitudes not observed by SAM II.

  5. Influence of aerosol spectrum and air pollutants on fog formation in urban environment of megacity Delhi, India.

    PubMed

    Mohan, Manju; Payra, Swagata

    2009-04-01

    Urban areas are facing increasing fog frequencies that may result due to increased air pollution emanating from variety of sources. The increased pollution levels may lead to the atmospheric reactions resulting into the formation of secondary pollutants that may also lead to increased aerosol number concentrations (ANC) in the atmosphere. This could cause enhanced water aerosols in the presence of favourable meteorological conditions and high relative humidity. This study deals with the atmospheric pollution and visibility during winter season of megacity Delhi in order to assess the relationship between the two specifically during fog episodes. Thus, this study analyses the levels of air pollutants, aerosol spectrum and meteorological conditions during one week each in the winter season of the years 2004 and 2006 in order to have an improved understanding of their role in fog formation in mega-city Delhi. More than 300 h of measurements which included episodes of dense, thick and moderate fogs of about 25 h, were studied. The measurements cover most of the accumulation mode and greater size spectrum of aerosols. Thus, the analysis is performed for the entire period, specifically, before the fog sets up, during and afterwards. In general, the relatively small variations in number concentration show larger variations in visibility prior and post dense fog formation than during dense fog episodes. Preliminary analysis of monthly averaged RSPM (Respirable Suspended particulate Matter or PM(10)) concentration values for four winter months for a period of 6 years (1996-2001) and visibility did not show a good correlation with total occurrences of fog. However, daily averaged RSPM concentration showed a good correlation with the occurrences of thick fog. Diurnal variation of Sulfur-dioxide and Nitrogen dioxide were found to have inverse relationship with visibility during fog which may be due to formation of secondary pollutants such as sulfate and to a lesser extent

  6. 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 μM-C). OH radicals (3.5E-2 μM [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

  7. Impact of new particle formation on the concentrations of aerosol number and cloud condensation nuclei around Beijing

    SciTech Connect

    Matsui, H.; Koike, Makoto; Kondo, Yutaka; Takegawa, Nobuyuki; Wiedensohler, A.; Fast, Jerome D.; Zaveri, Rahul A.

    2011-10-13

    New particle formation (NPF) is one of the most important processes in controlling the concentrations of aerosol number (condensation nuclei, CN) and cloud condensation nuclei (CCN) in the atmosphere. In this study, we introduced a new aerosol model representation with 20 size bins between 1 nm and 10 {mu}m and activation-type and kinetic nucleation parameterizations into the WRF-chem model (called NPF-explicit WRF-chem). Model calculations were conducted in the Beijing region in China for the periods during the CARE-Beijing 2006 campaign conducted in August and September 2006. Model calculations successfully reproduced the timing of NPF and no-NPF days in the measurements (21 of 26 days). Model calculations also reproduced the subsequent rapid growth of new particles with a time scale of half a day. These results suggest that once a reasonable nucleation rate at a diameter of 1 nm is given, explicit calculations of condensation and coagulation processes can reproduce the clear contrast between NPF and no-NPF days as well as further growth up to several tens nanometers. With this reasonable representation of the NPF process, we show that NPF contributed 20-30% of CN concentrations (> 10 nm in diameter) in and around Beijing on average. We also show that NPF increases CCN concentrations at higher supersaturations (S > 0.2%), while it decreases them at lower supersaturations (S < 0.1%). This is likely because NPF suppresses the increases in both the size and hygroscopicity of pre-existing particles through the competition of condensable gases between new particles and pre-existing particles. Sensitivity calculations show that a reduction of primary aerosol emissions, such as black carbon (BC), would not necessarily decrease CCN concentrations because of an increase in NPF. Sensitivity calculations also suggest that the reduction ratio of primary aerosol and SO2 emissions will be key in enhancing or damping the BC mitigation effect.

  8. Radon potential, geologic formations, and lung cancer risk

    PubMed Central

    Hahn, Ellen J.; Gokun, Yevgeniya; Andrews, William M.; Overfield, Bethany L.; Robertson, Heather; Wiggins, Amanda; Rayens, Mary Kay

    2015-01-01

    Objective Exposure to radon is associated with approximately 10% of U.S. lung cancer cases. Geologic rock units have varying concentrations of uranium, producing fluctuating amounts of radon. This exploratory study examined the spatial and statistical associations between radon values and geological formations to illustrate potential population-level lung cancer risk from radon exposure. Method This was a secondary data analysis of observed radon values collected in 1987 from homes (N = 309) in Kentucky and geologic rock formation data from the Kentucky Geological Survey. Radon value locations were plotted on digital geologic maps using ArcGIS and linked to specific geologic map units. Each map unit represented a package of different types of rock (e.g., limestone and/or shale). Log-transformed radon values and geologic formation categories were compared using one-way analysis of variance. Results Observed radon levels varied significantly by geologic formation category. Of the 14 geologic formation categories in north central Kentucky, four were associated with median radon levels, ranging from 8.10 to 2.75 pCi/L. Conclusion Radon potential maps that account for geologic factors and observed radon values may be superior to using observed radon values only. Knowing radon-prone areas could help target population-based lung cancer prevention interventions given the inequities that exist related to radon. PMID:26844090

  9. Using stable isotopes to trace sources and formation processes of sulfate aerosols from Beijing, China

    PubMed Central

    Han, Xiaokun; Guo, Qingjun; Liu, Congqiang; Fu, Pingqing; Strauss, Harald; Yang, Junxing; Hu, Jian; Wei, Lianfang; Ren, Hong; Peters, Marc; Wei, Rongfei; Tian, Liyan

    2016-01-01

    Particulate pollution from anthropogenic and natural sources is a severe problem in China. Sulfur and oxygen isotopes of aerosol sulfate (δ34Ssulfate and δ18Osulfate) and water-soluble ions in aerosols collected from 2012 to 2014 in Beijing are being utilized to identify their sources and assess seasonal trends. The mean δ34S value of aerosol sulfate is similar to that of coal from North China, indicating that coal combustion is a significant contributor to atmospheric sulfate. The δ34Ssulfate and δ18Osulfate values are positively correlated and display an obvious seasonality (high in winter and low in summer). Although an influence of meteorological conditions to this seasonality in isotopic composition cannot be ruled out, the isotopic evidence suggests that the observed seasonality reflects temporal variations in the two main contributions to Beijing aerosol sulfate, notably biogenic sulfur emissions in the summer and the increasing coal consumption in winter. Our results clearly reveal that a reduction in the use of fossil fuels and the application of desulfurization technology will be important for effectively reducing sulfur emissions to the Beijing atmosphere. PMID:27435991

  10. Using stable isotopes to trace sources and formation processes of sulfate aerosols from Beijing, China

    NASA Astrophysics Data System (ADS)

    Han, Xiaokun; Guo, Qingjun; Liu, Congqiang; Fu, Pingqing; Strauss, Harald; Yang, Junxing; Hu, Jian; Wei, Lianfang; Ren, Hong; Peters, Marc; Wei, Rongfei; Tian, Liyan

    2016-07-01

    Particulate pollution from anthropogenic and natural sources is a severe problem in China. Sulfur and oxygen isotopes of aerosol sulfate (δ34Ssulfate and δ18Osulfate) and water-soluble ions in aerosols collected from 2012 to 2014 in Beijing are being utilized to identify their sources and assess seasonal trends. The mean δ34S value of aerosol sulfate is similar to that of coal from North China, indicating that coal combustion is a significant contributor to atmospheric sulfate. The δ34Ssulfate and δ18Osulfate values are positively correlated and display an obvious seasonality (high in winter and low in summer). Although an influence of meteorological conditions to this seasonality in isotopic composition cannot be ruled out, the isotopic evidence suggests that the observed seasonality reflec