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Sample records for aerosol organic carbon

  1. Carbonaceous aerosols influencing atmospheric radiation: Black and organic carbon

    SciTech Connect

    Penner, J.E.

    1994-09-01

    Carbonaceous particles in the atmosphere may both scatter and absorb solar radiation. The fraction associated with the absorbing component is generally referred to as black carbon (BC) and is mainly produced from incomplete combustion processes. The fraction associated with condensed organic compounds is generally referred to as organic carbon (OC) or organic matter and is mainly scattering. Absorption of solar radiation by carbonaceous aerosols may heat the atmosphere, thereby altering the vertical temperature profile, while scattering of solar radiation may lead to a net cooling of the atmosphere/ocean system. Carbonaceous aerosols may also enhance the concentrations of cloud condensation nuclei. This paper summarizes observed concentrations of aerosols in remote continental and marine locations and provides estimates for the fine particle (D < 2.5 {mu}m) source rates of both OC and BC. The source rates for anthropogenic organic aerosols may be as large as the source rates for anthropogenic sulfate aerosols, suggesting a similar magnitude of direct forcing of climate. The role of BC in decreasing the amount of reflected solar radiation by OC and sulfates is discussed. The total estimated forcing depends on the source estimates for organic and black carbon aerosols which are highly uncertain. The role of organic aerosols acting as cloud condensation nuclei (CCN) is also described.

  2. Organic aerosols

    SciTech Connect

    Penner, J.E.

    1994-01-01

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

  3. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol.

    PubMed

    Kroll, Jesse H; Donahue, Neil M; Jimenez, Jose L; Kessler, Sean H; Canagaratna, Manjula R; Wilson, Kevin R; Altieri, Katye E; Mazzoleni, Lynn R; Wozniak, Andrew S; Bluhm, Hendrik; Mysak, Erin R; Smith, Jared D; Kolb, Charles E; Worsnop, Douglas R

    2011-02-01

    A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.

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

    SciTech Connect

    Paulson, S E

    2012-05-30

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

  5. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    SciTech Connect

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  6. Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

    SciTech Connect

    Mazurek, M.A. ); Hildemann, L.M. . Dept. of Civil Engineering); Cass, G.R.; Rogge, W.F. ); Simoneit, B.R.T. . Coll. of Oceanography)

    1990-10-01

    Organic aerosols comprise approximately 30% by mass of the total fine particulate matter present in urban atmospheres. The chemical composition of such aerosols is complex and reflects input from multiple sources of primary emissions to the atmosphere, as well as from secondary production of carbonaceous aerosol species via photochemical reactions. To identify discrete sources of fine carbonaceous particles in urban atmospheres, analytical methods must reconcile both bulk chemical and molecular properties of the total carbonaceous aerosol fraction. This paper presents an overview of the analytical protocol developed and used in a study of the major sources of fine carbon particles emitted to an urban atmosphere. 23 refs., 1 fig., 2 tabs.

  7. Determination of stable carbon isotopes of organic acids and carbonaceous aerosols in the atmosphere.

    PubMed

    Fisseha, R; Saurer, M; Jäggi, M; Szidat, S; Siegwolf, R T W; Baltensperger, U

    2006-01-01

    A wet oxidation method for the compound-specific determination of stable carbon isotopes (delta(13)C) of organic acids in the gas and aerosol phase, as well as of water-soluble organic carbon (WSOC), is presented. Sampling of the organic acids was done using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to an ion chromatography (IC) system. The method allows for compound-specific stable carbon isotope analysis by collecting different fractions of organic acids at the end of the IC system using a fraction collector. delta(13)C analyses of organic acids were conducted by oxidizing the organic acids with sodium persulfate at a temperature of 100 degrees C and determining the delta(13)C value of the resulting carbon dioxide (CO(2)) with an isotope ratio mass spectrometer. In addition, analysis of delta(13)C of the WSOC was performed for particulate carbon collected on aerosol filters. The WSOC was extracted from the filters using ultrapure water (MQ water), and the dissolved organic carbon was oxidized to CO(2) using the oxidation method. The wet oxidation method has an accuracy of 0.5 per thousand with a precision of +/-0.4 per thousand and provides a quantitative result for organic carbon with a detection limit of 150 ng of carbon.

  8. Aerosol organic carbon to black carbon ratios: Analysis ofpublished data and implications for climate forcing

    SciTech Connect

    Novakov, T.; Menon, S.; Kirchstetter, T.W.; Koch, D.; Hansen, J.E.

    2005-07-11

    Measurements of organic carbon (OC) and black carbon (BC)concentrations over a variety of locations worldwide, have been analyzed to infer the spatial distributions of the ratios of OC to BC. Since these ratios determine the relative amounts of scattering and absorption, they are often used to estimate the radiative forcing due to aerosols. An artifact in the protocol for filter measurements of OC has led to widespread overestimates of the ratio of OC to BC in atmospheric aerosols. We developed a criterion to correct for this artifact and analyze corrected OC to BC ratios. The OC to BC ratios, ranging from 1.3to 2.4, appear relatively constant and are generally unaffected by seasonality, sources or technology changes, at the locations considered here. The ratios compare well with emission inventories over Europe and China but are a factor of two lower in other regions. The reduced estimate for OC/BC in aerosols strengthens the argument that reduction of soot emissions maybe a useful approach to slow global warming.

  9. Direct radiative effect due to brownness in organic carbon aerosols generated from biomass combustion

    NASA Astrophysics Data System (ADS)

    Rathod, T. D.; Sahu, S. K.; Tiwari, M.; Pandit, G. G.

    2016-12-01

    We report the enhancement in the direct radiative effect due the presence of Brown carbon (BrC) as a part of organic carbon aerosols. The optical properties of organic carbon aerosols generated from pyrolytic combustion of mango tree wood (Magnifera Indica) and dung cake at different temperatures were considered. Mie codes were used to calculate absorption and scattering coefficients coupled with experimentally derived imaginary complex refractive index. The direct radiative effect (DRE) for sampled organic carbon aerosols was estimated using a wavelength dependent radiative transfer equation. The BrC DRE was estimated taking virtually non absorbing organic aerosols as reference. The BrC DRE from wood and dung cake was compared at different combustion temperatures and conditions. The BrC contributed positively to the direct top of the atmosphere radiative effect. Dung cake generated BrC aerosols were found to be strongly light absorbing as compared to BrC from wood combustion. It was noted that radiative effects of BrC from wood depended on its generation temperature and conditions. For BrC aerosols from dung cake such strong dependence was not observed. The average BrC aerosol DRE values were 1.53±0.76 W g-1 and 17.84±6.45 W g-1 for wood and dung cake respectively. The DRE contribution of BrC aerosols came mainly (67-90%) from visible light absorption though they exhibited strong absorption in shorter wavelengths of the UV-visible spectrum.

  10. Methods of analysis for complex organic aerosol mixtures from urban emission sources of particulate carbon

    SciTech Connect

    Mazurek, M.A. ); Hildemann, L.M. . Dept. of Civil Engineering); Cass, G.R.; Rogge, W.F. . Dept. of Environmental Engineering Science); Simoneit, B.R.T. . Coll. of Oceanography)

    1990-04-01

    Extractable organic compounds having between 6 to 40 carbon atoms comprise an important mass fraction of the fine particulate matter samples from major urban emission sources. Depending on the emission source type, this solvent-soluble fraction accounts for <20% to 100% of the total organic aerosol mass, as measured by quantitative high-resolution has chromatography (HRGC) with flame ionization detection. In addition to total extract quantitation, HRGC can be applied to further analyses of the mass distributions of elutable organics present in the complex aerosol extract mixtures, thus generating profiles that serve as fingerprints'' for the sources of interest. This HRGC analytical method is applied to emission source samples that contain between 7 to 12,000 {mu}g/filter organic carbon. It is shown to be a sensitive technique for analysis of carbonaceous aerosol extract mixtures having diverse mass loadings and species distributions. This study describes the analytical chemical methods that have been applied to: the construction of chemical mass balances based on the mass of fine organic aerosol emitted for major urban sources of particulate carbon; and the generation of discrete emission source chemical profiles derived from chromatographic characteristics of the organic aerosol components. 21 refs., 1 fig., 2 tabs.

  11. Spectroscopic characteristics and organic carbon contents in the aerosols collected in Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Potter, H. J.; Kasaba, T.

    2015-12-01

    Organics in the atmospheric aerosols occupy 20 to 70% of the total mass. Since the proportion of organics is so large that it's important to understand their detailed characteristics. Polymeric compounds called HUmic-Like Substance (HULIS) are known to be present in the atmospheric aerosols. Biomass burning can be a source of HULIS. In this study, atmospheric aerosols were collected at Cape Hedo, a northern tip of Okinawa Island, and we characterized overall features of the organics collected in different seasons. In Okinawa, continental air mass prevails in spring, fall and winter, while maritime air mass from Pacific Ocean prevails in summer. Thus, it is relatively straightforward to identify sources of organics in different seasons. We measured total organic carbon (TOC) and water soluble organic carbon (WSOC) concentrations, and absorbance and fluorescence intensity for the aerosol samples collected during Nov 2012 and July 2014 (n=90). As a result, TOC and WSOC showed almost the same trend, higher concentrations when continental air mass prevailed in fall and winter, while lower concentrations in summer. Percentages of WSOC in TOC accounted for 33-44%. Absorption efficiency, absorbance per 1 ppm organic carbon concentration, of the samples showed higher values in winter and fall, and lower values in summer. Fluorescence efficiency, normalized fluorescence with quinine sulfate per 1 ppm organic carbon concentration, were also different, it is likely that different types of organics were present in the aerosols from different seasons. We are also planning to measure HULIS in the aerosols and will be discussed a link between their contribution and trans-boundary air pollution in Asia.

  12. Concentrations and sources of organic carbon aerosols in the free troposphere over North America

    NASA Astrophysics Data System (ADS)

    Heald, Colette L.; Jacob, Daniel J.; Turquety, SolèNe; Hudman, Rynda C.; Weber, Rodney J.; Sullivan, Amy P.; Peltier, Richard E.; Atlas, Eliot L.; de Gouw, Joost A.; Warneke, Carsten; Holloway, John S.; Neuman, J. Andrew; Flocke, Frank M.; Seinfeld, John H.

    2006-12-01

    Aircraft measurements of water-soluble organic carbon (WSOC) aerosol over NE North America during summer 2004 (ITCT-2K4) are simulated with a global chemical transport model (GEOS-Chem) to test our understanding of the sources of organic carbon (OC) aerosol in the free troposphere (FT). Elevated concentrations were observed in plumes from boreal fires in Alaska and Canada. WSOC aerosol concentrations outside of these plumes average 0.9 ± 0.9 μg C m-3 in the FT (2-6 km). The corresponding model value is 0.7 ± 0.6 μg C m-3, including 42% from biomass burning, 36% from biogenic secondary organic aerosol (SOA), and 22% from anthropogenic emissions. Previous OC aerosol observations over the NW Pacific in spring 2001 (ACE-Asia) averaged 3.3 ± 2.8 μg C m-3 in the FT, compared to a model value of 0.3 ± 0.3 μg C m-3. WSOC aerosol concentrations in the boundary layer (BL) during ITCT-2K4 are consistent with OC aerosol observed at the IMPROVE surface network. The model is low in the boundary layer by 30%, which we attribute to secondary formation at a rate comparable to primary anthropogenic emission. Observed WSOC aerosol concentrations decrease by a factor of 2 from the BL to the FT, as compared to a factor of 10 decrease for sulfate, indicating that most of the WSOC aerosol in the FT originates in situ. Despite reproducing mean observed WSOC concentrations in the FT to within 25%, the model cannot account for the variance in the observations (R = 0.21). Covariance analysis of FT WSOC aerosol with other measured chemical variables suggests an aqueous-phase mechanism for SOA generation involving biogenic precursors.

  13. Role of Black Carbon and Absorbing Organic Carbon Aerosols in Surface Dimming Trends

    NASA Astrophysics Data System (ADS)

    Feng, Y.; Ramanathan, V.; Kotamarthi, V. R.

    2010-12-01

    Solar radiation reaching at the Earth’s surface plays an essential role in driving both atmosphere hydrological and land/ocean biogeochemical processes. Measurements have shown significant decreases in surface solar radiation (dimming) in many regions since 1960s. At least half of the observed dimming could be linked to the direct radiative effect of anthropogenic aerosols, especially absorbing aerosols like black carbon (BC) due to their strong atmospheric absorption. However, previous model-data comparisons indicate that absorption by aerosols is commonly and significantly underestimated in current GCM simulations by several factors over regions. Using a global chemical transport model coupled with a radiative transfer model, we include a treatment for absorbing organic carbons (OC) from bio-fuel and open biomass burnings in optical calculations and estimate aerosol radiative forcings for two anthropogenic aerosol emission scenarios representative of 1975 and 2000. Assumptions about aerosol mixing and the OC absorption spectrum are examined by comparing simulated atmospheric heating against aircraft optical and radiation measurements. The calculated aerosol single scattering albedo distribution (0.93+/-0.044) is generally comparable to the AERONET data (0.93+/-0.030) for year 2001, with best agreements in Europe and N. America, while overestimated in E. Asia and underestimated in the S. American biomass burning areas. On a global scale, inclusion of absorbing OC enhances the absorption in the atmosphere by 11% for July. The estimated aerosol direct radiative forcing at TOA (-0.24 W/m2) is similar to the average value of the AeroCom models based on the same 2000 emissions, but significantly enhanced negatively at surface by about 53% (-1.56 W/m2) and the atmosphere absorption is increased by +61% (+1.32 W/m2). About 87% of the estimated atmosphere absorption and 42% of the surface dimming is contributed by BC. Between 1975 and 2000, the calculated all-sky flux

  14. In-situ measurement of aerosol organic and elemental carbon, Southern California Air Quality Study. Final report

    SciTech Connect

    Turpin, B.J.; Huntzicker, J.J.

    1989-09-09

    An in situ carbon analyzer measured particulate organic and elemental carbon with two hour time resolution during the Southern California Air Quality Study. Organic and elemental carbon concentrations showed strong diurnal variations. Peak concentrations occurred during the daylight hours in the summer and at night in the fall. The maximum concentrations observed in the fall (maximum total carbon = 88 micrograms carbon per cubic meter) were two to three times higher than the summer maxima (maximum total carbon = 36 micrograms carbon per cubic meter). On several summer days the profiles of organic and elemental carbon were quite similar, and good correlations, comparable to those observed during the fall, were observed between organic and elemental carbon, suggesting that the organic aerosol on those days was principally primary. Comparison of the diurnal profile of organic carbon with those of elemental carbon and ozone provided evidence for considerable secondary formation of organic aerosol during three sampling periods.

  15. Size-resolved parameterization of primary organic carbon in fresh marine aerosols

    SciTech Connect

    Long, Michael S; Keene, William C; Erickson III, David J

    2009-12-01

    Marine aerosols produced by the bursting of artificially generated bubbles in natural seawater are highly enriched (2 to 3 orders of magnitude based on bulk composition) in marine-derived organic carbon (OC). Production of size-resolved particulate OC was parameterized based on a Langmuir kinetics-type association of OC to bubble plumes in seawater and resulting aerosol as constrained by measurements of aerosol produced from highly productive and oligotrophic seawater. This novel approach is the first to account for the influence of adsorption on the size-resolved association between marine aerosols and OC. Production fluxes were simulated globally with an eight aerosol-size-bin version of the NCAR Community Atmosphere Model (CAM v3.5.07). Simulated number and inorganic sea-salt mass production fell within the range of published estimates based on observationally constrained parameterizations. Because the parameterization does not consider contributions from spume drops, the simulated global mass flux (1.5 x 10{sup 3} Tg y{sup -1}) is near the lower limit of published estimates. The simulated production of aerosol number (2.1 x 10{sup 6} cm{sup -2} s{sup -1}) and OC (49 Tg C y{sup -1}) fall near the upper limits of published estimates and suggest that primary marine aerosols may have greater influences on the physiochemical evolution of the troposphere, radiative transfer and climate, and associated feedbacks on the surface ocean than suggested by previous model studies.

  16. Seasonal and diurnal variations of black carbon and organic carbon aerosols in Bangkok

    NASA Astrophysics Data System (ADS)

    Sahu, L. K.; Kondo, Y.; Miyazaki, Y.; Pongkiatkul, Prapat; Kim Oanh, N. T.

    2011-08-01

    Measurements of black carbon (BC) and organic carbon (OC) were conducted in Bangkok during 2007-2008. Annual trends of BC and OC show strong seasonality with lower and higher concentrations during wet and dry seasons, respectively. Flow of cleaner air, wet removal, and negligible biomass burning resulted in the lowest concentrations of aerosols in the wet season. In addition to anthropogenic sources, long-range transport and biomass burning caused higher concentrations in the dry and hot seasons, respectively. Despite extensive biomass burning in the hot season, moderate levels of aerosols were due to the mixing with air masses from the Pacific Ocean. Diurnal distributions exhibit peaks during rush hour marked by minima in the OC/BC ratio and stagnant wind flow. The lowest concentrations in the afternoon hours could be due to deeper planetary boundary layer and reduced traffic. Overall, the concentrations of both BC and OC decrease with the increase in wind speed. The weekend effects, due to reduced emission during weekends, in the concentrations of both BC and OC were significant. Therefore, stricter abatement in vehicular emissions could substantially reduce pollution. A slope of ΔBC/ΔCO of 9.8 ngm-3 ppbv-1 for the wet season represents the emission ratio from vehicular sources. The highest of ΔOC/ΔBC (3 μg μg-1) in the hot season was due to the predominant influence of biomass burning and significant formation of secondary OC. The levels of BC and OC in Bangkok fall within the ranges of their concentrations measured in the major cities of East Asia.

  17. Dual carbon isotope characterization of total organic carbon in wintertime carbonaceous aerosols from northern India

    NASA Astrophysics Data System (ADS)

    Bikkina, Srinivas; Andersson, August; Sarin, M. M.; Sheesley, R. J.; Kirillova, E.; Rengarajan, R.; Sudheer, A. K.; Ram, K.; Gustafsson, Örjan

    2016-05-01

    Large-scale emissions of carbonaceous aerosols (CA) from South Asia impact both regional climate and air quality, yet their sources are not well constrained. Here we use source-diagnostic stable and radiocarbon isotopes (δ13C and Δ14C) to characterize CA sources at a semiurban site (Hisar: 29.2°N, 75.2°E) in the NW Indo-Gangetic Plain (IGP) and a remote high-altitude location in the Himalayan foothills (Manora Peak: 29.4°N, 79.5°E, 1950 m above sea level) in northern India during winter. The Δ14C of total aerosol organic carbon (TOC) varied from -178‰ to -63‰ at Hisar and from -198‰ to -1‰ at Manora Peak. The absence of significant differences in the 14C-based fraction biomass of TOC between Hisar (0.81 ± 0.03) and Manora Peak (0.82 ± 0.07) reveals that biomass burning/biogenic emissions (BBEs) are the dominant sources of CA at both sites. Combining this information with δ13C, other chemical tracers (K+/OC and SO42-/EC) and air mass back trajectory analyses indicate similar source regions in the IGP (e.g., Punjab and Haryana). These results highlight that CA from BBEs in the IGP are not only confined to the atmospheric boundary layer but also extend to higher elevations of the troposphere, where the synoptic-scale circulations could substantially influence their abundances both to the Himalayas and over the downwind oceanic regions such as the Indian Ocean. Given the vast emissions of CA from postharvest crop residue combustion practices in the IGP during early Northeast Monsoon, this information is important for both improved process and model understanding of climate and health effects, as well as in guiding policy decision aiming at reducing emissions.

  18. Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples.

    PubMed

    El-Zanan, Hazem S; Lowenthal, Douglas H; Zielinska, Barbara; Chow, Judith C; Kumar, Naresh

    2005-07-01

    The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.

  19. Radiocarbon source apportionment of urban and wildfire black and organic carbon aerosols

    NASA Astrophysics Data System (ADS)

    Mouteva, G.; Fahrni, S. M.; Santos, G.; Randerson, J. T.; Czimczik, C. I.

    2013-12-01

    Fossil and non-fossil sources of black carbon (BC) and organic carbon (OC) in carbonaceous aerosols can be quantified unambiguously by radiocarbon (14C) measurements. However, accurate 14C-based source apportionment requires a clear and reproducible physical separation of OC and BC, as well as minimal sample contaminations with non-sample carbon. To achieve a clear separation, we used a thermo-optical aerosol analyzer (Sunset Laboratory Inc, USA) with a newly established protocol (Swiss_4S protocol, Zhang et al., 2012), specifically optimized to completely separate the OC and BC fractions with minimal charring and maximum BC recovery. A simple and efficient vacuum line was coupled to the analyzer to trap produced CO2 with high yields and low carbon blanks. Upon trapping, CO2 samples sealed into glass ampoules were converted to graphite and measured for their radiocarbon content at the Keck Carbon Cycle Accelerator Mass Spectrometry Laboratory at the University of California, Irvine. Here, we present the results from the radiocarbon analysis of a set of 14C reference materials, blanks and inter-comparison samples for both OC and BC with sample sizes as small as 5 μg C. We will also present initial results from a set of urban aerosol samples from Salt Lake City, collected throughout 2012 and 2013, and from interior Alaska, collected during the summer of 2013 near the Stuart Creek 2 wildfire.

  20. Elemental and organic carbon in aerosols over urbanized coastal region (southern Baltic Sea, Gdynia).

    PubMed

    Lewandowska, Anita; Falkowska, Lucyna; Murawiec, Dominika; Pryputniewicz, Dorota; Burska, Dorota; Bełdowska, Magdalena

    2010-09-15

    Studies on PM 10, total particulate matter (TSP), elemental carbon (EC) and organic carbon (OC) concentrations were carried out in the Polish coastal zone of the Baltic Sea, in urbanized Gdynia. The interaction between the land, the air and the sea was clearly observed. The highest concentrations of PM 10, TSP and both carbon fractions were noted in the air masses moving from southern and western Poland and Europe. The EC was generally of primary origin and its contribution to TSP and PM 10 mass was on average 2.3% and 3.7% respectively. Under low wind speed conditions local sources (traffic and industry) influenced increases in elemental carbon and PM 10 concentrations in Gdynia. Elemental carbon demonstrated a pronounced weekly cycle, yielding minimum values at the weekend and maximum values on Thursdays. The role of harbors and ship yards in creating high EC concentrations was clearly observed. Concentration of organic carbon was ten times higher than that of elemental carbon, and the average OC contribution to PM 10 mass was very high (31.6%). An inverse situation was observed when air masses were transported from over the Atlantic Ocean, the North Sea and the Baltic Sea. These clean air masses were characterized by the lowest concentrations of all analysed compounds. Obtained results for organic and elemental carbon fluxes showed that atmospheric aerosols can be treated, along with water run-off, as a carbon source for the coastal waters of the Baltic Sea. The enrichment of surface water was more effective in the case of organic carbon (0.27+/-0.19 mmol m(-2) d(-1)). Elemental carbon fluxes were one order of magnitude smaller, on average 0.03+/-0.04 mmol m(-2) d(-1). We suggest that in some situations atmospheric carbon input can explain up to 18% of total carbon fluxes into the Baltic coastal waters.

  1. Stable isotopes measurements reveal dual carbon pools contributing to organic matter enrichment in marine aerosol

    PubMed Central

    Ceburnis, Darius; Masalaite, Agne; Ovadnevaite, Jurgita; Garbaras, Andrius; Remeikis, Vidmantas; Maenhaut, Willy; Claeys, Magda; Sciare, Jean; Baisnée, Dominique; O’Dowd, Colin D.

    2016-01-01

    Stable carbon isotope ratios in marine aerosol collected over the Southern Indian Ocean revealed δ13C values ranging from −20.0‰ to −28.2‰. The isotope ratios exhibited a strong correlation with the fractional organic matter (OM) enrichment in sea spray aerosol. The base-level isotope ratio of −20.0‰ is characteristic of an aged Dissolved Organic Matter (DOM) pool contributing a relatively homogeneous background level of DOM to oceanic waters. The range of isotope ratios, extending down to −28.2‰, is characteristic of more variable, stronger, and fresher Particulate Organic Matter (POM) pool driven by trophic level interactions. We present a conceptual dual-pool POM-DOM model which comprises a ‘young’ and variable POM pool which dominates enrichment in sea-spray and an ‘aged’ but invariant DOM pool which is, ultimately, an aged end-product of processed ‘fresh’ POM. This model is harmonious with the preferential enrichment of fresh colloidal and nano-gel lipid-like particulate matter in sea spray particles and the observed depleted δ13C ratio resulting from isotope equilibrium fractionation coupled with enhanced plankton photosynthesis in cold water (−2 °C to +8 °C). These results re-assert the hypothesis that OM enrichment in sea-spray is directly linked to primary production and, consequently, can have implications for climate-aerosol-cloud feedback systems. PMID:27819297

  2. Stable isotopes measurements reveal dual carbon pools contributing to organic matter enrichment in marine aerosol

    NASA Astrophysics Data System (ADS)

    Ceburnis, Darius; Masalaite, Agne; Ovadnevaite, Jurgita; Garbaras, Andrius; Remeikis, Vidmantas; Maenhaut, Willy; Claeys, Magda; Sciare, Jean; Baisnée, Dominique; O’Dowd, Colin D.

    2016-11-01

    Stable carbon isotope ratios in marine aerosol collected over the Southern Indian Ocean revealed δ13C values ranging from ‑20.0‰ to ‑28.2‰. The isotope ratios exhibited a strong correlation with the fractional organic matter (OM) enrichment in sea spray aerosol. The base-level isotope ratio of ‑20.0‰ is characteristic of an aged Dissolved Organic Matter (DOM) pool contributing a relatively homogeneous background level of DOM to oceanic waters. The range of isotope ratios, extending down to ‑28.2‰, is characteristic of more variable, stronger, and fresher Particulate Organic Matter (POM) pool driven by trophic level interactions. We present a conceptual dual-pool POM-DOM model which comprises a ‘young’ and variable POM pool which dominates enrichment in sea-spray and an ‘aged’ but invariant DOM pool which is, ultimately, an aged end-product of processed ‘fresh’ POM. This model is harmonious with the preferential enrichment of fresh colloidal and nano-gel lipid-like particulate matter in sea spray particles and the observed depleted δ13C ratio resulting from isotope equilibrium fractionation coupled with enhanced plankton photosynthesis in cold water (‑2 °C to +8 °C). These results re-assert the hypothesis that OM enrichment in sea-spray is directly linked to primary production and, consequently, can have implications for climate-aerosol-cloud feedback systems.

  3. Temporal variations in sources and concentrations of black and organic carbon aerosols in the LA Basin

    NASA Astrophysics Data System (ADS)

    Mouteva, G.; Kearney, J.; Fahrni, S.; Santos, G. M.; Czimczik, C. I.

    2012-12-01

    Temporal variations in sources and concentrations of black and organic carbon aerosols in the LA Basin Black carbon (BC), derived from incomplete combustion of fossil and biogenic fuels and vegetation fires, is a crucial component of the aerosol pool, but sources as well as atmospheric transport and lifetime remain poorly constrained by measurements. We characterized the composition of carbonaceous aerosols emitted from urban areas by quantifying the temporal variations in the concentrations and sources of BC and organic carbon (OC) in PM-10 and PM-2.5 from two locations in the Los Angeles basin. Using the radiocarbon signatures in BC and OC allowed us to apportion emissions into fossil and modern contributions. We separated and quantified BC and OC using a modified Sunset OC-EC analyzer coupled to a vacuum line and cryogenically trapped the evolving CO2 (Zhang et al. In Prep.). The instrument and method were tested with well-defined radiocarbon standards to determine background, accuracy and precision. The purified CO2 was converted to graphite and measured at the Keck-AMS facility on unknown samples as small as ≥5 μg C. Preliminary results suggest that radiocarbon content can be used to apportion BC into fossil and modern sources. BC concentrations are on the order of 6-31% total carbon, with 48 to 96% fossil contribution. In the OC fraction we detected several super-modern samples, suggesting local production of radiocarbon, e.g. from medical waste incinerators. Thus, the radiocarbon-based approach cannot be used to quantify sources of OC and bulk carbonaceous aerosols in urban areas. Our measurements contribute to a comprehensive quantification of temporal and spatial variations in urban BC, a key uncertainty in constraining BC sources and transport in North America. References: Zhang YL, Perron N, Zotter P, Minguillón MC, Wacker L, Prévôt ASH, Baltensperger U, Szidat S. In Prep. On the isolation of OC and EC and the optimal strategy of radiocarbon

  4. Water-soluble organic carbon (WSOC) and its temperature-resolved carbon fractions in atmospheric aerosols in Beijing

    NASA Astrophysics Data System (ADS)

    Tang, Xiong; Zhang, Xiaoshan; Wang, Zhangwei; Ci, Zhijia

    2016-11-01

    Investigation of temperature-resolved carbon fractions of water-soluble organic carbon (WSOC) can improve our understanding of the chemical properties, formation processes and sources of WSOC in aerosols. We developed a method that can examine different temperature-resolved carbon fractions of WSOC and used this method to characterize aerosol samples (n = 102) collected from an urban site in Beijing in 2010-2011. The aerosol composition data including inorganic ions, elements and temperature-resolved carbon fractions of WSOC were used as input of positive matrix factorization (PMF) model to investigate the sources of WSOC. The results showed that the mean concentrations of WSOC were 10.2 μg m- 3 with increased values in winter and decreased values in summer, while WSOC/OC ratios (mean: 51.7%) were higher in spring and summer than in fall and winter. The sampling artifacts of WSOC (18.2%) were higher than those of OC (13.4%). Though WSOC was significantly influenced by biomass burning in spring and winter, the strong correlations between WSOC and other secondary components suggested that WSOC was secondary in nature. Results of temperature-resolved carbon fractions of OC and WSOC showed that WSOC/OC ratios for different carbon fractions had the highest value of 0.92 and lowest value of 0.30. PMF analysis identified four factors, three of which were associated with three organic polar compounds groups (low, medium, and high molecular weight compounds) based on their thermal evolution features, and one of which was attributed to inorganic secondary formation processes. Annually, the contributions of four factors were 20.5%, 46.2%, 12.4% and 20.9%, respectively.

  5. Stable carbon isotopic compositions of total carbon, dicarboxylic acids and glyoxylic acid in the tropical Indian aerosols: Implications for sources and photochemical processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.; Tachibana, Eri

    2011-09-01

    The tropical Indian aerosols (PM10) collected on day- and nighttime bases in winter and summer, 2007 from Chennai (13.04°N; 80.17°E) were studied for stable carbon isotopic compositions (δ13C) of total carbon (TC), individual dicarboxylic acids (C2-C9) and glyoxylic acid (ωC2). δ13C values of TC ranged from -23.9‰ to -25.9‰ (-25.0 ± 0.6‰; n = 49). Oxalic (C2) (-17.1 ± 2.5‰), malonic (C3) (-20.8 ± 1.8‰), succinic (C4) (-22.5 ± 1.5‰) and adipic (C6) (-20.6 ± 4.1‰) acids and ωC2 acid (-22.4 ± 5.5‰) were found to be more enriched with 13C compared to TC. In contrast, suberic (C8) (-29.4 ± 1.8‰), phthalic (Ph) (-30.1 ± 3.5‰) and azelaic (C9) (-28.4 ± 5.8‰) acids showed smaller δ13C values than TC. Based on comparisons of δ13C values of TC in Chennai aerosols to those (-24.7 ± 2.2‰) found in unburned cow-dung samples collected from Chennai and isotopic signatures of the particles emitted from point sources, we found that biofuel/biomass burning are the major sources of carbonaceous aerosols in South and Southeast Asia. The decrease in δ13C values of C9 diacid by about 5‰ from winter to summer suggests that tropical plant emissions also significantly contribute to organic aerosol in this region. Significant increase in δ13C values from C4 to C2 diacids in Chennai aerosols could be attributed for their photochemical processing in the tropical atmosphere during long-range transport from source regions.

  6. Carbonyl sulfide as an inverse tracer for biogenic organic carbon in gas and aerosol phases

    NASA Astrophysics Data System (ADS)

    de Gouw, J. A.; Warneke, C.; Montzka, S. A.; Holloway, J. S.; Parrish, D. D.; Fehsenfeld, F. C.; Atlas, E. L.; Weber, R. J.; Flocke, F. M.

    2009-03-01

    Carbonyl sulfide (COS) is a long-lived trace gas in the atmosphere with an oceanic source and a surface sink through the uptake by vegetation and soils. We demonstrate the use of COS as an inverse tracer for the impact of biogenic emissions on an air mass including the formation of secondary organic aerosol (SOA). Using airborne data from the summer of 2004 over the northeastern U.S., we find that air masses with reduced COS in the continental boundary layer had on average higher mixing ratios of biogenic VOCs (isoprene, monoterpenes, methanol) and their photo-oxidation products (methacrolein, methyl vinyl ketone, methyl furan and MPAN, a peroxyacyl nitrate derived from isoprene). Measurements of water-soluble organic carbon were only weakly correlated with COS, indicating that SOA formation from biogenic precursors was a small contribution to the total.

  7. Organic and Elemental Carbon Aerosol Particulates at the Southern Great Plains Site Field Campaign Report

    SciTech Connect

    Cary, Robert

    2016-04-01

    The purpose of this study was to measure the organic carbon (OC) and elemental carbon (EC) fractions of PM2.5 particulate matter at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) sampling site for a 6-month period during the summer of 2013. The site is in a rural location remote from any populated areas, so it would be expected to reflect carbon concentration over long-distance transport patterns. During the same period in 2012, a number of prairie fires in Oklahoma and Texas had produced large plumes of smoke particles, but OC and EC particles had not been quantified. In addition, during the summer months, other wild fires, such as forest fires in the Rocky Mountain states and other areas, can produce carbon aerosols that are transported over long distances. Both of these source types would be expected to contain mixtures of both OC and EC.

  8. Effects of surface-active organic matter on carbon dioxide nucleation in atmospheric wet aerosols: a molecular dynamics study.

    PubMed

    Daskalakis, Vangelis; Charalambous, Fevronia; Panagiotou, Fostira; Nearchou, Irene

    2014-11-21

    Organic matter (OM) uptake in cloud droplets produces water-soluble secondary organic aerosols (SOA) via aqueous chemistry. These play a significant role in aerosol properties. We report the effects of OM uptake in wet aerosols, in terms of the dissolved-to-gas carbon dioxide nucleation using molecular dynamics (MD) simulations. Carbon dioxide has been implicated in the natural rainwater as well as seawater acidity. Variability of the cloud and raindrop pH is assumed in space and time, as regional emissions, local human activities and geophysical characteristics differ. Rain scavenging of inorganic SOx, NOx and NH3 plays a major role in rain acidity in terms of acid-base activity, however carbon dioxide solubility also remains a key parameter. Based on the MD simulations we propose that the presence of surface-active OM promotes the dissolved-to-gas carbon dioxide nucleation in wet aerosols, even at low temperatures, strongly decreasing carbon dioxide solubility. A discussion is made on the role of OM in controlling the pH of a cloud or raindrop, as a consequence, without involving OM ionization equilibrium. The results are compared with experimental and computational studies in the literature.

  9. Reactivity of liquid and semisolid secondary organic carbon with chloride and nitrate in atmospheric aerosols

    SciTech Connect

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

    2015-05-14

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

  10. Sources and light absorption of water-soluble organic carbon aerosols in the outflow from northern China

    NASA Astrophysics Data System (ADS)

    Kirillova, E. N.; Andersson, A.; Han, J.; Lee, M.; Gustafsson, Ö.

    2014-02-01

    High loadings of anthropogenic carbonaceous aerosols in Chinese air influence the air quality for over one billion people and impact the regional climate. A large fraction (17-80%) of this aerosol carbon is water-soluble, promoting cloud formation and thus climate cooling. Recent findings, however, suggest that water-soluble carbonaceous aerosols also absorb sunlight, bringing additional direct and indirect climate warming effects, yet the extent and nature of light absorption by this water-soluble "brown carbon" and its relation to sources is poorly understood. Here, we combine source estimates constrained by dual carbon isotopes with light-absorption measurements of water-soluble organic carbon (WSOC) for a March 2011 campaign at the Korea Climate Observatory at Gosan (KCOG), a receptor station in SE Yellow Sea for the outflow from northern China. The mass absorption cross section at 365 nm (MAC365) of WSOC for air masses from N. China were in general higher (0.8-1.1 m2 g-1), than from other source regions (0.3-0.8 m2 g-1). However, this effect corresponds to only 2-10% of the radiative forcing caused by light absorption by elemental carbon. Radiocarbon constraints show that the WSOC in Chinese outflow had significantly higher fraction fossil sources (30-50%) compared to previous findings in S. Asia, N. America and Europe. Stable carbon (δ13C) measurements were consistent with aging during long-range air mass transport for this large fraction of carbonaceous aerosols.

  11. Polar and non-polar organic aerosols from large-scale agricultural-waste burning emissions in Northern India: Implications to organic mass-to-organic carbon ratio.

    PubMed

    Rajput, Prashant; Sarin, M M

    2014-05-01

    This study focuses on characteristics of organic aerosols (polar and non-polar) and total organic mass-to-organic carbon ratio (OM/OC) from post-harvest agricultural-waste (paddy- and wheat-residue) burning emissions in Northern India. Aerosol samples from an upwind location (Patiala: 30.2°N, 76.3°E) in the Indo-Gangetic Plain were analyzed for non-polar and polar fractions of organic carbon (OC1 and OC2) and their respective mass (OM1 and OM2). On average, polar organic aerosols (OM2) contribute nearly 85% of the total organic mass (OM) from the paddy- and wheat-residue burning emissions. The water-soluble-OC (WSOC) to OC2 ratio, within the analytical uncertainty, is close to 1 from both paddy- and wheat-residue burning emissions. However, temporal variability and relatively low WSOC/OC2 ratio (Av: 0.67±0.06) is attributed to high moisture content and poor combustion efficiency during paddy-residue burning, indicating significant contribution (∼30%) of aromatic carbon to OC2. The OM/OC ratio for non-polar (OM1/OC1∼1.2) and polar organic aerosols (OM2/OC2∼2.2), hitherto unknown for open agricultural-waste burning emissions, is documented in this study. The total OM/OC ratio is nearly identical, 1.9±0.2 and 1.8±0.2, from paddy- and wheat-residue burning emissions.

  12. Organic carbon in the sea surface microlayer and in submicron aerosol particles - measurements from the Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    van Pinxteren, Manuela; Wadinga Fomba, Kanneh; Müller, Konrad; Barthel, Stefan; von Tümpling, Wolf; Herrmann, Hartmut

    2016-04-01

    The export of organic compounds from the oceans can establish a considerable carbon flux in the Earth system. The detailed transport processes and especially the impact of environmental drivers in the organic carbon transfer are not yet fully understood. Here we present a broad study of measured dissolved organic carbon (DOC) and particulate organic carbon (POC) concentrations and enrichment in the sea surface microlayer (SML) as well as equivalent measurements in marine aerosol particles. For the first time, enrichment factors of organic carbon in marine ambient aerosol are reported that based on concerted measurements of seawater and aerosol particles. The measurements were conducted at different field campaigns in the Atlantic Ocean: at the Cape Verde islands, during two Atlantic transects with the RV Polarstern, and during a campaign at the Raune Fjord in Bergen, Norway. In oceanic water, concentration of DOC were in average 161 μmol/L in bulk water and 225 μmol/L in the SML. Average POC concentrations were 13 μmol/L in bulk water and 17 μmol/L in the SML. Instead of a constant enrichment of DOC or POC there are rather two pattern: high enrichment in samples with low concentrations and low enrichment when concentration were high. In seawater (bulk water and SML) small, mostly insignificant effects, concerning concentration and enrichment of DOC and POC were found regarding the impact of wind stress and chl-a concentrations. Differences between SML and bulk water concentrations are more pronounced at times of high chl-a, but all in all these effects are not strong. The thickness of the SML is affected by biological activity but probably caused by a more surface-active part of the DOC/POC pool and this is not reflected in the sum parameters. In the ambient marine aerosol particles water-soluble organic carbon (WSOC) and water-insoluble organic carbon (WISOC) concentrations were in average about 0.2 μg m-3, respectively. Higher concentration differences of

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  14. Natural abundance 13C and 14C analysis of water-soluble organic carbon in atmospheric aerosols.

    PubMed

    Kirillova, Elena N; Sheesley, Rebecca J; Andersson, August; Gustafsson, Örjan

    2010-10-01

    Water-soluble organic carbon (WSOC) constitutes a large fraction of climate-forcing organic aerosols in the atmosphere, yet the sources of WSOC are poorly constrained. A method was developed to measure the stable carbon isotope (δ(13)C) and radiocarbon (Δ(14)C) composition of WSOC for apportionment between fossil fuel and different biogenic sources. Synthetic WSOC test substances and ambient aerosols were employed to investigate the effect of both modern and fossil carbon contamination and any method-induced isotope fractionation. The method includes extraction of aerosols collected on quartz filters followed by purification and preparation for off-line δ(13)C and Δ(14)C determination. The preparative freeze-drying step for isotope analysis yielded recoveries of only ∼70% for ambient aerosols and WSOC probes. However, the δ(13)C of the WSOC isolates were in agreement with the δ(13)C of the unprocessed starting material, even for the volatile oxalic acid probe (6.59 ± 0.37‰ vs 6.33 ± 0.31‰; 2 sd). A (14)C-fossil phthalic acid WSOC probe returned a fraction modern biomass of <0.008 whereas a (14)C-modern sucrose standard yielded a fraction modern of >0.999, indicating the Δ(14)C-WSOC method to be free of both fossil and contemporary carbon contamination. Application of the δ(13)C/Δ(14)C-WSOC method to source apportion climate-affecting aerosols was illustrated be constraining that WSOC in ambient Stockholm aerosols were 88% of contemporary biogenic C3 plant origin.

  15. Contribution of methane to aerosol carbon mass

    NASA Astrophysics Data System (ADS)

    Bianchi, F.; Barmet, P.; Stirnweis, L.; El Haddad, I.; Platt, S. M.; Saurer, M.; Lötscher, C.; Siegwolf, R.; Bigi, A.; Hoyle, C. R.; DeCarlo, P. F.; Slowik, J. G.; Prévôt, A. S. H.; Baltensperger, U.; Dommen, J.

    2016-09-01

    Small volatile organic compounds (VOC) such as methane (CH4) have long been considered non-relevant to aerosol formation due to the high volatility of their oxidation products. However, even low aerosol yields from CH4, the most abundant VOC in the atmosphere, would contribute significantly to the total particulate carbon budget. In this study, organic aerosol (OA) mass yields from CH4 oxidation were evaluated at the Paul Scherrer Institute (PSI) smog chamber in the presence of inorganic and organic seed aerosols. Using labeled 13C methane, we could detect its oxidation products in the aerosol phase, with yields up to 0.09

  16. Predicting ambient aerosol Thermal Optical Reflectance (TOR) measurements from infrared spectra: organic carbon

    NASA Astrophysics Data System (ADS)

    Dillner, A. M.; Takahama, S.

    2014-11-01

    Organic carbon (OC) can constitute 50% or more of the mass of atmospheric particulate matter. Typically, the organic carbon concentration is measured using thermal methods such as Thermal-Optical Reflectance (TOR) from quartz fiber filters. Here, methods are presented whereby Fourier Transform Infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE or Teflon) filters are used to accurately predict TOR OC. Transmittance FT-IR analysis is rapid, inexpensive, and non-destructive to the PTFE filters. To develop and test the method, FT-IR absorbance spectra are obtained from 794 samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites sampled during 2011. Partial least squares regression is used to calibrate sample FT-IR absorbance spectra to artifact-corrected TOR OC. The FTIR spectra are divided into calibration and test sets by sampling site and date which leads to precise and accurate OC predictions by FT-IR as indicated by high coefficient of determination (R2; 0.96), low bias (0.02 μg m-3, all μg m-3 values based on the nominal IMPROVE sample volume of 32.8 m-3), low error (0.08 μg m-3) and low normalized error (11%). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision and accuracy to collocated TOR measurements. FT-IR spectra are also divided into calibration and test sets by OC mass and by OM / OC which reflects the organic composition of the particulate matter and is obtained from organic functional group composition; this division also leads to precise and accurate OC predictions. Low OC concentrations have higher bias and normalized error due to TOR analytical errors and artifact correction errors, not due to the range of OC mass of the samples in the calibration set. However, samples with low OC mass can be used to predict samples with high OC mass indicating that the

  17. Predicting ambient aerosol thermal-optical reflectance (TOR) measurements from infrared spectra: organic carbon

    NASA Astrophysics Data System (ADS)

    Dillner, A. M.; Takahama, S.

    2015-03-01

    Organic carbon (OC) can constitute 50% or more of the mass of atmospheric particulate matter. Typically, organic carbon is measured from a quartz fiber filter that has been exposed to a volume of ambient air and analyzed using thermal methods such as thermal-optical reflectance (TOR). Here, methods are presented that show the feasibility of using Fourier transform infrared (FT-IR) absorbance spectra from polytetrafluoroethylene (PTFE or Teflon) filters to accurately predict TOR OC. This work marks an initial step in proposing a method that can reduce the operating costs of large air quality monitoring networks with an inexpensive, non-destructive analysis technique using routinely collected PTFE filter samples which, in addition to OC concentrations, can concurrently provide information regarding the composition of organic aerosol. This feasibility study suggests that the minimum detection limit and errors (or uncertainty) of FT-IR predictions are on par with TOR OC such that evaluation of long-term trends and epidemiological studies would not be significantly impacted. To develop and test the method, FT-IR absorbance spectra are obtained from 794 samples from seven Interagency Monitoring of PROtected Visual Environment (IMPROVE) sites collected during 2011. Partial least-squares regression is used to calibrate sample FT-IR absorbance spectra to TOR OC. The FTIR spectra are divided into calibration and test sets by sampling site and date. The calibration produces precise and accurate TOR OC predictions of the test set samples by FT-IR as indicated by high coefficient of variation (R2; 0.96), low bias (0.02 μg m-3, the nominal IMPROVE sample volume is 32.8 m3), low error (0.08 μg m-3) and low normalized error (11%). These performance metrics can be achieved with various degrees of spectral pretreatment (e.g., including or excluding substrate contributions to the absorbances) and are comparable in precision to collocated TOR measurements. FT-IR spectra are also

  18. Laboratory Measurements of the Effect of Sulfuric and Organic Acid Coatings on the Optical Properties of Carbon Soot Aerosols

    NASA Astrophysics Data System (ADS)

    Xue, H.; Khalizov, A.; Zhang, R.

    2008-12-01

    Aerosol particles perturb the Earth-atmosphere radiative balance through scattering and absorption of the solar energy. Soot or black carbon, produced during combustion of fossil fuels and biofuels, is the major component responsible for light absorption by aerosol particles. The variation in the reported mass-specific absorption cross-sections (MAC) of fresh soot and increased light absorption by aged soot aerosols internally mixed with non-absorbing materials are the major factors leading to large uncertainties in the evaluation of the aerosol optical effects. We have investigated the optical properties of submicron carbon soot aerosols during simulated atmospheric processing with sulfuric acid and dicarboxylic organic acids. Internally mixed soot particles with known size, morphology, and the mixing state were produced by exposing the size-classified, flame-generated soot to sulfuric acid and organic acid vapor. Light extinction and scattering by fresh and internally mixed soot were measured at 532 nm wavelength using a cavity ring-down spectrometer and an integrating nephelometer, respectively; light absorption was derived as the difference between extinction and scattering. Mass-specific absorption cross-sections for fresh and internally mixed soot aggregates were calculated using the measured effective densities of soot cores. The optical properties of fresh soot were independent of the relative humidity (RH). Internally mixed soot exhibited significant enhancement in light absorption and scattering, increasing with the mass fraction of the coating material and RH. Sulfuric acid was found to cause greater enhancement in soot optical properties than organic acids. The higher absorption and scattering resulted in the increased single scattering albedo of coated soot aerosol. The measurements indicate that the irreversible restructuring of soot aggregates to more compact globules is a major contributor to the enhanced optical properties of internally mixed soot.

  19. On the gas-particle partitioning of soluble organic aerosol in two urban atmospheres with contrasting emissions: 1. Bulk water-soluble organic carbon

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaolu; Liu, Jiumeng; Parker, Eric T.; Hayes, Patrick L.; Jimenez, Jose L.; de Gouw, Joost A.; Flynn, James H.; Grossberg, Nicole; Lefer, Barry L.; Weber, Rodney J.

    2012-09-01

    The partitioning of semi-volatile compounds between the gas and particle phase influences the mass, size and chemical composition of the secondary organic aerosols (SOA) formed. Here we investigate the partitioning of water-soluble organic carbon (WSOC) and the formation of SOA in Los Angeles (LA), California and Atlanta, Georgia; urban regions where anthropogenic volatile organic compound (VOC) emissions are dominated by vehicles, but are contrasted by an additional large source of biogenic VOCs exclusive to Atlanta. In Atlanta, evidence for WSOC partitioning to aerosol water is observed throughout the day, but is most prevalent in the morning. During drier periods (RH < 70%), the WSOC partitioning coefficient (Fp) was in proportion to the organic mass, suggesting that both particle water and organic aerosol (OA) can serve as an absorbing phase. In contrast, despite the higher average RH, in LA the aerosol water was not an important absorbing phase, instead, Fp was correlated with OA mass. Particle water concentrations from thermodynamic predictions based on measured inorganic aerosol components do not indicate significant differences in aerosol hygroscopicity. The observed different WSOC partitioning behaviors may be attributed to the contrasting VOC mixture between the two cities. In addition, different OA composition may also play a role, as Atlanta OA is expected to have a substantially more aged regional character. These results are consistent with our companion studies that find similar partitioning differences for formic acid and additional contrasts in SOA optical properties. The findings provide direct evidence for SOA formation through an equilibrium partitioning process.

  20. On the gas-particle partitioning of soluble organic aerosol in two urban atmospheres with contrasting emissions: 1. Bulk water-soluble organic carbon

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaolu; Liu, Jiumeng; Parker, Eric T.; Hayes, Patrick L.; Jimenez, Jose L.; Gouw, Joost A.; Flynn, James H.; Grossberg, Nicole; Lefer, Barry L.; Weber, Rodney J.

    2011-11-01

    The partitioning of semi-volatile compounds between the gas and particle phase influences the mass, size and chemical composition of the secondary organic aerosols (SOA) formed. Here we investigate the partitioning of water-soluble organic carbon (WSOC) and the formation of SOA in Los Angeles (LA), California and Atlanta, Georgia; urban regions where anthropogenic volatile organic compound (VOC) emissions are dominated by vehicles, but are contrasted by an additional large source of biogenic VOCs exclusive to Atlanta. In Atlanta, evidence for WSOC partitioning to aerosol water is observed throughout the day, but is most prevalent in the morning. During drier periods (RH < 70%), the WSOC partitioning coefficient (Fp) was in proportion to the organic mass, suggesting that both particle water and organic aerosol (OA) can serve as an absorbing phase. In contrast, despite the higher average RH, in LA the aerosol water was not an important absorbing phase, instead, Fp was correlated with OA mass. Particle water concentrations from thermodynamic predictions based on measured inorganic aerosol components do not indicate significant differences in aerosol hygroscopicity. The observed different WSOC partitioning behaviors may be attributed to the contrasting VOC mixture between the two cities. In addition, different OA composition may also play a role, as Atlanta OA is expected to have a substantially more aged regional character. These results are consistent with our companion studies that find similar partitioning differences for formic acid and additional contrasts in SOA optical properties. The findings provide direct evidence for SOA formation through an equilibrium partitioning process.

  1. Fossil and Nonfossil Sources of Organic and Elemental Carbon Aerosols in the Outflow from Northeast China.

    PubMed

    Zhang, Yan-Lin; Kawamura, Kimitaka; Agrios, Konstantinos; Lee, Meehye; Salazar, Gary; Szidat, Sönke

    2016-06-21

    Source quantification of carbonaceous aerosols in the Chinese outflow regions still remains uncertain despite their high mass concentrations. Here, we unambiguously quantified fossil and nonfossil contributions to elemental carbon (EC) and organic carbon (OC) of total suspended particles (TSP) from a regional receptor site in the outflow of Northeast China using radiocarbon measurement. OC and EC concentrations were lower in summer, representing mainly marine air, than in other seasons, when air masses mostly traveled over continental regions in Mongolia and northeast China. The annual-mean contribution from fossil-fuel combustion to EC was 76 ± 11% (0.1-1.3 μg m(-3)). The remaining 24 ± 11% (0.03-0.42 μg m(-3)) was attributed to biomass burning, with slightly higher contribution in the cold period (∼31%) compared to the warm period (∼21%) because of enhanced emissions from regional biomass combustion sources in China. OC was generally dominated by nonfossil sources, with an annual average of 66 ± 11% (0.5-2.8 μg m(-3)), approximately half of which was apportioned to primary biomass-burning sources (34 ± 6%). In winter, OC almost equally originated from primary OC (POC) emissions and secondary OC (SOC) formation from fossil fuel and biomass-burning sources. In contrast, summertime OC was dominated by primary biogenic emissions as well as secondary production from biogenic and biomass-burning sources, but fossil-derived SOC was the smallest contributor. Distinction of POC and SOC was performed using primary POC-to-EC emission ratios separated for fossil and nonfossil emissions.

  2. Black carbon surface oxidation and organic composition of beech-wood soot aerosols

    NASA Astrophysics Data System (ADS)

    Corbin, J. C.; Lohmann, U.; Sierau, B.; Keller, A.; Burtscher, H.; Mensah, A. A.

    2015-10-01

    Soot particles are the most strongly light-absorbing particles commonly found in the atmosphere. They are major contributors to the radiative budget of the Earth and to the toxicity of atmospheric pollution. Atmospheric aging of soot may change its health- and climate-relevant properties by oxidizing the primary black carbon (BC) or organic particulate matter (OM) which, together with ash, comprise soot. This atmospheric aging, which entails the condensation of secondary particulate matter as well as the oxidation of the primary OM and BC emissions, is currently poorly understood. In this study, atmospheric aging of wood-stove soot aerosols was simulated in a continuous-flow reactor. The composition of fresh and aged soot particles was measured in real time by a dual-vaporizer aerosol-particle mass spectrometer (SP-AMS). The dual-vaporizer SP-AMS provided information on the OM and BC components of the soot as well as on refractory components internally mixed with BC. By switching the SP-AMS laser vaporizer off and using only the AMS thermal vaporizer (at 600 °C), information on the OM component only was obtained. In both modes, OM appeared to be generated largely by cellulose and/or hemicellulose pyrolysis and was only present in large amounts when new wood was added to the stove. In SP-AMS mode, BC signals otherwise dominated the mass spectrum. These signals consisted of ions related to refractory BC (rBC, C1-5+), oxygenated carbonaceous ions (CO1-2+), potassium (K+), and water (H2O+ and related fragments). The C4+ : C3+ ratio, but not the C1+ : C3+ ratio, was consistent with the BC-structure trends of Corbin et al. (2015c). The CO1-2+ signals likely originated from BC surface groups: upon aging, both CO+ and CO2+ increased relative to C1-3+ while CO2+ simultaneously increased relative to CO+. Factor analysis (positive matrix factorization) of SP-AMS and AMS data, using a modified error model to address peak-integration uncertainties, indicated that the surface

  3. A new approach for the fractionation of water-soluble organic carbon in atmospheric aerosols and cloud drops

    NASA Astrophysics Data System (ADS)

    Andracchio, Antonella; Cavicchi, Catia; Tonelli, Domenica; Zappoli, Sergio

    A novel approach is described for the fractionation of water-soluble organic carbon (WSOC) in atmospheric aerosols and cloud drops. The method is based on the preliminary adsorption of the sample, acidified at pH 2, on a polymeric styrene-divinylbenzene resin (XAD-2) and subsequent elution with a series of solvents, which leads to the fractionation of the sample into three classes of compounds. The method was set up using synthetic mixtures of organic compounds and then applied to selected samples of atmospheric aerosols and cloud drops. All samples and collected fractions were analysed using size exclusion chromatography (SEC). This method proved particularly useful both in providing information on the organic content of the samples and for the characterisation of the macromolecular compounds (MMCs) in the samples. Synthetic samples were prepared using humic, fulvic and tannic acid to simulate naturally occurring MMCs. In the first fraction, eluted with HCl, only the most soluble organic compounds (oxalic acid, formic acid and acetic acid) were collected. In the second fraction, eluted with methanol, the major part of the organic material was collected together with the more hydrophilic constituents of the humic substances. In the third fraction, it was possible to separately recover the more hydrophobic component of the humic substances. A large number of atmospheric samples (fog, aerosol, cloud) were then analysed using SEC. Most of these samples evidenced a noteworthy chromatogram at 254 nm. Moreover, the chromatographic area evidenced a clear linear correlation with the total organic carbon (TOC) values. The fractionation method on XAD-2 was finally applied to selected atmospheric samples, yielding three classes of organic compounds. In each sample, a non-negligible amount of compounds with dimensional and chemical properties similar to humic substances were collected in the third fraction. The carbon content in this latter fraction was estimated both by TOC

  4. Influence of sample composition on aerosol organic and black carbon determinations

    SciTech Connect

    Novakov, T.; Corrigan, C.E.

    1995-07-01

    In this paper we present results on characterization of filter-collected redwood (Sequoia sempevirens)-needle and eucalyptus smoke particles by thermal, optical, and solvent extraction methods. Our results demonstrate that organic and black carbon concentrations determined by thermal and optical methods are not only method dependent, but also critically influenced by the overall chemical composition of the samples. These conclusions are supported by the following: (1) the organic fraction of biomass smoke particles analyzed includes a component, ranging in concentration from about 6-20% of total carbon or from 16-30% of organic carbon, that is relatively non-volatile and has a combustion temperature close to that of black carbon; (2) presence of K or Na in biomass smoke samples lowers the combustion temperatures of this organic component and of black carbon, making their combustion properties indistinguishable; (3) about 20% of total organic material is nonvolatile when heated to 550{degrees}C in an inert atmosphere. Consequently, thermal methods that rely on a specific temperature to separate organic from black carbon may either underestimate or overestimate the black and organic carbon concentrations, depending on the amounts of Na and K and on the composition and concentration of organic material present in a sample. These analytical uncertainties and, under some conditions, absorption by organic material may contribute to the variability of empirically derived proportionality between light transmission through filter deposits and black carbon concentrations.

  5. PRIMARY AND SECONDARY ORGANIC AEROSOLS OVER THE UNITED STATES: ESTIMATES ON THE BASIS OF OBSERVED ORGANIC CARBON (OC) AND ELEMENTAL CARBON (EC), AND AIR QUALITY MODELED PRIMARY (OC/EC) RATIOS

    EPA Science Inventory

    The temporal and spatial distributions of primary and secondary organic carbon aerosols (OC) over the continental US during June 15 to August 31, 1999, were estimated by using observational OC and elemental carbon (EC) data from Interagency Monitoring of Protected Visual Environm...

  6. Water-soluble organic carbon, dicarboxylic acids, ketoacids, and α-dicarbonyls in the tropical Indian aerosols

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka; Swaminathan, T.

    2010-06-01

    Tropical aerosol (PM10) samples (n = 49) collected from southeast coast of India were studied for water-soluble dicarboxylic acids (C2-C12), ketocarboxylic acids (C2-C9), and α-dicarbonyls (glyoxal and methylglyoxal), together with analyses of total carbon (TC) and water-soluble organic carbon (WSOC). Their distributions were characterized by a predominance of oxalic acid followed by terephthalic (t-Ph), malonic, and succinic acids. Total concentrations of diacids (227-1030 ng m-3), ketoacids (16-105 ng m-3), and dicarbonyls (4-23 ng m-3) are comparative to those from other Asian megacities such as Tokyo and Hong Kong. t-Ph acid was found as the second most abundant diacid in the Chennai aerosols. This feature has not been reported previously in atmospheric aerosols. t-Ph acid is most likely derived from the field burning of plastics. Water-soluble diacids were found to contribute 0.4%-3% of TC and 4%-11% of WSOC. Based on molecular distributions and backward air mass trajectories, we found that diacids and related compounds in coastal South Indian aerosols are influenced by South Asian and Indian Ocean monsoons. Organic aerosols are also suggested to be significantly transported long distances from North India and the Middle East in early winter and from Southeast Asia in late winter, but some originate from photochemical reactions over the Bay of Bengal. In contrast, the Arabian Sea, Indian Ocean, and South Indian continent are suggested as major source regions in summer. We also found daytime maxima of most diacids, except for C9 and t-Ph acids, which showed nighttime maxima in summer. Emissions from marine and terrestrial plants, combined with land/sea breezes and in situ photochemical oxidation, are suggested especially in summer as an important factor that controls the composition of water-soluble organic aerosols over the southeast coast of India. Regional emissions from anthropogenic sources are also important in megacity Chennai, but their influence is

  7. Quality assurance and quality control for thermal/optical analysis of aerosol samples for organic and elemental carbon.

    PubMed

    Chow, Judith C; Watson, John G; Robles, Jerome; Wang, Xiaoliang; Chen, L-W Antony; Trimble, Dana L; Kohl, Steven D; Tropp, Richard J; Fung, Kochy K

    2011-12-01

    Accurate, precise, and valid organic and elemental carbon (OC and EC, respectively) measurements require more effort than the routine analysis of ambient aerosol and source samples. This paper documents the quality assurance (QA) and quality control (QC) procedures that should be implemented to ensure consistency of OC and EC measurements. Prior to field sampling, the appropriate filter substrate must be selected and tested for sampling effectiveness. Unexposed filters are pre-fired to remove contaminants and acceptance tested. After sampling, filters must be stored in the laboratory in clean, labeled containers under refrigeration (<4 °C) to minimize loss of semi-volatile OC. QA activities include participation in laboratory accreditation programs, external system audits, and interlaboratory comparisons. For thermal/optical carbon analyses, periodic QC tests include calibration of the flame ionization detector with different types of carbon standards, thermogram inspection, replicate analyses, quantification of trace oxygen concentrations (<100 ppmv) in the helium atmosphere, and calibration of the sample temperature sensor. These established QA/QC procedures are applicable to aerosol sampling and analysis for carbon and other chemical components.

  8. Identification of absorbing organic (brown carbon) aerosols through Sun Photometry: results from AEROCAN / AERONET stations in high Arctic and urban Locations

    NASA Astrophysics Data System (ADS)

    Kerr, G. H.; Chaubey, J. P.; O'Neill, N. T.; Hayes, P.; Atkinson, D. B.

    2014-12-01

    Light absorbing organic aerosols or brown carbon (BrC) aerosols are prominent species influencing the absorbing aerosol optical depth (AAOD) of the total aerosol optical depth (AOD) in the UV wavelength region. They, along with dust, play an important role in modifying the spectral AAOD and the spectral AOD in the UV region: this property can be used to discriminate BrC aerosols from both weakly absorbing aerosols such as sulfates as well as strongly absorbing aerosols such as black carbon (BC). In this study we use available AERONET inversions (level 1.5) retrieved for the measuring period from 2009 to 2013, for the Arctic region (Eureka, Barrow and Hornsund), Urban/ Industrial regions (Kanpur, Beijing), and the forest regions (Alta Foresta and Mongu), to identify BrC aerosols. Using Dubovik's inversion algorithm results, we analyzed parameters that were sensitive to BrC presence, notably AAOD, AAODBrC estimated using the approach of Arola et al. [2011], the fine-mode-aerosol absorption derivative (αf, abs) and the fine-mode-aerosol absorption 2nd derivative (αf, abs'), all computed at a near UV wavelength (440 nm). Temporal trends of these parameters were investigated for all test stations and compared to available volume sampling surface data as a means of validating / evaluating the sensitivity of ostensible sunphotometer indicators of BrC aerosols to the presence of BrC as measured using independent indicators. Reference: Arola, A., Schuster, G., Myhre, G., Kazadzis, S., Dey, S., and Tripathi, S. N.: Inferring absorbing organic carbon content from AERONET data, Atmos. Chem. Phys., 11, 215-225, doi:10.5194/acp-11-215-2011, 2011

  9. Development of a preparation system for the radiocarbon analysis of organic carbon in carbonaceous aerosols in China

    NASA Astrophysics Data System (ADS)

    Zhang, Y. L.; Liu, D.; Shen, C. D.; Ding, P.; Zhang, G.

    2010-09-01

    Carbonaceous aerosols comprising a large fraction of elemental carbon (EC) and organic carbon (OC) are considered to affect both global climate and human health. Radiocarbon measurements have been proved to be a useful isotopic tracer for distinguishing contemporary and fossil emissions. An optimized system of a two-step thermal preparation system for radiocarbon ( 14C) measurement of OC/TC is firstly established in China. In this system, OC/TC are converted into carbon dioxide under a pure oxygen flow at 340 °C/650 °C and then reduced to graphite for AMS target using the method of zinc reduction. Afterwards, radiocarbon measurements of the targets performed by the NEC Compact AMS System at the Institute of Heavy Ion Physics, Peking University. The measured results for estimated reference martial including HOx I, HOx II and IAEA-C6 are consistent with internationally accepted values. The radiocarbon-based source appointment of carbonaceous aerosols in China would be much more convenient and faster with the preparation system developed in this work.

  10. Influence and efficiency of catalytic stripper in organic carbon removal from laboratory generated soot aerosols

    EPA Science Inventory

    A catalytic stripper (CS) is a device used to remove the semi-volatile, typically organic carbon, fraction by passing raw or diluted exhaust over an oxidation catalyst heated to 300˚C. The oxidation catalyst used in this study is a commercially available diesel oxidation ca...

  11. Historical emissions of black and organic carbon aerosol from energy-related combustion, 1850-2000 - article no. GB2018

    SciTech Connect

    Bond, T.C.; Bhardwaj, E.; Dong, R.; Jogani, R.; Jung, S.K.; Roden, C.; Streets, D.G.; Trautmann, N.M.

    2007-05-15

    We present an emission inventory of primary black carbon (BC) and primary organic carbon (OC) aerosols from fossil fuel and biofuel combustion between 1850 and 2000. We reconstruct fossil fuel consumption and represent changes in technology on a national and sectoral basis. Our estimates rely on new estimates of biofuel consumption, and updated emission factors for old technologies. Emissions of black carbon increase almost linearly, totaling about 1000 Gg in 1850, 2200 Gg in 1900, 3000 Gg in 1950, and 4400 Gg in 2000. Primary organic carbon shows a similar pattern, with emissions of 4100 Gg, 5800 Gg, 6700 Gg, and 8700 Gg in 1850, 1900, 1950, and 2000, respectively. Biofuel is responsible for over half of BC emission until about 1890, and dominates energy-related primary OC emission throughout the entire period. Coal contributes the greatest fraction of BC emission between 1880 and 1975, and is overtaken by emissions from biofuel around 1975, and by diesel engines around 1990. Previous work suggests a rapid rise in BC emissions between 1950 and 2000. This work supports a more gradual increase between 1950 and 2000, similar to the increase between 1850 and 1925; implementation of clean technology is a primary reason.

  12. Hygroscopic growth of water soluble organic carbon isolated from atmospheric aerosol collected at US national parks and Storm Peak Laboratory

    NASA Astrophysics Data System (ADS)

    Taylor, Nathan F.; Collins, Don R.; Lowenthal, Douglas H.; McCubbin, Ian B.; Gannet Hallar, A.; Samburova, Vera; Zielinska, Barbara; Kumar, Naresh; Mazzoleni, Lynn R.

    2017-02-01

    Due to the atmospheric abundance and chemical complexity of water soluble organic carbon (WSOC), its contribution to the hydration behavior of atmospheric aerosol is both significant and difficult to assess. For the present study, the hygroscopicity and CCN activity of isolated atmospheric WSOC particulate matter was measured without the compounding effects of common, soluble inorganic aerosol constituents. WSOC was extracted with high purity water from daily high-volume PM2.5 filter samples and separated from water soluble inorganic constituents using solid-phase extraction. The WSOC filter extracts were concentrated and combined to provide sufficient mass for continuous generation of the WSOC-only aerosol over the combined measurement time of the tandem differential mobility analyzer and coupled scanning mobility particle sizer-CCN counter used for the analysis. Aerosol samples were taken at Great Smoky Mountains National Park during the summer of 2006 and fall-winter of 2007-2008; Mount Rainier National Park during the summer of 2009; Storm Peak Laboratory (SPL) near Steamboat Springs, Colorado, during the summer of 2010; and Acadia National Park during the summer of 2011. Across all sampling locations and seasons, the hygroscopic growth of WSOC samples at 90 % RH, expressed in terms of the hygroscopicity parameter, κ, ranged from 0.05 to 0.15. Comparisons between the hygroscopicity of WSOC and that of samples containing all soluble materials extracted from the filters implied a significant modification of the hydration behavior of inorganic components, including decreased hysteresis separating efflorescence and deliquescence and enhanced water uptake between 30 and 70 % RH.

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  14. Emission and Chemistry of Organic Carbon in the Gas and Aerosol Phase at a Sub-Urban Site Near Mexico City in March 2006 During the MILAGRO Study

    SciTech Connect

    de Gouw, Joost A.; Welsh-Bon, Daniel; Warneke, Carsten; Kuster, W. C.; Alexander, M. L.; Baker, Angela K.; Beyersdorf, Andreas J.; Blake, D. R.; Canagaratna, Manjula R.; Celada, A. T.; Huey, L. G.; Junkermann, W.; Onasch, Timothy B.; Salcido, A.; Sjostedt, S. J.; Sullivan, Amy; Tanner, David J.; Vargas-Ortiz, Leroy; Weber, R. J.; Worsnop, Douglas R.; Yu, Xiao-Ying; Zaveri, Rahul A.

    2009-05-28

    Volatile organic compounds (VOCs) and carbonaceous aerosol were measured at a sub-urban site near Mexico City in March of 2006 during the MILAGRO study (Megacity Initiative: Local and Global Research Objectives). Diurnal variations of hydrocarbons, elemental carbon (EC) and hydrocarbon-like organic aerosol (HOA) were dominated by a high peak in the early morning when local emissions accumulated in a shallow boundary layer, and a minimum in the afternoon when the emissions were diluted in a significantly expanded boundary layer and, in case of the reactive gases, removed by OH. In comparison, diurnal variations of species with secondary sources such as the aldehydes, ketones, oxygenated organic aerosol (OOA) and water-soluble organic carbon (WSOC) stayed relatively high in the afternoon indicating strong photochemical formation. Emission ratios of many hydrocarbon species relative to CO were higher in Mexico City than in the U.S., but we found similar emission ratios for most oxygenated VOCs and organic aerosol. Secondary formation of acetone may be more efficient in Mexico City than in the U.S., due to higher emissions of alkane precursors from the use of liquefied petroleum gas. Secondary formation of organic aerosol was similar between Mexico City and the U.S. Combining the data for all measured gas and aerosol species, we describe the budget of total observed organic carbon (TOOC), and find that the enhancement ratio of TOOC relative to CO is conserved between the early morning and mid afternoon despite large compositional changes. Finally, the influence of biomass burning is investigated using the measurements of acetonitrile, which was found to correlate with levoglucosan in the particle phase. Diurnal variations of acetonitrile indicate a contribution from local burning sources. Scatter plots of acetonitrile versus CO suggest that the contribution of biomass burning to the enhancement of most gas and aerosol species was not dominant and perhaps not dissimilar

  15. Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley

    PubMed Central

    Chalbot, M.-C. G.; Brown, J.; Chitranshi, P.; da Costa, G. Gamboa; Pollock, E. D.; Kavouras, I. G.

    2016-01-01

    The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5 % of particle mass for particles with δp > 0.96 μm and 10 % of particle mass for particles with δp < 0.96 μm. Non-exchangeable aliphatic (H–C), unsaturated aliphatic (H–C–C=), oxygenated saturated aliphatic (H–C–O), acetalic (O–CH–O) and aromatic (Ar–H) protons were determined by proton nuclear magnetic resonance (1H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m−3 for particles with 1.5 < δp < 3.0 μm to 73.9 ± 12.3 nmol m−3 for particles with δp < 0.49 μm. The molar H/C ratios varied from 0.48 ± 0.05 to 0.92 ± 0.09, which were comparable to those observed for combustion-related organic aerosol. The R–H was the most abundant group, representing about 45 % of measured total non-exchangeable organic hydrogen concentrations, followed by H–C–O (27 %) and H–C–C= (26 %). Levoglucosan, amines, ammonium and methanesulfonate were identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from −26.81 ± 0.18 ‰ for the smallest particles to

  16. Semicontinuous measurements of organic carbon and acidity during the Pittsburgh air quality study: implications for acid-catalyzed organic aerosol formation

    SciTech Connect

    S. Takahama; C.I. Davidson; S.N. Pandis

    2006-04-01

    Laboratory evidence suggests that inorganic acid seed particles may increase secondary organic aerosol yields secondary organic aerosol (SOA) through heterogeneous chemistry. Additional laboratory studies, however, report that organic acidity generated in the same photochemical process by which SOA is formed may be sufficient to catalyze these heterogeneous reactions. Understanding the interaction between inorganic acidity and SOA mass is important when evaluating emission controls to meet PM2.5 regulations. Semicontinuous measurements of organic carbon (OC), elemental carbon (EC), and inorganic species from the Pittsburgh Air Quality Study were examined to determine if coupling in the variations of inorganic acidity and OC could be detected. Significant enhancements of SOA production could not be detected due to inorganic acidity in Western Pennsylvania most of the time, but its signal might have been lost in the noise. If a causal relationship between inorganic acidity and OC is assumed, reductions in OC for Western Pennsylvania that might result from drastic reductions in inorganic acidity were estimated to be 2 {+-} 4% by a regression technique, and an upper bound for this geographic area was estimated to be 5 {+-} 8% based on calculations from laboratory measurements. 48 refs., 7 figs., 3 tabs.

  17. SECONDARY ORGANIC CARBON AND AEROSOL YIELDS FROM THE IRRADIATIONS OF ISOPRENE AND á-PINENE IN THE PRESENCE OF NO X AND SO 2

    EPA Science Inventory

    A laboratory study was carried out to investigate the secondary organic carbon (SOC) yields of a-pinene and isoprene in the presence of SO2, which produces acidic aerosol in the system. Experiments were based on irradiating each hydrocarbon (HC) with NOx in ...

  18. Effect of the secondary organic aerosol coatings on black carbon water uptake, cloud condensation nuclei activity, and particle collapse

    EPA Science Inventory

    The ability of black carbon aerosols to absorb water and act as a cloud condensation nuclei (CCN) directly controls their lifetime in the atmosphere as well as their impact on cloud formation, thus impacting the earth’s climate. Black carbon emitted from most combustion pro...

  19. Secondary formation of water-soluble organic acids and α-dicarbonyls and their contributions to total carbon and water-soluble organic carbon: Photochemical aging of organic aerosols in the Arctic spring

    NASA Astrophysics Data System (ADS)

    Kawamura, Kimitaka; Kasukabe, Hideki; Barrie, Leonard A.

    2010-11-01

    Water-soluble dicarboxylic acids (C2-C12), ketocarboxylic acids (C2-C6, C9), and α-dicarbonyls (glyoxal and methylglyoxal) were determined in the Arctic aerosols collected in winter to early summer, as well as aerosol total carbon (TC) and water-soluble organic carbon (WSOC). Concentrations of TC and WSOC gradually decreased from late February to early June with a peak in spring, indicating a photochemical formation of water-soluble organic aerosols at a polar sunrise. We found that total (C2-C11) diacids (7-84 ng m-3) increased at polar sunrise by a factor of 4 and then decreased toward summer. Their contributions to TC (average 4.0%) peaked in early April and mid-May. The contribution of total diacids to WSOC was on average 7.1%. It gradually increased from February (5%) to a maximum in April (12.7%) with a second peak in mid-May (10.4%). Although oxalic acid (C2) is the dominant diacid until April, its predominance was replaced by succinic acid (C4) after polar sunrise. This may indicate that photochemical production of C2 was overwhelmed by its degradation when solar radiation was intensified and the atmospheric transport of its precursors from midlatitudes to the Arctic was ended in May. Interestingly, the contributions of azelaic (C9) and ω-oxobutanoic acids to WSOC increased in early summer possibly due to an enhanced emission of biogenic unsaturated fatty acids from the ocean followed by photochemical oxidation in the atmosphere. An enhanced contribution of diacids to TC and WSOC at polar sunrise may significantly alter the hygroscopic properties of organic aerosols in the Arctic.

  20. Dicarboxylic acids and water-soluble organic carbon in aerosols in New Delhi, India, in winter: Characteristics and formation processes

    NASA Astrophysics Data System (ADS)

    Miyazaki, Yuzo; Aggarwal, Shankar G.; Singh, Khem; Gupta, Prabhat K.; Kawamura, Kimitaka

    2009-10-01

    Day- and nighttime aerosol samples were collected at an urban site in New Delhi, India, in winter 2006-2007. They were studied for low molecular weight dicarboxylic acids and related compounds, as well as total water-soluble organic carbon (TWSOC). High concentrations of diacids (up to 6.03 μg m-3), TWSOC, and OC were obtained, which are substantially higher than those previously observed at other urban sites in Asia. Daytime TWSOC/OC ratio (37%) was on average higher than that in nighttime (25%). In particular, more water-soluble OC (M-WSOC) to TWSOC ratio in daytime (50%) was twice higher than in nighttime (27%), suggesting that aerosols in New Delhi are photochemically more processed in daytime to result in more water-soluble organic compounds. Oxalic acid (C2) was found as the most abundant dicarboxylic acid, followed by succinic (C4) and malonic (C3) acids. Contributions of C2 to M-WSOC were greater (av. 8%) in nighttime than daytime (av. 3%). Positive correlations of C2 with malic acid (hC4), glyoxylic acid (ωC2), and relative humidity suggest that secondary production of C2 probably in aqueous phase is important in nighttime via the oxidation of both longer-chain diacids and ωC2. C2 also showed a positive correlation with potassium (K+) in nighttime, suggesting that the enhanced C2 concentrations are associated with biomass/biofuel burning. More tight, positive correlation between less water-soluble OC (L-WSOC) and K+ was found in both day- and nighttime, suggesting that L-WSOC, characterized by longer chain and/or higher molecular weight compounds, is significantly influenced by primary emissions from biomass/biofuel burning.

  1. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    PubMed

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-05

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  2. Use of levoglucosan, potassium, and water-soluble organic carbon to characterize the origins of biomass-burning aerosols

    NASA Astrophysics Data System (ADS)

    Urban, Roberta Cerasi; Lima-Souza, Michele; Caetano-Silva, Letícia; Queiroz, Maria Eugênia C.; Nogueira, Raquel F. P.; Allen, Andrew G.; Cardoso, Arnaldo A.; Held, Gerhard; Campos, Maria Lucia A. M.

    2012-12-01

    Three chemical species related to biomass burning, levoglucosan, potassium and water-soluble organic carbon (WSOC), were measured in aerosol samples collected in a rural area on the outskirts of the municipality of Ourinhos (São Paulo State, Brazil). This region is representative of the rural interior of the State, where the economy is based on agro-industrial production, and the most important crop is sugar cane. The manual harvesting process requires that the cane be first burned to remove excess foliage, leading to large emissions of particulate materials to the atmosphere. Most of the levoglucosan (68-89%) was present in small particles (<1.5 μm), and its concentration in total aerosol ranged from 25 to 1186 ng m-3. The highest values were found at night, when most of the biomass burning occurs. In contrast, WSOC showed no diurnal pattern, with an average concentration of 5.38 ± 2.97 μg m-3 (n = 27). A significant linear correlation between levoglucosan and WSOC (r = 0.54; n = 26; p < 0.0001) confirmed that biomass burning was in fact an important source of WSOC in the study region. A moderate (but significant) linear correlation between levoglucosan and potassium concentrations (r = 0.62; n = 40; p < 0.0001) was indicative of the influence of other sources of potassium in the study region, such as soil resuspension and fertilizers. When only the fine particles (<1.5 μm; typical of biomass burning) were considered, the linear coefficient increased to 0.91 (n = 9). In this case, the average levoglucosan/K+ ratio was 0.24, which may be typical of biomass burning in the study region. This ratio is about 5 times lower than that previously found for Amazon aerosol collected during the day, when flaming combustion prevails. This suggests that the levoglucosan/K+ ratio may be especially helpful for characterization of the type of vegetation burned (such as crops or forest), when biomass-burning is the dominant source of potassium. The relatively high

  3. Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols

    SciTech Connect

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

    2012-07-02

    The applicability of high resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in organic aerosols was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of secondary organic aerosol (SOA) were analyzed and corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of organic aerosols was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both (+) and (-) modes. A correlation was found between the ratio of the ionization efficiencies in the positive and negative ESI modes with the octanol-water partition constant, and more importantly, with the compound's O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (-) data for SOA produced by oxidation of limonene and isoprene and compared to online O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS methods is comparable to that of the AMS, with the added benefit of molecular identification of the aerosol constituents.

  4. 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.

  5. Spatial and seasonal variations of fine particle water-soluble organic carbon (WSOC) over the Southeastern United States: implications for secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Liu, Z.; Hecobian, A.; Zheng, M.; Frank, N. H.; Edgerton, E. S.; Weber, R. J.

    2012-04-01

    Secondary organic aerosol (SOA) in the Southeastern US is investigated by analyzing the spatial-temporal distribution of water-soluble organic carbon (WSOC) and other PM2.5 components from 900 archived 24 h Teflon filters collected at 15 urban or rural EPA Federal Reference Method (FRM) network sites throughout 2007. Online measurements of WSOC at an urban/rural-paired site in Georgia in the summer of 2008 are contrasted to the filter data. Based on FRM filters, excluding biomass-burning events (levoglucosan < 50 ng m-3), WSOC and sulfate were highly correlated with PM2.5 mass and both comprised a large mass fraction of PM2.5 (13% and 35%, respectively). Sulfate and WSOC both tracked ambient temperature throughout the year, suggesting the temperature effects were mainly on the photochemical processes that lead to secondary formation. FRM WSOC, and to a lesser extent sulfate, were spatially homogeneous throughout the region, yet WSOC was moderately enhanced (27%) in locations of greater predicted isoprene emissions in summer. A Positive Matrix Factorization (PMF) analysis identified two major source types for the summer WSOC; 22% of the WSOC were associated with ammonium sulfate, and 56% of the WSOC was associated with brown carbon and oxalate. A small urban excess of FRM WSOC (10%) was observed in the summer of 2007, however, comparisons of online WSOC measurements at one urban/rural pair (Atlanta/Yorkville) in August 2008 showed substantially greater difference in WSOC (31%) relative to the FRM data, suggesting a low bias for urban filters. The measured Atlanta urban excess, combined with the estimated boundary layer heights, gave an estimated Atlanta daily WSOC production rate in August of 0.55 mg C m-2 h-1 between mid-morning and mid-afternoon. This study characterizes the regional nature of fine particles in the Southeastern US, confirming the importance of secondary organic aerosol and the roles of both biogenic and anthropogenic emissions.

  6. A field measurement based scaling approach for quantification of major ions, organic carbon, and elemental carbon using a single particle aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Zhou, Yang; Huang, X. H. Hilda; Griffith, Stephen M.; Li, Mei; Li, Lei; Zhou, Zhen; Wu, Cheng; Meng, Junwang; Chan, Chak K.; Louie, Peter K. K.; Yu, Jian Zhen

    2016-10-01

    Single Particle Aerosol Mass Spectrometers (SPAMS) have been increasingly deployed for aerosol studies in Asia. To date, SPAMS is most often used to provide unscaled information for both the size and chemical composition of individual particles. The instrument's lack of accuracy is primarily due to only a fraction of particles being detected after collection, and the instrumental sensitivity is un-calibrated for various chemical species in mixed ambient aerosols. During a campaign from January to April 2013 at a coastal site in Hong Kong, the particle number information and ion intensity of major PM2.5 components collected by SPAMS were scaled by comparing with collocated bulk PM2.5 measurements of hourly or higher resolution. The bulk measurements include PM2.5 mass by a SHARP 5030 Monitor, major ions by a Monitor for Aerosols & Gases in ambient Air (MARGA), and organic carbon (OC) and elemental carbon (EC) by a Sunset OCEC analyzer. During the data processing, both transmission efficiency (scaled with the Scanning Mobility Particle Sizer) and hit efficiency conversion were considered, and component ion intensities quantified as peak area (PA) and relative peak area (RPA) were analyzed to track the performance. The comparison between the scaled particle mass assuming a particle density of 1.9 g cm-3 from SPAMS and PM2.5 concentration showed good correlation (R2 = 0.81) with a slope of 0.814 ± 0.004. Regression analysis results suggest an improved scaling performance using RPA compared with PA for most of the major PM2.5 components, including sulfate, nitrate, potassium, ammonium, OC and EC. Thus, we recommend preferentially scaling these species using the RPA. For periods of high K+ concentrations (>1.5 μg m-3), under-estimation of K+ by SPAMS was observed due to exceeding the dynamic range of the acquisition board. When only applying the hit efficiency correction, data for sulfate, nitrate, ammonium, potassium and OC were in reasonably good correlation (R2 = 0

  7. [Aerosol size distribution of organic carbon and elemental carbon on the top of coke oven and in the plant area].

    PubMed

    Liu, Xiao-Feng; Peng, Lin; Bai, Hui-Ling; Mu, Ling; Song, Chong-Fang

    2013-08-01

    In order to investigate the characteristic of organic carbon (OC) and elemental carbon (EC) in particles on the top of coke oven and in the plant area, the particle matter samples of five size fraction including < or = 1.4 microm, 1.4-2.1 microm, 2.1-4.2 microm, 4.2-10.2 microm and > or = 10.2 microm were collected using Staplex234 cascade impactor, and OC and EC were analyzed by Elementar Analysensysteme GmbH vario EL cube. The mass concentrations of OC and EC associated with TSP on the top of coke oven were 291.6 microg x m(-3) and 255.1 microg x m(-3), while those in the plant area were 377.8 microg x m(-3) and 151.7 microg x m(-3). The mass concentration of secondary organic carbon (SOC) in particles with size of < or = 1.4 microm was 147.3 microg x m(-3) in the plant area. The value of OC/EC in particles less than 2.1 microm was 1.3 on the top of coke oven. The mass concentration of EC in TSP in the plant area was lower than that on the top of coke oven, while the mass concentration of OC in the plant area was significantly higher than that on the top of coke oven. The mass concentrations of OC and EC associated with particles less than 10.2 microm in the plant area were far higher than those in the atmosphere of area where the coke plant is located. The OC and EC in particles, which were collected both on the top of coke oven and in the plant area, were mainly enriched in fine particles. The size distribution of OC showed a clear distinction between the coke oven top and the plant area, which revealed that OC in the plant area was more preferably enriched in fine particles than that on the top of coke oven, and the same size distribution of EC was found on the top of coke oven and in the plant area. In the plant area, the mass concentration of SOC and the contribution of SOC to OC increased with the decreasing diameter in particles with diameter of less than 10.2 microm.

  8. Black carbon aerosol dynamics and isotopic composition in Alaska linked with boreal fire emissions and depth of burn in organic soils

    NASA Astrophysics Data System (ADS)

    Mouteva, G. O.; Czimczik, C. I.; Fahrni, S. M.; Wiggins, E. B.; Rogers, B. M.; Veraverbeke, S.; Xu, X.; Santos, G. M.; Henderson, J.; Miller, C. E.; Randerson, J. T.

    2015-11-01

    Black carbon (BC) aerosol emitted by boreal fires has the potential to accelerate losses of snow and ice in many areas of the Arctic, yet the importance of this source relative to fossil fuel BC emissions from lower latitudes remains uncertain. Here we present measurements of the isotopic composition of BC and organic carbon (OC) aerosols collected at two locations in interior Alaska during the summer of 2013, as part of NASA's Carbon in Arctic Reservoirs Vulnerability Experiment. We isolated BC from fine air particulate matter (PM2.5) and measured its radiocarbon (Δ14C) content with accelerator mass spectrometry. We show that fires were the dominant contributor to variability in carbonaceous aerosol mass in interior Alaska during the summer by comparing our measurements with satellite data, measurements from an aerosol network and predicted concentrations from a fire inventory coupled to an atmospheric transport model. The Δ14C of BC from boreal fires was 131 ± 52‰ in the year 2013 when the Δ14C of atmospheric CO2 was 23 ± 3‰, corresponding to a mean fuel age of 20 years. Fire-emitted OC had a similar Δ14C (99 ± 21‰) as BC, but during background (low fire) periods OC (45 to 51‰) was more positive than BC (-354 to -57‰). We also analyzed the carbon and nitrogen elemental and stable isotopic composition of the PM2.5. Fire-emitted aerosol had an elevated carbon to nitrogen (C/N) ratio (29 ± 2) and δ15N (16 ± 4‰). Aerosol Δ14C and δ13C measurements were consistent with a mean depth of burning in organic soil horizons of 20 cm (and a range of 8 to 47 cm). Our measurements of fire-emitted BC and PM2.5 composition constrain the end-member of boreal forest fire contributions to aerosol deposition in the Arctic and may ultimately reduce uncertainties related to the impact of a changing boreal fire regime on the climate system.

  9. Stable carbon isotopic compositions of low-molecular-weight dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and fatty acids: Implications for atmospheric processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Lin; Kawamura, Kimitaka; Cao, Fang; Lee, Meehye

    2016-04-01

    Stable carbon isotopic compositions (δ13C) were measured for 23 individual organic species including 9 dicarboxylic acids, 7 oxocarboxylic acids, 1 tricarboxylic acid, 2 α-dicarbonyls, and 4 fatty acids in the aerosols from Gosan background site in East Asia. δ13C values of particle phase glyoxal and methylglyoxal are significantly larger than those previously reported for isoprene and other precursors. The values are consistently less negative in oxalic acid (C2, average -14.1‰), glyoxylic acid (-13.8‰), pyruvic acid (-19.4‰), glyoxal (-13.5‰), and methylglyoxal (-18.6‰) compared to other organic species (e.g., palmitic acid, -26.3‰), which can be explained by the kinetic isotope effects during atmospheric oxidation of pre-aged precursors (e.g., isoprene) and the subsequent gas-particle partitioning after the evaporation of clouds or wet aerosols. The δ13C values of C2 is positively correlated with C2 to organic carbon ratio, indicating that photochemical production of C2 is more pronounced than its degradation during long-range atmospheric transport. The isotopic results also suggest that aqueous phase oxidation of glyoxal and methylglyoxal is a major formation process of oxalic acid via the intermediates such as glyoxylic acid and pyruvic acid. This study provides evidence that organic aerosols are intensively photochemically aged in the western North Pacific rim.

  10. Stable carbon isotopic compositions of low-molecular-weight dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and fatty acids: implications for atmospheric processing of organic aerosols

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Kawamura, K.; Cao, F.; Lee, M.

    2015-12-01

    Stable carbon isotopic compositions (δ13C) were measured for 23 individual organic species including 9 dicarboxylic acids, 7 oxocarboxylic acids, 1 tricarboxylic acid, 2 α-dicarbonyls and 4 fatty acids in the aerosols from Gosan background site in East Asia. δ13C of particle-phase glyoxal and methylglyoxal are significantly higher than those previously reported for isoprene and other precursors, associated with isotope fractionation during atmospheric oxidation. 13C is consistently more enriched for oxalic acid (C2), glyoxylic acid, pyruvic acid, glyoxal and methylglyoxal compared to other organic compounds identified, which can be explained by the kinetic isotope effects during aqueous-phase processing and the subsequent gas-particle partitioning after clouds or wet aerosols evaporation δ13C of C2 is positively correlated with C2 and organic carbon ratio, indicating that a photochemical production of C2 is more pronounced than its degradation process during long-range transport. The 13C results also suggest that aqueous-phase oxidation of glyoxal and methylglyoxal is major formation process of oxalic acid production via the major intermediates glyoxylic acid and pyruvic acid. This study provides evidence that organic aerosols are intensively photo-chemically aged in this region.

  11. Molecular Characterization of Brown Carbon (BrC) Chromophores in Secondary Organic Aerosol Generated From Photo-Oxidation of Toluene

    SciTech Connect

    Lin, Peng; Liu, Jiumeng; Shilling, John E.; Kathmann, Shawn M.; Laskin, Julia; Laskin, Alexander

    2015-09-28

    Atmospheric Brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365nm = 0.78 m2 g-1) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

  12. Present and potential future contributions of sulfate, black and organic carbon aerosols from China to global air quality, premature mortality and radiative forcing

    NASA Astrophysics Data System (ADS)

    Saikawa, E.; Naik, V.; Horowitz, L. W.; Liu, J.; Mauzerall, D. L.

    2008-12-01

    Aerosols are harmful to human health and have both direct and indirect effects on climate. China is a major contributor to global emissions of sulfur dioxide (SO2), a sulfate (SO42-) precursor, organic carbon (OC), and black carbon (BC) aerosols. Although increasingly examined, the effect of present and potential future levels of these emissions on global premature mortality and climate change has not been well quantified. Through both direct and indirect effects, SO42- and OC exert negative radiative forcing (cooling) while BC exerts positive forcing (warming). We analyze the effect of China's emissions of SO2, SO42-, OC and BC in 2000 and for three emission scenarios in 2030 on global surface aerosol concentrations, premature mortality, and radiative forcing. Using global models of chemical transport (MOZART-2) and radiative transfer (GFDL RTM), and combining simulation results with gridded population data, mortality rates, and concentration-response relationships from the epidemiological literature, we estimate the contribution of Chinese aerosols to global annual premature mortality and to radiative forcing in 2000 and 2030. In 2000, we estimate these aerosols cause 385,320 premature deaths in China and an additional 18 240 globally. In 2030, aggressive emission controls lead to a reduction in premature deaths to 200,370 in China and 7,740 elsewhere, while under a high emissions scenario premature deaths would increase to 602,950 in China and to 29,750 elsewhere. Because the negative radiative forcing from SO42- and OC is larger than the positive forcing from BC, the Chinese aerosols lead to global net direct radiative forcing of -74 mW m-2 in 2000 and between -15 and -97 mW m-2 in 2030 based on the emissions scenario. Our analysis suggests that environmental policies that simultaneously improve public health and mitigate climate change would be highly beneficial (eg. reductions in BC emissions).

  13. Sugars as source indicators of biogenic organic carbon in aerosols collected above the Howland Experimental Forest, Maine

    NASA Astrophysics Data System (ADS)

    Medeiros, Patricia M.; Conte, Maureen H.; Weber, John C.; Simoneit, Bernd R. T.

    Bulk aerosols (>1 μm) were collected continuously above the canopy at the Howland Experimental Forest, Maine, USA from May to October 2002. Each sample integrated over an approximately 2-week period. Mono- and disaccharide sugars were extracted using a microscale technique and were analyzed as their TMS derivatives by gas chromatography-mass spectrometry (GC-MS). Concentrations of total aerosol sugars ranged from 10 to 180 ng m -3. Glucose was the most abundant sugar (40-75% of the total sugars). The monosaccharides arabinose, fructose, galactose, mannose, arabitol and mannitol, and the disaccharides sucrose, maltose and mycose (aka trehalose) were also present in lower concentrations. The sugar composition in the aerosols varied seasonally. Fructose and sucrose were prevalent in early spring and decreased in relative abundance as the growing season progressed. Sugar polyols (arabitol and mannitol) and the disaccharide mycose (a fungal metabolite) were more prevalent in autumn during the period of leaf senescence. The changes in the sugar composition in the aerosol samples appear to reflect the seasonality of sugar production and utilization by the ecosystem. Plant waxes were present as significant components also indicating an input from biogenic background. Smoke plumes from Quebec forest fires passed over the Howland site in early July 2002. Levoglucosan, a biomarker of biomass burning, increased by an order of magnitude in the aerosol samples collected during this time. Glucose, mannose, arabinose, galactose, and also, plant waxes increased in concentration by factors of 2-5 in the smoke-impacted samples, indicating that wildfires enhance atmospheric emissions of uncombusted organic compounds. In contrast, concentrations of fructose, sugar polyols and disaccharides were not significantly higher in the smoke-impacted samples and indicated that biomass burning was not a significant source of these compounds in the aerosols.

  14. Spatial and Temporal Distribution of Water-Soluble Anions and Organic Carbons in Bulk Aerosols Collected at the Ryukyu Islands, Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Somada, Y.; Azechi, S.; Ijyu, M.; Nakaema, F.; Handa, D.; Oshiro, Y.; Miyagi, Y.; Arakaki, T.; Tanahara, A.; Furukawa, M.

    2011-12-01

    Atmospheric aerosols pose health risks to humans and change global climate. Ryukyu Islands in Japan are mainly covered with maritime air mass in summer and continental air mass for the rest of the seasons. Thus, it is possible to estimate the origins of chemical components, in particular transboundary air pollutants from East Asia. Ryukyu Islands are one of the best locations for monitoring the changes in Asia's atmosphere. This study tried to elucidate the spatial and temporal distribution of water-soluble anions and organic carbons, and chemical changes during the transportation processes. Aerosol samples were collected at Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS, Sep. 2005 - Dec. 2010), Kume Island (KM, ca. 100 km from Naha), and Minami-Daitou Island (MD, ca. 350 km from Naha) from June 2008 to June 2010 on quartz filters by using identical high-volume air samplers. The sample filters were exchanged every week. The concentrations of water-soluble anions (Cl-,Br-,NO3-,NO2-,SO42-) and water-soluble organic carbon (WSOC) were determined by using ion chromatography and total organic carbon analyzer, respectively. And, concentrations of non-sea-salt SO(nss-SO42-) were calculated based on the concentrations of Na+. For the samples collected at CHAAMS, seawater component accounted for on average 56±5% of total aerosol mass. Monthly mean concentrations of nss-SO42- showed distinctive difference among the sampling sites (KM>CHAAMS>MD) during Jan. to May, suggesting that distance from Asian continent affected on its behavior. Yearly average concentrations of NO3- and nss-SO42- showed +42% and +16% increase, respectively between 2005 and 2011. Annual rate of NO3- increase was much faster than that of nss-SO42-, probably reflecting changes in lifestyles in Asian continent.

  15. Water soluble organic carbon in aerosols (PM1, PM2.5, PM10) and various precipitation forms (rain, snow, mixed) over the southern Baltic Sea station.

    PubMed

    Witkowska, Agnieszka; Lewandowska, Anita U

    2016-12-15

    In the urbanized coastal zone of the Southern Baltic, complex measurements of water soluble organic carbon (WSOC) were conducted between 2012 and 2015, involving atmospheric precipitation in its various forms (rain, snow, mixed) and PM1, PM2.5 and PM10 aerosols. WSOC constituted about 60% of the organic carbon mass in aerosols of various sizes. The average concentration of WSOC was equal to 2.6μg∙m(-3) in PM1, 3.6μg∙m(-3) in PM2.5 and 4.4μg∙m(-3) in PM10. The lowest concentration of WSOC was noted in summer as a result of effective removal of this compound with rainfall. The highest WSOC concentrations in PM2.5 and PM10 aerosols were measured in spring, which should be associated with developing vegetation on land and in the sea. On the other hand, the highest WSOC concentrations in PM1 occurred in winter at low air temperatures and greatest atmospheric stability, when there were increased carbon emissions from fuel combustion in the communal-utility sector and from transportation. WSOC concentrations in precipitation were determined by its form. Mixed precipitation turned out to be the richest in soluble organic carbon (5.1mg·dm(-3)), while snow contained the least WSOC (1.7mg·dm(-3)). Snow and rain cleaned carbon compounds from the atmosphere more effectively when precipitation lasted longer than 24h, while in the case of mixed precipitation WSOC was removed most effectively within the first 24h.

  16. On the implications of aerosol liquid water and phase separation for organic aerosol mass

    NASA Astrophysics Data System (ADS)

    Pye, Havala O. T.; Murphy, Benjamin N.; Xu, Lu; Ng, Nga L.; Carlton, Annmarie G.; Guo, Hongyu; Weber, Rodney; Vasilakos, Petros; Wyat Appel, K.; Hapsari Budisulistiorini, Sri; Surratt, Jason D.; Nenes, Athanasios; Hu, Weiwei; Jimenez, Jose L.; Isaacman-VanWertz, Gabriel; Misztal, Pawel K.; Goldstein, Allen H.

    2017-01-01

    Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM / OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM / OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM / OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model-measurement gap. When taking into account deviations from ideality, including both inorganic (when RH > SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from

  17. On the Importance of Organic Oxygen for Understanding OrganicAerosol Particles

    SciTech Connect

    Pang, Y.; Turpin, B.J.; Gundel, L.A.

    2005-04-01

    This study shows how aerosol organic oxygen data could provide new information about organic aerosol mass, aqueous solubility of organic aerosols, formation of secondary organic aerosol (SOA) and the relative contributions of anthropogenic and biogenic sources. For more than two decades atmospheric aerosol organic mass (OM) concentration has been estimated by multiplying the measured carbon content by an assumed (OM)-to-organic carbon (OC) factor, usually 1.4. However, this factor can vary from 1.0 to 2.5 depending on location. This large uncertainty about aerosol organic mass limits our understanding of the influence of organic aerosol on climate, visibility and health. New examination of organic aerosol speciation data shows that the oxygen content is responsible for the observed range in the OM-to-OC factor. When organic oxygen content is excluded, the ratio of non-oxygen organic mass to carbon mass varies very little across different environments (1.12 to 1.14). The non-oxygen-OM-to-OC factor for all studied sites (urban and non-urban) averaged 1.13. The uncertainty becomes an order of magnitude smaller than the uncertainty in the best current estimates of organic mass to organic carbon ratios (1.6 {+-} 0.2 for urban and 2.1 {+-} 0.2 for non-urban areas). This analysis suggests that, when aerosol organic oxygen data become available, organic aerosol mass can be quite accurately estimated using just OC and organic oxygen (OO) without the need to know whether the aerosol is fresh or aged. In addition, aerosol organic oxygen data will aid prediction of water solubility since compounds with OO-to-OC higher than 0.4 have water solubilities higher than 1 g per 100 g water.

  18. Evolved gas analysis of secondary organic aerosols

    SciTech Connect

    Grosjean, D.; Williams, E.L. II; Grosjean, E. ); Novakov, T. )

    1994-11-01

    Secondary organic aerosols have been characterized by evolved gas analysis (EGA). Hydrocarbons selected as aerosol precursors were representative of anthropogenic emissions (cyclohexene, cyclopentene, 1-decene and 1-dodecene, n-dodecane, o-xylene, and 1,3,5-trimethylbenzene) and of biogenic emissions (the terpenes [alpha]-pinene, [beta]-pinene and d-limonene and the sesquiterpene trans-caryophyllene). Also analyzed by EGA were samples of secondary, primary (highway tunnel), and ambient (urban) aerosols before and after exposure to ozone and other photochemical oxidants. The major features of the EGA thermograms (amount of CO[sub 2] evolved as a function of temperature) are described. The usefulness and limitations of EGA data for source apportionment of atmospheric particulate carbon are briefly discussed. 28 refs., 7 figs., 4 tabs.

  19. Combined effects of organic aerosol loading and fog processing on organic aerosols oxidation, composition, and evolution.

    PubMed

    Chakraborty, Abhishek; Gupta, Tarun; Tripathi, S N

    2016-12-15

    Chemical characterization of ambient non-refractory submicron aerosols (NR-PM1) was carried out in real time at Kanpur, India. The measurements were performed during the winter (December 2014 to February 2015), and comprised of two very distinct high and low aerosol loading periods coupled with prevalent foggy conditions. The average non-refractory submicron aerosol loading varied significantly from high (HL, ~240μg/m(3)) to low loading (LL, ~100μg/m(3)) period and was dominated by organic aerosols (OA) which contributed more than half (~60%) of the measured aerosol mass. OA source apportionment via positive matrix factorization (PMF) showed drastic changes in the composition of OA from HL to LL period. Overall, O/C (oxygen to carbon) ratios also varied significantly from HL (=0.59) to LL (=0.69) period. Fog episodes (n=17) studied here seem to be reducing the magnitude of the negative impact of OA loading on O/C ratio (OA loading and O/C ratio are anti-correlated, as higher OA loading allows gas to particle partitioning of relatively less oxidized organics) by 60% via aqueous processing. This study provided new insights into the combined effects of OA loading and fog aqueous processing on the evolution of ambient organic aerosols (OA) for the first time.

  20. Present and potential future contributions of sulfate, black and organic carbon aerosols from China to global air quality, premature mortality and radiative forcing

    NASA Astrophysics Data System (ADS)

    Saikawa, Eri; Naik, Vaishali; Horowitz, Larry W.; Liu, Junfeng; Mauzerall, Denise L.

    Aerosols are harmful to human health and have both direct and indirect effects on climate. China is a major contributor to global emissions of sulfur dioxide (SO 2), a sulfate (SO 42-) precursor, organic carbon (OC), and black carbon (BC) aerosols. Although increasingly examined, the effect of present and potential future levels of these emissions on global premature mortality and climate change has not been well quantified. Through both direct radiative effects and indirect effects on clouds, SO 42- and OC exert negative radiative forcing (cooling) while BC exerts positive forcing (warming). We analyze the effect of China's emissions of SO 2, SO 42-, OC and BC in 2000 and for three emission scenarios in 2030 on global surface aerosol concentrations, premature mortality, and radiative forcing (RF). Using global models of chemical transport (MOZART-2) and radiative transfer (GFDL RTM), and combining simulation results with gridded population data, mortality rates, and concentration-response relationships from the epidemiological literature, we estimate the contribution of Chinese aerosols to global annual premature mortality and to RF in 2000 and 2030. In 2000, we estimate these aerosols cause approximately 470 000 premature deaths in China and an additional 30 000 deaths globally. In 2030, aggressive emission controls lead to a 50% reduction in premature deaths from the 2000 level to 240 000 in China and 10 000 elsewhere, while under a high emissions scenario premature deaths increase 50% from the 2000 level to 720 000 in China and to 40 000 elsewhere. Because the negative RF from SO 42- and OC is larger than the positive forcing from BC, Chinese aerosols lead to global net direct RF of -74 mW m -2 in 2000 and between -15 and -97 mW m -2 in 2030 depending on the emissions scenario. Our analysis indicates that increased effort to reduce greenhouse gases is essential to address climate change as China's anticipated reduction of aerosols will result in the

  1. Major 20th century changes of the content and chemical speciation of organic carbon archived in Alpine ice cores: Implications for the long-term change of organic aerosol over Europe

    NASA Astrophysics Data System (ADS)

    Legrand, M.; Preunkert, S.; May, B.; Guilhermet, J.; Hoffman, H.; Wagenbach, D.

    2013-05-01

    Dissolved organic carbon (DOC) and an extended array of organic compounds were investigated in an Alpine ice core covering the 1920-1988 time period. Based on this, a reconstruction was made of the long-term trends of water-soluble organic carbon (WSOC) aerosol in the European atmosphere. It is shown that light mono- and dicarboxylates, humic-like substances, and formaldehyde account together for more than half of the DOC content of ice. This extended chemical speciation of DOC is used to estimate the DOC fraction present in ice that is related to WSOC aerosol and its change over the past. It is suggested that after World War II, the WSOC levels have been enhanced by a factor of 2 and 3 in winter and summer, respectively. In summer, the fossil fuel contribution to the enhancement is estimated to be rather small, suggesting that it arises mainly from an increase in biogenic sources of WSOC.

  2. Determination of multiple organic matter sources in aerosol PM10 from Wrocław, Poland using molecular and stable carbon isotope compositions

    NASA Astrophysics Data System (ADS)

    Górka, Maciej; Rybicki, Maciej; Simoneit, Bernd R. T.; Marynowski, Leszek

    2014-06-01

    from coupling of organic tracer analysis and carbon isotopic data of PM10 was that the total carbon (including insoluble soot) is likely derived from fossil fuel combustion, while the extractable organic matter is a mixture from different sources with significant inputs of biomass burning. We have also shown that dominant organic tracers do not always represent the major input source in aerosol PM and the unresolved part of the organic matter (soot) is important in the carbon budget.

  3. Radiocarbon-Based Source Apportionment of the Water-Soluble Organic Carbon (wsoc) of Atmospheric Aerosols in South and East Asia

    NASA Astrophysics Data System (ADS)

    Kirillova, E. N.; Sheesley, R. J.; Andersson, A.; Gustafsson, O.; Safai, P. D.; Budhavant, K.; Rao, P. S.; Kang, E.; Han, J.; Lee, M.

    2011-12-01

    The air quality and regional climate in South and East Asia are considerably affected by atmospheric aerosols produced by anthropogenic activities. Recent studies have investigated the sources of the black carbon aerosol component in these regions. This study seeks to make progress in apportioning the sources of the water soluble organic carbon (WSOC) component, which makes up 20-65% of the carbonaceous aerosol mass in these areas. WSOC is important as it enhances the ability of particles to serve as cloud condensation nuclei (CCN) and, therefore, has an impact on regional climate and radiative forcing. Atmospheric particulate matter was collected during fifteen-month continuous sampling campaigns Jan 2008 - March 2009 at both the Maldives Climate Observatory at Hannimaadho (MCOH) and at the Sinhagad hilltop sampling site of the Indian Institute of Tropical Meteorology (SIN) in central-western India. The radiocarbon method is an ideal approach to identify fossil sources (14C "dead") compared to biogenic and biomass combustion products (with a contemporary 14C signal). WSOC is a large fraction of organic aerosols and its annual average contribution to TOC during 2008 is 26% at MCOH and 40% at SIN. There is a distinct seasonal variability in WSOC concentrations at both sites with high concentrations during the winter season (0.92±0.49μg m-3 at MCOH and 3.5±2.0μg m-3 at SIN) and very low concentrations during the summer monsoon season (0.08±0.04μg m-3 at MCOH and 0.27±0.20μg m-3 at SIN). The radiocarbon source apportionment of WSOC in winter dry season was similar at MCOH and SIN with 80-85% from biogenic/biomass combustion and the rest from fossil fuel precursors. For the rest of the year, the biogenic/biomass contribution to WSOC is higher at the Indian Ocean site (86-93%) compared to the Indian site (74-83%). In March 2011 the GoPoEx2011 intensive sampling campaign at the Gosan ABC Superstation, Jeju Island, South Korea was dedicated to study atmospheric

  4. Spatial and seasonal variations of fine particle water-soluble organic carbon (WSOC) over the southeastern United States: implications for secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Zhang, X.; Liu, Z.; Hecobian, A.; Zheng, M.; Frank, N. H.; Edgerton, E. S.; Weber, R. J.

    2012-07-01

    Secondary organic aerosol (SOA) in the southeastern US is investigated by analyzing the spatial-temporal distribution of water-soluble organic carbon (WSOC) and other PM2.5 components from 900 archived 24-h Teflon filters collected at 15 urban or rural EPA Federal Reference Method (FRM) network sites throughout 2007. Online measurements of WSOC at an urban/rural-paired site in Georgia in the summer of 2008 are contrasted to the filter data. Based on FRM filters, excluding biomass-burning events (levoglucosan < 50 ng m-3), WSOC and sulfate were highly correlated with PM2.5 mass (r2~0.7). Both components comprised a large mass fraction of PM2.5 (13% and 31%, respectively, or ~25% and 50% for WSOM and ammonium sulfate). Sulfate and WSOC both tracked ambient temperature throughout the year, suggesting the temperature effects were mainly linked to faster photochemistry and/or synoptic meteorology and less due to enhanced biogenic hydrocarbon emissions. FRM WSOC, and to a lesser extent sulfate, were spatially homogeneous throughout the region, yet WSOC was moderately enhanced (27%) in locations of greater predicted isoprene emissions in summer. A Positive Matrix Factorization (PMF) analysis identified two major source types for the summer WSOC; 22% of the WSOC were associated with ammonium sulfate, and 56% of the WSOC were associated with brown carbon and oxalate. A small urban excess of FRM WSOC (10%) was observed in the summer of 2007, however, comparisons of online WSOC measurements at one urban/rural pair (Atlanta/Yorkville) in August 2008 showed substantially greater difference in WSOC (31%) relative to the FRM data, suggesting a low bias for urban filters. The measured Atlanta urban excess, combined with the estimated boundary layer heights, gave an estimated Atlanta daily WSOC production rate in August of 0.55 mgC m-2 h-1 between mid-morning and mid-afternoon. This study characterizes the regional nature of fine particles in the southeastern US, confirming the

  5. Accuracy and precision of 14C-based source apportionment of organic and elemental carbon in aerosols using the Swiss_4S protocol

    NASA Astrophysics Data System (ADS)

    Mouteva, G. O.; Fahrni, S. M.; Santos, G. M.; Randerson, J. T.; Zhang, Y.-L.; Szidat, S.; Czimczik, C. I.

    2015-09-01

    Aerosol source apportionment remains a critical challenge for understanding the transport and aging of aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and non-fossil sources to organic carbon (OC) and elemental carbon (EC) in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C) content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal-optical analysis (TOA) protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA) coupled to a vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2) in pure oxygen (O2). On average, 91 % of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS). To test the accuracy of our setup, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted) carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC) and contemporary standards (oxalic acid for OC and rice char for EC) as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2.5) samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our setup were 0.8 ± 0.4 and 0.67 ± 0.34 μg C, respectively

  6. Accuracy and precision of 14C-based source apportionment of organic and elemental carbon in aerosols using the Swiss_4S protocol

    NASA Astrophysics Data System (ADS)

    Mouteva, G. O.; Fahrni, S. M.; Santos, G. M.; Randerson, J. T.; Zhang, Y. L.; Szidat, S.; Czimczik, C. I.

    2015-04-01

    Aerosol source apportionment remains a critical challenge for understanding the transport and aging of aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and non-fossil sources to organic carbon (OC) and elemental carbon (EC) in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C) content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal-optical analysis (TOA) protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA) coupled to vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2) in pure oxygen (O2). On average 91% of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS). To test the accuracy of our set-up, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted) carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC) and contemporary standards (oxalic acid for OC and rice char for EC) as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2.5) samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our set-up were 0.8 ± 0.4 and 0.67 ± 0.34 μg C, respectively

  7. Characterizing the formation of secondary organic aerosols

    SciTech Connect

    Lunden, Melissa; Black, Douglas; Brown, Nancy

    2004-02-01

    Organic aerosol is an important fraction of the fine particulate matter present in the atmosphere. This organic aerosol comes from a variety of sources; primary organic aerosol emitted directly from combustion process, and secondary aerosol formed in the atmosphere from condensable vapors. This secondary organic aerosol (SOA) can result from both anthropogenic and biogenic sources. In rural areas of the United States, organic aerosols can be a significant part of the aerosol load in the atmosphere. However, the extent to which gas-phase biogenic emissions contribute to this organic load is poorly understood. Such an understanding is crucial to properly apportion the effect of anthropogenic emissions in these rural areas that are sometimes dominated by biogenic sources. To help gain insight on the effect of biogenic emissions on particle concentrations in rural areas, we have been conducting a field measurement program at the University of California Blodgett Forest Research Facility. The field location includes has been used to acquire an extensive suite of measurements resulting in a rich data set, containing a combination of aerosol, organic, and nitrogenous species concentration and meteorological data with a long time record. The field location was established in 1997 by Allen Goldstein, a professor in the Department of Environmental Science, Policy and Management at the University of California at Berkeley to study interactions between the biosphere and the atmosphere. The Goldstein group focuses on measurements of concentrations and whole ecosystem biosphere-atmosphere fluxes for volatile organic compounds (VOC's), oxygenated volatile organic compounds (OVOC's), ozone, carbon dioxide, water vapor, and energy. Another important collaborator at the Blodgett field location is Ronald Cohen, a professor in the Chemistry Department at the University of California at Berkeley. At the Blodgett field location, his group his group performs measurements of the

  8. Aerosol from Organic Nitrogen in the Southeast United States

    EPA Science Inventory

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

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

    PubMed

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

    2014-01-01

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

  10. How Important Is Organic Aerosol Hygroscopicity to Aerosol Indirect Forcing?

    SciTech Connect

    Liu, Xiaohong; Wang, Jian

    2010-12-07

    Organics are among the most abundant aerosol components in the atmosphere. However, there are still large uncertainties with emissions of primary organic aerosol (POA) and volatile organic compounds (VOCs) (precursor gases of secondary organic aerosol, SOA), formation and yield of SOA, and chemical and physical properties (e.g., hygroscopicity) of POA and SOA. All these may have significant impacts on aerosol direct and indirect forcing estimated from global models. In this study a modal aerosol module (MAM) in the NCAR Community Atmospheric Model (CAM) is used to examine sensitivities of aerosol indirect forcing to hygroscopicity (“κ” value) of POA and SOA. Our model simulation indicates that in the present-day condition changing “κ” value of POA from 0 to 0.1 increases the number concentration of cloud condensational nuclei (CCN) at supersaturation S=0.1% by 40-60% over the POA source regions, while changing “κ” value of SOA by ±50% (from 0.14 to 0.07 and 0.21) changes the CCN within 30%. Changes in the in-cloud droplet number concentrations (CDNC) are within 20% in most locations on the globe with the above changes in “κ” value of POA and SOA. Global annual mean anthropogenic aerosol indirect forcing (AIF) between present-day (PD) and pre-industrial (PI) conditions change by 0.4 W m-2 with the control run of -1.3 W m-2. AIF reduces with the increase hygroscopicity of organic aerosol, indicating the important role of natural organic aerosol in buffering the relative change of CDNC from PI to PD.

  11. Light-absorbing soluble organic aerosol in Los Angeles and Atlanta: A contrast in secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaolu; Lin, Ying-Hsuan; Surratt, Jason D.; Zotter, Peter; Prévôt, Andre S. H.; Weber, Rodney J.

    2011-11-01

    Light absorption spectra and carbon mass of fine particle water-soluble components were measured during the summer of 2010 in the Los Angeles (LA) basin, California, and Atlanta, Georgia. Fresh LA secondary organic carbon had a consistent brown color and a bulk absorption per soluble carbon mass at 365 nm that was 4 to 6 times higher than freshly-formed Atlanta soluble organic carbon. Radiocarbon measurements of filter samples show that LA secondary organic aerosol (SOA) was mainly from fossil carbon and chemical analysis of aqueous filter extracts identified nitro-aromatics as one component of LA brown SOA. Interpreting soluble brown carbon as a property of freshly-formed anthropogenic SOA, the difference in absorption per carbon mass between these two cities suggests most fresh secondary water-soluble organic carbon formed within Atlanta is not from an anthropogenic process similar to LA. Contrasting emissions of biogenic volatile organic compounds may account for these differences.

  12. Concentration, sources, and degradation of organic aerosol at Summit, Greenland

    NASA Astrophysics Data System (ADS)

    von Schneidemesser, Erika

    Characterization and understanding of the carbonaceous portion of the aerosol in the Arctic is limited. The objective of the research presented in this thesis was to improve the scope of knowledge pertaining to carbonaceous aerosols, in terms of atmospheric and snow concentrations, sources, and post-depositional processing. An extraction technique was developed to quantitatively identify a suite of organic compounds, typically observed in aerosol samples, at trace level concentrations in snow melt water samples. A field campaign of sampling and exposure experiments was carried out at Summit, Greenland. A 3-meter snow pit, sampled at 20 cm intervals, was analyzed for organic compounds and total organic carbon (TOC). The average concentration of TOC for the entire pit was 64 mug C kg-1. The quantified organic compounds comprised 6 to 24% of TOC throughout the layers. Median concentrations of the water insoluble individual organic compounds ranged from 0.14 ng kg-1 (hopane) to 2200 ng kg-1 (alkanoic acid) at any one depth. High-volume aerosol samples were collected over a six month period and analyzed for organics. Median concentrations ranged from 0.00045 ng kg-1 (hopane) to 0.23 ng kg-1 (levoglucosan) in the air samples. Source apportionment results from the aerosol samples indicate anthropogenic influence at Summit from biomass burning, fossil fuels, and vegetative detritus. The majority (>90%) of the organic carbon in the aerosol was estimated to be secondary organic aerosol. To investigate the post-depositional processing of organic compounds in snow, contaminant labeled snow was produced and exposed for up to 72 hours on the surface of the Greenland ice sheet at Summit. Degradation of alkanes, acids, and PAHs to a threshold concentration was observed. The threshold concentration, at which no further degradation was observed, ranged from 10 to 60% of the original (non-exposed) snow concentrations, depending on the reaction rate. This would indicate that a

  13. The organic aerosols of Titan

    NASA Technical Reports Server (NTRS)

    Khare, B. N.; Sagan, C.; Thompson, W. R.; Arakawa, E. T.; Suits, F.; Callcott, T. A.; Williams, M. W.; Shrader, S.; Ogino, H.; Willingham, T. O.

    1984-01-01

    The optical properties and chemical composition of thiolin, an organic solid synthesized by high-energy-electron irradiation in a plasma discharge (Sagan et al., 1984) to simulate the high-altitude aerosols of Titan, are investigated experimentally using monochromators, ellipsometers, and spectrometers (on thin films deposited by continuous dc discharge) and sequential and nonsequential pyrolytic gas chromatography/mass spectrometry (of the volatile component), respectively. The results are presented in tables and graphs and characterized. The real and imaginary elements of the complex refractive index in the visible are estimated as 1.65 and 0.004-0.08, respectively, in agreement with observations of Titan, and the IR absorption features include the nitrile band at 4.6 microns. The molecules identified in the volatile part of thiolin include complex species considered important in theoretical models of the origin of life on earth.

  14. Black carbon in aerosol during BIBLE B

    NASA Astrophysics Data System (ADS)

    Liley, J. Ben; Baumgardner, D.; Kondo, Y.; Kita, K.; Blake, D. R.; Koike, M.; Machida, T.; Takegawa, N.; Kawakami, S.; Shirai, T.; Ogawa, T.

    2003-02-01

    The Biomass Burning and Lightning Experiment (BIBLE) A and B campaigns over the tropical western Pacific during springtime deployed a Gulfstream-II aircraft with systems to measure ozone and numerous precursor species. Aerosol measuring systems included a MASP optical particle counter, a condensation nucleus (CN) counter, and an absorption spectrometer for black carbon. Aerosol volume was very low in the middle and upper troposphere during both campaigns, and during BIBLE A, there was little aerosol enhancement in the boundary layer away from urban areas. In BIBLE B, there was marked aerosol enhancement in the lowest 3 km of the atmosphere. Mixing ratios of CN in cloud-free conditions in the upper troposphere were in general higher than in the boundary layer, indicating new particle formation from gaseous precursors. High concentrations of black carbon were observed during BIBLE B, with mass loadings up to 40 μg m-3 representing as much as one quarter of total aerosol mass. Strong correlations with hydrocarbon enhancement allow the determination of a black carbon emission ratio for the fires at that time. Expressed as elemental carbon, it is about 0.5% of carbon dioxide and 6% of carbon monoxide emissions from the same fires, comparable to methane production, and greater than that of other hydrocarbons.

  15. Black carbon in aerosol during BIBLE B

    NASA Astrophysics Data System (ADS)

    Liley, J. Ben; Baumgardner, D.; Kondo, Y.; Kita, K.; Blake, D. R.; Koike, M.; Machida, T.; Takegawa, N.; Kawakami, S.; Shirai, T.; Ogawa, T.

    2002-02-01

    The Biomass Burning and Lightning Experiment (BIBLE) A and B campaigns over the tropical western Pacific during springtime deployed a Gulfstream-II aircraft with systems to measure ozone and numerous precursor species. Aerosol measuring systems included a MASP optical particle counter, a condensation nucleus (CN) counter, and an absorption spectrometer for black carbon. Aerosol volume was very low in the middle and upper troposphere during both campaigns, and during BIBLE A, there was little aerosol enhancement in the boundary layer away from urban areas. In BIBLE B, there was marked aerosol enhancement in the lowest 3 km of the atmosphere. Mixing ratios of CN in cloud-free conditions in the upper troposphere were in general higher than in the boundary layer, indicating new particle formation from gaseous precursors. High concentrations of black carbon were observed during BIBLE B, with mass loadings up to 40 μg m-3 representing as much as one quarter of total aerosol mass. Strong correlations with hydrocarbon enhancement allow the determination of a black carbon emission ratio for the fires at that time. Expressed as elemental carbon, it is about 0.5% of carbon dioxide and 6% of carbon monoxide emissions from the same fires, comparable to methane production, and greater than that of other hydrocarbons.

  16. Organic aerosols in the southeastern United States: Speciated particulate carbon measurements from the SEARCH network, 2006-2010

    NASA Astrophysics Data System (ADS)

    Blanchard, C. L.; Chow, J. C.; Edgerton, E. S.; Watson, J. G.; Hidy, G. M.; Shaw, S.

    2014-10-01

    This study describes and analyzes measurements of 119 non-polar organic compounds in PM2.5 samples from three urban sites in the Southeastern Aerosol Research and Characterization (SEARCH) network: Jefferson Street in Atlanta, Georgia (JST), Birmingham, Alabama (BHM), and Hinton, Texas (HIN). Daily 24-h PM2.5 samples were collected on quartz-fiber filters from January 2006 through 2007 at HIN and from March 2006 through 2010 at JST and BHM. PM2.5 sampling at BHM and JST is ongoing. The measured species are associated with directly emitted particles and potentially serve as tracers of specific types of emissions. PM2.5 organic measurements include 28 n-alkanes (C15-C42), 18 iso-/anteiso-alkanes (C29-C37), 2 methyl alkanes, 3 branched alkanes, 5 cycloalkanes, 32 PAH compounds, 18 hopanes, 12 steranes, and 1 alkene, many of which are constituents of motor-vehicle exhaust and other anthropogenic PM2.5 emissions. Predominantly anthropogenic origins of the measured compounds are indicated by weekly and seasonal cycles that are identified with known emission patterns, especially for motor vehicle usage. Annual mean concentrations of each class of compounds declined by 60-90% from 2006 through 2009, then increased in 2010 to concentrations comparable to 2008. These changes are similar to 40% reductions of on-road and non-road motor-vehicle exhaust PM2.5 emissions between 2006 and 2010. Year-to-year variations in OC correlated with year-to-year variations in measured non-polar compound concentrations. Regression of OC against the sums of measured n-alkanes, iso-/anteiso-alkanes, PAHs, hopanes, and steranes indicates that 32 ± 7% of OC at BHM and 35 ± 4% of OC at JST derived from sources emitting the measured non-polar compounds. The reductions in measured concentrations of EC, OC, and non-polar OC species represent an important improvement in air quality in the southeastern U.S. that can be attributed by the long-term measurement program to PM2.5 emission reductions.

  17. The organic aerosols of Titan

    NASA Technical Reports Server (NTRS)

    Khare, B. N.; Sagan, C.; Thompson, W. R.; Arakawa, E. T.; Suits, F.; Calcott, T. A.; Williams, M. W.; Shrader, S.; Ogino, H.; Willingham, T. O.

    1986-01-01

    A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan prepared by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from X-ray to microwave frequencies. Values of n (approx. 1.65) and k (approx. 0.004 to 0.08) in the visible are consistent with deductions made by groundbased and spaceborne observations of Titan. Many infrared absorption features are present in k(lambda), including the 4.6 micrometer nitrile band. Molecular analysis of the volatile components of this tholin was performed by sequential and nonsequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycylic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition,acid hydrolysis produces a racemic mixture of biological and nonbiological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

  18. Recent Studies Investigating Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Weber, R. J.

    2009-05-01

    The metropolitan areas of Mexico City and Atlanta have very different emissions and meteorology, yet in both cities secondary organic aerosol (SOA) comprises a significant fraction of fine particle mass. SOA in Mexico City is predominately from anthropogenic emissions and a number of studies have investigated the role of dicarbonyl partitioning to aerosol liquid water as a SOA formation route [Volkamer et al., 2006; 2007]. Hennigan et al. [2008] noted a high correlation between SOA (measured as water-soluble organic carbon) and fine particle nitrate in Mexico City and used this to estimate the volatility of both species during periods of rapidly decreasing RH in late morning. Secondary aerosol may also form when particles are much drier. In Mexico City, both nitrate and SOA were also frequently observed and highly correlated in late afternoon when RH was below 30 percent. A thermodynamic model could reproduce the observed morning nitrate under high RH when equilibrium was between nitric acid and dissolved nitrate, whereas equilibrium between vapor and crystalline ammonium nitrate was predicted in the afternoon [Fountoukis et al., 2007]. By analogy, these results may suggest two different SOA partitioning mechanisms in Mexico City, occurring at different times of the day. In contrast, measurements suggest that SOA in the southeastern United States is largely from biogenic precursors, and there is evidence that liquid water also plays a role. The stability of dissolved organic aerosol in response to loss of liquid water is currently being investigated and preliminary data suggest that like Mexico City, there is some degree of volatility. Recent experiments comparing data from rural-urban sites shows that there are periods when anthropogenic emissions also substantially contribute to SOA in the Atlanta metropolitan region. However, the mechanisms, or organic precursors involved, are yet to be determined. Results from these various ongoing studies will be presented

  19. Single-particle laser-induced-fluorescence spectra of biological and other organic-carbon aerosols in the atmosphere: Measurements at New Haven, Connecticut, and Las Cruces, New Mexico

    NASA Astrophysics Data System (ADS)

    Pan, Yong-Le; Pinnick, Ronald G.; Hill, Steven C.; Rosen, James M.; Chang, Richard K.

    2007-12-01

    This study focuses on organic carbon (OC) aerosols, including natural biological aerosols, in the Earth's troposphere, and on laser-induced fluorescence (LIF) spectral methods for studying these aerosols. LIF spectra of atmospheric OC and biological aerosols (having diameters greater than approximately 3 μm) measured at New Haven, Connecticut, and Las Cruces, New Mexico, are reported. A hierarchical clustering method was used to cluster approximately 90% of the single-particle LIF spectra into 8-10 groups. Some of these groups have spectra that are similar to spectra of some important classes of atmospheric aerosol, such as humic/fulvic acids and humic-like substances, bacteria, cellulose, marine aerosol, and polycyclic aromatic hydrocarbons (PAH). A comparison with previous measurements made at Adelphi, Maryland, reveals that the most highly populated clusters found at Adelphi, and some of the less populated ones, also appear in the LIF spectra at New Haven and Las Cruces, even though the regional climates at these locations is different (New England/Atlantic Coastal, for New Haven and Adelphi, and Chihuahuan Desert for Las Cruces), and the measurements were made in different seasons. The results are consistent with some (perhaps most) of the fluorors in OC and biological atmospheric aerosols being common to these three sites. On average, spectra characteristic of humic/fulvic acids and humic-like substances (HULIS) comprise 28-43% of fluorescent particles at all three sites; whereas cellulose-like spectra contribute only 1-3%.

  20. Condensing Organic Aerosols in a Microphysical Model

    NASA Astrophysics Data System (ADS)

    Gao, Y.; Tsigaridis, K.; Bauer, S.

    2015-12-01

    The condensation of organic aerosols is represented in a newly developed box-model scheme, where its effect on the growth and composition of particles are examined. We implemented the volatility-basis set (VBS) framework into the aerosol mixing state resolving microphysical scheme Multiconfiguration Aerosol TRacker of mIXing state (MATRIX). This new scheme is unique and advances the representation of organic aerosols in models in that, contrary to the traditional treatment of organic aerosols as non-volatile in most climate models and in the original version of MATRIX, this new scheme treats them as semi-volatile. Such treatment is important because low-volatility organics contribute significantly to the growth of particles. The new scheme includes several classes of semi-volatile organic compounds from the VBS framework that can partition among aerosol populations in MATRIX, thus representing the growth of particles via condensation of low volatility organic vapors. Results from test cases representing Mexico City and a Finish forrest condistions show good representation of the time evolutions of concentration for VBS species in the gas phase and in the condensed particulate phase. Emitted semi-volatile primary organic aerosols evaporate almost completely in the high volatile range, and they condense more efficiently in the low volatility range.

  1. Secondary Organic Aerosol and Brown Carbon Formation in the Sunlit Aqueous Phase: Aldehyde Photooxidation in the Presence of Ammonium Salts and Amines

    NASA Astrophysics Data System (ADS)

    De Haan, D. O.; Galloway, M. M.; Sharp, K. D.; Jiménez, N. G.

    2014-12-01

    The chemistry of water-soluble carbonyl compounds in clouds is now acknowledged as an important source of secondary organic aerosol. These reactive carbonyl compounds are oxidized to carboxylic acids and form oligomers by radical-radical reactions and by "dark reactions" with ammonium salts (AS) and/or amines. The latter class of reactions also produces light-absorbing brown carbon compounds, especially reactions involving methylglyoxal or glyoxal and amines. However, recent work has found that UV light fades the color of glyoxal + AS and methylgyloxal + AS reaction mixtures. We recently studied aldehyde-AS-amine reactions in sunlight and in control vessels at the same temperature to determine the effects of solar radiation on the aqueous-phase production of brown carbon. In sunlight, methylglyoxal reaction mixtures lost their initial color and failed to brown, indicating the photolytic loss of reactants and/or pre-brown intermediates. In many other reactions, brown products are lost to photolysis, reducing the overall browning of solutions exposed to sunlight. In other experiments, hydrogen peroxide was added to generate OH radicals by photolysis. In the presence of OH radicals, some carbonyl compound mixtures (e.g. those containing hydroxyacetone or glycolaldehyde) browned more rapidly when exposed to sunlight. This indicates the existence of uncharacterized photooxidative browning pathways involving aqueous-phase OH radicals, carbonyls, ammonium salts, and/or amine compounds.

  2. EVIDENCE FOR ORGANOSULFATES IN SECONDARY ORGANIC AEROSOL

    EPA Science Inventory

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

  3. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

    PubMed

    Hicks, Raea K; Day, Douglas A; Jimenez, Jose L; Tolbert, Margaret A

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

  4. 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

  5. Emissions of organic aerosol mass, black carbon, particle number, and regulated and unregulated gases from scooters and light and heavy duty vehicles with different fuels

    NASA Astrophysics Data System (ADS)

    Chirico, R.; Clairotte, M.; Adam, T. W.; Giechaskiel, B.; Heringa, M. F.; Elsasser, M.; Martini, G.; Manfredi, U.; Streibel, T.; Sklorz, M.; Zimmermann, R.; DeCarlo, P. F.; Astorga, C.; Baltensperger, U.; Prevot, A. S. H.

    2014-06-01

    A sampling campaign with seven different types of vehicles was conducted in 2009 at the vehicle test facilities of the Joint Research Centre (JRC) in Ispra (Italy). The vehicles chosen were representative of some categories circulating in Europe and were fueled either with standard gasoline or diesel and some with blends of rapeseed methyl ester biodiesel. The aim of this work was to improve the knowledge about the emission factors of gas phase and particle-associated regulated and unregulated species from vehicle exhaust. Unregulated species such as black carbon (BC), primary organic aerosol (OA) content, particle number (PN), monocyclic and polycyclic aromatic hydrocarbons (PAHs) and a~selection of unregulated gaseous compounds, including nitrous acid (N2O), ammonia (NH3), hydrogen cyanide (HCN), formaldehyde (HCHO), acetaldehyde (CH3CHO), sulfur dioxide (SO2), and methane (CH4), were measured in real time with a suite of instruments including a high-resolution aerosol time-of-flight mass spectrometer, a resonance enhanced multi-photon ionization time-of-flight mass spectrometer, and a high resolution Fourier transform infrared spectrometer. Diesel vehicles, without particle filters, featured the highest values for particle number, followed by gasoline vehicles and scooters. The particles from diesel and gasoline vehicles were mostly made of BC with a low fraction of OA, while the particles from the scooters were mainly composed of OA. Scooters were characterized by super high emissions factors for OA, which were orders of magnitude higher than for the other vehicles. The heavy duty diesel vehicle (HDDV) featured the highest nitrogen oxides (NOx) emissions, while the scooters had the highest emissions for total hydrocarbons and aromatic compounds due to the unburned and partially burned gasoline and lubricant oil mixture. Generally, vehicles fuelled with biodiesel blends showed lower emission factors of OA and total aromatics than those from the standard fuels

  6. Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol

    NASA Astrophysics Data System (ADS)

    Hicks, Raea K.; Day, Douglas A.; Jimenez, Jose L.; Tolbert, Margaret A.

    2016-11-01

    Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres.

  7. Characterization of Ambient Black Carbon Aerosols

    NASA Astrophysics Data System (ADS)

    Zhang, R.; Levy, M. E.; Zheng, J.; Molina, L. T.

    2013-12-01

    Because of the strong absorption over a broad range of the electromagnetic spectra, black carbon (BC) is a key short-lived climate forcer, which contributes significantly to climate change by direct radiative forcing and is the second most important component causing global warming after carbon dioxide. The impact of BC on the radiative forcing of the Earth-Atmosphere system is highly dependent of the particle properties. In this presentation, emphasis will be placed on characterizing BC containing aerosols in at the California-Mexico border to obtain a greater understanding of the atmospheric aging and properties of ambient BC aerosols. A comprehensive set of directly measured aerosol properties, including the particle size distribution, effective density, hygroscopicity, volatility, and several optical properties, will be discussed to quantify the mixing state and composition of ambient particles. In Tijuana, Mexico, submicron aerosols are strongly influenced by vehicle emissions; subsequently, the BC concentration in Tijuana is considerably higher than most US cities with an average BC concentration of 2.71 × 2.65 g cm-3. BC accounts for 24.75 % × 9.44 of the total submicron concentration on average, but periodically accounts for over 50%. This high concentration of BC strongly influences many observed aerosol properties such as single scattering albedo, hygroscopicity, effective density, and volatility.

  8. Chemical composition of emissions from urban sources of fine organic aerosol

    SciTech Connect

    Hildemann, L.M.; Markowski, G.R.; Cass, G.R. )

    1991-04-01

    A dilution source sampling system was used to collect primary fine aerosol emissions from important sources of urban organic aerosol, including a boiler burning No. 2 fuel oil, a home fireplace, a fleet of catalyst-equipped and noncatalyst automobiles, heavy-duty diesel trucks, natural gas home appliances, and meat cooking operations. Alternative dilution sampling techniques were used to collect emissions from cigarette smoking and a roofing tar pot, and grab sample techniques were employed to characterize paved road dust, brake lining wear, and vegetative detritus. Organic aerosol constituted the majority of the fine aerosol mass emitted from many of the sources tested. Fine primary organic aerosol emissions within the heavily urbanized western portion of the Los Angeles Basin were determined to total 29.8 metric ton/day. Over 40% of these organic aerosol emissions are from anthropogenic pollution sources that are expected to emit contemporary (nonfossil) aerosol carbon, in good agreement with the available ambient monitoring data.

  9. Climatic Effects of Marine Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Xu, J.; Meskhidze, N.; Zhang, Y.; Gantt, B.; Ghan, S. J.; Nenes, A.; Liu, X.; Easter, R. C.; Zaveri, R. A.

    2009-12-01

    Recent studies suggest that the emissions of primary organic matter (POM) of marine biogenic origin and secondary organic aerosol (SOA) from phytoplankton-produced volatile organic compounds can lead to changes of chemical composition and size distribution of marine aerosol, thus modifying the cloud droplet activation potential and affecting climate. In this study, the effects of marine organic aerosol emissions and the dissolved marine organic aerosol components as surfactant are explored using the National Center of Atmospheric Research’s Community Atmosphere Model, coupled with the Pacific Northwest National Laboratory’s Modal Aerosol Model (CAM-MAM). Primary marine organic aerosol emissions are separated into sub- and super-micron modes, and calculated based on wind speed-dependent sea-spray mass flux and remotely-sensed surface chlorophyll-a concentration. Two distinct sea spray emission functions used in this study yield different amounts and spatial distributions of sub-micron marine POM mass flux. The super-micron sea-spray flux is determined based on simulated sea-spray number flux. Both sub and super-micron marine POM are assumed to be mostly water-insoluble and added in the accumulation mode and coarse sea-salt mode, respectively. A prescribed soluble mass fraction of 50% is assumed for marine SOA, formed from phytoplankton-emitted isoprene and allowed to be condensed on existing aerosols in different modes. Surfactant effects from the soluble part of sub-micron marine POM are included in the cloud droplet activation parameterization by some modifications based on the mass fraction of dissolved marine POM. 10 year model simulations are conducted to examine the effects of marine organic aerosols on cloud microphysical and optical properties. Analyses of model results show that different marine aerosol emissions and cloud droplet activation mechanisms can yield 9% to 16% increase in global maritime mean cloud droplet number concentration. Changes

  10. On the implications of aerosol liquid water and phase separation for organic aerosol mass

    EPA Science Inventory

    Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to org...

  11. Aerosol and graphitic carbon content of snow

    SciTech Connect

    Chy-acute-accentlek, P.; Srivastava, V.; Cahenzli, L.; Pinnick, R.G.; Dod, R.L.; Novakov, T.; Cook, T.L.; Hinds, B.D.

    1987-08-20

    Snow samples from southern New Mexico, west Texas, Antarctica, and Greenland were analyzed for aerosol and graphitic carbon. Graphitic carbon contents were found to be between 2.2 and 25 ..mu..g L/sup -1/ of snow meltwater; water-insoluble aerosol content varied between 0.62 and 8.5 mg L/sup -1/. For comparison, two samples of Camp Century, Greenland, ice core, having approximate ages of 4,000 and 6,000 years, were also analyzed. Ice core graphitic carbon contents were found to be 2.5 and 1.1 ..mu..g L/sup -1/. copyrightAmerican Geophysical Union 1987

  12. Optical Properties of Polymers Relevant to Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Marrero-Ortiz, W.; Gomez-Hernandez, M. E.; Xu, W.; Guo, S.; Zhang, R.

    2014-12-01

    Atmospheric aerosols play a critical role in climate directly by scattering and absorbing solar radiation and indirectly by modifying the cloud formation. Currently, the direct and indirect effects of aerosols represent the largest uncertainty in climate predictions models. Some aerosols are directly emitted, but the majority are formed in the atmosphere by the oxidation of gaseous precursors. However, the formation of aerosols at the molecular level is not fully characterized. Certain category of secondary organic aerosols (SOA), which represent a significant fraction of the total aerosol burden, can be light-absorbing, also known as brown carbon. However, the overall contribution of SOA to the brown carbon and the related climate forcing is poorly understood. Such incomplete understanding is due in part to the chemical complexity of SOA and the lack of knowledge regarding SOA formation, transformation, and optical properties. Based on previous laboratory experiments, field measurements, and modeling studies, it has been suggested that the polymers and oligomers play an important role in the SOA formation. Atmospheric polymers could be produced by the hydration or heterogeneous reactions of epoxides and small α-dicarbonyls. Their aqueous chemistry products have been shown to give light-absorbing and high molecular weight oligomeric species, which increase the SOA mass production and alter the direct and indirect effect of aerosols. In this paper, the aerosol chemistry of small α-dicarbonyl compounds with amines is investigated and the associated optical properties are measured using spectroscopic techniques. The differences between primary, secondary and tertiary amines with glyoxal and methylglyoxal are evaluated in terms of SOA browning efficiency. Atmospheric implications of our present work for understanding the formation of light-absorbing SOA will be presented, particularly in terms of the product distribution of light-absorbing SOA formed by aqueous phase

  13. Filter-based measurements of UV-vis mass absorption cross sections of organic carbon aerosol from residential biomass combustion: Preliminary findings and sources of uncertainty

    NASA Astrophysics Data System (ADS)

    Pandey, Apoorva; Pervez, Shamsh; Chakrabarty, Rajan K.

    2016-10-01

    Combustion of solid biomass fuels is a major source of household energy in developing nations. Black (BC) and organic carbon (OC) aerosols are the major PM2.5 (particulate matter with aerodynamic diameter smaller than 2.5 μm) pollutants co-emitted during burning of these fuels. While the optical nature of BC is well characterized, very little is known about the properties of light-absorbing OC (LAOC). Here, we report our preliminary findings on the mass-based optical properties of LAOC emitted from the combustion of four commonly used solid biomass fuels - fuel-wood, agricultural residue, dung-cake, and mixed - in traditional Indian cookstoves. As part of a pilot field study conducted in central India, PM2.5 samples were collected on Teflon filters and analyzed for their absorbance spectra in the 300-900 nm wavelengths at 1 nm resolution using a UV-Visible spectrophotometer equipped with an integrating sphere. The mean mass absorption cross-sections (MAC) of the emitted PM2.5 and OC, at 550 nm, were 0.8 and 0.2 m2 g-1, respectively, each with a factor of ~2.3 uncertainty. The mean absorption Ångström exponent (AǺE) values for PM2.5 were 3±1 between 350 and 550 nm, and 1.2±0.1 between 550 and 880 nm. In the 350-550 nm range, OC had an AǺE of 6.3±1.8. The emitted OC mass, which was on average 25 times of the BC mass, contributed over 50% of the aerosol absorbance at wavelengths smaller than 450 nm. The overall OC contribution to visible solar light (300-900 nm) absorption by the emitted particles was 26-45%. Our results highlight the need to comprehensively and accurately address: (i) the climatic impacts of light absorption by OC from cookstove emissions, and (ii) the uncertainties and biases associated with variability in biomass fuel types and combustion conditions, and filter-based measurement artifacts during determination of MAC values.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  15. Evolution of Organic Aerosols in the Atmosphere.

    SciTech Connect

    Jimenez, J. L.; Canagaratna, M. R.; Donahue, N. M.; Prevot, A. S. H.; Zhang, Qi; Kroll, Jesse H.; DeCarlo, Peter F.; Allan, James D.; Coe, H.; Ng, N. L.; Aiken, Allison; Docherty, Kenneth S.; Ulbrich, Ingrid M.; Grieshop, A. P.; Robinson, A. L.; Duplissy, J.; Smith, J. D.; Wilson, K. R.; Lanz, V. A.; Hueglin, C.; Sun, Y. L.; Tian, J.; Laaksonen, A.; Raatikainen, T.; Rautiainen, J.; Vaattovaara, P.; Ehn, M.; Kulmala, M.; Tomlinson, Jason M.; Collins, Donald R.; Cubison, Michael J.; Dunlea, E. J.; Huffman, John A.; Onasch, Timothy B.; Alfarra, M. R.; Williams, Paul I.; Bower, K.; Kondo, Yutaka; Schneider, J.; Drewnick, F.; Borrmann, S.; Weimer, S.; Demerjian, K.; Salcedo, D.; Cottrell, L.; Griffin, Robert; Takami, A.; Miyoshi, T.; Hatakeyama, S.; Shimono, A.; Sun, J. Y.; Zhang, Y. M.; Dzepina, K.; Kimmel, Joel; Sueper, D.; Jayne, J. T.; Herndon, Scott C.; Trimborn, Achim; Williams, L. R.; Wood, Ezra C.; Middlebrook, A. M.; Kolb, C. E.; Baltensperger, Urs; Worsnop, Douglas R.

    2009-12-11

    Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework that describes the atmospheric evolution of OA and is constrained and motivated by new, high time resolution, experimental characterizations of their composition, volatility, and oxidation state. OA and OA-precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of large amounts of oxygenated organic aerosol (OOA) mass that has comparable concentrations to sulfate aerosol over the Northern Hemisphere. Our new model framework captures the dynamic aging behavior observed in the atmosphere and the laboratory and can serve as a basis for improving parameterizations in regional and global models.

  16. THERMAL PROPERTIES OF SECONDARY ORGANIC AEROSOLS

    EPA Science Inventory

    Volume concentrations of steady-state secondary organic aerosol (SOA) were measured in several hydrocarbon/NOx irradiation experiments. These measurements were used to estimate the thermal behavior of the particles that may be formed in the atmosphere. These laborator...

  17. Organosulfate Formation in Biogenic Secondary Organic Aerosol

    EPA Science Inventory

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

  18. Organic Aerosols in Rural and Remote Atmospheric Environments: Insights from Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Jimenez, J.; Ulbrich, I.; Dunlea, E.; Decarlo, P.; Huffman, A.; Allan, J.; Coe, H.; Alfarra, R.; Canagaratna, M.; Onasch, T.; Jayne, J.; Worsnop, D.; Takami, A.; Miyoshi, T.; Shimono, A.; Hatakeyama, S.; Weimer, S.; Demerjian, K.; Drewnick, F.; Schneider, J.; Middlebrook, A.; Bahreini, R.; Cotrell, L.; Griffin, R.; Leaitch, R.; Li, S.; Hayden, K.; Rautiainen, J.

    2006-12-01

    Organic matter usually accounts for a large fraction of the fine particle mass in rural and remote atmospheres. However, little is known about the sources and properties of this material. Here we report findings on the characteristics and the major types of organic aerosols (OA) in urban downwind, high elevation, forested, and marine atmospheres based on analyses of more than 20 highly time resolved AMS datasets sampled from various locations in the mid-latitude Northern Hemisphere. Organic aerosol components are extracted from these datasets using a custom multiple component mass spectral analysis technique and the Positive Matrix Factorization (PMF) method. These components are evaluated according to their extracted mass spectra and correlations to aerosol species, such as sulfate, nitrate, and elemental carbon, and gas-phase tracer compounds, such as CO and NOx. We have identified a hydrocarbon-like organic aerosol (HOA) component similar in mass spectra to the hydrocarbon substances observed at urban locations. We have also identified several oxygenated OA (OOA) components that show different fragmentation patterns and oxygen to carbon ratios in their mass spectra. Two OOA components a highly oxygenated that has mass spectrum resembling that of fulvic acid (a model compound representative for highly processed/oxidized organics in the environment) and a less oxygenated OOA component, whose spectrum is dominated with ions that are mainly associated with carbonyls and alcohols, are very frequently observed at various rural/remote sites. The oxygenated OOA component is more prevalent at downwind sites influenced by urban transport and the less oxygenated shows correlation to biogenic chamber OA at some locations. Compared to the total OOA concentration, HOA is generally very small and accounts for < 10% of the total OA mass at rural/remote sites. The comparisons between the concentrations of HOA and primary OA (POA) that would be predicted according to inert

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

    PubMed

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

    2016-05-03

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

  20. Black carbon aerosol size in snow.

    PubMed

    Schwarz, J P; Gao, R S; Perring, A E; Spackman, J R; Fahey, D W

    2013-01-01

    The effect of anthropogenic black carbon (BC) aerosol on snow is of enduring interest due to its consequences for climate forcing. Until now, too little attention has been focused on BC's size in snow, an important parameter affecting BC light absorption in snow. Here we present first observations of this parameter, revealing that BC can be shifted to larger sizes in snow than are typically seen in the atmosphere, in part due to the processes associated with BC removal from the atmosphere. Mie theory analysis indicates a corresponding reduction in BC absorption in snow of 40%, making BC size in snow the dominant source of uncertainty in BC's absorption properties for calculations of BC's snow albedo climate forcing. The shift reduces estimated BC global mean snow forcing by 30%, and has scientific implications for our understanding of snow albedo and the processing of atmospheric BC aerosol in snowfall.

  1. Organic Aerosols from SÃO Paulo and its Relationship with Aerosol Absorption and Scattering Properties

    NASA Astrophysics Data System (ADS)

    Artaxo, P.; Brito, J. F.; Rizzo, L. V.

    2012-12-01

    The megacity of São Paulo with its 19 million people and 7 million cars is a challenge from the point of view of air pollution. High levels of organic aerosols, PM10, black carbon and ozone and the peculiar situation of the large scale use of ethanol fuel makes it a special case. Little is known about the impact of ethanol on air quality and human health and the increase of ethanol as vehicle fuel is rising worldwide An experiment was designed to physico-chemical properties of aerosols in São Paulo, as well as their optical properties. Aerosol size distribution in the size range of 1nm to 10 micrometers is being measured with a Helsinki University SMPS (Scanning Mobility Particle Sizer), an NAIS (Neutral ion Spectrometer) and a GRIMM OPC (Optical Particle Counter). Optical properties are being measured with a TSI Nephelometer and a Thermo MAAP (Multi Angle Absorption Photometer). A CIMEL sunphotometer from the AERONET network measure the aerosol optical depth. 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. The ACSM was operated for 3 months continuosly during teh wintertime of 2012. The measured total particle concentration typically varies between 10,000 and 30,000 cm-3 being the lowest late in the night and highest around noon and frequently exceeding 50,000 cm-3. Clear diurnal patterns in aerosol optical properties were observed. Scattering and absorption coefficients typically range between 20 and 100 Mm-1 at 450 nm, and between 10 to 40 Mm-1 at 637 nm, respectively, both of them peaking at 7:00 local time, the morning rush hour. The corresponding single scattering albedo varies between 0.50 and 0.85, indicating a significant contribution of primary absorbing particles to the aerosol population. During the first month a total of seven new particle formation events were observed with growth rates ranging from 9 to 25

  2. 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.

  3. Black carbon reduction will weaken the aerosol net cooling effect

    NASA Astrophysics Data System (ADS)

    Wang, Z. L.; Zhang, H.; Zhang, X. Y.

    2014-12-01

    Black carbon (BC), a distinct type of carbonaceous material formed from the incomplete combustion of fossil and biomass based fuels under certain conditions, can interact with solar radiation and clouds through its strong light-absorption ability, thereby warming the Earth's climate system. Some studies have even suggested that global warming could be slowed down in a short term by eliminating BC emission due to its short lifetime. In this study, we estimate the influence of removing some sources of BC and other co-emitted species on the aerosol radiative effect by using an aerosol-climate coupled model BCC_AGCM2.0.1_CUACE/Aero, in combination with the aerosol emissions from the Representative Concentration Pathways (RCPs) scenarios. We find that the global annual mean aerosol net cooling effect at the top of the atmosphere (TOA) will be enhanced by 0.12 W m-2 compared with present-day conditions if the BC emission is reduced exclusively to the level projected for 2100 based on the RCP2.6 scenario. This will be beneficial for the mitigation of global warming. However, the global annual mean aerosol net cooling effect at the TOA will be weakened by 1.7-2.0 W m-2 relative to present-day conditions if emissions of BC and co-emitted sulfur dioxide and organic carbon are simultaneously reduced as the most close conditions to the actual situation to the level projected for 2100 in different ways based on the RCP2.6, RCP4.5, and RCP8.5 scenarios. Because there are no effective ways to remove the BC exclusively without influencing the other co-emitted components, our results therefore indicate that a reduction in BC emission can lead to an unexpected warming on the Earth's climate system in the future.

  4. Light absorption of organic aerosol from pyrolysis of corn stalk

    NASA Astrophysics Data System (ADS)

    Li, Xinghua; Chen, Yanju; Bond, Tami C.

    2016-11-01

    Organic aerosol (OA) can absorb solar radiation in the low-visible and ultra-violet wavelengths thereby modifying radiative forcing. Agricultural waste burning emits a large quantity of organic carbon in many developing countries. In this work, we improved the extraction and analysis method developed by Chen and Bond, and extended the spectral range of OC absorption. We examined light absorbing properties of primary OA from pyrolysis of corn stalk, which is a major type of agricultural wastes. Light absorption of bulk liquid extracts of OA was measured using a UV-vis recording spectrophotometer. OA can be extracted by methanol at 95%, close to full extent, and shows polar character. Light absorption of organic aerosol has strong spectral dependence (Absorption Ångström exponent = 7.7) and is not negligible at ultra-violet and low-visible regions. Higher pyrolysis temperature produced OA with higher absorption. Imaginary refractive index of organic aerosol (kOA) is 0.041 at 400 nm wavelength and 0.005 at 550 nm wavelength, respectively.

  5. OH-initiated heterogeneous aging of highly oxidized organic aerosol

    SciTech Connect

    Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.; Smith, Jared D.; Leone, Stephen R.; Kolb, Charles E.; Worsnop, Douglas R.; Wilson, Kevin R.; Kroll, Jesse H.

    2011-12-05

    The oxidative evolution (“aging”) of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter, but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicron particles composed of model oxidized organics—1,2,3,4-butanetetracarboxylic acid (C{sub 8}H{sub 10}O{sub 8}), citric acid (C{sub 6}H{sub 8}O{sub 7}), tartaric acid (C{sub 4}H{sub 6}O{sub 6}), and Suwannee River fulvic acid—were oxidized by gas-phase OH in a flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.

  6. Field and Laboratory Studies of Atmospheric Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Coggon, Matthew Mitchell

    these conditions to all measurements conducted during E-PEACE demonstrated that a large fraction of cloud droplet (72%) and dry aerosol mass (12%) sampled in the California coastal study region was heavily or moderately influenced by ship emissions. Another study investigated the chemical and physical evolution of a controlled organic plume emitted from the R/V Point Sur. Under sunny conditions, nucleated particles composed of oxidized organic compounds contributed nearly an order of magnitude more cloud condensation nuclei (CCN) than less oxidized particles formed under cloudy conditions. The processing time necessary for particles to become CCN active was short ( 4 hr). Laboratory chamber experiments were also conducted to evaluate particle-phase processes influencing aerosol phase and composition. In one study, ammonium sulfate seed was coated with a layer of secondary organic aerosol (SOA) from toluene oxidation followed by a layer of SOA from α-pinene oxidation. The system exhibited different evaporative properties than ammonium sulfate seed initially coated with α-pinene SOA followed by a layer of toluene SOA. This behavior is consistent with a shell-and-core model and suggests limited mixing among different SOA types. Another study investigated the reactive uptake of isoprene epoxy diols (IEPOX) onto non-acidified aerosol. It was demonstrated that particle acidity has limited influence on organic aerosol formation onto ammonium sulfate seed, and that the chemical system is limited by the availability of nucleophiles such as sulfate. Flow tube experiments were conducted to examine the role of iron in the reactive uptake and chemical oxidation of glycolaldehyde. Aerosol particles doped with iron and hydrogen peroxide were mixed with gas-phase glycolaldehyde and photochemically aged in a custom-built flow reactor. Compared to particles free of iron, iron-doped aerosols significantly enhanced the oxygen to carbon (O/C) ratio of accumulated organic mass. The primary

  7. Emissions of Black Carbon Aerosols from Alaskan Boreal Forest Wildfires

    NASA Astrophysics Data System (ADS)

    Mouteva, G.; Fahrni, S. M.; Rogers, B. M.; Wiggins, E. B.; Santos, G.; Czimczik, C. I.; Randerson, J. T.

    2014-12-01

    Boreal wildfires are a major source of carbonaceous aerosols. Emissions from wildfires in Alaska represent ~ 33% of all open biomass combustion emissions of black carbon (BC) in the United States. BC contributes to atmospheric warming and accelerates melting of ice and snow. With fire frequency and burned area projected to increase in boreal regions, BC has the potential to become an important positive feedback to climate change. Quantifying the emissions, constraining the sources and better understanding the transportation patterns of BC to the polar regions are therefore critical for constraining the strength of this feedback. We present results from direct measurements of BC from wildfires in Alaska during the summer of 2013 collected as a part of NASA's Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) campaign. Fine aerosol particulate matter (PM2.5) was collected at two locations: Caribou-Poker Creek Research Watershed and Delta Junction Agricultural and Forestry Experimental Site. Using a Sunset OCEC analyzer, we separated BC from organic carbon aerosols, measured concentrations and analyzed the radiocarbon (14C) content with accelerator mass spectrometry. We also analyzed the total carbon (C) and nitrogen (N) elemental and stable isotope composition of the bulk PM2.5 with EA-IRMS. We compared the temporal dynamics of BC concentrations and isotopic composition with active fire/thermal anomaly information from MODIS. Our results show that boreal forest fire emissions in interior Alaska increased BC concentrations by up to an order of magnitude above background levels. The mean Δ14C value of fire-emitted BC was 120‰ with a range of +99‰ to +149‰ after correcting for contributions from background BC. This range was in good agreement with measurements of the depth of burn in soil organic carbon layers from interior wildland fires, and Δ14C profiles. High fire periods also corresponded to elevated C:N ratios. The δ15N of the aerosols was

  8. Aerosol generation and measurement of multi-wall carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Myojo, Toshihiko; Oyabu, Takako; Nishi, Kenichiro; Kadoya, Chikara; Tanaka, Isamu; Ono-Ogasawara, Mariko; Sakae, Hirokazu; Shirai, Tadashi

    2009-01-01

    Mass production of some kinds of carbon nanotubes (CNT) is now imminent, but little is known about the risk associated with their exposure. It is important to assess the propensity of the CNT to release particles into air for its risk assessment. In this study, we conducted aerosolization of a multi-walled CNT (MWCNT) to assess several aerosol measuring instruments. A Palas RBG-1000 aerosol generator applied mechanical stress to the MWCNT by a rotating brush at feed rates ranging from 2 to 20 mm/h, which the MWCNT was fed to a two-component fluidized bed. The fluidized bed aerosol generator was used to disperse the MWCNT aerosol once more. We monitored the generated MWCNT aerosol concentrations based on number, area, and mass using a condensation particle counter and nanoparticle surface area monitor. Also we quantified carbon mass in MWCNT aerosol samples by a carbon monitor. The shape of aerosolized MWCNT fibers was observed by a scanning electron microscope (SEM). The MWCNT was well dispersed by our system. We found isolated MWCNT fibers in the aerosols by SEM and the count median lengths of MWCNT fibers were 4-6 μm. The MWCNT was quantified by the carbon monitor with a modified condition based on the NIOSH analytical manual. The MWCNT aerosol concentration (EC mass base) was 4 mg/m3 at 2 mm/h in this study.

  9. 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

  10. Shaken, not Stirred: Mixing Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Donahue, N. M.; Robinson, E.; Trump, E. R.; Saleh, R.

    2013-12-01

    For organic vapors to condense onto or into existing particles in the atmosphere, the compounds must have a positive thermodynamic driving force. Their activity (saturation ratio) in the gas phase must exceed their activity (modified mole fraction) at the particle surface. Organic-aerosol production rates are generally quite small -- a few μg m-3 per hour at most -- and thus gas-phase saturation ratios are correspondingly small. Most experiments are conducted with far higher production rates and thus far higher saturation ratios. Consequently, experiments may or may not constrain whether organics coat particles in the real world. In addition, surface activity is often assumed to equal bulk activity for most species, meaning that particles are well mixed. However, if particles are viscous and coating rates high, diffusion through the bulk of even 100 nm particles may be slow. Again, matching experimental timescales to real-world timescales is important. Here we describe organic particle mixing experiments in which two organic particle populations are prepared separately and then intermingled by transferring the contents of one preparation chamber into another. Constituents of one population are isotopically labeled, making the mass spectra of the two particle types completely orthogonal. Following the intermingling, single-particle mass spectra allow us to track individual particle composition as the populations mix via gas-phase exchange. This allows us to explore the mixing and coating behavior of organic-aerosol populations under conditions much closer to concentrations found in the real world.

  11. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols.

    PubMed

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-13

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  12. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  13. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    PubMed Central

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-01-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks. PMID:27733773

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

    SciTech Connect

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

    2013-10-25

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

  15. Modeling global organic aerosol formation and growth

    NASA Astrophysics Data System (ADS)

    Tsimpidi, Alexandra; Karydis, Vlasios; Pandis, Spyros; Lelieveld, Jos

    2014-05-01

    A computationally efficient framework for the description of organic aerosol (OA)-gas partitioning and chemical aging has been developed and implemented into the EMAC atmospheric chemistry-climate model. This model simulates the formation of primary (POA) and secondary organic aerosols (SOA) from semi-volatile (SVOC), intermediate-volatile (IVOC) and volatile organic compounds (VOC). POA are divided in two groups with saturation concentrations at 298 K 0.1, 10, 1000, 100000 µg m-3: OA from fossil fuel combustion and biomass burning. The first 2 surrogate species from each group represent the SVOC while the other surrogate species represent the IVOC. Photochemical reactions that change the volatility of the organics in the gas phase are taken into account. The oxidation products from each group of precursors (SVOC, IVOC, and VOC) are lumped into an additional set of oxidized surrogate species (S-SOA, I-SOA, and V-SOA, respectively) in order to track their source of origin. This model is used to i) estimate the relative contributions of SOA and POA to total OA, ii) determine how SOA concentrations are affected by biogenic and anthropogenic emissions, and iii) evaluate the effect of photochemical aging and long-range transport on OA budget over specific regions.

  16. Refractive Index and Absorption Attribution of Highly Absorbing Brown Carbon Aerosols from an Urban Indian City-Kanpur

    NASA Astrophysics Data System (ADS)

    Shamjad, P. M.; Tripathi, S. N.; Thamban, Navaneeth M.; Vreeland, Heidi

    2016-11-01

    Atmospheric aerosols influence Earth’s radiative balance, having both warming and cooling effects. Though many aerosols reflect radiation, carbonaceous aerosols such as black carbon and certain organic carbon species known as brown carbon have the potential to warm the atmosphere by absorbing light. Black carbon absorbs light over the entire solar spectrum whereas brown carbon absorbs near-UV wavelengths and, to a lesser extent, visible light. In developing countries, such as India, where combustion sources are prolific, the influence of brown carbon on absorption may be significant. In order to better characterize brown carbon, we present experimental and modeled absorption properties of submicron aerosols measured in an urban Indian city (Kanpur). Brown carbon here is found to be fivefold more absorbing at 365 nm wavelength compared to previous studies. Results suggest ~30% of total absorption in Kanpur is attributed to brown carbon, with primary organic aerosols contributing more than secondary organics. We report the spectral brown carbon refractive indices along with an experimentally constrained estimate of the influence of aerosol mixing state on absorption. We conclude that brown carbon in Kanpur is highly absorbing in nature and that the mixing state plays an important role in light absorption from volatile species.

  17. Refractive Index and Absorption Attribution of Highly Absorbing Brown Carbon Aerosols from an Urban Indian City-Kanpur.

    PubMed

    Shamjad, P M; Tripathi, S N; Thamban, Navaneeth M; Vreeland, Heidi

    2016-11-24

    Atmospheric aerosols influence Earth's radiative balance, having both warming and cooling effects. Though many aerosols reflect radiation, carbonaceous aerosols such as black carbon and certain organic carbon species known as brown carbon have the potential to warm the atmosphere by absorbing light. Black carbon absorbs light over the entire solar spectrum whereas brown carbon absorbs near-UV wavelengths and, to a lesser extent, visible light. In developing countries, such as India, where combustion sources are prolific, the influence of brown carbon on absorption may be significant. In order to better characterize brown carbon, we present experimental and modeled absorption properties of submicron aerosols measured in an urban Indian city (Kanpur). Brown carbon here is found to be fivefold more absorbing at 365 nm wavelength compared to previous studies. Results suggest ~30% of total absorption in Kanpur is attributed to brown carbon, with primary organic aerosols contributing more than secondary organics. We report the spectral brown carbon refractive indices along with an experimentally constrained estimate of the influence of aerosol mixing state on absorption. We conclude that brown carbon in Kanpur is highly absorbing in nature and that the mixing state plays an important role in light absorption from volatile species.

  18. Refractive Index and Absorption Attribution of Highly Absorbing Brown Carbon Aerosols from an Urban Indian City-Kanpur

    PubMed Central

    Shamjad, P. M.; Tripathi, S. N.; Thamban, Navaneeth M.; Vreeland, Heidi

    2016-01-01

    Atmospheric aerosols influence Earth’s radiative balance, having both warming and cooling effects. Though many aerosols reflect radiation, carbonaceous aerosols such as black carbon and certain organic carbon species known as brown carbon have the potential to warm the atmosphere by absorbing light. Black carbon absorbs light over the entire solar spectrum whereas brown carbon absorbs near-UV wavelengths and, to a lesser extent, visible light. In developing countries, such as India, where combustion sources are prolific, the influence of brown carbon on absorption may be significant. In order to better characterize brown carbon, we present experimental and modeled absorption properties of submicron aerosols measured in an urban Indian city (Kanpur). Brown carbon here is found to be fivefold more absorbing at 365 nm wavelength compared to previous studies. Results suggest ~30% of total absorption in Kanpur is attributed to brown carbon, with primary organic aerosols contributing more than secondary organics. We report the spectral brown carbon refractive indices along with an experimentally constrained estimate of the influence of aerosol mixing state on absorption. We conclude that brown carbon in Kanpur is highly absorbing in nature and that the mixing state plays an important role in light absorption from volatile species. PMID:27883083

  19. Laboratory and field measurements of organic aerosols with the photoionization aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Dreyfus, Matthew A.

    . The high-time resolution data shows that rapid concentration changes of a common individual species can be lost with traditional bulk sampling, and a time resolution of 30 minutes is suggested to accurately represent these changes. Using the mass spectra collected from the extended sampling campaign, source apportionment was performed with positive matrix factorization (PMF). The resulting model features six factors either correlated to specific sources (meat cooking, car emissions/road dust, diesel exhaust) or types of compounds (phthalates, alkanes/alkanoic acids, PAHs). The high-time resolution data allowed for the observation of specific trends in each factor's behavior as a function of time and wind direction relative to the receptor site. Elemental carbon/organic carbon (EC/OC) data is used to calculate the percentages of primary and secondary organic aerosol. Primary organic aerosol (POA) constituted the vast majority of the total carbon at 91% (an average of 2.8 +/- 1.1mug/m 3); 30% of which came from combustion, and 70% from non-combustion sources. These results can be explained by the PIAMS data: the diesel factor contributes to the combustion-related POA; the car/road dust, meat cooking, and alkane/alkanoic acid factors contribute the majority of non-combustion POA. The remaining factors represent <5% of the remaining OC. Considering the compatibility of data from the EC/OC and PIAMS, the ability of PIAMS to yield molecular species information to further define the primary and secondary organic aerosol factions is a distinct advantage in describing the behavior of the Wilmington organic aerosol. PIAMS was also applied to laboratory experiments. These experiments simulated complex environmental processes in order to focus on answering a central question. By mixing cholesterol aerosol with ozone in a smog chamber, and monitoring the concentration of cholesterol with PIAMS, the rate of reaction was determined. This rate indicates that cholesterol aerosol

  20. Modeling of secondary organic aerosols from mobile sources in Mexico City

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    Mobile sources are significant contributors of emissions of CO, NOx, hydrocarbons and particle matter (PM) that constitute critical precursors of ozone as well as secondary organic and inorganic particles that decisively impact the photochemical levels and aerosol loadings in the atmosphere. Currently there are large uncertainties in regional air quality models during the treatment of aerosol formation from aerosol precursors via the production of condensable organic gases. As a result, the modeling of the concentrations and properties of aerosols resulted from mobile emissions sources is an important challenge. In this study we compare aerosol simulations using the PM-CAMx air quality model linked to the SAPRC99 chemical mechanism with measured aerosol data obtained during the MILAGRO/MCMA-2006 field campaign in Mexico City. The PM-CAMx modeling framework is based on the volatility-basis approach: both primary and secondary organic components are assumed to be photochemically reactive and are logarithmically distributed in volatility bins. The distinction of the volatility properties of aerosols precursors is particularly important for diesel and gasoline emission sources due to their different organic carbon speciation emissions profiles. Using this volatility-basis technique, we will present results on the relative contributions from both gasoline and diesel vehicle fleet emission sources to the formation of secondary organic aerosols in an urban area.

  1. The impact of biogenic carbon emissions on aerosol absorption inMexico City

    SciTech Connect

    Marley, N; Gaffney, J; Tackett, M J; Sturchio, N; Hearty, L; Martinez, N; Hardy, K D; Machany-Rivera, A; Guilderson, T P; MacMillan, A; Steelman, K

    2009-02-24

    In order to determine the wavelength dependence of atmospheric aerosol absorption in the Mexico City area, the absorption angstrom exponents (AAEs) were calculated from aerosol absorption measurements at seven wavelengths obtained with a seven-channel aethalometer during two field campaigns, the Mexico City Metropolitan Area study in April 2003 (MCMA 2003) and the Megacity Initiative: Local and Global Research Observations in March 2006 (MILAGRO). The AAEs varied from 0.76 to 1.56 in 2003 and from 0.54 to 1.52 in 2006. The AAE values determined in the afternoon were consistently higher than the corresponding morning values, suggesting the photochemical formation of absorbing secondary organic aerosols (SOA) in the afternoon. The AAE values were compared to stable and radiocarbon isotopic measurements of aerosol samples collected at the same time to determine the sources of the aerosol carbon. The fraction of modern carbon (fM) in the aerosol samples, as determined from {sup 14}C analysis, showed that 70% of the carbonaceous aerosols in Mexico City were from modern sources, indicating a significant impact from biomass burning during both field campaigns. The {sup 13}C/{sup 12}C ratios of the aerosol samples illustrate the significant impact of Yucatan forest fires (C-3 plants) in 2003 and local grass fires (C-4 plants) at site T1 in 2006. A direct comparison of the fM values, stable carbon isotope ratios, and calculated aerosol AAEs suggested that the wavelength dependence of the aerosol absorption was controlled by the biogenically derived aerosol components.

  2. Inorganic markers, carbonaceous components and stable carbon isotope from biomass burning aerosols in Northeast China.

    PubMed

    Cao, Fang; Zhang, Shi-Chun; Kawamura, Kimitaka; Zhang, Yan-Lin

    2016-12-01

    To better characterize the chemical compositions and sources of fine particulate matter (i.e. PM2.5) in Sanjiang Plain, Northeast China, total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions as well as stable carbon isotopic composition (δ(13)C) were measured in this study. Intensively open biomass burning episodes are identified from late September to early October by satellite fire and aerosol optical depth maps. During the biomass-burning episode, concentrations of PM2.5, OC, EC, and WSOC are increased by a factor of 4-12 compared to those during the non-biomass-burning period. Non-sea-salt potassium is strongly correlated with PM2.5, OC, EC and WSOC, demonstrating an important contribution from biomass-burning emissions. The enrichment in both the non-sea-salt potassium and chlorine is significantly larger than other inorganic species, suggesting that biomass-burning aerosols in Sanjiang Plain are mostly fresh and less aged. In addition, the WSOC-to-OC ratio is lower than that reported in biomass-burning aerosols in tropical regions, further supporting that biomass-burning aerosols in Sanjiang Plain are mostly primary and secondary organic aerosols may be not significant. A lower average δ(13)C value (-26.2‰) is observed during the biomass-burning period, indicating a dominant contribution from combustion of C3 plants in the studied region.

  3. Ultraviolet Absorption by Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Secondary organic aerosols (SOA) are typically formed in the atmosphere by the condensation of a myriad of intermediates from the photo-oxidation of volatile organic compounds (VOCs). Many of these partly oxidized molecules have functional groups (chromophores) that absorb at the ultraviolet (UV) wavelengths available in the troposphere (λ ≳ 290 nm). We used the explicit chemical model GECKO-A (Generator of Explicit Chemistry and Kinetics for Organics in the Atmosphere) to estimate UV absorption cross sections for the gaseous and particulate components of SOA from different precursors (biogenic and anthropogenic) and formed in different environments (low and high NOx, day and night). Model predictions are evaluated with laboratory and field measurements of SOA UV optical properties (esp. mass absorption coefficients and single scattering albedo), and implications are presented for surface UV radiation trends, urban actinic flux modification, and SOA lifetimes.

  4. Effects of aerosol organics on cloud condensation nucleus (CCN) concentration and first indirect aerosol effect

    SciTech Connect

    Wang, J. X.; Lee, Y.- N.; Daum, Peter H.; Jayne, John T.; Alexander, M. L.

    2008-11-03

    Abstract. Aerosol microphysics, chemical composition, and CCN properties were measured on the Department of Energy Gulfstream-1 aircraft during the Marine Stratus/ Stratocumulus Experiment (MASE) conducted over the coastal waters between Point Reyes National Seashore and Monterey Bay, California, in July 2005. Aerosols measured during MASE included free tropospheric aerosols, marine boundary layer aerosols, and aerosols with high organic concentration within a thin layer above the cloud. Closure analysis was carried out for all three types of aerosols by comparing the measured CCN concentrations at 0.2% supersaturation to those predicted based on size distribution and chemical composition using K¨ohler theory. The effect of aerosol organic species on predicted CCN concentration was examined using a single hygroscopicity parameterization.

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

    SciTech Connect

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

    1999-06-07

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

  6. Implementation and initial application of new chemistry-aerosol options in WRF/Chem for simulating secondary organic aerosols and aerosol indirect effects for regional air quality

    NASA Astrophysics Data System (ADS)

    Wang, Kai; Zhang, Yang; Yahya, Khairunnisa; Wu, Shiang-Yuh; Grell, Georg

    2015-08-01

    Atmospheric aerosols play important roles in affecting regional meteorology and air quality through aerosol direct and indirect effects. Two new chemistry-aerosol options have been developed in WRF/Chem v3.4.1 by incorporating the 2005 Carbon Bond (CB05) mechanism and coupling it with the existing aerosol module MADE with SORGAM and VBS modules for simulating secondary organic aerosol (SOA), aqueous-phase chemistry in both large scale and convective clouds, and aerosol feedback processes (hereafter CB05-MADE/SORGAM and CB05-MADE/VBS). As part of the Air Quality Model Evaluation International Initiative (AQMEII) Phase II model intercomparison that focuses on online-coupled meteorology and chemistry models, WRF/Chem with the two new options is applied to an area over North America for July 2006 episode. The simulations with both options can reproduce reasonably well most of the observed meteorological variables, chemical concentrations, and aerosol/cloud properties. Compared to CB05-MADE/SORGAM, CB05-MADE/VBS greatly improves the model performance for organic carbon (OC) and PM2.5, reducing NMBs from -81.2% to -13.1% and from -26.1% to -15.6%, respectively. Sensitivity simulations show that the aerosol indirect effects (including aqueous-phase chemistry) can reduce the net surface solar radiation by up to 53 W m-2 with a domainwide mean of 12 W m-2 through affecting cloud formation and radiation scattering and reflection by increasing cloud cover, which in turn reduce the surface temperature, NO2 photolytic rate, and planetary boundary layer height by up to 0.3 °C, 3.7 min-1, and 64 m, respectively. The changes of those meteorological variables further impact the air quality through the complex chemistry-aerosol-cloud-radiation interactions by reducing O3 mixing ratios by up to 5.0 ppb. The results of this work demonstrate the importance of aerosol indirect effects on the regional climate and air quality. For comparison, the impacts of aerosol direct effects on both

  7. Black Carbon, Aerosols, and the Tooth Fairy

    NASA Astrophysics Data System (ADS)

    Buseck, P. R.; Adachi, K.; Posfai, M.

    2012-12-01

    Black carbon (BC) is widely cited in the atmospheric literature as a major aerosol particle type with significant effects on climate warming. Several analytical techniques are used for its determination, primarily through optical absorption measurements. A recently developed and widely used method is single particle soot photometry (SP2). During attempts to obtain reliable BC samples for study using transmission electron microscopy (TEM), it became apparent that no such samples exist. Instead, surrogate materials such as graphite, fullerene, Aquadag, and perhaps other things are used as calibration standards. It became rapidly evident that BC is an inferred rather than actual, identifiable substance with distinct material properties other than its absorption spectrum and refractory character (accounting for the subset of refractory black carbon, or rBC). Since climate effects depend on optical properties, and these are estimated for BC, it may not be critical at this time whether or not it is a discrete material. However, the same term is also used by other environmental communities for things that are distinctly different. Such imprecision in terms can lead to unnecessary confusion. The situation is summarized in the Table. We propose that 1) the term BC should be restricted to light-absorbing refractory carbonaceous matter of uncertain character and 2) the uncertainty be stated explicitly. We also propose a more precise definition for soot as a specific material, which we call ns-soot, where "ns" refers to carbon nanospheres. We define ns-soot as particles that consist of nanospheres, typically with diameters <100 nm, that possess distinct structures of concentrically wrapped, graphene-like layers of carbon and with grape-like (acinoform) morphologies.;

  8. A novel aerosol mass spectrometric approach - Analysis of the organic molecular signature of PM by coupling of thermal EC/OC-carbon analysis to photo-ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Zimmermann, R.; Grabowski, J.; Streibel, T.; Sklorz, M.; Chow, J.

    2012-12-01

    Carbonaceous material in airborne particulate matter (PM) is of increasing interest e.g. due to its adverse health effects and its potential influence on the climate. Its analytical assessment on a molecular level is still very challenging. Hence, analysis of carbonaceous fractions for many studies is often solely carried out by determining sum parameters such as the overall content of organic carbon (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC). The used thermal procedure, however, allows getting additional interesting information: By defining different thermal OC fractions (i.e. temperature steps) also information on the refractory properties of the carbonaceous material is obtained. In this context it is particularly interesting to investigate the release and formation behaviors of the molecular species responsible for the different OC and EC fractions. Thus after initial promising results of pre-studies [1,2] in the current work an EC/OC carbon analyzer (Model DRI 2000) and a homebuilt photo-ionization time-of-flight mass spectrometer (PI-TOFMS) were hyphenated and applied to investigate individual organic compounds especially from the different OC fractions. The carbon analyzer enables the stepwise heating of PM loaded filter samples and provides the sum values of the "carbon" release ("Improve protocol" [2]: OC1 - 120 °C, OC2 - 250°C, OC3 - 450°C OC4 - 550°C). With the on-line coupled PI-TOFMS evolved organic compounds, as released during the thermal program, are detectable in real time. This is possible by MS with soft photo ionization methods (SPI - single photon ionization and REMPI - resonance-enhanced multi photon ionization). Soft ionization suppresses fragmentation upon the ionization step and generates molecular signatures in the MS. The EC/OC-analyzer-PI-TOFMS instrument was applied to several types of PM samples, such as ambient aerosol, emission samples (gasoline/diesel car, wood combustion) or

  9. Los Angeles Basin airborne organic aerosol characterization during CalNex

    NASA Astrophysics Data System (ADS)

    Craven, J. S.; Metcalf, A. R.; Bahreini, R.; Middlebrook, A.; Hayes, P. L.; Duong, H. T.; Sorooshian, A.; Jimenez, J. L.; Flagan, R. C.; Seinfeld, J. H.

    2013-10-01

    We report airborne organic aerosol (OA) measurements over Los Angeles carried out in May 2010 as part of the CalNex field campaign. The principal platform for the airborne data reported here was the CIRPAS Twin Otter (TO); airborne data from NOAA WP-3D aircraft and Pasadena CalNex ground-site data acquired during simultaneous TO flybys are also presented. Aerodyne aerosol mass spectrometer measurements constitute the main source of data analyzed. The increase in organic aerosol oxidation from west to east in the basin was sensitive to OA mass loading, with a greater spatial trend in O:C associated with lower mass concentration. Three positive matrix factorization (PMF) components (hydrocarbon-like organic aerosol (HOA), semi-volatile oxidized organic aerosol (SVOOA), and low volatility oxidized organic aerosol (LVOOA)) were resolved for the one flight that exhibited the largest variability in estimated O:C ratio. Comparison of the PMF factors with two optical modes of refractory black carbon (rBC)-containing aerosol revealed that the coating of thinly coated rBC-containing aerosol, dominant in the downtown region, is likely composed of HOA, whereas more thickly coated rBC-containing aerosol, dominant in the Banning pass outflow, is composed of SVOOA and LVOOA. The correlation of water-soluble organic mass to oxidized organic aerosol (OOA) is higher in the outflows than in the basin due to the higher mass fraction of OOA/OA in the outflows. By comparison, the average OA concentration over Mexico City MILAGRO (Megacity Initiative: Local and Global Research Observations) campaign was ˜7 times higher than the airborne average during CalNex.

  10. A naming convention for atmospheric organic aerosol

    NASA Astrophysics Data System (ADS)

    Murphy, B. N.; Donahue, N. M.; Robinson, A. L.; Pandis, S. N.

    2014-06-01

    While the field of atmospheric organic aerosol scientific research has experienced thorough and insightful progress over the last half century, this progress has been accompanied by the evolution of a communicative and detailed yet, at times, complex and inconsistent language. The menagerie of detailed classification that now exists to describe organic compounds in our atmosphere reflects the wealth of observational techniques now at our disposal as well as the rich information provided by state-of-the-science instrumentation. However, the nomenclature in place to communicate these scientific gains is growing disjointed to the point that effective communication within the scientific community and to the public may be sacrificed. We propose standardizing a naming convention for organic aerosol classification that is relevant to laboratory studies, ambient observations, atmospheric models, and various stakeholders for air-quality problems. Because a critical aspect of this effort is to directly translate the essence of complex physico-chemical phenomena to a much broader, policy-oriented audience, we recommend a framework that maximizes comprehension among scientists and non-scientists alike. For example, to classify volatility, it relies on straightforward alphabetic terms (e.g., semivolatile, SV; intermediate volatility, IV; etc.) rather than possibly ambiguous numeric indices. This framework classifies organic material as primary or secondary pollutants and distinguishes among fundamental features important for science and policy questions including emission source, chemical phase, and volatility. Also useful is the addition of an alphabetic suffix identifying the volatility of the organic material or its precursor for when emission occurred. With this framework, we hope to introduce into the community a consistent connection between common notation for the general public and detailed nomenclature for highly specialized discussion. In so doing, we try to maintain

  11. Secondary organic aerosol formation from the irradiation of simulated automobile exhaust.

    PubMed

    Kleindienst, T E; Corse, E W; Li, W; McIver, C D; Conver, T S; Edney, E O; Driscoll, D J; Speer, R E; Weathers, W S; Tejada, S B

    2002-03-01

    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 (SOA) and how well their formation is described by recently developed models for SOA formation. The quality of a surrogate was tested by comparing its reactivity with that from irradiations of authentic automobile exhaust. Experiments for secondary particle formation using the surrogate were conducted in a fixed volume reactor operated in a dynamic mode. The mass concentration of the aerosol was determined from measurements of organic carbon collected on quartz filters and was corrected for the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. A functional group analysis of the aerosol made by Fourier transform infrared (FTIR) spectroscopy indicated

  12. On the Physicochemical Processes Controlling Organic Aerosol Hygroscopicity

    NASA Astrophysics Data System (ADS)

    Petters, Sarah Suda

    Aerosol particles in the atmosphere can influence air quality and climate through their interaction with water. Aerosols are an important factor in cloud formation because they serve as cloud condensation nuclei (CCN). Organic compounds contribute a large fraction of the atmospheric aerosol mass but their ability to serve as CCN is less certain relative to inorganic compounds. Limitations of the measurement techniques and theoretical gaps in understanding have prevented agreement between predicted and measured CCN. One way to quantify a compound's CCN activity is by the hygroscopicity parameter, kappa. This dissertation presents research towards constraining the variability of organic aerosol kappa at the process level using three approaches: developing a measurement technique; measuring the dependence of kappa on molecular functional groups; and measuring the effect of surface active molecules on kappa for mixtures. Chapter 2 presents a Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) instrument to measure aerosol water uptake at high relative humidity (RH). Measurements up to 99% RH were achieved by improving the precision of aerosol sizing, actively controlling temperature, and calibrating RH between measurements. Osmotic coefficients were obtained within +/-20% for organic aerosols sized between 30 and 200 nanometers. These results may improve water uptake models by providing accurate data at high RH. Chapter 3 presents a study of the sensitivity of kappa to changes in molecular functional group composition for pure compounds. Molecules were synthesized via gas and liquidphase reactions varying the type and location of functional groups, purified by High Performance Liquid Chromatography (HPLC), and routed for CCN measurement. The hydroxyl (-OH) and carbon chain length (-CH2-) changed kappa most, where hydroxyl groups increase kappa and longer carbon chains decrease kappa. This suggests that hydroxyl groups and molecular size dominate the

  13. Quantification of black carbon mixing state from traffic: Implications for aerosol optical properties

    SciTech Connect

    Willis, Megan D.; Healy, Robert M.; Riemer, Nicole; West, Matthew; Wang, Jon M.; Jeong, Cheol -Heon; Wenger, John C.; Evans, Greg J.; Abbatt, Jonathan P. D.; Lee, Alex K. Y.

    2016-04-14

    The climatic impacts of black carbon (BC) aerosol, an important absorber of solar radiation in the atmosphere, remain poorly constrained and are intimately related to its particle-scale physical and chemical properties. Using particle-resolved modelling informed by quantitative measurements from a soot-particle aerosol mass spectrometer, we confirm that the mixing state (the distribution of co-emitted aerosol amongst fresh BC-containing particles) at the time of emission significantly affects BC-aerosol optical properties even after a day of atmospheric processing. Both single particle and ensemble aerosol mass spectrometry observations indicate that BC near the point of emission co-exists with hydrocarbon-like organic aerosol (HOA) in two distinct particle types: HOA-rich and BC-rich particles. The average mass fraction of black carbon in HOA-rich and BC-rich particle classes was  < 0.1 and 0.8, respectively. Notably, approximately 90 % of BC mass resides in BC-rich particles. This new measurement capability provides quantitative insight into the physical and chemical nature of BC-containing particles and is used to drive a particle-resolved aerosol box model. Lastly, significant differences in calculated single scattering albedo (an increase of 0.1) arise from accurate treatment of initial particle mixing state as compared to the assumption of uniform aerosol composition at the point of BC injection into the atmosphere.

  14. Quantification of black carbon mixing state from traffic: Implications for aerosol optical properties

    DOE PAGES

    Willis, Megan D.; Healy, Robert M.; Riemer, Nicole; ...

    2016-04-14

    The climatic impacts of black carbon (BC) aerosol, an important absorber of solar radiation in the atmosphere, remain poorly constrained and are intimately related to its particle-scale physical and chemical properties. Using particle-resolved modelling informed by quantitative measurements from a soot-particle aerosol mass spectrometer, we confirm that the mixing state (the distribution of co-emitted aerosol amongst fresh BC-containing particles) at the time of emission significantly affects BC-aerosol optical properties even after a day of atmospheric processing. Both single particle and ensemble aerosol mass spectrometry observations indicate that BC near the point of emission co-exists with hydrocarbon-like organic aerosol (HOA) inmore » two distinct particle types: HOA-rich and BC-rich particles. The average mass fraction of black carbon in HOA-rich and BC-rich particle classes was  < 0.1 and 0.8, respectively. Notably, approximately 90 % of BC mass resides in BC-rich particles. This new measurement capability provides quantitative insight into the physical and chemical nature of BC-containing particles and is used to drive a particle-resolved aerosol box model. Lastly, significant differences in calculated single scattering albedo (an increase of 0.1) arise from accurate treatment of initial particle mixing state as compared to the assumption of uniform aerosol composition at the point of BC injection into the atmosphere.« less

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

    EPA Science Inventory

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

  16. Water absorption by secondary organic aerosol and its effect on inorganic aerosol behavior

    SciTech Connect

    Ansari, A.S.; Pandis, S.N.

    2000-01-01

    The hygroscopic nature of atmospheric aerosol has generally been associated with its inorganic fraction. In this study, a group contribution method is used to predict the water absorption of secondary organic aerosol (SOA). Compared against growth measurements of mixed inorganic-organic particles, this method appears to provide a first-order approximation in predicting SOA water absorption. The growth of common SOA species is predicted to be significantly less than common atmospheric inorganic salts such as (NH{sub 4}){sub 2}SO{sub 4} and NaCl. Using this group contribution method as a tool in predicting SOA water absorption, an integrated modeling approach is developed combining available SOA and inorganic aerosol models to predict overall aerosol behavior. The effect of SOA on water absorption and nitrate partitioning between the gas and aerosol phases is determined. On average, it appears that SOA accounts for approximately 7% of total aerosol water and increases aerosol nitrate concentrations by approximately 10%. At high relative humidity and low SOA mass fractions, the role of SOA in nitrate partitioning and its contribution to total aerosol water is negligible. However, the water absorption of SOA appears to be less sensitive to changes in relative humidity than that of inorganic species, and thus at low relative humidity and high SOA mass fraction concentrations, SOA is predicted to account for approximately 20% of total aerosol water and a 50% increase in aerosol nitrate concentrations. These findings could improve the results of modeling studies where aerosol nitrate has often been underpredicted.

  17. Distribution of dicarboxylic acids and carbon isotopic compositions in aerosols from 1997 Indonesian forest fires

    NASA Astrophysics Data System (ADS)

    Narukawa, M.; Kawamura, K.; Takeuchi, N.; Nakajima, T.

    Fine aerosol particles collected in Southeast Asia during 1997 Indonesian forest fires were studied for the concentrations of total carbon (TC), water-soluble organic carbon (WSOC) and low molecular weight dicarboxylic acids (C2-C12) as well as carbon isotopic ratios of TC (δ13CTC). TC and WSOC showed a large increase during the heavy forest fire event. At the same period, dicarboxylic acids, dominated by oxalic (C2) followed by succinic (C4) and malonic (C3) acids, also showed a concentration increase. Furthermore, the δ13CTC showed a decrease from ca. -25.5 to -27.5‰ during an intensified forest fire event, suggesting an addition of organic aerosols derived from C3 plants whose δ13C are lighter. These results indicate that the aerosol particles in Southeast Asia were significantly affected by the combustion processes of vegetations during the 1997 Indonesian forest fires that were extensively induced by El Ninõ event.

  18. The Organic Aerosols of Titan's Atmosphere

    NASA Technical Reports Server (NTRS)

    Sotin, Christophe; Lawrence, Kenneth; Beauchamp, Patricia M.; Zimmerman, Wayne

    2012-01-01

    One of Titan's many characteristics is the presence of a haze that veils its surface. This haze is composed of heavy organic particles and determining the chemical composition of these particles is a primary objective for future probes that would conduct in situ analysis. Meanwhile, solar occultations provide constraints on the optical characteristics of the haze layer. This paper describes solar occultation observations obtained by the Visual and Infrared Mapping Spectrometer (VIMS) onboard the Cassini spacecraft. These observations strongly constrain the optical characteristics of the haze layer. We detail the different steps involved in the processing of these data and apply them to two occultations that were observed at the South Pole and at the equator in order to investigate the latitudinal dependence of optical properties. The light curves obtained in seven atmospheric windows between 0.933-microns to 5-microns allow us to characterize atmospheric layers from 300 km to the surface. Very good fits of the light curves are obtained using a simple profile of number density of aerosols that is characterized by a scale height. The main difference between the South Pole and the equator is that the value of the scale height increases with altitude at the South Pole whereas it decreases at the equator. The vertically integrated amount of aerosols is similar at the two locations. The curve describing the cross-section versus wavelength is identical at the two locations suggesting that the aerosols have similar characteristics. Finally, we find that the two-way vertical transmission at 5-microns is as large as 80% at both locations.

  19. Water uptake impedance of glassy organic aerosols

    NASA Astrophysics Data System (ADS)

    Peter, T.; Zobrist, B.; Krieger, U. K.; Luo, B. P.; Soonsin, V.; Marcolli, C.; Koop, T.

    2009-04-01

    Depending on their concentration and composition, aerosols affect various atmospheric properties and processes, such as atmospheric chemistry and Earth's radiative budget. The atmospheric aerosol itself is a complex mixture of various inorganic and organic components, whereas the organic fraction can represent more than 50% of the total aerosol mass. It was recently shown that aerosols high in organics may be present in a glassy state (Zobrist et al., ACP, 8, 5221-5244, 2008). The glassy nature of the aerosols may influence their properties and restrict their functionalities severely, e.g. their water uptake, heterogeneous chemical reactions in their bulk or on their surfaces, as well as ice nucleation and ice crystal growth. Here, we present the first experiments on the water uptake by single levitated glassy aerosol particles using an electrodynamic balance (EDB). Sucrose was chosen as a model substance, which comprises functional groups typical of organic species in the atmosphere. In addition we developed a microphysical model, which enables us to calculate the liquid diffusion inside a glassy particle using water diffusion coefficients in aqueous sucrose particles adapted from the literature. As the diffusion coefficient of water in the particle, D(cH2O), depends on the water concentration cH2O itself, the solution of the diffusion equation presents an interesting non-linear problem. The combined experimental and modelling approach allows describing in detail the water uptake by glassy aerosols at atmospherically relevant temperatures and relative humidities (RH). Hygroscopicity cycles were perfomed in the EDB starting from a crystalline (non-spherical) sucrose particle at 291 K. No water uptake was observed while RH was increased until the particle deliquesces at roughly 85% RH leading to a liquid (spherical) particle. In the subsequent drying cycle, surprisingly no efflorescence was observed when the particle was dried to below 5% and it remained spherical

  20. Small molecules as tracers in atmospheric secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Yu, Ge

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

  1. THERMODYNAMIC MODELING OF LIQUID AEROSOLS CONTAINING DISSOLVED ORGANICS AND ELECTROLYTES

    EPA Science Inventory

    Many tropospheric aerosols contain large fractions of soluble organic material, believed to derive from the oxidation of precursors such alpha-pinene. The chemical composition of aerosol organic matter is complex and not yet fully understood.

    The key properties of solu...

  2. Source contributions to organic aerosol in the eastern United States

    NASA Astrophysics Data System (ADS)

    Lane, Timothy Edward

    Organic aerosols (OA) and elemental carbon (EC) are important components of atmospheric particulate matter (PM), potentially posing health hazards and contributing to global climate change. Secondary organic aerosol (SOA) is formed when condensable products from the oxidation of volatile organic compounds (VOCs) in the gas phase partition into the aerosol phase. Implementation of effective control strategies for organic PM2.5 (organic particles with diameters less than 2.5 mum) requires the quantification of the contribution of each source to the ambient OA and EC concentrations. The overall goal of this work is to determine which sources contribute the most to the organic aerosol concentrations across the eastern US. First, a source-resolved model is developed to predict the contribution of eight different sources to primary organic aerosol concentrations. Primary organic aerosol (OA) and elemental carbon (EC) concentrations are tracked for eight different sources: gasoline vehicles, non-road diesel vehicles, on-road diesel vehicles, biomass burning, wood burning, natural gas combustion, road dust, and all other sources. The results of the source-resolved model are compared to the results of chemical mass balance (CMB) models for Pittsburgh and multiple urban/rural sites from the Southeastern Aerosol Research and Characterization (SEARCH) network. Significant discrepancies exist between the source-resolved model and the CMB model predictions for several of the sources. There is strong evidence that the organic PM emissions from natural gas combustion are overestimated. Other similarities and discrepancies between the source-resolved model and the CMB model for primary OA and EC are discussed along with problems in the current emission inventory for certain sources. Next, the importance of isoprene as a source of SOA is determined using PMCAMx to predict the isoprene SOA concentration across the eastern US. Isoprene, the most abundant non-methane hydrocarbon

  3. CARES Helps Explain Secondary Organic Aerosols

    SciTech Connect

    Zaveri, Rahul

    2014-03-28

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

  4. CARES Helps Explain Secondary Organic Aerosols

    ScienceCinema

    Zaveri, Rahul

    2016-07-12

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

  5. 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.

  6. 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

  7. 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

  8. Atmospheric aerosol brown carbon in the high Himalayas

    NASA Astrophysics Data System (ADS)

    Kirillova, Elena; Decesari, Stefano; Marinoni, Angela; Bonasoni, Paolo; Vuillermoz, Elisa; Facchini, M. Cristina; Fuzzi, Sandro

    2016-04-01

    Anthropogenic light-absorbing atmospheric aerosol can reach very high concentrations in the planetary boundary layer in South-East Asia ("brown clouds"), affecting atmospheric transparency and generating spatial gradients of temperature over land with a possible impact on atmospheric dynamics and monsoon circulation. Besides black carbon (BC), an important light-absorbing component of anthropogenic aerosols is the organic carbon component known as 'brown carbon' (BrC). In this research, we provided first measurements of atmospheric aerosol BrC in the high Himalayas during different seasons. Aerosol sampling was conducted at the GAW-WMO Global station "Nepal Climate Observatory-Pyramid" (NCO-P) located in the high Khumbu valley at 5079 m a.s.l. in the foothills of Mt. Everest. PM10 aerosol samples were collected from July 2013 to November 2014. The sampling strategy was set up in order to discriminate the daytime valley breeze bringing polluted air masses up to the observatory and free tropospheric air during nighttime. Water-soluble BrC (WS-BrC) and methanol-soluble BrC (MeS-BrC) were extracted and analyzed using a UV/VIS spectrophotometer equipped with a 50 cm liquid waveguide capillary cell. In the polluted air masses, the highest levels of the BrC light absorption coefficient at 365 nm (babs365) were observed during the pre-monsoon season (1.83±1.46 Mm-1 for WS-BrC and 2.86±2.49 Mm-1 for MeS-BrC) and the lowest during the monsoon season (0.21±0.22 Mm-1 for WS-BrC and 0.32±0.29 Mm-1 for MeS-BrC). The pre-monsoon season is the most frequently influenced by a strong atmospheric brown cloud (ABC) transport to NCO-P due to increased convection and mixing layer height over South Asia combined with the highest up-valley wind speed and the increase of the emissions from open fires due to the agricultural practice along the Himalayas foothills and the Indo-Gangetic Plain. In contrast, the monsoon season is characterized by a weakened valley wind regime and an

  9. New Insights On The Link Between Oceanic Vegetation and Marine Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Facchini, M.; Rinaldi, M.; Decesari, S.; Finessi, E.; Carbone, C.; Fuzzi, S.; Ceburnis, D.; O'Dowd, C.

    2008-12-01

    Until a few years ago the link between vegetation and aerosol particles in marine environment was centered on the DMS emission from phytoplankton and the sulphur cycle. More recently, observation carried out in the North Atlantic as well as in other marine locations evidenced a seasonal dependence of sub micron particle chemical composition on biological oceanic activity and a potentially important marine aerosol organic component from primary and/or secondary formation processes associated to marine vegetation and its seasonal cycle. Here we show recent results obtained within the EC project MAP which allowed to discriminate primary and secondary organic marine aerosol components of biogenic origin. Bubble-mediated experiments carried out during phytoplankton blooms in the North Atlantic revealed that organic carbon in nascent submicron spray particles was highly enriched in the finest fraction, constituting up to 77 % in mass of the aerosol in the 0.125-0.25 micrometer size range and was almost entirely water insoluble (96% on average). 1H NMR analysis showed that WIOM in nascent marine aerosol forms from aggregation of lipopolysaccharides exuded by phytoplankton. Being marine aerosol WIOC mainly associated to primary production mechanisms, a direct consequence of this observation is that the water soluble fraction (WSOC) is mainly accounted for by secondary organic aerosol. This fact was also clearly evidenced by the analysis of the WSOC fraction of marine aerosol samples collected during MAP. The aerosol WSOC was dominated by MSA and two organic N species (ammonium salts of biogenic amines) and by several oxygenated species (mainly carboxylic acids and ketons). These results evidence the important contribution of organic nitrogen in North Atlantic marine SOA.

  10. MATRIX-VBS Condensing Organic Aerosols in an Aerosol Microphysics Model

    NASA Technical Reports Server (NTRS)

    Gao, Chloe Y.; Tsigaridis, Konstas; Bauer, Susanne E.

    2015-01-01

    The condensation of organic aerosols is represented in a newly developed box-model scheme, where its effect on the growth and composition of particles are examined. We implemented the volatility-basis set (VBS) framework into the aerosol mixing state resolving microphysical scheme Multiconfiguration Aerosol TRacker of mIXing state (MATRIX). This new scheme is unique and advances the representation of organic aerosols in models in that, contrary to the traditional treatment of organic aerosols as non-volatile in most climate models and in the original version of MATRIX, this new scheme treats them as semi-volatile. Such treatment is important because low-volatility organics contribute significantly to the growth of particles. The new scheme includes several classes of semi-volatile organic compounds from the VBS framework that can partition among aerosol populations in MATRIX, thus representing the growth of particles via condensation of low volatility organic vapors. Results from test cases representing Mexico City and a Finish forrest condistions show good representation of the time evolutions of concentration for VBS species in the gas phase and in the condensed particulate phase. Emitted semi-volatile primary organic aerosols evaporate almost completely in the high volatile range, and they condense more efficiently in the low volatility range.

  11. Organic Composition and Morphology of Sea Spray Aerosols as a Function of Biological Life during IMPACTS

    NASA Astrophysics Data System (ADS)

    Pham, D.; Moffet, R.; Fraund, M. W.; O'Brien, R.; Laskina, O.; Prather, K. A.; Grassian, V. H.; Beall, C.; Wang, X.; Forestieri, S.; Cappa, C. D.

    2015-12-01

    Aerosols influence climate by directly reflecting or absorbing sunlight, or indirectly by affecting clouds. A major source of aerosols is from oceanic wave breaking. Due to their complexity, the effects of marine aerosol on climate are uncertain. To provide more detailed measurements of the chemical composition of marine aerosols, Scanning Transmission X-Ray Microscopy coupled with Near Edge X-Ray Absorption Fine Structure (SXTM-NEXAFS) was used to give spatially resolved molecular information for carbon and oxygen. Application of STXM/NEXAFS to particles collected during a mesocosm study using a unique wave channel facility to generate aerosols shows that the organic volume fraction of aerosols at the aerodynamic diameter size range of 0.18-0.32 μm are a direct function of the biological activity in the sea water. Aerosol organic volume fraction increased from 0.32 for particles generated from seawater containing low biolife to 0.49 and 0.40 for particles produced during phytoplankton blooms. However, the organic volume fraction of aerosols at the aerodynamic diameter size range of 0.56-1 μm did not change with biological activity. Measurements also show that different types of organics can concentrate into aerosols depending on the enzyme activity expressed at the time. Enhanced spectral signatures for aliphatic hydrocarbons were observed during the first phytoplankton bloom compared to a second phytoplankton bloom occurring directly thereafter. The decreased signature of aliphatic organics in the second phytoplankton bloom was correlated with increased lipase activity from heterobacteria. Organic aggregates having similar morphology also differ in composition from their carbon spectra from the two blooms. For July 17, organic aggregates were much richer in hydrocarbons, which showed a remarkably intense C-H absorbance and a broad C-C absorbance. Organic aggregates observed for July 26-27, did not have the C-H and C-C signatures, but contained more polar

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

    PubMed

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

    2007-01-01

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

  13. 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

  14. Organic Mass Fragments and Organic Functional Groups in Aged Biomass Burning and Fossil Fuel Combustion Aerosol

    NASA Astrophysics Data System (ADS)

    Day, D. A.; Hawkins, L. N.; Russell, L. M.

    2009-12-01

    Organic functional group concentrations in submicron aerosol particles collected from 27 June to 17 September at the Scripps Pier in La Jolla, California as part of AeroSCOPE 2008 were quantified using Fourier Transform Infrared (FTIR) spectroscopy. Organic and inorganic non-refractory components in the same air masses were quantified using a Quadrupole Aerosol Mass Spectrometer (Q-AMS). Previous measurements at the Scripps pier indicate that a large fraction of submicron particle mass originates in Los Angeles and the port of Long Beach. Additional particle sources to the region include local urban emissions and periodic biomass burning during large wildfires. Three distinct types of organic aerosol components were identified from organic composition and elemental tracers, including biomass burning, fossil fuel combustion, and polluted marine components. Fossil fuel combustion organic aerosol was dominated by unsaturated alkane and was correlated with sulfur, vanadium, and nickel supporting ship and large trucks in and around the Los Angeles/Long Beach region as the dominant source. Biomass burning organic aerosol comprised a smaller unsaturated alkane fraction and larger fractions of non-acid carbonyl, amine, and carboxylic acid and was correlated with potassium and bromine. Polluted marine organic aerosol was dominated by organic hydroxyl and unsaturated alkane and was not correlated with any elemental tracers. Mass spectra of the organic aerosol support the aerosol sources determined by organic functional groups and elemental tracers and contain fragments commonly attributed to oxygenated organic aerosol (OOA), hydrocarbon-like organic aerosol (HOA), and biomass burning organic aerosol (BBOA). Comparisons of the PMF-derived Q-AMS source spectra with FTIR source spectra and functional group composition provide additional information on the relationship between commonly reported organic aerosol factors and organic functional groups in specific organic aerosol

  15. Can scooter emissions dominate urban organic aerosol?

    NASA Astrophysics Data System (ADS)

    El Haddad, Imad; Platt, Stephen; Huang, Ru-Jin; Zardini, Alessandro; Clairotte, Micheal; Pieber, Simone; Pfaffenberger, Lisa; Fuller, Steve; Hellebust, Stig; Temime-Roussel, Brice; Slowik, Jay; Chirico, Roberto; Kalberer, Markus; Marchand, Nicolas; Dommen, Josef; Astorga, Covadonga; Baltensperger, Urs; Prevot, Andre

    2014-05-01

    In urban areas, where the health impact of pollutants increases due to higher population density, traffic is a major source of ambient organic aerosol (OA). A significant fraction of OA from traffic is secondary, produced via the reaction of exhaust volatile organic compounds (VOCs) with atmospheric oxidants. Secondary OA (SOA) has not been systematically assessed for different vehicles and driving conditions and thus its relative importance compared to directly emitted, primary OA (POA) is unknown, hindering the design of effective vehicle emissions regulations. 2-stroke (2S) scooters are inexpensive and convenient and as such a popular means of transportation globally, particularly in Asia. European regulations for scooters are less stringent than for other vehicles and thus primary particulate emissions and SOA precursor VOCs from 2S engines are estimated to be much higher. Assessing the effects of scooters on public health requires consideration of both POA, and SOA production. Here, we quantify POA emission factors and potential SOA EFs from 2S scooters, and the effect of using aromatic free fuel instead of standard gasoline thereon. During the tests, Euro 1 and Euro 2 2S scooters were run in idle or simulated low power conditions. Emissions from a Euro 2 2S scooter were also sampled during regulatory driving cycles on a chassis dynamometer. Vehicle exhaust was introduced into smog chambers, where POA emission and SOA production were quantified using a high-resolution time-of-flight aerosol mass spectrometer. A high resolution proton transfer time-of-flight mass spectrometer was used to investigate volatile organic compounds and a suite of instruments was utilized to quantify CO, CO2, O3, NOX and total hydrocarbons. We show that the oxidation of VOCs in the exhaust emissions of 2S scooters produce significant SOA, exceeding by up to an order of magnitude POA emissions. By monitoring the decay of VOC precursors, we show that SOA formation from 2S scooter

  16. Global distribution and climate forcing of marine organic aerosol: 1. Model improvements and evaluation

    SciTech Connect

    Meskhidze, N.; Xu, J.; Gantt, Brett; Zhang, Yang; Nenes, Athanasios; Ghan, Steven J.; Liu, Xiaohong; Easter, Richard C.; Zaveri, Rahul A.

    2011-11-23

    Marine organic aerosol emissions have been implemented and evaluated within the National Center of Atmospheric Research (NCAR)'s Community Atmosphere Model (CAM5) with the Pacific Northwest National Laboratory's 7-mode Modal Aerosol Module (MAM-7). Emissions of marine primary organic aerosols (POA), phytoplanktonproduced isoprene- and monoterpenes-derived secondary organic aerosols (SOA) and methane sulfonate (MS{sup -}) are shown to affect surface concentrations of organic aerosols in remote marine regions. Global emissions of submicron marine POA is estimated to be 7.9 and 9.4 Tg yr{sup -1}, for the Gantt et al. (2011) and Vignati et al. (2010) emission parameterizations, respectively. Marine sources of SOA and particulate MS{sup -} (containing both sulfur and carbon atoms) contribute an additional 0.2 and 5.1 Tg yr{sup -1}, respectively. Widespread areas over productive waters of the Northern Atlantic, Northern Pacific, and the Southern Ocean show marine-source submicron organic aerosol surface concentrations of 100 ngm{sup -3}, with values up to 400 ngm{sup -3} over biologically productive areas. Comparison of long-term surface observations of water insoluble organic matter (WIOM) with POA concentrations from the two emission parameterizations shows that despite revealed discrepancies (often more than a factor of 2), both Gantt et al. (2011) and Vignati et al. (2010) formulations are able to capture the magnitude of marine organic aerosol concentrations, with the Gantt et al. (2011) parameterization attaining better seasonality. Model simulations show that the mixing state of the marine POA can impact the surface number concentration of cloud condensation nuclei (CCN). The largest increases (up to 20 %) in CCN (at a supersaturation (S) of 0.2 %) number concentration are obtained over biologically productive ocean waters when marine organic aerosol is assumed to be externally mixed with sea-salt. Assuming marine organics are internally-mixed with sea

  17. 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.

  18. 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...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-09-01

    The reaction of isoprene (C5H8) with hydroxyl radicals has been studied in the absence of nitrogen oxides (NOx) to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (ΔHvapeff), organic peroxide fraction, and the aerosol yield. The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols) were found to form in the absence of acidic sulfate aerosol. However, reaction conditions did not favor the production of HO2 radicals, thus allowing RO2+RO2 reactions to proceed more readily than if higher HO2 levels had been generated. SOA/SOC (i.e. OM/OC) was found to average 1.9 in the absence of NOx. The effective enthalpy of vaporization was measured as 38.6 kJ mol-1, consistent with values used previously in modeling studies. The yields in this work (using an independent technique than used previously) are lower than those of Kroll et al. (2006) for similar aerosol masses. SOC yields reported in this work range from 0.5-1.4% for carbon masses between 17 and 49 μgC m-3.

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    The reaction of isoprene (C5H8) with hydroxyl radicals has been studied in the absence of nitrogen oxides (NOx) to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (ΔHvapeff), the organic peroxide fraction, and the aerosol yield. The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols) were found to form in the absence of acidic sulfate aerosol. A re-evaluation of field samples in Research Triangle Park, North Carolina, during the summers of 2000 and 2001 indicated in the presence of the methyl butenediols from gas-phase denuder samples taken at the time. SOA/SOC (i.e., OM/OC) was found to average 1.9 in the absence of NOx. The effective enthalpy of vaporization was measured as 38.6 kJ mol-1, consistent with values that have previously been used in modeling studies. The yields in this work (using an independent technique than that previous) are lower than those of Kroll et al. (2006) for similar aerosol masses. SOC yields reported in this work range from 0.5-1.4% for carbon masses between 17 and 49 μgC m-3.

  2. Anthropogenic aerosols as a source of ancient dissolved organic matter in glaciers

    USGS Publications Warehouse

    Stubbins, Aron; Hood, Eran; Raymond, Peter A.; Aiken, George R.; Sleighter, Rachel L.; Hernes, Peter J.; Butman, David; Hatcher, Patrick G.; Striegl, Rob; Schuster, Paul F.; Abdulla, Hussain A.N.; Vermilyea, Andrew W.; Scott, Durelle T.; Spencer, Robert G.M.

    2012-01-01

    Glacier-derived dissolved organic matter represents a quantitatively significant source of ancient, yet highly bioavailable carbon to downstream ecosystems. This finding runs counter to logical perceptions of age–reactivity relationships, in which the least reactive material withstands degradation the longest and is therefore the oldest. The remnants of ancient peatlands and forests overrun by glaciers have been invoked as the source of this organic matter. Here, we examine the radiocarbon age and chemical composition of dissolved organic matter in snow, glacier surface water, ice and glacier outflow samples from Alaska to determine the origin of the organic matter. Low levels of compounds derived from vascular plants indicate that the organic matter does not originate from forests or peatlands. Instead, we show that the organic matter on the surface of the glaciers is radiocarbon depleted, consistent with an anthropogenic aerosol source. Fluorescence spectrophotometry measurements reveal the presence of protein-like compounds of microbial or aerosol origin. In addition, ultrahigh-resolution mass spectrometry measurements document the presence of combustion products found in anthropogenic aerosols. Based on the presence of these compounds, we suggest that aerosols derived from fossil fuel burning are a source of pre-aged organic matter to glacier surfaces. Furthermore, we show that the molecular signature of the organic matter is conserved in snow, glacier water and outflow, suggesting that the anthropogenic carbon is exported relatively unchanged in glacier outflows.

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

    SciTech Connect

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

    2009-09-22

    The meso-scale chemistry-transport model CHIMERE is used to assess our understanding of major sources and formation processes leading to a fairly large amount of organic aerosols [OA, including primary OA (POA) and secondary OA (SOA)] observed in Mexico City during the MILAGRO field project (March 2006). Chemical analyses of submicron aerosols from aerosol mass spectrometers (AMS) indicate that organic particles found in the Mexico City basin have a large fraction of oxygenated organic species (OOA), which have strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled here by the first-generation oxidation of anthropogenic (i.e., aromatics, alkanes) and biogenic (i.e., monoterpenes and isoprene) precursors and their partitioning into both organic and aqueous phases. The near-surface model evaluation shows that predicted OA correlates reasonably well with measurements during the campaign, however it remains a factor of 2 lower than the measured total OA. Fairly good agreement is found between predicted and observed POA within the city suggesting that anthropogenic and biomass burning emissions are reasonably captured. Consistent with previous studies in Mexico City, large discrepancies are encountered for SOA species, with a factor of 5-10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two the sharp increase in SOA concentrations during the late morning at both urban and near-urban locations. However, predicted SOA concentrations were unrealistically low when photochemistry was not active, especially overnight. These nighttime discrepancies were not significantly reduced when greatly enhanced partitioning to the aerosol phase was assumed. Model sensitivity results suggest that observed nighttime SOA concentrations are strongly influenced by the regional background (~2µg/m3) from biogenic origin, which is transported

  4. Updating CMAQ secondary organic aerosol properties relevant for aerosol water interactions

    EPA Science Inventory

    Properties of secondary organic aerosol (SOA) compounds in CMAQ are updated with state-of-the-science estimates from structure activity relationships to provide consistency among volatility, molecular weight, degree of oxygenation, and solubility/hygroscopicity. These updated pro...

  5. Characterization of Organic Nitrogen in the Atmosphere Using High Resolution Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ge, X.; Sun, Y.; Chen, M.; Zhang, Q.

    2015-12-01

    Despite extensive efforts on characterizing organic nitrogen (ON) compounds in atmospheric aerosols and aqueous droplets, knowledge of ON chemistry is still limited, mainly due to its chemical complexity and lack of highly time-resolved measurements. This work is aimed at optimizing the method of using Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) to characterize ON compounds in atmospheric aerosols. Seventy-five pure nitrogen-containing organic compounds covering a variety of functional groups were analyzed with the HR-AMS. Our results show that ON compounds commonly produce NHx+, NOx+, which are usually attributed to inorganic N species such as ammonium and nitrate, and CH2N+ at m/z = 28, which is rarely quantified in ambient aerosol due to large interference from N2+ in the air signal. As a result, using the nitrogen-to-carbon (N/C) calibration factor proposed by Aiken et al. (2008) on average leads to ~ 20% underestimation of N/C in ambient organic aerosol. A new calibration factor of 0.79 is proposed for determining the average N/C in organics. The relative ionization efficiencies (RIEs) of different ON species, on average, are found to be consistent with the default RIE value (1.4) for the total organics. The AMS mass spectral features of various types of ON species (amines, amides, amino acids, etc.) are examined and used for characterizing ON composition in ambient aerosols. Our results indicate that submicron organic aerosol measured during wintertime in Fresno, CA contains significant amounts of amino-compounds whereas more diversified ON species, including N-containing aromatic heterocycle (e.g., imidazoles), are observed in fog waters collected simultaneously. Our findings have important implications for understanding atmospheric ON behaviors via the widespread HR-AMS measurements of ambient aerosols and droplets.

  6. Interactions of Gas-Phase Nitric/Nitrous Acids and Primary Organic Aerosol in the Atmosphere of Houston, TX

    NASA Astrophysics Data System (ADS)

    Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Whitlow, S. I.; Lefer, B. L.; Flynn, J.; Rappenglück, B.

    2007-12-01

    Concentrations of aerosol and gas-phase pollutants were measured on the roof of an 18-story building during the Texas Air Quality Study II Radical and Aerosol Measurement Project (TRAMP) from August 15 through September 28, 2006. Aerosol measurements included size-resolved, non-refractory mass concentrations of ammonium, nitrate, sulfate, chloride, and organic aerosol in submicron particles using an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS). Particulate water-soluble organic carbon (PWSOC) was quantified using a mist chamber/total organic carbon analysis system. Concentration data for gas-phase pollutants included those for nitric acid (HNO3), nitrous acid (HONO), and hydrochloric acid (HCl) collected using a mist chamber/ion chromatographic technique, oxides of nitrogen (NOx) collected using a chemiluminescent method, and carbon monoxide (CO) collected using an infrared gas correlation wheel instrument. Coincident increases in nitrate and organic aerosol mass concentrations were observed on many occasions throughout the measurement campaign, most frequently during the morning rush hour. Based on the lack of organic aerosol processing (defined by the ratio of m/z = 44/57 in the Q-AMS spectra), strong correlation with NOx and CO, and a lack of significant increase in PWSOC concentration, the spikes in organic aerosol were likely associated with primary organic aerosol (POA). During these events, gas-phase HNO3 concentration decreases were observed simultaneously with increases in gas-phase HONO concentrations. These data likely indicate uptake of HNO3 and subsequent heterogeneous conversion to HONO involving POA. Preliminary calculations show that HNO3 partitioning could account for the majority of the observed HONO and aerosol nitrate concentrations during these events. Q-AMS chloride and HCl data also indicate uptake of chloride by particles during these events. This phenomenon was also observed during the night, but these nocturnal events were less

  7. Light Absorption of Brown Carbon Aerosol in the Pearl River Delta Region of China

    NASA Astrophysics Data System (ADS)

    Huang, X.

    2015-12-01

    X.F. Huang, J.F. Yuan, L.M. Cao, J. Cui, C.N. Huang, Z.J. Lan and L.Y. He Key Laboratory for Urban Habitat Environmental Science and Technology, School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055, ChinaCorresponding author. Tel.: +86 755 26032532; fax: +86 755 26035332. E-mail address: huangxf@pku.edu.cn (X. F. Huang). Abstract: The strong spectral dependence of light absorption of brown carbon (BrC) aerosol has been recognized in recent decades. The Absorption Angstrom Exponent (AAE) of ambient aerosol was widely used in previous studies to attribute light absorption of brown carbon at shorter wavelengths, with a theoretical assumption that the AAE of black carbon (BC) aerosol equals to unit. In this study, the AAE method was improved by statistical extrapolation based on ambient measurements in the polluted seasons in typical urban and rural areas in the Pearl River Delta (PRD) region of China. A three-wavelength photoacoustic soot spectrometer (PASS-3) and an aerosol mass spectrometer (AMS) were used to explore the relationship between the ambient measured AAE and the ratio of organic aerosol to BC aerosol, in order to extract the more realistic AAE by pure BC aerosol, which were found to be 0.86, 0.82 and 1.02 at 405nm and 0.70, 0.71, and 0.86 at 532nm in the campaigns of urban-winter, urban-fall, and rural-fall, respectively. Roadway tunnel experiment results further supported the effectiveness of the obtained AAE for pure BC aerosol. In addition, biomass burning experiments proved higher spectral dependence of more-BrC environment and further verified the reliability of the instruments' response. Then, the average light absorption contribution of BrC aerosol was calculated to be 11.7, 6.3 and 12.1% (with total relative uncertainty of 7.5, 6.9 and 10.0%) at 405nm and 10.0, 4.1 and 5.5% (with total relative uncertainty of 6.5, 8.6 and 15.4%) at 532nm of the three campaigns, respectively. These results indicate that the

  8. Fluorescent water-soluble organic aerosols in the High Arctic atmosphere

    PubMed Central

    Fu, Pingqing; Kawamura, Kimitaka; Chen, Jing; Qin, Mingyue; Ren, Lujie; Sun, Yele; Wang, Zifa; Barrie, Leonard A.; Tachibana, Eri; Ding, Aijun; Yamashita, Youhei

    2015-01-01

    Organic aerosols are ubiquitous in the earth’s atmosphere. They have been extensively studied in urban, rural and marine environments. However, little is known about the fluorescence properties of water-soluble organic carbon (WSOC) or their transport to and distribution in the polar regions. Here, we present evidence that fluorescent WSOC is a substantial component of High Arctic aerosols. The ratios of fluorescence intensity of protein-like peak to humic-like peak generally increased from dark winter to early summer, indicating an enhanced contribution of protein-like organics from the ocean to Arctic aerosols after the polar sunrise. Such a seasonal pattern is in agreement with an increase of stable carbon isotope ratios of total carbon (δ13CTC) from −26.8‰ to −22.5‰. Our results suggest that Arctic aerosols are derived from a combination of the long-range transport of terrestrial organics and local sea-to-air emission of marine organics, with an estimated contribution from the latter of 8.7–77% (mean 45%). PMID:25920042

  9. Black carbon and other light-absorbing aerosols in snow

    NASA Astrophysics Data System (ADS)

    Wang, X.; Doherty, S. J.; Warren, S. G.; Fu, Q.

    2011-12-01

    Black carbon (BC), organic carbon (OC), and mineral dust are the most important light-absorbing aerosols (LAA) in snow. The physical, chemical and optical properties of these aerosols differ greatly; the different spectral dependences of their light-absorption can be used to quantify their concentrations in snow. A field campaign was conducted in January and February of 2010 to measure the LAA in snow across northern China. About 400 snow samples were collected at 46 sites in 6 provinces (Huang et al. 2011). Light absorption by mineral dust is due to iron oxides, so iron was determined by chemical analysis of filters and meltwater. To obtain concentrations of the absorbers, BC, OC, and Fe were assumed to have mass absorption cross-sections at 550 nm of 6.3, 0.3, and 0.9 m2/g respectively, and absorption Ångstrom exponents of 1.1, 6, and 3. The lowest values of all LAA are in the remote northeast, at latitude 51°N on the border of Siberia.Median values in surface snow there are 75 ppb BC, 150 ppb OC, and 45 ppb Fe. Farther south, in the industrial northeast, median values are 1000 ppb BC, 4200 ppb OC, and 500 ppb Fe. The grassland of Inner Mongolia is dominated by OC in soil dust of local origin: 560 ppb BC, 8000 ppb OC, 430 ppb Fe. In the Qilian Mountains at the northern boundary of the Tibetan Plateau the surface snow has 70 ppb BC, 2800 ppb OC, and 550 ppb Fe. The fraction of light absorption due to Fe is ~30% in the Qilian Mountains. Elsewhere BC and OC dominate the absorption, so Fe contributes <10% even though the Fe concentrations are as high as the Qilian values.

  10. Implementing marine organic aerosols into the GEOS-Chem model

    NASA Astrophysics Data System (ADS)

    Gantt, B.; Johnson, M. S.; Crippa, M.; Prévôt, A. S. H.; Meskhidze, N.

    2014-09-01

    Marine organic aerosols (MOA) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOA observed during the summertime at an inland site near Paris, France. Our study shows that MOA have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having > 10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly-emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.

  11. Implementing marine organic aerosols into the GEOS-Chem model

    NASA Astrophysics Data System (ADS)

    Gantt, B.; Johnson, M. S.; Crippa, M.; Prévôt, A. S. H.; Meskhidze, N.

    2015-03-01

    Marine-sourced organic aerosols (MOAs) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem (Global Earth Observing System Chemistry) model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOAs observed during the summertime at an inland site near Paris, France. Our study shows that MOAs have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having >10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.

  12. Implementing marine organic aerosols into the GEOS-Chem model

    DOE PAGES

    Gantt, B.; Johnson, M. S.; Crippa, M.; ...

    2015-03-17

    Marine-sourced organic aerosols (MOAs) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem (Global Earth Observing System Chemistry) model. The implemented emission scheme improved the large underprediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Modelmore » predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOAs observed during the summertime at an inland site near Paris, France. Our study shows that MOAs have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having >10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.« less

  13. Implementing Marine Organic Aerosols Into the GEOS-Chem Model

    NASA Technical Reports Server (NTRS)

    Johnson, Matthew S.

    2015-01-01

    Marine-sourced organic aerosols (MOA) have been shown to play an important role in tropospheric chemistry by impacting surface mass, cloud condensation nuclei, and ice nuclei concentrations over remote marine and coastal regions. In this work, an online marine primary organic aerosol emission parameterization, designed to be used for both global and regional models, was implemented into the GEOS-Chem model. The implemented emission scheme improved the large under-prediction of organic aerosol concentrations in clean marine regions (normalized mean bias decreases from -79% when using the default settings to -12% when marine organic aerosols are added). Model predictions were also in good agreement (correlation coefficient of 0.62 and normalized mean bias of -36%) with hourly surface concentrations of MOA observed during the summertime at an inland site near Paris, France. Our study shows that MOA have weaker coastal-to-inland concentration gradients than sea-salt aerosols, leading to several inland European cities having > 10% of their surface submicron organic aerosol mass concentration with a marine source. The addition of MOA tracers to GEOS-Chem enabled us to identify the regions with large contributions of freshly-emitted or aged aerosol having distinct physicochemical properties, potentially indicating optimal locations for future field studies.

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

    PubMed

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

    2014-02-27

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

  15. 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.

  16. Quantification and radiocarbon source apportionment of black carbon in atmospheric aerosols using the CTO-375 method

    NASA Astrophysics Data System (ADS)

    Zencak, Zdenek; Elmquist, Marie; Gustafsson, Örjan

    To make progress towards linking the atmosphere and biogeosphere parts of the black carbon (BC) cycle, a chemothermal oxidation method (CTO-375), commonly applied for isolating BC from complex geomatrices such as soils, sediments and aquatic particles, was applied to investigate the BC also in atmospheric particles. Concentrations and 14C-based source apportionment of CTO-375 based BC was established for a reference aerosol (NIST RM-8785) and for wintertime aerosols collected in Stockholm and in a Swedish background area. The results were compared with thermal-optical (OC/EC) measurements. For NIST RM-8785, a good agreement was found between the BC CTO-375 concentration and the reported elemental carbon (EC) concentration measured by the "Speciation Trends Network—National Institute of Occupational Safety and Health" method (EC NIOSH) with BC CTO-375 of 0.054±0.002 g g -1 and EC NIOSH of 0.067±0.008 g g -1. In contrast, there was an average factor of ca. 20 difference between BC CTO-375 and EC NIOSH for the ambient Scandinavian wintertime aerosols, presumably reflecting a combination of BC CTO-375 isolating only the recalcitrant soot-BC portion of the BC continuum and the EC NIOSH metric inadvertently including some intrinsically non-pyrogenic organic matter. Isolation of BC CTO-375 with subsequent off-line radiocarbon analysis yielded fraction modern values (fM) for total organic carbon (TOC) of 0.93 (aerosols from a Swedish background area), and 0.58 (aerosols collected in Stockholm); whereas the fM for BC CTO-375 isolates were 1.08 (aerosols from a Swedish background area), and 0.87 (aerosols collected in Stockholm). This radiocarbon-based source apportionment suggests that contribution from biomass combustion to cold-season atmospheric BC CTO-375 in Stockholm was 70% and in the background area 88%.

  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. Organic Aerosol Component (OACOMP) Value-Added Product Report

    SciTech Connect

    Fast, J; Zhang, Q; Tilp, A; Shippert, T; Parworth, C; Mei, F

    2013-08-23

    Significantly improved returns in their aerosol chemistry data can be achieved via the development of a value-added product (VAP) of deriving OA components, called Organic Aerosol Components (OACOMP). OACOMP is primarily based on multivariate analysis of the measured organic mass spectral matrix. The key outputs of OACOMP are the concentration time series and the mass spectra of OA factors that are associated with distinct sources, formation and evolution processes, and physicochemical properties.

  19. On the Implications of aerosol liquid water and phase separation for modeled organic aerosol mass

    EPA Science Inventory

    Current chemical transport models assume that organic aerosol (OA)-forming compounds partition mostly to a water-poor, organic-rich phase in accordance with their vapor pressures. However, in the southeast United States, a significant fraction of ambient organic compounds are wat...

  20. The effect of organic aerosol material on aerosol reactivity towards ozone

    NASA Astrophysics Data System (ADS)

    Batenburg, Anneke; Gaston, Cassandra; Thornton, Joel; Virtanen, Annele

    2015-04-01

    After aerosol particles are formed or emitted into the atmosphere, heterogeneous reactions with gaseous oxidants cause them to 'age'. Aging can change aerosol properties, such as the hygroscopicity, which is an important parameter in how the particles scatter radiation and form clouds. Conversely, heterogeneous reactions on aerosol particles play a significant role in the cycles of various atmospheric trace gases. Organic compounds, a large part of the total global aerosol matter, can exist in liquid or amorphous (semi)solid physical phases. Different groups have shown that reactions with ozone (O3) can be limited by bulk diffusion in organic aerosol, particularly in viscous, (semi)solid materials, and that organic coatings alter the surface interactions between gas and aerosol particles. We aim to better understand and quantify how the viscosity and phase of organic aerosol matter affect gas-particle interactions. We have chosen the reaction of O3 with particles composed of a potassium iodide (KI) core and a variable organic coating as a model system. The reaction is studied in an aerosol flow reactor that consists of a laminar flow tube and a movable, axial injector for the injection of O3. The aerosol-containing air is inserted at the tube's top. The interaction length (and therefore time), between the particles and the O3 can be varied by moving the injector. Alternatively, the production of aerosol particles can be modulated. The remaining O3 concentration is monitored from the bottom of the tube and particle concentrations are measured simultaneously, which allows us to calculate the reactive uptake coefficient γ. We performed exploratory experiments with internally mixed KI and polyethylene glycol (PEG) particles at the University of Washington (UW) in a setup with a residence time around 50 s. Aerosol particles were generated in an atomizer from solutions with varying concentrations of KI and PEG and inserted into the flow tube after they were diluted and

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  2. a Study of the Origin of Atmospheric Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Hildemann, Lynn Mary

    1990-01-01

    The sources of ambient organic particulate matter in urban areas are investigated through a program of emission source measurements, atmospheric measurements, and mathematical modeling of source/receptor relationships. A dilution sampler intended to collect fine organic aerosol from combustion sources is designed to simulate atmospheric cooling and dilution processes, so that organic vapors which condense under ambient conditions will be collected as particulate matter. This system is used to measure the emissions from a boiler burning distillate oil, a home fireplace, catalyst and noncatalyst automobiles, heavy-duty diesel trucks, natural gas home appliances, and meat cooking operations. Alternate techniques are used to sample the particulate matter emitted from cigarette smoking, a roofing tar pot, paved road dust, brake lining wear, tire wear, and vegetative detritus. The bulk chemical characteristics of the fine aerosol fraction are presented for each source. Over half of the fine aerosol mass emitted from automobiles, wood burning, meat cooking, home appliances, cigarettes, and tar pots is shown to consist of organic compounds. The organic material collected from these sources is analyzed using high-resolution gas chromatography. Using a simple analytical protocol, a quantitative, 50-parameter characterization of the elutable fine organic aerosol emitted from each source type is obtained, which proves to be a unique fingerprint that can be used to distinguish most sources from each other. A mathematical model is used to predict the characteristics of fine ambient organic aerosol in the Los Angeles area that would prevail if the primary organic emissions are transported without chemical reaction. The model is found to track the seasonal variations observed in the ambient aerosol at the three sites studied. Emissions from vehicles and fireplaces are identified as significant sources of solvent-extractable organic aerosol. Differences between the model

  3. 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.

  4. Radiocarbon measurements of black carbon in aerosols and ocean sediments

    NASA Astrophysics Data System (ADS)

    Masiello, C. A.; Druffel, E. R. M.; Currie, L. A.

    2002-03-01

    Black carbon (BC) is the combustion-altered, solid residue remaining after biomass burning and fossil fuel combustion. Radiocarbon measurements of BC provide information on the residence time of BC in organic carbon pools like soils and sediments, and also provide information on the source of BC by distinguishing between fossil fuel and biomass combustion byproducts. We have optimized dichromate-sulfuric acid oxidation for the measurement of radiocarbon in BC. We also present comparisons of BC 14C measurements on NIST aerosol SRM 1649a with previously published bulk aromatic 14C measurements and individual polycyclic aromatic hydrocarbon (PAH) 14C measurements on the same NIST standard. Dichromate-sulfuric acid oxidation belongs to the chemical class of BC measurement methods, which rely on the resistance of some forms of BC to strong chemical oxidants. Dilute solutions of dichromate-sulfuric acid degrade BC and marine-derived carbon at characteristic rates from which a simple kinetic formula can be used to calculate concentrations of individual components (Wolbach and Anders, 1989). We show that: (1) dichromate-sulfuric acid oxidation allows precise, reproducible 14C BC measurements; (2) kinetics calculations give more precise BC yield information when performed on a % OC basis (vs. a % mass basis); (3) kinetically calculated BC concentrations are similar regardless of whether the oxidation is performed at 23°C or 50°C; and (4) this method yields 14C BC results consistent with previously published aromatic 14C data for an NIST standard. For the purposes of intercomparison, we report % mass and carbon results for two commercially available BC standards. We also report comparative data from a new thermal method applied to SRM 1649a, showing that thermal oxidation of this material also follows the simple kinetic sum of exponentials model, although with different time constants.

  5. Physical and Chemical Properties of Anthropogenic Aerosols: An Overview

    EPA Science Inventory

    Aerosol chemical composition is complex. Combustion aerosols can comprise tens of thousands of organic compounds, refractory brown and black carbon, heavy metals, cations, anions, salts, and other inorganic phases. Aerosol organic matter normally contains semivolatile material th...

  6. Role of Aerosol Liquid Water in Secondary Organic Aerosol Formation from Volatile Organic Compounds.

    PubMed

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

    2017-02-07

    A key mechanism for atmospheric secondary organic aerosol (SOA) formation occurs when oxidation products of volatile organic compounds condense onto pre-existing particles. Here, we examine effects of aerosol liquid water (ALW) on relative SOA yield and composition from α-pinene ozonolysis and the photooxidation of toluene and acetylene by OH. Reactions were conducted in a room-temperature flow tube under low-NOx conditions in the presence of equivalent loadings of deliquesced (∼20 μg m(-3) ALW) or effloresced (∼0.2 μg m(-3) ALW) ammonium sulfate seeds at exactly the same relative humidity (RH = 70%) and state of wall conditioning. We found 13% and 19% enhancements in relative SOA yield for the α-pinene and toluene systems, respectively, when seeds were deliquesced rather than effloresced. The relative yield doubled in the acetylene system, and this enhancement was partially reversible upon drying the prepared SOA, which reduced the yield by 40% within a time scale of seconds. We attribute the high relative yield of acetylene SOA on deliquesced seeds to aqueous partitioning and particle-phase reactions of the photooxidation product glyoxal. The observed range of relative yields for α-pinene, toluene, and acetylene SOA on deliquesced and effloresced seeds suggests that ALW plays a complicated, system-dependent role in SOA formation.

  7. Dual-wavelength-excitation single-particle fluorescence spectrometer/particle sorter for real-time measurement of organic carbon and biological aerosols

    NASA Astrophysics Data System (ADS)

    Pan, Yong-Le; Pinnick, Ron G.; Hill, Steven C.; Huang, Hermes; Chang, Richard K.

    2008-10-01

    We report the development of a Single-Particle Fluorescence Spectrometer (SPFS) system capable of measuring two UV-laser excited fluorescence spectra from a single particle on-the-fly. The two dispersed fluorescence spectra are obtained from excitation by two lasers at different wavelengths (263 nm and 351 nm). The SPFS samples single particles with sizes primarily in the 1-10 μm range. The fluorescence spectra are recorded from 280 nm to 600 nm (in 20 channels) for 263 nm excitation and from 370 nm to 700 nm (in 22 channels) for 351 nm excitation. The elastic scattering (channel 4 and 9) is also recorded for sizing each particle. A time stamp for single particles is marked with a variable time interval resolution from 10 ms to 10 minutes. The SPFS employs a virtual-impactor concentrator to concentrate respirable-sized particles with a resulting (size-dependent) effective flow rate of around 100 liters/min. The SPFS can measure single-particle spectra at a maximum rate of 90,000/sec, although the highest rates we have experienced for the ambient are only several hundred/sec. When the SPFS is combined with an aerodynamic deflector (puffer) to sort particles according to their fluorescence spectral characteristics, the SPFS/puffer system can selectively deflect and collect an enriched sample of targeted particles (at rates limited by the puffer) of 1200 particles/sec, for further examination. In laboratory tests, aerosol particles with similar UV-LIF spectra (e.g. B. subtilis and E.coli) are puffed into the reservoir of a micro-fluidic cell, where fluorescent-labeled antibodies bind to them and were classified by their labeled fluorescence. Measurements of the background ambient aerosol with the SPFS system made at sites with different regional climate (Connecticut, Maryland, and New Mexico) were clustered (unstructured hierarchical analysis) into 8-10 groups, with over 90% of all the fluorescent particles contained within these clusters (threshold dot product=0

  8. Cloud activation properties of organic aerosols observed at an urban site during CalNex-LA

    NASA Astrophysics Data System (ADS)

    Mei, F.; Hayes, P. L.; Ortega, A. M.; Jimenez, J.; Wang, J.

    2010-12-01

    Atmospheric aerosols strongly influence the global energy budget by scattering and absorbing sunlight (direct effects) and by changing the microphysical structure, lifetime, and coverage of clouds (indirect effects). Currently, the indirect effects of aerosols remain the most uncertain components in forcing of climate change over the industrial period. This large uncertainty is in part due to our incomplete understanding of the ability of aerosol particles to form cloud droplets under climatically relevant supersaturations. During CalNex study, size-resolved cloud condensation nuclei (CCN) spectrum and aerosol chemical composition were measured at an urban supersite in Pasadena, California from May 15 to June 6, 2010. Monodispersed aerosol particles are first classified using a differential mobility analyzer at sizes ranging from 25 to 320 nm. The activation efficiency of the classified aerosol, defined as the ratio of its CCN concentration (characterized by a DMT CCN counter) to total CN concentration (measured by a condensation particle counter, TSI 3771), is derived as a function of both particle size and supersaturation, which ranges from 0.08% to 0.39%. Aerosol chemical composition was characterized using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). In most of days, increases in aerosol mode diameter, organics mass loading, and aerosol organics volume fraction were observed from 10:00 AM to 15:00 PM. These increases are attributed to formation of secondary organic aerosols through photochemical reactions. On average, the aerosol was dominated by organics (~65% by volume), with the contribution from ammonium sulfate (~20%) and ammonium nitrate (~15%), and the balance being made up of elemental carbon. Positive matrix factorization (PMF) analysis shows the oxygenated organic aerosol (OOA) (~75%) was the dominant organics component. Additionally, the organics O:C ratio was within a narrow range of 0.50±0.12. Particle overall

  9. Apportionment of Primary and Secondary Organic Aerosols in Southern California During the 2005 Study of Organic Aerosols in Riverside (SOAR-1)

    EPA Science Inventory

    Ambient sampling was conducted in Riverside, California during the 2005 Study of Organic Aerosols in Riverside to characterize the composition and sources of organic aerosol using a variety of state-of-the-art instrumentation and source apportionment techniques.

  10. Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere

    NASA Astrophysics Data System (ADS)

    Kroll, Jesse H.; Seinfeld, John H.

    2008-05-01

    Secondary organic aerosol (SOA), particulate matter composed of compounds formed from the atmospheric transformation of organic species, accounts for a substantial fraction of tropospheric aerosol. The formation of low-volatility (semivolatile and possibly nonvolatile) compounds that make up SOA is governed by a complex series of reactions of a large number of organic species, so the experimental characterization and theoretical description of SOA formation presents a substantial challenge. In this review we outline what is known about the chemistry of formation and continuing transformation of low-volatility species in the atmosphere. The primary focus is chemical processes that can change the volatility of organic compounds: (1) oxidation reactions in the gas phase, (2) reactions in the particle phase, and (3) continuing chemistry (in either phase) over several generations. Gas-phase oxidation reactions can reduce volatility by the addition of polar functional groups or increase it by the cleavage of carbon-carbon bonds; key branch points that control volatility are the initial attack of the oxidant, reactions of alkylperoxy (RO2) radicals, and reactions of alkoxy (RO) radicals. Reactions in the particle phase include oxidation reactions as well as accretion reactions, non-oxidative processes leading to the formation of high-molecular-weight species. Organic carbon in the atmosphere is continually subject to reactions in the gas and particle phases throughout its atmospheric lifetime (until lost by physical deposition or oxidized to CO or CO2), implying continual changes in volatility over the timescales of several days. The volatility changes arising from these chemical reactions must be parameterized and included in models in order to gain a quantitative and predictive understanding of SOA formation.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    To study formation of secondary organic aerosol (SOA) in the air outflowed from the Chinese continent and its fraction in an urban city located in downwind, we have conducted field studies at two background sites and one urban site in the western Japan: the Cape Hedo Aerosol and Atmospheric Monitoring Station (26.9˚N, 128.3˚E), the Fukue Atmospheric Monitoring Station (32.8˚N, 128.7˚E), and Fukuoka University (33.6˚N, 130.4˚E), respectively. During the studies, stable carbon isotope ratio (δ13C) of low-volatile water-soluble organic carbon (LV-WSOC) was measured in 24 h collected filter samples of total suspended particulate matter. Concentration of fine organic aerosol and the proportion of the signal at m/z 44 (ions from the carboxyl group) in the organic mass spectra (f44) were also measured by Aerodyne aerosol mass spectrometers. Limited to the Fukue site only, mixing ratios of trace gas species, such as aromatic hydrocarbons, NOx, and NOy, were also measured using GC-FID and NOx and NOyanalyzers for estimation of photochemical age (t[OH]). A case study in December 2010 showed that plots of δ13C versus f44 showed systematic variations at Hedo and Fukue. However, their trends were opposite. At Fukue the trend was consistent in the plot of δ13C of LV-WSOC versus t[OH] estimated by the NOx/NOy or the hydrocarbon ratios, indicating influence of SOA. The systematic trends aforementioned qualitatively agreed with a binary mixture model of SOA with background LV-WSOC having the f44 of ~0.06 and the δ13C of -17‰ or higher, implication of some influence of primary emission associated with C4plants. Given that the LV-WSOC at the urban Fukuoka site was a binary mixture, a mass balance for δ13C was constructed below. In the equation, δ13CMix, δ13CLocal, δ13CTrans, and FLocal are δ13C of binary LV-WSOC mixture, δ13C of LV-WSOC from local emission origin, δ13C of LV-WSOC from transboundary pollution origin, and a fraction of LV-WSOC from local emission

  12. Kinetics, products, and mechanisms of secondary organic aerosol formation.

    PubMed

    Ziemann, Paul J; Atkinson, Roger

    2012-10-07

    Secondary organic aerosol (SOA) is formed in the atmosphere when volatile organic compounds (VOCs) emitted from anthropogenic and biogenic sources are oxidized by reactions with OH radicals, O(3), NO(3) radicals, or Cl atoms to form less volatile products that subsequently partition into aerosol particles. Once in particles, these organic compounds can undergo heterogenous/multiphase reactions to form more highly oxidized or oligomeric products. SOA comprises a large fraction of atmospheric aerosol mass and can have significant effects on atmospheric chemistry, visibility, human health, and climate. Previous articles have reviewed the kinetics, products, and mechanisms of atmospheric VOC reactions and the general chemistry and physics involved in SOA formation. In this article we present a detailed review of VOC and heterogeneous/multiphase chemistry as they apply to SOA formation, with a focus on the effects of VOC molecular structure on the kinetics of initial reactions with the major atmospheric oxidants, the subsequent reactions of alkyl, alkyl peroxy, and alkoxy radical intermediates, and the composition of the resulting products. Structural features of reactants and products discussed include compound carbon number; linear, branched, and cyclic configurations; the presence of C[double bond, length as m-dash]C bonds and aromatic rings; and functional groups such as carbonyl, hydroxyl, ester, hydroxperoxy, carboxyl, peroxycarboxyl, nitrate, and peroxynitrate. The intention of this review is to provide atmospheric chemists with sufficient information to understand the dominant pathways by which the major classes of atmospheric VOCs react to form SOA products, and the further reactions of these products in particles. This will allow reasonable predictions to be made, based on molecular structure, about the kinetics, products, and mechanisms of VOC and heterogeneous/multiphase reactions, including the effects of important variables such as VOC, oxidant, and NO

  13. Long-Term Measurements of Carbon Monoxide and Aerosols at the ZOTTO tall tower, Siberia

    NASA Astrophysics Data System (ADS)

    Andreae, M. O.; Birmili, W.; Chi, X.; Heimann, M.; Heintzenberg, J.; Mikhailov, E.; Panov, A.

    2012-04-01

    coefficients with SSA values reaching 0.97. These aerosols were present in airmasses from northern Siberia with low CO mixing ratios, which suggests that they are predominantly of biogenic origin. The lowest particle number concentrations (averaging ~430 cm-3) were present in northern Siberian and Arctic airmasses, with similar values in summer and winter. Chemical analysis shows that sulfates and "black" carbon are elevated in the winter aerosol, while organic carbon from biomass burning and terpenoid oxidation dominate in summer. The measurements at ZOTTO are being continued, in the expectation that long-term variations in the continental background signal could give new insights into the feedback of ecosystems on a continental scale to changing climatic conditions.

  14. Optical Properties and Aging of Light Absorbing Secondary Organic Aerosol

    SciTech Connect

    Liu, Jiumeng; Lin, Peng; Laskin, Alexander; Laskin, Julia; Kathmann, Shawn M.; Wise, Matthew E.; Caylor, Ryan; Imholt, Felisha; Selimovic, Vanessa; Shilling, John E.

    2016-10-14

    The light-absorbing organic aerosol (OA), commonly referred to as “brown carbon (BrC)”, has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various VOC precursors, NOx concentrations, photolysis time and relative humidity (RH) on the light absorption of selected secondary organic aerosols (SOA). Light absorption of chamber generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficients (MAC) value is observed from toluene SOA products formed under high NOx conditions at moderate RH, in which nitro-aromatics were previously identified as the major light absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organonitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible and UV light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed-SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.

  15. Cloud condensation nuclei activity of isoprene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

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

    PubMed

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

    2010-10-14

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

  17. Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles

    SciTech Connect

    Lin, Peng; Aiona, Paige K.; Li, Ying; Shiraiwa, Manabu; Laskin, Julia; Nizkorodov, Sergey A.; Laskin, Alexander

    2016-11-01

    Emissions from biomass burning are a significant source of brown carbon (BrC) in the atmosphere. In this study, we investigate the molecular composition of freshly-emitted biomass burning organic aerosol (BBOA) samples collected during test burns of selected biomass fuels: sawgrass, peat, ponderosa pine, and black spruce. We characterize individual BrC chromophores present in these samples using high performance liquid chromatography coupled to a photodiode array detector and a high-resolution mass spectrometer. We demonstrate that both the overall BrC absorption and the chemical composition of light-absorbing compounds depend significantly on the type of biomass fuels and burning conditions. Common BrC chromophores in the selected BBOA samples include nitro-aromatics, polycyclic aromatic hydrocarbon derivatives, and polyphenols spanning a wide range of molecular weights, structures, and light absorption properties. A number of biofuel-specific BrC chromophores are observed, indicating that some of them may be used as potential markers of BrC originating from different biomass burning sources. On average, ~50% of the light absorption above 300 nm can be attributed to a limited number of strong BrC chromophores, which may serve as representative light-absorbing species for studying atmospheric processing of BrC aerosol. The absorption coefficients of BBOA are affected by solar photolysis. Specifically, under typical atmospheric conditions, the 300 nm absorbance decays with a half-life of 16 hours. A “molecular corridors” analysis of the BBOA volatility distribution suggests that many BrC compounds in the fresh BBOA have low volatility (<1 g m-1) and will be retained in the particle phase under atmospherically relevant conditions.

  18. Real time in situ detection of organic nitrates in atmospheric aerosols.

    PubMed

    Rollins, Andrew W; Smith, Jared D; Wilson, Kevin R; Cohen, Ronald C

    2010-07-15

    A novel instrument is described that quantifies total particle-phase organic nitrates in real time with a detection limit of 0.11 microg m(-3) min(-1), 45 ppt min(-1) (-ONO(2)). Aerosol nitrates are separated from gas-phase nitrates with a short residence time activated carbon denuder. Detection of organic molecules containing -ONO(2) subunits is accomplished using thermal dissociation coupled to laser induced fluorescence detection of NO(2). This instrument is capable of high time resolution (seconds) measurements of particle-phase organic nitrates, without interference from inorganic nitrate. Here we use it to quantify organic nitrates in secondary organic aerosol generated from high-NO(x) photooxidation of limonene, alpha-pinene, Delta-3-carene, and tridecane. In these experiments the organic nitrate moiety is observed to be 6-15% of the total SOA mass.

  19. Assessment of the Aerosol Generation and Toxicity of Carbon Nanotubes

    PubMed Central

    O’Shaughnessy, Patrick T.; Adamcakova-Dodd, Andrea; Altmaier, Ralph; Thorne, Peter S.

    2014-01-01

    Current interest in the pulmonary toxicity of carbon nanotubes (CNTs) has resulted in a need for an aerosol generation system that is capable of consistently producing a CNT aerosol at a desired concentration level. This two-part study was designed to: (1) assess the properties of a commercially-available aerosol generator when producing an aerosol from a purchased powder supply of double-walled carbon nanotubes (DWCNTs); and (2) assess the pulmonary sub-acute toxicity of DWCNTs in a murine model during a 5-day (4 h/day) whole-body exposure. The aerosol generator, consisting of a novel dustfeed mechanism and venturi ejector was determined to be capable of producing a DWCNT consistently over a 4 h exposure period at an average level of 10.8 mg/m3. The count median diameter was 121 nm with a geometric standard deviation of 2.04. The estimated deposited dose was 32 µg/mouse. The total number of cells in bronchoalveolar lavage (BAL) fluid was significantly (p < 0.01) increased in exposed mice compared to controls. Similarly, macrophages in BAL fluid were significantly elevated in exposed mice, but not neutrophils. All animals exposed to CNT and euthanized immediately after exposure had changes in the lung tissues showing acute inflammation and injury; however these pathological changes resolved two weeks after the exposure.

  20. DETERMINATION OF THE ORGANIC MASS TO ORGANIC CARBON RATIO IN IMPROVE SAMPLES. (R831086)

    EPA Science Inventory

    The ratio of organic mass (OM) to organic carbon (OC) in PM2.5 aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM2.5 mass and chemical constituents...

  1. Chemical and Spatial Microscopy of Individual Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Tivanski, Alexei V.; Hopkins, Rebecca J.; Gilles, Mary K.

    2008-03-01

    Carbonaceous particles originating from biomass burning can account for a large fraction of organic aerosols in a local environment. Presently, their composition, physical, and chemical properties as well as their environmental effects are largely unknown. A distinct type of biomass burn particles, called ``tar balls'', have been observed in a number of field campaigns, both in fresh and aged smoke. They are characterized by their spherical morphology, high carbon content and ability to efficiently scatter and absorb light. Here, a combination of scanning transmission x-ray microscopy and near edge x-ray absorption fine structure spectroscopy is used to determine the shape, structure and size-dependent chemical composition of 150 individual tar ball particles ranging in size from 0.15 to 1.2 μm. Oxygen is present primarily as carboxylic carbonyls and oxygen-substituted alkyl functional groups. The observed chemical composition is distinctly different from black carbon and more closely resembles high molecular weight humic-like substances. A detailed examination of the carbonyl intensity as a function of particle size reveals the presence of a thin oxygenated interface layer on the tar balls, indicative of atmospheric processing of biomass burn particles.

  2. On the source of organic acid aerosol layers above clouds.

    PubMed

    Sorooshian, Armin; Lu, Miao-Ling; Brechtel, Fred J; Jonsson, Haflidi; Feingold, Graham; Flagan, Richard C; Seinfeld, John H

    2007-07-01

    During the July 2005 Marine Stratus/Stratocumulus Experiment (MASE) and the August-September 2006 Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS), the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter probed aerosols and cumulus clouds in the eastern Pacific Ocean off the coast of northern California and in southeastern Texas, respectively. An on-board particle-into-liquid sampler (PILS) quantified inorganic and organic acid species with < or = 5-min time resolution. Ubiquitous organic aerosol layers above cloud with enhanced organic acid levels were observed in both locations. The data suggest that aqueous-phase reactions to produce organic acids, mainly oxalic acid, followed by droplet evaporation is a source of elevated organic acid aerosol levels above cloud. Oxalic acid is observed to be produced more efficiently relative to sulfate as the cloud liquid water content increases, corresponding to larger and less acidic droplets. As derived from large eddy simulations of stratocumulus underthe conditions of MASE, both Lagrangian trajectory analysis and diurnal cloudtop evolution provide evidence that a significant fraction of the aerosol mass concentration above cloud can be accounted for by evaporated droplet residual particles. Methanesulfonate data suggest that entrainment of free tropospheric aerosol can also be a source of organic acids above boundary layer clouds.

  3. Water soluble organic constituents in Arctic aerosols and snow pack

    SciTech Connect

    Li, Shaomeng ); Winchester, J.W. )

    1993-01-08

    Eight water-soluble organic anions were measured in 70 aerosol samples and 10 snow samples at Barrow, Alaska in March-April, 1989. The ranking of the ions in aerosols according to total (coarse + fine aerosol) median concentrations was acetate (44 ng m[sup [minus]3]), oxalate (27), benzoate (23), formate (22), propionate (6), methanesulfonate (5), lactate (4), and pyruvate (4). When added up, the median organic anion mass was 156 ng m[sup [minus]3]. The organic anions/nssSO[sub 4][sup =] mass ratio had a median of 0.18 and 0.07 in the coarse (>1 [mu]m) and fine (<1 [mu]m) size fractions, respectively, but can be very high on occasions. On average, the organic anions made up more than 10% of the water-soluble aerosol mass. A similar ranking in concentration was also found for the organic ions in the snow pack samples. The organic anion/nssSO[sub 4][sup =] mass ratio in these samples was >0.5, substantially higher than in aerosols. 18 refs., 2 tabs.

  4. Direct radiative forcing from black carbon aerosols over urban environment

    NASA Astrophysics Data System (ADS)

    Badarinath, K. V. S.; Madhavi Latha, K.

    There is growing evidence that the earth’s climate is changing and will likely continue to change in the future. It is still debated whether these changes are due to natural variability of the climate system or a result of increases in the concentration of greenhouse gases in the atmosphere. Black carbon (BC) has become the subject of interest for a variety of reasons. BC aerosol may cause environmental as well as harmful health effects in densely inhabited regions. BC is a strong absorber of radiation in the visible and near-infrared part of the spectrum, where most of the solar energy is distributed. Black carbon is emitted into the atmosphere as a byproduct of all combustion processes, viz., vegetation burning, industrial effluents and motor vehicle exhausts, etc. In this paper, we present results from our measurements on black carbon aerosols, total aerosol mass concentration and aerosol optical depth over an urban environment namely Hyderabad during January to May, 2003. Diurnal variations of BC indicate high BC concentrations during 6:00 9:00 and 19:00 23:00 h. Weekday variations of BC concentrations increase gradually from Monday to Wednesday and gradually decrease from Thursday to Sunday. Analysis of traffic density along with meteorological parameters suggests that the primary determinant for BC concentration levels and patterns is traffic density. Seasonal variations of BC suggest that the BC concentrations are high during dry season compared to rainy season due to the scavenging by air. The fraction of BC to total mass concentration has been observed to be 7% during January to May. BC showed positive correlation with total mass concentration and aerosol optical depth at 500 nm. Radiative transfer calculations suggests that during January to May, diurnal averaged aerosol forcing at the surface is -33 Wm2 and at the top of the atmosphere (TOA) above 100 km it is observed to be +9 Wm-2. The results have been discussed in detail in the paper.

  5. Climate Impacts of Atmospheric Sulfate and Black Carbon Aerosols

    SciTech Connect

    Qian, Yun; Song, Qingyuan; Menon, Surabi; Yu, Shaocai; Liu, Shaw C.; Shi, Guangyu; Leung, Lai R.; Luo, Yunfeng

    2008-09-19

    Although the global average surface temperature has increased by about 0.6°C during the last century (IPCC, 2001), some regions such as East Asia, Eastern North America, and Western Europe have cooled rather than warmed during the past decades (Jones, 1988; Qian and Giorgi, 2000). Coherent changes at the regional scale may reflect responses to different climate forcings that need to be understood in order to predict the future net climate response at the global and regional scales under different emission scenarios. Atmospheric aerosols play an important role in global climate change (IPCC 2001). They perturb the earth’s radiative budget directly by scattering and absorbing solar and long wave radiation, and indirectly by changing cloud reflectivity, lifetime, and precipitation efficiency via their role as cloud condensation nuclei. Because aerosols have much shorter lifetime (days to weeks) compared to most greenhouse gases, they tend to concentrate near their emission sources and distribute very unevenly both in time and space. This non-uniform distribution of aerosols, in conjunction with the greenhouse effect, may lead to differential net heating in some areas and net cooling in others (Penner et al. 1994). Sulfate aerosols come mainly from the oxidation of sulfur dioxide (SO2) emitted from fossil fuel burning. Black carbon aerosols are directly emitted during incomplete combustion of biomass, coal, and diesel derived sources. Due to the different optical properties, sulfate and black carbon affect climate in different ways. Because of the massive emissions of sulfur and black carbon that accompany the rapid economic expansions in East Asia, understanding the effects of aerosols on climate is particularly important scientifically and politically in order to develop adaptation and mitigation strategies.

  6. Characterization of organic aerosols in Beijing using an aerodyne high-resolution aerosol mass spectrometer

    NASA Astrophysics Data System (ADS)

    Zhang, Junke; Wang, Yuesi; Huang, Xiaojuan; Liu, Zirui; Ji, Dongsheng; Sun, Yang

    2015-06-01

    Fine particle of organic aerosol (OA), mostly arising from pollution, are abundant in Beijing. To achieve a better understanding of the difference in OA in summer and autumn, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS, Aerodyne Research Inc., USA) was deployed in urban Beijing in August and October 2012. The mean OA mass concentration in autumn was 30±30 μg m-3, which was higher than in summer (13±6.9 μg m-3). The elemental analysis found that OA was more aged in summer (oxygen-to-carbon (O/C) ratios were 0.41 and 0.32 for summer and autumn, respectively). Positive matrix factorization (PMF) analysis identified three and five components in summer and autumn, respectively. In summer, an oxygenated OA (OOA), a cooking-emission-related OA (COA), and a hydrocarbon-like OA (HOA) were indentified. Meanwhile, the OOA was separated into LV-OOA (low-volatility OOA) and SV-OOA (semi-volatile OOA); and in autumn, a nitrogen-containing OA (NOA) was also found. The SOA (secondary OA) was always the most important OA component, accounting for 55% of the OA in the two seasons. Back trajectory clustering analysis found that the origin of the air masses was more complex in summer. Southerly air masses in both seasons were associated with the highest OA loading, while northerly air masses were associated with the lowest OA loading. A preliminary study of OA components, especially the POA (primary OA), in different periods found that the HOA and COA all decreased during the National Day holiday period, and HOA decreased at weekends compared with weekdays.

  7. Characterization of polar organic compounds and source analysis of fine organic aerosols in Hong Kong

    NASA Astrophysics Data System (ADS)

    Li, Yunchun

    Organic aerosols, as an important fraction of airborne particulate mass, significantly affect the environment, climate, and human health. Compared with inorganic species, characterization of individual organic compounds is much less complete and comprehensive because they number in thousands or more and are diverse in chemical structures. The source contributions of organic aerosols are far from being well understood because they can be emitted from a variety of sources as well as formed from photochemical reactions of numerous precursors. This thesis work aims to improve the characterization of polar organic compounds and source apportionment analysis of fine organic carbon (OC) in Hong Kong, which consists of two parts: (1) An improved analytical method to determine monocarboxylic acids, dicarboxylic acids, ketocarboxylic acids, and dicarbonyls collected on filter substrates has been established. These oxygenated compounds were determined as their butyl ester or butyl acetal derivatives using gas chromatography-mass spectrometry. The new method made improvements over the original Kawamura method by eliminating the water extraction and evaporation steps. Aerosol materials were directly mixed with the BF 3/BuOH derivatization agent and the extracting solvent hexane. This modification improves recoveries for both the more volatile and the less water-soluble compounds. This improved method was applied to study the abundances and sources of these oxygenated compounds in PM2.5 aerosol samples collected in Hong Kong under different synoptic conditions during 2003-2005. These compounds account for on average 5.2% of OC (range: 1.4%-13.6%) on a carbon basis. Oxalic acid was the most abundant species. Six C2 and C3 oxygenated compounds, namely oxalic, malonic, glyoxylic, pyruvic acids, glyoxal, and methylglyoxal, dominated this suite of oxygenated compounds. More efforts are therefore suggested to focus on these small compounds in understanding the role of oxygenated

  8. Inferring Absorbing Organic Carbon Content from AERONET Data

    NASA Technical Reports Server (NTRS)

    Arola, A.; Schuster, G.; Myhre, G.; Kazadzis, S.; Dey, S.; Tripathi, S. N.

    2011-01-01

    Black carbon, light-absorbing organic carbon (often called brown carbon) and mineral dust are the major light-absorbing aerosols. Currently the sources and formation of brown carbon aerosol in particular are not well understood. In this study we estimated globally the amount of light absorbing organic carbon and black carbon from AERONET measurements. We find that the columnar absorbing organic carbon (brown carbon) levels in biomass burning regions of South-America and Africa are relatively high (about 15-20 magnesium per square meters during biomass burning season), while the concentrations are significantly lower in urban areas in US and Europe. However, we estimated significant absorbing organic carbon amounts from the data of megacities of newly industrialized countries, particularly in India and China, showing also clear seasonality with peak values up to 30-35 magnesium per square meters during the coldest season, likely caused by the coal and biofuel burning used for heating. We also compared our retrievals with the modeled organic carbon by global Oslo CTM for several sites. Model values are higher in biomass burning regions than AERONET-based retrievals, while opposite is true in urban areas in India and China.

  9. Combined effects of organic aerosol loading and fog processing on organic aerosols oxidation and composition

    NASA Astrophysics Data System (ADS)

    Chakraborty, Abhishek; Tripathi, Sachchida; Gupta, Tarun

    2016-04-01

    Fog is a natural meteorological phenomenon that occurs throughout the world, it contains substantial quantity of liquid water and generally seen as a natural cleansing agent but it also has the potential to form highly oxidized secondary organic aerosols (SOA) via aqueous processing of ambient aerosols. On the other hand higher organic aerosols (OA) loading tend to decrease the overall oxidation level (O/C) of the particle phase organics, due to enhanced partitioning of less oxidized organics from gas to particle phase. However, combined impact of these two parameters; aqueous oxidation and OA loading, on the overall oxidation ratio (O/C) of ambient OA has never been studied. To assess this, real time ambient sampling using HR-ToF-AMS was carried out at Kanpur, India from 15 December 2014 - 10 February 2015. In first 3 weeks of this campaign, very high OA loading is (134 ± 42 μg/m3) observed (termed as high loading or HL period) while loading is substantially reduced from 2nd January, 2016 (56 ± 20 μg/m3, termed as low loading or LL period) . However, both the loading period was affected by several fog episodes (10 in HL and 7 in LL), thus providing the opportunity of studying the combined effects of fog and OA loading on OA oxidation. It is found that O/C ratio is very strongly anti-correlated with OA loading in both the loading period, however, slope of this ant-correlation is much steep during HL period than in LL period. Source apportionment of OA revealed that there is drastic change in the types of OA from HL to LL period, clearly indicating difference in OA composition from HL to LL period. During foggy night continuous oxidation of OA is observed from early evening to early morning with 15-20% enhancement in O/C ratio, while the same is absent during non-foggy period, clearly indicating the efficient fog processing of ambient OA. It is also found that night time fog aqueous oxidation can be as effective as daytime photo chemistry in oxidation of OA. Fog

  10. Nuclear magnetic resonance spectroscopy for determining the functional content of organic aerosols: a review.

    PubMed

    Chalbot, Marie-Cecile G; Kavouras, Ilias G

    2014-08-01

    The knowledge deficit of organic aerosol (OA) composition has been identified as the most important factor limiting our understanding of the atmospheric fate and implications of aerosol. The efforts to chemically characterize OA include the increasing utilization of nuclear magnetic resonance spectroscopy (NMR). Since 1998, the functional composition of different types, sizes and fractions of OA has been studied with one-dimensional, two-dimensional and solid state proton and carbon-13 NMR. This led to the use of functional group ratios to reconcile the most important sources of OA, including secondary organic aerosol and initial source apportionment using positive matrix factorization. Future research efforts may be directed towards the optimization of experimental parameters, detailed NMR experiments and analysis by pattern recognition methods to identify the chemical components, determination of the NMR fingerprints of OA sources and solid state NMR to study the content of OA as a whole.

  11. Characterization of the sunset semi-continuous carbon aerosol analyzer.

    PubMed

    Bauer, Jace J; Yu, Xiao-Ying; Cary, Robert; Laulainen, Nels; Berkowitz, Carl

    2009-07-01

    The field-deployable Sunset Semi-Continuous Organic Carbon/Elemental Carbon (Sunset OCEC) aerosol analyzer utilizes the modified National Institute for Occupational Safety and Health thermal-optical method to determine total carbon (TC), organic carbon (OC), and elemental carbon (EC) at near real-time. Two sets of OC and EC are available: thermal OC and EC, and optical OC and EC. The former is obtained by the thermal-optical approach, and the latter is obtained by directly determining EC optically and deriving optical OC from TC. However, the performance of the Sunset OCEC is not yet fully characterized. Two collocated Sunset OCEC analyzers, Unit A and Unit B, were used to determine the pooled relative standard deviation (RSD) and limit of detection (LOD) between September 18 and November 6, 2007 in Richland, WA. The LOD of Unit A was approximately 0.2 microgC/m3 (0.1 microgC/cm2) for TC, optical OC, and thermal OC, and 0.01 microgC/m3 (0.01 microgC/cm2) for optical EC. Similarly, Unit B had an LOD of approximately 0.3 microgC/m3 (0.2 microgC/cm2) for TC, optical OC, and thermal OC, and 0.02 microgC/m3 (0.01 microgC/cm2) for optical EC. The LOD for thermal EC is estimated to be 0.2 microgC/m3 (0.1 microgC/cm2) for both units. The pooled RSDs were 4.9% for TC (carbon mass loadings 0.6-6.0 microgC/cm2), 5.6% for optical OC (carbon mass loadings 0.6-5.4 microgC/cm2), 5.3% for thermal OC (carbon mass loadings 0.6-5.3 microgC/ cm2), and 9.6% for optical EC (carbon mass loadings 0-1.4 microgC/cm2), which indicates good precision between the instruments. The RSD for thermal EC is higher at 24.3% (carbon mass loadings 0-1.2 microgC/cm2). Low EC mass loadings in Richland contributed to the poor RSD of EC. The authors found that excessive noise from the nondispersive infrared (NDIR) laser in the Sunset OCEC analyzer could result in a worsened determination of OC and EC. It is recommended that a "quieter" NDIR laser and detector be used in the Sunset OCEC analyzer to improve

  12. Gas and aerosol fluxes. [emphasizing sulfur, nitrogen, and carbon

    NASA Technical Reports Server (NTRS)

    Martens, C. S.

    1980-01-01

    The development of remote sensing techniques to address the global need for accurate distribution and flux determinations of both man made and natural materials which affect the chemical composition of the atmosphere, the heat budget of the Earth, and the depletion, of stratospheric ozone is considered. Specifically, trace gas fluxes, sea salt aerosol production, and the effect of sea surface microlayer on gas and aerosol fluxes are examined. Volatile sulfur, carbon, nitrogen, and halocarbon compounds are discussed including a statement of the problem associated with each compound or group of compounds, a brief summary of current understanding, and suggestions for needed research.

  13. Modeling biogenic and anthropogenic secondary organic aerosol in China

    NASA Astrophysics Data System (ADS)

    Hu, Jianlin; Wang, Peng; Ying, Qi; Zhang, Hongliang; Chen, Jianjun; Ge, Xinlei; Li, Xinghua; Jiang, Jingkun; Wang, Shuxiao; Zhang, Jie; Zhao, Yu; Zhang, Yingyi

    2017-01-01

    A revised Community Multi-scale Air Quality (CMAQ) model with updated secondary organic aerosol (SOA) yields and a more detailed description of SOA formation from isoprene oxidation was applied to study the spatial and temporal distribution of SOA in China in the entire year of 2013. Predicted organic carbon (OC), elemental carbon and volatile organic compounds agreed favorably with observations at several urban areas, although the high OC concentrations in wintertime in Beijing were under-predicted. Predicted summer SOA was generally higher (10-15 µg m-3) due to large contributions of isoprene (country average, 61 %), although the relative importance varies in different regions. Winter SOA was slightly lower and was mostly due to emissions of alkane and aromatic compounds (51 %). Contributions of monoterpene SOA was relatively constant (8-10 %). Overall, biogenic SOA accounted for approximately 75 % of total SOA in summer, 50-60 % in autumn and spring, and 24 % in winter. The Sichuan Basin had the highest predicted SOA concentrations in the country in all seasons, with hourly concentrations up to 50 µg m-3. Approximately half of the SOA in all seasons was due to the traditional equilibrium partitioning of semivolatile components followed by oligomerization, while the remaining SOA was mainly due to reactive surface uptake of isoprene epoxide (5-14 %), glyoxal (14-25 %) and methylglyoxal (23-28 %). Sensitivity analyses showed that formation of SOA from biogenic emissions was significantly enhanced due to anthropogenic emissions. Removing all anthropogenic emissions while keeping the biogenic emissions unchanged led to total SOA concentrations of less than 1 µg m-3, which suggests that manmade emissions facilitated biogenic SOA formation and controlling anthropogenic emissions would result in reduction of both anthropogenic and biogenic SOA.

  14. Total organic carbon analyzer

    NASA Astrophysics Data System (ADS)

    Godec, Richard G.; Kosenka, Paul P.; Smith, Brian D.; Hutte, Richard S.; Webb, Johanna V.; Sauer, Richard L.

    The development and testing of a breadboard version of a highly sensitive total-organic-carbon (TOC) analyzer are reported. Attention is given to the system components including the CO2 sensor, oxidation reactor, acidification module, and the sample-inlet system. Research is reported for an experimental reagentless oxidation reactor, and good results are reported for linearity, sensitivity, and selectivity in the CO2 sensor. The TOC analyzer is developed with gravity-independent components and is designed for minimal additions of chemical reagents. The reagentless oxidation reactor is based on electrolysis and UV photolysis and is shown to be potentially useful. The stability of the breadboard instrument is shown to be good on a day-to-day basis, and the analyzer is capable of 5 sample analyses per day for a period of about 80 days. The instrument can provide accurate TOC and TIC measurements over a concentration range of 20 ppb to 50 ppm C.

  15. Total organic carbon analyzer

    NASA Technical Reports Server (NTRS)

    Godec, Richard G.; Kosenka, Paul P.; Smith, Brian D.; Hutte, Richard S.; Webb, Johanna V.; Sauer, Richard L.

    1991-01-01

    The development and testing of a breadboard version of a highly sensitive total-organic-carbon (TOC) analyzer are reported. Attention is given to the system components including the CO2 sensor, oxidation reactor, acidification module, and the sample-inlet system. Research is reported for an experimental reagentless oxidation reactor, and good results are reported for linearity, sensitivity, and selectivity in the CO2 sensor. The TOC analyzer is developed with gravity-independent components and is designed for minimal additions of chemical reagents. The reagentless oxidation reactor is based on electrolysis and UV photolysis and is shown to be potentially useful. The stability of the breadboard instrument is shown to be good on a day-to-day basis, and the analyzer is capable of 5 sample analyses per day for a period of about 80 days. The instrument can provide accurate TOC and TIC measurements over a concentration range of 20 ppb to 50 ppm C.

  16. Equilibration timescale of atmospheric secondary organic aerosol partitioning

    NASA Astrophysics Data System (ADS)

    Shiraiwa, Manabu; Seinfeld, John H.

    2012-12-01

    Secondary organic aerosol (SOA) formed from partitioning of oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs) accounts for a substantial portion of atmospheric particulate matter. In describing SOA formation, it is generally assumed that VOC oxidation products rapidly adopt gas-aerosol equilibrium. Here we estimate the equilibration timescale, τeq, of SOA gas-particle partitioning using a state-of-the-art kinetic flux model. τeq is found to be of order seconds to minutes for partitioning of relatively high volatility organic compounds into liquid particles, thereby adhering to equilibrium gas-particle partitioning. However, τeq increases to hours or days for organic aerosol associated with semi-solid particles, low volatility, large particle size, and low mass loadings. Instantaneous equilibrium partitioning may lead to substantial overestimation of particle mass concentration and underestimation of gas-phase concentration.

  17. Final Report, The Influence of Organic-Aerosol Emissions and Aging on Regional and Global Aerosol Size Distributions and the CCN Number Budget

    SciTech Connect

    Donahue, Neil M.

    2015-12-23

    We conducted laboratory experiments and analyzed data on aging of organic aerosol and analysis of field data on volatility and CCN activity. With supplemental ASR funding we participated in the FLAME-IV campaign in Missoula MT in the Fall of 2012, deploying a two-chamber photochemical aging system to enable experimental exploration of photochemical aging of biomass burning emissions. Results from that campaign will lead to numerous publications, including demonstration of photochemical production of Brown Carbon (BrC) from secondary organic aerosol associated with biomass burning emissions as well as extensive characterization of the effect of photochemical aging on the overall concentrations of biomass burning organic aerosol. Excluding publications arising from the FLAME-IV campaign, project research resulted in 8 papers: [11, 5, 3, 10, 12, 4, 8, 7], including on in Nature Geoscience addressing the role of organic compounds in nanoparticle growth [11

  18. 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

  19. A study of the origin of atmospheric organic aerosols

    SciTech Connect

    Hildemann, L.M.

    1990-01-01

    The sources of ambient organic particulate matter in urban areas are investigated through a program of emission source measurements, atmospheric measurements, and mathematical modeling of source/receptor relationships. A dilution sampler intended to collect fine organic aerosol from combustion sources is designed to simulate atmospheric cooling and dilution processes, so that organic vapors which condense under ambient conditions will be collected as particulate matter. This system is used to measure the emissions from a boiler burning distillate oil, a home fireplace, catalyst and noncatalyst automobiles, heavy-duty diesel trucks, natural gas home appliances, and meat-cooking operations. Alternate techniques are used to sample the particulate matter emitted from cigarette smoking, a roofing tar pot, paved road dust, brake lining wear, tire wear, and vegetative detritus. The bulk chemical characteristics of the fine aerosol fraction are presented for each source. Over half of the fine aerosol mass emitted from automobiles, wood burning, meat cooking, home appliances, cigarettes, and tar pots is shown to consist of organic compounds. The organic material collected from these sources is analyzed using high-resolution gas chromatography. Using a simple analytical protocol, a quantitative, 50-parameter characterization of the elutable fine organic aerosol emitted from each source type is obtained, which proves to be a unique fingerprint that can be used to distinguish most sources from each other. A mathematical model is used to predict the characteristics of fine ambient organic aerosol in the Los Angeles area that would prevail if the primary organic emissions are transported without chemical reaction. The model is found to track the seasonal variations observed in the ambient aerosol at the three sites studied.

  20. Toward Investigating Optically Trapped Organic Aerosols with CARS Microspectroscopy

    NASA Astrophysics Data System (ADS)

    Voss, L. F.

    2009-12-01

    The Intergovernmental Panel on Climate Change notes the huge uncertainty in the effect that atmospheric aerosols play in determining overall global temperature, specifically in their ability to nucleate clouds. To better understand aerosol chemistry, the novel coupling of gradient force optical trapping with broad bandwidth coherent anti-Stokes Raman scattering (CARS) spectroscopy is being developed to study single particles suspended in air. Building on successful designs employed separately for the techniques, this hybrid technology will be used to explain how the oxidation of organic compounds changes the chemical and physical properties of aerosols. By trapping the particles, an individual aerosol can be studied for up to several days. Using a broad bandwidth pulse for one of the incident beams will result in a Raman vibrational spectrum from every laser pulse. Combined with signal enhancement due to resonance and coherence of nonlinear CARS spectroscopy, this technique will allow for acquisition of data on the millisecond time scale, facilitating the study of dynamic processes. This will provide insights on how aerosols react with and absorb species from the gas phase. These experiments will increase understanding of aerosol oxidation and growth mechanisms and the effects that aerosols have on our atmosphere and climate. Progress in efforts developing this novel technique to study model systems is presented.

  1. 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 ...

  2. Atmospheric oxidation of isoprene and 1,3-Butadiene: influence of aerosol acidity and Relative humidity on secondary organic aerosol

    EPA Science Inventory

    The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA)have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ per m3 air s...

  3. Composition of carbonaceous smoke particles from prescribed burning of a Canadian boreal forest: 1. Organic aerosol characterization by gas chromatography

    SciTech Connect

    Mazurek, M.A.; Laterza, C.; Newman, L.; Daum, P.; Cofer, W.R. III; Levine, J.S.; Winstead, E.L.

    1995-06-01

    In this study we examine the molecular organic constituents (C8 to C40 lipid compounds) collected as smoke particles from a Canadian boreal forest prescribed burn. Of special interest are (1) the molecular identity of polar organic aerosols, and (2) the amount of polar organic matter relative to the total mass of aerosol particulate carbon. Organic extracts of smoke aerosol particles show complex distributions of the lipid compounds when analyzed by capillary gas chromatography/mass spectrometry. The molecular constituents present as smoke aerosol are grouped into non-polar (hydrocarbons) and polar {minus}2 oxygen atoms) subtractions. The dominant chemical species found in the boreal forest smoke aerosol are unaltered resin compounds (C20 terpenes) which are abundant in unburned conifer wood, plus thermally altered wood lignins and other polar aromatic hydrocarbons. Our results show that smoke aerosols contain molecular tracers which are related to the biofuel consumed. These smoke tracers can be related structurally back to the consumed softwood and hardwood vegetation. In addition, combustion of boreal forest materials produces smoke aerosol particles that are both oxygen-rich and chemically complex, yielding a carbonaceous aerosol matrix that is enriched in polar substances. As a consequence, emissions of carbonaceous smoke particles from large-scale combustion of boreal forest land may have a disproportionate effect on regional atmospheric chemistry and on cloud microphysical processes.

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

    NASA Astrophysics Data System (ADS)

    Aregahegn, Kifle; Nozière, Barbara; George, Christian

    2013-04-01

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

  5. 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

  6. Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles.

    PubMed

    Lin, Peng; Aiona, Paige K; Li, Ying; Shiraiwa, Manabu; Laskin, Julia; Nizkorodov, Sergey A; Laskin, Alexander

    2016-11-01

    Emissions from biomass burning are a significant source of brown carbon (BrC) in the atmosphere. In this study, we investigate the molecular composition of freshly emitted biomass burning organic aerosol (BBOA) samples collected during test burns of sawgrass, peat, ponderosa pine, and black spruce. We demonstrate that both the BrC absorption and the chemical composition of light-absorbing compounds depend significantly on the type of biomass fuels. Common BrC chromophores in the selected BBOA samples include nitro-aromatics, polycyclic aromatic hydrocarbon derivatives, and polyphenols spanning a wide range of molecular weights, structures, and light absorption properties. A number of biofuel-specific BrC chromophores are observed, indicating that some of them may be used as source-specific markers of BrC. On average, ∼50% of the light absorption in the solvent-extractable fraction of BBOA can be attributed to a limited number of strong BrC chromophores. The absorption coefficients of BBOA are affected by solar photolysis. Specifically, under typical atmospheric conditions, the 300 nm absorbance decays with a half-life of ∼16 h. A "molecular corridor" analysis of the BBOA volatility distribution suggests that many BrC compounds in the fresh BBOA have low saturation mass concentration (<1 μg m(-3)) and will be retained in the particle phase under atmospherically relevant conditions.

  7. Organic Aerosol Component (OACOMP) Value-Added Product

    SciTech Connect

    Fast, J; Zhang, Q; tilp, A; Shippert, T; Parworth, C; Mei, F

    2013-08-23

    Organic aerosol (OA, i.e., the organic fraction of particles) accounts for 10–90% of the fine aerosol mass globally and is a key determinant of aerosol radiative forcing. But atmospheric OA is poorly characterized and its life cycle insufficiently represented in models. As a result, current models are unable to simulate OA concentrations and properties accurately. This deficiency represents a large source of uncertainty in quantification of aerosol effects and prediction of future climate change. Evaluation and development of aerosol models require data products generated from field observations. Real-time, quantitative data acquired with aerosol mass spectrometers (AMS) (Canagaratna et al. 2007) are critical to this need. The AMS determines size-resolved concentrations of non-refractory (NR) species in submicrometer particles (PM1) with fast time resolution suitable for both ground-based and aircraft deployments. The high-resolution AMS (HR-AMS), which is equipped with a high mass resolution time-of-flight mass spectrometer, can be used to determine the elemental composition and oxidation degrees of OA (DeCarlo et al. 2006).

  8. On the mixing and evaporation of secondary organic aerosol components.

    PubMed

    Loza, Christine L; Coggon, Matthew M; Nguyen, Tran B; Zuend, Andreas; Flagan, Richard C; Seinfeld, John H

    2013-06-18

    The physical state and chemical composition of an organic aerosol affect its degree of mixing and its interactions with condensing species. We present here a laboratory chamber procedure for studying the effect of the mixing of organic aerosol components on particle evaporation. The procedure is applied to the formation of secondary organic aerosol (SOA) from α-pinene and toluene photooxidation. SOA evaporation is induced by heating the chamber aerosol from room temperature (25 °C) to 42 °C over 7 h and detected by a shift in the peak diameter of the SOA size distribution. With this protocol, α-pinene SOA is found to be more volatile than toluene SOA. When SOA is formed from the two precursors sequentially, the evaporation behavior of the SOA most closely resembles that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA resembles a core of SOA from the initial precursor coated by a layer of SOA from the second precursor. Such a core-and-shell configuration of the organic aerosol phases implies limited mixing of the SOA from the two precursors on the time scale of the experiments, consistent with a high viscosity of at least one of the phases.

  9. Hygroscopicity of Black-Carbon-Containing Aerosol in Wildfire Plumes

    NASA Astrophysics Data System (ADS)

    Perring, A. E.; Schwarz, J. P.; Markovic, M. Z.; Fahey, D. W.; Yokelson, R. J.; Jimenez, J. L.; Campuzano Jost, P.; Day, D. A.; Palm, B. B.; Wisthaler, A.; Ziemba, L. D.; Anderson, B. E.; Diskin, G. S.; Huey, L. G.; Gao, R. S.

    2015-12-01

    Water uptake by black carbon (BC) containing aerosol has been quantified in wildfire plumes of varying age (from 1 to ~40 hr old) sampled in North America during the NASA SEAC4RS mission of 2013. Measurements were made in flight using parallel single-particle soot photometers (SP2) that simultaneously detected the BC component of the ambient aerosol ensemble under contrasting humidity conditions. The hygroscopicity parameter, κ, of material internally mixed with BC derived from this data set is consistent with previous estimates of bulk aerosol hygroscopicity from biomass burning sources. We explore the temporal evolution of κ during aging of the Yosemite Rim Fire plume to constrain the rate of conversion of BC-containing aerosol from hydrophobic to hydrophilic modes in these emissions. We also investigate the relationship between κ values for BC-containing particles and the oxidation state and hygroscopicity of the bulk aerosol. These observations have implications for BC transport and removal in biomass burning plumes and provide important constraints on model treatment of BC optical and microphysical properties from wildfire sources in ambient conditions.

  10. Observation of hydration of single, modified carbon aerosols

    NASA Technical Reports Server (NTRS)

    Wyslouzil, B. E.; Carleton, K. L.; Sonnenfroh, D. M.; Rawlins, W. T.; Arnold, S.

    1994-01-01

    We have compared the hydration behavior of single carbon particles that have been treated by exposure to gaseous H2SO4 with that of untreated particles. Untreated carbon particles did not hydrate as the relative humidity varied from 0 to 80% at 23 C. In contrast, treated particles hydrated under subsaturation conditions; mass increases of up to 30% were observed. The mass increase is consistent with sulfuric acid equilibration with the ambient relative humidity in the presence of inert carbon. For the samples studied, the average amount of absorbed acid was 14% +/- 6% by weight, which corresponds to a surface coverage of approximately 0.1 monolayer. The mass fraction of surface-absorbed acid is comparable to the soluble mass fraction observed by Whitefield et al. (1993) in jet aircraft engine aerosols. Estimates indicate this mass fraction corresponds to 0.1% of the available SO2 exiting an aircraft engine ending up as H2SO4 on the carbon aerosol. If this heterogeneous process occurs early enough in the exhaust plume, it may compete with homogeneous nucleation as a mechanism for producing sulfuric acid rich aerosols.

  11. Black carbon aerosol optical properties are influenced by initial mixing state

    NASA Astrophysics Data System (ADS)

    Willis, M. D.; Healy, R. M.; Riemer, N.; West, M.; Wang, J. M.; Jeong, C. H.; Wenger, J.; Abbatt, J.; Lee, A.

    2015-12-01

    Incomplete combustion emits teragram quantities of black carbon (BC) aerosol to the troposphere each year, resulting in a significant warming effect on climate that may be second only to carbon dioxide. The magnitude of BC impacts on a global scale remains poorly constrained and is intimately related to its particle-scale physical and chemical properties. Using particle-resolved modeling informed by novel quantitative measurements from an Aerodyne soot-particle aerosol mass spectrometer (SP-AMS), we show that initial mixing state (or the distribution of co-emitted components amongst fresh BC-containing particles) significantly affects BC-aerosol optical properties even after a day of atmospheric processing. Both single particle and ensemble observations indicate that BC near emission co-exists with hydrocarbon-like organic aerosol (HOA) in two distinct particle types: HOA-rich and BC-rich particles. The average mass fraction of black carbon (mfBC) in HOA- and BC-rich particle types was 0.02-0.08 and 0.72-0.93, respectively. Notably, positive matrix factorization (PMF) analysis of ensemble SP-AMS measurements indicates that BC-rich particles contribute the majority of BC mass (> 90%) in freshly emitted particles. This new measurement capability provides quantitative insight into the physical and chemical nature of BC-containing particles and is used to drive a particle-resolved aerosol box model. Significant differences in calculated single scattering albedo (an increase of 0.1) arise from accurate treatment of initial particle mixing state as compared to the assumption of uniform aerosol composition at the point of BC injection to the atmosphere.

  12. 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...

  13. Limited influence of dry deposition of semivolatile organic vapors on secondary organic aerosol formation in the urban plume

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

    The dry deposition of volatile organic compounds (VOCs) and its impact on secondary organic aerosols (SOA) are investigated in the Mexico City plume. Gas-phase chemistry and gas-particle partitioning of oxygenated VOCs are modeled with the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) from C3 to C25 alkanes, alkenes, and light aromatics. Results show that dry deposition of oxidized gases is not an efficient sink for SOA, as it removes <5% of SOA within the city's boundary layer and ~15% downwind. Dry deposition competes with the gas-particle uptake, and only gases with fewer than ~12 carbons dry deposit while longer species partition to SOA. Because dry deposition of submicron aerosols is slow, condensation onto particles protects organic gases from deposition, thus increasing their atmospheric burden and lifetime. In the absence of this condensation, ~50% of the regionally produced mass would have been dry deposited.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  15. Atmospheric Carbon Dioxide and Aerosols: Effects of Large Increases on Global Climate

    ERIC Educational Resources Information Center

    Science, 1971

    1971-01-01

    Mathematical models indicate increasing atmospheric carbon dioxide causes an increase in surface temperature at a decreasing rate, and the rate of temperature decrease caused by increasing aerosols increases with aerosol concentration. (AL)

  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. The uptake of HO2 radicals to organic aerosols

    NASA Astrophysics Data System (ADS)

    Matthews, Pascale; Krapf, Manuel; Dommen, Josef; George, Ingrid; Whalley, Lisa; Ingham, Trevor; Baeza-Romero, Maria Teresa; Ammann, Markus; Heard, Dwayne

    2014-05-01

    HOx (OH + HO2) radicals are responsible for the majority of the oxidation in the troposphere and control the concentrations of many trace species in the atmosphere. There have been many field studies where the measured HO2 concentrations have been smaller than the concentration predicted by model calculations [1,2]. The difference has often been attributed to HO2 uptake by aerosols. Organics are a major component of aerosols accounting for 10 - 70 % of their mass [3]. However, there have been very few laboratory studies measuring HO2 uptake onto organic aerosols [4]. Uptake coefficients (γ) were measured for a range of aerosols using a Fluorescence Assay By Gas Expansion (FAGE) detector combined with an aerosol flow tube. HO2 was injected into the flow tube using a moveable injector which allowed first order HO2 decays to be measured along the flow tube both with and without aerosols. Laboratory generated aerosols were made using an atomiser or by homogeneous nucleation. Secondary organic aerosols (SOA) were made using the Paul Scherrer Institute smog chamber and also by means of a Potential Aerosol Mass (PAM) chamber. The total aerosol surface area was then measured using a Scanning Mobility Particle Sizer (SMPS). Experiments were carried out on aerosols containing glutaric acid, glyoxal, malonic acid, stearic acid, oleic acid and squalene. The HO2 uptake coefficients for these species were measured in the range of γ < 0.004 to γ = 0.008 ± 0.004. Humic acid was also studied, however, much larger uptake coefficients (γ = 0.007 - 0.09) were measured, probably due to the fact that these aerosols contained elevated levels of transition metal ions. For humic acid the uptake coefficient was highly dependent on humidity and this may be explained by the liquid water content of the aerosols. Measurements were also performed on copper doped aerosols containing different organics. An uptake coefficient of 0.23 ± 0.07 was measured for copper doped ammonium sulphate

  18. Absorbing Aerosols: Field and Laboratory Studies of Black Carbon and Dust

    NASA Astrophysics Data System (ADS)

    Aiken, A. C.; Flowers, B. A.; Dubey, M. K.

    2011-12-01

    Currently, absorbing aerosols are thought to be the most uncertain factor in atmospheric climate models (~0.4-1.2 W/m2), and the 2nd most important factor after CO2 in global warming (1.6 W/m2; Ramanathan and Carmichael, Nature Geoscience, 2008; Myhre, Science, 2009). While most well-recognized atmospheric aerosols, e.g., sulfate from power-plants, have a cooling effect on the atmosphere by scattering solar radiation, black carbon (BC or soot) absorbs sunlight strongly which results in a warming of the atmosphere. Dust particles are also present globally and can absorb radiation, contributing to a warmer and drier atmosphere. Direct on-line measurements of BC and hematite, an absorbing dust aerosol, can be made with the Single Particle Soot Photometer (SP2), which measures the mass of the particles by incandescence on an individual particle basis. Measurements from the SP2 are combined with absorption measurements from the three-wavelength photoacoustic soot spectrometer (PASS-3) at 405, 532, and 781 nm and the ultraviolet photoacoustic soot spectrometer (PASS-UV) at 375 nm to determine wavelength-dependent mass absorption coefficients (MACs). Laboratory aerosol samples include flame-generated soot, fullerene soot, Aquadag, hematite, and hematite-containing dusts. Measured BC MAC's compare well with published values, and hematite MAC's are an order of magnitude less than BC. Absorbing aerosols measured in the laboratory are compared with those from ambient aerosols measured during the Las Conchas fire and BEACHON-RoMBAS. The Las Conchas fire was a wildfire in the Jemez Mountains of New Mexico that burned over 100,000 acres during the Summer of 2011, and BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Biogenic Aerosol Study) is a field campaign focusing on biogenic aerosols at the Manitou Forest Observatory near Colorado Springs, CO in Summer 2011. Optical properties and size

  19. Model evaluation of marine primary organic aerosol emission schemes

    NASA Astrophysics Data System (ADS)

    Gantt, B.; Johnson, M. S.; Meskhidze, N.; Sciare, J.; Ovadnevaite, J.; Ceburnis, D.; O'Dowd, C. D.

    2012-09-01

    In this study, several marine primary organic aerosol (POA) emission schemes have been evaluated using the GEOS-Chem chemical transport model in order to provide guidance for their implementation in air quality and climate models. These emission schemes, based on varying dependencies of chlorophyll a concentration ([chl a]) and 10 m wind speed (U10), have large differences in their magnitude, spatial distribution, and seasonality. Model comparison with weekly and monthly mean values of the organic aerosol mass concentration at two coastal sites shows that the source function exclusively related to [chl a] does a better job replicating surface observations. Sensitivity simulations in which the negative U10 and positive [chl a] dependence of the organic mass fraction of sea spray aerosol are enhanced show improved prediction of the seasonality of the marine POA concentrations. A top-down estimate of submicron marine POA emissions based on the parameterization that compares best to the observed weekly and monthly mean values of marine organic aerosol surface concentrations has a global average emission rate of 6.3 Tg yr-1. Evaluation of existing marine POA source functions against a case study during which marine POA contributed the major fraction of submicron aerosol mass shows that none of the existing parameterizations are able to reproduce the hourly-averaged observations. Our calculations suggest that in order to capture episodic events and short-term variability in submicron marine POA concentration over the ocean, new source functions need to be developed that are grounded in the physical processes unique to the organic fraction of sea spray aerosol.

  20. Influence of Slightly Soluble Organics on Aerosol Activation

    SciTech Connect

    Abdul-Razzak, Hayder; Ghan, Steven J.

    2005-03-22

    This paper examines the effects of slightly soluble organics on aerosol activation in a parcel of air rising adiabatically. Slightly soluble organics can affect aerosol activation by three mechanisms: lowering surface tension, altering the bulk hygroscopicity, and delaying the growth of particles due to their lower solubilities. Here, we address the third mechanism by simulating the activation process of aerosol particles modeled using a single lognormal size distribution and consisting of an internal uniform chemical mixture of adipic acid (representing slightly soluble organics having extremely low solubility) and ammonium sulfate. The simulations were carried out using measured solubility of adipic acid spanning a wide range of physical and dynamical parameters. The same conditions were re-simulated but assuming fully soluble aerosols. Results of the simulations show that although that the low solubility of the adipic acid alters Köhler curves and increases critical supersaturation of the smaller particles (Köhler curves of the larger particles are not effected since these particles are completely dissolved at the initial supersaturation of zero), it has minimal to no effect on the parcel’s supersaturation except for particles consisting of more than 95% adipic acid. Accordingly, since aerosols in realistic atmospheric conditions do not contain more than 90% organics, we conclude that it is not necessary to retune the parameterization of aerosol activation previously developed and modified to address the other two mechanisms. The slightly soluble organics can thus be assumed to be fully soluble for the purpose of predicting the fraction of activation and the maximum supersaturation with negligible error.

  1. Method for characterization of low molecular weight organic acids in atmospheric aerosols using ion chromatography mass spectrometry.

    PubMed

    Brent, Lacey C; Reiner, Jessica L; Dickerson, Russell R; Sander, Lane C

    2014-08-05

    The structural composition of PM2.5 monitored in the atmosphere is usually divided by the analysis of organic carbon, black (also called elemental) carbon, and inorganic salts. The characterization of the chemical composition of aerosols represents a significant challenge to analysts, and studies are frequently limited to determination of aerosol bulk properties. To better understand the potential health effects and combined interactions of components in aerosols, a variety of measurement techniques for individual analytes in PM2.5 need to be implemented. The method developed here for the measurement of organic acids achieves class separation of aliphatic monoacids, aliphatic diacids, aromatic acids, and polyacids. The selective ion monitoring capability of a triple quadropole mass analyzer was frequently capable of overcoming instances of incomplete separations. Standard Reference Material (SRM) 1649b Urban Dust was characterized; 34 organic acids were qualitatively identified, and 6 organic acids were quantified.

  2. Optical and Physicochemical Properties of Brown Carbon Aerosol: Light Scattering, FTIR Extinction Spectroscopy, and Hygroscopic Growth.

    PubMed

    Tang, Mingjin; Alexander, Jennifer M; Kwon, Deokhyeon; Estillore, Armando D; Laskina, Olga; Young, Mark A; Kleiber, Paul D; Grassian, Vicki H

    2016-06-23

    in the mid-IR range (800 to 7000 cm(-1)) also showed no significant changes in either the real or the imaginary parts of the refractive indices for brown carbon aerosol particles when compared to ammonium sulfate. Therefore, changes in the optical properties of ammonium sulfate in the mid-IR spectral range due to reaction with methylglyoxal appear to be insignificant. In addition to these measurements, we have characterized additional physicochemical properties of the brown carbon aerosol particles including hygroscopic growth using a tandem-differential mobility analyzer. Compared to ammonium sulfate, brown carbon aerosol particles are found to have lower deliquescence relative humidity (DRH), efflorescence relative humidity (ERH), and hygroscopic growth at the same relative humidities. Overall, our study provides new details of the optical and physicochemical properties of a class of secondary organic aerosol which may have important implications for atmospheric chemistry and climate.

  3. Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

    SciTech Connect

    Madronich, Sasha

    2015-12-09

    The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

  4. Organic compounds in aerosols from selected European sites - Biogenic versus anthropogenic sources

    NASA Astrophysics Data System (ADS)

    Alves, Célia; Vicente, Ana; Pio, Casimiro; Kiss, Gyula; Hoffer, Andras; Decesari, Stefano; Prevôt, André S. H.; Minguillón, María Cruz; Querol, Xavier; Hillamo, Risto; Spindler, Gerald; Swietlicki, Erik

    2012-11-01

    Atmospheric aerosol samples from a boreal forest (Hyytiälä, April 2007), a rural site in Hungary (K-puszta, summer 2008), a polluted rural area in Italy (San Pietro Capofiume, Po Valley, April 2008), a moderately polluted rural site in Germany located on a meadow (Melpitz, May 2008), a natural park in Spain (Montseny, March 2009) and two urban background locations (Zurich, December 2008, and Barcelona, February/March 2009) were collected. Aliphatics, polycyclic aromatic hydrocarbons, carbonyls, sterols, n-alkanols, acids, phenolic compounds and anhydrosugars in aerosols were chemically characterised by gas chromatography-mass spectrometry, along with source attribution based on the carbon preference index (CPI), the ratios between the unresolved and the chromatographically resolved aliphatics, the contribution of wax n-alkanes, n-alkanols and n-alkanoic acids from plants, diagnostic ratios of individual target compounds and source-specific markers to organic carbon ratios. In spite of transboundary pollution episodes, Hyytiälä registered the lowest levels among all locations. CPI values close to 1 for the aliphatic fraction of the Montseny aerosol suggest that the anthropogenic input may be associated with the transport of aged air masses from the surrounding industrial/urban areas, which superimpose the locally originated hydrocarbons with biogenic origin. Aliphatic and aromatic hydrocarbons in samples from San Pietro Capofiume reveal that fossil fuel combustion is a major source influencing the diel pattern of concentrations. This source contributed to 25-45% of the ambient organic carbon (OC) at the Po Valley site. Aerosols from the German meadow presented variable contributions from both biogenic and anthropogenic sources. The highest levels of vegetation wax components and biogenic secondary organic aerosol (SOA) products were observed at K-puszta, while anthropogenic SOA compounds predominated in Barcelona. The primary vehicular emissions in the Spanish

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

    EPA Science Inventory

    Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles,...

  6. Direct radiative forcing from black carbon aerosols over urban environment

    NASA Astrophysics Data System (ADS)

    Madhavi Latha, K.; Badarinath, K. V. S.

    There is growing evidence that the earth's climate is changing and will likely continue to change in the future. It is still debated whether these changes are due to natural variability of the climate system or a result of increases in the concentration of greenhouse gases in the atmosphere. Black carbon (BC) has become the subject of interest for a variety of reasons. BC aerosol may cause environmental as well as harmful health effects in densely inhabited regions. BC is a strong absorber of radiation in the visible and near-infrared part of the spectrum, where most of the solar energy is distributed. Black carbon is emitted into the atmosphere as a byproduct of all combustion processes viz., vegetation burning, industrial effluents and motor vehicle exhausts etc. In this paper, we present results from our measurements on black carbon aerosols, total aerosol mass concentration and aerosol optical depth over an urban environment namely Hyderabad during January to May, 2003. Diurnal variations of BC suggests that high BC concentrations observed during 6:00-9:00hrs and 19:00-23:00hrs. Weekday variations of BC suggest that the day average BC concentrations increases gradually from Monday to Wednesday and gradually decreased from Thursday to Sunday. Analysis of traffic density along with meteorological parameters suggests that the primary determinant for BC concentration levels and patterns is traffic density. Seasonal variations of BC suggest that the BC concentrations are high during dry season compared to rainy season due to scavenging effects of BC during rainy season. Fraction of BC to total mass concentration has been observed to be 7% during January to May. BC showed positive correlation with total mass concentration and aerosol optical depth at 500nm. Radiative transfer calculations suggests that during January to May, diurnal averaged aerosol forcing at the surface calculated to be -33Wm -2 and at the top of the atmosphere (TOA) it is observed to +9 Wm -2. The

  7. Multi-walled carbon nanotubes: sampling criteria and aerosol characterization

    PubMed Central

    Chen, Bean T.; Schwegler-Berry, Diane; McKinney, Walter; Stone, Samuel; Cumpston, Jared L.; Friend, Sherri; Porter, Dale W.; Castranova, Vincent; Frazer, David G.

    2015-01-01

    This study intends to develop protocols for sampling and characterizing multi-walled carbon nanotube (MWCNT) aerosols in workplaces or during inhalation studies. Manufactured dry powder containing MWCNT’s, combined with soot and metal catalysts, form complex morphologies and diverse shapes. The aerosols, examined in this study, were produced using an acoustical generator. Representative samples were collected from an exposure chamber using filters and a cascade impactor for microscopic and gravimetric analyses. Results from filters showed that a density of 0.008–0.10 particles per µm2 filter surface provided adequate samples for particle counting and sizing. Microscopic counting indicated that MWCNT’s, resuspended at a concentration of 10 mg/m3, contained 2.7 × 104 particles/cm3. Each particle structure contained an average of 18 nanotubes, resulting in a total of 4.9 × 105 nanotubes/cm3. In addition, fibrous particles within the aerosol had a count median length of 3.04 µm and a width of 100.3 nm, while the isometric particles had a count median diameter of 0.90 µm. A combination of impactor and microscopic measurements established that the mass median aerodynamic diameter of the mixture was 1.5 µm. It was also determined that the mean effective density of well-defined isometric particles was between 0.71 and 0.88 g/cm3, and the mean shape factor of individual nanotubes was between 1.94 and 2.71. The information obtained from this study can be used for designing animal inhalation exposure studies and adopted as guidance for sampling and characterizing MWCNT aerosols in workplaces. The measurement scheme should be relevant for any carbon nanotube aerosol. PMID:23033994

  8. Characterization and source apportionment of organic aerosol using offline aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Daellenbach, K. R.; Bozzetti, C.; Křepelová, A.; Canonaco, F.; Wolf, R.; Zotter, P.; Fermo, P.; Crippa, M.; Slowik, J. G.; Sosedova, Y.; Zhang, Y.; Huang, R.-J.; Poulain, L.; Szidat, S.; Baltensperger, U.; Prévôt, A. S. H.; El Haddad, I.

    2015-08-01

    Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make impractical its deployment at sufficient sites to determine regional characteristics. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, PM10) collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g. AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60-91 %) achieved using this technique, together with low detection limits (0.8 μg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon, oxygen containing and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g. filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially-resolved long-term datasets.

  9. Characterization and source apportionment of organic aerosol using offline aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Daellenbach, K. R.; Bozzetti, C.; Křepelová, A.; Canonaco, F.; Wolf, R.; Zotter, P.; Fermo, P.; Crippa, M.; Slowik, J. G.; Sosedova, Y.; Zhang, Y.; Huang, R.-J.; Poulain, L.; Szidat, S.; Baltensperger, U.; El Haddad, I.; Prévôt, A. S. H.

    2016-01-01

    Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make its deployment at sufficient sites to determine regional characteristics impractical. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, and PM10, i.e., PM with aerodynamic diameters smaller than 1, 2.5, and 10 µm, respectively), collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g., AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60-91 %) achieved using this technique, together with low detection limits (0.8 µg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon ions, ions containing oxygen, and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning, and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g., filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially resolved long-term data sets.

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

    NASA Astrophysics Data System (ADS)

    Preunkert, S.; Legrand, M.

    2013-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Preunkert, S.; Legrand, M.

    2013-02-01

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

  12. Aqueous-phase mechanism for secondary organic aerosol ...

    EPA Pesticide Factsheets

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observati

  13. Evolution of secondary inorganic and organic aerosols during transport: A case study at a regional receptor site.

    PubMed

    Peng, Jianfei; Hu, Min; Gong, Zhaoheng; Tian, Xudong; Wang, Ming; Zheng, Jing; Guo, Qingfeng; Cao, Wei; Lv, Wei; Hu, Weiwei; Wu, Zhijun; Guo, Song

    2016-11-01

    Understanding the evolution of aerosols in the atmosphere is of great importance for improving air quality and reducing aerosol-related uncertainties in global climate simulations. Here, a unique haze episode at a regional receptor site near the East China Sea was examined as a case study of the aging process of atmospheric aerosols during transport. An increase in photochemical age from 5 h to more than 25 h and a progressive increase in the fitted mean particle diameter from 70 nm to approximately 300 nm were observed. According to the pollution features and meteorology conditions involved, pollution accumulation (PA), sea breeze (SB), and land breeze (LB) periods were identified. Concentrations of black carbon (BC), hydrocarbon-like organic aerosols (HOA), semi-volatile oxidized organic aerosols (SV-OOA), and nitrate increased by 7-fold up to 39-fold when the air masses passed through Taizhou, a nearby city. In addition, nitrate and SV-OOA dominated the aerosol composition in the urban outflow plumes (52% and 18%, respectively), yet they gradually decreased in concentration during transport. In contrast, sulfate and the low-volatile oxidized organic aerosols (LV-OOA) exhibited more regional footprints and potentially have similar formation mechanisms. The atomic oxygen-to-carbon (O/C) ratio also increased from 0.45 to 0.9, thereby suggesting that rapid formation of highly oxidized secondary organic aerosols (SOA) occurred during transport. Overall, these results provide valuable insight into the evolution of the chemical and physical features of aerosol pollution during transport and also highlight the need for regulatory controls of nitrogen oxides, sulfur dioxide, and VOCs to improve air quality on different scales.

  14. 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...

  15. Black Carbon Concentration from Worldwide Aerosol Robotic Network (AERONET)

    NASA Technical Reports Server (NTRS)

    Schuster, Greg; Dubovik, Oleg; Holben, Brent; Clothiaux, Eugene

    2008-01-01

    Worldwide black carbon concentration measurements are needed to assess the efficacy of the carbon emissions inventory and transport model output. This requires long-term measurements in many regions, as model success in one region or season does not apply to all regions and seasons. AERONET is an automated network of more than 180 surface radiometers located throughout the world. The sky radiance measurements obtained by AERONET are inverted to provide column-averaged aerosol refractive indices and size distributions for the AERONET database, which we use to derive column-averaged black carbon concentrations and specific absorptions that are constrained by the measured radiation field. This provides a link between AERONET sky radiance measurements and the elemental carbon concentration of transport models without the need for an optics module in the transport model. Knowledge of both the black carbon concentration and aerosol absorption optical depth (i.e., input and output of the optics module) will enable improvements to the transport model optics module.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  17. Organic aerosol sources an partitioning in CMAQv5.2

    EPA Science Inventory

    We describe a major CMAQ update, available in version 5.2, which explicitly treats the semivolatile mass transfer of primary organic aerosol compounds, in agreement with available field and laboratory observations. Until this model release, CMAQ has considered these compounds to ...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  19. SECONDARY ORGANIC AEROSOL FORMATION FROM MIXTURES OF BIOGENIC HYDROCARBONS

    EPA Science Inventory

    In this work the influence of hydrocarbon mixtures on the overall Secondary Organic Aerosol yield is investigated. Photochemical reaction experiments were conducted using mixtures of a-pinene, isoprene and propene in the presence of NOx. Results of the experiments show...

  20. Black carbon aerosols and the third polar ice cap

    SciTech Connect

    Menon, Surabi; Koch, Dorothy; Beig, Gufran; Sahu, Saroj; Fasullo, John; Orlikowski, Daniel

    2010-04-15

    Recent thinning of glaciers over the Himalayas (sometimes referred to as the third polar region) have raised concern on future water supplies since these glaciers supply water to large river systems that support millions of people inhabiting the surrounding areas. Black carbon (BC) aerosols, released from incomplete combustion, have been increasingly implicated as causing large changes in the hydrology and radiative forcing over Asia and its deposition on snow is thought to increase snow melt. In India BC emissions from biofuel combustion is highly prevalent and compared to other regions, BC aerosol amounts are high. Here, we quantify the impact of BC aerosols on snow cover and precipitation from 1990 to 2010 over the Indian subcontinental region using two different BC emission inventories. New estimates indicate that Indian BC emissions from coal and biofuel are large and transport is expected to expand rapidly in coming years. We show that over the Himalayas, from 1990 to 2000, simulated snow/ice cover decreases by {approx}0.9% due to aerosols. The contribution of the enhanced Indian BC to this decline is {approx}36%, similar to that simulated for 2000 to 2010. Spatial patterns of modeled changes in snow cover and precipitation are similar to observations (from 1990 to 2000), and are mainly obtained with the newer BC estimates.

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

    SciTech Connect

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

    2014-06-17

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

  2. Light absorption by organic carbon from wood combustion

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Bond, T. C.

    2009-09-01

    Carbonaceous aerosols affect the radiative balance of the Earth by absorbing and scattering light. While BC is highly absorbing, some organic compounds also have significant absorption, which is greater at near-ultraviolet and blue wavelengths. To the extent that OC absorbs visible light, it may be a non-negligible contributor to direct aerosol radiative forcing. In this work, we examine absorption by primary OC emitted from solid fuel pyrolysis. We provide absorption spectra of this material, which can be related to the imaginary refractive index. This material has polar character but is not fully water-soluble: more than 92% was extractable by methanol or acetone, compared with 73% for water and 52% for hexane. Water-soluble organic carbon contributed to light absorption at both ultraviolet and visible wavelengths. However, a larger portion came from organic carbon that is extractable only by methanol. The spectra of water-soluble organic carbon are similar to others in the literature. We compared spectra for material generated with different wood type, wood size and pyrolysis temperature. Higher wood temperature is the main factor creating organic aerosol with higher absorption, causing about a factor of four increase in mass-normalized absorption at visible wavelengths. A simple model suggests that, despite the absorption, both high-temperature and low-temperature carbon have negative climate forcing over a surface with average albedo.

  3. Quantifying the Relationship between Organic Aerosol Composition and Hygroscopicity/CCN Activity

    SciTech Connect

    Ziemann, Paul J.; Kreidenweis, Sonia M.; Petters, Markus D.

    2013-06-30

    The overall objective for this project was to provide the data and underlying process level understanding necessary to facilitate the dynamic treatment of organic aerosol CCN activity in future climate models. The specific objectives were as follows: (1) employ novel approaches to link organic aerosol composition and CCN activity, (2) evaluate the effects of temperature and relative humidity on organic aerosol CCN activity, and (3) develop parameterizations to link organic aerosol composition and CCN activity.

  4. Regional signatures in the organic composition of marine aerosol particles

    NASA Astrophysics Data System (ADS)

    Frossard, Amanda A.; Russell, Lynn M.; Keene, William C.; Kieber, David J.; Quinn, Patricia K.; Bates, Timothy S.

    2013-05-01

    Marine aerosol particles play an important role in the earth's radiative balance, yet the sources and composition of the organic fraction remain largely unconstrained. Recent measurements have been made in order to characterize the sources, composition, and concentration of aerosol particles in the marine boundary layer. The organic composition of submicron particles derived from multiple seawater regions have been measured using Fourier Transform Infrared (FTIR) spectroscopy. Cluster analysis of FTIR organic spectra suggest different spectral signatures based on collection location, seawater composition, and ambient conditions. Measurements including non-refractory aerosol composition from a high-resolution time of flight aerosol mass spectrometer (HR-ToF-AMS), seawater composition, and wind speed were used to interpret the cluster results, depending on the availability from each campaign. FTIR spectra of ambient particles are compared to FTIR spectra of primary marine particles generated from model ocean systems to infer the ambient particle production mechanisms and aging processes. Recent measurements used in the comparison include ambient and generated marine aerosol particles measured off the coast of California during CalNex in May and June 2010. Remote ambient marine aerosol particles were collected 100 miles off the coast of Monterey in the eastern Pacific during the EPEACE experiment in July 2011. Ambient and generated marine particles were measured in two different seawater types during WACS 2012 including colder, more productive water off the coast of the northeastern United States and warmer, oligotrophic water in the Sargasso Sea. These particles are also compared with those measured in the southeastern Pacific during VOCALS and the north Atlantic during ICEALOT.

  5. Simulations of organic aerosol concentrations during springtime in the Guanzhong Basin, China

    NASA Astrophysics Data System (ADS)

    Feng, Tian; Li, Guohui; Cao, Junji; Bei, Naifang; Shen, Zhenxing; Zhou, Weijian; Liu, Suixin; Zhang, Ting; Wang, Yichen; Huang, Ru-jin; Tie, Xuexi; Molina, Luisa T.

    2016-08-01

    The organic aerosol (OA) concentration is simulated in the Guanzhong Basin, China from 23 to 25 April 2013 utilizing the WRF-CHEM model. Two approaches are used to predict OA concentrations: (1) a traditional secondary organic aerosol (SOA) module; (2) a non-traditional SOA module including the volatility basis-set modeling method in which primary organic aerosol (POA) is assumed to be semivolatile and photochemically reactive. Generally, the spatial patterns and temporal variations of the calculated hourly near-surface ozone and fine particle matters agree well with the observations in Xi'an and surrounding areas. The model also yields reasonable distributions of daily PM2.5 and elemental carbon (EC) compared to the filter measurements at 29 sites in the basin. Filter-measured organic carbon (OC) and EC are used to evaluate OA, POA, and SOA using the OC / EC ratio approach. Compared with the traditional SOA module, the non-traditional module significantly improves SOA simulations and explains about 88 % of the observed SOA concentration. Oxidation and partitioning of POA treated as semivolatile constitute the most important pathway for the SOA formation, contributing more than 75 % of the SOA concentrations in the basin. Residential emissions are the dominant anthropogenic OA source, constituting about 50 % of OA concentrations in urban and rural areas and 30 % in the background area. The OA contribution from transportation emissions decreases from 25 % in urban areas to 20 % in the background area, and the industry emission OA contribution is less than 6 %.

  6. Modeling the influence of alkane molecular structure on secondary organic aerosol formation.

    PubMed

    Aumont, Bernard; Camredon, Marie; Mouchel-Vallon, Camille; La, Stéphanie; Ouzebidour, Farida; Valorso, Richard; Lee-Taylor, Julia; Madronich, Sasha

    2013-01-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapor pressure. Intermediate Volatility Organic Compounds (IVOC) emitted to the atmosphere are expected to be a substantial source of SOA. These emitted IVOC constitute a complex mixture including linear, branched and cyclic alkanes. The explicit gas-phase oxidation mechanisms are here generated for various linear and branched C10-C22 alkanes using the GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) and SOA formation is investigated for various homologous series. Simulation results show that both the size and the branching of the carbon skeleton are dominant factors driving the SOA yield. However, branching appears to be of secondary importance for the particle oxidation state and composition. The effect of alkane molecular structure on SOA yields appears to be consistent with recent laboratory observations. The simulated SOA composition shows, however, an unexpected major contribution from multifunctional organic nitrates. Most SOA contributors simulated for the oxidation of the various homologous series are far too reduced to be categorized as highly oxygenated organic aerosols (OOA). On a carbon basis, the OOA yields never exceeded 10% regardless of carbon chain length, molecular structure or ageing time. This version of the model appears clearly unable to explain a large production of OOA from alkane precursors.

  7. Source apportionment of carbonaceous aerosols over South and East Asia using dual carbon isotopes

    NASA Astrophysics Data System (ADS)

    Gustafsson, O.; Kirillova, E. N.; Andersson, A.-; Kruså, M.; Sheesley, R. J.; Tiwari, S.-; Lee, M.; Chen, B.; Du, K.

    2012-12-01

    Emissions of black carbon (BC) and other components of carbonaceous aerosols affect both climate and health in South and East Asia, yet substantial uncertainties exist regarding their sources. The relative contribution to atmospheric BC from fossil fuel versus biomass combustion is important to constrain both to direct mitigation and as their different properties make their effects on climate forcing and respiratory health different. This study approached the sourcing challenge by applying microscale radiocarbon measurements to aerosol particles collected in both source regions and at regional receptor observatories of both S Asia (New Delhi and the Maldives Climate Observatory) and of E Asia (Beijing, Shanghai, South China Coastal Observatory and the Korea Climate Observatory - Gosan, KCO-G, Jeju Island). The radiocarbon approach is ideally suited to this task as fossil sources are void of 14C whereas biomass combustion products hold a contemporary 14C signal. For S Asia, the 14C-based observations suggest that biomass combustion contributes half to two-thirds of the BC loading. In contrast, for E Asia, fossil fuel combustion account for four-fifths of the BC emitted from China. This source-diagnostic radiocarbon signal in the ambient aerosol over East Asia establishes a much larger role for fossil fuel combustion than suggested by all fifteen BC emission inventory models. There are also poor constraints on the sources of water-soluble organic carbon (WSOC), a large hydrophilic component of carbonaceous aerosols that enhances the propensity of aerosols to form clouds. In a 15-mo continuous campaign in S Asia, radiocarbon-based source apportionment of WSOC shows the dominance of biogenic/biomass combustion sources but also a substantial anthropogenic fossil-fuel contribution (about 20%). WSOC in E Asia reaching KCO-G were 50% from fossil sources. Aerosols reaching the Maldives after long-range over-ocean transport were enriched by 3-4‰ in δ13C-WSOC. This is

  8. 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

  9. Wintertime aerosol chemical composition and source apportionment of the organic fraction in the metropolitan area of Paris

    NASA Astrophysics Data System (ADS)

    Crippa, M.; DeCarlo, P. F.; Slowik, J. G.; Mohr, C.; Heringa, M. F.; Chirico, R.; Poulain, L.; Freutel, F.; Sciare, J.; Cozic, J.; Di Marco, C. F.; Elsasser, M.; Nicolas, J. B.; Marchand, N.; Abidi, E.; Wiedensohler, A.; Drewnick, F.; Schneider, J.; Borrmann, S.; Nemitz, E.; Zimmermann, R.; Jaffrezo, J.-L.; Prévôt, A. S. H.; Baltensperger, U.

    2013-01-01

    The effect of a post-industrial megacity on local and regional air quality was assessed via a month-long field measurement campaign in the Paris metropolitan area during winter 2010. Here we present source apportionment results from three aerosol mass spectrometers and two aethalometers deployed at three measurement stations within the Paris region. Submicron aerosol composition is dominated by the organic fraction (30-36%) and nitrate (28-29%), with lower contributions from sulfate (14-16%), ammonium (12-14%) and black carbon (7-13%). Organic source apportionment was performed using positive matrix factorization, resulting in a set of organic factors corresponding both to primary emission sources and secondary production. The dominant primary sources are traffic (11-15% of organic mass), biomass burning (13-15%) and cooking (up to 35% during meal hours). Secondary organic aerosol contributes more than 50% to the total organic mass and includes a highly oxidized factor from indeterminate and/or diverse sources and a less oxidized factor related to wood burning emissions. Black carbon was apportioned to traffic and wood burning sources using a model based on wavelength-dependent light absorption of these two combustion sources. The time series of organic and black carbon factors from related sources were strongly correlated. The similarities in aerosol composition, total mass and temporal variation between the three sites suggest that particulate pollution in Paris is dominated by regional factors, and that the emissions from Paris itself have a relatively low impact on its surroundings.

  10. Anthropogenic and biogenic organic compounds in summertime fine aerosols (PM2.5) in Beijing, China

    NASA Astrophysics Data System (ADS)

    Yang, Fan; Kawamura, Kimitaka; Chen, Jing; Ho, Kinfai; Lee, Shuncheng; Gao, Yuan; Cui, Long; Wang, Tieguan; Fu, Pingqing

    2016-01-01

    Ambient fine aerosol samples (PM2.5) were collected at an urban site (PKU) in Beijing and its upwind suburban site (Yufa) during the CAREBEIJING-2007 field campaign. Organic molecular compositions of the PM2.5 samples were studied for seven organic compound classes (sugars, lignin/resin acids, hydroxy-/polyacids, aromatic acids, biogenic SOA tracers, fatty acids and phthalates) using capillary GC/MS to better understand the characteristics and sources of organic aerosol pollution in Beijing. More than 60 individual organic species were detected in PM2.5 and were grouped into different compound classes based on their functional groups. Concentrations of total quantified organics at Yufa (469-1410 ng m-3, average 1050 ng m-3) were slightly higher than those at PKU (523-1390 ng m-3, 900 ng m-3). At both sites, phthalates were found as the most abundant compound class. Using a tracer-based method, the contributions of the biogenic secondary organic carbon (SOC) to organic carbon (OC) were 3.1% at PKU and 5.5% at Yufa, among which isoprene-SOC was the dominant contributor. In addition, most of the measured organic compounds were higher at Yufa than those at PKU, indicating a more serious pollution in its upwind region than in urban Beijing.

  11. Comparative Climate Responses of Anthropogenic Greenhouse Gases, All Major Aerosol Components, Black Carbon, and Methane, Accounting for the Evolution of the Aerosol Mixing State and of Clouds/Precipitation from Multiple Aerosol Size Distributions

    NASA Astrophysics Data System (ADS)

    Jacobson, M. Z.

    2005-12-01

    Several modeling studies to date have simulated the global climate response of anthropogenic greenhouse gases and bulk (non-size-resolved) sulfate or generic aerosol particles together, but no study has examined the climate response of greenhouse gases simultaneously with all major size- and composition resolved aerosol particle components. Such a study is important for improving our understanding of the effects of anthropogenic pollutants on climate. Here, the GATOR-GCMOM model is used to study the global climate response of (a) all major greenhouse gases and size-resolved aerosol components, (b) all major greenhouse gases alone, (c) fossil-fuel soot (black carbon, primary organic matter, sulfuric acid, bisulfate, sulfate), and (d) methane. Aerosol components treated in all simulations included water, black carbon, primary organic carbon, secondary organic carbon, sulfuric acid, bisulfate, sulfate, nitrate, chloride, ammonium, sodium, hydrogen ion, soil dust, and pollen/spores. Fossil-fuel soot (FFS) was emitted into its own size distribution. All other components, including biofuel and biomass soot, sea-spray, soil dust, etc., were emitted into a second distribution (MIX). The FFS distribution grew by condensation of secondary organic matter and sulfuric acid, hydration of water, and dissolution of nitric acid, ammonia, and hydrochloric acid. It self-coagulated and heterocoagulated with the MIX distribution, which also grew by condensation, hydration, and dissolution. Treatment of separate distributions for FFS allowed FFS to evolve from an external mixture to an internal mixture. In both distributions, black carbon was treated as a core component for optical calculations. Both aerosol distributions served as CCN during explicit size-resolved cloud formation. The resulting clouds grew by coagulation and condensation, coagulated with interstitial aerosol particles, and fell to the surface as rain and snow, carrying aerosol constituents with them. Thus, cloud

  12. Analysis of the chemical and physical properties of combustion aerosols: Properties overview

    EPA Science Inventory

    Aerosol chemical composition is remarkably complex. Combustion aerosols can comprise tens of thousands of organic compounds and fragments, refractory carbon, metals, cations, anions, salts, and other inorganic phases and substituents [Hays et al., 2004]. Aerosol organic matter no...

  13. Secondary organic aerosol formation during June 2010 in Central Europe: measurements and modelling studies with a mixed thermodynamic-kinetic approach

    NASA Astrophysics Data System (ADS)

    Langmann, B.; Sellegri, K.; Freney, E.

    2013-10-01

    Until recently secondary organic carbon (SOC) aerosol mass concentrations have been systematically underestimated by three-dimensional atmospheric-chemistry-aerosol models. With a newly proposed concept of aging of organic vapours more realistic model results for organic carbon aerosol mass concentrations could be achieved. Applying a mixed thermodynamic-kinetic approach for SOC aerosol formation shifted the aerosol size distribution towards particles in the cloud condensation nuclei size range, thereby emphasising the importance of SOC aerosol formation schemes for modelling realistic cloud and precipitation formation. The additional importance of hetero-molecular nucleation between H2SO4 and organic vapours remains to be evaluated in three-dimensional atmospheric-chemistry-aerosol models. Here a case study is presented focusing on Puy-de-Dôme, France in June 2010. Even though nucleation events at Puy-de-Dôme were rare during the chosen period of investigation a weak event in the boundary layer could be reproduced by the model when nucleation of low-volatile secondary organic vapour is included. Differences in the model results with and without nucleation of organic vapour are visible in the lower free troposphere over several days of the period. Taking into account nucleation of organic vapour leads to an increase in accumulation mode particles due to coagulation of nucleation and aitken mode particles. Moreover, the measurements indicate a considerable increase in SOC aerosol mass concentration during the measurement campaign, which could be reproduced by modelling using a simplified thermodynamic-kinetic approach for SOC aerosol formation and increased biogenic VOC precursor emissions. Comparison with a thermodynamic SOC aerosol formation approach shows a huge improvement in modelled SOC aerosol mass concentration with the thermodynamic-kinetic approach for SOC aerosol formation and a slight improvement of modelled particle size distribution.

  14. Amphiphobic Polytetrafluoroethylene Membranes for Efficient Organic Aerosol Removal.

    PubMed

    Feng, Shasha; Zhong, Zhaoxiang; Zhang, Feng; Wang, Yong; Xing, Weihong

    2016-04-06

    Polytetrafluoroethylene (PTFE) membrane is an extensively used air filter, but its oleophilicity leads to severe fouling of the membrane surface due to organic aerosol deposition. Herein, we report the fabrication of a new amphiphobic 1H,1H,2H,2H-perfluorodecyl acrylate (PFDAE)-grafted ZnO@PTFE membrane with enhanced antifouling functionality and high removal efficiency. We use atomic-layer deposition (ALD) to uniformly coat a layer of nanosized ZnO particles onto porous PTFE matrix to increase surface area and then subsequently graft PFDAE with plasma. Consequently, the membrane surface showed both superhydrophobicity and oleophobicity with a water contact angle (WCA) and an oil contact angle (OCA) of 150° and 125°, respectively. The membrane air permeation rate of 513 (m(3) m(-2) h(-1) kPa(-1)) was lower than the pristine membrane rate of 550 (m(3) m(-2) h(-1) kPa(-1)), which indicates the surface modification slightly decreased the membrane air permeation. Significantly, the filtration resistance of this amphiphobic membrane to the oil aerosol system was much lower than the initial one. Moreover, the filter exhibited exceptional organic aerosol removal efficiencies that were greater than 99.5%. These results make the amphiphobic PTFE membranes very promising for organic aerosol-laden air-filtration applications.

  15. Adsorptive uptake of water by semisolid secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Pajunoja, Aki; Lambe, Andrew T.; Hakala, Jani; Rastak, Narges; Cummings, Molly J.; Brogan, James F.; Hao, Liqing; Paramonov, Mikhail; Hong, Juan; Prisle, Nønne L.; Malila, Jussi; Romakkaniemi, Sami; Lehtinen, Kari E. J.; Laaksonen, Ari; Kulmala, Markku; Massoli, Paola; Onasch, Timothy B.; Donahue, Neil M.; Riipinen, Ilona; Davidovits, Paul; Worsnop, Douglas R.; Petäjä, Tuukka; Virtanen, Annele

    2015-04-01

    Aerosol climate effects are intimately tied to interactions with water. Here we combine hygroscopicity measurements with direct observations about the phase of secondary organic aerosol (SOA) particles to show that water uptake by slightly oxygenated SOA is an adsorption-dominated process under subsaturated conditions, where low solubility inhibits water uptake until the humidity is high enough for dissolution to occur. This reconciles reported discrepancies in previous hygroscopicity closure studies. We demonstrate that the difference in SOA hygroscopic behavior in subsaturated and supersaturated conditions can lead to an effect up to about 30% in the direct aerosol forcing—highlighting the need to implement correct descriptions of these processes in atmospheric models. Obtaining closure across the water saturation point is therefore a critical issue for accurate climate modeling.

  16. Secondary Organic Aerosol Formation over Coastal Ocean: Inferences from Atmospheric Water-Soluble Low Molecular Weight Organic Compounds.

    PubMed

    Bikkina, Srinivas; Kawamura, Kimitaka; Sarin, Manmohan

    2017-04-07

    A lack of consensus on the distributions and formation pathways of secondary organic aerosols (SOA) over oceanic regions downwind of pollution sources limits our ability to assess their climate impact globally. As a case study, we report here on water-soluble SOA components such as dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls in the continental outflows from the Indo-Gangetic Plain (IGP) and Southeast Asia (SEA) to the Bay of Bengal. Oxalic acid (C2) is the dominant species followed by succinic (C4) and glyoxylic acids (ωC2) in the outflow. Nonsea-salt SO4(2-) also dominates (∼70%) total water-soluble inorganic constituents and correlates well with aerosol liquid water content (LWC) and C2, indicating their production through aqueous phase photochemical reactions. Furthermore, mass ratios of dicarboxylic acids (C2/C4, C2/ωC2), and their relative abundances in water-soluble organic carbon and total organic carbon are quite similar between the two continental (IGP and SEA) outflows, indicating the formation of SOA through aqueous phase photochemical reactions in LWC-enriched aerosols, largely controlled by anthropogenic SO4(2-).

  17. Urban organic aerosols measured by single particle mass spectrometry in the megacity of London

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Harrison, R. M.

    2012-05-01

    During the month of October 2006, as part of the REPARTEE-I experiment (Regent's Park and Tower Environmental Experiment) an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed at an urban background location in the city of London, UK. Fifteen particle types were classified, some of which were already discussed (Dall'Osto et al., 2009a,b; Harrison et al., 2012). In this manuscript the origins and properties of four unreported particle types postulated to be due to locally generated aerosols, independent of the air mass type advected into London, are examined. One particle type, originating from lubricating oil (referred to as Ca-EC), was associated with morning rush hour traffic emissions. A second particle type, composed of both inorganic and organic species (called Na-EC-OC), was found enhanced in particle number concentration during evening time periods, and is likely to originate from a source operating at this time of day, or more probably from condensation of semi-volatile species. A third class, internally mixed with organic carbon and sulphate (called OC), was found to spike both in the morning and evenings although it could not unambiguously associated with a specific source or atmospheric process. The fourth class (Secondary Organic Aerosols - Polycyclic Aromatic Hydrocarbon; SOA-PAH) exhibited maximum frequency during the warmest part of the day, and a number of factors point towards secondary aerosol production from traffic-related volatile aromatic compounds. Single particle mass spectra of this particle type showed an oxidized polycyclic aromatic compound signature. A comparison of ATOFMS particle class data is then made with factors obtained by Positive Matrix Factorization and PAH signatures obtained from Aerosol Mass Spectrometer (AMS) data (Allan et al., 2010). Both the Ca-EC and OC particle types correlate with primary Hydrocarbon-like Organic Aerosol (HOA, R2 = 0.65 and 0.50 respectively), and Na-EC-OC correlates weakly with the AMS

  18. Formation mechanisms of water-soluble organic compounds in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Huang, Xiaofeng

    the formation of secondary organic aerosols. (2) Size distributions of water-soluble organic carbon and oxalate in ambient aerosols were measured in Shenzhen in the summer and the winter of 2005. (Abstract shortened by UMI.)

  19. Intercomparison of measurement methods for black carbon aerosols

    NASA Astrophysics Data System (ADS)

    Hitzenberger, R.; Jennings, S. G.; Larson, S. M.; Dillner, A.; Cachier, H.; Galambos, Z.; Rouc, A.; Spain, T. G.

    In this study, two method intercomparisons were performed. One thermal and two optical methods for the measurement of black carbon (BC) were applied to laboratory generated aerosols containing only BC. For the optical measurements, an aethalometer (Hansen et al., 1984. Science of Total Environment 36, 191-196) and an integrating sphere technique (Hitzenberger et al., 1996b. Journal of Geophysical Research 101, D14, 19 601-19 606) were used. The thermal method was described by Cachier et al. (1989a. Tellus 41B, 379-390). In an additional comparison, the integrating sphere was compared to a thermal optical technique (Birch and Cary, 1996. Aerosol Science Technology 25, 221-241) on ambient aerosol samples. The absorption coefficients were obtained from transmission measurements on filter samples for both the aethalometer and the integrating sphere. The BC mass concentration for the aethalometer was derived from this absorption measurement. The BC mass concentration for the integrating sphere, however, was obtained using an independent calibration curve. The agreement between the absorption coefficient σa obtained for the BC test aerosol on parallel filters with the aethalometer and the integrating sphere was satisfactory. The slope of the regression lines depended on filter type. A comparison between BC mass concentrations, however, showed that the aethalometer values were only 23% of those obtained by the integrating sphere technique indicating that for pure BC aerosols, the standard aethalometer calibration should not be used. Compared to the thermal method, the integrating sphere gave an overestimation of the BC mass concentrations by 21%. For the ambient samples, the integrating sphere and the thermal optical methods for BC mass concentration determination showed agreement within 5% of the 1 : 1 line, although the data were not so well correlated.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  1. Production, Organic Characterization, and Phase Transformations of Marine Particles Aerosolized from a Laboratory Mesocosm Phytoplankton Bioreactor

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Previous studies have shown that particles emitted from bubble bursting and wave breaking of ocean waters with high biological activity can contain sea salts associated with organic material, with smaller particles containing a larger mass fraction of organics than larger particles. This likely indicates a link between phytoplankton productivity in oceans and particulate organic material in marine air. Once aerosolized, particles with significant amount of organic material can affect cloud activation and formation of ice crystals, among other atmospheric processes, thus influencing climate. This is significant for clouds and climate particularly over nutrient rich polar seas, in which concentrations of biological organisms can reach up to 109 cells per ml during spring phytoplankton blooms. Here we present results of bubble bursting aerosol production from a seawater mesocosm containing artificial seawater, natural seawater and unialgal cultures of three representative phytoplankton species. These phytoplankton (Thalassiosira pseudonana, Emilianaia huxleyi, and Nannochloris atomus), possessed siliceous frustules, calcareous frustules and no frustules, respectively. Bubbles were generated employing recirculating impinging water jets or glass frits. Dry and humidified aerosol size distributions and bulk aerosol organic composition were measured as a function of phytoplankton growth, and chlorophyll composition and particulate and dissolved organic carbon in the water were determined. Finally, particles were collected on substrates for ice nucleation and water uptake experiments, their elemental compositions were determined using computer controlled scanning electron microscopy and energy dispersive analysis of X-rays (CCSEMEDAX), and their carbon speciation was determined using scanning transmission X-ray microscopy and near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Particle size distributions exposed to dry and humidified air employing

  2. Visibility-reducing organic aerosols in the vicinity of Grand Canyon Nationl Park: 1. Properties observed by high resolution gas chromatography

    SciTech Connect

    Mazurek, M.A.; Mason-Jones, M.; Mason-Jones, H. |

    1995-12-31

    During the summer of 1989, an air monitoring program was established within the Grand Canyon and on the South Rim to define summertime organic aerosol concentration and composition as a function of elevation in the canyon. Supporting information was collected on the composition of the inorganic portion of the atmospheric aerosol to help place the relative importance of organics in perspective. The present paper describes the ambient air monitoring experiment, quantifies the bulk chemical composition of the fine (dp< 2.1=135m) and total aerosol components, distinguishes carbonaceous aerosols according to their organic carbon, elemental carbon and carbonate content, and then examines those characteristics of the organic aerosol that can be defined via capillary gas chromatography using flame ionization detection (GC-FID). At both Indian Gardens (in-canyon, IG) and at Hopi Point (South Rim, HP), the largest contributors to the fine aerosol consist of sulfate and associated ammonium ion plus aerosol carbon species. At IG, sulfate and ammonium ion account for 25.5% and 7.5% of the fine aerosol, respectively, nearly equaled by the 29.9% of the sample composed of organic compounds and 1% contributed by elemental carbon. Somewhat more than half of the fine aerosol at HP can be explained by sulfate ion, ammonium ion, organic compounds and elemental carbon, again with roughly equal mass concentrations due to the ionic versus carbonaceous components. Monthly average mass concentrations for fine aerosol organics were 1.1 = B5gm -3(IG) and 1.3 =135gm-3 (HP), while the total organics monthly average mass concentrations were 1.9 =135gm-3 (IG) and 2.1 =135gm-3 (HP). The fraction of aerosol organics that could be evaluated by GC-FID (elutable organics) constituted 27% to 53% of the total organics mass collected as fine or total aerosol. For the fine particle monthly composites, the elutable organics were present in mass concentrations of 0.28 =B5gm-3 (IG) and 0.46 =135gm-3 (HP).

  3. Quantifying organic aerosol single scattering albedo over the tropical biomass burning regions

    NASA Astrophysics Data System (ADS)

    Chu, Jung-Eun; Ha, Kyung-Ja

    2016-12-01

    Despite growing evidence of light-absorbing organic aerosols (OAs), their contribution to the Earth's radiative budget is still poorly understood. In this study we derived a new empirical relationship that binds OA single scattering albedo (SSA), which is the ratio of light scattering to extinction, with sulfate + nitrate aerosol optical depth (AOD) and applied this method to estimate OA SSA over the tropical biomass burning regions. This method includes division of the attribution of black carbon (BC) and OA absorption aerosol optical depths from the Aerosol Robotic Network (AERONET) observation and determination of the fine-mode ratio of sea-salt and dust AODs from several atmospheric chemistry models. Our best estimate of OA SSA over the tropical biomass burning regions is 0.91 at 550 nm. Uncertainties associated with observations and models permit a value range of 0.82-0.93. Furthermore, by using the estimated OA SSA and comprehensive observations including AERONET, Moderate Resolution Imaging Spectroradiometer (MODIS) and Multi-angle Imaging Spectroradiometer (MISR), we examined the first global estimate of sulfate + nitrate AOD through a semi-observational approach. The global mean sulfate + nitrate AOD of 0.017 is in the lower range of the values obtained from 21 models participated in AeroCom phase II. The results imply that most aerosol models as well as climate models, which commonly use OA SSA of 0.96-1.0, have so far ignored light absorption by OAs and have overestimated light scattering by sulfate + nitrate aerosols. This indicates that the actual aerosol direct radiative forcing should be less negative than currently believed.

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

    NASA Astrophysics Data System (ADS)

    Yu, F.; Luo, G.

    2014-12-01

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

  5. Single particle characterization of biomass burning organic aerosol (BBOA): evidence for non-uniform mixing of high molecular weight organics and potassium

    NASA Astrophysics Data System (ADS)

    Lee, A. K. Y.; Willis, M. D.; Healy, R. M.; Wang, J. M.; Jeong, C.-H.; Wenger, J. C.; Evans, G. J.; Abbatt, J. P. D.

    2015-11-01

    Biomass burning is a major source of black carbon (BC) and primary organic aerosol globally. In particular, biomass burning organic aerosol (BBOA) is strongly associated with atmospheric brown carbon (BrC) that absorbs near ultraviolet and visible light, resulting in significant impacts on regional visibility degradation and radiative forcing. The mixing state of BBOA can play a critical role in the prediction of aerosol optical properties. In this work, single particle measurements from a soot-particle aerosol mass spectrometer coupled with a light scattering module (LS-SP-AMS) were performed to examine the mixing state of BBOA, refractory black carbon (rBC) and potassium (K+, a tracer for biomass burning aerosol) in an air mass influenced by aged biomass burning. Cluster analysis of single particle measurements identified five BBOA-related particle types. rBC accounted for 3-14 w.t. % of these particle types on average. Only one particle type exhibited a strong ion signal for K+, with mass spectra characterized by low molecular weight organic species. The remaining four particle types were classified based on the apparent molecular weight of the BBOA constituents. Two particle types were associated with low potassium content and significant amounts of high molecular weight (HMW) organic compounds. Our observations indicate non-uniform mixing of particles within a biomass burning plume in terms of molecular weight and illustrate that HMW BBOA can be a key contributor to low-volatility BrC observed in BBOA particles.

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

    PubMed

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

    2009-05-15

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

  7. The Composition of Organic Aerosols in Southeast Asia During The 2006 Haze Episode

    NASA Astrophysics Data System (ADS)

    Jun, H.; Zielinska, B.; Balasubramanian, R.

    2007-12-01

    The regional smoke haze in Southeast Asia is a recurring air pollution problem. Uncontrolled forest fires from land-clearing activities in Sumatra and Borneo, and to a lesser extent Malaysia, have occurred almost every dry season since the late 1990s. The smoke haze that took place in October 2006 shrouded an estimated 215,000 square miles of land on Indonesia's islands of Sumatra and Borneo, and persisted for several weeks. Satellite pictures showed numerous hotspots in both Sumatra and Kalimantan. The prevailing, South-Southwesterly, winds blew smoke from land and forest fires in central and south Sumatra to Singapore, affecting the regional air quality significantly and reducing atmospheric visibility. During this haze episode, we carried out an intensive field study in Singapore to characterize the composition of organic aerosols, which usually account for a large fraction of airborne particulate matter (PM). A total of 17 PM samples were collected while the hazy atmospheric conditions persisted in Singapore, and subjected to accelerated solvent extraction with dichloromethane and acetone. The extracted compounds were grouped into three major fractions (n-alkanes, polycyclic aromatic hydrocarbons, and polar organic compounds). More than 180 particulate-bound organic compounds were determined using gas chromatography/mass spectrometry (GC-MS). In order to investigate the origin of organic species, the carbon preference indexes as well as diagnostic ratios were used. The compositional differences of organic aerosols between the haze- and non- haze periods will be presented. The atmospheric implications of the composition of organic aerosols of biomass burning origin will be discussed. Keywords: smoke haze, organic aerosols, n-alkanes, polycyclic aromatic hydrocarbons, polar organic compounds

  8. Modeling organic aerosols in a megacity: comparison of simple and complex representations of the volatility basis set approach

    NASA Astrophysics Data System (ADS)

    Shrivastava, M.; Fast, J.; Easter, R.; Gustafson, W. I., Jr.; Zaveri, R. A.; Jimenez, J. L.; Saide, P.; Hodzic, A.

    2011-07-01

    The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) is modified to include a volatility basis set (VBS) treatment of secondary organic aerosol formation. The VBS approach, coupled with SAPRC-99 gas-phase chemistry mechanism, is used to model gas-particle partitioning and multiple generations of gas-phase oxidation of organic vapors. In addition to the detailed 9-species VBS, a simplified mechanism using 2 volatility species (2-species VBS) is developed and tested for similarity to the 9-species VBS in terms of both mass and oxygen-to-carbon ratios of organic aerosols in the atmosphere. WRF-Chem results are evaluated against field measurements of organic aerosols collected during the MILAGRO 2006 campaign in the vicinity of Mexico City. The simplified 2-species mechanism reduces the computational cost by a factor of 2 as compared to 9-species VBS. Both ground site and aircraft measurements suggest that the 9-species and 2-species VBS predictions of total organic aerosol mass as well as individual organic aerosol components including primary, secondary, and biomass burning are comparable in magnitude. In addition, oxygen-to-carbon ratio predictions from both approaches agree within 25 %, providing evidence that the 2-species VBS is well suited to represent the complex evolution of organic aerosols. Model sensitivity to amount of anthropogenic semi-volatile and intermediate volatility (S/IVOC) precursor emissions is also examined by doubling the default emissions. Both the emission cases significantly under-predict primary organic aerosols in the city center and along aircraft flight transects. Secondary organic aerosols are predicted reasonably well along flight tracks surrounding the city, but are consistently over-predicted downwind of the city. Also, oxygen-to-carbon ratio predictions are significantly improved compared to prior studies by adding 15 % oxygen mass per generation of oxidation; however, all modeling cases still under

  9. Modeling organic aerosols in a megacity: comparison of simple and complex representations of the volatility basis set approach

    NASA Astrophysics Data System (ADS)

    Shrivastava, M.; Fast, J.; Easter, R.; Gustafson, W. I., Jr.; Zaveri, R. A.; Jimenez, J. L.; Saide, P.; Hodzic, A.

    2010-12-01

    The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) is modified to include a volatility basis set (VBS) treatment of secondary organic aerosol formation. The VBS approach, coupled with SAPRC-99 gas-phase chemistry mechanism, is used to model gas-particle partitioning and multiple generations of gas-phase oxidation of organic vapors. In addition to the detailed 9-species VBS, a simplified mechanism using 2 volatility species (2-species VBS) is developed and tested for similarity to the 9-species VBS in terms of both mass and oxygen-to-carbon ratios of organic aerosols in the atmosphere. WRF-Chem results are evaluated against field measurements of organic aerosols collected during the MILAGRO 2006 campaign in the vicinity of Mexico City. The simplified 2-species mechanism reduces the computational cost by a factor of 2 as compared to 9-species VBS. Both ground site and aircraft measurements suggest that the 9-species and 2-species VBS predictions of total organic aerosol mass as well as individual organic aerosol components including primary, secondary, and biomass burning are comparable in magnitude. In addition, oxygen-to-carbon ratio predictions from both approaches agree within 25%, providing evidence that the 2-species VBS is well suited to represent the complex evolution of organic aerosols. Model sensitivity to amount of anthropogenic semi-volatile and intermediate volatility (S/IVOC) precursor emissions is also examined by doubling the default emissions. Both the emission cases significantly under-predict primary organic aerosols in the city center and along aircraft flight transects. Secondary organic aerosols are predicted reasonably well along flight tracks surrounding the city, but are consistently over-predicted downwind of the city. Also, oxygen-to-carbon ratio predictions are significantly improved compared to prior studies by adding 15% oxygen mass per generation of oxidation; however, all modeling cases still under

  10. Deliquescence behavior of organic/ammonium sulfate aerosol

    NASA Astrophysics Data System (ADS)

    Brooks, Sarah D.; Wise, Matthew E.; Cushing, Melinda; Tolbert, Margaret A.

    2002-10-01

    Recent studies have shown that tropospheric aerosols composed of internal mixtures of organics with sulfates are quite common with the organic composing up to 50% of the particle mass. The influences of the organics on the chemical and physical properties of the aerosol are not known. In this paper, we report the solubility of a series of dicarboxylic acids in saturated ammonium sulfate solution as a function of temperature. We also report the deliquescence relative humidity (DRH) of the pure dicarboxylic acids and of mixtures of dicarboxylic acids with ammonium sulfate. For the systems studied, we find that the presence of water-soluble dicarboxylic acids caused deliquescence to occur at a lower relative humidity (RH) than pure ammonium sulfate. In contrast, the less soluble dicarboxylic acids had no measurable effect on the deliquescence relative humidity of ammonium sulfate.

  11. Functional Group Composition of Semivolatile Compounds Present in Submicron Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Ruggeri, G.; Modini, R. L.; Iannarelli, R.; Rossi, M. J.; Takahama, S.

    2014-12-01

    Semivolatile organic compounds can partition between gas and particle phase in atmospheric conditions and can be volatilized and lost when the aerosol sampling is performed onto PTFE filters (Eatough et al., 1993). In this work, semivolatile compounds are collected onto carbon impregnated glass fiber-cellulose filters placed in series after an activated carbon denuder and PTFE filter which collects submicron aerosol particles of low volatility (Subramanian et al., 2004). The semivolatile compounds accumulated on the cellulose-glass fiber filters are desorbed by vacuum and injected into a stainless steel chamber that enables cold-trapping. The vapors in this chamber are condensed onto a low-temperature silicon window, and the composition of deposited vapors are analysed by transmission-mode Fourier Transform Infrared (FTIR) spectroscopy (Delval and Rossi, 2004). Functional group composition of semivolatile compounds that can be desorbed from the aerosol phase and its relationship with the apparent low-volatile fraction composition will be presented. Eatough, D.J., Wadsworth, A., Eatough, D.A., Crawford, J.W., Hansen, L.D., Lewis, E.A., 1993. A multiple-system, multi-channel diffusion denuder sampler for the determination of fine-particulate organic material in the atmosphere. Atmospheric Environment. Part A. General Topics 27, 1213-1219. Subramanian, R., Khlystov, A.Y., Cabada, J.C., Robinson, A.L., 2004. Positive and negative artifacts in particulate organic carbon measurements with denuded and undenuded sampler configurations. Aerosol Science and Technology 38, 27-48. Delval, C., Rossi, M.J., 2004. The kinetics of condensation and evaporation of H2O from pure ice in the range 173-223 K: a quartz crystal microbalance study. Physical Chemistry Chemical Physics 6, 4665-4676.

  12. Ambient Observations of Organic Nitrogen Compounds in Submicrometer Aerosols in New York Using High Resolution Aerosol Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Ge, X.; Xu, J.; Sun, Y.; Zhang, Q.

    2015-12-01

    Organic nitrogen (ON) compounds, which include amines, nitriles, organic nitrates, amides, and N-containing aromatic heterocycles, are an important class of compounds ubiquitously detected in atmospheric particles and fog and cloud droplets. Previous studies indicate that these compounds can make up a significant fraction (20-80%) of the total nitrogen (N) content in atmospheric condensed phases and play important roles in new particle formation and growth and affecting the optical and hygroscopicity of aerosols. In this study, we report the observation of ON compounds in submicrometer particles (PM1) at two locations in New York based on measurements using Aerodyne high-resolution time-of-flight mass spectrometer (HR-ToF-AMS). One study was conducted as part of the US Department of Energy funded Aerosol Lifecyle - Intensive Operation Period (ALC-IOP) campaign at Brookhaven National Lab (BNL, 40.871˚N, 72.89˚W) in summer, 2011 and the other was conducted at the Queen's College (QC) in New York City (NYC) in summer, 2009. We observed a notable amount of N-containing organic fragment ions, CxHyNp+ and CxHyOzNp+, in the AMS spectra of organic aerosols at both locations and found that they were mainly associated with amino functional groups. Compared with results from lab experiments, the C3H8N+ at m/z = 58 was primarily attributed to trimethylamine. In addition, a significant amount of organonitrates was observed at BNL. Positive matrix factorization (PMF) analysis of the high resolution mass spectra (HRMS) of organic aerosols identified a unique nitrogen-enriched OA (NOA) factor with elevated nitrogen-to-carbon (N/C) at both BNL and QC. Analysis of the size distributions, volatility profiles, and correlations with external tracer indicates that acid-base reactions of amino compounds with sulfate and acidic gas were mainly responsible for the formation of amine salts. Photochemical production was also observed to play a role in the formation of NOA. Bivariate polar

  13. Contribution of methyl group to secondary organic aerosol formation from aromatic hydrocarbon photooxidation

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Qi, Li; Cocker, David R.

    2017-02-01

    The complete atmospheric oxidation pathways leading to secondary organic aerosol remain elusive for aromatic compounds including the role of methyl substitutes on oxidation. This study investigates the contribution of methyl group to Secondary Organic Aerosol (SOA) formation during the photooxidation of aromatic hydrocarbons under low NOx condition by applying methyl carbon labeled aromatic hydrocarbons ((13C2) m-xylene and (13C2) p-xylene). Particle and gas phase oxidation products are analyzed by a series of mass spectrometers (HR-TOF-AMS, PTR-MS and SIFT-MS). The methyl group carbon containing oxidation products partition to the particle-phase at a lower rate than the carbons originating from the aromatic ring as a result of ring opening reactions. Further, the methyl carbon in the original aromatic structure is at least 7 times less likely to be oxidized when forming products that partition to SOA than the aromatic ring carbon. Therefore, oxidation of the methyl group in xylenes exerts little impact on SOA formation in current study. This study provides supporting evidence for a recent finding - a similarity in the SOA formation and composition from aromatic hydrocarbons regardless of the alkyl substitutes.

  14. Water-Soluble Organic Species in Biomass Burning Aerosols in Southern Africa: Their Chemical Identification and Spatial Distribution

    NASA Astrophysics Data System (ADS)

    Gao, S.; Hegg, D. A.; Hobbs, P. V.; Kirchstetter, T. W.; Magi, B.

    2001-12-01

    During the SAFARI-2000 field campaign, 14 aerosol samples were collected from an aircraft in plumes from biomass fires (under both flaming and smoldering conditions), at various distances from the fire source. Also collected were 36 aerosol samples in haze layers ranging from the surface to 16,000 feet, some of which could be associated with specific fires. The samples were collected on teflon membrane filters (lower size limit of about 30nm in diameter) which were analyzed for total aerosol mass loading and chemical composition using several analytical techniques. Particular effort was made to speciate the water-soluble portion of the aerosol organics. Seven organic acids and seven carbohydrate species (and their possible stereoisomers) were identified and quantified, along with three inorganic anions and five inorganic cations. The identified organic species accounted for up to 32% of the total aerosol mass; compared with concurrent total carbon and organic carbon measurements, the identified organics constituted at least 5% to 30% of the mass of the total aerosol organics. A number of conspicuous spatial distribution patterns were observed for these species. For instance, using K+ to correct for dilution, it was found that gluconate, oxalate, succinate, and glutarate, along with sulfate and nitrate, all increased significantly in mass concentration from the fire source going downwind. This suggests secondary formation of these species during aerosol aging. On the other hand, formate and acetate showed decreasing trends downwind, probably due to the loss of these volatile species to the gas phase. Another striking pattern is that anhydrosugars (e.g. levoglucosan) had the highest aerosol mass fraction near smoldering fires but a very low fraction in the haze layers, whereas, dicarboxylic acids showed an almost opposite trend. This implies possible chemical reaction processes converting intermediate organic products, such as levoglucosan, to smaller products like

  15. MATRIX-VBS (v1.0): implementing an evolving organic aerosol volatility in an aerosol microphysics model

    NASA Astrophysics Data System (ADS)

    Gao, Chloe Y.; Tsigaridis, Kostas; Bauer, Susanne E.

    2017-02-01

    The gas-particle partitioning and chemical aging of semi-volatile organic aerosol are presented in a newly developed box model scheme, where its effect on the growth, composition, and mixing state of particles is examined. The volatility-basis set (VBS) framework is implemented into the aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves mass and number aerosol concentrations and in multiple mixing-state classes. The new scheme, MATRIX-VBS, has the potential to significantly advance the representation of organic aerosols in Earth system models by improving upon the conventional representation as non-volatile particulate organic matter, often also with an assumed fixed size distribution. We present results from idealized cases representing Beijing, Mexico City, a Finnish forest, and a southeastern US forest, and investigate the evolution of mass concentrations and volatility distributions for organic species across the gas and particle phases, as well as assessing their mixing state among aerosol populations. Emitted semi-volatile primary organic aerosols evaporate almost completely in the intermediate-volatility range, while they remain in the particle phase in the low-volatility range. Their volatility distribution at any point in time depends on the applied emission factors, oxidation by OH radicals, and temperature. We also compare against parallel simulations with the original scheme, which represented only the particulate and non-volatile component of the organic aerosol, examining how differently the condensed-phase organic matter is distributed across the mixing states in the model. The results demonstrate the importance of representing organic aerosol as a semi-volatile aerosol, and explicitly calculating the partitioning of organic species between the gas and particulate phases.

  16. MATRIX-VBS (v1.0): Implementing an Evolving Organic Aerosol Volatility in an Aerosol Microphysics Model

    NASA Technical Reports Server (NTRS)

    Gao, Chloe Y.; Tsigaridis, Kostas; Bauer, Susanne E.

    2017-01-01

    The gas-particle partitioning and chemical aging of semi-volatile organic aerosol are presented in a newly developed box model scheme, where its effect on the growth, composition, and mixing state of particles is examined. The volatility-basis set (VBS) framework is implemented into the aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves mass and number aerosol concentrations and in multiple mixing-state classes. The new scheme, MATRIX-VBS, has the potential to significantly advance the representation of organic aerosols in Earth system models by improving upon the conventional representation as non-volatile particulate organic matter, often also with an assumed fixed size distribution. We present results from idealized cases representing Beijing, Mexico City, a Finnish forest, and a southeastern US forest, and investigate the evolution of mass concentrations and volatility distributions for organic species across the gas and particle phases, as well as assessing their mixing state among aerosol populations. Emitted semi-volatile primary organic aerosols evaporate almost completely in the intermediate-volatility range, while they remain in the particle phase in the low-volatility range. Their volatility distribution at any point in time depends on the applied emission factors, oxidation by OH radicals, and temperature. We also compare against parallel simulations with the original scheme, which represented only the particulate and non-volatile component of the organic aerosol, examining how differently the condensed-phase organic matter is distributed across the mixing states in the model. The results demonstrate the importance of representing organic aerosol as a semi-volatile aerosol, and explicitly calculating the partitioning of organic species between the gas and particulate phases.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  18. Organic Aerosol Formation and Processing in the Los Angeles Basin: Role of Gasoline vs. Diesel Emissions

    NASA Astrophysics Data System (ADS)

    Bahreini, R.; Middlebrook, A. M.; De Gouw, J. A.; Warneke, C.; Trainer, M.; Brown, S. S.; Dube, B.; Holloway, J. S.; Perring, A. E.; Schwarz, J. P.; Spackman, J. R.; Stark, H.; Wagner, N.; Parrish, D. D.

    2011-12-01

    During the CalNex-2010 field project in May-June 2010, the NOAA WP-3D aircraft performed flights up- and down-wind of metropolitan, industrial, agricultural and animal feeding sites in central-southern California. Here airborne data on organic aerosol (OA) properties as measured by a compact time-of-flight aerosol mass spectrometer along with measurements of trace gases affecting secondary production of aerosols in the Los Angeles Basin are presented. The analysis presented indicates that the ratio of organic aerosol to carbon monoxide (OA/CO) is significantly higher than the previously observed ratios of primary OA/CO downwind of urban areas, indicating that even on short time scales of transport within the basin, there is significant production of secondary organic aerosol (SOA). The increase in the ratio of OA/CO is also accompanied by an increase in the fraction of oxygenated species of OA, providing evidence for production of more oxidized SOA as air masses are photochemically processed. Despite a smaller contribution from Diesel vehicles to traffic on weekends, analysis of the weekend vs. weekday data indicates that similar values of ΔOA/ΔCO are observed on the weekends compared to weekdays, for air masses with similar degrees of photochemical processing. This indicates that emissions of gas phase organic species from Diesel vehicles are not significant for OA production in the LA Basin. Our calculated steady-state concentrations of hydroxyl radical (OH) indicate that OH concentrations at mid-day are substantially higher on weekends compared to weekdays, indicating faster chemical processing of air masses during a fixed length of time on the weekends compared to weekdays.

  19. In situ measurements of water uptake by black carbon-containing aerosol in wildfire plumes

    NASA Astrophysics Data System (ADS)

    Perring, Anne E.; Schwarz, Joshua P.; Markovic, Milos Z.; Fahey, David W.; Jimenez, Jose L.; Campuzano-Jost, Pedro; Palm, Brett D.; Wisthaler, Armin; Mikoviny, Tomas; Diskin, Glenn; Sachse, Glen; Ziemba, Luke; Anderson, Bruce; Shingler, Taylor; Crosbie, Ewan; Sorooshian, Armin; Yokelson, Robert; Gao, Ru-Shan

    2017-01-01

    Water uptake by black carbon (BC)-containing aerosol was quantified in North American wildfire plumes of varying age (1 to 40 h old) sampled during the SEAC4RS mission (2013). A Humidified Dual SP2 (HD-SP2) is used to optically size BC-containing particles under dry and humid conditions from which we extract the hygroscopicity parameter, κ, of materials internally mixed with BC. Instrumental variability and the uncertainty of the technique are briefly discussed. An ensemble average κ of 0.04 is found for the set of plumes sampled, consistent with previous estimates of bulk aerosol hygroscopicity from biomass burning sources. The temporal evolution of κ in the Yosemite Rim Fire plume is explored to constrain the rate of conversion of BC-containing aerosol from hydrophobic to more hydrophilic modes in these emissions. A BC-specific κ increase of 0.06 over 40 h is found, fit well with an exponential curve corresponding to a transition from a κ of 0 to a κ of 0.09 with an e-folding time of 29 h. Although only a few percent of wildfire particles contain BC, a similar κ increase is estimated for bulk aerosol and the measured aerosol composition is used to infer that the observed κ change is driven by a combination of incorporation of ammonium sulfate and oxidation of existing organic materials. Finally, a substantial fraction of wildfire-generated BC-containing aerosol is calculated to be active as cloud condensation nuclei shortly after emission likely indicating efficient wet removal. These results can constrain model treatment of BC from wildfire sources.

  20. Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

    NASA Astrophysics Data System (ADS)

    Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

    2016-11-01

    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, and health. 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 additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus

  1. Water soluble organic aerosols in the Colorado Rocky Mountains, USA: composition, sources and optical properties

    PubMed Central

    Xie, Mingjie; Mladenov, Natalie; Williams, Mark W.; Neff, Jason C.; Wasswa, Joseph; Hannigan, Michael P.

    2016-01-01

    Atmospheric aerosols have been shown to be an important input of organic carbon and nutrients to alpine watersheds and influence biogeochemical processes in these remote settings. For many remote, high elevation watersheds, direct evidence of the sources of water soluble organic aerosols and their chemical and optical characteristics is lacking. Here, we show that the concentration of water soluble organic carbon (WSOC) in the total suspended particulate (TSP) load at a high elevation site in the Colorado Rocky Mountains was strongly correlated with UV absorbance at 254 nm (Abs254, r = 0.88 p < 0.01) and organic carbon (OC, r = 0.95 p < 0.01), accounting for >90% of OC on average. According to source apportionment analysis, biomass burning had the highest contribution (50.3%) to average WSOC concentration; SOA formation and motor vehicle emissions dominated the contribution to WSOC in the summer. The source apportionment and backward trajectory analysis results supported the notion that both wildfire and Colorado Front Range pollution sources contribute to the summertime OC peaks observed in wet deposition at high elevation sites in the Colorado Rocky Mountains. These findings have important implications for water quality in remote, high-elevation, mountain catchments considered to be our pristine reference sites. PMID:27991554

  2. Water soluble organic aerosols in the Colorado Rocky Mountains, USA: composition, sources and optical properties

    NASA Astrophysics Data System (ADS)

    Xie, Mingjie; Mladenov, Natalie; Williams, Mark W.; Neff, Jason C.; Wasswa, Joseph; Hannigan, Michael P.

    2016-12-01

    Atmospheric aerosols have been shown to be an important input of organic carbon and nutrients to alpine watersheds and influence biogeochemical processes in these remote settings. For many remote, high elevation watersheds, direct evidence of the sources of water soluble organic aerosols and their chemical and optical characteristics is lacking. Here, we show that the concentration of water soluble organic carbon (WSOC) in the total suspended particulate (TSP) load at a high elevation site in the Colorado Rocky Mountains was strongly correlated with UV absorbance at 254 nm (Abs254, r = 0.88 p < 0.01) and organic carbon (OC, r = 0.95 p < 0.01), accounting for >90% of OC on average. According to source apportionment analysis, biomass burning had the highest contribution (50.3%) to average WSOC concentration; SOA formation and motor vehicle emissions dominated the contribution to WSOC in the summer. The source apportionment and backward trajectory analysis results supported the notion that both wildfire and Colorado Front Range pollution sources contribute to the summertime OC peaks observed in wet deposition at high elevation sites in the Colorado Rocky Mountains. These findings have important implications for water quality in remote, high-elevation, mountain catchments considered to be our pristine reference sites.

  3. Large historical changes of fossil-fuel black carbon aerosols

    SciTech Connect

    Novakov, T.; Ramanathan, V.; Hansen, J.E.; Kirchstetter, T.W.; Sato, M.; Sinton, J.E.; Sathaye, J.A.

    2002-09-26

    Anthropogenic emissions of fine black carbon (BC) particles, the principal light-absorbing atmospheric aerosol, have varied during the past century in response to changes of fossil-fuel utilization, technology developments, and emission controls. We estimate historical trends of fossil-fuel BC emissions in six regions that represent about two-thirds of present day emissions and extrapolate these to global emissions from 1875 onward. Qualitative features in these trends show rapid increase in the latter part of the 1800s, the leveling off in the first half of the 1900s, and the re-acceleration in the past 50 years as China and India developed. We find that historical changes of fuel utilization have caused large temporal change in aerosol absorption, and thus substantial change of aerosol single scatter albedo in some regions, which suggests that BC may have contributed to global temperature changes in the past century. This implies that the BC history needs to be represented realistically in climate change assessments.

  4. Organic composition and source apportionment of fine aerosol at Monterrey, Mexico, based on organic markers

    NASA Astrophysics Data System (ADS)

    Mancilla, Y.; Mendoza, A.; Fraser, M. P.; Herckes, P.

    2016-01-01

    Primary emissions from anthropogenic and biogenic sources as well as secondary formation are responsible for the pollution levels of ambient air in major urban areas. These sources release fine particles into the air that negatively impact human health and the environment. Organic molecular markers, which are compounds that are unique to specific PM2.5 sources, can be utilized to identify the major emission sources in urban areas. In this study, 43 representative PM2.5 samples, for both daytime and nighttime periods, were built from individual samples collected in an urban site of the Monterrey metropolitan area (MMA) during the spring and fall of 2011 and 2012. The samples were analyzed for organic carbon, elemental carbon, and organic molecular markers. Several diagnostic tools were employed for the preliminary identification of emission sources. Organic compounds for eight compound classes were quantified. The n-alkanoic acids were the most abundant, followed by n-alkanes, wood smoke markers, and levoglucosan/alkenoic acids. Polycyclic aromatic hydrocarbons (PAHs) and hopanes were less abundant. The carbon preference index (0.7-2.6) for n-alkanes indicates a major contribution of anthropogenic and mixed sources during the fall and the spring, respectively. Hopanes levels confirmed the contribution from gasoline and diesel engines. In addition, the contribution of gasoline and diesel vehicle exhaust was confirmed and identified by the PAH concentrations in PM2.5. Diagnostic ratios of PAHs showed emissions from burning coal, wood, biomass, and other fossil fuels. The total PAHs and elemental carbon were correlated (r2 = 0.39-0.70) across the monitoring periods, reinforcing that motor vehicles are the major contributors of PAHs. Cholesterol levels remained constant during the spring and fall, showing evidence of the contribution of meat-cooking operations, while the isolated concentrations of levoglucosan suggested occasional biomass burning events. Finally, source

  5. 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 ...

  6. 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).

  7. 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.; ...

    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

  8. 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

  9. Carbon Isotopic Measurements and Aerosol Optical Determinations during CARES: Indications of the Importance of Background Biogenic Aerosols

    NASA Astrophysics Data System (ADS)

    Gaffney, J. S.; Marley, N. A.; Begum, M.; Sturchio, N. C.; Guilderson, T. P.

    2011-12-01

    High volume size-fractionated aerosol samples were obtained in Cool, CA during the Carbonaceous Aerosol and Radiative Effects Study (CARES) in June of 2010. This site was chosen to study the regional impacts of carbonaceous aerosols originating from the Sacramento area. Samples were collected for 6 to 24 hour time periods on quartz fiber filters by using slotted impactors to allow for collection of sample size cuts above and below one micron. Both total carbon content and carbon isotopic composition, including 13C/12C and 14C, were determined on the samples. In addition, Ångstrom absorption exponents (AAEs) were determined for the region of 300-900 nm on the sub-micron size cut by using state of the art diffuse reflectance UV-visible spectroscopy with integrating sphere technology. The overall carbonaceous aerosol loadings were found to be quite low and relatively constant during the study, suggesting that most of the aerosols at the site were locally formed background aerosols. The 14C data is consistent with a substantial fraction (~80 %) being from modern carbon sources and 13C/12C results indicate that the carbon source was from C-3 plants. This is consistent with a significant fraction of the aerosols in the area arising from secondary formation from biogenic precursor emissions from trees, most likely mono- and sesquiterpenes. These results are compared to past results obtained in Mexico City and discussed in terms of the potential importance of biogenic emissions to UV absorbing aerosols as these are anticipated to increase with climate change. This work was supported by the Office of Science (BER), U.S. Department of Energy, Grant No. DE-FG02-07ER64328 and Grant No. DE-FG02-07-ER64329 as part of the Atmospheric Systems Research program.

  10. Recalcitrant dissolved organic carbon fractions.

    PubMed

    Hansell, Dennis A

    2013-01-01

    Marine dissolved organic carbon (DOC) exhibits a spectrum of reactivity, from very fast turnover of the most bioavailable forms in the surface ocean to long-lived materials circulating within the ocean abyss. These disparate reactivities group DOC by fractions with distinctive functions in the cycling of carbon, ranging from support of the microbial loop to involvement in the biological pump to a hypothesized major source/sink of atmospheric CO(2) driving paleoclimate variability. Here, the major fractions constituting the global ocean's recalcitrant DOC pool are quantitatively and qualitatively characterized with reference to their roles in carbon biogeochemistry. A nomenclature for the fractions is proposed based on those roles.

  11. Uptake of Ambient Organic Gases to Acidic Sulfate Aerosols

    NASA Astrophysics Data System (ADS)

    Liggio, J.; Li, S.

    2009-05-01

    The formation of secondary organic aerosols (SOA) in the atmosphere has been an area of significant interest due to its climatic relevance, its effects on air quality and human health. Due largely to the underestimation of SOA by regional and global models, there has been an increasing number of studies focusing on alternate pathways leading to SOA. In this regard, recent work has shown that heterogeneous and liquid phase reactions, often leading to oligomeric material, may be a route to SOA via products of biogenic and anthropogenic origin. Although oligomer formation in chamber studies has been frequently observed, the applicability of these experiments to ambient conditions, and thus the overall importance of oligomerization reactions remain unclear. In the present study, ambient air is drawn into a Teflon smog chamber and exposed to acidic sulfate aerosols which have been formed in situ via the reaction of SO3 with water vapor. The aerosol composition is measured with a High Resolution Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS), and particle size distributions are monitored with a scanning mobility particle sizer (SMPS). The use of ambient air and relatively low inorganic particle loading potentially provides clearer insight into the importance of heterogeneous reactions. Results of experiments, with a range of sulfate loadings show that there are several competing processes occurring on different timescales. A significant uptake of ambient organic gases to the particles is observed immediately followed by a slow shift towards higher m/z over a period of several hours indicating that higher molecular weight products (possibly oligomers) are being formed through a reactive process. The results suggest that heterogeneous reactions can occur with ambient organic gases, even in the presence of ammonia, which may have significant implications to the ambient atmosphere where particles may be neutralized after their formation.

  12. Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

    PubMed Central

    Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A.

    2016-01-01

    Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas–particle equilibrium and (ii) have a short particle-phase lifetime (∼2–4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. PMID:26811465

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  14. 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

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

    NASA Astrophysics Data System (ADS)

    Zhang, Hongliang; Ying, Qi

    2011-06-01

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

  16. Light Absorption Properties of Brown Carbon from Fresh and Aged Biomass Burning Aerosols Characterized in a Smog Chamber

    NASA Astrophysics Data System (ADS)

    Saleh, R.; Chuang, W.; Hennigan, C.; McMeeking, G. R.; Coe, H.; Donahue, N. M.; Robinson, A. L.

    2011-12-01

    Black carbon is an important particulate phase light absorber in the atmosphere. Recent studies have shown that some organic matter also absorb visible light, especially at short wavelengths. These organic compounds are referred to as "brown carbon". Biomass burning is a major contributor to brown carbon in atmospheric particulate matter; however, its optical properties are poorly characterized. We have conducted smog chamber experiments to investigate light absorption properties of brown carbon in primary and aged biomass burning emissions, namely the imaginary refractive index. The aging was performed in a smog chamber, where dilute emissions were exposed to UV lights to initiate photo-oxidation, which often produced substantial secondary organic aerosol. The experiments took place at Carnegie Mellon University (CMU) and at the US Fire Science Laboratory in Missoula, MT as part of the Fire Lab at Missoula field campaign (FLAME 2009). The CMU experiments simulated household wood burning (oak), and the FLAME experiments simulated wildland fires with fuels including gallberry, lodgepole pine, black spruce and ponderosa pine. Absorption coefficients were measured using an Aethalometer (Magee Scientific) at 7 different wavelengths ranging between 370 nm and 950 nm. The black carbon size distributions were measured using a Single Particle Soot Photometer (SP2, DMT), and total aerosol size distributions were measured using a Scanning Mobility Particle Sizer (SMPS, TSI). The absorption coefficients of both the fresh and aged aerosol were significantly larger, and had stronger wavelength dependence than what would be expected for black carbon alone, and for a black carbon core with a non-absorbing shell. This indicates that biomass burning organic aerosol should be classified as brown carbon. A (black carbon) core - (brown carbon) shell absorption model based on Mie theory was optimized to determine the shell imaginary refractive index which produces model outputs that

  17. Observations and analysis of organic aerosol evolution in some prescribed fire smoke plumes

    NASA Astrophysics Data System (ADS)

    May, A. A.; Lee, T.; McMeeking, G. R.; Akagi, S.; Sullivan, A. P.; Urbanski, S.; Yokelson, R. J.; Kreidenweis, S. M.

    2015-06-01

    Open biomass burning is a significant source of primary air pollutants such as particulate matter (PM) and non-methane organic gases (NMOG). However, the physical and chemical atmospheric processing of these emissions during transport is poorly understood. Atmospheric transformations of biomass burning emissions have been investigated in environmental chambers, but there have been limited opportunities to investigate these transformations in the atmosphere. In this study, we deployed a suite of real-time instrumentation on a Twin Otter aircraft to sample smoke from prescribed fires in South Carolina, conducting measurements at both the source and downwind to characterize smoke evolution with atmospheric aging. Organic aerosol (OA) within the smoke plumes was quantified using an aerosol mass spectrometer (AMS); refractory black carbon (rBC) was quantified using a single-particle soot photometer, and carbon monoxide (CO) and carbon dioxide (CO2) were measured using a cavity ring-down spectrometer. During the two fires for which we were able to obtain aerosol aging data, normalized excess mixing ratios and "export factors" of conserved species (rBC, CO, CO2) suggested that changes in emissions at the source did not account for most of the differences observed in samples of increasing age. An investigation of AMS mass fragments indicated that the in-plume fractional contribution (fm/z) to OA of the primary fragment (m/z 60) decreased downwind, while the fractional contribution of the secondary fragment (m/z 44) increased. Increases in f44 are typically interpreted as indicating chemical aging of OA. Likewise, we observed an increase in the O : C elemental ratio downwind, which is usually associated with aerosol aging. However, the rapid mixing of these plumes into the background air suggests that these chemical transformations may be attributable to the different volatilities of the compounds that fragment to these m/z in the AMS. The gas-particle partitioning behavior

  18. Inorganic Salt Interference on CO2(+) in Aerodyne AMS and ACSM Organic Aerosol Composition Studies.

    PubMed

    Pieber, Simone M; El Haddad, Imad; Slowik, Jay G; Canagaratna, Manjula R; Jayne, John T; Platt, Stephen M; Bozzetti, Carlo; Daellenbach, Kaspar R; Fröhlich, Roman; Vlachou, Athanasia; Klein, Felix; Dommen, Josef; Miljevic, Branka; Jiménez, José L; Worsnop, Douglas R; Baltensperger, Urs; Prévôt, André S H

    2016-10-04

    Aerodyne aerosol mass spectrometer (AMS) and Aerodyne aerosol chemical speciation monitor (ACSM) mass spectra are widely used to quantify organic aerosol (OA) elemental composition, oxidation state, and major environmental sources. The OA CO2(+) fragment is among the most important measurements for such analyses. Here, we show that a non-OA CO2(+) signal can arise from reactions on the particle vaporizer, ion chamber, or both, induced by thermal decomposition products of inorganic salts. In our tests (eight instruments, n = 29), ammonium nitrate (NH4NO3) causes a median CO2(+) interference signal of +3.4% relative to nitrate. This interference is highly variable between instruments and with measurement history (percentiles P10-90 = +0.4 to +10.2%). Other semi-refractory nitrate salts showed 2-10 times enhanced interference compared to that of NH4NO3, while the ammonium sulfate ((NH4)2SO4) induced interference was 3-10 times lower. Propagation of the CO2(+) interference to other ions during standard AMS and ACSM data analysis affects the calculated OA mass, mass spectra, molecular oxygen-to-carbon ratio (O/C), and f44. The resulting bias may be trivial for most ambient data sets but can be significant for aerosol with higher inorganic fractions (>50%), e.g., for low ambient temperatures, or laboratory experiments. The large variation between instruments makes it imperative to regularly quantify this effect on individual AMS and ACSM systems.

  19. 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

  20. New insights on aerosol sources and properties of Organics in the west Mediterranean basin

    NASA Astrophysics Data System (ADS)

    Nicolas, José B.; Sciare, Jean; Petit, Jean-Eudes; Bonnaire, Nicolas; Féron, Anais; Dulac, François; Hamonou, Eric; Gros, Valérie; Mallet, Marc; Lambert, Dominique; Sauvage, Stéphane; Léonardis, Thierry; Tison, Emmanuel; Colomb, Aurélie; Fresney, Evelyn; Pichon, Jean-Marc; Bouvier, Laetitia; Bourrianne, Thierry; Roberts, Gregory

    2013-04-01

    The Mediterranean basin exhibits high PM concentrations for a marine area, in particular during the dry season (summer), associated with high photochemistry. The large population of the basin is impacted by both natural and anthropogenic aerosols of various sources from Europe and North Africa. Simulations predict significant climate changes in that area, with less precipitation and hotter temperatures, reinforced by an increasing anthropogenic pressure, which will be linked by higher emissions of pollutants and also by higher impacts on the health. Nevertheless the aerosol models in that area currently suffer from large uncertainties, due to a lack of knowledge in organic aerosol (OA) sources and processes. As part of the French program ChArMEx (The Chemistry-Aerosol Mediterranean Experiment, http://charmex.lsce.ipsl.fr), a 5-week intensive campaign has been performed in June - July 2012 at the new Cape Corsica station (see Dulac et al. in that session), and aiming at a better characterization of anthropogenic versus biogenic aerosols, long range transport versus local influence, with a focus on fine OA. A complete instrumental strategy was deployed thanks to the contribution of a large French community: PM1 concentration every 6 min with a TEOM-FDMS 1405 (Thermo), major aerosol components in PM1 every 30 min (Organics, SO4, NO3, NH4) by Aerosol Chemical Speciation Monitor (Aerodyne), Equivalent Black Carbon every 5 min with a 7-? aethalometer AE31 (Magee Scientific), on-line major anions and cations (incl. light organics like oxalate & MSA) every 10 min with Particle-Into-Liquid Sampler (PILS, Metrohm) coupled with Ion Chromatographs (Dionex), on-line water-soluble organic carbon (WSOC) every 4 min with a PILS (Applikon) coupled with a Total Organic Carbon instrument (Ionics). Filter sampling in PM2.5 and PM10 was also performed every 12h for quality purposes (PM, EC/OC, ions) and for complementary measurements (metals by ICP-MS and organic tracers by LC

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  2. Effect of photochemical self-action of carbon-containing aerosol: Wildfires

    NASA Astrophysics Data System (ADS)

    Konovalov, I. B.; Berezin, E. V.; Beekmann, M.

    2016-05-01

    It has been shown by numerical simulation that the rate of formation of secondary organic aerosols (SOAs) in smoke plumes caused by vegetation and peat fires under real conditions can significantly depend on the aerosol optical thickness (AOT). The AOT determines the photodissociation rate and hydroxyl radical concentration, which in turn determines the rate of SOA generation as a result of oxidation of semivolatile organic compounds. Quantitative analysis has been carried out for the situation that took place in European Russia during the 2010 Russian wildfires. The state-of-the-art 3D chemical transport model is used in this study; the simulations are optimized and validated using the data of monitoring of the particulate matter in the Moscow region and Finland. The findings indicate that it is important to allow for this effect in studies focused on the analysis and prediction of air pollution due to wildfires, as well as climate and weather studies, whose results may depend on the assumptions about the content and properties of atmospheric carbon-containing aerosol.

  3. Gas uptake and chemical aging of semisolid organic aerosol particles.

    PubMed

    Shiraiwa, Manabu; Ammann, Markus; Koop, Thomas; Pöschl, Ulrich

    2011-07-05

    Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.

  4. Oxidative Evolution of Organic Aerosol during the Southern Oxidant and Aerosol Study 2013

    NASA Astrophysics Data System (ADS)

    Williams, B. J.; Martinez, R.; Hagan, D.; Zhang, Y.; Kreisberg, N. M.; Hering, S. V.; Isaacman, G. A.; Yee, L.; Goldstein, A. H.

    2013-12-01

    Previous studies on the formation mechanisms and atmospheric evolution of ambient organic aerosol (OA) have largely focused on individual biogenic or anthropogenic precursor sources. More recently, it has been shown that chemical reaction mechanisms and resulting oxidative evolution of OA behaves differently when there is a mixture of both biogenic and anthropogenic precursor gases. Addressing the need for improved understanding of this mixed source chemistry and a general improvement of OA chemical analysis, we deployed the Volatility and Polarity Separator (VAPS), capable of hourly (to half-hourly) measurements of volatility and polarity resolved OA, to the Centerville, AL ground site during the Southern Oxidant and Aerosol Study, a region impacted by both biogenic and anthropogenic sources. The VAPS instrument increases the mass throughput of ambient OA in comparison to traditional GC due to shorter transfer paths and passivated coatings, and utilizes high-resolution time-of-flight mass spectrometry to obtain aerosol elemental composition. VAPS data is explored to provide new insight into the underlying chemistry and chemical evolution of anthropogenically influenced biogenic secondary OA.

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    Laboratory experiments investigated the relationship between degree of oxidation and hygroscopic properties of secondary organic aerosol (SOA) particles. The hygroscopic growth factor (HGF), the CCN activity (κCCN) and the degree of aerosol oxidation (represented by the atomic O:C ratio) were measured for α-pinene, 1,3,5-trimethylbenzene (TMB), m-xylene and α pinene/m-xylene mixture SOA generated via OH radical oxidation in an aerosol flow reactor. Our results show that both HGF and κCCN increase with O:C. The TMB and m-xylene SOA were, respectively, the least and most hygroscopic of the system studied. An average HGF of 1.25 and a κCCN of 0.2 were measured at O:C of 0.65, in agreement with results reported for ambient data. The HGF based κ(κHGF) under predicted the κCCN values of 20 to 50% for all but the TMB SOA. Within the limitations of instrumental capabilities, we define the extent to which the hygroscopic properties of SOA particles can be predicted from their oxidation level and provide parameterizations suitable for interpreting ambient data.

  6. 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.

  7. NMOC, ozone, and organic aerosol in the southeastern United States, 1999-2007: 3. Origins of organic aerosol in Atlanta, Georgia, and surrounding areas

    NASA Astrophysics Data System (ADS)

    Blanchard, C. L.; Hidy, G. M.; Tanenbaum, S.; Edgerton, E. S.

    2011-02-01

    Carbonaceous compounds constitute a major fraction of the fine particle mass at locations throughout North America; much of the condensed-phase organic carbon (OC) is produced in the atmosphere from NMOC reactions as "secondary" OC (SOC). Ten years of particulate carbon and speciated non-methane organic compound (NMOC) data combined with other measurements from Southeastern Aerosol Research and Characterization (SEARCH) and other sites provide insight into the association between elemental carbon (EC), OC and NMOCs. Data are analyzed to characterize the OC and SOC contrasts between urban Atlanta, Georgia, and nearby non-urban conditions in the Southeast. Analysis of the monitoring record indicates that the mean Atlanta urban excess of total carbon (TC) is 2.1-2.8 μg m -3. The OC/EC ratio of the Atlanta urban excess is in the range 1.3 to 1.8, consistent with OC/EC ratios observed in motor vehicle emissions and a fossil carbon source of urban excess TC. Carbon isotope analysis of a subset of particle samples demonstrates that the urban excess is mainly fossil in origin, even though the majority of the TC is modern at both urban and non-urban sites. Temperature-dependent partitioning of OC between gas and condensed phases cannot explain the observed diurnal and seasonal variations of OC/CO, EC/CO, and OC/EC ratios. Alternatively, a hypothesis involving vertical mixing of OC-enriched air from aloft is supported by the seasonal and diurnal OC, isopentane, aromatic and isoprene observations at the ground. A statistical model is applied to indicate the relative significance of aerometric factors affecting OC and EC concentrations, including meteorological and pollutant associations. The model results demonstrate strong linkages between fine particle carbon and pollutant indicators of source emissions compared with meteorological factors; the model results show weaker dependence of OC on meteorological factors than is the case for ozone (O 3) concentrations.

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

    NASA Astrophysics Data System (ADS)

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

    2008-06-01

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

  9. Investigating types and sources of organic aerosol in Rocky Mountain National Park using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L., Jr.

    2015-01-01

    The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m-3, avg. = 5.13 ± 2.72 μg m-3) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM1 on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9% and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (m/z 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ~10 years of meteorological, particle composition, and fire data.

  10. Investigating types and sources of organic aerosol in Rocky Mountain National Park using aerosol mass spectrometry

    NASA Astrophysics Data System (ADS)

    Schurman, M. I.; Lee, T.; Sun, Y.; Schichtel, B. A.; Kreidenweis, S. M.; Collett, J. L., Jr.

    2014-07-01

    The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m-3, avg. = 5.13 ± 2.72 μg m-3) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM1 on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9 and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (m/zs 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time (LST) when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ∼10 years of meteorological, particle composition, and fire data.

  11. Water Activity Limits the Hygroscopic Growth Factor of Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Rodriguez, L. I.; Cabrera, J. A.; Golden, D.; Tabazadeh, A.

    2007-12-01

    In this work we study the hygroscopic behavior of organic aerosols, which has important implications for Earth's climate. The hygroscopic growth factor (HGF) is defined as the ratio of the diameter of a spherical particle when it is exposed to dry conditions to that at humid conditions. We present a new formulation to express the HGF of an aerosol particle as a function of water activity (aw) in the aqueous phase. This new formulation matches reported HGFs for common inorganic salts and water-miscible organic particles that are known to deliquesce into aqueous drops at high relative humidities (RH). Many studies use tandem differential mobility analyzers (TDMA) to determine the HGF of organic aerosols. For example, Brooks et al. used a TDMA to measure a HGF of 1.2 for 2 μm phthalic acid (PA) particles at 90% RH (aw= 0.9). However, water activity limits the growth of a particle that can be attributed to water uptake. We have assembled a vapor pressure apparatus to measure aw of aqueous solutions at room temperature. Measured water activities for PA, used in our growth formulation, yield a HGF of ~ 1.0005 for 2 μm PA particles at 90% RH. Comparing our results against Brooks et al. suggests that TDMA experiments may grossly overestimate the HGF of PA particles since water activity limits this growth to below 1.0005. Alternatively, we suggest that the adsorption of a negligible mass of water by a highly porous PA particle can lead to an apparent growth in particle size by changing its morphology. Other studies also use TDMAs to measure HGFs of secondary organic aerosols (SOAs). HGFs reported for SOAs are very similar to PA, suggesting that the observed growth may be due to morphological changes in particle size rather than water uptake as commonly assumed. We built a smog chamber where an organic precursor, such as d-limonene, reacts with nitrogen oxides under UV radiation to produce SOAs. We compare the HGFs for SOAs obtained with our method to those obtained with

  12. Gas-phase CO2 subtraction for improved measurements of the organic aerosol mass concentration and oxidation degree by an aerosol mass spectrometer.

    PubMed

    Collier, S; Zhang, Q

    2013-12-17

    The Aerodyne aerosol mass spectrometer (AMS) has been widely used for real-time characterization of the size-resolved chemical composition of sub-micrometer aerosol particles. The first step in AMS sampling is the pre-concentration of aerosols while stripping away the gas-phase components, which contributes to the high sensitivity of this instrument. The strength of the instrument lies in particle phase measurement; however, ion signals generated from gas-phase species can influence the interpretation of the particle-phase chemistry data. Here, we present methods for subtracting the varying contributions of gas-phase carbon dioxide (CO2) in the AMS spectra of aerosol particles, which is critical for determining the mass concentration and oxygen-to-carbon (O/C) ratio of organic aerosol. This report gives details on the gaseous CO2 subtraction analysis performed on a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) data set acquired from sampling of fresh and diluted vehicle emissions. Three different methods were used: (1) collocated continuous gas-phase CO2 measurement coupled with periodic filter tests consisting of sampling the same particle-free air by the AMS and the CO2 analyzer, (2) positive matrix factorization (PMF) analysis to separate the gas- and particle-phase signals of CO2(+) at m/z 44, and (3) use of the particle time-of-flight (PTOF) size-resolved chemical information for separation of gas- and particle-phase signals at m/z 44. Our results indicate that these three different approaches yield internally consistent values for the gas/particle apportionment of m/z 44, but methods 2 and 3 require certain conditions to be met to yield reliable results. The methods presented are applicable to any situation where gas-phase components may influence the PM signal of interest.

  13. Aerosol black carbon over Svalbard regions of Arctic

    NASA Astrophysics Data System (ADS)

    Gogoi, Mukunda M.; Babu, S. Suresh; Moorthy, K. Krishna; Thakur, Roseline C.; Chaubey, Jai Prakash; Nair, Vijayakumar S.

    2016-03-01

    In view of the climate impact of aerosol Black Carbon (BC) over snow covered regions (through enhanced absorption of radiation as well as snow-albedo forcing), and in view of the increasing anthropogenic presence and influence in the northern polar regions, continuous long term measurements of airborne BC have been undertaken from the Svalbard region of Norwegian Arctic (Ny-Ålesund, 79°N, 12°E, 8 m a.s.l.). This study, employing data over a period of 4-years (2010-2013) have shown a consistent spring-time enhancement in BC concentrations, having a (climatological) seasonal mean value of ∼50.3 ± 19.5 ng m-3, nearly 3-times higher than the lowest BC concentrations in summer (∼19.5 ± 6.5 ng m-3). Spectral variation of absorbance indicates that long-range transported biomass burning aerosols contribute as high as 25% to the high BC concentrations in the Arctic atmosphere in spring. Concurrent estimates of BC concentrations in the Arctic snow (for an ensemble of snow samples collected over a period of time during spring) showed values ranging from 0.6 ppb to 4.1 ppb. These values have been used to estimate the BC scavenging ratio (SR). Our studies revealed a mean value of SR ∼98 ± 46, which varied over wide range from 40 to 184 for individual samples. In a broader perspective, the seasonal variations of atmospheric BC concentrations at the Arctic are similar to those seen at the high altitude Himalayas; even though the concentrations are much lower at Arctic. It is found that synoptic conditions mainly influence the high altitude Himalayas, while the influences of local anthropogenic influences are not negligible at the Arctic in modulating the seasonal variations of absorbing aerosols.

  14. Multiphase OH oxidation kinetics of organic aerosol: The role of particle phase state and relative humidity

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H.; Knopf, Daniel A.

    2014-07-01

    Organic aerosol can exhibit different phase states in response to changes in relative humidity (RH), thereby influencing heterogeneous reaction rates with trace gas species. OH radical uptake by laboratory-generated levoglucosan and methyl-nitrocatechol particles, serving as surrogates for biomass burning aerosol, is determined as a function of RH. Increasing RH lowers the viscosity of amorphous levoglucosan aerosol particles enabling enhanced OH uptake. Conversely, OH uptake by methyl-nitrocatechol aerosol particles is suppressed at higher RH as a result of competitive coadsorption of H2O that occupies reactive sites. This is shown to have substantial impacts on organic aerosol lifetimes with respect to OH oxidation. The results emphasize the importance of organic aerosol phase state to accurately describe the multiphase chemical kinetics and thus chemical aging process in atmospheric models to better represent the evolution of organic aerosol and its role in air quality and climate.

  15. Photochemical evolution of organic aerosols observed in urban plumes from Hong Kong and the Pearl River Delta of China

    NASA Astrophysics Data System (ADS)

    Zhou, Shengzhen; Wang, Tao; Wang, Zhe; Li, Weijun; Xu, Zheng; Wang, Xinfeng; Yuan, Chao; Poon, C. N.; Louie, Peter K. K.; Luk, Connie W. Y.; Wang, Wenxing

    2014-05-01

    Organic aerosols influence human health and global radiative forcing. However, their sources and evolution processes in the atmosphere are not completely understood. To study the aging and production of organic aerosols in a subtropical environment, we measured hourly resolved organic carbon (OC) and element carbon (EC) in PM2.5 at a receptor site (Tung Chung, TC) in Hong Kong from August 2011 to May 2012. The average OC concentrations exhibited the highest values in late autumn and were higher during the daytime than at night. The secondary organic carbon (SOC) concentrations, which were estimated using an EC-tracer method, comprised approximately half of the total OC on average. The SOC showed good correlation with odd oxygen (Ox = O3 + NO2) in the summer and autumn seasons, suggestive of contribution of photochemical activities to the formation of secondary organic aerosols (SOA). We calculated production rates of SOA using the photochemical age (defined as -Log10(NOx/NOy)) in urban plumes from the Pearl River Delta (PRD) region and Hong Kong during pollution episodes in summer and autumn. The CO-normalized SOC increased with the photochemical age, with production rates ranging from 1.31 to 1.82 μg m-3 ppmv-1 h-1 in autumn and with a larger rate in summer (3.86 μg m-3 ppmv-1 h-1). The rates are in the range of the rates observed in the outflow from Mexico City, the eastern U.S. and Los Angeles. Microscopic analyses of the individual aerosol particles revealed large contrasts of aerosol physico-chemical properties on clean and smoggy days, with thick organic coatings internally mixed with inorganic sulfate for all particle sizes in the aged plumes from the PRD region.

  16. Updated aerosol module and its application to simulate secondary organic aerosols during IMPACT campaign May 2008

    NASA Astrophysics Data System (ADS)

    Li, Y. P.; Elbern, H.; Lu, K. D.; Friese, E.; Kiendler-Scharr, A.; Mentel, Th. F.; Wang, X. S.; Wahner, A.; Zhang, Y. H.

    2013-07-01

    The formation of Secondary organic aerosol (SOA) was simulated with the Secondary ORGanic Aerosol Model (SORGAM) by a classical gas-particle partitioning concept, using the two-product model approach, which is widely used in chemical transport models. In this study, we extensively updated SORGAM including three major modifications: firstly, we derived temperature dependence functions of the SOA yields for aromatics and biogenic VOCs (volatile organic compounds), based on recent chamber studies within a sophisticated mathematic optimization framework; secondly, we implemented the SOA formation pathways from photo oxidation (OH initiated) of isoprene; thirdly, we implemented the SOA formation channel from NO3-initiated oxidation of reactive biogenic hydrocarbons (isoprene and monoterpenes). The temperature dependence functions of the SOA yields were validated against available chamber experiments, and the updated SORGAM with temperature dependence functions was evaluated with the chamber data. Good performance was found with the normalized mean error of less than 30%. Moreover, the whole updated SORGAM module was validated against ambient SOA observations represented by the summed oxygenated organic aerosol (OOA) concentrations abstracted from aerosol mass spectrometer (AMS) measurements at a rural site near Rotterdam, the Netherlands, performed during the IMPACT campaign in May 2008. In this case, we embedded both the original and the updated SORGAM module into the EURopean Air pollution and Dispersion-Inverse Model (EURAD-IM), which showed general good agreements with the observed meteorological parameters and several secondary products such as O3, sulfate and nitrate. With the updated SORGAM module, the EURAD-IM model also captured the observed SOA concentrations reasonably well especially those during nighttime. In contrast, the EURAD-IM model before update underestimated the observations by a factor of up to 5. The large improvements of the modeled SOA

  17. Relating hygroscopicity and composition of organic aerosol particulate matter

    SciTech Connect

    Duplissy, J.; DeCarlo, P. F.; Dommen, J.; Alfarra, M. R.; Metzger, A.; Barmpadimos, I.; Prevot, A. S. H.; Weingartner, E.; Tritscher, T.; Gysel, M.; Aiken, A. C.; Jimenez, J. L.; Canagaratna, M. R.; Worsnop, D. R.; Collins, D. R.; Tomlinson, J.; Baltensperger, U.

    2011-01-01

    A hygroscopicity tandem differential mobility analyzer (HTDMA) was used to measure the water uptake (hygroscopicity) of secondary organic aerosol (SOA) formed during the chemical and photochemical oxidation of several organic precursors in a smog chamber. Electron ionization mass spectra of the non-refractory submicron aerosol were simultaneously determined with an aerosol mass spectrometer (AMS), and correlations between the two different signals were investigated. SOA hygroscopicity was found to strongly correlate with the relative abundance of the ion signal m/z 44 expressed as a fraction of total organic signal (f44). m/z 44 is due mostly to the ion fragment CO2+ for all types of SOA systems studied, and has been previously shown to strongly correlate with organic O/C for ambient and chamber OA. The analysis was also performed on ambient OA from two field experiments at the remote site Jungfraujoch, and the megacity Mexico City, where similar results were found. A simple empirical linear relation between the hygroscopicity of OA at subsaturated RH, as given by the hygroscopic growth factor (GF) or "κorg" parameter, and f44 was determined and is given by κorg = 2.2 × f44 - 0.13. This approximation can be further verified and refined as the database for AMS and HTDMA measurements is constantly being expanded around the world. Finally, the use of this approximation could introduce an important simplification in the parameterization of hygroscopicity of OA in atmospheric models, since f44 is correlated with the photochemical age of an air mass.

  18. Formation of secondary organic aerosols from the ozonolysis of dihydrofurans

    NASA Astrophysics Data System (ADS)

    Diaz-de-Mera, Yolanda; Aranda, Alfonso; Bracco, Larisa; Rodriguez, Diana; Rodriguez, Ana

    2017-02-01

    In this work we report the study of the ozonolysis of 2,5-dihydrofuran and 2,3-dihydrofuran and the reaction conditions leading to the formation of secondary organic aerosols. The reactions have been carried out in a Teflon chamber filled with synthetic air mixtures at atmospheric pressure and room temperature. The ozonolysis only produced particles in the presence of SO2. Rising relative humidity from 0 to 40 % had no effect on the production of secondary organic aerosol in the case of 2,5-dihydrofuran, while it reduced the particle number and particle mass concentrations from the 2,3-dihydrofuran ozonolysis. The water-to-SO2 rate constant ratio for the 2,3-dihydrofuran Criegee intermediate was derived from the secondary organic aerosol (SOA) yields in experiments with different relative humidity values, kH2O/kSO2 = (9.8 ± 3.7) × 10-5. The experimental results show that SO3 may not be the only intermediate involved in the formation or growth of new particles in contrast to the data reported for other Criegee intermediate-SO2 reactions. For the studied reactions, SO2 concentrations remained constant during the experiments, behaving as a catalyst in the production of condensable products. Computational calculations also show that the stabilised Criegee intermediates from the ozonolysis reaction of both 2,5-dihydrofuran and 2,3-dihydrofuran may react with SO2, resulting in the regeneration of SO2 and the formation of low-volatility organic acids.

  19. 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...

  20. 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

  1. 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.

  2. Laboratory studies of oxidation of primary emissions: Oxidation of organic molecular markers and secondary organic aerosol production

    NASA Astrophysics Data System (ADS)

    Weitkamp, Emily A.

    vehicle markers. Aerosol composition is a key influence on reaction rate constants, perhaps more significant than external influences. Alkenoic acid concentrations in the meat grease particles appear to influence cholesterol oxidation rates. Also, the reaction rate constants for new motor oil were faster than those of the more viscous used motor oil. The measured reaction rate constants were used to oxidize source profiles that were subsequently run in the Chemical Mass Balance (CMB) model. Oxidizing the molecular markers in the meat-cooking profile led to unrealistically high meat-cooking aerosol contributions to the total organic carbon (OC), often more than 100%. This suggests that there is either unaccounted for sources of meat-cooking molecular markers in the ambient samples, or there is some property of atmospheric aerosols that significantly inhibits reaction that was not captured in this study. Oxidation of motor vehicle profiles led to both higher estimates of total vehicle OC and a quadrupling of gasoline OC, while the diesel contribution changed very little. The increase in gasoline OC changes gasoline vehicle emissions from a relatively minor source to a major one. Thus, oxidation of molecular markers can have a significant impact on receptor model predictions. The second objective was to investigate SOA formation from the photo-oxidation of whole diesel exhaust. Diluted exhaust from a diesel engine was photo-oxidized in a smog chamber to investigate SOA production. Photochemical oxidation rapidly produced significant SOA, almost doubling the organic aerosol contribution of primary emissions after several hours of processing. Less than 10% of the SOA mass could 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. Aerosol Mass Spectrometer (AMS) mass spectra reveal that the

  3. Source forensics of black carbon aerosols from China.

    PubMed

    Chen, Bing; Andersson, August; Lee, Meehye; Kirillova, Elena N; Xiao, Qianfen; Kruså, Martin; Shi, Meinan; Hu, Ke; Lu, Zifeng; Streets, David G; Du, Ke; Gustafsson, Örjan

    2013-08-20

    The limited understanding of black carbon (BC) aerosol emissions from incomplete combustion causes a poorly constrained anthropogenic climate warming that globally may be second only to CO2 and regionally, such as over East Asia, the dominant driver of climate change. The relative contribution to atmospheric BC from fossil fuel versus biomass combustion is important to constrain as fossil BC is a stronger climate forcer. The source apportionment is the underpinning for targeted mitigation actions. However, technology-based "bottom-up" emission inventories are inconclusive, largely due to uncertain BC emission factors from small-scale/household combustion and open burning. We use "top-down" radiocarbon measurements of atmospheric BC from five sites including three city sites and two regional sites to determine that fossil fuel combustion produces 80 ± 6% of the BC emitted from China. This source-diagnostic radiocarbon signal in the ambient aerosol over East Asia establishes a much larger role for fossil fuel combustion than suggested by all 15 BC emission inventory models, including one with monthly resolution. Our results suggest that current climate modeling should refine both BC emission strength and consider the stronger radiative absorption associated with fossil-fuel-derived BC. To mitigate near-term climate effects and improve air quality in East Asia, activities such as residential coal combustion and city traffic should be targeted.

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

    EPA Science Inventory

    Seasonal and regional variations of primary (OCpri) and secondary (OCsec) organic carbon aerosols across the continental U.S. for the year 2001 were examined by a semi-empirical technique using observed OC and elemental carbon (EC) data from 142 routine moni...

  5. Evaluating Simulations of Primary Anthropogenic and Biomass Burning Organic Aerosols using Aerosol Mass Spectrometer Data and Positive Matrix Factorization Analysis

    NASA Astrophysics Data System (ADS)

    Fast, J.; Aiken, A.; Alexander, L.; Canagaratna, M.; Decarlo, P.; Herndon, S.; Jimenez, J.; Kleinman, L.; Ochoa, C.; Onasch, T.; Song, C.; Wiedinmyer, C.; Yu, X.; Zaveri, R.

    2008-12-01

    Most model predictions of organic matter are currently underestimated because the processes contributing to secondary organic aerosol (SOA) formation and transformation are not well understood. Since research associated with developing a better framework to improve the representation of specific gas-to-particle partitioning processes controlling SOA based on new measurements and theoretical relationships is on- going, this study seeks to determine whether 3-D models can adequately predict concentrations of primary organic aerosols (POA). If one assumes POA is non-volatile, then errors in POA predictions will results from uncertainties in the emission inventories and errors in transport and mixing processes. The WRF-chem model is used to predict POA in the vicinity of Mexico City during the 2006 MILAGRO field campaign. Particulate matter emission rates were obtained from urban and regional Mexican emission inventories and from biomass burning estimates derived from MODIS "hotspot" and vegetation databases. Organic aerosol predictions are evaluated using data from Aerodyne Aerosol Mass Spectrometer (AMS) instruments deployed at four ground sites and on two research aircraft and from Sunset Laboratory OCEC instruments deployed at two ground sites. Positive Matrix Factorization (PMF) has recently been applied to derive components of organic aerosols including: hydrocarbon-like organic aerosol (HOA), oxidized organic aerosol (OOA), and biomass burning organic aerosols (BBOA). The temporal variation of HOA is often similar to primary emissions of other species in urban areas. PMF analysis is currently available for three of the ground sites and for some of the aircraft flights. We found that the predicted POA was consistently lower than the measured organic matter at the ground sites, which is consistent with the expectation that SOA should be a large fraction of the total organic aerosol mass. A much better agreement was found when predicted POA was compared with HOA

  6. Organic Aerosol Nucleation and Growth at the CERN CLOUD chamber

    NASA Astrophysics Data System (ADS)

    Tröstl, Jasmin; Lethipalo, Katrianne; Bianchi, Federico; Sipilä, Mikko; Nieminen, Tuomo; Wagner, Robert; Frege, Carla; Simon, Mario; Weingartner, Ernest; Gysel, Martin; Dommen, Josef; Baltensperger, Urs

    2014-05-01

    It is well known that atmospheric aerosols influence the climate by changing Earth's radiation balance (IPCC 2007 and 2013). Recent models have shown (Merikanto et al. 2009) that aerosol nucleation is one of the biggest sources of low level cloud condensation nuclei. Still, aerosol nucleation and growth are not fully understood. The driving force of nucleation and growth is sulfuric acid. However ambient nucleation and growth rates cannot be explained by solely sulfuric acid as precursor. Recent studies have shown that only traces of precursors like ammonia and dimethylamine enhance the nucleation rates dramatically (Kirkby et al. 2011, Almeida et al., 2013). Thus the role of different aerosol precursor needs to be studied not only in ambient but also in very well controlled chamber experiments. The CLOUD (Cosmics Leaving OUtdoor Droplets) experiment enables conducting experiments very close to atmospheric conditions and with a very low contaminant background. The latest CLOUD experiments focus on the role of organics in aerosol nucleation and growth. For this purpose, numerous experiments with alpha-pinene have been conducted at the CERN CLOUD chamber. Several state-of-the-art instruments were used to cover the whole complexity of the experiment. Chamber conditions were set to 40% relative humidity and 5° C. Atmospheric concentrations of SO2, O3, HONO, H2O and alpha-pinene were injected to the chamber. Different oxidation conditions were used, yielding different levels of oxidized organics: (1) OH radicals, (2) Ozone with the OH scavenger H2 (pure ozonolysis) and (3) both. SO2 was injected to allow for sulfuric acid production. Optical UV fibers were used to enable photochemical reactions. A high field cage (30 kV) can be turned on to remove all charged particles in the chamber to enable completely neutral conditions. Comparing neutral conditions to the beam conditions using CERN's proton synchrotron, the fraction of ion-induced nucleation can be studied. Using

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids, to phase-separated particles, to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40-90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids, (2) forcing a single phase, but accounting for non-ideal interactions through activity coefficient calculations, and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation between the inorganic and organic components is assumed at all RH values, with water-uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    Recent work has demonstrated that organic and mixed organic-inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic-inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii-Stokes-Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid-liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF

  10. The link between organic aerosol mass loading and degree of oxygenation: an α-pinene photooxidation study

    NASA Astrophysics Data System (ADS)

    Pfaffenberger, L.; Barmet, P.; Slowik, J. G.; Praplan, A. P.; Dommen, J.; Prévôt, A. S. H.; Baltensperger, U.

    2013-07-01

    A series of smog chamber (SC) experiments was conducted to identify factors responsible for the discrepancy between ambient and SC aerosol degree of oxygenation. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer is used to compare mass spectra from α-pinene photooxidation with ambient aerosol. Composition is compared in terms of the fraction of particulate CO2+, a surrogate for carboxylic acids, vs. the fraction of C2H3O+, a surrogate for aldehydes, alcohols and ketones, as well as in the Van Krevelen space, where the evolution of the atomic hydrogen-to-carbon ratio (H : C) vs. the atomic oxygen-to-carbon ratio (O : C) is investigated. Low (near-ambient) organic mass concentrations were found to be necessary to obtain oxygenation levels similar to those of low-volatility oxygenated organic aerosol (LV-OOA) commonly identified in ambient measurements. The effects of organic mass loading and OH (hydroxyl radical) exposure were decoupled by inter-experiment comparisons at the same integrated OH concentration. An OH exposure between 3 and 25 × 107 cm-3 h is needed to increase O : C by 0.05 during aerosol aging. For the first time, LV-OOA-like aerosol from the abundant biogenic precursor α-pinene was produced in a smog chamber by oxidation at typical atmospheric OH concentrations. Significant correlation between measured secondary organic aerosol (SOA) and reference LV-OOA mass spectra is shown by Pearson's R2 values larger than 0.90 for experiments with low organic mass concentrations between 1.2 and 18 μg m-3 at an OH exposure of 4 × 107 cm-3 h, corresponding to about two days of oxidation time in the atmosphere, based on a global mean OH concentration of ~ 1 × 106 cm-3. α-Pinene SOA is more oxygenated at low organic mass loadings. Because the degree of oxygenation influences the chemical, volatility and hygroscopic properties of ambient aerosol, smog chamber studies must be performed at near-ambient concentrations to accurately simulate

  11. Stable Carbon Isotope Ratio of OC and TC in Aerosol Particles at Urban, Marine and Forest Sites

    NASA Astrophysics Data System (ADS)

    Masalaite, Agne; Dusek, Ulrike; Holzinger, Rupert; Röckmann, Thomas; Remeikis, Vidmantas

    2014-05-01

    Atmospheric aerosols contain up to 50 % (of) organic substances, thus substantially contributing to aerosol climate forcing and affecting human health. In addition to health and climate impacts, aerosol particulate matter is increasingly recognized for its role in biogeochemical cycles. δ13C value of carbonaceous aerosols is a useful tracer for distinguishing the origin of carbonaceous materials. Stable carbon isotope ratios were determined for organic carbon (OC) fraction and total carbon (TC) of PM1 collected on quartz fiber filters in Lithuania in March 2013 at three sites: the urban location of Vilnius, the coastal location of Preila and forest location of Rugsteliskis. The isotope values varied from -27.5 o to -25.5 o for OC and -27.9 o to -25.4 o for TC. δ13C values of TC of the marine site were depleted with some exceptions, at the forest site they were most enriched and the values of the city were in between. The city had the narrowest variation in TC indicating one main source of aerosol particles. The situation was different for OC values. δ13C values of the marine and the forest sites were relatively depleted, meanwhile the city site values were enriched and OC had a highest variability (1.6 o). The city samples had the best correlation (TC via OC). The marine values varied over a wide range (1.5 o) compared to the forest ones. The difference between TC and OC was not as high at the marine and city sites as at the forest site (the variation was about 5 times larger - the average OC was 1 o depleted). This indicates that VOC had a different origin than TC in the forest and in the city. Meanwhile marine aerosol particles had more or less the same source of OC and TC.

  12. Urban organic aerosols measured by single particle mass spectrometry in the megacity of London

    NASA Astrophysics Data System (ADS)

    Dall'Osto, M.; Harrison, R. M.

    2011-02-01

    During the month of October 2006, as part of the REPARTEE-I experiment (Regent's Park and Tower Environmental Experiment) an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed at an urban background location in the city of London, UK. Fifteen particle types were classified, some of which were accompanied by Aerosol Mass Spectrometer (AMS) quantitative aerosol mass loading measurements (Dall'Osto et al., 2009a, b). In this manuscript the origins and properties of four particle types associated with locally generated aerosols, independent of the air mass type advected into London, are examined. One particle type, originating from lubricating oil (referred to as Ca-EC), was associated with morning rush hour traffic emissions. A second particle type, composed of both inorganic and organic species (called Na-EC-OC), was found enhanced in particle number concentration during evening time periods, and is likely to originate from a source operating at this time of day, or more probably from condensation of semi-volatile species, and contains both primary and secondary components. A third class, internally mixed with organic carbon and sulphate (called OC), was found to spike both in the morning and evenings. The fourth class (SOA-PAH) exhibited maximum frequency during the warmest part of the day, and a number of factors point towards secondary production from traffic-related volatile aromatic compounds. Single particle mass spectra of this particle type showed an oxidized polycyclic aromatic compound signature. Finally, a comparison of ATOFMS particle class data is made with factors obtained by Positive Matrix Factorization from AMS data.. Both the Ca-EC and OC particle types correlate with the AMS HOA primary organic fraction (R2 = 0.65 and 0.50 respectively), and Na-EC-OC, but not SOA-PAH, which correlates weakly with the AMS OOA secondary organic aerosol factor (R2 = 0.35). A detailed analysis was conducted to identify ATOFMS particle type(s) representative

  13. 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.

  14. Quantifying the Indirect Effect of Sulfate Aerosol on Climate Change Through the Carbon Cycle

    NASA Astrophysics Data System (ADS)

    Cadule, P.; Friedlingstein, P.; Bopp, L.; Piao, S.; Ciais, P.

    2008-12-01

    Elevated atmospheric concentrations of greenhouse gases will continue to warm the Earth's climate in the coming century. Coupled climate-carbon models have demonstrated a significant climate-induced reduction of natural carbon sinks, which acts as a positive feedback on the atmospheric CO2 concentration (between +20 and +220 ppm in 2100, for the SRES A2 emission scenario). Sulfate aerosols are known to affect climate through a radiative direct effect and a series of indirect effects involving the atmospheric water cycle. However, the effects of sulfate aerosols and non-CO2 greenhouse gases were neglected in these coupled climate-carbon cycle models. Here we performed new coupled climate-carbon simulations wherein the evolution of sulfate aerosols and non-CO2 greenhouse gases were explicitly represented. We show a hitherto undocumented indirect effect of aerosols on climate, via the carbon cycle. While sulfate aerosols cool the climate by 0.79°C globally, this cooling reduces land carbon sinks, leaving additional CO2 in the atmosphere. At mid-to-high northern latitudes, the aerosol-induced cooling is responsible for a decline in photosynthesis and land carbon uptake (-63 PgC by 2100). On the other hand, a variety of processes yields increased tropical carbon uptake (+28 PgC) in response to aerosol induced cooling, which is insufficient to balance the decline in the northern hemisphere. Overall, including non- CO2 greenhouse gases and sulfate aerosols, in coupled simulations, doubles the additional quantity of CO2 accumulating in the atmosphere due to climate change. Our results demonstrate that any climate mitigation policy that aims to reduce warming via sulfate aerosols must also account for their indirect warming effect, which arises from interactions between climate and the carbon cycle.

  15. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

    NASA Astrophysics Data System (ADS)

    Gilardoni, Stefania; Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Chiara Pietrogrande, Maria; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-09-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1-0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4-20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate.

  16. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

    PubMed Central

    Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Pietrogrande, Maria Chiara; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-01-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1–0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4–20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate. PMID:27551086

  17. 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.

  18. 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.

  19. Photochemical aging of secondary organic aerosols: effects on hygroscopic growth and CCN activation

    NASA Astrophysics Data System (ADS)

    Buchholz, A.; Mentel, Th. F.; Tillmann, R.; Schlosser, E.; Mildenberger, K.; Clauss, T.; Henning, S.; Kiselev, A.; Stratmann, F.

    2009-04-01

    Plant emitted volatile organic carbons (VOCs) are a major precursor of secondary organic aerosols (SOA), an important constituent of atmospheric aerosols. The precursors are oxidized via ozonolysis, photooxidation, or by NO3 and form aerosol particles. Due to further oxidation of the organic matter the composition of the SOA may age with time. This will also change the hygroscopic growth (HG) and cloud condensation nuclei (CCN) activation of the particles. In this study we generated and aged SOA in the SAPHIR chamber at the Research Centre Juelich under near atmospheric conditions: natural sunlight, low precursor and O3 concentrations, and long reaction times. As precursor we used a mixture of 5 monoterpenes (MT) or 5 MT with 2 sesquiterpenes which had been identified as major constituents of plant emissions in previous experiments. Concentrations ranged between 4 and 100 ppb MT and the total reaction time was 36h. HG was measured at RH=10-97% by a Hygroscopic Tandem Differential Analyser (HTDMA, FZ Juelich) and at RH=97-99% by the Leipzig Aerosol Cloud Interaction Simulator (LACIS-mobile, IfT Leipzig). The agreement between HTDMA and LACIS-mobile data was generally good. CCN properties were measured with a continuous flow CCN Counter from DMT. SOA particles generated on a sunny day were more hygroscopic and had a lower activation diameter (Dcrit) than SOA formed under cloudy conditions. With aging it became more hygroscopic and Dcrit decreased. Sunlight enhanced this effect. But the change in HG and Dcrit due to aging was less than the difference between SOA generated under different conditions (i.e. sunny or cloudy). We did not observe a dependence of the HG on the precursor concentration.

  20. Dosimeter for monitoring vapors and aerosols of organic compounds

    DOEpatents

    Vo-Dinh, Tuan

    1987-01-01

    A dosimeter is provided for collecting and detecting vapors and aerosols of organic compounds. The dosimeter comprises a lightweight, passive device that can be conveniently worn by a person as a badge or placed at a stationary location. The dosimeter includes a sample collector comprising a porous web treated with a chemical for inducing molecular displacement and enhancing phosphorescence. Compounds are collected onto the web by molecular diffusion. The web also serves as the sample medium for detecting the compounds by a room temperature phosphorescence technique.

  1. Dosimeter for monitoring vapors and aerosols of organic compounds

    DOEpatents

    Vo-Dinh, T.

    1987-07-14

    A dosimeter is provided for collecting and detecting vapors and aerosols of organic compounds. The dosimeter comprises a lightweight, passive device that can be conveniently worn by a person as a badge or placed at a stationary location. The dosimeter includes a sample collector comprising a porous web treated with a chemical for inducing molecular displacement and enhancing phosphorescence. Compounds are collected onto the web by molecular diffusion. The web also serves as the sample medium for detecting the compounds by a room temperature phosphorescence technique. 7 figs.

  2. Sources and atmospheric transformations of semivolatile organic aerosols

    NASA Astrophysics Data System (ADS)

    Grieshop, Andrew P.

    Fine atmospheric particulate matter (PM2.5) is associated with increased mortality, a fact which led the EPA to promulgate a National Ambient Air Quality Standard (NAAQS) for PM2.5 in 1997. Organic material contributes a substantial portion of the PM2.5 mass; organic aerosols (OA) are either directly emitted (primary OA or POA) or formed via the atmospheric oxidation of volatile precursor compounds as secondary OA (SOA). The relative contributions of POA and SOA to atmospheric OA are uncertain, as are the contributions from various source classes (e.g. motor vehicles, biomass burning). This dissertation first assesses the importance of organic PM within the context of current US air pollution regulations. Most control efforts to date have focused on the inorganic component of PM. Although growing evidence strongly implicates OA, especially which from motor vehicles, in the health effects of PM, uncertain and complex source-receptor relationships for OA discourage its direct control for NAAQS compliance. Analysis of both ambient data and chemical transport modeling results indicate that OA does not play a dominant role in NAAQS violations in most areas of the country under current and likely future regulations. Therefore, new regulatory approaches will likely be required to directly address potential health impacts associated with OA. To help develop the scientific understanding needed to better regulate OA, this dissertation examined the evolution of organic aerosol emitted by combustion systems. The current conceptual model of POA is that it is non-volatile and non-reactive. Both of these assumptions were experimental investigated in this dissertation. Novel dilution measurements were carried out to investigate the gas-particle partitioning of OA at atmospherically-relevant conditions. The results demonstrate that POA from combustion sources is semivolatile. Therefore its gas-particle partitioning depends on temperature and atmospheric concentrations; heating and

  3. Secondary Organic Aerosol Production from Cloud Processing of Glycolaldehyde

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  4. 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

  5. Gas and aerosol carbon in California: comparison of ...

    EPA Pesticide Factsheets

    Co-located measurements of fine particulate matter (PM2.5) organic carbon (OC), elemental carbon, radiocarbon (14C), speciated volatile organic compounds (VOCs),and OH radicals during the CalNex field campaign provide a unique opportunity to evaluate the Community Multiscale Air Quality (CMAQ) model's representation of organic species from VOCs to particles. Episode average daily 23 h average 14C analysis indicates PM2.5 carbon at Pasadena and Bakersfield during the CalNex field campaign was evenly split between contemporary and fossil origins. CMAQ predicts a higher contemporary carbon fraction than indicated by the 14C analysis at both locations. The model underestimates measured PM2.5 organic carbon at both sites with very little (7% in Pasadena) of the modeled mass represented by secondary production, which contrasts with the ambient-based SOC/OC fraction of 63% at Pasadena. The National Exposure Research Laboratory’s (NERL’s) Human Exposure and Atmospheric Sciences Division (HEASD) conducts research in support of EPA’s mission to protect human health and the environment. HEASD’s research program supports Goal 1 (Clean Air) and Goal 4 (Healthy People) of EPA’s strategic plan. More specifically, our division conducts research to characterize the movement of pollutants from the source to contact with humans. Our multidisciplinary research program produces Methods, Measurements, and Models to identify relationships between and characterize processe

  6. Uptake of nitric acid, ammonia, and organics in orographic clouds: mass spectrometric analyses of droplet residual and interstitial aerosol particles

    NASA Astrophysics Data System (ADS)

    Schneider, Johannes; Mertes, Stephan; van Pinxteren, Dominik; Herrmann, Hartmut; Borrmann, Stephan

    2017-01-01

    Concurrent in situ analyses of interstitial aerosol and cloud droplet residues have been conducted at the Schmücke mountain site during the Hill Cap Cloud Thuringia campaign in central Germany in September and October 2010. Cloud droplets were sampled from warm clouds (temperatures between -3 and +16 °C) by a counterflow virtual impactor and the submicron-sized residues were analyzed by a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), while the interstitial aerosol composition was measured by an high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). During cloud-free periods, the submicron out-of-cloud aerosol was analyzed using both instruments, allowing for intercomparison between the two instruments. Further instrumentation included black carbon measurements and optical particle counters for the aerosol particles as well as optical sizing instrumentation for the cloud droplets. The results show that, under cloud conditions, on average 85 % of the submicron aerosol mass partitioned into the cloud liquid phase. Scavenging efficiencies of nitrate, ammonium, sulfate, and organics ranged between 60 and 100 %, with nitrate having, in general, the highest values. For black carbon, the scavenging efficiency was markedly lower (about 24 %). The nitrate and ammonium mass fractions were found to be markedly enhanced in cloud residues, indicating uptake of gaseous nitric acid and ammonia into the aqueous phase. This effect was found to be temperature dependent: at lower temperatures, the nitrate and ammonium mass fractions in the residues were higher. Also, the oxidation state of the organic matter in cloud residues was found to be temperature dependent: the O : C ratio was lower at higher temperatures. A possible explanation for this observation is a more effective uptake and/or higher concentrations of low-oxidized water-soluble volatile organic compounds, possibly of biogenic origin, at higher temperatures. Organic nitrates were observed

  7. The link between organic aerosol mass loading and degree of oxygenation: an α-pinene photooxidation study

    NASA Astrophysics Data System (ADS)

    Pfaffenberger, L.; Barmet, P.; Slowik, J. G.; Praplan, A. P.; Dommen, J.; Prévôt, A. S. H.; Baltensperger, U.

    2012-09-01

    A series of smog chamber (SC) experiments was conducted to identify driving factors responsible for the discrepancy between ambient and SC aerosol degree of oxygenation. An Aerodyne high resolution time-of-flight aerosol mass spectrometer is used to compare mass spectra from α-pinene photooxidation with ambient aerosol. Composition is compared in terms of the fraction of organic mass measured at m/z 44 (f44), a surrogate for carboxylic/organic acids as well as the atomic oxygen-to-carbon ratio (O : C), vs. f43, a surrogate for aldehydes, alcohols and ketones. Low (near-ambient) organic mass concentrations were found to be necessary to obtain oxygenation levels similar to those of low-volatility oxygenated organic aerosol (LV-OOA) commonly identified in ambient measurements. The effects of organic mass loading and OH (hydroxyl radical) exposure were decoupled by inter-experiment comparisons at the same integrated OH concentration. On average, an OH exposure of 2.9 ± 1.3 × 107 cm-3 h is needed to increase f44 by 1% during aerosol aging. For the first time, LV-OOA-like aerosol from the abundant biogenic precursor α-pinene was produced in a smog chamber by oxidation at typical atmospheric OH concentrations. Significant correlation between measured secondary organic aerosol (SOA) and reference LV-OOA mass spectra is shown by Pearson's R2 values larger than 0.90 for experiments with low organic mass concentrations between 1.5 and 15 μg m-3 at an OH exposure of 4 × 107 cm-3 h, corresponding to about two days oxidation time in the atmosphere, based on a global mean OH concentration of ∼1 × 106 cm-3. Not only is the α-pinene SOA more oxygenated at low organic mass loadings, but the functional dependence of oxygenation on mass loading is enhanced at atmospherically-relevant precursor concentrations. Since the degree of oxygenation influences the chemical, volatility and hygroscopic properties of ambient aerosol, smog chamber studies must be performed at near

  8. T-matrix calculations of fractal black carbon atmospheric aerosol particle optical scattering

    NASA Astrophysics Data System (ADS)

    Smith, Anna; Boness, David

    2008-05-01

    To better constrain global climate change computer models, and thereby to more fully understand the full extent of anthropogenic climate change, it is necessary to understand the physics of light scattering from those atmospheric aerosol particles that are caused by human activities. The IPCC AR4 report on the physical basis of climate change lists uncertainty in the effects of black carbon aerosol particles, caused by burning fossil fuels and organic matter, as one of the greatest uncertainties in current climate change understanding. This study hopes to increase the knowledge of how aerosols contribute to radiative forcing by using more realistic modeling of scattering properties. We use D. W. Mackowski's T- matrix code on fractal aggregates of uniform spherical monomers and compare this with fractal scattering predicted by the Raleigh-Debye-Gans approximation. The T-matrix code is checked for accuracy with one spherical particle as found with Mie theory. Scattering properties found using the T-matrix method are performed as a function of fractal dimension and number of monomers. Preliminary results will be presented. Future work will involve comparison with soot particle optical scattering measurements made at Seattle University.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  10. Molecular composition of organic aerosols in central Amazonia: an ultra-high-resolution mass spectrometry study

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Godoi, Ricardo H. M.; Connors, Sarah; Levine, James G.; Archibald, Alex T.; Godoi, Ana F. L.; Paralovo, Sarah L.; Barbosa, Cybelli G. G.; Souza, Rodrigo A. F.; Manzi, Antonio O.; Seco, Roger; Sjostedt, Steve; Park, Jeong-Hoo; Guenther, Alex; Kim, Saewung; Smith, James; Martin, Scot T.; Kalberer, Markus

    2016-09-01

    The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen- and/or sulfur-containing organic species contributed up to 60 % of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen- and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  13. Aerosols

    Atmospheric Science Data Center

    2013-04-17

    ... article title:  Aerosols over Central and Eastern Europe     View Larger Image ... last weeks of March 2003, widespread aerosol pollution over Europe was detected by several satellite-borne instruments. The Multi-angle ...

  14. Carbon cycle: Ocean dissolved organics matter

    NASA Astrophysics Data System (ADS)

    Amon, Rainer M. W.

    2016-12-01

    Large quantities of organic carbon are stored in the ocean, but its biogeochemical behaviour is elusive. Size-age-composition relations now quantify the production of tiny organic molecules as a major pathway for carbon sequestration.

  15. Airborne measurements of black carbon aerosol over the Southeastern U.S. during the Southeast Atmosphere Study (SAS) experiment

    NASA Astrophysics Data System (ADS)

    Markovic, M. Z.; Perring, A. E.; Schwarz, J. P.; Fahey, D. W.; Gao, R.; Watts, L.; Holloway, J.; Graus, M.; Warneke, C.; De Gouw, J. A.; Veres, P. R.; Roberts, J. M.; Middlebrook, A. M.; Welti, A.; Liao, J.

    2013-12-01

    The Southeast Atmosphere Study (SAS) field campaign was a large-scale, collaborative project, which took place in the Southeastern U.S. in June and July of 2013. The goal of the campaign was to investigate the impacts of biogenic and anthropogenic gases and aerosols on the formation of haze and anomalous climate cooling in the region. During SAS, a NOAA Single Particle Soot Photometer (SP2) instrument was utilized onboard NOAA WP-3D research aircraft for measurements of black carbon (BC) aerosol mass and microphysical properties. BC aerosol is emitted into the atmosphere from biomass burning (BB) and incomplete combustion of fossil and biofuel. Hence, BC sources are strongly linked to anthropogenic activity. BC aerosol is currently the second largest anthropogenic climate forcing agent after CO2(g), and its climate impacts, which depend on vertical burden and internal mixing, are not fully understood. In the Southeast, BC aerosol is expected to provide surface area for the condensation of semi-volatile products of VOC oxidation and subsequent formation of secondary organic aerosol (SOA). Hence, BC is expected to impact the haze formation and regional climate. In this work we present an overview of BC measurements during Southeast Nexus (SENEX) study, the NOAA contribution to SAS. Geographical variations in mass mixing ratios, mass size distributions, and mixing state of BC over the Southeast U.S. are discussed. Relationships of BC with carbon monoxide (CO), acetonitrile (ACN) and other trace gases are used to investigate the impacts of urban, BB, natural gas development, and power plant emissions on the distribution and properties of BC aerosol in the region. Among studied urban centers, St. Louis and Atlanta were determined to be the largest source regions of BC. A clear weekend effect in BC mass mixing ratios and microphysical properties was observed in the metropolitan Atlanta region. Compared to BB and urban centers, power plants and natural gas developments

  16. Introductory lecture: atmospheric organic aerosols: insights from the combination of measurements and chemical transport models.

    PubMed

    Pandis, Spyros N; Donahue, Neil M; Murphy, Benjamin N; Riipinen, Ilona; Fountoukis, Christos; Karnezi, Eleni; Patoulias, David; Skyllakou, Ksakousti

    2013-01-01

    The formation, atmospheric evolution, properties, and removal of organic particulate matter remain some of the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Here, we summarize our recent efforts to deal with the chemical complexity of the tens of thousands of organic compounds in the atmosphere using the volatility-oxygen content framework (often called the 2D-Volatility Basis Set, 2D-VBS). Our current ability to measure the ambient OA concentration as a function of its volatility and oxygen to carbon (O:C) ratio is evaluated. The combination of a thermodenuder, isothermal dilution and Aerosol Mass Spectrometry (AMS) together with a mathematical aerosol dynamics model is a promising approach. The development of computational modules based on the 2D-VBS that can be used in chemical transport models (CTMs) is described. Approaches of different complexity are tested against ambient observations, showing the challenge of simulating the complex chemical evolution of atmospheric OA. The results of the simplest approach describing the net change due to functionalization and fragmentation are quite encouraging, reproducing both the observed OA levels and O : C in a variety of conditions. The same CTM coupled with source-apportionment algorithms can be used to gain insights into the travel distances and age of atmospheric OA. We estimate that the average age of OA near the ground in continental locations is 1-2 days and most of it was emitted (either as precursor vapors or particles) hundreds of kilometers away. Condensation of organic vapors on fresh particles is critical for the growth of these new particles to larger sizes and eventually to cloud condensation nuclei (CCN) sizes. The semivolatile organics currently simulated by CTMs are too volatile to condense on these tiny particles with high curvature. We show that chemical aging reactions converting these semivolatile

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phen